THE 
 
 RADICAL THEORY 
 
 IN 
 
 CHEMISTRY. 
 
 BY 
 
 JOHN JOSEPH GRIFFIN, F.C.S., 
 
 HONORARY MEMBER OF THE PHILOSOPHICAL SOCIETY OF GLASGOW. 
 
 LONDON: 
 
 PUBLISHED BY JOHN JOSEPH GRIFFIN, 
 
 119 BUNHILL ROW. 
 
 1858. 
 
 [Th* Author Reserves the Riyht of Publishing Translations in France, and Germany.' 
 
LONDON : PRINTED BY W. CLOWES AND SONS, STAMFORD STREET. 
 
- 
 
 PREFACE. 
 
 Ix this work I propose to prove that the laws of Organic 
 Chemistry are as simple and orderly as the laws of Inorganic 
 Chemistry, and that the confusion which prevails in the former 
 is attributable in no degree to irregularity in organic com- 
 pounds, but to a disregard of the true laws of the science and 
 a devotion to false hypotheses. 
 
 The work includes a critical inquiry into the authority and 
 importance of the doctrines which are commonly accepted by 
 chemists as sound, and of others, which I recommend for 
 adoption, as better proved and of more universal application. 
 
 1 cannot enumerate these new doctrines without encroaching 
 upon the Table of Contents, but I may specify a few ex- 
 amples : 
 
 A new theory of the constitution and atomic measure of 
 
 gaseous salts and radicals. 
 A method of determining the atomic measures and specific 
 
 gravities of compound gases, from their formulas alone. 
 A theory of the origin and metamorphoses of organic 
 
 radicals. 
 
 A theory of vice-radicals. 
 A theory of salts, free from acids and bases. 
 A consistent theory of ammoniums and amidogens, and of 
 
 the salts which are formed by those radicals. 
 A theory of anhydrides, explanatory of the constitution of 
 
 those salts in which both radicals are acid radicals. 
 An explanation of the constitution of the salts which are 
 
 commonly assumed to be produced by certain imaginary 
 
 compounds, called polybasic and conjugated acids. 
 
 a 2 
 
V PREFACE. 
 
 Proof that the results of electrolytic experiments justify 
 
 the adoption of radicals. 
 A demonstration of the impolicy of attempting to separate 
 
 Organic from Inorganic Chemistry. 
 
 A systematic nomenclature, applicable to every descrip- 
 tion of chemical compound. 
 
 I adduce evidence to prove that the following Hypotheses 
 (among many others) propagate Fallacies for Truths, and 
 thereby obstruct the progress of the science : 
 
 That water contains only one atom of each of its two 
 
 elements. 
 
 That elementary atoms combine in multiple proportions. 
 That salts contain acids and bases. 
 That such things exist as sesquioxides, polyatomic 
 
 alcohols, and conjugated and poly basic acids. 
 That all salts are formed on the model of water. 
 That all compounds which contain azote are formed on 
 
 the model of ammonia. 
 That isolated elements do not exist, so that free chlorine 
 
 and free hydrogen are binary compounds. 
 
 Every experiment quoted in this work is derived from the 
 writings of the chemists, whose theories I oppose. The argu- 
 ments rest therefore upon facts which will not be impugned. 
 
 I treat all unsettled and disputed doctrines as if the reader 
 intended to form an independent and impartial opinion upon 
 them. I pay no respect to any other Authority than that of 
 Facts and the Probabilities which arise from concurrent circum- 
 stantial evidence. 
 
 The adoption of the Radical Theory would put an end to 
 much false philosophy, would speedily extend our knowledge 
 of organic compounds, and facilitate the study and improvement 
 of eveiy department of the science. 
 
 Lwigton Lodge, Sy den ham, 
 24th December, 1857. 
 
CONTENTS. 
 
 PAGE 
 
 On the Proximate Constitution of Acids, Bases, and 
 
 Salts . .3 
 
 Reference to the publication by the Author of the theory of hydration of 
 acids and bases in 1834 claim to its recent discovery by M. Gerhardt 
 Professor Clark's original publication of part of the theory in 1826 
 detailed evidence against M. Gerhardt's claim to originality notice of 
 the invention of unitary formulae. 
 
 The Binary Theory of Salts . . . .18 
 
 Dumas's account of the merits and demerits of Lavoisier's theory of acids 
 and bases Davy's theory of salts, page 21, resumed at page 128. 
 
 The Radical Theory 25 
 
 Principles of the radical theory classification of oxygen salts in accordance 
 with the radical theory, 
 
 Atomic Weights of the Elements . . .28 
 
 Table of atomic weights choice of a standard the English formula for 
 water = HO repudiated ; H + HO chosen ; reasons why double equi- 
 valents of certain elements, adopted after Gerhardt basylous and 
 basylic atoms both kinds are radicals illustrations salts of iron. 
 Inquiry, what is meant by protoxides and peroxides ? Sesquioxides 
 repudiated condition of iron in double salts of the so-called sesquioxides 
 investigation of the double and triple cyanides in respect to their 
 proportions of iron great simplification produced in the formulae of the 
 cyanides by using the symbols of the basylic radicals inquiry, whether 
 hydrocyanic acid is monobasic or polybasic ? 
 
 Table of Examples of Compound Organic Radicals 
 and Salts that contain them . . . .44 
 
 Composition, Specific Gravities, Atomic Weights, 
 and Atomic Measures of Gases and Vapours . 49 
 
 Catalogue of 280 gases, showing their composition, atomic weights, atomic 
 measures, theoretical specific gravities H = 1 ; observed specific gravities 
 H 1, and also air = 1; examination of the facts exhibited in the table 
 arrangement of the compounds in eleven groups characters of these 
 groups general results radicals have an atomic measure of one 
 volume salts an atomic measure of two volumes oxides containing 
 one radical are irregular in measure oxygen measures nothing in its 
 
VI CONTENTS. 
 
 PAGE 
 
 gaseous salts inquiry into the power of oxygen considered as an acid- 
 former oxygen never acts as a radical, nor as part of a radical, nor 
 does it affect the equivalence of radicals. 
 
 Examination of the Properties of Organic Radicals . 70 
 
 Table of Radicals arranged in the order of their basicity and acidity 
 importance of the neutral radical vinyl = CH* discrimination of basic 
 radicals from acid radicals reduction of basic radicals to acid radicals 
 reduction of acid radicals to basic radicals experimental reduction of 
 radicals the ketones the aldehydes the vinyl series of radicals a 
 short Catechism for Organic Chemists. 
 
 The Model of Water 82 
 
 What is meant by the model of water great abuse of the term gro- 
 tesque caricatures of the formula by Gerhardt, Odling, and Buff. 
 
 The Construction of Formulae . . . 84 
 
 Systematic Nomenclature . . . . .86 
 The object sought to be attained is an exact and easy method of reading 
 chemical formulae the nomenclature therefore merely proposes to 
 nominate and enumerate the constituents of each compound as set forth 
 in its formula It involves no hypotheses other than those involved in 
 the formulae special contrivance for distinguishing the number of atoms 
 of oxygen examples of names applied to the 11 groups of gaseous salts, 
 previously represented with the ordinary names. 
 
 The Doctrine of Chemical Types and Substitutions . 91 
 Discussion between Berzelius and Dumas how their conflicting views as to 
 radicals and types may be harmonized constitution of the compound 
 chlorine radicals the last subject is resumed at page 131. 
 
 Inquiry into the Causes which modify the Atomic 
 
 Measure of Compound Gases . . . .94 
 Powers of different elements and radicals as exercised in gases carbon, 
 vinyl, succinyl, salicyl, and other gases which have an even number of 
 atoms of hydrogen sulphur nitrogen ammonia gaseous salts of 
 ammonia chlorine, and other halogens and their salts phosphorus 
 arsenic antimony bismuth boron silicon tin titanium tellu- 
 rium selenium zinc mercury determination as to each element or 
 radical f what its atomic measure is when isolated what its measure is 
 when in salts and what condensing power it possesses over the radicals 
 with which it combines. Tabular view of results, which show how to 
 find the specific gravity and atomic measure of a gas, when only its for- 
 mulae is given total insufficiency of the methods in general use for 
 that purpose laws that regulate the atomic mctosure of the vapours of 
 polybasic acids, as enunciated by M. Gerhardt exposition of the falla- 
 cies involved in those laws. 
 
 Applications of the Radical Theory . . .117 
 
 Anhydrides, or anhydrous acids compound anhydrides discussion of 
 the theory of the anhydrides resumed at pages 377 and 480 degrees of 
 oxidation of radicals intermediate metallic oxides aldides, or alde- 
 hydes in general the chromates, illustrating the combination of anhy- 
 drous acids with neutral salts. 
 
CONTENTS. Vii 
 
 PAGE 
 
 Distinction between Analytical Formulae and Synop- 
 tical Formulae . . . . . .127 
 
 The flexibility of the new nomenclature allows names to be written to 
 suit either description of formulae. 
 
 Vice-Radicals 131 
 
 Chloric-radicals zotic-radicals sulphic-radicals metallic vice-radicals. 
 
 The Phosphates 138 
 
 Discussion respecting the nature of bibasic and terbasic salts the three 
 
 kinds of phosphates are models of three forms of salts that frequently 
 
 occur in organic chemistry. 
 
 The Phosphites and Hypophosphites . . .143 
 
 Their composition not yet satisfactorily ascertained. 
 
 The Sulphates 144 
 
 Discussion of the general question respecting the constitution of bibasic 
 salts examination of the arguments by which it has been attempted to 
 prove that sulphuric acid is bibasic Gerhardt's arguments William- 
 son's arguments classification of polybasic sulphates : monobasic, 
 bibasic, tribasic, tetrabasic, pentabasic, hexabasic, heptabasic, and octa- 
 basic conclusion drawn that sulphuric acid is monobasic, and given to 
 form multiple salts nomenclature of the sulphates. 
 
 The Polythionates 156 
 
 Investigation of the individual acids and salts of this extensive series the 
 pentathionates tetrathionates trithionates hyposulphates hypo- 
 sulphites sulphites sulphenetes question whether a multiple number 
 of atoms of sulphur ever acts as a single negative radical importance 
 of strictly discriminating the state of hydration of salts of this series 
 new views respecting these salts and their relations to one another 
 nomenclature of the complex oxy- sulphur salts peculiarities in the 
 saturating capacities of the oxy-sulphur salts. 
 
 The Oxalates 177 
 
 Argument against the alleged bibasic nature of the oxalates classification 
 of multiple oxalates, which are known to be 1, 2, 3, 4, 5, 6, 7, 8, 10, 
 11, and 18 basic conclusion drawn that oxalic acid is monobasic 
 nomenclature. 
 
 The Carbonates . . . . . .183 
 
 The carbonates and bicarbonates shown to be equally bibasic. 
 
 The Chlorides . 186 
 
 The chlorides are salts of a monobasic acid, but occur single, double, 
 triple, and quadruple. 
 
 Theory of Azotic Radicals 189 
 
 Sketch of a new Theory terms defined amidogen ammonium vice- 
 amidogens vice-ammoniums nomenclature 'of vice-amids and vice- 
 ammons varieties limits of the scheme discrimination of vice-amids 
 and vice-ammons relation of the amids to the ammons reciprocal 
 conversion of one into the other double salts that contain ammons 
 
Vlll CONTEXTS. 
 
 PAGE 
 
 and amids nomenclature of such double salts gaseous salts of amido- 
 gen non-volatile salts of ammonium ammoniated salts. 
 
 Examples of Azotic Radicals .... 199 
 
 Three classes of ammonias four classes of salts of vice-ammoniums. 
 
 Investigation of the Compounds which are produced 
 by the abstraction of Water from the normal salts 
 of Ammonia . . . . . . 208 
 
 Amids produced by the abstraction of one atom of HHO from the neutral 
 oxalates of vice-ammoniums amids produced by the abstraction of one 
 atom of HHO from the neutral salts that are formed by normal ammonium 
 with organic acids amids produced by the abstraction of one atom of 
 HHO from the neutral salts that are formed by ammonams with organic 
 acids non-oxidised salts of amids compounds of amids with ammons 
 nitriles investigation of the nitrile theory transmutations of nitro- 
 gen from the ammoniacal condition into the cyanogen condition and 
 back again carbamide imidogen compounds imides aiiiles ami- 
 dogen or amidated acids oxamates oxanilates amidogen acids with 
 compound radicals anilidogen acids with compound radicals. 
 
 Hydramides 228 
 
 Sulphates with Inorganic Vice-Ammons . . 229 
 
 Sulphates of Organic Vice-Ammons and Vice- Amids 231 
 
 Polythionates of Ammonia ..... 233 
 
 Sulphites containing Vice- Amids and Vice-Ammons 237 
 Hyposulphates containing Vice-Amids and Vice- 
 Ammons . . . . . . . 240 
 
 Hyposulphites containing Vice-Ammons and Vice- 
 Amids ';;.' 242 
 
 Sulphenetes containing Vice-Amids . . . 243 
 
 The Cyanides 243 
 
 Single cyanides double cyanides triple cyanides foxu-fold cyanides 
 cyanides in double salts conjugated cyanogen is repudiated. 
 
 The Sulphocyanides 247 
 
 The sulphocyanides explained as double sulphides sulphocyanogen con- 
 sidered to be unreal and unnecessary. 
 
 The Cyanates . . 250 
 
 The Nitrates 251 
 
 The nitrates can be monobasic, terbasic, and bibasic, like the phosphates. 
 They are properly monobasic. , 
 
 The Nitrites 253 
 
 The Oxides and Hydrates of Nitrogen . . 255 
 
 Azotic Radicals in Series . ... 256 
 
CONTENTS. ix 
 
 PACK 
 
 Indigo . . . 257 
 
 The radical is indyl = CH 3 , which produces numerous vice-indyls by 
 substitution of Cl, Br, and S for atoms of H objections to Berzelius's 
 radicals section 1, salts in which indyl is the negative radical section 2, 
 salts in which indylac ZH,CH 3 is the negative radical 'Section 3, 
 salts in which indylac and indylam (ZH 3 ,C 8 H 3 ) act as positive radicals 
 with sulphur as a negative radical section 4, salts in which sulphic- 
 indyl C 8 H 2 S is the negative radical. 
 
 The salts of the last two sections are subject to a modification of the for- 
 mulae in consequence of the recent discovery referred to at pages 
 376, 480, 490. according to which the indyl contained in these salts 
 should be described as being in the condition of a positive radical, and 
 not as in that of a conjugated sulphic acid. The argument respecting 
 the constitution of sulphacetic acid at page 489 explains the difference. 
 
 Aniline . . ... . 274 
 
 Importance of the aniline theory new theory proposed aniline assumed 
 to be the hydride of phenylac = ZH,CH 5 ;H table of the salts of 
 aniline critical notes on the salts of aniline investigation of aniline 
 and its chloric, bromic, and iodic compounds new formulae and new 
 systematic names applied to all the salts of this series - relation of salts 
 of phenylac ZH,C (; H 5 to salts of phenylam ZH 3 ,C 6 H 5 , explaining how 
 hydrated acids convert aniline into normal salts of phenylam. Thus: 
 ZH,C 6 H 5 ;H + H,C1 = ZH 3 ,C 6 H 5 ;C1- details of such normal salts of 
 phenylam, both without and with oxygen sulphanilic acid oxanilide 
 oxanilamide formanilide oxanilic acid nitraniline theory of nitra- 
 niline examined cyanilide melaniline, and its salts varieties of Hof- 
 mann's formulas for melaniline examination of his melaniline theory 
 dicyanomelaniline varieties of formulae given for this salt examination 
 of Hofmann's theory respecting dicyanomelaniline Cyaniline examina- 
 tion of Hofmann's theory of cyaniline anilo-urea, or carbamide-carbani- 
 lide investigation of Hofmann's carbanilide theory its defects the 
 theory that urea is cyanate of ammonia shown to be more in accordance 
 with facts metamorphoses of dicyanomelaniline melanoximide Hof- 
 mann's theory of its production another explanation preferred theory 
 of anilocyanic acid the anilocyanates are probably terbasic cyanates 
 products of the decomposition of melanoximide. 
 
 The Platinum Bases 308 
 
 Theory of the platinum bases causes of the errors which commonly prevail 
 respecting them necessity of admitting the distinction of platous and 
 platic radicals mischiefs caused by the adoption of imaginary acids and 
 bases monstrous formulae given to the imaginary platinum bases 
 platous salts platic salts salts of platousam salts of platicam. 
 
 The Urea Theory 338 
 
 Non-permanent cyanate of ammonia' permanent cyanate of ammonia 
 urea theory chemical reactions of urea summary of evidence respect- 
 ing the constitution of urea proof that it is cyanate of ammonia ex- 
 amples of ureas theory of compound ureas salts of urea. 
 
 Terbasic Cyanates ...... 348 
 
 Examples of terbasic cyanates inquiry into their nature uncertainties 
 respecting them. 
 
X CONTENTS. 
 
 PAGE 
 
 The Carbonates of Ammonia .... 355 
 
 Investigation of twelve varieties of carbonate of ammonia, all shown to be 
 neutral carbonate, or bicarbonate, or mixtures when dried, they are 
 reduced more or less to amidogen salts. 
 
 Carbamie Acid, and the Carbamates . . . 359 
 
 The Ureides 360 
 
 The ureicles are compound ureas, or cyanates of ammonams, which contain 
 an acid radical, and therefore contain one atom of oxygen more than is 
 contained in ureas that are formed by basic radicals this theory is 
 explained at pages 376 and 480. 
 
 The Allophanates or Tetrabasic Cyanates . . 362 
 Table of allophanates inquiry respecting tetrabasic cyanates biuret. 
 
 The Doctrine of Polyatomic Alcohols . . .366 
 Glycol, the Biatomic Alcohol . . .366 
 
 Method of production constitution proof adduced that glycol, the 
 
 biatomic alcohol, is merely vinyl, the monatomic alcohol, disguised under 
 
 a doubled formula. 
 
 The Hydrocarbons which contain an even number of 
 atoms of hydrogen ...... 368 
 
 Professor Miller's argument that these hydrocarbons are equivalent to 
 radicals, and rank between the basic and acid radicals the fallacy of 
 that argument proof adduced that these hydrocarbons are always pairs 
 of radicals examination of examples salts of vinyl acetal propylic 
 glycol and amylic glycol fallacies respecting them. 
 
 Glycerin, the Teratomic Alcohol .... 374 
 
 Argument led, that glycerin is not a teratomic alcohol, but what in cur- 
 rent phraseology is called aterbasic acid table of compounds of glycerin, 
 in eight groups the radical glycyl = C a H 5 , shown to act as the radical 
 of a polybasic acid investigation of forty-three salts of the glycylic 
 acid -glycerides fats theory of their constitution, and transforma- 
 tions uselessness of unitary formulae and of formulae on the model of 
 water the doctrine of polyatomic alcohols is a delusion. 
 
 Recent Proceedings in the French Academy of 
 
 Sciences, respecting the Teratomic Alcohols . 386 
 Attempt to prove that glycerin is a teratomic alcohol, which can combine 
 at once with three different acids. Examples given course of the 
 argument total failure of the evidence to prove the truth of the too 
 hasty assumption of the existence of teratomic powers. 
 
 Theory of Polybasi and Conjugated Acids . . 395 
 Precautions to be taken in the investigation of this subject apparent pro- 
 duction of bibasic and terbasic acids by doubling and tripling the 
 formulae of monobasic acids polybasic acids thus produced are shams, 
 and such shams must be guarded against discrimination of salts which 
 contain uneven numbers of basic and acid radicals. There are two kinds : 
 the bibasic and monacid; the monobasic and biacid reference to the 
 phosphates as standards of monobasic, bibasic, and terbasic salts. 
 
CONTENTS. XI 
 
 PAGE 
 
 Bisulphates of Alcohol Radicals .... 399 
 
 Theory of conjugated sulphates its fallacies Guthrie's electrolytic 
 researches respecting these salts his failure to prove the existence of 
 conjugated acids. 
 
 Professor Kolbe's Copulated Oxalates . . .408 
 The Malic Group of Sails 411 
 
 The malic acid erroneously assumed to be bibasic constitution of the 
 malates the conjugated malates aspartates asparagine maleates 
 funiarates mal-amides and phenyl-amides evidence advanced to prove 
 that malic acid is a double monobasic acid, and that none of the acids 
 of this group are either polybasic or conjugated. 
 
 The Citric Group of Salts . . , . . 424 
 Examples of citrates conjugated citrates citraniles aconites citraoo- 
 nates amidogen and aniline salts of this group investigation of these 
 salts evidence adduced that citric acid is a triple acid, not a tribasic 
 acid, and that it forms no conjugated acids. 
 
 The Succinic Group . . . . . .441 
 
 The succinates adipates suberates sebates proof advanced that these 
 are monobasic the pyrotartrates pimelates anchoates proof that 
 all these are double salts the sulpho -succinates shown to be double or 
 triple salts, but not polybasic nor conjugated. 
 
 The Salicylic Group 455 
 
 Normal salicylates hippurates benzo-glycollates benzo-lactates 
 formo-benzoylates the so-called conjugated silicylates all these salts 
 are shown to be normal salicylates, bibasic in the manner of the car- 
 bonates, and not conjugated. 
 
 The Tartrates 461 
 
 Great variety in the constitution of the tartrates normal, neutral, or 
 monobasic tartrates terbasic tartrates acid tartrates amidogen salts 
 double tartrates conjugated tartrates tetrabasic tartrates double 
 tartrates containing vice-tartryls complex tartrates simplification of 
 the formulae of the tartrates resulting from the use of the symbols of 
 the basylic radicals the tartrates shown to be salts of a monobasic acid, 
 and to enter into no conjugated acids. 
 
 The Xanthates 470 
 
 Sulphocarbonates or sulphoxanthates xanthomethylates xanthates 
 xanthamylates xanthopropylates xanthocetylates sulpho-car- 
 bamates binoxysulphocarbonates oxyxanthates xanthamides con- 
 sideration of the questions, whether sulphide of carbon is a radical 
 or not, and whether sulphic radicals exist xanthates containing basy- 
 lous and basylic radicals remarkable diversity in the common synonyms 
 and formulae of the salts of this group proof that no acid of this group 
 is conjugated. 
 
 The Conjugated Sulpho- Acids ..... 480 
 
 Suroxidation of sulphates which contain acid radicals in place of basic 
 radicals table of salts bisulphates of basic radicals bisulphates of 
 acid radicals double hyposulphates amidogen hyposulphates sul- 
 
Xii CONTEXTS. 
 
 PAGE 
 
 phites containing organic radicals amidogen sulphites methylodi- 
 thionates ethylotrithionates consideration of the question whether the 
 hydrogen of hydrocarbon radicals is replaceable by other complete 
 hydrocarbons consideration of the question whether, in the sulph- 
 acetates, the radical acetyl is present as a basic radical or an acid radical 
 inquiry into the constitution of Buckton and Hofmann's new conju- 
 gated acids the disulphometholic acid, and others of the same series 
 conclusion drawn that these acids are double hyposulphates considera- 
 tion of the conjugated acids formed by organic radicals with sulphurous 
 acid these acids shown to be sulphites total failure of evidence to 
 prove the existence of any conjugated sulpho-acids. 
 
 The Silicates 500 
 
 Recent researches on silica gaseous salts containing silicon determina- 
 tion of the atom, or radical, of silicon constitution of the silico-fluorides 
 simplification of formulae effected by using the basylic radicals con- 
 stitution of silicic acid theoretical constitution of silicates constitution 
 of the chief varieties of known mineral silicates relations of the oxygen 
 in natural silicates rational formulae of the silicates easy transforma- 
 tion of Berzelius's formulae of the silicates into those required by the 
 radical theory resulting simplification unitary formulae most suitable 
 for the silicates investigation of several complex silicates augite lime 
 chabasite soda chabasite vesuvian fuchsite. 
 
 The Aluminous and Aluminic Radicals . .518 
 
 Evidence towards proving the separate existence of an aluminous and an 
 aluminic radical. 
 
 Thoughts on the Origin and Metamorphoses of 
 Organic Radicals . . . . . .519 
 
 The nutriment of plants: sugars, starch, gum, woody fibre metamor- 
 phoses of sugar into fruit essences table of the products of the meta- 
 morphoses of sugar demonstration of the worthlessness of unitary 
 formulae in organic chemistry development of the doctrine of meta- 
 merism suggestion of systematic names for hydrocarbons classifica- 
 tion of organic radicals table of the relations which the organic radicals 
 bear to one another division of organic radicals into fifteen groups 
 theory of the origin of radicals description of each group of radicals 
 distinctions between bases and radicals metamorphoses of radicals 
 conversion of acid radicals into basic radicals and basic radicals into acid 
 radicals splitting up of complex radicals into simpler radicals neces- 
 sity of reform in the formulae and names of compounds belonging to 
 physiological chemistry. 
 
 Daltonism The Atomic Theory The Law of Com- 
 bination in Multiple Proportions . . . 537 
 Professor Miller's account of these laws the law of combination in mul- 
 tiple proportions considered to be fallacious grounds of that opinion 
 the atomic theory unable to prove how much of any single element 
 constitutes a single combining proportion it must consequently be un- 
 able to prove how much constitutes a multiple proportion Dr. Henry's 
 estimation of Dal ton's theory Dalton's matured views and final teaching 
 the radical defect in the atomic theory relation of the atomic weights 
 of elements to the specific gravities of their gases the densities of four 
 
CONTENTS. Xiii 
 
 PAGE 
 
 elementary gases taken as the foundation of a system of atomic weights 
 mode of determining the combining proportions of fixed elements 
 security of this process nature of radicals and of salts fallacies de- 
 pendent upon the law of multiple proportions salts of the sesquioxides 
 general formula of salts inability of the law of multiple proportions 
 to account for the origin of compound organic radicals. 
 
 The Evidence of Electrolysis in favour of the 
 Radical Theory . . . . .547 
 
 Magnus's electrolytic researches Faraday's results Gmelin's summary 
 of facts and arguments particular facts application of electrolytic 
 facts to the support of the radical theory Magnus's experiments prove 
 that chemical radicals are the same as galvanic equivalents investiga- 
 tion of the decomposition of various salts in the galvanic circuit 
 examination of Faraday's laws of electrolysis their failure to prove 
 that water is HO their incompatibility with Magnus's results electro- 
 lytic evidence against the law of combination in multiple proportions 
 reason why Daniell failed to prove the composition of sulphuric acid to 
 be H+SO 4 reconcilement of all the results with the radical theory 
 proof afforded that the formula of water is H+HO, and that all electro- 
 lytic results are in accordance with this formula. 
 
 Catalysis. 560 
 
 Index . . 561 
 
A MEMOIR, containing a succinct account of the principles of the Radical 
 Theory, accompanied by historical notes, in disproof of M. Gerhardt's claim 
 to the invention of the theory of hydration of acids and bases, was presented 
 to the Chemical Society in the month of June, 1855. 
 
 The printing of this Volume was commenced in the Spring of 1856. The 
 Author's illness occasioned an interruption of nearly a year. The work was 
 afterwards slowly proceeded with until the end of the year 1857. 
 
 In consequence of this interruption, and of the progress of the science 
 during the years 1856 and 1857, it happens that the earlier sections of the 
 work are not always in strict accordance with the later sections. Thus, the 
 theory of the Anhydrides and that of the Conjugated Sulpho-acids, as first 
 described, undergo important modifications in the article which commences at 
 page 480. In such cases, the Author's opinions are to be taken as they are 
 expressed in the latest statements. 
 
The Radical Theory in Chemistry. 
 
 On the Proximate Constitution of Acids, Bases, and 
 
 Salts. 
 
 TWENTY-THREE years ago I read, before the Philosophical Society of 
 Glasgow, a paper on " The Proximate Constitution of Chemical Com- 
 pounds," and in the year 1854, I published that Paper, as part of a 
 work entitled "Chemical Recreations''' 
 
 The chemical doctrines which I then advocated differed considerably 
 from the doctrines that were entertained by most chemists of that period, 
 and they met with the hostility which constituted authorities commonly 
 oppose to radical theories and organic changes. The book was well re- 
 ceived by the public, and the edition of 3,000 copies was exhausted in 
 two years ; but as the chief purpose of the work was to teach experi- 
 mental chemistry, when it was reprinted, the theoretical chapter was 
 omitted, and, though I never abandoned my radical theories, I have, 
 from that time to the present, ceased to press them upon the attention 
 of chemists. Even now, after a silence of nearly a quarter of a century, 
 I return to the subject only because I am provoked to it by a challenge 
 from Mr. Charles Gerhard t. I hope, for these reasons, that I shall not 
 be considered importunate, especially as the subject to be discussed is 
 one upon which the minds of philosophers are wholly unsettled, and 
 upon which it is desirable that some intelligible and comprehensive 
 theory should replace the multiform and misty hypotheses by which 
 the chemical world is now governed. 
 
 Mr. Gerhardt's challenge is contained in a paper that was published 
 in Liebig's Annalen der Chemie, for August, 1854, and it runs thus: 
 
 " Mr. Kolbe glows with indignation over what he calls * Williamson's 
 Theory of Water, Ethers, and Acids.' I do not comprehend, how a 
 theory, whose first and weightiest points were demonstrated by me 
 several years ago, is suddenly become * Williamson's ' theory. Now, 
 
 B 2' 
 
4 THEORIES CLAIMED BY ME. GERHARDT. 
 
 who was it that first said, that water was H 2 O, and not HO ; that hy- 
 drate of potash was KHO and not KO,HO ; that oxide of potassium was 
 K 2 O and not KO ; that ether was Ae 2 O and not AeO ; that the so-called 
 aqueous nitric acid was NHO 3 and not K0 5 ,HO, and so forth? Who 
 was it that devised the method of writing which is employed by Wil- 
 liamson and the other English chemists to exhibit the differences of these 
 methods of combination ? 
 
 '* The main point which now divides chemists into two parties, lies in 
 tJie relative atomic weights between oxides and their hydrates, ether and 
 alcohol, the so-called anhydrous and their corresponding hydrated mono- 
 basic acids. According to the old school, all hydrated oxides alcohol 
 as well as the hydrated monobasic acids contain the elements of water. 
 This now did I, before all other chemists, deny. Caustic potash, alcohol, 
 acetic acid, I said, contained no water: Berzelius and the old school 
 doubled the atomic weights of these bodies, and declared that they con- 
 tained water. This is the fundamental difference between the two 
 theories. 
 
 " For a long time, I and Laurent were the only advocates of my 
 opinions. Afterwards Chancel adopted them, and at a later period 
 Williamson." 
 
 Such are Mr. Gerhardt's claims. 
 
 I undertake to reply to them, because I can prove that he has no title 
 to the theories which he so boldly claims. 
 
 As the question must be treated historically, I begin by inquiring, 
 when it was that Mr. Gerhardt himself first published these theories ? 
 He tells us, 1 that it was in the year 1842. I ask, then, did any one else 
 publish the same theories before that year? That is the question to 
 which I am about to reply. 
 
 In the year 1826, Dr. Thomas Clark published in Glasgow, for the 
 use of his students in the Mechanics' Institution, a series of Tables of 
 Chemical Formulse, a copy of which I now reprint. The formulae given 
 in these Tables for water is HO,H ; that for anhydrous potash is PO,P ; 
 that for alcohol is HO ; CH,H ; CH,H,H. Ether and hydrate of potash 
 do not appear in Dr. Clark's Tables ; but the formulae of the hydrated 
 acids, namely of aquafortis, oil of vitriol, oxalic acid, acetic acid, &c., 
 show that all these contain as base a single atom of hydrogen, and are 
 without water. 
 Examples : 
 
 Aquafortis . . . AO,O,0 ; H 
 
 Oil of vitriol . . SO,O; H 
 
 Oxalic acid . . . CO,O ; II 
 
 Acetic acid . . . CH,H,H; CO,O; H 
 
 Comptes Rendus des Travaux de Chimie, 1850, p. 428. 
 
TABLES 
 
 ILLUSTRATIVE OF 
 
 MR. CLARK'S CHEMICAL LECTURES, 
 
 DELIVEEED TO THE 
 
 GLASGOW MECHANICS' INSTITUTION, 
 
 SESSIONS 1826-7, & 1827-8. 
 
 Atomic Weights, or Primitive Combining Proportions of Simple Substances. 
 
 
 
 SIGN. 
 
 
 Aluminum - 
 
 - - 
 
 Al 
 
 7 
 
 Magnesium 
 
 [Ammoniacum (A 
 
 H, H, H, H) 
 
 Am 
 
 9] 
 
 Manganese 
 
 Antimony - 
 
 - 
 
 An 
 
 22 
 
 Mercury 
 
 Arsenic - 
 
 - - 
 
 As 
 
 38 
 
 Molybden 
 
 Azote 
 
 - - 
 
 A 
 
 7 
 
 Nickel 
 
 Barium 
 
 _ 
 
 Ba 
 
 35 
 
 Osmium 
 
 Bismuth 
 
 _ 
 
 Bs 
 
 36 
 
 Oxygen 
 
 Boron 
 
 _ _ 
 
 B 
 
 11 
 
 Palladium 
 
 Bromine 
 
 _ 
 
 Br 
 
 38 
 
 Phosphorus 
 
 Cadmium 
 
 - 
 
 Cd 
 
 28 
 
 Platinum 
 
 Calcium 
 
 _ _ 
 
 Ca 
 
 10 
 
 Potassium 
 
 Carbon - 
 
 _ _ 
 
 C 
 
 6 
 
 Khodium 
 
 Cerium 
 
 _ _ 
 
 Ce 
 
 23 
 
 Selenium 
 
 Chlorine 
 
 _ _ 
 
 Ch 
 
 18 
 
 Silicon 
 
 Chrome 
 
 _ _ 
 
 Chr 
 
 14 
 
 Silver 
 
 Cobalt 
 
 _ _ 
 
 Cb 
 
 15 
 
 Sodium 
 
 Columbium - 
 
 _ _ 
 
 Cl 
 
 92 
 
 Strontium 
 
 Copper - 
 
 - 
 
 Cp 
 
 16 
 
 Sulphur 
 
 Fluorine 
 
 - 
 
 F 
 
 9 
 
 Tellurium 
 
 Glucinum - 
 
 _ _ 
 
 Gc 
 
 13 
 
 Tin - 
 
 Gold 
 
 _ 
 
 G 
 
 33 
 
 Titanium 
 
 Hydrogen - 
 
 
 
 H 
 
 1 
 
 Tungsten 
 
 Iodine - 
 
 _ 
 
 I 
 
 62 
 
 Uranium 
 
 Iridium 
 
 _ _ 
 
 Id 
 
 
 Yttrium 
 
 Iron 
 
 _ _ 
 
 Ir 
 
 14 
 
 Zinc - 
 
 Lead 
 
 _ _ 
 
 Ld 
 
 52 
 
 Zirconium 
 
 Lithium - 
 
 - 
 
 Li 
 
 5 
 
 
 SIGN. 
 
 - 
 
 Mg 
 
 6 
 
 - 
 
 Mn 
 
 14 
 
 _ 
 
 Mr 
 
 50 
 
 _ 
 
 Mo 
 
 24 
 
 _ 
 
 Ni 
 
 15 
 
 _ 
 
 Os 
 
 
 _ 
 
 
 
 8 
 
 _ 
 
 Pd 
 
 28 
 
 _ 
 
 Ph 
 
 16 
 
 _ 
 
 Pt 
 
 24 
 
 _ 
 
 P 
 
 20 
 
 _ 
 
 R 
 
 ? 
 
 _ 
 
 Se 
 
 20 
 
 _ 
 
 Si 
 
 8 
 
 - 
 
 Sv 
 
 55 
 
 _ 
 
 So 
 
 12 
 
 _ 
 
 Sr 
 
 22 
 
 _ 
 
 s 
 
 8 
 
 _ 
 
 Te 
 
 32 
 
 _ 
 
 Tu 
 
 29 
 
 _ 
 
 Tt 
 
 16 
 
 - 
 
 Tg 
 
 48 
 
 _ 
 
 U 
 
 72 
 
 _ 
 
 Y 
 
 16 
 
 _ 
 
 Zn 
 
 16 
 
 - 
 
 Zr 
 
 17 
 
 Gases and Vapours of which one volume corresponds with one atom. 
 
 SIGN. 
 
 Oxygen 
 
 Azote - 
 
 Hydrogen 
 
 Chlorine 
 
 Iodine - - 
 
 Mercury 
 
 Prussine, or Cyanogen 
 
 Sulphurous acid 
 
 Sulphuretted hydrogen 
 
 
 
 A 
 
 H 
 
 Ch 
 
 I 
 
 Mr 
 
 CA 
 
 SO 
 
 SH 
 
 8 
 7 
 
 IS* 
 
 62 
 50 
 13 
 16 
 
 8* 
 

 SIGN. 
 
 
 Seleniuretted hydrogen - - . 
 
 SeH 
 
 
 Nitrous acid - - - 
 
 A 0,0 
 
 23 
 
 Perchloride of tin - 
 
 Ch Tn, Ch 
 
 65 
 
 Perchloride of titanium 
 
 ChTt,Ch 
 
 52 
 
 Chloride of silicium - - 
 
 ChSi,Ch 
 
 44 
 
 Fluoride of silicium 
 
 FSi, F 
 
 26 
 
 Gases and Vapours of which 
 
 two volumes correspond with one atom. 
 
 
 Water - - - - 
 
 HO,H 
 
 9 
 
 Nitric oxide - _ - 
 
 AO 
 
 15 
 
 Nitrous oxide - 
 
 AO.A 
 
 22 
 
 Carbonic oxide _ _ - 
 
 CO 
 
 14 
 
 Carbonic acid _ _ - 
 
 C0,0 
 
 22 
 
 Deutoxide of chlorine 
 
 Ch 0, 
 
 34 
 
 Gas of marshes _ - - 
 
 CH,H,H,H 
 
 8 
 
 Olefiant gas - - 
 
 CH,H,H,H; C 
 
 14 
 
 Alcohol - 
 
 HO; CH,H; C,H,H,H 
 
 23 
 
 Sulphuret of carbon - - 
 
 C S, S, S, S 
 
 38 
 
 Muriatic acid - 
 
 Ch,H 
 
 18^ 
 
 Hydriodine acid - - - 
 
 IH 
 
 62t 
 
 Hydroprussine acid - - 
 
 CA,H 
 
 13^ 
 
 Ammonia - 
 
 AH,H,H 
 
 81 
 
 Phosphuretted hydrogen - 
 
 PhH,H,H? (Dumas) 
 
 17t 
 
 Arseniuretted hydrogen - 
 
 AsH, H,H ( Do. ) 
 
 39' 
 
 Protochloride of phosphorus 
 Protochloride of arsenic - 
 
 Ch, Ph, Ch, Ch 
 Ch As, Ch, Ch 
 
 70 
 93 
 
 Chloride of boron - - - 
 
 Ch B, Ch, Ch 
 
 65 
 
 Fluoride of boron - 
 
 FB,F,F 
 
 28 
 
 Chloride of cyanogen - - 
 
 Ch, C A 
 
 31 
 
 Chloride of carbonic oxide - 
 
 Ch,CO; Ch 
 
 50 
 
 Chloride of olefiaut gas 
 
 Ch(CH,H,H,H; C;)Ch 
 
 5 
 
 Gases and Vapours of which four volumes correspond with one atom. 
 
 Phosphuretted hydrogen, (spon- 1 ph H phHH p hHHH? (Dumas) 51 
 taneously inflammable) / 
 
 Oxides of Lead. 
 
 Brown ----- LdO 60 
 
 Yellow - - LdO, Ld 112 
 
 Intermediate? - LdO,Ld; LdO 172 
 
 Red - - LdO,Ld; LdO; LdO 232 
 
 Peroxide of tin Tn 7 
 
 Protoxide of tin - - TnO,Tn 66 
 
 Titanic acid - - TtO 24 
 
 Silica ----- Si 16 
 
 Sulphurous acid - - - SO 16 
 
 Carbonic acid - - - - C0,0 
 
 Nitrous acid A 0,0 23 
 
 Hydrosulphur acid - - - S H 
 
 Muriatic acid - - - - Ch H 
 
 Hydriodine acid - - - - I H 62 
 
 Hydroprussine acid - - - CA, H 13 
 
 Oil of vitriol SO,0;H 24^ 
 
 Aquafortis - A 0,0, ; H 31 
 
 Chromic acid - - - ChrO,0;H 30 
 
Oxalic acid - - 
 
 Formic acid 
 
 Succinic acid .- - 
 
 Acetic acid - 
 
 Tartaric acid 
 
 Sulphuret of sodium 
 
 Sulphuret of potassium 
 
 Sulphuret of ammoniacum - - 
 
 Sulphuret of barium - 
 
 (The above sulphurets are soluble, 
 Sulphuret of antimony - 
 Sulphuret of copper 
 Sulphuret of copper, with copper - 
 Sulphuret of iron - 
 
 Bisulphuret of lead (pyrites) 
 Sulphuret of lead (galena) 
 Sulphuret of lead, with lead 
 Cinnabar - - - - - 
 
 Ethiop's mineral - - - 
 
 Sulphuret of tin - 
 Mosaic gold - 
 
 Zinc blende - - - 
 
 Copper pyrites - - 
 
 Chloride of sodium - - 
 
 Chloride of potassium - 
 
 Sal ammoniac - 
 
 Chloride of barium - 
 
 Chloride of copper - - - 
 
 Chloride of copper, with copper - 
 
 Chloride of gold - - 
 
 Protochloride of iron - 
 
 Perchloride of iron 
 
 Chloride of lead - 
 
 Corrosive sublimate - - 
 
 Calomel - 
 
 Protochloride of tin - 
 
 Perchloride of tin - 
 
 Chloride of zinc - - 
 
 Sulphate of soda - 
 
 Sulphate of potash 
 
 Sulphate of ammonia 
 
 Sulphate of lead - 
 
 Sulphate of barytes - - - 
 
 Sulphate of lime (alabaster) 
 
 Sulphate of copper 
 
 Sulphate of manganese 
 
 Sulphate of iron - - - - 
 
 Sulphate of zinc - 
 
 Sulphate of magnesia - - 
 
 Sulphate of mercury 
 
 Do. with mercury - - 
 
 Bisulphate of tin - 
 
 Persulphate of iron - - 
 
 Persulphate of manganese - 
 
 Sulphate of chrome 
 
 Sulphate of alumina 
 
 SIGN. 
 
 
 CO,0;H 
 
 22 
 
 H,CO,0 ; H 
 
 23 
 
 CH,H ; C0,0 ; H 
 
 29^- 
 
 CH,H,H ; C0,0 ; H 
 
 30 - 
 
 CH,H; C0,0,0; H? 
 
 37 
 
 SSo 
 
 20 
 
 SP 
 
 28 
 
 SAm 
 
 17 
 
 SBa 
 
 43 
 
 the following are insoluble.} 
 
 
 SAn 
 
 30 
 
 SCp 
 
 24 
 
 SCp,Cp 
 
 40 
 
 Sir 
 
 22 
 
 SIr,S 
 
 30 
 
 SLd 
 
 60 
 
 SLd,Ld 
 
 112 
 
 SMr 
 
 58 
 
 SMr,Mr 
 
 108 
 
 STn 
 
 37 
 
 STn,S 
 
 45 
 
 SZn 
 
 24 
 
 SCp,SIr 
 
 46 
 
 ChSo 
 
 30 
 
 ChP 
 
 38 
 
 ChAm 
 
 27 
 
 ChBa+ W = 53 + 9 
 
 = 62 
 
 ChCp + 1^ W = 34 + 13^ 
 
 = 47* 
 
 ChCp,Cp 
 
 50 
 
 ChG 
 
 51 
 
 Chlr 
 
 32 
 
 Chlr; ChIr,Ch 
 
 82 
 
 ChLd 
 
 70 
 
 ChMr 
 
 68 
 
 ChMr,Mr 
 
 118 
 
 ChTn+2W = 47 + 18 
 
 = 65 
 
 ChTn,Ch 
 
 65 
 
 ChZn 
 
 34 
 
 S0,0; So+5 W = 36 + 45 
 
 = 81 
 
 SO,0;P 
 
 44 
 
 SO,0;Am 
 
 33 
 
 SO,0;Ld 
 
 76 
 
 SO,0;Ba 
 
 59 
 
 SO,0;Ca + W = 34+9 
 
 = 43 
 
 SCsO;Mn + 2j W = 38 + 22^ 
 
 = 6oJ 
 
 SO,0;Ir +3 W = 38 + 27 
 
 = 65 
 
 SO,0;Zn +3i W = 40 + 31 
 SO,0;Mg+3f W = 30 + 3l| 
 SO,0;Mr 
 
 = 6lJ 
 
 74 
 
 SO,0;Mr;Mr 
 
 124 
 
 SO,0;Tn: S0,0 
 
 77 
 
 SO,0;Ir: SO,0;Ir; S0,0 
 
 100 
 
 SO,0;Mn: SO,0;Mn; S0,0 
 
 100 
 
 SO,0;Chr: SO,0;Chr, S0,0 
 
 100 
 
 SO,0;A1: 30,0; Al; S0,0 
 
 86 
 
SIGN. 
 
 Potash alum SO,0;P+SO,0; 
 
 A1;SO,0;A1; S0,0 + 12 W = 44 + 86 + 108 = 
 
 238 
 
 Nitrate of lead 
 
 A0,0 0; Ld 
 
 83 
 
 Nitrate of barytes - - 
 
 A0,0,0; Ba 
 
 66 
 
 Nitrate of strontites 
 
 A0,0,0; Sr + 2 W = 53 + 18 = 
 
 71 
 
 Nitrate of iron 
 
 A0,0,0; Ir + 3* W = 45 + 31* 
 
 76* 
 
 Nitrate of copper - 
 
 A0,0,0; Cp + 3* W = 47 + 31 1 
 
 78| 
 
 Nitrate of potash 
 
 A0,0,0; P 
 
 51 
 
 Nitrate of ammonia - 
 
 A0,0,0; Am 
 
 40 
 
 Nitrate of soda 
 
 A 0,0,0; So 
 
 43 
 
 Nitrate of silver 
 
 A0,0,0; Sv 
 
 86 
 
 Yellow chromate of potash - 
 
 ChrO,0; P 
 
 50 
 
 Yellow chromate of lead 
 
 ChrO,0; Ld 
 
 82 
 
 Oxalate of ammonia - 
 
 C0,0; Am 
 
 31 
 
 Oxalate of lime 
 
 C0,0; Ca 
 
 32 
 
 Acetate of lead 
 
 CH,H,H;CO,0; Ld + 1W = 81* + 13* = 
 
 95 
 
 Acetate of soda 
 
 CH,H,H;CO,0; So + 3 W = 41* + 27 - = 
 
 68* 
 
 Acetate of lime 
 
 CH,H,H;CO,0; Ca -f- 3 W = 394 + 27 = 
 
 66* 
 
 Acetate of copper - 
 
 CH,H,H;CO,0; Cp + W = 45 J + 4^ = 
 
 50 
 
 Tartrate of potash - 
 
 CH,H;CO,0,0; P 
 
 57 
 
 
 Examples of Acid Salts. 
 
 
 Hydrosulphurate of potassium 
 Supersulphate of potash 
 
 SH,SP 
 SO,0;H: SO,0;P 
 
 36* 
 86} 
 
 Red chromate of potash - 
 
 ChrO,0; H: ChrO,0;P ? 
 
 80} 
 
 Cream of tartar 
 
 CH,H;CO,0,0; H: CH,H;CO,0,0; P 
 
 94 
 
 
 Examples of Sub-salts. 
 
 
 Goulard's extract - - 
 
 CH,H,H;CO,0;Ld: LdO,Ld 
 
 193* 
 
 Red chromate of lead 
 
 ChrO,0;Ld: LdO,Ld: ChrO,0;Ld 
 
 276 
 
 Examples of Double Salts. 
 
 Sulphate of potash and magnesia SO,0;P: SO,0;Mg -f- 3 W = 74 + 27 = 
 
 110 
 
 Sulphate of potash and zinc 
 
 SO,0;P: SO,0;Zn + 3W=84 + 27 = 
 
 111 
 
 Ferroprusside of potassium - 
 
 CA,lr;CA,P: CA,P + 1$ W = 93 + l.> = 
 
 106 
 
 Carbonate of lead - . * 
 
 C0,0; Ld 0,Ld 
 
 134 
 
 Carbonate of barytes * - ' 
 
 C0,0; Ba 0,Ba 
 
 100 
 
 Carbonate of strontites 
 
 C0,0; Sr 0,Sr 
 
 74 
 
 Carbonate of lime - 
 
 CO,0;CaO,Ca 
 
 50 
 
 Carbonate of magnesia 
 
 C0,0; MgO,Mg 
 
 42 
 
 Carbonate of iron - 
 
 C0,0; Ir 0,Ir 
 
 58 
 
 Carbonate of manganese 
 
 C0,0; MnO,Mn 
 
 58 
 
 Carbonate of zinc - 
 
 C0,0; Zn 0,Zn 
 
 52 
 
 Carbonate of soda - - 
 
 C0,0; So 0,So + 10 W = 45 + 90 
 
 144 
 
 Do. 
 
 C0,0; So 0,So + 7 W = 54 + 63 
 
 117 
 
 Do. 
 
 C0,0; So 0,So + W = 54 + 9 
 
 63 
 
 Carbonate of potash 
 
 C0,0; P 0,P + 2 W = 70 + 18 
 
 88 
 
 Carbonate of ammonia 
 
 C0,0; AmO; Am 
 
 48 
 
 Supercarbonate of potash - C0,0; HO,H: CO,0;PO,P 
 
 = 101 
 
 E. KIIULL & SON, PRINTERS. 
 
DISPROOF OF GERHARDT'S CLAIMS. 9 
 
 The theories indicated by these formulae were fully developed in Dr. 
 Clark's lectures. I heard some of those lectures delivered ; I had at the 
 period referred to, frequent discussions with Dr. Clark on these subjects ; 
 it is easy to prove the genuineness of the printed tables, because the 
 printer's name is attached ; and the proof is therefore conclusive, that 
 some of the fundamental theories, which Mr. Gerhardt claims to have 
 first published in 1842, were publicly taught by Dr. Clark to the 
 mechanics of Glasgow sixteen years previously. 
 
 All these theories were minutely described in my publication of 1834, 
 with many additions that had occurred to me during several years' con- 
 sideration of the subject. That book attracted the special notice of 
 another French chemist M. Dumas, who, in a course of lectures de- 
 livered in Paris in 1837,* treated it with frequent and unsparing ridicule. 
 Five years afterwards, Mr. Gerhardt discovered the theories of which my 
 book, thus publicly condemned in Paris, contained the full development. 
 
 I shall quote two or three passages from that book to show the won- 
 derful coincidence between Mr. Gerhardt's theories of 1842 and mine of 
 
 1834. 
 Firs 
 
 ?irst example, respecting the Hydrate of Potash. This compound is 
 not contained in Dr. Clark's Tables. Mr. Gerhardt's formula for it is 
 KHO, and he states it to be one of the strong points of his theory, that 
 the hydrated protoxides contain no water. Upon that fundamental idea is 
 founded the modern method of representing the composition of salts in 
 reference to the composition of water, taken as a model. The three 
 formulas 
 
 H Q K o K o 
 
 H U K U H 
 
 contain the essence of this system. Mr. Gerhardt declares that he 
 originated that theory in 1 842 ; but here is my account of it, published 
 eight years previously : 
 
 I quote from Chemical Recreations : 
 
 " The hydrate of a metallic protoxide contains one atom of oxygen, 
 one atom of hydrogen, and one atom of metal. 
 
 " Every chemist but myself assumes the hydrates of metallic 
 protoxides to consist of metallic protoxides combined with water. They 
 make this assumption even in cases where the hydrates have been 
 exposed, under common atmospheric pressure, to a red heat, without 
 suffering decomposition or giving off a particle of steam. . . . But my 
 opinion is, that the hydrates of the metallic protoxides contain neither 
 protoxides nor water, but are constituted of one atom each of metal, 
 oxygen, and hydrogen. This is the ultimate constitution what the 
 proximate constitution is, I cannot tell. It may be KH+O, or KO-}-H, 
 
 1 Lecons sur la Philosophise Chimique, 8vo. Paris, 1837. 
 
10 ON PROXIMATE AND ULTIMATE CONSTITUTION. 
 
 or K+HO; we have no means of determining which. I rest upon the 
 ultimate constitution." l 
 
 What I meant by the difference between the PROXIMATE and ULTI- 
 MATE constitution of a compound, is explained in the following quo- 
 tation : * 
 
 *' I have denounced the doctrine of proximate constitution as the ever- 
 flowing source of chemical blunders, whilst in treating of the limits of 
 combination, and in the discrimination of positive and negative sub- 
 stances, I have admitted the doctrine in its substantial features. Permit 
 me to reconcile these apparent contradictions. 
 
 " According to my theoretical notions, every compound is formed of 
 a positive substance and a negative substance, each of which may be either 
 an element or a compound. Thus the compound AB contains the posi- 
 tive element A and the negative element B. The compound AAB con- 
 tains the positive element A and the comparatively negative compound 
 AB. The compound ABB contains the comparatively positive com- 
 pound AB and the negative element B. Yet this is all matter of theory 
 and opinion, for I am unable to prove that the compound AAB is not 
 formed by the direct combination of AA with B, and the compound 
 ABB by the direct combination of A with BB. The latter is the pre- 
 vailing theory the theory of DALTON ; and though I disbelieve it, and 
 consider it utterly inconsistent with the facts of chemistry, it may be 
 true. But even admitting its truth, the light it throws on chemical 
 composition is a feeble one ; for what does it discover when brought to 
 bear upon the compound ABC ? Does this compound arise from the 
 simultaneous combination of the three elements, or does AB combine 
 with C, or AC with B, or A with BC? And in the case of the com- 
 pound ABCC is this constituted of A+BCC, or AB+CC, or ABC+C, 
 or AC+BC, or AAC+BBCCC? These are cases of perplexity, in the 
 disentanglement of which the atomic theory is of no service. It boots 
 not that we know how many elementary atoms of A,B, and C are contained 
 in a given compound. These are but the ultimate constituents ; and 
 what we want to know is, how these are combined together into proxi- 
 mate constituents. 
 
 " This is a problem for future times to solve, and it is a problem of 
 that importance that we are not warranted in assuming its solution, 
 merely for the purpose of grounding a nomenclature and a system of 
 arrangement upon the assumed solution. Yet this is done in the anti- 
 phlogistic nomenclature and theory. It is assumed that sulphate of 
 barytes contains barytes and sulphuric acid, that nitrate of potash contains 
 potash and nitric acid, that caustic soda contains protoxide of sodium and 
 water; and these assumptions form the groundwork of the French 
 
 1 GRIFFIN, J. J., Chemical Recreations, 7th edit. 1834, page 229. 
 8 Ibid, page 242. 
 
ON PROXIMATE AND ULTIMATE CONSTITUTION. 11 
 
 theory and nomenclature the groundwork of the theory adopted by the 
 gifted Berzelius, who has spent twenty years in vain attempts to esta- 
 blish it. The root of the system of this chemist is, that in the sulphate 
 of lead the oxygen is so divided between the sulphur and the lead, that 
 the portion combined with the former bears to the portion combined 
 with the latter the ratio of 3 to I . I hesitate not to say that this is an 
 assumption incapable of proof. 
 
 " Let us examine the formation of sulphate of lead with a view to 
 discover its proximate constituents : l 
 
 a. When 4 parts of sulphur are converted into sulphuric acid by 
 digestion with nitric acid, and the solution is precipitated by a solution 
 of lead, the resulting sulphate of lead weighs 38, containing 26 of lead, 
 and consequently 8 of oxygen. 
 
 b. When 26 parts of lead are dissolved in nitric acid, and the solution 
 is precipitated by sulphuric acid, or by the solution of a sulphate, the 
 resulting sulphate of lead weighs 38, containing 4 of sulphur, and 8 of 
 oxygen. 
 
 c. When 30 parts of sulphuret of lead, containing lead 26 and sul- 
 phur 4, are converted by oxidation into sulphate of lead, the weight of 
 the product is 38, including 8 of oxygen. 
 
 d. When 35 parts of chloride of lead, which contain chlorine 9 and 
 lead 26, are precipitated by sulphuric acid, the resulting sulphate of lead 
 weighs 38, and contains 4 of sulphur and 8 of oxygen. 
 
 e. When 30 parts of brown oxide of lead, which contains lead 26, 
 oxygen 4, are exposed to an atmosphere of sulphurous acid gas, they 
 absorb 8 parts of that acid, equal to oxygen 4 and sulphur 4, and pro- 
 duce 3 8 parts of sulphate of lead. 
 
 " The information afforded by the above experiments is, that sulphate 
 of lead is composed of 
 
 Lead 26 
 
 Sulphur 4 
 
 Oxygen 8 
 
 38 
 
 But none of these experiments afford the least insight into the manner 
 in which these elements are combined together. The assumption that 
 one-fourth of the oxygen is combined with the lead and three-fourths 
 with the sulphur, is perfectly gratuitous. 
 
 '* The most direct of the whole five experiments, e, is in favour of the 
 
 1 In one of Mr. Gerhardt's publications (his " Introduction to the 
 Study of Unitary Chemistry ") he follows precisely this line of argu- 
 ment, with the single difference of using sulphate of barytes, instead of 
 sulphate of lead, as his illustration. 
 
12 THE NATURE OF HYDRATED ACIDS. 
 
 conclusion that sulphate of lead is PbO-f-SO, a conclusion very different 
 from that which BERZELIUS comes to, but which agrees precisely with 
 my opinion that 26 parts of lead is the quantity which is equivalent in 
 combination to a volume of hydrogen. 
 
 "It is very well to admit the doctrine of proximate constitution in 
 theory, because it is useful in explaining a variety of phenomena, such as 
 chemical combinations, electrical decompositions, and the like. But 
 when we come to arrange the products of chemistry into a system, and 
 to give them systematic names, the only safe way to view them is in 
 relation to their ultimate constitution. It is only by founding a nomen- 
 clature upon this basis, that we can hope to avoid the perplexities which 
 arise from the guess-work of the proximatists. 
 
 " But, it may be said, in rejecting proximate constitution, and stating 
 only the ultimate constitution of compounds, you give false notions of 
 secondary compounds, the properties of which depend upon the nature 
 of their proximate constituents. Thus, sulphate of barytes derives its 
 properties from the sulphuric acid and barytes which compose it. 
 
 " I reply, No ! Sulphate of barytes derives its properties from the 
 barium, sulphur, and oxygen which compose it, just as sulphuric acid 
 and barytes, considered as distinct compounds, derive their properties 
 from the same ultimate elements. In short, viewed in any light, it is 
 the ultimate elements which determine the character of the compounds. 
 There is a fashion, but no utility, in assuming proximate constitution, as 
 the basis of a systematic nomenclature." 
 
 Second Example. Mr. Gerhardt states that he was the first to deny, 
 that the hydrated acids contained the elements of water. In that, how- 
 ever, he is mistaken. Dr. Clark's Tables prove him to have taught that 
 doctrine sixteen years previously, and I will now quote from my Paper 
 of 1834 a full development of the theory which considers hydrated acids 
 as salts of hydrogen. 
 
 [In making this quotation I have changed figures that represent 
 weights of ultimate elements for symbols that represent atoms the 
 change being made according to the atomic weights given in another 
 part of the same book.] 
 
 " The following Table exhibits the constitution of a variety of com- 
 pounds in which hydrogen is an essential constituent. I have inserted a 
 few compounds which contain no hydrogen, for the purpose of contrast- 
 ing their constitution with that of particular hydrogen compounds some- 
 what related to them : 
 
ACIDS SHOWN TO BE SALTS OF HYDROGEX. 
 
 13 
 
 H 
 
 
 
 _ 
 
 Peroxide of Hydrogen. 
 
 H 2 
 
 
 
 _ 
 
 Water. 
 
 H 
 H 
 
 - 
 
 s 
 
 Cl 
 
 Sulphuretted Hydrogen Gas. 
 Muriatic Acid Gas. . 
 
 H 
 
 O 3 
 
 Cl 
 
 Hydrate of Chloric Acid. 
 
 H 
 
 O 3 
 
 N 
 
 Nitric Acid. 
 
 
 Q5 
 
 N 2 
 
 Dry Nitric Acid (chimerical). 
 
 
 O 3 
 
 N,K 
 
 Nitrate of Potash. 
 
 H 
 
 O 2 
 
 N 
 
 Hydrate of Hyponitrous Acid. 
 
 H 
 
 O 2 
 
 S 
 
 Sulphuric Acid. 
 
 
 O 2 
 
 S,K 
 
 Sulphate of Potash. 
 
 H 
 
 O 2 
 
 C 
 
 Effloresced Oxalic Acid. 
 
 H 
 
 
 
 c 
 
 Bicarburet of Hydrogen. 
 
 H 2 
 
 _ 
 
 C 
 
 Olefiant Gas. 
 
 H 4 
 
 _ 
 
 c 
 
 Gas of Marshes. 
 
 H 
 
 - 
 
 C,N 
 
 Prassic Acid. 
 
 H 3 
 
 _ 
 
 N 
 
 Ammonia Gas. 
 
 H 4 
 
 _ 
 
 N 
 
 Ammonium (imaginary). 
 
 H 4 
 
 - 
 
 N,C1 
 
 Sal Ammoniac (Chloride of Ammonium.) 
 
 H 4 
 
 O 3 
 
 N 2 
 
 Nitrate of Ammonia. 
 
 H 
 
 O 
 
 K 
 
 Caustic Potash. 
 
 H 
 
 
 
 Ca 
 
 Hydrate of Lime (Slaked Lime). 
 
 
 
 
 Ca 2 
 
 Anhydrous Lime (Quick Lime). 
 
 H 
 
 O 
 
 Si 
 
 Hydrate of Silica. 
 
 
 
 
 Si 2 
 
 Silica. 
 
 " I beg to call the student's particular attention to this Table, and to 
 the following two memoranda : 
 
 " I. The difference between an ACID (namely, a Tiydrated acid, and a 
 SALT, is this : The former contains one combining proportion of hy- 
 drogen, where the latter, instead of this hydrogen, contains exactly one 
 combining proportion of a metal, all other constituents, both of the acid 
 and salt, remaining the same : 
 
 Examples : 
 
 S,O 2 ,H = Sulphuric Acid. 
 S ,0 2 , K = Sulphate of Potash. 
 
 N,O 3 , H = Nitric Acid. 
 N,O 3 ,K = Nitrate of Potash. 
 
 C,0 2 ,H = Oxalic Acid 
 
 C ,0 s , K = Oxalate of Potash. 
 
14 THEORY OF HYDRATED PROTOXIDES. 
 
 Cl, , H = Muriatic Acid. 
 Cl, , K = Muriate of Potash. 
 
 C1,0 3 ,H = Chloric Acid. 
 C1,O 3 ,K = Chlorate of Potash. 
 
 Numberless illustrations of this sort could be given, but these suffice to 
 confirm the above proposition, viz., that the hydrated acids are simply 
 salts of hydrogen. The reason why I wish to direct the student's atten- 
 tion to this subject is, that in every chemical book which falls into his 
 hand, he will find the absurd proposition gravely inculcated, that the 
 salts CONTAIN acids ; that, for example 
 
 Sulphate of potash contains sulphuric acid, 
 Nitrate of potash contains nitric acid, 
 Oxalate of potash contains oxalic acid, 
 Muriate of potash contains muriatic acid, 
 Chlorate of potash contains chloric acid ; 
 
 all of which assertions are destitute of the smallest foundation in truth, 
 and are, indeed, self-evident impossibilities. In fact, it would be quite 
 as correct to say, that sulphuric acid contains sulphate of potash, as to 
 say that sulphate of potash contains sulphuric acid. The truth is, that 
 they are two distinct compounds, each of which contains the same 
 number of constituent atoms, but neither of which does, or can, form 
 part of the other. 
 
 " II. Secondly, the difference between a hydrate of a protoxide of a 
 metal (such as slaked lime) and an anhydrous protoxide of a metal (such 
 as quicklime) is this : The former contains a combining proportion of 
 hydrogen where the latter contains a combining proportion of a metal. 
 The difference between a hydrated protoxide and an anhydrous protoxide 
 is, therefore, the same as the difference between an acid and a salt. In 
 both cases, one of the compounds contains a combining proportion of 
 hydrogen, which is replaced in the other by a combining proportion of a 
 metal. 
 
 EXAMPLE : 
 
 Ca,H,O Hydrate of lime. 
 
 Ca,Ca,0 .... Anhydrous lime. 
 
 *' This is the case with all the metallic protoxides. It is needless to 
 incumber the reasoning with illustrations. 
 
 " These hydrates of protoxides contain no water, for they contain but 
 one proportion of hydrogen, whereas water contains two proportions. 
 Yet they give off water when exposed to heat, and they produce nothing 
 else than anhydrous protoxides. There is no difficulty in ascertaining 
 how this effect is produced, or in showing the source of the constituents 
 from which the water is produced by this experiment : 
 
CLASSIFICATION OF OXYGEN SALTS. 15 
 
 Two proportions of Hydrate of 
 Lime. 
 CaHO 
 CaHO 
 
 What they produce by expo- 
 sure to heat. 
 CaCaO 
 HHO 
 
 " The greater part of the numerous acids and salts which contain 
 oxygen as a constituent, appear to fall within the limits of the following 
 scheme, in which M signifies the metal or hydrogen (i. e. the electro- 
 positive constituent), R the radical of the salt, and the oxygen ; the 
 figures denoting the number of atoms present of the element after which 
 they stand : 
 
 CLASS I. MMRK) 1 . Silicates. Many of the salts in which both M 
 
 and R are metals. Hyposulphites. 
 II. M'R'O 2 . Sulphates. Oxalates. Chlorites. Hyponitrites 
 
 (Nitrites). Manganesates. Seleniates. 
 III. M'R'O 3 . Nitrates. Chlorates, lodates. Bromates. 
 IV. M'R 1 4 . Perchlorates. 
 ,, V. M 2 R 1 O 3 . These are a species of basic salts of Class 2, 
 
 namely, MO + RO + MO. Carbonates. 
 VI. M 1 R 2 O 3 . These are a species of acid salts of Class 2, 
 
 namely, MO -f RO -f RO. Many metallic 
 
 salts. Hyposulphates. 
 ,,VH. M^O 3 . Sulphites. Selenites. 
 
 " The SUPEK- or El-salts commonly contain an atom of a metallic salt 
 and an atom of a hydrogen salt. Thus, bisulphate of potash contains an 
 atom of sulphate of potash, and an atom of oil of vitriol ; binoxalate of 
 soda contains an atom of oxalic acid, and an atom of oxalate of soda. 
 
 " I think that the word ACID, taken as a substantive name, ought to 
 be disused in chemistry. It has done mischief. It ought to be em- 
 ployed only as denoting a quality." l 
 
 Such is the theory of acids and salts, as advocated by me in 1834. 
 With what justice can M. Gerhard t proclaim, that the first and 
 weightiest points of this theory were originally demonstrated by him in 
 1842? 
 
 I have yet another claim to examine. " Who was it," asks M. Ger- 
 hardt, " that devised the method of writing, which is employed by 
 Williamson and the other English chemists to exhibit the differences of 
 these methods of combination ?" 
 
 Now there are two " methods of writing " to be noticed in M. Ger- 
 hardt's publications. The first consists in writing the formulae of 
 
 1 GRIFFIN, J. J., Chemical Recreations, 7th edit., 1834, pp. 92-6. 
 
16 METHODS OF WRITING FORMULA. 
 
 chemical compounds in a ternary form, as if the symbols were placed at 
 the three angles of a triangle, ^ O. 
 
 The other method of writing consists in constructing formulae in the 
 manner which Gerhardt and Laurent term UNITARY fwmulce. These 
 formulas are framed in accordance with the following hypotheses: 
 namely, that salts do not consist of acids and bases ; that we know 
 nothing of the proximate constitution of salts ; that it is impossible to 
 determine in what manner the atoms of the ultimate elements of salts are 
 grouped together ; that, consequently, the construction of dualistic for- 
 mulae, which affect to explain the constitution of salts, is unwarranted ; 
 and, finally, that the symbols composing each formula should be made 
 to represent only a single molecule. 
 
 Here then we have two decidedly different methods of writing. We 
 have the unitary system, founded upon the know-nothing principle, and 
 we have the ternary system, founded upon that perfect knowledge of 
 proximate constitution, which enables the chemist unerringly to divide 
 the components of every salt into three distinct portions, upon the model 
 of water. 
 
 I am not quite certain which of these two " methods of writing " it is 
 that M. Gerhardt claims to have invented; but, if I may judge from 
 the formulae commonly employed by Professor Williamson, I must con- 
 clude that it is the triangular system to which he refers. The invention 
 of that kind of formula may, for aught I know, be due to M. Gerhardt. 
 It certainly does not belong to me ; and, for reasons that I shall hereafter 
 state, I disapprove of it. 
 
 But the ternary formulae are only of recent invention. The formulae 
 that M. Gerhardt used for years previously, and which he strongly re- 
 commended in his Journal, are the unitary formulae, in the construction 
 of which he recommends especial care to be taken, to give no indication 
 of the proximate constitution of the compounds which the formulae are 
 meant to represent. 
 
 In expressing an opinion adverse to such unitary formulae, I no doubt 
 agree with the general body of chemists ; but treating the question, as I 
 do now, historically, truth obliges me to admit, that, for their introduc- 
 tion to chemists, it is not M. Gerhardt, but I that am responsible. The 
 evidence of this fact is contained in the extract from my Romance of 
 Chemistry, which I have quoted at page 10. In that article I dis- 
 cussed the question of proximate and ultimate constitution, and after 
 showing that the theory which assumes that salts consist of acids and 
 bases, is one that does not admit of proof, I recommended that the for- 
 mulae of compounds should in all cases be made to represent only their 
 ultimate elements. I added, indeed, that such formula? should be written 
 in a systematic manner (and not designedly hap-hazard as Mr. Laurent 
 advises), but still I recommended the formulae to be so written as to express 
 
CONCLUSIVE EVIDENCE AGAINST UNITARY FORMULAE. 17 
 
 no theory of the proximate constitution of the compounds ; and in order 
 to show that the system thus recommended was quite practical, I pre- 
 sented in Chemical Recreations a series of tables of unitary formulae, re- 
 presenting nearly 800 of the then best known compounds of inorganic 
 chemistry, to which department of chemistry alone, did I apply the 
 unitary system. That was in the year 1834. Reconsidering the matter 
 in 1856, and including in the reconsideration what is now known of the 
 nature and constitution of the hydrocarbons and other compound 
 radicals, I am of opinion that unitary formulae are equally inapplicable to 
 organic and to inorganic compounds. We now possess, thanks to the 
 discoveries made in organic chemistry, many of them due to Gerhardt, 
 much positive knowledge of the proximate constitution of chemical com- 
 pounds, and this knowledge the use of unitary formulae would hide or 
 mystify. A mere glance at Gmelin's account of Isomerism, Polymerism, 
 and Metamerism, 1 affords conclusive evidence of the worthlessness of 
 unitary formulae in organic chemistry, since the cases are numerous in 
 which a single unitary formula would indicate two, three, or four dif- 
 ferent organic compounds. Thus, the formula C 6 H 12 O 2 would repre- 
 sent 
 
 Butyrate of ethyl . . . C 2 H 5 ,C 4 H 7 2 . 
 
 Formiateofamyl . . . C 5 H l ',CHO a . 
 
 Valerate of methyl . . CH 3 ,C 5 H 9 O 2 . 
 
 Hydrated caproic acid . H,C 6 H U O 2 . 
 
 In this case, eight well-known radicals possessed of highly-characteristic 
 properties would be smothered by the unitary formula, C 6 H 12 O 2 . Whole 
 pages of similar difficulties could be quoted ; but it is needless to quote 
 them, when a single example extinguishes all faith in the precision and 
 perspicuity of that " method of writing," which is called unitai~y. 
 
 These particulars constitute my reply to Mr. Gerhardt's challenge. 
 
 He asked, who first published the unitary theory of hydration ? I 
 reply, that the unitary theory of hydrated Acids was first published by 
 Dr. Clark, and that of hydrated Bases by me. Mr. Gerhardt took up 
 these theories when they were neglected or decried by other chemists, 
 and, in conjunction with Laurent, applied them to organic chemistry, 
 and used them as a guide to numerous and brilliant discoveries. That 
 is a real merit, which I esteem. He did chemists another important 
 service, which many have ridiculed and few have properly appreciated. 
 He sho\ved how they could get rid of those troublesome hypothetical 
 compounds, the sesquioxides. For that service chemists will yet thank 
 him. But his challenge to the world, to disprove his claim to the 
 invention of the theories of hydration that I have cited in these pages is 
 unjust to Dr. Clark and to me. 
 
 1 Gmelin's Handbook of Chemistry, vii. 66. 
 
 C 
 
18 
 
 The Binary Theory of Salts. 
 
 I have already mentioned that my attack on Lavoisier's theory of the 
 salts was treated by M. Dumas with ridicule ; but, notwithstanding his 
 expressed contempt, my speculations appear to have roused him to con- 
 sider how far they might endanger the continued acceptability of Lavoi- 
 sier's theory. He describes himself to have been actuated by the argu- 
 ments of Davy and Dulong ; but these chemists had published their 
 theories twenty years before, and I might ask, how it happened that 
 they remained without reply from 1816 to 1837? Was it not that my 
 paper first brought the subject distinctly into public notice? That I 
 may not be charged with undue presumption in claiming the credit of 
 having first drawn attention to this subject, I will point out the fact, 
 that none of the following systematic works contain any allusion to the 
 binary theory of the salts as propounded by Davy and Dulong, or 
 express any doubt of the absolute perfection of the theory of Lavoisier. 
 Dumas, Traite de Chimie appliquee aux arts. Liege, 1848. Reprinted 
 
 from the Paris edition of about 1830. 
 Thenard, Traite de Chimie Elementaire. Paris, 1827. 
 Gay-Lussac, Cours de Chimie, professe a la Faculte des Sciences, com- 
 prenant 1'histoire des sels, la Chimie veg^tale et animale. Paris, 
 1833. The lectures were delivered in 1828. 
 Berzelius, Lehrbuch der Chemie, ubersetzt von F. Wohler. Dresden, 
 
 1831. 
 
 Gmelin, Handbuch der theoretischen Chemie. Frankfort, 1827. 
 Scliubarih, Elemente der technischen Chemie. Berlin, 1835. 
 Brande, Manual of Chemistry. London, 1830. 
 Henry ) Elements of Experimental Chemistry. London, 1829. 
 Thomson, System of Chemistry of Inorganic Bodies. London, 1831. 
 
 If the Binary Theory of Salts was clearly explained, and Lavoisier's 
 theory as clearly refuted by Davy and Dulong in 1815 and 1816, how 
 came all these eminent compilers of systems to take no notice of circum- 
 stances so remarkable ? 
 
 M. Dumas discussed the question as follows : 
 " I do not," he says, 1 " undertake to demonstrate that the system of 
 Lavoisier on the constitution of the salts is exact. It was established 
 on a principle of convenience. It is not based upon peremptory proofs ; 
 but I willingly undertake to show that, before all other systems that 
 have been proposed, there rise objections of still greater force than those 
 which rest against the theory of Lavoisier. 
 
 " Let us commence with the system of Davy, to the support of 
 
 1 Dumas, Leons sur la Philosophic Chimique. 8vo. Paris, 1837, 
 P- 337- 
 
THE BINARY THEORY OF SALTS. 19 
 
 which Dulong has lent his powerful aid. According to Lavoisier there 
 are only oxygen acids. Davy said, I will show you that all acids are 
 hydrogen acids. You believe, said he, that the compound denoted by 
 SO 3 is an acid. In that belief you are entirely mistaken. SO 3 is not 
 an acid. I defy you to show me the characters of an acid in that com- 
 pound. And strange to say, if we accepted Davy's challenge, we 
 should be powerless ; for it is really impossible to prove that anhydrous 
 sulphuric acid is an acid. 
 
 " The true acid, said Davy, is the ordinary liquid acid, SO 3 , H ? O. 
 But he wrote it in another manner, thus, SO 4 4-H 2 . You will readily 
 conceive that this acid in contact with the bases ought to behave like 
 other hydracids. Its hydrogen would form water with the oxygen of 
 the base, and its radical SO 4 would combine with the metal ; so that 
 the substance that we call sulphate of lead, would not be constituted like 
 SC^+PbO, but like S0 4 +Pb. 
 
 " Dulong supported the ideas of Davy by considerations on the 
 oxalates which, on Davy's system, would result from the combination of 
 carbonic acid with the metals ; a view which gives a ready explanation 
 of the properties of the oxalates. 
 
 "It is difficult to attack this theory of Davy's. It appears to be 
 so well founded. It is so rational. It so greatly simplifies chemistry. 
 It leaves us none but hydracids. All saline compounds are brought to 
 one formula, or rather salts are abolished, and we have only binaries; for 
 the bodies regarded as salts become the analogues of chloride of sodium. 
 
 " We are tempted to adopt this theory, or at least to remain undecided 
 between it and the theory of Lavoisier. 
 
 " Nevertheless, reflection shows us two motives that repel this system ; 
 motives so powerful, that to me they appear decisive. 
 
 " The first objection is, that it is necessary to admit the existence of a 
 number of bodies that we have never seen, and which we need never 
 expect to see per-sulphuric acid, per-nitric acid, per-carbonic acid, &c. 
 In a word, every oxacid would presume the existence of another com- 
 pound containing one extra proportion of oxygen. Now, I declare, that 
 whenever a theory requires the admission of unknown bodies, we ought 
 to distrust it. We ought to give no assent to it, except with the 
 greatest reserve. We should not assent until it is impossible to abstain 
 from doing so, or at least we should assent only in presence of the most 
 pressing analogies. The more a theory gives origin to imaginary bodies, 
 the more we should control our credence. By acting otherwise, we 
 should fall back into the inconveniences of phlogiston ; and, in this case, 
 we should not have merely one phlogiston to trouble us, we should 
 have a cloud of phlogistons. The unknown compounds would be 
 nearly as numerous as the known compounds ; and thence would arise 
 a confusion and embarrassment for science to which we ought not to 
 resign ourselves, except in obedience to a real and imperative necessity. 
 
 c2 
 
 \ 
 
20 THE BINARY THEORY OF SALTS. 
 
 *' There is another reason which augments the improbability of these 
 hypotheses. Recently, it has been shown that phosphoric acid, dissolved 
 in water, can assume three different states, in each of which it manifests 
 peculiar properties. In fact, it forms three distinct hydrates 
 
 Ph 2 5 , 3 H 2 O Ph 2 5 , 2H 2 Ph 2 5 ,H 2 0: 
 
 The first of these hydrates has received the name of common phosphoric 
 acid ; the second, of pyrophosphoric acid ; and the third, of metaphos- 
 phoric acid. These three acids produce three different sorts of salts, in 
 which the water originally combined with the acids, is replaced by bases, 
 atom for atom, either partially or totally. Moreover, the three varieties 
 of acid pass readily from any one condition into the others, either from 
 loss of water by calcination, or from gain of water by prolonged contact 
 with that liquid. There consequently exists, on the one hand, incon- 
 testable differences among them, and on the other hand, indications of 
 great natural resemblances. The simple formulas commonly assigned to 
 these acids, exhibiting differences which we may compare to those that 
 exist between alcohol and ether, present an intelligible account of their 
 common features of agreement. But if, instead of considering these 
 compounds as hydrates of the same oxacid, we treat them as different 
 hydracids, the formulae become 
 
 Ph 2 8 ,H 6 Ph 2 7 ,H 4 Ph 2 6 ,H 2 . 
 
 Here we perceive grave changes in nature for bodies that pass so easily 
 from one state to the other. We admit differences in composition of the 
 first importance to explain differences in properties of very secondary im- 
 portance. The effect is by no means in proportion to the cause. 
 
 " I insist upon these arguments, because I can find no others to oppose 
 to the system maintained by Davy and Dulong. The question is there- 
 fore not decided. It is possible that this theory may suddenly rise 
 triumphant, supported by some discovery of a nature to give it new 
 force. But at present, I think it should be rejected, because of that 
 innumerable multitude of imaginary compounds which it calls into exist- 
 ence. If I could see only a part of these compounds, I should have less 
 reluctance to believe in the existence of the rest." 
 
 In this passage Dumas ascribes the binary theory of salts to Davy, 
 into whose mouth he puts a speech, which would doubtless have 
 astonished the Fellows of the Royal Society, unused as they are to thea- 
 trical displays. I have looked in vain through Davy's work to find the 
 challenge which Dumas ascribes to him. Most chemists who have dis- 
 cussed this subject, since Dumas published the remarks which I have 
 quoted, refer to Davy as the originator of the binary theory, but neither 
 Graham, nor Kane, nor Miller, quote, or even refer to, the terms in 
 which Davy set forth his doctrine. The following passages are the most 
 explicit on this subject that I can find in Davy's works. 
 
SIR H. DAVY'S THEORY OF SALTS. 21 
 
 " It appears that this new substance [one of the gaseous compounds 
 of chlorine and oxygen], though it contains four proportions of oxygen, 
 is not an acid ; and hence it is probable, that the acid fluid compound 
 of oxygen, chlorine, and water, which M. Gay Lussac calls chloric acid, 
 owes its acid powers to combined hydrogen, and that it is analogous to 
 the other hyperoxymuriates [chlorates], which are triple compounds of 
 inflammable bases, chlorine, and oxygen, in which the base and the 
 chlorine determine the character of the compound. Muriate of potassa 
 is a perfectly neutral body ; and when six proportions of oxygen are 
 added to it, it still remains neutral. Muriatic acid (chlorine and hy- 
 drogen) is a strong acid ; and according to the relation above stated, it 
 ought not to lose its acid powers by the addition of six proportions of 
 oxygen. Till a pure combination of chlorine and oxygen is obtained, 
 possessed of acid properties, we have no right to say that chlorine is 
 capable of being acidified by oxygen, and that an acid compound exists 
 in the hyperoxymuriates. We know that chlorine is capable of being 
 converted into an acid by hydrogen, and, as I mentioned in my last 
 paper, where this principle exists, its energies ought not to be over- 
 looked ; and all the new facts confirm an opinion which I have more 
 than once before submitted to the consideration of the Society, namely, 
 that acidity does not depend upon any peculiar elementary substance, but 
 upon peculiar combinations of various substances." Phil. Trans., read 
 May 4, 1815. 
 
 " I have discovered a gaseous combination of four proportions of 
 oxygen, and one of chlorine, which has no acid properties. M. Gay 
 Lussac has discovered a compound of two proportions of hydrogen, one 
 of chlorine, and six of oxygen, which has acid properties ; but he con- 
 siders this substance merely as chlorine acidified by oxygen, and neglects 
 the hydrogen, without which, however, he allows it cannot exist. He 
 supposes that this acid of one proportion of chlorine and five of oxygen, 
 exists in all the hyperoxymuriates, but he does not support his suppo- 
 sition by any proof. The hyperoxymuriates are, as I showed six years 
 ago, composed of one proportion of chlorine, one of a basis, and six of 
 oxygen. Hydrogen, in M. Gay Lussac's chloric acid, may be considered 
 as acting the part of a base ; and it is an important circumstance in the 
 law of definite proportions, that when one metallic or inflammable basis 
 combines with certain proportions of a compound, all others combine 
 with the same proportions. 
 
 " M. Gay Lussac states, that if chloric acid be not admitted as a pure 
 combination of chlorine and oxygen, neither can the nitric or sulphuric 
 acids be admitted as pure combinations of oxygen. This is perfectly 
 obvious. An acid composed of five proportions of oxygen and one of 
 nitrogen is altogether hypothetical ; and it is a simple statement of facts 
 to say that liquid nitric acid is a compound of two proportions of hy- 
 drogen, one of azote, and six of oxygen ; and, as I showed long ago, the 
 
22 SIR H. DAVY'S THEORY OF SALTS. 
 
 only difference between nitre and hyperoxymuriate of potasli is, that one 
 contains a proportion of azote, and the other a proportion of chlorine. 
 
 " There are very few of the substances which have always been con- 
 sidered as neutral salts, that really contain the acids and the alkalies from 
 which they are formed. The muriates and fluates must be admitted to 
 contain neither acid nor alkaline bases. Most of the prussiates, M. Gay 
 Lussac has lately shown, are in the same case. Nitric and sulphuric 
 acids cannot be procured from nitrates and sulphates without the inter- 
 vention of some body containing hydrogen ; and if nitrate of ammonia 
 were to be judged of from the results of its decomposition, it must be 
 regarded as a compound of water and nitrous oxide. 
 
 " Only those acids which are compounded of oxygen and inflammable 
 bases appear to enter into combination with the fixed alkalies and alka- 
 line earths without alteration, and it is impossible to define the nature 
 of the arrangement of the elements in their neutral compounds. The 
 phosphate and carbonate of lime have much less the character attributed 
 to neutro-saline bodies than calcane (muriate of lime), and yet this last 
 body is not known to contain acid or alkaline matter. The chloriodic 
 acid, the phosganic acid, and the binary acids containing hydrogen, com- 
 bine with ammonia without decomposition, but they appear to be de- 
 composed in acting upon the fixed alkalies or alkaline earths ; and yet 
 the solid substances they form have all the characters which were for- 
 merly regarded as peculiar to neutral salts, consisting of acids and 
 alkalies, though they none of them contain the acids, and only the two 
 first of the series the alkalies, from which they are formed. 
 
 " The substitution of analogy for fact is the bane of chemical philo- 
 sophy ; the legitimate use of analogy is to connect facts together, and to 
 guide to new experiments." On the Constitution of Acids. Journal of 
 Science and the Arts (1816), Vol. I. art. xviii. 
 
 These passages show that Davy disputed the doctrine that salts con- 
 sist of acids and bases, but they cannot be said to show, that he formally 
 and explicitly recommended any other doctrine. He confines himself 
 to statements of the ultimate composition of salts. He does not say, as 
 Dumas and his later commentators make him say, that the oxygen of a salt 
 is all combined with the acid radical, that nitre is K-J-NO 6 , and that chlorate 
 of potash is K-f-CIO 6 . What he says is, that chlorate of potash is 
 Cl l + K l -f-O 6 , that nitre is N l -fK x +O 8 , that liquid nitric acid is H 2 + 
 N l -f-0 6 . He thus makes two proportions of hydrogen equivalent to 
 one proportion of potassium. He says also that the chlorates are triple 
 compounds, not that they are Unary compounds of K+C1O 6 . It is, 
 however, to this paper of Davy's, on the Constitution of the Acids, that 
 Gmelin 1 refers, as containing his suggestion of the binary theoiy of 
 salts, and I have failed to find any more explicit statement elsewhere in 
 
 1 Handbook of Chemistry, ii. 15. 
 
LOXGCHAMP'S THEORY OF SALTS. 23 
 
 Davy's works. It consequently appears to me that Davy had no specific 
 theory in his mind, and that his main intention was to dispute the 
 accuracy of M. Gay Lussac's proposition, that chlorine could be acidified 
 by oxygen ; but at any rate his views, as expressed in these quotations, 
 differ essentially from those subsequently published by Dr. Clark and 
 myself, and which have been appropriated and claimed by Mr. Gerhardt. 
 Davy certainly did not double the atomic weight of oxygen so as to reduce 
 the total number of atoms of oxygen contained in the chlorates and 
 nitrates from six to three, nor did he show that the acids corresponding 
 to these salts contained a single atom of hydrogen as base and no water, 
 nor that the hydrate of potash contained a single atom of hydrogen and 
 no water. The peculiar theory of hydration first published by Dr. Clark, 
 afterwards developed by myself, and now claimed by Mr. Gerhardt, is 
 consequently a different theory from that suggested by Davy and dis- 
 cussed by Dumas. I have not seen the paper published by Dulong. 
 
 After discussing Davy's theory of the salts, M. Dumas proceeded to 
 discuss another theory, which, he says, is due to M. Longchamp. I do 
 not know where the original is to be found, and cannot tell whether or 
 not M. Longchamp's theory is explained fairly. But here is M. Dumas' 
 account of it, written in terms which I presume were intended to encou- 
 rage M. Longchamp in the pursuit of science. 
 
 " We have seen," he says, 1 " that Davy, in adjusting the composition 
 of the salts, took the oxygen of the base to add it to that of the acid. 2 
 M. Longchamp has inverted that process. He wishes us to carry from 
 the acid to the base as much oxygen as that which it already contains. 
 According to him, sulphuric acid and protoxide of lead, combine to pro- 
 duce a compound of sulphurous acid and brown oxide of lead, the 
 formula of which ought to be written thus SO 2 ,PbO 2 . The sulphuric 
 acid of commerce becomes a combination of sulphurous acid and oxy- 
 genated water: SO 2 ,H' 2 O 2 . This is therefore the hypothesis of Davy 
 turned topsy-turvy. 
 
 " According to this plan, if you take sulphate of sesquioxide of man- 
 ganese, which is represented by 3SO 3 ,Mn 2 O 3 , you are to see in it what 
 is indicated by the formula 3S0 2 ,Mn 9 O 6 . After this transformation, you 
 perceive that you have a very strong acid, the manganic acid, playing 
 the part of base vis-a-vis to a very weak acid, the sulphurous acid ; and, 
 above all, that these are two acids which cannot exist together, since 
 sulphurous acid reduces manganic acid to the state of protoxide of man- 
 ganese. 
 
 " Again, suppose you have sulphate of alumina. That salt is no 
 longer 3S0 3 ,A1 2 3 , it is become 38O 2 ,AP0 6 . Here behold A1 2 O 6 , a 
 
 1 Le9ons sur la Philosophic Chimique, 8vo. Paris, 1837, p. 344. 
 
 2 It would be just as accurate to say that he took the oxygen of the 
 acid to add it to that of the base. J. J. G. 
 
24 LONGCHAMP'S THEORY OF SALTS. 
 
 compound that nobody knows, and the existence of which lias never 
 been suspected. There would be a multitude of similar changes ; for it 
 would be necessary that every salifiable oxide had a corresponding oxide 
 containing double the quantity of oxygen, while for each acid susceptible 
 of combination with bases, it would be necessary to find another com- 
 pound possessing an atom of oxygen less. We should be forced to admit 
 the existence of FeO 2 , FeO 6 , G1 2 6 , MgO 2 , KO 2 , c., &c., and of Ph 2 O 4 , 
 Ph 2 2 , &c. 
 
 *' It is useless to insist farther on the improbabilities of this theory, so 
 much less happy than that of Davy, and which presents nothing philo- 
 sophical." 
 
 I shall not dwell on the sarcastic style, but consider the substance of 
 this criticism. 
 
 According to Dumas, it is monstrously absurd to suppose that sul- 
 phate of lead contains sulphurous acid and brown oxide of lead. It is 
 monstrously absurd to suppose that oil of vitriol contains sulphurous acid 
 and oxygenated water. According to Dumas, you ought to crucify at 
 the Sorbonne the man who proposes things so improbable and so unphi- 
 losophical. But let us appeal from rhetoric to facts : 
 
 " The peroxide of lead gives rise to some peculiar and remarkable 
 reactions ; sulphurous acid converts it instantly into sulphate of lead. 
 There is even ignition at the moment of combination." DUMAS, Traite 
 de Chimie (Liege, 1848), torn. III., p. 401. 
 
 " Scarcely is sulphurous acid brought into contact with peroxide of 
 hydrogen, even diluted with much water, when its odour disappears, 
 and it passes into the state of sulphuric acid." THENAUD, Traite de 
 Chimie, (Paris, 1827), torn. II, p. 87. 
 
 The exact opposition of the facts to the rhetoric renders comment un- 
 necessary. 
 
 Dumas's other examples are equally extravagant. The formula of the 
 sulphate of sesquioxide of manganese, 3S0 3 ,Mn 2 3 is, as he admits, a 
 thing of " convenience," not the representation of a fact. As a mere 
 hypothesis, it is liable to be dealt with unceremoniously. I shall 
 show in the course of this inquiry, that the quantity of manganese con- 
 tained in this salt, in combination with 3 atoms of sulphur, is not 2 
 atoms, but 3 atoms of manganese ; that the quantity of oxygen is not 
 j 2 atoms but 6 atoms ; that the ultimate elements are therefore, 
 S 3 Mn 3 O 6 , which formula divided by 3, gives SMnO*, or according to the 
 despised theory of M. Longchamp, MnO + SO, in which we have not, as 
 M. Dumas affirmed, " a very strong acid, the manganic acid, playing 
 the part of base vis-a-vis to a very weak acid, the sulphurous acid." 
 We have no manganic acid at all. We have an oxidised basic radical, 
 MnO, combined with an oxidised acid radical, SO, and we can actually 
 produce MnO + SO, the sulphate of manganese, by heating MnO with 
 hydrated SO. M. Dumas's ridicule is therefore entirely misplaced. 
 
THE RADICAL THEORY. 25 
 
 The same remarks apply to the tersulphate of alumina, the proper 
 formula for which, as I shall show elsewhere, is AlcSO 2 , or AlcO,SO. 
 
 The question of the constitution of the salts might be conveniently 
 discussed in reference to any one of them. We might select oil of vitriol, 
 and inquire, shall we write this compound HO+SO 3 , according to 
 Lavoisier, or H + SO 4 , according to the binary theory? or, shall we 
 double the atomic weight of oxygen, and write it H-f-SO 2 , according to 
 the binary theory, or HO-j-SO, according to the theory ascribed to 
 Longchamp ? It appears to me, and I hope to bring the readers of this 
 essay to my opinion, that the doubling of the atomic weight of oxygen 
 is absolutely essential, and that consequently one of the last two formulas 
 must be adopted as the truest representation of the composition of oil 
 of vitriol ; but it does not seem to be possible, either by experiment or 
 by argument, to determine, whether the two atoms of oxygen are com- 
 bined, both with the acid radical, or one with each of the radicals. I 
 think it probaUe that the latter is the case, but there is no evidence to 
 prove it ; and we are consequently at liberty to use either the formula 
 H,S0 2 , or the formula HO,SO, according as one or the other may best 
 answer a given purpose. 
 
 The chemists who have discussed the constitution of salts, since 
 M. Dumas published his lectures, have, with the exception of M. 
 Gerhardt, confined themselves to the single case discussed by Dumas, 
 of HO + SO 3 versus H-f-SO 4 . They have not considered the important 
 effects that result from the adoption of Dr. Clark's proposal to double the 
 atomic weights of oxygen and carbon. It seems, therefore, to be un- 
 necessary to quote either their arguments or conclusions, which do not, 
 in the main, differ from those of Dumas. The theory of Lavoisier is 
 " permitted" to remain in fashion because the existing race of chemists, 
 though aware of its fallacies, and suffering from its defects, want the 
 courage to overthrow it, or the ability to organise a better. 
 
 The Eadical Theory. 
 
 The principles of the Radical Theory may be stated in a few 
 words : 
 
 Every salt is composed of two radicals, simple or compound, oxidised 
 or not oxidised. 
 
 Every element can act as a radical, except oxygen. Oxygen never 
 acts as a simple radical, nor forms part of a compound radical. Some of 
 the metallic elements form two radicals, which differ in weight and pro- 
 perties. 
 
 Compound radicals consist of (i) carbon and hydrogen, or (2) carbon 
 and nitrogen, or (3) combinations of other elements, with the fore- 
 going. For the most part, and when not otherwise expressed, the argu- 
 
26 CLASSIFICATION OF OXYGEN SALTS. 
 
 ments in the following pages refer to radicals that contain carbon and hy- 
 drogen only. 
 
 The quantity of an element which constitutes a radical is an atom, or 
 as much as forms a single volume of gas. 
 
 The quantity of a compound which constitutes a radical is as much as 
 forms a single volume of gas. When the compound is not gaseous, the 
 radical quantity is as much as is equivalent to a single volume of 
 hydrogen or of chlorine. 
 
 Every gaseous salt measuress two volumes, which is the measure 
 of its two radicals. When salts contain oxygen, that element adds to 
 their weight, but not to the measure of their gas. 
 
 Though a compound radical that measures one volume in the state of 
 gas, still measures one volume when combined with one or more atoms 
 of oxygen, the oxygen is not to be considered as a constituent part of 
 the radical, but only as an addition to it. 
 
 Muriatic acid, HC1, may be taken as the model of a salt. Any basic 
 radical, simple or compound, may replace H, and produce a chloride = 
 MCI, such as chloride of potassium = KC1, or chloride of methyl = CH 3 ,C1. 
 Any acid radical, simple or compound, may replace Cl, and produce 
 another hydride, such as HBr, HS, or H,C 6 H 5 . 
 
 When either or both radicals are oxidised, the compound is an oxygen 
 salt. It is in all cases impossible to determine whether the oxygen of 
 a salt is combined exclusively with either of the two radicals, or divided, 
 equally or unequally, between them. In framing equations for the 
 purpose of explaining theoretical opinions respecting the constitution 
 or transformations of compounds, we may place the oxygen in that 
 manner which best answers our special intention ; but in the construction 
 of formulae for purposes of classification or nomenclature, the oxygen 
 should, in all cases, be put together at the end of the formula?. 
 
 Since all gaseous salts that contain two radicals form two volumes of 
 gas, whether the radicals are simple or compound, oxidised or not 
 oxidised, it is assumed, that every compound radical, if isolated and 
 brought into the gaseous state, would measure one volume. In justifica- 
 tion of this assumption, it may be added, that every compound radical 
 that has yet been isolated measures one volume, and is the equivalent of 
 one volume of hydrogen or of chlorine. 
 
 Salts combine with one another, so as to form double, triple, quad- 
 ruple, and other forms of compound salts. 
 
 Classification of Oxygen Salts. 
 
 Referring to the classification of oxygen salts, which I published in 
 1834 (see page 15), I have to remark, that that system requires 
 scarcely any amendment, to adapt it to the Radical Theory of 1 8 5 6. 
 
CLASSIFICATION OF OXYGEN SALTS. 27 
 
 A. SIMPLE SALTS. 
 
 CLASS I. M-f-RO is an important class of salts, comprehending water 
 H,HO; the protoxides, K,KO; their hydrates, K,HO; many organic 
 compounds, such as alcohol, H,C 2 H 5 0, and ether, C 2 H 5 , C 2 H 5 0; the 
 silicates, M,SiO ; the borates, M,BO ; and such compounds as chloro- 
 sulphuric acid, C1SO, and the oxychloride of chromium, CrClO. 
 
 CLASS II. M-fRO 2 , the rational formula for which may possibly be 
 MO+RO, comprehends the sulphates, oxalates, nitrites, chlorites, and 
 most of the salts of organic acids, such as the acetates, formiates, ben- 
 zoates, valerianates, &c. 
 
 CLASS III. M+RO 3 . Rational formula, probably MO -fROO. The 
 nitrates, chlorates, iodates, bromates, metaphosphates, and several salts 
 of compound organic radicals. I am also disposed to put into this class 
 many of the anhydrides, such as anhydrous sulphuric acid = S + SO 3 , or 
 SO+SOO; anhydrous acetic acid = C^+C'ITO 3 , orC f H 8 O+C 2 H 8 OO ; 
 anhydrous benzocinnamic acid = C 7 H 5 +C 9 H 7 O 3 , O r C 7 H 5 0+C 9 H 7 OO. 
 
 CLASS IV. M+RO 4 . Perchlorates. 
 
 B. DOUBLE SALTS, 
 
 CLASS V. MM +R0 3 . Probable composition, MO,RO+MO. The 
 
 salts of this class are bibasic, because the acid radical is indivisible. 
 Examples : 
 
 KK ; CO 3 . . Neutral carbonate of potash. 
 KH; CO 3 . . Bicarbonate of potash. 
 CaMg; CO 3 . Bitterspar. 
 
 The compound of sulphuric acid with peroxide of hydrogen, belongs 
 to this class, HO,SO+HO = HH ; SO 3 . 
 
 CLASS VI. M-f-R 2 O 3 . Probable composition, MO,RO+RO. As the 
 salts of Class V are basic salts of Class II, so the salts of this class 
 are acid salts of Class II. -the relations of the three kinds being as 
 follows : 
 
 Class V MO,MO,RO. 
 
 II MO,RO. 
 
 VI MO,RO,RO. 
 
 The hyposulphates belong to this class. 
 
 CLASS" VII. M 2 +R 2 O 3 . Probable composition, MO,RO+M,RO ; 
 namely, a compound of a salt of Class I. with a salt of Class II. The 
 sulphites belong to this class, the salts of which, like those of Class V., 
 are necessarily bibasic : 
 
 KK ; S'O 3 . . Neutral sulphite of potash. 
 
 KH; S 2 O 3 . . Bisulphite of potash. 
 
 KNa ; S 2 O 8 . . Sulphite of potash and soda. 
 
28 
 
 CLASSIFICATION OF OXYGEN SALTS. 
 
 It has been erroneously assumed that the carbonates and sulphites are 
 of similar constitution : they are both bibasic, and both contain 3 atoms 
 of oxygen ; but with those relations the similarity ends. The carbonates 
 contain one acid radical, and the sulphites contain two acid radicals ; so 
 that their constitution is essentially different. 
 
 CLASS VIII. M 3 +RO 4 . Probable composition, MO,ROO+M,MO. 
 Example : the terbasic phosphates. 
 
 The full discussion of the composition of these, and other classes of 
 salts, will take place in subsequent sections. 
 
 In order to develop the Radical Theory in the shortest and 
 clearest manner, I have arranged the facts upon which I propose to found 
 my arguments in the form of Tables, to which I shall add a running 
 Commentary. 
 
 I shall first bring under your notice, a Table of the Atomic Weights, 
 or Chemical Equivalents, of the Elements. Secondly, a Table containing 
 Examples of Compound Organic Radicals and Salts which contain them. 
 Thirdly, a Table of Gases and Vapours. After explaining these Tables, 
 I shall apply the facts they contain to the explanation and illustration of 
 some problems of general chemical interest. These applications must 
 necessarily be restricted in number, because I do not propose to write a 
 system of chemistry, but only an account of certain philosophical prin- 
 ciples, and I shall limit the examples to such as afford the illustrations 
 requisite for the establishment of those principles. 
 
 Atomic Weights of the Elements. 
 
 ELEMENTS. 
 
 
 Griffin. 
 
 Miller. 
 
 Abridged Names. 1 
 
 Aluminum . 
 
 Al 
 Ale 
 
 13.60 
 91 
 
 *3-7 
 
 Al- ous. 
 Al- ic 
 
 Antimony . 
 
 Sb 
 Sbc 
 
 * 
 
 I2 9 . 
 
 4.2. 
 
 129. 
 
 Stib ous. 
 Stib- ic. 
 
 Arsenic .... 
 
 As 
 Asc 
 
 tD* 
 
 75- 
 25. 
 
 75- 
 
 Ars ous. 
 Ars- ic. 
 
 Barium .... 
 Bismuth .... 
 
 - Ba 
 Bi 
 Bic 
 
 68.5 
 213. 
 
 71. 
 
 68.5 
 213. 
 
 Baryt. 
 Bism- ous. 
 Bism ic. 
 
 Boron .... 
 Bromine .... 
 Cadmium . . . 
 Calcium .... 
 Carbon .... 
 
 B 
 Br 
 
 Cd 
 Ca 
 C 
 
 3 " 6 
 
 80. 
 
 55-7 
 
 20. 
 12. 
 
 10.9 
 80. 
 55-7 
 
 20. 
 
 6. 
 
 Bor. 
 
 Brom. 
 Cadm. 
 Calc. 
 Carb. 
 
 1 The use of these abridged names will be explained in the section on 
 Nomenclature. 
 
ATOMIC WEIGHTS OF THE ELEMENTS. 
 
 29 
 
 ELEMENTS. 
 
 
 Griffin. 
 
 Miller. 
 
 Abridged Names. 
 
 Cerium .... 
 
 Ce 
 Cec 
 
 4 6. 
 
 3O.66 
 
 4 6. 
 
 Cer- ous. 
 Cer ic 
 
 Chlorine .... 
 Chromium . 
 
 Cl 
 Cr 
 Crc 
 
 j 
 
 35-5 
 
 27- 
 1 8. 
 
 35-5 
 26.3 
 
 Chlor. 
 Chrom- ous. 
 Chrom ic 
 
 Cobalt .... 
 
 Co 
 Coc 
 
 29.5 
 
 IQ 7 
 
 29.5 
 
 Cob- ous. 
 Cob- ic 
 
 Copper .... 
 
 Cu 
 Cue 
 
 jy.y 
 
 64. 
 32. 
 
 3I.7CJ 
 
 Cupr- ous. 
 Cupr ic 
 
 Didymium . . . 
 Erbium .... 
 Fluorine .... 
 Gluclnum 
 Gold 
 
 D 
 E 
 F 
 G 
 
 An 
 
 48.. 
 19- 
 
 4-7 
 
 IQ6 ^ 
 
 j 1 J 
 
 4 8. 
 
 I 9 . 
 
 1 06 6 
 
 Didym. 
 Erb. 
 Fluor. 
 Glue. 
 Aur ous 
 
 
 Auc 
 
 1 ^ u -> 
 
 6^x 
 
 
 Aur ic 
 
 Hydrogen . 
 Ilmenium . . . 
 Iodine .... 
 Iridium .... 
 
 H 
 11 
 I 
 Ir 
 Ire 
 
 v j*j 
 
 i. 
 
 127. 
 99. 
 66. 
 
 i. 
 
 127. 
 98.6 
 
 Hydr. 
 Ilm. 
 lod. 
 Irid- ous. 
 Irid ic 
 
 Iron 
 
 Fe 
 
 28 
 
 28 
 
 Ferr ous 
 
 
 Fee 
 
 1 8.66 
 
 
 Ferr ic 
 
 Lantanium . 
 Lead 
 
 La 
 Pb 
 
 46. 
 
 IOA. 
 
 46. 
 103 6 
 
 Lant. 
 Plumb 
 
 Lithium .... 
 Magnesium . . . 
 Manganese . 
 
 Mercury .... 
 
 L 
 Mg 
 
 Mn 
 Mnc 
 Hg 
 Hc 
 
 * T 
 
 6-5 
 
 12. 
 
 2 7 .6 
 18.4 
 200. 
 IOO. 
 
 6 - 5 < 
 
 12. 16 
 
 27.6 
 
 IOO 
 
 Lith. 
 Magn. 
 Mang- ous. 
 Mang- ic. 
 Mer- ous. 
 M^er ic 
 
 Molybdenum 
 
 Mo 
 
 Moc 
 
 46. 
 
 I ^.33 
 
 45. 
 
 Molybd- ous. 
 Molybd ic 
 
 Nickel .... 
 
 Ni 
 Nic 
 
 J J J 
 29.55 
 IQ 7 
 
 29-5. 
 
 Niccol- ous. 
 Niccol ic 
 
 Niobium .... 
 Nitrogen .... 
 Osmium .... 
 
 Nb 
 N 
 Os 
 Osc 
 
 *7' I 
 
 14. 
 
 & 
 
 14. 
 99-4 
 
 Niob. 
 Nitr. 
 Osm- ous. 
 
 Oxygen .... 
 Palladium . . . 
 
 
 Pd 
 Pdc 
 
 1 6. 
 
 n 
 
 8. 
 53.2 
 
 Ox. 
 
 Pall- ous. 
 Pall ic 
 
 Pelopium . . . 
 
 Pe 
 
 
 
 Pelop. 
 
30 
 
 ATOMIC WEIGHTS OF THE ELEMENTS. 
 
 ELEMENTS. 
 
 
 Griffin. 
 
 Miller. 
 
 Abridged Names. 
 
 Phosphorus . . . 
 Platinum 
 
 P 
 Pt 
 
 Ptc 
 
 3 1 - 
 99. 
 
 AQ Z 
 
 98.6 
 
 Phosph. 
 Plat- ous. 
 Plat ic 
 
 Potassium . 
 Rhodium . . . 
 
 K 
 Rh 
 Rhc 
 
 *TrJ 
 
 39- 
 52. 
 
 2A. 66 
 
 39- 
 52.2 
 
 Potass. 
 Rhod- ous. 
 Rhod ic 
 
 Ruthenium . . . 
 
 Ru 
 
 Rue 
 
 yt* v ^ > 
 
 52. 
 
 7 A f\f\ 
 
 52. 
 
 Ruth- ous. 
 Ruth ic 
 
 Selenium 
 Silicon .... 
 Silver .... 
 Sodium .... 
 Strontium . 
 Sulphur .... 
 Tantalum . . . 
 Tellurium . . . 
 
 Se 
 Si 
 Ag 
 Na 
 Sr 
 S 
 Ta 
 Te 
 Tec 
 
 J^.UU 
 4 0. 
 
 7-5 
 1 08. 
 
 23. 
 44. 
 1 6. 
 
 6 4 . 
 
 2 2 
 
 39.6 
 14.24 
 
 108. 
 
 23 'o 
 
 43.8 
 
 1 6. 
 64. 
 
 Sel. 
 Sil. 
 Argent. 
 Nate. 
 
 Stront. 
 Sulph. 
 Tant. 
 Tellur- ous. 
 Tellur ic 
 
 Terbium .... 
 Thorinum . . . 
 Tin 
 
 Tb 
 
 Th 
 Sn 
 
 D*' 
 
 59-5 
 
 en. 
 
 59-5 
 
 8 8 
 
 Terb. 
 r rhor. 
 
 St ous 
 
 
 Snc 
 
 7> 
 
 20.^ 
 
 j <J 
 
 St- ic. 
 
 Titanium 
 Tungsten . . . 
 Uranium .... 
 
 Ti 
 W 
 U 
 
 Uc 
 
 "7J 
 
 12. 
 
 T 
 60. 
 
 A.O 
 
 24.2 
 92. 
 60. 
 
 Tit 
 
 Tungst. 
 Ur- ous. 
 Ur- ic 
 
 Vanadium . . . 
 
 V 
 
 Vc 
 
 ^^' 
 68.4 
 22 8 
 
 68.5 
 
 V- ous. 
 V- ic 
 
 Yttrium .... 
 
 Y 
 
 Zn 
 
 32. "? 
 
 ^2.^ 
 
 Yttr. 
 Zinc. 
 
 Zirconium . . . 
 
 Zr 
 
 j } 
 22.4 
 
 5 J 
 
 33.6 
 
 Zirc. 
 
 Atomic Weights of the Elements. 
 
 By the term atomic weight, I mean a chemical combining proportion. 
 By the term equivalent I mean the same thing. I set aside all physical 
 and metaphysical speculations respecting the nature of matter and atoms. 
 I mean by atom only a chemical combining quantity. I acknowledge no 
 equivalent that differs from an atom. 
 
 To put this principle into practice, that is to say, to act upon the 
 principle that atoms and equivalents are alike, I assume that the atomic 
 
ATOMIC WEIGHTS OF THE ELEMENTS. 31 
 
 weights of oxygen, hydrogen, nitrogen, and chlorine, are represented by 
 the specific gravities of their gases. In other words, that one volume of 
 each of these elements in the state of gas, is one atom or one equi- 
 valent. 
 
 This method of determining what constitutes an atom depends upon 
 Gay Lussac's discovery, that gases combine in equal volumes. Assuming 
 that volumes represent atoms, the different densities of the elementary 
 gases give the relative weights of the atoms. All theories and all equi- 
 valents incompatible with this assumption are sacrificed. There can be 
 no compromise between this and other theories. The half-measures 
 adopted years ago by Berzelius such as the crossed atoms of the 
 metalloids, the construction of sesquioxides, and other similar expedients 
 have proved useless. I propose then to abandon half measures, and 
 to bring equivalents and atoms into strict harmony ; to set aside, for the 
 moment, a variety of common chemical hypotheses respecting crossed 
 atoms, sesquioxides, anhydrous acids, anhydrous bases ; peroxidation 
 and protoxidation ; and, dispensing with these hypotheses, and looking 
 at the facts of chemistry from another point of view, I propose to 
 examine whether it is not possible to free our theories from some of their 
 present complications. 
 
 If a single volume of oxygen and of hydrogen represents an atom of 
 each, it follows that an atom of water contains two atoms of hydrogen 
 and one atom of oxygen. Is water really so constituted ? That is the 
 fundamental problem in theoretical chemistry, and until that problem is 
 solved, no other important theoretical problem, no difficulty respecting 
 radicals, or salts, or acids, or bases, or hydrates, or ethers, or alcohols, 
 can be considered as being finally disposed of. For this reason much of 
 what I have to say in this essay, will bear, directly or indirectly, upon 
 that single point. 
 
 We have at present four theories of the constitution of water. First, 
 the common English theory, that it contains one atom of hydrogen and 
 one atom of oxygen. Secondly, Berzelius's theory, that it contains 
 two atoms of hydrogen combined directly and together, with one 
 atom of oxygen. Thirdly, Gerhardt's theory, that it contains two 
 atoms of hydrogen combined separately, but equally, with one atom 
 of oxygen. And, fourthly, Clark's theory, that water contains one 
 atom of HYDROGEN, combined with one atom of OXIDE OF HYDROGEN. 
 The evidence in support of this view, will be brought forward in a suc- 
 ceeding chapter, but in the meantime I assume theoretically and subject 
 to future discussion that water is a compound of two radicals, one of 
 them oxidised, and the other not oxidised, its formula being H,HO. If 
 the facts that I have to bring forward in favour of this theory be con- 
 sidered valid, one effect will be to remove the difficulty in the way of 
 assimilating equivalents to atoms, a difficulty which is inseparable from 
 the theory, that the gaseous atom of hydrogen has twice the volume of 
 
32 SOME ELEMENTS HAVE TWO CHEMICAL ATOMS. 
 
 the gaseous atom of oxygen. The atomic weights in my table are based 
 upon the principle that one volume of each of these elements is equal to 
 one atom. Every number in the table represents as much of a given 
 element as, in my opinion, is chemically equivalent to one volume of 
 hydrogen, and every symbol is consequently equal to one H. 
 
 The Table contains, as a standard of comparison, the atomic weights 
 of Professor Miller (the latest published in England), where hydrogen 
 is i. The atomic weights, or equivalents, which I propose to adopt, 
 are placed in juxta-position with these. On comparing the two scales, 
 we find, that the weights of the metalloids, and of the alkaline metals, 
 remain unaltered, but that oxygen is made 16 instead of 8, and carbon 
 12 instead of 6. These alterations are made in the usual atomic 
 weights of carbon and oxygen, in order that the constitution of the pro- 
 toxides, and the hydrates of the protoxides, may be assimilated to that 
 of water, according to the general formula, M,MO. 
 
 I come now to describe a great divarication from prevalent systems. 
 I propose to adopt, for some of the acidifiable metals, and for the 
 elements that produce the compounds commonly termed sesquioxides, 
 two atomic weights two equivalents two quantities, EACH CHEMICALLY 
 EQUIVALENT to one atom of hydrogen. This proposal is, of course, 
 founded upon Mr. Gerhardt's suggestion of double equivalents, a sug- 
 gestion of great importance, and deserving of more attention than 
 chemists have yet bestowed upon it. Twenty years ago, when I reduced 
 the formulae of alumina, silica, and boracic acid, from APO 3 , SiO 3 , and 
 BO 3 , to Al'O, Si 2 O, and B 2 O, in order that they might agree with other 
 protoxides, I halted at the red oxide of iron, because a similar reduction 
 of Fe'O 3 to Fe*O, gave a formula that was incompatible with that of the 
 ferrous oxide, and inconsistent with that part of the atomic theory which 
 is called the law of combination in multiple proportions. Mr. Gerhardt, 
 coming to the same difficulty, cut the gordian knot, which, like me, he 
 was unable to untie, and, boldly disregarding the law of multiple pro- 
 portions, advocated the adoption of double equivalents. After a careful 
 consideration of the bearings of this proposal, I have come to the con- 
 clusion that Mr. Gerhardt is in the right, except in the following par- 
 ticular : while he adopts two equivalents for one metal, he still retains 
 one atomic weight, and he seems simply to intimate that the two equiva- 
 lents are different proportions of the same kind of metal. He says 
 " When we speak of the equivalent of a body, we should always indicate 
 to what other body, to what functions, to what properties, that equi- 
 valent corresponds." 1 Now, I hold the opinion, that when the change 
 in the atomic weight occurs, a change takes place simultaneously in the 
 quality of the atom; so that, for example, the mercuric atom is not 
 merely of half the weight of the mercurous atom, but is endowed with 
 
 1 Introduction to Unitary Chemistry, p. 78. 
 
THE FALLACIOUS DOCTKINE OF SESQU10XIDES. 33 
 
 different chemical properties, and capable of producing compounds which 
 also differ in properties from the compounds of the mercurous atom ; so, 
 also, that the ferric atom is not merely two-thirds of the quantity of iron 
 that is contained in the ferrous atom, but is a different chemical agent, 
 possessing properties that are peculiar to irself, and not the same as the 
 properties of the ferrous atom. The characteristics of the ferrous and 
 ferric atoms do not, on this view, depend upon their relations to other 
 bodies, nor upon the equivalents of other bodies, but are inherent and 
 not conditional properties. Each is a single complete chemical atom, and 
 neither of them is an equivalent in any other sense. 
 
 By the adoption of double equivalents, we get rid of the complicated 
 formulas and the perplexities that encumber all theories of the constitu- 
 tion of the salts of those metals that give two series such as the ferrous 
 and ferric salts of iron, and the mercurous and mercuric salts of mer- 
 cury, &c. ; above all, we get rid of the hypothetical SESQUIOXIDES. I 
 say hypothetical, because I consider them to be the creatures of a fiction. 
 I do not believe in their existence. I know the red oxide of iron. That 
 is a reality. But the sesquioxide of iron is a mere phrase, a technical 
 term which expresses a particular hypothesis. It has only an arith- 
 metical existence, and vanishes when you adopt a different calculation. 
 
 I propose then, in the case of iron, and I take that metal as an 
 example of the entire class of elements that produce sesquioxides, to 
 have two atomic weights two equivalents. One of these atoms, weighing 
 on the hydrogen scale 28, is the radical of the ferrous salts, and I mark 
 it Fe. The other atom, weighing 18*66, or two-thirds of the first atom, 
 is the radical of the ferric salts, and I mark it Fee. The atoms Fe and 
 Fee are each equivalent to one another, and to one atom of hydrogen, 
 each capable of combining with one atom of chlorine ; and consequently 
 their oxides, hydrates, and chlorides, should be indicated by correspond- 
 ing formulae : 
 
 Ferrous Compounds. 
 
 Fe,FeO Ferrous oxide. 
 
 H, FeO Hydrate of Ferrous oxide. 
 
 FeCl Ferrous chloride. 
 
 FeCy Ferrous cyanide. 
 
 Ferric Compounds. 
 Fec,FecO Ferric oxide. 
 H,FecO Hydrate of Ferric oxide. 
 FecCl Ferric chloride. 
 FecCy Ferric cyanide. 
 
 The elements for which I propose to adopt two equivalents are the 
 following: aluminum, antimony, arsenic, bismuth, cerium, chromium, 
 cobalt, copper, gold, iron, manganese, mercury, molybdenum, nickel, 
 platinum, and the other metals of that series, tellurium, tin, uranium, 
 and vanadium. 
 
 I propose to distinguish the two atoms of the same element by calling 
 the heavier the basylous atom, and the lighter the lasylic atom, and by 
 adding to the symbol of the basylic atom the letter c. Thus, 
 
 D 
 
34 IRON FORMS TWO CHEMICAL ATOMS. 
 
 Au = Aurous atom. 
 
 Auc = Auric atom. 
 
 Hg = Mercurous atom. 
 
 Hgc = Mercuric atom. 
 
 Mn = Manganous atom. 
 
 Mnc = Manganic atom. 
 
 Cu = Cuprous atom. 
 
 Cue = Cupric atom. 
 
 This nomenclature is borrowed from the system proposed some years 
 ago by Berzelius, and used by Mr. Watts in his translation of Gmelin's 
 Handbook of Chemistry. 
 
 Of course, this theory is, to a certain extent, inconsistent with the 
 atomic theory, and especially with the doctrine of combination in mul- 
 tiple proportions. That theory assumes that each element has a single 
 atomic weight, and that the single atom combines with other elements in 
 multiple proportions. Two atoms of iron, with three of oxygen, or with 
 three of chlorine, and so on. 
 
 My view of the matter is as follows : The element iron can, under 
 different circumstances, form two molecules, differing from one another in 
 weight, and in all those physical properties that depend upon the quan- 
 tity of ponderable matter, but agreeing with one another in having the 
 same chemical power, in being each a chemical equivalent, in exercising 
 the functions of a complete single atom ; the chemical properties of one 
 equivalent and of its salts being, at the same, time quite different from 
 those of the other equivalent. 
 
 Nothing is easier than to produce compounds either of the ferrous or 
 the ferric atom, to convert either into the other, to combine either with 
 oxygen, or sulphur, or chlorine, or to make either of them pass into 
 salts, both organic and inorganic. In all these circumstances each atom 
 is chemically equivalent to the other. The two chemical atoms of iron 
 can be treated like atoms of two different metals. Their atomic weight 
 is different, and they produce compounds having different properties, and 
 but for the circumstance that they are both known to be iron, and can 
 be easily converted from one condition into the other, they might be taken 
 for two different elements. Their compounds differ from one another as 
 much as the salts of cobalt do from those of nickel, or the salts of barium 
 from those of strontium. I shall examine a few of these transformations 
 of iron, because, next to the constitution of water, this question of 
 double equivalents of -the metals is the most important theoretical 
 point that can occupy our attention. I hope, by a complete elucidation 
 of this subject, to dispel what 1 1 must call the illusion that there is 
 something in the nature of equivalents which renders them different 
 from atoms. These two words have, or ought to be held to have, 
 under all circumstances, the same meaning. 
 
 If we dissolve iron in diluted hydrochloric acid, hydrogen is set free, 
 and we obtain ferrous chloride : 
 
 HCl+Fe = FeCl+H. 
 If we combine ferrous chloride with half as much chlorine as it already 
 
HOW FERROUS ATOMS ARE CONVERTED INTO FERRIC ATOMS. 35 
 
 contains, we produce ferric chloride. According to the atomic theory, 
 this transformation is explained as follows : 
 
 2FeCl+Cl = Fe 2 Cl 3 . 
 
 Two compounds, each containing one atom of iron and one atom of 
 chlorine, are decomposed, another atom of chlorine is taken up, and a 
 new compound is formed in which two atoms of iron are combined 
 directly with three atoms of chlorine 
 
 (Fe+Fe) + (C1+C1+C1). 
 
 This explanation is completely at variance with the electro-chemical 
 theory, and it is fallacious in a strictly chemical point of view. The 
 fallacy lies in this, that only a part of the change that takes place is 
 accounted for, while the equation pretends to account for the entire 
 change. The increase in the quantity of chlorine which is taken up by 
 the iron, is by no means the whole change that takes place in this trans- 
 formation. The iron goes into the new compound, not merely in that 
 increased quantity which is held to be a multiple proportion, but 
 changed in its chemical nature. The perchloride of iron differs essentially 
 in its chemical reactions from the protochloride of iron. The perchloride 
 of iron, therefore, does not contain a multiple proportion of the same iron 
 that is contained in the protochloride of iron, but it contains a different 
 chemical substance ; and strict logic demands that that different chemical 
 substance should be admitted to be different, and that the difference 
 should be denoted by a different chemical name. The doctrine of com- 
 bination in multiple proportions, takes no cognisance of the change that 
 occurs in the chemical properties of metals, when they enter into com- 
 bination in what are called multiple proportions. It simply points out 
 the physical condition of change in weight. This appears to me to be a 
 radical defect in this important law of the atomic theory. 
 
 The explanation of this process of the conversion of protochloride of 
 iron into perchloride, in accordance with the proposed theory of double 
 equivalents, is as follows : 
 
 Fed FecCl. 
 
 Fed = FecCl. 
 
 Cl FecCl. 
 
 The free chlorine converts two ferrous atoms into three ferric atoms ; 
 in other words, two chemical equivalents of one description of iron 
 become three chemical equivalents of another description of iron ; and 
 since every chemical equivalent of iron, whether ferrous or ferric, requires 
 one equivalent of chlorine to form a chloride, the two equivalents of 
 ferrous chloride require, after the transformation, a third equivalent of 
 chlorine, and produce three equivalents of ferric chloride. Here we 
 
 D 2 
 
36 HOW FERRIC ATOMS ARE CONVERTED INTO FERROUS ATOMS. 
 
 distinctly perceive the change that occurs in the number of atoms of the 
 iron, and that there is a corresponding change in the chemical nature of 
 the iron, can be made abundantly manifest by the action of every suit- 
 able chemical reagent. As to the theory of combination in multiple 
 proportions, there is here no evidence in support of it. The ferric chlo- 
 ride, or perchloride of iron, is on the theory of double equivalents, not 
 a compound of a multiple quantity of iron with a multiple quantity of 
 chlorine = Fe 2 with Cl 3 , but, like the ferrous chloride, is a binary compound 
 of two radicals : 
 
 The ferrous chloride being Fe Cl. 
 
 The ferric chloride being FecCl. 
 
 This theory is in complete accordance with the electro-chemical theory. 
 
 Let us now examine what occurs in the well-known experiment of the 
 reduction of perchloride of iron to protochloride by means of metallic 
 copper, an analytical process of frequent use in the laboratory : 
 
 FecCl \ FeCl. 
 
 FecCl \ + Cue = FeCl. 
 FecCl j CucCl. 
 
 Under the influence of the copper a free basic radical three ferric 
 atoms become transformed into two ferrous atoms, and one atom of 
 chlorine is given up to the cupric atom. 
 
 Thus, we perceive that when ferrous atoms are in presence of an 
 excess of a free acid radical, they are resolved into ferric atoms, which 
 can neutralize one-half more of the free acid radical, than can be neu- 
 tralized by the ferrous atoms. Conversely, when ferric atoms are in 
 presence of an excess of a free basic radical, they are resolved into ferrous 
 atoms, giving up one-third of their acid radical to the free basic radical. 
 An excess of an electro-positive substance, acting upon an electro-negative 
 substance or vice versa tends to produce an equality in the number 
 of positive and negative equivalents. Thus, FeCl -f- FeCl -f Cl produce 
 FecCl+FecCl+FecCl, and FecCl+FecCl-f FecCl -f Cue produces FeCl 
 _j_FeCl-f-CucCl. The phenomena are precisely of the same character 
 as many of the transformations of organic radicals, which take place 
 when they are subjected to the action of chemical agents. 
 
 The following diagrams show what occurs in the PEROXIDATION of 
 ferrous sulphate by means of hydrated nitric acid. 
 
 First, when no free sulphuric acid is present : 
 
 Before. After. 
 
 FeSO 2 FecSO 2 Persulphate of iron. 
 FeSO 2 = FecSO 2 Persulphate of iron. 
 HNO 3 FecHO Hydrate of peroxide of iron. 
 NO 2 Peroxide of nitrogen. 
 
THERE ARE NO SALTS CONTAINING SESQUIOXIDES. 37 
 
 Two atoms of ferrous sulphate and one atom of hydrated nitric acid, 
 produce two atoms of ferric sulphate, one atom of hydrated ferric oxide, 
 and one atom of peroxide of nitrogen. 
 
 Secondly, when free sulphuric acid is present : 
 
 Before. After. 
 
 FeSO 2 FecSO 2 ) 
 
 FeSO 8 = FecSO 2 I Persulphate of iron. 
 
 HSO 2 FecSO 8 ] 
 
 HNO 3 H HO Water. 
 
 NO 2 Peroxide of nitrogen. 
 
 Two atoms of ferrous sulphate, one atom of hydrated sulphuric acid, 
 and one atom of hydrated nitric acid, produce three atoms of ferric sul- 
 phate, one atom of water, and one atom of peroxide of nitrogen. 
 
 I hope the reader will do justice to the explanations of these trans- 
 formations, by examining the terms in which the facts are explained in 
 the systems of chemistry based on the ordinary theory. In most cases, 
 the peroxidation and protoxidation of iron salts are described about as 
 clearly as the alchemists were wont to describe the transmutation of lead 
 into gold. 
 
 Condition of Iron in double salts of Peroxide of Iron. Example : The 
 oxalate of potash and of peroxide of iron. I copy the usual formula from 
 Graham's Chemistry : 
 
 3 (KO,CA) + FeA, 3 C 2 3 + 6HO. 
 
 This formula indicates the following ultimate atoms, according to the 
 proposed new equivalents, in which the atomic weights of carbon and 
 oxygen are doubled : 
 
 K 3 Fec 3 C 6 12 
 
 Dividing these numbers by 3, we obtain K,Fec; C 2 O 4 -j-Aq, or KC0 8 -f- 
 FecCO 8 +Aq. That is to say, the salt is a double oxalate of the sim- 
 plest possible form, and in which the ferric atom Fee, is perfectly equi- 
 valent to the potassium atom K. There is absolutely no evidence to 
 prove the presence of sesquioxide of iron in this salt ; though the heap- 
 ing together of six equivalents of oxalic acid, six equivalents of water, 
 and three equivalents of potash, all take place in consequence of the 
 assumption that sesquioxide of iron forms an essential and indivisible 
 part of this compound. The salt, in fact, is made up after Berzelius's 
 law, that when electro-negative oxides combine with electro-positive 
 oxides, the oxygen of the former (in neutral compounds) is a multiple 
 by a whole number of the oxygen in the latter. The adoption of double 
 ^equivalents will render this law obsolete. 
 
 The greater part of the organic salts of peroxide of iron stand in 
 
38 OCCULT CHEMISTRY. 
 
 exactly similar circumstances to this oxalate. They are made to contain 
 3 atoms of acid without the slightest necessity. In Gmelin's and in 
 Gerhardt's Chemistry, there are scores of complicated formulas that imme- 
 diately are simplified if you adopt the ferric atom, and abandon the lum- 
 bering sesquioxide of iron, which, in fact, cannot be proved to exist in 
 any salt whatever. 
 
 Finally, let us apply these views to the investigation of some of the 
 cyanides that contain iron. 
 
 First of all, we must come to an understanding as to the meaning of 
 the words cyanide and cyanogen. According to Mr. Gerhardt, 1 the com- 
 position of cyanogen is expressed by the formula C 4 N 4 = Cy'Cy 2 . He 
 tells us, that most chemists represent free cyanogen by the formula 
 C 2 N 2 = 2 volumes ; but that, in his opinion, cyanogen is the cyanide of 
 cyanogen, just as hydrocyanic acid is the cyanide of hydrogen : 
 
 Cyanide of hydrogen Cy 2 1 Cyanide of cyanogen Cy 2 1 
 (4 volumes). H 2 j (4 volumes). Cy 2 / 
 
 That line of argument is beyond my comprehension. I understand 
 the statement that cyanide of hydrogen contains cyanogen as an acid 
 radical, combined with hydrogen as a basic radical ; but I must inquire, 
 if there is no such thing as free cyanogen, what can possibly be the con- 
 stituents, either of the cyanide of hydrogen or the cyanide of cyanogen ? 
 Mr. Gerhardt's theory of free cyanogen, if extended to the elements, as 
 some chemists seem desirous of extending it, leads to very singular con- 
 clusions. With vast propriety, we then declare that iron is not free iron, 
 but the ferride of iron ; that hydrogen is not free hydrogen, but the 
 hydride of hydrogen ; that oxygen is not free oxygen, but the oxide of 
 oxygen. Proceeding in this manner, we get rid of all the elements, 
 replacing each by a hypothetical compound of an imaginary -f- element, 
 combined with an imaginary element. Such are some of the 
 fashionable whimsies of men of science. 
 
 My notion of free cyanogen is, that it consists of one atom of carbon 
 combined with one atom of nitrogen ; that it forms a compound which 
 in the gaseous state measures one volume, weighs 26 on the hydrogen 
 scale, and has the power to combine with one atom, or one volume, 
 of any element or of any compound. That is a plain prosaic account of 
 cyanogen. I denote it by CN or Cy. Hence, 
 
 HCy = Hydrocyanic acid. 
 KCy = Cyanide of potassium. 
 
 When I am told that this cyanogen, which I can make, and isolate, 
 and test, and weigh, and measure, and cause to go into compounds and 
 to come out of them, and to be again the same isolated cyanogen, with 
 
 1 Traite de Chimie, I. 288. 
 
SINGLE CYANIDES. DOUBLE CYANIDES. 39 
 
 the same properties, the same weight, and the same measure ; when I 
 am told that I am to believe that this compound which I know is not 
 free cyanogen, but that free cyanogen is cyanide of cyanogen, a com- 
 pound of two other cyanogens, which I do not know, which I cannot 
 make, and which nobody ever saw, then I begin to think that I am 
 listening to a lecture on exoteric chemistry delivered by a philosopher of 
 Ancient Egypt, whose intention it is that I shall acquire no knowledge 
 of esoteric chemistry, and who has been constituted an authority under 
 the conservative opinion that the proper use of a chemical theory is to 
 enable a chemist to conceal his knowledge. 
 
 Passing by this occult philosophy, let us proceed to examine the 
 compounds of cyanogen. 
 
 I quote the following two formulas from Gmelin's Chemistry : 
 
 Protocyanide of iron, or ferrous cyanide C 6 N 3 Fe 3 = Fe Cy. 
 Sesquicyanide of iron, or ferric cyanide C 6 N 3 Fe 2 = Fe 2 Cy 3 . 
 
 According to the Radical Theory, these formulas are transformed as 
 follows : 
 
 Ferrous cyanide = Fe Cy. 
 
 Ferric cyanide = FecCy. 
 
 These symbols are not only simple,- but they show what the old 
 symbols do not show, that the iron in the two salts is not only present in 
 a different quantity, but in a different condition. There is no reason 
 whatever why the ferric atom should not be divided in this manner. 
 No fact forbids it. No experiment is opposed to it. The only argu- 
 ment that can be urged is, that it does not agree with Dalton's theory 
 of combination in multiple proportions. That is unlucky. But I must 
 reply, that if Dalton's theory is found to be inconsistent with truth, or 
 comes to be a cause of perplexity, instead of a help, to chemists, they 
 will have to consider whether that theory must not be amended or aban- 
 doned. 
 
 All the single cyanides can be expressed in the same manner as the 
 above ; even these containing compound radicals and organic radicals, 
 such as 
 
 CH 3 , Cy = Cyanine of methyl. 
 
 NH 3 Pt, Cy Ammonio-protocyanide of platinum. 
 
 AsC 2 H 6 ,Cy = Cyanide of cacodyl. 
 
 The next three formulas are quoted from Gmelin : 
 
 Hydroferricyanic acid ... 3 HCy, Fe ? Cy 3 = C 6 N 3 H 3 , C 6 N 3 Fe 8 . 
 Turnbull's Prussian blue . . ^FeCy,Fe 2 Cy 3 = C 6 N 3 Fe 3 ,C 6 N 3 Fe f . 
 
 By 'adopting separate symbols for the ferrous and ferric atoms, both 
 
40 DOUBLE CYANIDES. TRIPLE CYANIDES. 
 
 of which occur in Turnbull's Prussian blue, and then dividing every- 
 thing in these formulae by 3, we are enabled to simplify them thus : 
 
 Ferricyanide of potassium . . . K Cy,FecCy. 
 Hydroferricyanic acid . . . . H Cy,FecCy. 
 Tumbull's Prussian blue. . . . FeCy,FecCy. 
 
 Thus a series of compounds which require very complex formulae, 
 according to every theory hitherto produced, demand, upon the radical 
 theory, formula?, of the simplest possible character. All the double 
 cyanides that correspond with the red prussiate of potash have this very 
 simple constitution. They are double cyanides, having one basylous 
 atom and one basylic atom, and in all cases of double decomposition the 
 basylic atom accompanies the two atoms of cyanogen. Among the basylic 
 atoms which produce salts of this kind are Ag, Au, Cd, Coc, Crc, Cue, 
 Fee, Hg, Mnc, Ni, Pt, Zn. Any of these may have hydrogen as the 
 basylous atom, producing acids corresponding to the hydroferricyanic 
 acid. 
 
 These double cyanides may be strictly compared with the oxalates in 
 their form and their mode of action : 
 
 Red prussiate of potash . . KCy,FecCy = K,FecCy 2 . 
 Oxalate of potash . . . . KO, C O = K,C O 2 . 
 
 The following formulae of triple cyanides are quoted from Gmelin : 
 
 Ferrocyanide of potassium or) ^ = 
 
 yellow prussiate or potash . J 
 Hydroferrocyanic acid . . . H 2 FeCy 3 = C 6 N 3 FeH 2 . 
 Common Prussian blue . . C 6 N 3 Fe 3 ,2C 6 N 8 Fe 2 
 
 = 3FeCy,2Fe 2 Cy 3 (.rHO). 1 
 
 The complexity of this last formula is ludicrous. The simple fact is, 
 that the K 2 and H 2 of the two first salts is, in a case of double decom- 
 position, exchanged for two ferric atoms = Fee 2 ; but the prevailing 
 theory of the sesquioxides, enjoining the use of three times that quantity 
 of iron, and presenting no other solution of the difficulty, the entire 
 formula has to be enlarged to accommodate the theory. The above three 
 salts would be written with the new equivalents as follows : 
 
 Yellow prussiate of potash . . . K Cy,K Cy,FeCy = K 2 FeCy 3 . 
 Hydroferrocyanic acid . . . . H Cy,H Cy,FeCy = IP FeCy 3 . 
 Common Prussian blue .... FecCy,FecCy,FeCy = Fec 2 FeCy 3 . 
 
 I omit the water, as of no moment in this inquiry. 
 
TRIPLE CYANIDES. FOURFOLD CYANIDES. 41 
 
 Just as the last class of cyanides (the double cyanides) may be com- 
 pared with the oxalates, so may this class of triple cyanides be compared 
 with the carbonates : 
 
 Yellow prussiate of potash . KCy,KCy,FeCy = K 2 FeCy 3 . 
 Carbonate of potash . . . KO, KO, C O = K 2 C O 3 . 
 
 And in cases of double decomposition, just as the carbon and oxygen of 
 the carbonate CO 3 go together, so do the ferrous atom and the cyanogen 
 of the cyanide FeCy 3 go together. 
 
 Examples. Formation of Prussian blue with yellow prussiate of 
 potash and ferric sulphate : 
 
 KK,FeCy 3 . 
 Fee, SO 2 - 
 Fee, SO 2 - 
 
 Formation of Prussian blue with red prussiate of potash and ferrous 
 sulphate : 
 
 K,FecCy 2 . 
 
 Fe,S0 2 - 
 
 The two varieties of Prussian blue are therefore, 
 
 Fec,Fec; Fe Cy 3 = FecCy,FecCy,FeCy. 
 Fe,FecCy 2 = FecCy,FeCy. 
 
 The action of chlorine, in converting yellow prussiate of potash into 
 red prussiate of potash, is easy of explanation by means of the proposed 
 equivalents : 
 
 KFecCy 2 . 
 KFecCy 2 . 
 
 Cl 
 
 KC1. 
 
 Namely, the chlorine converts 2 ferrous atoms into 3 ferric atoms; 
 these, with 3 atoms of potassium and 6 atoms of cyanogen, produce 
 3 atoms of the double cyanide or red prussiate of potash. The super- 
 fluous 4th atom of potassium combines with an atom of chlorine to form 
 chloride of potassium. 
 
 There is a class of fourfold cyanides, of which Prussian green may be 
 taken as an example. Gmelin's formula of that compound is C 6 N 3 Fe 3 , 
 3C 6 N 3 Fe 2 + 1 2 HO = FeCy,Fe 2 Cy 3 + 4HO. This is another case where 
 iron occurs in both conditions. The reduction of the formula gives 
 
 FeFec 3 Cy 4 + 2H 2 O. 
 
42 IS HYDROCYANIC ACID MONOBASIC OR POLYBASIC ? 
 
 Finally, I must bestow a few words upon the question whether hydro- 
 cyanic acid is monobasic or polybasic. 
 
 a. If we take a quantity of hydrocyanic acid equal to HCy, 1 we can, by 
 replacing H by a basic radical, produce a great variety of cyanides of 
 this form, MCy. 
 
 The hydrocyanic acid is therefore MONOBASIC. 
 
 b. If we take a quantity of the acid equal to HHCy 2 , we can, by 
 replacing HH, either singly or together, produce a great variety of acid 
 or neutral salts, such as 
 
 HFecCy 2 . . . Hydroferricyanic acid. 
 
 KFecCy 2 . . . Red prussiate of potash. 
 
 HCrcCy 2 . . . Hydrochromidcyanic acid. 
 
 H Ag Cy 2 . . . Argentoprassic acid. 
 
 KAg Cy 2 . . . Argentocyanide of potassium. 
 
 The hydrocyanic acid is therefore BIBASIC. 
 
 c. If we take a quantity of the acid equal to HHHCy 3 , and replace 
 HHH partly or entirely with basic radicals, we can produce such 
 salts as 
 
 HHFeCy 3 . . . Hydroferrocyanic acid. 
 
 KKFeCy 3 . . . Yellow prussiate of potash. 
 
 C 8 H 5 ,C 2 H 5 ; FeCy 8 . . . Ferrocyanide of ethyl. 
 
 ZnZnBaCy 3 . . . Cyanide of zinc and barium. 
 
 The hydrocyanic acid is therefore TRIBASIC. 
 
 d. If we take a quantity of the acid equal to HHHHCy 4 , and replace 
 HHHH by basic radicals, we produce such salts as 
 
 Fe, Fee, Fee, Fee; Cy 4 . * . Prussian green. 
 
 K, Na, Fee, Fee; Cy 4 . . . Cyanide of potassium, sodium, and 
 
 ferricum. 
 
 Cu, Ag, Ag, Ag; Cy 4 . . . Cuprocyanide of silver. 
 K, Auc,Auc,Auc; Cy 4 . . . Auridcyanide of potassium. 
 
 The hydrocyanic acid is therefore TETRABASIC. 
 
 It appears to be probable that the nitro-prussides discovered by Dr. 
 Lyon Play fair contain octabasic cyanides. 
 
 Pray tell me, then, is hydrocyanic acid monobasic, bibasic, tribasic, 
 tetrabasic, or octabasic ? 
 
 H = i, C = 12, N = 14. HCy = 27. 
 
COXCLUSIONS RESPECTING THE SESQUIOXIDES. 43 
 
 The cyanides of iron, of all classes, single, double, triple, and quad- 
 ruple, contain iron in its two chemical conditions, and in such propor- 
 tions as seem not only to justify the assumption of the existence of the 
 ferrous and ferric atoms, but to render the prevalent hypothesis of the 
 indivisibility of that quantity of iron which corresponds to the sesquioxide 
 altogether improbable and untenable. I have shown that we can have 
 complete salts with one atom of Fee, with two atoms, and with three 
 atoms. The resolution adopted by chemists of making it appear that 
 all the " persalts " of iron contain three atoms of Fee, is at variance 
 with the plainest, straightforward method of representing the facts as 
 they stand out clearly in our view. It serves only to sustain the credit 
 of an unnecessary and extravagant hypothesis. The time will come 
 when chemists will hold the doctrine of the sesquioxides in the same 
 respect as they now hold the doctrine of phlogiston, which is its exact 
 parallel in common sense and practical utility. 
 
 The limits of this essay forbid an extension of these illustrations, 
 either in relation to iron or to the equivalents of other elements. Besides, 
 they will occur in abundance to any reflecting chemist who turns his 
 attention to this subject. 
 
44 
 
 COMPOUND ORGANIC RADICALS. 
 
 Examples of Compound Organic Radicals and the Salts that contain 
 
 them. 
 
 c. 
 
 H. 
 
 Kadicals. 
 
 Salts. 
 
 I 
 
 I 
 
 Formyl 
 
 H,CH0 2 . . . 
 
 Formic Acid. 
 
 
 
 
 CH,CHO . . 
 
 Pyrogallic Acid. 
 
 
 
 
 Pb,CHO . . 
 
 Pyrogallate of Lead. 
 
 I 
 
 2 
 
 Vinyl . . 
 
 CH 2 . . . . 
 
 [Olefiant Gas.] 
 
 I 
 
 3 
 
 Methyl . . 
 
 CH 3 ,CH 3 O . . 
 
 Methylic Ether. 
 
 
 
 
 H,CH 3 . . . 
 
 Marsh Gas. 
 
 
 
 
 CH 8 ,S0 2 . . . 
 
 Methylic Sulphate. 
 
 2 
 
 i 
 
 
 H^HO 2 . . 
 
 Aconitic Acid. 
 
 2 
 
 i 
 
 
 H,C 2 HO a . . 
 
 Fumaric Acid. 
 
 2 
 
 i 
 
 
 H,C 2 H0 8 . . 
 
 Maleic Acid. 
 
 2 
 
 2 
 
 
 H,C 2 H 2 2 . . 
 
 Succinic Acid. 
 
 2 
 
 2 
 
 
 H,C 2 H 2 3 . . 
 
 Tartaric Acid. 
 
 2 
 
 3 
 
 Acetyl . . 
 
 H,C 2 H 3 . . 
 
 Aldehyde. 
 
 
 
 
 H,C 2 H 3 2 . . 
 
 Acetic Acid. 
 
 2 
 
 3 
 
 
 H,C 2 H 3 3 . . 
 
 Homolactic Acid. 
 
 2 
 
 3 
 
 
 H,C 2 H 3 3 . . 
 
 Glycollic Acid. 
 
 2 
 
 5 
 
 Ethyl . . 
 
 H,C 2 H 5 O . . 
 
 Alcohol. 
 
 
 
 
 C"H 8 ,C'H 8 . 
 
 Ether. 
 
 3 
 
 3 
 
 Aciyl? . . 
 
 H,C 3 H 3 O . . 
 
 Acroleine. 
 
 J 
 
 J 
 
 
 H,C 3 H 3 O 2 . . 
 
 Acrylic Acid. 
 
 T> 
 
 2 
 
 
 HjCflEPO 8 . . 
 
 Pyruvic Acid. 
 
 j 
 
 3 
 
 J 
 
 3 
 
 Pteleyl . . 
 
 C 3 H 3 ,NO 2 . . 
 
 fNitrite of Pteleyl. 
 
 J 
 
 3 
 
 4 
 
 
 H,C 8 H 4 O 4 . . 
 
 Mucic Acid. 
 
 _/ 
 2 
 
 i 
 
 4 
 
 
 H,C 3 H 4 0* . . 
 
 Adipic Acid. 
 
 J 
 
 T^ 
 
 
 C 2 H 5 ,C 8 H 4 2 . 
 
 Adipate of Ethyl. 
 
 3 
 
 5 
 
 Aciyl? . . 
 
 H,C 3 H 5 . . 
 
 Acrylic Alcohol. 
 
 J 
 
 TL 
 
 5 
 
 Allyl . . 
 
 C 3 H 5 ,C 3 H 5 O . 
 
 Oxide of AUyl. 
 
 J 
 
 3 
 
 J 
 
 5 
 
 Propionyl- . 
 
 H,C 3 H 5 O . . 
 
 Propionic Aldide. 
 
 J 
 
 
 
 H,C 3 H 5 . . . 
 
 Propylene. 
 
 
 
 
 H,C 3 H 5 O a . . 
 
 Propionic Acid, hydrate. 
 
 
 
 
 C 3 H 5 ,C 3 H 5 O 3 . 
 
 Propionic Acid, anhydr. 
 
 2 
 
 ; 
 
 
 H^H^ . . 
 
 Lactic Acid. 
 
 J 
 
 3 
 
 j 
 5 
 
 
 H.CflBW . . 
 
 Metacetonic Acid. 
 
 _/ 
 
 3 
 
 J 
 
 1 
 
 Propyl . . 
 
 C 8 H 7 ,C 3 H 5 2 . 
 H^IFO . . 
 
 Propylal. 
 Propylic Alcohol. 
 
 
 
 
 CPIF.NH 1 . . 
 
 Propylamine. 
 
 3 
 
 7 
 
 Lipyl . . 
 
 H,OTP<? . . 
 
 Glycerine. 
 
 j 
 
 4 
 
 2 
 
 
 H,C 4 H 2 O . . 
 
 Phtalic Acid. 
 
COMPOUND ORGANIC RADICALS. 
 
 45 
 
 c. 
 
 H. 
 
 Radicals. 
 
 Salts. 
 
 4 
 
 2 
 
 
 H 4 ,C 4 H 2 O 6 . . 
 
 Tartaric Acid. 
 
 4 
 
 2 
 
 
 H 2 ,C 4 H 2 5 ? . 
 
 Tartrelic Acid. 
 
 4 
 
 3 
 
 
 H, C 4 H 3 5 ? . 
 
 Tartrelic Acid. 
 
 4 
 
 4 
 
 
 H 2 ,C 4 H 4 8 . . 
 
 Metatartaric Acid. 
 
 4 
 
 4 
 
 
 H 2 ,C 4 H 4 O 5 . . 
 
 Malic Acid. 
 
 
 
 
 Ag 2 ,C 4 H 4 5 . 
 
 Malate of Silver. 
 
 4 
 
 6 
 
 Suberyl . 
 
 H,C 4 H 6 O 2 . . 
 
 Suberic Acid. 
 
 4 
 
 7 
 
 Butyryl . 
 
 H,C 4 H 7 O . . 
 
 Butyral. 
 
 
 
 
 H,C 4 H 7 2 . . 
 
 Butyric Acid. 
 
 4 
 
 9 
 
 Butyl . . 
 
 H,C 4 H 9 . . 
 
 Butylic Alcohol. 
 
 
 
 (Valyl) . 
 
 C 4 H 9 ,NO 2 . . 
 
 Nitrite of Butyl. 
 
 5 
 
 3 
 
 
 H,C 5 H 3 O 2 . . 
 
 Furfurol. 
 
 5 
 
 3 
 
 
 H,C 5 W0 3 . . 
 
 Pyromeconic Acid. 
 
 5 
 
 3 
 
 
 H,C 5 H 3 O 3 . . 
 
 Pyromucic Acid. 
 
 5 
 
 4 
 
 
 H 2 ,C 5 H 4 4 . . 
 
 Citraconic Acid. 
 
 5 
 
 4 
 
 Naphthaline 
 
 C 5 H 4 ,C1 . . . 
 
 Chloride of Naphtha- 
 
 
 
 
 
 line. 
 
 5 
 
 6 
 
 
 H 2 ,C 5 H 6 4 . . 
 
 Pyrotartaric Acid. 
 
 5 
 
 7 
 
 Angelyl 
 
 H,C 5 H 7 O 2 . . 
 
 Angelic Acid. 
 
 5 
 
 7 
 
 Camphoryl. 
 
 H,C 5 H 7 O 2 . . 
 
 Camphoric Acid. 
 
 
 
 
 C 5 H 9 ,C 5 H 7 O . 
 
 Camphor. 
 
 
 
 
 C 5 H 9 ,C 5 H 7 . . 
 
 Turpentine. 
 
 5 
 
 8 
 
 
 H,C 5 H 8 2 . . 
 
 Sebacic Acid. 
 
 5 
 
 9 
 
 Valeryl . . 
 
 H,C 5 H 9 O . . 
 
 Valeral. 
 
 ./ 
 
 
 
 H^ITO 2 . . 
 
 Valerianic Acid. 
 
 5 
 
 ii 
 
 Amyl . . 
 
 H,C 5 H U O . . 
 
 Amylic Alcohol. 
 
 6 
 
 6 
 
 2 
 
 3 
 
 
 H 2 ,C 6 H 2 O 5 ?. .) 
 H,C 6 H 3 5 ?. .] 
 
 Comenic Acid. 
 
 6 
 
 5 
 
 
 H 3 ,C 6 H 5 7 . . 
 
 Citric Acid. 
 
 6 
 
 5 
 
 Phenyl . . 
 
 H,C 6 H 5 O . . 
 
 Phenole (Phenic Acid). 
 
 
 
 
 H,C 6 H 5 . . . 
 
 Benzine. 
 
 
 
 
 H,C 6 H 5 ;S 2 O 4 . 
 
 Phenyl-Sulphuric Acid. 
 
 6 
 
 ii 
 
 
 H,C 6 H 11 6 . . 
 
 Glucic Acid. 
 
 6 
 
 ii 
 
 Caproyl 
 
 H,C 6 H n O a . . 
 
 Caproic Acid. 
 
 
 
 
 H,C 6 H 11 O . . 
 
 Capral. 
 
 6 
 
 J 3 
 
 Hexyl . 
 
 H,C 6 H !3 . . 
 
 Caproic Alcohol. 
 
 7 
 
 i 
 
 
 H 3 ,C 7 H0 7 . . 
 
 Meconic Acid. 
 
 7 
 7 
 
 3 
 
 4 
 
 
 H 3 ,C 7 H 3 O 5 ?) 
 H a ,C 7 H 4 O 5 ?f ' 
 
 Gallic Acid. 
 
 7 
 
 5 
 
 Salicyl . . 
 
 H,C 7 H 5 2 ?. . 
 
 Salicylous Acid. 
 
 
 
 
 HCOPO 1 ?. . 
 
 Salicylic Acid. 
 
 
 
 
 H,C 7 H 5 4 ?. . 
 
 Salicylic Acid. ? 
 
46 
 
 COMPOUND ORGANIC RADICALS. 
 
 c. 
 
 H. 
 
 Radicals. 
 
 Salts. 
 
 7 
 
 5 
 
 Benzyl . . 
 
 H,C'H 5 . . 
 
 Oil of Bitter Almonds. 
 
 
 
 
 H,C 7 H 5 O 2 , 
 
 Benzoic Acid. 
 
 
 
 
 C 7 H 5 ,C10 . . 
 
 Chloride of Benzoyl. 
 
 7 
 
 7 
 
 Toluenyl . 
 
 H,C 7 H 7 . . . 
 
 Toluine. 
 
 
 
 
 C 7 H 7 ,C1 . . . 
 
 Chloride of Toluenyl. 
 
 
 
 
 C 7 H 7 ,NO 2 . . 
 
 Nitrotoluine. 
 
 7 
 
 9 
 
 
 H 3 ,C 7 H 9 6 . . 
 
 Quinic Acid. 
 
 7 
 
 10 
 
 
 H 2 ,C 7 H 10 4 . . 
 
 Pimeiic Acid. 
 
 7 
 
 T 3 
 
 (Enanthyl . 
 
 H,C 7 H 13 . . 
 
 (Enanthol. 
 
 
 
 
 H,C 7 H 13 2 . . 
 
 (Enanthylic Acid. 
 
 7 
 
 15 
 
 Heptyl? . 
 
 H,C 7 H 15 . . 
 
 Castor-oil Alcohol. 
 
 
 
 
 C 2 H 5 ,C 7 H 15 . 
 
 Ethyl-O3nanthyl Ether. 
 
 
 
 
 C'H^CWO?. 
 
 Caprylone. 
 
 8 
 
 7 
 
 Toluyl . . 
 
 H,C 8 H 7 2 . . 
 
 Toluic Acid. 
 
 8 
 
 7 
 
 Anisyl . . 
 
 H,C 8 H 7 O 3 . . 
 
 Anisic Acid. 
 
 
 
 
 C 8 H 7 ,C10 2 . . 
 
 Chloride of Anisyl. 
 
 8 
 
 15 
 
 Capryl . . 
 
 H,C 8 H 15 2 . . 
 
 Caprylic Acid. 
 
 
 
 
 H,C 8 H 15 O . . 
 
 Caprylic Aldehyde. 
 
 
 
 
 H,C 8 H 15 . . . 
 
 Caprylene. 
 
 8 
 
 J 7 
 
 Octyl . . 
 
 H,C 8 H 17 O . . 
 
 Caprylic Alcohol. 
 
 
 
 
 C 8 H 17 ,C*H 3 2 . 
 
 Acetate of Octyl. 
 
 
 
 
 H,C 8 H 17 ; S 2 O 4 . 
 
 Sulphocaprylic Acid. 
 
 9 
 
 7 
 
 Cinnamyl . 
 
 H,C 9 H 7 2 , . 
 
 Hydride of Cinnamyl. 
 
 
 
 
 H,C 9 H 7 8 . . 
 
 Cinnamic Acid. 
 
 
 
 
 C 9 H 7 ,C10 . . 
 
 Chloride of Cinnamyl. 
 
 9 
 
 9 
 
 Styryl . . 
 
 C 9 H 9 ,C 9 H 7 2 . 
 
 Cinnamate of Styryl. 
 
 
 
 
 H,C 9 H 9 . . 
 
 Sty rone. 
 
 9 
 
 9 
 
 
 H,C 9 H 9 2 . . 
 
 Xylitic Acid. 
 
 9 
 
 ii 
 
 Mesityl . . 
 
 H,C 9 H U . . . 
 
 Mesitylol. 
 
 >/ 
 
 Q 
 
 ii 
 
 Cumenyl . 
 
 H,C 9 H n . . . 
 
 Cumene. 
 
 ^ 
 
 
 
 H,C 9 H ll ; S 2 3 . 
 
 J Cumenyl-Sulphurous 
 \ Acid. 
 
 9 
 
 '7 
 
 Pelargyl . 
 
 H,C 9 H 17 2 . . 
 
 Pelargonic Acid. 
 
 IO 
 
 ii 
 
 Cumyl . . 
 
 H,C 10 H 11 2 . . 
 
 Cuminic Acid. 
 
 
 
 
 H,C 10 H 11 O . . 
 
 Hydrate of Cumyl. 
 
 
 
 
 K,C 10 H"0 . . 
 
 Cumilide of Potassium. 
 
 IO 
 
 ii 
 
 
 H,C 10 H 11 . . 
 
 Essence of Anis. 
 
 IO 
 
 13 
 
 Thymyl . 
 
 H,C 10 H 13 O . . 
 
 Hydrate of Thymyl. 
 
 
 
 
 H,C 10 H 13 ; S 2 4 . 
 
 ! Thymyl- Sulphuric 
 Acid. 
 
 10 
 
 j- 
 
 Camphyl . 
 
 H,C'H I7 2 . . 
 
 Campholic Acid. 
 
 10 
 
 19 
 
 Rutyl . . 
 
 H,C 10 H 19 0' . . 
 
 Rutic Acid. 
 
COMPOUND ORGANIC RADICALS. 
 
 47 
 
 c. 
 
 H. 
 
 Radicals. 
 
 Salts. 
 
 10 
 
 J 9 
 
 Rutyl . . 
 
 Am,C 10 H 19 ;S 2 \ 
 
 Sulphite of Rutyl. 
 
 
 
 
 3 + 2Aq J 
 
 Ammonium. 
 
 10 
 
 J 9 
 
 
 H,C IO H 19 2 . . 
 
 Capric Acid. 
 
 II 
 
 21 
 
 
 H,C 11 H 21 O 2 . . 
 
 Margaritic Acid. 
 
 12 
 
 23 
 
 Lauryl . . 
 
 H,C lf HO i . . 
 
 Laurie Acid. 
 
 J 3 
 
 25 
 
 Cocinyl . . 
 
 H,C 13 H 25 2 . . 
 
 Cocinic Acid. 
 
 *-4 
 
 27 
 
 Myristyl 
 
 H^H^O 2 . . 
 
 Myristic Acid. 
 
 *5 
 
 29 
 
 
 H,C 15 H 29 O 2 . . 
 
 Benic Acid. 
 
 1 5 
 
 3 1 
 
 
 C I5 H 3l ,C 16 H 31 O. 
 
 Palmitone. 
 
 16 
 
 3 1 
 
 Palmityl . 
 
 H,C 16 H 31 O 2 . . 
 
 Palmitic Acid. 
 
 
 
 
 H,C I6 H 31 . . 
 
 Cetene. 
 
 
 
 
 C 5 H 11 ,C 16 H 31 2 . 
 
 Palmitate of Amyl. 
 
 16 
 
 33 
 
 Cetyl . . 
 
 H,C W H JB . . 
 
 Ethal. 
 
 
 
 
 H,C I6 H 33 ; S 2 4 . 
 
 Cetyl-Sulphuric Acid. 
 
 l l 
 
 33 
 
 
 H,C 17 H 33 0* . . 
 
 Margaric Acid. 
 
 
 
 
 C 2 H 5 ,C 17 H 33 2 . 
 
 Margarate of Ethyl. 
 
 18 
 
 33 
 
 
 H,C I8 H? B B . . 
 
 Oleic Acid. 
 
 18 
 
 33 
 
 
 H?C1 8 H 33 3 f f 
 
 Ricinolic Acid. 
 
 18 
 
 35 
 
 
 H,C 18 H 35 8 . . 
 
 Stearic Acid. 
 
 
 
 
 C 5 H ll ,C 18 H 35 8 . 
 
 Stearate of Amyl. 
 
 T 9 
 
 37 
 
 
 H,C 19 H 37 2 . . 
 
 Balenic Acid. 
 
 20 
 
 39 
 
 
 H,GH0 I ^ 
 
 Butynic Acid. 
 
 21 
 
 4 1 
 
 
 H,C 21 H 41 O 2 . . 
 
 Behenic Acid. 
 
 27 
 
 53 
 
 
 H,C*H M O . . 
 
 Cerotic Acid. 
 
 27 
 
 55 
 
 Ceryl . . 
 
 H^H^O . . 
 
 Hydrate of Ceryl. 
 
 30 
 
 59 
 
 Melissyl 
 
 H,C 30 H M O 2 . . 
 
 Melissic Acid. 
 
 3 
 
 61 
 
 Myricyl . 
 
 H,C" ) H n O . . 
 
 Hydrate of Myricyl. 
 
 
 
 
 C 30 H 6I ,C 16 H 31 O 2 
 
 Palmitate of Myricyl. 
 
 Compound Organic Eadicals. 
 
 The compound radicals contained in this Table are compounds of 
 carbon and hydrogen only. They are free from oxygen, nitrogen, 
 chlorine, and sulphur. They vary greatly in composition, from For- 
 myl = CH to Myricyl = OTH". 
 
 To some of these radicals I have applied the names by which they 
 are commonly known ; to others the names that are sometimes applied 
 to what I should call their oxides ; while many of them are still without 
 names. To assist in their identification, I have cited a variety of salts 
 
48 COMPOUND ORGANIC RADICALS. 
 
 that are commonly assumed to contain them. The formulae of these salts 
 are written according to the plan advocated in this paper, and to be ex- 
 plained in a subsequent section. 
 
 A difficulty in applying names to these radicals arises from the fact, 
 that the same combination of carbon and hydrogen apparently acts as a 
 radical in salts of very different character. Thus, the compound C 3 !! 5 
 seems to represent acryl, allyl, propionyl, and the radicals of the lactic 
 and metacetonic acids. So also C 6 H 5 represents phenyl and the radical 
 of the citric acid. Whether in such cases we have to do with one 
 radical or with more than one, it is at present impossible to determine. 
 It is not unlikely that some of these are synonymous terms for the same 
 thing, and may hereafter be dispensed with. 
 
 I accept these radicals, theoretically, as the chemical equivalents of 
 atoms of the elements. Whatever may be the complexity of the 
 constitution of a radical whatever the number of its atoms of carbon 
 and hydrogen I consider that it forms one molecule ; that its chemical 
 action is that of one atom or one equivalent ; that when it acts as an 
 acid radical, it replaces one volume of chlorine or combines with one 
 volume of hydrogen ; that when it is a basic radical, it combines with 
 one volume of chlorine, or replaces one volume of hydrogen. A com- 
 pound radical is in all respects the chemical equivalent of one atom, or 
 one volume, of any element, except oxygen. 
 
 The assumption of the existence of these radicals"is purely theoretical. 
 The evidence in support of the assumption is to be given in the following 
 pages. 
 
 Let me repeat, that I speak of radicals that contain carbon and 
 hydrogen only. Compounds that contain oxygen or nitrogen are of a 
 totally different character. 
 
 The materials for this table have been principally derived from 
 GMELIN'S Handbook of Chemistry and GERHARDT'S Traite de Chimie 
 Organique. The table is not to be considered as presenting anything 
 more than a selection of examples to illustrate what I mean by com- 
 pound radicals and their combinations. Those who desire more detailed 
 information may consult the two systematic works that I have just 
 named. 
 
49 
 
 Composition, Specific Gravities, Atomic Weights, and 
 Atomic Measures of Gases and Vapours. 
 
 The compounds named in this Table exceed three hundred. They 
 are arranged alphabetically, according to the names in common use. 
 They have formulae according to the system described in this Essay. The 
 following particulars are given of each compound : 
 
 1. The observed specific gravity of the gas, stated against that of 
 atmospheric air taken as unity ; with the name of the observer. 
 
 2. The observed specific gravity stated against the specific gravity of 
 hydrogen gas taken as unity. 
 
 3 . The atomic weight of each compound on the hydrogen scale. 
 
 4. The theoretical specific gravity on the same scale. 
 
 5. Under the head of atomic measure I have given the number of 
 volumes which contain an atom, or equivalent, of each gas. 
 
 In connection with the proposal to mark the specific gravities of 
 gases in numbers relating to their atomic weights, I take this opportunity 
 of suggesting, that the vessels in which chemists are accustomed to 
 measure gases, might be graduated in such a manner as to indicate the 
 weight of the gases. This can be effected by adopting, as a standard gas 
 measure, a vessel that contains one grain of hydrogen gas, the volume of 
 which at 60 F., and 30 ins. Bar., is 46-7 cubic inches. This vessel may 
 be divided into 100 spaces, each of which will contain T i n grain of 
 hydrogen gas. A vessel, one-tenth of that size, =4! cubic inches, 
 divided into 100, would have divisions, each = TJS \ V grain of hydro- 
 gen gas. The weight of any gas measured in these vessels would be 
 found by multiplying the measure of the gas by its specific gravity, 
 according to the theoretical number given in the following Table. Thus, 
 80 measures of dry nitrogen gas collected in the small tube, at 30 ins. 
 Bar. and 60 F., would weigh O'oSox 14 = I'I2 grain. Of course, 
 corrections upon the measure of a gas, collected over water at another 
 temperature, and under a different pressure, would have to be made as 
 usual. Vessels thus graduated would be useful for class experiments, 
 as well as for analytical purposes. To give one example, A receiver 
 for showing the combustion of phosphorus in oxygen gas, may be 
 known to contain TO grains of hydrogen gas. The question is, 'how 
 much chlorate of potash will afford oxygen gas sufficient to fill it. 10 
 grains of H = 10 atoms of H = 10 atoms of O. The formula of 
 chlorate of potash being KC1O 3 , the quantity required is 3^ atoms, and 
 taking the atom of this salt at 122*5 g ra i ns we find that I22 X 3g = 
 408^ grains of the chlorate of potash will give the requisite quantity of 
 oxygen gas. 
 
50 COMPOSITION, SPECIFIC GRAVITIES, ATOMIC WEIGHTS, 
 
 
 
 
 
 N- INN 
 
AND ATOMIC MEASURES OF GASES AND VAPOURS. 
 
 51 
 
 
 
 
 
 l 
 
 O 
 
 r u-v ro m r- <M HI ON c>* VO VO VO u-" O ON 
 
 n v/^CO mVQ rf- O -^ t~- ro\Q KH VO <N 1-1 ONCO VTN m r^oo m 1-1 VO 
 
 rn O 
 
 *-* ^ rrAO 
 
 O 11 
 
 
 
 VO 
 M vrs<M 
 
 M cqco O O O "^ M 
 
 r- vj->! rnCD CTN v,o vo 
 
 o>vo vo hi 
 
 r-C-q I^-VQ O O CO O CD Q 
 
 oo_ ^ P 
 
 tf5 O O i i 
 
 a M-H-M-H- 
 
 C^ W oo W w 
 
 ^ 
 
 S O M 
 
 O O CJ O 
 
 
 .i.i<i *. 
 
 4-3 1 1 i i i i i i i i i^w ulm 
 
52 
 
 COMPOSITION, SPECIFIC GRAVITIES, ATOMIC WEIGHTS, 
 
 
 
 
 - 
 
 CO xo r~- CM CM M xo> t~~ m rn O\ 
 
 r-* o^ r~co vo -^t- 1-1 T^- rovo >-< v*\ r^-co 
 
 O 
 
 t- CM VO ro 
 
 >-< o> N o> 
 
 CO HH 
 
 ONVO 
 
 VO c^ M 
 
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 CX) CO O CO 
 
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 xr^ CM r~-VO CT\ 
 
 1-1 O M O O>oo m o O "tf- t-i r-oo r- Osco Vo CM <-< 
 
 OO OO VO t~~ xo, vn mGO rt~VO 
 
 rooo vo ^i- 
 
 CM m '?J- 
 
 
 II 
 
 vo xr>, M VO 
 
 i-iCM ovo O>MO I-COCM r-vo 
 
 VO <N ^O mCMOOOO CM rj- xr> w 
 
 r^- CM -^- m O i^vo CM co 
 
 ro O>CO OO O> CM 
 
 H 
 
 ; JJ ">5;-G "00 
 
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 pqpqpqpqpq | | I 1 I 1 pq pq pq PQ 
 
AND ATOMIC MEASUEES OF GASES AND VAPOURS. 
 
 a a 
 
 $ 
 
 bo 
 
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 Q Q 
 
 3 2 a s-t -<' 
 
 1 ^ J * -s 
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 M t~> vo vo 
 
 
 $* 
 
 VO 
 
 t-~ u^ o M 
 
 Vo r-^ <N 
 
 r-vo vo 
 
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 oiuio^y 
 
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 >-HM vo 
 
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 Vo 
 
 00 
 
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 "^ r~\ 
 
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 aa 
 
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54 
 
 COMPOSITION, SPECIFIC GRAVITIES, ATOMIC WEIGHTS, 
 
 . 
 
 
 is! 
 
 So c Sb'fj 
 
 
 x/-> co 
 CO I~~ 
 
 I""** CT^^O 
 
 _ _ r- mvq 
 
 co cr\vo 
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 co rt- m 
 
 Tj-OOCTN 
 
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 x^oo >-tVO 
 
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 Oimo;y 
 
 
 C bfi 
 
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 rf X/-N 
 M mV 
 
 r- CO 
 CO i-( ^H 
 
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 ffioooo W 
 
 Cet 
 
 g ijrgljf'211'f nil?'! 
 
 a^few^oSfSs^gsoaH 
 
ATOMIC MEASURES OF GASES AND VAPOURS. 
 
 55 
 
56 
 
 COMPOSITIOX, SPECIFIC GRAVITIES, ATOMIC WEIGHTS, 
 
 ' c5 C3 c3 *~\ -c3 <?3 cJ 
 
 ! II II I II 
 
 , 11 11 
 
 ^2^^ 
 g- fr 1 fr 5* 
 
 I co xo r 
 
 O r~- r<-> 
 
 VO rt-i-i 
 
 VO 
 
 M t 
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 1-1 mCT\ 
 
 g 
 
 B 
 
 v^q 
 
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 C i-" vo 
 
 t-i CO <N 
 
 ro Tj-co QO HI 1-1 
 
 1-1 01 rf- 
 
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 r~- HH cvi \ovo cq O *H ro ON r- m 
 
 xoVO O t c<j ^-O (~<*^ CA M 
 
 i-iCO VO O^COI^~O> 
 
 O "i ' vo ON ro r-vo O 
 
 O O 
 
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 (Ml mi-. xr\co r OO 
 
 O ooocovovo 1-1 M r-O\ rj-vo 
 
 - O 
 
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 lll 
 
AND ATOMIC MEASURES OF GASES AND VAPOURS. 
 
 57 
 
 i 
 
 o 
 
 "d T* 
 
 o c ^ 
 
 ^3 C3 H 3 
 
 CG co Si ^ 
 
 BS S ~ 
 
 QQ 
 
 'Ill ^ ^ 
 
 S Ifll 
 
 lo 
 
 do 
 
 m xr-, u->i m 
 
 CO <N CO CM 
 
 -tf-co ^f- --d- ONOO t-i oo 
 
 i- M CO m M XO CM ONVO CO 
 
 cMr^- c\ *sf-i-icocMcoM o Xj T |T: f' v O < T 1 
 
 OO H^ CM "^"VO XO f^*. CM t"~* X/^ X/^OO 
 
 ^O rn ON ON r<""> O 'x'^ r<" t~^ M r~~ 
 
 oratory 
 
 CM CM CM CM CM CM 
 
 CM CM CM CM CM CM 
 
 ._ 
 
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 55 
 
 99 
 wo 
 
 OOPQ 
 
 6699^- - - - 
 j w w w w w &M 8 j & 5 1 o s 
 
 6? 
 
 000 
 
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 ^ S % 
 
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 6 o o 6 
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 Cyanate 
 Cyanurate 
 
 ^ -2 
 S cs 
 
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58 COMPOSITION, SPECIFIC GRAVITIES, ATOMIC WEIGHTS, 
 
 11 
 
 i-^ "75 
 
 
 
 vor^ ON co 
 
 cs OO vr> M c<l t I-H CO I-H 
 
 m r 
 
 i-ioocx)m(v)Vo 
 
 vo, r<^ t ^'"N fS t~~ 
 
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 ON moo cs M rr>oo CO V3 "-" 
 
 1 t~~ (*") t-i t~-~vo "5" O 
 -^ VO u-i roVO t^-VO O t-- ^ VN 
 
 
 
 
 moo m *-i vo 
 
 l5 5 2 ||p 
 
 566 
 
 
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 1 1 1 1 1 1 111 
 
AND ATOMIC MEASURES OF GASES AND VAPOURS. 
 
 59 
 
 .a .s .a ^ .s .s T-; . ^ g ^ ^ 
 
 s |l^sJ||i|Jl|Jl|Jllllll 
 
 <N VO 
 
 vo 
 
 ON O r- M ONVO co ^rocsvo M r- <*o ONVO r~- M ON 
 ro ro O VO vo M c<i O ^~ CN t^CO ONCO O t*^ ON vr O ^~ f O ^ ON 
 ^ " rnCO M MVO'VO* "tf--^-!-i OVO* OVOM 6 oXoN voCO roVO* t^CO <S 
 
 M M l-l M M M V) 
 
 K ? ^T 
 
 roco HS ci x/**\ r~^- xf* ^" CTN O O 1^** O ^"^ f^* t^ 1 " O *-^CO r^VO t^"CO 
 <N -^f- rt-CO <N VO mVO O ^- M CO m cvj t VO M MM mVO 
 
 Hm 
 
 OICUO^Y <N<MM<NMMMCSMMC^CS|MMMMMMCSCSICqMC^ 
 
 2 " 
 
 ^3 VO VO f VO 
 
 6X3 vo vd M ^f- vo r^-cd co o> (D (D vo o 10 r^-vo* O vovo* vo* 
 Tj-ON cococqcqVOVOOco mco m <N M csi M M 
 
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60 
 
 COMPOSITION, SPECIFIC GRAVITIES, ATOMIC WEIGHTS, 
 
 jgt 
 
 s- 
 
 d 
 
 S 
 
 E 
 
 cs^ 
 S 
 
 -w 
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 oo 
 
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AND ATOMIC MEASURES OF GASES AND VAPOURS. 
 
 61 
 
 
 
 m O>00 
 M VD CO 
 
 vq q CTNCO 
 
 C<1 I-I -^j- (N Th V^ *~l "H 
 
 M o CTN <N 
 
 
 
 <N rnvo CTs ro CT\ <s <N ro -^fco 'vh r-VO 
 
 vo> M O O O CO -^-VO m r^ <N O vo,VO CJ 
 
 r-~vo,i-ii-ixo>-i'<^-<svo, rf COLO, QN^O i-i VO O m -o ro O 
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 CO VO.GO h-rj-i-i 
 ro H-I VO -^}-VO CO *-i CM M 
 
 rn COVO, t^-VO H VO ON w >-t <N CO 
 cvj (-<VOvo,t-i-^-rc,ro vo,VQ VO VO 
 
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 vo M r-i-tco i-c 
 
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 mm 
 
 6 W 
 
 - -+00 -- -^5 
 
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62 
 
 COMPOSITION, SPECIFIC GRAVITIES, ATOMIC WEIGHTS, 
 
 
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 fiitfmliili 
 
 .5 -S .S -S 3 .2 o a % ~ 5* 
 P-i^PQCwQCuiCOQp3^P3O 
 
 1 
 
 CO ONVO M 
 
 r-vo O "-" 
 
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 CO VT-N 
 
 ONCO Vo ^N ON w m r^ 
 
 O ON m rt- cs o r^ ONVO O mvncs vo 
 
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 co rj- tf^ r~~-<x> 
 
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 O CO l~~ O t~- O ON t~~ w> >M ^H co O 
 
 mcs 
 
 to t-VO ON m TJ- cvj M 
 
 ONO t~--i -i 
 
 i-VO HM VO r<~>m mvo cs O 
 
 vrs I--VO ON m ^t- cs 
 
 oirao^y 
 
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 M vr>^o M O 
 
 ONVO VQ f O 
 O <N M mco 
 
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 s.tfi-si.s-^ 
 
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 IS I 
 
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 l<gl| I I I 
 
AND ATOMIC MEASURES OF GASES AND VAPOURS. 
 
 63 
 
 CftCC 
 
 1 j 
 
 II 1 
 
 r2 *^3 
 
 1 ^ 
 
 8-1 O! O 
 
 x^ M x^ O\VO 
 
 CO oo VO ON u"> ON mVO rnVo CO r<^ xo, ^00 
 
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 TJ- ^- TJ- t~- mco i Vo co 
 VO '^OVO VO 
 
 M ON O 
 
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 xrs xo, i . 
 
 HH VO 
 
 oiraojy 
 
 vo\VO w O VO mVO 
 
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 O^ rn r-~oo QO O> I-H Q M i-i VO 
 
 . . o 
 
 CQ 
 Oft 
 
 + 
 
 
 
 
 
 
 
64 GASEOUS COMPOUND ORGANIC RADICALS. 
 
 No hypothetical specific gravities are given in this Table. No gases 
 are admitted but such as have been actually produced, and, with a few 
 exceptions, weighed. Hence carbon, fluorine, boron, silicon, antimony, 
 zinc, tellurium, &c., are excluded. The Table therefore represents in its 
 weights and measures, a mass of facts. The formulae alone are theo- 
 retical. It enables us to take a comprehensive and trustworthy survey 
 of that chemical region which consists of gases and vapours. It shows 
 us on experimental evidence the weight, the measure, and the ultimate 
 composition, and theoretically the proximate constitution, of above three 
 hundred well-known volatile bodies. Of that large field we have an ac- 
 curate bird's-eye view. WHAT DO WE SEE THERE ? 
 
 First of all we perceive, that all the hydrocarbons that act as radicals, 
 all those which in combination displace an atom of hydrogen or of chlo- 
 rine, have, in an isolated state, an atomic measure of one volume. They 
 are consequently the equivalents of one volume of one atom of one 
 equivalent of hydrogen. That is the case with all the radicals that have 
 yet been isolated; with methyl whose specific gravity is 15, with ethyl 
 = 29, with acryl =41, with butyl = 57, and with amyl, whose spe- 
 cific gravity is 7 1 ; all these radicals differing so greatly in their density, 
 have an atomic measure equal to that of hydrogen, whose specific gravity 
 is I. Dr. Frankland fixed the atomic measures of ethyl, of methyl, and 
 of amyl, at two volumes each, and Dr. Hofmann argued that it ought 
 to be four volumes. But from the peculiar point of view which is 
 recommended in this Essay, the theoretical measure is seen to be only 
 one volume, and the experimental evidence proves that each compound 
 radical is equivalent to one volume of hydrogen. 
 
 Secondly, it appears that there are 121 compounds two-fifths of the 
 whole which have in common these two properties : they form two 
 volumes of vapour, and they contain two radicals. These radicals are 
 in some cases simple, in others compound ; sometimes they are oxidised ; 
 sometimes not oxidised ; but the compounds all agree in the two leading 
 characters, that there are two radicals in every compound, and that every 
 compound forms two volumes of gas. 
 
 By arranging these compounds in groups, we shall show clearly the 
 evidence, and the peculiarities, of their binary constitution. 
 
 First Group. Combinations of compound radicals with one another. 
 7 examples: 
 
 C 4 H 9 ,C 5 H U .... Butyl-amyl. 
 C 4 H 9 ,C 6 H 13 .... Butyl-hexyl. 
 C 2 H 5 ,C 4 H 9 ..... Ethyl-butyl. 
 C 2 H 5 ,C 5 H 11 .... Ethyl-amyl. 
 OH 3 ,C e H 13 ..... Methyl-hexyl. 
 
 ' ' Cam P holene - 
 C 9 H'',C 7 H 5 Retiiiole. 
 
GASEOUS COMPOUND ORGANIC RADICALS. 65 
 
 All these radicals belong individually to the class of basic radicals, yet 
 the differences between them are sufficient to enable them to act as basic 
 and acid in respect to one another. The electro-chemical force is still 
 present, perhaps in feeble action, but in action quite sufficient for the 
 purpose of ensuring combination. 
 
 Second Group. Compounds of hydrogen with a compound radical. 
 {Hydrides.) 
 
 1 8 Examples : 
 
 H,CH 3 .... Methyl hydride (marsh gas). 
 
 H,C 2 H 5 . . . Ethyl hydride. 
 
 H,C 3 H 5 . . . Propylene. 
 
 H,C 4 H 7 . . . Butyrine. 
 
 H,C 4 H 9 . . . Butyl hydride. 
 
 H,C 5 H 7 . . . Likene. 
 
 H,C 5 H 9 . . . Valerine (Amylen). 
 
 H,C 3 H U . . . Amyl hydride. 
 
 H,C 6 H 5 . . . Phenyl hydride (Benzine). 
 
 H,C 6 H 11 . . . Hexylene. Caproiline. 
 
 H,C 7 H r "... Toluine. 
 
 H,C 7 H 7 . . . Retinnaphtha. t 
 
 H,C 9 H U . . . Mesitylol. 
 
 H,C 9 H U . . . Retinyl? 
 
 H,C 8 H 15 . . . Caprylene. Octylene. 
 
 H,C 9 H U . . . Cumenyl hydride. 
 
 H,C 10 H 13 . . . Thymyl hydride. 
 
 H,C 16 H 31 . . . Cetene. Palmityl hydride. 
 Third Group. Compounds of hydrogen with an oxide of a compound 
 radical ; or, it may be, compounds of a compound radical with oxide of 
 
 hydrogen, thus CH 3 ,HO, &c. {Alcohols. Hydrated oxides. Aldides.) 
 1 8 Examples: 
 
 H,CH 3 O . . . Methylic alcohol. 
 
 H,C 2 H 3 . . . Aldehyd. 
 
 H,C 2 H 5 . . . Alcohol. 
 
 H,C 3 H 3 O . . . Acroleine. 
 
 H,C 3 H 5 . . . Acrylic alcohol. \ ? 
 
 H,C 3 H 5 O . . . Propionic aldide. J' 
 
 H,C 3 H'O . . . Propylic alcohol. 
 
 H,C 4 H 7 O . . . Butyral. 
 
 H,C 4 H 9 O . . . Butylic alcohol. 
 
 H T C 5 H 7 O . . . Angelyl hydrate. 
 
 H,C 5 HO . . . Valeral. 
 
 H,C 5 H U O . . . Amylic alcohol. 
 
 H,C 8 H 13 O . . . Caproic alcohol. 
 
 H,C 7 H 13 O. . . Oenanthol. 
 
 H,C 7 H I5 O . . . Castor oil alcohol. 
 
 . . Caprylic alcohol. 
 
66 GASEOUS COMPOUND ORGANIC RADICALS. 
 
 H,C 10 H II O . . . Cumyl hydrate. 
 H,C i0 H ll O . . . Essence of anis. 
 
 Fourth Group. Compounds consisting of a compound radical, com- 
 bined with an oxide of the same radical. (Ethers. Oxides.) 
 3 Examples ; 
 
 CH 3 ,CH 3 . . . Methylic ether. 
 C 2 H 5 ,C 2 H 5 O. . . Ether. 
 AsC 2 H 6 ,AsC 2 H 8 . Oxide of cacodyl. 
 
 Fifth Group. Compounds containing a compound radical, combined 
 with an oxide of a different compound radical. (Compound Ethers and 
 Ketones.) 
 
 1 2 Examples : 
 
 CH 3 ,C 2 H 3 . . . Acetone [methyl and acetyl.] 
 CH 3 ,CH 2 O . . . Lignone. 
 CH 3 ,C 2 H 5 O . . . Ethylate of methyl. 
 CH^IT'O. . . Amylate of methyl. 
 C 2 H 5 ,C 5 H ll O . . Amylate of ethyl. 
 C 2 H 5 ,C 7 H 15 O . . Ethyl-heptyl ether. 
 C 3 H 7 ,C 4 H 7 O . . Butyrone. 
 C*H 5 ,CNO . . . Cyanate of ethyl. 
 C 5 H 9 ,C 5 H 7 0. . . Camphor. 
 C 5 H ll ,C 5 H 9 O 9 . . Peppermint Camphor. 
 C 8 H 14 ,C 8 H 12 O? . . Cedrole. 
 C 4 H 8 ,C 4 H 6 O? . . Suberone. 
 
 Sixth Group. Compounds containing oxide of hydrogen, combined 
 with an oxide of a compound radical. Thus : HO + CHO = H,CHO*. 
 (Hydrated Organic Acids.) 
 9 Examples : 
 
 H,CHO*. . . . Formic acid. 
 H,C 8 H 3 O* . . . Acetic acid. 
 H,C 4 H 7 O 8 . . . Butyric acid, 
 H,C 5 H 3 O 8 . . . Furfurol. 
 H^IFO 2 . . . Valerianic acid. 
 H,C 8 H U O 2 . . . Caproicacid. 
 H,(7H 5 O* . . . Benzoicacid. 
 H,C 7 H 13 O 2 . . . Oenanthylic acid. 
 H,C 10 H' 7 O 8 . . . Campholic acid. 
 
 Seventh Group. Compounds containing an oxide of a compound 
 radical, combined with an oxide of a different compound radical. Thus : 
 CH 3 O+CHO = CH 8 ,CHO 2 . (Salts of Methyl, Ethyl, Amyl, Butyl, 
 $c., with Organic Acids.) 
 21 Examples: 
 
 CH 3 ,CH0 9 . . . ' Methyl, formiate. 
 CH 3 ,C 2 H 8 8 . . Methyl, acetate. 
 . Methylal. 
 
GASEOUS COMPOUND ORGANIC RADICALS. 67 
 
 CH 3 ,C 4 H 7 2 . . Methyl, butyrate. 
 
 CH 3 ,CH U O 2 . . Methyl, caproate. 
 
 CH 3 ,C 7 H 5 2 . . Methyl, benzoate. 
 
 CH 3 ,C 8 H 15 O 2 . . Methyl, caprylate. 
 
 C 2 H 5 ,CH0 2 . . Ethyl, formiate. 
 
 C 2 H 5 ',C 2 H 3 2 . . Ethyl, acetate. 
 
 C 2 H 5 ,C 4 H 7 O 2 . . Ethyl, butyrate. 
 
 C 2 H 5 ^IPO 2 . . Ethyl, butylate. 
 
 C 2 H 5 ,C 5 H 9 2 . . Ethyl, valerianate. 
 
 C 2 H 5 ,C 6 H 11 2 . . Ethyl, caproate. 
 
 C 2 H 5 ,C 7 H 5 2 . . Ethyl, benzoate. 
 
 C 2 H 5 ,C 8 H 15 2 . . Ethyl, caprylate. 
 
 C 2 H 5 ,C 9 H 7 O 2 . . Ethyl, cinnamate. 
 
 C 2 H 5 ,C 10 H n 2 . . Ethyl, eliminate. 
 
 C 2 H 5 ^^ETO 2 . . Ethyl, laurate. 
 
 C 4 H 9 ,C 2 H 3 2 . . Butyl, acetate. 
 
 C 5 H ll ,C 2 H 3 2 . . Amyl, acetate. 
 
 C 5 H U ,C 5 H 9 2 . . Amyl, valerianate. 
 
 Eighth Group. Compounds containing an oxide of a metalloid, com- 
 bined with an oxide of a compound radical. (Nitrites.) 
 4 Examples : 
 
 C 7 H 7 ,N0 2 . . . Nitrite of toluine (nitrobenzoene). 
 
 C 2 H 5 ,NO 2 . . . Nitrite of ethyl. 
 
 C 6 H 5 ,N0 2 . . . Nitrite of phenyl (nitrobenzide). 
 
 C 5 H U ,N0 2 . . . Nitrite of amyl. 
 
 Ninth Group. Compounds consisting of a compound radical, com- 
 bined with a metalloid. (Chlorides, Iodides, Bromides, Fluorides., 
 and Cyanides.) 
 21 Examples: 
 
 <?R 3 ,C\ .... Chloride of acetyl. 
 
 C 5 H U ,C1 .... Chloride of amyl. 
 
 C 4 H 9 ,C1 .... Chloride of butyl. 
 
 AsC 2 H 6 ,Cl .... Chloride of cacodyl. 
 
 C 2 H 5 ,C1 .... Chloride of ethyl.' 
 
 CH 3 ,C1 .... Chloride of methyl. 
 
 C 2 H 3 ,Br . . . . Bromide of acetyl. 
 
 C 4 H 9 ,Br . . . . Bromide of butyl. 
 
 C*H 5 ,Br .... Bromide of ethyl. 
 
 C H 3 ,Br .... Bromide of methyl. 
 
 C 2 H 3 ,I .... Iodide of acetyl. ' 
 
 C 5 H U ,I .... Iodide of amyl. 
 
 C 4 H 9 ,I .... Iodide of butyl. 
 
 C 2 H 5 ,I .... Iodide of ethyl. 
 
 CH 8 ,I .... Iodide of methyl. 
 
 CH 3 ,F . . . . Fluoride of methyl. 
 
 F2 
 
68 OXYGEN HAS NO MEASURE IN GASEOUS SALTS. 
 
 C 5 H u ,Cy . . . Cyanide of amyl. 
 AsC 2 H 6 ,Cy . . . Cyanide of cacodyl. 
 
 C H 3 ,Cy . . . Cvanide of methyl. 
 
 C 4 H 9 ,Cy . . . Cyanide of butyl. 
 
 C 6 H 5 ,Cy . . . Cyanide of phenyl. 
 
 Tenth Group. Compounds containing a compound radical, combined 
 with an oxide of a metalloid. (Oxychlorides, &c.) 
 2 Examples : 
 
 C 7 H 5 ,C1O . . . Chloride of benzoile. 
 
 C 2 H 3 ,C1O . . . Oxy chloride of acetyl. 
 
 Eleventh Group. Compounds of various orders, all containing three 
 atoms of oxygen. 
 6 Examples : 
 
 C 2 H 3 ,C 2 H 3 O 8 . . Anhydrous acetic acid. 
 
 C'lF^H'O 3 . . Anhydrous batyric acid. 
 
 C*H 5 ,C*H 5 ; C O 3 . Carbonate of ethyl. 
 
 C*H 5 ,C*H 5 ; S*0 8 . Sulphite of ethyl. 
 
 C 2 H 5 ,C 5 H 3 O 3 . . Pyromucate of ethyl. 
 
 CH 3 ,N0 3 . . . Nitrate of methyl. 
 
 The compounds enumerated in these eleven groups amount to 121. 
 Their properties are remarkable. They all contain two radicals. They 
 all produce two volumes of gas. Most of them contain two compound 
 radicals. A few contain one simple and one compound radical. When 
 these radicals are isolated, each of them (as far as our knowledge ex- 
 tends), forms a single volume of gas : consequently, they all combine 
 with one another without suffering condensation. The relation of the 
 compounds to oxygen is as follows : 46 of them contain no oxygen ; 3 5 
 contain one atom ; 34 contain two atoms ; and 6 contain three atoms of 
 oxygen. Whatever the quantity of oxygen present, each compound 
 lias merely the gaseous volume that is proper to its two radicals. This 
 is equally the case, whether the radicals are simple or compound, 
 whether the quantity of oxygen is one, or two, or three atoms, or none. 
 The oxygen increases the weight of the radical, but adds nothing to its 
 measure. With hydrogen the results are entirely different. Any quan- 
 tity of carbon and hydrogen, which is combined by the organising powers 
 of nature into a compound radical,- from two atoms (Formyl = CH) up 
 to thirty-Jive atoms (Lauryl = C 12 !! 23 ) is condensed into a single volume 
 of gas, which is chemically equivalent to a single volume of hydrogen ; 
 but we cannot experimentally combine with one of these radicals 
 another volume of hydrogen without producing a hydride which measures 
 two volumes. Thus, oxygen, which, when separated from other elements, 
 can be obtained only in the state of gas when it goes into gaseous com- 
 bination with compound radicals, loses its volume, and adds only to the 
 weight of the compound, and nothing to the measure. How is it that 
 this remarkable fact has hitherto escaped the notice of chemists ? Is it 
 
A SALT IS A BINARY COMPOUND OF TWO RADICALS. 69 
 
 not a powerful argument in support of the theory of the separate exist- 
 ence of the compound radicals ? The difference between oxygen and all 
 other elements proves clearly that oxygen is not a radical, and is never 
 the equivalent of a radical ; not one of the 1 2 1 salts enumerated in the 
 foregoing groups, can exchange either of its radicals for oxygen, though 
 radicals can be substituted for radicals, either single or compound, to any 
 extent whatever. Hence, all the arguments that have been urged in 
 favour of the hypotheses, that one volume of oxygen is the equivalent 
 of two volumes of hydrogen and of two volumes of chlorine, fall to the 
 ground. . 
 
 From the facts disclosed by this survey, I think w r e may draw the 
 general conclusions, that all salts are BINARY ; that they are compounds 
 formed of two radicals, which may be simple or compound, oxidised or 
 not oxidised. 
 
 The evidence that has been brought forward in support of this theory 
 is twofold ; first, that which consists in an attempted refutation of the 
 hypothesis of sesquioxides, and secondly, the evidence supplied by the 
 physical constitution of the gases, and which may be termed the argu- 
 ment from gaseous volumes. The evidence that would be obtained by 
 comparing the compounds that are volatile, with the immense mass of 
 corresponding organic compounds that are not volatile, may be called the 
 argument from analogy. It is an argument of great weight, but its 
 comprehensiveness unfits it for the limits of this Essay. I shall in the 
 following pages adduce a few, but only a few, illustrations of this 
 character. 
 
 The radical theory modifies in a peculiar degree the chemical character 
 which is usually ascribed to oxygen. Hitherto, chemists have been 
 accustomed to consider oxygen as a centre round which all other elements 
 gyrated the sun of the chemical planetary system. But the radical 
 theory proves to us, that the substantive elements of a salt, whether it 
 is acid, alkaline, or neutral, are the two radicals which it contains. 
 Without two radicals there can be no salt. Without oxygen we can 
 have many salts. Any two radicals, simple or compound, can form a 
 salt, with no oxygen, with one atom, or two, or three, or four atoms of 
 oxygen. The equivalency of the radicals is not affected by the presence 
 or absence of oxygen. Those salts which have no oxygen are as perfect 
 in their characters as those which have much oxygen. Those salts which 
 are gaseous have no increase in volume from the acquisition of oxygen. 
 A volume of hydrogen in combination (not forming part of a radical) 
 measures a volume, so does a volume of chlorine. One, two, or three 
 volumes of oxygen in combination, measure nothing. Oxygen, therefore, 
 is not a radical, or salt-former, in the sense in which hydrogen, chlorine, 
 the metals, and the hydrocarbons are radicals. A volume of it is not 
 the equivalent, either of one volume, or of two volumes of hydrogen or 
 of chlorine. Its action is peculiar to itself, and not a property which it 
 holds in common with other elements. In forming our notions of salts, 
 
70 
 
 DISCRIMINATION OF BASIC FROM ACID RADICALS. 
 
 and in framing our plans for their classification, we should consequently 
 do so without regard to the presence or absence of oxygen. For that 
 reason, we say that a compound of two radicals is a salt, whether the 
 radicals are oxidised or not. And by enlarging our conception of the word 
 " radical," so that it signifies either elements or compound radicals, we 
 are provided with a theory of the salts that applies equally to inorganic 
 and to organic chemistry. 
 
 Oxygen is not only unnecessary to the existence of a salt, but it is not 
 even the acid-former in the sense that many chemists so consider it. 
 Even among inorganic compounds, oxygen, as was many years ago 
 pointed out by Davy, is not the cause of acidity. Chlorate of potassium 
 = KC1 is a neutral salt, and when three atoms of oxygen are added, 
 producing chlorate of potash = KC1O 3 , the salt is still neutral. The 
 hydrate of chloric acid = HC10 3 is an acid. Remove all the oxygen, 
 leaving hydrochloric acid = HC1, and the compound is still acid. So, 
 among compound organic radicals, the presence or the quantity of oxygen 
 is not the cause of acidity. An acid requires the presence of an acid 
 radical. An acid radical can sometimes be produced by the action of 
 oxygen on non-acid compounds, but even then the acid is seldom the 
 result of the mere addition of oxygen. Other circumstances operate to 
 this end, and, among these, one of the most important, as respects the 
 hydrocarbons, is the right apportionment of their hydrogen to their 
 carbon. In illustration of this point, the following Table presents a 
 selection of compound radicals, arranged in such a mariner as to show this 
 relation the radicals which contain the greatest relative quantity of 
 hydrogen being placed first in the list : 
 
 Ratios. 
 
 Formulae. 
 
 Radicals. 
 
 Salts containing 
 the Radicals. 
 
 C. H. 
 
 
 
 
 1 3* 
 
 C H 3 
 
 . Methyl. 
 
 
 I 2-5 
 
 C 2 H 5 
 
 Ethyl. 
 
 
 I 2-333 
 
 (C 3 H 7 
 IC 3 ^ 
 
 Propyl. 
 Lipyl. 
 
 
 I 2-25 
 
 C 4 H 9 
 
 Butyl. 
 
 
 I 2'2 
 
 C 5 H 11 
 
 Amvl. 
 
 
 I ' 2-167 
 
 C 6 H 13 
 
 Hexyl. 
 
 
 I 2-143 
 
 C 7 H 15 
 
 Heptyl. 
 
 
 1 2-125 
 
 CH 17 
 
 Octyl. 
 
 
 I 2*067 
 
 C 15 H 31 
 
 
 Palmitone. 
 
 1 2 '062 
 
 C^M 33 
 
 Cetyl. 
 
 
 I 2-037 
 
 C^H 55 
 
 Ceryl. 
 
 
 I | 2-033 
 
 C 30 H 61 
 
 Myricyl. 
 
 
 * J 
 I ' 2- 
 
 C H 8 
 
 Olefiant Gas (Vinyl). 
 
 
DISCRIMINATION OF BASIC FROM ACID RADICALS. 
 
 71 
 
 Ratios. 
 
 Formulae. 
 
 Radicals. 
 
 Salts containing 
 the Radicals. 
 
 C. 
 
 H. 
 
 
 
 
 I 
 
 1-967 
 
 C 30 H 59 
 
 Melissyl 
 
 Melissic Acid. 
 
 I 
 
 1-963 
 
 Q27JJ53 
 
 . 
 
 Cerotic Acid. 
 
 I 
 
 1-952 
 
 C 2I H 41 
 
 . 
 
 Behenic Acid. 
 
 I 
 
 1-95 
 
 C 20 H 39 
 
 . 
 
 Arachidic Acid. 
 
 I 
 
 1-947 
 
 C 19 H 37 
 
 . 
 
 Balenic Acid. 
 
 I 
 
 1-944 
 
 C 18 H35 
 
 . 
 
 Stearic Acid. 
 
 I 
 
 1-941 
 
 C 17 !! 33 
 
 . 
 
 Margaric Acid. 
 
 I 
 
 I'937 
 
 C 16 H 31 
 
 Palmityl 
 
 Palmitic Acid. 
 
 I 
 
 1-933 
 
 C 15 H 29 
 
 . . 
 
 Benic Acid. 
 
 I 
 
 1-928 
 
 Q14JJ27 
 
 Myristyl 
 
 Myristic Acid. 
 
 I 
 
 1-923 
 
 QI3JJ25 
 
 Cocinyl . 
 
 Cocinic Acid. 
 
 I 
 
 1*916 
 
 C 12 !! 23 
 
 Lauryl . 
 
 Laurie Acid. 
 
 I 
 
 1-909 
 
 C L1 H 21 
 
 . 
 
 Margaritic Acid. 
 
 I 
 
 1-9 
 
 C l H 19 
 
 Rutyl . 
 
 Rutic Acid. 
 
 
 
 
 
 Capric Acid. 
 
 I 
 
 1-889 
 
 C 9 H 17 
 
 Pelargyl 
 
 Pelargonic Acid. 
 
 I 
 
 1-875 
 
 C8JJ15 
 
 Capryl . 
 
 Caprylic Acid. 
 
 I 
 
 1-857 
 
 C 7 H 13 
 
 Oenanthyl 
 
 Oenanthylic Acid. 
 
 
 
 !C 6 H U 
 
 J Caproyl . 
 
 Caproic Acid. 
 
 
 1-822 
 
 
 I 
 
 Glucosic Acid. 
 
 
 i j3 
 
 Q18JJ33 
 
 J 
 
 Oleic Acid. 
 
 
 
 
 I 
 
 Ricinolic Acid. 
 
 I 
 
 1-8 
 
 C 5 H 9 
 
 Valeryl . 
 
 Valerianic Acid. 
 
 I 
 
 1-75 
 
 C 4 H 7 
 
 Butyryl . 
 
 Butyric Acid. 
 
 I 
 
 1*7 
 
 Q10JJ17 
 
 Camphyl 
 
 Campholic Acid. 
 
 
 
 
 Acryl? . 
 
 Acrylic Alcohol. 
 
 
 
 
 Allyl ? 
 
 
 I 
 
 1-667 
 
 C 3 H 5 
 
 < Propionyl . 
 
 Propionic Acid. 
 
 
 
 
 1 
 
 Lactic Acid. 
 
 
 
 
 1 
 
 Metacetonic Acid. 
 
 I 
 
 1-6 
 
 C 5 H 8 
 
 
 Sebacic Acid. 
 
 
 
 JC 2 H 3 
 
 fAcetyl . 
 s 
 
 Acetic Acid. 
 Home-lactic Acid. 
 
 I 
 
 r 5 
 
 
 1 
 
 Glycollic Acid. 
 
 
 
 C 4 H 6 
 
 Suberyl . 
 
 Suberic Acid. 
 
 I 
 
 1-429 
 
 C 7 H 10 
 
 . 
 
 Pimelic Acid. 
 
 I 
 
 
 C 5 H 7 
 
 (Angelyl 
 [ Camphoryl 
 
 Angelic Acid. 
 Camphoric Acid. 
 
 
 
 
 r 3 H 4 
 
 I 
 
 Mucic Acid. 
 
 
 333 
 
 V> JTJL 
 
 . 
 
 Adipic Acid. 
 
 I 
 
 r 3 
 
 C 10 H 13 
 
 Thymyl. 
 
 
72 
 
 DISCRIMINATION OF BASIC FROM ACID RADICALS. 
 
 Ratios. 
 
 Formulas. 
 
 Radicals. 
 
 Salts containing 
 the Radicals. 
 
 C. 
 
 H. 
 
 
 
 
 I 
 
 1-286 
 
 C7H 9 
 
 
 Kinic Acid. 
 
 I 
 
 1-25 
 
 C^H 5 
 
 , 
 
 Isotartaric Acid. 
 
 I 
 
 1-222 
 
 C 9 H U 
 
 Cumenyl. 
 
 
 
 
 C 9 H U 
 
 Mesityl. 
 
 
 I 
 
 J'2 
 
 C 5 H 6 
 
 . 
 
 Pyrotartaric Acid. 
 
 I 
 
 I'l 
 
 C io H u 
 
 Cumyl . 
 
 Cuminic Acid. 
 
 
 
 C l H l 
 
 Formyl . 
 
 Formic Acid. 
 
 
 
 C'H 1 
 
 Pteleyl. 
 
 
 
 
 P2TT2 
 
 t 
 
 Succinic Acid. 
 
 
 
 H 
 
 . 
 
 Tartaric Acid. 
 
 I 
 
 r 
 
 C 3 H 3 
 
 Acryl? . 
 
 Acrylic Acid. 
 Pyravic Acid. 
 
 
 
 p4 TT4 
 
 f . 
 
 Malic Acid. 
 
 
 
 CJ H 
 
 . 
 
 Metatartaric Acid. 
 
 
 
 C 7 H 7 
 
 Toluenyl. 
 
 
 
 
 [C 9 H 9 
 
 Styryl. 
 
 
 I 
 
 0-875 
 
 C"H 7 
 
 |Anisyl . 
 fToluyl . 
 
 Anisic Acid. 
 Toluic Acid. 
 
 I 
 
 0-833 
 
 C 8 H 5 
 
 [Phenyl . 
 
 Citric Acid. 
 Phenic Acid. 
 
 I 
 
 0-8 
 
 C 5 H* 
 
 . 
 
 Citraconic Acid. 
 
 I 
 
 0-778 
 
 C 9 H 7 
 
 Cinnamyl 
 
 Cinnamic Acid. 
 
 I 
 
 0-75 
 
 C 4 H 3 
 
 . 
 
 Tartrelic Acid. 
 
 I 
 
 0714 
 
 C 7 H 5 
 
 Benzyl . 
 
 Benzoic Acid. 
 
 
 
 
 f 
 
 Pyromeconic Acid. 
 
 I 
 
 0-6 
 
 C'H 8 
 
 i 
 
 Pyromucic Acid. 
 
 
 
 
 I 
 
 Furfurol. 
 
 I 
 
 0-571 
 
 C 7 H 4 
 
 Salicyl . 
 
 Salicylic Acid. 
 
 
 
 
 f 
 
 Aconitic Acid. 
 
 
 
 C^H 1 
 
 ; 
 
 \ 
 
 Fumaric Acid. 
 
 
 
 
 1 . .. 
 
 Maleic Acid. 
 
 I 
 
 0-5 
 
 
 f ' 
 
 Phtalic Acid. 
 
 
 
 ]C 4 H S 
 
 J 
 
 \ 
 
 Tartaric Acid. 
 
 
 
 
 1 
 
 Tartrelic Acid. 
 
 
 
 C 6 !! 3 
 
 
 Comenic Acid ? 
 
 I 
 
 0-429 
 
 C 7 H 3 
 
 ' 
 
 Gallic Acid? 
 
 I 
 
 0-333 
 
 C 6 H a 
 
 . 
 
 Comenic Acid? 
 
 I 
 
 0-143 
 
 (7H l 
 
 I : : 
 
 Meconic Acid. 
 Chrysammic Acid. 
 
DISCRIMINATION OF BASIC FROM ACID RADICALS. 73 
 
 Taking into consideration the properties and the composition of the 
 compounds named in this list, we seem to be warranted in drawing the 
 following conclusions : 
 
 1. That carbon acts as an acid radical; that hydrogen acts as a basic 
 radical ; and that radicals containing the two elements act as acid or basic, 
 according as the carbon or the hydrogen exceeds a certain proportion. 
 
 2. That the compound CH 2 is one in which the acid properties of the 
 carbon are neutralized by the basic properties of the hydrogen. This 
 compound is olefiant gas, called by Berzelius elayl, and by Gmelin vine, 
 a term which might with convenience be translated into VINYL, which 
 term I propose to employ. 
 
 3. Compound radicals that contain any proportion of hydrogen 
 greater than that of H 2 to C l , are BASIC. Those that contain any pro- 
 portion of hydrogen less than that of H 2 to C 1 , are add. Thus 
 
 C 3o H ei = Myricyl . . A basic radical. 
 CH 2 = Vinyl . . Neutral. 
 C so H 59 = Melissyl . . An acid radical. 
 
 Hence the basic radicals occur in the above list before Vinyl, and the 
 acid radicals after it. I speak only in a general sense, and do not mean 
 to give to this observation the character of a fixed and absolute law. But 
 supposing the law to be only approximately true, this list, notwith- 
 standing its irregularities, may serve in organic chemistry the same pur- 
 pose that Berzelius's electro-chemical arrangement of the elements serves 
 in inorganic chemistry, namely, as a formal guide in the arrangement of 
 basic and acid radicals. Notwithstanding the irregularities, it is evident 
 that we may, with propriety, decide between any two radicals, that the 
 one which contains the greater proportion of hydrogen is the more basic 
 of the two. According to this rule, methyl is more basic than ethyl, 
 ethyl than propyl, propyl than amyl, and so on, through the whole 
 range of the hydrocarbons. There are exceptions to this rule, but 
 perhaps not more than occur in Berzelius's electro-chemical list of the 
 elements. It is a great point gained, if, setting oxygen aside, we can, 
 from the mere inspection of the formulae of the hydrocarbons, distinguish 
 the basic from the acid. 
 
 The present uncertain practice of chemists in their dealings with salt 
 radicals, shows the necessity of adopting some decisive method of dis- 
 tinguishing the basic radicals from the acid. When Professor Williamson 
 discovered his compound ethers, he was unable to name them in accord- 
 ance, with any commonly understood system ; and consequently he gave 
 to each compound a series of synonymes. Thus the compound which 
 
 C 2 H 5 
 contained ^jr 3 was called the three carbon ether, the efhylate of methyle, 
 
 and the methylate of ethyle. Now upon the principle that we have just 
 laid down, methyl must, in all cases, be held to be basic against ethyl, 
 
74 REDUCTION OF BASIC RADICALS TO ACID RADICALS. 
 
 the relation of the hydrogen to the carbon being 3 to I against 2% to i. 
 Hence, the difficulty of naming the compound is avoided, and our 
 memories are spared the infliction of useless synonymes. 
 
 It would be easy to refer to innumerable examples in the writings of 
 Gerhardt, which show the want of this principle of classification. He 
 finds, for example, a compound containing benzyl and acetyl, with three 
 atoms of oxygen, 1 =C 2 H 3 -f-C 7 H 5 -f O 3 , and he calls it "acetic benzoate 
 or benzoic acetate" Again, he finds a similar compound containing 
 acetyl and cumenyl =C 2 H 3 +C 10 H ll -f-0 3 , and he is uncertain whether 
 to call it acetic cuminate or cuminic acetate. Such difficulties are imme- 
 diately resolved by the rule that has been proposed, according to which 
 acetyi is to be considered as decidedly basic towards both benzyl and 
 cuminyl. 
 
 It is not proposed to investigate in systematic detail the proximate 
 composition of the compound radicals, but in reference to the question 
 whether oxygen is the acidifying principle, and to one or two doctrines 
 that depend upon the answer to that question, it will be useful to adduce 
 a few special illustrations. 
 
 Reduction of Basic Radicals to Acid Radicals. 
 
 A remarkable relation exists between many basic radicals and acid 
 radicals, taken in pairs. Vinyl = CH 2 being the point of neutrality, 
 certain basic radicals taken from above it in the list, are related to par- 
 ticular acid radicals taken from below it, the difference in composition 
 between the pair being that of two atoms of hydrogen. Examples : 
 Basic Radicals. Acid Radicals. 
 
 Methyl = C H 3 - H 2 = C H = Formyl. 
 
 Ethyl = C 2 H 5 - H 2 = C 2 H 8 = Acetyl. 
 
 Propyl = C 3 H 7 - H 2 = C 8 H 5 = Propionyl. 
 
 Butyl = C 4 H 9 - H 2 = C 4 H 7 = Butyryl. 
 
 Amyl = C 5 H 11 - H 9 = C 5 H 9 = Valeryl. 
 
 Myricyl = C 30 H 61 - H 2 = C 3n H 59 = Melissyl. 
 
 From this it appears that a BASIC Hydrocarbon no matter what 
 may be the complexity of its composition, is, according to theory, con- 
 vertible into an ACID Hydrocarbon by any process which withdraws from 
 it two atoms of hydrogen, that being the constant difference between a 
 basic radical of the kind referred to and its corresponding acid radical. 
 
 Is this theoretical vision practically true ? Can we convert a basic 
 radical into an acid radical, by withdrawing from it two atoms of hydro- 
 gen ? If the answer to that question is yes, then the process of acidifi- 
 cation I am speaking of the acidification of hydrocarbons only consists, 
 
 1 Quarterly Journal of the Chemical Society (1852), V. 227. 
 
REDUCTION OF ACID RADICALS TO BASIC RADICALS. 75 
 
 not simply in the addition of oxygen, but primarily and essentially in the 
 abstraction of two atoms of hydrogen from the compound radical that is 
 to be acidified. The answer to the inquiry is, practically, in the affirma- 
 tive, as regards a considerable class of radicals. Any chemical agent, 
 or even a physical agent, such as the galvanic current, which can sepa- 
 rate from a basic radical of the kind referred to two atoms of hydrogen 
 produces an acid radical, or performs the essential part of the operation 
 which is termed acidification. Oxygen, therefore, though the common 
 agent of acidification, and chiefly because of the facility with which it 
 converts two atoms of hydrogen into an atom of water and so removes 
 them, is not essentially the acidifying principle. Chlorine can be made 
 an acidifying principle ; the galvanic-battery can be made an acidifying 
 principle ; for both can separate hydrogen from a basic radical, and so 
 convert it into an acid radical. 
 
 Beduction of Acid Eadicals to Basic Kadicals. 
 
 If we examine in a cursory manner the composition of the radicals 
 just referred to, we find that the basic radicals appear to consist of a 
 multiple of vinyl = CH 2 , added to a single atom of hydrogen = H, 
 while the acid radicals appear to consist of a multiple of vinyl = CH 2 , 
 added to a single atom of formyl = CH. It follows, that if we can 
 take from an acid radical a single atom of carbon = C, we can destroy 
 its chemical character, and convert it into a basic radical. Take the 
 cases just cited : 
 
 Acid Radicals. Basic Eadicals. 
 
 Formyl = C H - C = H = Hydrogen. 
 
 Acetyl = C 2 H 3 - C = C H 3 = Methyl. 
 
 Propionyl = C 3 H 5 - C = C 4 H 5 = Ethyl. 
 
 Butyryl = C 4 H 7 - C = C 3 H 7 = Propyl. 
 
 Valeryl = C 5 H 9 - C = C 4 H 9 = Butyl. 
 
 Hence we have it, theoretically, in our power, by an alternate abstrac- 
 tion from a radical of H 2 and C 1 to make it alternately acid or basic, 
 through a regular course of reductions till we come at last to the 
 elementary basic radical H ; for 
 
 Amyl - H 2 is Valeryl. 
 Valeryl - C , Butyl. 
 
 Butyl - H 2 
 
 Butyryl - C 
 
 Propyl - H 2 
 
 Propionyl C 
 
 Ethyl - H 2 
 
 Acetyl C 
 
 Methyl - H 2 
 
 Formyl - C 
 
 , Butyryl. 
 , Propyl. 
 , Propionyl. 
 , Ethyl. 
 , Acetyl. 
 , Methyl. 
 , Formyl. 
 , Hydrogen. 
 
( 76 ) 
 Experimental Eeduction of Radicals. 
 
 What is here assumed to be theoretically possible, can, to a certain 
 extent I do not know to how limited an extent be performed expe- 
 rimentally. Kolbe has shown 1 that by the electrolysis of a valerianate 
 = K,C 5 H 9 2 , valeryl = C 5 H 9 is converted into butyl "= C 4 H 9 , and that by 
 the electrolysis of an acetate = K,C 2 H 3 O 2 , acetyl = C*H 3 is converted 
 into methyl = CH 3 , the extra atom of carbon being driven off in the 
 state of carbonic acid. 
 
 " Particular interest," says Professor Miller, 2 "is attached to these 
 researches, owing to the circumstance that in each case the compounds 
 obtained by the electrolysis belong to a series related to an alcohol 
 different from that which was submitted to decomposition. The vale- 
 rianic acid thus yields an ether of the butylic series ; and acetic acid, 
 which is a derivative of wine alcohol, furnishes the carbo-hydrogen 
 which belongs to the wood-spirit series." 
 
 Brazier and Gossleth have shown 3 that by the electrolysis of a caproate 
 = K, C 6 H U 2 , caproyl = C'H U is converted into amyl = C 5 H", and 
 that by the electrolysis of an cenanthylate = K, C 7 H 13 O 2 , oenanthyl = 
 C 7 H 13 is converted into hexyl = C 6 H 13 , with evolution of carbonic acid. 
 
 In all these examples, acid radicals are reduced to basic radicals by the 
 abstraction of C l . 
 
 Similar transformations can be effected chemically ; as, for example, by 
 the joint action of heat and fixed alkalies. Thus, Professor Brodie, by 
 heating the hydrate of myricyl = H, C 30 H 61 O, with lime and potash con- 
 verted it into melissate of potash = K, C :HO H 59 O 2 , in which process the 
 basic radical C^H 61 loses two atoms of hydrogen, and is reduced to 
 the acid radical C^H 59 . In the same manner, the hydrate of ceryl = 
 H^H^O was converted into cerotate of potash = K, C* r H 53 O 2 , where 
 the radical ceryl = C 27 H 55 is reduced by the abstraction of H 2 to another 
 radical not yet named = C 27 !! 53 . Dumas and Stas, by acting in this 
 manner on ethal, or hydrate of cetyl = H, C I8 H 38 O converted it into pal- 
 mitate of potash = K, C I6 H 31 O where the radical cetyl = C 16 H 33 is re- 
 duced to the radical palmityl = C 16 H 31 . In all these examples basic 
 radicals are reduced to acid radicals by the abstraction of H 2 . This pro- 
 cess in the ordinary language of organic chemistry is called " oxidation." 
 
 The Ketones. 
 
 In this manner also the KETONES are prepared. 4 Here, again, we 
 have acid radicals reduced to basic radicals by the abstraction of C l . 
 
 1 Chemical Soc. Quarterly Journal, II., 157. 
 
 2 Elements of Chemistry (1856), Part II., H2O. 
 
 3 Chemical Soc. Quarterly Journal, III., 210. 
 
 4 Gmelin, Handbook of Chemistry, VII., 136. 
 
THE KETONES. 
 
 77 
 
 Compounds exposed to Heat. 
 
 A. K,C S H 3 2 + K,C 2 H 3 2 
 
 B. K,C 3 H 5 O 2 + K,C 3 H 5 O 2 
 
 C. K,C 4 H 7 O 2 + K,C 4 H 7 O 2 
 
 D. K,C 5 H 9 2 + K,C 5 H 9 2 
 
 E. K,C 7 H 5 O 2 + K,C 7 H 5 O 2 
 
 F. K,C'H 17 2 + K,C 10 H 17 2 
 
 G. I^C^H^O 2 -f- K,C 17 H 33 O 2 
 H. K,C 5 H 9 O 2 + K,C 2 H 3 O 2 
 
 K 2 C0 3 
 
 Compounds produced. Constant product. 
 
 = C H 3 , C 2 H 3 1 
 
 = C 2 H 5 ,C 3 H 5 
 
 = C 3 H 7 , C 4 H 7 O 
 
 = C 4 H 9 ,C 5 H 9 
 
 = C 6 H 5 , C 7 H 5 O 
 
 = C 9 H I7 ,C 10 H 17 
 
 = C Ifl H 88 ,C 17 H 38 O 
 
 = C 4 H 9 , C s H 3 O 
 In every example two atoms of salt are decomposed, because the car- 
 bonate of potash to be produced is bibasic = KKCO 3 . The salts are 
 submitted to dry distillation ; the ketones form a distillate, and the fixed 
 carbonate of potash remains behind. One of the compounds loses a 
 single atom of carbon, and is thus reduced from an acid radical to a 
 basic radical. Three atoms of oxygen go off with the carbon, leaving 
 one atom with the ketone, which therefore consists in each case of an 
 unoxidised basic radical, combined with an oxidised acid radical, con- 
 stituting a compound of the same nature as the compound ethers 
 described in Group 5, page 66. 
 In A. Acetyl 
 
 B. Propionyl = 
 
 C. Butyryl = 
 
 D. Valeryl 
 
 E. Benzyl 
 
 F. Camphyl 
 
 G. Margaryl 
 H. Valeryl 
 
 The names usually given to these ketones are as follow : A, acetone. 
 B, propione. C,butyrone. D, valerone. E, benzone. F, campholone. 
 G, margarone. H. There is a difficulty respecting this ketone, because 
 it is unknown whether the atom of carbon is abstracted from the valeryl 
 
 or the acetyl. Williamson gives the formula n TT CO, which admits the 
 
 L/ 4 -tl 9 
 
 ketone to contain butyl, methyl, and oxide of carbon, a composition that 
 is by no means probable. Gerhardt says of it, 2 that " it is evidently the 
 valeride of methyl or the acetylide of butyl," a description which suffi- 
 ciently shows the difficulty of choice. However, whether this particular 
 ketone is to be written C<H 9 ,C*H 3 0, or CH 3 ,C 5 H 9 O, the result is the 
 same in regard to my present argument, which is to prove that certain 
 acid radicals can be reduced to basic radicals by the abstraction of one 
 atom of carbon. 
 
 1 H is the result of an experiment made by Professor Williamson, 
 Quarterly Journal Chem. Soc. IV., 239. 
 8 Traite de Chimie Organique, II., 650. 
 
 = C 2 H 3 is red 
 = C 3 H 5 
 = C 4 H 7 
 = C 5 H 9 
 = C 7 H 5 
 = C 10 H lf 
 = C I7 H 
 = C d H 9 
 
 uced to Methyl = C H 3 
 Ethyl = C 2 H 5 
 Propyl = C 3 H 7 
 Butvl = C 4 H 9 
 Phenyl = C 6 H 5 
 Pelargyl = C 9 H 17 
 Cetyl = C ie H" 
 Butyl = C 4 H 9 
 
( 78 ) 
 
 The Aldehydes. 
 
 Experiments of a character precisely similar to the foregoing have 
 been described by Limpricht and Hitter, 1 in reference to the production 
 of the class of compounds called aldehydes or aldides. If formiate of 
 lime = Ca,CH0 2 is heated with the lime-salt of another acid, the formyl 
 is decomposed. Its carbon produces carbonic acid, and its hydrogen 
 becomes a basic radical to the acid radical of the other salt. Thus 
 
 Ca, CHO 2 -f Ca, C 2 H 3 8 = CaCa, CO 3 + H, C 2 H 3 O 
 Formiate of lime. Acetate of lime. Carbonate of lime. Aldehyde. 
 
 According to Ritter this reduction of formyl to hydrogen has been 
 effected experimentally with all the following compounds : 
 
 Ca, CHO 8 + Ca, C J H 5 2 = CaCa, CO 3 + H, C 3 H 5 O 
 
 Propionate of lime. Propylaldehyde . 
 
 Ca, CHO 2 + Ca,C 5 H 9 O 2 = CaCa, CO 3 + H, C 5 H 9 O 
 Valerate of lime. Valeraldehyde. 
 
 Ca, CHO 2 + Ca, C 7 H"0 2 = CaCa, CO 3 + H, C 7 H I3 
 Oenanthylate of lime. Oenardhol. 
 
 Ca, CHO 2 + Ca, C 8 H 15 O 2 = CaCa, CO 3 + H, C 8 H 15 
 Caprylate of lime. Caprylaldehyde. 
 
 In all these cases an acid radical is reduced to a basic radical by the 
 abstraction of C 1 . 
 
 This evidence to prove the experimental reduction of compound radi- 
 cals from acid to basic, and from basic to acid, by the alternate abstrac- 
 tion of C 1 and H 2 , has been adduced because the subject does not appear 
 to be clearly apprehended by many chemists. Even Gmelin advances 
 opinions that are in some respects adverse to these facts. Thus, in 
 speaking of the transformations of organic compounds, he says, 2 that 
 " they may take place by the complete or partial abstraction of one or 
 more constituents (CARBON EXCEPTED)." And, again, " The carbon of 
 an organic compound cannot be removed by substitution; for this 
 element is the one essential principle of organic compounds ; the number 
 of its atoms determines their character, and no other substance can take 
 its place. Without carbon nothing organic can exist ! Even the diminution 
 of the number of its atoms in a compound would immediately remove 
 that compound into another series, and alter its character entirely." 
 
 The Vinyl Series of Radicals. 
 
 It would take me too far into details to enter into the consideration of 
 the transformation of organic radicals generally. The facts that I have 
 
 1 Quarterly Journal of the Chemical Society (1856), IX., 188. 
 
 2 Handbook of Chemistry, VII., 71. 
 
THE VINYL SERIES OF BASIC AND ACID RADICALS. 
 
 79 
 
 adduced show evidently the distinction of radicals into basic and acid ; how 
 each kind can be converted into the other, and how totally independent 
 of mere oxidation is the discrimination of radicals into these two classes. 
 It is, however, so highly interesting to observe the relationship of the 
 hydrocarbons one to another, that I must bring forward a single complete 
 SERIES, in order to collect and confirm, the facts which I have brought 
 forward in detail. 
 
 Radicals. Their Salts. 
 
 C 30 H 61 
 Q30JJ59 
 
 - 
 
 H 2 
 
 C 
 
 = 
 
 C 30 H 61 
 
 C 30 H 5tf 
 C 29 H 59 
 
 Myricyl 
 
 Melissyl 
 
 Hydrate of myricyl 
 Melissic acid 
 
 Q29JJ59 
 
 
 
 H 2 
 
 
 
 C i9 H 57 
 
 
 
 C 29 H 57 
 
 
 
 C 
 
 = 
 
 C 28 H 57 
 
 
 
 C 28 H 57 
 
 
 
 H 2 
 
 = 
 
 C2 8 H 55 
 
 
 
 C 28 H 35 
 C 27 H 55 
 
 
 
 C 
 H 2 
 
 =5 
 
 C 27 H 55 
 C 27 H 53 
 
 Ceryl 
 
 Hydrate of ceryl 
 Cerotic acid 
 
 C^H 53 
 
 
 
 C 
 
 
 
 C 26 H 53 
 
 
 
 C*H 
 
 
 
 H 2 
 
 
 
 C 26 H M 
 
 
 
 C 26 H 51 
 
 
 
 C 
 
 
 
 C i5 H 51 
 
 
 
 CH 51 
 
 
 
 H 2 
 
 ; 
 
 C 85 H 49 
 
 
 
 C 25 H 49 
 
 
 
 C 
 
 = 
 
 C 24 H 49 
 
 
 
 OH 49 
 
 
 
 H 8 
 
 = 
 
 C 24 H 47 
 
 
 
 C 24 H 47 
 
 _ 
 
 C 
 
 -at 
 
 C 23 H 47 
 
 
 
 C 23 H 47 
 
 
 
 H 2 
 
 
 
 C 43 H 45 
 
 
 
 C 23 H 45 
 
 
 
 C 
 
 as 
 
 C 22 H 45 
 
 
 
 C 2-2 H 45 
 
 
 
 H 2 
 
 
 
 Q22JJ43 
 
 
 
 C 22 H 43 
 
 
 
 C 
 
 
 
 C 21 H 43 
 
 
 
 C 21 H 43 
 
 
 
 H 2 
 
 = 
 
 C 21 H 41 
 
 . 
 
 Behenic acid 
 
 C 21 H 41 
 
 
 
 C 
 
 = 
 
 C 20 H 41 
 
 
 
 C 20 H 41 
 
 
 
 H 2 
 
 
 
 C -20 H 39 
 
 v 
 
 Arachidic acid 
 
 C *0 H 39 
 
 
 
 C 
 
 
 
 Q19JJ89 
 
 
 
 C 19 H 39 
 
 
 
 H 3 
 
 = 
 
 C 19 H 3 7 
 
 g 
 
 Balenic acid 
 
 C 19 H 8 7 
 
 
 
 C 
 
 
 
 C 18 H 37 
 
 
 
 Q18JJ37 
 
 
 
 H 2 
 
 
 
 C 18 H 35 
 
 . 
 
 Stearic acid 
 
 C 18 H 35 
 
 
 
 C 
 
 rz 
 
 C 17 H 35 
 
 
 
 C I7 H 35 
 
 C 17 H 33 
 C 16 H 33 
 C 16 H 3l 
 
 
 
 H 2 
 C 
 H 2 
 C 
 
 = 
 
 C 17 H 33 
 
 C ,e H 33 
 
 C 16 H 31 
 C 15 H 31 
 
 Margaryl 
 Cetyl 
 Palmityl 
 
 Margaric acid 
 Ethal is its hydrate 
 Palmitic acid 
 Palmitone 
 
 (.ISJJSl 
 
 - 
 
 H 2 
 
 : 
 
 C 15 H 29 
 
 
 Benic acid 
 
 C 15 H 29 
 
 
 
 C 
 
 
 
 C 14 H 29 
 
 
 
 C 14 H 29 
 C I4 H 7 
 C 13 H 17 
 C 13 H 25 
 
 - 
 
 H 2 
 C 
 H 2 
 C 
 
 = 
 
 C 14 H 27 
 
 C 13 H87 
 
 C 13 H 25 
 
 C 12 H 25 
 
 Myristyl 
 Cocinyl 
 
 Myristic acid 
 Myristone 
 Cocinic acid 
 
80 
 
 THE VINYL SERIES OF BASIC AND ACID RADICALS. 
 
 C 12 H* 5 
 
 - H 8 
 
 
 
 C'- 2 H 23 
 
 C 12 H' 3 
 
 - C 
 
 = 
 
 C U H *3 
 
 C U H 43 
 
 - H 2 
 
 = 
 
 C 11 H 21 
 
 C U H 21 
 
 - C 
 
 _ 
 
 C 10 H 81 
 
 C l H 81 
 
 - H 2 
 
 
 
 C l H 19 
 
 C'"H 19 
 
 - C 
 
 
 
 C 9 H 19 
 
 C 9 H 19 
 
 - H* 
 
 = 
 
 C 9 H 17 
 
 C 9 H , 7 
 
 - C 
 
 - 
 
 C 8 H i 7 
 
 C 8 H 17 
 
 - H 2 
 
 
 
 C 8 H ,5 
 
 C 3 H 15 
 
 - C 
 
 
 
 C 7 H 15 
 
 C 7 H 15 
 
 - H 2 
 
 = 
 
 C 7 H 13 
 
 C 7 H 13 
 
 - C 
 
 - 
 
 C 6 H .3 
 
 C 8 H 13 
 
 - H 2 
 
 = 
 
 C 6 H U 
 
 C 8 H n 
 
 - C 
 
 = 
 
 C 5 H U 
 
 C 5 H U 
 
 - H 2 
 
 
 
 C 5 H 9 
 
 C 5 H 9 
 
 - C 
 
 = 
 
 C 1 W 
 
 C 4 H 9 
 
 - H 2 
 
 = 
 
 C 4 H 7 
 
 C'H 7 
 
 - C 
 
 = 
 
 C 3 H 7 
 
 C J H 7 
 
 - H 2 
 
 
 
 C 3 H 5 
 
 C 3 H 5 
 
 - C 
 
 = 
 
 C 2 H 5 
 
 C 2 H 5 
 
 - H 3 
 
 
 
 C 2 H 3 
 
 C 2 H 3 
 
 - C 
 
 = 
 
 C 1 H 3 
 
 C'H 3 
 
 - H 8 
 
 = 
 
 C'H 1 
 
 C l H l 
 
 - C 
 
 = 
 
 H 1 
 
 Lauryl 
 
 Rutyl 
 
 Laurie acid 
 Laurone 
 Margaritic acid 
 
 Rutic acid 
 
 Pelargyl Pelargonic acid 
 
 Octyl Caprylic alcohol 
 
 Capryl Caprylic acid 
 
 Heptyl Castor oil alcohol 
 
 (Enanthyl (Enanthylic acid 
 Hexyl Caproic alcohol 
 
 Caproyl Caproic acid 
 
 Amyl 
 
 Valeryl Valerianic acid 
 
 Butyl 
 
 Butyryl Butyric acid 
 
 Propyl 
 
 Propionyl Propionic acid 
 Ethyl 
 
 Acetyl Acetic acid 
 
 Methyl 
 
 Formyl Formic acid 
 
 Hydrogen 
 
 Commencing with a known radical of very complex constitution, 
 myricyl = C 30 !! 61 , which is equal to 30 atoms of Vinyl, plus I atom 
 of hydrogen = CH 2 x 30 + H 1 , the Table shows the entire range of 
 radicals which would be produced from the original complex radical by 
 the alternate abstraction of H 2 and C l until the components of the radical 
 were exhausted. I have affixed the names of such existing compounds as 
 agree with the successive stages of this reduction, as far as I know 
 them. The list could probably be completed by a careful examination of 
 known organic compounds. As it is, we perceive that this purely theo- 
 retical abstract accords wonderfully well with the known products of 
 experimental investigation. The radicals are basic and acid alternately. 
 Out of 30 acid radicals which would complete the list, certainly not less 
 than 23 are known. The existence of the series of basic radicals is not 
 so evident, but the bases have not been so carefully looked for as the 
 acids. Near the lower end of the Table the series is complete, and in 
 respect to these lower members, the evidence is also conclusive, that the 
 acid and basic radicals can be experimentally procured from the radicals 
 next above them, by the abstraction of C 1 or H 2 . It would be rash to 
 declare that this is the case throughout the series, but as it has been 
 proved to be true in regard to myricyl, to ceryl, and to cetyl, as well as 
 to the lower members, it is probably true of the whole. 
 
THE NATURE OF CERTAIN ORGANIC SALTS. 81 
 
 It would, perhaps, be possible to arrange all the known compound 
 radicals in a few such Tables as the foregoing, and thus exhibit 
 their mutual relationship, distinguish the members that are known, 
 and mark the places of those that are unknown. Schedules of this 
 sort would be as useful to a chemical investigator as charts are to a 
 navigator. 
 
 Some of the direct uses of this Table may be briefly noticed : 
 
 It shows the principle upon which any basic radical can be reduced to 
 the acid radical next below it on the list, namely, by the abstraction of 
 H 2 ; and also upon which every acid radical can be reduced to the basic 
 radical next below it, namely, by the abstraction of C l . Of course, in 
 another series of radicals having a different progression, the rate of 
 abstraction of C and H would be different. 
 
 The discrimination of the radicals is sufficiently clear to render it 
 unnecessary for chemists to confound with one another, as they now 
 frequently do, the basic and acid radicals that are closely related ; such 
 as propionyl C 3 H 5 and propyl = C 3 H 7 ; butyryl = C 4 H 7 and butyl 
 = C 4 H 9 ; caproyl = C 6 H 11 and hexyl = C e H 13 ; capryl - C 8 H 15 and 
 octyl = C 8 H 17 , &c. If we adopt radicals, we should treat them fairly, 
 and not call some of them by names that have been allotted to others. 
 
 The Table supplies short answers to several questions that are rather 
 puzzling to answer if you object to believe in the existence of compound 
 radicals. 
 
 What constitutes an alcohol ? 
 
 A basic radical 4- H 1 + O 1 . Example : H,C 2 H 5 = alcohol. 
 
 What constitutes an aldide ? 
 
 An acid radical + H 1 + O 1 . Example : H,C 2 H 3 O = aldehyd. 
 
 What constitutes an ether ? 
 
 Two basic radicals of the same kind + O 1 . Example : C 2 H 5 ,C 2 H 
 = ether. 
 
 What constitutes a compound ether ? 
 
 Two basic radicals, one containing CH 2 less than the other -f- O 1 . 
 Example : CH 3 ,C 2 H 5 O = ethylate of methyl. 
 
 What constitutes a ketone ? 
 
 An acid radical + a basic radical, containing C 1 less than the acid 
 radical + O 1 . Example : CH 3 ,C 2 H 3 = acetone. 
 
 What constitutes a hydrated organic acid ? 
 
 An acid radical -f- H 1 + O 2 (sometimes O 3 or more). Example : 
 H,C 2 H 3 O 2 = hydrated acetic acid. 
 
 What constitutes an anhydride or anhydrous organic acid ? 
 
 Two acid radicals of the same kind + O 3 . Example : C 2 H 3 ,C 2 H 3 O a 
 = anhydrous acetic acid. 
 
 What constitutes a compound anhydride ? 
 
 Two different acid radicals -f- O 3 . 
 
 What constitutes an organic salt ? 
 
 G 
 
82 THE MODEL OF WATER. 
 
 One acid radical + one basic radical -|~0 2 or O 3 . Example: C 4 H 9 , 
 C^IPO* = acetate of butyl. 
 
 The Model of Water. 
 
 Let us return for a moment to the question of the constitution of 
 water. Is it H+O, or H S 0, or ^O, or H+HO? See page 31. The 
 
 evidence that has been adduced in favour of the existence of compound 
 radicals, and explanatory of their modes of combination, is decidedly in 
 favour of the last of these formula?, H-f-HO. Water differs in no respect, 
 physically, from the gaseous compounds of the fourth group the ethers 
 or dioxides of radicals. It contains two radicals ; its atomic measure is 
 two volumes ; its radicals, when isolated, measure each one volume ; it 
 contains one volume of oxygen, which adds nothing to its atomic mea- 
 sure. It is readily divisible into hydrogen = H and oxide of hydrogen 
 = HO, both of which enter largely into organic and inorganic salts. In 
 short, it may be taken as the model of a salt consisting of two radicals, 
 with one atom of oxygen. There is, I think, nothing to be said in 
 favour of the other formulae at all approaching in force to the positive 
 evidence in favour of the formula H-f-HO. 
 
 As water is undoubtedly the equivalent of the metallic protoxides, 
 such as anhydrous lime, every argument that can be urged to show that 
 the formula of water is H,HO serves equally to show that the formula of a 
 metallic protoxide is M,MO, and the formula of the corresponding hydrate 
 either M,HO, or H,MO. Which of the two latter is the proper formula ? 
 is a question that presents some difficulty, not, indeed, as respects the 
 hydrates of the metallic protoxides, but as respects the hydrates of com- 
 pound radicals. I do not hesitate to write CaHO for hydrate of lime, 
 because I consider hydrogen to be an acid radical against calcium, but if 
 I am to write a formula for alcohol, I hesitate to write C 2 H 5 ,HO, because 
 I consider hydrogen to have, more than any hydro-carbon, the nature 
 of a basic radical, and for that reason I would write the formula 
 H,C 2 H 5 0. This practice I would generalise, considering H to be an acid 
 radical against any metal, and a basic radical against any hydro- 
 carbon. 
 
 The reason that I object to the triangular formulae, by which Mr. 
 Gerhardt and Professor Williamson indicate the salts that are formed on 
 the model of water, is now evident. I consider all such compounds to 
 be Unary, and that for Unary compounds, ternary formula are im- 
 proper. 
 
 For the same reason, I do not concur in Professor Williamson's 
 opinion, that most salts can be designated by formulae framed on the 
 model of the formula of water Of the eleven groups of salts described 
 
THE MODEL OF WATER. 
 
 83 
 
 between pages 64 and 68, only the third, fourth, fifth, and tenth groups 
 are, in my opinion, formed on the model of water. The other groups 
 cannot be fairly reduced to that form. Water consists of one oxidised 
 radical and another radical not oxidised ; whereas the radicals of the great 
 majority of salts are either not oxidised at all, or are both oxidised. Of 
 the 121 binary compounds, gaseous in two volumes, described in these 
 eleven groups, 3 5 only are formed on the model of water, and 86 on 
 other models ; and even of those which are formed on the model of water, 
 namely, those which contain a single atom of oxygen, the evidence is 
 strongly in favour of the view that their constitution is binary = M -f- MO, 
 
 1VT 
 
 and not ternary -i\rO. 
 
 Professor Williamson's views on this subject are explained in his 
 Paper on the Constitution of Salts. 1 It is unnecessary to examine his 
 illustrations in detail, because my general objection applies to the whole 
 of them. In the following examples, the separation of a certain quantity 
 of oxygen from the rest of it is arbitrary and incapable of demonstration, 
 as is also the proposal to consider the compounds CIO, CIO 8 , and CIO 3 , 
 to be each equivalent to one atom of hydrogen, and the compound SO' 2 
 to be equivalent to H 2 , K 2 , and HK. The function of oxygen in salts is 
 ignored in these assumptions. That element is never the equivalent of a 
 radical, and all formulae in which oxidised compounds are represented in 
 the equivalents of single volumes of hydrogen are, in my judgment, con- 
 structed on an erroneous principle. Equivalents must be sought for in 
 the radicals alone, independent of their oxygen. 
 
 Examples of Professor Williamson's formulae : 
 
 SO 
 
 H, 
 
 S0 2( 
 K 2 
 
 S0 2 . 
 HK 
 
 2 O 2 Sulphuric acid. 
 
 Neutral sulphate 
 of potash. 
 
 Acid sulphate of 
 potash. 
 
 (C10) 
 (C10 2 ) 
 (CK) 3 ) 
 
 Chlorous acid. 
 
 Perch i oric ackl 
 
 According to the radical theory these salts would require the following 
 formulae : 
 
 HSO 2 Sulphuric acid. 
 KSO* Sulphate of potash. 
 KS0 2 +HSO 8 . Bisulphate of potash 
 
 HC10 2 Chlorous acid. 
 HC1O 3 Chloric acid. 
 HC10 4 Perchloric acid. 
 
 In all cases of double decomposition, the sulphur, or acid radical, and 
 all the oxygen of these salts go together. There is no evidence to prove 
 
 1 Quarterly Journal of the Chemical Society (1852), iv. 350. 
 
 G 2 
 
84 THE CONSTRUCTION OF FORMULAE. 
 
 that such a division of the oxygen takes place as the triangular formulae 
 show us. 
 
 Professor Williamson has recently somewhat changed his views 
 respecting the formulae of the sulphates, and I shall refer to his latest 
 opinions when I come to discuss the question, whether sulphuric acid is 
 bibasic or monobasic. But, before I quit the " model of water," I must 
 copy a few fashionable formulae to show to what extent that unfortunate 
 model has been recently tormented, and what strange varieties of fan- 
 tastic aspect the triangular formulae, on the model of water, are made to 
 assume. 
 
 Gerhard t's " Succinate of methylo-salicyl, or oxide of succinyl and 
 methylo-salicyl." ' 
 
 C 7 H 4 (CH 3 )0 8 \ 
 
 C 7 H 4 (CH 3 )Oj U ' 
 C 4 HA,0. 
 
 Odling's bichromate of potash : 2 
 
 CrA" OA 
 2K r 2K' 
 
 H. L. Buff's succinic acid : 3 
 
 C 4 (C 4 H 4 )0 4 
 
 H. L. Buff's succinamide . s 
 
 H 
 H 
 
 |C 4 (C 4 H 4 )0 4 
 H 
 H 
 
 The dense clouds of philosophical mist which hang over these vast and 
 intricate edifices prevent my seeing their relation to the model of water, 
 and I must refer the reader. who wishes to understand them to the 
 descriptions given by their respective architects descriptions which 
 appear to me to be particularly difficultly intelligible. 
 
 The Construction of Formulae. 
 
 It may, perhaps, be not out of place here to make a few remarks re- 
 specting symbols and formulae. It should be adopted by chemists as an 
 
 1 Quar. J. Chem. Soc. (1855), vii. 62. 2 Ibid., page 12. 
 
 8 Communicated to the Royal Society by Professor A. W. Hofmann, 
 June 10, 1856. Proceedings Roy. Soc., viii. 195. 
 
THE CONSTRUCTION OF FORMULAE. 85 
 
 inflexible rule, to use no letters, figures, or other symbols in writing for- 
 mulae, but such as can be printed by the types commonly kept in every 
 printing office. There should be no crossed letters, and no brackets, or 
 copulas that require an unusual description of type. 
 
 The theory of the constitution of the salts which I have advocated in 
 this Essay, namely, that every salt consists of two radicals, simple or 
 compound, oxidised or not oxidised, is one that leads to a simple and 
 regular method of writing formulae. For example, the benzoate of 
 methyl contains the two radicals benzyl and methyl, combined with two 
 atoms of oxygen. We may consider the two radicals to be each com- 
 bined with one atom of oxygen, and may represent the salt as a 
 combination of the two oxidised radicals CH 3 O -f- C 7 H 5 O ; but, con- 
 sidering that, in cases of double decomposition, the division of the com- 
 ponents of this salt seems to take place, not where the sign -{- is placed, 
 in the above formulae, but in the following manner : CH 3 -j- O,C 7 H 5 O, 
 so that all the oxygen appears to go with the acid radical, it is expedient 
 in this and all cases of oxidised salts, to put the whole of the oxygen 
 together at the end of the formula, thus : CH 3 ,C 7 H 5 O 2 . We have here 
 distinctly placed before us the two acting substances of the salt ; first, 
 the basic radical, and next, the acid radical, while the subjunctive oxygen 
 is thrown to the end. It is not to be understood, from this proposal, 
 that I wish it to be considered an ascertained fact, that in every salt the 
 oxygen is wholly combined with the acid radical. It may be so, but we 
 have no proof that it is so, and I do not pretend to decide this difficult 
 question. The proposal to indicate all the oxygen in one sum is simply 
 to give regularity to the formula, and, as I shall show presently, to 
 facilitate the construction of a systematic nomenclature. 
 
 When there are several radicals, as in all cases of compound salts, they 
 are to be written in a straight line, separating them from one another by 
 a comma, and placing a semicolon before the acid radical. Thus 
 
 Na, C 3 H 9 ; S 2 3 . . . Sulphite of soda and valeryl. 
 Ag, C 2 H 5 ,H; C 7 H0 7 . . Acid ethylomeconate of silver. 
 
 This method of writing formulae is equally applicable to the salts of 
 inorganic radicals. Thus, the sulphates are MSO 2 , the oxalates MCO 2 , 
 the carbonates M,M ; CO 3 , the nitrates MNO 3 , &c. 
 
 It does not appear to me to be advisable to adopt abridged symbols 
 for the hydrocarbon radicals, such as Et for ethyl, A for acetic acid, and 
 the like. The full symbol for such compounds is only C m H n , so that 
 little is gained by abridgment, while we lose the important advantage 
 presented to the eye by the factors which belong to the full symbols. 
 One need not object to Cy instead of CN, because it does not tax the 
 memory, but the symbols of the basic and acid radicals should never be 
 abridged. 
 
Systematic Nomenclature. 
 
 I have defined a salt to be a compound of two radicals, simple or 
 compound, with or without oxygen. I proceed to show in what manner 
 such compounds can be provided with simple and accurate names. 
 
 The name of each salt is to consist of two words, the first of which is 
 to designate the basic radical, and the second to designate the acid 
 radical, and to specify the number of atoms of oxygen, if any is present. 
 The names of simple radicals are, of course, to be the names of elements 
 or some convenient abridgments of them, such as I have proposed for 
 consideration in the last column of the Table at page 28. The names 
 of compound radicals of the hydrocarbon series, may be such words as 
 ethyl, acetyl, and benzyl. Of these there must be one for every hydro- 
 carbon known to exist. In the selection of such names, it is advisable 
 to avoid those which indicate numbers : trityl, octyl, and the like. 
 
 The atoms of oxygen are to be indicated by a change in the termina- 
 tion of the name of the acid radical of each salt. The numerals which I 
 propose for this purpose are as follow : 
 
 ate. 6 aze. n abate. 16 abaze. 
 
 ete. 7 eze. 12 abete. 17 abeze. 
 
 ite. 8 ize. 13 abite. 18 abize. 
 
 ote. 9 oze. 14 abote. 19 aboze. 
 
 ute. 10 uze. 15 abute. 20 abuze. 
 
 This system is sufficient for all compounds that consist of two radicals 
 in combination with oxygen ; but in order to provide names for com- 
 pounds that contain more than two radicals, and for those which contain 
 no oxygen, it is necessary to provide terminal numerals which are to be 
 used for radicals only, and are not to indicate oxygen. I propose the 
 following : 
 
 a, an, or ane. 
 e, en, ene. 
 i, in, ine. 
 o, on, one. 
 u, un, une. 
 6 ad or ade. 
 ed ede. 
 id ide. 
 od ode. 
 nd ude. 
 
 8 
 
 9 
 10 
 
 II aban 
 
 or abane. 
 
 12 aben 
 
 abene. 
 
 13 abin 
 
 abine. 
 
 14 abon 
 
 abone. 
 
 15 abun 
 
 abune. 
 
 1 6 abad 
 
 abade. 
 
 17 abed 
 
 abede. 
 
 1 8 abid 
 
 abide. 
 
 19 abod 
 
 abode. 
 
 20 abud 
 
 abude. 
 
 It does not appear to be expedient to provide names to indicate num- 
 bers above 20, because they would be rarely used, and from want of use, 
 
SYSTEMATIC NOMENCLATURE. 87 
 
 their significance would escape the memory. The system, however, is 
 capable of application to compounds with high numbers of atoms, if it 
 is considered advisable so to apply it. We should have merely to change 
 the consonant of the syllable ab, and thus provide a series of numbers for 
 the tens up to 100: 
 
 10 ab. 
 20 af. 
 30 ak. 
 
 40 al. 
 50 am. 
 60 an. 
 
 70 ap. 
 80 ar. 
 90 av. 
 
 Such of the elements as give two radicals already possess characteristic 
 terminations ous and ic, which must not be displaced by the numerals. 
 See the table of elements at page 28. I propose to insert the numerals 
 between the root of each name and its terminal ous or ic. Thus : 
 
 Ferranous = Ferr-an-ous = one ferrous atom. 
 Ferrinic = Ferr-in-ic = three ferric atoms. 
 
 But when only one atom is spoken of, the numeral may in all ordinary 
 cases be omitted, and without causing any doubt to arise, we may 
 say 
 
 Ferrous . . for one ferrous atom. 
 
 Ferric . . for one ferric atom. 
 
 In some compound words it may be proper, for the sake of brevity, to 
 omit the terminal ous, but the same liberty must never be taken with 
 the terminal ic, otherwise the distinction between the two kinds of radi- 
 cals would be lost. 
 
 When speaking in a general sense of the non-oxidised salts, I propose 
 to use the termination ane, as in the following examples : 
 
 Present Names. Proposed Names. 
 
 Fluorides or hydrofluates = Fluoranes. 
 
 Chlorides or hydrochlorates = Chloranes. 
 
 Iodides or hydriodates = lodanes. 
 
 Bromides or hydrobromates = Bromanes. 
 
 Sulphides or hydrosulphates = Sulphanes. 
 
 Phosphides or phosphurets = Phosphanes. 
 
 Carbides or carburets = Carbanes. 
 
 But in speaking of individual compounds of this kind, I prefer the use of 
 the termination a. Thus : 
 
 Muriatic acid = HC1 = Hydra chlora. 
 
 Chloride of sodium = NaCl = Natra chlora. 
 
 Sulphuret of potassium = KS = Potassa sulpha. 
 
 Fluoride of calcium = CaF = Calca fluora. 
 
88 SYSTEMATIC NOMENCLATURE. 
 
 The following examples show the relation of the names required for 
 oxidised salts to those required for non-oxidised salts : 
 
 Hydrochloric acid = HC1 = Hydra chlora. 
 Hydrated chloric acid = HC1O 3 = Hydra chlorite. 
 
 Chloride of barium = BaCl = Baryta chlora. 
 
 Chlorate of barytes = BaCIO 3 = Baryta chlorite. 
 
 Sulphuretted hydrogen = HS = Hydra sulpha. 
 Hydrated sulphuric acid = HSO 2 = Hydra sulphete. 
 
 Sulphuret of iron = FeS = Ferrous sulpha. 
 Protosulphate of iron = FeSO 2 = Ferrous sulphete. 
 
 Hydrocyanic acid = HCy = Hydra cyana. 
 Hydrated cyanic acid = HCyO = Hydra cyanate. 
 
 Cyanide of potassium = KCy = Potassa cyana. 
 Cyanate of potash = KCyO = Potassa cyanate. 
 
 To denote WATER OF CRYSTALLIZATION, I propose to abridge the term 
 aqua to AQU, and to add the terminals of the oxygen series. Thus : 
 
 Aquate will signify one atom of water. 
 Aquete two atoms ,, 
 
 Aquite ,, three atoms 
 
 Aqueze ,, seven atoms 
 
 Aquabete twelve atoms ,, 
 
 The names which this system provides for the organic compounds of 
 the eleven groups described between pages 64 and 68, are as 
 follows : 
 
 First group, page 64, the names given in the list may remain as 
 they are written, or the terminal a may be added to each word, so as to 
 produce Ethyla butyla, &c. 
 
 Second group, p. 65, the hydrides : 
 
 H^H 3 Methyl hydride = Hydra methyla. 
 H,C 6 H 5 Benzine = Hydra phenyla. 
 
 HjCTH 7 Toluine ' = Hydra tolnenyla. 
 
 Third group, p. 65. The alcohols and the aldides. In this case we 
 have to indicate one atom of oxygen, for which purpose the acid radical 
 must have the termination ate : 
 
 H,CH 8 O Methylic alcohol = Hydra methylate. 
 H,C 2 H 3 Aldehyd = Hydra acetylate. 
 
 H,C*H*O Alcohol = Hydra ethylate. 
 
 It is useless to quote more examples, because the names would all be 
 
SYSTEMATIC NOMENCLATURE. 89 
 
 as regular as the formulae, which cannot be said of the names that appear 
 in page 65. 
 
 Fourth group, p. 66. The ethers : 
 
 C 2 H 5 ,C 2 H 5 O Ether = Ethyla ethylate. 
 
 AsC 2 H 6 ,AsC 2 H 6 Oxide of cacodyl = Cacodyla cacodylate. 
 
 Fifth group, p. 66. Compound ethers and ketones : 
 
 CH 3 ,C 2 H 3 O Acetone = Methyla acetylate. 
 
 CH 3 ,C 2 H 5 O Ethylate of methyl = Methyla ethylate. 
 C 3 H 7 ,C 4 H 7 O Butyrone = Propyla butyrylate. 
 
 The third, fourth, and fifth groups are named in a similar manner, 
 because their constitution is similar 
 
 Alcohol = H, C 2 H 5 = Hydra ethylate. 
 
 Ether = C 2 H 5 ,C'H 5 = Ethyla ethylate. 
 
 Ethylate of methyl = CH 3 , C 2 H 5 O = Methyla ethylate. 
 
 These evidently all belong to the class of ethylates, and differ from one 
 another only in their basic radical. The non- volatile substance called 
 potassium alcohol, belongs to the same class, K,C 2 H 5 O = potassa 
 ethylate. 
 
 The prevalent theory of chemistry, and the prevalent prejudices of 
 chemists, are opposed to the adoption of salts which contain only a single 
 atom of oxygen for division between "the base" and " the acid," but 
 such salts nevertheless exist in abundance, and must eventually be gene- 
 rally recognized. These, indeed, are the true salts on the " model of 
 water." Attempts to graft on this model salts that have more than two 
 radicals, or more than one atom of oxygen, are mere delusions. 
 
 The ketones described at page 77 belong to this order of salts, and 
 must be named accordingly : 
 
 Acetone C H 3 ,C 2 H 3 O = Methyla acetylate. 
 
 Propione C 2 H 5 ,C 3 H 5 O = Ethyla propionylate. 
 
 Butyrone C 3 H 7 ,C 4 H 7 O = Propyla butyrylate. 
 
 Valerone C 4 H 9 ,C 5 H 9 O = Butyla valerylate. 
 
 Benzone C 6 H 5 ,C 7 H 5 O = Phenyla benzylate. 
 
 Campholene C 9 H I7 ,C 10 H 17 O = Pelargyla camphylate. 
 
 Margarone C l6 H 88 ,C l7 H a8 O = Cetyla margarylate. 
 
 H. C 4 H 9 ,C 2 H 3 O = Butyla acetylate. 
 
 Sixth group, p. 66. Hydrated organic acids. In this group, two 
 atoms of oxygen have to be indicated; which requires the terminal 
 ete : 
 
 H,CHO 2 Hydrated formic acid = Hydra formylete. 
 H,C 2 H 3 2 Hydrated acetic acid = Hydra acetylete. 
 H,C 7 H 5 2 Hydrated benzoic acid = Hydra benzylete. 
 
90 SYSTEMATIC NOMENCLATURE. 
 
 When a hydrated acid becomes a salt, the basic hydrogen is replaced 
 by a basic radical, the name of which takes the place of the word hydra, 
 while the name which indicates the acid part of the salt, and enumerates 
 the oxygen, remains unchanged, as is shown by the next group. 
 
 Seventh group, p. 66. Organic salts, in which both of the radicals 
 are compound, and in which there are two atoms of oxygen : 
 
 CH 3 ,CHO 2 Methyl formiate = Methyla formylete. 
 
 CH 3 ,C 2 H 3 O 2 Methyl acetate = Methyla acetylete. 
 
 CH 3 ,(7H 5 O 2 Methyl benzoate = Methyla benzylete. 
 
 CH 3 ,C 2 H 5 2 Methylal = Methyla ethylete. 
 
 Eighth group, p. 67. Nitrites : 
 
 OTPjNO 8 Nitrobenzid, or nitrite of phenyl = Phenyla nitrete. 
 Ninth group, p. 67. Haloids: 
 
 C 2 H 3 ,C1 Chloride of acetyl = Acetyla chlora. 
 
 CH 3 ,Cy Cyanide of methyl = Methyla cyana. 
 
 Tenth group, p. 68. Oxy chlorides : 
 
 Chloride of benzoile = Benzyla chlorate. 
 Oxy chloride of acetyl = Acetyla chlorate. 
 
 Eleventh group, p. 68. Miscellaneous compounds, containing three 
 atoms of oxygen. The acid radical requires the terminal ite, which 
 signifies three atoms of oxygen : 
 
 Anhydrous acetic acid = Acetyla acetylite. 
 Anhydrous butyric acid = Butyryla butyrylite. 
 
 The nature of these anhydrous acids will be discussed under the head 
 of " ANHYDRIDES." 
 
 C 2 H 5 ,C 2 H 5 ; CO 3 Carbonate of ethyl = Ethylene carbite. The 
 
 termination ene, in the word ethylene, shows the salt to be 
 
 bibasic. 
 C 2 H 5 ,C 2 H 5 ; S 2 0* Sulphite of ethyl = Ethylene sulphen ite. In 
 
 the last word the syllable en indicates two atoms of sulphur, and 
 
 the syllable ite three atoms of oxygen. 
 CH 3 ,NO 8 Nitrate of methyl = Methyla nitrite. 
 
 Examples of the application of this nomenclature to other more com- 
 plex substances than those named in the above groups, will be given 
 when the formula? of these compounds are explained. 
 
 In the designation of double salts, I propose to express the phrase 
 " combined idth " by the Latin word cum. 
 
The Doctrine of Chemical Types and Substitutions. 
 
 To illustrate the subject of TYPES and SUBSTITUTIONS, I take the 
 example that was first used by Dumas in developing his theory, and 
 afterwards by Berzelius in his critical condensation of that theory. Here 
 is the account given by Berzelius : 
 
 " To give an idea," says he, 1 " of the views of atomic composition 
 which arise from the theory of chemical types, I will quote an example 
 given by Dumas of the chemical type to which the oil of bitter almonds 
 belongs, represented by the chemical formulas required by this theory, in 
 which the elements that play the same part are placed vertically the one 
 above the other 
 
 1. Oil of bitter almonds ..... C 14 H 6 O 2 
 
 2. Binacichloride (chloride) of benzoyle C 14 
 
 3. Benzoic acid . ...... 
 
 {H 5 1 
 S r 
 {H 5 
 
 " Amongst these very different compounds, the rational composition of 
 which is expressed by the names here employed, it is not only presumed 
 that chlorine, sulphur, and oxygen play the same part, but that this is 
 likewise the case with hydrogen ; they are therefore supposed to occupy 
 the same position as one equivalent of hydrogen in the oil of bitter 
 almonds, or in their prototype. The fifth example presents the most 
 remarkable circumstance, that the same space which in oil of bitter 
 almonds is occupied by i equivalent of hydrogen, suffices not only for 2 
 equivalents of hydrogen, but in addition for i equivalent of nitrogen. 
 The mechanical impossibility is no obstacle to this theory, and the sup- 
 porters of metalepsy find no difficulty in replacing an equivalent of 
 hydrogen by 4 atoms or equivalents of oxygen and i equivalent of ni- 
 trogen, or by 2 atoms of oxygen and I atom of sulphur." 
 
 It is a proof of the soundness of the theory which I am advocating, 
 that it is able to clear up readily a point which for years served as basis 
 for a controversy between two such chemists as Berzelius and Dumas. 
 Before I proceed to write the formulae for these compounds, according to 
 my system, I must point out that in the formula, No. 3, benzoic acid, 
 there is a fallacy which I must let Dumas himself explain. He says : 
 
 1 Taylor's Scientific Memoirs (1846), vol. iv. p. 670. 
 
92 CHEMICAL TYPES AND SUBSTITUTIONS. 
 
 " The oil of bitter almonds C*H 10 O -f H 2 , when exposed to air loses 
 H a , and ought in consequence to gain O, and be converted into benzoic 
 acid CTTO 3 , which actually occurs." Traite de Chimie, 1847, I. 76. 
 
 " The essence of bitter almonds can be transformed into benzoic acid 
 by the action of oxygen or of air, or the effect of any oxidising cause 
 whatever. The action takes place at the ordinary temperature, and is 
 rapid in sunshine. The conversion is complete, and immediately pro- 
 duces hydrated benzoic acid, containing precisely the quantity of water 
 which it retains after sublimation." Idem, p. 144. 
 
 These extracts show that the formula for No. 3 requires an atom of 
 water to be added, making it, according to Dumas's numbers, C 28 H 10 4 
 -f- H 2 , or according to Berzelius's numbers 
 
 HM 
 2 f C 
 
 JHO 2 
 
 According to my notation these compounds are constituted as 
 follows : 
 
 1 . Oil of bitter almonds . . H, C^O. 
 
 2. Chloride of benzoyle . . Cl, C 7 H 5 O. 
 
 3. Benzoic acid .... HO, (7H 5 O. 
 
 4. Sulphuret of benzoyle . S, C 7 H 5 0. 
 
 5. Benzamide NH 2 ,C 7 H 5 O. 
 
 Looking from this point of view at the explanations given by both 
 parties, it would appear that Dumas was evidently right in supposing 
 that the C1,HO,S, and NH 2 , were respectively substituted for AN atom 
 of hydrogen, and that Berzelius was equally right in supposing that this 
 series of compounds contained, all through, the compound (TH 5 O. But, 
 on the other hand, Dumas was wrong in supposing that the atom of 
 hydrogen which he replaced was any one atom taken indifferently from 
 the mass of atoms of hydrogen contained in the oil of bitter almonds. 
 He failed to perceive that the hydrogen which he replaced was a radical, 
 equal in chemical power, not to each of the other atoms of hydrogen 
 present in the compound, but to all the rest of the hydrogen and all the 
 carbon taken together ; for the radical benzyl = (JW is but one molecule, 
 the equivalent of one volume of hydrogen, and this molecule remained 
 undecomposed while the compound underwent all the transformations 
 which formed the basis of the great controversy between these chemists. 
 Berzelius failed equally to notice this peculiarity, so strikingly confirma- 
 tive of his hypothesis of compound radicals. He was also wrong in 
 urging it as a mechanical impossibility that an atom of amidogen should 
 replace an atom of hydrogen ; for, as far as analogy can be trusted, the 
 volume of NH 2 in gaseous combination is exactly the same as that of H ; 
 and it has been proved by evidence in the preceding pages, that there is- 
 no mechanical hindrance to the replacement of a single volume of hy- 
 
CHEMICAL TYPES AND SUBSTITUTIONS. 93 
 
 drogen by a single volume of a compound of several atoms, since it is 
 proved that a heavy complex hydrocarbon, such as lauryl = C^H 23 , 
 whose elements probably measure 35 times, and certainly weigh 167 
 times, as much as hydrogen, can be obtained in the volume of a single 
 atom of hydrogen; for the laurate of ethyl = C 2 H 5 ,C 12 H 83 2 , the atomic 
 weight of which is 228, has a specific gravity of 114, and an atomic 
 measure of two volumes, which is equal to that of its two radicals, the 
 oxygen, as usual, measuring nothing. 
 
 The five compounds which form the subject of the foregoing criticism, 
 would, in accordance with the radical theory, be formulated and named 
 as follows : 
 
 1. H, C 7 H 5 O = Hydra benzylate. 
 
 2. C 7 H 5 ,C10 = Benzyla chlorate. 
 
 3. H, C 7 H 5 O 2 = Hydra benzylete. 
 
 4. C7H 5 SO = Benzyla sulphate. 
 
 5. NH 2 ,C 7 H 5 = Amida benzylate. 
 
 Compound Chlorine Eadicals. 
 
 In the case of this TYPE of oil of bitter almonds, the SUBSTITUTION 
 that occurs affects only the different radicals with which the oxidised 
 benzyl successively combines. Hydrogen gives place to chlorine, that to 
 oxidised hydrogen, that to sulphur, and that to amidogen ; but all 
 through the series of transformations the benzyl remains unchanged. 
 
 There is, however, a species of substitution of an entirely different 
 character from the former, and which has not always been so clearly dis- 
 tinguished from it by chemical writers as it ought to have been. I allude 
 to that species where hydrocarbons, such as methyl and ethyl, are so 
 acted upon by chlorine, bromine, and iodine, as to lose their original 
 composition, and to produce new compounds, which still act as radicals, 
 but are constituted as follows : 
 
 From Methyl = CH 3 . From Ethyl = C 2 H 5 . 
 
 CH'Cl. C 2 H 4 C1. 
 
 CHC1 2 . C 2 H 3 C1 2 . 
 
 CC1 3 . C 2 H 2 C1 3 . 
 
 C 2 HC1 4 . 
 C 2 CP. 
 
 In these compounds the energetic acid radical chlorine acts the part of 
 the basic radical hydrogen. Bromine and iodine act to some extent in 
 the same way. The above complex compounds form each only a single 
 ladical, and it will be seen, on consulting the Table of Gases, under 
 J ' Chlorine Compounds" at page 54, that each chlorine radical, however 
 Iteavy, forms only a single volume of gas, and that when they form 
 
94 
 
 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 gaseous salts by combining with other radicals, the salts, whether oxidised 
 or not oxidised, produce only two volumes of gas ; the chlorine radicals 
 thus agreeing in their general characteristics with the hydrogen radicals 
 from which they are derived, only diminishing progressively in basic 
 intensity as the proportion of chlorine increases. 
 
 In subsequent sections, I shall show that sulphur, nitrogen, and 
 certain metals are also subject to act vicariously for hydrogen in 
 compound radicals. 
 
 In regard to the nomenclature of such radicals, I venture to propose 
 that each should retain the name of its original hydrocarbon, with a 
 prefix to denote the number of atoms of chlorine, or other element, intro- 
 duced into it by substitution. This will show the relationship of the 
 derived to the original radical, and also the extent of the change effected. 
 Examples : 
 
 Ethyl Series. 
 
 CH 4 C1 = Chloric-ethyl. 
 
 COTCl 2 .= Chlorenic-ethyl. 
 
 C 2 H 2 C1 3 = Chlorinic-ethyl. 
 
 = Chloronic-ethyl. 
 
 = Chlorunic-ethyl. 
 
 cmci 4 
 
 C"C1* 
 
 Methyl Series. 
 
 CH 2 C1 = Chloric-methyl. 
 CHC1 2 = Chlorenic-methyl. 
 CCi 3 = Chlorinic-methyl. 
 
 Acetyl Series. 
 (TCI 3 = Chlorinic-acetyl. 
 
 When nitrogen is an element in a compound radical, I propose to 
 indicate it by the symbol Z and the syllable Zot, derived from Azote, 
 excepting in the case of CN. 
 
 Inquiry into the Causes which modify the Atomic 
 Measure of Compound Gases. 
 
 It is a fundamental principle of the radical theory that a gaseous 
 element has an atomic measure of one volume. Accordingly, one 
 volume is the measure allotted in the Table of Gases to one atom of 
 oxygen, hydrogen, nitrogen, and chlorine. 
 
 A second axiom of the radical theory is, that every compound 
 radical which acts as the equivalent of an atom of hydrogen or of 
 chlorine, measures, in the gaseous state, like its equivalents, one volume. 
 In all cases, where these compound radicals have been isolated and 
 weighed, they have been found to agree with this axiom. Thus one 
 volume has been found by experiment to be the atomic measure of the 
 following compounds : 
 
 CH Formyl. 
 C H 2 Vinyl. 
 CH 3 Methyl- 
 C 8 H 5 Ethyl. 
 C 3 H 5 Acryl. 
 
 C 4 I ' Butyl. 
 C 5 H 7 Camphogene. 
 C 5 H 9 Menthene. 
 C 5 H 11 Amyl. 
 C'H 18 Hexyl. 
 
 Cedrone. 
 C 10 H 16 Petrolene. 
 C 10 H 21 Paraffine. 
 sC^H 6 Cacodyl. 
 
 CN Cyanogen. 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 95 
 
 In the third place, compounds of two radicals, whether the radicals 
 are simple or compound, oxidised or not oxidised, are assumed to form 
 two volumes of vapour, because their two radicals combine without con- 
 densation. The groups of compounds between pages 64 and 68, show 
 121 proofs of the correctness of this assumption, to which I may now 
 add the following compounds, which are equally regular, and were only 
 excluded from the former groups because they are not hydrocarbons, 
 and it appeared to be desirable to keep the argument respecting the 
 hydrocarbons free from extraneous considerations. The following com- 
 pounds form two volumes of gas : 
 
 HHO Water. 
 
 HC1 Chlorhydric acid. 
 
 HBr Bromhydric acid. 
 
 HI lodhvdric acid. 
 
 HCy Cyanhydric acid. 
 CyBr Bromide of cyanogen. 
 CyCl Chloride of cyanogen. 
 C'H 5 ,Cy Cyanide of phenyl. 
 
 So far the atomic measures, both of elements and compounds, are all 
 regular. There is one volume for an atom of a radical, and two volumes 
 for an atom of a compound of two radicals. But the above compounds 
 amount to less than half the number that are contained in the Table of 
 Gases, and we have now to consider the compounds whose measures 
 are apparently irregular. 
 
 The fact has already been pointed out, that oxygen, which, in the 
 free state, measures one volume, measures nothing when in combination 
 with two radicals, but serves only to increase the weight of the com- 
 pounds into which it enters. I cannot account for that fact, and will 
 not dwell upon it, but proceed to the consideration of the properties of 
 other elements. 
 
 CARBON. Carbon, occurring as an acid radical, in combination with 
 other radicals measures nothing. The oxalate of amyl = C 5 H U O,CO, 
 and the oxalate of ethyl = C^H'OjCO, each measure one volume, which 
 is due to the amyl and methyl they contain. The double oxalate of 
 ethyl and methyl = CH 3 ,C 2 H 5 ; C 2 4 measures two volumes, because it 
 contains two basic radicals. The carbonate of ethyl = C 2 H 5 ,C 2 H 5 ; CO 3 
 also measures two volumes, and for the same reason. In all these cases 
 the radical carbon and the oxygen measure nothing. On the other 
 hand, carbonic oxide = CO, and carbonic acid = CO 2 , when uncom- 
 bined with other radicals, both measure two volumes. In the case of 
 CO 2 this is the measure of the oxygen, but in the case of CO, the 
 volume is twice the measure of the oxygen. These measures are there- 
 fore irregular. . In combination with other radicals all combinations of 
 C with O measure nothing. 
 
 The reader, in examining the facts and arguments of this section, will 
 do well to bear in mind the particulars of these irrregular and excep- 
 tional compounds, which occur, not only among the oxides of carbon, 
 but also among the oxides of nitrogen, sulphur, and chlorine. It will 
 
96 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 be seen, that the most irregular gases are among the best known 
 inorganic compounds, and that the great multitude of organic vapours 
 present scarcely any irregularities. 
 
 VINYL. Olefiant gas, or vinyl = CH 2 (see page 73) has an atomic 
 measure of one volume. 
 
 The facts with which my arguments are interspersed, between pages 
 64 and 8 1 , show the important relationship that exists between vinyl and 
 an extensive series of volatile radicals. The basic radicals are composed 
 as if I am now entering upon the boundary of conjecture, as if each 
 was composed of a multiple number of atoms of vinyl plus a single 
 atom of hydrogen = H, and the acid radicals appear as if they contained 
 a multiple number of atoms of vinyl, plus a single atom of formyl 
 = CH. Now these compound radicals, basic and acid, from the simplest 
 to the most complex, all measure one volume, which is precisely the same 
 measure as that of the single atoms of H and of CH. Then, as we have 
 found that carbon measures nothing when in combination, with the ex- 
 ception of CO and CO 2 , it follows that the atom of carbon in the com- 
 pound CH, may measure nothing, and that the single atom of hydrogen 
 which is present alike in the basic and acid radicals, over and above the 
 quantity necessary to the constitution of the multiples of vinyl, is the 
 only thing which MEASURES in the state of gas. All the vinyl, however 
 great the quantity, from one atom up to thirty atoms, measures nothing, 
 and the odd atom of carbon in the acid radicals also measures nothing. 
 The vinyl and the carbon increase the WEIGHT of the gas, but the MEA- 
 SURE is that of the single atom of hydrogen. This atom of hydrogen is 
 essential to the existence of every member of the great class of radicals 
 exhibited in the Table at page 79, and probably to the existence of 
 most of the basic and acid radicals that are volatile ; and when it is not 
 essential to their existence its absence appears to be marked by some 
 peculiar characteristic. 
 
 The following are examples of such a peculiarity : 
 
 C 2 H 5 ,C 2 H 2 O 2 = Succinate of ethyl = Ethyla succinylete. 
 C H 3 ,C 2 H 2 2 = Succinate of methyl = Methyla succinylete. 
 
 These two salts have an atomic measure of only one volume, which is 
 the measure of their basic radicals ; the succinyl, which is probably con- 
 stituted thus: CH 2 +C, for want of the odd atom of hydrogen measures 
 nothing. For the same reason, the following salt, which contains 3 
 radicals, measures only two volumes. 
 
 H,H ; (7H 4 2 = Salicylous acid = Hydren salicylete. 
 
 Regnault's bibromide of ethylene = C 2 H 4 ,Br 2 , with the atomic weight 
 of 1 88, and the specific gravity of 94, is quite irregular, showing two 
 volumes and three radicals. But if we divide this compound by 2, and 
 consider it as bromide of vinyl = CH 2 ,Br, the atomic weight and specific 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 97 
 
 gravity are both 94, and the measure is one volume, which, on the 
 assumption that vinyl has no measure in combination is correct, one 
 volume being the measure of the bromine. 
 
 Unfortunately we know yet too little of the constitution of compounds 
 of this kind, to be able to settle difficult cases so readily ; and as an 
 example of the uncertainty that attends such arrangements of atoms, I 
 may mention that this compound is susceptible of even a third grouping, 
 which has a great appearance of truth. If we represent it by the 
 formula C 2 (H 4 Br), Br, it seems to be a bromide of a variety of ethyl in 
 which one atom of hydrogen has been replaced by one atom of bromine, 
 similar to the chlorine compound that I have described at page 93. 
 Such a compound should weigh 188, and measure two volumes, and 
 have a specific gravity of 94, in all which respects the gas and the for- 
 mula agree. 
 
 Upon the whole it seems probable that no hydrocarbon radical mea- 
 sures anything in its gaseous salts, unless it contains an odd atom of 
 hydrogen, or of chlorine (or other element) in substitution for hydrogen. 
 The number of apparent radicals that contain an even number of atoms 
 of hydrogen is very small, and may possibly be diminished when the 
 compounds are better understood. 
 
 The expression of these decided opinions respecting the odd atom of 
 hydrogen which characterises both the basic and acid radicals of the 
 hydrocarbon series, will, no doubt, lead many persons to inquire, what 
 I think of Laurent and Gerhardt's LAW of EVEN NUMBERS OF ATOMS ? 
 According to that law, nearly all organic compounds contain an even 
 number of atoms of carbon, and an even number of atoms of hydrogen. 
 The law requires the atomic weight of every compound to be so estab- 
 lished, that the vapour of its atom may occupy four volumes. This 
 law is explained more fully in Gmeliiis Chemishy, vol. vii., p. 6, and 
 in Laurent's Chemical Method, pages 46 to 129. 
 
 My opinion of the law is, that it is quite true and utterly useless. 
 The reason is, that the compounds to which it refers are all complete in 
 two volumes. The atoms included in that measure must, in every in- 
 stance, either be even or odd. The law requires the measure to be taken 
 at four volumes. If the original numbers are even, multiplication by 
 two (to make two volumes into four) LEAVES them even. If the numbers 
 are odd, multiplication by two MAKES them even. The law therefore is 
 a mere artifice of arithmetic, and instead of holding a place in our sys- 
 tems of chemistry, it ought to be transferred to the pages of Button's 
 Mathematical Recreations. 
 
 SULPHUR. An atom of sulphur in the state of vapour measures one- 
 sixth part of a volume ; but this measure disappears when the sulphur 
 is in combination with other radicals. The sulphur then adds to the 
 weight of the compound but not to the gaseous volume. When one 
 or more atoms of sulphur are combined with a single radical, the 
 
 H 
 
98 
 
 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 compound measures one volume ; when they 
 radicals, the compound measures two volumes. 
 adds nothing to the measure. 
 Examples : 
 
 a. Compounds forming 
 r\ r7 7 ^ ft 
 One volume of Gas. 
 
 Methyl, sulphide = 
 
 Methyl, bisulphide = 
 
 Methyl, sulphate = 
 
 Ethyl, sulphide = 
 
 Ethyl, bisulphide = 
 
 C 4 H"S Amyl, sulphide = 
 
 AsC 2 H 6 ,S = Cacodyl, sulphide = 
 
 HS = Hydrosulphuric acid = 
 
 CIS = Chloride of sulphur = 
 
 CIS 2 = Dichloride of sulphur = 
 
 C1SO Chlorosulphuric acid = 
 
 C H 3 
 C H 3 
 C H 3 
 C 2 H 5 
 C 2 H 5 
 
 S 
 S 2 
 
 SO 2 
 
 S 
 S 2 
 
 Two Volumes o Gas. 
 
 H,C 2 H 5 ; 
 H,C*H U ; 
 C 2 H 5 ,C 2 H 5 
 H,C 4 H 9 ; 
 
 S 2 
 S 2 
 
 S 2 3 
 S 2 
 
 = Mercaptan = 
 
 = Hydrosulphideofamyl= 
 
 = Sulphite of ethyl = 
 
 = Butylic mercaptan = 
 
 are combined with two 
 The presence of oxygen 
 
 D , AT 
 
 Proposed Names. 
 
 Methyla sulpha. 
 Methyla sulphene. 
 Methyla sulphete. 
 Ethyla sulpha. 
 Ethyla sulphene. 
 Amyla sulpha. 
 Cacodyla sulpha. 
 Hydra sulpha. 
 Chlora sulpha. 
 Chlora sulphene. 
 Chlora sulphate. 
 
 p d y 
 
 Hydra ethyla sulphene. 
 Hydra amyla sulphene. 
 Ethylene sulphenite. 
 Hydra butyla sulphene. 
 Chlorinic methyla sul- 
 
 r . 
 
 CCP.SOH-C1SO = SU c fdeo f f can = 
 
 v ( sulphate. 
 
 SO = the atom of sulphurous acid gas, measures one volume, al- 
 though S and O in combination with other elements measure nothing. 
 8,8(5* = anhydrous sulphuric acid, and HSO 2 = hydra ted sulphuric 
 acid, both measure two volumes. The volume of these three compounds 
 when uncombined with other radicals, is therefore quite regular ; that is 
 to say, the sulphur measures as -a radical, and the oxygen has no measure. 
 SO 2 and SO 3 in combination with radicals, measure nothing. 
 
 The compound CS 4 , commonly called bisulphide of carbon, but which 
 I propose to call xanthyl, has an atomic measure of two volumes ; but 
 when it is in combination, it measures nothing. The following three 
 gaseous salts contain each two compound organic radicals, besides oxygen 
 and xanthyl, and each measures only two volumes : 
 
 CH 3 ,CH 3 ; CS 4 O = Methylene xanthylate. 
 CH 3 ,CH 3 ; CS 4 S 2 = Methylene xanthyla sulphene. 
 CH 8 ,C 2 H 5 ; CS 4 O = Methyla ethyla xanthylate. 
 
 In these cases the basic radicals retain their full measure: the carbon, 
 sulphur, and oxygen, measure nothing. 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 99 
 
 NITROGEN. The specific gravity of nitrogen gas is 14, which being- 
 taken as its atomic weight, its atomic measure is one volume. 
 
 When it combines with oxygen it forms three gases which measure 
 two volumes each : 
 
 Protoxide of nitrogen = N,NO. 
 Deutoxide of nitrogen = NO. 
 Peroxide of nitrogen = NOO. 
 
 The first of these three compounds is regular, namely, the measure of 
 the two radicals is retained, and that of the oxygen is lost. But the last 
 two have twice the measure that they would have, if the oxygen, ac- 
 cording to its usual practice on entering into combination, disappeared. 
 The irregularity of these two compounds is similar to that which cha- 
 racterises CO and COO. When in combination with other radicals, NO 
 and NOO measure one volume, the oxygen disappearing. 
 
 There are two other compounds of nitrogen and oxygen, the measures 
 of which have not been determined. These are anhydrous nitrous acid 
 = N,NO 3 , and anhydrous nitric acid = N,N0 5 . We have, however, 
 the atomic measure of one of the hydrates of nitric acid = 2HN0 3 -f- 
 3HHO. The measure is ten volumes, which is regular; namely, four 
 volumes for the two atoms of HNO 3 , and six volumes for the three 
 atoms of water. The nine atoms of oxygen present in this compound 
 measure nothing. 
 
 AMMONIA. Ammonia contains N-J-H 3 , which weigh 17 ; its specific 
 gravity is 8*5, and its atomic measure is consequently two volumes. It 
 is, in my opinion, not a radical, but a salt ; the components of which are 
 H-f-NH 2 . The compound NH 2 is a radical. It has been named 
 amidogen, or briefly amid. It cannot be prepared in a free state, but its 
 progress can be traced through a multitude of salts, in which it evidently 
 acts as a basic radical. I assume, therefore, that amid is a radical, and 
 that its atomic measure is one volume. 
 
 The compound NH" 2 ,H = amida hydra, or the hydride of amid, 
 commonly called ammonia, is in that case a salt, containing two radicals, 
 and having therefore an atomic measure of two volumes. 
 
 The radical NH 2 = amid, and the salt NH 2 ,H = ammonia, are subject 
 to have part, or the whole, of their hydrogen replaced by compound 
 radicals. The following are examples : 
 
 NH,C 2 H 3 ; H = Acetylamine. 
 
 NH,C 2 H 5 ; H = Ethylamine. 
 
 NH,CH 3 ; H = Methylamine. 
 
 NH,C 6 H 5 ; H = Phenylamine (Aniline). 
 
 NH,C 5 H 9 ; H = Piperidine. 
 
 NCH 3 ,C 5 H 9 ; H = Methylopiperidine. 
 
 NC 2 H 5 ,C 5 H 9 ; H = Ethylopiperidine. 
 
 n 2 
 
100 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 These salts may all be considered as the equivalents of ammonia, and 
 they each possess an atomic measure of two volumes. 
 
 A great number of compounds of this description are formed by the 
 combination of nitrogen with non-volatile radicals. My illustrations are 
 here restricted to compounds that form gases. 
 
 It is possible that the compound called nicotine = NC 5 H 7 , the atomic 
 measure of which is one volume, may be an amid = NH,C 5 H 6 . 
 
 Compounds of Ammonia. Ammonia, as I have said, is a salt and not 
 a radical. When it goes into combination, it does not combine as a 
 basic radical with an acid radical to produce a simple salt, but it com- 
 bines as a salt with another salt, to produce a compound salt. The 
 result is, that the volatile double salts of ammonia form gases whose 
 atomic measure is four volumes, because each double salt contains four 
 radicals. The only exceptions to this measure are where the radicals 
 lose their measure in combination, as is the case with sulphur. 
 
 Examples : 
 
 H,NH 2 + HC1 .... Hydrochlorate of ammonia. 
 
 H,NH 2 -f- HCy .... Hydrocyanate of ammonia. 
 
 H,NH 2 + HTe Hydrotellurate of ammonia. 
 
 H,NH 2 + HS + HS . . . Bi-hydrosulphate of ammonia. 
 
 In the last case, the amid and the three atoms of hydrogen make up the 
 four volumes, the sulphur having no measure. In the third example we 
 find that hydrotelluric acid, which alone measures only one volume, 
 produces two volumes when in combination. The neutral hydro- 
 sulphate of ammonia = H,NH 2 -|- HS, has an atomic measure of three 
 volumes, because the sulphur measures nothing, and the measure is made 
 up of one volume of amidogen and two volumes of hydrogen. 
 
 The study of the constitution and nomenclature of the ammoniacal 
 salts will be resumed in a subsequent section. 
 
 When nitrogen combines with carbon to form the compound radical 
 cyanogen = CN, the product measures one volume, the nitrogen retain- 
 ing its measure, and the carbon, as usual, losing it. 
 
 In the cyanides and cyanates the atomic measure of the cyanogen is 
 retained; but the following examples show that this is not the case 
 with the cyanurates : 
 
 Gaseous chloride of cyanogen CICy = 2 volumes. 
 
 Solid chloride of cyanogen CICy = $ volume. 
 
 Cyanate of ethyl C 2 H 5 ,CyO = 2 volumes. 
 
 Cyanurate of ethyl C 2 H 5 ,CyO = -g- volume. 
 
 Cyanide of methyl C H 8 ,Cy = 2 volumes. 
 
 Cyanurate of methyl C H 3 ,CyO = - volume. 
 
 These relations lead to the inference that cyanogen exists in the cyanates 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 
 
 101 
 
 and the. cyanurates under different physical conditions, and that, in 
 the latter, it possesses the properties, common to several elements, of 
 having in combination an atomic measure of -g- volume, with the power 
 of condensing the measure of all radicals with which it combines from 
 one volume each to half a volume ; whence it follows that, as is shown 
 in the above table, its salts have a common measure of -f- volume. It is 
 probable that cyanogen exists in this condensed condition in its fulmi- 
 nating salts, but their explosive decomposition by heat renders the 
 determination of their measure impossible. I propose to distinguish, in 
 formulae and names, the cyanogen of the cyanurates from that of the 
 cyanides and cyanates, by giving to the former the sign Cyl and the 
 name cyanyl. The three gaseous salts referred to above as measuring 
 each - volume, will then become : 
 
 Cl Cyl = Chlora cyanyla. 
 C 2 H 5 ,CylO = Ethyla cyanylate. 
 C H 3 ,CylO = Methyla cyanylate. 
 
 CHLORINE, BROMINE, IODINE, FLUORINE. These elements when 
 acting as radicals, and combining with compound organic radicals, or 
 with hydrogen, retain their atomic measure undiminished. See group 
 nine, page 67. But when they become constituents of radicals, acting 
 as substitutes for hydrogen (see page 93), they become subject to the 
 same law as hydrogen, and lose their atomic measure. See the proof of 
 this fact under the head of "Chlorine Compounds" in the Table of 
 Gases, page 54. I will quote a few comparative examples of hydrogen 
 and chlorine radicals: 
 
 Usual Names. 
 
 C 2 H 3 ,C1 O = Oxychloride of acetyl = 2 volumes. 
 
 C 2 CP,C1 = Chloraldehyd = 2 volumes. 
 
 H,C 2 H 3 O a = Acetic acid = 2 volumes. 
 
 H,C 2 CPO a = Chioracetic acid = 2 volumes. 
 
 H,C 2 H 3 O = Aldehyd = 2 volumes. 
 
 H,C 2 C1 3 O = Chloral ; = 2 volumes. 
 
 C 2 H 5 , Cl = Chloride of ethyl = 2 volumes. 
 
 C 2 H 4 C1 ,C1 = Monochlorinated ditto = 2 volumes. 
 
 C 2 H 3 C1 2 ,C1 = Bichlorinated ditto = 2 volumes. 
 
 C 2 H 2 C1 3 ,C1 = Terchlorinated ditto = 2 volumes. 
 
 C 2 H C1 4 ,C1 = Quadrichlorinated ditto = 2 volumes. 
 
 C*CP ,C1 = Sesquichloride of carbon ? = 2 volumes. 
 
102 
 
 INQUIRY IXTO THE CAUSES WHICH MODIFY 
 
 CH 3 ,C1 
 CC1 3 ,C1 
 
 H,CH 3 
 H,CC1 3 
 
 CH 3 
 CC1 3 
 CHC1 2 
 CH 2 C1 
 
 CH 2 
 CC1* 
 CHC1 
 
 = Chloride of methyl 
 
 = Bichloride of carbon 
 
 = Marsh gas 
 
 = Chloroform 
 
 = Methyl 
 
 = Sesquichloride of carbon ? 
 
 = Perchloride of formyl 
 
 = Dutch liquid 
 
 = Vinyl (olefiant gas) 
 
 = Protochloride of carbon 
 
 = Chloride of formyl 
 
 = 2 volumes. 
 = 2 volumes. 
 
 = 2 volumes. 
 = 2 volumes. 
 
 = I volume, 
 volume, 
 volume, 
 volume. 
 
 volume, 
 volume, 
 volume. 
 
 Here it is seen, that one, two, three, four, or five volumes of chlorine 
 may, as substitutes for equal volumes of hydrogen, become part of a 
 compound radical, which radical measures altogether only one volume ; 
 while the same salt which contains that compound radical, may also con- 
 tain, as a simple radical, chlorine, retaining its full measure of one 
 volume for one atom. 
 
 The compounds of chlorine with oxygen present some peculiarities. 
 Hypochlorous acid = C1,C1O measures two volumes, and is therefore 
 regular, the oxygen measuring nothing. Chloric oxide, or the peroxide 
 of chlorine = CIO 2 , also measures two volumes, which is irregular, as it 
 contains only one radical. This irregularity resembles that which occurs 
 with carbonic acid = CO 8 , and the peroxide of nitrogen = KO 2 . All 
 these compounds become regular when they become part of salts. The 
 volume of the oxygen then disappears. Chlorous acid = C1C10 3 , appa- 
 rently forms three volumes of vapour, but the specific gravity of the gas 
 has probably not been correctly determined. Chlorosulphuric acid 
 = C1SO measures one volume; the double salt CCFSO -f Cl SO mea- 
 sures two volumes. Both of these salts are regular, on the supposition 
 that CC1 3 is a compound radical (vicarious methyl), and that S and O 
 measure nothing. 
 
 Chlorochromic acid = CICrO also measures one volume, which seems 
 to intimate that CHROMIUM, like sulphur, measures nothing when in com- 
 bination with other radicals. 
 
 On the other hand, chloro-nitrous gas = C1NO measures two volumes 
 which is regular, because neither nitrogen nor chlorine lose their measure 
 in combination ; while here, as in all cases, the volume of the oxygen 
 
 PHOSPHORUS. The atomic weight of phosphorus is 3 1 , and the spe- 
 cific gravity of its vapour is 62, so that its atomic measure is half a 
 volume. The atom of phosphorus, on combining with other radicals, 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 103 
 
 reduces the measure of the whole of them from a volume each to half a 
 volume, and then adds to the product its own half volume. 
 Examples : 
 
 H 3 P. The measure is 2 volumes = | -f i- 
 Phosphuretted hydrogen = Hydrine phospha. 
 
 CPP. The measure is 2 volumes = f -f . 
 Terchloride of phosphorus = Chlorine phospha. 
 
 CPP. The measure is 3 volumes = -| -f i. 
 
 Pentachloride of phosphorus = Chlorune phospha. 
 
 CPPO. The measure is 2 volumes = | + -|-. 
 
 Oxychloride of phosphorus = Chlorine phosphate. 
 
 C 2 H 5 ,C 2 H 5 ,C 2 H 5 ; PO 3 . The measure is 2 vols = f + J. 
 Tribasic phosphite of ethyl = Ethyline phosphite. 
 
 This is a remarkable case. The three atoms of ethyl are all reduced 
 from one volume each to half a volume, so that phosphorus has the same 
 power of reduction over compound radicals that it has over elementary 
 radicals. The oxygen as usual disappears. 
 
 H 3 P,HI. The atomic measure is four volumes. I regard this as a 
 double salt. The measure of H 3 P, as shown above, is two volumes 
 = -| -f- ^.. The measure of HI, as shown at page 59, is two volumes. 
 These two salts combine without farther condensation. Hydriodate of 
 phosphuretted hydrogen = hydrine phospha cum hydra ioda. 
 
 H 3 P,HBr. Similar to the preceding. The measure is four volumes. 
 Hydrine phospha cum hydra broma. 
 
 ARSENIC. The atom of arsenicum = Asc, atomic weight = 25, 
 measures one-sixth of a volume in the state of gas, for its specific gravity 
 is 150. When arsenic combines with another radical, it causes the 
 atomic measure of that other radical to be reduced from a volume to half 
 a volume = three-sixths of a volume, to which the arsenic adds its one- 
 sixth of a volume, producing in all four-sixths of one volume. The 
 atomic measure of all the following examples is therefore four-sixths of a 
 volume : 
 
 AscCl Chloride of arsenic = Arsanic chlora. 
 
 AscI Iodide of arsenic = Arsanic ioda. 
 
 AscH Arseniuretted hydrogen = Arsanic hydra. 
 
 AscC 2 H 5 Arsentriethyl = Ethyla arsanic. 
 
 Arsenious acid in the state of gas measures two-sixths of a volume, or 
 only half as much as the other compounds of arsenic. This is easy of 
 explanation. Its formula is Asc,AscO, namely, it contains two arsenic 
 
10-1 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 atoms, each measuring one-sixth of a volume, and one atom of oxygen, 
 which measures nothing. The systematic name of Asc, AscO is arsanic 
 arsanicate. 
 
 Cacodyl contains one arsanous atom, weighing 75, and two atoms of 
 methyl, weighing in all 105. This compound might be expected to 
 measure |- -f- 2 volumes ; but its measure is exactly one volume. The 
 reason of this is, that this compound is a radical, and has the measure, 
 as it is the equivalent, of one volume of hydrogen. All the compounds 
 of cacodyl are regular in their atomic measure, even the oxychloride = 
 6 [AsC 2 H 6 ,Cl] + [AsC*H 6 j 2 O, which contains six atoms of chloride of 
 cacodyl, with one atom of oxide of cacodyl ; for it has the remarkable 
 atomic measure of fourteen volumes, being two volumes for each of the 
 seven regular salts which compose it. 
 
 Contrary to the opinion usually entertained by chemists, the action of 
 arsenic in gaseous compounds, whether we refer to the arsanic atom or 
 the arsanous atom, is different from the action of phosphorus. If we 
 adapted another atom of phosphorus = PC, weighing 10.33, which 
 would be the equivalent of i volume of hydrogen, they would be 
 brought into harmony. 
 
 ANTIMONY. We do not know the atomic measure of antimony, be- 
 cause it is not volatile, but we can examine its action upon other radicals, 
 and we then find that the stibanic atom acts precisely in the same 
 manner as the arsanic atom, its compounds presenting the atomic mea- 
 sure of four-sixths of a volume, exactly as they would do if the measure 
 of the stibanic atom was one-sixth of a volume, and it had the same 
 power that is possessed by the arsanic atom, of reducing the measure of 
 other radicals in combination with it, from a volume to three-sixths of a 
 volume, and then adding to the result its own one-sixth of a volume, 
 making in all four-sixths of a volume. Examples : 
 
 SbcCl = Terchloride of antimony = Stibanic chlora. 
 SbcH = Antimoniuretted bydrogen = Hydra stibanic. 
 SbcC 2 H 5 = Stib-ethyl = Ethyla stibanic. 
 
 BISMUTH. The measure and condensing power of the bismanic 
 atom are, apparently, the same as those of the stibanic and arsanic atoms, 
 the measure of the following compound being four-sixths of a volume : 
 
 BicCl. Chloride of bismuth = bismanic chlora. 
 
 BORON. Boron is not volatile when isolated. Its atom has, appa- 
 rently, the same atomic measure and condensing properties as the arsanic 
 atom, namely, it reduces other radicals to three-sixths of a volume, and 
 then adds its own one-sixth of a volume. Hence, all its compounds 
 measure four-sixths of a volume. Examples : 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 105 
 
 BC1 Chloride of boron = Bora chlora. 
 
 BF Fluoride of boron = Bora fluora. 
 
 C*H 5 , BO Borate of ethyl = Ethyla borate. 
 
 C 5 H ll ,BO Borate of amyl = Amy la borate. 
 
 C H 3 , BO Borate of methyl = Methyla borate. 
 
 SILICON. The atomic measure of silicon is unknown. When it 
 is in combination, it reduces the measure of the radical it is combined 
 with, from a volume to half a volume, adding nothing for its own 
 volume. The following examples all measure half a volume : 
 
 SiCl = Chloride of silicon = Sila chlora. 
 
 SiF = Fluoride of silicon = Sila fluora. 
 
 C 2 H 5 , SiO = Silicate of ethyl = Ethyla silate. 
 
 C 5 H u ,SiO = Silicate of amyl = Amyla silate. 
 
 There is another gaseous compound containing silicon, the atomic 
 measure of which is one volume and a half. This compound is the 
 chlorosulphide of silicon = Si 3 CPS, the atomic weight of which is 109-5, 
 and the specific gravity 73. To account for this singular atomic volume, 
 I imagine that this compound contains CIS, which measures one 
 volume, SiCl, which measures half a volume, and Si 2 which measure 
 nothing, making one volume and a half together. 
 
 Carbon, boron, and silicon, all differ from one another in their power 
 of modifying the atomic measure of compound gases. 
 
 TIN. Tin is not volatile, and its volume is unknown. The stanic 
 atom appears to measure nothing in combination, and to have the power 
 to reduce the radical it combines with, from a volume to half a volume, 
 which is the measure of the following compound : 
 
 SncCl. Stannic chloride = Stanic chlora. 
 
 TITANIUM. The same as tin. The following salt measures half a 
 volume : 
 
 TiCl. Chloride of titanium = Tita chlora. 
 
 TELLURIUM. The atomic measure of tellurium is unknown. It 
 seems, like sulphur, to lose its volume in combination, without altering 
 the volume of the radical with which it combines. The atom of the fol- 
 lowing gas measures one volume : 
 
 HTe. Telluretted hydrogen = Hydra tellura. 
 
 But this gas exhibits another character when in combination with 
 ammonia (see page 100). 
 
 SELENIUM. Selenium, like tellurium and sulphur, has no measure 
 
106 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 when in combination, and it leaves unaltered the radical with which it 
 combines. An atom of each of the following gases measures one volume, 
 so that selenium, like sulphur, retains its volume when combined with 
 oxygen, though it loses it in all other cases. 
 
 HSe. Seleniuretted hydrogen = Hydra sela. 
 SeO. Selenious acid = Selate. 
 
 ZINC. If we may judge from the single gaseous compound of it that 
 is known, zine acts like sulphur, namely, it loses its measure in com- 
 bination, without condensing the radical with which it combines. Hence 
 the following gas measures one volume : 
 
 ZnC 2 H 5 . Zinc ethyl = Ethyla zinca. 
 
 " The vapour volume of zincethyl," says Frankland, 1 " is highly re- 
 markable, and almost compels us to conclude that the vapour volume of 
 the double atom of zinc is only equal to that of oxygen, instead of cor- 
 responding with the volume of hydrogen, in accordance with the gene- 
 rally received supposition. Zincethyl, therefore, appears to belong to 
 the so-called water type, and to consist of two volumes of ethyl and one 
 volume of zinc vapour ; the three volumes being condensed to two ; for 
 if we were to assume that an equivalent of zinc occupies the same 
 vapour volume as an equivalent of hydrogen, we should then have the 
 anomaly of the combination of equal volumes of two radicals being 
 attended by condensation." 
 
 If Dr. Frankland will compare zinc ethyl with sulphide of ethyl, he 
 will perceive that the vapour volume of zincethyl is in no respect more 
 remarkable than that of sulphide of ethyl. In both salts, the ethyl 
 retains its measure of one volume. In both salts, the combined radical, 
 sulphur in the one and zinc in the other, loses its volume. It is of 
 no use to trouble ourselves with a suppositions atomic measure of zinc 
 vapour, because we can neither prove nor disprove any possible con- 
 jecture respecting it, and therefore can apply the conjecture to no useful 
 end. Our knowledge of the actual atomic measure of the vapour of sul- 
 phur is of no service to us in explaining the constitution of the sulphur- 
 ous gases, because its measure in combination has no relation to its 
 volume in the free state. But on examining the compounds of sulphur 
 and zinc with ethyl, it is easy to see that the ethyl of each retains its 
 measure, while the measure of the sulphur and the zinc are both lost. 
 
 The volume of a compound gas has no constant relation to the 
 volumes of its radicals per se. It depends upon the measure which the 
 radicals retain in combination, and upon the condensing power which each 
 can exercise upon the other. 
 
 Proceedings of the Royal Society (1855), VII. 304. 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 107 
 
 MERCURY. I have assumed that there are two chemical atoms of 
 mercury : the mercurous atom weighing 200, and the mercuric atom 
 weighing 100. The specific gravity of gaseous mercury is 100, which 
 corresponds to the mercuric atom and to the atomic measure of one 
 volume. When the mercuric atom combines with a radical, it loses its 
 own measure, but leaves the measure of the radical with which it com- 
 bines unchanged. Consequently, the following compounds have all a 
 measure of one volume, which is due to the metalloid : 
 
 HgcCl Mercuric chloride = Mercuric chlora. 
 HgcBr Mercuric bromide = Mercuric broma. 
 Hgcl Mercnric iodide = Mercuric ioda 4 
 
 When the mercurous atom goes into combination with a radical, it 
 adds one volume to the measure of the radical. Hence the following 
 compounds measure two volumes : 
 
 HgCl Mercurous chloride* = Mercurous chlora. 
 HgBr Mercurous bromide = Mercurous broma. 
 
 The compound of the mercuric atom with sulphur, the mercuric sul- 
 phide, or cinnabar, has an atomic measure of one volume and a half. In 
 this case the mercuric atom retains its volume, and the sulphur triples 
 its volume. It is one of the few examples of apparent expansion. The 
 specific gravity is given on the authority of Mitscherlich, but it is pos- 
 sibly incorrect : 
 
 HgcS. Mercuric sulphide = Mercuric sulpha. 
 
 SUMMARY. Notwithstanding the differences that exist in the powers 
 of the various elements, and the irregularities that occur in special gases, 
 the causes which modify the atomic measure of compound gases, are 
 neither imperceptible nor incapable of reduction to systematic order. I 
 have attempted to give them a useful arrangement in the Table on the 
 next page. 
 
 I have limited this summary to the specification of three peculiarities 
 of each element or radical. First, its atomic measure in the free state, 
 wherever it has been ascertained. Secondly, its measure when in com- 
 bination with other radicals. Thirdly, the condensing power possessed 
 by one atom of each element or radical, on each volume of every radical 
 with which it combines. 
 
 Oxygen, though not a radical, is placed at the head of the list, as a 
 standard of comparison. 
 
108 
 
 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 
 
 2 
 
 g 
 
 
 
 
 11 
 
 | OT . 
 
 Condensing Power of one 
 
 Radicals 
 
 Atomic 
 
 
 g^ 
 
 Atom of the Radical on 
 
 which produce Gases. 
 
 Weight. 
 
 is 
 
 _O fl 
 
 each Volume of every 
 Radical with which it 
 
 
 
 J! 
 
 1 
 
 combines. 
 
 Oxygen . . . O 
 
 16 
 
 I 
 
 
 
 0. 
 
 Carbon . . . C 
 
 12 
 
 
 
 
 0. 
 
 Sulphur . . . S 
 
 16 
 
 1 
 
 
 
 O. 
 
 Selenium . . Se 
 
 4 
 
 
 o 
 
 0. 
 
 Tellurium . . Te 
 
 64 
 
 
 
 
 0. 
 
 Zinc . . . . Zn 
 
 32.5 
 
 
 
 
 0. 
 
 Chromium . . Cr 
 
 27 
 
 
 o 
 
 0. 
 
 Hydrogen . . H 
 
 i 
 
 
 
 0. 
 
 Chlorine . . . Cl 
 
 35-5 
 
 
 
 0. 
 
 Bromine. . . Br 
 
 80 
 
 
 
 O. 
 
 Iodine ... I 
 
 127 
 
 
 
 0. 
 
 Fluorine . . . F 
 
 
 
 
 O. 
 
 Nitrogen. . . N 
 
 H 
 
 
 
 0. 
 
 Mercury. . . Hgc 
 
 100 
 
 
 o 
 
 o. 
 
 . . . Hg 
 
 200 
 
 
 I 
 
 0. 
 
 Phosphorus. . P 
 
 3 1 
 
 1 
 
 * 
 
 I volume to volume. 
 
 Arsenic . . . Asc 
 
 25 
 
 T 
 
 i 
 
 I volume to volume. 
 
 Antimony . . Sbc 
 
 43 
 
 
 i 
 
 I volume to ^ volume. 
 
 Bismuth. . . Bic 
 
 7 1 
 
 
 I 
 
 I volume to volume. 
 
 Boron . . . B 
 
 3.6 
 
 
 -L 
 
 I volume to volume. 
 
 Silicon ... Si 
 
 7-5 
 
 
 
 
 I volume to volume. 
 
 Titanium. . . Ti 
 
 12 
 
 
 
 
 I volume to volume. 
 
 Tin .... Snc 
 
 29.5 
 
 
 
 
 I volume to ^ volume. 
 
 COMPOUNDS. 
 
 
 
 
 
 Radicals . . C n H 2n+I 
 
 
 I 
 
 I 
 
 o. 
 
 Radicals . . C n H 2n -' 
 
 
 I 
 
 I 
 
 o. 
 
 Radicals . . C m H 2n 
 
 
 
 o 
 
 o. 
 
 Vinyl . . CH 2 
 
 H 
 
 I 
 
 
 
 0. 
 
 Succinyl . . C 2 H 2 
 
 26 
 
 
 o 
 
 o. 
 
 Amidogen . NH 2 
 
 16 
 
 
 I 
 
 0. 
 
 Cyanogen Cy = CN 
 
 26 
 
 I 
 
 I 
 
 0. 
 
 Cyanyl Cyl = CN 
 
 26 
 
 
 * 
 
 I volume to volume. 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 
 
 109 
 
 
 
 <D 
 
 2 
 
 
 
 
 13 
 
 D 
 
 Condensing Power of one 
 
 Radicals 
 which produce Gases. 
 
 Atomic 
 Weight. 
 
 o 
 
 i! 
 
 Atom of the Radical on 
 each Volume of every 
 Radical with which it 
 
 
 
 ll 
 
 i 
 
 combines. 
 
 EXCEPTIONS AMONG 
 
 
 
 
 
 INORGANIC GASES. 
 
 
 
 
 
 Carbonic Oxide . CO 
 
 28 
 
 2 
 
 
 
 O. 
 
 Carbonic Acid . CO 2 
 
 44 
 
 2 
 
 
 
 0. 
 
 Deutoxide of K TQ 
 JNitrogen . .) 
 
 3 
 
 2 
 
 i 
 
 0. 
 
 Peroxide of 1 NQ2 
 JNitrogen . .) 
 
 46 
 
 2 
 
 i 
 
 0. 
 
 Sulphurous Acid SO 
 
 32 
 
 I 
 
 
 
 O. 
 
 Selenious Acid . SeO 
 
 56 
 
 I 
 
 o 
 
 0. 
 
 Sulphuric Acid,) csc^ 3 
 Anhydrous / bSC 
 
 80 
 
 2 
 
 o 
 
 0. 
 
 Hydrated . HSO 2 
 
 49 
 
 2 
 
 I 
 
 0. 
 
 Chloric Oxide . CIO 2 
 
 67.5 
 
 2 
 
 I 
 
 0. 
 
 Xanthyl . . . CS 4 
 
 76 
 
 2 
 
 
 
 0. 
 
 A few of the Organic Salts present exceptions to the above-stated 
 general rules, but it is probable that most of them are attributable to 
 our imperfect knowledge of the composition of the substances which 
 exhibit the irregularities. They are as follow : 
 
 ORGANIC GASES WITH IRREGULAR ATOMIC MEASURES. 
 
 1. Benzoile, chlorohydride 
 
 = H,C 7 H 5 ; Cl 2 
 
 2. Ethyl, tribasic formiate 
 
 = (C 2 H 5 ) 3 ; CHO 3 
 
 3. Ethyl, renan thy late 
 
 = C 2 H 5 ,C 7 H 13 2 -f-C 2 H 5 ,C 7 H l3 
 
 4. Methyl, tribasic formiate 
 
 = (CH 3 ) 8 ; CHO 3 
 
 5. Terchlorinated methylic ether 
 
 = CC1 3 ,CC1 3 
 
 6. Terchlorinated methylic sulphide 
 
 = CC1 3 ,S 
 
 Theoretical 
 Atomic 
 Measure. 
 
 Experimental 
 Atomic 
 Measure. 
 
 4 volumes. 
 
 2 volumes. 
 
 4 volumes. 
 
 2 volumes. 
 
 4 volumes. 
 
 2 volumes. 
 
 4 volumes. 
 
 3 volumes. 
 
 2 volumes. 
 
 4 volumes. 
 
 i volume. 
 
 2 volumes. 
 
110 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 Number 5 in this list would become regular if formulated thus : 
 CC1 2 ,C1+CC1 2 ,C1O, where CC1 2 represents bichlorinated vinyl ; and, for 
 the same reason, number 6 would be regular if formulated CCl a ,ClS. 
 
 METHOD COMMONLY EMPLOYED BY CHEMISTS TO FIND THE SPECIFIC 
 GRAVITY OF COMPOUND GASES. The usual method of calculating the 
 specific gravities of compound gases, is described by Sir Robert Kane as 
 follows. 1 " The simplicity shown to exist between the volumes of the 
 constituent and compound vapours, enables us very often to calculate 
 beforehand what the specific gravity of a vapour should be, and thus to 
 ascertain how closely the numbers found experimentally approach to 
 absolute correctness. . . . The general rule is to multiply the 
 specific gravities of the simple gases or vapours respectively, by the 
 volumes in which they combine, to add these products together, and 
 then to divide the sum by the number of volumes of the compound gas 
 produced." 
 
 To be able to put this rule into practice, we must know the specific 
 gravities of the gases, as commonly expressed in terms referring to the 
 density of air as unity, and we must also know the assumed combining 
 volume of each elementary gas, and the measure of the compound gas. 
 
 On the radical theory, we require only the formula of the compound 
 gas, and the data presented in the above Table, to be able to calculate 
 not only the specific gravity of the compound gas, but its atomic mea- 
 sure also, which is a quantity that the ordinary rule requires to be given 
 as one of the data from which to calculate the specific gravity. 
 
 Examples : 
 
 HHO = Water. Atomic weight 1 + 1 + 16=18. The two atoms 
 of hydrogen measure two volumes in combination, and the oxygen 
 measures nothing. Hence the atomic measure is two volumes, and the 
 specific gravity is 1 8 -f- 2 = 9. To find the specific gravity in terms 
 referring to air taken at roo, the specific gravity 9 must be divided by 
 14-47. 
 
 SncCl = Chloride of Tin. Atomic weight 29-5 + 35-5 = 65. The 
 atom of tin measures nothing in combination, and it reduces the mea- 
 sure of the chlorine from one volume to half a volume. Hence the 
 atomic measure of the salt is half a volume, and as it requires two 
 atoms of the compound to complete one volume, the specific gravity is 
 65 X 2 = 130. 
 
 C 2 H 5 ,S + HS. Mercaptan. The hydrosulphate of sulphide of ethyl. 
 Atomic weight, 29+16 + 1+16 = 62. The atom of ethyl, like all 
 the compound organic radicals, measures one volume in combination. 
 The atom of hydrogen measures one volume. The two atoms of sulphur 
 
 1 Elements of Chemistry (1849), page 290. 
 
THE ATOMIC MEASURE OF COMPOUND GASES. Ill 
 
 measure nothing. No condensing power is present. The total measure 
 is consequently two volumes, and the specific gravity is 62 -4- 2 = 31. 
 
 H,C 2 H 5 O. Alcohol Atomic weight, i + 29 -f- 16 = 46. The hy- 
 drogen and the ethyl measure in combination one volume each, and the 
 oxygen measures nothing. Hence the atomic measure of alcohol is two 
 volumes, and its specific gravity is 46 -f- 2 = 23. 
 
 It is unnecessary to quote other examples, because the Table of Gases, 
 and the discussion which I have just concluded, present them in abund- 
 ance. 
 
 In contrast with the simplicity of the mode of calculation afforded by 
 the radical theory, I will quote Poggendorff's account 1 of the gaseous 
 constitution of the last two compounds, the aspect of which shows the 
 difficulties and uncertainties of the ordinary mode of reckoning : 
 
 Component Volumes in Condensa- Atoms Specific 
 
 1 Vol. of Compound. tion. in 1 Vol. Gravity. 
 
 Mercaptan <^-C 2 H 5 S^--f-HS-i- i 
 
 CH 3 Oi 9 
 
 Alcohol UC 2 H 5 (H+HO* i 
 
 2 
 
 6 
 
 iV i 2,15822 
 
 i> i 1,60049 
 
 One of the marvels of modern chemistry is the persistence of its 
 professors in the practice of comparing the specific gravities of gases 
 with that of common air taken as unity. To be consistent, they should 
 adopt the additional absurdity of taking the composition of common air 
 as the standard of the atomic weights. Just look at these two examples 
 of specific gravities ! The atomic weight of mercaptan is 62 , and its 
 specific gravity is 31 ; the atomic weight of alcohol is 46, and its specific 
 gravity is 2 3 ; but these numbers are too simple to have the proper 
 look of philosophical profundity, so The Authorities of our science fix the 
 specific gravity of mercaptan at 2*15822, and of alcohol at i '60049' 
 beautiful numbers ! which contain the quantity of Egyptian darkness 
 necessary to render them grand and mysterious, and which confer upon 
 the scientific world the remarkable advantages that always flow from 
 the statement of simple facts in terms w r hich no memory can retain. 
 
 THE LAWS. THAT REGULATE THE ATOMIC MEASURE OF THE VAPOURS 
 OF POLYBASIC ACIDS, AS ENUNCIATED BY PROFESSOR GfiRHARDT. 
 Before closing my inquiry into the causes which modify the atomic 
 measure of compound gases, I must consider certain propositions that 
 
 1 Handworterbuch der Chemie, Band II, pp. 478, 488. 
 
112 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 have been laid down by M. Gerhardt. I copy them from his recently- 
 published Traite de Chimie Organique, tome iv. I may, premise, that 
 the objects which M. Gerhardt has in view, are to establish certain laws 
 by which monobasic, bibasic, and tribasic acids may be distinguished 
 from one another, and, in particular, to demonstrate that sulphuric acid 
 and oxalic acid are bibasic acids. To this end, he lays down certain 
 absolute laws, and adduces such examples as he considers sufficient to 
 prove their accuracy and universality. I shall quote the laws and proofs, 
 and then examine their trustworthiness. 
 
 " Considered in the state of vapour and in the same volume, the neu- 
 tral ethers of bibasic acids contain twice the radical of the alcohol, where 
 the neutral ethers of monobasic acids contain [only once that radical." 
 Page 653. 
 
 I. 2. 3. 4. 
 
 n j(7H 5 O n |C 2 H 3 O n2 JS0 2 rvJ c * 2 
 
 U [C 2 H 5 U \CH 3 U \(CH 3 ) 2 ((C*H 5 ) 2 
 
 2 volumes 2 volumes 2 volumes 2 volumes 
 
 Benzoate of Acetate of Sulphate of Oxalate of 
 Ethyl. Methyl. Methyl. Ethyl. 
 
 " Considered in the state of vapour and in the same volume, the 
 chlorides of bibasic acids (the dichlorides) contain twice the radical chlo- 
 rine, where the chlorides of monobasic acids contain it only once." 
 Pages 653 and 724. 
 
 C^CPH'O C1,C 2 H 3 O C1 2 ,S0 2 C1 2 ,CO 
 
 2 volumes 2 volumes 2 volumes 2 volumes 
 
 Chloride of Chloride of Chloride of Chloride of 
 
 Benzoyle. Acetyle. Sulphury le. Carbonyle. 
 
 " Considered in the state of vapour, and in the same volume, the 
 neutral ethers of tribasic acids contain three times the radical of the 
 alcohol, where the neutral ethers of bibasic acids contain that radical only 
 twice, and those of monobasic acids contain it only once" Pages 658 
 and 694. 
 
 9. 10. ii. 
 
 :C 2 H 5 02 J(C 2 H 5 ) 2 n3 J(C*H 5 ) 3 
 
 [C 2 H 3 O u }C 2 O 2 (Cy 3 
 
 2 volumes 2 volumes 2 volumes 
 
 Acetate of Oxalate of Cyanurate of 
 
 Ethyl. Ethyl. Ethyl. 
 
 " Considered in the state of vapour, and in the same volume, the 
 chlorides of tribasic acids (the trichlorides) contain three times the radical 
 chlorine, where the chlorides of bibasic acids contain that radical only 
 twice, and the chlorides of monobasic acids contain it only o?ice." Pages 
 658 and 725. 
 
 j 
 \ 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 113 
 
 12. 
 
 CP,B 
 2 volumes 
 Chloride of 
 Boron. 1 
 
 *3 
 
 C1 3 ,P 
 2 volumes 
 Chloride of 
 Phosphorus. 
 
 14. 
 CP,PO 
 2 volumes 
 Chloride of 
 Phosphoryle. 
 
 CP,Cy 3 
 2 volumes 
 Chloride of 
 Cyanuryle." 
 
 These laws are evidently founded upon the examples which M. Ger- 
 hardt has adduced to support them. According to him, the examples 
 prove that bibasic and tribasic acids affect the atomic measure of com- 
 pound gases, or gaseous salts, in a manner entirely different from that in 
 which they are affected by monobasic acids ; so that, if you examine 
 two volumes of the vapour of a salt, and find therein one, or two, or 
 three basic radicals, the acid is with certainty known to be monobasic, 
 bibasic, or tribasic, according to the number of the basic radicals which 
 your examination discloses in the two volumes of vapour. In the same 
 manner, the examination of two volumes of a gaseous chloride, and the 
 discovery therein of one, or two, or three atoms of chlorine, proves to 
 M. Gerhardt, that the radical with which the chlorine is combined, is 
 that of a monobasic, bibasic, or tribasic acid, according to the number of 
 atoms of chlorine that are discovered to be present in the two volumes 
 of vapour that are submitted to examination. 
 
 The examples that I have quoted seem to support these doctrines ; 
 for the facts are accurate, and M. Gerhardt's inferences are plausible. 
 But I cannot, upon evidence of this description, and of this limited ex- 
 tent, jump at once, with that chemist, to the conclusion, that, because 
 two volumes of sulphate of methyl contain two atoms of methyl, sul- 
 phuric acid is bibasic, or that, because two volumes of oxalate of ethyl 
 contain two atoms of ethyl, oxalic acid is bibasic. True as the facts are, 
 these inferences do not necessarily follow. 
 
 Let us check M. Gerhardt's examples by what we have ascertained, in 
 another manner, to be true in regard to the measure of compound gases. 
 Let us see why his formula? agree in all cases with two volumes of 
 vapour, and yet fail to prove the truth of his propositions. 
 
 No. i. Benzoate of Ethyl = C 2 H 5 ,C 7 H 5 2 . There are two volumes 
 of vapour because there are two radicals. 
 
 In this and all the examples the oxygen measures nothing. 
 
 No. 2. Acetate of Methyl = CH 3 ,C 2 H 3 O 2 . Again, there are two vo- 
 lumes of vapour because there are two radicals. 
 
 No. 3. Sulphate of Methyl = CH 3 ,SO 2 . M. Gerhardt arbitrarily 
 doubles the atomic weight of sulphur. I reduce it to 1 6, the usual weight. 
 The salt, according to the corrected formula, CH 3 ,S0 2 , has two radicals, 
 
 1 M. Gerhardt's atomic weight of sulphur is twice as much as mine, 
 and that of boron three times as much. The weights of the other 
 elements agree with mine. 
 
 I 
 
114 INQUIRY INTO THE CAUSES WHICH MODIFY 
 
 one acid and one basic; but I have shown (page 97) that sulphur, when 
 acting as an acid radical in a gaseous salt, measures nothing. The salt 
 is therefore complete in one volume ; and the reason that two volumes 
 of the vapour contain two atoms of methyl, is because two volumes of 
 the vapour contain two complete atoms of the salt. If the weight 
 of one atom of sulphur could be proved to be 32, that is to say, the 
 .equivalent of two atoms of hydrogen, then M. Gerhardt would have 
 some ground for his doctrine, but as all attainable evidence proves 
 the atomic weight of sulphur to be 1 6, or the equivalent of one atom of 
 hydrogen, the examination of this gaseous salt affords no proof that sul- 
 phuric acid is bibasic. 
 
 No. 4. Oxalate of Ethyl = C 2 H 5 ,C0 2 . This salt is complete in one 
 volume, because the radical carbon measures nothing when combined 
 with other radicals. Two volumes of vapour contain two atoms of ethyl, 
 because they contain two atoms of oxalate of ethyl. The salt therefore 
 lends no support to the notion that oxalic acid is bibasic. M. Gerhardt 
 makes the oxalates appear to be bibasic by doubling the quantities of 
 all the components. His formula is not a demonstration but an assump- 
 tion. 
 
 No. 5. Chloride of Benzoyle = CPH^CIO. Two volumes of vapour 
 contain two radicals uncondensed. 
 
 No. 6. Chloride of Acetyle = C 2 H 3 ,C10. Two volumes of vapour 
 contain two radicals uncondensed. 
 
 No. 7. The compound which M. Gerhardt calls Chloride of Sul- 
 phuryle = C1 2 ,SO 2 , is that which I have described at page 56, under the 
 designation of chlorosulphuric acid = C1SO. An atom of this salt 
 = CISO, measures one volume, because the chlorine alone retains its 
 measure, the sulphur and oxygen losing theirs. Two volumes of this 
 compound contain two complete atoms of the salt, and therefore two 
 atoms of chlorine. M. Gerhardt's inference, that the two volumes of 
 vapour contain one atom of bibasic sulphuryle, is a fallacy, founded upon 
 the arbitrary assumption that one atom of sulphur weighs 32. 
 
 No. 8. The salt which M. -Gerhardt calls chloride of carbonyle = 
 C1 2 ,CO, is that which, at page 55 of this work, is called phosgene gas 
 = CC1,C1O, according to which formula the salt is an oxychloride of 
 chloricformyl. Upon either supposition, the salt should have an atomic 
 measure of two volumes ; in the first case, because CO measures nothing 
 in combination, and Cl 2 are uncondensed, and measure two volumes ; in 
 the second case, because CC1 = an atom of formyl that contains Cl 1 , in- 
 stead of H 1 , measures one volume, and CIO also measures one volume. 
 The measure of two volumes is therefore due solely to the two volumes 
 of chlorine, the carbon and oxygen measuring nothing. There is DO 
 evidence to prove that the compound which M. Gerhardt calls carbonyle 
 = CO is a bibasic acid radical. 
 
 It does not appear that M. Gerhardt knew, or duly appreciated, the 
 
THE ATOMIC MEASURE OF COMPOUND GASES. 115 
 
 fact that oxygen, carbon, and sulphur have no gaseous measure when 
 combined with radicals to form salts ; and that, in the salts which con- 
 tain these elements, it is the basic radicals alone that make up the mea- 
 sure of the compound gases. The consequence is, that his laws re- 
 specting the measure of salts that contain the so-called bibasic acids, 
 founded as they are upon the examination of those salts only that con- 
 tain sulphur and carbon as radicals, are fallacious. They apply, to the 
 exceptional cases upon which they are founded, and to nothing else. 
 The three hundred gases described between pages 50 and 63 do net 
 afford a single example to justify them. 
 
 I pass to the consideration of the laws that relate to tribasic acids. 
 The Example No. 9 is equivalent to No. 2. No. 10 is a repetition of 
 No. 4. No. 1 1 is a salt, the composition of which I have already dis- 
 cussed at page toi, where I have attempted to show that its proper 
 measure is not two volumes, but % volume. See farther particulars on 
 this head in the account of Example No. 15. M. Gerhardt might have 
 brought forward a more striking example in support of his law. This 
 is the tribasic formiate of ethyl No. 2 in the Table of Irregular Gases, 
 formulated at page 109. This salt agrees perfectly with the law in 
 question: C 2 H 5 ,C 2 H 5 ,C 2 H 3 ; CHO 3 ; atomic weight, 148; sp. gr. 74; 
 atomic measure, two volumes ; number of basic radicals, three. Un- 
 luckily, the conformity of this salt is neutralised by the nonconformity 
 of the parallel salt No. 4 in the same Table, namely, the tribasic formiate 
 of methyl = CH 3 ,CH 3 ,CH 3 ; CHO 3 ; atomic weight, 103 ; sp. gr. 35-33 ; 
 number of basic radicals, three ; atomic measure, three volumes. Upon 
 two examples which neutralise one another we cannot prudently found 
 a law having pretensions to general applicability. 
 
 The next law relates to the chlorides of tribasic acids. 
 
 No. 12. Chloride of Boron. I divide M. Gerhardt's atomic weight of 
 boron by 3, which converts his formula from C1 3 B to C1 3 B 3 . This for- 
 mula no doubt represents two volumes of the gas, but, as it appears to me, 
 it also represents three atoms of the salt ; the small atom of boron is the 
 equivalent of one atom of hydrogen or of chlorine. No advantage is 
 obtained by treating as trichlorides compounds which can be just as well 
 treated as simple chlorides. I therefore write C1B as the proper formula 
 of the compound described at pages 52 and 104 in this work. Boron, 
 as I understand it, is the base of a monobasic and not of a tribasic acid, 
 and I will show in another section, that all the chemical reactions in 
 which boron plays a part, can be described accurately and simply by 
 equations that refer to it in its monobasic character. 
 
 No. 13. Chloride of Phosphorus = CPP. 
 
 No. 14. Oxy chloride of Phosphorus CPPO. I have shown at page 
 I O2 how it happens that three atoms of chlorine, in combination with an 
 atom of phosphorus, produce two volumes of vapour, either in the pre- 
 sence or absence of oxygen : it is because phosphorus in all cases con- 
 
 i2 
 
116 INQUIRY INTO THE CAUSES WHICH MODIFY, ETC. 
 
 denses the radicals it combines with from one volume each to half a 
 volume, adding thereto its own measure of half a volume. It acts thus 
 not only with chlorine but with hydrogen and with ethyl, and when the 
 action takes place upon three atoms, the result is favourable to M. Ger- 
 hardt's law. But in this case, as in the cases of carbon and sulphur, the 
 law depends for support upon a peculiar property of an individual sub- 
 stance. There is no evidence that all tribasic acid radicals have this 
 power of condensation : yet the law is founded upon the assumption of 
 its universal applicability. 
 
 No. i 5. Chloride of Cyanyl = CICyl. The compound in question is 
 the solid chloride of cyanogen, the nature of which has been discussed 
 at page 101. Two volumes of it certainly contain three atoms of Cyl 
 because two volumes contain three atoms of the complete salt. If we 
 admit that the compound CylCl, measuring -- volume, is a complete salt, 
 the radical Cyl is monobasic. The question, whether any advantage is 
 gained by tripling the atom, and considering it polybasic, will be con- 
 sidered when I come to investigate the properties of the so-called poly- 
 basic acids. The point for consideration here is the influence of polybasic 
 acid radicals upon the measure of their gaseous salts. According to 
 M. Gerhardt, a bibasic acid radical in all cases condenses two basic 
 radicals, and a tribasic acid radical in all cases condenses three basic radi- 
 cals into a gaseous salt, having an atomic measure of two volumes. On 
 the other hand, my view of this matter is, that all the radicals which 
 produce gases have individually certain unalterable properties, such as 
 their measure in an isolated state their measure when combined in salts 
 the power possessed by certain radicals of condensing to one-half the 
 volume of all radicals with which they combine. These properties they 
 possess as against all other radicals ; and as the properties are constant, 
 we can foresee what will occur hi the various combinations of these 
 radicals one with another. This is the view which I have attempted to 
 express in the Table given at page 108. The examples of salts upon 
 which M. Gerhardt has founded his laws are all such as can be easily 
 interpreted by these principles, and when interpreted, they prove, as I 
 think, that M. Gerhardt's laws have not that accuracy, precision, and 
 general applicability which he attributed to them. Founded on spe- 
 cialties, they apply to similar specialties and to nothing more. 
 
 A question which has been largely debated is, whether the atomic 
 measures of all gases, simple and compound, ought to be fixed at TWO 
 volumes or, as some have it, at FOUR volumes. Upon this question I 
 will not waste a word. No man whose judgment is unprejudiced can 
 examine the facts that are detailed in this section, and in the Table given 
 at pages 50-63, without coming to the conclusion, that the adoption of 
 one uniform atomic measure for gases and vapours of every description 
 is absurd. 
 
Applications of the Eadical Theory. 
 
 The object of this Essay is to show the reasonableness of the Radical 
 Theory, and the advantages which it possesses over every other theory, 
 in the clearness of the explanations which it affords of the proximate 
 constitution of chemical compounds. I have dwelt at considerable length 
 upon the compounds that produce gases and vapours, because we have 
 in the examination of these compounds the double advantage of being 
 able to measure and to weigh both the components and the compounds. 
 The examination has afforded evidence more decisively favourable to the 
 Radical Theory than any that has ever before been submitted to the 
 consideration of chemists. I hope that the effect will be to induce them 
 to adopt it, and to throw aside many of the limited and limiting 
 hypotheses by which the science is now hampered. The theory of 
 Lavoisier, that salts are composed of acids and bases ; Berzelius's 
 doctrines respecting the salts of the sesquioxides and the relations 
 supposed to exist between the oxygen of bases and the oxygen of acids ; 
 the theory of nuclei, as developed by Laurent and Gmelin ; Gerhardt's 
 notion that "free elements" are binary compounds; and the proposal 
 to make all salts agree with the model of water are among the hypo- 
 theses that may be advantageously discarded as unsuited to the present 
 condition of chemical science. The explanations of particular facts, and 
 the generalisations which they provide, are, as I think, in all cases inferior 
 to those that are afforded by the Radical Theory ; while the formula? and 
 nomenclature to which they lead are so intricate and puzzling, that only 
 a few professional chemists pretend to be able to understand them. 
 This evil is so great, that an annual complaint is made at the meetings 
 of the British Association, that organic chemists employ an unknown 
 tongue, and render their science unintelligible and inaccessible to men 
 of science of other denominations. 
 
 If the principles of the Radical Theory were adopted, there would 
 remain for performance the duty of carrying the theory into practical 
 operation that is to say, of showing in detail its effects, firstly, upon 
 the Classification and Nomenclature of chemical compounds; and, 
 secondly, upon the views that ought to be taken of the proximate con- 
 stitution of different varieties of compound salts ; for it is upon these 
 points that the existing theories and the Radical Theory most strikingly 
 divaricate. That duty cannot be performed in a work of the limited extent 
 of this Essay. My task is that of advocating a principle. I adduce 
 such facts as serve to prove the truth of the statements that I advance, 
 but I avoid details that would require a series of volumes for their 
 complete exposition. Nevertheless, as it is necessary for the proper 
 comprehension of the doctrines that I am advocating to show what 
 effect the adoption of the Radical Theory would have upon the com- 
 
118 ANHYDRIDES, OR ANHYDROUS ACIDS. 
 
 monly-received formulae and names of several important classes of 
 chemical compounds, I shall make a selection of such compounds, and 
 apply to them the Formulas, the Names, and the Explanations, which 
 would come into effect on the adoption of the Radical Theory, as that 
 theory is set forth in the preceding pages. Let it, however, be borne 
 in mind, that the NOMENCLATURE which I have suggested, though it is 
 framed upon the Radical Theory, forms no essential part of that theory ; 
 so that the Theory and the Nomenclature must be judged of independ- 
 ently of each other. 
 
 Among the examples which I propose to describe, I shall select some 
 that will give me an opportunity of discussing several questions that have 
 not hitherto come before us ; such, for instance, as relate to the doctrines 
 of polybasic and conjugated acids ; of amids, ammonias, ammoniums, 
 and other organic bases ; of vice-radicals, anhydrides, and double salts. 
 These examples will enable us to grapple with, and dispose of, some of 
 the most startling difficulties in theoretical chemistry. 
 
 Anhydrides, or Anhydrous Acids. 
 
 As the distinction of the proximate elements of salts into ACIDS and 
 BASES is not recognised by the Radical Theory, it is necessary to show 
 what view is to be taken of the compounds that are commonly called 
 Anhydrous Acids ; that is to say, the oxidised negative radicals, which 
 can be procured in a separate state, or uncombined with water or me- 
 tallic bases. 
 
 . The following diagram exhibits examples of anhydrous acids, con- 
 trasted with hydrated acids : 
 
 i. HO, SO 
 (HO,SO 
 
 lHO,so 
 
 HO,POO 
 HO,POO 
 
 [The atomic weights of the elements in the Table are, = 16, H = i , 
 S=i6, C = i2, P = 3i.] 
 
 The compound represented by No. 1 is one atom of oil of vitriol, or 
 hydrated sulphuric acid, the proposed systematic name for which, in 
 accordance with the Radical Theory, and framed on the formula H,S0 2 , 
 is HYDRA SULPHETE. 
 
 No. 2 represents two atoms of hydrated sulphuric acid. If we con- 
 sider these two atoms to be decomposed, by proper chemical means, 
 into the two compounds distinguished by the different character of the 
 types in the diagram, we have, as products, one atom of water = H,HO, 
 
 . 
 
 ' lHO,c 2 H a o 
 
 f HO,C 7 H 5 O 
 
 3 ' I HO,c io H u o 
 
ANHYDRIDES, OR ANHYDROUS ACIDS. 119 
 
 and one atom of anhydrous sulphuric acid = 0,SO, or SO -f- SOO or 
 
 SO 
 
 S,SQ 3 . I regard this anhydrous compound, not as an acid, for it has no 
 acid reactions, but as a SALT, consisting of two radicals ; the basic radical 
 being one atom of sulphur combined with one atom of oxygen ; the acid 
 radical being one atom of sulphur combined with two atoms of oxygen. 
 This apportionment of the oxygen is, however, only conjectural. It 
 is quite as possible that all the oxygen may be combined with one of the 
 atoms of sulphur, and that the true formula of the compound may be 
 S,S0 3 . I name this salt SULPHA SULPHITE. 
 
 It may be objected to this proposal, that chemists have always repre- 
 sented sulphur as an acid radical, and that there is no precedent for con- 
 sidering it a basic radical. But, on the other hand, it may be remarked, 
 that chemists have never hesitated to account for certain intermediate 
 metallic oxides by admitting them to be salts, consisting of a protoxide 
 acting as a base, and a sesquioxide or a peroxide of the same metal act- 
 ing as an acid, combined together. Why should the argument run 
 in two opposite ways ? If a metal, brought into different states of 
 oxidation, can form both positive and negative radicals, and these can 
 combine to produce a salt, why may not a metalloid, placed in similar 
 circumstances, act in a similar manner? Moreover, we have to take 
 into consideration the fact, that this salt S,S0 3 has, equally with the 
 salt HSO 2 , the power of combining with neutral salts to form multiple 
 salts. This fact is proved by the following well-known compounds, and 
 is corroborated by the existence of similar double salts, formed by anhy- 
 drous chromic acid with metallic chromates, and even by anhydrous 
 acetic acid with anhydrous acetate of potash. 
 
 Sulphate. Bisulphate. 
 
 KSO 2 KSO 2 KSO 2 KSO 2 
 
 HSO 2 KSO 2 KSO 2 
 
 HSO 8 SSO 3 
 
 I shall show, in a subsequent section, that there is another acid of 
 sulphur, -which differs from hydrated sulphuric acid only in having one 
 atom less of oxygen, so that it requires the formula H,SO ; and that 
 this acid has, like sulphuric acid, the property of forming an anhydride : 
 
 H,SO } __ j^jjQ and gjgo 
 
 This anhydrous compound must also be considered as a salt of sulphur ; 
 the unoxidised atom S being the positive radical, and the oxidised atom 
 SO being the negative radical of the salt. 
 
120 ANHYDRIDES, OR ANHYDROUS ACIDS. 
 
 Comparison of the two series of Acids. 
 
 H,SO = Hydra sulphate. I H,SO 2 = Hydra sulphete. 
 S, SO = Sulpha sulphate. | S, SO 3 = Sulpha sulphite. 
 
 Diagram No. 3 exhibits the relation of hydrated phosphoric acid to 
 anhydrous phosphoric acid. What I have said of sulphuric acid applies 
 with equal force to phosphoric acid. The anhydrous compound POO 
 -f- POOO or P,PO 5 is a salt in which phosphorus acts both as a 
 basic radical and an acid radical, the two radicals being probably in 
 different states of oxidation. This compound ought not to be called an 
 acid. Its name, on the proposed system, and agreeing with the formula 
 last quoted, P,P0 5 , will be PHOSPHA PHOSPHUTE. 
 
 The other anhydrous inorganic oxygen acids may be treated precisely 
 in the same way. Anhydrous nitric acid is formed from two atoms of 
 the hydrated acid; H,N0 3 -f H,N0 8 producing H,HO + N,N0 5 = 
 NITRA NITRUTE ; and Chromic acid, only known, and easily procured, 
 in the anhydrous state, in beautiful red crystals, is Cr,Cr0 3 = 
 CHROMOUS CHROMITE. 
 
 In all these examples, as in all salts, the quantity of oxygen is expressed 
 by the terminal of the name of the negative radical. 
 
 No. 4 in the diagram represents the hydrated and the anhydrous 
 acetic acid. Notwithstanding that this substance contains a compound 
 organic radical, I propose to deal with it precisely in the same manner 
 as with the salts that contain simple inorganic radicals ; for I consider it 
 to be in the highest degree inexpedient to subject organic and inorganic 
 radicals to different laws ; and, by so doing, to make a chasm between 
 organic and inorganic Chemistry, and separate two branches of know- 
 ledge, which ought to be one and indivisible. 
 
 The anhydrous acetic acid is to be considered as a salt having 
 protoxide of acetyl = C 2 H 3 O for its base, and binoxide of acetyl = 
 Q2jj3Q f or j tg ac j^ j tg f ormu ] a) on that view of its constitution, will 
 be C*ITO,(?H 8 O i , or C 2 H 3 ,C 2 H 3 3 , and the systematic name for the 
 latter will be ACETYLA ACETYLITE. 
 
 All the anhydrides of organic acids, of which a considerable number 
 have recently been discovered, may be treated in the same way. 
 
 M. Gerhardt has given to anhydrous acetic acid the name of Acetic 
 acetate, and as he has adopted the same system of nomenclature for the 
 anhydrides of organic acids generally applying, for example, such terms 
 as Benzoic benzoate, and Cuminic cuminate, to compounds that consist 
 of two radicals with three atoms of oxygen I take leave to point out 
 the unfitness of such names. The acetates, benzoates, and eliminates, 
 contain respectively only two atoms of oxygen. The names proper to such 
 salts ought not to be given to compounds which, containing three atoms 
 of oxygen, evidently belong to a different series from that to which the 
 
ANHYDRIDES, OR ANHYDROUS ACIDS. 121 
 
 acetates, benzoates, and eliminates belong. When the characters of a 
 class of salts have been distinctly defined, the name of that class ought 
 undoubtedly to be confined to compounds that agree with the definition. 
 The present proposal, to consider the anhydrides as salts, in which the 
 same negative radicals, in different states of oxidation, are assumed to 
 act as positive and negative towards one another, being applicable to all 
 anhydrides, whether their radicals be simple or compound, presents, at 
 least, the good qualities of simplicity, uniformity, and precision, both in 
 formulae and nomenclature. 
 
 {TTO C 7 H 5 Ol 
 fro C IO H II O I i 
 
 a compound procured lately by M. Gerhardt. This is a double anhy- 
 dride of a kind that appears to be as plentiful as the anhydrides of 
 the individual organic acids. The radicals represented in No. 5 are 
 benzyl = C 7 H 5 and cumyl = C 10 H U . These are combined, with three 
 atoms of oxygen, into a compound of the same structure as anhydrous 
 acetic acid. The origin of the compound is to be explained exactly 
 in the same manner as that of the simple anhydrides; namely, two 
 atoms of hydrated acid produce one atom of water and one atom of the 
 anhydride : 
 
 = H,C 7 H 5 O 2 \ J C 7 H 5 O 2 1 f H 
 id = H,C 10 H n 2 } == \ C 10 H U O j + { HO 
 
 Benzoic acid = H,C 7 H 5 O 2 
 Cumenic acid 
 
 M. Gerhardt calls this anhydride by the following names : " Anhydrous 
 Benzo-cuminic acid," " Cuminate of Benzoile," and " Benzoate of Cumyl." 
 For want of a System of Nomenclature which would indicate to him a 
 single satisfactory name, he begins with a profusion of synonymes. This 
 is an example of the manner in which our books on Organic Chemistry 
 become incumbered with useless or mischief-making names. 
 
 The terms " eliminate of benzoile" and " benzoate of cumyl" are 
 both improper, for the reasons urged in reference to the names of the 
 simple anhydrous acids ; namely, because eliminates and benzoates are 
 salts that contain each only two atoms of oxygen, and it is contrary to 
 chemical logic to apply the same names to salts that contain three atoms 
 of oxygen. 
 
 The term " anhydrous benzo-cuminic acid" is improper for another 
 reason, namely, because it is not an acid, and does not give rise to a 
 series of salts in which " benzo-cumyl " forms the acid radical. On the 
 contrary, when the anhydride is placed in the presence of basic radicals, 
 the benzyl and cumyl fall apart, and produce benzoates and cuminates. 
 In fact, this anhydride differs in no respect from the compound ethers 
 and acetones that are described in group 5, page 66, excepting that its 
 radicals are in a higher state of oxidation. I propose, therefore, to con- 
 sider it as a salt, in which the radical with the greater proportion of 
 
122 DEGREES OF OXIDATION OF RADICALS. 
 
 hydrogen shall, on the principle explained at page 73, be taken to be the 
 basic radical, and the one with the lesser proportion of hydrogen shall 
 be taken to be the acid radical. The analytical formula of the salt will 
 then be C'H 11 O,C 7 H 5 O 2 ; its synoptical formula will be C 10 H U ,C 7 H 5 3 ; 
 and its systematic name will be CQMYLA BENZYLITE. 
 
 All the anhydrides that contain two organic radicals, combined with 
 three atoms of oxygen, may be formulated and named in accordance with 
 this example. The following compounds of this class have been recently 
 discovered by MM. Gerhardt and Chiozza. 1 
 
 C 9 H 1 /, C 7 H 5 O 3 = Pelargyla Benzylite. 
 
 C 7 H 13 , C IO H0 = (Enanthyla Cumylite. 
 
 C^H 9 , C7H 5 3 = Valeryla Benzylite. 
 
 C 2 H 8 , C 10 H U 8 = Acetyla Cumylite. 
 
 C 2 !! 3 , C 9 H 7 O 3 = Acetyla Cinnamylite. 
 
 C 2 H 3 , C 7 H 5 3 = Acetyla Benzylite. 
 
 C l H a , C 7 H 5 O 3 = Cumyla Benzylite. 
 
 C 9 H 7 , C 7 H 5 O 3 = Cinnamyla Benzylite, 
 
 Degrees of Oxidation of Eadicals. 
 
 The compound radicals appear to have the same degrees of oxidation 
 as the elementary radicals. If R is the radical, we have the series : 
 
 1. R,RO 
 
 2. RO 
 
 3. RO,ROO = R,RO 3 
 
 4. ROO 
 
 No. I is what we now term a protoxide, namely, the oxide formed on 
 the model of water. 
 
 No. 2 is the oxide that exists in the salts that have the formula 
 MRO 2 or MO -f- RO, but which is rarely obtained in a separate state. 
 Professor Williamson has given to an oxide of this description, a name 
 which entirely differs from that of its characteristic radical. He desig- 
 nates the protoxide of acetyl = C 2 H 3 O by the term OTHYL. If this 
 precedent is followed, we must have a pair of names for every radical ; 
 one name for the radical alone, and another, entirely different, for one of 
 its oxides. The evil may not stop there. If RO is to have a name 
 essentially different from that of R, why may not RRO, ROO, R^O 3 , 
 and all other oxides of the radical, also be distinguished by widely-dif- 
 ferent names ? Surely it is better to adopt a system of names, which 
 shall not lose sight of each radical by the time we reach its first oxide. 
 
 1 Quarterly Journal of the Chemical Society. V. 127, 226. VI. 
 182, 184. 
 
. INTERMEDIATE METALLIC OXIDES. 123 
 
 According to the nomenclature which I have proposed, C 2 H 3 will be 
 named ACETYLATE, which, without special definition, signifies one atom 
 of acetyl and one atom of oxygen. Such words as othyl must require 
 definition individually ; for othyl indicates neither acetyl nor oxygen. 
 
 It may be replied to this objection, that the reason why two different 
 names are given to the compounds in question is, that acetyl = C 2 H 3 and 
 othyl = C 2 H 3 O are two different radicals. That reply rests, however, 
 not on a matter of fact, but on a matter of opinion. According to the 
 radical theory, as I understand it, othyl is not a radical, but the oxide 
 of a radical, and it has no right to any other name than that which de- 
 clares it to be the oxide of a radical. 
 
 The oxides, No. 3, = RO, ROO, or R,RO 3 , are the anhydrides of 
 which I have just treated. 
 
 No. 4, = ROO. This oxide probably occurs in the salts that contain 
 O 3 and 0*. 
 
 Thus: MO,ROO = M,R0 3 
 MOO,ROO = M,R0 4 
 
 Intermediate Metallic Oxides. 
 
 In reference to the classification of oxides, I may say a few words 
 respecting those metallic oxides which occur between the protoxides and 
 the sesquioxides, and which commonly receive the formulas M 3 O 4 and 
 MO -f M 2 O 3 ; the latter representing the compounds as salts in which 
 different oxides of the same metal act as base and acid to one another. 
 The following formulas represent examples of such oxides : 
 
 Fe O 4- Fe 2 O 3 = Fe 3 O 4 Magnetic oxide of iron. 
 MnO -f Mn 8 3 = Mn 3 4 Red oxide of manganese. 
 Cr O -f- Cr 2 O 3 = Cr 3 O 4 Chromoso-chromic oxide. 
 
 M. Laurent accounts for salts of this description, by adopting a third 
 equivalent of the metals w T hich they contain. But this proposal is inad- 
 missible, because the fourth part of the metal contained in such com- 
 pounds is not the equivalent of a single volume of hydrogen, nor does 
 it make a series of salts, corresponding to those which are made by the 
 basylous and basylic equivalents of the respective metals. I consider these 
 oxides to be compounds of the basylous and basylic oxides, according 
 to the following general formula : 
 
 McMcO + McMO = Mc 3 M0 2 . Thus, 
 
 Magnetic oxide of iron = FecFecO,FecFeO = Fec 3 FeO a 
 Red oxide of manganese = MncMncO,MncMnO = Mnc 3 Mn0 2 
 Chromoso-chromic oxide = CrcCrcO,CrcCrO = Crc 3 CrO 8 
 
124 ALDIDES, OR ALDEHYDES IN GENERAL. 
 
 Corresponding nomenclature : 
 
 Fec 3 FeO 2 = Ferrinic ferrete. 
 Mnc 3 Mn0 2 = Manginic manganete. 
 Crc 3 Cr0 2 = Chrominic chromete. 
 
 Aldides, or Aldehydes in general. 
 
 Gmelin describes l the aldides as follows : " When Liebig, by with- 
 drawing two atoms of hydrogen from alcohol, converted it into the com- 
 pound C 4 H 4 O 2 , he called that compound aldehyde, from alcohol and 
 deAyJrogenated. More recently a considerable number of other com- 
 pounds have been discovered, possessing a certain analogy with Liebig's 
 aldehyde, and to these the same name has been extended. To avoid 
 this confusion, I propose to- denote all these compounds by the generic 
 term Aldide, reserving the original title of aldehyde for the aldide of the 
 ethyl series." 
 
 He then goes into a description, classification, and enumeration of the 
 aldides : see the work referred to. It will suffice for my purpose to 
 extract a few examples from his list. Let me premise, that the funda- 
 mental experiment, referred to above, of the production of aldehyde 
 from alcohol is, on the radical theory, to be explained as follows : 
 
 H,C 8 H 5 O - H 2 = H,C*fPO. 
 
 Namely, the radical ethyl is reduced to the radical acetyl by the abstrac- 
 tion of two atoms of hydrogen. See the explanation of this theory at 
 page 74. Both alcohol and aldehyde are salts of the same structure: 
 they belong to the hydrated oxides, of which examples are given in 
 group 3, page 65. Many of Gmelin's aldides are precisely of this cha- 
 racter. I have treated, at page 78, of the production of aldides of this 
 class. Several of Gmelin's aldides belong to the anhydrides described 
 in the last section ; others belong to the oxychlorides, of which examples 
 are given in group 10, page 68 ; and others are of the class of amids, of 
 which I shall treat in a subsequent section. In short, the aldides, as 
 grouped by Gmelin, are compounds belonging to many different series 
 of salts, transformed into the so-called aldides by the abstraction, not 
 only of hydrogen, but of carbon or oxygen, or sometimes of all three ; 
 and having scarcely any common relation : 
 
 Handbook of Chemistry. VII. 192. 
 
THE CHEOMATES. 
 
 125 
 
 Gmelin's Names. Proposed Formulae. 
 a. Hydrates. 
 
 Aldehyde .... E^CTPO . 
 
 Acrolein .... H,C 3 H 3 O . 
 
 Butyric aldide . . H,C 4 H 7 O . 
 
 Valeric aldide . . . H,C 5 H 9 O . 
 
 Phenous acid . . . H,C 6 H 5 O . 
 
 Oil of bitter almonds H,C 7 H 5 O . 
 
 (Enanthol .... H,C 7 H 13 O . 
 
 O 
 
 Proposed Names. 
 
 Hydra acetylate. 
 Hydra aery late. 
 Hydra butyrylate. 
 Hydra valerylate. 
 Hydra phenylate. 
 Hydra benzylate. 
 Hydra (Enanthylate. 
 
 5. Anhydrous Acids. 
 
 
 
 Lactic acid . . . 
 Maleic Acid . . 
 
 . C 3 H 5 ,C 3 H 5 5 . 
 . C 2 H,C 2 H0 3 . 
 
 . Lactyla lactylute. 
 . Maleyla maleylite. 
 
 c. Oxychlorides. 
 
 
 
 Chloraldehyde . . 
 Chlorobenzoyl . . 
 
 . C 2 C1 3 ,C1O . 
 . C 7 H 5 ,C10 . 
 
 . Chlorinic-acetyla cl 
 . Benzyla chlorate. 
 
 d. Cyanates. 
 
 
 
 Cyanic acid . . . 
 
 . H,CyO . . 
 NH 4 ,CyO . 
 
 . Hydra cyanate. 
 . Ammona cyanate. 
 
 e. Amids. 
 
 
 
 Oxamide . . . 
 
 . NH 2 ,CO . . 
 
 . Amida Carbate. 
 
 At page 8 1 I have defined aldide in terms intended to fix its mean- 
 ing and restrict its use. 
 
 The Chromates. 
 
 I introduce the chromates in this place, because they exhibit some 
 striking examples of the combination of anhydrides with neutral salts. 
 The anhydrous crystallized chromic acid is composed of 
 
 Chromium . . 54 = Cr 2 
 Oxygen . . . 48 = O 3 
 
 It consequently belongs to the class of Anhydrides, and requires the 
 formula Cr,CrO 3 , and the name Chromous chromite. The solid hydrate 
 of this acid is unknown, although the anhydrous acid readily dissolves 
 in water, and the solution may be supposed to contain HCrO* ; agree- 
 ably to the equation, 
 
 H,HO 4. Cr,GW = HCrO 8 + HCrO a 
 
126 THE CHROMATES. 
 
 The acid in this aqueous solution combines with peroxide of hydrogen 
 = HO. The compound has a deep indigo-blue colour, but it is unstable, 
 and cannot be separated from the water of solution. Its composition is 
 probably 
 
 HO,CrO + HO = H,H; CrO 8 . 
 
 There are three combinations of chromic acid with potash, which have 
 the following composition : 
 
 Chromate of Potash. Usual formula, KO,Cr0 3 . Doubling the atomic 
 weight of the oxygen we have KCrO 2 . 
 
 Bichromate of Potash. Usual formula KO, CrO 3 , CrO 3 Doubling the 
 atomic weight of the oxygen we have iK,2Cr,3^0. Doubling the 
 formula, to get rid of fractions, we have K 2 Cr 4 O 7 . 
 
 Terchromate of Potash. Usual formula, KO^CrO 8 . Doubling the 
 atomic weight of the oxygen, this gives us KCr 3 O 5 . 
 
 If we regard the chromate as the normal salt = KCrO 2 , the terchro- 
 mate is a compound of normal chromate and chromic acid, atom to 
 atom, and the bichromate is a compound of the normal chromate with 
 the terchromate. 
 
 Chromate = KCrO 2 = KCrO 2 
 
 Bichromate = KCrO 2 + (KCrO 2 + CrCrO 3 ) = K 2 Cr 4 7 
 Terchromate = KCrO 3 + CrCrO 3 = K Cr 3 5 
 
 This series is similar to that of the three kinds of phosphates, excepting 
 that, in the present case, it is' the add radical which is variable, while in 
 the phosphates it is the basic radical that is variable. 
 The systematic names of these salts are as follow : 
 
 Chromate of potash . . K Cr O 2 = Potassa chromete. 
 Terchromate of potash . K Cr 3 5 = Potassa chrominute. 
 Bichromate of potash . . K*Cr*0 7 = Potassen chromoneze. 
 
 There is a salt formed by means of chromic acid and chloride of 
 potassium which has given theoretical chemists a great deal of trouble. 
 Here are two of its formulae and names : 
 
 KC1. 2 CrO 3 = Bichromate of chloride of potassium. 
 
 I 2> \ 
 
 KO. (Cr < j J CrO 3 - Chrombioxychlorid-chromate of potash. 
 
 This salt is probably a compound of neutral chromate of potash = 
 KCrO 2 , with the oxychloride of chromium = CICrO, so that its formula 
 may be KCrO 2 + CICrO or K,C1; Cr 2 O 3 . The systematic name, accord- 
 ing to this last formula, is Potassa chlora chromenite. 
 
ANALYTICAL FORMULA AND SYNOPTICAL FORMULAE 127 
 
 There is a corresponding salt containing sulphur instead of chromium 
 the sulphur bioxychlorid-sulphate of potash, 
 
 This salt is probably a compound of neutral sulphate of potash = KSO 2 
 with the oxychloride of sulphur = C1SO, producing the compound 
 KSO 2 + C1SO or K,C1 ; S 8 O 3 , the name for which is Potassa chlora 
 sulphenite. 
 
 The chromates combine with one another to produce compound salts : 
 
 Double : KCrO 2 + CaCrO 2 = K,Ca ; (CrO 2 ) 2 . 
 Triple: 2KCrO 2 + NaCrO 8 = K 2 Na; (CrO 2 ) 3 . 
 Sextuple: AmCrO 2 + 5HCr0 2 = Am,H 5 ; (CrO 2 ) 6 . 
 
 Is the chromic acid monobasic, bibasic, tribasic, or sexbasic ? 
 
 Distinction between Analytical Formulae and 
 Synoptical Formulae. 
 
 In the preceding pages I have frequently shown, that the radical 
 theory permits of the representation of salts by two kinds of formulae ; 
 as a simple example of which I may quote the formulas employed to 
 represent the sulphates, viz. : 
 
 MO,SO and MSO 2 . 
 
 The formula MSO 2 is that which expresses all that we certainly know of 
 the constitution of the sulphates, and the arrangement of the symbols is 
 conventional. We agree (that is the strongest ground that we can put 
 it upon we agree} to put first the electro-positive or basic radical, and, 
 after it, the electro-negative or acid radical ; and, at the end, we put the 
 oxygen, because we do not know where else to put it. This formula 
 gives a synoptical view of our knowledge of this compound, and I propose 
 to call it a synoptical formula. 
 
 In the other formula, MO, SO, we show what we conjecture to be the 
 proximate constitution of the sulphate. In our mental analysis of this 
 salt, we figure to ourselves, that it is a compound of oxidised metal and 
 oxidised sulphur, atom to atom. But mental analysis is purely theo- 
 retical, and we cannot experimentally establish the truth of this formula. 
 Nevertheless, the analytical view of the compound assists our compre- 
 hension of many phenomena that occur when the salt is decomposed by 
 reaction with other salts ; and, in many theoretical inquiries, where our 
 judgment must be entirely guided by circumstantial evidence, the 
 analytical formulae of salts are important. 
 
 The systematic nomenclature which I have proposed for adoption is 
 
128 DAVY'S THEORY OF SALTS. 
 
 founded upon the synoptical formulae, partly because these are less sub- 
 ject to variation than the analytical formulae, and partly because they 
 yield shorter and simpler names. It is, however, always possible, 
 whenever it is considered desirable, to give names to the conjectured 
 components of a salt as set forth in an analytical formula. Thus, we 
 may call the sulphate of barytes : 
 
 Synoptical formulas : BaSO 8 . . Baryta sulphete. 
 Analytical formulae : BaO,SO . Barytate sulphate. 
 
 The power of writing names to suit either formula is frequently useful, 
 particularly in the discrimination of multiple salts. 
 
 Sir Humphry Davy on the Composition of Sulphates 
 and Salts in General. 
 
 Since the article on the binary theory of salts, at page 18, went to 
 press, a chemical friend has directed my notice to another note of Sir H. 
 Davy's, respecting the question there discussed. As I desire to do 
 justice to that great chemist, I copy the article in full : 
 
 " The extensive class of bodies called neutral salts," says Davy, 1 " are 
 formed by the mutual action of acids and oxides, alkalies and earths ; 
 and in general those oxidated bodies that contain least oxygen are such 
 as most readily enter into combination with acids ; thus the peroxides 
 generally are either insoluble in acids, or require the abstraction of a 
 portion of oxygen to become soluble ; and, in general, two inflammable 
 bodies, in combining with oxygen, unite to less than the added sums of 
 the quantity they would separately combine with to saturation. Many 
 of the neutral salts may be considered either as combinations of per- 
 oxides with inflammable bases or as alkalies united to acids, or as per- 
 oxides united to oxides; for instance, the compound formed from 
 sulphurous acid gas and potassa consists of potassium and sulphur, with 
 three proportions of oxygen, and may be regarded as a compound of 
 peroxide of potassium and sulphur. Sulphate of potassa contains four 
 proportions of oxygen, and might be regarded as a compound of per- 
 oxide of potassium and oxide of sulphur. They are, in fact, all com- 
 pounds of oxygen with double bases; and when one fixed alkali, or 
 earth, or oxide, separates another, it may be supposed that the basis 
 only is changed : thus, where hydrate of potassa separates lime from its 
 nitric solution, it may be conceived that the potassium only takes the 
 place of calcium, and that the oxygen and water of the hydrate of 
 
 1 Elements of Chemical Philosophy, Collected Works (1840), vol. iv. 
 page 368. First published in 1812. 
 
129 
 
 potassium unite to this metal, and that the potassium unites to the 
 oxygen, nitrous acid and water of the solution. 
 
 " It is very easy to estimate the composition of any of the com- 
 binations of alkalies, earths, or oxides with acids, by adding together 
 the numbers representing their elements : thus, sulphate of soda is 
 composed of 60 sulphur, 90 oxygen, which make two proportions of 
 sulphuric acid ; and 88 of sodium and 30 of oxygen, which make one 
 proportion of soda. Carbonate of lead is composed of two proportions 
 of carbonic acid, equal to 82*8, two proportions of oxygen 30, and one 
 of lead 398. Sulphate of lead is composed of two proportions of sul- 
 phuric acid 1 50, two of oxygen 30, and one of lead 398 : sulphate of 
 nickel of two proportions of sulphuric acid 1 50, and one of oxide of nickel 
 141 ; and these proportions agree almost precisely with the best analysis. 
 
 " It appears that in the neutrosaline compounds, in which there is a 
 perfect harmony between the proportions of the elements, the result is 
 neutralisation; and that in this case a crystalline compound or an 
 insoluble compound is usually formed. Thus, in the instances above 
 mentioned, in the sulphates of soda and lead, the sulphur is a binary 
 proportion, and the oxygen a binary proportion, or a multiple of a 
 binary proportion ; and in the carbonate of lead the carbon is a binary 
 proportion, and the oxygen a multiple of a binary proportion ; and, to 
 give another instance, in the sulphate of barytes the sulphur is a single 
 proportion, and the oxygen a single proportion, or a multiple. 
 
 " When, on the contrary, there is a want of harmony in the pro- 
 portions, the excess either of acid or basis seems to be shown in the 
 properties of the result, and it is seldom a crystallized body. Thus, in 
 the soluble red sulphate of iron, the number of proportions of oxygen in 
 the oxide are three, and those of the sulphur in the acid are four, and 
 this body is strongly acid and uncrystallizable." 
 
 This note, printed in 1812, does not essentially differ from the notes 
 subsequently published in 1815 and 1816, and which I have quoted at 
 page 21. Davy had, previous to any of these dates, proved that 
 chloride of sodium contained only chlorine and sodium ; that no oxygen 
 was present, and therefore no soda ; no hydrogen, and therefore no 
 hydrochloric acid. The substance that was par excellence a SALT, was 
 .found to contain neither acid nor base. This discovery naturally led him 
 to form generalisations respecting other salts. He might reasonably ask 
 these questions : Since we know that muriate of soda contains neither 
 muriatic acid nor soda, what certainty have we that sulphate of soda 
 contains sulphuric acid and soda ? May not this salt, and all salts, be 
 composed in a manner analogous to muriate of soda ? These were very 
 natural suggestions, and the evidence before us proves that they passed 
 through Davy's mind, and that he was the first to point out the fact, 
 that Lavoisier's theory of acids and bases did not rest on a logical basis, 
 But it does not appear to me that Davy went much beyond this expres- 
 
 K 
 
130 DAVY'S THEORY OF SALTS. 
 
 sion of his conviction that the existing theory of the salts was bad, and 
 that it was desirable to have a better theory. He opens the case for 
 discussion very clearly. He says, " Many of the neutral salts may be 
 considered either as 
 
 a. Combinations of peroxides with inflammable bases, or as 
 6. Alkalies united to acids, or as 
 c. Peroxides united to oxides." 
 
 In proposition a, he allots all the oxygen to the basic radical = MO + R. 
 In 6, the usual theory is accepted = MO -f- RO 3 I* 1 c the oxygen is 
 supposed to be equally divided between the positive and negative 
 radicals, MO 4- RO ; and this last proposition is illustrated by sup- 
 posing the sulphate of potash to be composed of peroxide of potassium 
 and sulphurous acid = KO 2 + SO 2 . This last was certainly a most 
 valuable suggestion. There is no statement in these propositions, nor 
 anywhere in the note, that Davy supposed the sulphates to be so con- 
 stituted, that all the oxygen was combined with the sulphur ; according 
 to the formula which Dumas assigned to him = K -f- SO 4 . 
 
 But after opening the case for inquiry, Davy did not pursue it with 
 much precision. He states, first, that sulphate of potash contains four 
 proportions of oxygen ; then, that the sulphates of soda, lead, and nickel 
 contain each two proportions of sulphur, eight proportions of oxygen, 
 and one proportion of metal; and, finally, that in the sulphate of 
 barytes the sulphur is a single proportion, and the oxygen a single 
 proportion, or a multiple. The most important sentence in the note 
 is that where he says, that " the salts are, in fact, all compounds of 
 oxygen with double bases ; and when one fixed alkali, or earth, or oxide, 
 separates another, it may be supposed that the basis only is changed : 
 thus, where hydrate of potassa separates lime from its nitric solution, it 
 may be conceived that the potassium only takes the place of calcium." 
 With this exception, there is in this note no distinct setting forth of 
 any new and peculiar theory of the salts ; and it remains to be shown 
 whether any such theory was published by Davy, or anybody else, 
 between 1816 and the date of Dr. Clark's Syllabus of 1826. 
 
 One of Davy's instances deserves special notice : " Sulphate of 
 potash contains four proportions of oxygen, and might be regarded as a 
 compound of peroxide of potassium and oxide of sulphur." The theory 
 contained hi this sentence, instead of being the binary theory, = K -j- 
 SO 4 , which Dumas attributes to Davy (see page 19), is precisely the 
 theory KO + SO, which he attributes to Longchamp (see page 23), 
 and which he calls " the hypothesis of Davy turned topsy-turvy ;" so 
 that, actually, the praises which Dumas bestowed upon Sir H. Davy 
 belong to Dr. Clark, while the sneers which he lavished upon M. Long- 
 champ are the property of Sir H. Davy. 
 
Vice-Badicals. 
 
 In explaining the doctrine of chemical types and substitutions, I 
 stated that the hydrocarbon radicals produced a series of secondary 
 radicals, by exchanging part or the whole of their hydrogen, atom for 
 atom, for chlorine, bromine, or iodine ; and, in the inquiry respecting 
 gaseous volumes, I showed that the secondary radicals, thus produced, 
 acted in salts the same part as the radicals from which they were derived, 
 excepting only that the basic energy of the positive radicals diminished 
 in proportion to the increase in the number of the substituting atoms of 
 the negative metalloid. The reader will consult pages 93 and 101 for a 
 detailed illustration of these general principles. 
 
 The compound chlorine radicals, produced in the manner that I have 
 described, and having the property of acting vicariously, or as substitutes, 
 for the original radicals from which they are derived doing the duty of 
 those radicals more or less imperfectly, as the duties of principals com- 
 monly are done by substitutes form but one division of a series of 
 Vicarial or Vice-Radicals that are found among the compounds of 
 organic chemistry. The chlorine radicals were first referred to, because 
 many of them are volatile, and it was necessary that we should under- 
 stand their constitution, in order to comprehend certain doctrines re- 
 specting the measure of the gases ; but I shall now give a short notice of 
 such radicals taken generally, and including those which are fixed, as 
 well as those which are volatile. They may be arranged in four classes. 
 i. Vice-radicals, in which the hydrogen of the original radicals is re- 
 placed by chlorine. These I shall call Chloric Radicals. The iodic- and 
 bromic-radicals, form parallel series, belonging to the same class. 2, 
 Those in which the hydrogen is replaced by nitrogen. These I shall 
 call Zotic Radicals. 3. Those in which the hydrogen is replaced by 
 sulphur, which I shall call Sulphic Radicals. 4. Those in which the 
 hydrogen is replaced by metals, which may be distinguished as Metallic 
 Vice-Radicals. 
 
 I. Chloric Eadicals. 
 
 The account of the chloric radicals, already given at pages 93 and 
 1 01, leaves but a few remarks unsaid. When the chlorine is introduced 
 into a negative or acid radical, the vice-radical is also negative, and in 
 forming salts with positive radicals, it acts in the same manner as the 
 original radicals. In being monobasic or bibasic, in forming salts with 
 one atom of oxygen, or with two atoms or three atoms, and in similar 
 particulars, the vicar and the principal radical agree perfectly. Generally, 
 also, the salts of the chloric radical have the same external appearance as 
 those of the hydro-carbon radical. Their solutions do not give a pre- 
 
 K2 
 
132 
 
 ZOTIC KADICALS. 
 
 cipitate with solutions of silver, and the presence of the chlorine can 
 only be demonstrated by a process which destroys the compound. The 
 following are examples of salts that contain chloric radicals, placed in 
 juxtaposition with the corresponding salts of the original radicals. The 
 nomenclature has been explained at page 94 : 
 
 Radicals. 
 
 Salts. 
 
 r c*H 3 
 
 Acetyl < 
 
 C 2 C1 8 
 
 f C 5 H 9 
 
 ValeryH 
 
 I C>H 5 C1 4 
 
 f C 7 H 5 
 Benzyl { 
 
 [ C 7 H 4 C1 
 
 Phenyl 
 
 H,C 2 H 3 2 
 
 {Hydrated acetic acid. 
 Hydra acetylete. 
 
 H remarks I Hydrated trichloracetic acid. 
 ,\j \ji \j . < TT j , i . . i 
 
 [ Hydra chlorimc-acetylete. 
 
 tr nsure i Hydrated valenanic acid. 
 Jn,L/Ml O . < Tj- 7 , , , . 
 [ Hydra valerylete. 
 
 H C 5 H 5 Cl*O a I Hydrated quadrichlorovaleric acid. 
 | Hydra chloronic-valerylete. 
 
 f Hydrated benzoic acid. 
 1 Hydra benzylete. 
 H C 7 H 4 C1O 8 I Hydrated chlorobenzoic acid. 
 { Hydra chloric-benzylete. 
 
 H.C'H'O 
 
 C 6 H 3 C1 2 
 C 6 H 2 C1 3 
 C 6 C1 5 
 
 H,C 6 C1 5 O 
 
 f Hydrated phenic acid. 
 
 I Hydra phenylate. 
 
 J Hydrated bichlorophenic acid. 
 
 \ Hydra chlorenic-phenylate. 
 
 ) Hydrated trichlorophenic acid. 
 Hydra chlorinic-phenylate. 
 j Hydrated quintichlorophenic acid. 
 \ Hydra chlorunic-phenylate. 
 
 The vice-radicals formed by iodine and bromine are similar in consti- 
 tution and functions to those formed by chlorine. I refer the reader for 
 examples to the sections on Indigo and Aniline. 
 
 II. Zotic Eadicals. 
 
 The acids of zotic radicals are generally produced by dissolving certain 
 organic acids in fuming nitric acid, or in a mixture of nitric acid and 
 concentrated sulphuric acid. The reaction may be represented as 
 follows : 
 
ZOTIC RADICALS. 133 
 
 Employed. Produced. 
 
 Benzole acid . . H,C'H 5 2 H,C 7 H 4 N0 4 . 
 
 Nitric acid . . . H,N O 3 H, H O. 
 
 Namely, an atom of hydrated benzoic acid and an atom of hydrated 
 nitric acid, produce an atom of water and an atom of hydrated nitroben- 
 zoic acid. 
 
 In contemplating the composition of this new acid, we perceive two 
 remarkable peculiarities : In the first place, the radical benzyl = C 7 H 5 is 
 converted, by the substitution of an atom of nitrogen for an atom of 
 hydrogen, into the vice-radical C 7 H 4 N, or, as I have proposed to formu- 
 late it (page 94), into C 7 H 4 Z ; for which formula the systematic name 
 will be zotic-benzyl. In the second place, we perceive that the acid 
 formed by the vice-radical contains two atoms more of oxygen than are 
 contained in the acid formed by the original radical. This is not a pro- 
 perty belonging to this individual example, but is a characteristic of all 
 the zotic radicals which contain carbon. For every atom of nitrogen 
 which is carried into any radical, in substitution for an atom of hydrogen, 
 two atoms of oxygen are carried into the salts of that radical ; and this 
 is continued to the amount of three atoms of nitrogen, beyond which 
 number substitution by this element rarely extends. The following are 
 therefore the proportions and general limits of the zotic radicals : 
 
 Expelled from the 
 original Radicals. 
 
 Zotic radicals . . . . H 1 . 
 Zotenic radicals . . . H 2 . 
 Zotinic radicals . H 3 . 
 
 Substituted. 
 
 Z 1 + O 2 . 
 Z 2 + O 4 . 
 Z 3 4. O 6 . 
 
 In two respects the zotic radicals differ essentially from the chloric 
 radicals. The first is, that in the latter there is no limitation to the 
 number of atoms of chlorine that can replace atoms of hydrogen : sub- 
 stitution may proceed till all the hydrogen of any radical is replaced by 
 chlorine. The second point of difference is, that the salts of the chloric 
 radicals contain in all cases the same quantity of oxygen as the salts of 
 the primary radicals from which they are formed. 
 
 The circumstance that every atom of nitrogen that goes into a zotic 
 radical is accompanied in its transit by two atoms of oxygen has 
 induced many chemists to conclude, that the actual substitute for each 
 atom of hydrogen which nitric acid expels from a radical is not an atom 
 of nitrogen = N, but an atom of peroxide of nitrogen = NO 2 , and this 
 conclusion has induced them to formulate the salts of the zotic radicals 
 in such a manner as to show that two atoms of oxygen in company with 
 each atom of nitrogen are situated in the body of the compound radical. 
 Thus : 
 
 | C7 H 4 ( N 2 ) I _ Hydrated nitrobenzoic acid. 
 
134 ZOTIC RADICALS. 
 
 This symbol affects to show us, that there is in this salt one atom of 
 oxygen that is equally combined, on the one hand, with a single atom of 
 basic hydrogen, and on the other hand, with a complex acid radical. 
 This complex acid radical is itself an oxide containing one atom of oxygen 
 in combination with a nitro-conjugated radical = C 7 H 4 (NO 2 ) -f- O. This 
 nitro-conjugated radical = C 7 H 4 (NO 2 ) is fundamentally benzyl = (7H 5 , 
 but it is benzyl which contains peroxide of nitrogen, instead of one 
 atom of hydrogen = C 7 H 4 -f NO 8 . Here, therefore, we have oxygen 
 represented to be distributed in three places, combined with three 
 different degrees of intensity, to the radicals of the salt we have, con- 
 sequently, assumptions upon assumptions three deep, which can be jus- 
 tified or established by no evidence, and which serve no useful purpose. 
 
 {(THYNO^O ) 
 ^ JT i* > is an affectation of knowledge a pre- 
 
 tentious accuracy in a matter where accurate knowledge is unattain- 
 able. It serves neither to register nor to convey knowledge, for it 
 represents nothing but a speculation. I should not quarrel with it, if it 
 were confessedly a speculation. What I complain of is, the practice too 
 common among organic chemists, of stating such speculative views as 
 if they represented demonstrated facts. Until we learn something certain 
 respecting the distribution of oxygen between the positive and negative 
 radicals of a salt, the honest, modest, prudent course for us to follow is, 
 to put the oxygen together, and frankly confess that we do not divide it 
 between the radicals, because we do not know how to do so with the 
 slightest pretensions to accuracy and truth. 
 
 Applying this notion to the nitrobenzoic acid, the formula becomes 
 
 The leading properties of the salts of the zotic radicals are as follow : 
 They are all monobasic. They have usually a yellow colour. Bitter. 
 Commonly decomposed by heat, so that they do not form gases. The 
 decomposition by heat is generally explosive. It is possible, therefore, 
 that the nitrogen which they contain may be present in that condensed 
 condition which I have referred to in the article on Cyanyl (page 101). 
 
 Examples of Salts containing Zotic Radicals. 
 
 Radicals. 
 
 Salts. 
 
 fCPH 5 
 Propionyl < 
 I C 3 H 4 Z 
 
 H.C'HPO 1 . 
 H,C 3 H 4 Z0 4 
 
 f Hydrated propionic acid. 
 ( Hydra propionylete. 
 {Hydrated nitropropionic acid. 
 Hydra zotic-propionylote. 
 
ZOTIC EADICALS. 
 
 135 
 
 Kadicals. 
 
 Salts. 
 
 
 rc 6 H 5 
 
 H,C 6 H 5 O . 
 
 ( Hydrated phenic acid. 
 ( Hydra phenylate. 
 
 Phenyl . 
 
 < C 6 H 3 Z 8 
 
 H,C 6 H 3 Z 2 5 
 
 ( Hydrated binitrophenic acid. 
 ( Hydra zotenic-phenylute. 
 
 
 [ COTZ 8 
 
 H,C"H 2 Z 3 7 
 
 {Hydrated trinitrophenic acid. 
 Hydra zotinic-phenyleze. 
 
 
 r cm 5 
 
 H,C 7 H 5 2 . 
 
 (Hydrated benzoic acid. 
 Hydra benzylete. 
 
 Benzyl . 
 
 < C7H 4 Z 
 
 H,C 7 H 4 Z0 4 
 
 I Hydrated nitrobenzoic acid. 
 ( Hydra zotic-benzylote. 
 
 
 [ C 7 H 3 Z 2 
 
 H,C 7 H 3 Z 2 O 6 
 
 f Hydrated binitrobenzoic acid. 
 \ Hydra zotenic-benzylaze. 
 
 Cinnamyl 
 
 rc 9 H 7 
 
 1 C 9 H 6 Z 
 
 H,CH 7 O 2 . 
 H^H'ZO 4 
 
 J Hydrated cinnamic acid 
 { Hydra cinnamylete. 
 {Hydrated nitrocinnarnic acid. 
 Hydra zotic-cinnamylote. 
 
 Lest it should be imagined that I lose sight of the difficulties that 
 attend the management of the zotic radicals, I will cite a couple of very 
 perplexing examples from an article on the Benzoates, written by Dr. 
 H. Kolbe. 1 
 
 " Benzoate of oxide of phenyl (benzophenid of Laurent and Ger- 
 hardt) (C 12 H 5 )0,C 14 H 5 3 ." Kolbe. 
 
 According to my notation this compound is C 6 H 5 ,C 7 H 5 O 2 , name phe- 
 nyla benzylete. 
 
 " Benzoate of oxide of binitrophenyl. (Binitrobenzophenid of Laurent 
 and Gerhardt.) 
 
 3 " Kolbe - 
 
 According to this formula, three-fourths of the oxygen of the salt is 
 combined with the basic radical and one-fourth with the acid radical. 
 According to my notation, the synoptical formula is C 6 H 3 Z 2 ,C 7 H 5 O 6 , and 
 the systematic name is zotenic-phenyla benzylaze. 
 
 " Benzoate of oxide of trinitrophenyl. (Trinitrobenzophenid of Lau- 
 rent and Gerhardt.) 
 
 ma; 
 
 (NO 4 )' 
 
 .jo. 
 
 C 14 H 5 O 3 ." Kolbe. 
 
 1 S 
 
 Supplemente zum Handwbrterbuche der Chemie (1852), p. 503. 
 
136 SULPHIC RADICALS. 
 
 According to this formula, thirteen-sixteenths of the oxygen of the 
 salt is combined with the basic radical, and only three-sixteenths with 
 the acjd radical. According to my notation, the synoptical formula is 
 C 6 H 2 Z 3 ,C 7 H 5 O 8 , and the systematic name is zotinic-phenyla benzylize. 
 
 If I wanted to make analytical formulae for the last two compounds, 
 I should reason in this way : The analytical formula of the phenic acid 
 is H,C 6 H 5 O, and that of the benzoic acid is HC^C'TPO. If the basic H 
 in the last formula is replaced by phenyl, we have the salt C 6 H 5 O, 
 C 7 H 5 O, as exhibited in the first of the above three examples. 
 
 If the replacing radical is zotenic-phenyla = CWZ 2 , the resulting 
 salt must account for the four atoms of oxygen which always accompany 
 Z 2 , when acting as substitute for H 2 , and we have consequently the 
 analytical formula CTCZK^OTPO. The O 5 consists of the O l belonging 
 to the original phenylate, and the O 4 brought into the compound by 
 the Z a . 
 
 In like manner, the vice-radical C e H 2 Z 3 gives rise to a compound 
 which requires the analytical formula C 6 H 2 Z 3 O 7 ,C 7 H 5 O. 
 
 The inspection of these analytical formulae gives rise to an important 
 question. Can the oxidised radical (7H 5 O act as an acid radical against 
 such oxidised radicals as C 6 H 3 Z 8 O 5 and C 6 H 2 Z 3 O 7 taken as basic radicals ? 
 Is such an action certain is it possible probable plausible ? No ! 
 certainly not. It would be just as extravagant to assume that, in sul- 
 phate of potash, SO 3 acted as a base against KO as an acid. But what 
 opinion ought we to form of these salts ? 
 
 The salts in question are produced by the action of chloride of benzyl 
 (CFIPCIO) upon binitrophenic acid = H,C 6 H 3 Z 2 O 5 and trinitrophenic 
 acid = H,C e H 2 Z 3 O 7 . But the action which takes place is such as throws 
 the benzyl out of the condition of a basic radical into the condition of an 
 acid radical, because the salts finally produced contain respectively six 
 and eight atoms of oxygen, whereas if phenyl were the acid radical, the 
 atoms of oxygen in the salts would be respectively five and seven. I 
 think therefore that in the formation of these salts, the nitrogen passes 
 from the phenyl radicals into the benzyl radicals, and that the final pro- 
 ducts of the two processes are as follows : 
 
 C 6 H 5 0,C7H 3 Z 2 5 = C 8 H 5 ,C 7 H 8 Z 2 6 = Phenyla zotenic-benzylaze. 
 C 6 H 5 O,C 7 H 2 Z 3 7 = C 6 H 5 ,C 7 H 2 Z 3 O 8 = Phenyla zotinic-benzylize. 
 
 The salts formed by zotic radicals are all monobasic, because there is 
 present in each of them only one acid radical, whatever may be the 
 quantity of azote they contain. 
 
 III. Sulphic Eadicals. 
 
 The salts that contain the sulphic radicals are produced by subjecting 
 organic acids to the action of anhydrous sulphuric acid, or of oil of 
 
METALLIC VICE-RADICALS. 137 
 
 vitriol. Each sulphic radical consists of one atom of an organic negative 
 radical minus one atom of hydrogen plus one atom of sulphur ; and in 
 its salts there is always present one atom more of oxygen than belongs 
 to salts of the same organic radical in its normal state. The production 
 of these sulphic radicals may be explained as follows. I use the radical 
 benzyl as an example : 
 
 a. Reaction when Hydrated Sulphuric Acid is used. 
 
 Hydrated benzoic acid . H,C 7 H 5 O 2 ) f H,C 7 H 4 S0 3 . 
 
 Hydrated sulphuric acid . H,S0 2 J ( (H,HO set free.) 
 
 b. Reaction when Anhydrous Sulphuric Acid is used. 
 
 }H,C 7 H 5 OM (H,C 7 H 4 S0 3 . 
 Hydrated benzoic acid . < TT ^TTT* I ) TT VBTTC 
 
 > = 
 
 Anhydrous sulphuric acid S,S0 3 j [ (H,HO set free.) 
 
 As an atom of water is thrown off in each case, the proportions of the 
 acting ingredients are regulated by that contingency. 
 
 But the sulphic radicals, thus produced, never give monobasic salts 
 agreeing with the formula H,C 7 H 4 SO 3 . Formed, as they are, in the 
 presence of an excess of sulphuric acid, they always combine with an 
 atom of that acid, and produce a double salt of the formula : 
 
 H,C 7 H 4 S0 3 + HSO a = H,H ; C 7 H 4 S 2 5 . 
 
 This formula represents the structure of all the salts that contain sulphic 
 radicals. As exhibited by the analytical formula, they are double salts ; 
 as exhibited by the synoptical formula they are bibasic salts ; and as 
 respects their nomenclature, we have the choice of naming them in 
 accordance with either of these formulae. I shall give no examples of 
 such salts in this section ; because the sulphic radicals will again come 
 tinder our consideration in the discussion of the Constitution of Con- 
 jugated Acids and elsewhere. 
 
 IV. Metallic Vice-Kadicals. 
 
 There are two kinds of metallic vice-radicals : ist. Amidogen = ZH 2 , 
 and ammonium ZH 4 , are subject to exchange part, or the whole, of their 
 hydrogen for metals, and thus produce compound basic radicals which 
 may be called metallic vice-amidogens and metallic vice-ammoniums. 
 These will come under our consideration in a subsequent section. 
 
 2ndly. Many basic compound radicals of the hydrocarbon series ex- 
 change part of their hydrogen for metals, and thus produce compound 
 radicals metallic vice-radicals of a special character. These are at 
 present scarcely recognised by chemists, but in subsequent sections of 
 
138 THE PHOSPHATES. 
 
 this Essay, I trust to be able to satisfy the reader that they actually 
 exist. In the meantime, I shall quote a single example, in order to ex- 
 plain the proposed nomenclature of these metallic vice-radicals. 
 
 CH 2 Ba represents methyl in which an atom of hydrogen is replaced 
 by an atom of barium. The name proposed for it is barytic-methyla. 
 
 The Phosphates. 
 
 The following diagram exhibits the constitution of the phosphates : 
 Graham's Formulae. 1 Proposed Formulae. 2 
 
 No. i. KO,P0 5 = KPO 3 . 
 
 2. KO,KO,PO> = KPO 3 + K 3 P0 4 = K 4 P 2 7 . 
 
 3. KO,KO,KO,P0 5 = KPO 3 + KKO = K 8 P0 4 . 
 
 No. i in this Table is the metaphosphate or monobasic phosphate. 
 No. 2 is the pyrophosphate or bibasic phosphate. No. 3 is the ordinary 
 or tribasic phosphate. The second column represents the formulse which 
 I am inclined to give to these salts. 
 
 According to this view, the metaphosphate is the normal phosphate 
 containing one basic radical and one acid radical, both oxidised 
 = KO,POO. The terbasic phosphate is a compound of the normal 
 phosphate = KO,POO, with a dioxide, or salt on the model of water 
 = H,HO, or M,MO, or M,HO ; producing the following double 
 salts : 
 
 Analytical Formulse. Synoptical Formula. 
 
 MPO 3 -f HHO = MHH, PO 4 . 
 MPO 3 + MHO = MMH,P0 4 . 
 MPO 3 + MMO = MMM,PO 4 . 
 
 The synoptical formulae describe the terbasic phosphate as if it were 
 really a terbasic salt, namely, a salt in which one acid radical is combined 
 directly with three basic radicals. I do not admit the truth of that theory. 
 On the contrary, I consider the constitution of the terbasic phosphate to 
 be represented by the analytical formula : 
 
 KO,POO -f K,KO. 
 
 It is, namely, a double salt, the two components of which have each its 
 basic and its acid radical. When we transpose this analytical formula 
 into the synoptical formula K 3 PO 4 , we no longer express the true 
 chemical constitution of the salt, but we obtain a formula that is useful 
 in explaining those cases of double decomposition in which the phos- 
 phates bear a part. I have already said, and I repeat it, that, in the 
 
 1 K = 39; P = 31; 0= 8. 2 K = 39; P = 31; O = 1 6. 
 
THE PHOSPHATES. 139 
 
 present state of chemical knowledge, a clear distinction should be made 
 between our conjectures respecting the proximate constitution of salts 
 and our mechanical construction of chemical formulae to be used in the 
 registry and communication of our experience. We have knowledge 
 enough of the transformations which the phosphates undergo, to be able 
 to construct formulae that can accurately represent and record those 
 transformations ; but of the internal constitution of the phosphates we 
 KNOW nothing. Our analyses prove that in terbasic phosphate of potash, 
 we have potassium, phosphorus, and oxygen. Using Mr. Graham's 
 atomic weights, the atoms are K 3 P 1 O 8 . Using the atomic weights that 
 are advocated in this Essay, the atoms are KT'O 4 . Of the manner in 
 which the oxygen is distributed among the other elements, and in which 
 it is combined with them, we know absolutely nothing. Mr. Graham's 
 groupment of the elements into KO,KO,KO,P0 5 , and my groupment of 
 them into KO,POO + K,KO, are both conjectures : nothing more ! It 
 is consequently impossible to give an incontestable, rational formula for 
 the phosphates, and therefore I conclude it to be best to give such a 
 formula as is likely to be most useful in practice, and, as regards the 
 proximate constitution of the salt, to hold my mind at liberty to form 
 opinions as analogies and the light of circumstantial evidence may direct. 
 I give therefore to the terbasic phosphates a terbasic formula, but I be- 
 lieve that the terbasic phosphates are dout&e salts composed of two 
 simple monobasic salts, and agreeing therefore with the doctrine which I 
 am attempting to establish, that every simple salt is a binary compound 
 of two radicals. 
 
 The pyrophosphate seems to be a compound of the other two phos- 
 phates, atom to atom. Thus : KPO 8 -f- K 3 PO 4 . There appear also to 
 be other combinations of metaphosphates with terbasic phosphates, in 
 proportions differing from those that constitute the pyrophosphate ; such 
 as 
 
 4(AgP0 3 ) + AgAgO = Ag 4 P 2 7 + 2AgP0 8 . 
 
 3(AgP0 3 ) + AgAgO = Ag 4 P 2 O 7 -f- AgPO 3 . 
 
 io(AgP0 3 ) + AgAgO = Ag 4 P 2 7 + SAgPO 3 . 
 
 If the pyrophosphates are formulated synoptically as K 4 P 2 O 7 , they are 
 made to appear as tetrabasic salts, which notion may, for the reasons 
 which I have just given, be accepted for its mechanical convenience, but 
 is not to be considered as expressing a chemical fact. The proximate 
 constitution of the pyrophosphates, like that of the terbasic phosphates, 
 is absolutely unknown. My opinion of it is expressed by the following 
 analytical formula : 
 
 (KO,POO + K,KO) + KO,POO. 
 
 The transformation and reduction of this analytical formula to the synop- 
 
140 THE PHOSPHATES. 
 
 tical formula K 4 P 2 O 7 , is simply with a view to practical or mechanical 
 utility. 
 
 The basylic equivalents given in this Essay greatly simplify the for- 
 mulas of the phosphates of the compounds which are commonly called 
 sesquioxides. Thus : 
 
 Instead of 
 
 A1 2 3 , 3 P0 5 . 
 
 Fe 2 8 , 3 P0 5 . 
 
 Cr 2 3 , 3 P0 5 . 
 
 2Cr 8 O 3 , 3 PO 5 . 
 
 We have 
 AlcSO 3 . 
 FecPO 3 . 
 CrcPO 3 . 
 CrcPO 8 Crc 8 P0 4 . 
 
 By adopting a proper atomic weight for the basylic radical of every ses- 
 quioxide, we are freed from the necessity of making their salts triple. In 
 fact, three atoms of phosphoric acid were required in such salts merely 
 because chemists took three atoms of base, instead of one atom, to com- 
 pose each salt, and by a perverse ingenuity made the three atoms appear 
 to be only one atom, and that one atom of such a kind that three atoms 
 of acid were necessary to neutralise it. 
 
 According to the theory which I have endeavoured to explain in this 
 Essay, there is but one kind of phosphoric acid, and that is monobasic. 
 The normal phosphate is the metaphosphate, which is composed of one 
 basic radical and one acid radical. The terbasic phosphate is a combina- 
 tion of the normal phosphate with a salt of the formula M,MO, and the 
 bibasic phosphate is a compound of the monobasic with the terbasic 
 phosphates. All other phosphates contain these three varieties variously 
 combined ; or with the addition of #HHO, #MHO, or 2-MMO. 
 
 I insist upon this method of accounting for the composition of the 
 three classes of phosphates, because it is the only reasonable manner of 
 replying to these objections to the binary theory of salts which 
 M. Dumas founded expressly upon the constitution of the phosphates. 
 See page 20 of this work. The propositions that the metaphosphates 
 are M,PO 3 , that the tribasic phosphates are M^PO 3 + MMO ; and that 
 the pyrophosphates are M,PO 8 + M 3 PO 4 , are so much in accordance 
 with our knowledge of numerous double salts of similar constitution, 
 that we can admit the theory without much hesitation. But the case is 
 entirely different when we formulate the phosphates expressly as mono- 
 basic, bibasic, and tribasic salts, thus : 
 
 M,PO 3 = monobasic. 
 M 4 ,P 2 7 = bibasic. 
 M 8 ,PO 4 = tribasic. 
 
 According to this diagram, taking the phosphorus and oxygen to- 
 gether, we have before us three totally different kinds of phosphates, 
 those with PO 3 , P'O 7 , and PO 4 , and we have no longer for adoption the 
 
THE PHOSPHATES. 141 
 
 simple case where one and the same acid radical combines with different 
 quantities of the same basic radical. Then again, we have to consider 
 the probability of the occurrence of such combinations between radicals 
 as those which are represented in the diagram by (M -}- M -j- M -j- M) 
 -f- (P + P) and (M -f- M -J- M) -f- P. A glance at the numerous for- 
 mulas of gaseous salts which appear in the preceding pages will show 
 the extreme unlikelihood of the formation of such compounds as these, 
 and will suggest the almost unavoidable conclusion, that phosphoric acid 
 is neither bibasic nor tribasic, but only subject to form those peculiar 
 double salts, that SEEM to be bibasic and tribasic while considered as 
 compounds of fictitious acids and bases. 
 
 When monobasic phosphoric acid is boiled in water, it is converted 
 into tribasic acid, without passing through the intermediate stage of 
 bibasic acid. That experiment cannot be explained on the acid theory, 
 but it agrees perfectly with the radical theory. The tribasic acid is the 
 result of the direct combination of the monobasic acid with water, atom 
 to atom, HPO 3 -f- HHO. The bibasic acid is a secondary compound 
 that demands the previous formation of the tribasic acid, for it cannot 
 be made by the direct combination of the monobasic acid with water, 
 because it is physically impossible to boil HPO 3 + HPO 3 in HHO, and 
 when more HHO is used you produce the tribasic acid. This reaction is 
 consequently in favour of the view that I am advocating of the constitu- 
 tion of the phosphates. 
 
 In conclusion, I admit the varieties of phosphates to be as follows : 
 
 Analytical Formulae. Synoptical Formulas. 
 Monobasic, or ) 
 metaphosphate f 
 
 Tribasic or com- ) =KPO* 
 
 mon phosphate j 
 
 The Nomenclature of the phosphates has proved to be difficult upon 
 every theory that has been applied to them. Comprehending many 
 bases, and in diversities of number, the salts require names that are 
 necessarily long, and for that reason subject to be uncouth. No sys- 
 tematic nomenclature can give short names to double, triple, and 
 quadruple salts, without abridgments that must introduce ambiguity 
 with brevity. The nomenclature now proposed is fully equal to the 
 exact expression of the composition indicated by the symbols of the dif- 
 ferent phosphates, but it does not escape the evils of length and com- 
 plexity to which all systematic names of the phosphates must ever be 
 liable. 
 
 The acid radicals and the oxygen of the three classes of phosphates 
 will in all cases be indicated thus : 
 
142 THE PHOSPHATES. 
 
 Monobasic, or metaphosphates by PO 3 = Phosphite. 
 Tribasic, or common phosphates by PO 4 = Phosphote. 
 Bibasic, or pyrophosphates by P 2 7 = Phospheneze. 
 
 The substantive portion of the names is therefore simple. The difficulty 
 lies in the adjective portion of the name, which must nominate all the 
 basic radicals that are present in each salt. 
 
 EXAMPLES OF PHOSPHATES. 
 
 Common Formulae. Proposed Formulae. Proposed Names. 
 
 a. Metaphosphates. 
 
 NaO,PO 5 .... NaPO 3 . . . Natra phosphite. 
 
 AgO,PO 5 .... AgPO 8 . . . Argenta phosphite. 
 
 A1 2 O 3 ,3PO 5 . . . AlcPO 8 . . . Alanic phosphite. 
 
 Cr y O 3 ,3PO 5 . . . CrcPO 3 . . . Chromic phosphite. 
 
 b. Tribasic Phosphates. 
 
 3KO,PO 5 .... K 3 P0 4 . . . Potassine phosphote. 
 
 2KO,HO,PO 5 . . K 2 H,P0 4 . . Potassen hydra phosphote. 
 
 KO,2HO,P0 5 . . KH 2 ,PO 4 . . Potassa hydren phosphote. 
 
 3NaO, PO 5 + i2Aq Na 3 PO 4 + Aq 6 Natrine phosphote aquaze. 
 
 ^AgO,P0 5 . . . Ag 3 PO 4 . . . Argentine phosphote. 
 
 NH 4 O,NaO,HO,PO 5 Na,NH 4 ,H,P0 4 Natra ammona hydra phosphote, 
 
 -f- 8Aq. -f- Aq 4 . aquote. 
 
 2 HO,C 4 H 5 0,P0 5 . . C 2 H 5 ,H 2 ; PO 4 . Ethyla hydren phosphote. 
 HO^C'H'CXPO 5 . . (C 2 H 5 ), 2 H ; PO 4 Ethylen hydra phosphote. 
 
 3 C 4 H 5 O,P0 5 . . . (C 2 H 5 ) 3 P0 4 . Ethyline phosphote. 
 
 c. Pyrophosphates. 
 
 2 C 4 H 5 O,P0 5 . . . (C 8 H 5 ) 4 P 8 7 . Ethylone phospheneze. 
 2KO,PO> .... K 4 P 2 O 7 . . . Potassone phospheneze. 
 2Cr 2 O 3 ,3P0 5 . . . Crc 4 P 2 O 7 . . Cromonic phospheneze. 
 
 The above names give a necessary, and a very unfavourable, example 
 the application of the proposed nomenclature to compound salts. The 
 critic will instantly perceive that " microcosmic salt " is a much shorter 
 term than " natra ammona hydra phosphote aquote ; and that " ordinary 
 phosphate of soda" (Gmelin's name) is far easier than " natrine phos- 
 phote aquaze ;" but then, the short and easy names do not express the 
 constitution of the compounds, and in regard to such complex substances 
 it will perhaps be ever impossible to find words that will accurately 
 state their composition, and yet be short and easy. Any systematic 
 nomenclature must be judged of by its general applicability and not by 
 its failure in a few special and non-important instances. 
 
( 143 ) 
 The Phosphites. 
 
 According to the researches of Railton 1 and Williamson, 2 a phosphite 
 requires the following formula 
 
 M,M,M; PO 3 . 
 
 Comparing this constitution with that of a metaphosphate = MPO 3 , we 
 observe the striking peculiarity, that with the same acid radical and the 
 same amount of oxygen in each salt, we have in the metaphosphate one 
 basic radical, and in the phosphite three basic radicals. At first sight, 
 such a result appears improbable ; but a little investigation removes the 
 apparent difficulty. The constitution of the metaphosphate is 
 
 MO + POO. 
 
 That of the phosphite is 
 
 MO,PO + M,MO. 
 
 Namely, it is a double salt, where MO,PO = MPO 2 is of the same form 
 of constitution as the oxalates and sulphates, and M,MO of the same 
 constitution as water H,HO, These two salts combine to form terbasic 
 phosphite, just as MPO 3 and MMO combine to form a terbasic phos- 
 phate. But the normal salt MPO 2 is unknown. 
 The following are examples of phosphites : 
 
 Ba,C 2 H 5 ,C 2 H 5 ; PO 3 Baryta ethylen phosphite. 
 
 Ba,Ba,C 2 H 5 ; PO 3 Baryten ethyla phosphite. 
 
 Ba,Ba,H ; PO 3 Baryten hydra phosphite. 
 
 OTFWHWH 11 ; PO 3 Amyline phosphite. 
 
 C 2 H 5 ,C 2 H 5 ,C 2 H 5 ; PO 3 Ethyline phosphite. 
 
 Pb,C*H 5 ,H ; PO 3 Plumba ethyla hydra phosphite. 
 
 Ba,C 8 H 5 ,H; PO 8 Baryta ethyla hydra phosphite. 
 
 Sn,Sn,H; PO 3 Stenous hydra phosphite. 
 
 No inorganic normal phosphite contains three atoms of metal. They 
 have all two atoms of metal and one atom of hydrogen. Rose considers 
 them to be bibasic, but always containing water of crystallization ; and 
 Wurtz has attempted to prove that they are bibasic,* with a compound 
 acid radical consisting of PH. That theory seemed to be probable when 
 we judged from the composition of the mineral phosphites, in all of which 
 we find H l ; but Railton's discovery of the salts 
 
 Ba,C 2 H 5 ,C 2 H 5 ; PO 3 . 
 
 Ba,Ba,C 2 H 5 ; po 3 . 
 
 C 2 H 5 ,C 2 H 5 ,C 2 H 5 ; PO 3 . 
 
 1 Quarterly Journal of the Chemical Society (1854), VII. 216. 
 * Proceedings of the Royal Society (1854), VII. 131. 
 
144 THE SULPHATES. 
 
 seems to overturn Wurtz's theory. Yet it is remarkable that Railton 
 tried in vain to produce the salt 
 
 Ba,Ba,Ba; PO 3 , 
 
 and that in those cases of inorganic basic salts, where there is present a 
 great excess of metal, there is also always present as much hydrogen or 
 water as gives at least possibility to the theory of the presence of the 
 compound radical PH in all inorganic phosphites. 
 
 The Hypophosphites. 
 
 The composition of the hypophosphites is uncertain. Many of the 
 inorganic hypophosphites seem to be 
 
 MPO + H,HO 
 equal to M,H,H; PO 2 . 
 
 But they cannot be deprived of this hydrogen or water, and the normal 
 salt = MPO is unknown. Wurtz has suggested that they contain a 
 compound acid radical = PH 2 , and that the proper formulae of the salts 
 
 M,PH 2 2 . 
 
 On the other hand, Kane has pointed out the existence of a salt contain- 
 ing hypophosphite of barytes and acetone, equal to 
 
 ; PO 2 = Baryta methyla acetyla phosphete. 
 and a similar salt containing soda 
 
 ; PO 2 = Natra methyla acetyla phosphete. 
 
 If, on this ground, we admit the hypophosphites to be tribasic, we have 
 still the difficulty of accounting for the circumstance that the three basic- 
 radicals of the inorganic salts are always MHH, and never j\DLM. 
 
 The Sulphates. 
 
 According to the radical theory, the composition of hydrated sul- 
 phuric acid is as follows : 
 
 Analytical Formula. Synoptical Formula. 
 
 HO,SO. HSO* 
 
 Where H = i, S = 16, = 16. 
 
THE SULPHATES. 145 
 
 According to M. Gerhardt, sul- 
 phuric acid is composed thus : l 
 
 posed thus : 2 
 S0 a 
 H 2 
 
 According to Professor Wil- 
 liamson, sulphuric acid is com- 
 
 H 
 
 where H = i, S = 32, O = 16. 
 
 According to the radical theory, sulphuric acid is monobasic, that is 
 to say, it contains one atom of hydrogen replaceable by a metal. Ac- 
 cording to Messrs. Gerhardt and Williamson, sulphuric acid is bibasic, 
 that is to say, it contains two atoms of hydrogen which are both or 
 either replaceable by metals. The compound which on the theory of 
 Gerhardt and Williamson is a single bibasic sulphate, is, on the radical 
 theory, a double salt composed of two monobasic sulphates. These 
 theories are consequently antagonistic. I believe that the radical theory 
 is the true one, and I shall endeavour to show that the arguments by 
 which the bibasic theory is advocated are such as cannot command our 
 assent. 
 
 M. Gerhardt's first and main argument* depends upon the atomic 
 measure of the gaseous sulphates. He points out that when you ex- 
 amine a gaseous salt, of a kind that is admitted to be monobasic, such 
 as an acetate or a benzoate, you find that two volumes of it contain one 
 basic radical, but that when you examine a gaseous sulphate, you find 
 that two volumes of it contain two basic radicals ; whence he infers, that 
 sulphuric acid is bibasic. 
 
 This argument is worthless, because it leaves out of consideration the 
 fact, that the radical sulphur in the gaseous sulphates measures nothing. 
 The consequence of that property is, that a gaseous sulphate is complete 
 in one volume, and that if you examine two volumes of the gas, you 
 find two basic radicals because you operate upon two complete sulphates. 
 This attempt to prove that sulphates are bibasic is consequently 
 abortive. 
 
 M. Gerhardt's second argument depends upon the properties of the 
 gases that contain chlorine with sulphur. Thus he points out that 
 
 P f Chloride of acetyle contain C1,C 2 H 3 O. 
 2 volumes 01 < ^, -, . -. r , ; , ~ 10 ,-. ~. 
 
 \ Chloride of sulphury le contain C1 2 ,SO*. 
 
 From which, as before, he concludes that sulphur is bibasic, and acetyle 
 monobasic. But this argument rests on no better foundation than the 
 former. The oxy chloride of sulphur (chlorosulphuric acid) SC1O, or 
 C1SO, is complete in one volume, because S and O measure nothing ; 
 
 Traite de Chimie Organique (1856), torn. iv. p. 642. 
 Quarterly Journal of the Chemical Society (1854), VII. 182. 
 Vide the Traite de Chimie already cited. 
 
 L 
 
146 THE SULPHATES. 
 
 and in two volumes of vapour you have two complete salts, and there- 
 fore two radicals of each kind. This and the preceding argument have 
 been so fully discussed at pages 98, 102, and 113, that farther criticism 
 is needless. 
 
 Third argument. " Whereas monobasic acids give but one compound 
 ether, sulphuric acid gives two, one neutral and one acid. Whereas 
 monobasic acids give but one amide, sulphuric acid gives several." 
 
 My reply to this argument is, that the compounds in question depend 
 upon the property which sulphur possesses of forming numerous com- 
 pound salts, not only double, but triple, fourfold, fivefold, and varieties 
 still more complex. The property of producing compound salts is quite 
 a different thing from the property of bibasicity, meaning by the latter 
 term the power possessed by one acid radical of combining with two 
 basic radicals. This is the property which, in my opinion, does not 
 belong to sulphuric acid; and no mere enumeration of the ethers, the 
 amides, and other double salts, which sulphuric acid unquestionably does 
 form, can affect the point at issue, which stated in plain terms, is the 
 assertion that two basic radicals can combine with one atom of oxidised 
 sulphur to form a sulphate. This is the point that I deny, and M. Ger- 
 hardt only evades the real question, when he doubles the atomic weight 
 of sulphur, and when he adduces double salts, namely, pairs of sulphates, 
 containing ethyl, amidogen, and other bases, to prove that one sulphate 
 contains two basic radicals. 
 
 Fourth argument. " If we determine what are the smallest possible 
 quantities of the radical acetyl and the radical sulphury 1 which occasion 
 chemical metamorphoses, we find that these radicals are C 2 H 8 O equi- 
 valent to H, and SO 2 equivalent to H 2 . This naturally leads us to 
 represent the molecule of acetic acid as monatomic, and the molecule of 
 sulphuric acid as biatomic" Traite, iv. p. 643. 
 
 Monatomic, in Gerhardt's language, signifies " derived from one atom 
 of water;" and biatomic signifies "derived from two atoms of water." 
 The former has one replacable atom of basic hydrogen, the latter has 
 two such atoms. The " sulphuryl " referred to in this argument as SO 8 
 = H 2 , contains 3 2 parts of sulphur, and is therefore what I should call 
 SO X 2. It is equivalent to H 2 simply because it contains S 2 . The 
 oxygen has nothing to do with the question of basicity. Here M. Ger- 
 hardt first assumes that two atoms of sulphur are one atom, and then 
 finding that this so-called one atom is equivalent to two basic radicals, 
 he calls it bibasic. The question at issue turns, therefore, upon the 
 mere matter of fact whether 32 parts of sulphur is the " smallest pos- 
 sible quantity " which has the power of chemical action. To dispose of 
 that question, I shall show in this book that all the classes of salts of 
 which sulphur is a constituent can be simply and effectively represented 
 by formulas in which S 1 will in all cases signify 16, and not 32, parts of 
 sulphur. If I do that, it will show that the assumption of 32 is 
 
THE SULPHATES. 147 
 
 improper, and, as a consequence, that this fourth argument is fallacious. 
 I may, moreover, point out the remarkable circumstance that the com- 
 pounds that are commonly called sulphides or sulphurets, all contain 
 one atom each of M and S, where M signifies one metallic radical or 
 one atom of a hydrocarbon radical, and S equals 1 6 parts of sulphur. 
 The consequence of this relationship is, that when M. Gerhardt treats 
 of these compounds, instead of using the simple formula MS, he is 
 
 forced to use the bibasic formula S j ]yr ; that is to say, he is forced to 
 
 make the sulphides all double, because he has doubled the atom of 
 sulphur. See his account of the sulphurets, Traite de Chimie Organique, 
 torn. iv. p. 700. 
 
 Fifth and final argument. This argument is founded on the reaction 
 of nitric and sulphuric acids with benzoic acid reactions resulting in 
 the production of nitrobenzoic acid and sulphobenzoic acid. I have 
 discussed this subject under the heads of sulphic vice-radicals and con- 
 jugated acids, to which sections I must ask the reader to refer for intimate 
 details. In this place I will briefly quote the results. Benzyl and 
 nitrogen produce a deputy or vice-radical, in which the primary radical 
 benzyl exchanges an atom of hydrogen for an atom of nitrogen, and this 
 altered radical produces a salt, or, if you please to call it so, an acid, of 
 this form : 
 
 H.OTPZO 4 = Nitrobenzoic acid, 
 
 which shows one replaceable atom of basic hydrogen. Benzyl and sul- 
 phur also produce a vice-radical, in which benzyl exchanges an atom of 
 hydrogen for an atom of sulphur, and this vice-radical produces a double 
 salt, or double acid, of the form 
 
 H,C7H 4 S0 3 + H,S0 2 = Sulphobenzoic acid, 
 
 where there are two replaceable atoms of basic hydrogen. 
 
 The main facts to be observed here are, that nitric acid, which rarely 
 forms double salts, true to its ordinary character, forms no double salt 
 with nitrobenzoic acid ; whereas sulphuric acid, which has an extraor- 
 dinary tendency to produce double salts, particularly in combination 
 with organic radicals, true to its ordinary character, forms a double salt 
 with the sulphobenzoic acid. The nitrobenzoic acid is monobasic, 
 because it contains one acid radical. The sulphobenzoic acid is bibasic, 
 because it contains two acid radicals, namely, sulphic benzyl and normal 
 sulphur. But M. Gerhardt insists upon it that sulphobenzoic acid is 
 bibasic, because it contains one acid radical, the one acid radical contain- 
 ing, according to him, one atom of sulphur, that one atom of sulphur 
 weighing 32, and the salt being bibasic, in consequence of the presence 
 of that one heavy atom of sulphur. But M. Gerhardt goes a great deal 
 too fast. His argument proves nothing, unless you admit that 32 parts 
 
 L2 
 
148 THE SULPHATES. 
 
 is one atom of sulphur. This is the grand point which he assumes to 
 be true, which, however, it is the great object of his arguments to prove 
 to be true, and to do which they all signally fail. Yet he seems to 
 have satisfied himself that the force of his arguments amounted to 
 demonstration. 
 
 " Mr. Graham," he says, 1 " was the first to admit the existence of 
 polybasic acids in his work On the Modifications of Phosphoric Acid, 
 formulating them according to the ancient dualistic theory. A German 
 chemist [Liebig] sought to apply the same ideas to certain organic 
 acids ; but this chemist depending, like his predecessor, only on the 
 composition of the salts, was unable to fix precisely the characters of the 
 acids endowed with different degrees of basicity. I consider that I have 
 better defined these characters by resting on the properties of correspond- 
 ing volatile bodies (the chlorides and compound ethers). The law of 
 the saturation of conjugated acids has, above all, permitted me to put 
 in evidence the well-marked differences which exist between certain 
 mineral and organic acids in respect of their basicity." 
 
 I have gone over M. Gerhardt's arguments in detail, because he 
 admits that " the whole question of polybasic acids" is comprised in 
 those arguments. The arguments appear, however, to me, to be emi- 
 nently futile ; and unless other admirers of polybasic acids have some- 
 thing stronger to say, I fancy that modern chemists must content 
 themselves, as their grandfathers did, with the possession of monobasic 
 acids. 
 
 Let us next listen to Professor WILLIAMSON ; " Chemists," he 
 says, 2 " have long been aware of the fact, that some acids unite with 
 bases in one proportion only, others in two or more proportions. Thus 
 a given quantity of nitric acid forms, with what is termed its equivalent 
 of potash, a definite nitrate of potash ; if less than this equivalent quan- 
 tity of potash were added to the nitric acid, the product would be a 
 mechanical mixture of the same nitrate of potash with uncombined 
 nitric acid; if more than the equivalent of potash were added, the 
 excess of alkali would remain uncombined. Sulphuric acid, on the 
 other hand, is capable of forming two compounds with potash, and it 
 depends upon the proportions in which the two substances are brought 
 together, whether the neutral or acid sulphate is formed. 
 
 " The number of compounds which an acid forms with one base is 
 now considered as indicating its atomic weight. The weights of sul- 
 phuric and nitric acids, which are respectively susceptible of neutralising 
 the same quantity of potash, are termed equivalent, but these are by no 
 means the same as their atomic weights. Sixty-three parts of nitric 
 
 1 Traite de Chimie Organique, torn. iv. p. 646. 
 8 Proceedings of the Royal Society, VII. 1 1 ; and Quarterly Journal 
 of the Chemical Society (1855), VII. 180. 
 
THE SULPHATES. 149 
 
 acid (nitrate of water) contain the same quantity of hydrogen as forty- 
 five [forty-nine?] parts of sulphuric acid, and when they are neutralised 
 by potash the whole of this hydrogen is removed, and replaced by 
 potassium ; and if neither of the acids would combine in any other pro- 
 portion with potash, their atomic weights would be the same as their 
 equivalent weights. But sulphuric acid also forms a potash-compound 
 in which half of its hydrogen is replaced by potassium, the other half 
 remaining in the compound, whereas the smallest particles of nitric 
 acid either exchange the whole or none of their hydrogen for potassium. 
 
 " This fact is expressed in the simplest possible manner by the state- 
 ment that the smallest indivisible particles of sulphuric acid contain two 
 atoms of hydrogen, whilst those of nitric acid only contain one. Thus 
 it is, that whereas the equivalent weights of the two acids are the quan- 
 tities which contain the same amount of basic hydrogen, their atomic 
 weights must be in the proportion of two equivalents of sulphuric to 
 one of nitric acid. The simplest expression for one atom of nitric acid 
 being empirically N0 3 H, we shall accordingly represent an atom of 
 sulphuric acid by the formula SO 4 H 2 . In like manner an atom of 
 common phosphoric acid, being tribasic, is expressed empirically by the 
 formula PO 4 H 3 . The labours of Messrs. Laurent and Gerhardt greatly 
 contributed to the establishment of these results, which are uncon- 
 troverted" 
 
 I will endeavour to do away with this last reproach by offering a 
 little con tro version. 
 
 I hold that the distinction drawn by Professor Williamson between 
 the equivalent and the atom of sulphuric acid is unnecessary and inju- 
 rious ; that the smallest indivisible particle of sulphuric acid contains 
 only one atom of hydrogen, not two atoms ; that the simplest expres- 
 
 HQ 
 
 sion for an atom of sulphuric acid is HSO 2 , not S0 2 n ; that sulphuric 
 
 H U 
 
 acid is monobasic, not bibasic ; and that the atom of sulphur weighs 
 only 1 6, and not 32. These opinions are supported by the following 
 reasons : 
 
 Every atom of sulphuric acid contains one atom of sulphur and one 
 atom of hydrogen. These atoms are perfectly equivalent to one another, 
 and either of them can be replaced by one atom, that is to say, by one 
 equivalent, of another radical. The argument, that you can take a cer- 
 tain quantity of hydrated sulphuric acid, and replace half its hydrogen 
 by one radical and the other half by another radical, and thus produce 
 a bibasic sulphate, is a good argument as far as it goes ; but when it is 
 offered, as Professor Williamson offers it, as a conclusive argument 
 embracing the whole question, it is a fallacy of that class, where what is 
 stated truly of a part of a thing is assumed as being truly stated of the 
 whole of a thing ; for you can also take a quantity of hydrated sulphuric 
 
150 
 
 THE SULPHATES. 
 
 acid and replace its hydrogen by one, or three, or four, or five, or six, or 
 seven, or eight different radicals, and procure crystallised sulphates that 
 contain all or any number of these radicals, and which, therefore, accord- 
 ing to Professor Williamson's argument, ought to be called monobasic, 
 tribasic, tetrabasic, pentabasic, hexabasic, heptabasic, and octabasic 
 sulphates. 
 
 Let us look at the evidence that shows, from experimental grounds, 
 what is the constitution of the sulphates. 
 
 In the following Table H=i,S = i6, O=i6. 
 
 Monobasic Sulphates formed from H,S0 2 . 
 
 HSO 8 . . . Oil of vitriol. 
 KSO 8 . . . Sulphate of potash, 
 
 and perhaps nine-tenths of all the sulphates that are known to exist. 
 
 Bibasic Sulphates formed from H 2 ,S 2 4 . 
 
 K,H; S 2 O 4 . 
 K,G ; S*0 4 . 
 
 Mg,Alc ; S 2 4 . 
 Na,Mn; S 2 O 4 . 
 
 K,Cr; S 2 O 4 .1 
 Am,Fe; 
 
 Tribasic Sulphates formed from H 3 ,S 8 O 6 . 
 
 Fe,Fe,Fec; S 3 O. 
 Ba.Ba,Ca; S 3 O 6 . 
 K,K,H ; S 3 6 . 
 
 Fe,Fe,H; S 3 6 .l 
 Fe,Fec,Fec;S 3 6 .| 
 Mg,Zn,Mn; "" 2 
 
 Tetrabasic Sulphates 
 
 Am,Am,Am,H 
 Alc,Alc,Alc,H; S 4 O 8 . 
 K,Fec,Fec,Fec; S'O 8 . 
 Zn,Zn,Zn,H; S 4 O 8 . 
 K,Alc,Alc,Alc ; S^. 
 Mg,Co,Co,Co ; S'O 8 . 
 Am,Am,Zn,Fe; S 4 O 8 . 
 Am,Am,Mg,Cuc; S'O 8 . 
 Am,Am,Cuc,Fe ; S^ 8 . 
 K,K,Cuc.Fe ; S*O 8 . 
 Am^m^^CucjS'O 8 . 
 K,K,Mg,Cuc; S 4 8 . 
 
 formed from H 4 ,S 4 O 8 . 
 
 Zn,Alc,Alc,Alc; 
 
 K,Crc,Crc,Crc; 
 
 Na,Crc,Crc,Crc; 
 
 Am,Crc,Crc,Crc; 
 
 Fe,Fe,Fe,H ; 
 
 Fec,Fec,Fec,H; 
 
 K,Cuc,Cuc,Cuc; 
 
 K,K,Ni,Cuc; 
 
 Am,Am,Zn,aic; 
 
 Am,Am,Zn,Fe; 
 
 K,K,Co,Cuc ; 
 
 K,K,Mn,Cuc; 
 
 S 4 O 8 .1 
 
 S 4 O 8 . 
 
 S 4 O 8 . 
 
 S 4 O 8 . 
 
 S 4 O 8 . 
 
 S'O 8 . 
 
 S 4 O 8 .J 
 
 S 4 O 8 . 
 
 S 4 O". 
 
 S 4 O 8 . 
 
 S 4 O 8 . 
 
 Pentabasic Sulpltates formed from H 5 ,S 5 O 10 . 
 Cuc,Cuc,Cuc,Cuc,H; S 5 O 10 . l 
 
 Laurent, Chemical Method, pages 116-123. 
 Vohl, Liebig's Annalen der Chemie, April, 1855, 
 
THE SULPHATES. 
 
 Heccdbasic Sulphates formed from H 6 ,S 6 O 1Z . 
 
 K,K,K,Mg,Mn,Cuc; S 6 12 . 2 
 [There are several salts agreeing with this formula.] 
 
 ffeptdba*ic Sulphates formed from H 7 ,S 7 U . 
 K,K,K,K,K,H,H; S 7 O U . r 
 
 Octabasic Sulphatesformed from H 8 ,S 8 O 16 . 
 
 K,K,K,K,Mg,Zn,Co,Cuc ; S 8 O 16 ) 
 
 K,K,Alc,Alc,Alc,Crc,Crc,Crc ; S 8 O 16 V * 
 Am,Am,Alc,Alc,Alc,Crc,Crc,Crc ; S 8 O 16 J 
 
 With these examples before us, we can estimate the force of Pro- 
 fessor Williamson's argument. He pitches upon the second group in the 
 above Table, and he says, " Here we have a quantity of sulphuric acid 
 which we may call two equivalents, because it contains two replaceable 
 atoms of hydrogen ; but we can replace half of its hydrogen by potas- 
 sium, the other half remaining in the compound. We thus procure a 
 complete crystallizable sulphate one sulphate containing, therefore, 
 one atom of sulphuric acid and one atom of sulphur, but having two 
 bases, being consequently bibasic, and agreeing with the formula 
 S0 4 H 2 ." 
 
 Change the ground a little, and apply this argument to the octabasic 
 sulphate. " We have here," we may say, " a quantity of sulphuric 
 acid which represents eight equivalents, because it contains eight re- 
 placeable atoms of hydrogen. We replace these atoms of hydrogen by 
 eight atoms of different metals, and we produce a complete neutral crys- 
 tallisable salt, whose composition is stated in the simplest possible 
 manner by the formula 
 
 K,K,K,K,Mg,Zn,Co,Cuc; S 8 O 16 ; 
 
 whence it follows, that this is one sulphate one atom of a sulphate 
 containing one atom of sulphuric acid, and therefore one atom of sul- 
 phur ; and, consequently, sulphuric acid is proved to be octabasic, and 
 the atom of sulphur is proved to weigh 128 (= 16 x 8)." 
 
 This argument applies equally well to every one of the eight groups 
 of sulphates arranged in the above table, and consequently proves so 
 much, that it proves nothing at all. It would be absurd to admit 
 that an acid is proved to be bibasic by an argument which is equally 
 powerful in proving it to be octabasic, heptabasic, pentabasic, tri- 
 basic, &c., &c., &c. 
 
 1 See p. 1 50. 2 Ibid. 
 
152 THE SULPHATES. 
 
 I proceed, however, to adduce the experimental evidence by means of 
 which Professor Williamson attempts to establish his theory. I quote 
 from the journal previously referred to : 
 
 " In some papers published in the Journal of the Chemical Society 
 two or three years ago, I endeavoured to show that the constitution of 
 salts may be reduced to the type of water ; that acids and bases, being 
 truly acid salts and basic salts, are perfectly conformable to the same 
 principle ; and that, amongst other things, the difference between mono- 
 basic and bibasic acids, &c., admits of a simple and easy explanation by 
 it. The leading propositions in those papers have been adopted by 
 several eminent chemists in this country and in France ; and M. Ger- 
 hardt speedily enriched science with a series of brilliant and striking 
 illustrations of their truth. As regards the constitution of bibasic acids, 
 M. Gerhardt's results were, however, at variance with that theory ; and 
 he was led to represent them by formulae equally inconsistent with his 
 own previous views on the subject. I believe that this discrepancy is 
 satisfactorily removed by the facts I have the honour of submitting to 
 the consideration of the Society. 
 
 " An atom of nitric acid, being eminently monobasic, is, as we have 
 
 TT 
 
 already shown, represented in the monobasic type water jrO by the for- 
 mula * TJ 0, in which peroxide of nitrogen (NO 2 ) replaces one atom 
 
 /"TT \ 
 
 of hydrogen. In like manner, hydrate of potash ( ^-0 J is obtained by 
 
 replacing one atom of hydrogen in the type by its equivalent of po- 
 tassium ; and nitrate of potash ( ,^O ) by a simultaneous substitution 
 
 of one atom of hydrogen by protoxide of nitrogen and the other by 
 potassium. 
 
 " Sulphuric acid is formed from two atoms of 
 
 H o 
 
 H 
 
 water p ; one of hydrogen from each is removed, and the two re- 
 
 f) 
 H U 
 
 placed by the indivisible radical S0 a . The series 
 
 Sulphuric Acid. Acid Sulphate of Potash. Neutral Sulphate of Potash. 
 
 H H K O 
 
 SO 2 SO 2 SO 2 
 
 H K K 
 
 explains itself. 
 
 " Chemists have long known how to remove the basylous con- 
 stituents H, K, &c. of these salts, and to replace them by others ; but 
 
THE SULPHATES. 153 
 
 it is only recently that they have learnt to remove the chlorous radicals 
 SO 2 , NO 2 , &c. in a similar manner. To obtain the chloride of potassium 
 from its sulphate, it is sufficient to bring the latter into liquid contact 
 with chloride of barium ; but the same reagent would be powerless for 
 the preparation of the chlorides of the radicals SO* or NO 2 . 
 
 " M. Cahours has shown us a reagent (the pentachloride of phos- 
 phorus) which is capable of forming from a great number of monobasic 
 acids the chlorides of the acid radicals. Whilst extending our know- 
 ledge of the action of the body on monobasic and organic acids, and pre- 
 paring numerous compounds of their radicals with one atom of chlorine, 
 M. Gerhardt examined also the nature of its action upon bibasic acids 
 and their compounds; and states that it consists of two successive 
 phases first, the liberation of the anhydrous acid ; secondly, the sub- 
 stitution of two atoms of chlorine for one of oxygen in that anhydrous 
 acid. These facts, if correct, would be unfavourable to the above view 
 of the constitution of sulphuric and other bibasic acids ; and M. Ger- 
 hardt adopted accordingly the old formulas, representing in their com- 
 position an atom of water ready-formed, SO 3 H 2 O. 
 
 " Confining my remarks for the present to the case of sulphuric acid, 
 whose decomposition is doubtless typical of that of other bibasic acids, I 
 may state as the result of numerous experiments with the most varied 
 proportions of pentachloride and acid, performed on a scale of consider- 
 able magnitude, that the first action of the pentachloride consists in re- 
 moving one atom of hydrogen and one of oxygen (empirically, peroxide 
 of hydrogen) from the acid, putting in an atom of chlorine in their 
 
 H 
 
 place, and forming the compound SO 2 , which is strictly intermediate 
 
 Cl 
 
 between the hydrated acid and the final product S0 2 C1 2 formed by a 
 repetition of the same process of substitution of chlorine for peroxide 
 of hydrogen. The existence and formation of this body, which we may 
 call chloro-hydrated sulphuric acid, furnishes the most direct evidence 
 of the truth of the notion, that the bibasic character of sulphuric acid 
 is owing to the fact of one atom of its radical SO 2 replacing or (to use 
 the customary expression) being equivalent to two atoms of hydrogen. 
 Had this radical been divisible like an equivalent quantity of a mono- 
 basic acid, we should have obtained a mixture, not a compound, of the 
 chloride with the hydrate or, at least, the products of decomposition 
 of that mixture. 
 
 " Chloro-hydrated sulphuric acid boils at 145 cent., distilling with- 
 out decomposition. The intensity of its action upon water varies ac- 
 cording to the manner in which the two bodies are brought together. 
 When poured rapidly into a large quantity of cold water, a portion of 
 it sinks to the bottom, and only gradually dissolves as a mixture of hy- 
 drochloric and sulphuric acids. When a small quantity of water is added 
 
154 THE SULPHATES. 
 
 to the compound, the same decomposition takes place with explosive 
 violence. The acid dissolves chloride of sodium on the application of a 
 gentle heat, with evolution of hydrochloric acid, giving rise to a com- 
 
 Na 
 
 pound of the formula SO 2 0." 
 Cl 
 
 I have quoted Professor Williamson's entire argument, because I agree 
 with him, that sulphuric acid is typical of other bibasic acids, so that if 
 he fails to establish the bibasic nature of sulphuric acid, the failure 
 extends to bibasic acids in general. My conviction is, that his failure in 
 this point is complete. 
 
 Throughout his argument, Professor Williamson assumes, but never 
 proves, that the atom of sulphur weighs 32 and not 16. If you admit 
 this assumption as a truth, you virtually admit that the smallest possible 
 quantity of sulphuric acid, being that which contains one atom of sul- 
 phur, and therefore that which contains 32 parts of sulphur, is con- 
 sequently that which contains the equivalent of two atoms of hydrogen. 
 The admission, then, that the atomic weight of sulphur is 32, is prac- 
 tically the admission that sulphuric acid is bibasic. This, however, is 
 the entire question. I ask, therefore, that Dr. Williamson should prove 
 this point, and not assume it to be true without proof ; as he lias done in 
 the Paper from which I quote. 
 
 I shall now show that his facts all agree with the notion, that the 
 atom of sulphur weighs 16, and that sulphuric acid is monobasic. 
 
 First action of the pentachloride. A quantity of hydrated sulphuric 
 acid which contains H 2 , gives off HO and takes up Cl. My interpreta- 
 tion of the experiment is as follows : 
 
 HSO 2 , p, _ C1SO wn 
 HSO 2 4 = HSO 2 H 
 
 Namely, one atom of monobasic hydrated sulphuric acid HSO 2 or 
 HO, SO, is converted into C1SO, which combines with another atom 
 of monobasic hydrated sulphuric acid, and produces the double salt 
 C1SO+HSO 2 , or H,C1 ; S 2 O 8 . This salt has a constitution exactly similar 
 to that of a bisulphite, and it is monobasic, that is to say, it has one 
 replaceable atom of hydrogen, which, as Dr. Williamson has proved, can 
 be replaced by sodium, so as to produce a neutral salt, represen table by 
 the formula Na,Cl ; S^O 3 , or C1SO -f- NaSO 2 . When treated with 
 water, the double salt C1SO -f- HSO 2 produces hydrochloric and sul- 
 phuric acids. Thus : 
 
 H,HO + C1,SO + HSO 2 = HC1 + HSO 2 + HSO 2 . 
 
 Final product of the action of the pentachloride. All the sulphuric 
 acid is converted into C1SO ; namely 
 
THE SULPHATES. 155 
 
 HO,SO + Cl = HO + C1SO. 
 HO,SO + Cl = HO + C1SO. 
 
 Dr. Williamson writes this final product SO 2 C1 2 , but that is merely be- 
 cause he doubles the atomic weight of sulphur ; otherwise, he must write 
 it S 2 O 2 C1 2 = SOC1. This compound is the chlorosulphuric acid referred 
 to at pages 56 and 102 of this work, as a gas having the atomic mea- 
 sure of one volume. Dr. Williamson shows us that it has the faculty 
 of combining with hydrated sulphuric acid, and Professor Rose had pre- 
 viously shown that it combines also with anhydrous sulphuric acid. See 
 page 63. 
 
 M. Gerhardt's experiment, if it is correct, which Dr. Williamson 
 seems to deny, may also be explained, as indeed he admits, on the 
 notion that sulphuric acid is monobasic. Two atoms of the hydrated 
 sulphuric acid yield one atom of water and one of anhydrous sulphuric 
 acid : 
 
 HO,SO + HO,SO = H,HO + S,SOOO. 
 
 If we substitute, in this last product, two atoms of chlorine for one atom 
 of oxygen, we have SSC1C1OO, which, being divisible by two, yields 
 SC1O or C1SO. 
 
 Here we have all the transformations that occur in the cited experi- 
 ments all the tangible facts duly accounted for on the supposition 
 that S weighs 16, and that sulphuric acid is monobasic; and these 
 results are expressed in formulas and equations that are of extreme sim- 
 plicity. Why are we to renounce an easy and satisfactory system, and 
 jump, without necessity and without a shadow of proof, to the various 
 conclusions, that the atom of sulphur weighs 32 ; that an atom is equal 
 to two equivalents ; that sulphuric acid is bibasic ; that its smallest indi- 
 visible particle contains two atoms of hydrogen ; that it is formed from 
 two atoms of water ; that all bibasic acids are formed from two atoms of 
 water ; and that on the model of one, or two, or more atoms of water, 
 all salts whatever are formed ? For my part, I oppose these conclusions 
 with a very decided negative. 
 
 I do not know whether Professor Williamson attributes any logical 
 force to the positions given to the symbols in the scattered formulae by 
 which the constitution of the so-called bibasic sulphates on the model of 
 water are depicted. With what relative degrees of intensity are the 
 respective members of the following compounds combined with one 
 another ? 
 
 **0 H 
 
 and SO 2 
 
 H H 
 
 If, in the single atom of water, O is combined with equal intensity to 
 
156 THE POLYTHIONIC ACIDS. THE MANY-SULPHURED ACIDS. 
 
 each of the two atoms of H, then SO 2 which replaces H -f H, must 
 possess the same combining force as H + H do collectively. But in 
 that case S first of all monopolises O 2 entirely, and then takes up half of 
 each of the other two atoms of O. So that, in fact, in an atom of hy- 
 drated bibasic sulphuric acid, S 1 exercises a combining power over 75 
 per cent, of the oxygen, and the remaining HH, a combining power 
 over 25 per cent. I am at a loss to perceive in what respect this final 
 result differs from the old theory, that hydrated sulphuric acid consists 
 of anhydrous acid = SO 3 plus water = H*O. We have merely the old 
 system of acids and bases reproduced in another form. An old friend is 
 presented to us with a new face. There appears to be no practical ad- 
 vantage obtainable by departing from the old symbols, if we are to retain 
 the old ideas. On the radical theory, the notion that the oxygen of a 
 sulphate is divided between the basic radical and the acid radical in the 
 unequal proportions of 75 to 25, is repudiated. Without that repudia- 
 tion, distinctly agreed to, we had better retain the old formula. 
 
 NOMENCLATURE OF THE SULPHATES. 
 
 Proposed Names. 
 
 Hydrated sulphuric acid H,S0 2 Hydra sulphete. 
 
 [Anhydrous sulphuric acid S,SO 3 Sulpha sulphite.] 
 
 Sulphate of potash K,SO 2 Potassa sulphete. 
 
 Protosulphate of iron Fe,SO 2 Ferrous sulphete. 
 
 Persulphate of iron Fec,SO 2 Ferric sulphete. 
 
 Bisulphate of potash K,H ; S 2 O 4 Potassa hydra sulphenote. 
 
 or K,H; 2 SO 2 Potassa hydra bisulphete. 
 
 A tribasic sulphate Ba 2 ,H; 3 SO 2 Baryten hydra trisulphete. 
 
 It is immaterial whether the double sulphates (bisulphates) are called 
 sulphenote or bisulphete, but all sulphates of a more complex constitu- 
 tion will be most conveniently named if called n-sulphete, tetra-, penta-, 
 bexa-, hepta-, or oca-sulphete ; the bases being particularised in the 
 commencement of the name. It is evident, however, that systematic 
 names for such complex compounds as octasulphates will never come 
 into use. If ever any salt of this description should come to be of im- 
 portance in the arts, it will immediately acquire a trivial name, just as 
 the tetrasulphate of potash and alumina is at present commonly desig- 
 nated by the short word ALUM. 
 
 The Polythionic Acids. The Many-Sulphured Acids. 
 
 The term polythionic acids has been applied to a series of oxidised acids 
 of sulphur which are said to be distinguished by the property of contain- 
 ing more than one atom of sulphur. They are as follows : 
 
THE POLYTHIONIC ACIDS. THE MANY-SULPHURED ACIDS. 157 
 
 THE ANHYDROUS ACJDS. THE METALLIC SALTS. 
 
 All of which are hypothetical. All considered to be monobasic. 
 
 Pentathionic acid S 5 5 Pentathionate MO,S 5 5 
 
 Tetrathionic acid S 4 O 5 Tetrathionate MO,S 4 O 5 
 
 Tritliionic acid S 3 O 5 Trithionate MO,S 3 O 5 
 
 Hyposulphate MO,S 2 O> 
 
 Hyposulphurous acid I S2Q2 Hyposulphite 
 Dithionous acid j 
 
 The value of the symbols in the above Table is S = 16, = 8. If 
 I raise O to 1 6, and write synoptical formulas of the salts in accordance 
 with the radical theory, they come out as follows : 
 
 Pentathionate = M,S 5 O 3 
 
 Tetrathionate = M,S 4 8 
 
 Trithionate = M,S 3 3 
 
 Hyposulphate = M.S'O" 
 
 Hyposulphite = M 2 ,S 4 3 
 
 I am obliged to double the formula of the hyposulphite, because the 
 three atoms of oxygen cannot, like the six atoms in the other examples, 
 be divided by 2. 
 
 This Table includes all the commonly -received oxidised salts of sul- 
 phur, except the sulphates and the sulphites. These two are excluded 
 on the ground that they both contain only one atom of sulphur. That 
 reason is valid for the sulphates, but not for the sulphites. The follow- 
 ing is the formula by which a sulphite is usually represented : 
 
 MO,S0 2 , where O = 8. 
 
 Performing the same operation upon this salt as upon the hyposul- 
 phite, namely, doubling the atoms, making O = 16, and throwing the 
 symbols into a synoptical formula, the sulphite becomes M 2 ,S 2 3 . This 
 formula, added to those in the above Table, completes the series of the 
 so-called POLYTHIONATES. 
 
 I have, in the course of this Essay, pointed it out as being generally 
 a fact, and I have laid much stress upon that fact as an important 
 element in the radical theory, that every salt contains two radicals, and 
 only two ; one positive radical and one negative radical; that this is true 
 whether the salt contains oxygen or no oxygen ; and that deviations 
 from this general fact only occur when a salt (already containing two 
 radicals) combines with another positive radical, as in the case of the 
 carbonates = MO,CO + MO, or with another negative radical, as in 
 the case of the hyposulphates = MO, SO -j- SO, to form bibasic or biacid 
 
158 THE PENTATHIONATES. 
 
 salts of a peculiar and very definite character. See page 27, double 
 salts, Classes 5 and 6. 
 
 But, as if in contradiction to these facts, or, if you prefer the ex- 
 pression, to these opinions, we have in the formulae that profess to show 
 the composition of the polythionates, a statement that one basic radical 
 can combine, not only with one atom of sulphur, but with two, three, 
 four, or five atoms. The question which arises upon that statement is 
 this : Are we to consider these multiples of sulphur, S 2 , S 3 , S 4 , S 5 , as 
 being each a single negative radical, or are we to explain the composition 
 of the polythionates in some manner that is more in accordance with the 
 leading doctrines of the radical theory? Is it possible to show that 
 these polythionates consist of simple sulphur salts formed by single 
 radicals ? My reply to those questions is, that the multiples of sulphur, 
 S 2 , S 3 , S 4 , S 5 , act in no case as single negative radicals ; that the above- 
 framed synoptical formulae give erroneous notions of the proximate con- 
 stitution of the salts under consideration ; arid that it is possible to 
 adduce facts to prove that sulphur acts like all other negative radicals, 
 and produces salts with positive radicals, by combining therewith atom 
 to atom. With these subjects for consideration before us, the reader will 
 accompany me, with as much patience as possible, in the examination of 
 a variety of instances and arguments upon which these theories turn. 
 
 The Pentathionates. 
 
 According to Wackenroder, 1 " five atoms of sulphurous acid and five 
 atoms of hydrosulphuric acid, react upon one another in such a manner 
 as to form one atom of pentathionic acid, five atoms of water, and five 
 atoms of sulphur, which separate in the solid state: 5S0 2 4- 5HS = 
 S 5 O 5 -f- 5HO + 58." 
 
 The acid thus produced can be concentrated over a water-bath till it 
 obtains the spec. grav. of 1*3, and in vacuo the spec. grav. of r6o, but 
 it cannot be deprived of water, and its composition at the concentration 
 of i 5 is about one atom of S'O 5 to nine atoms of H 2 O. 
 
 Upon the radical theory, I account for this reaction as follows : 
 
 SO + HS = HSO -f S. 
 
 This simple view of the reaction accounts for all the facts, and is, I 
 think, the true one. The compound HSO is the simplest form of the 
 series of oxidised sulphur salts, and it bears to the sulphates the same 
 relation that aldehyde bears to the acetates. In short, to borrow a 
 phrase from organic chemistry, it is the ALDIDE of the sulphur series, and 
 this relation holds true even to the double salts of the two radicals that 
 
 1 Gmelin's Handbook of Chemistry, II. 163. 
 
THE PENTATHIONATES. 159 
 
 are produced by the combination of the aldehydes with the hydrated 
 acids, or by the corresponding salts with metallic radicals : 
 
 Acetic Series. Sulphuric Series. 
 Aldehyde M,C 2 H 3 O M,SO 
 
 Acid M,C 2 H 3 8 M,SO 2 
 
 Aldehydate M 2 ,(C 2 H 3 ) 2 3 
 
 Sulphite M 2 ,S 2 3 . 
 
 Another method of producing a pentathionate is by the action of 
 aqueous solution of sulphurous acid on dichloride (subchloride) of sul- 
 phur CIS 2 . Thus : 
 
 CIS 2 4- SO + 1 J HC1 
 HHO,HHO I \ 3HSO 
 
 A pentathionate can also be produced by the action of chloride of sul- 
 phur CIS upon water, the presence of sulphurous acid not being 
 essential : 
 
 CIS + HHO = HC1 + HSO. 
 
 According to Kessler, 1 Persoz obtained pentathionic acid by decom- 
 posing hyposulphite of lead with hydrosulphuric acid. 
 
 EXPLANATION : 
 
 Supposing the hyposulphite Supposing the hyposulphite 
 
 to be hydrated. to be anhydrous. 
 
 PbHS 2 2 T jPbS Pb 2 S 4 3 ) ( 2PbS 
 
 + HS [ \2HSO H 2 S 2 } = UHSO 
 
 HHO ) I 
 
 The hydrated pentathionic acid produced by these different reactions 
 is sufficiently explained by the formula HSO, which, in the nomencla- 
 ture proposed in this work, would be called HYDRA SULPHATE. This 
 compound, you will observe, can actually be obtained in the state of a 
 concentrated solution, of the specific gravity of 1*6. But chemists, in 
 their wonderful love for what is occult, rarely scruple to sacrifice the 
 known and the simple, to favour the unknown and the complex. They 
 ignore this hydrated acid, which has been procured experimentally, which 
 anybody can make, and which has this simple formula, and they insist 
 upon recognising an imaginary anhydrous pentathionic acid, which is 
 said to agree with the formula S 5 O 5 , but which they have never seen, 
 which nobody can make, and of which they probably will never have 
 the least knowledge. 
 
 The pentathionic acid, or, as I may perhaps be allowed the liberty 
 
 1 Liebig and Kopp's Annual Report (1847-8), I. 287. 
 
160 THE HYPOSULPHITES. 
 
 of calling it, HYDRA SULPHATE, is a very unstable compound, and to this 
 circumstance must be attributed the fact of its not having forced che- 
 mists to give greater attention to it. A substance that comes frequently 
 before us might be supposed to be able to command our notice ; but 
 when it has the property of disappearing as soon as its presence is 
 announced, it goes not only out of sight but out of mind. Thus it is 
 with hydra sulphate, the decomposition of which follows so closely upon 
 its formation, that we have no time to make a satisfactory acquaintance 
 with it. 
 
 In consequence of the instability of this acid, it is impossible to con- 
 vert HSO into MSO. When we attempt to do so, by adding, for 
 example, KHO to HSO, instead of producing, by double decomposition, 
 the products KSO and HHO, we decompose HSO, drive off more or 
 less of its sulphur, and give rise to the so-called tetrathionates, tri- 
 thionates, and other varieties of sulphur salts which we have presently 
 to examine. But the acid which is so unstable when alone becomes 
 stable when brought into combination, and we are consequently enabled 
 to procure, by indirect means, a variety of salts in which MSO and 
 HSO occur, not only in combination with one another, but with other 
 sulphur salts in great variety and in greatly-varying proportions. 
 
 The Anhydrous Acid S,SO corresponding to the Hydrated Acid H,SO. 
 
 I have, at page 119, explained the relation that exists between the 
 hydrated and the anhydrous sulphuric acids. I have shown that these 
 are both to be considered as normal salts, and that the latter is produced 
 by the decomposition of two atoms of the former : 
 
 HSO 2 + HSO 2 = HHO + S,SO 8 . 
 
 Precisely the same relationship exists between the acid HSO and the 
 anhydride S,SO ; for 
 
 HSO + HSO = HHO + S,SO. 
 
 This compound, which I may call SULPHA SULPHATE, is of great im- 
 portance for the elucidation of the salts of the polythionic acids, but it is 
 unknown in the free state, and we can only infer its existence from the 
 composition and the properties of the salts of which it is a component. 
 But supposing that we could isolate it, we should have a salt on the 
 model of water, in which S would be an unoxidised positive radical, and 
 SO an oxidised negative radical, together = S,SO. 
 
 The Hyposulphites. 
 
 The formula commonly given to the hyposulphites is KO,S 2 O 2 , where 
 O = 8. If we double this formula to raise O to 1 6, and at the same 
 
THE HYPOSULPHITES. 161 
 
 time transpose the oxygen, we have the formula K^O 3 . But this. for- 
 mula does not describe the greater part of the hyposulphites. Most of 
 them contain H 2 O in addition to what is expressed in the above formula ; 
 and Rose and other chemists have expressed a doubt whether it is pos- 
 sible for hyposulphites, free from water, to exist. It is, however, a 
 question whether the hydrogen which is found in these salts exists 
 there in the state of water. The quantity of it is always peculiar. It 
 rarely agrees with the quantity of water of crystallisation which is com- 
 monly found with salts of different bases, but bears a specific relation to 
 the quantity of sulphur which is present in each hyposulphite. 
 
 If we add together the above two formula? (K 2 S 4 O 3 and HHO), we 
 have K 8 H 2 S 4 4 , or, reduced to its simplest form, KHS 2 O 2 . This com- 
 pound seems to be equivalent to an acid salt agreeing with the formula 
 KSO -f- HSO, namely, a double or acid salt of the pentathionic acid. 
 But if the hyposulphites were thus constituted, we might reasonably 
 expect to find neutral salts of the formula KSO. Yet these salts only 
 occur in cases where the basic radical is a metalloid or a negative hydro- 
 carbon ; such as 
 
 Chlorosulphuric acid = C1SO = Chlora sulphate. 
 
 Sulphobenzide = O fl H 5 ,SO = Phenyla sulphate. 
 
 Sulphonaphthaline = C IO H 7 ,SO = Naphtyla sulphate. 
 
 Sulphide of benzoyle = C 7 H 5 ,SO = Benzyla sulphate. 
 
 Sulphide of acetyl = C 2 H 3 ,SO = Acetyla sulphate. 
 
 We find no metallic salts of this formula, but we find an abundance 
 both of organic and inorganic salts of the formula KHS 2 O 2 , not only 
 simple but double, and even of more complex varieties. There are also 
 plenty of anhydrous hyposulphites of the form K S S 4 3 , and many com- 
 pounds which appear to be constituted of these two forms of the salt, 
 combined with one another in various proportions. 
 
 It is commonly said, that no such compound is known as hypo- 
 sulphurous acid, either anhydrous or hydrated ; but here, I think, we can 
 derive some benefit from our investigation of the so-called pentathionic 
 acid. Let us gather the facts together : 
 
 HSO is certainly the composition of the hydrated pentathionic 
 acid. 
 
 SSO is probably its corresponding anhydride. 
 
 MSO is the neutral salt which corresponds to the acid HSO, 
 and which has been procured in salts where M is 
 a negative radical, but not where M is a positive 
 radical. 
 
 Then, KSO + HSO = KH,S 2 0* is the double salt, or acid salt, of 
 the series ; and this is the composition of the hydrated 
 hyposulphites, which can be procured in great variety. 
 
 M 
 
162 THE HYPOSULPHITES. 
 
 If we join together two atoms of hydrated hyposulphite, and deprive 
 the compound of one atom of water, we produce the 
 anhydrous hyposulphite, which also occurs plentifully: 
 
 KSO 4- HSO ) J H O 1 J KSO + S ) 
 KSO + HSO f "" \H f == \ KSO + SO f : 
 
 According to these relations, the well-known but misunderstood hydrated 
 pentathionic acid = HSO is, in fact, the " undiscovered" hydrated hypo- 
 sulphurous acid ; the compound SSO is the non-isolated anhydrous 
 hyposulphurous acid ; and the hydrated hyposulphite KSO + HSO is 
 a double or acid pentathionate. These are sad complications in terms, 
 and I will, therefore, simplify the matter by throwing aside the penta- 
 thionic theory, and stating the facts in other words, thus : 
 
 HSO = HYDRA SULPHATE is the fundamental acid, or rather hydrogen 
 salt, of the series of oxy-salts of sulphur. SSO is its anhydride. 
 
 KSO would be the normal salt of the series, but we cannot get it 
 except with negative radicals, C 2 H 8 ,SO, &c. 
 
 KSO 4- HSO = KH(SO) 8 . POTASSA HYDRA BISULPHATE is the 
 double salt or acid salt of the series, and this can be procured in great 
 variety, constituting the salts now considered to be hyposulphites 
 combined with water, according to the formula 
 
 5 " * KSO,HSO. 
 
 fKSO] 
 
 The anhydrous salt K 8 S 4 O 3 = < KSO I is a triple salt, which bears to 
 
 [ssoj 
 
 the salt KSO 4- HSO the same relation that the anhydrous bisulphate 
 
 (KSOM 
 of potash = < KSO 8 > bears to two atoms of the hydrated bisulphate of 
 
 ( SSOJ 
 
 potash = 2 (KSO 2 -f- HSO 2 ), according to the theory that I have 
 explained at page 119. The relation is also the same as that which 
 bichromate of potash bears to neutral chromate of potash, as is explained 
 in the article on the " Chromates," page 126. 
 
 THE PENTATHIONATE OF BARYTA. The only salt of the pentathionic 
 acid which has been analysed is that of baryta. According to Lenoir, 1 
 this salt, obtained in crystals by precipitation with alcohol, contains 
 
 BaO,S 5 5 4- 2HO equal to Ba,S 5 3 4- HHO. 
 ( where O = 8.) (where O = 16.) 
 
 The relation of the pentathionate of barytes to the hydrated penta- 
 thionic acid is shown in the following diagram : 
 
 Liebig and Kopp's Annual Report (1847-8), I. 286. 
 
THE HYPOSULPHITES. 163 
 
 HSO BaSO BaSO BaSO 
 
 HSO HSO HSO SSO 
 
 HSO HSO HSO SSO 
 
 HSO HSO SSO 
 
 HSO HSO 
 
 5 atoms of the i atom of the I atom of the i atom of the 
 
 Hydrated Acid Baryta-salt Baryta-salt theoretical 
 
 commonly called as it exists in in crystals. Anhydrous-salt. 
 
 i Acid -f 2 Water. solution. 
 
 The connection of the hyposulphites with the pentathionates is remark- 
 ably illustrated by the following comparisons : 
 
 BaSO 
 
 BaSO 
 
 BaSO 
 
 BaSO 
 
 HSO 
 
 HSO 
 
 SSO 
 
 BaSO 
 
 HSO 
 
 
 SSO 
 
 SSO 
 
 SSO 
 
 
 
 
 Crystallised 
 
 Crystallised 
 
 Theoretical 
 
 Anhydrous 
 
 Pentathionate 
 
 Hyposulphite 
 
 Anhydrous 
 
 Hyposulphite 
 
 of Barytes. 
 
 of Barytes. 
 
 Pentathionate 
 
 of Barytes. 
 
 
 
 of Barytes. 
 
 
 I conclude from these examples, that the hyposulphites and penta- 
 thionates are both composed by the intercombination of simple salts of 
 the formulae HSO, MSO, SSO, and that no such thing exists as a 
 pentathionic acid of the form HO,S 5 O 5 , and that there are no penta- 
 thionates, but such as are, like the hyposulphites, compounds of MSO 
 with HSO and SSO. 
 
 The following processes illustrate the formation of the hyposul- 
 phites : 
 
 1 . When zinc is dissolved in an aqueous solution of sulphurous acid, 
 we obtain, without liberation of hydrogen gas, a mixture of sulphite of 
 zinc and hyposulphite of zinc, 
 
 a. Supposing Water not to Act. 
 
 7 * _L <^OV - J Zn2 S 2 O 3 = Neutral sulphite. 
 
 = \ Zn 2 ,S 4 3 = Anhydrous hyposulphite. 
 
 b. Supposing Water to Act. 
 Zn 2 \ \ ZnH,S 2 3 = Bisulphite. 
 
 (SO) 4 + HHOj lZnH,S 2 O 8 = Hydrous hyposulphite. 
 
 2. A hyposulphite is also produced when an aqueous solution of an 
 alkaline sulphite is heated in a close vessel with an excess of sulphur. 
 
 a. Supposing Water not to Act. 
 
 = Na*,S 4 O 3 = Anhydrous hyposulphite. 
 
 M2 
 
164 THE HYPOSULPHITES. 
 
 b. Supposing Water to Act. 
 
 Na 2 ,S*0 3 \ (NaHS 2 OM 
 
 S* > = < M Tj'osns t Hydrous hyposulphite, 2 atoms. 
 HHOJ 
 
 In the presence of water, the hyposulphites are probably always 
 formed in agreement with the formula MSO,HSO. Many of them 
 crystallise in that state. This is the case with the hyposulphite of soda, 
 perhaps the most important salt of the series, in consequence of its 
 employment in the art of photography. This salt crystallises from its 
 solution with so much water as to agree with the formula 
 
 NaSO,HSO + 2H 2 O. 
 
 The hyposulphite of barytes and many others also crystallise in the 
 form MSO,HSO. When these salts are dried they gradually lose their 
 water, and pass, by intermediate stages, into the form of the anhydrous 
 hyposulphites agreeing with the formula M 8 S 4 O 3 . As an example of 
 these progressive changes I may refer to a crystallised salt of potash, 
 which has the formula KH,(SO)* = KSO,HSO. When this salt has 
 been dried in vacuo, its composition is K 8 H,S 6 O 5 ; and when h has been 
 deprived of all its water, it is K 2 ,S 4 O 3 . These relations are shown in 
 the following diagram : 
 
 3 atoms original Salt. Partially dried. 
 
 KSO + HSO) [ KSO -f HSO ) . v , , 
 
 KSO + HSO I = | KSO + SO I + H,HO { Ex P elled from 
 KSO + HSO J (KSO+ S J l 3 a 
 
 2 atoms original Salt. Wholly dried. 
 
 KSO + HSO ) J KSO + SO \ , TT Tr n j Expelled from 
 KSO + HSO j == I KSO + S J " n ' nu \ 2 atoms. 
 
 These examples prove that the salts of this series have, like the silicates, 
 an extraordinary power of combining with one another, and also of com- 
 bining with additional atoms of what is commonly, but improperly, 
 called the anhydrous ACID. In this case, and in all such cases, the com- 
 pound S,SO appears to me to be a perfect salt, and to combine as such 
 with the other salts. 
 
 Although unwilling to multiply details, I must quote a few examples 
 of hyposulphites, because I feel that the reader will naturally desire to 
 see the important positions which I have advanced established firmly 
 by sufficient evidence. Most of the hyposulphites agree with the two 
 formulae that I have explained, MSO + HSO and M 2 S 4 O 3 . I shall not 
 refer again to salts agreeing with those ordinary formulae, but select 
 those of more complex constitution. 
 
THE HYPOSULPHITES. 
 
 16i 
 
 EXAMPLES OF COMPLEX HYPOSULPHITES. 
 
 Assumed proximate Constituents. 
 
 Ultimate Constituents. 
 
 Hydrous Salts. 
 
 Anhydrous Salts. 
 
 I. Am 3 ,H; 
 
 S 6 5 = 
 
 AmH,S 2 O 2 4- 
 
 Am 2 S 4 3 . 
 
 2 pU TT3 
 
 cs r\e 
 
 (2(AmH,S 2 2 ). 
 
 
 ^ " > ? J 
 
 
 | PbH,S 2 O 2 . 
 
 
 3. Na 4 ,Pb 2 ; 
 
 S 12 9 = 
 
 ... =s 
 
 ]2(Na 2 S 4 3 ). 
 I Pb 2 S 4 3 . 
 
 4. K 4 ,Pb 2 ,H 4 ; 
 
 S 12 n = 
 
 4 (KH,S 2 2 ) + 
 
 Pb 2 S 4 3 . 
 
 5 . K,Cu,H 2 ; 
 
 S 4 4 = 
 
 1 KH,S 2 2 . 
 ( CuH,S 2 O 2 . 
 
 
 6. K 6 ,Cu 2 ,H 6 ; 
 
 S 16 O 15 = 
 
 6(KH,S 2 2 ) + 
 
 Cu 2 S 4 3 . 
 
 7. Na 3 ,Cu,H 2 ; 
 
 S 8 7 = 
 
 2(NaH,S 2 2 ) 4- 
 
 NaCu,S 4 O 3 . 
 
 8. Na 2 ,Cu 3 ,H 5 ; 
 
 s>o" = 
 
 J2(NaH,S 2 2 ). 
 |3(CuH,S 2 O 8 ). 
 
 
 
 
 
 f2(Cu 2 S 4 O 3 ) 
 
 9. Cu',Hg 3 ; 
 
 S 18 O 12 = 
 
 . 
 
 { CuHg,S 4 3 . 
 
 
 
 
 I Hg 2 S 4 3 . 
 
 10. Am 8 ,Hg 2 ,H 4 ; 
 
 S 20 17 = 
 
 4(AmH,S 2 O 2 ) + 
 
 J 2 (Am 2 S 4 3 ). 
 \ Hg 2 S 4 3 . 
 
 ii. Na 2 ,Ag 2 ,H 2 ; 
 
 S 8 7 = 
 
 2(NaH,S 2 2 ) 4- 
 
 Ag 2 S 4 O 3 . 
 
 12. Na 4 ,Ag 2 ,H 4 ; 
 
 S 12 U = 
 
 4(NaH,S 2 2 ) 4- 
 
 Ag 2 S 4 3 . 
 
 13. Na 4 ,Ag 2 ; 
 
 S 12 9 = 
 
 . . . 
 
 |2(Na 2 S 4 O 3 ). 
 1 (Ag 2 S 4 3 ). 
 
 AUTHORITIES. (The references are to GMELIN'S Handbook of Che- 
 mistry.^) 
 
 1. Rammelsberg, II. 454. Hyposulphite of ammonia = 3(NH 4 O,S 2 O 8 ) 
 
 4- HO. 
 
 2. Rammelsberg, V. i 59. Hyposulphite of lead-oxide and ammonia 
 
 = 2(NH 4 0,S 2 O 2 ) 4- PbO,S 2 2 4- 3Aq. 
 
 3. Lens, V. 162. Hyposulphite of lead-oxide and soda = 2(NaO, 
 
 S 2 O 8 ) 4- PbO,S 2 O 2 . 
 
 4. Rammelsberg, V. 161. Hyposulphite of lead-oxide and potash 
 
 = 2 (KO,S 2 8 ) 4- PbO,S 2 2 4. 2Aq. 
 
 5. Rammelsberg, V. 459. Hyposulphite of cuprous-oxide and potash; 
 
 with i atom of potash-salt = KO,S 2 O 2 4- Cu 2 O,S 2 O 2 4- 2Aq. 
 
 6. Rammelsberg, V. 459. Hyposulphite of cuprous-oxide and potash ; 
 
 with 3 atoms of potash-salt = 3 (KO,S 2 2 ) 4- Cu 2 0,S 2 0* 4- 
 
166 THE HYPOSULPHITES. 
 
 7. Lenz, V. 492. Hyposulphite of cuprous-oxide and soda ; with i 
 
 atom of copper-salt to 3 atoms of soda-salt = 2(NaO,S 2 2 ) -+ 
 Cu 8 0,S 2 2 + 2Aq. 
 
 8. Lenz, V. 462. Hyposulphite of cuprous-oxide and soda; with 3 
 
 atoms of copper-salt to 2 atoms of soda-salt = 2 (NaO,S 2 O 2 ) -f- 
 3(Cu 2 0,S 2 2 ) 
 
 9. Rammelsberg, VI. 131. Hyposulphite of mercurous and cuprous- 
 
 oxide = 5(Cu 2 0,S 8 2 ) + 3(Hg 2 0,S*0 2 ). 
 IO. Rammelsberg, VI. 78. Hyposulphite of mercuric-oxide and am- 
 
 monia = 4(NH 4 0,S 2 2 ) -}- HgO,S 2 2 + 2 Aq. 
 IT. Lenz, VI. 180. Hyposulphite of silver-oxide and soda = NaO,S 2 O 8 
 
 + AgO,S 2 O 2 -f Aq. 
 
 12. Lenz, VI. 180. Hyposulphite of silver-oxide and soda = 2(NaO, 
 
 S 2 2 ) + AgO,S 2 2 + 2Aq. 
 
 13. Sir John Herschel, VI. 179. Hyposulphite of silver-oxide and 
 
 soda = 2(NaO,S 2 2 ) + AgO,S 2 O 2 . 
 
 14. Fordos and Ge"lis, VI. 231. Hyposulphite of aurous-oxide and soda 
 
 = 3(NaO,S 8 2 ) + AuO,S 2 2 
 
 Except among the silicates and the salts of the metallic acids, it would 
 perhaps be difficult to find a series of salts of more complicated relations 
 than the series exhibited in the preceding Table. The complication 
 arises from the circumstance that the normal salt MSO, which is the 
 basis of the series, though unstable when isolated, acquires stability when 
 in combination, and, like all the oxy-salts of sulphur, has an unlimited 
 tendency to form complex salts. 
 
 In considering the facts that are exhibited in this Table, we speedily 
 come to the question, What is the condition of the hydrogen in these 
 salts ? Does it act as base to the oxidised radical SO, or does it, as all 
 the authorities that I have quoted assume, exist in the condition of 
 water ? I admit that the last view simplifies the formulas materially ; 
 but the mere simplification of formula? is not the sole object of our in- 
 quiry. What we want mainly to understand is the intimate nature of 
 the composition of these salts ; how it is in what order the elements 
 of which they are composed are combined with one another. Looking 
 at the whole series, at all the kinds of the salts of the polythionic acid, 
 it seems to me that there is no probability that the hydrogen exists in 
 the state of water, but that there is throughout a constant recurrence of 
 the salts HSO, MSO, SSO, and that of these elementary salts the 
 hyposulphites and pentathionates are made up. We perceive every- 
 where in this Table, that if we consider SO as an oxidised negative 
 radical, there is for every atom of it a corresponding positive radical 
 sometimes H, sometimes M, sometimes S ; all of them unoxidised. This 
 is consequently a demonstration of the truth of the proposition, which I 
 enunciated at page 158, that with certain specified exemptions, one 
 
THE HYPOSULPHITES. 167 
 
 positive radical never combines with a multiple number of oxidised sul- 
 phur atoms considered as one negative radical ; but that every single 
 oxidised sulphur atom acts as a negative radical, and combines with one 
 positive radical. 
 
 But what, it may be asked, shall we gain by admitting the divisibility 
 of these compounds into innumerable little normal salts ? I will endea- 
 vour to answer this question. It is admitted, that plants feed on water 
 = HHO, carbonic acid = CO 2 , ammonia = NH 3 , with minute quantities 
 of S and other inorganic elements. We know also that animals feed on 
 plants. But when we come, in the practice of physiological chemistry, 
 to examine the component parts of animals, we find, of course, the 
 elements upon which the plants feed, but we find them in the condition 
 of substances that have the following composition : 
 
 Total atoms. 
 
 Albumen . . C^H'^N^S'O 68 = 482 
 Caseine . . . C lar H MB N M SW = 644 
 Flesh fibrine . C^H'^N^S'O 68 = 482 
 Blood fibrine . C 298 H 22r N T40 S 2 O 92 = 660 
 
 I copy these formulae from Professor GREGORY'S Handbook of Organic 
 Chemistry, published in 1856. They represent therefore the present 
 state of chemical knowledge as respects these compounds. We have 
 here a statement of the ultimate constitution of a number of important 
 compounds, but no statement of their proximate constitution. We can- 
 not tell how these multitudes of atoms are combined with one another, 
 or of what innumerable little normal salts the complex salts are com- 
 posed. Between the food of plants CO 2 , HHO, NH 3 , S and blood 
 fibrine C^H^N^S^ 92 , there is an immense chasm. We desire to bridge 
 it over. We want to know how the raw material has been worked up 
 into this finished manufacture. We would fain follow the original 
 elements, C, and H, and N, and S, through all their transmigrations and 
 metamorphoses till they united to form the complex animal compound 
 which so much perplexes and astonishes us. 
 
 Well, then, the proper course to pursue is certainly not that of 
 massing the elements into vast clumps, and forbearing to inquire 
 whether these clumps are not divisible into smaller, and smaller, and 
 smaller groups. On the contrary, the duty of the chemist is to examine 
 the works of Nature with the greatest minuteness, to watch, as far as his 
 power permits, the working of every atom of the substances which he 
 undertakes to examine, and not to satisfy himself with looking at them 
 cursorily and in the gross. These are the reasons which have induced 
 me to point out what I consider a defect in the manner in which 
 chemists have examined the salts of sulphur. They have stopped too 
 readily after having grouped the elements into clumps, and have not 
 examined with proper care in what manner these clumps are constituted. 
 
168 THE TETRATHIONATES AND TRITHIONATES. 
 
 By persisting in such a course with salts in general, they will never 
 arrive at the comprehension of the constitution of such compounds as 
 albumen, caseine, and fibrine, and never properly appreciate the physio- 
 logical chemistry either of animals or plants. This is why I propose 
 that we should push our analytical inquiries into the constitution, not 
 only of the oxy-salts of sulphur, but of all salts, to the extremest possible 
 extent of minuteness. 
 
 The Tetrathionates. 
 
 The Tetrathionates are produced by the action of iodine on solutions 
 of the hyposulphites. Thus : 
 
 JKSO-f-HSCM J SO + HSO) 
 
 t KSO + HSO f " " t KSO + HSOf 
 
 2 atoms Hyposulphite. I atom Tetrathionate. 
 
 Supposing the tetrathionate thus formed to be dried and deprived of one 
 atom of water = HHO, it becomes KSO,SO + SSO = KS'O 8 . 
 
 The following tetrathionates are nearly all that have been analysed 
 
 Analytical Formulae. Synoptical Formulae. 
 
 BaSO,SO + 2HSO = BaH 2 ; S 4 O 4 = BaS 4 O 3 + Aq. 
 
 PbSO,SO + 2HSO = PbH 2 ; S 4 O 4 = PbS 4 O 3 + Aq. 
 
 SrSO,SO + 2HSO + Aq 2 = SrH 6 ; S 4 O 6 = Sr SKP + Aq 8 . 
 K SO,SO + SSO = K ; S'O 3 = K S*O. 
 
 The synoptical formula seem to show the presence of the poly-sulphur 
 radical S 4 , but the analytical formulae account for the salts in another 
 manner. They are, namely, compounds of the normal sulphates HSO, 
 MSO, and SSO with SO, and there is apparently no such compound 
 as the assumed tetrathionic acid HO,S 4 O 5 , the real acid being composed 
 as follows: H r SO,SO + HSO -f HSO = H 3 S<O 4 ; where H r is the 
 only atom that is replaceable by a metal. 
 
 The Trithionates. 
 
 The trithionates are produced by digesting, for three or four days, a 
 saturated solution of bisulphite of potash on flowers of sulphur. The 
 products vary according to the duration of the digestion, the heat at 
 which it is effected, and other circumstances. They are, generally, 
 trithionate of potash, more or less of sulphate and of hyposulphite, a 
 quantity of sulphurous acid which is evolved during the digestion, and 
 a solution from which free sulphur is afterwards deposited. The variety 
 and variableness of these products render it impossible to explain the 
 
THE TEITHIONATES. 169 
 
 operation in an equation ; but the chief points can be satisfactorily 
 accounted for. 
 
 1. The formula of bisulphite of potash, according to the radical 
 theory, is KSOO + HSO. With S, this can produce KSO + HSO 
 = hyposulphite of potash + SO = sulphurous acid. 
 
 2. Two atoms of bisulphite of potash are equal to one atom each of 
 trithionate of potash and sulphate of potash, thus : 
 
 KSO 2 + HSO 1 ( KSO 2 + HSO + HSO = Trithionate. 
 KSO 2 + HSO J := ( KSO 2 = Sulphate. 
 
 3. If water is presumed to take part in the operation, and a little 
 oxygen is taken up from the air during the prolonged digestion, the 
 action may be represented thus : 
 
 KSO 2 + HSO ) f KSO 2 + HSO + HSO. 
 KSO 2 + HSO I = { KSO 2 + HSO + HSO. 
 S 2 + HHO 4- J ( 
 
 4. The trithionates can also be prepared by exposing a solution of 
 hyposulphite of zinc to spontaneous decomposition : 
 
 ZnSO,HSO 1 Q I ZnSOO. 1 
 ZnSO,HSO I = ' i (HSO) 2 f 
 
 The composition of crystallized trithionate of barytes has been found to 
 be BaH 2 S 3 O 4 , which is equal to BaSO 2 + (HSO/. The formulae of the 
 crystallized anhydrous trithionate of potash is KSO 2 -f SSO, orKS 3 3 . 
 Hence, the analytical formulae of these salts are as follow : 
 
 The anhydrous trithionates are = 
 M,SOO 
 
 s,so. 
 
 The hydrous trithionates are = 
 M,SOO 
 H,SO 
 
 
 H,SO. 
 
 Their synoptical formulae are, 
 
 Anhydrous trithionates = M,S 8 O 3 
 
 = MH 2 ,S 3 4 
 
 ^^ 
 
 J 
 
 Hydrous trithionates < ' 
 
 When the trithionate of potash is made red hot, it is decomposed into 
 one atom each of sulphur, sulphurous acid, and sulphate of potash. 
 Langlois. 
 
 KSO 2 -f- S,SO = KSO 2 + S + SO. 
 
 When a solution of trithionate of potash is boiled, it is resolved into 
 sulphate of potash, sulphurous acid, and sulphur. Pelouze. 
 
 KSO 2 + HSO + HSO = KSO 2 + SO -f S+HHO. 
 
170 THE SULPHENETES. 
 
 The synoptical formulas seem to indicate the existence of the multiple 
 radical S 3 , but all other circumstances discredit that assumption. 
 
 The aqueous pentathionic acid, when acted on by an alkali, suffers de- 
 composition, liberates water and one or two atoms of sulphur, and pro- 
 duces a tetrathionate or trithionate : 
 
 KH 4 ,S 5 5 less S and H*O = KH 2 ,S 4 O 4 = Tetrathionate. 
 KH 4 ,S 5 O* less S 8 and H 8 O = KH 2 ,S 3 O 4 = Trithionate. 
 
 The Sulphenetes. 
 
 In the proposed nomenclature a SULPHENETE would be a salt con- 
 taining two atoms of sulphur and two atoms of oxygen = S 2 O 2 . No 
 such salts are at present recognised, but I have no doubt that we shall 
 find them hereafter. In tracing the constitution of the tetrathionates, I 
 have shown that they may be considered to consist of a biacid salt, of 
 the form MSO,SO in combination with S,SO or with HSO,HSO. This 
 biacid salt MSO,SO, if isolated, would be a sulphenete. Thus, KSO,SO 
 = KS 2 O* = Potassa sulphenete. Now, though I cannot point out any 
 single salts of this composition, I can refer to a double salt, which will 
 explain my view of its composition. I copy the following equation from 
 Gerhardt's discussion of the " type ammonia." 1 In this equation S 
 signifies what I call S 8 . The other symbols agree with mine. 
 
 A. B. C. D. 
 
 fC 6 H 5 S0 8 fC 6 H 5 SO a 
 
 N \ Ag + C1,SH 5 S0 8 = N \ C 6 H 5 S0 2 + ClAg. 
 
 (H I H 
 
 Azoture of Chloride of Azoture of 
 
 Sulpho-phenyle Sulpho-phenyle. Disulpho-phenyle 
 
 of Silver and Hydrogen, 
 and of Hydrogen. 
 
 It is absurd to consider oxidised double salts like these as " ammonias," 
 and I shall arrange the symbols in a different manner : 
 
 A is a salt of the class that I have pointed out as double sulphates 
 (using that word in its new sense), in which one of the basic radicals is 
 silver and the other an amidogen containing one atom of phenyl = 
 Ag; SO + ZH,OT[ 5 ; SO. 
 
 B is a similar double sulphate, in which the basic radicals are chlorine 
 and phenyl = Cl ; SO + CH - ; SO. 
 
 1 Traite de Chimie Organique, torn. iv. 770. 
 
THE SULPHITES. 171 
 
 When these two salts act upon one another, chloride of silver (D) is 
 produced, and the other elements all rest in combination to form the 
 salt C. 
 
 A + B. D. C. 
 
 A = AgSO + ZH,C 6 H 5 ; SO 1 f Ag 1 f SO + ZH,C 6 H 5 ; SO 
 B = Cl SO + C 6 H 5 ; SO j == | Cl f '" \ SO + C 6 H 5 ; SO. 
 
 This last salt (C) is consequently the double sulphenete, ZH,C 6 H 5 ; 
 S*O* + C 6 H 5 ; S 2 O*. The normal sulphenete will no doubt soon be 
 found, if it is searched for, 
 
 The Sulphites. 
 
 The composition of the sulphites, according to the radical theory, and 
 on the assumption that the atomic weight of sulphur is 16, is repre- 
 sented by the following formulae : 
 
 Analytical Formula. Synoptical Formula. 
 
 MO,SO + M,SO " M,M ; S 2 3 
 
 These formulae, however, represent the Neutral Sulphites. The Acid 
 Sulphites, or Bisulphites, are constituted as follows : 
 
 Analytical Formula. Synoptical Formula. 
 
 MO,SO+H,SO M,H; S 2 O 3 . 
 
 There is no hydrated acid corresponding to these sulphites. According 
 to the synoptical formula, a sulphite is a bibasic salt. According to the 
 analytical formula, it is a double salt consisting of a sulphate MSO 2 , in 
 combination with a salt on the model of water containing only one atom 
 of oxygen = MSO. Hence the hydrated acid would be a compound of 
 hydrated sulphuric acid with hydrated pentathionic acid 
 
 HO,SO + HSO = H,H; S 2 3 . 
 
 NOMENCLATURE OF THE TWO KINDS OF SULPHITE. 
 
 Neutral sulphite : K,K ; S*O 3 POTASSEN SULPHENITE. 
 Acid sulphite : K,H ; S'O 8 POTASSA HYDRA SULPHENITE. 
 
 The sulphites are prepared by passing sulphurous acid gas = SO into 
 solutions of caustic alkalies or carbonates of alkalies. The reactions that 
 take place are shown by the following equations : 
 
 a. KHO + SO -f SO = K,H; S 8 8 
 
 b. KHO + SO) JK,K; S 2 O 3 
 KHO + SO ( == | H,HO. 
 
 c. K,K;C0 3 \ jE^KjS'O 3 
 SO + SO j == \ C O 2 . 
 
172 THE HYPOSULPHATES. 
 
 According to a), one atom of caustic potash and two atoms of sul- 
 phurous acid produce one atom of bisulphite of potash. According to 
 b\ two atoms of caustic potash and two atoms of sulphurous acid pro- 
 duce one atom of water and one atom of neutral sulphite of potash. 
 According to c) , one atom of carbonate of potash and two atoms of sul- 
 phurous acid produce one atom of neutral sulphite of potash and one 
 atom of carbonic acid. 
 
 The sulphites of the alkaline earths (Ba, Sr, Ca) which are insoluble 
 in water, dissolve in an aqueous solution of sulphurous acid. The reason 
 of this is, that the insoluble neutral sulphites become converted into 
 soluble bisulphites : 
 
 Ba,Ba;S 9 3 + ) lBa,H;S 8 O 3 
 
 SO + SO + HHOj := }Ba,H;S 2 3 . 
 
 Many neutral sulphites are decomposed by ignition into sulphate 
 and i sulphide : 
 
 Pb,Pb; S 2 3 \ j 3(PbS0 4 ) 
 Pb,Pb; S 8 3 j " \ PbS. 
 
 When sulphites are treated with hydrochloric acid, sulphurous acid 
 gas is liberated, and no sulphates are formed : 
 
 Ag,Ag,S 8 8 ) JAgCl,Agd 
 H,H,C1 2 f " \ SO,SO + HHO. 
 
 When sulphites are treated with nitric acid in the cold, sulphurous 
 acid gas is liberated : 
 
 K,K; S'OM (K,NO 3 
 H,N0 3 V = K,N0 8 
 
 SO,SO + HHO. 
 
 When a mixture of sulphites and nitric acid is boiled, peroxide of 
 nitrogen is expelled and sulphates are formed : 
 
 K,K;S 8 3 1 fKSO* 
 HO,NO 8 V = < KSO 2 
 HO,N0 8 J I NO 2 ,NO 8 , + HHO. 
 
 The Hyposulphates. 
 
 The hyposulphates are constituted as follows : 
 
 Analytical Formula. Synoptical Formula. 
 
 KO,SO; SO K,S 8 3 
 
SATURATING CAPACITIES OF OXY-SULPHUR ACIDS. 173 
 
 The hyposulphate of manganese is produced by passing sulphurous acid 
 gas into water containing peroxide of manganese in suspension : 
 
 MnO + SO,SO = MnO,SO + SO = MnS'O 3 . 
 
 When heated, the hyposulphates give off one atom of sulphurous acid 
 and leave a sulphate of the base : 
 
 MnS'O 3 = MnSO 8 + SO. 
 
 A boiling solution of a hyposulphate, when acted on by chlorine or 
 nitric acid, produces two atoms of sulphuric acid for each atom of base. 
 Thus : 
 
 With Nitric Acid. 
 
 KO,SOM fKO,SO. 
 SO f V = <^ HO,SO. 
 
 HO,NOOJ NOO. 
 
 With Chlorine. 
 
 KO,SO \ 
 SOJ 
 H,HO 
 
 Cl 
 
 KO,SO. 
 HO,SO. 
 
 H,C1. 
 
 Hyposulphuric acid can be procured in the state of hydrate = HS'O 8 
 HYDRA SULPHENITE. 
 
 Peculiarities in the Saturating Capacities of the 
 Oxy-Sulphur Acids. 
 
 i]. On comparing together the synoptical formulae of the sulphites 
 and hyposulphates, we observe a very remarkable coincidence : 
 
 K,K; S 2 8 = Sulphite. 
 K, S ? O 3 = Hyposulphate. 
 
 Here are two classes of salts, both having acid radicals of the same 
 nature and quantity, and both with the same number of atoms of oxygen, 
 yet differing essentially in the important circumstance, that the salts of 
 the one class are monobasic, and those of the other class, bibasic. The 
 synoptical formulae show nothing to explain this peculiarity, but the 
 analytical formula clear up all mystery ; 
 
 KO,SO + KSO = Sulphite. 
 KO,SO + SO = Hyposulphate. 
 
 Namely, the sulphite is both bibasic and biacid. The hyposulphate is 
 biacid but not bibasic. 
 
 This explanation of the rational composition of the sulphites and 
 hyposulphates is totally lost, if, following MM. Gerhardt and William- 
 son, we fix the atomic weight of sulphur at 3 2 ; for then we have the 
 formulae KKSO 3 and KSO 3 ; one representing a bibasic, and the other a 
 
174 SATURATING CAPACITIES OF OXY-SULPHUR ACIDS. 
 
 monobasic salt, with no clue to the significance of so remarkable a pecu- 
 liarity. 
 
 The proportions of sulphur and oxygen which are present in the 
 sulphites and hyposulphates, are the same as the proportions which con- 
 stitute the compound called anhydrous sulphuric acid : 
 
 Anhydrous Neutral Hyposulphate 
 
 Sulphuric Acid. Sulphite of Potash. of Potash. 
 
 SO K,SO SO 
 
 SOO K,SOO K,SOO 
 
 These relations explain many phenomena that occur when sulphuric acid 
 acts upon organic radicals. 
 
 2]. A similar anomaly, as to saturating power, appears when we com- 
 pare together the anhydrous tetrathionates and the anhydrous hyposul- 
 phites, expressed in synoptical formulae : 
 
 = Tetrathionate, 
 KK,S 4 O 3 = Hyposulphite. 
 
 The cause of this difference is shown in the analytical formulae : 
 
 KSO -f SO + SSO = The Anhydrous tetrathionate. 
 KSO + KSO -f SSO = The Anhydrous hyposulphite. 
 
 3]. The following salts exhibit a third pair of examples of this pecu- 
 liarity : 
 
 M; 8*0* = Sulphenete (Hypothetical). See page 170. 
 MH ; S 8 O 2 = Hydrous hyposulphite. 
 
 The analytical formulae of which salts are : 
 
 MSO + SO = Sulphenete. 
 
 MSO + HSO = Hydrous hyposulphite. 
 
 4]. I might even notice a fourth pair of such salts : 
 
 ZH^H 5 ; C'H 5 ; S 4 O 4 = Double sulphenete. See page 170. 
 K,H,H ; S 4 4 = Hydrous tetrathionate. 
 
 The analytical formulas of this pair of salts are : 
 
 (ZH,C 6 H 5 ; SO + SO) n . , 
 
 1 CTP; SO + SO | Double sul P henete - 
 
 I KSO,SO + H,SO I Hydrous tetrathionate. 
 
 Facts of this sort should not be forgotten when you inquire, What is 
 the nature of the bibasic and biacid power ? 
 
 How are you to know a sulphite from a hyposulphate ? Both contain 
 
NOMENCLATURE OF THE POLYTHIONATES. 175 
 
 S 2 3 , but the sulphite contains two positive radicals, the hyposulphate 
 only one positive radical. The distinction seems to be almost self- 
 evident ; yet the terms sulphite and hyposulphate are applied frequently, 
 in books on organic chemistry, to compounds for which they are totally 
 unfit. Such cases occur even in Gmelin's Handbook. In discriminating 
 the oxy-sulphur salts, attention must always be paid to three particulars, 
 namely, the number of atoms of sulphur, of oxygen, and of the positive 
 radicals. The relation, not of any two of these, but of the whole, to one 
 another, determines the nature of the salt ; for we have seen, that the 
 acids S 2 O 3 , S 4 O 3 , and S 2 O 2 , can saturate either M or MM ; and that MM 
 can saturate either S 4 3 , S 2 O 3 , or S 2 O a , or twice that quantity of any one 
 of them. I repeat, therefore, that the relations of these three components 
 of the salts must be carefully determined in each case, and that the 
 various oxy-sulphur salts are to be formulated and named according to 
 such threefold determinations. Hence, the formula MS 2 3 will signify 
 a hyposulphate, and the formula MM,S*O 3 will signify a sulphite; so 
 also, MSO 8 will signify a sulphate, and MSO 8 + HSO 2 will signify a 
 bisulphate ; whatever may be the nature of the radical which is denoted by 
 M, provided always that it is a radical, and is known to act as a radical 
 in other cases. 
 
 Nomenclature of the Complex Oxy-Sulphur Salts. 
 
 An atom of sulphur weighing 16 combines with an atom of oxygen of 
 the same weight to produce an atom of sulphurous acid = SO. This is 
 the prime radical of all the oxysalts of sulphur. 
 
 SO combine with H, to produce the salt H,SO. This can be ob- 
 tained in aqueous solution of the specific gravity of i *6, but it cannot be 
 isolated. It has been called pentathionic acid. I call it hydra sulphate. 
 It can produce salts of the form MSO, where M is a negative radical, 
 but not where M is a positive radical. It can however produce acid 
 salts of the form MSO + HSO, where M is a positive radical. These 
 salts are now called hyposulphites. I propose to call them bisulphates. 
 Thus K,H ; (SO) 2 is potassa hydra bisulphate. Hydra sulphate produces 
 an anhydride of the form S,SO = sulpha sulphate. This combines with 
 salts of the form MSO to produce anhydrous hyposulphites of the form 
 PbSO, PbSO, SSO = Pb 8 S 4 O 3 , which may be called plumben sulphonite. 
 These simpler varieties of hyposulphites combine with one another to 
 produce a series of extremely complex salts of which I have given some 
 examples at page 165. I do not propose to apply systematic names to 
 these complex salts, because it is certain that they would never be used. 
 The names in present use, as given at page 165, are vague and in- 
 accurate ; one single term " hyposulphite " being applied to salts of 
 extremely different constitution. Such error-teaching names are worse 
 
176 NOMENCLATURE OF THE POLYTHIOXATES. 
 
 than useless. It is better to depend upon the formulas for information. 
 The new nomenclature could express every one of these salts with pre- 
 cision, but only in words of complexity corresponding to the complexity 
 of the salts upon whose formulae they would be framed. 
 
 I will, however, give a few examples of the names of these salts, 
 specifying the proximate constituents as they appear in the text at page 
 165: 
 
 1. AmH,S 2 O* 4- Am 8 S 4 O 3 . Ammona hydra bisulphate cum am- 
 
 monen sulphonite. 
 
 2. 2(AmH,S 2 O*) + PbH,S*O*. Bis ammona hydra bisulphate cum 
 
 plumba hydra bisulphate. 
 
 3. 2(Na 2 S 4 O 3 ) + Pb'S'O 3 . Bis natren sulphonite cum plwmben sul- 
 
 phonite. 
 
 4. 4(KH,S 2 O 8 ) 4- Pb 2 S 4 O 3 . Tetrakis plumba hydra bisulphate cum 
 
 plumben sulphonite. 
 
 The critic who feels disposed to censure the length of these names 
 will be pleased to bear in mind that they are not merely hard meaning- 
 less words, but that they contain an account of the composition of the 
 respective salts, and so render it needless to state that composition in the 
 description of the salts. 
 
 The pentathionates are compound salts of the kind that I propose to 
 call sulphates, such as BaSO,HSO,HSO,SSO, or BaSO,SSO,SSO. See 
 page 163. The names expressive of these two formulae are 
 
 ~BaSO,(HSO) 2 ,SSO. Baryta sulphate bis hydra sulphate cum sulpha 
 
 sulphate. 
 BaSO,(SSO) a . Baryta sulphate, bis sulpha sulphate. 
 
 But if the formula? of these salts are thrown into the closest synoptical 
 form, (which, however, hides the proximate constitution,) they become 
 
 BaH 8 ,S 5 0*. Baryta hydren sulphunote. 
 Ba,S 5 3 . Baryta sulphunite. 
 
 The tetrathionates are BaSO,SO 4- HSO,HSO. The first division of 
 this formula consists of BaSO combined with SO, just in the same 
 manner as the hyposulphates (page 172) consist of BaSO 8 combined 
 with SO. The other part of the formula consists of two atoms of the 
 hydrated acid HSO. These two atoms of acid seem to be liable to pro- 
 duce an anhydride, and so form the salt KSO,SO 4- SSO. 
 
 BaS*O*,(HSO) 2 . Baryta bisulphate bis hydra sulphate. 
 BaS*O*,SSO. Baryta bisulphate cum sulpha sulphate. 
 
 Expressed synoptically, these two salts will be 
 
THE OXALATES. 177 
 
 BaH 2 ,(SO) 4 = Baryta liydren ietrasulpliate. 
 Ba,S 4 O 3 = Baryta sulphonite. 
 
 The trithionates are ZnSO 1 + (HSO) 2 or ZnSO 4 + SSO. The first 
 part of this formula signifies the compound which is called at present 
 a sulphate, but which the new nomenclature changes to sulphete. The 
 other part of the formulas is similar to that of the tetrathionates. The 
 proposed nomenclature of the trithionates is as follows : 
 
 ZnH 2 S 3 O 4 = Zinca Jiydren sulphinote. 
 ZnS 3 O 3 = Zinca sulphinite. 
 
 The above classes of sulphur salts are, at present, of very little import- 
 ance in comparison with the following : 
 
 a). The salts which are now called SULPHATES, but which I propose 
 to term SULPHETES. 
 
 b). The salts now called SULPHITES. These are compounds of MSO 
 with MSO 8 , that is to say, of the two salts that, in the new nomencla- 
 ture, are called sulphates and sulphetes. The double salt assumes the 
 character of a bibasic salt K,K ; S*0 3 = POTASSEN SULPHENITE. 
 
 c). The salts that are at present called HYPOSULPHATES. These salts 
 ore composed of the salts now called sulphates, in combination with sul- 
 phurous acid. Thus KSO* + SO = K,S 8 O 3 = POTASSA SULPHENITE. 
 
 The Oxalates. 
 
 According to Professor Miller, the formula of hydrated oxalic acid is 
 HO, C 2 3 , and that of the oxalate of silver is AgO,C 2 O 3 . If I double 
 the atomic weight of the carbon and oxygen, these formulae become : 
 
 H, CO* = HYDRA CAEBETE. 
 Ag,CO 2 = ARGEXTA CARBETE. 
 
 Professor Miller gives the following account of the different classes of 
 oxalates : " With the alkalies, oxalic acid forms three classes of salts, 
 one of which contains one equivalent of base to one equivalent of acid, of 
 which the oxalate of ammonia (H 4 NO,C' 2 3 -|-aq) is an example. The 
 second class contains two equivalents of acid to one of a fixed base. Bin- 
 oxalate of potash, or the salt of sorrel (KO,HO, 2C 2 3 -f 2aq) is an 
 instance of this description; whilst the third class, which is exemplified 
 by quadroxalate of potash (KO,3HO,4C 2 3 -f4 aq), contains the unusual 
 proportion of four equivalents of acid to one of a fixed base. It is very 
 probable that oxalic acid belongs to the class of acids termed bibasic." 
 ELEMENTS OF CHEMISTRY, ii., p. 645. 
 
 R 
 
178 THE OXALATES. 
 
 On the Radical Theory, these salts may be represented thus : 
 
 ZH 4 , CO 8 -f- -- aq = Ammona carbete demi-aquate. 
 K,H ; (CO 2 ) 2 + aq = Potassa hydra bicarbete aquate. 
 K,H 3 ; (CO 2 ) 4 + 2 aq = Potassa hydrine tetracarbete aquete. 
 
 Gerhardt's account of the oxalates is as follows : 
 " Oxalic acid is a most energetic bibasic acid. 
 
 " The composition of the neutral oxalates is represented, in a general 
 manner, by 
 
 = C 4 6 = 2 (C 2 3 ,MO). 
 
 The binoxalates, or acid oxalates, contain 
 
 C 4 HM0 8 = C 4 6 = (C 2 3 ,HO + C 2 3 ,MO). 
 
 " There also exist quadroxalates ; that is to say, combinations of 
 oxalic acid with binoxalates : 
 
 C 4 HM0 8 
 
 o 8 ] 
 
 C 4 O 6 
 
 (M01 
 
 IHO 
 
 (HO 
 
 = (3C ? 3 ,HO + C 2 3 ,MO)." 
 
 IHO 
 
 Traite de Chimie Organique, torn. I. 243. 
 
 According to the radical theory, these salts are formulated as fol- 
 lows : 
 
 Neutral Oxalates. Acid Oxalates. Quadroxalates. 
 
 MCO 8 MCO 8 + HCO 8 , MCO 2 + 3CHCO 8 ), 
 
 or or 
 
 MH (CO 2 ) 2 MH 8 (C0 2 ) 4 . 
 
 The question whether oxalic acid is MONOBASIC or BIBASIC, is analo- 
 gous to the similar inquiry respecting sulphuric acid. The arguments 
 that have been maintained for and against the bibasicity of the latter bear 
 equally upon the bibasicity of the former. If the arguments of MM. 
 Gerhardt and Williamson, which I have quoted between | pages 144 
 and 156, prove to the reader that sulphuric acid is bibasic, then he 
 may assume at once that oxalic acid also is bibasic. If the arguments 
 which I have urged in reply to those chemists prove that sulphuric acid 
 is monobasic, they serve equally well to prove that oxalic acid is mo- 
 nobasic. I consider the question, therefore, as sufficiently examined, and 
 I assume the decision upon it to be that oxalic acid is MONOBASIC. 
 
THE OXALATES. 
 
 179 
 
 EXAMPLES OF OXALATES. 
 a. Oxalates with ONE basic radical : 
 
 H, CO 4 
 Am, CO* 
 K, CO 8 
 Na, CO 8 
 Ca, CO* 
 
 Ag, CO 8 
 Pb, CO 2 
 Zn, CO 8 
 Cuc,CO 8 
 Alc,C0 2 
 
 Fe, CO 8 
 Fee, CO 8 
 Hg, CO 8 
 Hgc,C0 8 
 Crc, CO 8 
 
 Co, CO 2 
 Ni, CO 8 
 U, CO* 
 CH 3 ,C0 2 
 C*H 5 ,CO* 
 
 b. Oxalates with TWO basic radicals : 
 
 AmCrc;C 2 4 
 AmMn ; C 2 O 4 
 KCuc; C^ 4 
 KZn ; C 2 4 
 KCrc; C^ 4 
 
 KSbc; C 2 4 
 KFec; C 2 O 4 
 NaAlc ; C 2 4 
 NaFec; C 2 O 4 
 NaCrc; C 2 4 
 
 BaAlcjC^ 4 
 BaFec; C*0 4 
 CaCrc; C 2 O 4 
 AgCrc; C 2 O 4 
 PbCrc;C 2 O 4 
 
 c. Oxalates with THREE basic radicals : 
 
 Am 2 ,Zn; (CO 2 ) 3 CaCrc* 
 
 d. Oxalates with FOUR basic radicals : 
 
 (CO 8 ) 3 
 
 CoCoc 3 ; (CO 8 ) 4 
 
 (ZH 3 Mn) 3 ,H; (CO 8 ) 4 
 
 AmH 3 ; (CO 3 ) 4 KCrc 3 ; (CO 8 ) 4 
 
 KH 3 ; (CO 2 ) 4 AmMg 3 ; (CO 2 ) 4 
 
 AmCrc 3 ; (CO 8 ) 4 
 
 e. Oxalates with FIVE basic radicals : Am 4 Cd ; (CO 8 ) 5 . 
 
 f. Oxalates with six basic radicals : Am 5 Mg ; (CO 8 ) 6 . 
 
 g. Oxalates with SEVEN basic radicals : 
 
 K 8 Sbc 8 H 8 ; (CO 2 ) 7 | Am 6 Mg; (CO 1 ) 7 . 
 
 A. Oxalates with EIGHT basic radicals : MgMn 7 ; (CO 8 ) 8 . 
 i. Oxalates with TEN basic radicals : 
 
 KWCuc 5 ; (CO 2 ) 10 | Am'Co; (CO 2 ) 10 . 
 
 j. Oxalates with ELEVEN basic radicals : 
 
 K 5 Sbc s ; (CO 2 ) 11 | Na 5 Sbc 6 ; (CO 8 ) 11 . 
 
 k. Oxalates with EIGHTEEN basic radicals: Am^Mg 5 ; (CO 2 ) 18 . 
 
 The particulars of these salts will be found in the following works : 
 Gmelin's Handbook of Chemistry, Vols. IX and X; Liebig's Handwor- 
 terbuch der Chemie, Band V., article Oxalsaure Salze; Gerhardt, 
 Traite de Chimie Organique ; and Liebig's Annalen for July, 1856. 
 
 The preceding Table shows that the oxalates, like the sulphates, com- 
 bine with one another to produce a great variety of complex salts. 
 
 N 2 
 
180 THE OXALATES. 
 
 They not only produce double salts, as is urged by the advocates of the 
 bibasic theory, who call the double salts, bibasic salts, but they produce 
 three-fold, five-fold, seven-fold, eleven-fold, and eighteen-fold oxalates, 
 which are by no means easy to reconcile with the bibasic theory. Nay, 
 even the salts with an even number of acid radicals, are often more 
 difficultly explicable on the bibasic than on the monobasic theory. Such 
 salts are : 
 
 AmCO 2 -f 3(MgC0 2 ) CoCO 2 + 9 (AmCO 2 ) 
 
 MgCO 2 + 7(MnC0 2 ) 
 
 CoCO 2 + 3(CocCO 2 ). 
 
 The formulas of the multiple oxalates which are given in the above 
 table, are much simpler than the formulae that are usually ascribed to 
 them. This is particularly the case with the salts of the BASYLIC 
 Metallic Radicals, which are distinguished in the Table by the final "c" of 
 their symbols. See page 3 3 . How this simplification of the formula? 
 is effected, I have explained by an example given at page 37 ; but in 
 order to leave no doubt on this subject, I will now examine one or two 
 more examples of complex oxalates. 
 
 " Chromic oxalate forms, with the oxalates of the alkalies and earths, 
 two series of salts, viz., dark-blue salts, which form bluish-green solu- 
 tions in water, and cherry-red or garnet-coloured salts, forming cherry- 
 red solutions in water. The formula of the blue salts is 3(MO,C 2 O : ') + 
 Cr 2 O 3 ,3C' J O 3 = C l8 M 3 Cr 2 O- 4 ; that of the red salts is MO,C 2 3 -f Cr 2 3 , 
 3 C 2 O 3 = C 8 MCr 2 16 ." Gmelin, Handbook of Chemistry, ix., 137. 
 
 Blue ammonia-chromic oxalate, 3(NH 4 0,C ? 3 ) + Cr'C^C'O 3 + 6aq. 
 Mitscherlich. This is equal to 
 
 N 3 H 12 Cr 2 C l2 24 + aq 6 . 
 
 I consider Cr 2 to be replaceable by Crc 3 , and I double the atomic weight 
 of the carbon and oxygen. The number of atoms then becomes : 
 
 N 3 H 12 Crc 3 C 6 12 + aq 3 . 
 
 All these numbers are divisible by 3, which reduces the atoms thus : 
 NH 4 CrcC 2 O 4 + aq 1 . 
 
 This gives us NH 4 CO 8 + CrcCO 8 + aq, or ZH 4 ,Crc; (CO 2 ) 2 -f aq, 
 which represents a double oxalate with one atom of water of crystal- 
 ization. All of the blue salts are of the same construction, and belong 
 to group b in the above Table. 
 
 ' 
 
 Red ammonia-chromic oxalate, NEPO,C 8 8 + Cr'O'^C'O 3 -f- 8 aq = 
 C"(NH 4 ,Cr 4 )O 16 + 8 aq, Gmelin. This is equal to 
 
 + aq 8 . 
 
THE OXALATES. 181 
 
 Making the same corrections as before, this becomes 
 
 NEPCrc^O 8 + Aq 4 . 
 
 These numbers are indivisible, and the compound requires the formula : 
 NH 4 C0 2 + 3(Crc,CO 2 ) -f- aq 4 = ZH 4 ,Crc 3 ; (CO 8 ) 4 + aq 4 . 
 
 This salt is therefore a quadroxalate, and belongs to group d in the 
 above Table. 
 
 Oxalate of magnesia and ammonia, with excess of the ammonia-salt. 
 2[C 4 (2NH 4 )0 8 ] + C 4 (Mg,NH 4 )O 8 + 4 aq. 
 
 The ultimate constituents of this compound are 
 
 N 5 H 20 Mg l C :2 24 + Aq 4 . 
 
 After doubling the atomic weight of carbon and oxygen, they become 
 NHMg l O'O u + Aq 2 . 
 
 These numbers are indivisible, and they consequently produce the 
 compound, (ZH 4 ) 5 Mg ; (CO 2 ) 6 + aq 2 = 5(ZH 4 ,CO<) + Mg CO* + aq' ; 
 which is the salt marked group f in the Table ; the aq 8 being 
 neglected. 
 
 Normal oxalate of alumina. = A1 2 O 3 , 3C*0 8 , Berzelius. = C 18 A1'0* 4 
 6W/w. = C 4 AlfO 8 , Gerhardt. 
 
 After substituting Ale 3 for Al a (see page 28), the formula A1 2 3 , 
 3C*0 3 becomes Alc 3 C 6 O 12 . After doubling the atomic weight of C and O, 
 this formula becomes Alc 3 C 3 6 . After division by 3, we have the 
 simple formula, AlcCO*, which brings the salt into group a. 
 
 Oxalate of alumina and baryta. 3(BaO,C 2 O 3 ) -f (A1 ? O 3 ,3C*0 3 ) 4. 
 10 aq and + 30 aq. [ = C 12 Ba"Al*0 24 -f- 10 and -f 30 aq.] Gmelin. 
 
 This salt is evidently of the same structure as the blue chromic 
 oxalates, and is liable to a similar reduction. 
 
 Ba 3 Al 2 C l2 24 = Ba 8 Alc 3 C 6 O 12 = BaAlcC^ 4 . 
 
 Consequently the salt belongs to group 6. 
 
 Ammonio-manganous oxalate. C 4 (NH 4 ,Mn)0 8 + 4 aq, Gmelin. This 
 formula is equal to ZH 4 ,Mn,(CO*) 2 + aq 2 . Group b. 
 
 Basic ammonio-manganous oxalate. 2NH 3 -}- C 4 (NH 4 ,Mn)0 8 + 
 C 4 MnO" + 8 aq, Gmelin. 
 
 These elements may be arranged thus : 
 
 'O 16 H 8 0", 
 
 And, after doubling the atomic weight of C and 0, they become 
 Z 3 H 9 l\In 8 H'C 4 O 8 H 8 O 4 ; 
 
182 THE OXALATES. 
 
 And these atoms may be grouped into a quadruple oxalate, thus : 
 ZH 3 Mn,C0 8 
 
 ZH 3 Mn,C0 8 
 
 ZH 3 Mn,C0 2 
 
 H,C0 8 
 
 aq 4 = (ZH 3 Mn) 3 ,H ; (CO 2 ) 4 + aq 4 . Group d. 
 
 The radical ZH 8 Mn is an ammonium, in which H l is replaced by 
 Mn l . The constitution of this class of azotised compounds will be 
 explained in a subsequent section. 
 
 These examples of oxalates are sufficient to show what clear and 
 intelligible formulae: can be given to the whole of them, when you 
 adopt the monobasic theory and abandon the hypothesis which assumes 
 that they contain the lumbering bases that are called sesquioxides. 
 
 NOMENCLATURE OF THE COMPLEX OXALATES. 
 
 AmCrc (CO 2 ) 8 Ammona chromic bicarbete. 
 Ba Ale (CO 8 ) 8 Baryta alic bicarbete. 
 Am 2 Zn (CO 2 ) 3 Ammonen zinca tricarbete. 
 AmCrc 3 (CO 2 ) 4 Ammona chrominic tetracarbete. 
 Am 4 Cd (CO 2 ) 5 Ammonon cadma pentacarbete. 
 Am 5 Mg(CO 2 ) 6 Ammonun magna hexacarbete. 
 
 It does not seem to be advisable to apply names to very complex 
 oxalates ; such as those contained in groups g to k. 
 
 TRIBASIC OXALATES. Besides the multiple salts of normal oxalates, 
 there exist some others of which a brief notice may be taken. The 
 following are tribasic salts, formed, like the tribasic phosphates, by the 
 combination of a normal salt, with a salt on the model of water : 
 
 a. H CO 2 + HHO = H 3 CO 3 Hydrine carbite. 
 
 b. UcCO 8 + UclJcO = Uc'CO 3 Urinic carbite. 
 
 c. PbCO 2 -f- PbPbO = Pb'CO 3 Plumbine carbite. 
 
 Salt a is the ordinary crystallized oxalic acid = C 4 H 2 8 + 4 aq, Gme- 
 lin. b is the normal uranic oxalate = C 4 ( 2 U 2 O 2 )0 8 , Gmelin. c is the 
 basic oxalate of lead = 4?bO-f C'Pb'O 8 , Gmelin. 
 
 TETRABASIC OXALATES. These are of similar constitution to the 
 pyrophosphates namely, they are compounds of normal oxalates with 
 tribasic oxalates. Examples : 
 
 a. AmCO 2 +Uc C0 8 ,UcUcO = AmUc 3 ,C 2 O 5 Ammona urinic carbenute. 
 
 b. K CO 2 +Uc C0 2 ,UcUcO = KUc 3 , CW Potassa urinic carbenute. 
 
 c. AmCO 2 +H CO 2 , HHO = AmH 3 , C^ 5 Ammona hydrinecarbenute. 
 
 d. Bic CO 2 -f Bic CO 2 , BicHO = HBic 3 , C 2 5 Hydra bisminic carbenute. 
 
 e. SbcC0 8 + SbcCO 2 ,SbcHO = HSbc 3 , CW Hydra stibinic carbenute. 
 
THE CARBONATES. 183 
 
 Usual names. a = oxalate of uranyle and ammonia = C 4 (U 2 0*)(NH 4 )O 3 , 
 Gerhardt. b - oxalate of uranyle and potash = C 4 K(IPO 2 )O 8 , Gerhardt. 
 c = acid oxalate of ammonia = C 4 (H,NH 4 )0 8 -f- 2 aq, Gmelin ; sometimes 
 called binoxalate of ammonia; in accordance with which we can, on the 
 radical theory, write the formula thus : AmCO 8 -{- HCO 2 -f- aq. There is 
 also a quadroxalate of ammonia, which Gmelin describes as the hyperacid 
 salt = C 4 (H,NH 4 )0 8 ,C 4 H*0 8 + 4 aq. This can be formulated either as 
 a quadroxalate, thus : AmCO 2 + 3HC0 8 + aq 2 , or as a double tetrabasic 
 oxalate, thus : 
 
 AmCO 8 + HC0 2 ,HHO 1 j AmH 3 ,C 2 O 5 ) . 
 HCO 2 + HC0 2 ,HHO j " ( H 4 ,C 2 O 5 ( = 
 
 d = Oxalate of bismuth = 2Bi0 3 ,2C 4 O 6 ,2HO. 
 
 e = Antimonic oxalate = C 4 (H,SbO 2 )O 8 , Gmelin. 
 
 The Carbonates. 
 
 " Though but a feeble acid, the carbonic acid unites with the metallic 
 protoxides, and forms a numerous and important class of salts which 
 are monobasic ; that is, they contain one equivalent of the acid to one 
 equivalent of the base, like carbonate of lime (CaO,CO 2 ). In the case 
 of the alkalies, a second equivalent of carbonic acid may be combined 
 with the metallic oxide ; thus with potash there is a carbonate (KO, 
 CO 8 ), and a bicarbonate (KO,HO,2CO 8 ) .... The carbonates have 
 considerable tendency to combine with each other, and form double 
 salts, like dolomite, which is a double carbonate of lime and magnesia 
 (MgO,CO 8 + CaO,CO e )." Miller, Elements of Chemistry (1856), 
 ii., p. 480. 
 
 These are the common opinions of chemists concerning the car- 
 bonates. 
 
 If I double the atomic weight of carbon and oxygen, the formula 
 for carbonate of potash becomes KKCO 3 , that of bicarbonate of potash 
 becomes KHCO 3 , and that of dolomite becomes MgCaCO 3 . In short, 
 carbonic acid becomes BIBASIC ; not bibasic in the sense in which the 
 sulphates and oxalates are assumed to be bibasic ; not endowed with a 
 bibasicity, which is so doubtful as to require a million of plausible 
 arguments to be advanced in support of it, and yet remain desperately 
 uncertain after all, but bibasic in a direct sense, the truth of which is 
 demonstrable, if you admit the atomic weight of C to be 12, and that 
 of to be 1 6. 
 
 This result of doubling the atomic weights of carbon and oxygen was 
 pointed out to chemists by Dr. Clark in the year 1826 (see page 8), 
 and was repeatedly urged upon their attention in my essay of 1834; 
 yet up to this day the carbonates are assumed to be monobasic, 
 
184 THE CARBONATES. 
 
 simply because chemists will not double the atomic weights of carbon 
 and oxygen : they will be forced to do it ultimately. 
 
 The oxalates being constituted thus: MO, CO, the carbonates are 
 constituted thus : MO,CO + MO. They are consequently basic oxalates. 
 
 MO, CO = Neutral Oxalates. 
 MO 4- (MO, CO) = Neutral carbonates. 
 HO 4- (MO,CO) = Bicarbonates. 
 MO 4- (MO,CO) = Double carbonates (dolomite, &c.). 
 
 NOMENCLATURE OF THE CARBONATES. 
 The names are framed on the synoptical formulae. 
 
 1. CaCa, CO 3 ... Calcen carbite. 
 
 2. KH, CO 3 . . . Potassa hydra carbite. 
 
 3. MgCa, CO 3 . . . Magna calca carbite. 
 
 4. BaCa, CO 3 . . . Baryta calca carbite. 
 
 5. ZH 4 H, CO 3 . . . Ammona hydra carbite. 
 
 6. FeFe, CO 3 . . . Ferrenous carbite. 
 
 7. FeMg CO 3 . . . Ferrous magna carbite. 
 
 8. PbPb, CO 3 ... Plumben carbite. 
 
 9. CecCec,CO 3 . . . Cerenic carbite. 
 
 Usual names. i, Carbonate of lime. 2, Bicarbonate of potash. 
 3, Carbonate of lime and magnesia, or bitterspar. 4, Baryta-calcite. 
 5, Bicarbonate of ammonia. 6, Iron spar, or carbonate of iron. 7, Me- 
 sitine-spar. 8, White lead ore, or native carbonate of lead. 9, Ceric 
 carbonate. 
 
 BASIC CARBONATES. The carbonates not only combine with each 
 other, but with water, and with salts formed on the model of water, 
 and thus produce a great variety of complicated basic salts. 
 
 EXAMPLES. 
 
 1 1. ZH 4 Mg,C0 3 -}- a q 8 ' Ammona magna carbite aquete = carbonate of 
 
 magnesia and ammonia, 
 
 1 2. 2(MgMg,CO 3 )4- 3(CaCa,CO 8 ). Bis magnen carbite tris calcen carbite 
 
 = dolomite. 
 
 13. CaCa,CO 3 + 3(MgMg,C0 3 ). Calcen carbite tris magnen carbite 
 
 = conite. 
 
 14. CucCiiCjCO 3 4- CucHO. Cuprenic carbite cum cupric hydrate 1 
 
 = blue copper ore. 
 
 15. CucCu^CO 3 -f- 2 (CucHO). Cuprenic carbite bis cupric hydrate 
 
 = malachite. 
 
 1 6. PbPb,CO 3 + PbHO. Plumben carbite cum plumbic hydrate 
 
 = white lead. 
 
THE CARBONATES. 185 
 
 17. PbPb,CO 3 + 2PbHO. Plumben carbite bis plumbic hydrate 
 
 = dicarbonate of lead. 
 
 1 8. NaNajCO 3 -f 4(PbPbCO 3 ). ISatren carbite tetrakis plumben carbite 
 
 = carbonate of lead and soda. 
 i o. MgMgCO* + aq. Magnen carbite aquate = Magnesia alba. 
 
 In some cases, the basic salts of a single metal are very numerous, 
 and present combinations for which it is difficult to provide simple 
 names. The following is an example of such a series : 
 
 19. Zn 2 CO 3 . Zincen carbite. 
 
 20. Zn 8 C0 3 -fZn 3 H 3 O 3 . Zincen carbite tris zinca hydrate. 
 
 21. Zn 2 C0 3 +Zn 2 H 4 O 3 . Zincen carbite cum zincen hydronite. 
 
 22. Zn 8 C0 3 -f-Zn 6 H 4 5 . Zincen carbite cum zincad hydronute. 
 
 23. (Zn 2 C0 3 ) 8 -f Zn 4 H 8 5 . Bis zincen carbite cum zincon hydradute. 
 
 24. Zn 2 C0 3 -f-Zn u H 4 9 . Zincen carbite cum zincabon hydronoze. 
 
 No. 1 9 is the neutral carbonate of zinc, or zinc-spar ; the others are 
 basic carbonates. The water of such salts is usually reckoned apart. 
 In these formulae and names, the hydrogen is placed with the oxygen 
 which is in excess of the quantity that belongs to the normal salt, and 
 the metal is reckoned by itself. This method gives a clear account of 
 the salts, but produces names that have an awkward appearance. Ex- 
 treme convenience and extreme accuracy in nomenclature must always 
 be difficult of combination in relation to basic salts, and chemists have to 
 determine to what extent, and under what circumstances, convenience 
 and accuracy shall give way to each other. 
 
 CARBONATES WITH COMPOUND POSITIVE RADICALS. 
 
 25. C 2 H 5 ,C 2 H 5 ; CO 3 . . Ethylen carbite. 
 
 26. CH 3 ,C 2 H 5 ;CO 3 . . Metlryla ethyla carbite. 
 
 27. K,C 2 H 5 ; CO 3 . . . Potassa ethyla carbite. 
 
 28. C 5 H I1 .C 5 H U ; CO 3 . . Amylen carbite. 
 
 29. C 2 C1 3 ,C 2 C1 5 ; CO 3 . . Chlorunic-ethylen carbite. 
 
 30. Ba,CH 3 ; CO 3 . . . Baryta methy la carbite. 
 
 31. C 4 H 9 ,C 4 H 9 ; CO 3 . . Butylen carbite. 
 
 Usual names. 25, Carbonic ether = C 10 H'0 6 , Gerhardt. Carbonate 
 of ethyl = C 4 H 5 O,CO 2 , Gmelin. 26, Carbonate of ethyle and methyle, 
 or ethyl-methyl-carbonic ether = COTO 6 , Gerhardt = C 4 H S O,CO 2 + 
 C 2 H 3 0,'C0 8 , Kolbe. 27, Carbethylate of potash = KO,C 4 H 3 O,C 2 4 , Miller. 
 
 28, Carbonate of amyl, or amylcarbonic ether = C 22 H 2 *O 6 , Gerhardt. 
 
 29, Perchlorinated carbonic ether = C 5 CPO 8 , Gmelin. Perchlorocarbonic 
 ether, or carbonate of perchlorinated ethyle = C IO C1 1( 'O 8 , Gerhardt. 30, 
 Carbomethylate of bary tes. 3 1 , Carbonate of butyle = C 9 H 9 0" = C 8 H 9 O, 
 CO 2 , Gmelin. Wurtz gives us the following choice of formulae : 
 
186 THE CHLOKIDES. 
 
 C 18 H 18 6 - 
 
 The Chlorides. 
 
 The composition of hydrochloric acid is represented by the formula 
 HC1 ; that of the ordinary neutral chlorides is represented by MCI. 
 
 Is hydrochloric acid a monobasic or a poly basic acid ? 
 
 Almost every chemist will reply that it is monobasic. 
 
 Yet we find such compounds as these, PtCP and AuCl 3 , which are 
 produced thus : 
 
 H 8 ,CP - H 8 + Pt = PtCl 2 + H 2 disengaged. 
 H 3 ,CP - H 3 + Au = AuCl 3 + H 3 disengaged. 
 
 If the replacement of H 8 and H 3 by equivalent quantities of other 
 positive radicals, when considered in reference to other negative radicals, 
 constitutes the characters of libasidty and terbasidty, why do we not 
 give to bichlorides the title of bibasic salts, and to terchlorides the title 
 of terbasic salts? Why are PtCP and AuCl 3 not written Ptc 2 CP and 
 Auc 3 CP? 
 
 Most chemists take shelter from this difficulty under Dalton's law of 
 combination in multiple properties. " It frequently happens," says Pro- 
 fessor Miller, " that chlorine combines with the same metal in more 
 proportions than one ; for example, with iron a protochloride (Fed) 
 and a sesquichloride (Fe 2 CP) may be formed ; with platinum a proto- 
 chloride (P1C1) and a bichloride (P1CP) may be obtained ; and gene- 
 rally, for each oxide of the metal which is capable of uniting with acids 
 to form salts, a corresponding chloride exists." Elements of Chemistry, 
 ii. 520. 
 
 Gerhardt treats the question as follows : 
 
 " The chlorides which correspond to mineral bases are monatomic, 
 biatomic, or triatomic, according as the bases are derived from one, or 
 two, or three, molecules of water. 
 
 a. Chlorides of monatomic bases : 
 
 Chloride of potassium . . . C1K. 
 Chloride of silver ..... ClAg. 
 Chloride of platinosum . . . CIPt. 
 ( = Protochloride of platinum.) 
 
 b. Chlorides of biatomic bases : 
 
 Chloride of platinicum . . . CPPt = CP j &' 
 ( Bichloride of platinum). 
 
THE CHLORIDES. 187 
 
 c. Chlorides of triatomic bases : 
 
 fal. 
 Chloride of aluminium . . . Cl'Al* = CIV al. 
 
 u 
 
 fbi. 
 
 Chloride of bismuth . . . . CPBi = CIV bi. 
 
 Ibi. 
 
 (au. 
 au. 
 au." 
 Traite de Chimie Organique, tome iv. 712. 
 
 Gerhardt's theory appears to me to be much preferable to the theory 
 which is commonly received by chemists, and which is expressed in the 
 above quotation from Professor Miller. The doctrine that two, or three, 
 and even five or seven atoms of chlorine, can combine with one atom 
 of a metal to form a chloride, seems to rest on no good foundation. 
 It is much simpler to suppose that every chloride is a compound of 
 two radicals, one atom of chlorine and one atom of metal, and this 
 view is in accordance with the constitution of most chlorides, provided 
 we agree with the doctrine that it is possible for certain metals to form 
 two different chemical atoms, the basylous and basylic atoms, which I 
 have explained in the article at page 32. 
 
 This doctrine is expressed in Gerhardt's propositions, quoted above, 
 but it is almost smothered by the "model of water" theory with 
 which the " chloride" theory is needlessly intermixed. 
 
 The salts that are referred to by Miller and Gerhardt in the above 
 quotations, I should formulate and name as follows : 
 
 Miller's : Fe Cl = Fe Cl . , Ferrous chlora. 
 
 Fe 2 Cl 3 = Fee Cl . . Ferric chlora. 
 
 Pt Cl = Pt Cl . . Platous chlora. 
 
 Pt Cl 2 = Ptc Cl . . Platic chlora. 
 
 Gerhardt's : Cl K = K Cl . . Potassa chlora. 
 
 Cl Ag = Ag Cl . . Argenta chlora. 
 
 Cl Pt = Pt Cl . . Platous chlora. 
 Cl 2 Pt = PtcCl . . Platic chlora. 
 
 Cl 3 Al 8 =AlcCl . . Alic chlora. 
 CPBi = BicCl . . Bismic chlora. 
 
 Cl'Au = AucCl . . Auric chlora. 
 
 The value of these symbols is given in the Table at page 28. 
 
 In this manner, these chlorides are all representable as monatomic 
 chlorides, or salts of monobasic hydrochloric acid. I cannot perceive 
 that any advantage is derived from Gerhardt's triple formulae, such as : 
 
188 THE CHLORIDES. 
 
 al. f hi. f au. 
 
 Cl 3 <! al. Cl 3 1 bi. Cl 3 \ an. 
 
 al. ( bi. ( an. 
 
 These symbols remind one of the arithmetic of a savage, who can 
 only mark 3 by marking i three times. 
 
 The notion that every chloride is a salt containing but one atom of 
 chlorine is, no doubt, liable to certain exceptions such, for example, 
 as the pentachlorides of antimony and of phosphorous, which com- 
 pounds, like the pentasulphides, I confess myself unable to reconcile 
 with the common salts of the radical theory. I do not, indeed, be- 
 lieve that P 5 and S 5 ever combine directly with one atom of another 
 radical, yet I am not prepared to offer any other satisfactory explana- 
 tion of this difficulty. There is a discovery yet to be made in reference 
 to the functions of these multiples of S, Cl, and some other elements. 
 Some kind of compound radical is probably produced, but of a kind 
 that is not at present comprehended. 
 
 MULTIPLE CHLORIDES. The chlorides combine with each other to 
 produce double, triple, and quadruple chlorides. 
 
 EXAMPLES OF DOUBLE CHLORIDES. 
 
 1. ZH 4 ,Cuc; Cl 2 . . . Ammona cupric chloren. 
 
 2. ZH 3 Alc,Alc; Cl 8 , . Alicam alic chloren. 
 
 EXAMPLES OF TRIPLE CHLORIDES. 
 
 3. Am,Mg 2 ,Cl 3 .... Ammona rnagnen chlorine. 
 
 4. ZH 3 Alc,Alc 2 ,Cl 3 . . Alicam alenic chlorine. 
 
 5. K,Ptc 2 ,Cl 3 .... Potassa platenic chlorine. 
 
 6. Am,Ptc 2 ,Cl 3 .... Ammona platenic chlorine. 
 
 Usual names. i, Protochloride of copper and ammonium, NH 3 ,HC1 
 -f CuCl, Gmelin. 2, See azotic radicals, No. 60. 3, Double chloride of 
 magnesium and ammonium =NH 4 Cl,2MgCl. 4, See azotic radicals, 
 No. 61. 5, See platinum, No. 20. 6, See platinum, No. 22. All 
 these triple chlorides admit of another formula, viz., 
 
 AmCl + 2MgCl = Ammona chlora bis magna chlora. 
 
( 189 ) 
 
 Theory of Azotic Eadicals. 
 
 The radical azote combines with other radicals to produce compound 
 positive radicals. In doing this, it controls the affinities of those 
 radicals to such an extent, that their ordinary saturating capacities are 
 totally paralysed, and remain so as long as the combination endures. 
 This power of control azote exercises in two degrees. 
 
 First degree. ONE atom of azote combines with TWO radicals to 
 form a triple compound ; which may be represented by the formula 
 ZMM, which compound, consisting of three radicals, has a saturating 
 power equal to that of one radical ; in other words, the saturating 
 capacities of the two radicals, MM, are paralysed, and the radical Z 
 alone retains its saturating power. 
 
 Second degree. ONE atom of azote combines with FOUR radicals to 
 form a quintuple compound, which may be represented by the formula, 
 ZMMMM ; which compound, consisting of five radicals, has a saturat- 
 ing power equal to that of one radical ; so that here again the saturating 
 capacities of four radicals are paralysed. 
 
 The symbol M in these formulae signifies hydrogen, or any metal, or 
 any hydrocarbon which has, separately, the properties of a radical, 
 either positive or negative. 
 
 The metalloids, Cl,Br,I, the element oxygen, and all nitrogenous 
 compounds, are excluded from the number of the radicals that can com- 
 bine with azote to produce the compound radicals, now under con- 
 sideration. This exclusion is strictly insisted on ; because many chemists 
 allow themselves a great licence in this particular. But while Cl, Br, 
 and I are excluded, as radicals, from among the radicals that can replace 
 M in the compounds ZM 2 and ZM 4 , it is not intended to exclude the 
 vice-radicals of which these metalloids are constituents by substitution. 
 See page 131. No hydrocarbons are excluded from the replacing radi- 
 cals, for even those of the most powerful negative energies are capable 
 of producing ammoniums, and lose their saturating capacities while 
 under the domination of azote. 
 
 This governing power is exercised by azote only in these two degrees, 
 and the products of its action are so far under the control of the che- 
 mist, that he can at pleasure experimentally convert the compound 
 ZM 2 into the compound ZM 4 , and the compound ZM 4 into the compound 
 ZM 2 ; but this he can do only while the compounds are in combination 
 with other radicals. He is unable to isolate either ZM 2 or ZM 4 , and 
 their existence is consequently not to be proved by experiment, but only 
 to be inferred from circumstantial evidence, the nature and extent of 
 which we proceed to take into consideration. 
 
 It is to be understood, therefore, that this " theorv of the azotic 
 
190 THEORY OF AZOTIC RADICALS. 
 
 radicals" is not to be a bare enumeration of facts, but is to include the 
 exposition of a " THEORY " of the azotic radicals, and a theory, too, 
 which differs in a great many respects from any that has hitherto been 
 submitted to the consideration of chemists. After tracing the outline 
 of the theory, I shall adduce a multitude of facts and examples to sup- 
 port it. 
 
 When an azotic radical of the first order = ZM 2 contains hydrogen 
 only, it produces the compound ZH 8 , which is commonly called ami- 
 dogen. This term it is proposed to abridge to AMID, which is then to 
 be made subject to the numeral terminals which have been proposed for 
 all radicals, namely 
 
 ZH 2 . (ZH 2 ) 2 . (ZH 2 ) 3 . 
 
 Amida. Amiden. Amidine. 
 
 When this radical assumes the form ZHM or ZMM, it is to be con- 
 sidered as a VICE- AMID, or substitute for the normal amid, ZH 2 . 
 
 When an azotic radical of the second order ZM 4 contains hydrogen 
 only, it produces the compound ZH 4 , which is commonly called 
 ammonium. This term it is proposed to abridge to AMMON, which is to 
 be made subject to the usual numeral terminals ; thus 
 
 ZH 4 . (ZH 4 ) 2 . (ZH 4 ) 3 . 
 
 Ammona. Ammonen. Ammonine. 
 
 When the radical ZH 4 assumes any of the forms ZH 3 M, ZH'M 8 , 
 ZHM 8 , ZM 4 , it is to be considered as a ViCE-AMMON, or substitute for 
 the normal ammon ZH 4 . 
 
 The symbol M in the above formulae signifies either a metallic radical 
 or a hydrocarbon radical. 
 
 NOMENCLATURE OF VICE-AMIDS AND VICE-AMMONS. 
 
 Since the vice-amids and vice-ammons differ from normal amid and 
 normal ammon only by containing metallic radicals, or compound radi- 
 cals, in place of hydrogen, atom for atom, it follows, that if the names 
 of such vice-amids and vice-ammons can be made to nominate and enu- 
 merate the replacing radicals, they will give all the information that is 
 requisite for the accurate discrimination of the respective compounds. 
 Such a nomenclature can be arranged as follows : 
 
 A. Discrimination of Vice-Amids. 
 
 Case a. Suppose H 1 in ZH 2 to be replaced by a hydrocarbon, say 
 phenyl C^H 5 , so as to produce the vice-amid ZH,C 6 H 5 . The name is 
 to be PHENYLAC, where phenyl indicates the replacing radical ; a shows 
 
NOMENCLATURE OF VICE-AMIDS AND VICE-AMMONS. 191 
 
 the number of replacing atoms, and c is an arbitrary sign which sig- 
 nifies a vice-amid. 
 
 Case b. Suppose H 2 in ZH 2 to be replaced by two atoms of the same 
 hydrocarbon, say (C 6 H 5 ) 2 , producing a vice-amid of the form Z^H 5 , 
 C 8 H 5 , or Z(C 6 H 5 ) 2 . The name is to be PHENYLEC, which differs from 
 the former only in having the letter e to intimate the presence of 
 two atoms of phenyl, instead of the letter a to intimate a single 
 atom. 
 
 Case c. When H 2 in ZH 2 are replaced by two different hydrocarbons, 
 say Methyl CH 3 and Amyl C 5 H U , producing the vice-radical, Z^H 3 , 
 (FIT 1 . The name is to be METHYLIC-AMYLAC, where the name of the 
 more basic of the two radicals is used as an adjective to qualify the 
 name imposed on the vice-amid by the other more acid radical. See 
 page 73. 
 
 Case d. When the replacing radical is a metal. The name is then 
 derived from the abridged names of the metals that are given in the last 
 column of the Table of Elements, printed at page 28. Examples : 
 
 ZHK = POTASSAC. ZHAg = ARGENTAC. ZKK = POTASSEC. 
 
 But if the replacing metal is one of those which have two different 
 chemical atoms (the basylous and basylic atoms), the distinctive marks 
 of those different atoms must be retained in the name of the vice-amid. 
 See pages 33 and 87. Examples: 
 
 ZHHg - MEKOUSAC. ZHHgc = MERICAC. 
 
 B. Discrimination of Vice-Ammons. 
 
 The vice-ammons can be distinguished from one another by a nomen- 
 clature exactly similar in principle to that which has been applied to 
 the vice-amids, only changing the arbitrary terminal of each name from 
 e to m. 
 
 Case e. The vice-ammon is represented by the formula ZH 3 ,C 2 H R . 
 Name : ACETYLAM. This name indicates an ammonium in which one 
 atom of hydrogen is replaced by one atom of acetyl = C 2 H 3 . Any other 
 hydrocarbon may occur in place of acetyl. This is the most numerous 
 and most important class of the vice-ammons. 
 
 Case/. The replacing radical is a metal. Formula : ZH 3 Ag. Name : 
 ARGENTAM. 
 
 Case g. The replacing radical is a basylous metal. Formula : ZEPCu. 
 Name : CUPROUSAM. 
 
 Case h. The replacing radical is a basylic metal. Formula : ZH 3 Ptc. 
 Name: PLATICAM. 
 
 Case i. The replacement of PTjEP.H 8 ,!! 4 , in ZH 4 , by a similar 
 number of other radicals, produces a series of compounds which require 
 
192 THEORY OF AZOTIC RADICALS. 
 
 names of the following forms ; methyl is taken as an example, but any 
 other radical may occur instead. 
 
 ZH 3 ,CH 3 . Name: METHYLAM. 
 
 ZH*(CH 3 ) 2 . METHYLEM. 
 
 ZH (CH 3 ) 3 . METHYLI.M. 
 
 Z (CH 3 ) 4 . METHYLOM. 
 
 Case k. When the hydrogen in ZH 4 is replaced by two different 
 radicals. The names are regulated in this case on the principle that has 
 been described under case c. 
 
 Examples : 
 
 Z,CH 3 ,(C 2 H 5 ) 3 . Name : METHYLIC-ETHYLIM. (a.) 
 
 ZH*,C 2 H 3 ,C 6 H 5 . ACETYLIC-PHENYLAM. (b.) 
 
 ZH.Cfl^CW.C'H 7 . TOLUENYLIC-ETHYLEM. (c.) 
 
 The name (a) intimates that the vice-ammon is an ammonium in which 
 H s have been replaced by three atoms of ethyl (C 2 H 5 ) 3 , and which would 
 therefore simply require the name etliylim ; but, as the fourth atom of 
 hydrogen has been replaced by methyl CH 3 , it is necessary to qualify the 
 name of the vice-ammon by the prefix methylic-. In like manner, the 
 name (6) intimates the modification that is made in a phenylam, or an 
 ammonium that contains one atom of phenyl, by the replacement of 
 another atom of its hydrogen by acetyl. Finally, the name (c) intimates 
 that the vice-ammon contains two atoms of ethyl and one atom of 
 toluenyl. In this case, the name of the single atom is used to qualify 
 the name afforded by the two atoms. This is with a view to simplicity 
 in nomenclature. But as toluenyl is an acid radical, this practice is con- 
 trary to the rule laid down under case c ; to which rale, however, it is 
 easy to conform by describing ZH,C 2 H 5 ,C 2 H 5 ,C 7 H 7 as ethylenic-tolu- 
 enylam. 
 
 Case I. When a vice-ammon contains more than two kinds of radicals 
 besides hydrogen, the name must at present consist of a mere enumera- 
 tion of its constituents. 
 
 Examples : 
 
 Z,CH 3 ,C 2 H 5 ,C 2 H 5 , C 5 H U . Name : Zot-methyla-ethylen-amyla. 
 Z,CH 3 ,C 2 H 5 ,C 5 H U ,C 6 H 5 . Zot-methyla-ethyla-amyla-phenyla. 
 
 The name now applied to Z,CH 3 ,C 2 H 5 ,C 2 H 5 ,C 5 H 11 is methylodiethyl- 
 amylammonium, so that in this case, the new nomenclature is merely 
 not retrograding. When we know a greater number of the compounds 
 of this class, we may be able to form a more compendious nomenclature 
 for them. 
 
 The terminals applied to the names of zotic radicals can never be mis- 
 taken for those that are recommended to be applied to radicals proper, 
 
KELATION OF AMIDS TO AMMONS. 193 
 
 or to oxidised radicals. See page 86. The names are therefore not only 
 short, but in every case exact and free from doubt. 
 
 For the sake of the convenience which is afforded when we can speak 
 of different classes of compounds in general terms, it is proper to add the 
 following definitions : 
 
 Amid is the normal compound ZH 2 . The vice-amids are of two 
 kinds ; amidacs, in which H 1 is replaced by another radical = ZHM ; 
 and amidecs in which H 2 are replaced by two other radicals = ZMM. 
 
 Amman is the normal ammonium ZH 4 , with which the common 
 symbol Am is equivalent. The vice-ammons are of four kinds : 
 
 Ammonam = ZH 3 M. 
 Ammonem = ZH 2 M 2 . 
 
 Ammonim = ZHM 
 Ammonom = ZM 4 . 
 
 When M in these formula is replaced by the symbol of a compound 
 radical, the words amid and ammon in the corresponding names, are to 
 be replaced by the names of the replacing radicals; Thus : 
 
 ZH,C 6 H 5 = Phenylac. 
 Z(C 5 H 11 ) 2 = Amylec. 
 
 ZH 3 ,C 6 H 5 = Phenylam. 
 Z(C 5 H U ) 4 = Amyiom. 
 
 RELATION OF THE AMIDS TO THE AMMONS. 
 
 The amids and ammons of every description usually act in salts as 
 positive radicals. The basic properties of the ammons are stronger than 
 those of the amids ; hence the amids can act as negative radicals towards 
 the ammons. Different amids can also act as negative and positive 
 radicals towards one another. Generally, but not always, nor necessarily, 
 the salts of the amids with oxygen acids, contain one atom less of 
 oxygen than is contained in the corresponding salts formed by the 
 ammons. The reason of this is, that the governing power of the azote 
 is, so to speak, expansive and contractive, and can be made, at the will 
 of the chemist, to control either MM or MMMM ; in consequence of 
 which property, the salts of the amids and ammons are reciprocally con- 
 vertible the one into the other by reactions that are expressed in the 
 following equations : 
 
 (a.) (ZMMMM)O + RO = [(ZMM) + RO] + M,MO; 
 
 or, synoptically, ZM 4 ,RO 2 = ZM 2 ,RO + M,MO. 
 (6.) [(ZMM) + RO] + M,MO = (ZMMMM)O + RO; 
 
 or, synoptically, ZM 2 ,RO + M,MO = ZM 4 ,RO 2 . 
 
 w r here R signifies any acid radical ; M = H or any equivalent of H. 
 
 In reaction a, two radicals are removed from the salt in company 
 with one atom of oxygen. The salt is thereby reduced to a lower degree 
 of oxidation, and the ammon is converted into an amid. In reaction 6, 
 the operation is reversed. 
 
 o 
 
194 THEORY OF AZOTIC RADICALS. 
 
 Conversion of Ammons into Amids. 
 These equations may be illustrated by a special example : 
 
 Let ZH 4 = Ammonium. 
 ZH 2 = Amidogen. 
 
 Let K^CO 2 = Oxalic acid. 
 H,HO = Water. 
 
 The radical ZH 4 can be made to displace the radical H in oxalic acid 
 H,CO*, and to produce the salt ZH 4 ,C0 2 , or, as it may be expressed in an 
 analytical formula, ZH 4 O,CO. This salt is commonly called oxalate of 
 ammonia, or oxalate of oxide of ammonium. By an experiment, the 
 details of which do not belong to the question under consideration, the 
 oxalate of ammonia can be decomposed into two other salts, thus : 
 
 ZH 4 + CO = ZH 2 ,CO + H,HO. 
 
 Oxalate of Ammonia. Oxamid. Water. 
 
 In oxalate of ammonia we have a salt that is NOT formed on the model 
 of water ; for whereas water contains one oxidised radical and one un- 
 oxidised radical, this salt contains two oxidised radicals. In process a, 
 one of these radicals, ZH 4 , is split up, by chemical means, into three 
 radicals, ZH 2 ,H,H, ; and these three radicals, with the single atom of 
 carbon and the two atoms of oxygen, produce two salts that are really 
 formed on the model of water ; one of them being actually water H,HO, 
 and the other a salt whose structure is similar to that of water ZH 2 ,CO. 
 This salt is commonly called oxamid. In accordance with the proposed 
 new nomenclature, it would be called AMIDA CARBATE ; this name 
 serving to indicate one atom of unoxidised amidogen acting as a basic 
 radical against one atom of carbon, acting as an acid radical in combina- 
 tion with one atom of oxygen. The doctrine of the formation of salts on 
 the model of water is particularly valuable in aiding the explanation of 
 the precise action of the azotic radicals. There cannot be the least doubt 
 that as water is the hydrate of hydrogen = H + HO, namely, a salt con- 
 taining two radicals, so oxamid is the carbate of amidogen = ZH 2 -f- CO, 
 also a salt containing two radicals ; and as this explanation of the equa- 
 tion a applies, not only to salts of normal amidogen and normal ammo- 
 nium, but to salts of all the varieties of vice-amids and vice-ammons, it 
 is of great importance. 
 
 Conversion of Amids into Ammons. 
 
 In regard to equation 6), it needs only to be remarked, that the ex- 
 planation of it is, like the formula, only the inversion of that of equation 
 a). When oxamid ZH 2 ,CO is subjected, by proper chemical means, to 
 the action of H,HO, the governing power of Z is enlarged, the non- 
 oxidised amid ZH 2 becomes reconverted into the oxidised ammon ZH 4 O, 
 
DOUBLE SALTS OF AMIDS AND AMMONS. 195 
 
 and the original salt, the oxalate of ammonia, ZH 4 O,CO or ZH 4 ,C0 2 , is 
 thoroughly reconstituted. 
 
 Double Salts containing Ammons and Amids. 
 
 The salts of the amids and the salts of the ammons have a great ten- 
 dency to combine with one another, and thus to produce double salts. 
 Hence, oxamid ZH 2 ,CO combines with oxalate of ammonia ZH 4 ,C0 2 , to 
 produce the double salt which is represented by the following for- 
 mulas : 
 
 This salt is commonly called oxamate of ammonia, in consequence of 
 the prevalence of a notion that it is the ammonia-salt of an acid which 
 is called OXAMIG ACID, and which acid is assumed to contain amidogen as 
 PART of its Acid Radical, The radical theory repudiates the idea that 
 any acid radical can contain amidogen as one of its constituents, and ac- 
 cording to the radical theory, oxamic acid is a double salt, consisting of 
 oxamid and hydrated oxalic acid, thus : 
 
 ZH 2 ,CO + H r ,C0 2 = H r ,ZH 2 ; C 2 O 3 . 
 
 Present ) Q id + Oxalic add = Qxamic acid. 
 
 Names. \ 
 
 rop& I Amida carbate + Hydra carbete = Hydra amida carbenite. 
 
 In these formulas, H r signifies an atom of hydrogen that is replaceable 
 by a positive radical, either a metal or a hydrocarbon. 
 
 This double salt can, like oxamid, have its unoxidised amid experi- 
 mentally enlarged by the addition of HHO to oxidised ammon ; the 
 consequence of which enlargement is, that the so-called oxamic acid is 
 converted into binoxalate of ammonia. Thus : 
 
 H* ZH* C*0 3 or I ZH2 ' CO 1 + HHO - \ ZH4 ' C 2 
 \ ,Z,1 , O U , or | H jC()2 j - i H ,C0 2 . 
 
 What has been said here respecting the metamorphoses of the ammon 
 and amid of a salt that has carbon for its acid radical, is equally true of 
 salts that have negative hydrocarbons for their acid radicals ; of which 
 fact numerous examples will appear in the following Tables : 
 
 NOMENCLATURE OF THE DOUBLE SALTS OF AMIDS AND AMMONS. 
 
 The name of a double salt which contains a salt of an amid combined 
 either with a neutral salt of an ammon, or of any single radical, may be 
 
 02 
 
196 THEORY OF AZOTIC RADICALS. 
 
 framed either on the analytical formula or the synoptical formula. The 
 latter gives the most compendious name, and will be generally used. 
 Examples : 
 
 a. Where the Acid Radical is Carbon. 
 
 H, ZH 2 ; C 2 O 3 = Hydra amida carbenite. 
 ZH*,ZH 2 ; C*O 3 = Ammona amida carbenite. 
 Ag, ZH 2 ; C 2 O 3 = Argenta amida carbenite. 
 CH 3 ,ZH 2 ; C 2 3 = Methyla amida carbenite. 
 
 b. Where the Acid Radical is a Hydrocarbon. 
 
 H, ZH 2 ; (C 2 HW = Hydra amida succinylenite. 
 
 Ag,ZH 2 ; (C 2 H 2 ) 2 O 3 = Argenta amida succinylenite. 
 
 H; ZH,C 6 H 5 ; (C 5 H 7 ) 2 3 = Hydra phenylac camphorylenite. 
 
 The analytical formula of the last salt is as follows : 
 
 ZH,C 6 H 6 ; C 5 H 7 + H,C 5 H 7 O S . 
 Name : Phenylac camphorylate cum Hydra camphorylete. 
 
 Some of the salts that contain amids are volatile. None of the salts 
 that contain ammons are volatile. Some of the double salts that con- 
 tain both amids and ammons are volatile ; but they have not yet been 
 thoroughly examined. 
 
 GASEOUS SALTS OF AMIDOGEN. 
 
 In the preceding development of the theory of the azotic radicals, the 
 word ammonia has been intentionally avoided. But it it is now time to 
 explain what is meant by that word, and I commence by requesting the 
 reader to examine the notice of ammonia that has been already given 
 at page 99. It is there stated, and it is to be here repeated, that am- 
 monia is not a radical, but a SALT. Its composition is commonly 
 represented by the formula NH 3 . M. Gerhardt gives it as 
 
 H. 
 H 
 
 H 
 
 In accordance with the present theory, it is ZH 2 + H, which formula 
 represents it to be a salt ; namely, a hydride of the radical ZH 2 . This 
 salt ammonia has, in the state of gas, an atomic measure of two volumes, 
 which in itself is almost a proof, and certainly affords a strong pre- 
 sumption, that the gas is a compound of two radicals. All the volatile 
 hydrides of vice-amids, which are represented at page 99, agree with 
 ammonia in this characteristic property of having an atomic measure of 
 
SALTS OF AMIDS AND AMMONS DISCRIMINATED. 197 
 
 two volumes, and there is probably no exception to this general rule. 
 It is reasonable to infer, therefore, that all the hydrides of vice-amids 
 are, like ammonia, not radicals, but salts compounds of two radicals. 
 
 In page 100, another table is given of a series of the gaseous com- 
 pounds, which are commonly called salts of ammonia, of which salts, 
 the one named sal-ammoniac, or hydrochlorate of ammonia, may be 
 taken as the model. These salts have each, in t^ie gaseous state, an 
 atomic measure of four volumes, which is an indication of the presence 
 of four radicals, or the constituents necessary to produce a double salt 
 in each compound. When we examine the formula of sal-ammoniac, 
 we find it to be ZH 2 ,H -f- H,C1. We have here the whole materials of 
 two salts, the hydride of amidogen, which of itself is known to mea- 
 sure two volumes, and the hydride of chlorine, or hydrochloric acid, 
 which also is known to measure two volumes. These two salts, known to 
 exist separately, and each having the measure of two volumes, combine 
 without condensation to produce the double salt, the hydrochlorate of 
 ammonia, which has consequently an atomjc measure of four volumes, 
 because it is a compound of four radicals = (ZH 2 -f- H) + (H -f Cl). 
 
 But upon this explanation there follows a difficulty. When sal- 
 ammoniac is brought into the state of solid crystals, it forms a com- 
 pound which, in its form, and in many of its chemical characters, closely 
 agrees with the salt that is called chloride of potassium. Now, chlo- 
 ride of potassium is considered to be a direct compound of potassium 
 with chlorine, a Unary compound in accordance with the formula KC1 ; 
 and we have to account for the peculiar circumstance, how it is, that 
 a compound of two radicals, a simple salt = KC1, should appear to be 
 the counterpart of a salt, the gaseous properties of which indicate it to 
 be a double salt of the formula ZH 2 ,H + H,C1. The only rational ex- 
 planation of this difficulty seems to be, that the elements which consti- 
 tute sal-ammoniac form in fact, under different circumstances, two dif- 
 ferent salts. In the gaseous state, they produce a double salt the 
 hydrochlorate of ammonia = ZH' 2 ,H -f- H,C1, and in the solid and aque- 
 ous states they produce a simple salt = the chloride of ammonium, 
 ZH 4 -f- CL In other words, the gaseous salt contains amidogen, and 
 the solid salt contains ammonium. In the solid state, the government 
 of azote is exercised over H 4 ; in the gaseous state it is limited to H 2 . 
 Admitting the facts, that the salts of the vice-amids are frequently vola- 
 tile, and those of the vice-ammons are always fixed, this explanation is 
 quite in accordance with our experimental evidence, and approaches as 
 nearly to demonstration as circumstantial evidence can be reasonably 
 expected to do. 
 
of Ammonium. 
 
 198 THEORY OF AZOTIC RADICALS. 
 
 SALTS OF AMMONIUM. 
 
 The theory which I have just explained applies to all the compounds 
 that are commonly called salts of Ammonia and Ammonium ; in fact to 
 all the salts that are formed by the combination of ammonia with 
 hydrated acids, whether oxidised or non-oxidised. Thus it applies to 
 the following salts : 
 
 Proposed Names. Present Names. 
 
 ZH 4 ,C1 = Ammona chlora = Chloride 
 
 ZH 4 ,Br = Ammona broma = Bromide 
 
 ZH 4 ,I = Ammona ioda = Iodide 
 
 ZH 4 ,Cy = Ammona cyana = Cyanide 
 
 ZH 4 ,S0 2 = Ammona sulphete = Sulphate 
 
 ZH^NO 3 = Ammona nitrite = Nitrate f A 
 
 ZH 4 ,C0 2 = Ammona carbete = Oxalate ofAmmonia - 
 
 ZH^ITO 8 = Ammona acetylete = Acetate 
 
 The salts that are produced by the combination of ammonia with 
 anhydrous oxygen acids will be described in the course of the following 
 investigation. 
 
 AMMONIATED SALTS. 
 
 Under the head of ammoniated salts, chemists commonly place a series 
 of compounds which have not been alluded to in the preceding theory. 
 They consist of neutral salts, either of hydracids or oxacids, combined 
 with two atoms of ammonia. The following are examples of such salts 
 expressed in the formulae in common use : 
 
 a. Ammoniated chloride of silver = AgCl + 2H 3 N. 
 6. Ammoniated nitrate of silver = AgO,NO 5 + 2H 3 N. 
 c. Ammoniated sulphate of copper = CuO,S0 3 -f- 2H 3 N. 
 
 [In these formulas = 8.] 
 
 The formulae provided for these compounds by the theory now under 
 discussion are as follow : 
 
 a. ZH 8 Ag,Cl + ZH 2 ,H = Argentam chlora cum Amida hydra. 
 
 b. ZiPAg^O 3 4- ZH 2 ,H = Argentam nitrite cum Amida hydra. 
 
 c. ZH 3 Cuc,SO 2 + ZH 2 ,H = Cupricam sulphete cum Amida hydra. 
 
 According to the new theory, these compounds are all regular double 
 salts. Half the ammonia converts the metal of each salt into an ammo- 
 nam. The other half combines as a salt, the hydride of amidogen, with 
 the ammonium salt, to produce a compound salt. This method of ex- 
 planation will be found to clear away a variety of difficulties which ac- 
 company the ordinary theories respecting the compound mercury and 
 platinum bases. See the section on salts of platousam. 
 
( 199 ) 
 
 Examples of Azotic Eadicals. 
 
 Having briefly explained the proposed theory of azotic radicals, I 
 proceed to support its principles, and develop its details, by adducing a 
 number of examples. 
 
 The salts which contain azotic radicals are so numerous and varied, 
 and they figure in chemical books under so many different names and 
 formulae, and are made the foundation of so much classification and 
 theorizing, that it is difficult to compress a lucid account of them into 
 the narrow space which is necessarily allotted to them in this Essay. 
 
 I have to prove that the proposed theory is of general applicability ; 
 that its formulas are accurate ; and that its nomenclature is sufficiently 
 flexible and comprehensive to answer the purpose for which it is recom- 
 mended. 
 
 This proof requires a considerable number of examples. I have col- 
 lected nearly a thousand. They do not by any means constitute a com- 
 plete catalogue of the salts of the azotic radicals, but they afford 
 specimens of the most characteristic varieties. I have arranged them in 
 groups which will exhibit the different classes of salts of the azotic 
 radicals. I have given them the names and formulae that are demanded 
 by the radical theory, and I have added a series of explanatory notes, 
 which contain the ordinary names and formulae of the selected salts, and 
 serve not merely to identify them, but to lead to the discussion of a 
 series of knotty questions respecting azotic radicals, upon which at 
 present the opinions of chemists are either divided or unsettled. 
 
 These notes will, however, neither depict all the formulae, nor recite 
 all the synonymes, which the ingenuity of chemists has contrived for these 
 so-called " organic bases," which substances infinitely exceed all other 
 chemical compounds in the variety of the fancy costumes in which they 
 have been made to masquerade. 
 
 Ammonias. 
 
 SECTION i. AMMONIAS, in WHICH H l is REPLACED by ANOTHER 
 RADICAL. HYDRIDES of AMIDACS. 
 
 1. ZH,C 5 H U 
 
 2. ZH,C 2 H 3 
 
 3. ZH,C 4 H 9 
 
 4. ZH,C 8 H 13 
 
 5. ZH,C 9 H 11 
 
 6. ZH,C 2 H 5 
 
 H . . . Amylac hydra. 
 
 H . . . Acetylac hydra. 
 
 H . Butylac hydra. 
 
 H . . . Conylac hydra. 
 
 H . . . Cumenylac hydra. 
 
 H . . . E thy lac hydra. 
 
 7. ZH,C 2 H 3 P;H . . . lodenic-ethylac hydra. 
 
 8. ZH,C H; H . . . Formylac hydra. 
 
 9. ZH,C 9 H 5 ; H . . . Leukylac hydra. 
 
200 AMMONIAS, 
 
 10. ZH,CH 3 ; H ... Methylac hydra. 
 
 11. ZH,C 10 H 7 ; H . . . Naphtylac hydra. 
 
 12. ZH,Na; H .... Natrac hydra. 
 
 13. ZH,C 8 H 17 ; H . . . Octylac hydra. 
 
 14. ZH,C 6 H 5 ;H . . . Phenylac hydra. 
 
 15. ZH,C 6 H 4 C1;H . . . Chloriophenylac hydra. 
 
 1 6. ZH,C 6 H 3 Cl 2 ; H . . Chlorenic-phenylac hydra. 
 
 17. ZH^H'Br; H . . . Bromiopheny lac hydra. 
 
 1 8. ZH,C 6 H 3 B 2 ; H . . . Bromenic-phenylac hydra. 
 
 19. ZH,C 6 H 4 I;H . . . lodic-pheny lac hydra. 
 
 20. ZHK ; H .... Potassac hydra. 
 
 21. ZH,C 3 H 7 ; H . . . Propylac hydra. 
 
 22. ZH,C 7 H 7 ;H . . . Tolueny lac hydra. 
 
 23. ZH,C 5 H 9 ;H . . . Valerylac hydra. 
 
 24. ZH^H^H . . . Xylenylac hydra. 
 
 SECTION 2. AMMONIAS in WHICH H 2 ARE REPLACED by OTHER 
 
 RADICALS. 
 
 A). AMIDACS COMBINED WITH ACID RADICALS. 
 
 25. ZH,C 2 H 5 ; C 2 H 3 . . . Ethylac acetyla. 
 
 26. ZH,C 6 H 5 ; C 7 H 5 . . . Phenylac benzyla. 
 
 27. ZH,CH 3 ; C 2 H 5 . . . Methylac ethyla, 
 
 28. ZH,C 2 H 3 ; C 6 H 5 . . . Acetylac phenyla. 
 
 29. ZH,C 5 H U ; C 6 H 5 . . . Amylac phenyla. 
 
 30. ZH^H 5 ; C 6 H 5 . . . Ethylac phenyla. 
 
 31. ZH,C 2 H 5 ; C 6 H 4 C1 . . Ethylac chloric-phenyla. 
 
 32. ZH,C H 3 ; C'H 5 . . . Methylac phenyla. 
 
 33. ZH, K;C 6 H 5 . . . Potassac phenyla. 
 
 34. ZH^H 5 ; (^H 7 . . . Ethylac propy la. 
 
 35. ZH,C 2 H 5 ; C 7 !! 7 . . . Ethylac toluenyla. 
 
 B). HYDRIDES OF AMIDECS. 
 
 36. Z,C 5 H U ,C 5 H U ; H . . Amylec hydra. 
 
 37. Z,C a H 5 ,C 2 H 5 ; H . . Ethylec hydra. 
 
 38. Z,CH 3 ,CH 3 ; H. . . Methylec hydra. 
 
 39. Z^H^H 7 ; H . . Propylec hydra. 
 
 SECTION 3. AMMONIAS IN WHICH H 3 ARE REPLACED BY OTHER 
 
 RADICALS. 
 
 SALTS OF AMIDECS. 
 a. The three Radicals are unlike. 
 
 40. Z,C H 3 ,C 2 H 5 ; C 5 H 11 . Methylic-ethylac amyla. 
 
 41 . Z,C 2 H 5 ,C 5 H U ; C 6 H 5 . . Ethylic-amylac phenyla. 
 
 42. Z,C H 3 ,C 2 H 5 ; C 6 H 5 . . Methylic-ethylac phenyla. 
 
AMMONIAS. 201 
 
 b. The three Radicals are alike. 
 
 43. Z,C 5 H U ,C 5 H 11 ; C 5 H 11 . . Amylec amyla. 
 
 44. Z^H^H 33 ; C 16 H 33 . . Cetylec cetyla. 
 
 45. Z,C 2 H 5 , C 2 H 5 ; C 2 H 5 . . Ethylec ethyla. 
 
 46. Z,CH 3 ,CH 3 ; CH 3 .... Methylec methyla. 
 
 47. ZCu,Cu; Cu ..... Cuprousec cuprous. 
 
 48. ZHgc,Hgc; Hgc. . . . Mericcec meric. 
 
 49. Z K,K ; K ...... Potassec potassa. 
 
 c. Two basic and one acid Radical. 
 
 50. Z,C 2 H 5 , C 2 H 5 ; C 5 H U . . . Ethylec amyla. 
 
 51. Z,C 5 H U ,C 5 H U ; C 2 H 5 . . . Amylec ethyla. 
 
 52. Z,C 2 H 5 , C 2 H 5 ; C H 3 . . . Ethylec methyla. 
 
 53. Z,C 5 H ll ,C 5 H H ; C 6 H 5 . . . Amylec phenyla. 
 
 54. Z^H 5 , C 2 H 5 ; C 6 H 5 . . . Ethylec phenyla. 
 
 55. Z,C 2 H 5 , C 2 H 5 ; C 6 H 4 C1 . . Ethylec chloric-phenyla. 
 
 56. Z,C 2 H 5 , C 2 H 5 ; C 7 H 7 . . . Ethylec toluenyla. 
 
 USUAL NAMES AND FORMULAE OF THE AMMONIAS. 
 
 No. i. ZH,C 5 H n ; H is commonly denoted by one of the three fol 
 lowing formulae : 
 
 C l H n 
 C 10 H 13 N, or C 10 H U ,H 2 N, or N H 
 
 These three formulas (in which C = 6) may be taken as models of 
 the formulae that are usually given to the ammonias Nos. I to 24 in the 
 list, and it is consequently needless to quote them all. In the same way, 
 the ammonias have not only a variety of formula?, but a variety of 
 names; No. i, for example, being called amylamine, amylia, and 
 azoture (or nitride) of amyl and of hydrogen. I shall, for the sake of 
 brevity, only quote such of these names as serve either to identify the 
 compounds, or to exhibit some of the vagaries of chemists, or to illustrate 
 important or disputed doctrines: i, Amylamine. 2, Acetylamine ; 
 acetylia. 3, Butylamine; butyria; tetrylia. 4, Conine; conia. 5, Cu- 
 midine. 6, Ethylamine ; ethylia. 7, lodethylamine. 8, Formylia. 
 9, Leukol; quinoline. i o, Methylamine ; methylia. 1 1 , Naphtylamine. 
 12, Azoture of sodium and hydrogen. 13, Octylia; caprylia. 14, Ani- 
 line ; phenylamine ; phenylia ; phenylamide ; crystalline ; krystallin ; 
 kyanol; benzidam. 15, Chloraniline. 16, Bichloraniline. 17, Bro- 
 maniline. 18, Bibromaniline. 19, lodaniline. 20, Amidide of potas- 
 
202 SALTS OF VICE-AMMONIUMS. 
 
 slum. 21, Propylamine; tritylia ; tritylamine; metacetamine ; ceny- 
 lam ine. 22, Toluidine. 23, Piperidine. 24, Xylidine. 
 
 25, Ethyl-acetylia. 26, Benz-anilide. 27, Methyl-ethylamine. 28, 
 Phenylacetylia. 29, Amylophenylamine ; amylaniline. 30, Ethylaniline, 
 ethyphenylamine. 31, Ethyl-chloraniline. 32, Methylaniline. 33, 
 Anilide of potassium. 34, Ethyl-propylamine. 35, Ethyl-toluidine. 
 
 36, Diamylamine. 37, Diethylamine ; diethylia. 38, Dimethyla- 
 mine; dimethylia. 39, Dipropylamine. 
 
 40, Methyl-ethyl-amylamine. 41, Ethyl-amylo-phenylamine. 42, 
 Methyl-ethylo-phenylamine. 43, Triamylamine ; triamylia. 44, Tri- 
 cetylia; tricetylamine. 45, Triethylamine. 46, Trimethylamine. 47, 
 Azoture of cuprosum. 48, Nitride of mercury. 49, Azoture of potas- 
 sium. 
 
 50, Biethylo-amylamine. 51, Biamylo-ethylamine. 52, Methyl-die- 
 thylamine. 53, Diamylo-phenylamine. 54, Biethylaniline. 55, Bie- 
 thyl-chloraniline. 56, Diethyltoluidine. 
 
 Salts of Yice-Ammons. 
 
 The following is a list of Salts of VICE-AMMONS ; that is to say, of 
 Salts of Ammonium, in which the Hydrogen has been more or less re- 
 placed by other Radicals. 
 
 GROUP A. AMMONAMS = ZH 3 M. 
 
 57. ZHV^ 3 ; Cl .... Acetylam chlora. 
 
 58. ZH 3 ,C 2 H 3 ;HO. . . . Acetylam hydrate. 
 
 59. ZH 3 ,Alc; Cl .... Alicam chlora. 
 
 60. ZH 3 ,Alc; Cl -f- AlcCl . . Alicam chlora cum alic chlora. 
 
 61. ZH 3 ,Alc; Cl + 2 AlcCl . Alicam chlora bis alic chlora. 
 
 62. ZH 3 ,Ag; C B H 8 8 . . . Argentam indylite. 
 
 63. ZH 3 ,Ag ; CrO 8 + ZH J H . Argentam chromete cum amida 
 
 hydra. 
 
 64. ZH 3 Ba ; C 8 H 8 O 8 . . . Barytam indylite. 
 
 65. ZH 3 ,C 4 H 9 ; Cl . . . . Butylam chlora. 
 
 66. ZH 8 ,Coc ; CO 2 + ZIFH . Cobalticam carbete cum amida 
 
 hydra. 
 
 67. ZH 3 ,Cuc; CO 9 . . . . Cupricam carbete. 
 
 68. ZH 3 ,Cuc ; CO* -f CucCO 2 Cupricam carbete cum cupric 
 
 carbete. 
 
 69. CucCO 2 + ZH 4 ,C0 2 . . Cupric carbete cum ammona 
 
 carbete. 
 
 70. ZH 3 ,C 2 H 5 ; CO 2 . . . . Ethylam carbete. 
 
 71. ZH 3 ,C*H 5 ; HO. . . . Ethylam hydrate. 
 
 72. ZH 3 ,C 2 H 5 ; Cl .... Ethylam chlora. 
 
SALTS OF VICE-AMMONIUMS. 
 
 203 
 
 73- ZH 3 ,C 2 H 5 ; Br . . . . 
 
 Ethylam broma. 
 
 74. ZH 3 ,C' 2 H 5 ; Cl + 3AucCl 
 
 Ethylam chlora tris auric chlora. 
 
 75. ZH 3 ,C 2 H 5 ; Cl + HgcCl . 
 
 Ethylam chlora cum meric 
 
 
 chlora. 
 
 76. ZH 3 ,CH 3 ;C0 2 .... 
 
 Methylam carbete. 
 
 77. ZH 3 ,CH 3 ; CO 2 + HCO 2 . 
 
 Hydra methylam bicarbete. 
 
 78. ZH 3 ,CH 3 ;C1 .... 
 
 Methylam chlora. 
 
 79. ZH 3 ,CH 3 ; Br . . . . 
 
 Methylam broma. 
 
 80. ZH 3 ,CH 3 ; I .... 
 
 Methylam ioda. 
 
 81. ZH 3 ,CH 3 ; Cl + HgcCl . 
 
 Methylam chlora cum meric 
 
 
 chlora. 
 
 82. ZH 3 ,CH 3 ; Cl + 3AucCl . 
 
 Methylam chlora tris auric 
 
 
 chlora. 
 
 83. ZH 3 ,C 10 H 7 ; Cl . . . . 
 
 Naphtylam chlora. 
 
 84. ZH 3 ,C 10 H 7 ; Br . . / . 
 
 Naphtylam broma. 
 
 85. ZH 3 ,C 10 H 7 ; I .... 
 
 Naphtylam ioda. 
 
 86. ZH 3 ,Ni; CO* 4- NiCO* . 
 
 Nicollousam carbete cum ni- 
 
 
 collous carbete. 
 
 87. ZH 3 ,C 6 H 5 ; CO 2 ... 
 
 Phenylam carbete. 
 
 88. ZH 3 ,C 6 H 4 Br; CO 8 . . . 
 
 Bromic-phenylam carbete. 
 
 89. ZH 3 ,C 6 H 4 I ; CO 2 . . . 
 
 lodic-phenylam carbete. 
 
 90. ZH 3 ,C 6 H 5 ;Br .... 
 
 Phenylam broma. 
 
 91. ZH 3 ,C 6 H 5 ; Cl . . . . 
 
 Phenylam chlora. 
 
 92. ZH 3 ,C 6 H 5 ; I .... 
 
 Phenylam ioda. 
 
 93. ZH 3 ,C 6 H 4 Br;Cl . . . 
 
 Bromic-phenylam chlora. 
 
 94. ZH 3 ,C 6 H 4 C1; Cl . . . 
 
 Chloric-phenylam chlora. 
 
 95. ZH 3 ,C 6 H 4 I;C1. . . . 
 
 lodic-phenylam chlora. 
 
 96. ZH 3 ,C 6 H 5 ;Cl + 2PtcCl . 
 
 Phenylam chlora bis platic 
 
 
 chlora. 
 
 97. ZH 3 ,C 6 H 5 ; PO 3 ... 
 
 Phenylam phosphite. 
 
 98. (ZH 3 ,C 6 H 5 V,H; PO 4 . . 
 
 Phenylamen hydra phosphote. 
 
 99. ZH 3 ,C 6 H 5 ;H*;P0 4 . . 
 
 Phenylam hydren phosphote. 
 
 100. (ZH 3 ,C 6 H 5 ) 2 ,H* ; P*0 7 
 
 Phenylamen hydren phos- 
 
 
 pheneze. 
 
 1 01. ZH 3 ,K ; C 8 H 3 3 . . . 
 
 Potassam indylite. 
 
 102. ZH 3 ,C 7 H 7 ; Cl . . . . 
 
 Toluenylam chlora. 
 
 103. ZH 3 ,C 7 H 7 ; Cl-f 2 PtcCl . 
 
 Toluenylam chlora bis platic 
 
 
 chlora. 
 
 104. ZH 3 ,C 7 H 7 ; Cl + 3AucCl 
 
 Toluenylam chlora tris auric 
 
 
 chlora. 
 
 105. ZH 3 ,C 7 H 7 ; CO 2 + HCO 2 
 
 Hydra toluenylam bicarbete. 
 
 GROUP B. AMMONEMS = ZH 2 M 2 . 
 
 106. ZH 2 ,Hgc 8 ; Cl . . . . 
 
 Mericcem chlora. 
 
 107. ZH*(CH 3 ) 2 ; I .... 
 
 Methylem ioda. 
 
204 
 
 SALTS OF VICE-AMMONIUMS. 
 
 108. ZH 2 ,C 2 H 5 ,C 10 H 7 ;I . . Ethylic-naphtylam ioda. 
 
 109. ZH 2 ,Hgc,C 6 H 5 ; Cl . . Meric-phenylam chlora. 
 no. ZH 2 (C 7 H 5 ) 2 ;HO . . . Benzylem hydrate. 
 
 in. ZH 2 ,C*H 5 ,C 6 H 5 ; Br . . Ethylic-phenylam broma. 
 H2. ZH 2 ,C 2 H 5 ,C 7 H 7 ; Cl-f 2 PtcCl Ethylic-toluenylam chlora bis 
 
 platic chlora. 
 
 GROUP C. AMMONIMS = ZHM 3 . 
 
 113. ZH,(C 5 H U ) 8 ;CI . . 
 
 114. ZH,(CH 3 ) 3 ;I . . . 
 
 115. ZH,C 2 H 5 ,C 2 H 5 ,C 6 H 5 ;Br 
 
 1 1 6. ZH,C 2 H 5 ,C 2 H 5 ,(7H 7 ; I 
 ZH,C 2 H 5 ,C 2 H 5 ,C 5 H U ; Cl 
 
 117. 
 
 2PtcCl 
 
 Amylim chlora. 
 Methyl im ioda. 
 Phenylic-ethylem broma. 
 Toluenylic-ethylem ioda. 
 Amylic-ethylem chlora bis 
 platic chlora. 
 
 GROUP D. AMMONOMS ZM 4 . 
 
 ii8. 
 119. 
 
 1 20. 
 
 121. 
 122. 
 I2 3 . 
 
 124. 
 125 
 
 ZH 4 
 ZH 4 
 ZH 4 
 ZH 4 
 ZH 4 
 ZH 4 
 
 HO . . 
 Cl . . 
 CO 2 . . 
 H;(CO 2 ) 2 
 
 H 3 ; (CO 2 ) 4 
 C 8 H 3 3 . 
 
 Z(C 5 H M ) 4 ; I . 
 
 Z(C 5 H a ) 4 ;HO 
 
 126. Z(C 2 H 5 ) 4 ; Cl . 
 
 127. Z(C 2 H 5 ) 4 ;I . 
 
 128. Z(C 2 H 5 ) 4 ;HO . 
 
 129. Z(C 8 H 5 ) 4 ;C1 + 
 
 130. Z(C 2 H 5 ) 4 ; 
 
 131. Z(CH 3 ) 4 ;I. 
 
 132. Z(CH 3 ) 4 ; HO 
 
 133. Z(CH 3 ) 4 ; Cl 
 
 , ZCC'H'^C'H 11 
 
 136. 
 
 . Z(C 2 H 5 ) 8 ,C 5 H 11 
 2PtcCl 
 
 2PtcCl 
 
 I. 
 
 H 
 
 C1 
 
 138. 
 139. 
 140. 
 
 ; HO 
 
 2PtcCl 
 
 Ammona hydrate. 
 Ammona chlora. 
 Ammona carbete. 
 Hydra ammona bicarbete. 
 Hydrine ammona tetracarbete. 
 Ammona indylite. 
 Amylom ioda. 
 Amy lorn hydrate. 
 Ethylom chlora. 
 Ethylom ioda. 
 Ethylom hydrate. 
 Ethylom chlora bis platic 
 
 chlora. 
 Ethylom chlora tris auric 
 
 chlora. 
 
 Methylom ioda. 
 Methylom hydrate. 
 Methylom chlora bis platic 
 
 chlora. 
 
 Mericom carbete. 
 Amylic-ethylim ioda. 
 Amylic-ethylim hydrate. 
 Amylic-ethylim chlora bis 
 
 platic chlora. 
 
 Phenylic-ethylim hydrate. 
 Toluenylic-ethylim hydrate. 
 Toluenylic-ethylim chlora bis 
 
 platic chlora. 
 
SALTS OF VICE-AMMONIUMS. 205 
 
 141. ZCH 3 ,(C 2 H 5 ) 3 ; I . . . . Methylic-ethylim ioda. 
 
 rrrms /^2Tj5 r<2TT5 n5Tjn T I Zot-methyla-ethylen-amyla 
 
 142. ZCH ,C tt ,O tt , C i ; J < . , 
 
 lOvlci* 
 
 143. Z,CH 3 ,C 2 H 5 ,C 2 H 5 ,C 5 H U ; Cl J Zot-methyla-ethylen-amyla 
 
 -f- 2PtcCl | chlora bis platic chlora. 
 
 7 PUS n*TJ5 psTTn pews . T J Zot-methyla-^thyla-amyla- 
 
 1 44. Z,U ,0 M ,0 . 1 ,0 | phenyla ioda. 
 
 y PUS P2TT5 psTTii P6U5 WO J Zot-methyla-ethyla-amyla- 
 
 145. Z,LhL ,C H ,C i ,L U j p henyla hydrate. 
 
 146. Z,CH 3 ,C 2 H 5 ,C 5 H 11 ,C 6 H 5 ; Cl I Zot-methyla-ethyla-amyla-phe- 
 
 + 2PtcCl \ nyla chlora bis platic chlora. 
 
 USUAL NAMES AND FORMULA OF THE SALTS OF THE VICE- 
 AMMONS. 
 
 GEOUP A. AMMONAMS = ZH 3 M. Nos. 57 to 105. 
 
 57, Chlorhydrate of acetosamine. 58, Hydrated oxide of acetylium. 
 59, Chloride of alumina with ammonia = 3NH 3 ,APC1 3 . 60, Ditto, in- 
 termediate between 59 and 61. 61, Ditto = NH 3 ,A1 2 C1 3 . See Gmelin's 
 Handbook, hi. 320. 62, Isatate of silver, see Indigo, No. 7]. 63, 
 Argento-chromate of ammonia = NH 3 AgO -f- NH 3 ,CrO 3 , Gmelin. 64, 
 Indigo, 7]. 65, Hydrochlorate of butylamine = C"NH II ,HC1, Gmelin. 
 66, Cobaltic oxalate with ammonia = 1 2NH 3 + C'WO 24 + 6 aq., 
 Gmelin. The occurrence of a basylic atom in company with ammonia is 
 so uncommon that this analysis is probably incorrect. 67, Cupric oxalate 
 with two atoms of ammonia = 2NH 3 ,C 4 Cu 2 O 8 , Gmelin. 68, Ditto with 
 i atom ammonia = NH 3 ,C 4 Cu 2 O 8 , Gmelin. 69, Ammonio-cupric oxalate 
 = C 4 (NH 4 ,Cu)0 8 , Gmelin. 1 70, Oxalate of ethylamine = C 4 (C 4 H 8 N) 2 8 , 
 
 Gmelin. 71, Hydrate of ethyl-ammonium = O < AT/PSTTSNTTS Gerhardt. 
 
 72, Hydrochlorate of ethylamine, or chloride of ethylium = C 4 H 7 N,HC1 
 or C 4 H 8 N,C1, Gmelin. 73, Equivalent to 72. In this and similar cases 
 it seems needless to repeat the names and formulae merely to exchange 
 Cl for Br and I. 74, Chloro-aurate of ethylamine = C 4 H 7 N, HC1 
 + AuCl 3 or C*H 8 NCl,AuCl 8 ,- Gmelin. 75, Chloro-mercurate of ethyla- 
 mine = C 4 H 7 N,HC1 + HgCl, Gmelin. 76, Oxalate of methylamine 
 = C 4 (C 2 H 6 N) 2 8 , Gmelin. 77, Binoxalate of methylamine - C 4 (H, 
 (?BL*N)<y, Gmelin. 78, Chloride of methyl-ammonium = C1,N(CH 3 )H 3 , 
 GerJiardt. Hydrochlorate of methylamine = C 2 H 5 N,HC1, Gmelin. 79, 
 
 1 Nos. 67 and 69 contain water of crystallization, which is not ex- 
 pressed in the above formulee. I shall, for the sake of brevity, omjt 
 water of crystallization in all cases where it does not affect the argu- 
 ment. 
 
206 SALTS OF VICE-AMMONIUMS. 
 
 and 80, Equivalent to 78. 81, Chloro-mercurate of methylamine = 
 C*H 5 N, HC1, HgCl, Gmelin. 82, Chloro-aurate, equivalent to 81. 
 83, Chlorhydrate of naphtylaraine = C^H'NjHCl, Gerhardt. 84 and 
 85, Equivalent to 83. 86, Oxalate of nickel with ammonia = NH 3 
 4- CWC", Gmelin. 87, Oxalate of aniline = C 2 O 3 ,C 12 H 7 N + HO, 
 Hofmann, 88, Oxalate of bromaniline = C 2 3 ,C l2 (H 6 ,Br)N,HO, Hof- 
 mann. 89, Analogous to 88. 90 to 95, See Aniline, Nos. 12 to 17.' 
 96, Platinum-salt of the hydrochlorate of aniline. 97 to 100, See 
 Aniline, Nos. 32 to 35.] 101, Isatate of potash, see Indigo, No. 7.]' 
 I O2, Hydrochlorate of toluidine. 103, Platin-chloride of toluidine. 
 104, Aurochloride of toluidine. 105, Binoxalate of toluidine. 
 
 GROUP B. AMMONEMS = ZH 2 M 2 . Nos. 106 to 112. 
 1 06, Mercuric amido-chloride ; infusible white precipitate = Hg,NH" 
 + HgCl, Kane = H^N + HgCl + NH 4 C1, Rammelslerg = N ( 51)c9, 
 
 Watts. 107, Iodide of dimethylammonium = (H,H,C 2 H 3 ,C 2 H 3 )NI, 
 Hofmann. 108, Iodide of ethyl-naphthylammonium. 109, See Aniline 
 22J. 1 10. Dibenzoylimide = C^H^NO 2 , Robson. in, Hydrobro- 
 mate of ethylophenylamine. 112, Chloroplatinate of ethyl-toluidine. 
 
 GROUP C. AMMONIMS = ZHM 3 . Nos. 113 to 117. 
 
 1 1 3, Hydrochlorate of triamylamine = C SO H 83 N,HC1 = (C 10 H U ) 3 N,HC1, 
 Hofmann. 1 14, Iodide of trimethylammonium = (H,C 2 H 3 ,C 2 H 3 ,C 2 H 3 )NI, 
 Hofmann. 115, Bromide of diethylophenylammonium. 116, Iodide 
 of methyl-toluenylammonium. 117, Platinum-salt of diethylamylam- 
 monium. 
 
 GROUP D. AMMONOMS = ZM 4 . Nos. 1 1 8 to 1 46. 
 
 1 1 8, Hydrated oxide of ammonium, or solution of ammonia in water 
 = NH 3 ,HHO. 119, Chloride of ammonium, or hydrochlorate of 
 ammonia; see page 197. 120, Oxalate of ammonia; see page 194. 
 Normal salt = C 4 (2NH 4 )O 8 , Gmelin. 121, Acid oxalate of ammonia 
 = C 4 (H,NH 4 )O 8 , Gmelin. 122, Hyperacid oxalate of ammonia = 
 (7(H,NH 4 )0 B ,C*BW, Gmelin. 123, Isatic acid; see Indigo, 8.] 
 124, Iodide of tetramylammonium = (C 10 H U ) 4 NT, Hofmann. 125, 
 Hydrated oxide of tetramylammonium = (C l H n ) 4 NO,HO, Hofmann. 
 126, Chloride of tetrethylammonium = (C 4 H 5 ) 4 NC1. 127, Iodide of 
 tetrethylammonium = (C 4 H 5 ) 4 NI, Hofmann. 128, Hydrated oxide of 
 tetrethylammonium = (C 4 H 5 ) 4 NO,HO, Hofmann. 129, Platinum-salt 
 
 1 In the cases where compounds are fully explained in the sections 
 headed Indigo, Aniline, &c., instead of repeating the explanations, I 
 shall refer to them by numbers. 
 
SALTS OF VICE-AMMONIUMS. 
 
 207 
 
 of tetrethylammonium = (C 4 H 5 ) 4 NCl,PtCl 2 , Hofmann. 1 130, Gold salt 
 of tetrethylammonium = (C 4 H 5 ) 4 NCl,AuCl 3 , Hofmann. 131, Iodide of 
 tetramethylammonium = (C 2 H 3 ) 4 NI, Hofmann. 132, Hydrated oxide 
 of tetramethylammonium (C 2 H 3 ) 4 NO,HO. 133, Platinum-salt of tetra- 
 methylammonium = (C 2 H 3 ) 4 NC1, PtCl 2 , Hofmann. 134, Oxalate of 
 tetramercurammonium = (^(NHg 4 )^ 8 , GerJiardt. 135, Iodide of tri- 
 ethylamylammonium (C 4 H 5 ) 3 , C 10 H n , NI. 136, Hydrated oxide of 
 triethylamylammonium. 137? Platinum-salt of triethylamylammonium. 
 138, Hydrated oxide of triethylophenylammonium C 12 H 5 (C 4 H 5 ) 3 NO,HO, 
 Hofmann. Gmelin assumes in this salt the presence of a compound 
 which he calls trivinanilin = C^NH 19 = C 12 (C 4 H 5 ) 3 NH 2 ,H 2 . 139, Hy- 
 drated oxide of triethyl-toluenylammonium. 140, Chloroplatinate of 
 triethyl-toluenylammonium. 141, Iodide of triethylomethylammonium 
 = C 2 H 3 (C 4 H 5 ) 3 NI, Hofmann. 142, Iodide of methylodiethylamyl- 
 ammonium. 143, The platinum -salt of the chloride of methylodiethyl- 
 
 amylammonium = C^H^NCljPtCl 2 = 
 
 Q! H NCl,PtCl 2 , Hofmann. 
 
 
 C io H 1 
 
 
 C 2 H 3 
 
 
 144, Iodide of methylethylamylophenylammonium = 
 
 C 4 H 5 
 C io H u 
 
 NI, Hof- 
 
 mann. 145, The hydrated oxide of methylethylamylophenylammonium, 
 Hofmann. 146, The platinum-salt of the last base 
 
 C 2 H 3 
 C 4 H 5 
 
 QIOJJll 
 
 NCl,PtCl 2 , Hofmann. 
 
 1 Dr. Hofmann's formulas of the ammonoms are generally written in 
 the following style, which, in this instance, and in many other instances, 
 I have compressed in the text to save room : 
 
 |C 4 H 5 
 ^s NCl,PtCl 8 . 
 OH 5 
 
 What advantage is gained by inflating the formula of an ammonium 
 until it occupies four lines ? 
 
( 208 ) 
 
 Investigation of the Compounds which are produced 
 by the abstraction of Water from the Salts of 
 Ammonia. 
 
 " The salts of oxide of ammonium, both neutral and acid, when 
 subjected to the influence of heat, lose either two or four equivalents of 
 water, 1 four classes of compounds being thus produced ; neutral oxalate 
 of oxide of ammonium by the loss of two equivalents of water becomes 
 oxamide, while by the elimination of four equivalents of water cyanogen 
 or oxalo-nitrile is formed. Binoxalate of ammonia, when losing two 
 equivalents of water, is converted into oxamic acid. A compound arising 
 from the binoxalate by the loss of four equivalents of water has not as 
 yet been formed ; this term, however, is found to be represented among 
 the derivatives of the ammonia-salts of various other acids, e. #., of cam- 
 phoric and phthalic acids, camphorimide and phtalimide being bicam- 
 phorate and biphtalate of ammonia 4 equivalents of \vater. We 
 may thus distinguish as derived from the ammonia-salts by loss of 
 water 
 
 1 . Amides. 
 
 2. Nitriles. 
 
 3. Amidogen-acids. 
 
 4. Imidogen- compounds. (Imides)." 
 
 Hofmann, Quarterly Journal of the Chemical Society (1849), ii. 331. 
 
 I have copied Dr. Hofmann's classification, because it has been adopted 
 by several chemists. I propose to examine the constitution of the com- 
 pounds which constitute these four classes, and to show in what forms 
 they respectively appear when viewed in the light of the Radical 
 Theory. 
 
 1 In Hofmann's numbers two equivalents of water = HO + HO. 
 This is only one equivalent on the radical theory = H,HO. 
 
( 209 ) 
 
 Amids produced by the abstraction of one atom of 
 HHO from the Neutral Oxalates of Vice- Ammo- 
 niums. 
 
 147. ZH 2 ;CO ..... Amida carbate. 
 
 148. ZH,C 6 H 5 ; CO ... Phenylac; carbate. 
 JZH,C 6 H 5 ; CO) JPhenylac'carbate cum amida 
 
 I 49-|ZH 2 ; COf ' ' ' \ carbate. 
 
 150. ZH,C H 3 ; CO . . . Methylac carbate. 
 
 151. ZH,C 2 H 5 ; CO . . . Ethylac carbate. 
 
 152. ZH,C 5 H n ;CO . . . Amylac carbate. 
 
 USUAL NAMES OF THESE AMIDS. 
 
 C 4 O 4 1 
 
 147. Oxamide = H 2 NC 2 O a = 2(H 2 N)C 4 O 4 = H 2 U 2 , Miller. Ox- 
 
 H 2 J 
 
 (C'O 2 
 = N 2 < 
 
 amide, or diazoture of oxalyle and hydrogen = C 2 H 4 ITO 2 = N 2 < H 2 
 
 Gerhardt. tfAtfOW GmeUn. 
 
 The rationale of the production of this compound is given at page 
 1 94. I have included oxamide in this section, for the sake of showing 
 its relation to other amids. 
 
 DUMAS'S THEORY OF OXAMIDE. " It has been supposed that oxamide 
 might be represented by two binary elements oxide of carbon and a 
 particular azoture of hydrogen less hydrogenated than ammonia,, and 
 which has not yet been isolated. Oxamide under that form would be 
 
 C 4 2 + Az 2 H 4 . 
 
 Between these two components we have to find that which plays the 
 negative part, and our choice is readily directed by the following con- 
 sideration. We know that, in general, when a body decomposes water, 
 its negative element takes up the hydrogen and its positive element 
 the oxygen. Consequently, as oxamide decomposes water to pass to 
 the state of oxalate of ammonia, we see that the azoture of hydrogen, 
 which takes up the hydrogen, must be the negative element, and that 
 the oxide of carbon which unites to the oxygen must act as the positive 
 element in the compound." Dumas, Traite de Chimie appliquee aux 
 Arts (Liege, 1847), partie Organique, tome i. p. 64. 
 
 According to M. Dumas, amidogen, = ZH 2 , acts in oxamide the same 
 part that chlorine or cyanogen acts in neutral salts. It is the acid 
 radical ; while CO, or oxide of carbon, acts as the positive or metallic 
 
 p 
 
210 AMIDS FllOM THE NEUTRAL OXALATES OF VICE-AMMONIUMS. 
 
 radical. The sole ground for this opinion is, that oxamide combines 
 with water to produce oxalate of ammonia ; and M. Dumas infers thence, 
 that, since ZH 2 combines with H 8 , ZH 8 must needs be an acid radical. 
 That is his whole evidence, and very poor evidence it is. At the 
 time of the discovery of oxamide, M. Dumas could not, of course, trace 
 its true character as clearly as we can trace it now ; but the assumptions 
 that ZH 2 could be an acid radical, and that CO could be a basic radical, 
 seem to me to be extravagant even for that period. They certainly are 
 suggestions which would not have been listened to for an instant from a 
 man who had been less successful in the world than M. Dumas. 
 
 148, Oxanilide; aniloxamide. See Aniline, No. 40]. 149, Ox- 
 anilamide ; oxamid-aniloxamide. See Aniline, No. 41]. No. 148 is 
 the amide of the vice-ammon oxalate, No. 87 ; and No. 149 is a double 
 salt, composed of No. 147 and No. 148. 
 
 150, Dimethyl-oxamide, or f C*0 8 
 
 diazoture of dimethyle C 4 H 8 N 2 O 2 = N 2 1 (C H 3 ) 2 
 and oxalyle. I H 2 
 
 151, Diethyl - oxamide, or f C 2 O 2 
 diazoture of diethyle C 6 H 12 N 2 2 = N 2 <^ (C 2 H 5 ) 8 
 and oxalyle. I H 8 
 
 i<2, Diamyl - oxamide, or f C 2 2 
 
 diazoture of diamyle C 12 H 24 N 2 O 2 = N 2 ^(C 5 H 11 ) 2 
 and oxalyle. ( H 2 
 
 The last three names and formula? are Gerhardt's. In these formulas 
 everything is doubkd, because Gerhardt chose to consider oxalic acid as 
 bibasic. I have elsewhere shown the weakness of his arguments on that 
 point (see page 177). Independently of the bibasic fallacy, the present 
 examples are objectionable in another important particular: he formu- 
 lates oxidised salts as ammonias that is to say, as vice-ammonias, or 
 substitutes for ZH*,H'. In doing this, he assumes that the acid radical 
 of the salt with all the oxygen- is one of three forces which act equally 
 
 (CO 
 \CR 3 . 
 
 IB 
 
 upon the azotic atom. Thus, Z < CH 3 . This assumption is of course 
 
 IH 
 
 gratuitous: it gives rise to complicated, and therefore troublesome, 
 formulse ; and it conveys notions respecting the constitution, not only 
 of ammonias, but of salts in general, which, in my opinion, are quite 
 inaccurate, and which are totally at variance with the great principle of 
 the radical theory, that all salts are compounds of two radicals. For 
 these reasons I entirely reject Gerhardt's ammonia type. In simplicity 
 and comprehensiveness it is much inferior to the plan which is pro- 
 vided by the radical theory. 
 
( 211 ) 
 
 Amids produced by the abstraction of one atom of 
 HHO from the Neutral Salts that are formed by 
 Normal Ammonium with Organic Acids. 
 
 Proposed Names. Usual Names. 
 
 153. ZH 2 ,C 2 H 3 O Amida acetylate . . . Acetamide. 
 
 1 54. ZH 2 ,C 2 Cl 3 O Amida chlorinic-acetylate Trichloracetamide. 
 
 155. ZH 2 ,C 8 H 7 O Amida anisy late . . . Anisamide. 
 
 156. ZH 2 ,C 7 H 5 O Amida benzy late . . . Benzamide. 
 
 157. ZH 2 ,C 4 H 7 O Amida butyry late. . . Butyramide. 
 
 158. ZH 2 ,C 5 H 7 O Amida camphory late . . Camphoramide. 
 
 159. ZH 2 ,C 9 H 7 O Amida cinnamylate . . Cinnamide. 
 
 1 60. ZH 2 ,C 10 H U O Amida cumylate . . . Cuminamide. 
 
 161. ZH 2 ,C 2 H O Amida fumary late . . Fumaramide. 
 
 162. ZH 2 ,C 8 H 3 O Amida indylate . . . Indigo blue. 
 
 163. ZH 2 ,C 8 H 3 O 2 Amida indylete . . . Isatine. 
 
 164. ZH 2 ,C 3 H 5 O 2 Amida lactylete . . . Lactamide. 
 
 165. ZH 2 ,C 3 H 4 O 3 Amida mucylite . . . Mucamide. 
 
 1 66. ZH 2 ,C IO H 7 O Amida naphty late. . . Naphtylamide. 
 
 167. ZH 2 ,C 7 H 13 O Amida cenanthy late . . (Enanthamide. 
 
 1 68. ZH 2 ,C 3 H 5 O Amida propionylate . . Propionamide. 
 
 169. ZH 2 ,C 5 H 8 O Amida sebamylate . . Sebamide. 
 
 170. ZH 2 ,C 4 H 6 O Amida subery late . . . Suberamide. 
 
 171. ZH 2 ,C 2 H 2 O Amida succinylate. . . Succinamide. 
 
 172. ZH 2 ,C 2 H 2 O 2 Amida tartrylete . . . Tartramide. 
 
 173. ZH 2 ,C 5 H 9 O Amida valerylate . . . Valeramide. 
 
 It is unnecessary to quote more than the usual names of the 
 substances contained in this list. They all bear a similar relation to 
 corresponding salts of ammonia. Thus, No. 153] = ZH 2 ,C 2 H 3 amida 
 acetylate, is commonly called acetamide, and has the formula H 2 N,C 4 H 3 O 8 . 
 The addition of HHO to the new formula No. 153, converts it into 
 ZH 4 ,C*H 3 O 2 = ammona acetylete, which, in the usual language of 
 chemistry, is called acetate of ammonia, see page 198. 
 
 Practically, water is thus combined with these amids when they are 
 boiled with diluted acids and alkalies. 
 
 Many of these Salts have very complicated formulas commonly given 
 to them ; but it does not appear that any advantage results from that 
 practice. Gmelin's formula for mucamide = No. 165, amida mucylite, 
 given above as ZH 2 ,C 3 H 4 3 is 
 
 C 12 N 2 H 12 12 = C 12 Ad 2 H a 10 ,O 2 . 
 
 p 2 
 
212 PRODUCTION OF AMIDS FROM SALTS OF ORGANIC ACIDS. 
 
 Gerhardt's formula for lactamide, = No. 164, amida lactylete = 
 ZH 2 ,C 3 H 5 8 is 
 
 [(C 8 H 5 2 ) 8 
 
 H 8 
 
 N 2 | 
 
 These double quantities of atoms are given, because these chemists act 
 upon the notion that certain acids are bibasic, or that the salts ought to 
 be made equivalent to gases that have an atomic measure of four 
 volumes, or because some other theory prescribes the duplication. The 
 theory which I am advocating assumes all radicals to be equivalent to 
 one volume of hydrogen, which, as a general rule, makes their salts 
 equal to two volumes of vapour, and the practice which I pursue is that 
 of cutting down the formulae of all salts into accordance with this one 
 simple idea. 
 
 There are several methods of producing these amids ; such as, the 
 action of ammonia on the anhydrides ; the action of ammonia or car- 
 bonate of ammonia on the oxychlorides of organic acid radicals ; and the 
 action of ammonia on compound ethers. 
 
 They are neutral salts ; namely, they are neutral to test-papers ; they 
 do not combine with acids ; they are crystallizable. 
 
 M. Gerhardt says that " sometimes they behave like acids in regard 
 to certain oxides ; thus, benzamide forms a salt with mercury : 
 
 C 7 H 5 
 
 Benzamide. Mercuiy benzamide." 
 
 Traite de Chimie Organique, iv. 761. 
 
 This transformation would be represented in my notation thus : 
 
 HEP.COTO) , TT n (ZHHgc,(7H 5 0) 
 
 + H S cH g c = ' + 
 
 This process is simply the conversion of amid into mericae by the re- 
 placement of H 1 by Hgc 1 in each atom of the salt. 
 
 Voit gives the ammonia formula to the compound that is commonly 
 called binitrobenzamide, thus : 
 
 (C U H 8 (NO*) ? 8 
 N< H 
 
 But this salt is evidently a compound of the same order as No. 156 ii 
 the above Table : 
 
 No. 156.] ZH*,C 7 H 5 O = Benzamide. 
 
 ZH f ,C 7 H 3 Z ? 5 = Binitrobenzamide. 
 
PRODUCTION OF AMIDS FROM SALTS OF ORGANIC ACIDS. 213 
 
 In this example O 4 extra goes into the salt because Z 2 goes into the 
 radical instead of H 2 . See page 133. 
 
 I might add other examples of this kind, but they could only prove 
 the facts that have been detailed in the general notice of the properties of 
 vice-radicals. See page 132. 
 
 Amids produced by the abstraction of one atom of 
 HHO, from the Neutral Salts that are formed by 
 Ammonams with Organic Acids. 
 
 174. ZH,C 4 H 7 ;C 8 H 3 . . Butyrylac acetylate. 
 
 175. ZH,C 2 H 5 ; C 2 H 3 O . . Ethylac acetylate. 
 
 176. ZH,C 6 H 5 ; C'IFO . . Phenylac acetylate. 
 
 177. ZH,C 6 H 5 ; C 8 H 7 O 2 . . Phenylac anisylete. 
 
 178. ZB^C 7 !! 5 ; C 7 H 5 O . . Benzylac benzylate. 
 
 179. ZH,Hgc; C 7 H 5 O . . Mericac benzylate. 
 
 1 80. ZH,C 6 H 5 ; C 7 H 5 O . . Phenylac benzylate. 
 
 181. ZH,Hgc; C 4 H 7 O . . Mericac butyry late. 
 
 182. ZH,C 6 H 5 ;C 4 H 7 O . . Phenylac butyrylate. 
 
 183. ZH,C 6 H 5 ; C 9 H 7 O . . Phenylac cinnamy late. 
 
 184. ZH,C 6 H 5 ;C 10 H n O . . Phenylac cumylate. 
 
 185. ZH,C 2 H 5 ; C H O . . Ethylac formylate. 
 
 1 86. ZH,C 6 H 5 ;C HO.. Phenylac formylate. 
 
 187. ZH,Zn; C 2 H 3 O 2 . . Zincac glycollylete. 
 
 1 88. ZH,C 6 H 5 ; C 4 H 6 . . Phenylac suberylate. 
 
 189. ZH,C 6 H 5 ; C 2 H 2 O . . Phenylac succinylate. 
 
 190. ZH,C 6 H 5 ; C 5 H 9 O . . Phenylac valerylate. 
 
 Each of these salts of an amid may be considered to be convertible by 
 combination with HHO into the corresponding neutral salt of an 
 ammonam. Thus, the first on the list, No. 174] ZH,C 4 H 7 ; C 2 H 8 O = 
 butyrylac acetylate, if combined with HHO, would become ZH 8 ,C 4 H 7 ; 
 C*H 3 O 2 , namely, butyrylam acetylete, or the acetate of an ammonium 
 containing one atom of butyryl. But this change cannot always be 
 effected experimentally, for when these amids are boiled with mineral 
 alkalies, they suffer decomposition, the acid radical forming a salt with 
 the alkali, and the amid being separated as a hydride or an ammonia. 
 But though the corresponding salts of ammonams and amides cannot 
 always be produced, it is important to bear in mind the existence of 
 these relations. 
 
214 PRODUCTION OF AM1DS FROM SALTS OF ORGANIC ACIDS. 
 USUAL NAMES AND FORMULAE. 
 
 174, Butyric acetylamide = C*H 3 v N. Miller. 
 
 H 
 
 This formula is in accordance with Gerhardt's ammonia type, and is 
 therefore subject to the objections which I have urged at page 210. 
 
 175, Acetoethylide. 
 
 175, Ethyl-ace tamide, or Azoture (C 2 H 3 
 
 of ethyle, acetyle, and hy- C 4 H 9 NO = N^C'IFO 
 drogen. ( H 
 
 176, Phenyl-acetamide, Acetanilide, fC'H 5 
 
 or Azoture of phenyle, ace- COTNO = NJC 8 H 3 O 
 tyle, and hydrogen. ( H 
 
 The last two formulae and sets of names are Gerhardt's, written ac- 
 cording to his type ammonia. All the salts from Nos. 175 to 184 are 
 subject to the same treatment, but I think it useless to crowd this Essay 
 with more than specimens of these digitated formulae and their duplicate 
 or triplicate names. It will suffice if the reader understands the differ- 
 ence between Gerhardt's system, and the system now under considera- 
 tion. According to the radical theory, No. 176 is a direct binary com- 
 pound between phenylac = ZH,C 6 H 5 and acetylate = C 8 H 8 0, whereas, 
 according to Gerhardt, it is a compound of N acting with tripartite force 
 upon C 6 H S , and C*H 8 O, and H. It is the azoture of phenyl, of acetyle, 
 and of hydrogen. From these views I dissent entirely. 177, Anisani- 
 lide ; phenyl-anisamide. 178, Imabenzile. 179, Benzamidate of mer- 
 cury, Gerliardt; hydrargo-benzamide, Miller. 180, Benzanilide; anilo- 
 benzamide. See No. 223. 181, Mercury-salt of butyramide. 182, 
 Phenyl -bu ty ramide ; butyranilide. 183, Cinnanilide; anilo-cinnamide ; 
 phenyl-cinnamide. 184, Cumanilide; anilocuminamide. 185, Ethyl- 
 formiamide. 186, Phenyl-formiamide ; formanilide ; aniloformamide ; 
 azoture of phenyle, of formyle, and of hydrogen. 187, Combination of 
 sugar of gelatine and zinc = 2N(C*H 8 O 2 ,Zn,H). 188, Suberanilide ; 
 anilosuberamide ; diphenyl-suberamide, or diazoture of diphenyle and of 
 suberyle, Gerhardt. 189, Succinanilide ; anilosuccinamide, Hofmann; 
 diphenyl-succinamide, or diazoture of diphenyle, and of oxalyle, Ger- 
 hardt. 1 90. Phenyl-valeramide ; valeranilide, or azoture of phenyle, of 
 valeryle, and of hydrogen. 
 
( 215 
 
 Non-oxidised Salts of Amids. 
 
 191. ZH,C 7 H 5 ; Cl . . Benzylac chlora. 
 
 192. ZH,K; C 8 H 5 . . Potassac phenyla. 
 
 193. ZH,C 6 H 5 ; Cy . . Phenylac cyana. 
 
 194. Z,C 2 H 5 ,C 6 H 5 ; Cl . Ethylic-phenylac chlora. 
 
 195. Z,C 2 H 5 ,C 2 H 5 ; C 6 H 4 C1 Ethylec chloric-phenyla. 
 
 196. ZH,C 6 H 3 CP; Cl . Chlorenic-phenylac chlora, 
 
 197. ZH,C 6 H 8 Br 8 ; Cl . Bromenic-phenylac chlora. 
 
 198. ZH,C 6 H 3 Br*; Br . Bromenic-phenylac broma. 
 
 USUAL NAMES AND FORMULAE. 
 
 191, Chloride of benzamidyle = C1,C 7 H 6 N, Gerhardt. When heated, 
 it produces hydrochloric acid and cyanide of phenyle ZH,C 7 H 3 ; Cl = HC1 
 + C 6 H 5 ,CN. 192, see Aniline, No. ir]. 193, see Aniline, No. 62]. 
 
 H 
 
 {H 5 1 
 
 rn I "\r ^ 
 
 V^L > IN. TT 
 
 P4TT5 rUS/* 1 
 
 CM J O (p, 
 
 f H 4 
 
 195, Biethyl-chloraniline I p. 
 
 N. Hofmann. 
 
 C 4 H 5 
 
 N. Hofmann. 
 
 . 
 
 196, 197, 198; see Aniline, Nos. 9], 10], and 8]. 
 
 Examples of the Combination of Ammons and Amids 
 with one another. 
 
 199. ZH 3 ,C 7 H 7 + ZH,C 7 H 7 . . . Toluenylam toluenylac. 
 
 200. ZH*(C 7 H 5 ) 2 4- ZH,C 7 H 5 . . , Benzylem benzylac. 
 
 201. ZH 2 (C 9 H 7 ) 2 4- ZH,C 9 H 7 . . . Cinnamylem cinnamylac. 
 
 202. Z(CH 3 ) 2 (C 2 H 3 ) 2 4- ZCH 3 ,C 2 H 8 . Methylenic-acetylem cum 
 
 methylic-acetylac. 
 
 203. ZH 2 4- ZH,C 10 H 7 Amida naphtylac. 
 
 204. ZH 2 4-ZH,C 6 H 5 Amida phenylac. 
 
 USUAL NAMES AND FORMULAE. 
 
 199, Lutidine, a compound isomeric with toluidine, No. 22 ; that is 
 to say 
 
 No.22 two atoms = .. No. 1 9? < 
 
216 COMBINATION OF AMMONS WITH AMIDS. 
 
 Two atoms of toluenylac hydra = one atom of toluenylam toluenylac. 
 This accounts for the isomerism of these two salts, and supplies a hint 
 as to the probable explanation of other cases of isomerism. 200, Hy- 
 
 drobenzamide = C 21 H 18 N* = N^ Gerhardt. C 42 H 18 N 2 , Miller. 
 
 201, Cumhydramide = C^^N 2 = , Gerhardt. 
 
 Miller. 
 
 202, " Acetonine, or Acetonia, a new base = C 18 H 18 N 2 . Hydrochlo- 
 rate of acetonia forms with bichloride of platinum, an orange-yellow, 
 crystalline double salt, (C l8 H l8 N 2 ,HCl,PtCl 2 ). The binoxalate (HO, 
 C 18 H 18 N 2 ,HO ; C 4 6 + 2 Aq) is soluble in alcohol, and crystallises readily 
 from this soluble." Miller, narrating the researches of Steedeler, Elements 
 of Chemistry, Part iii, p. 312. I do not believe in the existence of this 
 assumed " new base." Acetone itself contains acetyl and methyl, see 
 page 77. Acetonia is composed of an ammon and an amid, including 
 the same radicals; and the platinum-salt and the binoxalate can be 
 explained (see Nos. 205, 206), without resorting to the expedient of 
 creating a hypothetical " new base" to meet the special circumstances, 
 an expedient to which organic chemists resort with a too-ready facility. 
 When compound salts can be clearly explained by means of well- 
 known existing radicals, what is the use of making imaginary bases ? In 
 the present case, three atoms of methyl, three atoms of acetyl, and two 
 atoms of azote, are rolled up into a giant base and called acetonia. This 
 method of practising chemical synthesis is becoming really alarming. 
 
 203, Azonaphtylamine ; or seminaphtalidam = C 20 H 10 N 2 , Gerhardt. 
 Seminaphtalidine,'or naphtidine = C IO H 5 N, Zinin. = C 20 H 6 (H 2 N) 2 , 
 Hofmann. 204, Semaniline = CH 4 N, Zinin. = C 12 H 4 (H 2 N) 2 , Hof- 
 mann. When hydrated acids act upon the double amids, such as are 
 represented by 203 and 204, they produce double salts which contain both 
 an amid and an ammon ; of which, Nos. 207 and 208 are examples : 
 
 (Z(CH 3 ) 3 Ptc; Cl) Platic-methylim chlora cum 
 {Z(C 2 H 3 ) 3 Ptc; Cl> - platic-acetylim chlora cum 
 H;Clj hydra chlora. 
 
 fZH(C H 3 ) 3 ; CO 2 ) , T t ,,. , 4 
 
 t Jyw)p2W3\3 m*l Methyhm carbete cum ace- 
 206. ja ; CO v : tylim carbefce aquate> 
 
 {7H 3 C IO H7 Cl ) 
 y-tra' ' n I = Naphtylam chlora cum amida chlora. 
 
 j 7TJ3 n lo i^7 SO 2 1 
 208 < 7TT2 ' CQ 2 I = ^ a P nt y^ am sulphetecum amida sulphete. 
 
 No. 207 is commonly called the bichlorhydrate of azonaphtylamine, 
 
NITRILES. 217 
 
 and No. 208 is the bisulpbate of the same base. The hydrogen of the 
 acids is, in each case, merely sufficient to convert one of the amids into 
 an ammon ; so that one amid remains still in the compound salt. It is 
 possible that the last two salts may require the following formulae : 
 
 207, ZH, C 10 H 7 ; Cl + ZH 4 , Cl 
 
 208, ZH, C 10 H 7 ; SO 2 + ZH 4 ; SO 2 
 
 The compounds 203 and 204 do not form salts by combining with a 
 single equivalent of H Cl or H SO 2 . 
 
 Nitriles. 
 
 209. CN Cyana [= Cyanogen]. 
 
 210. H,CN Hydra cyana [ = Hydrocyanic acid], 
 
 211. CH 3 ,CN Methyla cyana [= Cyanide of Methyl]. 
 
 When oxalate of ammonia = ZH 4 , CO 8 is deprived of two atoms of 
 HHO, it is reduced to the condition which is shown in the following 
 equation : 
 
 ZHHHH; COO - (HHO + HHO) = Z -f C. 
 
 Oxalate of ammonia. Water. Residues. 
 
 All that is left of the salt is the acid radical C, and the zotic atom 
 which was the prime agent of the positive radical. These two atoms 
 combine together and produce cyanogen, which is usually marked CN or 
 Cy. This compound is not a salt composed of two radicals, but a 
 single acid radical, energetic in its chemical powers, yet having the 
 saturating capacity of only one atom. This fact is worthy of particular 
 notice, because azote and carbon have each, separately, the saturating 
 capacity of one radical, though, when combined, they have together only 
 the saturating capacity of one radical. Thus azote, which, in positive 
 radicals, paralyses the saturating capacities of the two or four radicals 
 with which it produces amids and ammons, has its own saturating 
 capacity paralysed when it enters into a negative radical which contains 
 carbon. Even when two or three atoms of azote enter into a negative 
 radical in the presence of carbon, they all lose their saturating capacity, 
 that of the carbon radical alone remaining active. 
 
 See the account of the zotic radicals at page 132. 
 
 When formiate of ammonia = ZH 4 , CHO 8 , is deprived of two atoms 
 of HHO, the result is as follows : 
 
 ZHHHH ; CHOO - (HHO + HHO) = Z + CH. 
 
 Formiate of ammonia. Water. Residues. 
 
 These residues are nitrogen and formyl. 
 
218 NITRILES. 
 
 When acetate of ammonia = ZH 4 ,C 2 H 3 O 2 , is deprived of two atoms of 
 HHO, the result is this : 
 
 ZHHHH ; C 2 H 3 00 - (HHO 4. HHO) = Z + C 2 H 3 . 
 
 Acetate of ammonia. Water. Residues. 
 
 These residues are nitrogen and acetyl. 
 
 In both these cases the nitrogen combines with the other residue, and 
 in all similar cases, when the neutral ammonia-salt of an organic acid is 
 deprived of the hydrogen of its ammonium, and of all its oxygen, the 
 residual nitrogen combines with the residual acid radical, and produces 
 the compounds which are called NITRILES. 
 
 In an early part of this Essay, in treating of the reduction of acid 
 radicals to basic radicals, I have shown that if you can, by any process, 
 deprive an acid radical belonging to the vinyl series, of one atom of 
 carbon, you reduce it at once to a basic radical. See page 75. Now it 
 appears to me that, in the preparation of the nitriles, this reduction of an 
 acid radical to a basic radical takes place in every instance. It is aprM 
 improbable that the acid radical Z should combine with the acid radicals 
 CH and C 2 H 3 , both of which are energetic acid radicals, if the acid power 
 of the whole of them is supposed to be persistent ; but if Z is supposed 
 to abstract C from each of the hydrocarbons, the two pair of residues 
 then become 
 
 H + CN and CH 8 + CN. 
 
 = Hydrocyanic acid = cyanide of methyl. 
 
 That is to say, the two acid radicals Z + CH, become one basic radical 
 (hydrogen) and one acid radical (cyanogen), and these combine together 
 to produce a salt, the hydrocyanic acid. So, in the second example, the 
 two acid radicals Z -f- C 2 H 3 produce the strongly positive radical methyl 
 CH 3 and the strongly negative radical cyanogen CN, and these combine 
 to form the salt called cyanide of methyl = CH 8 ,CN. The evidence 
 which I have given to prove the possibility of this reduction of acid 
 radicals to basic radicals by the removal of an atom of carbon, is so con- 
 vincing, that no man can doubt the fact ; and when we couple with this 
 certainty, the fact that the products of the three processes which I have 
 supposed to yield the substances called oxalo-nitrile, formo-nitrile, and 
 aceto-nitrile, actually yield cyanogen, hydrocyanic acid, and cyanide of 
 methyl, we have reasons that are almost demonstrations to induce us to 
 believe that in all these instances the nitrogen and the carbon combine to 
 form cyanogen, and that this cyanogen produces a cyanide with the positive 
 radical which is formed by the residue of the decomposed acid radical. 
 
 I have referred expressly to those ammonia-salts that are produced 
 by the organic acids that belong to the vinyl series, page 79; .but the 
 formation of the so-called nitriles is not confined to radicals of that 
 particular series ; for the benzoate of ammonia yields cyanide of phenyl, 
 
NITRILES. 219 
 
 and eliminate of ammonia yields cyanide of cumenyl, the benzoic radical 
 being reduced to phenyl, that is to say = C 7 H 5 to C 6 H 5 , and the cumyl 
 radical to cumenyl = C 10 H 11 to C 9 H 11 , by the abstraction, in each case, of 
 C l to form cyanogen with the azotic residue of the destroyed ammonium. 
 
 According to this theory, azote, in the presence of sufficient radicals, 
 exercises its prerogative of producing amidogens and ammoniums, which 
 then form salts with oxidised carbon, with negative hydrocarbons, or with 
 any other acid radicals, oxidised or not oxidised, which are placed within 
 its reach. But neither amidogens nor ammoniums are produced in the 
 absence of negative radicals with which they can form salts. 
 
 When the radicals necessary to the existence of ammonium-salts are 
 half withdrawn from them, the salts are reduced to amides or amidogen- 
 salts. When they are all withdrawn, the salts are destroyed and the 
 azote is set free. When this happens in the presence of carbon, the 
 free azote combines with the carbon to form cyanogen. When it 
 happens in the presence of a negative hydrocarbon, it splits that negative 
 hydrocarbon into C l and a positive hydrocarbon, and produces therewith 
 a neutral cyanide. 
 
 This theory is quite consistent with well-ascertained facts respecting 
 the formation of cyanogen, and the importance of the subject warrants my 
 citing a few particulars, i]. When a mixture of carbonate of potash 
 and pure sugar-charcoal is heated red hot in a porcelain tube, and 
 common atmospheric air is passed through the tube, cyanide of potassium 
 is produced. 2]. Many vapours that contain carbon, if mixed with 
 vapours that contain azote, and passed through a red-hot tube, produce 
 cyanogen. 3]. When ammonia gas is passed over charcoal strongly 
 ignited in a porcelain tube, cyanide of ammonium and marsh gas are 
 produced, thus : 
 
 4 (ZH 2 H) ) f 2 (ZH 4 ,CN) 
 3 C | := 1 CH,H. 
 
 4]. Ammonia gas and carbonic oxide, passed through a red-hot tube, 
 produce cyanide of ammonium and water ; thus : 
 
 ZH 2 H,ZH 2 H + CO = ZH 4 ,CN + HHO. 
 
 5]. When refuse animal matter, such as horns, hides, hoofs, &c., 
 are heated red-hot in a close vessel with carbonate of potash and iron 
 filings, the triple cyanide of iron and potassium = K 2 FeCy 3 , is produced. 
 The phenomena that occur in this last example are complicated ; but 
 the final product alone is what we have to consider. It is evident that 
 the ammoniacal compounds which these animal substances contain in 
 large quantities with an excess of carbon are converted during the 
 operation into cyanogen, the hydrogen and oxygen of the compounds 
 being wholly disengaged, because the cyanogen combines with the 
 potassium and iron, without the intervention of oxygen. 
 
220 NITRILES. 
 
 RECONVERSION OF THE NITROGEN OF CYANOGEN INTO THE AMMONIACAL 
 
 CONDITION. 
 
 It is not only possible to remove nitrogen from amidogen or ammo- 
 nium into cyanogen; but to perform the reverse operation of forcing 
 the nitrogen of a cyanide to transmigrate into the ammoniacal condition. 
 Of course, these transmigrations result from the fact, that nitrogen can 
 act either negatively or positively, according to the pressure of the posi- 
 tive or negative forces that are made to control it, and that it changes 
 its condition with every sufficient change in those controlling forces. 
 
 Examples : 
 
 ]H,CN4-H,C1 ) JZH 4 ,C1: 
 [ ' \H,HO -h H,HOJ =: \ H,CH0 2 
 
 One atom of hydrocyanic acid, one atom of hydrochloric acid, and 
 two atoms of water produce, one atom of chloride of ammonium, and 
 one atom of hydrated formic acid. 
 
 One atom of cyanide of potassium, two atoms of hydrochloric acid, 
 and two atoms of water produce, one atom each of chloride of ammo- 
 nium, chloride of potassium, and hydrated formic acid. 
 
 , JK,CN 1 JK,CH0 8 
 
 3' \ H,HO + H,HO f == I ZH 2 ,H. 
 
 One atom of cyanide of potassium boiled in a close vessel with two 
 atoms of water produces one atom of ammonia and one atom of for- 
 miate of potash. 
 
 One atom of cyanate of potash, one atom of water, and two atoms 
 of hydrated sulphuric acid, produce one atom each of sulphate of 
 ammonia, sulphate of potash, and free carbonic acid. 
 
 . (ZH*,CNO 1 7TT47TT4PO. 
 
 5' { H,HO + H,HO f == ZH ' ZH ' C0 ' 
 
 One atom of urea (cyanate of ammonia) heated in a sealed tube 
 with two atoms of water, produces one atom of carbonate of am- 
 monia. 
 
 If we examine the nature and consequences of these various reactions, 
 and then ask ourselves the question, whether the nitriles consist of 
 
CARBAMIDE. 221 
 
 nitrogen combined directly with unchanged negative radicals, Z -{- CH, 
 Z + C 2 H 3 , Z + C 3 H 5 , Z + C 4 H 7 , Z + C 5 H 9 , Z + C 7 H 5 , &c., or whe- 
 ther they are cyanides of the corresponding positive radicals ? we can 
 scarcely come to any other conclusion than that which has been drawn 
 above, namely, that the NITRILES are in all cases to be considered as 
 CYANIDES, and that nitriles proper, or compounds of nitrogen with nega- 
 tive radicals, do not exist. 
 
 [Consult the investigation into the constitution of the compound com- 
 monly called anilocyanic acid, Article Aniline, No. 95.] 
 
 Carbamide. 
 
 212. ZH 4 ; CyO, Ammona cyanate = [carbamide or urea]. 
 
 213. ZH*(C 6 H 5 ) 2 ; CyO, Phenylem cyanate = [carbanilide]. 
 
 214. ZH 3 ,C 6 H 5 ; CyO, Phenylam cyanate = [carbamide-carbanilide]. 
 
 The following formulae represent the neutral carbonate of ammonia : 
 Analytical formula. Synoptical formula. 
 
 ZH 4 O + ZH 4 + CO ZH 4 ,ZH*,CO 3 . 
 
 If we imagine two atoms of HHO to be abstracted from this com- 
 pound, the residue will be as follows : 
 
 ZH 2 + ZH 2 + CO. 
 
 This formula represents CARBAMIDE. 
 
 If we ask ourselves the question, whether this formula probably 
 represents the constitution of this residue, we must, before we make 
 a reply, take into consideration the following particulars, which I have 
 in the preceding pages almost demonstrated to be matters of fact. 
 
 1. One atom of Z can, with facility, hold either H 2 or H 4 in the 
 form of a positive radical ; but H 4 more effectually than H 2 . 
 
 2. When Z is freed from H, in the presence of C, it combines with 
 C, and produces cyanogen. 
 
 3. If any positive radical is present, the resulting cyanogen com- 
 bines with it to form a salt. 
 
 What is to prevent the occurrence of these reactions among the 
 elements that constitute carbamide ? I can see no counteracting force 
 whatever, and I believe that, in the circumstances that are presented by 
 the process above described, azote would infallibly fulfil its usual func- 
 tions, and that the so-called carbamide, with the formula ZH 2 ,ZH 2 ,CO, 
 would become ZH 4 ,CNO, or ammona cyanate, a compound which, in 
 the usual language of chemists, is called cyanate of ammonia, or briefly 
 UREA. I can find no sufficient reason to retain either the name carba- 
 mide or the formula upon which that name is based. The opinions of 
 
222 IMIDOGEN COMPOUNDS. DUDES. ANILES. 
 
 chemists are at present divided upon this subject ; but I trust that the 
 facts and contingencies which I have pointed out in this Essay respecting 
 the properties of ammoniums, amidogens, and cyanogen compounds, 
 and the demonstration of the circumstances which regulate the amazing 
 power of transmigration possessed by the element azote, will bring 
 them to agree in the propriety of my conclusions. 
 
 The arguments which bear upon the constitution of carbamide axe 
 precisely similar to those which must be used if I were to enter into a 
 description respecting the constitution of the compounds which Dr. 
 Hofmann has called carbanilide and carbarn ide-carbanilide. The former of 
 these compounds is represented by No. 213, and the latter by No. 214. 
 I refer the reader for a complete investigation of these two compounds 
 to Aniline, No. 90], 
 
 The usual formula given to carbamide is H 2 N,CO, Hofmann; but 
 as the radical theory doubles the weight of the atoms of C and O, this 
 formula requires to be changed to H 2 N,H S N,CO, to express the same 
 percentage relations. 
 
 The constitution of "Urea" will be more fully discussed in a sub- 
 sequent section. 
 
 Imidogen Compounds. Imides. Aniles. 
 
 According to Dr. Hofmann, the IMIDES are produced by the abstrac- 
 tion of four equivalents of water [that is, two equivalents on the radical 
 theory] from an acid salt of ammonia. He tells us, that the imide 
 resulting from the binoxalate of ammonia has not as yet been formed ; 
 but that we have representatives of the imidogen compounds among 
 the derivatives of camphoric and phtalic acids. See page 208. 
 
 Let us first see, why the binoxalate of ammonia produces no imide : 
 
 Binoxalate of Ammonia. "Water. Residue. 
 
 } - (HHO.HHO) = { I 
 
 
 This residue produces hydrocyanic acid = H,CN, and carbonic acid 
 = CO 8 , which do not enter into combination ; and this is the reason 
 why oximide " has not as yet been formed," and why it never will be 
 formed. 
 
 Decomposition of Bicamphorate of Ammonia. 
 Bicamphorate of Ammonia. Water. Residue. 
 
 ZH 4 ; C 5 H 7 2 \ J HHO \ JZ + C'H 7 
 H ; C 5 H 7 2 j "" t HHO j == |H + C 5 H 7 8 . 
 
 What becomes of this residue ? According to Dr. Hofmann, it produces 
 camphorimide, the formula of which is HN,2C 10 H 7 O 2 . Correcting the 
 
IMIDOGEN COMPOUNDS. IMIDES. ANILES. 223 
 
 atomic weights of C and O, this formula becomes HN,2C 5 H 7 0. The 
 first part of this formula is Hofmann's " Imide " = HN. 
 
 I dissent from this theory entirely, and I consider that no such thing 
 as an imide exists. Let us compare the residues of the two processes 
 just referred to : 
 
 (Z + C ]Z + C 5 H 7 
 
 First residue, < H ' ^Q 2 Second residue, < jj ^_ Q 5 jj7Q2 
 
 If the three radicals Z -f- C 4- H can combine together, what is to 
 prevent the combination of the three radicals Z -j- C 5 H 7 -f- H, which are 
 placed in contact under precisely similar circumstances ? The reason 
 for the combination in the first case is the tendency of carbon and 
 nitrogen to form cyanogen. The reason for the combination in the 
 second case is the power of nitrogen in the presence of two free radicals 
 and an oxidised negative radical to produce a salt of an amidogen. The 
 result of the combination in the first case is an acid radical which 
 takes up the basic hydrogen left free by the disengagement of car- 
 bonic acid. The result of the combination in the second case is a 
 basic radical which combines with the camphoric acid left free by the 
 abstraction of the hydrogen, and the final product is a neutral salt 
 with a vice-amidogen base, thus : 
 
 ZH,C 5 H 7 ; C 5 H 7 2 = Camphorylac camphorylete. 
 
 Decomposition of BipJitalate of Ammonia. 
 
 Precisely the same thing takes place when biphtalate of ammonia is 
 decomposed. 
 
 ZH 4 ; C 4 H 2 2 1 ( HHO 1 J Z: C 4 H 2 
 H ; C 4 H 2 2 f " | HHO f : t H ; C 4 H 2 2 . 
 
 = ZH,C 4 H 2 ; C'H'O 2 = Phtalylac phtalylete. 
 Dr. Hofmann's name and formula for this compound are 
 HN, 2 C 8 H 2 O 8 = Phtalimide. 
 
 It is needless to give more examples of the imides, for they would 
 be repetitions of camphorimide, with the mere change of the acid 
 radical. It will suffice to quote a few varieties of these salts in a Table. 
 In all cases they are neutral salts, containing the full quantity of oxygen 
 required by the acid radical, but having a vice-amidogen as basic radical. 
 It may perhaps be urged that even my formula contain ZH, and that 
 the salts may therefore contain imidogen ; but since ZH must occur in 
 every amidogen and ammonium, in which all the hydrogen has not been 
 replaced, this argument proves nothing. There is no such thing as 
 isolated imidogen, and a theoretical one is not required. 
 
224 IMIDOGEN COMPOUNDS. JMIDES. ANILES. 
 
 EXAMPLES OF IMIDES AND ANILES. 
 a). Amidacs. (Imides.) 
 
 215. ZHjCPH 5 ; C 7 H 5 2 . . Benzylac benzylete. 
 
 216. ZH,Ba; C 7 H 5 2 . . Barytac benzylete. 
 
 217. ZH,Na; C 7 H 5 O 2 . . Natrac benzylete. 
 
 2 1 8. ZH,C 5 H 7 ; C 5 H 7 2 . . Camphory lac camphorylete. 
 
 219. ZH,C 2 H; C'HO 2 . . Fumarylac fumarylete. 
 
 220. ZH,C 4 H 2 ; C 4 H 2 O 2 . . Phtaly lac phtalylete. 
 
 221. ZH,C 2 H 2 ; C 2 H 2 2 . . Succinylac succinylete. 
 
 6). Amidecs. (Aniles, etc.) 
 
 222. Z,C 2 H 5 ,C 2 H 3 ; C 2 H 3 O a . . Ethylic-acetylac acetylete. 
 
 223. Z^EP^H 5 ; C 7 H 5 O 2 . . Benzylic-phenylac benzylete. 
 
 224. Z,C 5 H 7 ,C 6 H 5 ; C 5 H 7 O a . . Camphorylic-phenylac camphorylete. 
 
 225. Z,C 4 H 2 ,C 6 H 5 ;C 4 H 2 2 . . Phtalylic-phenylac phtalylete. 
 
 226. Z,C*H 2 ,C 6 H 5 ; C 2 H 2 2 . . Succinylic-phenylac succinylete. 
 
 SYNONYMES AND USUAL FORMULAE. 
 
 215. Benzimide = HN,2C 14 H 5 8 , Hofmann. 216, Amidobenzoate 
 of barytes = BaOC l4 H 4 NH 2 O 3 = C 14 H 4 Ba(NH 2 )0 4 , Voit. 217, Amido- 
 benzoate of soda = C l4 H 4 Na(NH 2 )O 4 , Voit. These two salts are liable 
 to another interpretation. See Tribasic cyanates. See also No. 474 in 
 this series. Voit's Memoir may be seen in the Quarterly Journal Chem. 
 Soc. ix., 268. 218. Camphorimide = HN, 2C 10 H 7 O 2 , Hofmann. 
 219. Fumarimide = C 8 H 8 NO 4 , Gerhardt. 220. Phtalimide = HN, 
 2C 8 H 2 2 , Hofmann. 221. Succinimide, or bisuccinamide 
 
 C 8 H 4 O 4 } 
 
 = C 8 H 5 NO 4 = 2(C 8 H 4 4 )H 2 N a = C 16 H 10 N 2 O 8 = C 8 H 4 4 I N 8 , Miller. 
 
 H 2 j 
 
 222. Ethyl-diacetamide, or azoture of ethyle and of diacetyle 
 
 ( C 2 H 5 
 
 = C 6 H U N0 2 = N { C 2 H 3 Gerhardt. 
 { C 2 H 3 
 
 223. Phenyl-dibenzamide, dibenzanilide, or azoture of phenyle and of 
 dibenzoile 
 
 C 6 H 5 
 = N I C'H'O Gerhardt. 
 
AMIDOGEN ACIDS. 225 
 
 Compare Dibenzanilide, No. 223, and Benzanilide, No. 180, with the 
 ammonium-salts to which they respectively correspond : 
 
 No. 223. ZC 7 H 5 ,C 6 H 5 ; CWO 2 I j ZH 3 ,C 6 H 5 ; C 7 H 5 2 
 
 H 2 ; H 2 2 ( == 1 H; C 7 H 5 2 
 
 No. 1 80. ZH,C 6 H 5 ; C 7 H 5 O 1 
 
 H; HO j : 
 
 224. Camphoranile; anilocamphorimide = C 32 H 19 NO 4 = C 12 H 5 N,2C 10 H 7 8 , 
 Hofmann. Phenyl-camphorimide, or azoture of phenyle and of cam- 
 phoryle 
 
 J14 8 Gerhardt. 
 
 225. Phenyl-phtalimide, phtalanile, or azoture of phenyle and phtalyle 
 = C 14 H 9 N0 2 = N f Gerhardt. 
 
 Phtalanile, or anilophtalimide = C 12 H 5 N,2C 8 H 2 O 2 , Hofmann. 226. Suc- 
 cinanile, or anilosuccinimide = C 20 H 9 N0 4 = C' 2 H 5 N,2C 4 H*0 2 , Hofmann. 
 Phenyl-succinimide, or azoture of phenyle and of succinyle 
 
 ^ f Gerhardt. 
 
 The compounds No. 223 to 226 belong to the class which Dr. Hof- 
 mann calls " aniles." They are derived from the acid salts of phe- 
 nylam : 
 
 ZH 3 ,C 6 H 5 ; (7H 5 O a I j H 2 O ) _ ZC 7 H 5 ,C 6 H 5 ; C 7 H 5 O 
 H; C 7 H 5 O 2 f " \ H 8 O ( : No. 223. 
 
 The salt No. 222 shows that this series is not confined to aniline, but 
 has a general character. The Anilidogen (C 6 H 5 N), which is commonly 
 assumed to be present in the " aniles," is a phantom. 
 
 Amidogen Acids. Amidated Acids. Amided Acids. 
 
 The amidated acids are produced when one atom of HHO is abstracted 
 from an acid salt of ammonia. Example : 
 
 Binoxalate of Ammonia. Water. Residue. 
 
 ZH 4 ; CO 8 ) TT nn _JZH 2 ; CO 
 H; C0 8 f " -] H; CO* 
 
 This residue is a double salt, consisting of an atom of normal hydrated 
 oxalic acid and an atom of a salt containing amidogen as a base. This 
 double salt is called oxamic acid. See page 195. The single atom of 
 hydrogen is replaceable by a positive radical, and all the other elements 
 
 Q 
 
226 OXAMATES. 
 
 of the salt pass into the new salt. We may apply a systematic name 
 to oxamic acid either according to its analytical or its synoptical formula, 
 thus : 
 
 ZH 2 ,CO+HCO 2 = amida carbate cum hydra carbete. 
 H,ZH 2 ; C 2 3 = hydra amida carbenite. 
 
 The latter is the briefest name, and it is sufficiently explicit. The follow- 
 ing are some of the salts of this " acid " : 
 
 A. OXAMATES. 
 
 227. H ; ZH 2 ; C 2 3 . . . Hydra amida carbenite. 
 
 228. Am; ZH 2 ; C*0 3 . . . Ammona amida carbenite. 
 
 229. Ba;ZH 2 ;C 2 O 3 . . . Baryta amida carbenite. 
 
 230. Ag;ZH 2 ;C 2 O 3 . . . Argenta amida carbenite. 
 
 231. CH 3 ; ZH 2 ; C 2 3 . . . Methyla amida carbenite. 
 
 232. C 8 H 5 ; ZH 2 ; C 2 3 . . Ethyla amida carbenite. 
 
 233. C 2 C1 5 ; ZH 2 ; C ? O 3 . . Chlorunic-ethyla amida carbenite. 
 2 34. C 5 H U ; ZH 2 ; C 2 O 3 . . Amyla amida carbenite. 
 
 235. CH 2 Ca; ZH 2 ; C 2 3 . . Calcic-methy la amida carbenite. 
 Analytical Formula; ZH 2 , CO + H r , CO 2 . 
 
 USUAL NAMES. 227. Oxamic acid = C 4 NH 3 O 6 . 228. Oxamate of 
 ammonia. 229. Oxamate of barytes. 230. Oxamate of silver. 231. 
 Oxamethylane ; oxalformamester = C 6 NH 5 O 6 = C 2 H 3 Ad,C 4 O 6 , Gmelin. 
 232. Oxamethane; oxalvinamester ; oxalovinate of ammonia = C 8 NH 7 O 6 
 = C 4 AdH 6 ', C 4 O 6 , Gmelin. 233. Chloroxamethane ; chloroxethamide = 
 C 8 NH 2 CP0 6 = C 4 AdCP,C 4 8 , Gmelin. 234. Oxamylane = C U H W NO, 
 Gerhardt. 235. Methyloxamate of lime = C 4 N (H, C 2 H 3 ,Ca) O 6 , Gmelin. 
 
 At No. 231, there is a remarkable divergence in the ordinary nomen- 
 clature of these salts. Organic chemists first introduce us to "Oxamic 
 acid," and then, the basic hydrogen of the " acid " being replaced by 
 Am, Ba, Ag, &c., we obtain salts which we are desired to term 
 oxamates. That course is quite proper if we admit the existence of 
 oxamic acid. But no sooner does a positive hydrocarbon appear in the 
 place of the basic radical, when, presto ! the oxamate vanishes and we 
 find that we are dealing w r ith an amethane ! " The amethanes formed 
 by wood-spirit are called methylanes or formamethanes ; these formed 
 by common alcohol, ethylanes, vinamethanes, or simply amethanes ; and 
 those formed by fusel-oil, amy lanes, or mylamethanes." Gmelin. And 
 what is the use of all these trivial, non-systematic names ? Why did 
 not oxamate of methyl, of ethyl, and of amyl, answer the purpose? 
 What good end is obtained by dividing the salts of oxamic acid sup- 
 posing we submit to have oxamic acid into two battalions, and calling 
 one of them oxamates and the other amethanes ? The first false step in 
 this course is that of applying the name " acid " to the double salt No. 
 
OXANILATES. 227 
 
 227 = ZH 2 ,CO-|-HC0 2 . That is an illogical commencement, and leads 
 to the vague and confused notions according to which the other names 
 are perpetrated. 
 
 B. OXANILATES. 
 
 236. H; ZH,C 6 H 5 ; C 2 3 . . . Hydra pheny lac carbenite. 
 
 237. Ba; ZH,C 6 H 5 ; C 2 O 3 . . Baryta pheny lac carbenite. 
 
 238. Ag; ZH, C 6 H 5 ; C 2 O 3 . . Argenta phenylac carbenite. 
 
 239. Am; ZH,C 6 H 5 ; C 2 O 3 . . Ammona phenylac carbenite. 
 J Am ; ZH,C 6 H 5 ; (TO 8 \ Ammona phenylac carbenite 
 
 2 4 a \H : ZH,C 6 H 5 ; C 2 3 ( cum hydra phenylac carbenite. 
 
 JZH 3 ,C 6 H 5 ; ZH,C 6 H 5 ; C 2 O 3 ( Pheny lam phenylac carbenite cum 
 [ ' \ H ; ZH,C 6 H 5 ; C 2 O 3 | hydra phenylac carbenite. 
 
 Analytical formula of No. 236: ZH,C 6 H 5 ; CO + H r ,CO* 
 
 SYNONYMES: 236. Oxanilic acid; anilo-oxamic acid = H,C*0 4 ; 
 C 12 H 6 N,C 2 2 = C 16 H 7 N0 6 = HO.C 2 O 3 ; C I2 HN,C 2 2 = HO.C 2 j ^l^N 
 
 C 2 3 . Hofmann. See Aniline, No. 50]. 237. See Aniline, 51], 238 
 and 239 are analogous salts to No. 237. 240. Acid-oxanilate of 
 
 ammonia = NH 4 0,C 2 1 ^^ C 2 3 + HO . C 2 j ^^ C 2 3 . Hof- 
 mann. 241. See Aniline, 52]. 
 
 The oxanilates differ from the oxamates by containing phenylac instead 
 of amid, I see nothing to prevent the occurrence of similar salts with 
 any other amidac, each salt being formed in agreement with the following 
 general formula : 
 
 H r ; ZH,M r ; C 2 3 = hydra amidac carbenite ; 
 in which formula M r signifies a replaceable radical = C m H n . 
 
 C. AMIDOGEN-ACIDS WITH COMPOUND EADICALS. 
 
 242. H; ZH 2 ; (C 5 H 7 ) 2 3 . . Hydra amida camphorylenite. 
 
 243. H; ZH 2 ; (C 4 H a ) 2 O 3 . . Hydra amida phtalylenite. 
 
 244. H; ZH 2 ; (C 5 H 8 ) 2 3 . . Hydra amida sebamylenite. 
 
 245. H; ZH 2 ; (C S H 2 ) 2 O 3 . . Hydra amida succinylenite. 
 
 246. Ag ; ZH 2 ; (C 2 H 2 ) 2 3 . Argenta amida succinylenite. 
 Analytical formula of No. 242 : ZH 2 ,C 5 H 7 O + H r ,C 5 IFO 8 . 
 
 These salts differ from the oxamates 227 to 235, only by containing 
 compound acid radicals instead of the simple carbon radical of the oxalic 
 acid. Their derivation and structure are perfectly analogous to those of 
 the oxamates. 
 
 USUAL NAMES. 242. Hydrated camphoramic acid = HO,H 2 N, 
 CH 14 O S , Miller. 243. Phtalamic acid = HO,H 2 N,C 16 H 4 O 5 , Miller. 
 244. Sebamic acid = C^H^NO 6 , Gerhardt. 245. Succinamic acid, 
 
 Q2 
 
228 HYDRAMIDES. 
 
 I H 
 
 or hydrate of succinylammonium = O < ,~ 4j4i\TT2 Gerhardt. 
 
 ^, 
 246. Succinamate of silver = | N/^jj^ixjp Gerhardt. 
 
 D. ANILIDOGEN-ACIDS WITH COMPOUND RADICALS. 
 
 247. H; ZH,C 6 H 5 ; (C 5 H 7 ) 8 3 . Hydra phenylac camphorylenite. 
 
 248. H; ZH,C 6 H 5 ; (C 4 H 8 ) 2 O 3 . Hydra phenylac phtalylenite. 
 
 249. H; ZH,C 6 H 5 ; (C 4 H 6 )*0 3 . Hydra phenylac suberylenite. 
 
 250. H; ZH,C 6 H 5 ; (C*H 2 ) 2 3 . Hydra phenylac succinylenite. 
 
 Analytical formula: ZH,C 6 H 5 ; C 5 H 7 O-f H r ; C'H 7 ^. 
 
 These compounds are Dr. Hofmann's anilic or anilidogen acids. They 
 differ from the salts of section C only in containing phenylac instead of 
 normal amid. Hofmann's names and formulae are as follow : 
 
 247. Camphoranilic acid = H,C 10 H 7 O 4 ; C 12 H 6 N,C 10 H 7 O 2 . 
 
 248. Phtalanilic acid . = H,C 8 H'O* ; C 12 H 6 N,C 3 ffO 2 . 
 
 249. Suberanilic acid . = H,C" H 6 O 4 ; C 12 H 6 N,C 8 H 6 8 . 
 
 250. Succinanilic acid . = H,C 4 H*0 4 ; C 12 H 6 N,C 4 H 2 2 . 
 
 This concludes the investigation of the four classes of dehydrated 
 compounds described by Hofmann at page 208. 
 
 Hydramides. 
 
 jZH* 
 
 \ZH,C 8 H 7 
 |ZH : 
 
 C 8 H 7 
 
 C 8 H 7 O 2 I ^ n ^ s } 7 ^ ac am ida anisylenite. 
 
 C 5 H 3 1 
 
 > Furfurylac amida furfurylenite. 
 
 C 7 H 5 O ) 
 
 rvTT5/-\2f Chlorinic-benzylac amida benzylenite. 
 
 \_> -Li. \_/ I 
 
 2 5 2 -\ZH,C 5 H 3 
 
 (ZH 2 
 2 53-{zH,C'H 2 Cl 3 
 
 C 7 H 5 O ) 
 
 /-vTT5/~v2Y Brominic-benzylac amida benzvlenite. 
 
 v^ i V_/ J ^ 
 
 GERHARDT'S NAMES AND FORMULAE. 
 
 251. Anishydramide = C^H^N 2 *} 3 = N 2 | ^ TT S ^ 
 
 252. Furfuramide = C 15 H 12 N 2 O 3 = N 2 K ) 3 
 
 253. Chlorosamide = C 21 H I5 C1 3 N 2 3 = N 2 K C7 2^ C ^^ 
 
 XX 
 
 2 54. Bromosamide = C 8l H 15 Br 8 N 2 3 = N*j ( C7 H 4 (Br)O) 3 
 These hydramides are double salts, each of them containing an 
 
SULPHATES WITH INORGANIC VICE-AMMONS. 
 
 229 
 
 "amide" similar to No. 153, with an "imide" similar to No. 215. 
 Only a few of them have been discovered, but there can be no doubt 
 that many more will be found, now that their nature is understood. 
 
 Sulphates with Inorganic Vice-Ammons. 
 GROUP A. 
 
 255. ZH 4 
 
 256. ZH 3 Zn 
 
 257. ZH 3 Cuc 
 
 258. ZH 3 Ag 
 
 259. ZH 3 Pt 
 
 SO 2 Ammona sulphete. 
 SO 2 Zincam sulphete. 
 SO 2 Cupricam sulphete. 
 SO 2 Argentam sulphete. 
 SO 2 Platousam sulphete. 
 
 USUAL NAMES AND FORMULA. 255, Sulphate of ammonia = 
 NH 4 0,SO 3 . 256 to 259, These salts are sulphates containing the vice- 
 ammoniums to which I have given the name of ammonam. See page 
 193. Namely, they are sulphates of normal ammonium in which H 1 
 has been replaced by M l . They are commonly considered as sulphates 
 of metallic protoxides combined with one atom of ammonia. For an 
 account of No. 259, see Platinum, No. 43. 
 
 GROUP B. 
 
 260. ZH 8 Mn; SO 2 + ZH 2 ,H Mangam sulphete cum amida hydra. 
 
 261. ZH 3 Zn ; SO 2 + ZH a ,H Zincam sulphete cum amida hydra. 
 
 262. ZH 3 Cd; S0 8 + (ZH 2 ,H) 2 Cadmam sulphete bis amida hydra. 
 
 263. ZH 3 Co; S0 2 + ZH 2 ,H Cobaltousam sulphete cum amida hydra. 
 
 264. ZH 3 Ni; S0 2 -f-ZH 2 ,H Niccolousam sulphete cum amida hydra. 
 
 265. ZH 3 Ag; S0 2 + ZH 2 ,H Argentam sulphete cum amida hydra. 
 
 These compounds are examples of the ammoniated salts, of which I 
 have given an account at page 198. It seems needless to quote their 
 ordinary names, as the formulas render them obvious. No. 260 is sul- 
 phate of manganese with two atoms of ammonia = MnO,SO 3 -{-2NH 3 . 
 The names of the others correspond to this example. 
 
 GROUP C. 
 
 266. ZH 4 
 
 268. 
 
 c 
 269. 
 
 
 SO 2 + H,S0 2 Hydra ammona bisulphete. 
 
 SO 2 
 SO 2 
 SO 2 
 SO 2 
 SO 2 
 SO 2 
 SO 2 
 SO 2 
 
 271 
 
 [ 4 ; SO 2 
 'e; SO 4 
 E 4 ; SO 2 
 xs; SO 2 
 SO 2 
 
 , ! > V 
 
 27 M Pb; SO 2 
 
 JZH 4 ; SO 2 
 
 2 "4' I Zn; SO 2 
 
 SO 2 
 SO 2 
 SO 2 
 SO 2 
 SO 2 
 
 277 ' JGuc'; SO 2 
 JZH 4 ; SO 2 
 
 2 7 8 'iH g c;S0 2 
 
 IZH 
 
230 SULPHATES WITH INORGANIC VICE-AMMONS. 
 
 This group consists of double sulphates, in each of which normal 
 ammonium is one of the positive radicals. The systematic names are 
 omitted, to save room. They may be found by substituting the name 
 of the characteristic radical in each salt for the word hydra in the model 
 name added to No. 266, thus : 
 
 No. 271 is Ferrous ammona bisulphete. 
 272 is Ferric ammona bisulphete. 
 
 The ordinary name of No. 266 is bisulphate of ammonia = NH 4 0,S0 3 
 4- HO, SO 3 . The usual name of No. 267 is sulphate of soda and 
 ammonia. 
 
 GROUP D. 
 
 279. ZH 4 ; SO 8 + 3(Alc,S0 8 ) + Aq 18 . 
 
 280. ZH 4 ; SO 2 + 3(Crc,S0 2 ) + Aq 12 . 
 
 281. ZH 4 ; S0 2 + 3(Mnc,S0 2 )+Aq 12 . 
 
 282. ZH 4 ; SO 2 + 3(Fec,S0 2 )-f Aq 12 . 
 
 This group 'consists of the compounds that are commonly called 
 AMMONIA- ALUMS. The systematic name for No. 279 is, ammona 
 sulphete tris alic sulphete cum aquabete. Its common name is sulphate 
 of alumina and ammonia, with 24 atoms of water of crystallization, 
 
 = (NH 4 0,SO 3 ) +(A1 2 8 ,3SO 8 ) + 24Aq. Gmelin. 
 
 = (HO,S0 3 ,HAd + 6Aq)+Al 2 3 ,3SO 3 + i8Aq. Kane. 
 
 These formulae apply equally to the other examples, only changing 
 Al 2 for Cr 2 , Mn 2 , and Fe 2 ; for in all these salts, the usual theory of 
 chemistry assumes the existence of a tersulphate of the sesquioxide of 
 the characterizing metal. 
 
 GROUP E. 
 
 f ZH 4 ,S0 2 ] 
 283. < Uc,SO 8 >Uric ammona bisulphete, bis uric hydrate. 
 
 I (Uc,HO) 2 j 
 
 j ZH 4 ,S0 8 1 Ammona sulphete cum ammona niccolou- 
 2b 4- \ ZH 4 ,NiO | sate. 
 
 J(ZH 3 Cuc,S0 2 ) 2 |Bis cupricam sulphete cum ammona am- 
 2b 5- JZH 4 ,ZH 4 f monate. 
 
 2864 I cf 3 UC ' SO* r^P*" 01 " 1 cu P ric bisulphete. 
 
 287. j H' HO [Merousim sulphete cum merous hydrate. 
 
 288. < TT^ C 'T T , >Mericcim sulphete cum meric hvdrate. 
 | Hgc,HO j 
 
 289. f C ' 2 platicamsul P netecum P latic sulphete. 
 
SULPHATES OF ORGANIC VICE-AMMOXS AND VICE-AMIDS. 
 
 231 
 
 USUAL NAMES AND FORMULAE. 283, Sulphate of uranic oxide and 
 ammonia = urano-ammonic sulphate = NH 4 O,SO 3 + U 2 O 3 ,S0 3 + 2Aq. 
 Gmelin. It may be well to put here the usual name of No. 269 : it is 
 Sulphate of uranous oxide and ammonia = uranoso-ammonic sulphate = 
 NH 4 O,S0 3 + UO,SO 3 . Gmelin. 284, Niccolo-sulphate of ammonia = 
 NH 4 O,NiO = NH 4 O,SO 3 . Gmelin. 285, Cupro-sulphate of ammonia ; 
 cuprum ammoniacale = NH 3 ,CuO + NH 4 O,SO 3 . Gmelin. 286, Sesqui- 
 basic sulphate of cupric oxide and ammonia = NH 3 ,2CuO,2SO 3 , or NH 3 , 
 CuO,SO 3 4- CuO,SO 3 . Gmelin. Observe, that Nos. 257, 277, 285 and 
 286, are all ammoniacal sulphates of copper. 287, Trisulphate of mer- 
 curous oxide with mercurous amide = Hg 2 ,NH 2 + 3Hg 2 0,S0 3 . Gmelin. 
 288, Trisulphate of mercuric oxide with mercuric amide, or ammoniacal 
 turpethum = Hg,NH 2 -f 3HgO,S0 3 . Gmelin. 289. See Platinum, 
 No. 8 1.] 
 
 Sulphates of Organic Yice-ammons and Yice-amids. 
 
 290. ZH 3 ,CH 3 ; 
 
 SO 2 . Methylam sulphete. 
 
 291. ZH 3 ,C 2 H 3 ; 
 
 SO 2 . Acetylam sulphete. 
 
 292. ZH 3 ,C 6 H 5 ; 
 
 SO 2 . Phenylam sulphete. 
 
 293. ZH 3 ,C 6 H 4 a ; 
 
 SO 2 . Chloric-phenylam sulphete. 
 
 294. ZH 8 ,C"H 4 I; 
 
 SO 2 . lodic-phenylam sulphete. 
 
 295. ZH 2 ,C 6 H 5 , Cue 
 
 ; SO 2 . Cupric-phenylam sulphete. 
 
 296. ZH 3 ,C 7 H 7 ; 
 
 SO 2 . Toluenylam sulphete. 
 
 297. | < H > C8 ^. 
 
 SO 2 1 
 ^^2 >Hydra indylac sulphenote. 
 
 2 9 8. { ZH ' C ^ 
 
 Q /^\2 "1 
 
 cr)a >Plumba indylac sulphenote. 
 
 299-f ZH3 ' C8] 
 
 SO 2 1 
 <^ 2 iHydra indylam sulphenote. 
 
 j ZH 8 ,C 10 H 7 
 3 i *7TJ2 
 
 co 2 [Naphtylam amida sulphenote. 
 
 f Z,C 2 H 2 ,C 7 H 5 
 
 SO 2 i Succiny lie - benzylac sulphete cum 
 
 \ C 8 H 5 
 
 SO 2 j phenyla sulphete. 
 
 JZ,C*H 2 ,C'H 2 
 
 SO 8 ISuccinylec sulphete cum phenyla 
 
 J ^ * 1 /^tfiTT^ 
 
 SO 8 f sulphete. 
 
 J ZjC^^C 7 !! 5 
 
 SO 2 JBenzylec sulphete cum phenyla 
 
 33- \ C 6 H 5 
 
 SO 2 f sulphete. 
 
 I Z,C 7 H*,C'H 3 
 
 SO 2 1 Acetylic - benzylac sulphete cum 
 
 jW^J.. "v /^6TJ5 
 
 SO 8 j phenyla sulphete. 
 
 (ZC'H U ,C 7 H 5 
 
 SO 2 tCumylic - benzylac sulphete cum 
 
 305- | C 6 H 5 
 
 SO 8 ) phenyla sulphete. 
 
 306. ZH,(CH 8 ) 3 ;S( 
 
 )' 2 + 3(Alc,SO 2 ) 4- Aq l8 = Methylim sulphete 
 
 
 tris alic sulphete cum aquabete. 
 
232 SULPHATES OF ORGANIC VICE-AMMONS AND VICE-AMJDS. 
 
 USUAL NAMES AND FORMULAE. 290, Sulphate of methylamine = 
 C 2 H 5 N,HSO 4 . 291, Neutral sulphate of acetosamine = 2C 4 H 5 N,2HO, 
 S 2 O 6 , Gerhardt. 292, See aniline 24]. 293, See aniline 26]. 294, 
 See aniline 27]. 295, See aniline 25]. 296, Sulphate of toluidine 
 = 2C 14 H 9 N,S 2 O 6 ,2HO, Gerhardt. 297, See indigo, 48]. 298, See 
 indigo, 49]. 299, See indigo, 46]. 300, Bisulphate of seminaphtalidam, 
 orbisulphate of azonaphtylamine = C 20 H 10 N 2 ,S 2 O 8 ,2HO, Gerhardt. See 
 No. 208. 
 
 301. 
 
 fc' 4 H> o 2 
 
 ( Diazoture of sulphophenyle, of C 14 H 5 O 2 
 
 { benzoile, and of succinyle " = N 8 C 12 H 5 S 8 O 4 Gerhardt. 
 [ = C 60 H 24 N 8 S 4 16 C 12 H 5 S 2 4 
 
 [C 8 H 4 
 
 I Azoture of sulphophenyle, and _ 
 3 2> | of succinyle = C 20 H 9 NS 2 8 = 
 
 Dibenzo - sulphophenylamide 
 = (C 40 H 15 N 8 8 N), or^ 
 
 303. 
 
 Azoture of sulphophenyle and 
 of benzoile = C 80 H r5 NSO 4 
 
 O 4 
 
 C 12 H 5 S 2 4 
 C 8 H 4 O 4 
 
 [C 14 H 5 
 
 (C 18 H 5 ,2SO 2 
 (C 6 H 5 S0 2 
 
 Gerhardt. 
 
 Miller. 
 
 Gerhardt. 
 
 (C 7 H 5 O 
 
 ;c i2 H 5 s 2 o 4 
 
 4 H S O 2 Gerhardt. 
 [C 14 H 5 2 
 For an account of the preparation of this salt, see No. 327. 
 
 Azoture of sulphophenyle, of 
 benzoile, and of benzoile 
 = C 40 H 15 NS 2 8 
 
 (" Azoture of sulphophenyle, of 
 304. < benzoile, and of acetyle = 
 
 Azoture of sulphophenyle, of 
 benzoile, and of cumyle = 
 = C 46 H 21 NS 2 O 8 
 
 C 12 H 5 S 2 O 4 
 
 305 
 
 C 4 H 3 O 2 
 C 12 H 3 S 2 4 
 
 ( = C^IFNSO 4 
 
 C 80 H 11 2 
 C 6 H 5 S0 2 
 
 Gerhardt. 
 
 Gerhardt. 
 
 Gerhardt. 
 
 306. The alum of trimethylamine 
 = S0 3 ,N 
 
 G IO H U O 
 
 - 3SO 8 ,A1 2 3 + 24 aq. 
 
 S 8 6 
 
 Gerhardt. 
 
 
 Professor Miller quotes No. 303 as an example of a " tertiary amide, 
 in which each equivalent of the hydrogen of ammonia is displaced by an 
 
THE POLYTHIONATES OF AMMONIA. 233 
 
 equivalent of an organic radicle," and he apologizes for its " inharmonious 
 and unwieldy name." It would, perhaps, have better suited the cir- 
 cumstances if he had apologized for the wildness of the theory which 
 gave rise not only to the name, but to the formula? ; or does Professor 
 Miller really believe in the proposition, that such compounds as C I4 H 5 2 , 
 and C 14 H 5 3 , and (more wonderful still) C 12 H 5 S 8 O 4 , can each replace 
 one of the three atoms of hydrogen which belong to ammonia, and in 
 company with the nitrogen, constitute an ammonia, merely an ammonia, 
 and not a salt ? Does he believe that the formulae which I have quoted 
 from Gerhardt to represent the compound No. 301, prove the constitu- 
 tion of that compound to be that of an ammonia ? It seems to me, that 
 this new " ammonia type " of Gerhardt's is a press by means of which 
 anything you wish to put out of your way hydrogen, metals, hydro- 
 carbons, metalloids, oxygen, nitrogen, and everything else is to be 
 screwed into the form of an " ammonia," without regard to possibility, 
 necessity, or utility. It is a short and sharp way of getting rid of 
 troublesome things, just as novelists 'and dramatists kill off characters 
 who become superfluous. The ammonia type is an accommodating 
 thing in its own way. Just as the bed of Procrustes suited all men, pro- 
 vided the short men were racked longer and the long men were cut 
 shorter, so the ammonia type suits all nitrogenous salts, provided they 
 are properly trimmed to fit it. 
 
 The Polythionates of Ammonia. 
 
 This section includes the salts that are formed by dry ammonia gas 
 with anhydrous oxy sulphur acids. 
 
 307. ZH 2 ,SO + ZH 4 ,SO . . Amida sulphate cum ammona 
 
 sulphate. 
 
 308. ZH 2 ,SO + H,SO . . Amida sulphate cum hydra 
 
 sulphate. 
 
 309. ZH 2 ,SO + ZH 4 C1 . . Amida sulphate cum ammona 
 
 chlora. 
 
 310. ZH 4 ,ZH 4 ; S 2 3 . . . Ammona ammona sulphenite. 
 
 311. H,ZH 4 ; S 2 O 3 . . . . Hydra ammona sulphenite. 
 
 312. H,ZH 2 ; S*0 3 . . . . Hydra amida sulphenite. 
 
 313. ZH 4 ,ZH 2 ; S 5 ^ 3 . . . Ammona amida sulphenite. 
 
 f H ; ZH 2 ; S 2 O 3 ) Hydra amida sulphenite cum 
 
 *- T 4 ZH 4 ; ZH 2 ; S 2 3 f ammona amida sulphenite. 
 
 315. ZH 4 ,S 2 O 2 4. ZH 2 ,S 2 O* . Ammona sulphenete cum amida 
 
 sulphenete. 
 
 316. ZH 4 ,S 2 O 3 Ammona sulphenite. 
 
 317. ZH 4 ,S 3 O 3 Ammona sulphinite. 
 
234 THE POLYTHIOXATES OF AMMONIA. 
 
 3170. ZH 4 ,S0 2 + (HSO) 2 . Ammona sulphete bis hydra 
 
 sulphate. 
 
 JZH 4 SO 4 HSO1 Hydra ammoiia bisulphate cum 
 
 3 ' | (ZH 4 ) 2 ; S 4 3 f ammonen sulphonite. 
 
 319. (ZH 4 ) 2 ,S 4 3 -f- -jAq Tris ammonen sulphonite cum 
 
 aquate. 
 
 USUAL NAMES AXD FORMULA. 
 
 307. ZH 2 ,SO -f- ZH 4 ,SO . . Amida sulphate cum ammona 
 
 sulphate. 
 
 According to Miller, this compound is produced by mixing dry sul- 
 phurous acid gas SO with an excess of dry ammoniacal gas. Two 
 volumes of SO and four volumes of ZH 2 H, that is to say, two atoms of 
 each compound, combine to form this salt. Miller calls it sulphurous 
 ammonide = H 3 N,S0 2 . Gmelin does not admit of its existence. 
 
 308. ZH 2 ,SO + H,SO . . Amida sulphate cum hydra 
 
 sulphate. 
 
 Miller informs us, that this compound is produced when an excess of 
 dry sulphurous acid gas is mixed with dry ammoniacal gas. Gmelin 
 states, on the authority of Rose, that in whatever proportions the two 
 gases are mixed, they always condense in equal volumes. Miller's for- 
 mula is H 3 N,2SO 2 . Gmelin gives it two formula, NH 3 ,2SO 2 and 
 NH 8 ,SO,SO 3 , and names it sulphit-ammon. 
 
 It differs from bisulphite of ammonia, No. 311, by one atom of water, 
 thus 
 
 Z H*' S O + HS [ = ZH4S 2 + HSO - 
 
 When it is dissolved in water, it speedily produces sulphate and trithio- 
 nate of ammonia 
 
 ZH 2 ,SO + HSO 
 ZH 2 ,SO 4 HSO 
 
 H 2 O 
 
 H 2 O 
 
 ZH 4 ,S0 2 \ 
 
 HSO > = Trithionate of ammonia. 
 
 HSO ) 
 ZH 4 ,SO 2 = Sulphate of ammonia. 
 
 Compare the note descriptive of No. 315. 
 
 309. ZH 2 ,SO 4 ZH 4 C1 . Amida sulphate cum ammona 
 
 chlora. 
 
 A mixture of sal-ammoniac and sulphamide = NH 2 ,S0 2 4 NH 3 C1, 
 Gmelin. A white soluble powder. Sulphamide = ZH 2 ,SO has not 
 been isolated. 
 
 310. ZH 4 ; ZH 4 ; S 2 O 3 . . Ammona ammona sulphenite. 
 
THE POLYTHIONATES OF AMMONIA. 235 
 
 Analytical formula = ZH 4 ; SO -fr- ZH 4 ,S0 2 . Usual name: Neutral 
 sulphite of ammonia. 
 
 311. H; ZH 4 ; S 2 O 3 . . Hydra ammona sulphenite. 
 
 Analytical formula = ZH 4 ,SO + H,S0 2 . Usual name: Bisulphite of 
 ammonia. 
 
 312. H ; ZH 2 ; S 2 3 . . Hydra amida sulphenite. 
 
 A hypothetical compound ; not yet produced. Its supposed constitu- 
 tion is = ZH 2 SO -f H r S0 2 ; the H r being replaceable by a positive 
 radical. Usual name : Sulphamic acid = HO,H 2 N,S 2 O 5 , Miller. The 
 formula of the sulphamates, according to the radical theory, is 
 ZH 2 SO + M r SO 2 , or M r ; ZH 2 ; S 2 O 3 . That is to say, they are common 
 bibasic sulphites, in which ZH 2 is constantly one of the two basic 
 radicals. According to Dr. Miller's formula, this acid is what I may 
 call an amidated hypos ulphate ; but we have not the slightest evidence 
 to show that the amidogen in this salt acts as part of the acid radical, 
 nor that the salt is a hyposulphate. In fact, if ZH 2 be admitted to be a 
 basic radical, then the existence of two positive radicals in the salt is suf- 
 ficient proof that it is not a hyposulphate. See the note on oxamic acid, 
 page 195, and in the oxamates, page 226. 
 
 313. ZH 4 ;ZH 2 ;S 2 3 . . Ammona amida sulphenite. 
 
 Analytical formula = ZH 2 ,SO + ZH 4 ,SO 2 . Produced by transmitting 
 a current of dry ammoniacal gas = ZH 2 H over anhydrous sulphuric 
 acid = S,SO 3 , keeping the latter in excess. Common names : Sulphuric 
 ammonide or Sulphat ammon = H 3 N,SO 3 , Miller. Sulphate of ammon 
 = NH 3 ,SO 3 , Gmelin. Sulphamide, Dumas. Sulphat ammon, Rose. 
 It is, of course, the ammonium salt of the hypothetical sulphamic acid, 
 No. 312; and it is sometimes called the sulphamate of ammonia. 
 Gmelin describes a " deliquescent sulphate of ammon," which seems 
 to agree with the formula ZH 4 ; ZH 2 ; S 2 O 3 + aq. 
 
 f H ; ZH 2 ; S 2 3 ) Hydra amida sulphenite cum 
 
 3 * 4- 1 ZH 4 ; ZH 2 ; S 2 3 j "ammona amida sulphenite. 
 
 " According to Jacquelain, this compound may be procured in beau- 
 tiful transparent crystals by transmitting the vapour of anhydrous sul- 
 phuric acid into ammoniacal gas in excess ; the solid compound thus 
 obtained is fused in a current of dry ammonia, and dissolved in water. 
 The crystals obtained on evaporation consist of 3(H 3 N) -}- 4SO 8 . Al- 
 though the solution of this compound has an acid reaction, it gives no 
 precipitate with salts of baryta." Miller. 
 
 Compare the three formulas 312, 313, 314. It is evident that 314 
 represents a double salt composed of 3 12 -j- 31 3. It is what might be 
 called, according to the ordinary theory, the acid sulphamate of ammonia ; 
 
236 THE POLYTHIONATES OF AMMONIA. 
 
 but Miller does not give it that name. The reader will find it important 
 to notice the evidence afforded by this salt of the existence of double 
 sulphites. The presence of the replaceable atom of H r is the cause of 
 the acid reaction. The non-precipitation of salts of baryta MAY be due 
 to the formation of a soluble double salt agreeing with the formula 
 
 j Ba;ZH 2 ; S 2 O 3 ) 
 tZH 4 ;ZH 2 ; S 2 OT 
 
 JZH 4 ; S 2 O 2 ) Ammona sulphenete cum 
 
 3 1 5 | ZH 2 ; S 2 O 2 j amida sulphenete. 
 
 I have alluded at page 1 70 to the existence of a class of oxysulphur 
 salts which agree with the formula H r ,SO + SO or H^SW This 
 compound may be a double salt of that series, but its composition is un- 
 certain. I have grouped the elements into a different formula at 
 No. 308. Other views of the composition of this salt are described in 
 Gmelin's Handbook of Chemistry, vol. ii., p. 456. It is possible that 
 salts may exist which agree with both formulae. 
 
 316. ZH 4 ; S 2 O 3 .... Ammona sulphenite. 
 
 A compound containing S 2 O 3 , with one positive radical, constituting 
 what Gmelin properly calls a hyposulphate. His formula is NH 4 0,S S O 5 , 
 (with aq 1 , which I have omitted in the above formula). 
 
 317. ZH 4 ; S 3 O 3 . . . Ammona sulphinite. 
 
 jZH 4 S0 2 | Ammona sulphete bis hydra 
 
 )(HSO) 2 [ sulphate. 
 
 Miller quotes H 4 NO,S 3 O 5 as the formula of the trithionate of ammonia 
 which is produced by the decomposition of the salt No. 308. This for- 
 mula would require No. 317; but in the presence of water, the compound 
 that would be produced is that which is represented by the formula 
 No. 317^. Consult the Theory of the Trithionates, page 168. 
 
 a JZH 4 SO + HSO) Ammona hydra bisulphate 
 3 |(ZH 4 )*; S 4 O 3 f * cum ammonen sulphonite. 
 319. (ZH 4 ) 2 ; S 4 O 3 -f- aq Tris ammonen sulphonite 
 
 cum aquate. 
 
 Gmelin's. hyposulphite of ammonia = 3(NH 4 O,S 2 2 ) -f- HO, admits 
 of explanation either by No. 318 or 319, according as it is considered to 
 be a hydrated or an anhydrous salt. See the Theory of the Hyposulphites, 
 page 1 60. 
 
( 237 ) 
 
 320. 
 
 CH 3 ; 
 
 ZH 2 ; 
 
 
 320*. 
 
 C 7 H 5 ; 
 
 ZH 4 ; 
 
 
 321. 
 
 H; 
 
 ZH, 
 
 C 6 H 5 
 
 322. 
 
 ZH 4 ; 
 
 ZH, 
 
 C 6 H 5 
 
 323. 
 
 Ag; 
 
 ZH, 
 
 C 6 H 5 
 
 324. 
 
 Ba; 
 
 ZH, 
 
 C 6 H 5 
 
 325. 
 
 C 7 H 3 ; 
 
 ZH, 
 
 C 6 H 5 
 
 326. 
 
 C io H ii 
 
 ;ZH, 
 
 C 6 H 5 
 
 327. 
 
 Ag; 
 
 ZC 7 H 5 
 
 ,C 8 H 5 
 
 328. 
 
 OH 5 ; 
 
 ZAg, 
 
 C 8 H 5 
 
 329. 
 
 H; 
 
 ZH, 
 
 C io H 7 
 
 33- 
 
 K; 
 
 ZH, 
 
 C'H 7 
 
 331. 
 
 K; 
 
 ZH, 
 
 C 7 H 7 
 
 332. 
 
 ZH 4 ; 
 
 ZH, 
 
 C 7 H 7 
 
 333- 
 
 (ZH 3 , 
 
 C 8 H 3 ) 2 ; 
 
 
 Sulphites containing Vice-Amids and Yice-Ammons. 
 
 The conditions of the existence of a sulphite are that it shall contain 
 two positive radicals, two atoms of sulphur, and three atoms of oxygen. 
 
 S 2 O 3 Methyla amida sulphenite. 
 
 S 2 O 3 Benzyla ammona sulphenite. 
 
 S 2 O 3 Hydra phenylac sulphenite. 
 
 S 2 O 3 Ammona phenylac sulphenite. 
 
 S 2 O 3 Argenta phenylac sulphenite. 
 
 S 2 O 3 Baryta phenylac sulphenite. 
 
 S 2 O 3 Benzyla phenylac sulphenite. 
 
 S 2 3 Cumyla phenylac sulphenite. 
 
 S 2 3 Argenta benzylic-phenylac sulphenite. 
 
 S 2 O 3 Benzyla argentic-phenylac sulphenite. 
 
 S 2 3 Hydra naphtylac sulphenite. 
 
 S 2 O 3 Potassa naphtylac sulphenite. 
 
 S 2 O 3 Potassa toluenylac sulphenite. 
 
 S 2 O 3 Ammona toluenylac sulphenite. 
 
 S a O 3 Indylarnen sulphenite. 
 
 USUAL NAMES AND FORMULAS. 
 
 320. CH 3 ; ZH 8 ; S 2 O 3 . Methyla amida sulphenite. Analytical 
 formula = ZH 2 SO + CH 3 ,S0 2 . This salt corresponds to 3 13, with the 
 exception that the replaceable positive radical is CH 3 instead of ZH 4 . 
 It is, therefore, according to the usual theory, the sulphamate of methyl, 
 the trivial name of which is sulphomethylane. Gmelin's new German 
 systematic name is Schwefel-Formamester = C 2 H 3 Ad,2SO 3 . He also 
 quotes the following formula = C 2 H 5 NS 2 O 6 and C 2 H 3 O,S 2 AdO 5 . Ger- 
 hardt's name and formulae are, Sulphamethylane, or sulphamate of 
 methyl = C 2 H 5 NS 2 6 
 
 INH 2 (SO 2 ) 2 O| 
 
 C 2 H 3 O| ' an( ^ ^ e a ^ s *^ e m f rma ti n > tnat " sulphamic acid 
 
 represents the hydrate of an oxide of ammonium in which H is replaced 
 by SO 2 ." I might reasonably inquire, whether " the hydrate of an oxide 
 of ammonium," in which H has been replaced by SO 2 , STILL REMAINS 
 " the hydrate of an oxide" of ammonium ? For my part, I consider an 
 ammonium having the formula (ZH,H,SO S ,S0 2 ) to be a monster whose 
 existence is impossible. 
 
 The following is Professor Gregory's account of this compound : 
 " When a current of ammonia is made to act on the neutral sulphate of 
 methyl, there is produced a crystalline compound C 2 H 3 NS 2 6 , which 
 
238 SULPHITES CONTAINING VICE-AM1DS AND VICE-AMMONS. 
 
 has been called sulphamethylane, and may be viewed as oxamethylane, 
 in which sulphamide, SO 2 ,NH 2 , has been substituted for oxamide, C 2 O 2 , 
 NH 2 ; or SO 2 , for C 2 e . It may also be considered, if oxamethylane 
 be the oxamate of oxide of methyl, C 2 H 3 O -f C 4 H 2 NO 5 , as composed 
 of oxide of methyle and a peculiar acid, formed of hyposulphuric acid 
 and amide, or rather of sulphuric acid and sulphamide, and which may 
 be called sulphamic acid ; and its formula will be C 2 H 3 O + (S 2 O 5 , 
 NH 2 ), or C 2 H 3 + (SO 3 + NH 2 ,SO 2 ). On this view, sulphamethylane 
 is the sulphamate of oxide of methyle." Handbook of Organic Che- 
 mistry (1856), page 179. 
 
 This paragraph contains an excellent summary of the views that are 
 now entertained by organic chemists in respect to this compound, and 
 these views manifest a state of bewilderment which is calculated to 
 inspire little confidence in the minds of chemical students. 
 
 320*. C'H 5 ; ZH 4 ; S 2 O 3 , Benzyla ammona sulphate. 
 
 Usual Name : Sulphite of benzosum and of ammonium 
 
 (SO 
 
 = C 7 H 5 (NH 4 )O,SO 2 = O 2 {C 7 W Gerhardt. 
 (NH 4 . 
 
 321. H; ZH,C 6 H 5 ; S 2 O 3 Hydra phenylac sulphenite. Analytical for- 
 mula = ZH,C 6 H 3 ; SO + H r SO 2 . Compare this formula with No. 312. 
 The salts are similarly constituted, excepting that one of them contains 
 amid as a constant basic radical, where the other has phenylac. In 
 both salts there is one replaceable atom of hydrogen, H r , which gives 
 rise to a series of neutral sulphites. 
 
 Usual names. Sulphanilic acid ; anilamic sulphuric acid, or anilosul- 
 phamic acid = C 12 H 7 NS*O 6 = HO . SO 3 ; C I2 H 6 N,SO 2 = HSO 4 C 12 H 6 N,SO 2 
 
 = HO . S | ^ SO 3 . Hofmann. 
 
 Sulphanilic acid, or phenyl-sulphamic acid = C 12 H 7 NS 2 6 , Gerhardt. 
 Sulphanilic acid = HO,C l2 H 6 NS 2 O 5 = HO,C 12 H 5 ,HN,S 2 5 , Miller. Sul- 
 phanilic acid is formed by heating aniline with strong sulphuric acid. 
 
 322. ZH 4 ; ZH,C 6 H 5 ; S 2 O 3 , Ammona phenylac sulphenite. 
 
 323. Ag; ZH,C 6 H 5 ; S 2 O 3 , Argenta phenylac sulphenite. 
 
 324. Ba; ZH,C 6 H 5 ; S 2 O 3 , Baryta phenylac sulphenite. 
 
 325. C7H 5 ; ZH,C 6 H 5 ; S'O 3 , Benzyla phenylac sulphenite. 
 
 326. C 10 H"; ZH,C C H 5 ; S 2 O 3 , Cumyla phenylac sulphenite. 
 
 These five salts are formed by the replacement of H, in the so-called 
 Sulphanilic "acid" No. 321, by the positive radicals that are exhibited 
 by the different formulae. Of course, these are the salts that are com- 
 monly called sulphanilates. I will nevertheless quote the ordinary 
 names and formulae of each salt. 
 
SULPHITES CONTAINING VICE-AMIDS AND VICE-AMMONS. 239 
 
 322, Sulphanilate of ammonia = C 12 H e (NH 4 )NS 2 O 6 , Gerhardt, 
 = NH^SJ^SO 3 , Hofmann. 
 
 323, Sulphanilate of silver = C 12 (H 6 Ag)NS 2 6 , Hofmann. 324, Sul- 
 phanilate of barytes = C 12 (H 6 Ba)NS 2 O 6 , Hofmann. 325, Analytical 
 ibrmuke, ZH,C 6 H 5 ; SO+C 7 H 5 ; SO 2 . Usual names : Benzo-sulphophe- 
 
 (C 12 H 5 , 2 S0 2 ) 
 nylamide = < C 14 H 5 O 2 V N, Miller. Azoture of sulphophenyle, of 
 
 (C 6 H 3 S0 2 
 benzoile, and of hydrogen = N < C 7 H 5 O Gerhardt. The following 
 
 I H 
 
 reaction exhibits the formation of this salt from No. 342, when acted 
 upon by the compound C 7 !! 5 , CIO = Benzyla chlorate, commonly called 
 chloride of benzoyl. 
 
 v JZH,C 6 H 5 ; SOU (ZH,C 6 H 5 ; SO ) v 
 
 *<> 342 { Ag ; SO }LJ w; so 2 }= No * 325> 
 
 C 7 H 5 ; ClOJ ( Ag; Cl 
 
 326, Azoture of sulphophenyle, of (C 6 H 5 SO 2 
 
 cumyle, and of hydrogen = N ^C 10 H U Gerhardt. 
 = C 16 H 17 NS0 3 I H 
 
 It is amusing to notice the varieties in the formulae which the 
 ingenuity of chemists has provided for the sulphanilates. The salts 
 are evidently formed on a single model, but the formulas are very agree- 
 ably diversified, and all in accordance with the well-known philosophical 
 axiom, that " the farthest way round is the nearest way there." 
 
 327, Ag; ZC 7 H 5 ,C 8 H 5 ; S 2 O 3 . Argenta benzylic-phenylac sulphenite. 
 
 328. C 7 H 5 ; ZAg,C 6 H 5 ; S 2 O 3 . Benzyla argentic-phenylac sulphenite. 
 Nos. 327 and 328 are different formulas to represent the sarne~com- 
 
 pound. The salt differs from No. 323, in havmg the amidec ZC 7 H 5 ,C 6 H 5 , 
 
 instead of the amidac ZH,C 6 H 5 . It may also be compared with the salt 
 
 No. 325, from which it is prepared, and from which it differs by con- 
 
 taining ZAg,C 6 H 5 instead of ZH,C 6 H 5 . Whether the silver acts as a 
 
 base per se, or is in the condition of argentic-phenylac is undetermined. 
 
 The following reactions are interesting, but undecisive in this particular : 
 
 (7H 5 ; ZH,C 6 H 5 ; S 2 O 3 ) JC 7 H 5 ; ZAg,C 6 H 5 ; S 2 O 3 
 
 Ag; N0 3 f \ H; NO 3 . 
 
 C 7 H 5 ; ZAg,C 6 H 5 ;S 2 3 ) JZC 7 H 5 ,C'H 5 ; SO 2 ] 
 
 C 7 H 5 ; CIO f := ) C 6 H 5 ; S0 2 [ 
 
 The product of the last reaction is the salt No. 303. 
 
 Usual name of No. 327 : 
 
 C 12 H 5 , 2 S0 2 
 Benzosulphophenylargentamide = C 14 H 5 O 2 [> N, Miller 
 
240 HYPOSULPHATES CONTAINING VICE-AMIDS AND VICE-AMMONS. 
 
 rc 6 H 5 so 2 
 
 Azoture of sulphophenyle, of 1 = N Q 
 
 benzoile and of silver. j . 
 
 329. H; ZH,C IO H 7 ; S 2 3 , Hydra naphty lac sulphenite; Analytical 
 formula = ZH,C 10 H 7 ; SO + H,SO 2 . 
 
 Thionaphtamic acid = C^H'NS^O 6 , Gerhardt. Compare with No. 337. 
 
 330. K; ZH,C W H 7 ; S 2 O 3 ; Potassa naphtylac sulphenite. 
 Thionaphtamate of potash, Gerhardt. Similar salts are formed with 
 
 ZH 4 ,Ba,Pb, instead of K. Compare with No. 338. 
 
 331. K; ZH^^E 7 ; S 2 3 . . . Potassa tolueny lac sulphenite. 
 
 332. ZH 4 ; ZH,C 7 H 7 ; S 2 3 . . Ammona toluenylac sulphenite. 
 
 These salts are called thiotolamates or thiotoluolates. Formula?.: 
 C 14 NH 8 KS*0 6 and C 14 NH 8 (NH 4 ) 2 SO 3 , Gmelin. The thiotolamic acid 
 has not been isolated. 
 
 333. (ZH 3 ,C 3 H 3 ) 2 ; S 2 3 , Indylamen sulphenite. See Indigo, No. 50.] 
 
 Hyposulphates containing Yice-Amids and Vice- 
 Ammons. 
 
 A hyposulphate must contain two atoms of sulphur, three atoms of 
 oxygen and one positive radical. 
 
 334- ' g Hydra phenylac bisulphenite. 
 
 (ZBa C 6 H 5 S 8 O 3 ) 
 
 335. -j R ' osQaf Baryta barytic-pheny lac bisulphenite. 
 
 336. < A ^' ' oQ3 > Argenta argentic-phenylac bisulphenite. 
 337- |^ Cl H7 ) 2 ; jp 3 3 i Naphtylem amida bisulphenite. 
 
 33 s ' |\ Cl H7 ^: gl^l Naphtylem argentec bisulphenite. 
 
 339. ZH 3 Zn; S S O 3 -f ZH 2 H Zincam sulphenite cum amida hydra. 
 
 340. ZH 3 Ni ; S 2 3 -f- 2ZH 2 H Niccolousam sulphenite bis amida 
 
 hydra. 
 
 USUAL NAMES AND FORMULA. 
 334. H; ZH,C 6 H 5 ; (S J O 3 ) 2 , Hydra phenylac bisulphenite. 
 
 Analytical formula (ZH,C 6 H 5 ; SO 2 + SOI 
 See page 172. \ H; SO 2 + SO) 
 
 Compare this compound with No. 321. The basic radicals H and 
 
HYPOSULPHATES COXTAINIXG V1CE-AMIDS AND VICE- A MM ON S. 241 
 
 ZH,C 6 H 5 , are combined in 321 with S 2 O 3 , in 334 with twice S 2 3 ; or, 
 reversing the standard, we have, to the same quantity of S 2 O 3 , in 321, 
 four basic radicals, in 334 two basic radicals. Hence, 321 is a sulphite 
 and 334 a double hyposulphate. This compound is produced by heating 
 dry sulphanilic acid with fuming sulphuric acid. It was discovered by 
 Buckton and Hol'mann, who call it disulphanilic acid, and give it the 
 formula C 12 H 7 NS 4 12 . According to these chemists, it is a peculiar 
 and perfectly new bibasic acid, which forms salts that agree with the 
 formula C 12 (H 5 M 2 )XS 4 12 . There is, however, no evidence to prove the 
 existence of this peculiar acid, or to warrant the formulating of the salts 
 which it produces as if they contained any new acid. They appear to be 
 double hyposulphates and nothing else. 
 
 (ZBa,C H H 5 ; S 2 O 3 \ ^ 
 335. < p ' 02Q3 \ -Baryta barytic-pheny lac bisulphemte. 
 
 336- \ AO-- S 8 O 3 I J ^- r enta argentic-pheriylac bisulphenite. 
 
 These are salts of the so-called "disulphanilic acid," No. 334. They 
 can be formulated in a more simple manner thus : 
 
 334. ZH 2 ; C 6 H 5 ; (S^ 3 ) 2 = Amida pheny la bisulphenite. 
 
 335. ZBa 2 ; C 6 H 5 ; (S 9 3 ) 2 = Barytec phenyla bisulphenite. 
 
 336. ZAg 2 ; C 6 H 5 ; (S 2 3 ) 2 = Argentec phenyla bisulphenite. 
 
 But these formula are founded on the notion of the complete disruption 
 of the aniline ; and I cannot tell, from the account which has been pub- 
 lished by Messrs. Buckton and Hofmann, whether this disruption takes 
 place or not. These formula? account, in a very simple manner, for the 
 bibasic property of disulphanilic acid. 
 
 
 (ZH 2 ,(C'H 7 ) 2 ; S 8 3 | AT , . , ., ,. . , . 
 
 337. wua. QS( Naphtylem amida bisulphemte. 
 
 ( ZH 2 ( 10 H 7N ) 2 S 9 3 ) 
 
 IZAffAo" g?Q 3 > ^aphtylem argentec bisulphenite. 
 
 When thionaphtamic acid (No. 329) is prepared, its mother-liquor 
 yields a compound having different properties, but the same percentage 
 composition as that acid. See Gerhardt, on the authority of Piria, Traite 
 de Chimie Organique, tome iii. 472. Gerhardt calls it Naphthionic acid 
 and Sulpho-naphtalidamic acid. His formula is OH 9 NS 2 6 ; and that 
 of the salts is C 20 H 8 MNS 2 6 . These formulae agree precisely with those 
 which he gives for the thiomiphtamates. We give, however, some sort 
 of reason for the isotnerism which is found here, if we ascribe to one set 
 of salts the formulas given at Nos. 329 and 330, and to the other set 
 those given at Nos. 337 and 338. It is favourable to this sugges- 
 tion, that the salts which I have formulated as hyposulphates are much 
 
 R 
 
242 HYPOSULPHITES WITH VICE-AMMONS AND VICE-AMIDS. 
 
 more difficult of decomposition than those which I have described as 
 sulphites. This power of withstanding the decomposing action of 
 reagents is characteristic of the hyposulphates generally. 
 
 339. ZH 3 Zn; S 2 O 3 -f- ZH 2 H. Zincam sulphenite, cum amida hydra. 
 
 Gmelin calls this salt the Ammonio-hyposulphate of zinc-oxide = 2NH 3 
 4- ZnO,S 2 O 5 . 
 
 340. ZH 3 Ni; S 2 O 3 -f- 2ZH 2 H. Niccolousam sulphenite cum amida 
 
 hydra. 
 
 Gmelin's name and formula : Ammonio-hyposulphate of nickel-oxide 
 = 3 NH 3 + NiO,S 2 5 . 
 
 Hyposulphites with Vice-Ammons and Vice-Amids. 
 
 341. ZH,C 6 H 5 ; SO -f HSO. Phenylac sulphate cum hydra sul- 
 
 phate. 
 
 342. ZH,C 6 H 5 ; SO + AgSO. Phenylac sulphate cum argenta 
 
 sulphate. 
 
 343. ZH,C 8 H* ; SO + C1SO. Phenylac sulphate cum chlora sul- 
 
 phate. 
 
 344. (ZH 3 Zn) 2 ; S 4 3 . Zincamen sulpifbnite. 
 
 USUAL NAMES AND FORMULA. 
 
 341. ZH,C 6 H 5 ; SO + HSO. Phenylac sulphate cum hydra sulphate. 
 
 Sulphophenylamide, or azoture of f C 6 H 5 SO 2 
 
 sulphophenyle and of hydrogen = N < H Gerhardt. 
 = C 6 H 7 NS0 2 ( H 
 
 342. ZH,C 6 H 5 ; SO -f AgSO. Phenylac sulphate cum argenta sulphate. 
 
 Azoture of sulpho-phenyle, of f C 6 H 5 SO 2 
 
 silver, and of hydrogen = = N < Ag Gerhardt. 
 C 6 H 6 NS0 2 I H 
 
 See No. 325. 
 
 343. ZH,C 6 H 5 ; SO-j-ClSO. Phenylac sulphate cum chlora sulphate 
 Chloride of sulpho-phenyle = C 12 H 5 S*0 4 C!, Gerlardt. 
 
 These three salts may also be formulated thus : 
 
 341. H; ZH,C 6 H 5 ; (SO) 2 . . Hydra phenylac bisulphate. 
 
 342. Ag; ZH,C 6 H 5 ; (SO) 2 . . Argenta phenylac bisulpbate. 
 
 343. Cl; ZH,C 6 H 5 ; (SO) 2 . . Chlora phenylac bisulphate. 
 
 344. (ZIFZnf; S 4 3 .... Zincamen sulphonite. 
 Ammonio-hyposulphite of zinc-oxide = NH 3 -f ZnO,S 2 2 , Gmelin. 
 
( 243 ) 
 
 Sulphenetes containing Yice-Amids. 
 
 j ZH,C 6 H 5 ; S 2 2 ) Phenylac sulphenete cum 
 
 345- \ C 6 H 5 ; S a 2 j phenyla sulphenete. 
 
 Gerhardt's name and formula for this salt are 
 
 (C 6 H 5 S0 2 
 
 Azoture of disulphophenyle and of hydrogen = N< C 6 H 5 SO 2 
 
 I H 
 
 This salt is procured from No. 342 by a reaction which I have de- 
 scribed at page 171. 
 
 The Cyanides. 
 
 The constitution of cyanogen and the cyanides has been already dis- 
 cussed, first in the investigation of the " sesqui oxides," at pages 38 to 
 43, and secondly in the article on the " nitriles," at pages 217 to 221. 
 A third discussion will be found in the inquiry into the nature of the 
 salts of "aniline," beginning with No. 62 in that series, and another in 
 the article on " Urea." There remain only a few particulars which 
 require illustration under this head, the most important of which is, 
 perhaps, nomenclature. 
 
 SINGLE CYANIDES. 
 
 
 346. HCy . . . Hydra cyana. 
 
 347. KCy . . . Potassa cyana. 
 
 348. AgCy . . . Argenta cyana. 
 
 349. FeCy . . . Ferrous cyana. 
 
 350. FecCy . . . Ferric cyana. 
 
 351. AuCy . . . Aurous cyana. 
 
 352. AucCy . . Auric cyana. 
 3^3. ZH 4 ,Cy . . Ammona cyana. 
 
 354. ZH 2 ,Cy . . Amida cyana. 
 
 355. ZH 3 Pt,Cy . Platousam cyana. 
 
 356. ZH 2 (C 7 H 5 ) 2 ,Cy Benzylem cyana. 
 
 357. AsC 2 H 6 ,Cy . Cacodyla cyana. 
 
 358. CH 3 ,Cy . . Methyla cyana. 
 3 59. ZH,CH 3 ; Cy . Methylac cyana. 
 
 360. C 5 H u ,Cy . . A my la cyana. 
 
 361. ZH,C 5 H U ; Cy Amylac cyana. 
 
 362. C 6 H 5 ,Cy . . Phenyla cyar- 
 
 363. ZH,C 6 H 5 ; Cy Phenylac cya 
 
 a. 
 cyana. 
 
 R2 
 
244 
 
 THE CYANIDES. 
 
 364. ZH,C r H 7 ; Cy Toluenylac cyana. 
 
 365. Z(C 2 H 5 ) 2 ; Cy Ethylec cyana. 
 
 366. Z,C 5 H u ,C 6 H 5 ;Cy Amylic-phenylac cyana. 
 
 DOUBLE CYANIDES. 
 
 367. HFecCy 2 . 
 368. KFecCy 2 . 
 369. HAgCv 2 . 
 370. KAgCy 2 . 
 371. HCocCv 2 . 
 372. AgCocCv 2 
 373. HCrcCy* . 
 374. FeFecCy 2 . 
 |ZH 3 ,C 7 H 7 ; 
 
 . Hydra ferric cyanen. 
 . Potassa ferric cyanen. 
 . Hydra argenta cyanen. 
 . Potassa argenta cyanen. 
 . Hydra cobaltic cyanen. 
 . Argenta cobaltic cyanen. 
 . Hydra chromic cyanen. 
 . Ferrous ferric cyanen. 
 
 ^ iToluenylam toluenylac cy 
 
 alien. 
 
 > \<7Tr natru. p" >Cumenylam cumenylac cyanen. 
 
 r. j^SSs ! p y |Phenylam phenylac cyanen. 
 [Lin. ,u 1 ; VX j 
 
 TRIPLE CYANIDES. 
 
 Hydren ferrous cyanine. 
 Potassen ferrous cyanine. 
 Ferrenic ferrous cyanine. 
 Cuprenous ferrous cyanine. 
 Cuprenic ferrous cyanine. 
 Ethylen ferrous cyanine. 
 Zincen baryta cyanine. 
 
 378. HHFeCy 3 . . 
 
 379. KKFeCy 3 . . 
 
 380. FecFecFeCy 3 . 
 
 381. CuCuFeCy 3 . . 
 
 382. CucCucFeCy 3 . 
 
 383. C 2 H 5 ,C 2 H 5 ,Fe,Cy 3 
 
 384. ZnZnBaCy 3 . . 
 
 FOURFOLD CYANIDES. 
 
 385. FeFec 3 Cy 4 . 
 
 386. KNaFec 2 Cy*. 
 
 387. CuAg 3 Cy 4 " . 
 
 388. KAuc 3 Cy 4 . 
 
 Ferrous ferrinic cyanone. 
 Potassa natra ferrenic cyanone 
 Cuprous argentine cyanono. 
 Potassa aurinic cyanone. 
 
 CYANIDES IN DOUBLE SALTS. 
 
 (ZH ,C 6 H 5 ; Cy) Phenylac cyana cum phenylac 
 3 b 9- |ZH,C 5 H 5 ; H | hydra. 
 
 j ZH ,C 7 H 7 ; Cy 1 Toluenylac cyana cum tolueny- 
 39- ] ZH ,C 7 H 7 ; H f lac hydra." 
 
 j ZH ,C 10 H 7 ; Cy ) Naphty'lac cyana cum naphty- 
 39 1 {ZH ,C 10 H 7 ; H f lac hydra.' 
 
THE CYANIDES. 245 
 
 (ZH,C 6 H 4 C1; Cyl Chloric-phenylac cyana cum 
 39 2 - \ZH,C (i H 4 Cl; H \ chloric-phenylac hydra. 
 
 I ZH C 6 H 5 Cv I 
 393' I ZH 3 'c 6 H 5 01 I Piien y lac C 7 ana cum phenylam chlora, 
 
 JZH ,C 7 H 7 ; Cy( Toluenylac cyana cum toluenylam 
 394- }ZH 3 ,C 7 H 7 ; Cl j chlora. 
 
 JZH ,C 10 H 7 ; Cy I Naphtylac cyana cum napthtylac 
 395-jZH 3 ,C 10 H 7 ; Cl j chlora. 
 
 USUAL NAMES AND FORMULAE OF THE CYANIDES. 
 
 SINGLE CYANIDES. 346, Hydrocyanic acid; prussic acid = C 2 NH 
 = HCy, Gmelin. 347, Cyanide of potassium = C 2 NK, Gmelin. 348, 
 Cyanid'e of silver = AgCy, Gmelin. 349, Protocyanide of iron; ferrous 
 cyanide ; ferrocyaneisen ; eisencyanur = C 6 N 3 Fe 3 or FeCy, Gmelin. 
 350, Sesquicyanide of iron; ferric cyanide; eisencyanid = C 6 N 3 Fe 2 
 = Fe 2 Cy 3 , Gmelin. See page 39 in this work. 351, Protocyanide of 
 gold; aurous cyanide = AuCy, Gmelin. 35 2 > Tercyanide of gold; auric 
 cyanide = AuCy 8 , Gmelin. 353, Cyanide of ammonium; hydrocyanate 
 of ammonia = NH 4 Cy = NH 3 ,HCy = C 2 N(NH 4 ), Gmelin. 354, Cy- 
 anamide, or azoture of cyanogen and hydrogen = CH 2 N 2 = N(CN,H,H), 
 Gerhardt. 355, see Platinum, 49]. 355, Unnamed substance 
 = OTBPN 2 , Robson, Quarterly Journal Chemical Society, iv. 228; 
 who supposed it to be benzhydramide (see No. 200). 357, Cyanide of 
 cacodyle = C 6 NAsH 6 = C 4 ArH 3 ,C 2 NH, Gmelin. 358, Acetonitrile 
 = C 2 H 3 C 2 N; cyanide of methyl, Hofmann. 359, Methyl-cyanamide, or 
 cyanic methylamide = C 2 H 4 N 2 = N(CH 3 ,Cy,H), Gerhardt. 360, Cya- 
 nide of amyle; capronitrile; cyanhydramilic ether; cyanmylafer = C 12 NH 1! 
 _ C 10 H',C 2 NH, Gmelin. 361, Amyl-cyanamide, or cyanic amylamide 
 = C 6 H U N 2 = N(C 5 H ll ,Cy,H), Gerhardt. 362, Benzonitrile ; cyanide 
 of phenyle = C 14 H 5 N, Gerhardt. 363* Phenyl-cyanamide ; cyananilide 
 = C 7 H 6 N 2 = N(C 6 H 5 ,Cy,H), Gerhardt. See Aniline, 62]. 364, To- 
 luyl-cyanamide = C 8 H 8 N 2 = N(C 7 H 7 ,Cy,H), Gerhardt. 365, Diethyl- 
 cyanamide = C 5 H'N 2 = N(C 2 H 5 ,C 2 H 5 ,Cy), Gerhardt. 366, see Ani- 
 line, No. 83]. 
 
 DOUBLE CYANIDES. 367, Hydroferricyanic acid; ferripmssic acid; 
 red forroprussic acid ; ter-hydrocyanate of ferric oxide = C 6 N 3 H 3 ,C 6 N 3 Fe 8 
 = 3HCy,Fe 2 Cy 3 , Gmelin. 368, Ferricyanide of potassium; red ferro- 
 cyanide of potassium ; red prussiate of potash ; red ferroprussiate of 
 potash = 3 KCy,Fe 2 Cy 3 = C ti N 3 K 3 ,C 6 N 3 Fe 2 , Gmelin. See page 40 of 
 this work. 369, Argentoprussic acid = HCy,AgCy, Gmelin. 370, Ar- 
 gentocyanide of potassium = KCy,AgCy, Gmelin. 371, Hydrocobaltid 
 cyanic acid = C 6 N 3 H 3 ,C 6 N 3 Co 2 = 3 HCy,Co 2 Cy 3 , Gmelin. 372, Cobaltid- 
 cyanideof silver = C 6 N 3 Ag 3 ,C 6 N 3 Co 2 = 3AgCy,Co 2 Cy 3 , Gmelin. 373, 
 Hydrochromidcyanic acid = 3 HCy,Cr 2 Cy 8 = C 8 N 3 H 3 ,C 6 N 3 Cr 2 , Gmelin. 
 
24G THE CYANIDES. 
 
 374, Prussian blue; Turnbull's Prussian blue = C 6 N 3 Fe 3 ,C 6 N 3 Fe 3 
 = 3FeCy,Fe 2 Cy 3 , Gmelin. See page 41. 37 5 > Cyanotoluidine 
 = Cy 9 C"H'K,- Hofmann. 376, Cyanociimidine = Cy,C i8 H' 8 N, Hof- 
 mann. 377> Cyaniline = Cy,C 12 H 7 N. See Aniline, 84], where the 
 reason for doubling the formulas of the salts 375, 376, and 377, is 
 given. 
 
 TRIPLE CYANIDES. 378, Hydroferrocyanic acid; ferroprussic acid; 
 ferruretted chyazic acid = 2HCy,FeCy = C 6 N 3 FeH 2 , Gmelin. 379, 
 Yellow prussiate of potash ; ferrocyanide of potassium ; ferroprussiate of 
 potash = K 2 FeCy 3 = OTFTeK 8 , Gmelin. 380, Ordinary Prussian blue 
 (not TurnbiuTs ; see No. 374, and refer to page 40) = C 6 N 3 Fe 3 , 
 2 C 6 N 3 Fe 2 = 3FeCy,2Fe 9 Cy 3 , Gmelin. 381, Cuprous ferrocyanide 
 = Cu 4 FeCy 3 , Gmelin. 382, Cupric ferrocyanide = Cu 2 FeCy 3 
 = C 6 N 3 FeCu 2 , Gmelin. 383, Ferrocyanide of ethyl = (C 4 H 5 )*FeCy 3 
 = C 6 N 3 FeAe 2 , Gmelin. 384, Cyanide of zinc and barium = BaCy, 
 2ZnCy, Gmelin. 
 
 FOURFOLD CYANIDES. 385, Prussian green; green cyanide of iron 
 = C 6 N 3 Fe 3 ,3C 6 N 3 Fe 2 , Gmelin. 386, Double salt, red prussiate of potash 
 and soda = K 3 Na 3 Fe 4 N 12 C 12 = C 2 N 8 feKiNa, Laurent. 387, Cupro- 
 cyanide of silver = 3AgCy,Cu 2 Cy, Gmelin. 388, Auridcyanide of po- 
 tassium = KCy,AuCy 3 , Gmelin. 
 
 CYANIDES IN DOUBLE SALTS. 389, Melaniline, see Aniline, 63]. 
 390, Metoluidine = C 30 !! 17 ]^ 3 , W. Wilson. 391, Menaphthalamine 
 = C 42 H ir N 3 , Hofmann. 
 
 These three compounds have evidently a corresponding structure. 
 Hence, the criticism given in the note to Aniline, 63] may be held to 
 apply to the whole of them. 392, see Aniline, 71]. 393, see Aniline, 
 64]. 394, Hydrochlorate of metoltiidine = C^IFN^HCl. 395, Hy- 
 drochlorate of menaphthalamine = C 42 H 17 N 3 HC1, Hofmann. 
 
 The theory, according to which I have formulated and named the 
 cyanides, does not require the assistance of any hypothetical secondary 
 radicals, such as cobalti cyanogen, chromicyanogen, platinocyanogen, 
 ferrocyanogen, ferricyanogen, &c. But it requires the acceptance of the 
 theory of basylous and basylic atoms, as it is described at pages 3 2 to 
 43. The ordinary theory, even with the aid of numerous secondary 
 radicals, provides the cyanides with formulae which are much more com- 
 plicated than those that are provided by the radical theory. 
 
( 247 ) 
 
 The Sulphocyanides. 
 
 396. H,Cy,S 2 . . . Hydra cyana sulphene. 
 
 397. K,Cy,S 2 . . . Potassa cyana sulphene. 
 
 398. ZH 4 ,Cy,S 2 . . Ammona cyana sulphene. 
 
 399. Cu,Cy,S 2 . . . Cuprous cyana sulphene. 
 
 400. Cuc,Cy,S 2 . . Cupric cyana sulphene. 
 
 401. Hg,Cy,S 2 . . Mercurous cyana sulphene. 
 
 402. Pt,Cy,S 2 . . . Platous cyana sulphene. 
 
 403. Bic,Cy,S 2 . . Bismic cyana sulphene. 
 
 404. C 2 H 5 ,Cy,S 2 . . E thy la cyana sulphene. 
 
 405. CH 3 ,Cy,S 2 . . Methyla cyana sulphene. 
 
 406. ZH 3 Zn,Cy,S 2 . Zincam cyana sulphene. 
 
 407. ZH 3 Pt,Cy,S 2 . Platousam cyana sulphene. 
 
 408. ZH 3 ,C 6 H 5 ; Cy ; S 2 Phenylam cyana sulphene. 
 
 409. ZH 2 (C 6 H 5 ) 2 ,Cy,S 2 Phenylem cyana sulphene. 
 
 410. ZH 3 ,C 3 H 5 ; Cy ; S 2 Allylam cyana sulphene. 
 
 411. Cu,Cuc,Cy s S 4 . Cuprous cupric cyanen sulphone. 
 
 412. K,Ag,Cy 2 ,S 4 . Potassa argenta cyanen sulphone. 
 
 413. H,Pt,Cy 2 S 4 . . Hydra platous cyanen sulphone. 
 
 414. K,Pt,Cy 2 ,S 4 . . Potassa platous cyanen sulphone. 
 
 415. Ag,Pt,Cy 2 ,S 4 . Argenta platous cyanen sulphone. 
 
 416. ZH 4 ,Cy 3 ,S 4 . . Ammona cyanine sulphone. 
 
 417. ZH 3 K,Cy 3 ,S 4 . Potassam cyanine sulphone. 
 
 418. ZH 3 Ag,Cy 3 ,S 4 . Argentam cyanine sulphone. 
 
 419. K,Hg*,Cy 3 ,S 6 . Potassa merenous cyanine sulphade. 
 
 420. H,Ptc 2 ,Cy 3 ,S 6 . Hydra platenic cyanine sulphade. 
 
 421. ZH 4 .Ptc 2 ,Cy 3 ,S 6 Ammona platenic cyanine sulphade. 
 
 422. K,Ptc 2 ,Cy 3 ,S 6 . Potassa platenic cyanine sulphade. 
 
 423. Ag,Ptc a ,Cy 3 ,S 6 . Argenta platenic cyanine sulphade. 
 
 424. Hg,Ptc 2 ,Cy 3 ,S 6 . Mercurous platenic cyanine sulphade. 
 
 425. Fe,Ptc 2 ,Cy 3 ,S 6 . Ferrous platenic cyanine sulphade. 
 
 426. H 2 ,Cy,S 3 . . . Hydren cyana sulphine. 
 
 427. H,ZH 4 ,Cy,S 3 . Hydra ammona cyana sulphine. 
 
 428. H,Cy,S 3 . . . Hydra cyana sulphine. 
 
 USUAL NAMES AND FORMULAE. 
 
 f jH,Cy,S 2 = Hydra cyana sulphene. 
 *' (HS -f- CyS = Hydra sulpha cum cyana sulpha. 
 
 This is the compound commonly called hydro-sulpho-cyanic acid, and 
 which is regarded by most chemists as a compound of hydrogen with a 
 hypothetical radical called sulpho-cyanogen H -f- CyS 2 . I do not believe 
 
248 THE SULPHOCYAX1DES. 
 
 in the existence of sulpho-cyanogen ; and I consider these compounds to 
 be double sulphides, containing sulphide of cyanogen in combination with 
 a sulphide of another radical = H r S -f- CyS. 
 
 397, Sulpho-cyanide of potassium = K,NC 2 S 2 or K,Scy, Miller. 
 
 = C 2 NK,S 2 , Gmelin. 398, Sulpho-cyanide of ammonium = NH 3 , 
 C*NHS 2 , Gmdin. 399, Cuprous sulpho-cyanide = C 2 NCu 2 ,S 2 , Gmelin. 
 400, Cupric sulpho-cyanide = C*NCuS 2 , Gmelin. See No. 411. 401, 
 Mercurous sulpho-cyanide = C 2 NHg 2 S 2 , Gmelin. 402, Protosulpho- 
 cyanide of platinum = PtCyS 2 , Buekton. 403, Sulpho-cyanide of bis- 
 muth = C 6 N 3 BiS 6 , Gmelin. The triple quantities of cyanogen and 
 sulphur are to accommodate the triple (basylous) atom of bismuth. Of 
 course, if the basylic atom is accepted, the triplication of the formula is 
 needless. 404, Sulpho-cyanide of ethyl, or hydro-sulpho-cyanic ether 
 
 = C S H 5 NS 2 = C 4 H 4 ,C 2 NHS 2 = C*H 5 S,C 2 NS, Gmelin. 405, Sulpho- 
 cyanide of methyl = C 2 H 3 S,C 2 NS = C 2 H 3 ,C 2 NS 2 , Gmelin. 406, Am- 
 monia-sulpho-cyanide of zinc = NH 3 ,C 2 NZnS 2 , Gmelin. Similar salts 
 are formed by ammonams containing cadmium, copper, &c. 407, Sul- 
 pho-cyanide of platos-ammonium = PtH 3 NCyS 2 , Buekton. 408, Hydro- 
 sulpho-cyanate of aniline = C 12 H 7 N,HC 2 NS 2 , Hofmann. 409, Sulpho- 
 carbanilide, or anilo-sulpho-carbamide = C 12 H 6 N,CS, Hofmann. Diphe- 
 nyl-sulpho-carbamide, or diazoture of diphenyle and of sulpho-carbonyle 
 
 f CS 
 = N 2 <^ (C 6 H 5 ) 2 , Gerhardt. 
 
 410, Thiosinamine, or sulphuretted diallyl-urea = C 4 H 8 N 2 S 
 
 [ CS 
 
 .= N*{<7H, Gerhardt. 
 \ W 
 
 411, Cuproso-cupric sulpho-cyanide, or Kupfer-rhodanur-rhodanid 
 - C 4 N 2 Cu 3 S 4 = C 2 NCu 2 S 2 ,C 2 NCiIS 2 , GmeKn. 412, Sulpho-cyanide of 
 
 silver and potassium = C 2 NKS a ,C 2 NAgS 2 , Gmelin. 
 
 413, Hydro-platino-bisulpho-cyanic acid =HPt2(CyS 2 ), Buekton. 
 41 4, Platino-bisulpho-cyanide of potassium = KPtC 4 N 2 S 4 or KPt 2 (CyS 2 ), 
 Buekton. 415, Platino-bisulpho-cyanide of silver = AgPt2(CyS 2 ), 
 Buekton. 416, Sulpho-mellonic acid = 
 
 . 
 N1H 4 ) fCy, Gerhardt. In other places he writes the for- 
 
 N H 
 
 mute = C 6 H 4 N 4 S 4 = (NCyH 2 ,2CyHS 2 ). 417 and 418 are sulpho- 
 mellonates or salts of the " acid," No. 416. If I reckon this acid as a 
 
THE SULPHOCYANIDES. 249 
 
 salt of ammonium (the " acids " of organic chemists are frequently 
 neutral salts of ammonium), then the salts 417 and 418 differ from the 
 acid 416, in containing ammonams instead of normal ammonium. In 
 417 it is potassam ZH 3 K; in 418 it is argentam ZH 3 Ag; but other 
 salts are known which contain the radicals ZH 3 Na,ZH 8 Ba,ZH 3 Sr, 
 ZH 3 Ca,ZH 3 Mg, &c. 419, Sulpho-cyanide of mercury and potassium 
 = C 2 NKS a ,2C a NHgS 2 , Gmelin. 420, Hydroplatino - tersulphocyanic 
 acid = H,Pt3CyS 2 , Buckton. 421, Platino-tersulphocyanide of ammo- 
 nium = NH 4 ,Pt3CyS 2 , Buckton. 422, Platino-tersulphocyanide of po- 
 tassium = KPtC 6 N 3 S 6 , or KPt 3CyS 2 , Buckton. 423, Platino-tersulpho- 
 cyanide of silver = Ag,Pt 3(CyS 2 ), Buckton, 424, Subplatino-tersul- 
 phocyanide of mercury = Hg 2 Pt 3(CyS 2 ), Buckton. 425, Platino-ter- 
 sulphocyanide of iron = FePt 3CyS 2 , Buckton. 
 
 426, H 2 CyS 3 , or according to the analytical formula HS + HS -+- 
 CyS. This compound seems to throw discredit upon the theory which 
 assumes the existence of sulphocyanogen ; for we have here a com- 
 bination of three sulphides, which view is corroborated by the constitu- 
 tion of the next salt in the list, No. 427, which contains HS + ZH 4 S 
 4- CyS. The salt No. 426 has given theoretical chemists a great deal 
 of trouble. Gmelin calls it Hydrothio-sulphoprussic acid, and gives it 
 all these formulae: C 2 NH 2 S 3 = C 2 NH,S 2 HS = C*AdS,S 2 = C 2 AdS 2 
 4-2CS 2 . He also quotes the following : C 2 NHS 2 ,HS, Zeise. C 2 NHS 2 
 4 HS, Berzetius, in which formula C 2 NH represents a peculiar radical, 
 Urene. C 2 AdS.S 2 , Laurent. 
 
 427, Hydrothio-sulphoprussiate of ammonia, or hydrothio-cyanide of 
 ammonium = NH 3 ,C*NH 8 S 8 = C 2 NH(NH 4 )S 3 , Gmelin. See preceding 
 note, 
 
 428, Hydropersulphocyanic acid, or sulphuretted hydrosulphocyanic 
 acid = C 2 NHS 3 = C 2 NHS 2 ,S = H,C 2 NS 3 - C 4 N 2 H 2 ,S 6 = C 2 NAdS 2 
 4 2CS 2 , Gmelin. Here is another compound which, in the relations of 
 Cy to S, does not agree with the sulphocyanogen theory. This, how- 
 ever, is one of those compounds with multiple atoms of sulphur, the 
 nature of which I do not understand. 
 
( 250 ) 
 The Cyanates. 
 
 429. H, CyO . . . Hydra cyanate. 
 
 430. Ag, CyO . . . Argenta cyanate. 
 
 431. CH 3 , CyO . . . Methy la cyanate. 
 
 432. C 2 H 5 , CyO . . . Ethyla cyanate. 
 
 433. C 5 H u ,CyO . . . Amyla cyanate. 
 
 434. C 6 H 5 , CyO . . . Phenyla cyanate. 
 
 435. ZH 4 , CyO . . . Ammona cyanate. 
 
 The cyanates are salts that are formed on the model of water, M r ,CyO, 
 
 M r ) 
 or T > 0, where M r signifies one replaceable positive radical, O = 16, 
 
 and Cy = (C = 12 and*N = 14). They are consequently equal to simple 
 cyanides plus one atom of oxygen. 
 
 USUAL NAMES AND FORMULAE. 
 
 429. Cyanic acid = CyO,HO, Gerhardt, or HO.CPNO, Miller. 
 
 430. Cyanide of silver, or argentic carbonimide = N| . , Gerhardt. 
 
 431. Methyl-cyanic ether = C 2 H 3 0,C 2 NO, Miller. 
 
 Cyanate of methyle ; methyl- 
 
 carbonimide; or azoture of = C(CH 3 )NO = 
 methyle and of carbonyle 
 
 also P | Q- i Gerhardt. 
 
 432. Cyanic ether = C 4 H 5 0,C I NO, Miller. 
 
 Cyanate of ethyle ; ethyl- , ~~ 
 
 carbonimide; or azoture of = C(C 2 H 5 )NO = N j 
 ethyle and of carbonyle 
 
 ako , Gerhardt. 
 
 433. Amyl-cyanic ether = C IO H II O,0 I NO, Miller. 
 
 {psrrii 
 g , Gerhardt. 
 
 434. Anilocyanic acid, Hofmann. See Aniline, 95]. 
 
 Cyanate of phenyle ; phenyl- , 
 
 carbonimide ; or azoture of = C(C 6 H 5 )NO = N | 
 phenyle and of carbonyle 
 Gerhardt. 
 
THE NITRATES. 251 
 
 435. Cyanate of ammonia. A full investigation of this compound is 
 given under the head of " The Urea Theory." 
 
 A variety of complex cyanates are described under " Aniline," Nos. 
 89] to 99]. 
 
 The Nitrates. 
 
 The formula usually given to a Nitrate is MO,N0 5 , where = 8. 
 Doubling the atomic weight of the oxygen, these proportions give us 
 analytically, MO -f NOO ; and synoptically, M,N0 3 . 
 
 As the nitrates have not formed the subject of conflicting discussion 
 among chemists, in consequence of the scarcity of their acid salts and 
 double salts, I shall trouble the reader with only a few notes and queries 
 respecting them. 
 
 436. H,N0 3 = Hydra nitrite. Usual name, hydrated nitric acid = 
 HO,N0 5 . 
 
 437. K,NO 3 = Potassa nitrite. Usual name, nitrate of potash = 
 KO,N0 5 . The change in the name from nitrate to nitrite is rather 
 unlucky, as there is, on the ordinary theory, another class of salts called 
 nitrites; but the change is unavoidable in carrying out a systematic 
 nomenclature. 
 
 438. PbNO 3 . Plumba nitrite. [ = Neutral nitrate of lead.] 
 
 | PbNO 3 -f PbPbO 
 439- { rPb 3 N0 4 
 
 ( PbNO 3 4. PbHO } , 
 44- } or PWH.N0 4 | Plumben 
 
 ( (PbNO 3 4- PbPbO) 4 PbNO 3 ) , 
 44 1 ' 1 or = Pb 4 N 2 O 7 f plumbone nitreneze. 
 
 These sub-salts correspond in their construction with the three varieties 
 of phosphates. They have not the permanency nor the properties of 
 the phosphates ; but they resemble them in their proximate constitution 
 in their atomic structure. 
 
 Phosphates. Nitrates. 
 
 Monobasic . . Pb P O 3 PbNO 8 
 
 T , . f Pb 3 P0 4 Pb 3 N0 4 
 
 Tbasic . . . 4 Pb 2 HN O 4 
 
 Bibasic . . . Pb 4 P 2 7 Pb 4 N 2 7 
 
 See the Article on the Constitution of the Phosphates, pp. 138-142,, 
 
 442. CH 3 ,XO 3 . . . Methyla nitrite. 
 
 443. ZH 3 ,CH 3 ;NO 3 . . Methylam nitrite. 
 
 444. C 2 H 5 ,NO 3 . . . Ethyla nitrite. 
 
252 THE NITRATES. 
 
 445. Z(C 2 H 5 ) 4 ; NO 3 . . Ethylom nitrite. 
 
 446. C 5 H U ,NO 3 . . . Amyla nitrite. 
 
 447. Z(C 5 H U ) 4 ; NO 3 . Am'ylom nitrite. 
 
 448. C 6 H 5 ,NO 3 . . . Phenyla nitrite. 
 
 449. ZH 8 ,C 6 H 5 ; NO 3 . Phenylam nitrite. 
 
 The salts 442 to 449 are examples of nitrates having as basic radical, 
 either a compound radical, or a vice-ammonium containing one or more 
 atoms of a compound radical. 
 
 USUAL NAMES. 442, Methylic nitrate. 443, Nitrate of methyla- 
 mine. 444, Nitrate of ethyle. 445, Nitrate of tetrethylammonium. 
 446, Nitrate of amyle. 447, Nitrate of tetramylammonium. 448, Nitro- 
 phenic acid, or nitrophenole. 449, Nitrate of aniline. As these salts 
 are cited here simply as examples of nitrates, I say nothing about their 
 bases, which are explained in other sections. 
 
 450. ZH 3 ,C 6 H 5 ; CyO + H NO 3 Phenylam cyanate cum hydra 
 
 nitrite. 
 
 451. ZH 3 ,C 6 H 5 ; CyO + AgNO 3 Phenylam cyanate cum argenta 
 
 nitrite. 
 
 USUAL NAMES. 450, Nitrate of carbanilamide. 451, Nitrate of 
 silveroxide carbanilamide. Cited as examples of nitrates in combination 
 with salts containing a different acid. 
 
 ARE THE FOLLOWING SALTS TO BE CONSIDERED AS DOUBLE Nl- 
 TRATES ? 
 
 452. C 7 H,NO 8 + H, NO 3 Chrysyla hydra bin itrite. 
 
 453. C 7 H,NO 3 -f K, NO 3 Chrysyla potassa binitrite. 
 
 454. C7H,N0 3 + Pb, NO 3 Chrysala plumba binitrite. 
 
 455. C 7 H,N0 3 + Pb 2 H, NO 4 Chrysyla nitrite cum plumben hydra 
 
 nitrote. 
 
 456. C7H,NO 3 + ZH 4 , NO 3 Chrysyla ammona binitrite. 
 
 457. (7H,N0 3 -f- ZH 2 , NO 2 Chrysyla nitrite cum amida nitrete. 
 
 458. C 7 H,NO 3 + ZH 3 Ba,N0 3 Chrysyla barytarn binitrite. 
 
 USUAL NAMES. 452, Chrysammic acid = C I4 H 2 (NO 4 ) 2 4 . 453, 
 Chrysammate of potash = C 14 HK(NO 4 ) 2 4 . 454, Chrysammate of lead 
 = C 14 HP(N0 4 ) 2 4 . 455, Sub-chrysammate of lead = C 14 HPb(NO 4 ) 2 O 4 , 
 PbO,HO. 456, Chrysamidic acid = C 14 H S (N0 4 ) 2 NO 4 . 457, Chry- 
 samide = C 14 H 3 (NO 4 ) 2 NO 2 . 458, Chrysamidate of barytes = C 14 H 4 Ba 
 (N0 4 ) 2 NO 4 . These names and formulae are by Gerhardt. 
 
 The salt No. 456 appears to be the neutral salt of ammonia corre- 
 sponding to the acid, No. 452, and to the potash salt, No. 453 ; and 
 the existence of the corresponding amide, No. 457, seems to prove the 
 truth of this idea. But it was found that the salt, No. 456, could 
 exchange H l for Ba 1 , and produce the salt No. 458 ; and for this 
 
THE NITRITES. 253 
 
 reason alone, the neutral salt, No. 456, was called an " acid." This 
 muddle, as in many similar cases, has arisen from a misconception of the 
 character of the radical (ZH 3 Ba). These metallic vice-ammoniums have 
 not hitherto been recognised by chemists ; but I trust that the evidence 
 which I shall bring together in the articles on Indigo and Platinum will 
 prove to chemists their existence and importance. See also pages 137 
 and 193. 
 
 459. C 2 H 5 ; Bi; (NO 3 ) 2 or C 2 H 5 ,N0 3 + BiNO 3 Ethyla bismous 
 
 binitrite. 
 
 Nitrate of bismuthethyle = C 4 H 5 Bi,O 2 ,2NO 5 , Gerhardt. 
 
 f j ZH, C 6 H 5 ; NO 3 ) Phenylac nitrite cum argentic-phenylac 
 4 60 ' \ ZAg,C 6 H 5 ; NO 3 j nitrite. 
 
 Binitrodiphenamate of silver = C 24 H U Ag(NO 4 ) 2 N 2 4 , Gerhardt. 
 
 There are various salts having the same formula as 460, with Ag 
 exchanged for another radical. 
 
 ANHYDROUS NITRIC ACID. The anhydrous nitric acid is derived from 
 the decomposition of two atoms of the hydrated acid, thus : 
 
 HO,NOO 1 . ( HO NOO } 
 
 HO,NOO( \H ~ 0,NOO( 
 
 The Nitrites. 
 
 The terms nitrous acid, hyponitrous acid, and hyponitric acid are used 
 by chemists with a perplexing vagueness. There is but one kind of 
 salt, though we have three kinds of name for it. Nitrites agree with 
 Nitrates in having the same positive and negative radicals, but Nitrites 
 have only two-thirds of the quantity of oxygen which is necessary to 
 constitute Nitrates. If Nitrates have the formula HO,NO 5 , Nitrites re- 
 quire the formula HO, NO 3 . According to the radical theory, these salts 
 are distinguished thus : 
 
 Nitrate of potash = KNO 3 = Potassa nitrite. 
 Nitrite of potash = KNO 2 = Potassa nitrete. 
 
 The following examples of Nitrites nearly all contain debateable 
 " bases," so that the usual formulae of the salts differ entirely from those 
 that are given here. I refer the reader, in those cases which are im- 
 portant, to the sections in which the evidence respecting the nature of 
 the bases is investigated. 
 
 461. ZH,C 2 H 5 ;N0 2 . . Ethylac nitrete. 
 
 462. ZZn,C 2 H 5 ; NO 2 . . Zinc-ethy lac nitrete. 
 
254 THE NITRITES. 
 
 463. ZZn 8 (C 2 H 5 ) 2 ; NO 2 . Zincen-ethylem nitrete. 
 
 464. ZH,CH 3 ; NO 8 . . Methy lac nitrete. 
 
 465. ZZn,CH 3 ; NO 2 . . Zinc-methylac nitrete. 
 
 466. ZZn 2 (CH 3 ) 2 ; NO 2 . Zincen-methylem nitrete. 
 
 467. ZH,C 7 H 7 ; NO 2 . . Toluenylac nitrete. 
 
 468. ZH,C 10 H 7 ; NO 2 . . Naphtylac nitrete. 
 
 469. ZH,C 6 H 5 ; NO 2 . . Phenylac nitrete. 
 
 . JZH,C 6 H 5 ; NO 2 ) Phenylac nitrete cum hvdra 
 
 47 't H ;CyOf ' cyanate. 
 
 47 1 . Z,C 2 H 5 ,C 6 H 5 ; NO 2 . Ethylic-phenylac nitrete. 
 
 472. ZH 3 ,C 7 H 5 ; NO 2 . . Benzylam nitrete. 
 
 (ZH 3 ,C 7 H 5 ; NO 2 ) Benzylam nitrete bis hydra 
 
 (H;Cl) 2 f ' chlora. 
 
 ZH 3 ,C7H 5 ; NO 2 ( Benzylam nitrete bis hydra 
 
 (H;SO 2 ) 2 ( sulphete. 
 
 USUAL NAMES AND FORMULAE : Nos. 461 to 466. Examples of 
 Professor Frankland's Dinitroethylates and Dinitromethylates. See 
 those sections in the article on Conjugated Acids. 467, Nitrotoluidine 
 = C 14 H 8 (NO 4 )N, Gerhardt. 468, Nitronaphtylamine = C 20 H 8 (N0 4 )N, 
 Gerhardt. 469, Nitraniline. See Aniline, No. 54]. 470, Carbamide 
 nitrocarbanilide. See Aniline, No. 58]. A variety of double salts, 
 containing No. 469 as a constituent, are described in the article 
 " Aniline," between Nos. 54] and 61]. It is important to observe that 
 I consider No. 461 = ZH,C 2 H 5 ; NO 2 as the same kind of salt with 
 No. 469 = ZH,C 6 H 5 ; NO 2 . Upon comparing this view with the theories 
 of Frankland and Hofmann respectively, very curious divergencies in the 
 mode of accounting for facts will be seen. 471, Ethyl-nitraniline 
 
 . J 
 474< t 
 
 fH> ) 
 
 = CTNOMN. 
 IC 4 H 5 ) 
 
 Hofmann. 
 
 472, Biamidobenzoic acid = C 14 H 4 (NH 2 ) 2 4 , Voit. 473, Hydro- 
 chlorate of biamidobenzoic acid = C 14 H 4 (NH 2 ) 2 O 4 ,2HC1, Voit. 474, 
 Sulphate of biamidobenzoic acid = C 14 H 4 (NH 2 ) 2 O 4 ,S 2 H 2 O 8 , Voit. In 
 Nos. 472 to 474 "it is remarkable that biamidobenzoic acid does not 
 combine with bases, but forms well-crystallized salts with acids, whence 
 the name of acid is not very appropriate for it," Voit. See his Memoir, 
 Quarterly Journal Chemical Society, ix. 271. It seems to me, that an 
 " acid " with such properties might be conveniently classed with sul- 
 phate of potash, which, on these grounds, has an equal right to be called 
 an "acid." The biamidobenzoic acid will be referred to more par- 
 ticularly in another section. 
 
( 255 ) 
 
 The Oxides and Hydrates of Nitrogen. 
 
 The formulae of the oxides and hydrated oxides of nitrogen are usually 
 written in accordance with the supposition that the atomic weights of 
 their elements are, N_= 14, H = i,O = 8. In this work, the atomic 
 weights of these elements are fixed at N = 14, H = i,O= 16. These 
 proportions necessarily give entirely new formulae to the compounds, and 
 it seems proper to give a short general notice of them, to prevent mis- 
 apprehension. 
 
 OXIDES. , CORRESPONDING HYDRATES. 
 
 475. NO = Nitrate. | 
 
 476. NO 2 = Nitrete. i 
 
 477. N,NO = Nitra nitrate. | 480. H,NO = Hydra nitrate. 
 
 478. N,NO 3 = Nitra nitrite. | 481. H,NO 2 = Hydra nitrete. 
 
 479. N,N0 5 = Nitra nitrate. I 482. H,NO 3 = Hydra nitrite. 
 
 According to the radical theory, all the compounds from No. 477 to 
 48 2 should be considered as salts. 
 
 USUAL NAMES AND FORMUL/E. 
 
 475, NO = Nitrate. 
 
 Nitric oxide, binoxide of nitrogen, deutoxide of nitrogen NO 2 . 
 Atomic weight, 30; specific gravity of gas, 15; atomic measure, 2. 
 Neutral to test papers. 
 
 476, NO 2 = Nitrete. 
 
 Peroxide of nitrogen ; hyponitric acid ; sometimes nitrous acid 
 = NO 4 . Atomic weight, 46; specific gravity of gas, 23 ; atomic mea- 
 sure, 2. Reddens litmus. 
 
 477, N,NO = Nitra nitrate. 
 
 Nitrous oxide ; protoxide of nitrogen ; laughing gas = NO. Atomic 
 weight, 44; specific gravity of gas, 22 ; atomic measure, 2. Neutral to 
 test papers. 
 
 478, N,N0 3 = Nitra nitrite. 
 
 Nitrous acid; sometimes hyponitrous acid; meaning, of course, the 
 anhydrous acid = NO 3 . Atomic weight, 76 ; specific gravity and 
 atomic measure of the gas not yet determined. 
 
 479, N,NO 5 = Nitra nitrate. 
 
 Anhydrous nitric acid = NO 5 . Atomic weight, 1 08 ; specific gravity 
 and atomic measure unknown. 
 
 480, H,NO = Hydra nitrate. 
 Unknown ; unrecognised ; unnamed. 
 
 481, H,N0 2 = Hydra nitrete. 
 
256 AZOTIC RADICALS IN SERIES. 
 
 Hydrated nitrous acid = HO,NO 3 . Atomic weight, 47. This is the 
 acid which corresponds to the nitrites, Kos. 461 to 474 in this series 
 
 482, H,NO 3 = Hydra nitrite. 
 
 Hydrated nitric acid = HO,NO 5 . Atomic weight, 63. This is the 
 acid already referred to at No. 436 in this series. 
 
 I have included among the hydrates a compound (No. 480) that is 
 not recognised by chemists, but which will, in all probability, be dis- 
 covered when it is looked for. It is the compound which corresponds 
 in the nitrogen series with the salt HSO ( = hydra sulphate or penta- 
 thionic acid) in the sulphur series. The corresponding anhydrous com- 
 pound is known in the nitrogen, though not known in an isolated state 
 in the sulphur series. There seems to be no reason why the hydrated 
 form of the acid should not exist in the nitrogen as well as the sulphur 
 series. The following equation represents a transformation that is, a 
 priori, by no means improbable : 
 
 No. 477 = N,NO\ JHN01 Two atoms of 
 Water = H,HOJ ' : 1HNOJ : No. 480. 
 
 I am not pleading that this compound HNO really exists. I am only 
 showing that the radical theory indicates its possible existence, which is 
 a sufficient reason to induce us to look for it, especially as it is required 
 to complete a series. 
 
 Azotic Eadicals in Series. 
 
 The next three sections contain the "bases" that are usually called 
 Indigo, Aniline, and Platinum. In these sections I shall show a com- 
 plete series of the salts of these " bases," which are unquestionably three 
 of the great " difficulties " in theoretical chemistry. I have chosen them 
 as examples because they are difficult ; because I wish to show that the 
 Theory and the Nomenclature which I am advocating, do not give way 
 under the pressure of difficulties ; and finally, because my conclusions 
 respecting these bases are so different from those of chemists in general, 
 that the results of the investigation may be taken as a fair example of 
 what may be expected from the application of the proposed radical 
 theory to chemistry in general. I have, in regard to these bases, quoted 
 the arguments fully and discussed them freely ; so that the reader will 
 find the cases stated ready for his judgment. He will have to answer 
 such questions as these : Are the Theory and Nomenclature that are 
 proposed for the salts of Indigo better or worse than those of Berzelius ? 
 Are those proposed for the salts of Aniline better or worse than those 
 of Hofmann? Are those proposed for the Platinum bases hotter or 
 worse than those of Gros, and Reiset, and Raewsky, and Gerhardt ? 
 
 Of course, the consideration of the replies proper to be made to these 
 
INDIGO. 257 
 
 questions, involves the consideration of the merit of the leading doctrines 
 of the radical theory and of the chemical nomenclature, which, though 
 forming no part of the radical theory, I have grafted upon it. 
 
 A peculiarity to which I must direct the reader's attention in refer- 
 ence to these three bases, is, that the salts of indigo, aniline, and pla- 
 tinum, though all salts of vice-ammons or vice-amids, differ in structure 
 from one another essentially. The general character of the indigo salts 
 agrees in no respects with that of the salts of aniline or platinum, and 
 the salts of aniline are throughout quite unlike the salts of platinum. So 
 also the theories which chemists have employed to explain these salts 
 are extremely different from one another, and the various nomenclatures 
 that have been proposed have scarcely any points in common. 
 
 But the radical theory and its nomenclature apply with equal facility 
 to the whole of these complicated and diversified salts. The compre- 
 hensiveness of the theory, and the flexibility of the nomenclature, satisfy 
 every demand ; and these are prime requisites in a theory and nomen- 
 clature that pretend to fulfil the requirements of a science which is so 
 eminently expansive and progressive as the science of chemistry. 
 
 Indigo. 
 
 The principal compound of the Indigo series is INDIGO BLUE, which is 
 represented by the empirical formula OWNO, where C = 12, H = i, 
 N = 14, O = 1 6. Gerhardt considered this oxidised compound to be 
 the radical of the indigo series, and he called it Indyle. Berzelius 
 thought it expedient to distinguish the compounds of indigo by a variety 
 of radicals, and he accordingly adopted the following : 
 
 C 16 H 3 N = Flavinden 
 C 16 H 4 N = Porrinden 
 C 16 H 5 N = Inden. 
 = Isaten. 
 
 C*H"N = Polinden. 
 C 32 H 12 N 2 = Eosinden. 
 C 3, H i 3]N T 2 = Xanthinden. 
 [In these formulas C = 6.] 
 
 For these radicals he provided formulae in which the svmbols were 
 written in Greek. 
 
 It is proposed, on the present occasion, to adopt, as the radical of the 
 Indigo series, a Hydrocarbon agreeing in composition with the formula 
 C 8 H 3 , and to call it INDYL. This radical is subject to have part, or the 
 whole, of its hydrogen replaced by chlorine, bromine, and sulphur ; and, 
 in this manner, to produce the following Vice-Radicals : 
 
 1 In all quotations of ordinary formulae, it is to be understood that 
 
 C = 6, O = 8, H = i,N = 14. 
 
 s 
 
258 
 
 INDIGO. 
 
 VlCE-lNDYLS. 
 
 C 8 H 8 S 
 C 8 HC1 2 
 C 8 HBr 2 
 
 C 8 HC1S 
 
 C 8 C1 2 S 
 
 C 8 Br 2 S 
 
 rC 8 H 2 Cl = Chloric-indyl. 
 Bromic-indyl. 
 Sulphic-indyl. 
 Chlorenic-indyl. 
 Bromenic-indyl. 
 Chloric-sulphindyl. 
 Chlorenic-sulphindyl. 
 Bromenic-sulphindyl. 
 
 The Vice-Radicals that contain chlorine and bromine without sulphur, 
 act like normal Indyl. They have the same saturating capacity, and 
 their salts have the same proportion of oxygen. The sulphic vice- 
 radicals, as usual, take additional oxygen, and form double salts. 
 
 The indigo series presents no other peculiar radical than indyl. They 
 all contain either amidogens or ammoniums, and in all of them the radical 
 indyl is found, sometimes as the negative radical, and sometimes as a 
 component of the vice-amid or vice-ammon, which forms the positive 
 radical. The indigo salts are quite regular in all other respects ; so that 
 Berzelius's army of Greek radicals may be dismissed as needless super- 
 numeraries. 
 
 Section i . SALTS IN WHICH INDYL is THE NEGATIVE RADICAL. 
 
 i]. ZH 2 ; C 8 H 3 = Amida indylate. 
 
 It is assumed that INDIGO BLUE or Indigotine is a salt which con- 
 tains the radical indyl, acting as an acid radical, in combination with one 
 atom of oxygen, and with normal amidogen acting as a basic radical ; 
 which combination requires the following formula and name : 
 
 ZH 2 ;C 8 H 3 = Amida indylate. 
 
 It is no part of the business of this Essay to describe either the pro- 
 perties or preparation of the substances to which allusion is made. I 
 may refer those who wish for detailed information respecting the Indigo 
 Salts, to the following works, in which are described all the compounds 
 that I shall refer to in this article. GMELIN, Handbuch der Chemie, 
 Band vi. LIEBIG'S Handworterbuch der Chemie, Band iv., several articles 
 written by STRECKER, from which I quote BERZELIUS'S names. GER- 
 HARDT, Traite de Chimie Organique, tome iii. Shorter notices will be 
 found in the Treatises on Organic Chemistry by Professors Gregory and 
 Miller. 
 
 -, JZH 4 ; CWC)) Ammona indylate cum amida 
 2 J' JZH 2 ; OTPOJ : indylate. 
 
 By certain chemical processes, indigo blue can be converted into a 
 substance which is called Indigogen, or WHITE INDIGO. The process 
 which effects this change is called " reduction," and the resulting com- 
 
IXDIGO. 259 
 
 pound is also called Reduced Indigo. The act of reduction consists in 
 adding one atom of hydrogen to one atom of blue indigo, and thereby 
 converting 
 
 ZH 2 ,C 8 H 3 O into ZH 3 ,C 8 H 3 O. 
 
 This new formula is not in accordance with the amidogen and ammonium 
 theories. H 3 forms neither an amidogen nor an ammonium. It is not 
 therefore immediately evident how the additional atom of hydrogen is 
 connected with the indigo blue, and chemists have given many different 
 explanations of this difficulty. Berzelius even resorted to the expedient 
 of adopting a special radical, Isaten = C 8 H 6 N to explain it. According 
 to him, indigo white should be called Isaten oxydul. 
 
 Nevertheless, what it is difficult to understand of this occurrence in 
 relation to one atom of the compound, becomes easy if we regard it as 
 taking place with two atoms ; for, if two atoms of indigo blue take up 
 two atoms of hydrogen, and produce a compound that agrees with the 
 following formula, we perceive that the difficulty is gone, and that we 
 are looking upon a change that is analogous to many that occur with 
 other compounds of the azotic series : 
 
 IZH*,C 8 H 3 O) Ammona indylate cum amida 
 Indigo white = | ZE[25C 8 H 3 } indylate< ' 
 
 According to this view of the transformation, indigo blue is a simple 
 indylate with an amidogen base, and indigo white is a double indylate, 
 with one amidogen base and one ammonium base. In so far as per 
 centage relations are in question, those formulae agree perfectly with the 
 analytical results ; but in respect to the assumed proximate constitutions 
 of these salts, the only evidence that can be offered in proof of their 
 accuracy is, that the relations of the salts to all other salts of the indigo 
 series are such as would exist if the constitutions that are assumed to be 
 true, could be proved to be true. The great assumption made in respect 
 to indigo white is, that it contains a salt of Ammonium combined with 
 a salt of Amidogen. Hitherto, such combinations have not been ad- 
 mitted, because they have been overlooked and misunderstood ; but the 
 numerous examples of their existence which I have cited in this Essay 
 must remove all reasonable doubts respecting the possibility of their 
 existence. 
 
 3], One of the agents employed to reduce indigo blue to indigo white 
 is grape sugar, and the process of reduction may be represented as 
 follows : 
 
 J_J1V1 
 
 r 7"tT2 (~ > 8yT 3 (~)') 
 \ZH 2 ic 8 H 3 0[ " 
 
 h CH 2 + H 2 0. 
 
 {: : ^}+H,CHO 
 
 Indigo blue, 
 
 Grape Water. 
 
 Indigo white, Formic 
 
 2 atoms. 
 
 sugar. 
 
 i atom. acid. 
 
 
 s2 
 
2GO INDIGO. 
 
 A more elaborate and intricate explanation of this process, founded on 
 the current theory of chemistry, is given in Professor Gregory's Hand- 
 book of Organic Chemistry, page 365. 
 
 Indigo white is subject to reconversion into indigo blue by a process 
 which is usually called " oxidation ;" that is to say, when it is exposed to 
 atmospheric air, O l of the air takes H 2 from the indigo to form water ; 
 the ammonium ZH 4 is thus " oxidised " into the amidogen ZH a , and the 
 indigo white again becomes indigo blue. 
 
 If the theory, according to which I am endeavouring to explain the 
 constitution of the indigo salts, is true, it shows, among other things, 
 that the processes which are commonly called oxidation and reduction, 
 are either incorrectly understood by chemists, or are described in veiy 
 awkward phraseology. Let us consider the present case in detail. We 
 convert two atoms of indigo blue into one atom of indigo white, by the 
 addition of two atoms of hydrogen, and we call this process " reduction." 
 What is reduced? Surely not the indigo. We reverse the operation. 
 We convert one atom of indigo white into two atoms of indigo blue, by 
 taking away two atoms of hydrogen, and this process we call " oxidation." 
 What is oxidised ? Certainly not the indigo. The ways and means by 
 which the results are brought about are, theoretically, of no moment. 
 The facts are, that hydrogen is either added or removed. The words 
 intimate that oxygen is added or removed. Many of the misty 
 hypotheses that have been published respecting the metamorphoses of 
 the various salts of indigo have no doubt had their origin in the 
 ambiguity that has been occasioned by the abuse of the words oxidation 
 and reduction. 
 
 4]. ZH 2 ; C 8 H 8 2 = Amida indylete. 
 
 Indigo blue, when submitted to the action of certain agents which 
 impart oxygen, such as nitric acid and chromic acid, takes up another 
 atom of oxygen, and produces the compound which is usually called 
 ISATINE, and which possesses the following constitution : 
 
 ZH 2 ;C"H 3 2 = Amida indylete. 
 
 This compound differs from indigo blue by containing an additional atom 
 of oxygen. Berzelius called it Indenoxyd. Gmelin's formula is 
 C 16 NH 5 2 ,O 2 - Laurent's formula C l6 H 5 Is T O 4 . 
 
 5]. ZHK ; C 8 H 3 2 = Potassac indylete. 
 6]. ZHAg; CH 8 O S = Argentac indylete. 
 
 When Amida indylete Isatine is acted on by a cold solution of 
 caustic potash, it exchanges an atom of hydrogen for an atom of potas- 
 sium, by which exchange its positive radical amida is converted into 
 potassac. 
 
 ZH 2 ; Cm) 2 + KHO = ZHK; C 8 H S 2 + HHO. 
 
IXDIGO. 261 
 
 A similar salt, 6], can be prepared with silver, and indeed the formula 
 ZHM r ; C 8 H 3 2 is that of a series of salts which contain amidac radicals. 
 These salts are called by different chemists, Isatites, Isatides, and Isati- 
 nides. Their usual formula is C 16 NH 4 MO 4 . 
 
 (ZH 3 K ; C 3 H 3 3 = Potassam indylite. 
 7], JzH 3 Ag; C 8 H 3 3 = Argentam indylite. 
 
 |ZH 3 Ba ; C 8 H 3 3 = Barytam indylite. 
 8]. ZH 4 ; C 8 H 3 O 3 = Ammona indylite. 
 
 When Amida indylete Isatine, No. 4] is acted on by a hot solu- 
 tion of caustic potash, the power of the azotic radical is enlarged, the 
 amida becomes potassam, and the salt assumes another atom of 
 oxygen. Thus : 
 
 ZH 2 ; C 8 H 3 2 + KHO = ZH 3 K ; C 8 H 3 3 . 
 
 By proper operations, the experimental details of which do not belong 
 to this investigation, the potassium in this salt can be replaced by 
 barium, silver, or hydrogen ; giving origin to salts that agree with the 
 formulae marked 7] and 8]. 
 
 It is important to notice the difference of the effects that are produced 
 by treating isatine with a hot and with a cold solution of caustic potash. 
 The relations of amidogens to ammoniums are often essentially changed 
 by circumstances that chemists overlook as insignificant. 
 
 By one of those misnomers that are so frequent in organic chemistry, 
 the normal salt of this series, represented by No. 8], is called an " ACID." 
 Gregory calls it ISATINIC ACID ; and Miller's name for it is ISATIC ACID. 
 The denomination " acid" is founded on the assumption, that the atom 
 of azote, and three out of the four atoms of hydrogen which are here 
 ascribed to the basic radical of the salt, all belong to the acid radical. Of 
 course, there is no evidence to support that notion. According to the 
 theory now under consideration, the Isatinic or Isatic acid corresponding 
 with the salts 7] and 8], would be constituted as follows, H'jOTPO 8 ; 
 but no such compound is known. The other salts cited above are com- 
 monly called Tsatate of potash, Isatate of silver, and Isatate of barytes. 
 The formula usually ascribed to the imaginary isatic acid is C I6 NH 7 O 6 , 
 or HO,C 16 H 6 N0 5 . 
 
 Formula 8] and formula 4] show, that hydrated isatic acid is the 
 neutral salt of ammonia of which isatine is the amide. That is, I believe, 
 the true relation of these two salts. It will be seen that a great many 
 of the salts of the indigo series differ from one another to the extent of 
 the difference in the quantity of hydrogen that is required to convert an 
 amid ZH 2 into an ammon ZH 4 ; all other constituents of the salts, ex- 
 cept oxygen, remaining the same. Of course, this peculiarity is not con- 
 fined to the indigo series, but is a general property of the azotic radicals. 
 
262 INDIGO. 
 
 -, (ZH 4 ; C 8 H 3 O 2 ) Ammona indylete cum amida 
 9J- |ZH 2 ;C 8 H 3 2 ( : indylete. 
 
 When " reducing" agents are made to act upon isatine = ZH 2 ; C 8 H 3 2 , 
 the result is exactly similar to that produced when they act upon blue 
 indigo ; namely, two atoms of isatine take up two atoms of hydrogen, 
 and produce a compound which has the composition represented by for- 
 mula 9]. This compound differs from white indigo by containing two 
 additional atoms of oxygen, just as isatine differs from blue indigo by 
 containing one additional atom of oxygen. The name that is usually 
 given to it is ISATHYDE. Berzelius called it Isatenoxyd. Its ordinary 
 formula is C 16 H 6 NO 4 . 
 
 -, JZH 4 ; OWO 2 ) Ammona indylete cum amida 
 IO J* \ZH 2 ; C 8 H 3 0( indylate. 
 
 The salt 9] rests upon the experiments of Laurent. Erdmann considers 
 the salt to have the composition that is indicated by the common 
 formula C 16 H 6 N0 3 , which is equivalent to formula No. 10]. A com- 
 pound of this per centage composition has been described under the name 
 of Isatan, which Berzelius rendered Isaten sesquioxydul. 
 
 1 proceed to quote a few examples of the salts of indigo that contain 
 the chloric and bromic vice-radicals. 
 
 11]. ZH 2 ;C 8 H 2 C10 2 = Amida chloric-indylete. 
 12]. ZHAg; C 8 H 2 C10 2 = Argentac chloric-indylete. 
 
 The salt No. 1 1] differs from the salt No. 4] only by containing chloric 
 indyl = C 8 H*C1, instead of normal indyl = C 8 H 3 . The salt No. 12] 
 differs from the salt No. 6] only by the same substitution. 
 
 The ordinary names for the salt No. n] are chlorisatine and chlo- 
 risatinase, and the formula is C 16 H 4 C1N0 4 . Berzelius's formula is 
 C 16 H 4 NO 3 ,C1O, and his name is Basisches unterchlorigsaures porrinden- 
 sesquioxydul ! 
 
 13]. ZH a ; C 8 H 2 Br0 2 = Amida bromic-indylete. 
 The common names are bromisatine and bromisatinase = C ie NBrH 4 4 . 
 14]. ZH 2 ; C 8 HC1 2 2 = Amida chlorenic-indylete. 
 
 Common name: Bichlorisatine = C I6 NC1 2 H 3 4 . Berzelius's formula 
 (translated from the Greek) is C 16 H 3 N0 2 ,2C1O. His name is Unter- 
 chlorigsaures flavindenoxydul. 
 
 A comparison of the formute No. u] and No. 14] with Berzelius's 
 
INDIGO. 263 
 
 names and formulae for the same compounds, will show how far that 
 great chemist was led astray by his misconception of the nature of the 
 compounds which I have called VICE-RADICALS. 
 
 15]. ZH 2 ; C^B^O 2 = Amida bromenic-indylete. 
 i6J. ZHK; C^B^O 2 = Potassac bromenic-indylete. 
 
 Common names : No. 1 5] is Bibromisatine, bromisatinese = C 16 NBr 2 H 3 4 , 
 Laurent. No. 16] is called Bibromisatite of potash C 16 H 2 KBr 2 N0 4 , 
 Gerhardt. 
 
 ZH 3 K ; C 8 H 2 C1O 3 = Potassam chloric-indylite. 
 
 ZH 3 Ba ; C 8 H 2 C10 3 = Barytam chloric-indylite. 
 
 ZH 3 Ag ; C?H 2 C1O 3 = Argentam chloric-indylite. 
 
 ZH 3 Pb ; (OT'CIO 3 = Plumbam chloric-indylite. 
 1 8]. ZH 4 ; C 8 H 2 C10 3 = Ammona chloric-indylite. 
 
 The salts represented by formulae 17] and 18] are commonly called 
 Chlorisatates and Chlorisatinates, and the usual formula is C I6 NC1H 5 M0 6 . 
 No. 1 8] is the Chlorisatic "Acid," in agreement with the formula 
 HO,C 16 H 5 NC10 5 . Berzelius's name for it is Indenoxydul chlorige Saure. 
 This "acid" cannot be separated from solution, and is, in fact, un- 
 known. 
 
 The series 17] and 18] agree precisely with the series 7] and 8], 
 except in containing chloric-indyl instead of normal indyl. 
 
 fZH 3 K ; C 8 HC1 2 8 = Potassam chlorenic-indylite. 
 ZH 3 Ba ; C 8 HC1 2 3 = Barytam chlorenic-indylite. 
 19]. JzH 3 Cuc; C 8 HC1 2 3 = Cupricam chlorenic-indylite. 
 ZH 3 Pb ; C 8 HC1 2 O 8 = Plumbam chlorenic-indylite. 
 (ZH 3 Ag ; C 8 HC1 2 3 = Argentam chlorenic-indylite. 
 20]. ZH 4 ; C 8 HC1 2 3 = Ammona chlorenic-indylite. 
 
 The salts represented by the formulae No. 19]] are commonly called 
 Bichlorisatinates. No. 20] is the Bichlorisatinic " Acid," answering to 
 the formula HO,C 16 H 4 C1 2 N0 5 or C I6 NCPH 5 O 6 . Berzelius's name for 
 this acid is Porrinden-chloric acid - C 16 H 4 ]N",C1 + CIO 5 -f, HO. 
 
 The relation of these salts to those represented by formulae 7], 8], 
 and 17], 1 8], is so evident, that it is needless to offer any discussion. 
 
 21]. ZH 4 ; C 8 H 2 Br0 3 - Ammona bromic-indylite. 
 Common name : Bromisatic acid = C 16 NBrH 6 O 6 . Compare it with 18]. 
 
 22]. ZH 3 K ; C 8 HBr 2 3 = Potassam bromenic-indy lite. 
 23]. ZH 4 ; C 8 HBr 8 O 3 = Ammona bromenic-indy lite. 
 
 Commonly called Bibromisatinates. No. 23 is the Bibromisatinic 
 " Acid"^HO,C 16 H 4 Br 8 N0 5 . Compare 22] with 19], and 23] with 20]. 
 
264 
 
 INDIGO. 
 
 No. 18" 
 
 . ZH 4 
 
 *.?! 
 
 . ZH 3 Ag 
 
 21 
 
 . ZH 4 
 
 20 
 
 . ZH 4 
 
 2 3 
 
 . ZH 4 
 
 22]. ZH a K 
 
 Ai <! ZH4; 
 
 2 4J' JZH 2 ; 
 
 COT 
 
 [No. ii 
 
 12 
 
 H 
 
 responding Amides. 
 . ZH 2 C 8 H 2 C1 O 2 
 . ZHAg C 8 H 2 C1 O 2 
 . ZH 2 C 8 H 2 Br0 2 
 . ZH 2 C 8 HC1 2 O 2 
 . ZH 2 C 8 HBr 2 2 
 . ZHK C 8 HBr 2 2 . 
 
 The relations existing between the following pairs of salts are so 
 evident, that it seems to be scarcely necessary to point them out : 
 
 Normal Salts of Ammoniums. 
 
 C 8 H 2 C1 O a 
 C 8 H 2 C1 O 3 
 C 8 H 2 Br O 3 
 C 8 HC1 2 O 3 
 C 8 H Br 2 3 
 C 8 H Br 2 3 
 
 C 8 H 2 C10 2 ) Ammona chloric-indylete cum amida 
 C 8 H 2 C1O 2 J chloric-indylete. 
 
 The ordinary names of this salt are as follow: Chlorisathyde = 
 C 32 H 10 C1 2 N 2 O 6 , Gerhardt. Chlorisathydase, Laurent. Basisches unter- 
 chlorigsaures indensesquioxydul = C 16 H 5 NO 8 + CIO, Berzelius. 
 
 1 j ZH 4 ; C 8 HC1 2 O 2 ) Ammona chlorenic-indylete cum amida 
 2 5> \ZH 2 ; CHCFO'I chlorenic-indylete. 
 
 Common names : Chlorisathydese, Laurent. Bichlorisathyde = 
 C 32 H 8 C1 4 N 2 O 8 . Unterchlorigsaures porrindenoxydul = C 16 H 4 N0 2 5 2C1O, 
 Berzelius. 
 
 Compare the salts No. 24] and 25] with normal isathyde, No. 9]. 
 It is evident that the three salts differ in no other respect than that, in 
 two of them, a portion of the hydrogen of the radical indyl is replaced 
 by chlorine. Yet Berzelius thought it proper to assume that these salts 
 contained three totally-different radicals isaten, inden, and porrinden ; 
 and that these radicals were present in remarkable conditions of com- 
 bination. Thus, 9] was the " peroxide of isaten ;" 24] was the " basic 
 hypochlorite of the sesquioxide of inden;" and 25] was the " hypo- 
 chlorite of the protoxide of porrinden." Here we see how things which 
 are naturally simple and regular can be distorted and made perplexing 
 by the vices of an erroneous hypothesis. Berzelius would not admit 
 that chlorine could replace hydrogen in radicals, and he was driven to 
 advance a host of assumptions, each of which was a thousand times 
 more incredible than the single assumption which he repudiated. 
 
 Section 2. SALTS IN WHICH INDYLAC is THE NEGATIVE EADICAL. 
 
 I mean by INDYLAC, a vice-amid which contains one atom of Indyl 
 = ZH,C 8 H 8 . 
 
 ZH 2 ; ZH,C 8 H 3 = Amida indylacate. 
 
 ZH 2 ; ZH.C'iraO = Amida chloric-indylacate. 
 , (ZH 2 ; ZH,C 8 H 3 ) Amida indylacate cum amida indy- 
 
 1- JZH 2 ; C 8 H 8 2 f ' lete. 
 
INDIGO. 265 
 
 Amida chloric-indylacate cum 
 amida chloric-indylete. 
 
 Amida bromenic-indylacate cum 
 amida bromenic-indylete. 
 
 Amida indylacate bis amida 
 iridylete. 
 
 Bis amida indylacate cum amida 
 indvlete. 
 
 Tris amida bromenic-indylacate 
 cum amida bromenic-indylete. 
 
 Amida indylacate cum ammona 
 indylaccete. 
 
 Amida chloric-indylacate cum 
 ammona chloric-indylaccete. 
 
 Amida chlorenic-indylacate cum 
 ammona chlorenic-indylaccete. 
 
 Ammona indylaccete cum amida 
 indvlete. 
 
 Ammona chloric-indylaccete cum 
 amida chloric-indylete. 
 
 Ammona chlorenic - indylaccete 
 cum amida chlorenic-indylete. 
 
 Barytam indylaccete cum amida 
 indylete. 
 
 Argentam chlorenic-indylaccete 
 cum amida chlorenic-indylete. 
 
 Ammona indylaccete. 
 Cupriccem indylaccete. 
 Argentam indylaccete. 
 Argentam chloric-indylaccete. 
 
 I have placed the above formulae together, in order to show the rela- 
 tionship of the multiple salts of indigo, and to draw attention to the 
 slight, but perfectly definite, differences by which they are individually 
 characterised. 
 
 All the formulae from 26] to 45], contain an assumption that appeared 
 
 29]. | Z TT 2 \ 
 
 ZH,C 8 H 2 C10) 
 C 8 H 2 C10 8 | 
 
 i (ZH 2 
 30]. | ZH2 
 
 ZH^HBi^O 1 
 C 3 HBr 2 2 
 
 (ZH 2 
 
 " ] - is 
 
 ZH,C 8 H 3 ) 
 C 8 H 3 2 } 
 C 8 H 3 2 J 
 
 fZH 2 
 32] ' JZH 2 
 
 ZH,C 8 H 3 ) 
 ZH,C 8 H 3 I 
 C 8 H 3 O 2 J 
 
 ZH 2 
 , ZH 2 
 333- ZH 2 
 ZH 2 
 
 ZH,C a HBr 2 
 ZH,C 8 HBr 2 
 ZH^HBi^O 
 C 8 HBr ? 2 
 
 i (ZH 2 
 34]- jzH 4 
 
 ZH,C 8 H 3 \ 
 ZH,C 8 H 3 O 2 j 
 
 -, ;ZH 2 
 
 35]- jzH 4 
 
 ZH,C 8 H 2 C1O } 
 ZH,C 8 H 2 C10 2 | 
 
 3 6 ]' {zH< 
 
 ZH,C 8 HC1 2 O ) 
 ZH,C 8 HC1 2 2 J 
 
 -i I ^-ti 
 37]- J Z H 
 
 ZH,C 8 H 3 2 1 
 C 8 H 3 O 2 j 
 
 3 8 1- JZH* 
 
 ZH,C 8 H 2 C10 2 1 
 C 8 H 2 C1 0'j 
 
 n (ZH 4 
 391- {zH 2 
 
 ZH,C 8 HC1 2 2 ) 
 C 8 H C1 2 2 ( 
 
 401 P 3 
 
 4 _!* i 7TT 2 
 
 ZH,C 8 H 3 2 1 
 H C 8 H 3 2 f 
 
 All | ZH3A S 
 4 1 -!' }ZH 2 
 
 ZH,C 8 HC1 2 8 I 
 C 8 HC1 2 2 | 
 
 42]. ZH 4 
 43]. ZH 2 Cuc 2 
 44]. ZH 3 Ag 
 45]. ZH 3 Ag 
 
 ZH,C 8 H 3 2 
 ZH,C 8 H 3 2 
 ZH,C 8 H 3 2 
 ZH,C 8 H 2 C10 2 
 
266 INDIGO. 
 
 in none of the formulas from i] to 25]. This consists in the employ- 
 ment of a vice-amidogen, INDYLAC -- ZH,C 8 H 3 , as an ACID RADICAL. I 
 shall be asked, how I justify so novel and irregular a proceeding ? I reply, 
 by the success with which it is followed. No assumption hitherto made 
 by chemists has availed to raise the formulae of the indigo salts out of 
 the mists of empiricism. With this assumption, their composition is 
 made intelligible and regular. The end justifies the means, because order 
 is better than muddle. 
 
 NOTICES OF THE INDIVIDUAL SALTS. 
 
 No. 26]. ZH 2 ;ZH,C 8 H 3 = Amida indylacate. 
 Compare with No. 4]. ZH 2 ; C 8 H 3 O 2 = Amida indylete (Isatine). 
 
 When isatine is treated with ammonia ZH 2 ,H, the compound No. 26] is 
 produced, one atom of water H,HO being given off. 
 
 ZH 2 ; OTTO* + ZH 2 H = ZH 2 ; ZH.CPEPO + H,HO. 
 
 In this operation, the residue of the ammonia ZH, combines with the 
 indyl C B H 3 to form the vice-amidogen Indylac. The resulting salt 26] 
 
 ZH 2 ) 
 if formulated " on the model of water " would look thus : ^JT najpf O. 
 
 If we contrast the radicals ZH 2 with ZH,C 8 H 3 , and ask which is the 
 more acid of the two, taking for our guidance the properties of radicals 
 which have been described at page 73 of this work, we come to the con- 
 clusion that ZH,C 8 H 3 is more acid than ZH 2 , and consequently that the 
 proper formula for the compound which contains both is that given in 
 26] = ZH 2 ; ZH,C 8 H 3 0. 
 
 The ordinary names of this compound are as follow : Imesatine 
 = C'-'H^O 2 , Gerhardt. Porrindenoxydulamid = C 16 H 4 NO 2 NH 2 , Ber- 
 zelius. 
 
 27]. ZH 2 ; ZH,C 8 H 2 C10 = Amida chloric-indylacate. 
 
 This salt differs from No. 26] only in containing chloric-indyl = 
 instead of indyl = C 8 H 3 . It is prepared by acting upon chlorisatine 
 instead of normal isatine. This remark applies to the salts of the vice- 
 indyls generally. Whatever compound salt you can make with indyl, 
 you can also make with chloric-, chlorenic-, bromic-, or bromenic-indyl. 
 I cannot go into experimental details, and it is needless to repeat this 
 general remark at the mention of every formula. 
 
 The ordinary names for No. 27] are chlorimesatine = C I6 H 5 C1N 8 2 , 
 Gerhardt. Imechlorisatinase, Laurent. 
 
 JZH 2 ; ZH,C 8 H 3 O 1 Amida indylacate cum 
 2BJ. J ZH . C 8 H 3 O 2 j amida indylete. 
 
 A compound of the two salts, 26] and 4], atom to atom. 
 
INDIGO. 267 
 
 Usual names: Imasatine = C 32 H U N 3 6 , Gerhardt. Polindenoxyd 
 = C 32 H U N 3 ,O 6 , Berzelius. 
 
 29]. The chlorine compound parallel to 28]. 
 
 Common name : Chlorimasatine = C 32 H 9 C1 2 N 3 6 , Gerhardt. Imachlo- 
 risatine, Strecker. 
 
 30]. The bromine compound parallel to 28]. 
 
 Usual names : Bibromimasatine = C 32 H 7 Br 4 N 3 6 , Gerhardt. Imabi- 
 bromisatine, Strecker. 
 
 Amida indylacate bis amida 
 
 indylete - 
 
 A compound of one atom of the salt 26] with two atoms of the salt 4], 
 Common name : Isatilime = C^IPN'O 10 , Laurent. 
 
 o-l 7TT ywrw Bis amida mdylacate cum 
 
 = amida i 
 
 A compound of two atoms of 26] with one atom of 4]. 
 
 The ordinary name of this salt is Isatimide = C^H^N'O 8 , Laurent. 
 Compare the single salt 26] with the three multiple salts 28], 31], 32]. 
 
 33], A salt, said to be very beautiful, accidentally obtained by 
 Laurent, but not producible at pleasure. His name and formula are, 
 Carmindine bibromee = C 64 H 15 Br 8 N 7 O 10 . 
 
 The most interesting circumstance respecting this salt is, that it seems 
 to indicate the existence of salts that belong to the series 26], 28], 31], 
 32], but extending beyond the last of these. 
 
 -, JZH 2 ; ZH,C 8 H 3 1 Amida indylacate cum ammona 
 34J-JZH 4 ; ZH,C 8 H 3 2 j : indylaccete. 
 
 This salt is procured by heating the isamate of ammonia No. 42]. HHO 
 is driven off, and No. 34] remains. 
 
 ZH 4 ; ZH,C 8 H 3 2 ) J ZH 2 ; ZH,C 8 H 3 O 1 + H,HO. 
 ZH 4 ; ZH,C 8 H 3 2 J == \ ZH ^ ZH,C 8 H 3 2 J 
 
 The compound thus procured contains one atom of the salt 26] and one 
 of the salt 42]. Compare 34] with 10]. The difference between the 
 two salts is, that the two atoms of indyl in 10] are replaced by two 
 atoms of indylac in 34]. 
 
 Common "names : Isamide, Amasatine = C 32 H 14 N 4 6 , Laurent and 
 Gerhardt. Polindenoxydammoniak = C 3 " 2 H U N 3 O 6 + NH 3 , Berzelius. 
 
 35], 36], These salts correspond to 34] but have chloric- and chlo- 
 renic-indyl instead of indyl. Common names : 
 
 No. 35]. Chlorisamide = C 32 H 12 C1 2 N 4 O 6 . 
 No. 36]. Bichlorisamide = C 32 H 10 C1 4 N 4 6 . 
 
268 IXDIGO. 
 
 ZH 4 ; ZH,C 8 H 3 2 1 _ Ammona indylaccete cum 
 ZH 2 ; OTTO 8 !" = amida indylete. 
 
 Compare with 9]. & 3 O 2 I = Amm ?? a . ^ vlete cum 
 ^ J (ZH 2 ; C 8 H 3 O 2 j amida indylete. 
 
 The only difference in the composition of the two salts, Nos. 9] and 37] 
 is, that in the latter one atom of indyl is replaced by one atom of 
 indylac. The salt 37] contains one atom of isamate of ammonia 42] 
 combined with one atom of isatine 4], It is procured by acting upon 
 isatine with ammonia. 
 
 ZH 2 ; C 8 H 3 O 2 + ZH 2 H) f ZH 4 ; ZH,C 8 H 3 O 2 
 ZH 2 ;C 8 H 3 2 f == IZH 2 ; C 8 H 3 2 
 
 The common names of this compound (No. 37) are as follow: Isamic 
 acid; Imasatic acid = C 32 H 13 N 3 O 8 , Gerhardt. Imasatinic acid, Laurent. 
 Isatinamic acid. Rubindenic acid, Berzelius. Isamsaure = HO, 
 C 32 H 12 N 3 7 , Strecker. 
 
 38] and 39] are salts similar to 37] but containing chloric and chlo- 
 renic-indyl instead of indyl. No. 38] is commonly called chlorisamic 
 acid = HO,C 32 H 10 C1 2 N 3 O 7 . No. 39] is called Bichlorisamic acid 
 
 40]. This is the barium salt of the Isamic acid, No. 37]. Between 
 the composition of No. 37] and No. 40], there is only the difference 
 that Ammona = ZH 4 is replaced by Barytam = ZEPBa. The or- 
 dinary name for the salt represented by No. 40] is Isamate of barytes 
 = BaO,C 32 H 12 N 3 O 7 . 
 
 41]. This is the silver salt of the "acid" formulated by No. 39]. 
 Its common name is the Bichlorisamate of silver. 
 
 42]. ZH 4 ; ZH,C 8 H 3 O 2 = Ammona indylaccete. 
 
 This is the ammonia salt of the " acid" formulated by No. 37]. It is 
 formed thus : 
 
 ZH 4 ; ZH,C 8 H 3 2 1 JZH 4 ; ZH,C 8 H 3 O 2 
 
 ZH 2 ; C 8 H 3 O 2 + ZH 2 ,Hf : '- JZH 4 ; Z 
 
 As I consider the salt No. 37] to be a compound of two salts, so I con- 
 sider the result of this reaction to be a product of two similar salts, and 
 therefore I limit the formula to what is given in 42]. 
 
 The common name of 42] is the isamate of ammonia. I have already 
 stated that when it is strongly dried, the loss of water transforms it into 
 the salt No. 34]. 
 
 43]. ZIPCuc 2 ; ZH,C 8 H 3 2 = Cupriccem indylaccete. 
 44]. ZH 8 Ag; ZH,C 8 H 3 2 = Argentam indylaccete. 
 
 These two salts are modifications of No. 42], the ammona of 42] being 
 
INDIGO. 269 
 
 replaced by Cupriccem in 43] and by Argentam in 44]. Common 
 names : No. 43] is Isatinkupferamrnonium = C 16 NH 2 (NH 4 )Cu 2 4 , or 
 C l6 N 2 H 6 Cu 2 O 4 , Gmelin. Isatinkupferoxydammoniak = 2CuO,C 16 H 3 N0 2 
 + NH 3 , Strecker. 
 
 No. 44] is Isatinsilverammonium = C 16 NH 3 (NH 4 )Ag0 4 , Gmelin. 
 C l6 NH 4 (NH 3 Ag)O 4 , Laurent. Isatinsilberoxydammoniak = AgO, 
 C 16 H 4 N0 3 + NH 3 , Strecker. 
 
 45]. ZH 3 Ag; ZH,C 8 H 2 C10 2 = Argentam chloric indylaccete. 
 This salt differs from No. 44] only by containing chloric-indyl instead of 
 indyl. Common names : Chlorisatinsilverammonium = C 16 NC1H 2 (NH 4 ) 
 AgO 4 , Gmelin. AgO.C 16 H 3 ClNO 3 + NH 3 , Strecker. Chlorisatite of 
 argentammonium = C l6 H 3 (NH 3 Ag)ClN0 4 , Gerliardt. 
 
 SECTION 3. SALTS IN WHICH INDYLAC AND INDYLAM ACT AS POSI- 
 TIVE RADICALS, WITH SULPHUR AS A NEGATIVE RADICAL. 
 
 Indylac, as already explained, is a vice-amid containing one atom of 
 Indyl = ZH,C 8 H 3 . Indylam is a vice-ammon containing one atom 
 of Indyl - ZH 3 ,C 8 H 3 . 
 
 A. Bisulphates. 
 
 <n JZH 3 ,C 8 H 3 ; S0 2 \ , . , , .. 
 
 4J- \ w. go 2 ! = ^y " 31 m dylam sulphenote. 
 
 n JZH 3 ,C 8 H 3 ; SO 2 ) 
 47 J' IZH 4 SO 2 1 = J ^ mmona m dylam sulphenote. 
 
 ZH,C 8 H 3 J SO 2 ) 
 
 | 2 > = Hydra indylac sulphenote. 
 
 01 ) 
 
 48]. < 
 
 Tb; ZH,C 8 H 3 ; 8 2 4 = Plumba indylac sulphenote. 
 49]. \ K ; ZH^H 3 ; S 2 4 = Potassa indylac sulphenote. 
 (Ba; ZH,C 8 H 3 ; S 2 O 4 = Baryta indylac sulphenote. 
 
 B. Sulphite. 
 (ZH 3 ,C 8 H 3 ;SO) ] 
 
 50]. {ZH 3 ,C 8 H 3 ; S0*( : \ = Indylamen sulphenite. 
 
 [= ZH 3 ,C 8 H 3 ; ZH 3 ,C 8 H 3 ; S 2 3 J 
 
 C. Hyposulphite? 
 51]. ZH 3 ,C 8 H 3 ; S 2 0? = Indylam sulphenate. 
 
 , (ZH 3 ,C 8 H 3 ; SO 2 ) = Hydra indylam sulphenote. 
 
 '* | H ; SO 2 ] " (or, Hydra indylam bisulphete.) 
 
 This salt is the Acide sulfisataneux of Laurent, the Sulfisatanige Saure o 
 Strecker. Formulae: HO,C 16 H 6 N0 3 ,2S0 2 . I cannot understand why 
 those proportions of sulphur, oxygen, and basic radicals which constitute 
 what is commonly called a sulphate should ever be considered to form a 
 sulphite. Organic chemists are too often guided in their opinion of what 
 
270 INDIGO. 
 
 a salt is, by their knowledge of the materials they use to make it, or the 
 products they obtain when they decompose it. A salt, while it exists, 
 is neither its antecedent nor its subsequent. Its name ought to state 
 what it is, and not allude to circumstances that attend its construction or 
 destruction. 
 
 A sulphate contains one positive radical, one atom of sulphur, and two 
 atoms of oxygen. A sulphite contains two positive radicals, two atoms 
 of sulphur, and three atoms of oxygen. These, at least, are the relations 
 insisted upon by the radical theory, but, under all theories, these salts 
 present differences which no chemist is entitled to overlook. 
 
 47]. ZH 4 ; ZH 3 ,C 8 H 3 ; S 2 4 = Ammona indylam sulphenote. 
 
 This is the ammonia-salt of the " acid" No. 46], Its usual names are 
 Sulfisatanite d'ammoniaque, Laurent. Sulfisatanigsaures ammoniak, 
 Strecher. Formula : C 16 H 10 N 2 S 2 O 8 (with 2Aq. omitted in the above for- 
 mula). This salt is not readily decomposed. Hydrochloric acid does 
 not disengage sulphurous acid from its solution. Salts of barium pro- 
 duce no precipitate therein. The salt No. 47] is prepared by mixing 
 bisulphite of ammonia with an alcoholic solution of sulphesatyde. 
 
 48]. H; ZH^H 3 ; S 2 4 = Hydra indylac sulphenote. 
 49]. K ; ZHjOTP ; S*0* = Potassa indylac sulphenote. 
 
 The " acid " No. 48] differs from the " acid " No. 46] only by con- 
 taining indylac instead of indylam ; all other things remaining the same. 
 The salts 49] differ from the salt 47] in the same particular. The dif- 
 ference is the same as that which distinguishes the Binoxalates from the 
 Oxamates. The acid 48] is prepared by digesting indigo blue in concen- 
 trated hydrated sulphuric acid in a close vessel : 
 
 ZH 2 ,C 8 H"0 ) f ZH,C 8 H 3 ; SO 8 ) N R1 
 H, S0 2 l = J H ; S0 2 f No ' 4 8 J' 
 
 H, SO 8 J t H ,HO = water. 
 
 With diluted acid, and free access of air, the salt No. 57] is produced. 
 The acid No. 48] has received a variety of names, and been the subject 
 of many different hypotheses. Sulphate of indigo; Gremlin-sulphuric 
 acid, W. Crum; Sulphindigotic acid; sometimes, hyposulphindigotic 
 acid ; indigblauschwefelsaure ; Schwefelsaurer indigo ; Losliches indig- 
 blau; Indylinschwefelsaure; Sulfindylsaure; Acidesulfindylique,DMmas; 
 Acide sulfmdigotique. Formula^. : C 16 NH 5 S 2 O 8 = C lfi NH 5 O 2 , 2 S0 3 , 
 Gmelin. HO,C 16 H 4 NO,2SO 3 ( = Sulphindylic acid), Milkr. The salts 
 49] are commonly called Sulphindylates. The usual formula of the 
 potash salt is KO,C 16 H 4 NO,S 2 O 6 . It has also been called Indigo carmine 
 and soluble indigo. 
 
 I copy the following passage from Dr. Gregory's account of the salts 
 No. 49]. " The sulphindigotate appears to be strictly a hyposulphin- 
 
INDIGO. 271 
 
 digotate, and its formula is in all probability, C 16 H 4 N0 2 ,S 2 5 + KO. 
 Dumas' view, according to which the salt is a double sulphate, analogous 
 to sulphovinate of potash, C 16 H 4 NO,SO 3 + KO,S0 3 , is not supported by 
 the chemical relations of these substances. Dumas conjectured that 
 indigo blue was analogous to alcohol, and that its formula was 
 C 16 H 4 N,0 + HO, the body C 16 H 4 N,O being analogous to oxide of ethyle. 
 But this view is far-fetched, and does not agree with the chemical rela- 
 tions of indigo. It would make, for example, white indigo C 16 H 4 N,O 
 + H + HO or C 16 NH 4 4- 2 HO, both most improbable formulas." Hand- 
 book of Organic Chemistry (1856), p. 367. 
 
 I disagree entirely with Dumas' view, that indigo blue has a structure 
 analogous to that of alcohol, and I have shown that its structure re- 
 sembles that of an amide : 
 
 H,C 2 H 5 = Alcohol. 
 ZH 2 ,C 8 H 3 O = Indigo blue. 
 ZH 2 ,C 2 H 3 O = Acetamide. 
 
 Nevertheless, I agree with Dumas, that the structure of sulphate of 
 indigo resembles that of sulphovinate of potash ; the two salts being for- 
 mulated in my notation as follow : 
 
 IT paws Q*n* _ J Sulphovinate of potash. 
 
 "\ Potassa ethyla sulphenote. 
 
 K . 7TT rspre . ca J In( %otate of potash. 
 
 K , ZH,C = j pota sa . nd ^ c sulphenote . 
 
 The sole difference exhibited by these two salts, is the replacement" of 
 ethyla by indylac, both of which are basic radicals. It is not very clear 
 what Dr. Gregory means by a hyposulphindigotate. The formula that 
 he proposes for the salt shows those proportions of S and O which con- 
 stitute a sulphate, not a hyposulphate ; moreover, a hyposulphate, though 
 it is biacid, is monobasic (see page 172), and it could only have indigo 
 and potassium together, as a base in the form of an amidogen or 
 ammonium. The respective quantities of the oxygen and sulphur, how- 
 ever, agree with the composition of nothing but a double sulphate. 
 
 50]. ZH 3 ,C 8 H 3 ; ZH 3 ,C 8 H 3 ; S 2 3 = Indylamen sulphenite. 
 
 This salt is what, in the existing nomenclature, would be called the 
 "neutral sulphite" of indylam. It is the Sulfasatyde, or Sulfisathyde 
 of Laurent and Erdmann ; the Isatenoxysulphuret of Berzelius. For- 
 mulae : C 16 H 6 N0 3 S, Laurent. C 32 H 12 N 2 O 6 S 2 , Gerhardt. 3C' 6 H 6 NO 4 + 
 C 16 H 6 NS 4 , Berzelius. 
 
 51]. ZH 3 ,C 8 H 3 ;S 2 = Indylam sulphenate. 
 
 This salt is given on the authority of Laurent, after whom it is copied 
 into all the works on Chemistry. The ordinary names and formulae are 
 
272 
 
 INDIGO. 
 
 Sulfesathyde, Isathyde bisulfuree = C 16 H 6 NO*S 2 , Laurent. Bisulfisa- 
 thyde = > 2 H 12 N 2 4 S 4 , Gerhardt. Isatenoxysulplmret = C 16 H 6 NO 4 
 -f- C 16 H 6 NO 4 , Berzelius. The salt is prepared by passing sulphuretted 
 hydrogen into a solution of isatine. The formula 51] is an uncommon 
 form of an oxysalt of sulphur, and I think that the true formula of the 
 salt is that of a hyposulphite : 
 
 f ZH 3 ,C 8 H 3 ; SO \ f | ZH 3 ,C 8 H 3 ; SO] 
 
 Either 
 
 or 
 
 H; SOf |ZH 3 ,C 8 H 3 ; SO 
 
 S: SO 
 
 See the account of the constitution of the hyposulphites, page 160. 
 Gmelin ascribes to this salt (ffandbuch der Chemie, Band vi., 423,) the 
 formula C 32 JS T2 H 12 O 4 S 2 , adding the authority of Erdmann and Laurent; 
 but I imagine that this is an error in quoting the figures ; otherwise we 
 should have the simple formula : 
 
 ZH 3 ,C 8 H 3 ;SO = Indylam sulphate. 
 
 SECTION 4. SALTS IN WHICH SULPHIC-INDYL is THE NEGATIVE 
 RADICAL. 
 
 The nature of sulphic vice-radicals has been explained at page 136. 
 The salts of sulphic-indyl have the usual characters of such radicals. 
 They are all double salts if viewed in relation to their analytical formulaa 
 and bibasic salts in accordance with their synoptical formulas. 
 
 Analytical Formula. Synoptical Formula. 
 
 5]- ill'; s H T} = ZH< ; ZH< = C H!S? 5 - 
 
 Ammona sulphic-indylite cum I = Ammona ammona indyl- 
 ammona sulphete. ) sulphenute. 
 
 52]. ZH 4 ; ZH 4 ; C 8 H 2 S 2 5 = Ammona ammona indylsulphenute. 
 
 53 J. K ; ZH 4 ; C 8 H 2 S 2 5 = Potassa ammona indylsulphenute. 
 
 54 j. K; ZH 4 ; C 8 HC1S 2 5 = Potassa ammona chloric-indyl- 
 
 sulphenute. 
 55], K; ZH 4 ; C 8 C1 2 S 2 5 = Potassa ammona chlorenic-indyl- 
 
 sulphenute. 
 56]. K; ZH 4 ; (/"BrtSFQ 5 = Potassa ammona bromenic-indvl- 
 
 sulphenute. 
 
 ZH 2 ; C 8 H 2 S0 3 ) _ Amida sulphic-indylite cum 
 ZH 8 , C 8 H 3 : S0 2 f = indylam sulphete. 
 
 573- 
 
 58]. 
 
 = ZH 2 ; ZH 3 ,C 8 H 3 ; C"H 1 S I S = Amida indylam indyl- 
 sulphenute. 
 
 ZHK ; C 8 H 2 SO 3 \ _ Potassac sulphic-indylite cum 
 ZH 3 ,C 8 H 3 ; S0 a f = indylam sulphete. 
 = ZHK ; ZH 3 ,C 8 H 3 ; C 8 H 2 S 2 6 5 = Potassac indylam 
 
 indylsulphenute. 
 
INDIGO. 273 
 
 52]. ZH 4 ; ZH 4 ; C 8 H 2 S 2 O 5 = Ammona ammona indylsulphenute. 
 The ordinary names and formulas of this salt are as follow : Isatosul- 
 phite of ammonia = C l6 H fi (NH 4 )NO 6 ,2SO 2 , Gerhardt. Isatinschweflig- 
 saures amrnoniak = C 16 NH 6 (NH 4 )O 6 ,2SO 2 , Gmelin. The Isatinosulphites 
 are formulated by several chemists thus : C 16 H 5 N0 4 ,2SO* + MO. But 
 this formula is deficient of HO. 
 
 53]. K ; ZH 4 ; C 8 H 2 S 2 O 5 = Potassa ammona indylsulphenute. 
 
 This is the potash-salt corresponding to the ammonia-salt No. 52]. Com- 
 mon names and formulae : The isatmosulphite of potash = C 16 H 6 KNO 6 , 
 2 SO' 2 , Gerhardt. Isatinschwefligsaures kali = C 16 NH 6 ,KO 6 ,2S0 2 , 
 Gmelin. This salt occurs with water of crystallization, which can be 
 driven off by heat ; but it is also possible to drive off so much of it that 
 the salt 53] becomes reduced to the salt 49]. Hence these two salts are 
 frequently confounded in chemical works. The Isatinosulphurous acid, 
 which would correspond to salts 52] and 53], is unknown. Gmelin 
 gives its formula as C 16 NH 7 S 2 O' - C 16 NH 7 O 6 ,2S0 2 , which would cor- 
 respond to the following : 
 
 H ; ZH 4 ; C 8 H 2 S 2 O 5 = Hydra ammona indylsulphenute. 
 
 54]. K; ZH 4 ; C 8 HC1S 2 O 5 = Potassa ammona chloric-indylsul- 
 
 phenute. 
 55]. K; ZH 4 ; C 8 C1 2 S 2 5 = Potassa ammona chlorenic-indyl- 
 
 sulphenute. 
 56]. K ; ZH 4 ; C 8 Bi- 2 S 2 5 = Potassa ammona bromenic-indyl- 
 
 sulphenute. 
 
 These three salts differ from 53] by having the hydrogen of the indyl 
 partly replaced by chlorine and bromine as well as by sulphur. In 5 5] 
 and 56] the hydrogen of the radical is entirely replaced. The vice- 
 radicals of the four salts are as follow : 
 
 53J 
 54 
 
 C 8 H 2 S = Sulphic-indyl. 
 
 C 8 HC1S = Chloric-sulphindyl. 
 
 C 8 C1 2 S = Chlorenic-sulphindyl 
 
 C 8 Br 2 S = Bromenic-sulphindyl. 
 
 These salts afford remarkable examples of the great substitution that can 
 take place in radicals, without disturbing the structure of their salts. 
 
 The ordinary name of No. 54] is the Chlorisatinsulphite of potash; 
 of No. 55] the Bichlorisatin sulphite of potash; and of No. 56] the Bi- 
 bromisatinsulphite of potash. 
 
 Hence, the ordinary names of the salts from No. 52] to 56] are quite 
 erroneous. A sulphite contains S 2 -f- O 3 ; but these salts contain 
 S' 2 -f- O 5 , and they are evidently double sulphates, including that addi- 
 tional atom of oxygen which always accompanies a sulphic vice-radical. 
 
 T 
 
274 ANILINE. 
 
 Each salt may receive a systematic name either according to the analytical 
 or the synoptical formula, as is shown at No. 52]. 
 
 Analytical Formula. Synoptical Formula. 
 
 57]- |zH<CH 3 ,- ^lo*} = { ZH " ; ZH 3 ' " 113 ; C'H'S'O 5 . 
 
 This salt is produced when indigo blue is stirred up with dilute sul- 
 phuric acid, with free access of atmospheric air. It has received the 
 following names : Sulphopurpuric acid ; Sulphophenicic acid ; Indig- 
 purpur; Purpurschwefelsaure. Formulas: HO.OTEPIW^SO 8 , Dumas. 
 C"H 10 N f O 4 ,S0 8 , Gerhardt. 
 
 58], ZHK; ZH 3 ,C 8 H 3 ; C 8 H 2 S 2 O 5 . Potassac indylam indylsulphenute. 
 
 This is the potash-salt of the so-called " acid" No. 57]. The two com- 
 pounds differ only in the circumstance that the radical Amida in 57] is 
 converted into Potassac in 58]. This substitution is effected by means 
 of caustic potash, thus : ZH 2 + KHO = ZHK -f HHO. 
 
 I have omitted from the preceding Table the compounds called 
 Indine, Hydrinden, and their derivatives. The composition commonly 
 ascribed to these compounds is such as does not admit of reduction to 
 exact formulae. For Indine we have C 16 H 6 NO 2 and C 16 H 5 NO 2 , one cor- 
 responding to indigo blue, and the other to indigo white. For Hydrin- 
 dine we have C 32 H 18 N 8 O 5 and C^IFN'O 10 . All these are given by 
 Laurent. The compounds that contain bromine and chlorine are equally 
 uncertain. I have also omitted Indelibrom for a like reason. 
 
 Aniline. 
 
 The compounds of aniline are to be reckoned by hundreds ; but they 
 are not the subjects of manufacture ; they are not articles of commerce ; 
 they are of no use in the arts ; they are applied to no purpose in 
 domestic economy; yet they have been the principal subject of dis- 
 cussion in all the chemical journals of Europe for nearly twelve 
 years. 
 
 The reason that these compounds have commanded so much of the 
 attention of chemists is, that they seemed to promise to afford informa- 
 tion which would lead to the solution of the great theoretical problem 
 which is expressed in the inquiry Wliat -is the nature of the Azotic 
 Bases ? That problem is of the very highest importance, because it is 
 
ANILINE. 275 
 
 impossible to make any decisive advances in physiological chemistry until 
 chemists obtain clearer notions than have hitherto prevailed respecting 
 the nature and functions of the compounds of azote. The researches of 
 Hofmann, carried out with admirable experimental dexterity, have sup- 
 plied a multitude of facts to aid in the solution of this problem. Yet, 
 notwithstanding his labours, and those of many other chemists in this 
 field, it cannot be said that the work in question has been accomplished, 
 and that the problem of the constitution of the azotic bases has been 
 logically solved. For that reason I take leave to call the attention of 
 chemists to a series of arguments, which constitute one more attempt to 
 clear away the difficulties which beset this question. 
 
 The " ANILINE THEORY," which I have to propose for the adoption 
 of chemists, is briefly as follows : a). The Radical of these compounds is 
 PHENYL = C 6 H 5 , which frequently undergoes substitution, and becomes 
 chloric-phenyl = C 6 H 4 C1, chlorenic-phenyl = C 6 H 3 C1 2 ; bromic-phenyl 
 = C 6 H 4 Br, bromenic-phenyl = C 6 H 3 Br; iodic-phenyl = C 6 H 4 I, &c. 
 6). In combination with azote and hydrogen, phenyl and the vice- 
 phenyls produce the radicals phenylac = ZH,C 6 H 5 , phenylam = ZH 3 ,C 6 H 5 , 
 phenylem = ZH 2 ,(C 6 H 5 ) 2 ; and the vice-phenylacs and vice-phenylams 
 which result from the substitution of chloric-, bromic-, or iodic-phenyl for 
 normal phenyl in such compounds, c). These vice-amids and vice-ammons 
 which, it is apparent, are part of the great system of vice-amids and vice- 
 ammons, and are in no respect peculiar to aniline, form salts by combining, 
 in the usual way, with negative radicals of every description, oxidised or 
 not oxidised ; so that, in this respect also, they have no property peculiar 
 to aniline, but act exactly like all other azotic radicals, d). The salts of 
 these compound radicals have a great tendency to form double salts, 
 especially salts which contain on the one part an amid and on the other 
 part an ammon. e). They also possess, and frequently exercise, the 
 power to produce triple and quadruple salts. 
 
 In this " theory " there is nothing improbable. The properties 
 ascribed to the aniline radicals, and the structure of their double and 
 triple salts, are such as are common to many other radicals and their 
 salts. The pretensions of this " theory " are, not to show that aniline 
 is wonderfully different from all other chemical compounds, but that it 
 is able to reduce to order and regularity a mass of facts which, as they 
 are commonly formulated and named in chemical books, are either in 
 confusion or helpless uncertainty. The points upon which the " theory " 
 rests are these.: The dismissal of all ammonias as " bases," and the 
 assumption of vice-amids and vice-ammons as "basic radicals," each of 
 these radicals, whatever its composition, being equivalent in chemical 
 power to H l , and exercising that power in the formation of an extensive 
 variety of single and multiple salts. Everything else follows as a matter 
 of course, in accordance with the general principles of the radical theory. 
 
 I proceed to adduce evidence in support of this aniline theory. It con- 
 
 T 2 
 
276 
 
 TABLE OF THE SALTS OF ANILINE. 
 
 sists, first, of a Table of examples selected from the most important aniline 
 compounds ; and, secondly, of a critical account of the names, formulae, 
 and theories applied to the same compounds by Hofmann and other 
 chemists. On looking over the Table, the reader will see the structure of 
 each salt; its relation to other salts of the series, and its systematic 
 name ; and on consulting the notes he will be supplied with the means 
 of judging whether or not the theory and nomenclature now proposed 
 are better or worse than those against which they are put in competition. 
 
 Table of the Salts of Aniline. 
 
 7. 
 8" 
 
 9j 
 10 
 ii 
 
 12 
 
 i8 
 
 *9J 
 
 2 7J 
 28]. 
 
 29]. 
 
 ZH,C 6 H 5 ;H 
 ZH,C 6 H 4 C1 ; H 
 ZH,C 6 H 4 Br; H 
 ZH,C 6 H 4 I;H 
 ZH^HW; H 
 ZC 5 H U ,C 6 H 5 ;H 
 ZC 2 H 5 ,C 6 H 5 ; H 
 ZH^HW; Br 
 ZH,C 8 H 3 C1 2 ; Cl 
 ZH, C 6 H 3 Br 2 ; Cl 
 ZH,K;C<H 5 
 ZH 3 ,C 6 H 5 ;C1 
 ZH 3 ,C 6 H 5 ; Br 
 ZH 3 ,C 6 H 5 ; I 
 ZH 3 ,C 6 H 4 C1 ; Cl 
 ZH 8 ,C 6 H 4 Br;Cl 
 ZH 3 ,C 6 H 4 I; Cl 
 ZH 3 ,C 6 H 4 I;I 
 ZH,C e BPBr*;Ca 
 (ZH 3 ,C 6 H 4 C1; Cl 
 Ptc 2 ;Cl 2 
 JZH 3 ,C 6 H 4 I; Cl\ 
 \ Ptc 2 ; C1 2 ( 
 
 ZH 2 ,C 6 H 5 ,Hgc;Cl 
 ZH 8 ,C 8 H 5 ; NO 3 
 ZH 3 ,C 6 H 5 ; SO 2 
 ZH 2 ,C 6 H 5 ,Cuc ; SO 2 
 ZH 3 ,C 6 H 4 C1 ; SO 2 
 ZH 3 ,C 6 H 4 I ; SO 2 
 ZH,C 6 H 5 ;SO\ 
 H; S0 2 f 
 = H;ZH,C'H 5 ; S 2 3 
 
 Phenylac hydra. 
 Chloric-phenylac hydra. 
 Bromic-phenylac hydra, 
 lodic-phenylac hydra. 
 Bromenic-phenylac hydra. 
 Amylic-phenylac hydra. 
 Ethylic-phenylac hydra. 
 Bromenic-phenylac broma. 
 Chlorenic-phenylac chlora. 
 Bromenic-phenylac chlora. 
 Potassac phenyla. 
 Phenylam chlora. 
 Phenylam broma. 
 Phenylam ioda. 
 Chloric-phenylam chlora. 
 Bromic-phenylam chlora. 
 lodic-phenylam chlora. 
 lodic-phenylam ioda. 
 Bromenic-phenylam chlora. 
 Chloric-phenylam chlora bis platic 
 
 chlora. 
 lodic-phenylam chlora bis platic 
 
 chlora. 
 
 Meric-phenylam chlora. 
 Phenylam nitrite. 
 Phenylam sulphete. 
 Cupric-phenylam sulphete. 
 Chloric-phenylam sulphete. 
 lodic-phenylam sulphete. 
 
 Hydra phenylac sulphenite. 
 Argenta phenylac sulphenite. 
 
TABLE OF THE SALTS OF ANILINE. 
 
 277 
 
 30]. Ag; Z,C 7 H 5 ,C 6 H 5 ;S 2 3 
 
 fZH,C 6 H 5 ; S 2 3 ) 
 3 i]JzH,C 6 H 5 ;S 2 3 I 
 
 I H;Cy J 
 
 32]. ZH 3 ,C G H 5 ;P0 3 
 33]. ZH 3 ,C 6 H 5 ; H 2 ; PO 4 
 34. (ZH 3 ,C 6 H 5 ) 2 ;H; PO 4 
 35]. (ZH a ,C 6 H 5 ) 8 ;H 2 ; P 2 7 
 
 36]. ZH 3 ,C 6 H 5 ; CO 2 
 37]. ZH 3 ,C 6 H 4 I; CO 2 
 38]. ZH 3 ,C 6 H 4 Br; CO 2 
 
 -, (ZH 3 ,C 6 H 4 C1; CO 8 1 
 39J- \ H;C0 2 [ 
 
 40]. ZH,C 6 H 5 ; CO 
 
 n JZH, CO \ 
 
 ^> ]ZH,C 6 H 5 ; CO f 
 42]. ZH,C 6 H 5 ;CHO 
 43]. ZH,C 6 H 5 ; C 2 H 2 O 
 44]. ZH,C 6 H 5 ; C 2 H 3 O 
 45J. ZH,C 6 H 5 ; C 4 H 7 O 
 46]. ZH,C 6 H 5 ; C 5 H 9 
 47]. ZH,C 6 H 5 ; OH^ 
 48]. ZH,C 6 H 5 ; C 8 H 7 O 2 
 49]. ZH,C 6 H 5 ; C 9 H 7 
 
 [ZH,C 6 H 5 ; CO) 
 50]. H;C0 2 f 
 
 l = H; ZH,C 6 H 5 ;C 2 3 
 51]. Ba; ZH,C 6 H 5 ; C 2 O 3 
 
 , (ZH 3 ,C e H 5 ; ZH,C 6 H 5 ; C 2 3 ) 
 52 J' \ H; ZH,C 6 H 5 ; C 2 O 3 j 
 
 fZH,C 6 H 3 ; C 2 H 2 01 ) 
 
 53]. H;C 2 H 2 2 f 
 
 ( = H ; ZH,C 6 H 5 ; (C 2 H 2 ) 2 3 J 
 54]. ZH,C 6 H 5 ;N0 2 
 n (ZH,C 6 H 5 ; NO 2 
 55J- { H;C1 
 
 <n (ZH,C 6 H 5 ;N0 2 ) 
 5 & > \HPtc 2 ; Cl 3 f 
 ZH,C 6 H 5 ;NO 2 ) 
 I; CO 2 ) f 
 
 2(H 
 H 5 
 H;CyO 
 
 ZH,C 6 H 5 ;N0 2 1 
 f 
 
 Argenta benzylic-phenylac sul- 
 phenite. 
 
 Bis phenylac sulphenite cum 
 hydra cyana. 
 
 Phenylam phosphite. 
 Phenylam hydren phosphote. 
 Phenylamen hydra phosphote. 
 Phenylamen hydren phos- 
 
 pheneze. 
 
 Phenylam carbete. 
 lodic-phenylam carbete. 
 Bromic-phenylam carbete. 
 Hydra chloric-phenylam car- 
 
 benote. 
 
 Phenylac carbate. 
 Phenylac carbate cum amida 
 
 carbate. 
 
 Phenylac formylate. 
 Phenylac succinylate. 
 Phenylac acetylate. 
 Phenylac butyrylate. 
 Phenylac valerylate. 
 Phenylac benzylate. 
 Phenylac anisylete. 
 Phenylac cinnamylate. 
 Phenylac carbate cum hydra 
 
 carbete ; or 
 
 Hydra phenylac carbenite. 
 Baryta phenylac carbenite. 
 Phenylam phenylac carbenite 
 cum hydra phenylac carbenite. 
 
 Hydra phenylac succinylenite. 
 
 Phenylac nitrete. 
 
 Phenylac nitrete cum hydra 
 
 chlora. 
 Phenylac nitrete cum hydra 
 
 platenic chlorine. 
 Phenylac nitrete bis hydra 
 
 carbete. 
 Phenylac nitrete cum hydra 
 
 cyanate. 
 
278 
 
 TABLE 
 
 c 
 
 (ZH,C 6 H 5 ;NOM 
 
 59]. ^ZH,C 6 H 5 ; NO 2 
 
 
 H;Cy J 
 
 
 60]., 
 
 !'7"tT /"^6"CJ5 !Vr > k2 
 Zji,v^ 1 ; I\LJ 
 ZH,C 6 H 5 ; NO 2 
 Cy;Cl 
 
 1 
 
 
 ZH,C 6 H 5 ; NO 2 
 
 
 61]. 
 
 ZH,C 6 H 5 ; NO 2 
 Cy;Cl 
 
 
 
 Ptc 2 ; Cl 2 
 
 
 62]. 
 
 ZH^H 5 ; Cy 
 
 
 6 , IZH,C 6 H*;Cy 1 
 & 3> JZH,C 6 H 5 ; H j 
 
 61 (ZH,C 6 H*;Cy 
 I' \ZH 3 ,C 6 H 5 ; Cl 
 
 I 
 
 6 , lZH,CH*;Cy 
 5J- \ZH 3 ,C 6 H 5 ; Br 
 
 1 
 
 66]., 
 
 (ZH,C 6 H 5 ; Cy 
 ZH 3 ,C 6 H 5 ; I 
 
 I 
 
 6 , (ZH,C 6 H*;Cy 
 7J \ZH 3 ,C 6 H 5 ; SO 2 
 
 I 
 
 681 (ZH,C 6 H*;Cy 
 6b > 1ZH 8 ,C 6 H 5 ;N0 3 
 
 ) 
 
 
 ZH, C 6 H 5 ; Cy 
 
 
 1 
 
 ZH, C 6 H 5 ;H 
 
 
 09]. 
 
 ZH, C 6 H 5 ; Cy 
 
 
 
 ZH 2 ,C 6 H 5 ,Ag;NO 3 
 
 
 fZH,C"H 5 ;Cy 
 
 ) 
 
 7 0]., 
 
 ZH 3 ,C 6 H 5 ; CO 2 
 H;C0 2 
 
 1 
 
 n JZH,C 6 H 4 C1; Cy 1 
 
 7 I J' {ZH,C 6 H 4 C1;H J 
 
 -, JZH,C 6 H 4 Br; Cy 
 
 } 
 
 7 2 J'\ZH,C 6 H 4 Br;H 
 
 
 -, (ZH^'H 4 !; Cy 
 73J- |ZH,C 6 H 4 I; H 
 
 I 
 
 -, (ZH,C 6 H 4 Br;Cy 1 
 74J- izH 3 ,C 6 H 4 Br;Cl j 
 
 (ZH,C 6 H 5 ;Cy ) 
 ]JZH 3 ,C 6 H 5 ;C1 I = 
 Ptc 2 ; Cl 2 J 
 
 TABLE OF THE SALTS OF AX1LIXK. 
 
 = Bis phenylac nitrete cum hydra cyana. 
 = Bis phenylac nitrete cum cyana chlora. 
 
 Bis phenylac nitrete cum cyana chlora 
 bis platic chlora. 
 
 = Phenylac cyana. 
 
 = Phenylac cyana cum phenylac hydra. 
 
 = Phenylac cyana cum phenylam chlora. 
 
 = Phenylac cyana cum phenylam broma. 
 
 = Phenylac cyana cum phenylam ioda. 
 
 = Phenylac cyana cum phenylam sulphete. 
 
 = Phenylac cyana cum phenylam nitrite. 
 
 Bis phenylac cyana cum phenylac hydra 
 cum argentic-phenylam nitrite. 
 
 Phenylac cyana cum hydra phenylam 
 bicarbete. 
 
 Chloric-phenylac cyana cum chloric-phe- 
 
 nylac hydra. 
 Bromic-phenylac cyana cum bromic- 
 
 phenylac hydra, 
 lodic-phenylac cyana cum iodic-phenylac 
 
 hydra. 
 Bromic-phenylac cyana cum bromic- 
 
 phenylam chlora. 
 
 Phenylac cyana cum phenylam chlora 
 bis platic chlora. 
 
TABLE OF THE SALTS OF ANILINE. 279 
 
 I Phenylac cyana cum phenylam 
 
 I Auc 3 ' CP I : Chl ra triS aUrk Chl ra * 
 
 !ZH, C 6 H 4 C1 ; Cy ) Chloric - phenylac cyana cum 
 
 ZH 3 ,C 6 H 4 C1; Cl \ = chloric-phenylam chlora bis 
 
 ^H Ptc 2 ; Cl 2 J platic chlora. 
 
 f ZH, C 6 H 4 Br; Cy | Bromic - phenylac cyana cum 
 
 78]. < ZH 3 ,C 6 H 4 Br; Cl V = bromic-phenylam chlora bis 
 
 I Ptc 2 ; Cl 2 J platic chlora. 
 
 79] . & 
 
 I H; Cy 
 
 ( 7TT f^TT 5 C*v \ 
 
 ai J r/ij XTTS ' r? _ Bis phenylac cyana cum cyana 
 
 79] r c : 
 
 | o 
 
 Q -, }(ZH, C 6 H 5 ; Cy) 8 { _ Tris phenylac cyana cum phe- 
 
 8 > I ZH, C 6 H 5 ; H / : nylac hydra. 
 
 81]. ZCH 3 ,C 6 H 5 ;Cy = Methylic-phenylac cyana. 
 
 82]. ZC 2 H 5 ,C 6 H 5 ; Cy = Ethylic-phenylac cyana. 
 
 83]. ZC 5 H U ,C 6 H 5 ; Cy = Amylic-phenylac cyana. 
 
 (7TT n 6 !^ 5 Pw 1 
 
 84]. |zH 3 ,C 6 H 5 ; Cy } = Phen y lam phenylac cyanen. 
 
 -, j ZH, C 6 H 5 ; Cy + HC1 1 _ Phenylam phenylac cyanen bis 
 
 b 5> JZH 3 ,C 6 H 5 ; Cy + HC1 J = hydra chlora. 
 
 Q/n JZH, C 6 H 5 ; Cy + HPtc'Cl 3 \ _ Phenylam phenylac cyanen bis 
 
 y& > |ZH 3 ,C 6 H 5 ; Cy + HPtc 2 Cl 3 J = hydra platenic chlorine. 
 
 -, JZH,C 6 H 5 ; Cy + HAuc 3 ClM _ Phenylam phenylac cyanen bis 
 
 8 7J- |ZH 3 ,C 6 H 5 ; Cy + HAuc 3 Cl 4 j ' hydra aurinic chlorone. 
 
 QQ1 JZH, C 6 H 5 ; Cy +HN0 3 \ _ Phenylam phenylac cyanen bis 
 
 |ZH 3 ,C 6 H 5 ; Cy + HNO 3 j = hydra nitrite. 
 
 8 9; 
 
 92. 
 
 ZH 3 ,C 6 H 5 ; CyO = Phenylam cyanate. 
 
 ZH 2 ,C 6 H 5 ,C 6 H 5 ; CyO = Phenylem cyanate. 
 
 ZH 3 ,C 6 H 5 ; Cy ; S 2 = Phenylam cyana sulphene. 
 
 ZH 2 ,C 6 H 5 ,C 6 H 5 ; Cy ; S s = Phenylem cyana sulphene. 
 
 CC 6 H 5 CvO ^ 
 
 1 Jc 6 H 5 'c = Bis pheny la cyanate cum hydra 
 
 I H/Cy " 
 
 c 6 H 5 CvO 
 
 ^ 
 
 I = 
 j " 
 
 'i 
 
 I = 
 
 I * rf I " cyana 
 
 I Ag,Cy ' 
 
 'i 
 
 I = Bis phenyla cyanate cum argenta 
 I " 
 
280 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 95]. C 6 H 5 ,CyO '= Phenyla cyanate. 
 
 ^1 (H,CH 3 O + C 6 H 5 ; CyO = Hydra methylate cum phenyla cy- 
 9 -I" 4 anate. 
 
 I = H,GH B ,C e H ; CyO 8 = Hydra methyla phenyla cyanete. 
 
 -, j H,C 2 H 5 O + C 6 H 5 ; CyO = Hydra ethylate cum phenyla cyanate. 
 97J- \H,C 2 H 5 ,C 6 H 5 ; CyO 2 = Hydra ethyla phenyla cyanete. 
 
 fi -, j H,C 5 H U 0+C 6 H 5 ; CyO = Hydra amylate cum phenyla cyanate. 
 9 8 > \H,C 5 H ll ,C 6 H 5 ; CyO 2 = Hydra amyla phenyla cyanete. 
 
 99-1* )CZHC 6 H 5 ' C Vi = ^ >nen y^ a cyanate tris phenylac cyana. 
 
 Critical Notes on the Salts of Aniline. 
 
 i]. ZH,C 6 H 5 ;H = Phenylac hydra. 
 
 This is the salt that is commonly called Aniline. It is prepared by 
 fusing hydrate of potash with isatine. See Indigo, 4]. The action is 
 represented in the following equation : 
 
 ZH 2 ,C 8 H S OM fZH,C 6 H 5 ;H 
 4 K,HO f = ^(KK,C0 3 ) 2 
 IIP 
 
 Ore atom of isatine and four atoms of hydrate of potash produce one 
 atom of aniline, two atoms of carbonate of potash, and two atoms of hy- 
 drogen. Hofmann, Memoirs of the Chemical Society (1845), iii., 271. 
 Many other names have been given to aniline: Kyanol, Crystalline, 
 Benzidam, Phenylamide, Amaphenase, Phenylia. It is formulated as 
 C 12 H 7 N and C 1S H 5 ,H 2 N. Hofmann, acting on the presumption that 
 aniline contained ammonia, endeavoured to prove that the composition 
 was C I2 H 4 -}- NH 3 ; but he did not succeed in procuring a radical of the 
 form C I8 H 4 ; although many of his formulae, as will hereafter be seen, 
 are framed on the assumption that the aniline salts contain such a 
 radical. 
 
 It is remarkable, that in the conversion of isatine into aniline, the 
 radical indyl = C 8 H 3 is converted into the radical phenyl = C^H 5 ; in 
 which transformation two atoms of carbon are abstracted from, and two 
 atoms of hydrogen are added to, the original radical. This transmutation 
 renders it probable that chemists may hereafter be able to effect consider- 
 able changes in the composition of the organic radicals which occur as 
 products of vegetable and animal life. 
 
 2]. ZH,C 6 H 4 C1;H = Chloric-phenylac hydra. 
 
CHLORANILINE, BROMANILIXE, IODANILINE. 281 
 
 Hofmann's names : Chloraniline and Amachlophenese. His formulae 
 
 H 
 
 \C1 
 
 N. 
 
 Prepared by acting upon chlorisatine, Indigo 1 1], with caustic potash : 
 
 ZH 2 ,C 8 H 2 C10 2 ) 
 4 K,HO f 
 
 (ZH,C 6 H 4 C1; H 
 { (KK,CO 3 ) 2 
 
 The reaction is quite parallel to that which occurs when normal isatine 
 is acted upon. See No. i. Hofmann remarks that "the capacity of 
 saturation of chloraniline is the same as that of aniline, although the atom 
 of the latter is lower than that of the former by the difference of the 
 equivalents of chlorine and hydrogen (442*65 12*50 = 430*15)." 
 Mem. Ch. Soc. ii., 277. Of course ! The capacity of saturation is the 
 same, because phenylac and chloric-phenylac are each one radical, with 
 the saturating capacity of one atom. All the vice-amids and vice-ammons, 
 whatever their composition or atomic weight, have the saturating capa- 
 city of one volume of hydrogen. 
 
 3]. ZH,C 6 H 4 Br; H = Bromic-pheny lac hydra. 
 Bromaniline ; Amabrophenese ; Bromophenylamine = C I2 (H 6 Br)N 
 
 H 
 H 
 
 C 12 
 
 N. Hofmann. 
 
 Prepared by the action of potash on bromisatine, Indigo 13], Hofmann. 
 
 4]. ZH,C 6 H 4 I;H = lodic-phenylac hydra, 
 lodaniline = C 12 (H 6 I)N. Hofmann. 
 
 5]. ZH,C 6 H 3 Br 2 ; H = Bromenic-phenylac hydra. 
 Dibromaniline ; amabrophenese ; Dibromophenylamine = C l2 (H 5 Br 2 )N 
 
 H 
 
 H 
 
 C 12 ( 
 
 N. Hofmann. 
 
 1 As I must refer to many of Dr. Hofmann's formulae, which are gene- 
 rally written in double or triple lines, I shall, to save room, write them 
 in a single line, thus : C I2 (H 6 ,C1)N, unless there appears reason to quote 
 them graphically. 
 
CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 6]. ZC 5 H U ,C 6 H 5 ; H = Amylic-phenylac hydra. 
 7]. ZC 2 H 5 ,C 6 H 5 ;H = Ethylic-phenylac hydra. 
 
 These two compounds contain amidogens, in which both atoms of 
 hydrogen are replaced by compound radicals. 
 
 Hofmann's names and formulae for No. 6] : Amylaniline ; Amylophe- 
 nylamine 
 
 c tie i f H 
 
 = C"H ir N = ( 
 
 His names and formulae for No. 7] : Ethylaniline ; Ethylophenylamine 
 = C 16 H 11 N = C 12 L^ 5 1 N = Jc i4 H 5 VN. 
 
 There exists a similar compound with CH 3 , instead of C 2 H 5 and C 5 H", 
 but which in other respects agrees with Nos. 6] and 7]. 
 
 The compounds fr6*ni No. i] to No. 7] are commonly called " bases." 
 They contain one atom of replaceable hydrogen. When this hydrogen 
 is replaced by an anhydrous radical, we obtain salts with an amidogen 
 base, such as Nos. 8] to n] ; but when the " base" combines with a 
 " hydrated acid," the hydrogen of the " acid," added to that of the 
 " base," is just sufficient to convert the amidogen into an ammonium. 
 Thus, Aniline i] = ZH,C 6 H 5 ; H, with hydrochloric acid = HC1, pro- 
 duces hydrochlorate of aniline = ZH 3 ,C 6 H 5 ; Cl, shown by No. 12] in 
 the Table. The " bases " which contain chloric and bromic-phenyl act 
 exactly in the same manner as those which contain normal phenyl ; and 
 hydrated oxygen acids act precisely like hydrochloric acid ; so that it is 
 possible to produce a great number of salts by preparing these bases, or 
 hydrides of vice-amids, and then simply combining them with hydrated 
 acids. The experimental processes are in some cases complicated ; but 
 so far as respects the theory of these compounds, nothing can be simpler. 
 The entire aniline series consists of salts of Phenylac and Phenylam 
 with double salts containing both of these radicals, and with a few mul- 
 tiple and irregular salts. The differences in the aniline salts depend, 
 either upon the nature of their negative radicals, or upon certain peculiar 
 forms of double and triple salts which admit of easy explanation. In 
 consequence of this great regularity, I shall pass over all duplicate salts 
 with a brief notice, and only dwell upon those prominent substances 
 which invite critical examination. Dr. Hofmann's series of papers on 
 aniline, in which the methods of preparation, and the properties of all 
 the salts are described in detail, being easily accessible, in the Quarterly 
 Journal of the Chemical Society, I shall not enter unnecessarily upon 
 those subjects, but confine myself, as closely as a clear identification of 
 the compounds will permit, to the discussion of formulae and names. 
 
THE SA.LTS OF ANILINE. 283 
 
 8]. ZH,C 6 H 3 Br 2 ; Br = Bromenic-phenylac broma. 
 Tribromaniline ; amabrophenose = C 12 (H 4 Br 3 )N. 
 
 H 
 
 Tribromophenylamine 
 
 N. Hofmann. 
 
 This is a neutral salt, not a base; a bromide of an amidogen con- 
 taining a bromenic radical. 
 
 9], ZH,C 6 H 3 C1 2 ; Cl = Chlorenic-phenylac chlora. 
 
 Trichloraniline ; amachlophenose = C 12 (H 4 Br 3 )N, Hofmann. Of similar 
 constitution to the preceding salt. 
 
 10]. ZH,C 6 H 3 Br 2 ;Cl = Bromenic-phenylac chlora. 
 Chlorodibromaniline ; amachlobrophenose = C 12 (H 4 ClBr 2 )N, Hofmann. 
 
 ii]. ZH,K;C 6 H 5 = Potassac phenyla. 
 Anilide of potassium = K,NH 2 ,C 12 H 4 , Hofmann. 
 
 12]. ZH 3 ,C 6 H 5 ;C1 = Phenylam chlora. 
 Hydrochlorate of aniline = C 12 NH 7 ,HC1, Fritzsche. 
 
 13]. ZH 3 ,C 6 H 5 ;Br = Phenylam broma. 
 Hydrobromate of aniline = C 12 H 7 N,HBr, Hofmann. 
 
 14]. ZH 3 ,C 6 H 5 ;I = Phenylam ioda. 
 Hydriodate of aniline = C 12 H 7 N,HI, Hofmann. 
 
 15]. ZH 3 ,C 6 H 4 C1;C1 = Chloric-phenylam chlora. 
 Hydrochlorate of chloraniline = C1H,C 12 (H 6 C1)N, Hofmann. 
 
 16]. ZH 3 ,C 6 H 4 Br;Cl = Bromic-phenylam chlora. 
 Hydrochlorate of bromaniline = ClH,C 12 (H 6 Br)N, Hofmann. 
 
 17]. ZH 3 ,C 6 H 4 I;C1 = lodic-phenylam chlora. 
 Hydrochlorate of iodaniline = C 12 (H 6 I)N,HC1, Hofmann. 
 
 1 8]. ZH 3 ,C 6 H 4 I;I = lodic-phenylam ioda. 
 Hydriodate of iodaniline = C 12 (H 6 I)N,HI, Hofmann. 
 
 19]. ZH 3 ,C 6 H 3 Br 2 ; Cl = Bromenic-phenylam chlora. 
 Hydrochlorate of dibromaniline = ClH,C 12 (H 5 Br 2 )N, Hofmann. 
 
 -, JZH 3 ,C 6 H 4 C1; Cl 1 _ Chloric-phenylam chlora 
 20J< { Ptc 2 ; Cl 2 ] : bis platic chlora. 
 
284 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 Chloraniline arid bichloride of platinum = C1H,C 18 (H 6 C1)N + Cl 8 Pt, 
 Hofmann. In this case, and in all similar cases, I use the platic atom, 
 in order that the number of positive radicals, = Ptc 8 , may equal the 
 number of negative radicals = Cl 2 , and that we may thus get rid of the 
 necessity of assuming the existence of ^chlorides. See the article on the 
 " Platinum Bases." 
 
 o -, IZH^C'H 4 !; Cl ) _ lodic-phenylam chlora bis 
 r \ Ptc 8 ; C1 8 | : platic chlora. 
 
 Bichloride of platinum and iodaniline = C 18 (H 6 I)N,HC1 + PtCl 8 , Hqf- 
 mann. 
 
 22]. ZH 8 ,C 6 H 5 ,Hgc; Cl = Meric-phenylam chlora. 
 
 Chlorquicksilver-aniline, Gmelin = C l2 NH 7 ,HgCl, Gerhardt. Hofmann 
 has analysed a salt of the following constitution : 
 
 ZH 2 ,C 6 H 5 ,Hgc ; C1+ 2(HgcCl) = Meric-phenylam chlora bis meric chlora. 
 23]. ZH 3 ,C 6 H 5 ;N0 3 = Phenylam nitrite. 
 
 Ordinary name : Nitrate of aniline. The composition is equivalent to 
 that of an atom of hydrated nitric acid combined with an atom of aniline ; 
 the hydrogen of these two compounds being just sufficient to convert 
 the amidogen into an ammonium ; as explained in the note to No. 7]. 
 
 ZH^H 5 ; H + HNO 3 = ZH 3 ,C 6 H 5 ; NO 3 . 
 
 Phenylac hydra -f- Hydra nitrite = Phenylam nitrite. 
 The compound called Nitraniline, No. 54, is the Amide of this salt. 
 
 24]. ZH 3 ,C 6 H 5 ;S0 2 = Phenylam sulphete. 
 
 Sulphate of aniline = C 12 NH 7 ,HO,SO 3 , Zinin. The composition is equi- 
 valent to that of a compound of an atom of hydrated sulphuric acid with 
 an atom of aniline : 
 
 5 ; H + HSO* = ZEP.OTP; SO 8 . 
 
 Phenylac hydra -f Hydra sulphete = Phenylam sulphete. 
 
 25]. ZH 2 ,C 6 H 5 ,Cuc; SO 2 = Cupric-pheny lam sulphete. 
 Sulphate of copperoxide-aniline = C 1? NH 7 ,CuO,SO 3 , Gmelin, Hofmann. 
 26]. ZH 3 ,C 6 H 4 C1;S0 8 = Chloric-phenylam sulphete. 
 
 Sulphate of chloraniline = S0 3 ,C 12 (H 6 C1)N + HO, Hofmann. Compare 
 the following two formulae : 
 
 No. 2]. ZH,C 6 H 4 C1;H 
 No. 26]. ZH 3 ,CH 4 C1; SO 8 . 
 
 Hofrnann calls No. 2] Chloraniline, and No. 26] Sulphate of chlora- 
 niline, and his formulae are : 
 
SULPHANILIC ACID. 285 
 
 C 12 | ^ } N and S0 3 ,C' 2 j **' | N + HO. 
 
 These names and formulae effectually hide the important fact, that 
 No. 2] is a salt of an amidogen, and No. 26] a salt of an ammonium. 
 Such is the result of the adoption of " bases " instead of "basic radicals." 
 They darken what they are intended to enlighten. 
 
 27]. ZH 3 ,C 6 H 4 I; SO 2 = lodic-phenylam sulphete. 
 Sulphate of iodaniline = C 12 (H 6 I)N,HSO 4 , Hofmann. 
 
 J28]. H; ZH,C 6 H 5 ; S 2 O 3 = Hydra pheny lac sulphenite. 
 29]. Ag; ZH,C 6 H 5 ; S 2 O 3 = Argenta phenylac sulphenite. 
 30]. Ag; Z,C 7 H 5 ,C 6 H 5 ; S 2 O 3 = Argenta benzylic-phenylac 
 
 sulphenite. 
 
 These three salts are all sulphites, and are, therefore, bibasic. See page 
 171. No. 28] has an atom of hydrogen replaceable by a positive 
 radical, and on that account is called by Hofmann an " acid." No. 29] 
 is the silver salt of that acid. No. 30] contains benzylic-phenyl in place 
 of normal phenyl, but in other respects it is the same as No. 29]. Hof- 
 mann's formula for No. 28] is HS0 4 C 12 H 6 N,SO 2 , and his name is Sul- 
 phanilic acid. Both name and formula ignore the existence of a sulphite. 
 Gerhardt calls it Phenyl-sulphamic acid, and gives it the formula 
 C 12 IFNS 2 6 . Miller gives two formulae: HO,C 12 H 5 ,HN,S 2 O 5 and 
 HO,C 12 H 6 NS 9 5 . Gerhardt's name and formula for No. 30] are as 
 follow : 
 
 [ C 12 H 5 S 2 O 4 Azoture of sulphopheny le 
 
 N^C 14 H 5 2 = of benzoile and "of 
 
 [Ag silver. 
 
 By this ingenious superstructure a bibasic neutral sulphite is made to 
 look like an ammonia. Gerhardt calls No. 29] Sulphanilate (or pheny 1- 
 sulphamate) of silver = C 12 H 6 AgNS 2 6 . Consult Azotic Radicals, 
 No. 321], also the section on Conjugated Acids. 
 
 31]. (ZH,C 6 H 5 ; S 2 O 3 ) 2 + HCy = Bis phenylac sulphenite 
 
 cum hydra cyana. 
 
 According to the formula, this salt is a compound of two atoms of a 
 hyposulphate see page 172 with one atom of hydrocyanic acid. 
 Hofmann gives the following account of it : " Concentrated sulphuric 
 acid forms with Melaniline (see No. 63) a copulated sulphuric acid, 
 which, as it appears, possesses this remarkable composition, C 26 H 13 N 3 S 4 12 , 
 which crystallises, and produces soluble salts with all bases." Supple- 
 mente zum ffandworterbuche der Chemie, 271. 
 
286 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 32] to 35] are phosphates of phenylam, which do not require par- 
 ticular notice ; No. 32] is the monobasic salt. Nos. 33] and 34] are 
 tribasic; and No. 35] is tetrabasic, or, as it is commonly called, bibasic. 
 See page 142. They are all given on the authority of Nicholson. 
 
 36]. ZH 3 ,C 6 H 5 ;CO a = Phenylam carbete. 
 
 Neutral oxalate of aniline = C 2 O 3 ,C 12 H 7 N + HO, Hofmann. The com- 
 position of this salt is equal to that of an atom of hydrated oxalic acid 
 and an atom of aniline : 
 
 H,C0 8 + ZH,C 6 H 5 ;H = ZH 3 ,C 6 H 5 ; CO 2 . 
 Hydra carbete -}- Phenylac hydra = Phenylam carbete. 
 
 37]. ZIPjOH 4 !; CO 2 = lodic-phenylam carbete. 
 Oxakteofiodaniline = C 12 (H 6 I)N,HC 2 O 4 , Hofmann. 
 
 38]. ZH 3 ,C 6 H 4 Br; CO 2 = Bromic-pheny lam carbete. 
 Oxalate of bromaniline = C 2 O 3 ,C l2 (H 6 Br)N,HO, Hofmann. 
 
 39]- { 
 
 ZH 3 ,C 6 H 4 C1; CO 2 1 Hydra chloric-pheny lam 
 H ; CO 2 ] : carbenote. 
 
 ) , 
 
 \Hofmann. 
 
 Binoxalate of chloraniHne = 2C 2 O 3 ,C I2 (H 6 C1)N + HO, Hofmann. 
 40]. ZH,C 6 H 5 ;CO = Phenylac carbete. 
 
 Oxanilide = C^N.W = C 14 H 6 NO 2 ) 
 = NH 2 ,C 2 2 ,C 12 H 4 
 
 Gerhardt's name is Diphenyl-oxamide or diazoture of diplienyle and 
 
 f C ? 2 
 hydrogen = C 14 H 12 N 2 2 = N 2 j(C 6 H 5 ) 2 
 
 Oxanilide is the amid of the ammonium-salt No. 36], viz. : 
 ZH 3 ,C 6 H 5 ; CO 2 - HHO = ZH,C 6 H 5 ; CO. 
 
 41]- { 
 
 ZH,C 6 H 5 ; CO) Phenylac carbete cum amida 
 ZH 2 ; CO | = carbete. 
 
 Oxanilamide = C 16 H 8 N 2 4 = C 12 H 6 N,C 2 O 2 ; H 2 N,C 2 O 2 , Hofmann. A 
 double salt containing the amid of the ammonium series and that of the 
 phenylam series. 
 
 42]. ZH,C 6 H 5 ;CHO = Phenylac formylate. 
 Formanilide ; phenyl-formiamide ; azoture of phenyl, of formyl, and of 
 
 fC 6 H 5 
 
 = N^CHO, 
 I H 
 
 hydrogen = (7H 7 NO = N <CHO, Gerhardt (Traite de Oh. iv. 775). 
 
OXANILIC ACID. 287 
 
 43] to 49]- For each of these seven salts Gerhardt has a pair of for- 
 mula?, and a set of three names on the model of those which I have cited 
 in the note to No. 42]. It is useless to quote them. In all salts 
 of this description he makes the negative radical plus the oxygen, equal 
 in chemical power to H l or to C 6 H 5 , as against the atom of N. Now 
 this is not accurate, because, as I am showing by hundreds of examples, 
 the chemical powers both of H and C 6 H 5 are paralysed as long as they 
 form part of an amidogen. The power of attraction exists therefore be- 
 tween the negative radical with its oxygen and Z considered with its 
 appendage of two radicals as one radical ; and it is quite wrong to re- 
 present H 1 and C 6 H 5 as having individually in these compounds the same 
 chemical power as the oxidised negative radical. The " type ammonia" 
 applied in this fashion is a mere Will-o'-the-wisp, which serves only to 
 lead one astray. See pages 209 to 214. 
 
 50]. H; ZH,C 6 H 5 ;C 2 3 = Hydra phenylac carbenite. 
 Oxanilic acid; phenyl-oxamic acid = C^HTNO 6 , Gerhardt. Oxanilidic 
 acid; aniloxamic acid = HO,C 2 3 ; CTFN^O 2 = HO,?|^fc 
 
 Hofmann. This is a double salt on the model of oxamic acid, being 
 formed of the amide ZH,C 6 H 5 ; CO, in combination with hydrated oxalic 
 acid HCO 2 . The hydrogen of the latter is replaceable by a metal, and 
 it gives rise to a variety of salts of which No. 51] is a model. They are 
 commonly called Oxanilates. See page 227. 
 
 51]. Ba; ZH,C 6 H 5 ; C 2 3 = Baryta phenylac carbenite. 
 
 There are numerous salts of similar constitution, containing ZH 4 ,Ag,Ca, 
 and other positive radicals, instead of Ba. See page 227. 
 
 52]. 
 
 ZH C 6 H 5 CO ) 
 
 ZH 3 'c 6 H 5 ' C0 2 |) P nen yl am phenylac carbenite 
 
 7H'c 6 H 5 ' CO 1 1 cum hydra phenylac car- 
 
 ' 
 
 benite - 
 
 An inspection of the formula convinces us that this is a double or acid 
 salt belonging to the series 50] and 51], Acid oxanilate of aniline 
 = C 16 H 6 (HC 12 H 7 N)N0 6 ,C 16 H 7 N0 6 , Gerhardt. C 12 NH 7 ,2C 16 NH 7 S , 
 Gmelin. The formula given by Hofmann is : 
 
 C' 2 H 7 N,HO,C 2 ' C 2 3 + HO,C 2 C 2 O 3 
 
 53]. H; ZH,C 6 H 5 ; (C 2 H 2 ) 2 3 = Hydra phenylac succinylenite. 
 
 This compound is similar in constitution to No. 50], excepting that its 
 acid radicals are succinyl instead of carbon. It is, of course, the amided 
 
288 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 acid that is formed by the abstraction of HHO from the bisuccinate of 
 phenylam : 
 
 JZH 3 ,C 6 H 5 ; C 2 H 2 2 1 JH,HO\ _ ]ZH,C 6 H 5 ; C'H'O ) 
 \ H r ; C 2 H 2 2 ( ~ \ f\ Hr ; C*H 2 2 ( 
 
 H r is replaceable by a positive radical. See page 228. The names 
 usually given to the salt No. 53] are Succinanilic acid, Anilo-succinamic 
 acid, and Phenyl-succinamic acid. Formulae: C NH"O 6 = C 18 (C 8 H 5 O 2 ) 
 AdH 4 ,0 4 , Gmelin. C 8 H 6 (C 12 H 5 )NO 6 , Gerhardt. 
 
 C^ff'NO 6 = HO.C 4 H 2 3 : C 12 H 6 N,C 4 H 2 2 = HO.C 4 H 2 1 /^C'lPO 8 
 
 (And 
 
 Hofmann. 
 
 54]. ZH,C 6 H 5 ;N0 2 = Phenylac nitrete. 
 Nitraniline = C 12 (H 6 NO 4 )N, Hofmann. 
 
 ZH,C 6 H 5 ; NO 2 ) _ Phenylac nitrete cum hydra 
 H; Cl f : chlora. 
 
 Hydrochlorate of nitraniline = C' 2 (H 6 NO 4 )N,HC1, Hofmann. 
 
 The formulae which I have given to 54] and 55] differ fundamentally 
 from those which are given to those salts by Dr. Hofmann. He con- 
 siders nitraniline to be, like aniline, a base, but a base in which H 1 is 
 replaced by NO 2 . That notion would cause the formula for 54] to be 
 ZH,C 6 H 4 N0 8 ; H; and, correspondingly, the formula for No. 55] to 
 be ZH 3 ,C 6 H 4 NO*; Cl. These two formulae present to us phenyl in the 
 condition of a vice-radical that contains NO 2 in place of H 1 ; the vice- 
 phenyl forming, as usual, a phenylac and a phenylam, thus : 
 
 No. 54]. = ZH,C 6 H 4 N0 2 ; H 
 No. 55]. = ZH 3 ,C 6 H 4 N0 2 ;C1 
 
 I consider that this method of looking at the transformation which this 
 salt undergoes is incorrect. I will not declare that NO 2 CANNOT, under 
 any circumstances, form part vf an amidogen or an ammonium, but I am 
 sceptical on the point, and I find no evidence to prove it in the case 
 of nitraniline. On the contrary, it seems to me, that nitraniline is a 
 neutral salt which has normal phenylac for its basic radical, and nitrogen 
 (with O 2 ) for its acid radical ; constituting what is commonly called a 
 " nitrite," with the radical (ZH,C 6 H 3 ) for its base. 
 
 Let us examine the characters of nitraniline : 
 
 " Nitraniline affords not the slightest reaction with test papers ; even 
 rose-paper, which is so exceedingly sensitive for alkalies, is not at all 
 
 affected by it Nitraniline displaces none of the metallic oxides 
 
 from their acid compounds; its basic properties are exceedingly wcik. 
 
 Aniline displaces this base from all its salts Although nitraniline 
 
 is so weak a base, it combines with acids, affording crystallizable salts, 
 
NITEANILIXE. 289 
 
 which possess the same constitution as the corresponding salts of aniline. 
 All its salts are decidedly acid to test papers. They are decomposed 
 by the caustic and carbonated alkalies, nitraniline separating in a crystal- 
 line form." Hofmann and Muspratt, Memoirs Chem. Soc., iii. 122. 
 
 I have formulated nitraniline as the amide which corresponds to Phe- 
 nylam nitrite No. 23], namely, to the salt which, in the usual language 
 of chemistry, is called Nitrate of aniline : 
 
 No. 23] = ZH 3 ,C 6 H 5 ; NO 3 - HHO = ZH,C 6 H 5 ; NO 2 = No. 54]. 
 
 The characteristics of nitraniline, quoted from Hofmann and Muspratt's 
 account of it, agree precisely with such an amide. It is neutral ; its 
 combinations with acids are very acid ; it cannot act as a base (a pre- 
 cipitant) ; and it is easily separated from the acids with which it com- 
 bines, by any base even by aniline. 
 
 I conclude from these particulars, that nitraniline is an amide, agreeing 
 with the formula ZH,C 6 H 5 ; NO 2 ; that it is not a base, and that there is 
 no proof that its radical phenyl = C 6 H 5 , is changed into C 6 H 4 NO 2 . The 
 salts of nitraniline, Nos. 55] to 58] are consistent with these opinions. 
 As each of them contains an atom of free hydrated acid, one can easily 
 account for their acid reactions in accordance with the description which 
 I have cited from Hofmann and Muspratt. 
 
 56]. ZH,C 6 H 5 ; NO 2 + HC1 + 2PtcCl = Phenylac nitrete cum 
 hydra chlora bis platic chlora. 
 
 Double salt of hydrochlorate of nitraniline and bichloride of platinum 
 = C 12 (H 6 N0 4 )N,HCl,PtCl 2 , Hofmann. 
 
 57]. ZH,C C H 5 ;N0 2 + 2HCO 2 = Phenylac nitrete bis 
 
 hydra carbete. 
 
 Binoxalate of nitraniline = C 12 (H 6 NO 4 )N,HO,2(C ? O 3 ,HO), Hofmann. 
 
 58]. ZH,C 6 H 5 ; N0 2 + HCyO = Phenylac nitrete cum 
 
 hydra cyanate. 
 
 This is a combination of nitraniline with hydrated cyanic acid. It is 
 produced during the action of chloride of cyanogen on nitraniline, and 
 subsequent treatment of the product with water. Hofmann calls it car- 
 bamide-nltrocarbanilide, and he gives it all the following formula?: 
 C 14 H 7 N 3 O 6 - C 14 (H 7 N0 4 )N 2 O 2 = NH 2 ,CO ; C 12 (H 5 NO 4 )N,CO. 
 
 This compound appears to me to be precisely analogous to No. 5,5], 
 and if that salt, is to be supposed to contain an ammonium, this salt 
 should also contain an ammonium; in which case 58] would be a urea 
 the cyanate of an ammonium, containing peroxide of nitrogen as sub- 
 stitute for H 1 , thus: ZH 2 ,C 6 H 5 , NO 2 ; CyO. Now, I am not disposed 
 to admit that the replacement of H in an ammonium is effected by N, 
 or O, or NO 2 , without much better evidence in support of that assump- 
 
 u 
 
290 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 tion than any that has yet been supplied. Hofmann, indeed, does not 
 describe this compound as containing an ammonium ; on the contrary, 
 he urges our acceptance of the idea, that it is a carbamide ; but there 
 exist precisely the same objections to the admission of NO 2 into an 
 amidogen as to its admission into an ammonium, and you can have no 
 carbamide without a pair of amidogens and probably none even with 
 them. See the carbamide theory, page 221. 
 
 59]. (ZH,C 6 H 5 ; NO 4 ) 8 + HCy = Bis phenylac nitrete cum 
 
 hydra cyana. 
 
 This salt is produced by the action of chloride of cyanogen upon 
 nitraniline. See Hofmann, Quarterly Journal of the Chemical Society 
 (1847), i. 305. Hofmann's name and formula are Dinitromelaniline 
 
 8 - But his 
 
 experimental per centage of H was 3 96. The theoretical per centage 
 of H u is 3 * 65, that of H 12 is 3 96, and that of H 13 is 4 * 29. Hofmann's 
 formula with H 12 produces the formula: ZH,C 6 H 5 ; NO 2 + ZH,C 6 H 5 ; 
 NO 2 + Cy. I cannot understand how Cy can be present in such a salt 
 with no radical in combination with it, and I assume that the true 
 quantity of H is H 13 , which number differs no more from the experimental 
 quantity, H 12 , than the theoretical number, H 11 , that was assumed by 
 Hofmann. H 13 gives us formula 59]. See the note to No. 60]. 
 
 60]. (ZH,C 6 H 5 ; NO 2 ) 2 ; CyCl = Bis phenylac nitrete cum cyana 
 
 chlora (or cyanyl chlora ?) 
 
 This salt was prepared in the same manner as No. 59]. Hofmann's 
 name and formula are : Hydrochlorate of dinitromelaniline 
 
 In this case Hofmann's formula agrees (in the number of ultimate atoms) 
 with mine, which confirms the propriety of the assumption of one addi- 
 tional atom of hydrogen which I have made to complete the formula for 
 No. 59]. 
 
 61]. (ZH,C 6 H 5 ; NO 2 ) 2 + CyCl -f 2PtcCl = Bis phenylac nitrete 
 cum cyana chlora bis platic chlora. 
 
 The platinum-salt of No. 6oJ. Hofmann's name and formula: Bi- 
 chloride of platinum and dinitrojnelaniline 
 
 = C12 {NO*} N ' C' 2 j^JNCy,HCl,PtCl 2 . 
 62]. ZI^C^ 5 ; Cy = Phenylac cyana. 
 Cyananilide ; phenyl-cyanamide ; anilide cyanique ; discovered by 
 
MELANILINE. 291 
 
 Cahours and Cloez = C 14 H 6 N 2 = N(C 12 H 5 )CyH, Gerhardt. Cyanilide 
 = C 12 H 6 NCy, Hofmann. 
 
 -, J ZH, C 6 H 3 ; Cy 1 _ Phenylac cyana cum phenylac 
 
 6 3J- JZH, C 6 H 5 ; H j = hydra. 
 
 ,- -, I ZH, C 6 H 5 ; Cy ) Phenylac cyana cum phenylam 
 
 6 4J- 1ZH 3 ,C 6 H_ 5 ; Cl ( : chlora. 
 
 / -i J ZH, C 6 H 5 ; Cy 1 _ Phenylac cyana cum phenylam 
 
 b 5> \ZH 3 ,C 6 H 3 ;Br j : broma. 
 
 67]. { 
 
 J ZH, C 6 H 5 ; Cy ) _ Phenylac cyana cum phenylam 
 \ZH 3 ,C 6 H 8 ; I ( " ioda. 
 ZH, C 6 H 5 ; Cy 1 _ Phenylac cyana cum phenylam 
 
 ZH 3 ,C 6 H 5 ; SO 2 j " sulphete. 
 <Q1 JZH, C 6 H 5 ; Cy 1 Phenylac cyana cum phenylam 
 6 b > JZH 3 ,C 6 H 5 ; N0 3 f " nitrite. 
 
 Here are half-a-dozen double salts that exhibit great similarity in com- 
 position. Their characteristic salt is Phenylac cyana, No. 62], which 
 occurs in all of them. The other salts of these compounds have been 
 already described individually. No. 63] contains No. i] ; No. 64] 
 contains No. 12] ; No. 65] contains No. 13] ; No. 66] contains No. 14] ; 
 No. 67] contains No. 24] ; No. 68] contains No. 23.] 
 
 If we begin our examination of these compounds with No. 63], we 
 perceive that this salt produces all the others by direct combination with 
 hydrated acids. Thus, 
 
 No. 63- 
 
 HC1 Hydrochloric acid = No. 
 
 -f. HBr Hydrobromic acid = 65 
 
 + HI Hydriodic acid = 66" 
 
 -f HSO 2 Sulphuric acid = 67' 
 
 + HNO 3 Nitric acid. 6S~_. 
 
 The hydrogen in phenylac hydra added to the hydrogen of each acid is 
 just enough to convert phenylac into phenylam, or produce an ammonium 
 from an amidogen. See the explanatory note after No. 7]. 
 
 Now let us turn to the account of those salts, that has been given by 
 Dr. Hofmann, their discoverer. You will find it in the Quarterly 
 Journal of the Chemical Society (1847), vol. i. p. 285. 
 
 No. 63] is called MELANILINE, and it is said to have these characters : 
 "It is a new conjugated alkaloid. A conjugated base which saturates 
 only one equivalent of acid. It has scarcely any action on vegetable 
 colours. It is only slightly soluble in cold water. It dissolves easily in 
 all acids, and with most of them forms crystallised salts. With respect 
 to its basic properties, melaniline is nearly allied to aniline. An aniline 
 salt cannot be decomposed by melaniline. nor has aniline any action on the 
 salts of the other base." Hofmann. 
 
 u2 
 
292 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 There is not one of these characters that is not perfectly consistent 
 with the formula which I have given to the compound in No. 63]. The 
 reason is evident why it saturates only one equivalent of acid ; namely, 
 because it contains only one replaceable atom of hydrogen. The action 
 of vegetable colours results from the presence of the H l of the aniline 
 atom, but as the compound is only slightly soluble, the solution can have 
 only a feeble action. Aniline has no action on salts of melaniline, because 
 phenylac can displace neither phenylac nor phenylam. 
 
 The name melaniline was adopted in consequence of a relationship or 
 an analogy which Dr. Hofmann supposed to exist between this body and 
 the compound that is usually called melamine. According to my way 
 of formulating these two compounds, they are as follow : 
 
 Melamine = ZH 2 ,Cyl = Amida cyanyla. 
 
 f ZH, C 6 H 5 ; Cyl Phenylac cyana cum 
 = tZH,C 6 H*;Hi = phenylac hydra. 
 
 The relationship that exists between these two compounds is certainly 
 very distant ; a sort of Scotch-cousinship a great many times removed. 
 
 Dr. Hofmann is, however, quite right in the following statement. 
 " From the mode in which it is formed (viz., by the action of chloride 
 of cyanogen on aniline) the basic atom of melaniline may be regarded as 
 an intimate combination of aniline with cyanilide, whence the rational 
 formula of the new compound assumes the following shape : 
 
 C 26 H i3 N 3 = c 12 H 6 NCy, C 12 H 7 N." 
 Melaniline. Cyanilide. Aniline. 
 
 This equation, transformed into my notation, is 
 
 5 ; H. 
 
 No. 63] = No. 62] + No. i]. 
 
 Hofmann's names and formulae for the salts Nos. 64] to 68] are as 
 follow : 
 
 . Hydrochlorate of melaniline = C 26 H 13 N 8 ,HC1. 
 
 65 
 
 66 
 
 68 
 
 . Hydrobromate of melaniline = C 26 H 18 N 3 ,HBr. 
 
 . Hydriodate of melaniline = C 86 H 13 N 3 ,HI. 
 
 . Sulphate of melaniline = C 26 H 18 N 8 ,HS< 
 
 . Nitrate of melaniline = C 2(! H 13 N 3 ,HNO 6 . 
 
 He has given another series of formula? for these salts similar to the 
 following example : 
 
 No. 64] = C' 2 H 7 N,C 12 H 6 NCy,HCl. 
 
MELANILIKE. 
 
 293 
 
 For melaniline, No. 63], he has proposed the five following formulas : 
 
 I. 
 
 2. H 
 
 H 
 
 C 12 
 
 3. C- 
 
 69]. 
 
 C 26 H 13 N 3 . 
 
 4. NH 3 + An 2 ,Ad,O. 
 
 wllPVP At! fl2TT4 
 
 1 H 1 
 
 IN, cy IN. 
 
 H 5 J C 12 H 5 J 
 
 Ad = NH 2 . 
 
 5. (C' 2 H 5 ) 2 ) 
 Cv N. 
 (H 4 N) J 
 
 Bis phenylac cyana cum 
 = phenylac hydra cum ar- 
 gentic-phenylam nitrite. 
 
 H 7 N,C 12 H 6 N,Cy. 
 
 (ZH, C 6 H 5 ;Cy\ 
 ZH, C 6 H 5 ; H j 
 ZH, C 6 H 5 ; Cy 1 
 ZH 2 ,C 6 H 5 , Ag;N0 3 ( 
 
 This compound will be understood by comparing the formula with 
 Nos. 63] and 68] ; considering it to be a compound of these two salts, 
 and that the radical phenylam of No. 68] is replaced in 69] by the 
 radical argentic-phenylam ; or, in other words, by supposing that two 
 atoms of No. 63] combine with one atom of nitrate of silver, Ag,NO 3 , 
 to form the double or acid salt No. 69]. Hofmann's names and formulae 
 are: Nitrate of silver and melaniline = 2 (C 26 H 13 N 3 ), Ag, NO 6 = 
 2(C 12 H 7 N,C 12 H 6 NCy,),AgN0 6 ; and, in another place, Nitrate of pro- 
 toxide of silver-melaniline = AgO,N0 5 ,2C 26 H 13 N 3 . He says the com- 
 position is " somewhat uncommon." It is, however, by no means 
 uncommon to find ammoniums that contain metallic radicals in sub- 
 stitution for hydrogen. It is only uncommon to find organic chemists 
 who admit the fact that such ammoniums exist. 
 
 fZH, C 6 H 5 ; Cy ] 
 
 70]. <ZH 3 ,C 6 H 5 ; CO a V 
 
 1 H ; CO 2 ] 
 
 Phenylac cyana cum 
 phenylam bicarbete. 
 
 hvdra 
 
 Hofmann's Binoxalate of melaniline = C 30 H 15 N 3 8 = C 26 H 13 N 3 ,HC 2 4 , 
 HC 2 4 = C 12 H 7 N,C 12 H 6 NCy,2(HC 2 4 ). 
 
 -i (ZH,C 6 H 4 C1; Cy) _ Chloric-phenylac cyana cum 
 7 1 -!' |ZH,C 6 H 4 C1; H J = chloric-phenylac hydra. 
 
 Hofmann's Dichloromelaniline = C 26 (H U C1 2 )N 3 . 
 
 -, JZH,C 6 H 4 Br; Cy) _ Bromic-phenylac cyana cum 
 7 2 > |ZH,C 6 H 4 Br; H f = bromic-phenylac hydra. 
 
 Hofmann's Dibromomelanilme = C 26 (H u Br 2 )N 3 . 
 
 -, JZH,C 6 H 4 I; Cy \ _ lodic-phenylac cyana cum 
 
 73J- |ZH,C 6 H 4 I;H J = iodic-phenylac hydra. 
 Hofmann's Diiodomelanilme 
 
 = C 12 l N, C 12 j^JNCy. 
 
294 CRITICAL NOTES OX THE SALTS OF ANILINE. 
 
 Compare Nos. 71], 72], 75] with No. 63]. They agree exactly, 
 excepting that the phenyl of 63] is replaced by chloric-, bromic-, and 
 iodic-phenyl in the other salts. The salts remain the same in structure 
 and in general properties. 
 
 -, JZH, C 6 H 4 Br; Cy) _ Bromic-phenylac cyana cum 
 ' (ZH 3 ,C 6 H 4 Br; Cl j = bromic-phenylam chlora. 
 
 Hofmann's Hydrochlorate of dibromomelaniline = C 8e (H ll Br 8 )jS T3 ,HCl 
 
 . -i I vtra /--6Tj5 ' r7 1 Phenylac cvana cum phenylam 
 
 / S . <ZJn,V^ 1 J V^l > SS . f - * . 
 
 Pt 2 n 2 1 chlora bis platic chlora. 
 
 Hofmann's Bichloride of platinum and melaniline = C 26 H I8 N 8 HCl,PtCl 2 
 = C l2 H 7 N,C' a H 6 NCy,HCl,PtCl 2 . 
 
 TZH, C 6 H 5 ; Cy 1 Phenylac cyana cum phe- 
 76]. ^ZIFjC'H 5 ; Cl I = nylam chlora tris auric 
 1 Auc 3 ; CT j chlora. 
 
 Hofmann's Terchloride of gold and melaniline = C !6 H 13 N 3 ,HCl,AuCl 3 
 = C u H 7 N,C w H 8 NCy,HCl, AuCl 8 . 
 
 fZH, C 6 H 4 C1 ; Cy) Chloric-phenylac cyana cum 
 77]. ZH 3 ,C 6 H 4 C1; Cl I = chloric -phenylam chlora 
 
 bis platic chlora. 
 
 , C 6 H 4 C1 ; Cy) 
 3 ,C 6 H 4 C1; Cl I = 
 Ptc 8 ; CPJ 
 
 Hofmann's Bichloride of platinum and dichloromelaniline 
 
 {TT6 | f TJ5 ) 
 
 j I N, C 12 j Q 1 N,Cy ,HCl,PtCl 8 
 
 TZH, C 6 H 4 Br; Cy] Bromic-phenylac cyana cum 
 78]. ^ZH 3 ,C 6 H 4 Br; Cl I = bromic-phenylam chlora 
 Ptc 2 ; C1 2 J bis platic chlora. 
 
 Hofmann's Bichloride of platinum and dibromomelaniline 
 
 = C 26 (H ll Br 2 ) N 8 ,HCl,PtCl 2 = C 12 H N, C 18 *l N,Cy,HCl,PtCl 2 . 
 
 cyana cum 
 
 This salt is produced by the action of cyanogen on melaniline, Hof- 
 mann gives it the name of Dicyanomelaniline, and liberally assigns to it 
 
D1CYANOMELANILIXE. 295 
 
 six different formulae, which give us certainly the opportunity of choice, 
 but necessarily accompanied by its embarrassments : 
 
 SP = Cy 2 ,C 26 H 13 N 3 = CyC l2 H 7 N;Cy,C 12 H 6 NCy 
 = C 12 H 7 N,C 12 H 6 NCy{^ = NH 3 (2AnCy,AdCy) 
 
 H ) rn \ 
 
 = Cy H IN, Cy^Cy 
 C 12 H 5 J (C 12 H 5 J 
 
 Grnelin's name and formulae are Bicyanmelanilin = C Z4 Cy 3 Ad 2 H 7 ,H 2 . 
 
 Compare No. 79] with No. 63.] There really seems to be no difficulty 
 in the matter, and no necessity to marshal such an army of formulae. 
 The transformation which takes place in this process is of the simplest 
 possible character. Two atoms of cyanogen, combine with one atom of 
 melaniline, converting H l from a negative into a positive radical, and pro- 
 ducing a triple cyanide. But let us listen to Dr. Hofmann : 
 
 " In dicyanomelaniline the basic properties of melaniline are still per- 
 ceptible : they appear, however, less prominent than in the descendants 
 of substitution. The cyanogen base dissolves with great facility in 
 dilute acids in the cold. On adding ammonia to the acid solution, a few 
 moments after it has been made, a white precipitate is thrown down, 
 consisting of unaltered dicyanomelaniline. I have, however, vainly tried 
 to prepare salts of this base" Hofmann, Quarterly Jour. Chem. Soc. 
 1848, i. 309. 
 
 " I have vainly endeavoured to produce crystallized combinations of 
 dicyanomelaniline with acids. In fact, the only experimental evidence 
 of the basic nature of this substance is the remarkable facility with which 
 it dissolves in mineral as well as vegetable acids." Idem, 1849, ii. 307. 
 
 Those who look at formula No. 79] will feel little surprise that 
 Dr. Hofmann should fail in preparing salts by adding acids to such a 
 " base." They will feel more surprise that he should attach to the word 
 " base " a meaning with so wide a latitude. 
 
 cum 
 
 (ZH,C 6 H 5 ; Cy } ~. 
 
 79 ]JzH,C 6 H 5 ;Cy I = Bls P hen ? ac 
 
 1 Cy ' Cl ) c y ana cnlora - 
 
 Discovered by Laurent. Chlorcyaniled ; formulas : C 30 N 5 C1H 12 
 C 24 Cy 3 Ad 2 H 7 ,HCl, Gmelin. 
 
 ZH,C 6 H 5 ; Cy ) _ 
 
 9 = Bl * r> hen y lac C 7 ana cum 
 
 70*1 ziLcm 9 cv 
 
 H;CyO ycra cyanate 
 
 Anilinammeline = C^N^H^O 8 , Gmelin. 
 
296 
 
 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 -, j(ZH,C 6 H 5 ; Cy) 3 l _ Tris phenylac 
 J * t ZH,C 6 H 5 ; H f : 
 
 cyana cum 
 phenylac hydra. 
 
 Compare with Nos. 62] and 63]. According to Hofmann, when 
 melaniline is heated, aniline distils over, and leaves a residue that has the 
 following composition: C 54 H 85 N 7 ; and he says, "The simplest inter- 
 pretation of this formula consists in regarding it as a compound of the 
 aniline-mellon with three equivalents of aniline. 
 Mellon . . . C 6 N 4 
 Aniline-mellon . C 6 N 4 (C 12 H 4 ) = C 13 H 4 N 4 
 
 C^IPN 7 = C 18 H 4 N 4 + 3 C 12 H 7 N. 
 
 " If this formula actually represents the composition of the body in 
 question, its formation would be the result of the separation of two 
 aniline atoms from three equivalents of melaniline. 
 
 3 C 26 H 13 N 3 
 2C 18 H 7 N 
 
 Quar. Jour. Chem. Soc. ii. 323. 
 
 This conclusion is correct ; but why does he go to it by so round- 
 about a process ? What have we to do with mellon or aniline-mellon, 
 or with C 6 H 4 , or C 12 H 4 , or C 18 H 4 N 4 ? The process and its interpretation 
 are extremely simple, and require none of these far-fetched luminaries 
 to enlighten them. Thus : 
 
 Used. 
 
 3 atoms of 
 No. 63] 
 
 ZH,C 6 H 5 ;Cy) 
 ZH,C 6 H 5 ; Cy( 
 ZH,C 6 H 5 ; Cy 
 ZH,C 6 H 5 ;H ) 
 ZH,C 6 H 5 ;H 1 
 ZH,C 6 H 5 ; H j 
 
 ZH,C 6 H 5 
 
 ZH,C 6 H 5 
 
 ZH,C 6 H 5 
 
 ZH,C 6 H 5 
 
 JZH,C 6 H 5 
 
 1ZH,C 6 H 5 
 
 Obtained. 
 Cy 
 Cy 
 Cy 
 H 
 HI 
 Hf 
 
 i atom of 
 No. 80]. 
 
 2 atoms of 
 
 No. il. 
 
 ZCH 3 ,C 6 H 5 ; Cy = Methylic-phenylac cyana. 
 ZC 2 H 5 ,C 6 H S ; Cy = Ethylic-pheny lac cyana. 
 ; Cy = Amylic-phenylac cyana. 
 
 81 
 82 
 
 83 
 
 These salts are so simple that they require no explanation, 
 names and formulas are as follow : 
 
 Gerhardt's 
 
 , 
 J 
 
 (Methyl-phenyl-cyanamide, or 
 I cyanic methylanilide /' 
 
 = 
 
 [CH 3 
 
 lcf 
 rc 2 H 5 
 
 C 6 H 
 C 
 
CYANILINE. 297 
 
 fC 5 H 11 
 
 8 -j fAmyl-phenyl-cyanamide, or l^iajjie^s _ ]S[Jc 6 H 5 
 *J' | cyanic amylanilide J | ^ 
 
 These three formulae exhibit the usual excellencies of Gerhard t's " type 
 ammonia," and make simple things complex with remarkable facility. 
 We are here called upon to believe (if we can) that cyanogen can replace 
 hydrogen in ammonia, and that the result is still an ammonia. 
 
 84]. I^'CTP,- Cy} = Phen y lam P hen 7 lac 
 
 This formula is intended to represent the compound which Dr. Hofmann 
 calls Cyaniline, and which he represents by the following formulas: 
 C 14 H 7 N 2 = Cy,C 12 H 7 N. 
 
 According to Dr. Hermann's opinion, cyaniline is formed by the 
 direct union of one equivalent of aniline and one equivalent of cyanogen. 
 Those materials produce ZH,C 6 H 5 ; H + Cy. But this formula repre- 
 sents the radical phenylac in combination at once with two different 
 radicals, H and Cy. To overcome this irregularity, I double the formula, 
 which produces No. 84], a double salt which is quite in accordance with 
 many other salts of phenylac. See Nos. 64] to 70]. The solutions of 
 cyaniline are perfectly neutral, and the compound resembles a neutral 
 salt much more than it does a base. 
 
 85] to 88]. These formulae represent examples of the compound salts 
 which are formed by cyaniline. This compound combines both with 
 hydrated acids and with the metallic chlorides, and always in such a 
 manner that the phenylac cyana and phenylam cyana are both combined 
 with the hydrated acid and the chloride. These relations are shown by 
 the formulae. 
 
 These compounds are prepared with difficulty, because cyaniline is 
 readily decomposed by water. " The constitution of the salts of 
 cyaniline," says Hofmann, " is similar to that of the aniline salts. These 
 compounds are, in fact, aniline salts, which have become associated with 
 tiie elements of cyanogen. I have, however, vainly tried to obtain a salt 
 of cyaniline by passing a current of cyanogen gas into an alcoholic solu- 
 tion of an aniline salt." 
 
 If, in accordance with Dr. Hermann's opinion, we formulate the salts 
 of cyaniline so as to be similar to the salts of aniline with cyanogen as 
 an adjunct, " associated," as he calls it, which I understand to mean, 
 not combined, but hanging on loosely, they will appear as follows : 
 
 ZH 3 ,C 6 H 5 ; Cl + Cy. 
 ZH 3 ,C 6 H 5 ; Cl + 2PtcCl + Cy. 
 ZH 3 ,C 6 H 5 ; Cl + 3 AucCl + Cy. 
 ZH 3 ,C 6 H 5 ; 
 
 8 5 
 86] 
 
 88 
 The hydrogen of the hydrated acids is just enough to convert the phe- 
 
298 CRITICAL NOTES OX THE SALTS OF ANILINE. 
 
 nylac into phenylam, and this simplifies the formula greatly. But what 
 is the function of the cyanogen in these salts after the hydrated acids 
 have converted them into salts of phenylam ? Is this a case where we 
 have biacid salts ; or is the cyanogen, as Hofmann assumes, a ** copula," 
 an unexplained and unexplainable adjunct of the phenylam? " The for- 
 mation of this base," he says, " offers one of the first instances in which 
 an organic alkali is found associated with another compound, the presence 
 of which does not affect its saturating capacity." What gives chlorine 
 the power in these special cases, and only in these special cases, to nullify 
 the saturating capacity of cyanogen ? Upon the whole, I am of opinion, 
 that it is safest to consider these compounds as quadruple salts, such as 
 they are exhibited by formula Nos. 85] to 88], page 279. The assump- 
 tions of Dr. Hofmann lead to consequences that are too important to be 
 admitted without sufficient evidence. I cannot understand the position 
 of an "associated" radical, which has no functions to perform. That is 
 not according to the common course of nature, which makes every atom 
 do its duty. 
 
 89]. ZEP.O'H 5 ; CyO = Phenylam cyanate. 
 
 Hofmann's Carbamide-carbanilide, or Anilo-urea. Procured by the action 
 of hydrated cyanic acid = HCyO upon aniline = ZH,C 6 H 5 ; H. 
 
 90]. ZH 2 ,C 6 H 5 ,C 6 H 5 ;CyO = Phenylem cyanate. 
 
 Hofmann's Carbanilide. 
 
 These two compounds belong to the class of Ureas, that is to say, 
 each of them is a cyanate of an ammonium ; and they differ from one 
 another onlyvin the circumstance, that the radical phenylem of No. 90] 
 contains twice as much phenyl as is contained in the radical, phenylam of 
 No. 89]. Nevertheless, these two salts form the subject of a special 
 theory by Dr. Hofmann, and as I consider that that theory is fallacious, 
 I shall quote his arguments in full. 
 
 " The method by means of which I first obtained anilo-urea, viz., the 
 action of hydrated cyanic acid on aniline, very naturally suggested the 
 idea that this compound must be considered as an analogue of urea ; as 
 urea containing the elements C 12 H 4 . 
 
 Urea NH 3 HC 2 N0 2 , 
 
 Anilo-urea . (C 12 H 4 )NH 3 HC 2 NO 2 , 
 
 and hence the name under which I have described it. 
 
 " This mode of regarding it is, however, not supported by the 
 chemical deportment of the compound ; in anilo-urea we no longer find 
 a remnant of basic properties, [i] I have vainly endeavoured to combine 
 it with acids, in order to produce compounds analogous to nitrate or 
 oxalate of urea. The presence of these acids does not increase the 
 solubility of the aniline compound in water, and the crystals deposited on 
 
CARBANILIDE. CARBAMIDE-CABBANILIDE. 299 
 
 cooling retain no acid. My attempts to form a platinum-salt have 
 likewise been unsuccessful. [2]. 
 
 " The formula of anilo-urea admits, however, of another interpretation, 
 which is strikingly supported by experimental evidence. The following 
 equation : 
 
 C 14 H 8 N 2 2 = NH 2 ,CO; C 12 H 6 N,CO, 
 
 shows that we may consider this substance, likewise, as a double com- 
 pound of carbamide with its conjugated analogue. The existence of such 
 double compounds is by no means isolated : in a Memoir on the Meta- 
 morphoses of Cyaniline, which I intend shortly to present to the Society, 
 I shall have to describe a body of perfectly similar construction, viz., a 
 compound of oxamide with oxanilide, corresponding in every respect to 
 the preceding substance. [3]. 
 
 Carbamide-carbanilide . . NH 2 ,C O ; C 12 H 6 N,C O . 
 Oxamide-oxanilide . . . NH 2 ,C 2 2 ; C l2 HN,C 2 2 . 
 
 I was very curious to submit this idea to the test of experiment, and 
 was fortunate enough to meet with a reaction, which leaves little doubt 
 regarding the structure of anilo-urea, or carbamide-carbanilide, as the 
 substance more properly should be called. I found that, when submitted 
 to the action of heat, this compound actually splits into its proximate 
 constituents ; one of which, the carbanilide, is the principal product of 
 the reaction, whilst the other, unable to exist at the temperature at 
 which the separation takes place, undergoes a further metamorphosis, and 
 can be recognized only in its derivatives. 
 
 " In submitting anilo-urea to the action of heat, the substance fuses 
 without decomposition ; on increasing, however, the temperature above 
 the fusing-point, torrents of ammonia are evolved, while the liquid in the 
 retort solidifies to a crystalline mass, which again liquifies, and ultimately 
 distils on a further elevation of the temperature. If the process be in- 
 terrupted as soon as the evolution of ammonia ceases, and the solid 
 begins to liquefy again, the residue in the retort consists of carbanilide 
 and cyanuric acid. On treating this mixture with a large quantity of 
 boiling water, the w r hole of the cyanuric acid, together with a small 
 quantity of the other substance, is dissolved. In order to obtain the 
 cyanuric acid, the aqueous solution is evaporated to dryness, and the 
 residue extracted w r ith alcohol, when carbanilide is dissolved, and the 
 acid remains in a state of purity. The properties of cyanuric acid are so 
 marked, that I have omitted to analyse the product ; its comportment 
 with solvents, and emitting also the well-known odour of cyanic acid 
 when heated, appearing quite sufficient to obviate all chance of mistake. 
 
 " The production of carbanilide, of ammonia, and of cyanuric acid in 
 this reaction, admits of an easy explanation, if we recollect that carbamide 
 is actually a submultiple of urea, which, as is well known, when sub- 
 
300 CRITICAL NOTES ON THE SALTS OF ANILIXE. 
 
 mitted to dry distillation, is converted into ammonia and cyanuric 
 acid. 
 
 " Two equivalents of the compound contain the elements of two equi- 
 valents of carbanilide and one of urea : [4] 
 
 2C 14 H 8 N 2 2 = 2C 13 H 6 NO 
 
 Carbamide- Carbanilide. Urea : 
 
 Carbanilide. 
 
 and the following equation exhibits the final results of the destruction of 
 carbamide-carbanilide by heat [5] : 
 
 6C U H 8 N 2 2 = 3 NH 3 + 6C I8 H 6 NO + H 3 ,C 6 N 3 6 . 
 
 Carbamide- Carbanilide. Cyanuric acid. 
 
 Carbanilide. 
 
 " The substance which I have described in the preceding pages claims 
 some interest, as the first conjugated amide which was discovered, and 
 as the first member of a class of compounds which has been enriched in 
 so remarkable a manner by the investigations of MM. Gerhardt and 
 Laurent." Quarterly Journal of the Chemical Society, 1848, ii., 42. 
 
 Remarks on the above statement. i] Anilo-urea is a neutral salt and 
 not a base ; and it has no replaceable hydrogen, except what constitutes 
 the ammonium. Why should it have " a remnant of basic properties?" 
 
 2]. The so-called salts of ordinary urea are not normal salts formed by 
 a base with an acid, but double salts containing two complete single 
 salts. It is not necessary that every urea should form double salts. 
 
 3]. These two salts are, as I view them, not perfectly similar, but 
 perfectly dissimilar. Just double the atomic weight of the carbon and 
 oxygen, and then examine how the two compounds are individually 
 affected by that simple operation, which, remember, is not a special 
 operation suggested for this occasion, but one to which all compounds 
 are made to submit, when brought under the rule of the radical theory. 
 The compounds are then : 
 
 NH 2 ; C 12 H 6 N,CO. 
 NH 2 ,CO; C 12 H 6 N,CO. 
 
 The second compound is No. 41] in the above Table. The first com- 
 pound is No. 89]. Surely there is no " perfect similarity" here? The 
 difference in the relative quantities of C and O, in the two compounds, 
 is a difference which produces a perfect dissimilarity in the compounds. 
 No. 41] can be a double oxamide; No. 89] cannot, because of the 
 absence of the necessary quantity of CO. No. 89] can be a cyanate, 
 having the necessary ingredients in the necessary preparations. No. 41] 
 cannot be a cyanate, because of the unsuitableness of the proportions of 
 its constituents. 
 
CARBANILIDE. CARBAM1DE-CARBANIL1DE. 301 
 
 4]. Even this short equation is more explicit when made according to 
 the radical theory. Two atoms of No. 89 produce one atom of No. 90, 
 and one of urea = ammona cyanate ZH 4 ,CyO. Thus: 
 
 ZH 3 ,C 6 H 5 ; CyO 1 ( ZH 2 , (C 6 H 5 ) 2 ; Cy 0. 
 
 ZH 3 ,C 6 H 5 ; CyOJ : (ZH 4 ; CyO. 
 
 5]. The following diagram shows the final results of the decom- 
 position. Thus exhibited, these results support the Urea theory, and 
 are adverse to Dr. Hofmann's opinions : 
 
 Acted upon. Produced. 
 
 ZH,CH>;Cvo 
 
 Thus, two atoms of 89] Phenylam cyanate, produce one atom of 90] 
 Phenylem cyanate, one atom of ammonia, and one atom of cyanuric acid. 
 I conclude therefore that the salts 89] and 90] are not examples of " con- 
 jugated amides," and that the terms carbamide-carbanilide and carbanilide 
 convey views that are erroneous. The urea theory is much simpler and 
 more probable, and is SUPPORTED, though Dr. Hofmann thinks otherwise, 
 by the chemical deportment of each of the compounds. 
 
 " Aniline, when introduced into an atmosphere of phosgene gas, 
 solidifies at once into a crystalline mixture of carbanilide and hydro- 
 chlorate of aniline : 
 
 " 2C 12 H 7 N + COC1 = C 12 H 7 N,HC1 + C 12 H 6 N,CO." Hofmann. 
 I prefer the following equation : 
 
 Used. Produced. 
 
 4(ZH,C 6 H 5 ; H) 1 f ZH 2 ,C 6 H 5 ,C 6 H 5 ; CNO 
 
 CC1,C10 [2(ZH 3 ,C 6 H 5 ; Cl). 
 
 91]. ZH 3 ,C 6 H 5 ;Cy;S 2 = Phenylam cyana sulphene. 
 92]. ZH 2 ,C 6 H 5 ,C 6 H 5 ;Cy; S 2 = Phenylem cyana sulphene, 
 
 On a comparison of the formulas Nos. 91] and 92] with Nos. 89] and 
 90], it will be perceived that these salts exactly correspond to one 
 another. No. 91] is the sulphocyanide of phenylam, and No. 92] is 
 the sulphocyanide of phenylem. 
 
 Dr. Hofmann's name for No. 91] is Hydrosulphocyanate of aniline, 
 and his formula is C 12 H 7 N,HC 2 NS 2 . His name for No. 92] is Sulpho- 
 carbanilide, and his formula is C 12 H 6 N,CS. The first formula, after 
 doubling the atomic weight of the carbon, agrees with No. 91] ; but, on 
 account of the odd atom of carbon in the last formula, I must double the 
 whole formula, which then agrees with No. 92]. 
 
302 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 The compound No. 92] can be procured by the action of aniline on 
 bisulphide of carbon ; thus : 
 
 v J ZH,C 6 H 5 ; m f ZH 2 ,C 6 H 5 ,C 6 H 5 ; CN ; S 2 = No. 92. 
 
 NO. I. - | ZH)C 6 H 5. H ( = I JJ. S 
 
 CS 4 J I H ; S 
 
 METAMORPHOSES OF DICYANOMELANILINE. " The products arising 
 from the decomposition of dicyanomelaniline (No. 79) belong to the 
 most remarkable substances which have been brought to light by this 
 investigation" p. e. of aniline and its derivatives], Hofmann. For this 
 reason I will add a short account of these products : 
 
 fC 6 H 5 ,CyO } 
 
 Bls 1611 c ' anate cum 
 
 93]. 'CvO = v 
 
 TT V I hydra cyana. 
 
 I H ,Cy J 
 
 The formula of dicyanomelaniline is given at No. 79], It is : 
 (ZH,C 6 H 5 ;Cy) 2 + HCy. 
 
 a). When dicyanomelaniline was heated with hydrochloric acid, it 
 produced a considerable quantity of chloride of ammonium, and a new 
 salt which Dr. Hofmann calls Melanoximide or Oxamelanile, and which 
 proved on analysis to have the following composition (in Hofmann's 
 numbers) : C 30 H U N 3 O 4 . " This formula," he says, " readily explains 
 the transformation of dicyanomelaniline under the influence of acids. 
 One equivalent of this substance assimilates four equivalents of water, 
 while two equivalents of ammonia combine with the acid. 
 
 Dicyano- Melanoximide. 
 
 melaniline. 
 
 6). " This determination leaves no doubt respecting the composition 
 of the new substance, and this is moreover supported by various pheno- 
 mena of transformation which I shall describe hereafter. The formula 
 derived from analysis, although correctly enumerating the elements 
 grouped in the compound, leaves us quite in the dark respecting their 
 actual arrangement, and consequently of the position which has to be 
 assigned to the substance. 
 
 c). "A rational interpretation of the analysis was, however, greatly 
 facilitated by the previous study of the decomposition of cyaniline. The 
 conversion of this substance into oxalates of aniline and ammonia, or 
 rather into compounds derived from those salts by elimination of water, 
 (oxanilide and oxamide,) at once gave the clue to the nature of the Me- 
 lanoximide. It may be considered as binoxalate of mclanilino, less four 
 equivalents of water : 
 
METAMORPHOSES OP DIG YANOMEL ANILINE. 303 
 
 C 26 H I3 N 3 ,HC ? 4 + HC 2 4 = C 30 H 15 N 3 8 
 C 30 H 15 N 3 8 - 4HO = C 30 H U N 3 4 
 
 Binoxalate of Melanoximide. 
 
 Melaniline. 
 
 cT). " Experiment supports this view in an unequivocal manner. On 
 adding ammonia or potash to an alcoholic solution of the compound, the 
 liquid readily solidifies into a crystalline mass. These crystals are 
 melaniline ; the mclLer liquor contains a considerable proportion of 
 oxalic acid." Quarterly Journal of the Chemical Society, ii. 310. 
 
 From these experiments Dr. Hofmann draws the conclusion that the 
 substance under examination is what, in an ammonia series, would be 
 called an Imide, and in the aniline series is an Anile ; i. e., the " bin- 
 oxalate of melaniline less 4 equivalents of water" I venture to show the 
 reader that the conclusions to which we are led by the radical theory, 
 though very different from these, are far simpler and more probable. I 
 shall explain the first reaction (a) by an equation : 
 
 Used. Produced. 
 
 fZH,C 6 H 5 ; CN 
 79]. {ZH,C 6 H* ; CN fC 6 H 5 ,CNO| No. 93]. 
 
 H, CN |C 6 H 5 ,CNO!> Melanoximide 
 
 Hydrochoric]H,Cl 
 Acid 1H,C1 
 
 H, CN J =C 15 H U N 3 O 2 . 
 ZH 4 , Cl ) Chloride of 
 
 vy IJLJL,J.J.W i ZH 4 , Cl I Ammonium. 
 
 Here we have the whole process completely developed. There is no 
 evidence that binoxalate of melaniline is first formed and then decomposed 
 to produce the new compound ; nor is it necessary to resort to * .ch an 
 assumption, nor to imagine that we have to deal either with an Imide or 
 an Anile. The salt 93] appears to be a compound of two atoms of 
 cyanate of phenyl and one atom of hydrocyanic acid. The predisposing 
 cause of the decomposition of the dicyanomelaniline is, probably, that 
 the two atoms of Z, in the presence of Cl arid of abundance of H, exer- 
 cise their usual function of enlarging their amidogens to ammoniums. 
 These ammoniums might be expected to include the phenyl that is 
 present in the salt under decomposition ; but they do not, and we may 
 reasonably infer thence, that the attachment of the phenyl to the 
 cyanogen prevents it. I have shown in other cases (see 85] to 88]) 
 the probability that phenylic radicals can combine with cyanogen in pre- 
 ference to chlorine, and in the presence of chlorides. I do not agree with 
 Dr. Hofmann, that we are " quite in the dark respecting the actual 
 arrangement of the elements in this compound," because his own 
 experiments make the grouping of the constituent salts tolerably clear. 
 
304 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 The experiment described in paragraph d) is perfectly in accordance 
 with the above explanation, and may be stated in an equation as follows : 
 
 fC 6 H 5 ,CNCM (ZH,C 6 H 5 ; CN) 
 93 1. I CTP.CNO ZH OTL* H \ 
 
 H,CN 
 
 Caustic j K,HO K,C0 8 \ Oxalate of 
 
 potash \ K,HO J [ K,CO 2 j potash. 
 
 J(C 6 H 5 ,CyO) 2 l Bis phenyla cyanate cum argenta 
 
 \ Ag,Cy f cyana." 
 
 This salt is the silver-salt of the preceding compound, No. 93], which 
 has merely changed its basic H for Ag. Dr. Hofmann's analysis 
 confirms this formula, but he is in great doubt about its propriety. 
 He says, " Several of the amidogen-compounds which have been ex- 
 amined, such as camphorimide and phtalimide, have the properties of 
 weak acids : they combine, for example, with protoxide of silver. The 
 actual nature of these combinations is scarcely understood. Some con- 
 sider them as compounds of the imides with the oxides ; others as imides 
 in which hydrogen is replaced by silver ; melanoximide is also feebly 
 acid .... and yields a precipitate with nitrate of silver." The metallic 
 compounds to which Dr. Hofmann alludes are the vice-radicals and vice- 
 amids which contain substituting metals. See pages 137 and 191. 
 His analysis leaves no doubt respecting the regularity of the salt 
 No. 94,], which may serve as an example to convince chemists " by 
 whom these compounds are scarcely understood," that it is quite pos- 
 sible to understand them perfectly, if they will take the trouble to 
 examine the facts which prove their existence and nature. 
 
 95]. C 6 H 5 ,CyO = Phenyla cyanate. 
 
 This compound was produced by the action of heat on melanoximide 
 No. 93], its relation to which is obvious at a glance. Dr. Hofmann 
 calls it ANILOCYANIC ACID. His formula is C 14 H 5 NO 2 . He informs us 
 that when this compound is treated with aniline it yields carbanilide 
 (a), and that when it is heated with ammonia it is converted into 
 carbamide-carbanilide (b). These transformations can be readily repre- 
 sented by the new formulae, thus : 
 
 \ J Na 95] = C 6 H 5 ,CyO 1 _ ZH 2 ,(C 6 H 5 ) 2 ; CyO = No. 90]. 
 a > JNo. ij = ZH,CH>; H ( = "cSSHSE" 
 
 (No. 95] = C 6 H 5 ;Cy01 = ZH 3 ,C 6 H 5 ; CyO = No. 89]. 
 \Ammonia = ZH 2 ; H / Carbamide-'carbanilide. 
 
 H,CH 3 -f C 6 H 5 ,CyO = Hydra methylate cum phenyla cyanate. 
 = H,CH 8 ,C 6 H 5 ; CyO 2 = Hydra methyla phenyla cyanete. 
 
ANILOCYANIC ACID. 305 
 
 -, (H,C 2 H 5 0+C 6 H 5 ; CyO = Hydra ethylate cum phenyla cyanate 
 97 > { =H,C 2 H 5 ,C 6 H 5 ; CyO 2 = Hydra ethyla phenyla cyanete. 
 
 JLJ.,^ j.j. ll O+C 6 H 5 ,CyO = Hydra amylate cum phenyla cyanate. 
 = H,C 5 H n ,C 6 H 5 ; CyO 2 = Hydra amyla phenyla cyanete. 
 
 " Anilocyanic acid dissolves in the alcohols with considerable evolution 
 of heat, clear liquids being formed, which, after some minutes, deposit 
 magnificent crystals, I have convinced myself by analysis that the ordi- 
 nary alcohols absorb one equivalent of anilocyanic acid, giving rise to the 
 production of the following series of compounds : 
 
 Methyl-compound C 16 H 9 NO 4 = C*H 4 O 2 + C 14 H 5 N0 2 
 Ethyl-compound C 18 H U NO 4 = C 4 H 6 O 2 + C 14 H 5 NO 2 
 Amyl-componnd C 24 H 17 NO 4 = C 10 H 12 O 2 + O' 4 H 5 NOV 
 
 Hofmann, Quarterly Journal of the Chemical Society, ii., 319. He 
 immediately afterwards suggests that these compounds may be carbani- 
 lates or anthranilates, such as C 4 H 5 ,C 14 H 6 NO 4 = Carbanilate or anthrani- 
 late of ethyl. 
 
 These salts are formed, experimentally, by the direct combination of 
 the salt C 6 H 5 ,CyO with the salts H,C'H 5 O, H,CH 3 O, and H,C 5 H"0; 
 precisely in the same manner as we produce a terbasic phosphate by 
 combining a monobasic phosphate with similar salts on the model of 
 water. I see no reason for doubting that these salts are terbasic cyanates, 
 any more than I do for doubting whether there are such compounds as 
 terbasic phosphates. 
 
 REACTIONS OF ANILOCYANIC ACID, or PHENYLA CYANATE, C 6 H 5 ; CyO. 
 The following reactions, (a) to (/), of the compound represented by 
 No. 95] = C 6 H 5 ; CyO, are given by Dr. Hofmann with a view to 
 prove that the compound is an ACID (Anilo-cyanic acid) analogous to 
 cyanic acid. Quarterly Journal of the Chemical Society, ii., 315. But 
 they seem to prove only the presence of cyanate of phenyl, a salt in which 
 H 1 of hydrated cyanic acid has been replaced by the radical phenyl C 6 H 3 . 
 
 a.) C 6 H 5 ,CNO) f 7 TT r 6TT5 TT XT i 
 
 ilTTTA I JZH,C 6 H 5 ; H = No. i] 
 
 Caustic potash J'JJQ J == | KK > C 3 
 
 The cyanogen is decomposed; its carbon takes the potassium and 
 oxygen, and forms carbonate of potash ; its nitrogen takes the phenyl and 
 hydrogen, and forms aniline or phenylac hydra, No. i]. Two atoms of 
 caustic potash are necessary to supply the quantity of K and O required 
 to complete the carbonate, and of H to complete the aniline. 
 
 *). C 6 H 5 ,CNO) UTTB , 
 
 Hydrochloric acid H, Cl } = \ ' ; JiJ 8 ,5 J 
 
 Water . . . H| HO J ( CO* set free. 
 
 x 
 
306 CRITICAL NOTES ON THE SALTS OF ANILINE. 
 
 In the presence of water and of the strong negative radical, Cl, first of 
 all phenylam is formed, and then phenylam chlora, No. 12], commonly 
 called Hydrochlorate of aniline ; while the carbon carries oft' the oxygen 
 in the state of carbonic acid. 
 
 c). CTP ; CNO) f ZH,CH> ; SO 1 N g1 
 
 Q . , . . , ]H,SOO Im'l H ; S0 2 f JNa 2b > 
 
 Sulphuric acid | Hjgoo | j ^ 
 
 In the presence of strong sulphuric acid, the cyanogen is decomposed, 
 carbonic acid is set free, and the azote forms phenylac and then sul- 
 phanilic acid, No. 28] = ZH,C 6 H 5 ; SO + HSO 2 , "or H; ZH,C 6 H 5 ; 
 S 9 3 . 
 
 cif). C 6 H 5 ; CNO) f ZH 2 ,(C 6 H 5 ) 2 ; CNO = No. gol 
 
 C 6 H 5 ;CNOI = \ CO 2 
 
 H ; HO j I 
 
 In the presence of water, the cyanogen is decomposed, slowly at mean 
 temperature, rapidly if heated ; carbonic acid is given off, and the azote 
 produces phenylem cyanate, No. 90], commonly called Carbanilide. 
 
 _\ r^PT 5 PNO 1 
 
 "/ ' *'"*"' I "7TJ2 /PCTTS'NS . PXrn "NTrv ^o,"i 
 
 No. i] =ZH,CH 5 ;H f* R '^ C 
 
 When No. 95] is treated with aniline, No. i], it produces carbanilide 
 (phenylem cyanate), No. 90]. 
 
 C ^ a [ \= ZH 3 ,C 6 H 5 ; CNO = No. 89]. 
 
 When No. 95] is treated with ammonia = ZH 2 H, it produces car- 
 bamide-carbanilide (phenylam cyanate), No. 89]. 
 
 These experiments do not prove that the compound C 6 H 5 ,CyO 
 is an acid; but what they do prove is, that nitrogen acts up to the 
 character that I have assigned to it as a constructor of radicals. When 
 it is in the presence of carbon, and without the materials necessary to 
 constitute an amid or an ammon, it forms cyanogen ; but so soon as 
 materials are placed within its reach, wherewith it can make a salt of an 
 amid or an ammon, it immediately forms such a salt, and leaves the 
 carbon to its destiny, which appears to be that of occupying and removing 
 the oxygen. What the precise result is, in each case, depends partly 
 upon the nature of the materials that are employed, partly upon their 
 relative quantities, and the manner of putting them together. In cases 
 a and c the materials produce phenylac ; in cases 6 and / they produce 
 phenylam ; in cases d and e they produce phenylem. In the presence of 
 potassium the carbonic acid remains in the state of carbonate of potash. 
 In the absence of positive radicals it flies off as gas. 
 
 On the subject of the transmigration of azote from amids and ammons 
 
MELAXOXIMIDE. 
 
 307 
 
 into cyanogen, and thence back again into amids and ammons, the reader 
 will find some additional particulars in the Article on " Nitriles," at 
 page 217. 
 
 At a later period (January, 1856,) Dr. Hofmann ascribed to anilo- 
 cyanic acid the formula C 14 H 6 NO 2 . Proceedings of the Royal Society, 
 viii. 13. But his analyses give C 14 H 5 NO 2 (November, 1849), Quar- 
 terly Journal of the Chemical Society (1850), ii. 314. 
 
 {C 6 H 5 CvO ) 
 /<7-LT per ! p \3 ( == Yhenjla, cyanate tris phenylac cyana. 
 
 When melanoximide is distilled, the compounds produced are carbonic 
 oxide gas, anilocyanic acid, and a residue having the following composition : 
 C 56 H 23 N ro* (Hofmann's numbers) = C" 8 H 23 N 7 O l = No. 99]. This de- 
 composition may be accounted for as follows : 
 
 Used. 
 
 Produced. 
 
 3 atoms of No. 93. 
 C s H 5 ,CyO 
 C 6 H 5 ,CyO 
 C 6 H 5 ,CyO 
 C 6 H 5 ,CyO -f HCy 
 C 6 H 5 ,CyO + HCy 
 C 6 H 5 ,CvO + HCv 
 
 JCO) Carbonic 
 ICO I oxide, 
 [CO] 3 atoms. 
 
 C 6 H 5 ,CyO) 2 atoms } 
 C 6 H 5 ,CyO| of 95]. 
 C 6 H 5 ,CyO 
 
 ZH,C 6 H 5 ,Cy I i atom 
 ZH,C 6 H 5 ,Cy ( of 99]. 
 ZH,C"H 5 ,Cy J 
 
 When water is present, additional reactions take place and complicate 
 the phenomena. Thus : 
 
 C 6 H 5 ,CyO) fZH 2 ,(C 6 H 5 ) 2 ; CyO - No. 90]. 
 C 6 H 5 ,CyOl = < CO* set free. 
 
 H, HO j I 
 
 Every atom of water decomposes two atoms of No. 95], C 6 H 5 ,CyO, and 
 their materials produce one atom of carbanilide, No. 90], ZH 2 ,(C 6 H 5 ) 2 ; 
 CvO, and one atom of carbonic acid, CO 2 . 
 
 In reviewing Dr. Hofmann's account of the compounds of aniline, I 
 have restricted my remarks to the individual substances selected for 
 examples, and I have not entered upon the general speculation, whether 
 the aniline bases are most consistent with Berzelius's idea that they all 
 contain ammonia = NH 3 , or with Liebig's, that they all contain amido- 
 gen = NH 2 , &c. On these points Dr. Hofmann does not appear to have 
 satisfied his own judgment, and his wavering arguments certainly settle 
 nothing. In 1844 he quotes aniline with the formula C 18 H 7 N. In 
 1 848 he is favourable to Berzelius's theory, and aniline is NH 3 ,(C 1S H 4 ). 
 In 1850, farther researches make him incline to Liebig's view, and aniline 
 
 H] 
 
 is quoted as H V N. In 1856, aniline becomes again what it was in 
 C 12 H 5 J 
 
 x 2 
 
308 THE PLATINUM BASES. 
 
 1 844, C 12 H 7 N. In most cases these formulae are given doubtingly, as if 
 the arguments that are urged to support them had riot appeared conclu- 
 sive to their author. 
 
 As the theory of azotic radicals which I have advanced in this Essay 
 is of wider application than any of the theories that have been advocated 
 by Dr. Hofmann, and as the aniline salts, if my views are correct, must 
 fall in with all other salts of azotic radicals, I leave it to the reader to 
 form his own opinion respecting them, when I have placed before him 
 the azotic theory in a more complete state. 
 
 The Platinum Bases. 
 
 It is impossible to examine the salts of platinum, and their distin- 
 guishing names and formula?, without being driven to the conclusion 
 that, on these matters, chemists are in a muddle. 
 
 Of course, the muddle is unnecessary, and might be removed. It does 
 not depend upon difficulties inherent in the salts ; for they are simple 
 and regular, and their transmutations are characteristic and intelligible. 
 The muddle is purely theoretical. It is the produce of the clumsy con- 
 trivances by which, from time to time, the salts of platinum have been 
 EXPLAINED. If we could get rid of these explanations, w r e should get 
 rid of the muddle, since the salts themselves are orderly ; but, unhappily, 
 chemists cherish two favourite dogmas, the retention of which perpetuates 
 the muddle. 
 
 These are the dogmas : 
 
 1. " There is only one chemical equivalent of platinum" 
 
 2. " The salts of platinum are composed of acids and bases." 
 
 REMARKS ox THE FIRST OF THESE DOGMAS. 
 
 M. Gerhardt, some years ago, showed chemists the propriety nay, 
 the necessity, of admitting the existence of two chemical equivalents of 
 platinum, and he proved to them that this would diminish the muddle 
 amcng its salts. Some ridiculed this notion, and some said it was " a 
 very ingenious theory ;" but I believe that no one, excepting Laurent, 
 admitted its truth. They preferred the muddle. 
 
 Now I cannot understand why chemists persist in playing the part of 
 Sphinx, and puzzling the world with philosophical riddles that require 
 an (Edipus to solve them, when a plain, simple, and useful course is 
 proposed for their adoption. I cannot perceive what principle of reason 
 guides their judgment in this matter. They will not admit the existence 
 of a " second equivalent" of platinum, and they will admit the exist- 
 ence of a score of *' platinum bases " of the most monstrous and extra- 
 vagant proportions and composition. And thus they encourage muddle. 
 
THE PLATINUM BASES. 309 
 
 I have collected for this section about a hundred of the principal salts 
 of platinum. I have arranged them in four classes, and given them the 
 formula which they ought to have in accordance with the radical theory. 
 I have added to each salt its ordinary formulae, its difficultly-pronounce- 
 able names, and such other information as is necessary to identify it, 
 and to contrast the existing system with that which is now offered to 
 replace it. 
 
 I admit the existence of two chemical equivalents of platinum. A 
 heavy atom which has the atomic weight of 99, and a light atom of half 
 that weight. The first is to be called the platous atom, and the second 
 the platic atom. 
 
 These two chemical atoms produce two distinct classes of salts, being 
 those which are commonly called salts of the protoxide, and salts of the 
 peroxide of platinum. An inspection of the formulae which I have given 
 in the following Table, Nos. i] to 33] will convince any one whose 
 judgment is unperverted by the " idols of the schools," that the separa- 
 tion of the salts Nos. i] to 15] from those of Nos. 1 6] to 33], on the 
 pretence that the former are salts of the protoxide, and the latter salts of 
 the peroxide of platinum, is an unqualified absurdity. Oxygen is power- 
 less in the matter. The real difference in the two classes of salts is 
 obviously in the PLATINUM and ONLY in the platinum; and the true 
 question for investigation is, What is the NATURE of that difference ? 
 
 The nature of that difference is, that the platous salts contain the 
 heavy atom of platinum, and the platic salts contain the light atom ; all 
 other elements of the salts remaining the same. 
 
 The difference that exists between the platous and platic salts, exists 
 also between the salts of platousam and platicam. By platousam, I 
 mean an ammonium which contains one platous atom ; by platicam, an 
 ammonium that contains one platic atom. These ammoniums act as 
 positive radicals, and each of them produces a variety of salts. These 
 salts are given in the following Table, where Nos. 34] to 68] are salts of 
 platousam, and Nos. 70] to 100] are salts of platicam. Throughout these 
 extended sets of salts, the characteristic of the first set is the presence .of 
 the platous atom, and of the last set the presence of the platic atom. 
 
 It is completely in the power of the chemist to produce at pleasure 
 either the platous or the platic atom. The certainty of the very exist- 
 ence of platinum is not greater than the certainty that the chemist has 
 it in his power to produce at will either platous salts or platic salts, 
 either salts of platousam or salts of platicam. And to do this, he must 
 produce either the platous or the platic atom. The following are the 
 facts which guide him : 
 
 1 . When platinum is acted on by a negative radical, in the presence 
 of an excess of positive radicals, the platous atom is produced. 
 
 2. When platimim is acted on by a negative radical, in the presence 
 of an excess of negative radicals, the platic atom is produced. 
 
310 THE PLATINUM BASES. 
 
 The salts that are described in the following Tables, are produced by 
 processes that are in perfect accordance with these facts. The salts of 
 platousam are all produced by the action of positive radicals in excess ; 
 and it is only in this class that we meet with those combinations of 
 neutral salts with ammonia, which in Gerhardt's language are called salts 
 of diplatosamine ; while on the other hand, we perceive in the salts of 
 platicam a total absence of an excess of ammonia, and in their formation 
 the constant recurrence of the splitting up of platous into platic atoms by 
 the energetic action of negative radicals presented to the platinum in 
 excess. It is scarcely possible to conceive the existence of evidence of a 
 circumstantial character more conclusive than is presented by the salts 
 that are described in these Tables in support of the principle which I am 
 advocating, that platinum has two different chemical atoms, that either 
 of them is producible, or convertible into the other, at the will of the 
 chemist, and that to the diversity of their reactions all the salts of pla- 
 tinum owe their peculiar characteristics. 
 
 What I have stated respecting the mutability of the chemical atom of 
 platinum is strictly in accordance with what I have stated in another 
 section see page 34 respecting the mutability of the chemical atom of 
 iron. I have shown there, that under the action of an excess of positive 
 radicals, the ferrous atom is formed, and that, under the pressure of an 
 excess of negative radicals, the ferric atom is produced. This kind of 
 reaction is no doubt common, in a greater or lesser degree, to all 
 elements which are endowed With the property of producing two dif- 
 ferent radicals. The natural tendency of matter to come to an 
 equilibrium occasions these peculiar chemical elements to form their 
 larger or their smaller radical according as the circumstances in which 
 they are placed demand the one or the other. The power to control the 
 elements, and make them produce the basylous or basylic atoms as he 
 requires them, depends entirely on the chemist's ability to arrange the 
 circumstances in which the elements are to be made to act. This was 
 the secret of the " wonderful lamp." When Aladdin rubbed the lamp, the 
 genius appeared to do his bidding. When the chemist desires to pro- 
 duce a particular chemical atom, he arranges the proper circumstances, 
 and nature does his bidding. 
 
 By admitting the mutability of elementary chemical radicals to be the 
 result of a natural law which is in continual operation, we are enabled to 
 account, in a simple and easy manner, for a great variety of complex 
 chemical phenomena, which are otherwise perfectly unaccountable. 
 Under these circumstances, it is extraordinary that chemists persist in 
 rejecting evidence which is clear and abundant, for no better reason than 
 that Dalton, fifty years ago, defined a chemical equivalent to be one in- 
 divisible atom. Why are we to be bound by a definition which never 
 rested on evidence stronger than a surmise, when that definition is con- 
 tradicted by the facts accumulated by fifty years of analytical research ? 
 
THE PLATINUM BASES. 311 
 
 We have to this day no evidence of the existence of indivisible atoms. 
 We have abundant evidence of the power possessed by more than 
 twenty elements to produce two different chemical atoms, each of them 
 having the power of a radical, and each being able to produce a series of 
 salts differing in quality from the salts produced by the other radical. 
 But fashions in chemistry are not always regulated by experimental 
 evidence. Dal ton's theory is become an " idol of the schools," and 
 sacrifices are made to it. 
 
 REMARKS ON THE SECOND DOGMA. 
 
 " The salts of platinum are composed of acids and bases" 
 The reader is requested to look over the formulae that accompany the 
 synonymes in the following Table of 99 salts of platinum. The doctrine 
 that every salt is composed of an acid and a base, has, in this case, led 
 its votaries to the adoption of some extraordinary absurdities. According 
 to that doctrine, a normal nitrate is composed thus: MO, NO 5 , where 
 MO is the base, and NO 5 is the acid. But here is an exquisite platinum- 
 nitrate, No. 85] : 4NH 3 ,Pt 2 ClO'\2N0 5 . That doctrine professes to dis- 
 countenance binitrates, but here it admits the existence of a binitrate. 
 That doctrine declares it to be a fundamental law, that in every salt the 
 number of atoms of anhydrous acid must be equal to the number of 
 atoms of oxygen in the base. Yet here we have five atoms of oxygen 
 in the base, and only two atoms of anhydrous acid to bring that base 
 into equilibrium. Then, what a base it is ! What a radical it contains ! 
 four atoms of nitrogen, twelve atoms of hydrogen, two atoms of platinum, 
 and one atom of chlorine are all conglomerated into one basic clump 
 that clump is oxidised into a base by five atoms of oxygen, and that one 
 base is then combined directly with two atoms of anhydrous nitric acid 
 to form a nitrate. This is gravely recorded as matter for belief by phi- 
 losophers who are too squeamish to admit the possibility that platinum 
 can produce two different chemical atoms. In order to escape this last 
 difficulty, and to do reverence to the Daltonian " idol," they take a salt 
 which, as formula 85] shows, contains four complete ammoniums and 
 four acid radicals, and which therefore is a quadruple salt ; and, after 
 setting aside as the "acid," the clump " 2NO 5 ," they cram all the other 
 ingredients into the " base," thus making a salt by a series of processes 
 every one of which is in violation of the laws that constitute the doctrine 
 which they pretend to support. I ask any independent thinker whether 
 this is not "muddle?" whether it is not a striking example of the 
 ability to swallow a camel and strain at a gnat ? 
 
 Here is another admirable example of theoretical architecture : 
 H 3 1 ' 
 PtCU 
 H 3 
 
312 THE PLATINUM BASES. 
 
 This salt, as I regard it, is formed on the model of sal-ammoniac ; a chlo- 
 ride of an ammonium, in which one atom of hydrogen has been replaced 
 by one platic atom, and which requires on the radical theory the simple 
 formula which I have given to it in No. 70], viz., ZEPPtc; Cl. But 
 this radical formula is very simple, and it contains the heterodox platic 
 atom; it is therefore doubly objectionable to the established chemical 
 authorities. The orthodox view of the salt is this : " It is the chloride 
 of an ammonium. This ammonium has one of its atoms of hydrogen 
 replaced by another ammonium. This other ammonium has one of its 
 atoms of hydrogen replaced by the protochloride of platinum, and thus 
 we obtain the compound : 
 
 NCI." 
 H 8 ' 
 
 But some of our orthodox chemists dissent from this view of the salt. 
 They do not admit the truth of this theory of involved ammoniums, 
 where the smaller is made to include the greater. Instead of grouping 
 the elements in that form, they put them side by side in regimental 
 order, thus : Pt 2 Cl 2 O 2 H 12 N 4 + O 2 , and they call this regiment a BASE 
 " Raewsky's base." The particular nature of this " base" is not made 
 by any means clear to us. Whether the elements are combined in any 
 special grouping, or whether they stand side by side like posts in a 
 pallisade, a series of chemical nullities waiting for the " acid " that is to 
 rail them into united action, we are not informed. 
 
 By similar processes, chemists manufacture a host of " platinum 
 bases," of which I will try to quote a few examples. I hope I shall 
 quote them satisfactorily, but it is so difficult to know when you have 
 the whole of a " platinum base," that in extracting it from its salts, you 
 are very liable to take away a few atoms too many, or leave behind a 
 few that ought to be taken. In the estimation of many orthodox 
 chemists, however, if we may judge from the following formula?, a few 
 atoms more or less in a platinum base seems to be considered a matter 
 of little importance : 
 
 1. Gros'sbase . . . PtClH'N 2 -f O or PtClH 8 N,NH 4 O. 
 
 2. Reiset's first base . PtH 6 N 2 + O or PtH 2 N,NH 4 O. 
 
 3. Reiset's second base . PtH 8 N -{- O or ^H NO. 
 
 4. Raewsky's first base Pt 2 Cl O 3 H 12 N 4 + O 2 . 
 
 5. Raewsky's second base Pt 8 Cl 2 O 2 H 12 N 4 + O 2 . 
 
 Grimm's Notation. Hofmann's Notation. 
 
 6. Gerhardt's Platosamine NH 2 Pt = ^lNO,HO. 
 
THE PLATINUM BASES. 313 
 
 Grimm's Notation. Hofmann's Notation. 
 
 H 4 N> NO HO 
 Pt j 
 
 8. Gerhardt's Platinamine . . NHpt 2 = I ^ } NO,HO. 
 
 f H ) 
 
 9. Gerhardt's Diplatinamine . N 2 H 4 pt 2 = 1 pt 2 V NO,HO. 
 
 [H 4 N] 
 
 The next six are given by Grimm on the authority of Kolbe : 
 
 {Pt } 
 TT3 >N. 
 
 N 
 
 1 1 . Ammon-Platammonium = < Pt > N. 
 
 12. Oxyplatammonium J IN. 
 
 H 4 N) 
 
 13. Amraon-Oxyplatammonium = <PtO>N. 
 
 IIP] 
 
 f PtCl ) 
 
 14. Chlorplatarnmonium = < p > N. 
 
 15. Ammon-Chlorplatammonium 
 
 (HN) 
 
 = ^PtCHN. 
 
 Iff j 
 
 All these bases, and as many more as can be produced by numerous 
 variations in the methods of writing the formulae, the student of 
 chemistry is led to believe to be necessary for the explanation of the salts 
 of platinum. 
 
 In the Renowned History of the Seven Champions of Christendom it 
 is recorded that the Necromancers of the middle ages no doubt, the 
 orthodox chemists of that period were in the practice of defending 
 unsafe positions by Fortifications and Giants and Dragons of hideous 
 aspect and ugly names, all constructed of MIST. It seems to me that 
 the Platinum Bases have been made of the same material by descendants 
 of those Necromancers in order to protect the rickety theory of acids and 
 bases which they delight to honour. 
 
 These " bases " are, actually, mere mist castles built in the air, with 
 no solid foundations. If you touch them with the inflexible rod of the 
 Radical Theory, it smashes them, and they vanish. The true platinum 
 
314 PLATOUS SALTS. 
 
 radicals which bear examination, and do not fly into mist, if you ask 
 them a question or two, are the following : the platous atom = Pt, the 
 platic atom = Ptc, platousam = ZH 3 Pt, and platicam = ZH 3 Ptc. With 
 these only, I proceed to formulate the entire series of the salts of this 
 malicious metal, which, acting the part of the chemical " Puck," has 
 hitherto led philosophers a pretty dance into all sorts of quagmires. 
 
 It is high time for orthodox chemists to unmuzzle their wisdom, 
 and begin to inquire whether "acids" and "bases" have not been 
 " idolized " a little too long ; and whether it is safe for them to continue 
 to treat with supercilious contempt all proposals to examine into the 
 constitution of salts, because the proposers decline to worship with them 
 the misty phantoms which were the progeny of the half-knowledge, half- 
 ignorance of a preceding generation. 
 
 Salts of Platinum. 
 
 DEFINITIONS OF THE PLATINUM RADICALS. 
 
 PLATOUS signifies the heavy chemical atom of platinum. Atomic 
 weight, 99. Symbol, Pt. 
 
 PLATIC signifies the light chemical atom of platinum. Atomic weight 
 49-5. Symbol, Ptc. 
 
 PLATOUSAM signifies an ammonium in which one atom of hydrogen 
 has been replaced by one platous atom. Symbol, ZH 3 Pt. 
 
 PLATICAM is an ammonium in which one atom of hydrogen has been 
 replaced by one platic atom. Symbol, ZH 3 Ptc. 
 
 Thes'e four Radicals produce four distinct Classes of Salts. 
 
 Class I. Platous Salts. 
 
 1. Pt,PtO . . . ' . . Platous platousate. 
 
 2. PtS Platous sulpha. 
 
 3. PtCl Platous chlora. 
 
 4. PtCl + ZH 4 C1 . . . Platous chlora cum ammona 
 
 chlora. 
 
 5. PtjZEFjS'O 8 . . . Platous ammona sulphenite. 
 
 6. PtI Platous ioda. 
 
 7. PtCy Platous cyana. 
 
 8. H,Pt,Cy 2 Hydra platous cyancn. 
 
 9. ZH*,Pt,Cy 2 .... Ammona platous cyanen. 
 
 10. K,Pt,Cy 8 Potassa platous cyanen. 
 
 1 1. (K,Pt,Cy 2 ) 5 + KCy . . Pentakis potassa platous cyanen 
 
 cum potassa cyana. 
 
PLATOUS SALTS. 315 
 
 1 2. (ZH 4 ,Pt,Cy 2 ) 5 4- ZH 4 Cy Pentakis ammona platous cyanen 
 
 cnm ammona cyana. 
 
 13. Pt,Cy,S 2 Platous cyana sulphene. 
 
 14. K,Pt,Cy 2 ,S 4 .... Potassa platous cyanen sul- 
 
 phone. 
 
 15. Ag,Pt,Cy, 2 S 4 . . . . Argenta platous cyanen sul- 
 
 phone. 
 
 USUAL NAMES AND FORMULAE OF THE PLATOUS SALTS. 
 In these Formula, O = 8. Pt = 99. 
 
 i, Protoxide of platinum; platinous oxide = PtO. 2, Protosulphide 
 of platinum; platinous sulphide = PtS. 3, Protochloride of platinum ; 
 platinous chloride ; chloroplatinous acid = PtCl. 4, Chloroplatinate of 
 ammonium = NH 4 Cl,PtCl, Peyrone. (This is the model of three series 
 of salts. In one of them, the chloroplatinites, ZH 4 is replaced by K or 
 some other metal. In the other two series, the two atoms of Cl are re- 
 placed by Br 2 or I 2 , giving rise to the bromoplatinites and iodoplatinites.) 
 
 5, Sulphite of platinous oxide and ammonia = NH 4 O,S0 2 -\- PtO, SO 2 . 
 
 6, Protoiodide of platinum ; platinous iodide ; iodoplatinous acid = PtI. 
 
 7, Protocyanide of platinum; platinous cyanide = PtCy. 8, Hydro- 
 platinocyanic acid = HCy,PtCy. 9, Platinocyanide of ammonium 
 
 = NH 4 Cy,PtCy. 10, Platinocyanide of potassium = KCy,PtCy. 
 Numbers 9 and 10 are models of a large class of salts, which differ only 
 in having, in the place of ZH 4 and K, one of these radicals, Ba, Ca, Mg, 
 Cue, Hgc, Ag. n, Platino-platinidcyanide of potassium = K 6 Pt 5 Cy 11 
 = KCy,5KPtCy 2 . 12, Platino-platinidcyanide of ammonium = 
 (NH 4 ) 6 Pt 5 Cy 11 = NH 4 Cy,5(NH 4 PtCy 2 ). There are many other salts 
 on the model of Nos. 1 1 and 1 2, in which ZH 4 and K give place to Na, 
 Ca, Mg, Pb, Fe, &c. 13, Sulphocyanide of platinum = PtCyS 2 . 14, 
 Platino-bisulphocyanide of potassium = KPtC 4 N 2 S 4 = KPt2(CyS 2 ). 
 15, Platino-bisulphocyanide of silver = AgPt 2(CyS 2 ). 
 
 Nos. i to 12 are given on the authority of Gmelin's Handbook of 
 Chemistry. Nos. 13 to 15 are on the authority of Buckton. 
 
( 316 ) 
 
 Class II. Platic Salts. 
 
 16. Ptc,PtcO . . . . Platic platicate. 
 
 17. Ptc,HO .... Platic hydrate. 
 
 1 8. PtcS Platic sulpha. 
 
 19. PtcCl Platic chlora. 
 
 20. KC1 4- 2PtcCl . Potassa chlora bis platic chlora. 
 
 21. NaCl 4- 2 PtcCl . Natra chlora bis platic chlora. 
 
 22. ZH 4 C1 + 2PtcCl . Ammona chlora bis platic chlora. 
 
 23. Ptcl Platic ioda. 
 
 24. ZH 4 I 4- 4PtcI . Ammona ioda tetrakis platic ioda. 
 
 25. H,Ptc 8 ; I 3 . . . Hydra platenic iodine. 
 
 26. Pt,Ptc 2 ; I 3 . . . Platous platenic iodine. 
 
 27. PtcSO* .... Platic sulphete. 
 
 28. KC1 4- 2PtcCy . Potassa chlora bis platic cyana. 
 
 29. ZH*C1 + 2PtcCy . Ammona chlora bis platic cyana. 
 
 30. ZH 4 , Ptc*,Cy 8 . . Ammona platenic cyariine. 
 
 3 1 . K,Ptc 2 ,Cy a . . . Potassa platenic cyanine. 
 
 32. ZH 4 ,Ptc 2 ,Cy 8 ,S 6 . . Ammona platenic cyanine sulphade. 
 
 33. K,Ptc 2 ,Cy 3 ,S 6 . . Potassa platenic cyanine sulphade. 
 
 USUAL NAMES AND FORMULA OF THE PLATIC SALTS. 
 In these formulae O = 8, Pt = 99. 
 
 1 6, Platinic oxide; bioxide of platinum = PtO 2 . 17, Hydrate of 
 platinic oxide; platinic hydrate = Pt0 2 ,2HO. 18, Bisulphide of pla- 
 tinum; platinic sulphide = PtS 2 . 19, Bichloride of platinum ; platinic 
 chloride ; chloroplatinic acid = PtCl 2 . 20, Chloroplatinate of potassium 
 = KCl,PtCl 2 . 2 1 , Chloroplatinate of sodium = NaCl,PtCl 8 . 22, Chloro- 
 platinate of ammonium = NH 4 Cl,PtCl 2 . There are other salts on the 
 model of Nos. 20 to 22. The salts that are called chloroplatinites are 
 formed on the model of No. 4. 23, Biniodide of platinum ; platinic 
 iodide; iodoplatinic acid = PtI 2 . 24, lodoplatinate of ammonium = 
 NH 4 I,2PtI 2 . (Instead of the name and formula which I have given in 
 the Table, we could also write ZH 4 ,Ptc 4 ,P = Ammona platonic iodune). 
 25, Hydriodate of platinic iodide = PtI 2 ,HI. 26, Sesqui-iodide of pla- 
 tinum = Pt 2 ! 3 . (This seems to be a salt precisely corresponding to 
 No. 25. There are equivalent salts with K,Na, &c., instead of Pt; and 
 a corresponding series with Br instead of I). 27, Sulphate of platinic 
 oxide; platinic sulphate = PtO 2 , 2 SO 3 . Two atoms of sulphuric acid 
 are required, because two atoms of oxygen are assumed to be present in 
 the base in combination with only one atom of metal ; so that eight 
 atoms of oxygen are demanded by the current theory, while two atoms 
 
SALTS OF PLATOUSAM. 317 
 
 suffice on the radical theory. 28, Bicyanide of platinum with chloride 
 of potassium = KCl,PtCv 2 . 29, Bicyanide of platinum with chloride of 
 ammonium = NH 4 Cl,PtCy 2 . 30, Platinidcyanide of ammonium = 
 NH 4 Cy, PtCy 2 . 31, Platinidcyanide of potassium = KCy, PtCy 2 . 
 32, Platino-tersulphocyanide of ammonium = NH 4 ,Pt 3 CyS 2 . 33, Pla- 
 tino-tersulphocyanide of potassium = KPtC 6 N 3 S 6 = KPt 3 CyS*. Nos. 
 32 and 33 are models of a series of salts in which K and ZH 4 are re- 
 placed by Fe, Hg, Ag, Pb, and H. See Buckton, Quarterly Journal 
 of the Chemical Society, vii. 22. The names and formulae from No. 16 
 to 31 are taken from Gmelm's Handbook of Chemistry . 
 
 Class III. Salts of Platousam - ZHTt. 
 
 34. ZH 3 Pt; Cl Platousam chlora. 
 
 35. ZHTt; Cl + ZH 2 ,H . . Platousam chlora cum amida hydra. 
 
 36. ZHTt; Br Platousam broma. 
 
 37. ZHTt ; Br + ZH 2 ,H . . Platousam broma cum amida hydra. 
 
 38. ZHTt; I Platousam ioda. 
 
 39. ZHTt; I + ZH 2 ,H . . Platousam ioda cum amida hydra. 
 
 40. ZHTt; HO' Platousam hydrate. 
 
 41. ZHTt; ZHTtO . . . Platousam platousam ate. 
 
 42. ZH 4 ; ZHTtO .... Ammona platousamate. 
 
 43. ZHTt; SO 2 Platousam sulphete. 
 
 44. ZHTt; SO 2 + ZH 2 ,H . Platousam sulphete cum amida 
 
 hydra. 
 
 45. ZHTt; NO 3 Platousam nitrite. 
 
 46. ZHTt ; NO 3 + ZH 2 ,H . Platousam nitrite cum amida 
 
 hydra. 
 
 47. ZH 4 ; ZHTt; CO 3 . . . Ammona platousam carbite. 
 
 ft (ZH 4 ; ZHTt; CO 3 . . .) Ammona platousam carbite cum 
 
 5< jZH 4 ; ZHTtO . . . .( ammona platousamate. 
 
 49. ZHTt ; Cy Platousam cyana. 
 
 50. ZHTt,Cy + AgCy = Platousam cyana cum argenta 
 
 cyana. 
 
 51. ZHTt,Cy 4- ZnCy Platousam cyana cum zinca cyana. 
 
 52. ZHTt,Cy + CoCy = Platousam cyana cum cobaltous 
 
 cyana. 
 
 53. ZHTt,Cy -f- Ni Cy = Platousam cyana cum niccolous 
 
 cyana, 
 
 54. ZHTt ; Cy ; S a . . . . Platousam cyana sulphene. 
 
 55. ZH 4 ; ZHTt ; S 2 O 3 . . . Ammona platousam sulphenite. 
 
 ^ j ZH 4 ; ZHTt ; S*0 3 . . I Ammona platousamine bisul- 
 50. | ZH 3p t . ZH 3 Ft . S20 3 ^ ^ j phenite. 
 
318 SALTS OF PLATOUSAM. 
 
 JZH 4 ; ZH 3 Pt; S'O 3 . . .\ 
 57'lZH 4 'zH 4 ' S 2 O 3 ( Anmionme platousam bisulpnenite. 
 
 8 I(ZH 4 ; ZH 3 Pt; S'KD 3 ) 2 ) i A Bis ammona platousam sulphenite 
 ' *(ZH 4 ;C1 j cum aramona chlora dcmi-aquate. 
 
 jZH 4 ; ZH 3 Pt; S 8 O 3 i A Ammona platousam sulphenite 
 * \ ZH 3 Pt ; Cl I" 1 " cum platousam chlora aquate. 
 
 60. ZH 3 Pt; Cl + ZH 3 Cuc ; Cl Platousam chlora cum cupricam 
 
 chlora. 
 
 61. ZH 3 Pt ; Cl + ZH 3 Hgc ; Cl Platousam chlora cum mericain 
 
 chlora. 
 
 62. ZH 3 Pt; Cl + ZH 3 Pb ; Cl Platousam chlora cum plumbam 
 
 chlora. 
 
 63. ZH 3 Pt; Cl -f ZH 8 Zn ; Cl Platousam chlora cum zincam 
 
 chlora. 
 
 64. ZH(CH 3 ) 8 Pt;Cl + ZH 2 ,H Platous - methylem chlora cum 
 
 amida hydra. 
 
 65. ZH^IPyPt; Cl + ZH 2 ,H Platous-ethylem chlora cum amida 
 
 hydra. 
 
 66. ZH(C 8 H 5 ) 2 Pt; C1 + ZH 8 ,H Platous - phenylem chlora cum 
 
 amida hydra. 
 
 67. ZH 2 ,C 6 H 5 ,Pt;Cl . . . Platous-pheriylam chlora. 
 
 68. ZH 3 ,C 6 H 5 ; Cl-f PtCl = Phenylam chlora cum platous 
 
 chlora. 
 
 USUAL NAMES AND FORMULA OF THE SALTS OF PLATOUSAM. 
 34]. ZH 3 Pt; Cl = Platousam chlora. 
 
 This formula represents a compound which contains the following pro- 
 portions of the respective elements : 
 
 Nitrogen. . . . i atom = 14 
 
 Hydrogen ... 3 atoms = 3 
 
 Platinum . . . i atom = 99 
 
 Chlorine . . . . i atom = 35*5 
 
 There are several ways of preparing a compound of this composition, 
 and the compounds thus prepared, though similar in their ultimate com- 
 position, have different properties, and give rise to the notion that they 
 differ in their proximate constitution. Three varieties may be specially 
 noticed : 
 
 a). TJie Green Salt of Magnus is prepared thus : A solution of proto- 
 chloride of platinum (3] Platous chlora) in hydrochloric acid is super- 
 saturated with ammonia. The platous atom undergoes no change, and 
 the quantity of chlorine remains the same, but they combine with 
 
SALTS OF PLATOUSAM. 319 
 
 ammonia, and the question is, in what manner are the four atoms, 
 Z -j- H 3 , connected with the two atoms Pt -f- Cl. In formula 34] it is 
 assumed that Z -f- H 3 + Pt have produced the vice-ammon platousam, 
 and that this is combined directly with the chlorine. But the facts 
 admit of various other explanations. Thus, we may assume that the 
 platous chlora PtCl combines directly with the ammonia salt to 
 salt and produces the double salt = PtCl -f- ZH 8 ,H ; and, since many 
 salts of platousam possess this property of combining with ZH 2 ,H (see 
 Nos. 35, 37, 39, 44, 46), it is not unreasonable to suppose that the 
 same power of combination may also exist in the platous salts. 
 
 Another explanation is, that the combination may be of the same 
 nature as the hydrochlorate of ammonia (see page 197); and, in that 
 view, may require the formula ZH,Pt ; H -f- HC1. In this formula 
 ZH,Pt represents a vice-amidogen ; the formula ZH,Pt ; H the cor- 
 responding ammonia, and the formula HC1 the hydrochloric acid requisite 
 to constitute a hydrochlorate of this peculiar ammonia. 
 
 One of the methods of preparing the compound under consideration 
 consists in adding platous chlora, = PtCl, to the salt represented by 
 formula 35] = ZH 3 Pt; Cl -f- ZH 2 H, which may thus produce a com- 
 pound of the following formula, (ZH 3 Pt; Cl -f ZH 2 H) -f PtCl. 
 
 Finally, we can imagine the existence in this compound of the radical 
 platousem = ZH 2 Pt 2 , which would then require the following formula : 
 ZH 2 Pt* ; Cl -f ZH 4 C1. 
 
 We have thus five formulas, all of which express the same quantities 
 of the same elements, but differ greatly in their proximate arrangement, 
 and every one of which has some claim to be considered the right 
 formula : 
 
 i). ZH 3 Pt;Cl. 
 
 2). PtCl + ZH 2 H. 
 
 3). ZH,Pt; H + HC1. 
 
 4). (ZH 3 ,Pt;Cl + ZH 2 H)+PtCl. 
 
 (ZH 2 Pt 2 ;Cl 
 1ZH 4 
 
 ) 
 .( 
 
 It is not unlikely that some of the duplicate salts of this series may 
 require formulae similar to No. 5), containing platousem instead of pla- 
 tousam ; but in the present state of our knowledge of these compounds, 
 while it is easy to construct such formulae, it is impossible to ascribe 
 them with any certainty to the proper compounds. 
 
 6). The Yellow Salt. Preparation i). The compound No. 35], 
 = ZEPPt ; Cl + ZH 2 H, is heated as long as it gives off ammonia. 
 2). The gree'n salt is dissolved in a boiling solution of sulphate of am- 
 monia. When the solution cools, the yellow salt is deposited. There 
 are several other methods, but none which gives any precise information 
 respecting the proximate constitution of the salt. When the yellow salt 
 is dissolved in aqueous ammonia, the salt No. 35] is reconstituted. The 
 yellow salt is sometimes called the hydrochlorate of Reiset's second base. 
 c.) Tlie Red Salt. Carbonate of ammonia is added, drop by drop, 
 
320 SALTS OF PLATOUSAM. 
 
 to a boiling solution of neutral protochloride of platinum, No. 3] : the 
 red salt crystallises when the solution cools. If carbonate of ammonia is 
 added at once in great excess to a cold solution of protochloride of 
 platinum, the yellow salt is produced. 
 
 There appear to be several other compounds of this same percentage 
 composition (see Gmelin's Handbook of Chemistry, vi. 300), but neither 
 the methods of preparing them, or of converting them into other com- 
 pounds, nor their properties or reactions, enable us to allot to them 
 with certainty any one of the above formulae in preference to the others. 
 The prevailing opinion of chemists is, that the green salt contains twice 
 as many atoms as the other salts, but this opinion does not rest on any 
 strong foundation. 
 
 Synonymes. Chloride of diplatosammonium, Buckton. Ammonio- 
 protochloride of platinum, with one atom of ammonia = NH 8 ,PtCl, 
 Gmelin. Hydrochlorate of platosamine = ClH,NH 2 Pt, Gerhardt ; but 
 according to him the green salt is chloroplatinite of diplatosamine 
 
 = PtCl 2 H,N 2 H 5 Pt. Platammoniumchlorur = 3 NCI, Grimm (the 
 
 fHN] 
 
 vellow salt). Ammon-Platammoniumchloriir-Platinchlorur = <\Pt > 
 
 Icr j 
 
 NCI + PtCl, Grimm (the green salt). 1 Miller calls the yellow salt 
 Hydrochlorate of platosamine (Reiset's second base) = PtH 3 N,Cl ; while 
 he calls the green salt Magnus's green salt (Reiset's first base) = 
 PtH 6 N*Cl + PtCl. This last formula agrees with No. 4) in the above 
 list of possible formulae. An objection to this particular formula is, that 
 it is difficult to understand how it happens that (ZH 3 Pt ; Cl + ZH 2 H) 
 + PtCl does not instantly become ZH 8 Pt; Cl + ZH 3 Pt; Cl, a com- 
 pound which requires formula i). 
 
 35]. ZIPPt; Cl 4- ZH 2 H . Platousam chlora cum amida hydra. 
 
 Under the head of " Ammoniated Salts," at page 198, I have ex- 
 plained the nature of the compounds that are formed by the combination 
 of ammonia with neutral salts. It is of importance to bear in mind that 
 these compounds are double salts, because it clears away one of the 
 difficulties in the theory of the platinum bases. Gmelin's name and 
 formula for this salt are Ammonio-protochloride of platinum, with two 
 
 1 Grimm's names and formulae are quoted from Liebig's Handworter- 
 buch der Chemie, Band vi. To save room, I shall here quote his ^-lino 
 formulae in one line, thus : (H 4 N,Pt,Cl 2 )NCl 4. PtCl. The reader will 
 understand, that the quantities that are placed within the parenthesis, 
 and pointed off by commas, must be placed in a column to represent 
 Grimm's formula. 
 
SALTS OF PLATOUSAM. 321 
 
 atoms of ammonia = 2NH 3 ,PtCl. He gives the following account of 
 its preparation. " Protochloride of platinum is immersed in aqueous 
 ammonia, and boiled with it, the liquid being frequently renewed till 
 the green compound of Magnus, which is formed at first with evolution 
 of heat, is dissolved, after which the solution is evaporated to the crys- 
 tallizing point. The green salt of Magnus may likewise be treated in a 
 similar manner. (Reisefy" These reactions seem pretty clear : 
 
 First reaction : PtCl + ZH 4 ,HO = ZH 3 Pt,Cl + HHO. 
 
 Second reaction : ZH 3 Pt,Cl + ZH 4 ,HO - ZH 3 Pt,Cl 4. ZH 2 H -f HHO. 
 
 Gerhardt's name for No. 35] is Hydrochlorate of diplatosamine 
 = HCl,N 2 H 5 Pt. Grimm calls it Ammon - Platammoniumchloriir 
 = (H 4 N,Pt,H 2 )NCl. Buckton's name is Chloride of diplatosammonium 
 = PtH 6 N 2 Cl. Miller calls it Hydrochlorate of diplatosamine (or Reiset's 
 first base) = PtH 6 N 2 ,Cl. 
 
 When this salt is heated in a tube, it gives off ZH 2 H, and produces 
 the yellovi variety of No. 34]. When its solution is mixed with solution 
 of No. 3], it produces the green variety of No. 34]. Buckton has de- 
 scribed a remarkable reaction with this salt. He mixed a solution of it 
 with sesquichloride of iron, expecting to obtain a double chloride similar 
 to those described at Nos. 60] to 63]. In that expectation he failed; 
 but he procured a precipitate which, on analysis, proved to be Platicam 
 chlora, No. 70] = ZH 3 Ptc,Cl. After precipitation of the iron solution 
 by an excess of the platinum salt, he found the solution to contain no 
 sesquichloride, but only protochloride of iron, the disengaged equivalent 
 of chlorine, having, according to him, united itself to the platinum 
 chloride, as represented in the following equation : 
 
 PtH 6 N 2 Cl 4 Fe 2 Cl 3 = PtClH 6 N 2 ,Cl + 2 (Fed). 
 According to my notation, this reaction is explained as follows : 
 ZH 3 Pt ; Cl 4- ZH 2 H + Fec 3 Cl 3 = ZH 3 Ptc ; Cl 4- ZH 3 Ptc ; Cl + Fe 2 Cl 2 . 
 
 That is to say, the three ferric atoms in the presence of a basic com- 
 pound become two ferrous atoms, and abandon one atom of chlorine. 
 This free chlorine converts the one platous atom into two platic atoms, 
 and sufficient hydrogen and nitrogen to form two vice-ammons being 
 present, the products are two atoms of platicam chlora, and two atoms 
 of ferrous chlora. 
 
 ZH 3 Pt; Br = Platousam broma 
 
 ZH 3 Pt ; Br 4 ZH 2 H = Platousam broma cum amida hydra. 
 
 ZH 3 Pt ; I = Platousam ioda. 
 
 39J. ZHTt; I 4. ZH 2 H = Platousam ioda cum amida hydra. 
 
322 SALTS OF PLATOUSAM. 
 
 These four salts are evidently the corresponding salts to 34] and 35], 
 the only difference being in the replacement of the negative radical Cl by 
 Br or I. It is consequently needless to enter into details respecting 
 them. 
 
 40]. ZH 3 Pt;HO = Platousam hydrate. 
 
 Dr. Hofmann, speaking of the Platosamine bases, says" The free base, 
 
 H 3 ) 
 
 which Brodie has recently produced, has the composition p } NO,HO, 
 
 r l ) 
 
 and is consequently a true Platosammoniumoxydhydrate." Supplemente 
 zum ffandworterbuche der Chemie, p. 473. I can find no account of this 
 substance. Compare No. 40] with No. 41]. Which of these salts did 
 Brodie discover ? 
 
 41], ZBPPt; ZH 3 PtO = Platousam platousamate. 
 This compound is produced when No. 42] is exposed to heat. 
 
 ZH 4 ; ZH 3 PtO 1 J ZH 8 Pt ; ZH 3 PtO 
 
 ZH 4 ; ZH 3 PtO) == \ZH 2 H + ZH 2 H + HHO. 
 
 This is the hydrate of Gerhardt's Platosamine, and Reiset's second base. 
 It forms a grey porous mass, insoluble in water and in ammonia. Dr. 
 Miller's formula for Platosamine is PtH 3 N,O. 
 
 42]. ZH 4 ; ZH 8 PtO = Ammona platousamate. 
 
 This compound is obtained by precipitating the solution of the sulphate 
 No. 44] with baryta-water : 
 
 ZH 3 Pt; SO 8 + ZH 2 H + BaHO = ZH 4 ; ZHTtO + BaSO 2 , 
 
 or by acting upon the salt No. 3 5] by oxide of silver (that is to say, 
 newly-precipitated, or in the state of hydrate) : 
 
 ZHTt; Cl + ZH 2 H + AgHO = ZH 4 ; ZHTtO + AgCl, 
 
 Gmelin gives it the formula 2NH 3 ,PtO,HO, and calls it Ammonio-pro- 
 toxide of platinum, or Platinite of ammonia, with two atoms of ammonia 
 and one. atom of water. According to Berzelius, the formula is 
 NH 8 PtO + NH^. If O is taken = 16, this formula agrees with mine. 
 Grimm calls it Ammon - platammoniumoxydhydrate = (H 4 N,Pt,H 2 ) 
 NO.HO. Gerhardt's formula is N 2 H 5 Pt + 2HO. The first division of 
 this formula = N 2 H 5 Pt, represents an imaginary base which Gerhardt 
 called Biplatosamine or Diplatosamine. Dr. Miller's formula for Dipla- 
 tosamine is PtH 6 N 8 ,O + HO. A name by which this compound is 
 frequently distinguished is "Reiset's first base." Reiset's "second" 
 base is the radical of No. 41]. Dr. Hofmann gives the following account 
 of the present compound. " The constitution of the base is not so 
 
SALTS OF PLATOUSAM. 323 
 
 simple as that of the Platosammoniumoxydhydrate (No. 40). It con- 
 tains the elements of that compound -f I equiv. ammonia 
 
 PtH 6 N 2 0,HO = * NO.HO -f H 3 N. 
 
 We have at this moment nothing to guide us in forming an opinion of 
 the manner in which this equivalent of ammonia is combined with the 
 Piatosammoniumoxydhydrate. If we adopt Graham's idea, that when 
 ammonia combines directly with bodies that contain hydrogen, it may be 
 considered as ammonium, replacing one atom of hydrogen, then we may 
 consider Platosamine as an ammonioplatosammoniurnoxyd, composed 
 according to the following formula : 
 
 H 2 I 
 
 H 4 N I NO.HO. 
 Pt j 
 
 I may remark that the tendency of bases to combine with a second 
 equivalent of ammonia is frequently manifested in complex compounds." 
 Supplemente zum Handudrterbuche der Chemie, 473. In this passage 
 Hofmann adopts the notion, that ammonium ZH 4 can replace H l in 
 ammonium, a notion which appears to me to be subversive of the very 
 idea of an ammonium. I have not met with Mr. Graham's advocacy of 
 this strange proposal. 
 
 The salt 42] has strong alkaline properties ; its solution is nearly as 
 corrosive as that of caustic soda ; and it rapidly attracts carbonic acid 
 from the atmosphere. The formula which I have given to it is equi- 
 valent to that of anhydrous soda : 
 
 ZH 4 ,ZH 3 PtO = the salt No. 42]. 
 Na ,Na O = anhydrous soda. 
 
 With hydrochloric acid, the salt 42] produces water and the chlorine 
 compound 3 5] : 
 
 ZH 4 ; ZHTtO + HC1 = (ZH 3 Pt; Cl + ZH 2 H) + HHO. 
 43]. ZH 3 Pt; SO 2 = Platousam sulphete. 
 
 Formed by boiling Platousam ioda, No. 38] = ZH 3 Pt,I, with aqueous 
 sulphate of silver. Gmelin calls it Ammonio-sulphate of platinous oxide y 
 with one atom of ammonia = NH 3 ,PtO,SO 3 + HO. He says that this 
 water cannot be separated. In that case, the formula 43] should be 
 ZH 3 Pt,S0 2 -f- $aq. The salt reddens litmus strongly. By solution in 
 ammonia, it is converted into No. 44] . Grimm describes it as Sulphate 
 of platosamine = (PtH 3 )NO.S0 3 . 
 
 44]. ZH 3 Pt; SO 2 + ZH 2 H = Platousam sulphete cum 
 
 amida hydra. 
 
 Y 2 
 
324 SALTS OF PLATOUSAM. 
 
 The preparation is described in the note to 43]. It can also be prepared 
 by adding strong sulphuric acid to Platousam chlora cum amida hydra, 
 No. 35] = ZH 3 Pt; Cl -f ZH 2 H. In the last case, the reaction' falls 
 entirely upon the chlorine of the salt : 
 
 Cl + HSO 2 = SO 2 + HC1. 
 
 The salt forms transparent square-based octahedrons, which have no 
 action on vegetable colours. Gmelin calls it Ammonio-sulphate of pla- 
 tinous oxide, with two atoms of ammonia = 2NH 3 ,PtO,SO 3 . Grimm 
 calls it Sulphate of ammon-platammoniumoxyd = (H 4 N,Pt,H 2 )NO.S0 3 . 
 Gerhardt's name is Sulphate of diplatosamine. 
 
 45]. ZH 3 Pt;N0 3 = Platousam nitrite. 
 
 Formed by boiling Platousam ioda, 38] = ZH 3 Pt; I, with aqueous 
 silver nitrate (AgNO 3 = argenta nitrite). The reaction is simply a case 
 of double decomposition : 
 
 ZH 3 Pt ; I + AgNO 3 = ZH 3 Pt ; NO 3 + Agl. 
 
 The solution of the crystallized salt reddens litmus strongly. It is con- 
 verted, by solution in ammonia, into the salt No. 46]. Gmelin calls it 
 Ammonio-Nitrate of platinous oxide, with one atom of ammonia 
 = NH 8 ,PtO,N0 5 . It is Gerhardt's Nitrate of platosamine = NH'Pt, 
 NHO 3 . Sometimes called the Nitrate of Reiset's second base. 
 
 46]. ZH 3 Pt; N0 3 + ZH 2 H = Platousam nitrite cum 
 
 amida hydra. 
 
 This salt is prepared by acting upon platousam chlora cum amida hydra, 
 No. 35] = ZH 3 Pt; Cl + ZH 2 H, either with nitrate of silver AgNO 3 , 
 or with nitric acid = HNO 3 , when double decomposition ensues. 
 Gmelin's name for this salt is Ammonio-nitrate of platinous oxide, with 
 two atoms of ammonia = 2NH 3 ,PtO,NO 5 . It is Gerhardt's Nitrate of 
 diplatosamine = N 2 H 5 Pt,NHO 3 . Grimm's name is Nitrate of ammon- 
 platammoniumoxyd = (H 4 N,Pt,H 2 )NO.NO 5 . Miller calls it Nitrate of 
 diplatosamine (Reiset's first base) = PtH 6 N 2 O,N0 5 . 
 
 47]. ZH 4 ; ZEPPt ; CO 3 = Ammona platousam carbite. 
 
 This formula represents a neutral carbonate, in which platousam and 
 ammona form the two positive radicals. These radicals are the same as 
 those which occur in the salt No. 42] = ZH 4 ; ZH 3 PtO. It is formed 
 when a solution of the salt No. 42] is exposed to a current of carbonic 
 acid gas : 
 
 ZH 4 ; ZH 3 PtO + CO 2 = ZH 4 ; ZH 3 Pt; CO 3 . 
 
 This salt is Gerhardt's Carbonate of diplatosamine, and Grimm's Car- 
 bonate of ammon-platammoniumoxyd = (H 4 N,Pt,H 2 )NO.C0 2 +HO.CO 2 . 
 This formula leads Grimm to call it the add salt, and he allots the term 
 
SALTS OF PLATOUSAM. 325 
 
 neutral salt to the one which I have formulated in No. 48], so that, in 
 my opinion, he misnames both. 
 
 gl JZH 4 ; ZH 3 Pt; C0 3 | _ Ammona platousam carbite 
 
 _ 
 4 ; ZH 3 PtO J " cum ammona platousamate. 
 
 or thus, as a tetrabasic salt : 
 
 (ZH 4 ) 2 ; (ZH 3 Pt) 2 ; CO 4 = Ammonen platousamen carbote. 
 
 This salt is a compound of No. 47] with No. 42]. It is produced by 
 exposing a solution of No. 42] to atmospheric air. Grimm's formula for 
 the so-called neutral salt is (H 4 N,Pt,H 2 )NO.C0 2 + HO. He also notices 
 a sesquicarbonate with the formula 
 
 (Pt NO. COM 
 \H* J / 
 
 + HO.CO 8 , 
 
 the occurrence of which is improbable. Miller, also, calls No. 47] Bi- 
 carbonate of diplatosamine (Reiset's first base) = HO,PtH 6 N 2 O,2CO 2 . 
 
 It is worthy of remark, that a salt which, on the Radical theory, is a 
 tibasic neutral carbonate, may, on the theory of " acids and bases," be 
 represented as a monobasic bicarbonate. 
 
 49]. ZH 3 Pt;Cy = Platousam cyana. 
 
 The cyanide of platousam. It is produced, in company with hydro- 
 cyanate of ammonia, by saturating the protoxide No. 42] with hydrocyanic 
 acid (HCy = hydra cyana). Thus : 
 
 ZH 4 ; ZH 3 Pt,0 + H 2 Cy 2 = ZH 4 Cy + ZH 3 Pt,Cy + HHO. 
 
 The products are platousam cyana, ammona cyana, and water. It is also 
 produced by passing cyanogen gas through a solution of No. 42]. The 
 separated oxygen gives rise to some secondary reactions. Buckton con- 
 siders the most convenient method of production to be that of decom- 
 posing Platousam chlora No. 34] = ZH 3 Pt; Cl by Potassa cyana 
 = KCy, which is a case of direct double decomposition : 
 
 ZH 3 Pt,Cl + KCy = ZH 3 Pt; Cy + KC1. 
 
 The decomposition of the salt No. 49] by nitrate of silver = AgNO, 
 argenta nitrite, is as follows : 
 
 ZH'Pt'cv 1 - I ZH3pt ' N 3 + ZH2H = No - 
 
 Ig,NO'i II AgCy + PtCy = No. o 
 
 TT 2 ) 
 Synonymes. Hydrocyanate of platosamine = p f [ N.HCy and Cyanide 
 
 p f 
 
 H 3 ) 
 of platosammonium = p > N.Cy, Buckton. 
 
326 SALTS OF PLATOUSAM. 
 
 5 
 
 5 1 
 
 52 
 
 53 
 
 . ZH 3 Pt ; Cy -f- AgCy = Platonsam cyana cum argenta cyana. 
 . ZH 3 Pt ; Cy -f- ZnCy = Platousam cyana cum zinca cyana. 
 . ZH 3 Pt ; Cy -f- CoCy = Platousam cyana cum cobaltous cyana. 
 . ZH 3 Pt ; Cy -f- NiCy = Platousam cyana cum niccolous cyana. 
 
 These are double cyanides, which differ from those that were described, 
 at Nos. 8] to 10] only by containing platousam instead of platous atoms. 
 They are procured by the action of platinocyanide of potassium, No. 10], 
 upon ammoniacal solutions of salts of the respective metals. 
 
 54]. ZH 3 Pt,Cy,S 2 = Platousam cyana sulphene. 
 
 Buckton calls this salt the Platino-bisulphocyanide of diplatosammonium 
 = PtH 6 N 2 ,Pt 2(CyS 2 ). It is similar in constitution to the salt No. 13], 
 excepting that it contains platousam instead of the platons atom ; but 
 Buckton doubles the constituents to make the salt agree with his double 
 sulphocyanides, Nos. 14] and 15]. The unsupported notion that half the 
 platinum is combined with the imaginary sulpho-cyanogen, and the 
 other half with the ammonia, does not warrant the doubling of the 
 formula?. 
 
 55]. ZH 4 ; ZH 8 Pt; S 2 3 = Ammona platousam sulphenite. 
 
 This sulphite, and the four compounds represented by Nos. 56] to 59], 
 are produced by the action of sulphite of ammonia on the different modi- 
 fications of platousam chlora, No. 34]. The compounds Nos. 56] and 
 57] are produced either by the red or the green salt; those represented 
 by Nos. 58] and 59] are produced by the yellow salt. The comparison 
 of these products with the various doubtful formulas attributable to the 
 salt 34] (see page 319), has not enabled me to clear away the difficulties 
 which rest on this point. 
 
 60]. ZH 8 Pt; Cl + ZH 3 Cuc ; Cl = Platousam chlora cum cupricani 
 
 chlora. 
 
 This salt is a double chloride of platousam and cupricam ; that is to say, 
 it contains chlorides of two vice-ammoniums, each of which contains one 
 metallic atom in place of one atom of hydrogen. The salts Nos. 61] to 
 63] are of similar constitution. Buckton, who discovered these salts, 
 describes them as compounds of chloride of diplatosammonium, No. 35], 
 with chlorides of the respective metals. Thus, No. 60] is chloride of 
 diplatosammonium combined with chloride of copper = PtH 6 N y Cl,CuCl, 
 Buckton. See his Memoir, Quarterly Journal of the Chemical Society, 
 v. 213. It is much more probable that they are double chlorides of 
 ammonams, in agreement with formulae 60 to 63]. 
 
 64]. ZH,CH 8 ,CH 3 ,Pt; Cl + ZH 2 H = Platous-methylem chlora 
 
 cum amida hydra. 
 
^Ethylammon-^thyl-Platammonium j C 4 H 5 
 
 SALTS OF PLATOUSAM. 327 
 
 This salt differs from No. 35], only by having two atoms of methyl in 
 the vice-ammon instead of H 2 . Hofmann's name and formula for this 
 salt are, Methylobiplatosammoniumchlorid = C*PtH l N 2 Cl, Grimm 
 calls it Methylammon-Methyl-Platammoniumchloriir, I C 2 H 3 ) 
 and he gives it this magnificent formula, which is JH 3 f 
 recommended by a high degree of improbability. The f C 2 H 3 ^ NCI. 
 existence of an ammonium within an ammonium is an < Pt 
 assumption to which I can in no case agree. [ H 
 
 65]. ZH,C 2 H 5 ,C 2 H 5 ,Pt; Cl + ZH 2 H = Platous-ethylem chlora 
 
 cum ami da hydra. 
 
 Similar to No. 64], excepting that it contains (C 2 H 5 ) 2 instead of (CH 3 ) 3 . 
 Hofmann's name : ^Ethylobiplatosammoniumchlorid = C 8 PtH l4 N 2 Cl. 
 Grimm's name and formula : 
 
 NCI. 
 
 66]. ZH,C 6 H 5 ,C 6 H 5 ,Pt; Cl + ZH 2 H = Platous-phenylem chlora 
 
 cum amida hydra. 
 
 Similar to 64] and 65], but having two atoms of phenyl instead of H 2 . 
 Grimm's name is Phenylammon-Phenyl-Platammonium chloriir, with a 
 five-line formula of similar architecture to the two that I have cited for 
 Nos. 64] and 65], and liable to the same objection. 
 
 67]. ZH 2 ,C 6 H 5 ,Pt ; Cl = Platous-phenylam chlora. 
 
 Similar in constitution to platousam chlora, No. 34], excepting that H 1 
 is replaced by C 6 H 5 . A salt of a violet colour. Discovered by Raewsky ; 
 said by him to correspond to the green salt of Magnus, and to be 
 capable, like that salt, of assuming a variety of isomeric conditions. If 
 that is the case, this compound may hereafter supply information which 
 may lead to the accurate discrimination of the compounds that I have 
 described in the note to No. 34]. 
 
 68]. ZH 8 ,C 6 H 5 ; Cl + PtCl = Phenylam chlora cum platous chlora. 
 
 A garnet-coloured compound, discovered by Raewsky. Formula = 
 C l2 H 7 N,PtCl.HCl, a form which, according to Hofmann, is not yet 
 represented in the ammonia series. 
 
( 328 ) 
 
 Class IV. Salts of Platicam = ZH 3 Ptc. 
 
 70]. ZH 3 Ptc ; Cl = Platicam chlora. 
 
 71]. ZH 3 Ptc; Cl -f PtcCl = Platicam chlora cum platic 
 
 chlora. 
 72]. ZHTtc; Cl + ZH 3 Ptc; Br = Platicam chlora cum pla- 
 
 ticam broma. 
 73]. ZHTtc; Cl + ZHTtc; SO 2 = Platicam chlora cum pla- 
 
 ticam sulphete. 
 74]. ZH 3 Ptc; Cl + ZHTtc; CO 8 = Platicam chlora cum pla- 
 
 ticam carbete. 
 75]. ZHTtc; Cl + ZHTtc; NO 3 = Platicam chlora cum pla- 
 
 ticam nitrite. 
 77]. ZHTtc ;C1 + (ZHTtc)TO 4 = Platicam chlora cum pla- 
 
 ticamine phosphote. 
 78]. ZHTtc; NO 3 + ZHTtc; CO 8 = Platicam nitrite cum pla- 
 
 ticam carbete. 
 80]. ZHTtc; HO -f PtcHO = Platicam hydrate cum platic 
 
 hydrate. 
 81]. ZHTtc; SO 2 + PtcSO 2 = Platicam sulphete cum 
 
 platic sulphete. 
 82]. ZHTtc; NO 3 + PtcNO 3 = Platicam nitrite cum platic 
 
 nitrite. 
 83]. ZHTtc; NO 3 + PtcHO + aq = Platicam nitrite cum platic 
 
 hydrate aquate. 
 
 ZHTtc ; CO 2 I,, _ Platicam carbete cum platic 
 
 p tc ; HO ( " hydrate demi-aquate 
 
 {ZHTtc; Cl ] Platicam chlora bis platicam 
 
 (ZHTtc; NO 8 ) 2 1 = nitrite cum ammona pla- 
 
 ZH 4 ;PtcO J ticate. 
 
 f ZHTtc ; Cl ] Platicam chlora cum pla- 
 
 8 6]. < (ZHTtc) 2 ; CO 3 V = ticamen carbite cum 
 
 ( ZH 4 ; PtcO J ammona platicate. 
 
 -, J ZHTtc ; NO 3 ) _ Platicam nitrite cum am- 
 
 b 7 J- 1 ZH 4 ; PtcO ) mona platicate. 
 
 , I (ZHTtc; NO 3 ) 3 ) Tris platicam nitrite cum 
 
 J'| ZH 4 ; PtcO f ammona platicate. 
 
 {ZHTtc ; NO 3 ] Platicam nitrite bis platicam 
 
 (ZHTtc ; CO 2 ) 2 I = carbete cum ammona pla- 
 
 ZH 4 ; PtcO ' ticate. 
 
 90]. ZH'^^Ptc; Cl = Platic-phenylam chlora. 
 
 Q -, J 
 b 4J- j 
 
SALTS OF PLATICAM. 329 
 
 91]. ZH 2 ,C 2 H 5 ,C 6 H 3 ; Cl + 2PtcCl = Phenylic - ethylam chlora 
 
 bis platic chlora. 
 92]. ZH,C 2 H 5 ,C 2 H 5 ,C 6 H 5 ; Cl+2PtcCl = Phenylic-ethylem chlora bis 
 
 platic chlora. 
 93]. Z(C 2 H 5 ) 3 ,C 6 H 5 ; Cl -f 2PtcCl = Phenylic-ethylim chlora bis 
 
 platic chlora. 
 94]. ZH 2 ,CH 3 ,C 6 H 5 ; Cl + 2PtcCl = Phenylic-methylam chlora 
 
 bis platic chlora. 
 95]. ZCH 3 ,C 2 H 5 ,C 5 H U ,C 6 H 5 ;C1 + 2PtcCl = Zot-methyla-ethyla-amyla- 
 
 phenyla chlora bis platic 
 
 chlora. 
 
 96]. Z,(CH 3 ) 4 ,C1 + 2PtcCl = Methylom chlora bis platic chlora. 
 97]- Z(C 2 H 5 ) 4 ,C1 + 2PtcCl = Ethylom chlora bis platic chlora. 
 98]. Z(C 5 H U ) 4 ,C1 + 2PtcCl = Amylom chlora bis platic chlora. 
 -, (ZC 2 H 5 ,C 6 H 5 ; NO 2 ) Ethylic-phenylac nitrete cum 
 
 99-J* I H,Ptc 2 ; Cl 3 ] hydra platenic chlorine. 
 
 100]. ZH 2 ,C 8 H 3 ,C 6 H 5 ; Cl + 2PtcCl = Phenylic -acetylam chlora 
 
 bis platic chlora. 
 
 USUAL NAMES AND FORMUL/E OF THE SALTS OF PLATICAM. 
 70]. ZH 3 Ptc ; Cl = Platicam chlora. 
 
 This salt is produced by the action of sesquichloride of iron = FecCl, on 
 the salt No. 35] = ZH 3 Pt; Cl + ZH 2 H. See the note descriptive of 
 No. 35]. It is also produced by the action of chlorine gas on the same 
 salt: 
 
 ZH 3 Pt; Cl + ZH 2 H + Cl = ZH 3 Ptc; Cl + ZH 3 Ptc; Cl. 
 
 There are many other methods of obtaining it. It is produced when- 
 ever basic power is removed from a salt of platousam and chloric 
 power applied instead. Pt 1 then becomes Ptc 2 . Also produced by 
 boiling No. 71] with ammonia, and by acting on No. 75] with strong 
 hydrochloric acid. 
 
 Synonymes. Ammonio-bichloride of platinum = 2NH 3 ,PtCl 2 , Gmelin. 
 Bihydrochlorate of diplatinamine = N 2 H 4 pt 2 ,2HCl, Gerliardt. Ammon- 
 chlorplatammoniumchlorur = (H 4 N,PtCl,H 2 )NCl, or else 
 
 Miller quotes a hydrochlorate of diplatinamine with the formula 
 PtH 5 N 2 ,Cl. I can find no account of such a salt. Miller also quotes the 
 hydrochlorate of Gros's base, with the formula PtClH 6 N*Cl. This 
 
330 SALTS OF TLATICAM. 
 
 agrees with No. 70]. Gros's base he gives as PtClH 6 N 2 O, not isolated. 
 The nitrate of Gros's base is No. 75]. 
 
 71]. ZH 3 Ptc; Cl + PtcCl = Platicam chlora cum platic chlora. 
 
 This salt is produced by the action of chlorine on Magnus's green salt, 
 No. 34] = ZH 3 Pt ; Cl. The chloric power converts Pt l into Ptc 2 , and 
 then produces the salt No. 71]. According to Gerhardt, there is an 
 intermediate salt produced, in the form of a red crystalline power, which 
 appears to be a compound of Nos. 34] and 71]. Thus, ZH 8 Pt,Cl 
 -f- (ZH 3 Ptc; Cl + PtcCl). He calls it chloroplatinate of diplatos- 
 amine. 
 
 Gerhardt's name and formula for No. 71] are Bichlorhydro-chloro- 
 
 ( PtPPTT ) 
 platinate of diplatinamine = -j ^^ > N 2 H 4 pt 2 . Grimm's name and 
 
 formula = Ammon-chlorplatammoniumchloriir-platinchlorid = (H 4 N, 
 PtCl,H 2 )NCl + PtCl 8 . Ammonio-bichloride of platinum = NH 8 ,PtCl*, 
 Gmelin. Bi-hydrochlorate of platinamine = NJIpt 2 ,2HCl, Gerhardt. 
 Miller's name and formula are Bihydrochlorate of platinamine (Ger- 
 hardt's base) = PtH 3 N,Cl 2 . 
 
 Gerhardt makes a distinction between the products of the action of 
 chlorine gas upon solutions of the yellow and the green variety of 
 platousam chlora, No. 34] ; and hence the different names and formula 
 which I have ascribed to him. The analytical results of the different 
 products are the same ; excepting that one salt is anhydrous, and the 
 other, when dried at 120 C, retains about two per cent, of water. In 
 other respects the evidence of differences in these products is not suf- 
 ficiently clear to remove any of the difficulties that have been described 
 in the note appended to No. 34]. 
 
 72]. ZH 3 Ptc; Cl + ZH 3 Ptc; Br = Platicam chlora cum 
 
 platicam broma. 
 
 Produced by adding bromine to the salt No. 35] = ZH 3 Pt ; Cl + ZH 2 H. 
 In this case Pt l becomes Ptc 2 , bromine is assumed, and thus the salt 72] 
 is formed. It has an orange-yellow colour, and its solution gives with 
 silver-solution a precipitate containing AgCl and AgBr. 
 
 The production of this salt affords clear evidence in support of the 
 opinion which I have expressed, that in the presence of an excess of 
 chloric, bromic, or iodic power, the platous atom becomes converted into 
 platic atoms. 
 
 Synonymes. Ammonio-chlorobromide of platinum = 2NH 3 ,PtClBr, 
 Gmelin. Ammon - Bromplatammoniumchlorur = Pt(Cl,Br)N 2 H 6 = 
 (H 4 N,PtBr,H 8 )NCl, Grimm. 
 
 73]. ZHTtc; Cl 4- ZH 8 Ptc; SO 8 = Platicam chlora cum 
 
 platicam sulphete. 
 
SALTS OF PLATICAM. 331 
 
 \ Produced when the salt No. 70] is dissolved in strong sulphuric acid and 
 heated to drive oft' muriatic acid : 
 
 2(ZH 3 Ptc ; Cl) + HSO 9 = ZH 3 Ptc ; Cl + ZH 3 Ptc ; SO 2 + HC1. 
 
 It is also produced when the salt No. 75] is heated with sulphuric acid, 
 in which case nitric acid is driven off. 
 
 Synonymes. Ammonio-sulphate of oxychloride of platinum = 2NH 3 , 
 PtC10,SO 3 , Gmelin. Bichlorhydro-sulphate of diplatinamine = N 2 H 4 pt 2 , 
 S0 4 H 2 + N*H 4 pt 2 ,2ClH, Gerhardt. Gros's sulphate. Sulphate of 
 Ammon-chlorplatammoniumoxyd = (H 4 N,PtCl,H 2 )NO.SO 3 , Grimm. 
 
 74]. ZH 3 Ptc; Cl -f- ZH 3 Ptc; CO 2 = Platicam chlora cum 
 
 platiaam carbete. 
 
 Produced by adding oxalic acid to the solution of the salts Nos. 73] or 
 75], Gros. 
 
 Synonymes. Ammonio-chloroplatinous oxalate. Ammonio-oxalate of 
 oxychloride of platinum = 4NH 3 + C 4 (PtCl) 8 O 8 , Gmelin. Bichlor- 
 
 2 EL 2 O 4 ) 
 hydro-oxalate of diplatinamine = , >2N 2 H 4 pt 2 , Gerhardt. Oxalate 
 
 of Ammon-chlorplatammoniumoxyd = (H 4 N,PtCl,H 2 )NO.C 2 3 , Grimm. 
 
 75]. ZH 3 Ptc; Cl + ZH 3 Ptc ; NO 3 = Platicam chlora cum 
 
 platicam nitrite. 
 
 Produced by the action of nitric acid on the salt No. 34] Magnus's 
 green salt thus : 
 
 ZH 3 Pt ; Cl ) f ZH 3 Ptc ; Cl + ZH 3 Ptc ; NO 3 
 
 ZH 3 Pt ; Cl V = < Pt, half the platinum thrown dawn, 
 H;N0 3 ] [Hd set free, Gros. 
 
 Synonymes. Ammonio-nitrate of oxychloride of platinum = 2NH 3 , 
 PtClO,NO 5 , Gmelin. Bichlorohydro-nitrate of diplatinamine = N 2 H 4 pt 2 , 
 NH0 3 ,C1H, Gerhardt. Nitrate of Ammon-chlorplatammoniumoxyd 
 = (H 4 N,PtCl,H 2 )NO.N0 5 , Grimm. Nitrate of Gros's base = PtClH 6 N 2 O, 
 NO 5 , and also (PtCl,2H 3 N,O)NO 5 , Miller. 
 
 " Gerhardt," says Professor Miller (Elements of Chemistry, part ii., 
 1066), " views the salts of Gros as biacid salts of diplatinamine, in some 
 of which two acids are present. A serious objection to this supposition, 
 however, is afforded by the fact that Gros's hydrochlorate abandons only 
 half its chlorine when mixed with the solution of nitrate of silver. It 
 ought to give up the whole were Gerhardt's theory correct." 
 
 Professor Miller's difficulty does not exist in the facts, but in the 
 erroneous theory which guides his reasoning. If I were to ask him to 
 explain WHY nitrate of silver, acting upon the salt No. 70], ought to 
 throw down all the chlorine ? the reply would, no doubt, be, that it is, 
 or rather should be, simply a case of double decomposition. ZH 3 Ptc ; 
 
[ 
 
 PtCl NO, I PtOVNO,HO 4- PO 5 4- HO, Grimm. 
 ( 
 
 332 SALTS OF PLATICAM. 
 
 Cl + AgNO 3 = AgCl + ZH 3 Ptc ; NO 3 . That reaction does not indeed 
 take place, but the cause of the different reaction that really takes place 
 is obvious. Thus : 
 
 ZH 3 Ptc;Cl ) [ZH 3 Ptc;Cl 1 XT 
 ZH 3 Ptc; Cl I = \ ZH 3 Plc; NO 8 f JNa 75- 
 Ag;N0 3 ] 1 Ag;Cl 
 
 This reaction is precisely analogous to that which takes place in the pre- 
 paration of No. 75], by adding nitric acid to No. 34], and to that which 
 occurs in the preparation of No. 73]. When the double salt No. 75] is 
 produced, it resists decomposition by nitric acid, by nitrate of silver, and 
 even by sulphuric acid. That is the solution of the problem. 
 
 77]. ZH 3 Ptc; Cl 4. (ZH 3 Ptc) 3 P0 4 = Platicam chlora cum 
 
 platicamine phosphote. 
 
 Synonymes. Sesquichlorhydro-phosphate of diplatinamine = N 2 H 4 pt 2 , 
 P0 4 H 3 4. N*H 4 pt 2 ,ClH, Gerhardt. Phosphate of Ammon-Chlorplatam- 
 moniumoxyd and Ammon-Oxyplatammoniumoxyd 
 
 H 4 N ) [ H 4 N] 
 
 tCl 1 NO, I PtOV 
 H 2 j ( fff 
 
 Phosphate of Raewsky's base = Pt 2 ClH 12 N 4 O 5 ,P0 5 ,HO, Miller. 
 
 78]. ZH 3 Ptc; NO 3 4- ZH 3 Ptc; CO 2 = Platicam nitrite cum 
 
 platicam carbete. 
 
 A combination of nitrate of platicam with oxalate of platicam. 
 
 Synonymes. Binitro-oxalate of diplatinamine = N 2 H 4 pt 2 ,C 2 H 2 O 4 4- 
 N 2 H 4 pt 2 ,2NHO 3 
 
 fC 4 H[NHpt 2 (NH 4 )]O 8 ) Bioxalate of diplatinammonium 
 = } NHO 6 Nitric acid 
 
 I N[NHpt 2 (NH 4 )]O 6 f Nitrate of diplatinammonium 
 = 2C 2 3 ,2N0 5 ,2PtO 2 ,4NH 3 . 
 
 All these formulas are given by Gerhardt. They are striking examples 
 of the exercise of the ingenious art of giving apparent complexity to 
 things which are naturally simple. 
 
 80]. ZH 3 Ptc; HO 4. PtcHO = Platicam hydrate cum platic 
 
 hydrate. 
 
 Produced by adding an excess of ammonia to a boiling solution of 
 nitrate of platinamine No. 83]. Small brilliant yellow crystals. Caustic 
 potash does not dissolve it, nor expel ammonia from it (because caustic 
 potash and this compound are both hydrated basic radicals of the same 
 order). It readily dissolves in acids. 
 
SALTS OF PLATICAM. 333 
 
 Synonymes. Platinamine = NHpt 2 -f 2Aq, Gerhardt. Oxyplatam- 
 moniumoxydhydrate = (PtO,H 3 )NO.HO + HO, Kolbe. Platinamine 
 - NH 3 ,PtO 2 + 2Aq, Gmelin. Miller ascribes to Platinamine (Ger- 
 hardt's base) the formula PtH 3 N,O a , which in my notation would be 
 either ZH 3 PtO, or ZH 3 Ptc,PtcO; but no such compound appears to 
 have been produced. Gerhardt's Platinamine requires the formula that 
 is given to No. 80]. 
 
 81]. ZH 3 Ptc; SO* + PtcSO 2 = Platicam sulphete cum platic 
 
 sulphete. 
 
 Produced by dissolving platinamine, No. 80] in sulphuric acid. Yellow 
 powder; acid; soluble. 
 
 Synonymes. Sulphate of platinamine = NH 3 ,Pt0 2 ,2SO 3 , Gmelin. Bi- 
 sulphate of platinamine = NHpt 2 ,SO 4 H 2 , Gerhardt. 
 
 82]. ZH 3 Ptc; NO 3 + PtcNO 3 = Platicam nitrite cum platic 
 
 nitrite. 
 
 Produced by mixing nitric acid with No. 83], and evaporating. A 
 yellow powder. 
 
 Binitrate of platinamine = NH 3 ,Pt0 2 ,2N0 5 , Gmelin. Binitrate of 
 platinamine = NHpt 2 ,2HN0 3 , Gerhardt. Binitrate of platinamine = 
 PtH 3 N,0 2 ,2N0 5 , Miller. 
 
 83]. ZH 3 Ptc; NO 3 + PtcHO + HHO (dried at I2OC) = Platicam 
 nitrite cum platic hydrate aquate. 
 
 Produced by boiling the chloride No. 71] with nitrate of silver, until the 
 chlorine is wholly abstracted by the silver. 
 
 Synonymes. Neutral nitrate of platinamine = NHpt 2 ,NHO 3 -f- 2 aq, 
 Gerhardt. Ammonio-nitrate of platinic oxide = NH 3 ,PtO 2 ,NO 5 4- 3 aq, 
 Gmelin. Nitrate of Oxyplatammoniumoxyd = (PtO,H 8 )N O.NO*-f 3HO, 
 Grimm. Neutral nitrate of platinamine = PtH 3 N,0 2 ,N0 5 3HO, Miller. 
 
 Q -, JZH 3 Ptc; CO 2 ) t _ Platicarn carbete cum platic 
 1 ' 1 Ptc ; HO j ~ hydrate demi-aquate. 
 
 Produced by adding oxalate of ammonia to No. 8 3]. Yellow crystals 
 which explode when heated. This is Gerhardt's neutral oxalate of pla- 
 tinamine = C 2 H 2 4 ,2NHpt 2 -f 3Aq. 
 
 [Query DOES PLATICCEM OCCUR AS A RADICAL AMONG THE PLATINUM 
 
 SALTS ? 
 
 PLATICCEM is the vice-ammon = ZH 2 Ptc 2 , produced by replacing H 2 
 in ammonium by two platic atoms. The five salts Nos. 80] to 84] can 
 IKJ conveniently formulated with such a radical. Thus : 
 
 No. 80 = ZHTtc 2 ; HO + Aq. Platiccem hydrate aquate. 
 
334 SALTS OF PLATICAM. 
 
 8 1 = ZH 2 Ptc 8 ; SO 8 -I- HSO 2 . Platiccem sulphete cum 
 
 hydra sulphete. 
 
 82 = ZH 2 Ptc 2 ;NO 3 +HN0 3 . Platiccem nitrite cum 
 
 hydra nitrite. 
 
 83 = ZH 2 Ptc 8 ; NO 3 + Aq 2 . Platiccem nitrite aquete. 
 
 84 = ZH*Ptc 2 ; CO 2 -f iAq. Platiccem carbete sesquiaquate. 
 
 These are the principal salts of the series to which Gerhardt ascribes his 
 " platinamine," which may hereafter be proved to beplaticcem, although 
 our present information is not conclusive on that point.] 
 
 (ZH 3 Ptc;Cl ) Platicam chlora bis platicam 
 85]. <(ZH 3 Ptc; NO 3 ) 2 > = nitrite cum ammona pla- 
 [ZH 4 ;PtcO j ticate. 
 
 Produced by the action of concentrated nitric acid on Magnus's green 
 salt, No. 34], Raewsky, whose formula is 4NH 3 ,Pt 2 ClO 5 ,2N0 5 . Pro- 
 duced by the action of nitrate of silver upon the salt No. 70]. Brilliant 
 yellow small hard rhombic crystals, which explode when heated. 
 
 The property of exploding when heated is apparently concurrent with 
 the presence of the compound ZH 4 ; PtcO. The salts which, in com- 
 bination with ZH 4 ; PtcO, compose the compounds Nos. 85 to 89, that 
 is to say, the chloride, nitrate, carbonate, and oxalate of platicam, do 
 not seem to be explosive either when isolated or when combined in 
 pairs, provided the salt ZH 4 ; PtcO is absent. But when this salt 
 forms part of a compound, the compound is explosive. It is on account 
 of this peculiarity that I prefer the formula ZH 4 ; PtcO to the formula 
 ZH 3 Ptc ; HO, which would make the several salts appear as basic salts. 
 But the formulae of these salts, as given by different chemists, are by no 
 means concurrent even as regards the ultimate constituents of the salts, 
 and while uncertainty prevails on that score, no satisfactory analytical 
 formulae can be written. 
 
 Synonymes. Ammonio-binitrate of oxy chloride of platinum, Gmelin. 
 Sesquichlorhydronitrate of diplatinamine = N 2 H 4 pt 2 ,2NHO 3 -f- N 2 H 4 pt 2 , 
 C1H, Gerhardt. Double Nitrate of Ammon-Chlorplatammoniumoxyd 
 and Ammon - Oxyplatammoniumoxyd = (H 4 N,PtCl,H 2 )NO.NO 5 + 
 (H*N,PtO,H 2 )NO.NO 5 -f HO, Grimm. Binitrate of Raewsky's base 
 = Pt 2 ClH 12 N 4 O 5 ,2N0 5 , Miller. 
 
 f ZHTtc ; Cl ] Platicam chlora cum platic- 
 86]. < (ZH 3 Ptc) 2 ; CO 3 V = amen carbite cum ammona 
 [ ZH 4 ; PtcO J platicate. 
 
 Synonymes. Raewsky's ammonio-carbonate of oxychloride of pla- 
 tinum = 4NH 8 ,Pt 2 ClO\2C0 2 , Gmelin. Sesquichlorhydro-carbonate of 
 diplatinamine = N 2 H 4 pt 2 ,CO 3 H 2 + N 2 H 4 pt 2 ,ClH + Aq, Gerhardt. Car- 
 
SALTS OF PLATICAM. 335 
 
 bonate of ammon-chlorplatammoniumoxyd and of ammon-oxyplatammo- 
 niumoxyd = (H 4 N,PtCl,H 2 )NO.CO 2 + (H 4 N,PtO,H 2 )NO.C0 2 4. HO, 
 Grimm. 
 
 3 3 Ptc ; NO 3 ) _ Platicam nitrite cum ammona 
 
 I 4 ; PtcO j = platicate. 
 
 Synonymes. Ammonio-nitrate of platinic-oxide = 2NH 3 ,Pt0 2 ,NO 5 
 4- Aq, Gmelin. Neutral nitrate of diplatinamine = N 2 H 4 pt 8 ,NH0 3 -f Aq, 
 Gerhardt. Neutral nitrate of ammon-oxyplatammoniumoxyd = (H 4 N, 
 PtO,H 2 )NO.N0 5 4 HO, Grimm. Neutral nitrate of diplatinamine 
 = PtH 6 N 2 2 ,NO 5 ,HO, Miller. 
 
 fift -, l(ZH 3 Ptc; NO 3 ) 3 ) _ Tris platicam nitrite cum 
 -J* { ZH 4 ; PtcO j = ammona platicate. 
 
 Synonymes. Ammonio-sesquinitrate of platinic oxide = 4NH 3 ,2Pt0 2 , 
 3 NO 5 4- Aq, Gmelin. Sesquinitrate of diplatinamine = 2N 2 H 4 pt 2 , 
 3NHO 3 + Aq, Gerhardt. Neutral nitrate of ammon-oxyplatammonium- 
 oxyd = (H 4 N,PtO,H 2 )NO.N0 5 4 HO, Grimm. Sesquinitrate of di- 
 platinamine = 2(PtH 6 N 2 O*),3N0 5 ,HO, Miller. 
 
 f ZH 3 Ptc ; NO 3 ) Platicam nitrite bis platicam 
 89]. ^(ZH 3 Ptc; CO 2 ) 2 1 = carbete cum ammona pla- 
 lZH 4 ;PtcO J ticate. 
 
 Synonymes. Sesquinitro-oxalate of diplatinamine 
 
 (C 4 H[NHpt 2 (NH 4 )]0 8 ) Bioxalate of diplatinammonium 
 = { \ + 2 aq. 
 
 [ N[NHpt 2 (NH 4 )]0 6 J Nitrate of diplatinammonium 
 
 = 2C 2 3 ,NO 5 ,2PtO a ,4NH 3 ,HO, Gerhardt. Compare this formula with 
 that quoted in the note to No. 78]. Grimm "calls this compound 
 Oanlate of ammon-oxyplatammoniumoxyd with nitric acid 
 
 /H 4 N) v 
 
 = 2 (PtO \ NO.C 2 3 ) 4 HO. NO 5 . 
 H J / 
 
 Grimm quotes the following as Gerhardt's formula? : 
 
 JC 4 H 2 O 8 .N 2 H 4 pt 2 l 
 \NH0 6 . N 2 H 4 pt 2 j " 
 
 90]. ZH 2 ,C 6 H 5 ,Ptc ; Cl = Platic-phenylam chlora. 
 
 A rose-red salt, discovered by Kaewsky. Formula quoted by Hofmann: 
 2(C 12 H 7 N),PtCl 2 . This salt is said to be produced by acting upon 
 
336 SALTS OF PLATICAM. 
 
 No. 67] with hydrochloric acid ; but other compounds must be formed 
 simultaneously, because this statement leaves H -}- Ptc unaccounted for. 
 
 91]. ZH 2 ,C 2 H 5 ,C 6 H 5 ; Cl + 2PtcCl = Phenylic-ethylam chlora 
 
 bis platic chlora. 
 
 Synonyme Ethylaniline-platinchloride = C 12 5 } N,HC1 -f PtCl 2 , 
 
 Hofmann. Chlorplatin-salzsaures vinanilin = C^NH'SHCl + PtCl 2 , 
 Ghnelin. 
 
 92]. ZH,C 2 H 5 ,C 2 H 5 ,C 6 H 5 ; Cl + 2PtcCl = Pheny lie-ethyl em chlora 
 
 bis platic chlora. 
 
 Synonymes. Biethylaniline-platinchloride = C 20 H 15 N.HCl.PtCl 2 , Hof- 
 mann. Chlorplatin-salzsaures bivinanilin = C^NH^HCl + PtCl 4 , Gmelin. 
 
 93]. Z(C 2 H 5 ) 3 ,C 6 H 5 ; Cl + 2PtcCl = Phenylic-ethylim chlora bis 
 
 platic chlora. 
 
 Synonymes. Chlorplatin-salzsaures trivinanilin = C 24 NH 19 ,HC1 -f- PtCl 2 
 (equal to Hofmann's C l2 H 5 (C 4 H 5 ) 3 NCl,PtCl 2 ), Gmelin. 
 
 94]. ZH*,CH 3 ,C 6 H 5 ; Cl + 2PtcCl = Phenylic-methylam chlora bis 
 
 platic chlora. 
 
 Synonymes. Methylaniline - platinchloride = C 12 (H 6 ,C 2 H 3 )N,HC1 + 
 PtCl 2 , Hofmann. 
 
 95]. ZCH 3 ,C 2 H 5 ,C 5 H 11 ,C 6 H 5 ;C1+ 2PtcCl = Zot-methyla-ethyla- 
 amyla-phenyla chlora bis platic chlora. 
 
 Synonyme. The platinum-salt of methylethylamylphenylammonium 
 
 = C 28 H S4 NCl,PtCl 2 
 
 C 2 H 3 
 
 C 4 H 5 
 C io H u 
 
 NCl,PtCl 2 , Hofmann. 
 
 C 12 H J 
 96]. Z(CH 3 ) 4 ,C1 -f 2PtcCl = Methylom chlora bis platic chlora. 
 
 Synonyme. The hydrochlorate of tetramethylammonium combined 
 with bichloride of platinum 
 
 cm 3 ) 
 
 = C"H 12 NCl,PtCl 2 = 
 
 C 2 H 8 
 C 2 H 3 
 C 2 H 3 J 
 
 1 NCl,PtCl 2 , Hofmann. 
 
SALTS OF PLATICAM. 337 
 
 97]. Z(C 2 H 5 ) 4 ; Cl 4- 2PtcCl = E thy lorn chlora bis platic chlora. 
 Synonyme. The platinum-salt of tetrethylammonium 
 
 C 4 H 5 
 C 4 H 5 
 
 C 16 H 20 NCl,PtCl 2 = 
 
 C 4 H 5 
 C 4 H 5 
 
 NCl,PtCl 2 , Hofmann. 
 
 98]. Z(C 5 H n ) 4 ; Cl + 2PtcCl = Amylom chlora bis platic chlora. 
 Synonyme. The platinum-salt of tetramylammonium 
 
 C 10 H U 
 
 C 10 H n 
 C io H u 
 
 C 10 H 11 
 
 NCl,PtCl 2 , Hofmann. 
 
 -, (ZC 2 H 5 ,C 6 H 3 ;N0 2 ) _ Ethylic-phenylac nitrete cum 
 99J- \ H, Ptc 2 ; Cl 3 j = hydra platenic chlorine. 
 
 Synonyme. Ethylnitranilm-platinchloride 
 
 f H5 1 
 = C 12 { NO 4 I N,HC1 + PtCl 2 , Hofmann. 
 
 Dr. Hofmann's " nitraniline " theory is discussed at page 288. The pos- 
 sibility of the existence of such an ammonium as is here represented, is 
 inadmissible : 
 
 r IP ) 
 
 P I NO 4 I N,H. 
 I C 4 H 5 j 
 
 i oo]. ZH 2 ,C 2 H 3 ,C 6 H 5 ;Cl 
 
 = Phenylic-acetylam chlora bis 
 platic chlora. 
 
 Synonyme. Chloroplatinate of phenyl - acetosamine = C*HYC 1S H 5 ) 
 N,HCl,PtCl 2 , Gerhardt. 
 
( 338 ) 
 
 The Urea Theory. 
 
 NON-PERMANENT CYANATE OF AMMONIA. When the vapour of 
 hydrated cyanic acid (= H,CyO) is passed into dry ammonia gas 
 ( = ZH 2 ,H), we obtain a white voluminous crystalline powder, which 
 chemists in general agree in calling CYANATE OF AMMONIA, and the 
 composition of which is stated to be H 4 NO,C*NO ( = ZH 4 ,CyO). This 
 powder is very soluble in water, and its cold solution, when freshly 
 prepared, has the following properties : 
 
 1. It disengages ammonia on the addition of a cold solution of caustic 
 potash : ZH 4 CyO + KHO = ZH 2 H + KCyO + HHO. 
 
 2. When treated with acids, it gives off cyanic acid (a) and carbonic 
 acid (6). 
 
 (a). ZH 4 ,CNO + H,S0 2 = ZH 4 ,S0 2 + H,CNO. 
 (6). ZH 4 ,CNO + H,HO ) J 2 (ZH 4 ,S0 2 ) 
 H,SO* + H,S0 2 j : 1 c 8 
 
 The first reaction is simply a case of double decomposition between 
 the cyanate of ammonia and the hydrated sulphuric acid. The seeond 
 reaction is owing to the circumstance, that hydrated cyanic acid is 
 readily decomposable by water into carbonic acid and ammonia : 
 
 H,CNO + H,HO = ZH 2 ,H + CO 2 . 
 
 This transformation is accelerated when a strong acid is present, which 
 can take up the ammonia and expel the carbonic acid as gas : 
 
 ZH*,H + HSO 8 = ZH 4 ,S0 2 . 
 
 In equation (&), these two reactions are represented as occurring 
 simultaneously. 
 
 PERMANENT CYANATE OF AMMONIA. When the solution of cyanate 
 of ammonia has been prepared two or three days ; or when, soon after 
 being prepared, it is either boiled or gently evaporated to the crystal- 
 lising point ; or when the white powder, described above, is exposed for 
 some days to the air, or is slightly fused, before being brought into 
 solution; then the resulting solution is found to contain a substance 
 which is possessed of other properties than those above described, and 
 this substance has received from chemists the name of UREA with the 
 clump formula C 2 H 4 N 2 O 2 ( = CH 4 N 2 O) and sometime that of CARBAMIDE, 
 first with the formula NH 8 + CO, and latterly with the formula 
 
 C 2 2 ) 
 
 H 2 }N 2 ( = ZH 2 ,ZH 2 ,CO). 
 H' 
 
THE UREA THEORY. 339 
 
 Berzelius represented it as a conjugated ammonia compound, having the 
 formula NH 3 ,C 2 HNO 2 , to which he gave the name of urenoxyd-ammonia ; 
 but this notion has not been adopted by other chemists. 
 
 UREA THEORY. Before I enter upon the examination of the proper- 
 ties that are said to distinguish Urea from the non-permanent Cyanate 
 of Ammonia, I may state that I consider the composition of the two 
 substances to bear to one another the same relation as that which is 
 borne by the gaseous salts of ammonia to the solid salts of ammonium. 
 See page 197. The non-permanent cyanate of ammonia, which is pro- 
 duced by the action of hydrated cyanic acid upon gaseous ammonia, 
 is a double salt, constituted in accordance with the formula ZH 2 , 
 H -f- H,CyO, while the permanent salt, into which it so soon changes, 
 is the true cyanate of ammonium, constituted according to the formula 
 ZH 4 ,CyO. The names of the two substances should be, in agree- 
 ment with this idea, as follow : 
 
 ZH 2 ,H + H,CyO = Amida hydra cum hydra cyanate. 
 ZH*,CyO = Ammona cyanate. 
 
 The supposition that urea should be esteemed to be carbamide 
 = ZH 2 ,ZH 2 ,CO, is not well sustained by facts, as I have shown in the 
 preceding pages, particularly in the arguments respecting the Nitriles, 
 page 217; Carbamide, page 221; the Imides, page 222; Anilo-urea 
 and Carbanilide, page 298, and in treating of various other compounds 
 of minor importance. 
 
 CHEMICAL EEACTIONS OF UREA. I proceed to show that the best- 
 known chemical reactions of Normal Urea (No. i in the table of 
 examples at page 349), and the Compound Ureas (Nos. 2 to 18), 
 justify the theory which is now advanced. 
 
 I. " Neither cyanic acid nor ammonia can be discovered in urea, but 
 if a solution containing a mixture of nitrate of silver and urea be boiled 
 for some time, it is partly resolved into cyanate of silver and nitrate of 
 ammonia." Miller (Elements of Chemistry, iii. 609). 
 
 This argument and illustration are ill-adjusted to one another. The 
 decomposition, when completed, is as follows : 
 
 ZH 4 ,CyO + Ag,NO 3 = ZH 4 ,N0 3 + Ag,CyO. 
 
 If urea is converted by nitrate of silver into cyanate of silver and nitrate 
 of ammonia, however slowly the operation proceeds, surely there is a 
 "discovery," both of cyanic acid and of ammonia in that salt, for 
 neither of these compounds are contained in the nitrate of silver. 
 Besides, we are told by Liebig and Wohler, that if the mixture of the 
 two salts is evaporated to dryness, the transformation is perfect. 
 Hence the opinion, so frequently expressed by chemists, that " neither 
 cyanic acid nor ammonia can be discovered in urea," is unwarranted by 
 experimental facts. 
 
 2 2 
 
340 THE UREA THEORY. 
 
 2. A cold solution of urea mixed with a cold solution of caustic 
 potash does not liberate ammonia. This is the experiment which 
 distinguishes urea from the non-permanent cyanate of ammonia, which, 
 under these circumstances, gives off ammonia. But it is a prodigious 
 jump from this characteristic (which is explained at page 342) to the 
 statement that " ammonia cannot be discovered in urea." 
 
 3. A complete decomposition of urea occurs when it is fused with 
 hydrate of potash ; the products being carbonate of potash and gaseous 
 ammonia : 
 
 ZH 4 ,CNO) fKK,C0 3 = Carbonate of potash. 
 K,HOl = 
 K,HOJ 
 
 Here the potassium carries off the carbon and oxygen, while the nitrogen 
 produces amids, and ultimately ammonias, with the hydrogen. 
 
 4. One atom of permanent cyanate of ammonia (urea) heated in a 
 sealed tube, with two atoms of water, produces one atom of carbonate 
 of ammonia : 
 
 ZH 4 ,CNO -f HHO,HHO = ZH 4 ,ZH 4 ; CO 3 . 
 
 At pages 219 and 220 I have fully explained the theory of this 
 reaction. 
 
 5. When urea is fused, it gives off ammonia gas, and leaves cyanuric 
 acid : 
 
 ZH 4 ,CyO = ZH 2 ,H + H,CylO. 
 
 When the heat is increased, the cyanuric acid volatilises as cyanic acid. 
 If this meets in the apparatus with gaseous ammonia, it again produces 
 the non-permanent variety of cyanate of ammonia = ZH 2 ,H -f- H,CyO, 
 in the form of a white powder. This is often referred to as being a 
 sublimate of undecomposed urea. Of course, it is readily inconvertible 
 into urea by the usual processes. 
 
 6. Chlorine, when transmitted into an aqueous solution of urea, 
 resolves the latter into carbonic acid and nitrogen, whilst hydrochloric 
 acid is formed : 
 
 ZH 4 ,CNO + HHO + 6C1 = CO 2 + 2N + 6HC1. 
 
 In this case the nitrogen is set free, in accordance with the observation 
 that was made at page 219, that ammoniums are only produced when 
 there are present, not only sufficient basic radicals to constitute the am- 
 monium, but also negative radicals with which the ammoniums can 
 instantly combine. It is true that water is present in this case, and 
 might be supposed able to supply the requisite hydrogen, but there is no 
 means of escape provided for the oxygen. 
 
 3. According to Wurtz, dry chlorine gas, passed through melted 
 
THE UREA THEORY. 341 
 
 urea, forms cyanuric acid, sal-ammoniac, hydrochloric acid, and nitrogen. 
 This decomposition may be represented in an equation, thus : 
 
 2(ZH 4 ,CyO)) (2(H,CylO) + ZH 4 C1. 
 
 3 C1 S :: l2(HCl ) + N. 
 
 8. Urea boiled with excess of oil of vitriol is completely resolved into 
 carbonic acid gas and sulphate of ammonia (Dumas) : 
 
 ZH 4 ,CNO 1 J2(ZH 4 ,SO 2 ) 
 
 2(HS0 2 ) + HHO( ; | CO 2 . 
 
 The cyanate of potash suffers decomposition in a similar manner. See 
 Reaction 4, page 22O. This comparative experiment proves that the 
 C and N of the cyanates can be separated from one another by an acid, 
 under production of carbonic acid gas. 
 
 9. According to Millon, one atom of urea decomposed by two atoms 
 of nitrous acid, produces carbonic acid, nitrogen, and water : 
 
 ZH 4 ,CNO] (CO 2 
 H,N0 2 l = <UN 
 H,NO 2 j ( 3 HHO 
 
 10. According to Williamson, when oxamide is heated with oxide 
 of mercury, the products are mercury, carbonic acid, and urea : 
 
 2(ZH 2 ,CO) + HgcHgcO = HgcHgc + CO 2 + ZH 4 ,CNO. 
 
 Oxamide. Urea. 
 
 11. Oxamide, passed in the state of vapour through a glass tube 
 heated to redness, yields, among other products, a large quantity of 
 urea : 
 
 ZH 2 ,CO + ZH 8 ,CO = ZH 4 ,CNO + CO. 
 
 Oxamide, 2 atoms. Urea. Carbonic oxide. 
 
 12. When carbonic ether is heated in a sealed tube, with an alcoholic 
 solution of ammonia, the excess of ammonia slowly converts the carbonic 
 ether into alcohol and urea. Natanson. 
 
 Carbonic ether = C 2 H 5 ,C 2 H 5 ; C0 a l Ir, T^ TT 
 
 A i r7TT4 TT-s/-J ZH .GNU = urea. 
 
 Ammonia in I ZH : CHO> = < / T r ^9TTn/-v\i AT 11 
 
 alcohol {zH<;C'H'OJ |(H,C'H'0)' = Alcohol. 
 
 SUMMARY OP THE EVIDENCE. The question to be answered is, 
 ought urea to be considered as carbamide = ZH 2 ,ZH 2 ,CO, or as cyanate 
 of ammonia = ZH 4 ,CNO ? It is needless to ask if it corresponds to the 
 clump formula CH 4 N 2 O, because that formula is confessedly a declara- 
 tion of ignorance of any form of proximate constitution. The decision, 
 then, lies between carbamide and cyanate of ammonia, and that decision 
 
342 THE UREA THEORY. 
 
 depends in a great measure upon considerations which I have fully 
 discussed in other parts of this work, and to which I have already asked 
 the reader to refer. 
 
 The main argument urged in favour of the carbamide theory, is, 
 that urea readily produces carbonic acid and ammonia when it is heated 
 with hydrated alkalies and strong acids. But that argument was 
 certainly not based upon a full consideration of the character of the 
 azotic radicals, and of the transmigrations which azote undergoes under 
 the pressure of different chemical forces. These transmigrations I have 
 traced in great detail, and I may say that it is demonstrated, that a 
 cyanate can give off carbonic acid as readily as if it contained carbonic 
 oxide or even carbonic acid ready formed, provided you supply the 
 radicals that are necessary to occupy the azote which the cyanate 
 liberates when it gives off the carbonic acid. It is simply a question 
 of the balance of the powers which are brought into simultaneous 
 operation. 
 
 Then, in regard to the disengagement of ammonia, we find that a cold 
 solution of an alkali does not liberate it, but that a hot solution liberates 
 it, and that fusion of the mixed salts in the dry state liberates it. A 
 corresponding action has been described in the treatment of isatine with 
 caustic potash. See page 261. In that case a cold solution of KHO 
 has this reaction : ZH 2 -f KHO = ZHK + HHO ; while a hot solution 
 has this reaction : ZH 2 -f KHO = ZH 3 KO. Applying this illustration 
 to urea, we may imagine that the mixture ZH 4 ,CyO -f- KHO (cold) pro- 
 duces ZH 3 K,CyO -f- HHO, in which case no ammonia is expelled ; but 
 that when KHO (hot) is applied, the reaction becomes ZH*,CyO -j- KHO 
 = KCyO + ZH 4 ,HO( = ZH 2 ,H + H,HO), which, of course, disengages 
 ammonia. In the presence of an excess of potash, the reaction does not 
 end here, but, as is shown by reaction 3, the cyanogen is next decom- 
 posed, and the final results of the decomposition of the urea are ammonia 
 and carbonate of potash. 
 
 To enter farther into details would be only to repeat what I have said 
 in the sections to which I have made reference. Briefly, I may 
 conclude, that every one of the reactions of urea agrees with the theory, 
 that its true constitution is that of cyanate of ammonia = ZH 4 ,CyO. 
 The notion that it is carbamide = ZH i ,ZH i! ,CO, is discordant with the 
 whole series of facts that have been disclosed in the course of this 
 investigation of the theory of the azotic radicals. 
 
( 343 ) 
 
 Examples of Ureas. 
 
 NORMAL UREA. 
 
 1. ZH 4 ; CyO . . . Ammona cyanate. 
 
 COMPOUND UREAS. Group A. 
 
 2. ZH 3 ,CH 3 ; CyO . . . Methylam cyanate. 
 
 3. ZH 3 ,C 2 H 5 ; CyO . . . Ethylam cyanate. 
 
 4. ZH 3 ,C 3 H 5 ; CyO . . . Allylam cyanate. 
 
 5. ZH 3 ,C 5 H U ; CyO . . . Amylam cyanate. 
 
 6. ZH 3 ,C 6 H 5 ; CyO . . . Phenylara cyanate. 
 
 7. ZH 3 ,C 7 H 7 ; CyO . . . Toluenylam cyanate. 
 
 8. ZH 3 ,C 10 H 7 ; CyO . . . Naphty lam cyanate. 
 
 COMPOUND UREAS. Group B. 
 
 9. ZH 2 (C H 3 ) 2 ; CyO . . . Methylem cyanate. 
 
 10. ZH 2 (C 2 H 5 ) 2 ; CyO . . . Ethylem cyanate. 
 
 11. ZH 2 (C 5 H 11 ) 2 ; CyO . . . Amylem cyanate. 
 
 12. ZH 2 (C 3 H 5 ) 2 ; CyO . . . Allylem cyanate. 
 
 13. ZH 2 (C 6 H 5 ) 2 ; CyO . . . Phenylem cyanate. 
 
 14. ZH 2 (C 10 H 7 ) 2 ; CyO . . . Naphtylem cyanate. 
 
 COMPOUND UREAS. Group C. 
 
 1 5. ZH 8 ,C H 3 ,C 2 H 5 ; CyO . . Methylic-ethylam cyanate. 
 
 1 6. ZH 2 ,C 2 H 5 ,C 5 H U ; CyO . . Ethylic-amylam cyanate. 
 
 17. ZH 2 ,C 2 H 5 ,C 6 H 5 ; CyO . . Ethylic-phenylam cyanate. 
 
 COMPOUND UREAS. Group D. 
 
 1 8. Z(C 2 H 5 ) 4 ; CyO . . , . E thy lorn cyanate. 
 
 SALTS OF UREA. 
 
 19. ZH 4 ,CyO + HNO 3 . . . Ammona cyanate cum hydra 
 
 nitrite. 
 
 20. ZH 4 ,CyO + AgNO 3 . . Ammona cyanate cum argenta 
 
 nitrite. 
 
 21. ZH 4 ,CyO + 2 AgNO 3 . . Ammona cyanate bis argenta 
 
 nitrite. 
 
 22. ZH 4 ,CyO -f HCO 2 . . . Ammona cyanate cum hydra 
 
 carbete. 
 
344 THEORY OF COMPOUND UREAS. 
 
 23. ZH 4 ,CyO -f HCyO . . . Ammona cyanate cum hydra 
 
 cyanate. 
 
 24. ZH 4 ,CyO -f- NaCl . . . Ammona cyanate cum natra 
 
 chlora. 
 
 25. H,CyO + HC1 . . . Hydra cyanate cum hydra 
 
 chlora. 
 
 26. ZH 3 ,CH 3 ; CyO + HNO 3 . Methylam cyanate cum hydra 
 
 nitrite. 
 
 27. ZH 3 ,C 6 H 5 ; CyO + AgNO 3 Pheriylam cyauate cum ar- 
 
 genta nitrite. 
 
 THEORY OF COMPOUND UREAS. 
 
 The Compound Ureas differ from Normal Urea precisely to the same 
 extent that all the salts of vice-ammoniums differ from the corresponding 
 salts of normal ammonium, namely, by the replacement of H l , H 2 , H 8 , 
 or H* of the ammonium by an equal number of equivalents of compound 
 radicals. The compound ureas are, therefore, in all probability, con- 
 structed in the same manner as normal urea, so that if the latter is to be 
 considered as a cyanate of ammonium, the former must be considered as 
 cyanates of vice-ammoniums. If it were in accordance with discovered 
 facts to consider normal urea as carbamide, it would be equally in 
 accordance with facts to represent the compound ureas as compound car- 
 bamides. This representation is, in fact, made by many chemists, and 
 I have quoted, between pages 298 and 301, the arguments by means of 
 which one of the most distinguished investigators of organic bases has 
 endeavoured to fix the character of carbamides upon the two salts that 
 are numbered 6 and 13 in the above Table. I have examined the 
 bearings of his arguments, and pointed out their weakness, and I have 
 drawn from that examination the conclusion, that the doctrine of car- 
 bamides is invalid, and that the chemical reactions of the two compounds 
 in question, demonstrate that they are undoubtedly cyanates of vice- 
 ammoniums. Dr. Hofmann, as I have shown, decides in favour of the 
 carbamide theory. Gerhardt admits that " as it is possible to represent 
 ordinary urea as a cyanate of ammonia, it is evident that compound 
 ureas can. be equally expressed by similar rational formulae;" but he 
 decides in favour of the " type ammonia," and gives to the ureas a series 
 of formula of which the following are examples : 
 
 {CO 
 < 
 
 Ethylamyl-urea . 1 _ 
 No. 1 6 in the Table f 
 
 CO 
 C 8 H 5 
 C 5 H" 
 
 H 2 
 
THEORY OF COMPOUND UREAS. 345 
 
 In these formulae C = 12, O = i6, and the symbol CO signifies an 
 oxidised radical, which Gerhardt calls carlonyle, and which he considers 
 to be the equivalent of H 2 . These formulas represent, therefore, a double 
 atom of ammonia, and neither a cyanate nor a carbamide. It is needless 
 to discuss this proposal, because I have explained, at page 233, the phi- 
 losophy, or rather the phantasy, of the ammonia type. 
 
 USUAL NAMES, FORMULAE, DERIVATIONS, &c., OF THE COMPOUND 
 UREAS. It would be a waste of time to go over the compound ureas, 
 one by one, and recite at length and examine critically the names, 
 formulae, and theories, that have been attached by different chemists to 
 each of them. A glance at the Table from No. 2 to No. 18, shows the 
 relative compositions of these salts, and how completely they all agree 
 with the two propositions, that they are cyanates, and that they contain 
 vice-ammoniums. In Group A, we have ammonams ; in Groups B and C 
 we have ammonems ; in Group D an ammonom. I shall quote a few 
 of the common names and formulae, in order to identify the compounds, 
 and refer to some of their modes of derivation and their characteristic 
 reactions ; but I assume, once for all, that I am speaking of cyanates of 
 vice-ammoniums, and I shall only quote other formulae to explain the 
 views of other chemists. 
 
 GROUP A. Nos. 2 to 8. Cyanates of Ammonams. 
 2. Methyl-urea = H 3 (C 2 H 3 )N 2 C 2 2 , Miller. 
 
 He describes it as being derived from methyl-cyanic ether (see No. 43 1 , 
 page 250,) and ammonia, thus : C 2 H 3 0,C 2 NO -f- H 3 N, and as being a 
 urea in which the place of one equivalent of hydrogen has been supplied 
 by one equivalent of the radical of the ether. Thus : 
 
 Ordinary urea = H'( H)NVO'| From hydrated cyanic acid 
 v ' ( and ammonia. 
 
 Methvl-urea = H 3 (C 2 H 3 )N 2 C 2 2 { Fram , me % lc y anic ether 
 ' I and ammonia. 
 
 It is evident, that this is a reaction, in which the cyanate of a compound 
 hydrocarbon is converted into the cyanate of an ammonam, by the 
 assumption of ammonia, thus : 
 
 ZH 2 H + CH 3 ,CyO = ZH 3 ,CH 3 ; CyO. 
 Gmelin gives the following formulae for methyl-urea : 
 
 C 4 H 6 N 2 O* = C 2 H 2 ,C 2 H 4 N 2 2 = 
 
 Gerhardt' s formula on the ammonia type I have quoted above from 
 vol. 4 of his Traitt. In vol. I he gives these two formulae : 
 
346 THEORY OF COMPOUND UREAS. 
 
 C 4 H 6 N 2 8 = N '' in which C = 6 ' = 
 
 The last of these formulae is formed on the model of water, in which one 
 of the atoms of hydrogen is assumed to be replaced by methyl, and the 
 other by the very strange compound NCyH 3 , which he calls cyanammo- 
 nium, a thing which exists only in symbols. 
 
 The examples Nos. 3 to 8 I may pass over without further notice, as 
 their usual names and formula? would be parallel to those of methyl-urea, 
 and exhibit the same crudeness. No. 6 is described at page 298!! 
 
 GROUP B. Nos. 9 to 14. Cyanates of Ammonems. 
 
 When the cyanates of basic radicals are placed in contact with water, 
 they evolve carbonic acid and produce cyanates of ammonems. Thus : 
 
 Methyla cyanate 1 _ JCH 3 ,CNO] fZH 2 ,CH 3 ,CH 3 ; CNO = No. 9. 
 No. 431, p. 250} ~ \CH 3 ,CNOl = \ CO 2 
 
 H,HOJ ( 
 
 The salts Nos. 10, n, and 12, are produced in the same way. 
 No. 13 has been fully discussed as No. 90 of the aniline series. No. 14 
 is produced by the action of heat on the oxalate of naphtylamine 
 ( = ZH 3 ,C'H 7 ; CO 2 = naphtylam carbete). Usual names : No. 9, Di- 
 methyl-urea. No. 10, Diethyl-urea. No. u, Diamyl-urea. No. 12, 
 Diallyl-urea ; diacryl-urea ; sinapoline. No. 13, Diphenyl-urea ; flavine; 
 and carbanilide. No. 14, Dinaphtyl-carbamide, or naphtalidamic carba- 
 mide. I will notice the usual formulae for one salt only, No. 13. Hof- 
 mann's formula I have quoted at page 300 : 
 
 Gerhardt's (vol. i) 
 
 ( CO 
 Gerhardt's (vol. 4) = C 13 H 12 N 8 O = N*j(C*H 
 
 Miller's = C^H'^O 2 = 2(C 12 H 5 )N 2 . 
 
 H'j 
 
 From these specimens it will be seen that while Hofmann advocates the 
 carbamide theory, Gerhardt first proposes the model of water, and then 
 the ammonia type, and that in the last form he is followed by Miller. 
 
 GROUP C. Nos. 15 to 17. Cyanates of Ammonems. 
 
 These salts differ from those in Group B merely by containing two 
 different compound radicals instead of two equivalents of the same com- 
 pound radical. Usual formulae for Ethyl-methyl-urea, No. 1 5 : 
 
SALTS OF UREA. 347 
 
 Gerhardt's (vol. i) = 
 
 Gerhardt's (vol. 4.) = C 4 H'N 2 O = N 2 
 
 CO 
 CH 3 
 C 2 H 5 
 H 2 
 C 2 2 
 
 Miller's = C 8 H'N 2 O 2 = 
 
 C 4 H 5 
 
 C 2 H 3 
 
 H 2 
 
 N 2 = 
 
 C 6 H 9 N, ) 
 HO,CyOj 
 
 Here, restricting ourselves to two authors, we have, first, the clump for- 
 mula, that innocent thing which resembles a direction-post with the 
 inscription rubbed out, and which does not send us astray only because 
 it does not tell us to go anywhere; secondly, we have the model of 
 water ; thirdly, the ammonia type ; to both of which I have given else- 
 where their proper modicum of praise ; and fourthly, we have a binary 
 formula, which assumes the salt to consist of hydrated cyanic acid, in 
 combination with the ammonia called methyl-ethylamine ( = methylac 
 ethyla, No. 27, page 200). The objection which I have to make to 
 this last formula is, that it represents an extreme improbability ; for the 
 amidogen salt ZH,CH 3 ; C 2 H 5 , put in contact with the hydrated acid 
 H,CyO, would produce the ammonium salt ZH 2 ,CH 3 ,C 2 H 5 ; CyO. We 
 cannot admit that the non-permanent cyanate of ammonia is rapidly 
 converted into the permanent cyanate of ammonium, and at the same 
 time insist that the permanent compound cyanates or ureas assume and 
 retain the form that belongs to the fugitive cyanates. 
 
 GROUP D. No. 1 8. Z(C 2 H 5 ) 4 ,CyO. Ethylam cyanate. 
 Miller's name for this salt is Tetrethyl-urea, and his formulae are : 
 
 C 2 O 2 1 
 
 C 18 H 20 N 2 2 = 2(C 4 H 5 )VN 2 = 
 2(C 4 H 5 )j 
 
 Gerhardt, vol. i = NCy * Vol. 4 = N 2 
 
 SALTS OF UREA. Nos. 19 to 27. 
 
 Normal urea and the compound ureas combine with hydrated acids 
 and with neutral salts, to form double salts, such as are represented in 
 the Table of examples, Nos. 19 to 27. All the compounds formed with 
 hydrated acids retain their acid reactions. There is, of course, no neu- 
 tralisation of the saturating capacities of the acids effected by the ureas, 
 which have been inconsiderately and improperly termed " bases." They 
 
348 TERBASIG CYANATES. 
 
 combine with acids, not in the sense in which anhydrous potash is 
 assumed to combine with anhydrous sulphuric acid, effecting the neu- 
 tralisation of its acidity ; but in the sense in which neutral sulphate of 
 potash combines with hydrated sulphuric acid, producing a double salt, 
 but not affecting the saturating capacity of the hydrated acid. The 
 application of the term " base " to a neutral salt when acting in this 
 manner has produced much of the ambiguity which pervades most 
 chemical writings on the subject of the salts which contain hydrogen. 
 
 It is needless to enter into details respecting these compounds indi- 
 vidually. Their composition is evident from the symbols, and I only 
 insist upon the broad fact, that these are double salts, and that to regard 
 them as compounds of acids with a base is improper. Urea is never, 
 under any circumstances, a " base." 
 
 Terbasic Cyanates. 
 
 In describing Dr. Hermann's Anilocyanates, I have suggested (see 
 page 305) that these salts may have the constitution of Terbasic 
 Cyanates, or be produced by the combination of a monobasic cyanate 
 with a salt formed on the model of water, H,CH 3 + C 6 H 5 ,CyO 
 = H,CH 3 ,C 6 H 5 ; CyO 2 . See Aniline, No. 96, and No. 3 in the follow- 
 ing Table. There are many other salts that have similar proportions of 
 ultimate constituents, and which are liable to a similar interpretation ; 
 while the processes by which some of them are prepared, and the pro- 
 ducts of their decomposition, give strength to this hypothesis. Never- 
 theless, many of the facts upon which we must build the theory of ter- 
 basic cyanates are liable to so many other interpretations, that I can 
 only state the hypothesis in a general form as one for consideration, and 
 not as one that is established. Certainly, the arguments which I have 
 adduced at pages 305 and 306 are strongly in favour of the supposition 
 that the anilocyanates are terbasic cyanates ; but the evidence respecting 
 some other of the compounds in the following Table is neither so direct 
 nor so conclusive as that respecting the anilocyanates, though, as it 
 appears to me, it is sufficiently affirmative to warrant my grouping the 
 compounds into a class for future investigation. 
 
 We cannot produce terbasic cyanic acid, because, as I have pointed 
 out at page 338, when hydrated cyanic acid = H,CNO acts upon 
 water = HHO, they are resolved into ammonia ZH 2 H and carbonic 
 acid = CO 2 . But this reaction is no disproof of the existence of terbasic 
 cyanates, containing other basic radicals than H,H,H; because we have 
 examples of the production of some of these salts by the direct action of 
 hydrated cyanic acid upon hydrated oxides formed on the model of water, 
 as will be seen in the following descriptions : 
 
( 349 ) 
 
 Examples of Terbasic Cjanates. 
 
 1. H, H, C 6 H 5 ; CyO 2 . Hydra hydra phenyla cyanete. 
 
 2. H, C 6 H 5 , C 6 H 5 ; CyO 8 . Hydra phenyla phenyla cyanete. 
 
 3. H, CH 3 , C 6 H 5 ; CyO 2 . Hydra methyla phenyla cyanete. 
 
 4. H, C 2 H 5 , C 6 H 5 ; CyO 2 . Hydra ethyla phenyla cyanete. 
 
 5. H, C 5 H U ,C 6 H 5 ; CyO 2 . Hydra amyla phenyla cyanete. 
 
 6. H, K, C 6 H 5 ; CyO 2 . Hydra potassa phenyla cyanete. 
 
 7. H, Na, C 6 H 5 ; CyO 2 . Hydra natra phenyla cyanete. 
 
 8. H, Ba, C 6 H 5 ; CyO 2 . Hydra baryta phenyla cyanete. 
 
 9. H, Sr, C 6 H 5 ; CyO* . Hydra stronta phenyla cyanete. 
 
 10. H, Ca, C 6 H 5 ; CyO 3 . Hydra calca phenyla cyanete. 
 
 1 1 . H, Mg, C 6 H 5 ; CyO 2 . Hydra magna phenyla cyanete. 
 
 12. H, Ag, C 6 H 5 ; CyO 2 . Hydra argenta phenyla cyanete. 
 
 13. H, Cue, C 6 H 5 ; CyO 2 . Hydra cupric phenyla cyanete. 
 
 14. H, H, CH 3 ; CyO 2 . Hydra hydra methyla cyanete. 
 
 15. H, Ag, CH 3 ; CyO 2 . Hydra argenta methyla cyanete. 
 1 6. H, Zn, CH 3 ; CyO 2 . Hydra zinca methyla cyanete. 
 17. H, H, C 2 H 5 ; CyO 2 . Hydra hydra ethyla cyanete. 
 
 1 8. H, C 2 H 5 , C 2 H 5 ; CyO 2 . Hydra ethyla ethyla cyanete. 
 
 19. H, H, C 5 H n ;Cy0 2 . Hydra hydra amyla cyanete. 
 
 20. H, H, C 4 H 9 ; CyO 2 . Hydra hydra butyla cyanete. 
 
 21. H, H, (JW ; CyO 2 . Hydra hydra tolueny la cyanete. 
 
 22. H, H, C 9 H 11 ; CyO 2 . Hydra hydra cumeny la cyanete. 
 
 23. CH 3 , CH 3 , ZH 4 ; CyO 2 . Methyla methyla ammona cyanete. 
 
 24. C 2 H 5 ,C 2 H 5 , ZH 4 ; CyO 2 . Ethyla ethyla ammona cyanete. 
 
 25. Hgc, Hgc, ZH 4 ; CyO 2 . Meric m eric ammona cyanete. 
 
 26. H, H, ZH 4 ; CyO 2 . Hydra hydra ammona cyanete. 
 
 USUAL NAMES AND FORMULAE OF THE TERBASIC CYANATES. 
 
 11. H,H,C 6 H 5 ; CyO 2 . Hydren phenyla cyanete. Anthranilic acid; 
 benzamic acid; carbanilidic acid = C 14 H 7 N0 4 = HO. CO 2 ; C 12 H 6 N, 
 CO = HO.C(O,C 12 H 6 N)C0 2 , Hofmann, who adds, that he considers 
 these three acids to be identic. Phenyl-carbamic, carbam'lic, or 
 
 anthranilic acid = C 14 H 7 N0 4 = \ Gerjiardtf 
 
 Anthranilic acid (HO,C 14 H 6 NO 3 ), Miller. Benzamic; carbanilic, or 
 amido-benzoic acid = C 14 H 7 NO 4 = HO,C 14 H 4 ,H 2 N,O 8 , Miller. A great 
 many other formulaa have been applied to those substances, the 
 proximate composition of which is not understood, nor is it yet even 
 
350 TERBASIC CYAN AXES. 
 
 decidedly ascertained whether there is one, or two, or three compounds 
 of different properties having the same ultimate composition = C 7 H 7 N0 2 . 
 
 While suggesting that the compound No. I may be a terbasic 
 cyanate, in agreement with the formula H,HO -f- C 6 H 5 ,CyO, it is proper 
 to place before the reader some of the other formulas, according to 
 which the ultimate composition may be interpreted. 
 
 a). C 6 H 5 ; ZH 2 ; CO 2 . This represents an amide derived from a neutral 
 carbonate, having one equivalent of ammonium and one of phenyl, thus : 
 
 C 6 H 5 ; ZH 4 ; C0 3 -HHO = C 6 H 5 ; ZH 2 ; CO 8 . 
 
 By some chemists the formula a) would be understood to signify the 
 carbamate of phenyl. 
 
 b). ZH,C 6 H 5 ; H; CO 2 . This represents an anilidogen acid derived 
 from the bicarbonate of phenylam by abstraction of HHO : 
 
 ZH 8 ,C 6 H 5 ; H; CO 3 -HHO = ZH,C 6 H 5 ; H; CO 2 . 
 
 c). ZH 2 ,C 7 H 5 2 . In this case all the carbon of the compound is 
 placed together so as to increase the acid energy of the negative radical, 
 and the nitrogen then forms an amid with the two basic radicals. Most 
 of the salts in the table are liable to this treatment, but it happens in 
 regard to many of them that the true amids having the same ultimate 
 composition are otherwise known, and have properties that differ from 
 those of the substances that are referred to in this Table. 
 
 The formulae which I have quoted from Miller, Hofmann, and 
 Gerhardt, represent acid radicals, which include carbon in combination 
 with amidogen or phenylac. It is needless to resort to the expedient 
 of framing imaginary conjugated radicals, while we have before us 
 several more probable and more simple methods, by means of which the 
 transformations of the compounds can be sufficiently explained. Of 
 these several formulae I prefer that which regards the compounds as 
 being terbasic cyanates ; but we have not sufficient knowledge of facts 
 to be able to decide exclusively in favour of this or of any one formula. 
 
 Anthranilic acid, when heated, produces aniline and carbonic acid 
 gas: 
 
 H,H,C 6 H 5 ; CNO 2 = ZH,C 6 H 5 ; H + CO 2 . 
 
 The formulae marked a), 6), c), suit this experiment equally well, so 
 that the experiment proves nothing beyond the accuracy of the clump 
 formula C 7 H 7 NO 2 . Benzamic acid is said not to produce aniline when 
 heated. 
 
 2]. H,C 6 H 5 ,C 6 H 5 ; CyO 8 . Hydra phenylen cyanete. A combination 
 of anilocyanic acid with hydrated oxide of phenyl. Hofmann. Thus : 
 
 C 6 H 5 ,CyO + H,C 6 H 9 O = H,CH 5 ,C 6 H 5 ; CyO 2 . 
 3]. H,CH 8 ,C 6 H 5 ; CyO 8 . Hydra methyla phenyla cyanete. See 
 
TERBASIC CYAN AXES. 351 
 
 Aniline 96]. A compound of the same composition, discovered by 
 Chancel, is called by Gerhardt the phenyl-carbamate of methyl, or 
 carbanimethylane. 
 
 4]. H,C 2 H 5 ,C 6 H 5 ; CyO 2 . Hydra ethyla phenyla cyanete. See Aniline 
 97], Also Chancel's compound, called by Gerhardt phenyl-carbamate 
 of ethyl, or carbanilethane. This last compound is converted by 
 ammonia into alcohol and anilo-urea (Aniline 89) : 
 
 H,C 2 H 5 ,C 6 H 5 ; CyO 2 ) (ZH 3 ,C 6 H 5 ; CyO = Anilo-urea. 
 ZH 2 H j : : j H,C 2 H 5 = Alcohol. 
 
 5]. H,C 5 H U ,C 6 H 5 ; CyO 2 . Hydra amyla phenyla cyanete. See 
 Aniline 98]. 
 
 6]. H,K,C 6 H 5 ; CyO 2 . Hydra potassa phenyla cyanete. Benzamate 
 of potash. Phenyl-carbamate of potash. Scarcely known. 
 
 7]. H,Na,C 6 H 5 ; CyO 2 . Hydra natra phenyla cyanete. Amido-ben- 
 zoate (Benzamate) of soda = C u H 4 Na(NH 2 )0 4 , Voit. Quart. Jaurn. 
 Cliem. Soc., ix. 269. 
 
 8, 9, 10, n]. Amido-benzoates or benzamates of barytes, strontia, 
 lime, and magnesia ; described by Voit, (loc. cit.) There is also a 
 phenyl-carbamate of lime, Chancel. 
 
 12]. H,Ag,C 6 H 5 ; CyO 2 . Hydra argenta phenyla cyanete. Carba- 
 nilate of silver ; anthranilate of silver ; benzamate of silver. 
 
 13]. H,Cuc,C 6 H 5 ; CyO 2 . Hydra cupric phenyla cyanete. Benza- 
 mate of copper ; carbanilate of copper. 
 
 14]. H,H,CH 3 ; CyO 2 . Hydren methyla cyanete. Two compounds 
 answer to this formula, both of which have undergone, and still undergo, 
 much discussion. Whether or not either of them belongs to this 
 category has yet to be finally determined. They are named urethylane, 
 (carbamate of methyl or carbomethylane) and glycocoli. 
 
 Urethylane is formed by saturating wood-spirit with the vapour 
 of cyanic acid. This reaction gives us H,CH 3 O -f- HCyO, which is 
 precisely the composition of a terbasic cyanate. It is also produced by 
 passing gaseous chloride of cyanogen into wood-spirit mixed with water, 
 which is also in accordance with this idea : 
 
 H,CH 3 + HHO + CyCl = H,H,CH 3 ; CyO 2 + HC1. 
 It suffers the following decompositions : 
 
 H,H,CH 3 ; CNO 2 ) fZH 4 ,S0 2 Sulphate of ammonia, 
 
 i ]. Sulphuric acid H; SO 8 1 = m,CH 3 O Wood spirit. 
 Water H; HO J [ CO 8 Carbonic acid. 
 
 H,H,CH 3 ; CNO 2 ) f KK,CO 3 Carbonate of potash. 
 
 , 1r ,. . , JK;HO } = M,CH 3 Wood spirit. 
 2 . Caustic potash < T7 - ' -r^ | ^ TT9 TT A 
 
 (K ; HO J [ ZH 2 ,H Ammonia. 
 
352 TERBASIC CYANATES. 
 
 These reactions are precisely such as arise from the decomposition of a 
 compound that contains cyanogen, and agree perfectly with Formula 14]. 
 
 Urethylane is also called carbamate of methyl, and is assumed to 
 contain the hypothetical carbamic acid. See page 359. 
 
 Glycocoll, or sugar of gelatine, is obtained by the action of alkalies 
 and acids upon gelatine. It combines with acids without neutralising 
 them ; its solution reddens litmus feebly ; these are characters which 
 agree very well with the above formula. It can exchange H l for a 
 metal, especially for Zn, Cue, Pb, Ba, and Ag. Nos. 15 and 16 in the 
 Table are examples of such salts. They can be formed by heating the 
 hydrated oxides of the metals with a solution of glycocoll : 
 
 H,H,CH 3 ; CyO 2 1 J H,Ba,CH 8 ; CyO 2 
 Ba; HO] : ( H;HO. 
 
 When glycocoll is boiled with acetate of copper, acetic acid is expelled, 
 and a compound of glycocoll with oxide of copper is obtained in solu- 
 tion : 
 
 H,H,CH 3 ; CyO 2 ) (H,Cuc,CH 3 ; CyO 8 
 Cue ; C 2 H 3 2 | : t H; C 2 H 3 2 . 
 
 15] and 1 6]. Salts of glycocoll. See last note. 
 
 17]. H,H,C 2 H 5 ; CyO 8 . Hydren ethyla cyanete. The clump for- 
 mulas of several known compounds agree with this formula. The most 
 important of these are urethane (or carbamate of ethyl), sarkosine, 
 alanine, and lactamide. But if there exist several acid radicals having 
 the formula C 3 H 5 , respecting which I have made some inquiries in the 
 section on glycerin, it is probable that there are several amides isomeric 
 with lactamide. The compounds that are here referred to, though 
 alike in ultimate composition, differ from one another in certain pro- 
 perties, but have not had their characters fully determined. It is 
 therefore impossible to say how many of them, if any, ought to be 
 embraced in the category of terbasic cyanates. I do not enter into 
 details, because I find among them no facts that point out conclusive 
 arguments respecting the proximate composition of these several salts. 
 
 1 8]. H,C 2 H 5 ,C 8 H 5 ; CyO 8 . Hydra ethylen cyanete. Ethylurethane, 
 or ethyl-carbamate of ethyle = C'H U NO 4 = C G H 6 (C 4 H 5 )NO 4 , Gerhardt. 
 Produced by heating cyanate of ethyl with alcohol in a closed glass tube, 
 thus: 
 
 H,C 2 H 5 O -f C 8 H 5 ,CyO = H,C B H 5 ,C 2 H 5 ; CyO 2 . 
 
 It is decomposed by caustic potash, which produces alcohol, cthylamine, 
 and carbonate of potash, thus : 
 
 + C'H'SCNO) [H,C 2 H 5 O Alcohol. 
 
 KHOV = ^ZH,C*H 5 ;H Ethylamine. 
 
 KHO I (KK,C0 3 Carbonate of potash. 
 
TERBASIC CYANATES. 353 
 
 When heated with concentrated sulphuric acid, it produces carbonic 
 acid, sulphate of ethylamine and sulphovinic acid : 
 
 ZH 3 ,C 2 H 5 ; SO 2 Sulphate of ethylamine. 
 - SO 2 } Sul P hovinic add ' 
 
 CO 
 
 H,C 2 H 5 ,C 2 H 5 ,CN0 2 
 H,S0 2 
 H,S0 2 
 H,S0 8 
 
 These reactions all agree with the theory that ethylurethane is a terbasic 
 cyanate, containing two atoms of ethyl. 
 
 19]. H,H,C 5 H U ; CyO 8 . Hydren amyla cyanete. Amylo-urethane, 
 or carbamate of amyle, discovered by Mr. Medlock ( Quart. Jour, of the 
 Chem. Soc., ii. 212). Formula?. : 
 
 = C 12 H 13 NO* = C l H 13 N + 2C0 2 = C 10 H n O,C 2 j N Il. 
 
 This salt was produced by the action of ammonia on the chloro-carbon- 
 ate (i. e. the chloric-formylete) of amyle, thus : 
 
 C 5 H H ,CC1O 2 ) J H,H,C 5 H n ; CNO 2 . 
 ZH 2 H + ZH 2 HJ : I ZH 4 ,C1. 
 
 When this salt is distilled with caustic baryta, it produces ammonia, 
 carbonic acid, and hydrated oxide of amyle : 
 
 H,H,C 5 H U ; CNO 2 ) fZH 2 H 
 
 BaHO I = BaBa,C0 3 . 
 BaHO j 
 
 When heated with sulphuric acid, it produces sulphamylic acid and 
 ammonia, with evolution of carbonic acid (and sulphurous acid ?) : 
 
 H,H,C 5 H U ; CNO 2 ) [C 5 H U ,S0 2 1 , , 
 
 HS0 2 i = \ H,S0 2 f Sul P h amyhc acid. 
 
 HSO 2 ) 
 
 The sulphurous acid must have proceeded from a subsequent decompo- 
 sition of part of the sulphamylic acid. 
 
 These reactions show that amylo-urethane agrees perfectly with the 
 character of a terbasic cyanate. 
 
 Another compound w r hich corresponds to the same formula as amylo- 
 urethane is leucine ; but though its reactions do not indicate so clearly as 
 those of amylo-urethane that its composition is that of a terbasic cyanate, 
 yet there are many points of resemblance. It combines with metals to 
 form salts, of which the following is an example : H,Pb,C 3 H a ; CyO 2 . 
 By dry distillation leucine produces amylamine and carbonic acid, thus 
 
 H,H,C 5 H n ; CNO 2 = ZH,C 5 H n ; H + CO 2 . 
 
 20]. H,H.C 4 H 9 ; CyO 2 . Hydren buty la cyanete. Carbamate of tetryle ; 
 
 2 A 
 
354 TERBASIC CYANATES. 
 
 butylic urethane ; tetrylic urethane = C 10 H U N0 4 , Gerhardt. It is pro- 
 duced, according to Humann, by acting on butylic alcohol with liquid 
 chloride of cyanogen : 
 
 4 (H,C 4 H 9 0)) 
 2(CNCl)l = 
 HHO 
 
 C 4 H 9 ,C 4 H 9 ; CO 3 = Carbonate of butyl. 
 H,H,C 4 H 9 ; CNO 2 = No. 20]. 
 
 C 4 H 9 ;C1 = Chloride of butyl. 
 
 ZH 4 ; Cl = Sal-ammoniac. 
 According to Humann, the formula is 
 
 ,. This is interpreted in Gmelin's Handbook (x. 149) 
 
 c H r 1 
 
 to signify that the salt is a compound of carbonate of butyl w r ith 
 carbamide = OTTO, CO" + CNH'O. The objections to this supposi- 
 tion are, that it includes belief in a compound of the existence of which 
 we have no evidence (carbamide, see page 22 1), and that, besides this, 
 the theory is less probable, and the formula more complex, than the 
 theory and corresponding formula now advanced. 
 
 21]. H,H,C 7 H 7 ; CyO 2 . Hydren toluenyla cyanete. The toluamic 
 acid of Cahours. 
 
 22]. H,H,C 9 H U ; CyO 2 . Hydren cumenyla cyanete. The cumin- 
 am ic acid of Cahours. 
 
 23]. CH 3 ,CH 3 ,ZH 4 ; CyO 2 . Methylen ammona cyanete. A com- 
 bination of methylic ether *= CH 3 ,CH 3 with cyanate of ammonia 
 = ZH 4 ,CyO. This is Gmelin's anhydrous carbonate of methylamine 
 = C 2 H 5 N,C0 2 . Gerhardt's formula are C 2 4 ,2C 2 H'N and C'H 4 
 (-HC :; H 5 N)NO 4 . He assumes in it the presence of a methyl-carbamic 
 acid = C 4 H 5 N0 4 , of the existence of which we have no proof, and for 
 which there is no necessity. The salt, 23], is produced by the com- 
 bination of two volumes of carbonic acid = CO 8 with four volumes of 
 methylamine, see page 61 = 2(ZH,CH 3 ; H), and the product might be 
 formulated thus : ZH 3 ,CH 3 ; ZH,CH 3 ; CO 2 , in which form it is analogous 
 to the anhydrous carbonate of ammonia. See No. i] in the series of 
 carbonates of ammonia on the next page. 
 
 24]. C 2 H 5 ,C 2 H 5 ,ZH 4 ; CyO 2 . Ethylen ammona cyanete. This salt 
 is of similar composition to No. 23], excepting that it contains methyl 
 instead of ethyl. It is subject to the same diversity of explanations, 
 and gives origin to another hypothetical acid, the ethyl-carbarn ic acid. 
 
 25]. Hgc, Hgc, ZH 4 ; CyO 8 . Merenic ammona cyanete. This salt 
 is formed when successive portions of red oxide of mercury suspended in 
 water are mixed with a warm solution of urea : 
 
 Hgc,HgcO + ZH 4 ,CyO = Hgc,Hgc,ZH 4 ; CyO 2 . 
 
THE CARBONATES OF AMMONIA. 
 
 355 
 
 26], H,H,ZH 4 ; CyO 2 . Hydren ammona cyanete. This salt looks 
 like the " acid " which corresponds to the three preceding salts. Its 
 occurrence is possible : H,HO + ZH 4 ,CyO, namely, an atom of cyanate 
 of ammonia combined with an atom of water ; nevertheless, I shall 
 show in the note to No. i] of the carbonates of ammonia, that this 
 compound has better claims to a different interpretation. 
 
 The Carbonates of Ammonia. 
 
 I. 
 
 ZH 4 , 
 
 ZH*,W 
 
 2. 
 
 ZH 4 , 
 
 ZH 4 ,CO 3 
 
 (ZH 4 , 
 
 ZH 4 ,CO 3 1 
 
 3' |ZH 4 , 
 
 ZH 2 ,C0 2 / 
 
 4- 
 
 H, 
 
 ZH 4 ,CO 3 
 
 
 
 ZH 4 ,CO 3 ) 
 
 5- < 
 
 'H 
 
 ZH 4 ,C0 3 
 
 
 ^ZH 4 , 
 
 ZH 2 ,C0 2 j 
 
 
 fZH 4 , 
 
 ZH 4 ,C0 3 
 
 
 ZH 4 , 
 
 ZH 4 ,C0 3 
 
 
 <ZH 4 , 
 
 ZH 4 ,CO 3 
 
 
 |H, 
 
 ZH 4 ,C0 3 
 
 
 IH, 
 
 ZH 4 ,CO 3 
 
 
 (ZH 4 , 
 
 ZH 4 ,CO 3 ' 
 
 
 ZH 4 , 
 
 ZH 4 ,C0 3 
 
 7 
 
 ft 
 
 ZH 4 ,CO 3 
 
 
 a, 
 
 ZH 4 ,C0 3 
 
 
 [ZH 4 , 
 
 ZH 2 ,C0 2 
 
 
 ZH 4 , 
 
 ZH 4 ,C0 3 
 
 Q 
 
 H, 
 
 ZH 4 ,C0 3 
 
 o 
 
 H, 
 
 ZH 4 ,CO 3 
 
 
 
 (2HHO) 
 
 9. < 
 
 XH, 
 
 ZH 4 ,C0 3 )\ 
 HHO j 
 
 10. < 
 
 f4(H, 
 
 ZH 4 ,C0 3 )) 
 TJtrrk- i 
 
 Ammona amida carbete. 
 
 Ammona ammona carbite. 
 
 Ammona ammona carbite cum ammona 
 
 amida carbete. 
 Hydra ammona carbite. 
 
 Bis hydra ammona carbite cum ammona 
 amida carbete. 
 
 Tris ammona ammona carbite bis hydra 
 ammona carbite. 
 
 Bis ammona ammona carbite bis hydra 
 ammona carbite cum ammona amida 
 carbete. 
 
 Ammona ammona carbite bis hydra am- 
 mona carbite cum aquete. 
 
 n. 
 
 12. 
 
 ammona carbite demi-aquate. 
 
 <4^ ' '/I Tetrakis hydra ammona carbite cum aquate. 
 
 J7H 4 ZH 4 CO 3 " 1 
 
 ^/TT r/TT-t' ^/-v.\ Ammona ammona carbite hexakis hydra 
 
 01 -ti, /Jxi ,ou ) > -,., 
 
 \ ' J \ onr>win'na rOTniro rnrn a ran lira 
 
 j ^ ' trHHOif ammona carbite curn aquute. 
 
 !Q/TT yTT4 r^O 3 *\ 
 ? CO 2 I ^ C ^i sn 7^ ra ammona carbite cum carbete 
 2(HHO)j 
 
 [In the above table, H = i, O = 16, C = 12, Z = 14.] 
 
 2 A 2 
 
356 THE CAKBOXATES OF AMMONIA. 
 
 These carbonates of ammonia are all described, after the researches of 
 Heinrich Rose, in Gmelin's Handbook of Chemistmj, vol. ii. pages 
 430 to 435. In Gmelin's formulae, C = 6 and O = 8. The difference 
 between these atomic weights and those which I have adopted, causes 
 great differences to appear in the formula? of the salts. 
 
 The salt No. i] = ZH 4 ,ZH 2 ,CO 2 is produced when carbonic acid gas 
 and ammonia gas act upon one another. In whatever proportions they 
 are mixed, they always combine and condense in the proportions of two 
 volumes of carbonic acid = i atom CO 2 and four volumes of ammonia 
 = 2 atoms or ZH*H -f ZH 2 H. This compound is noticed in the Table 
 at p. 50 as the hypothetical carbamate of ammonia. The atomic measure 
 is six volumes, which is the measure of its component gases. Gmelin calls 
 this salt anhydrous mono-carbonate of ammon = NH 3 ,CO 2 . Gerhardt 
 says of this salt, that " the density of its vapour has been found 
 equal to 0^9, Bineau, or to 0*8992, Rose, and that, consequently, the 
 formula C 2 4 2NH 3 corresponds to eight volumes, like those of 
 cyanhydrate, sulphhydrate, and chlorhydrate of ammonia," Traite de 
 Chimie, i. 196. This is, however, a mistake; the measure is six, not 
 eight, volumes, and it disagrees with the measure of the other gaseous 
 salts of ammonia. See pages 50 and 99. 
 
 The salt, No. i], may be conceived to be formed from the neutral 
 carbonate of ammonia, No. 2], by the abstraction of an atom of HHO, 
 thus : 
 
 (ZH 4 + ZH 4 + CO) - HHO = ZH 4 + ZH 2 CO. 
 
 2]. = ZH 4 ,ZH 4 ,C0 3 . This is the neutral carbonate of ammonia. It 
 is produced when the salt No. I is dissolved in water : 
 
 ZH 4 ,ZH 2 ,C0 2 -f HHO = ZH 4 ,ZH 4 ,C0 3 . 
 
 But it cannot be procured in the solid state. When the aqueous 
 solution is evaporated, ammonia = ZH 2 H escapes before the salt 
 crystallises, and a more acid product is left. 
 
 3]. ZH 4 ,ZH 4 ,CO 3 -f ZH 4 ,ZH 2 ,C0 2 . This is Gmelin's hydrated mono- 
 carbonate of ammonia = 2NH 3 ,HO,2CO 2 , or NH 3 ,C0 2 -f NH 8 ,HO,CO 2 . 
 " It is crystalline, it may be sublimed without change in composition ; 
 but if it is dissolved in water, it cannot be recovered from the solution ; 
 because, even at ordinary temperatures in vacuo, ammonia is disengaged 
 from 'it, and an acid salt is obtained." Gmelin. I consider the solution 
 to contain the salt, No. 2], because 
 
 ZH 4 ,ZH 4 ,CO 3 
 ZH 4 ,ZH 2 ,CO a +HHO 
 
 4]. H,ZH 4 ,C0 3 . This salt is Gmelin's bicarbonate of ammonia with 
 two atoms of water = NH 3 ,HO,C0 2 + HO,CO'. A crystalline salt, 
 less soluble and less volatile than the neutral salt No. 2]. 
 
 1 ofyw* 7 w* 
 f 
 
THE CARBONATES OF AMMONIA. 357 
 
 Of course, No. 2 and No. 4 are the two normal carbonates of ammo- 
 nium. All the other salts in the Table are modifications or combinations 
 of these two. 
 
 5]. 2(H,ZH 4 ,C0 3 ) + ZH 4 ,ZH*,CO 2 . A compound of two atoms of 
 the bicarbonate of ammonium No. 4], and one atom of the amidogen 
 salt No. i]. This is Gmelin's sesquicarbonate of ammonia with two 
 atoms of water = 2NH 3 ,2HO,3CO 2 , or according to Rose, NH 3 ,C0 2 
 + NH 3 , 2 CO 2 , 2 HO. It is the carbonate of ammonia of commerce. When 
 the vapour of anhydrous sulphuric acid is passed over this salt, carbonic 
 acid gas is disengaged, and ordinary sulphate of ammonia is produced. 
 
 f H, ZH 4 ,C0 3 1 fZH 4 ,SO 2 
 
 H, ZH 4 ,C0 3 
 [ZH 4 ,ZH 2 ,C0 2 ^ 
 S,SO 3 
 
 |ZH 4 ,S0 2 
 <{ZH 4 ,S0 5 
 ZH 4 ,SO 2 
 
 S,S0 3 J I 3 (C0 2 ) 
 
 " The salt effloresces in the air, forming a friable mass of bicarbonate 
 of ammonia, while anhydrous carbonate of ammon sublimes." Rose. 
 Thus: 
 
 ' jl 
 
 j 
 
 l 
 
 H,ZH 4 ,C0 3 = HZH'COS + ZH 4 ,ZH 2 ,C0 2 . 
 ZH 4 ,ZH 2 ,C0 2 J 1 H ' ZH ' C( 
 
 No. 5] = No. 4] -f- No. i]. 
 
 When the sesquicarbonate No. 5] is acted upon with small quantities of 
 water, neutral carbonate of ammonia is first dissolved, and bicarbonate 
 is left undissolved. By the action of successive small doses of water, a 
 series of solutions are obtained which differ in their relative contents of 
 monocarbonate and bicarbonate of ammonia. If, on the other hand, the 
 salt is dissolved in a large quantity of water, and the solution is heated, 
 carbonic acid is disengaged, and the proportion of monocarbonate of 
 ammonia is increased. The instability of these two salts, both in 
 aqueous solution and when exposed to air, gives origin to a great 
 variety of mixtures. 
 
 6]. 3(ZH 4 ,ZH 4 ,C0 3 ) + 2(H,ZH 4 ,CO 3 ). A compound of three atoms 
 of neutral carbonate of ammonia No. 2] with two atoms of bicarbonate 
 No. 4]. Gmelin's five-fourths carbonate of ammonia with five atoms of 
 water = 4NH 3 ,5C0 8 ,5HO. Sublimes when the salt No. 5] is slowly 
 heated. 
 
 7]. 2 (ZH 4 ,ZH 4 ,C0 3 ) + 2(H,ZH 4 ,C0 3 ) + ZH 4 ,ZH 2 ,CO 2 . Composed 
 of two atoms of No. 2], two atoms of No. 4], and one atom of No. i], 
 Gmelin's five-fourths carbonate of ammonia with four atoms of water 
 = 4NH 3 ,5CO 2 ,4HO, or 2(NH 3 ,HO,C0 2 ) + 2NH 3 ,2HO,3C0 2 ; or, ac- 
 cording to H. Rose, 3(NH 3 ,C0 2 ) -f- NH 4 O,2CO 2 . Produced by the 
 same process as No. 6]. There is, according to Rose, another salt, 
 which contains 1 2 atoms of water. 
 
358 THE CARBONATES OF AMMONIA. 
 
 8]. ZH 4 ,ZH 4 ,C0 3 4. 2 (H,ZH 4 ,C0 3 ) + 2 Aq. A compound of one 
 atom of neutral carbonate No. 2], two atoms of bicarbonate No. 4], and 
 two atoms of water. Gmelin's sesquicarbonate of ammonia with five 
 atoms of water = 2NH 3 , 3 CO 2 , 5 HO. 
 
 When the sesquicarbonate No. 5] is in solution in water, it may be 
 considered to be constituted as follows : 2(H,ZH 4 ,C0 3 ) + ZH 4 ,ZH 4 ,CO 3 . 
 9]. 2(H,ZH 4 ,C0 3 )+Aq. 
 
 10]. 4(H,ZH 4 ,CO 3 ) + Aq. 
 
 The bicarbonate of ammonia No. 4] combined with a little water of 
 crystallisation. 
 
 ii], ZH 4 ,ZH 4 ,CO 3 4- 6(H,ZH 4 ,C0 3 ) + 5Aq. A compound of six 
 atoms of bicarbonate of ammonia with one atom of neutral carbonate and 
 five atoms of water. Gmelin's seven-fourths carbonate of ammonia 
 = 4NH 3 , 7 C0 2 , i 2 HO, or probably = NH 3 ,HO,C0 2 -f- 3 (NH 3 ,HO, 
 2CO*) + 8HO. 
 
 I2j. 8(H,ZH 4 ,C0 3 ) 4- CO 2 + 2 Aq. 
 
 Eight atoms of bicarbonate of ammonia with one atom of carbonic 
 acid and two atoms of water. Gmelin's nine-fourths carbonate of 
 ammonia = 4NH 3 ,9CO 2 ,ioHO. Produced by evaporating the salt 
 No. 5] over oil of vitriol in vacuo. Probably only a mixture. 
 
 It appears from this investigation that the carbonates of ammonia 
 when in solution in water consist of the neutral carbonate No. 2] or the 
 bicarbonate No. 4], or mixtures of these two normal salts ; that the 
 sesquicarbonate No. 5] when in solution contains two atoms of bicar- 
 bonate and one atom of neutral carbonate, and that the various salts 
 upon being crystallised take up water, arid when sublimed lose water, 
 and are partly changed into amidogen salts. The instability of the 
 carbonates of ammonia, and their great tendency to combine with one 
 another, give rise to a series of complicated formulae ; but the theory 
 of their constitution is very simple. 
 
 The practice of representing multiple salts as containing all their 
 bases in a clump, directly combined with all their acids in another clump, 
 is one of those vicious practices grown out of the theory of " acids " 
 and " bases," which have produced great confusion in chemical theories, 
 and much impeded the progress of organic chemistry. While the 
 carlxmates of ammonia may all be represented as multiple salts contain- 
 ing the neutral carbonate, the bicarbonate, and the amidogen salt No. i], 
 f. e. the so-called carbamate, we find Gmelin representing them by such 
 formulae as these : 
 
 2NH 3 -f iHO -f 2C0 8 4NH 8 + 4HO + 5CO 2 . 
 
 2NH 3 -f- 2HO -f 3CO 8 2NH 8 -f 5HO + 3C0 2 . 
 
 4 NH 3 4. 5HO + 5C0 8 4NH 3 + loHO + 9CO 2 . 
 
 4NH 3 4- 1 2 HO 4 7 CO 2 . 
 
 These formula? show us the materials with which the salts are prepared, 
 
THE CARBAMATES. 359 
 
 or the products which result from their decomposition, but no power of 
 belief in the truth of the doctrine of combination in multiple proportions 
 can give plausibility to the notion that we have here before us true 
 representations of the proximate constitution of the different carbonates 
 of ammonia to which these formulaa refer. 
 
 The Carbamates. 
 
 If we suppose the neutral carbonate of ammonia No. 2] = ZH 4 ,ZH 4 , 
 CO 3 , to be deprived of an atom of water, we have as the result the 
 compound ZH 4 ,ZH 2 ,C0 8 , which I have described as No. i] of the 
 carbonates of ammonia. If we suppose the salt to be deprived of a 
 second atom of water, it is then reduced to ZH 2 ,ZH 2 ,CO, which is equal 
 to ZH 4 ,CNO, the last of these formula? representing cyanate of 
 ammonia, and the preceding one carbamide, both of which compounds 
 have been already fully discussed at pages 221 and 338. 
 
 If, on the other hand, we suppose an atom of water to be abstracted 
 from an atom of bicarbonate of ammonia, the resulting product is 
 H,ZH 2 ,CO a ; since 
 
 H,ZH 4 ,C0 3 - HHO = H,ZH 2 ,C0 2 . 
 
 This product does not appear among the many carbonates of ammonia, 
 nor has it been produced by any experiment whatever. Nevertheless 
 it forms an imaginary acid, which chemists have agreed to call Car- 
 bamic acid, and in which it is assumed that the amidogen and the 
 carbonic acid form together a conjugated acid which is in combination 
 with a replaceable atom of basic hydrogen = H r + ZH 2 ,C0 2 , or 
 H r O -j- ZH 2 ,CO. According to this theory, when H r is replaced by a 
 basic radical, we have a Carbamate, of which kind of salt the following 
 may serve as examples : 
 
 ZH 4 ,ZH 2 ,C0 2 = Carbamate of ammonia. 
 
 CH 3 ,ZH 2 ,CO 2 = Carbamate of methyl, or urethylane. 
 
 C*H 5 ,ZH 2 ,CQ 2 = Carbamate of ethyl, or urethane. 
 
 C 5 H U ,ZH 2 ,C0 2 = Carbamate of amyl, or amylurethane. 
 
 C 4 H 9 ,ZH 2 ,CO 2 = Carbamate of butyl, or butylic urethane. 
 
 The .view which it seems necessary to take of these salts, if we retain 
 the idea of the existence of carbamates, is, that they are direct 
 compounds of oxamide with oxides of the positive radicals. Thus : 
 ZH 4 + ZH 2 CO, and CH 3 O + ZH 2 CO. That appears to be not 
 an unlikely composition for the carbamate of ammonia, described above 
 as No. i of the carbonates of ammonia ; but as respects the other salts, 
 where we have no second atom of azote to deal with, this composition 
 seems to be less probable than that of terbasic cyanates, and I have ac- 
 
oOO THE URE1DES. 
 
 cordingly included the above four urethanes among the terbasic cyanates : 
 see Nos. 14, 17, 19, and 20 in that series. This operation enables 
 us to dispense with the hypothetical carbamic acid, which, having the 
 theoretical composition of one atom of ammonia combined with one 
 atom of carbonic acid, will probably never be produced, for the 
 same reason that it is impossible to form the terbasic cyanic acid. See 
 page 348. Even the carbamate of ammonia can be represented as a 
 probable member of the group of terbasic cyanates, as I have shown at 
 No. 26 in that series: ZH 4 ,ZH 2 ,C0 2 = H,H,ZH 4 ; CNO 2 . 
 
 The Ureides. 
 
 1. ZH 3 ,C 2 H 3 ; CyO 2 .... Acetylam cyanete. 
 
 2. ZH 8 ,C 4 H 7 ; CyO 2 .... Butyrylam cyanete. 
 
 3. ZH 3 ,(m 9 ; CyO 2 .... Valerylam cyanete. 
 
 4. ZH 8 ,<7H 5 ; CyO 2 .... Benzylam cyanete. 
 
 BlAMIDOBENZOIC ACID. 
 
 5. ZH^C 6 !! 5 ; CyO 2 .... Phenylam cyanete. 
 
 The ureides differ from the compound ureas by containing two atoms 
 of oxygen instead of one atom. That is the main difference. The 
 ureides all contain acid radicals in their ammoniums. The ureas some- 
 times contain acid radicals, but in general they contain basic radicals. 
 According to Miller (Elements of Chemistry, iii. 617), the ureides are 
 " salts of urea from which the elements of water have been abstracted;" 
 but if we look at the salts of urea formulated in the Table at page 343, 
 Nos. 19 to 27, we shall be puzzled to find a single example of a salt of 
 urea, which is convertible into a ureide by the abstraction of the 
 elements of water. Indeed, as every ureide is equivalent to an entire 
 compound urea + O l , it is evidently impossible to convert a compound 
 urea into a ureide by abstracting from it the elements of water. 
 
 The ureides No. I to No. 4 were formed by Zinin and Moldenhauer 
 by acting on urea with oxy chlorides of acid radicals. Thus : 
 
 ZH 4 ,CyO + C^CIO = ZH 8 ,C 2 H 3 ; CyO 2 -f HC1. 
 Ammona Acetyla _ Acetylam Hydra 
 
 cyanate. " " chlorate. ~" cyanate. "~ chlora. 
 
 Nos. 2,3, and 4 were formed in the same manner. 
 
 According to this view of the composition of the ureides, they are 
 Monobasic Cyanetes, which form a remarkable contrast with the 
 Terbasic Cyanetes ; there being to the same quantity of cyanogen com- 
 bined with the same quantity of oxygen, in the salts of one series, one 
 basic radical, and in those of the other series three basic radicals : 
 
 M,M,M;CyO 8 = Terbasic cyanate. [ ZH 4 ; CyO 2 = Ureide. 
 
THE UREIDES. 
 
 361 
 
 USUAL NAMES AXD FORMULAE OF THE UREIDES. 
 il. Acetureide = H 3 , C 4 H 3 2 ,N 2 C 2 2 ] 
 
 2]. Butyrureide = H 3 , C 8 H?O 2 ,N 2 C 2 2 [ - 
 A Valerureide = H 3 ,C 10 H 9 2 ,N 2 C 2 2 f 
 4]. Benzureide = H 3 ,C 14 H 5 2 ,N 2 C 2 2 ) 
 
 Gerhardt's names are i], Acetyl-urea; 2], Butyryl-urea; 3], Vale- 
 ryl-urea ; 4] , Benzoyl-urea. He gives two sets of formulae, both in 
 tome iv. of his Traite de Chimie. 
 
 At page 886. 
 
 il C 6 H 6 N 9 4 - NC ^ H3 1 
 ij. C H JN O - C 4 H 3 2 .O f 
 
 At page 765. 
 
 i]. C 3 H 6 N 2 8 = 
 
 2]. C 5 H IO N 2 2 = 
 
 3]. C 6 H 1S N 2 2 = 
 
 4]. C 8 H 8 N 2 2 = 
 
 CO 
 
 H 3 
 CO 
 
 H 3 
 CO 
 
 t H 3 
 CO 
 
 2]. 
 
 NCyH 3 \ 
 ~ C 8 H 7 2 .Of 
 
 C 10 H 9 2 .O 
 
 -i rH>W NC y H3 I 
 
 3J. c 1 IN < - n ioiT9n2nr 
 4]. C 
 
 NCyH 3 O \ 
 C 14 H 5 2 .O 
 
 Two authors thus supply us with five formulae for each of the ureides. 
 We have the clump formula?, both with large and with small atoms of 
 C and ; we have the model of water, including in each example the 
 impossible-ammonium NCyH 3 ; we have the double type ammonia ; and 
 finally, we have a series of formulas formed according to no type and 
 after no model. 
 
 Gerhardt quotes the following decompositions by heat as illustrating 
 the composition of these compounds : 
 
 3 C 6 H 6 N 2 4 
 Acetyl-urea. 
 
 = Cy 3 H 3 0* + 
 = Cyanuric acid. + 
 
 3 C 4 H 5 N0 2 . 
 
 Acetamide. 
 
 [ CO 
 
 2N 2 <C 2 H 3 
 \ H- 
 
 Acetyl-urea. 
 
 N3 ( ff + 
 
 Cyanuric acid. 
 
 rc 2 H 3 o 
 
 [ H 
 
 Acetamide. 
 
 3C 16 H 8 N 2 4 
 Benzoyl-urea. 
 
 = Cy 3 H 3 6 + 
 = Cyanuric acid. + 
 
 Benzamide. 
 
362 THE ALLOPHANATES. TETEABASIC CYANATES. 
 
 According to the radical theory, these decompositions can be repre- 
 sented in a far simpler manner : 
 
 ; CyO 2 H,CylO + ZH,C 2 H 3 ; H. 
 
 Acetylam cyanete = Hydra cyanylate -f- Acetylac hydra. 
 
 ZH 3 ,C7H 5 ; CyO 2 H,CylO + ZH,C 7 H 5 ; H. 
 
 Benzylam cyanete = Hydra cyanylate -j- Benzylac hydra. 
 
 The BIAMIDOBENZOIC ACID, which I have marked as No. 5 in the 
 Table of Ureides : 
 
 = ZH 3 ,C 6 H 5 ; CyO 2 Phenylam cyanete, 
 
 has been formulated in this work at No. 472, page 254, as a nitrete 
 = ZH 3 ,C 7 H 5 ; NO 8 . See the notice of the compound and reference 
 made to the discoverer's memoir. The formula given by him is 
 C 14 H 4 (NH 2 ) 2 4 , which signifies nothing, and which is capable of so many 
 re-arrangements, that, in the absence of a more extended account of the 
 chemical reactions of the compound than he has yet given, one can settle 
 it nowhere with certainty. It is only certain, that the substance has no 
 claim to the character of an acid. If it contains benzyl, it is probably a 
 nitrete. If it contains phenyl, it is more likely a monobasic cyanete. 
 
 The AHophanates. Tetrabasic Cyanates. 
 
 In accounting for the composition of the different kinds of phosphates, 
 I have shown (page 139) that what are termed bibasic phosphates are 
 compounds of monobasic phosphates with tribasic phosphates, and that 
 they therefore contain four basic radicals and two acid radicals. In the 
 same way, other tribasic salts combine with their corresponding mono- 
 basic salts, and produce compounds, each of which, like the tribasic 
 phosphates, contains four basic and two acid radicals, and which may be 
 called either bibasic or tetrabasic salts, according as we speak in reference 
 to one or to two atoms of their respective acids. 
 
 Among the acids which produce double salts of this description, I 
 think we may place the cyanic acid. The compounds to be cited in 
 evidence of the propriety of this suggestion are not very numerous, but 
 it is probable that their number will speedily increase if this suggestion 
 is found to bear uninjured that strict examination, which all suggestions 
 of this description are foredoomed to undergo. / 
 
 The structure of a tetrabasic cyanate may be shown thus : 
 
 Analytical formula. Synoptical formula. 
 
 = H,H,H,C>H ;Cy <0*. 
 
THE ALLOPHANATES. 363 
 
 The strongest objection to this theory exists in the fact that, in the pre- 
 sence of four positive radicals, the two atoms of azote might be expected 
 to produce two amidogens, and leave the carbon to take up the oxygen. 
 The above compound would then assume the following form : 
 
 f ZH 2 ;CO 1 
 |ZH,C 2 H 5 ; COO j 
 
 This is an amidogen salt, agreeing to a certain extent with the oxamates 
 described at page 226, but differing from those salts by having a vice- 
 ammon instead of a non-azotised radical in the oxalate, which, however, 
 is a difference which renders the existence of such an amidogen salt im- 
 probable. 
 
 Table of Allophanates.* 
 
 1 . H,H,H,C 2 H 5 ; Cy 2 O 3 . . . Hydrine ethyla cyanenite. 
 
 2. H,H,H,CH 3 ; Cy 2 3 . . . Hydrine methyla cyanenite. 
 
 3. H,H,H,C 5 H U ; Cy 2 O 3 . . . Hydrine amy la cyanenite. 
 
 4. H,H,H,Ba ; Cy 2 O 3 . . . Hydrine baryta cyanenite. 
 
 BIURET. 
 
 5. H,H,H,ZH 4 ; Cy 2 3 . . . Hydrine ammona cyanenite. 
 
 The first four of the salts in this Table have received a variety of 
 names, but at present they are called Allophanates. The last-named salt 
 is called Biuret, or bicyanate of ammonia. 
 
 i]. H 3 ,C 2 H 5 ; Cy ? O 3 . This salt is produced when the vapour of 
 hydrated cyanic acid is passed into alcohol or ether : 
 
 H,CNO 4- H,CNO + H,C 2 H 5 0. 
 
 Discovered by Liebig in 1846. It was originally called the Ureo-car- 
 bonate of ethyl, and was assumed to contain the ureo-carbonic acid, 
 which Gmelin (Handbook, vii. 377) describes as C 2 Ad 2 2 ,2CO 2 = 
 C 4 N 2 H 4 O a . No such acid is known, and subsequently Liebig and 
 Wohler ascribed to this salt the name of Allophanate of ethyl, or Allo- 
 phanic ether, which it still bears. Gmelin's formula for it is C B N 2 H 8 P 
 = C 4 H 5 0,C 4 N 2 H 3 O 5 . Gerhardt's formula is C 4 H 3 (C 4 H 5 )N 2 6 . When 
 decomposed by heat, the allophanic ether produces alcohol and cyanuric 
 acid : H 3 ,C 2 H 3 ; Cy 2 O 3 = H,C 2 H 5 O + 2HCylO. 
 
 The Allophanic Acid, which is assumed to be present in this salt, but 
 which has no separate existence, has these formulae assigned to it : 
 
 C 4 N 2 H 4 6 = C 4 Ad 2 O 8 ,O 4 , Gmelin. 
 Gerkardt. 
 
364 THE ALLOPHANATES. 
 
 O 5 , Miller. 
 NH 2 CO.C0 2 ,HO,(C 2 NH0 2 ), Hofmann. 
 HO.C 4 N 2 H 3 5 , 
 
 There appears to me to be little probability of truth in any of these 
 assumptions. The non-isolation of allophanic acid has been accounted 
 for by assuming that when it is separated from its salts by a stronger 
 acid, it immediately decomposes into carbonic acid and urea. I shall 
 examine this explanation in the note to the barytic salt, No. 4]. 
 
 2]. H 3 ,CH 3 ; Cy*0 3 . This compound is "formed by passing the 
 vapour of hydrated cyanic acid into pure wood spirit : 
 
 H,CyO + H,CyO + H,CH 3 0. 
 
 Discovered by Richardson in 1837; then called Ureo-carbonate of 
 methyl, and afterwards called Allophariate of methyl. The theory is the 
 same as that of the last example. 
 
 3]. H 3 ,C 5 H U ; Cy 2 3 . Formed in the same manner as the preceding 
 salts, by passing the vapour of cyanic acid into hydrated oxide of 
 amyle : 
 
 H,CyO + H,CyO + H,C 5 H"0. 
 
 When heated, it falls into its original constituents, save that the cyanic 
 acid becomes cyanuric acid. 
 
 4]. EP,Ba; Cy'O 3 . This salt is produced by acting on a solution of 
 allophanic ether, No. i], by a cold solution of hydrate of barytes: 
 
 No. i] = H 3 ,C 2 H 5 ; Cy'O 3 ) J H 3 ,Ba; Cy*O 3 = No. 4]. 
 Barytic water = Ba; HO f == \ C 2 H 5 ; HO = Alcohol. 
 
 When the solution of the barytic salt No. 4] is heated, the products are 
 as follow : 
 
 TT3 ~R r 2^3 ( Ba,Ba ; CO 3 = Carbonate of barytes. 
 
 TT3R ; fSrv 1 C 2 = Carbonic acid. 
 
 H 3 ,Ba ; Cy 5 !) 3 } = < 7TT 4 r m 
 
 H,HO J ZH 4 ',CyOf = Urea > 2 atoms ' 
 
 When the barytic salt is acted on by a strong acid, it disengages car- 
 bonic acid with brisk effervescence, and produces urea. Neither ammonia 
 nor free cyanic acid are disengaged : 
 
 Ba,CNO ) fZH 4 ,CNO 
 [,H,H,CNOOV = <^ COO 
 H,SOO J I Ba,SOO 
 
 This decomposition is quite in accordance with the general action of 
 hydrated sulphuric acid upon the cyanates. 
 
 It is commonly stated that, when allophanic acid is separated from its 
 salts by a stronger acid, it cannot be retained in an isolated state, because 
 
BIURET. 365 
 
 it has the property of immediately decomposing into carbonic acid and 
 urea. The ideal of allophanic acid is formed on certain properties be- 
 longing in part to ammonia, and in part to cyanic acid. The hydrated 
 allophanic acid, corresponding to the allophanates described in the above 
 Table, should have the formula H,H,H,H ; Cy s 3 . It is easy to foresee 
 what must occur if this acid was set free in an aqueous solution by the 
 action of hydrated sulphuric acid on the barytic salt No. 4]. I will put 
 the reaction into the form of an equation : 
 
 H 3 ,Ba; Cy 2 3 ) JH 4 ; Cy 2 O 3 
 H; S O 2 j : [Da; S O 2 
 
 That is the first reaction. But the following would immediately 
 follow : 
 
 H 4 ,Cy 2 3 = ZH 4 ,CyO + CO 2 . 
 
 The solution would then be ready to suffer any of the reactions described 
 under the article relating to the ureas. 
 
 It is evident, throughout these reactions, that we have to deal with 
 salts of cyanic acid, and with nothing else, and that there is no evidence 
 of the existence of an allophanic acid answering to any of the six formulas 
 which I have cited above from the writings of different chemists. 
 
 5]. H 3 ,ZH 4 ; Cy 2 3 . This compound, commonly called Biuret, and 
 sometimes Bicyanate of ammonia, has not been included in the list of 
 Allophanates. Miller gives it these two formulae : C 4 H 5 N 3 4 , 2 Aq = 
 HO,H 4 NO, 2CyO, 2 aq. It is prepared by keeping urea for some time in 
 a melted state at the temperature of 300. There is a simultaneous 
 production of ammonia, cyanuric acid, and melanuric acid. 
 
 When the salt No. 5] is strongly heated, it is decomposed into 
 ammonia, cyanuric acid, and water : 
 
 H 3 ,ZH 4 ; Cy 2 O 3 = 2H,CylO + ZH 2 H + HHO. 
 Biuret. = Cyanuric acid + Ammonia -f- Water. 
 
 With this section, I close my inquiry into the Theory of the Azotic 
 Radicals. 
 
( 366 ) 
 
 The Doctrine of Polyatomic Alcohols. 
 
 THE doctrine of polyatomic alcohols is founded upon the properties of 
 a substance described by M. Wurtz (Comptes Itendus, July, 1856) 
 under the name of glycol, and upon those of some compounds of glycerin 
 which have been investigated by M. Berthelot (Ann. de Chimie, iii., xli. 
 2 1 6). The polyatomic alcohols are said to possess the properties of 
 uniatomic alcohols, but to have the power of combining with more than 
 one equivalent of acid. Glycol is called a Biatomic alcohol and glycerin 
 a Teratomic alcohol. Professor Miller, the President of the Chemical 
 Society, in his Annual Address to that body in March, 1857, described 
 " WURTZ'S brilliant discovery of the biatomic alcohols, of which glycol is 
 the type" as one of the chemical memorabilia of the past year. I am 
 therefore bound to notice this new and important doctrine. 
 
 Grlycol, the Biatomic Alcohol. 
 
 According to M. Wurtz (loc. cit.), glycol is prepared by acting on 
 the iodide of ethylene, C 4 H 4 P (the iodised compound corresponding to 
 Dutch liquid) by dry acetate of silver ; one equivalent of the former to 
 two equivalents of the latter. There is a disengagement of carbonic 
 acid gas and olefiant gas ; iodide of silver is formed, and the resulting 
 mixture is submitted to distillation. The product then obtained is 
 called by Wurtz the diacetate of glycol, and is said to result from the 
 reaction depicted in the following equation : 
 
 C 4 H 4 1 
 
 4 F 2 O 8 ) = 2AgI + CWO'l O 4 
 Ag C 4 H 4 O 2 ) 
 
 Iodide of Acetate Iodide of Binacetate 
 ethylene. of silver. silver. of glycol. 
 
 [In this equation, C = 6, O = 8.] 
 
 Before proceeding farther with my notes from M. Wurtz, Jet me 
 draw the reader's attention to the fact that every article in this equation 
 is quoted in double proportions. We may ask, why are these double 
 quantities necessary ? Why not make use of single proportions ? We 
 have no evidence that iodide of ethylene is constituted thus : C 4 H 4 P. 
 It may be formed thus : C*H*I. In chemistry, what is true of double 
 proportions ought to be true of single proportions ; for nature acts the 
 same upon grains as upon tons. I will reduce the ingredients that are 
 named in the above equation uniformly to single proportions, correct the 
 atomic weights of C and O, and put the equation into the form that I 
 have commonly used throughout this volume, It then reads thus : 
 
GLYCOL, THE BIATOMIC ALCOHOL. 367 
 
 CH 2 ,I + Ag,C 2 H 3 2 = Ag,I + CH a ,C 2 H 3 2 . 
 Vinyla Argenta Argenta Vinyla 
 ioda. acetylete. ioda. acetylete. 
 
 This simple operation produces a magical effect. The glycol vanishes ! 
 Instead of binacetate of diatomic glycol, we see only neutral acetate of 
 uniatomic vinyl. 
 
 When a uniform reduction in the quantities of all the ingredients 
 concerned in a chemical reaction makes a fundamental change in the 
 nature of the products other conditions being alike the reaction is 
 one that demands a careful investigation. We cannot place unexplained 
 mysteries in the rank of established truths. It would be a new axiom 
 in philosophical chemistry to assume that Nature, operating upon 200 
 grains of a mixture, produces other results than when it operates upon 
 100 grains; that when it acts upon two atoms of a mixture, the 
 products are not the same as when it acts upon one atom. We must 
 make a clear distinction between effects that are produced by natural 
 operations and those which arise from the management of figures 
 arranged in equations. 
 
 I return to M. Wurtz : " If it is true that this body [t. e. the 
 binacetate of glycol] contains the elements of two equivalents of acetic 
 acid, or, if you'please, two equivalents of the radical acetyle [i. e. C 4 H 3 2 ], 
 as indicated by the formula, it is evident that, when it is decomposed 
 by the agency of alkalies, it ought to give two equivalents of acetic acid 
 for each equivalent of matter decomposed. This fundamental property 
 has been established by the following experiment." 
 
 I do not quote the experiment because I do not dispute the fact. As 
 much of the acetate of vinyl as contains two equivalents of acetyle 
 must necessarily yield to experiment two equivalents of acetic acid ; but 
 that fact respecting the acid does not prove the proposed doctrine 
 respecting the base, namely that C 2 H 4 represents One Radical that 
 two atoms of vinyl make one atom of glycol. 
 
 M. Wurtz finds that by distilling acetate of glycol with hydrate of 
 potash, pure glycol is produced. According to my notation this reaction 
 would be represented as follows : 
 
 KHO - K,C 2 H 3 O 2 + H,CH 2 O. 
 
 Vinyla Potassa __ Potassa Hydra 
 
 acetylete. ' hydrate. ~ acetylete. "" vinylate. 
 But M. Wurtz says that " the method of producing glycol shows that it 
 contains the group C 4 H 4 that is to say, olefiant gas, and that its con- 
 
 n4TT4 j 
 
 Stitution can be expressed by the formula TT 2 [0 4 , which represents a 
 
 TT2J 
 
 group of two molecules of water, TT 2 [0 4 , in which H 2 is replaced by 
 the diatomic radical C 4 H 4 ." 
 
368 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 This sentence, in which every quantity of the acting elements is doubled, 
 gives rise to the inquiry, Does C*H 4 , or, in corrected numbers, C 2 H 4 , 
 represent one atom of ethelene or two atoms of vinyl ? Why must we 
 double the proportions ? 
 
 I have, on several occasions in the course of this work, see pages 73, 
 79, 96, and 108 (which the reader will do well to re-consult), shown 
 the importance of the radical Vinyl, and the necessity of recognising it 
 under the formula CH 2 , which represents one volume of gas. I am 
 not aware that any experiment exists, or that any argument has been 
 advanced, which can establish, or even recommend, the formula C 2 H 4 as 
 of superior authority or utility to the formula CH 2 . For these reasons I 
 consider that ethylene and glycol are non-existent, and that the doctrine 
 of diatomic alcohols, founded upon their assumed existence, and owing 
 its sole authority to the apparent results of equations constructed with 
 double equivalents, is a fallacy. I am, nevertheless, rejoiced that 
 M. Wurtz has discovered the acetate and the hydrate of vinyl, because 
 they serve to show that the character which I assigned to vinyl was not 
 ill-founded. As the Neutral Radical, which stands between the positive 
 and the negative radicals as hydrogen stands between the metals and 
 the metalloids its importance cannot be overrated, and it is surprising 
 that chemists have not long since recognised this compound as the key 
 to the system of compound organic radicals. 
 
 CONSIDERATIONS RESPECTING THE HYDROCARBONS WHICH CONTAIN AN 
 EVEN NUMBER OF ATOMS OF HYDROGEN. 
 
 I copy the following observations from Professor MILLER'S Elements 
 of Chemistry, 1857, part iii., page 431 : 
 
 " Glycol is derived indirectly from olefiant gas, and there can be no 
 question that the hydrocarbons homologous with olefiant gas will, 
 before long, assume a much more important position in the theory of 
 organic chemistry than has hitherto been assigned to them. 
 
 *' A paper by Mr. Buff, communicated to the Royal Society by 
 Dr. Hofmann (Proceedings Roy. Soc., viii. 188), contains some important 
 observations on the derivatives of olefiant gas. There are, it must be 
 remarked, two classes of hydrocarbons which yield uniatomic alcohol 
 radicles ; one of these is homologous with ethyl, and is represented by 
 the formula (C n H B + j) ; this class has been long known and ex- 
 tensively investigated. The second series has only recently attracted 
 the notice of chemists ; it is homologous with allyl (C 6 H 5 ), and is repre- 
 sented by the formula (CJi^^. Allyl is the only member of this 
 series which has been carefully examined. 
 
 " These two groups of hydrocarbons are intimately related to each 
 other, and, probably, the members of the latter series will hereafter be 
 obtained from the former by a general method analogous to that by 
 
GLYCOL, THE BI ATOMIC ALCOHOL. 369 
 
 which Berthelot and De Luca have succeeded in obtaining allyl from 
 glycerin. 
 
 " Now, intermediate between these two groups is a third, which has 
 already been long recognised viz., the group of the hydrocarbons 
 which are homologous with defiant gas, represented by the general 
 formula (C 2n H 2n ) ; and which, it may be remarked, would be produced 
 by the combination of the corresponding terms of the two groups 
 previously alluded to, CJR^ -f (C n H n + 1 ) = (C 2n H 2ll ). It is only 
 recently that these hydrocarbons have been regarded as radicles ; yet 
 they are undoubtedly compounds of this nature, but they differ essen- 
 tially from the radicles of the two other groups, inasmuch as their 
 molecules are biatomic, or are capable of displacing two equivalents of 
 hydrogen ; whilst the radicles typified by ethyl and allyl are uniatomic, 
 and only represent one equivalent of hydrogen. 
 
 " We have already examined the nature of Dutch liquid a compound, 
 the molecular composition of which was then indicated by the formula 
 (C 4 H 3 C1,HC1): the view thus represented harmonizes well with the decom- 
 positions which Dutch liquid experiences when treated with potash ; but 
 the compound may also be regarded as the result of a combination of the 
 diatomic radicle (C 4 H 4 ) with two equivalents of chlorine, thus (C 4 H 4 )"C1 2 , 
 and as such it may be termed bichloride of ethylene ; the biatomic 
 character of ethylene (C 4 H 4 )" being indicated here by the notation (") 
 affixed to the radicle. Bromine and iodine also combine with olefiant 
 gas, and form corresponding compounds (C 4 H 4 )"Br 2 ; and (C 4 H 4 )"I 2 . 
 
 " There can be little doubt but that glycol is the type of a new 
 class of homologous alcohols, each of which will form the starting point 
 of numerous series of collateral derivatives." 
 
 REMARKS. The two classes of compounds which Professor Miller, 
 following MM. Wurtz and Buff, here refers to as having each an odd 
 atom of hydrogen, are those which at page 73 I have distinguished into 
 basic and acid radicals, according as the proportion of hydrogen which 
 each contains is above or below that which is demanded by its carbon 
 for the constitution of a multiple of vinyl. The third class of compounds 
 namely, those which have an even number of atoms of hydrogen 
 are characterised by Dr. Miller as being " undoubtedly compounds of 
 the nature of radicles," and as being " biatomic, or capable of displacing 
 two equivalents of hydrogen." This doctrine appears to me to be 
 unsound, for the following reasons : 
 
 I. Because such compounds are frequently not radicals, but salts 
 namely, pairs of radicals, consisting of hydrides of radicals, or compounds 
 of radicals with each other, of which compounds examples are given at 
 pages 64 and 65 of this work, under the head of First and Second 
 Group of Gaseous Salts. These compounds have in the state of vapour 
 twice the volume of radicals proper. Every compound formed by a 
 basic radical with an acid radical of the vinyl series, see page 79, and 
 
 2 B 
 
370 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 every compound formed either by a basic or an acid radical of this 
 series with hydrogen, must have an even number of atoms of 
 hydrogen, and yet will not be a radical, but a salt consisting of two 
 radicals. 
 
 2. Because there are examples of radicals which contain an even 
 number of atoms of hydrogen, but which are not necessarily biatomic ; 
 witness, vinyl = CH 2 , and succinyl = C 2 H 2 ; and which do not 
 displace two equivalents of hydrogen. In the vapour of the salts of 
 these radicals, the radical itself measures nothing. See page 96. 
 
 3. Because the practice of making uniatomic radicals appear to be 
 biatomic by the crude process of doubling the formulae is a violation of 
 the law of simplicity, a law which nature always follows, and which 
 science cannot disregard without ceasing to be science. 
 
 I might urge many other facts that tell against this doctrine ; but the 
 article on compound organic radicals, printed between pages 44 and 81 
 of this work, anticipates almost every argument that need be advanced. 
 For the reasons stated in those arguments, I do not consider that there 
 is A SERIES OF RADICALS intermediate between the positive and negative 
 radicals of the vinyl series. Vinyl itself is certainly intermediate ; but 
 the compounds that are called the homologues of this radical namely, 
 the hydrocarbons that are multiples of CH 2 are, for the most part, either 
 hydrides of positive or negative radicals, or salts composed of positive 
 combined with negative radicals ; and it is a mistake to ascribe to such 
 double compounds the character of single biatomic radicals. 
 
 The bichloride, bibromide, and biniodide of ethylene ought, in my 
 opinion, to be called the neutral chloride, bromide, and iodide of vinyl. 
 The existing evidence is entirely in favour of this assumption. The 
 Dutch liquid is composed of one volume each of chlorine and vinyl 
 (olefiarit gas). It has the specific gravity of 49*5 (see page 54), which 
 agrees with the atomic weight of the compound CH 2 ,C1, and with one 
 volume of vapour, which is the measure of the chlorine alone, since 
 vinyl measures nothing in its salts. Regnault's bibromide of ethylene 
 has the specific gravity of 94, which agrees with the formula CH 2 ,Br, 
 and with one volume of vapour. The iodide of ethylene does not 
 produce a gas ; but the double formula usually given to it (C 4 H 4 I 2 ) has 
 nothing to sustain it, and analogy justifies us in describing this salt with 
 greater simplicity and more accuracy as CH 2 ,I. 
 
 There is a sulphide of ethylene (C 4 H 4 S 2 ) which is equal to 
 CH 8 ,S = vinyla sulpha, and a sulphohydrate of ethylene (C 4 H 4 S 2 ,2HS), 
 which may be written CH 2 ,S + HS = H ; CH 2 ; S 8 = hydra vinyla 
 sulphene. This compound produces salts, of which an example may 
 be quoted in CH 2 ,S 4- PbS = Pb ; CH 8 ; S 8 = plumba vinyla sulphene. 
 
 I shall add a short notice of the compounds that have been recently 
 described by MM. Buff and Wurtz. 
 
 According to M. Buff", sulphocyanide of potassium decomposes both 
 
GLYCOL, THE BIATOMIC ALCOHOL. 
 
 371 
 
 chloride and bromide of ethylene, and produces sulphocyanide of ethy- 
 lene, according to the following equation : 
 
 C 4 H 4 C1 2 + 2KCyS 2 = 2KC1 + C 4 H 4 Cy 2 S 4 . 
 
 Is it not evident that a result is arrived at here, as in M. Wurtz's 
 argument, by a mere duplication of the ingredients which are named in 
 the formulas? Avoiding that duplication, the equation is as follows : 
 
 CH 2 ,C1 
 Vinyla 
 chlora. 
 
 K,Cy,S 2 
 Potassa 
 
 = KC1 + 
 Potassa 
 chlora. 
 
 CH 2 ,Cy,S 2 . 
 
 Vinvla 
 
 cyana cniora. cyana 
 
 sulphene. sulphene. 
 
 This equation is quite intelligible. We have proof of the existence of 
 vinyl and of its power to act as a radical, and to form salts with 
 chlorine, sulphur, cyanogen, &c. Why are we to renounce vinyl, in 
 order to believe in ethylene, of the existence of which we have less evi- 
 dence, and then to renounce ethylene to believe in glycol, of the existence 
 of which we have no evidence ? 
 
 The analyses of acetal by M. Stas, and by Baron von Liebig, showed 
 the composition of that compound to be C 12 H I4 4 , the atomic weight of 
 which is 1 1 8. M. Stas found the specific gravity of the vapour to be 
 59. Gmelin suggested (Handbuch der Chemie, Bd. iv. 807,) that the 
 composition represented a copulated compound of 2 atoms of ether with 
 I atom of aldehyde = 2C 4 H 5 O + C 4 H 4 O S = C 18 H 14 4 , but he admitted 
 that its behaviour with alkalies and solution of silver rendered the pre- 
 sence of aldehyde improbable ; and as it appeared to me to be difficult: 
 to account for its atomic measure of two volumes, on the supposition of 
 its containing so many radicals as Gmelin assumed, I suggested, at page 
 57 of this work, that it might contain ethyl and butyl, but I marked 
 it (?), because I had no facts or authority to support such a suggestion. 
 
 M. Wurtz now quotes the composition of acetal as 
 
 C 4 H 4 
 
 C 12 H 14Q4 = 
 
 C 4 H 5 
 C 4 H 5 
 
 O 4 , 
 
 which is similar to Gmelin's arrangement of the formulas, but M. Wurtz 
 considers the compound to be diethyline of glycol. By distilling a mix- 
 ture of alcohol and wood spirit with sulphuric acid and manganese, he 
 prepared two corresponding compounds containing methyl, making to- 
 gether the following series ; all of which he considers to be compounds 
 
 C 4 H 5 
 C 4 H 5 
 
 O 4 . 
 
 C 4 H 5 
 C 2 H 3 
 
 O 4 . 
 
 C 2 H 3 
 
 Q2JJ3 
 
 O 4 . 
 
 2B2 
 
372 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 If now, we correct the atomic weights of C and O, and reduce the 
 duplicate to single quantities, these relations justify the following for- 
 mulae : 
 
 A. C 2 H 5 ,CH 2 = Ethyla vinylate. 
 
 ^' I T H 3 'cH 2 O I = Ethyla vinylate cum methyla vinylate. 
 
 C. CH 3 ',CH 8 = Methyla vinylate. 
 
 The atomic weight of the compound A, which represents Acetal, is 
 according to this formula 59, which agrees with the specific gravity of 
 the vapour on the idea that it forms one volume, the ethyl alone retaining 
 its measure, and the vinyl and oxygen losing theirs. The atomic weight 
 of the compound B is 104. It ought to measure two volumes, and its 
 specific gravity should be *-%* = 52. Now M. Wurtz found the specific 
 gravity to be 3*475 against air = i, which is equal to 50*283 against 
 H = i. The atomic weight of the salt C is 45. Its vapour ought to 
 measure one volume, and its specific gravity ought to be 45. This is 
 equal to spec. grav. 3'!! against air = i. I do not know what 
 M. Wurtz found it to be. I have a note stating it to be 0*8535, wn ih 
 is evidently an error, either in the Comptes Rendus or in my transcrip- 
 tion, which I have no opportunity to correct. 
 
 " I find," says M. Wurtz, " that other salts of silver are decomposed 
 with great facility by the iodide of ethylene. The benzoate of silver 
 thus gave me an oleaginous neutral compound which is no doubt 
 benzoate of glycol. Consequently, the method which I have described 
 may produce an infinite number of neutral compounds, holding a middle 
 place between the ethers and the fats." 
 
 In the absence of exact information, I surmise that the reaction here 
 alluded to is as follows : 
 
 CH 2 ,I + Ag,C 7 H 5 2 = Ag,I + CH 2 ,C'H 5 2 
 Vinyla Argenta Argenta Vinyla 
 
 ioda. benzylete. ioda. benzylete. ] 
 
 PROPYLIC GLYCOL AND AMYLIC GLYCOL. 
 
 I copy from M. Wurtz : " I have proved the existence of propylic 
 glycol and amylic glycol. 
 
 A. " By acting upon acetate of silver with bromide of propyleno 
 C 6 H 6 Br 2 , I produced diacetate of propylic glycol. 
 
 C 6 H 6 ) 
 
 = C 4 H 3 2 lo* = C U H 12 O 8 . 
 C 4 H 3 2 \ 
 
 B. " I prepared diacetate of amylic glycol by acting on bromide of 
 arnylene C 10 H 10 Br 2 with acetate of silver. 
 
GLYCOL, THE BIATOMIG ALCOHOL. 373 
 
 C l H 10 ) 
 
 C 4 H 3 2 1 O 4 = C 18 H 16 8 ." Wurtz. 
 C 4 H 3 2 j 
 
 I confess that I do not understand the terms that are used in this 
 description, or rather, the sense in which the terms are used. Why is 
 the group of atoms C 6 H 6 called propylene when in combination with 
 bromine, and propylic glycol when in combination with acetyl and 
 oxygen ? Why is the group C 10 H 10 called in one form of combination 
 amylene and in another form amylic glycol ? Propyl is not present in 
 the first group, because an equivalent of propyl contains H 7 ; it is pro- 
 pionyl that is present in propylene. Amyl is not present in the last 
 group, because an equivalent of it contains H 11 . It is valeryl that is con- 
 tained in amylene. 
 
 Overlooking the latitudinarianism of these terms, I will state my view 
 of the reactions which they are used to describe. 
 
 Bromide of propylene I consider to be a double salt = C 3 H 5 ,Br -f- HBr 
 = H; C 3 !! 5 ; Br 2 = Hydra propionyla bromen, and the bromide of 
 amylene to be also a double salt = C 5 H 9 ,Br + HBr = H ; C 5 H 9 ; Br 2 = 
 Hydra valeryla bromen. The reactions described by M. Wurtz are, 
 according to my notation, as follow : 
 
 A JC 3 H 5 ,Br + HBr ) JC 3 H 5 ,C 8 H 3 2 + H,C 2 H 3 O 2 
 
 A 'lAg,C 2 H 3 2 + Ag,C 2 H 3 2 / l- \AgBr + AgBr 
 
 R ( C 5 H 9 ,Br + HBr 1 J C 5 H 9 ,C 2 H 3 2 + H,C 2 H 3 2 
 
 *' \ Ag,C 2 H 3 2 + Ag.OTPO 1 j : = t Ag Br + Ag Br 
 
 Both of these equations represent ordinary examples of double decom- 
 positions. 
 
 Supposing the experiments to be correct, which I do not question, in 
 each case, a BINACETATE is produced, but not a binacetate of a diatomic 
 alcohol. On the contrary, the first is a binacetate of propionyl and of 
 hydrogen, and the second a binacetate of valeryl and of hydrogen. There 
 is no evidence of the formation of such things as propylic glycol and 
 amylic glycol ; I do not even so much as understand what is meant by 
 those terms ; and I cannot admit that phantom compounds which result 
 from the mere duplication of formula?, are to be received as substantive 
 compounds, different from those that are exhibited by the same equations 
 when the ingredients are taken in single proportions. To admit that 
 the effects produced by the mere doubling of symbols is sufficient, in the 
 absence of corroborative evidence, to prove the existence of new sub- 
 stances, is to make chemistry a pastime for speculative arithmeticians. 
 It is remarkable that throughout these investigations into the biatomic 
 alcohols, by M. Wurtz, by M. Buffj and by Professor Miller, every 
 result is come at by means of equations that contain duplicate quantities 
 of all the acting substances, and that when you uniformly reduce the 
 
374 
 
 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 quantities from double to single, the biatomic-alcohol theory breaks 
 down ; glycol, stripped of its double, is seen to be vinyl ; propylic glycol 
 and amylic glycol become shadows of shades ; and the whole fabric and 
 its fairy creatures vanish like a mediaeval enchanted castle at the touch 
 of truth. The pen destroys them as the pen created them. 
 
 Glycerin, the Teratomic Alcohol. 
 
 I am so far from considering that GLYCERIN is a teratomic alcohol, 
 that I hold it to belong to that class of compounds which are commonly 
 called terbasic acids. Instead of being a base which requires three equi- 
 valents of acid to neutralise it, I think it is an acid which can neutralise 
 three equivalents of base. The following formulae are framed in accord- 
 ance with this opinion : 
 
 Group A. 
 
 1. H,H,H; C 3 H 5 3 . . . Hydrine glycylite. 
 
 2. C 3 H 5 ,C 3 H 5 O 3 .... Glycyla glycylite. 
 
 3. ZH 4 ,C 3 H 5 O 2 . . . . Ammona glycylete. 
 
 4. H,C 3 H 5 Hydra glycyla. 
 
 5. C 3 H 5 ,I Glycylaioda. 
 
 Group B. 
 
 C 3 H 5 4 
 C 3 H 5 4 
 C 3 H 6 O 4 
 
 6. H,H,C 2 H 3 
 
 7. H,H,C 7 H 5 
 8. 
 
 9. 
 
 10. H,H,C 16 H 31 
 u. H,H,C 5 H 8 
 
 12. H^C^H 35 
 
 13. H,H,C 5 H 9 
 
 14. H,(C*H 8 ) 9 ; C 8 H 5 5 
 
 15. H,(C a H') 2 ; C 3 H I 3 
 
 C 3 H 5 O 4 
 C 3 H 5 4 
 C 3 H 5 O 4 
 
 Hydren acetyla glycylote. 
 Hydren benzyla glycylote. 
 Hydren butyryla glycylote. 
 Hydren oleyla glycylote. 
 Hydren palmityla glycylote. 
 Hydren sebamyla glycylote. 
 Hydren stearyla glycylote. 
 Hydren valeryla glycylote. 
 
 Group C. 
 
 Hydra acetylen glycylute. 
 Hydra ethylen glycylite. 
 
 Group D. 
 
 16. H^H'O* + (H,C 4 H 7 O 8 ) 2 Hydra glycylete bis hydra 
 
 butyrylete. 
 
 17. H,C 3 H 5 O'+ (H^^H^O 2 ) 2 Hydra glycylete bis hydra 
 
 oleylete. 
 
GLYCERIN, THE TERATOMIC ALCOHOL. 
 
 375 
 
 18. H,C 3 H 5 2 +(H,C 16 H 31 O 2 ) 2 Hydra glycylete bis hydra 
 
 palmitylete. 
 
 19. H,C 3 H 5 2 -f- (H,C :8 H 35 O 2 ) 2 Hydra glycylete bis hydra 
 
 stearylete. 
 
 20. H,C 3 H 5 O 2 + (H,C 5 H 9 O 2 ) 8 Hydra glycylete bis hydra 
 
 valerylete. 
 
 21. H,(C 4 H 7 ) 2 
 
 22. H,(C 18 I 
 
 23. H,(C 16 H 31> 
 
 24. H,(C I8 H M ) 
 
 25. H,(C*H 9 ) 2 
 
 Group E. 
 
 C 3 H 5 O 5 . Hydra butyrylen glycylute. 
 
 C 3 H 5 O 5 . Hydra oleylen glycylute. 
 
 C 3 H 5 O 5 . Hydra palmitylen glycylute. 
 
 C 3 H 5 O 5 . Hydra stearylen glycylute. 
 
 C 3 H 5 O 5 . Hydra valerylen glycylute. 
 
 26. (C 2 H 3 ) 3 
 
 27. (C 7 H 5 ) 3 
 
 28. (C 4 H 7 ) 3 
 
 30! (C 16 H 31 ) 3 
 
 C 5 H 9 ) 
 
 Group F. 
 
 C 3 H 5 6 . . Acetyline glycylaze. 
 
 C 3 H 5 O 6 . . Benzyline glycylaze. 
 
 CPH'O 6 . . Butyryline glycylaze. 
 
 C 3 H 3 O 6 . . Oleyline glycylaze. 
 
 C 3 H 5 O 6 . . Palmityline glycylaze. 
 
 C 3 H 5 O 6 . . Stearyline glycylaze. 
 
 C 3 H 5 O 6 . . Valeryline glycylaze. 
 
 33. C H 5 ,C10 .... 
 
 34. C 3 H 5 ,C1O + HC1 . . 
 
 35. C 3 H 5 ,BrO + HBr . 
 
 36. H^H'O 2 + HC1 . 
 
 37. H^ffO 2 + C 3 H 5 ,IO 
 
 38. H,C 3 H 5 2 + C 2 H 3 ,C10 
 
 39. H,C 3 H 5 O 2 + (7H 5 ,C1O 
 
 Group G. 
 
 Glycyla chlorate. 
 
 Glycyla chlorate cum hydra chlora. 
 Glycyla bromate cum hydra broma. 
 Hydra glycylete cum hydra chlora. 
 Hydra glycylete cum glycyla iodate. 
 Hydra glycylete cum acetyla chlorate. 
 Hydra glycylete cum benzyla chlorate. 
 
 H,H,C 3 H 5 ;S0 4 ) 
 Ca r ;S0 2 f 
 !Ba r ;P0 3 ) 
 
 ^^^JH^a 1 ; CWO 3 } 
 
 42. H 3 ;C 3 H 3 Z 2 7 . 
 
 43. H 3 ; C 3 H 2 Z 3 9 . 
 
 Group H. 
 
 Hydren glycyla sulphote cum 
 
 calca sulphete. 
 Baryta phosphite cum hydren 
 
 baryta glycylite. 
 Hydrine zotenic-glycyleze. 
 Hydrine zotinic-glycyloze. 
 
376 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 I. H,H,H;C 3 H 5 3 = Hydrine glycylite. 
 
 The clump formula commonly given to glycerin is C 6 H 8 O 6 . Doubling 
 the atomic weights of C and O, this becomes C 3 H 8 O 3 . Chemists have 
 differed greatlv in their opinions respecting the proximate constitution of 
 this compound. For the sake of brevity, I will abstain from any his- 
 torical notice of such opinions, and only describe the theory which I am 
 about to use. I assume, then, that in glycerin there is an acid radical 
 which agrees with the formula C 3 H 5 , which is Gerhard t's GLYCYL with- 
 out the oxygen, and I adopt this name to distinguish it. 
 
 Glycyl can form salts with one basic radical and two atoms of oxygen, 
 an example of which is given in No. 3, = ZH 4 ,C 3 H 5 O 2 ; but hydrated 
 glycylic acid possesses, like hydrated phosphoric acid, the power of 
 forming terbasic salts by combining with water, or with salts formed on 
 the model of water. Thus : 
 
 H,C 3 H 5 2 + HHO = H 3 ,C 3 H 5 3 = No. i. 
 
 These three atoms of basic hydrogen are jointly and separately replace- 
 able by other radicals, and these may be either basic or acid radicals, but 
 are more frequently acid than basic. 
 
 On glancing over the above Table, it will be seen, that in many cases 
 where the salts are of similar structure, where, for example, one acid 
 radical is in combination with three basic radicals, there is a remarkable 
 difference in the complement of oxygen, the atoms of which vary- 
 according to the series 3,4, 5, and 6. 
 
 In the different orders of phosphates, the quantity of oxygen varies 
 with the number of basic radicals that are present in the salts ; but in 
 the glycylites (or glycerides, as they are usually termed), the quantity of 
 oxygen varies while the number of radicals remains unchanged. A little 
 consideration of the facts exhibited in the Table of Examples enables us 
 to explain this peculiarity. 
 
 The synoptical formula of terbasic glycylic acid, No. i (hydrine gly- 
 cylite), is H,H,H ; C 3 H 5 3 . When the atoms of hydrogen are replaced 
 by basic radicals, no change occurs in the quantity of oxygen required to 
 complete the glycylite; witness the salt No. 15, which contains two 
 atoms of ethyl, and the formula of which is H,C 2 H 5 ,C*H 5 ; (^IPO 3 . 
 But when the replacing radicals are such as, under ordinary circum- 
 stances, act as acid radicals, then each acid radical which goes into the 
 glycylite in the character of a basic radical, carries with it into the salt 
 one additional atom of oxygen. Thus, every salt in Group B has one 
 such pseudo-basic radical, and the oxygen is, in consequence, increased 
 from 3 atoms to 4 atoms in each salt. In No. 14 of Group C, and in 
 all the salts of Group E, there are two such radicals, and the oxygen is 
 increased in every instance from 3 atoms to 5 atoms. In the salts of 
 Group F there are three of these radicals, and the quantity of oxygen is, 
 
GLYCERIN, THE TERATOMIC ALCOHOL. 377 
 
 therefore, raised from 3 atoms to 6 atoms. In Group D, each compound 
 contains three acid radicals and three basic radicals, forming three com- 
 plete salts ; and there are present in all only 6 atoms of oxygen, namely, 
 two for each salt, because none of the acid radicals act as basic radicals. 
 In short, so far as this series of salts is concerned, the truth of this im- 
 portant fact is demonstrated. 
 
 The property thus shown to be possessed by acid radicals of taking an 
 additional atom of oxygen when they act the part of basic radicals, is not 
 restricted to the radicals which enter into the composition of the gly- 
 cerides. The inquiry into the constitution of the Anhydrides has taught 
 us otherwise. See page 118. When sulphur, or acetyl, or benzyl, 
 forms salts with hydrogen, or with any basic radical, either metallic or 
 compound, the salts require a complement of two atoms of oxygen ; but 
 when the same acid radicals form salts with an acid radical in the place 
 of a basic radical, the oxygen is always increased from two atoms to 
 three atoms. For that reason, all the anhydrous acids have O 3 where the 
 corresponding hydrated acids have O 2 , so also all the compound anhy- 
 drides, or salts composed of two different acid radicals, have s , though 
 the neutral salts of each of the same acid radicals have only O 2 when they 
 contain basic radicals. I am not declaring that this peculiar property of 
 the acid radicals is universal, but it is certainly exercised very frequently, 
 and it deserves more attention than chemists have hitherto been pleased 
 to bestow upon it. In subsequent sections relating to the constitution of 
 polybasic acids, I shall have to speak of it again. 
 
 2. C'H^IPO 3 . Glycyla glycylite. This compound is the anhy- 
 dride or anhydrous acid of the glycerine series. Gerhardt calls it the 
 oxide of glyceryle, and Professor Miller characterises it as " the supposed 
 glyceric ether." It is evidently derived, like other anhydrides, by the 
 abstraction of water from the monobasic hydrated glycylic acid. 
 
 H,C 3 H S 2 ) JC 3 H 5 ,C 3 H 5 3 
 H,C 3 H 5 2 ( | H,HO 
 
 The preceding paragraph accounts for the presence of O 3 in the anhy- 
 dride, when the hydrated acid contains only O 2 . It shows also the 
 exact accordance of this compound with the compounds called anhydrous 
 acids. I see no reason whatever for imagining it to belong to any 
 other class than this, and I am not surprised at the doubting state of 
 mind which led Professor Miller to call this compound the " SUPPOSED " 
 glyceric ether. 
 
 3. ZH 4 ,C 3 H 5 O 2 . Ammona glycylete. Professor Miller informs us 
 that, "When an alcoholic solution of bibromhydrin (C 6 H 6 Br 2 2 ) 
 [= No. 35 in the above Table] is submitted to the action of gaseous 
 ammonia, the hydrobromate of a new base, glyceramine, C 6 H 9 NO 4 (Ber- 
 thelot and De Luca) is produced, whilst bromide of ammonium is formed. 
 
378 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 The correctness of the formula given for this base is however question- 
 able." (Elements of Chemistry, iii. 383.) 
 
 If we admit that water takes part in the reaction, the equation 
 becomes intelligible, thus : 
 
 No. 35 = C 3 H 5 ,BrO + HBr] fZH 4 ,Br 
 ZH 3 + ZH 3 l = JZH 4 ,< 
 H,HO j (HBr. 
 
 The " hydrobromate of a new base " is merely a double salt of hydro- 
 bromic acid with the salt No. 3, which is the glyceramine. 
 
 4. H^H 5 = Hydra glycyla. 
 
 5. C 3 H 5 ,I = Glycyla ioda. 
 
 " Glycerine treated with biniodide of phosphorus yields gaseous 
 propylene C 6 H 6 , a distillate of water and iodopropylene, C 6 H 5 I, and a 
 residue containing certain oxygen-acids of phosphorus, together with free 
 iodine, undecomposed glycerine, and a trace of red phosphorus. The 
 formation of iodopropylene is due to a reducing action exercised by the 
 PP on the glycerine. The liberation of C 6 H 6 appears to be of 
 secondary importance." Berthelot and De Luca (in Gmelin's Hand- 
 book of Chemistry, ix. 489). 
 
 The compounds which are here called propylene and iodopropylene 
 appear to me to be the hydride and the iodide of glycyl; but the 
 variety in the names that are given to hydrocarbon radicals which are 
 isomeric, if not identical, with glycyl is very perplexing. Thus, C 3 H 5 , 
 occurring as an acid radical in a series of salts, has for some years been 
 called allyl. Latterly, Dr. Hofmann (Proceedings, Royal Society, viii. 33), 
 has changed the name to acryl, although acryl already had fixed upon it 
 the signification of C 3 H 8 , which formula indicates another radical, 
 produced, like allyl, from glycerine. The term Allyl is therefore 
 overthrown, and we are at liberty to use acryl to signify either C 3 H 3 or 
 (^H 5 , which, as these radicals are nearly related, and both producible 
 from glycerine, is a mighty convenient latitude, and highly conducive to 
 perspicuity. 1 
 
 The compound C 3 H 5 is also called mesityl; it is the radical of 
 Pseudo-acetic acid, which has also been called lutyroacetic acid; it is the 
 radical of metacetonic acid ; it is the radical of propylene ; it is the 
 radical of lactic acid; it is the radical of propionic acid and of propionic 
 
 1 A new number (26, vol. viii.) of the Proceedings of tlie Pioyal 
 Society, which has just appeared, contains a paper by Dr. Hofmann, 
 read i^th June, 1857, in which he returns to the old name of Allyl. 
 " It is never too late to mend." 
 
GLYCERIN, THE TERATOMIC ALCOHOL. 379 
 
 aldide ; it is propionyl ; it is sixe ; it is the hydride of tritylene ; it is the 
 radical ofpropylal ; &c., &c., &c. 
 
 When organic chemists can bring up their languid energies to the 
 point of acknowledging the existence of such things as radicals, taking 
 that word in the restricted sense in which it is used in this Essay, one of 
 their first subsequent labours must be that of identifying and dis- 
 criminating the radicals from one another. Is it creditable to the 
 present race of chemists that we should have nearly a score of names for 
 the hydrocarbon C 3 H 5 , and that these names should have attached to 
 them characteristics of classes of salts so ill made out that it is impossible 
 to say whether the formula C 3 H 5 represents one thing only, or twelve, or 
 twenty different things ? whether it indicates one performer assuming a 
 variety of characters, like Miss Horton or Mr. Woodin when playing 
 their monopolylogues, or is the representative of a whole company of 
 actors, each possessing an ascertainable individuality ? 
 
 Such a state of uncertainty should not and need not continue. 
 Looking at it from a business point of view, there is an obvious 
 solution of the problem. The radicals which constitute this mob can 
 either be distinguished from one another, or they cannot. They can be 
 proved to be alike, or to be different. If they can be distinguished, it 
 ought to be done, and their characters ought to be laid down with 
 precision ; if they cannot be distinguished, the useless duplicate names 
 should be abandoned ; for it is absurd to retain distinctions in words 
 where there are no differences in things. 
 
 At present, I confess that I am unable to identify the radical which 
 in the above formula, Nos. I to 5, I have called glycyl. It may be 
 glycyl ; it may be allyl ; it may be acryl ; it may be lactyl ; it may be 
 propionyl. In all probability these five names signify only one thing ; 
 and, in the mean time, I assume only that the formula C 3 H 5 represents 
 the hydrocarbon which transmigrates through the 44 salts that are 
 named in the above table, and that the word glycyl means this radical. 
 
 USUAL NAMES OF THE COMPOUNDS, Nos. 6 to 32. 
 
 Group B. 6, Monacetin. 7, Monobenzoicin. 8, Monobutyrin. 
 9, Monolein. 10, Monopalmitin. u, Sebacin. 12, Monostearin. 
 13, Monovalerin, 
 
 Group C. 14, Biacetin. 15, Biethylin. 
 
 Group D. 1 6, Bibutyrin. 17, Biolein. 18, Bipalmitin. 19,61- 
 stearin. 20, Bivalerin. 
 
 Group^. 21, Bibutyrin. 22, Biolein. 23, Bipalmitin. 24,61- 
 stearin. 25, Bivalerin. 
 
 Group F. 26, Teracetin. 27, Terbenzoicin. 28, Terbutyrin. 29, 
 Terolein. 30, Terpalmitin. 31, Terstearin. 32, Tervalerin. 
 
 " The most important compounds which result from the action of 
 
380 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 acids upon glycerin are those termed glycerides, which are analogous in 
 composition to the various fats and oils. Berthelot has recently suc- 
 ceeded in forming these bodies by the direct union of the acids with 
 glycerin, and has obtained, in the course of his investigation, not only a 
 large class of these bodies which were not previously known, but has 
 been successful in the attempt to re-combine glycerin with the fatty 
 acids, so as to reproduce several of the natural fats (Ann. de Chimie, 
 III., xli. 2 1 6). According to the researches of this chemist, stearic, 
 palmitic, and oleic acids, each forms three compounds by its union with 
 glycerin ; the act of combination is, however, attended by the separation 
 of water in each case. . . . The following Table contains a list of 
 these compounds with the formulas of the decomposition which appears 
 to attend their formation. For the sake of convenience, the formulas of 
 the hydrated acids are written without indicating the basic water in the 
 usual manner: thus, stearic acid (HOjC^fPO 3 ) is written 
 
 Stearic Acid. Glycerin. 
 
 Monostearin = C 42 H 42 8 = C^H^O 4 + C 6 H 8 O 6 - 2 HO 
 
 Bistearin = C^EPO 12 = 2(C 36 H 36 4 ) -f C 6 H 8 O 6 - 2HO ? 
 
 Terstearin = C U4 H U0 12 = 3 (C 36 H 36 O 4 ) -f C 6 H 8 6 - 6HO. 
 
 Acetic Acid. Glycerin. 
 
 Monacetin = C 10 H 10 O 8 = C 4 H 4 O 4 + C 6 H 8 O 6 - 2HO 
 
 Biacetin = C 14 H 18 O 10 = 2 (C 4 H 4 4 ) -f C 6 H 8 6 - 4 HO 
 
 Teracetin = C 18 H 14 O 12 = 3 (C 4 H 4 4 ) + C 6 H 8 6 - 6HO. 
 
 " It might have been expected, that in the formation of these com- 
 pounds the quantity of water separated should have been somewhat 
 different, and that the proportions in each of the three' compounds 
 should have been 2 HO in the first, 4.HO in the second, and 6HO in the 
 third, each equivalent of the hydrated acid losing an equivalent of 
 water, whilst the single equivalent of glycerin, in the act of combination, 
 should lose I, 2, and 3 equivalents of water, according to the number 
 of equivalents of acid with which it is combined. 
 
 "According to Berthelot, terstearin, terpalmitin, and terolein, are 
 identical with the stearin, palmitin, and olein of the natural fats, and 
 they are produced by the combination of 3 equivalents of the hydrated 
 fatty acids (C n H M O 4 ) with i equivalent of glycerin, the act of combination 
 being attended with the separation of 6 equivalents of water. 
 
 " All these neutral compounds of the fatty acids with glycerin are 
 insoluble in water, but are soluble to some extent in boiling alcohol, and 
 are readily soluble in ether. If treated with concentrated acids, they 
 are decomposed and acidified in the same manner as the natural fats ; 
 and they are all saponifiable that is, they are decomposed, like the 
 natural fats, into a fatty acid and glycerin, when boiled with an alkali. 
 It has been found that whether monacid, biacid, or teracid in composi- 
 
GLYCERIN, THE TERATOMIC ALCOHOL. 381 
 
 tion, these fats are all neutral in their reactions, and, moreover, when 
 decomposed, they all yield glycerin of the same composition and 
 condition of hydration." Miller {Elements of Chemistry, 1857, part iii. 
 381). 
 
 I have quoted only two examples from the Table given by Professor 
 Miller, because these are sufficient to show the amount of information 
 which they contain. They give us the relations of the acids and 
 glycerin to the resulting compounds, but they make no attempt to 
 explain, what we chiefly wish to have explained, the internal constitu- 
 tion of these compounds. Terstearin is merely said to be C I14 H 110 O 12 , 
 and we are left to guess, as we can, at the possible proximate constitution 
 of the salt which is represented by this great unhewn block of 236 
 ultimate atoms. 
 
 The following paragraph, which Professor Miller appends as a foot- 
 note to his phrase " supposed glyceric ether " {Elements of Chemistry, 
 iii. 383), contains the only hints towards a knowledge of the proximate 
 constitution of the glycerides which he ventures to advance : 
 
 " Glycerin, however, if it be an alcohol, cannot be a monatomic 
 alcohol, but it must be teratomic ; in which case it may be formed, as 
 Gerhardt suggests, upon the type of two double molecules of water, and 
 its radicle (C 6 H 5 O 2 ) may be named gtycyl, in order to distinguish it 
 from Liebig's glyceryl (C 6 H 7 ). The relation of the three acetins to 
 glycerin would then be the following : 
 
 Glycerin. Acetin. 
 
 p605r\2} TT) petrs/^si fjr\ 
 
 lo 2 lo 2 - in 2 lo 2 - 
 
 H j u 'H/ u ' C 4 H 3 2 j U 'H( U ' 
 
 Biacetin. Teracetin. 
 
 H |^"'C 4 H 3 2 ( 2; (>H 8 2 J Cr 'C*H 8 O s 
 " Wurtz, however, considers glycerin to be formed upon the type of 
 three double molecules of water, jj 3 |o 6 ; a view which is more con- 
 sistent with the general theory of these compounds; C 6 H 5 being 
 a teratomic radicle, or representing three equivalents of hydrogen, 
 thus :. 
 
 Glycerin. Glyceric ether. Acetin. Biacetin. Teracetin. 
 
 H 3 ' (C 6 H 5 )( 2 H 
 
 When I look at the real model of water HHO and compare its 
 
382 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 simplicity with the intricacy of these giant formula?, I marvel at the 
 latitude of interpretation in which organic chemists indulge! While 
 professing to account for the composition of these salts upon their 
 alleged resemblance to the model of water, we have here one chemist 
 extending his model to four atoms, and another to six atoms of water, 
 and twisting these into a variety of strange and fantastic forms. These 
 are not examples of adherence to a scientific standard, but of the play of 
 a capricious fancy. 
 
 The difficulty which Professor Miller starts in regard to the quantity 
 of water which is expelled during the reaction, gives rise to the double 
 set of formulas which I have given in Groups D and E. The com- 
 pounds in Group D represent the results of M. Berthelot's analyses ; and 
 which have been objected to, not only by Dr. Miller, but by M. Ger- 
 hardt, and by Mr. Watts (editor of Gmelin's Handbook). The salts of 
 Group E are the (presumed) same compounds formulated according to 
 a suggested correction of Gerhardt's, which consists in deducting HHO 
 from each salt (equal to 2HO according to Dr. Miller's notation). As 
 all the series of salts are formed by heating together the acids and 
 glycerin in closed glass tubes, for different lengths of time and at 
 different degrees of heat, and the effect produced is the gradual formation 
 and separation of water from the anhydrides that are formed simul- 
 taneously, it is possible that both sets of salts may be formed, though, 
 certainly, those of Group E seem to be of more probable occurrence 
 than those of Group D. 
 
 Let us now see how these various salts agree with the notion that 
 formula No. i = H,H,H; C 3 H 5 3 represents the true composition of 
 glycerin, according to which formula glycerin is a terbasic acid, and the 
 glycerides are salts in which the so-called fatty acids act the part of 
 bases against glycerin acting as an acid. 
 
 The following examples represent, in detail, the reactions which take 
 place when 'hydrated terbasic glycylic acid is heated with hydrated 
 acetic, butyric, and stearic acids, and with alcohol. 
 
 Group B. 
 
 H,H,H; C 3 H 5 O 8 \ (H,H,C 2 H 3 ; C 3 H 5 4 = No. 6. 
 Acetic acid. H ; C 8 H 3 O a J \ H ; HO 
 
 H,H,H ; C 3 H 5 O 3 I J H.H.C^H" ; C 3 H'O 4 = No. 1 2. 
 Stearic acid. H; C^ETO 2 ft H ; HO 
 
 Group C. 
 
 H,H,H; C 3 H 5 O 3 1 '_ JH,C ! H 3 ,C 2 H 3 ; CWO 5 = No. 14. 
 
 Acetic acid. 2(H ; C 2 H 3 O s ) f \ 2(H ; HO) 
 
 H,H,H; C'H'O 3 \ (H,C'H 5 ,C*H 5 ; C 3 H 5 3 = No. 15. 
 
 Alcohol. 2(H;C 2 H 5 O)( | 2 (H, HO) 
 
GLYCERIN, THE TERATOMIC ALCOHOL. 383 
 
 Group D. 
 
 H,H,H ; C 3 H 5 O 3 1 _ f 2(H,C 4 H 7 O 2 ) + H,C 3 H 5 O 2 = No. 16. 
 Butyric acid. 2 (H ; C 4 H 7 O 2 ) f " \ H ; HO 
 
 Group E. 
 
 H,H,H ; C 3 H 5 O 3 1 _ J H,C 4 H 7 ,C 4 H 7 ; C 3 H 5 5 = No. 2 1 . 
 Butyric acid. 2(H ; C 4 H 7 O 2 ) j " \ 2(H ; HO) 
 
 Group F. 
 
 H,H,H ; C 3 H 5 O 3 1 _ JC 2 H 3 ,C 2 H 3 ,C 2 H 3 ; C 3 H 5 O 6 = No. 26. 
 Acetic acid. 3 (H ; C 2 H 3 O 8 ) ) " \ 3 (H ; HO) 
 
 H,H,H ; C 3 H 5 O 3 j (C 18 H^C I8 H 35 ,C 18 H 35 ; C 3 H 5 O 6 = No. 31. 
 Stearic acid. 3 (H ; C 18 H 35 2 ) f " \ 3 (H ; HO) 
 
 It will be observed, that in the formation of these compounds there is 
 a gradual progression from the condition of normal hydrated acids to 
 that of perfect anhydrides. Thus, the salt No. 6 is equal to H,C 2 H 3 O 2 
 4- H,C 3 H 5 O 8 , or hydrated acetic acid plus hydrated glycylic acid ; and 
 the salt No. 31 is equal to (?W,C*B*<y -f C 18 H : *,C 3 H 5 O a or the 
 stearic anhydride plus the compound anhydride of stearyl and glycyl. 
 The other groups are intermediate, according to their deficiency of HHO. 
 
 At page 73 of this work I have given an arbitrary rule for arranging 
 the hydrocarbon radicals in the order of their basicity. According to 
 that rule, the radicals, which form the salts Nos. 6 to 32 in the Table of 
 glycerides, are to be arranged as follows : 
 
 1. Ethyl = C*H 5 
 
 2. Stearyl = C 18 H 35 
 
 3. Palmityl = C 16 H 31 
 
 4. Oleyl = C 18 H 33 
 
 5. Valeryl = C 5 H 9 
 
 6. Butyryl = C 4 H 7 
 
 7. Glycyl = C 3 H 5 
 
 8. Sebamyl = C 5 H 8 
 
 9. Acetyl = C 2 H 3 
 10. Benzvl = C 7 H 5 . 
 
 This relationship justifies me in placing the radicals of the fatty acids 
 as positive or basic against the radical of glycerine, considered as 
 negative or acid, and in overturning the notions which are commonly 
 attached to the components of the glycerides. I do not mean to say 
 that my arbitrary rule for discriminating positive from negative radicals 
 alone justifies my over-riding the opinions generally entertained on this 
 subject by organic chemists, but that this arbitrary rule leads to results 
 the importance of which justifies my classification. In fact, the notion 
 that glycerine is a teratomic alcohol leads to nothing beyond clump 
 formulae (save only the crude attempts to explain the compounds by the 
 model of water) ; whereas the assumption that it is a terbasic acid gives 
 rise to formulae that are regular, intelligible, and probable. 
 
 Let us now examine why it is that the fats, or glycerides, whether 
 
384 
 
 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 monacid, biacid, or teracid, when boiled with potash, all yield glycerin 
 of the same composition and condition of hydration. I will adduce the 
 different stearins as examples : 
 
 Monostearin. 
 
 No. 12]. H,H,C 18 H 35 ; C 3 H 5 OM JH,H,H; C 3 H 5 O 3 = No. i]. 
 K ; HO ft K ; C^H^O 2 
 
 Bistearin (according to Gerhardt). 
 No. 24]. H^^H 35 ^ 1 ^ 35 ; C 3 H 5 O 5 ) [H,H,H ; C 3 H 5 O 3 = No. i]. 
 
 I 35 ; C 3 H 5 O 5 ) ( H,H,H ; C 3 H 5 O 3 
 K ; H O I = \ K ; CVH^O 2 
 K; H Oj K; C 1H H 35 O 2 
 
 Terstearin. 
 
 No. 3 1]. (C 18 H 35 ) 3 ; C 3 H 5 O 6 ) JH,H,H ; C 3 H 5 O 3 = No. i]. 
 
 3 (K;HO) f t 3 (K;C' 8 H 35 2 ) 
 
 Bistearin (according to Berthelot). 
 
 No. 19]. 
 
 H ; C 18 H 35 2 1 
 H;C 3 H 5 2 } = 
 K; HO 
 K; HO 
 
 H,H,H ; C 3 H 5 3 = No. i], 
 K ; C 18 H 35 2 
 K; C 18 H 35 2 
 H: HO 
 
 These equations prove that every individual radical of the fatty acids 
 takes up K 1 from KHO (hydrate of potash), and that the quantity of HO 
 thus set free is in all cases exactly sufficient to convert the liberated glycyl 
 into the tribasic glycylic acid, H 3 ,C 3 H 5 O 3 . The radicals of the fatty 
 acids, which act positively against glycyl, act negatively against metallic 
 radicals and against hydrogen. The equations account for the disposal 
 of every atom which is concerned in each reaction. 
 
 The compounds represented in Groups G and H are of much less 
 importance than those which precede them ; but I will show briefly 
 that they are not inconsistent with the theory that I have advanced to 
 explain the more important compounds. 
 
 Group G. USUAL NAMES. 33, Epichlorhydrin = C 6 H 5 C10 a . 34, 
 Bichlorhydrin = C 6 H 6 C1 2 O 2 . 35, Bibromhydrin = C 6 HWO*. See 
 the note to No. 3]. 36, Monochlorhydrin = C 6 H 7 C10 4 . 37, lodhy- 
 drin = C 18 H U IO 6 . This compound is decomposed by caustic potash, 
 according to the following equation : 
 
 H,C 3 H 5 2 4- C 3 H 5 ,IO 
 H.OTPO 8 4- C 3 H 5 ,IO 
 K,HO 4- K,HO 
 4- H,HO 
 
 38,Acetochlorhydrin = C l H 9 C10 6 . 39, Benzochlorhydrin =C*H U C1O 6 . 
 
 fC 3 H 5 ,C 3 H 5 3 = No. 2" 
 = <! 2 (H 3 ,C 3 H 5 3 ) = No.i; 
 
GLYCERINE, THE TERATOMIC ALCOHOL. 385 
 
 Group H. USUAL NAMES. 40, Sulphogly cerate of Lime = CaO, 
 C 6 H 7 5 ,2SO 3 , Miller. Gerhardt's formula for the "acid," which he 
 'C 3 H 5 01 
 
 calls monobasic, is O 3 
 
 SO 2 >. There are similar salts with Ba, Ag, 
 
 H 3 . 
 
 and Pb instead of Ca. The formula No. 40 is founded upon the 
 notion that the compound is a double sulphate (Ca,SO 2 + H,H,C 3 H 5 ; 
 SO 4 ), the salt Ca,S0 2 is neutral and H,H,C 3 H 5 ; SO 4 is terbasic. There 
 are four atoms of oxygen in the latter instead of two ; one atom extra 
 because it is terbasic acid, and another atom because it contains an acid 
 radical acting as a basic radical. 
 
 41, Phosphoglycerate of Barytes = C 6 H 6 Ba 9 O 6 ,HO,P0 5 , Gmelin. 
 Gerhardt gives the following formula to phosphogly eerie acid, which he 
 
 fC 3 H 5 0) 
 calls bibasic: OVPO I. 42, Nitroglycerine = C 6 H 6 (N0 4 ) 2 6 , De 
 
 (H 4 . J 
 
 Vrij. 43, Nitroglycerine = C 6 H 5 (NO 4 ) 3 6 , Railton. When boiled 
 with aqueous potash, these compounds produce glycerine and nitrate of 
 potash : 
 
 No. 42]. H 3 ,C 3 H 3 Z*O 7 ) J2(KNO 3 ) 
 
 (K,HO) [ : (H 3 ,C 3 H 5 3 = No, i]. 
 
 No. 43]. H 3 ,C 3 H 2 Z 3 9 \ J 3 (K,N0 3 ) 
 
 (K,HO) 3 j : }H 3 ,C 3 H 5 3 = No. i]. 
 
 These two compounds, Nos. 42, 43, have been described as belonging 
 to the salts of zotic radicals described at page 132: but I shall show, 
 at page 394, that they admit of another and a better interpretation. 
 
 The Doctrine of " Polyatomic Alcohols " is now ready for the 
 reader's judgment. I have placed the evidence before him, and he is to 
 decide upon it. My summing up of it is as follows : 
 
 1. There is no such thing as Glycol meaning thereby a radical 
 different from Vinyl ; a radical that can produce a binacetate, but not a 
 monacetate. 
 
 2. There is consequently no biatomic alcohol, because the visionary 
 glycol is the only evidence to support the doctrine of biatomic alcohols. 
 
 3. It is easy to account for the composition of the glycerides on the 
 assumption that glycyl is the radical of a terbasic acid. 
 
 4. It is impossible to give a rational account of the composition of 
 the glycerides on the assumption that glycyl is the radical of a teratoraic 
 alcohol. 
 
 5. There is consequently no evidence to support the theory of 
 teratomic alcohols. 
 
 6. The Doctrine of Polyatomic Alcohols is a delusion. 
 
 2c 
 
386 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 Eecent Proceedings in the French Academy of Sciences, 
 respecting the Teratomic Alcohols. 
 
 Just as the final proof of the preceding article on POLYATOMIC 
 ALCOHOLS was about to be sent to press, I read in a French scientific 
 newspaper (La Lumiere, 29th August, 1857), the following Article, 
 No. I . The broad statements respecting the existence of acid quater- 
 nions, contained in this Article, and the strong approval of the 
 teratomic-alcohol theory attributed to M. Chevreul, induced me to 
 delay the printing of my Article until the arrival of the Comptes JRendus 
 of 1 7th August, 1857, from which I have extracted the Summary, 
 No. 2. These two papers give the reader the latest experimental 
 researches, and the newest doctrines, on the subject of the teratomic 
 alchohols. After reading them, I sent my Article, as it stood in 
 type, to press, considering it was needless to alter it, because its facts, 
 arguments, and conclusions, were in no respect invalidated by the new 
 discoveries. 
 
 No. i. 
 
 "AT THE SITTING OF THE ACADEMY OF SCIENCES, IN PARIS, ON 
 THE i7TH AUGUST, 1857, 
 
 " M. Chevreul communicated to the Academy, in the names of the 
 authors, MM. Berthelot and De Luca, a complete treatise on the com- 
 pounds which glycerine, considered as a teratomic alcohol, produces on 
 combining with chlorhydric, bromhydric, and acetic acids. 
 
 " It results from this investigation, that glycerine presents, in com- 
 parison with alcohol, precisely the same relations that phosphoric acid 
 presents in comparison with nitric acid. This latter acid forms with 
 bases only a single series of neutral salts, that is to say, the monobasic 
 nitrates; whereas phosphoric acid produces with bases three distinct 
 series of neutral salts, namely, the monobasic metaphosphates, the 
 bibasic pyrophosphates, and the ordinary tribasic phosphates. 
 
 " Similarly, alcohol produces with acids only a single series of 
 neutral compounds, namely, the Ethers, formed by the union of one 
 equivalent of alcohol with one equivalent of acid ; whereas glycerine 
 forms with acids three distinct series of neutral compounds. Among 
 these compounds, some result from the union of one equivalent of 
 glycerine with a single equivalent of acid, and correspond to the meta- 
 phosphates ; others result from the union of two equivalents of acid and 
 one equivalent of glycerine, and correspond to the pyrophosphates ; 
 whilst, finally, the third class, identic with the natural fatty bodies, 
 
GLYCERINE, THE TER ATOMIC ALCOHOL. 387 
 
 result from the action of one equivalent of glycerine with three equiva- 
 lents of acid, and correspond with the ordinary phosphates. 
 
 "MM. Berthelot and De Luca undertook the investigation of a 
 certain number of double and triple compounds, which result from the 
 simultaneous union of one equivalent of glycerine with two or even 
 with three different acids ; these complex compounds are so much the 
 more interesting, that their analogues are found among the natural 
 fatty bodies. The compounds of this order are easy of production, it 
 being only necessary to act upon glycerine with several acids at once. 
 The results at which the authors arrived, complete the study of the 
 glycerine compounds, considered as derivatives of a triatomic alcohol, 
 constituting the most complete and most general type which has ever 
 been made known, of the compounds formed by three acids combined 
 with glycerine, either singly, doubly, or triply. 
 
 " MM. Berthelot and De Luca have prepared a neutral compound, 
 which contains glycerine, bromhydric acid, and chlorhydric acid ; 
 another containing glycerine, chlorhydric acid, and acetic acid ; a third, 
 containing glycerine, bromhydric acid, and acetic acid. They have also 
 prepared several intermediate compounds ; and, finally, they have pro- 
 cured a compound which contains at the same time glycerine, chlor- 
 hydric acid, bromhydric acid, and acetic acid, and which is the first 
 compound ever prepared in which three different acids are combined 
 with a single equivalent of glycerine. 
 
 " M. Chevreul earnestly pressed upon the notice of the Academy the 
 importance of this new discovery, declaring it to be unprecedented, and 
 as throwing a flood of light upon the constitution of glycerine." 
 
 No. 2. 
 
 THE COMPOUNDS FORMED RY GLYCERINE WITH CHLORHYDRIC, BROM- 
 HYDRIC, AND ACETIC ACIDS. By MM. BERTHELOT and DE LUCA. 
 
 Comptes Rendus, i^th August, 1857. 
 
 " After different attempts to form complex compounds by the succes- 
 sive reactions of two or three distinct acids upon glycerine, we were 
 led, in order to avoid the formation of very complicated mixtures, to 
 cause the acids to act upon the glycerine simultaneously and in the 
 nascent state. We produced the above-named acids in equivalent pro- 
 portions, and at the cost of the glycerine itself, by treating that body 
 with acetic chloride and acetic bromide. It is known that these last 
 compounds, when treated with water, reproduce acetic acid in company 
 with chlorhydric or bromhydric acid : 
 
 C 4 H 3 C10 2 + 2HO = C 4 H 4 4 + HC1. 1 
 
 1 In my notation = C 2 H 3 ,C10 4- H,HO = H,C 2 H 3 0* + HC1. J. J. G. 
 
 2 c 2 
 
388 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 . " Tlie reaction of these bodies upon glycerine, even when cold, is 
 extremely violent. By operating upon pure glycerine, and sometimes 
 upon glycerine mixed with acetic acid, we have obtained : 
 
 Acetodichlorhydrine : 
 
 C 10 H 8 C1 2 O 4 = C 6 H 8 6 + C 4 H 4 4 + 2HC1 - 6HO, 
 
 a neutral compound, volatile at about 2O5C., decomposable by barytes 
 with regeneration of glycerine ; by alcohol and chlorhydric acid with 
 formation of acetic ether ; 
 
 AcetochlorTiydrine : 
 
 C l H 9 C10 6 = C 6 H 8 O 6 + C 4 H 4 4 + HC1 - 4HO, 
 a neutral body, volatile at about 250 C. ; 
 
 Diacetochl&rhydrine : 
 
 C 14 H U C10 8 = C 6 H 8 O 8 + 2C 4 H 4 4 + HC1 -6HO, 
 
 a body which volatilizes at about 245 C., and which it is difficult to 
 obtain free from triacetine. 
 
 " The acetic bromide gives origin to analogous compounds which it 
 did not appear to be necessary to examine in detail. 
 
 "Finally, glycerine, treated by a mixture of equal equivalents of 
 acetic chloride and acetic bromide, has furnished : 
 
 Acetochlorhydrdbromhydnne : 
 C lo H 8 ClBr0 4 = C 6 H 8 6 + C 4 H 4 O 4 + HC1 + HBr - 6HO, 
 
 a neutral compound, volatile at about 228 C., and the first compound in 
 which three distinct acids have been found combined at the same time 
 with a single equivalent of glycerine. 
 
 " According to these facts, and to those which we have already pub- 
 lished, the three acids, chlorhydric, bromhydric, and acetic, can, by 
 combining with glycerine, produce at least nineteen distinct neutral 
 compounds, of which the following is a list : 
 
GLYCERINE, THE TERATOMIC ALCOHOL. 
 
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390 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 " This is the most complete type that has ever been developed by 
 experiment of the complex compounds which can be produced by a 
 triatomic alcohol. Combinations of this order are always produced 
 when we act upon glycerine with two acids at once. It was thus that 
 one of us had previously obtained acetochlorhydrine by the simultaneous 
 action of chlorhydric and acetic acids ; benzochlorhydrine, valerochlor- 
 hydrine, stearochlorhydrine, butyrochlorhydrine, etc. By acting upon 
 glycerine with a mixture of butyric and sulphuric acids, we have 
 obtained a neutral compound which can be considered as a mixture of 
 equal parts of tributyrine and of a glycerine formed conjointly by the 
 two acids, butyric and sulphuric, 
 
 The Dibutyrosulphurine : 
 
 = C 6 H 8 O 6 2C 8 H 8 4 S0 4 H - 6HO. 
 
 " This explains a great number of facts that are observed in the 
 study of natural fatty bodies, and notably the existence, signalised by 
 MM. Pelouze and Boudet, of certain crystallisable complex products, in 
 which glycerine is combined at the same time with two fatty acids. 
 All these phenomena, the theoretical interpretation of which has hitherto 
 been obscure and incomplete, can now be explained by the properties of 
 polyatomic alcohols, in a manner the most simple and most conformable 
 to analogies. 
 
 " To show all the riches all the variety of compounds of which 
 this theory permits us to foresee the existence, it suffices to cite the 
 following numbers: glycerine, on combining with n acids in equal 
 equivalents, forms n neutral compounds; with 2 equivalents of these n 
 
 n (n-\- i) 
 acids, taken i to i, or 2 to 2, it can form - neutral com- 
 
 1.2 
 
 pounds; with 3 equivalents of these n acids, taken i to i, 2 to 2, 
 
 n (n+ i) (n + 2) 
 3 to 3, it can produce - - =*-* - neutral compounds. If we 
 
 admit the existence of a thousand distinct acids, a number that is cer- 
 tainly below the reality, the multitude of glycerine compounds of the 
 
 1000. 1001 .1002 
 
 third order will consequently be equal to - , that is to 
 
 1.2.3 
 say, pretty nearly two hundred millions. 
 
 " We see to what an almost infinite variety of complex compounds, 
 often analogous to, or identical with, certain natural substances, we can 
 give origin by combining a small number of compounds with the poly- 
 atomic alcohols." 
 
 If we are to have in one little corner of chemistry " two hundred 
 
GLYCERINE, THE TERATOMIC ALCOHOL. 391 
 
 millions" of complex compounds, bearing such names as chlorhy- 
 drobromhydrine, bromhydrodichlorhydrine, chlorhydrodibromhydrine, 
 acetochlorhydrobromhydrine, and dibutyrosulphurine, and having these 
 names explained by such awkward squads of symbols as constitute the 
 "unitary" formulae, which I have quoted on page 389, heaven help the 
 future student of chemistry, and give him a longer life and a better 
 memory than is allotted to mortal man in these days ! 
 
 If the discovery of these compounds throws so extraordinary a flood 
 of light over the constitution of glycerine, why is it that MM. Bert-helot 
 and De Luca have not dissected their unitary formula into rational 
 formulae? If that dissection is neglected while chemists are enlightened 
 by this flood of light, how is it ever to be effected afterwards ? Why 
 have these gentlemen not favoured us with an interpretation of the 
 formulae C l H 8 ClBrO 4 , which is assigned to the compound called Aceto- 
 chlorhydrobromhydrine, and of which compound it is said, that "it 
 contains at the same time glycerine, chlorhydric acid, bromhydric acid, 
 and acetic acid, and is the first compound ever prepared, in which three 
 different acids are combined with a single equivalent of glycerine ?" 
 
 As the authors have not answered that question, I will answer it. 
 Acetochlorhydrobromhydrine does not contain glycerine, it does not 
 contain chlorhydric acid, it does not contain bromhydric acid, it does not 
 contain acetic acid ; and yet it is said to contain all four. Here we 
 come upon a question of FACT, and that question must be settled before 
 we have any talk about theories. The authors take four hydrated acids, 
 which acids have among them six replaceable atoms of hydrogen, 
 which hydrogen is indispensable to the completion of the acids, as acids, 
 and cannot be separated from them without terminating their existence, 
 as acids. The authors separate from these four acids all the six atoms 
 of hydrogen, in company with three atoms of oxygen belonging to the 
 acetic and the glyceric acids, and they then combine together the residues 
 of the four acids left by the abstraction of these nine essential atoms, 
 and having done that, they affirm that this compound of the four residues 
 contains in fact all the four acids with which they commenced operations. 
 
 This method of philosophising reminds me of a joke to be found in 
 the pages of our old friend Joe Miller. You take, according to his 
 recommendation, the word " majesty." You abstract the two ends of it, 
 and having thus produced the residue, "a jest," you insist that this 
 residue is still " majesty," only minus its externals. In like manner, 
 our authors, in the present case, take the formula HC1, which represents 
 hydrocloric acid ; they remove H and leave Cl, and then they insist 
 that the residue, Cl, is still hydrochloric acid, having only undergone 
 the trifling abstraction of its external hydrogen. The blunder which 
 is committed by these gentlemen is that of treating the NEGATIVE 
 RADICALS of acids as if they were the SAME THINGS as the ACIDS IN A 
 STATE OF COMPLETENESS, and the blunder is one that vitiates the whole 
 
392 THE DOCTRINE OF POLYATOMIC ALCOHOLS. 
 
 train of their reasoning. In acetochlorhydrobromhydrine, instead of 
 having the four complete acids which are stated to be its constituents, 
 we have only the radical C 3 H 5 , the radical C 8 H 3 , the radical Cl, and the 
 radical Br, with two remaining atoms of oxygen. The simplest rational 
 formula for a compound containing only these residues is, 
 
 0^,310 + CTP.CIO; 
 
 according to which formula the compound is a combination of oxychlo- 
 ride of acetyl with oxy bromide of glycyl, and it contains not one of the 
 four acids which we are desired to believe to be collectively contained in 
 it. To offer such a compound as this, as evidence of the truth of the 
 theory, that glycerine is a teratomic alcohol, which can combine at once 
 with three different acids, is to suppose that we have lost the power to 
 observe facts, and the right to judge of their relations. If scientific 
 academicians admit such theories as this, proved by such evidence, to 
 be true philosophy, they ought to be punished by being made to commit 
 to memory the two hundred millions of hard words, which MM. Ber- 
 thelot and De Luca threaten to inflict upon us. 
 
 But, now, let it be understood, that I am making no objections to 
 the experiments and discoveries of these gentlemen, which are really 
 valuable. I object only to the ridiculous theory of polyatomic alcohols, 
 by which the interpretation of their results is caricatured. When the 
 new compounds are stripped of these dainty devices, we perceive their 
 value and utility. 
 
 Here follows a different interpretation of the 20 compounds described 
 in the above Table. Several of them have been already inserted at 
 pages 374, 375, namely, at Nos. 36, 6, 34, 35, 14, 38, and 26, in the 
 list there printed ; but I repeat them here, to facilitate, the comparative 
 view of the formula? and nomenclature of the whole set of compounds, 
 according to the two systems. 
 
 1. H,C 3 H 5 O a 4- HC1 . . Hydra glycylete cum hydra chlora. 
 
 2. H,C 3 H 5 O 2 4- HBr . . Hydra glycylete cum hydra broma. 
 
 3. H,H,C 2 H 3 ; C 3 H 5 4 . Hydren acetyla glycylote. 
 
 4. C 3 H 5 ,C1O 4- HC1 . . Glycyla chlorate cum hydra chlora. 
 
 5. C 3 H 5 ,BrO 4- HBr . . Glycyla bromate cum hydra broma. 
 
 6. C^^BrO 4- HC1 . . Glycyla bromate cum hydra chlora. 
 
 7. H,(C 2 H 3 ) 2 ; CWO 5 . . Hydra acetylen glycylute. 
 
 8. H,C 3 H 5 O 2 4- C 2 H a ,ClO. Hydra glycylete cum acetyla chlorate. 
 
 9. H,C 3 H 5 O 2 4- C 2 H 3 ,BrO Hydra glycylete cum acetyla bromate. 
 10. C 3 H 4 C1,C1 4- HC1 . . Chloric-glycyla chlora cum hydra chlora. 
 n. OTPBrjBr 4- HBr . . Bromic-glycyla broma cum hydra broma. 
 
 12. OTPB^Cl 4- HC1 . . Bromic-glycyla chlora cum hydra chlora. 
 
 13. C 3 H*Br,Cl 4- HBr . . Bromic-glycyla chlora cum hydra broma. 
 
 14. (C 2 H a ) 3 ; C 3 H 5 O 8 . . Acetyline glycylaze. 
 
GLYCERINE, THE TERATOMIC ALCOHOL. 393 
 
 15. C 3 H 5 ,C10 + C*H 3 ,C 2 H 3 O 3 Glycyla chlorate cum acetyla acetylite. 
 
 16.' C 3 H 5 .BrO+ C 2 H 3 ,C 2 H 3 O 3 Glycyla bromate cum acetyla acetylite. 
 
 17. C ? H 5 ,C1O -f- C 2 H 3 ,C1O . Glycyla chlorate cum acetyla chlorate, 
 
 j 8. C 3 H 5 ,BrO + C 2 H 3 ,BrO Glycyla bromate cum acetyla bromate. 
 
 19. C 3 H 5 ,BrO + C 2 H 3 ,C1O Glycyla bromate cum acetyla chlorate. 
 
 20. C 3 H 5 ,S0 3 -f C 4 H 7 ,C 4 H 7 O 3 Glycyla sulphite cum butyryla butyrylite. 
 
 [In this Table H = i, C = 12, = 16.] 
 
 These formulae do not exhibit the slightest trace of the existence of a 
 teratomic alcohol ; but, on the other hand, the cloud of smoke produced 
 by the unitary formulas being cleared away, we perceive that the com- 
 pounds are all double salts of very definite and intelligible constitution. 
 I need not repeat the arguments that have been already urged, but will 
 confine myself to a few explanatory notices. Nos. i and 2 are com- 
 pounds of monobasic glycylic acid with hydrogen acids. I might with 
 much safety declare that glycylic acid is allylic acid ; for these com- 
 pounds go far to prove that allyl and glycyl are identic. Nos. 3, 7, and 
 14, are the three acetines, which have been fully discussed at Nos. 6, 14, 
 and 26 of the former series. 4, 5, and 6, are compounds of oxy chloride 
 and oxybromide of glycyl with hydrogen acids. 8 and 9 are compounds 
 of monobasic glycylic acid with oxychloride and oxybromide of acetyl. 
 10, n, 12, 13 are bichlorides, bibromides, &c. of chloric-glycyl and 
 bromic-glycyl, that is to say, of glycyl in which H 1 has been replaced by 
 Cl l or Br l . This vice-radical is analogous in its constitution to the 
 bromic-phenyl and chloric-phenyl, which occur in the aniline series. See 
 page 276. 15 and 16 are compounds of oxychloride and oxybromide of 
 glycyl with anhydrous acetic acid. 17, 18, and 19, are all pairs of 
 compounds of oxychloride and oxybromide of acetyl, with oxychloride 
 and oxybromide of glycyl. No. 20 represents a double anhydride, each 
 containing two acid radicals and consequently three atoms of oxygen. It 
 will be seen, that the theoretical views which I have explained, give a 
 reason for the quantity of oxygen which is present in each compound, 
 and for its allotment to special salts. According to the unitary system, 
 the quantity of oxygen which remains in each compound is simplv what 
 the hydrogen did not require for its conversion into water ; but, accord- 
 ing to my view, the oxygen that remains is that which is demanded by 
 the number and the chemical powers of the residual radicals. 
 
 If the chemical quaternions which appear in the above list were 
 really, as MM. Berthelot and De Luca describe them, quadruple hy- 
 drated acids, it would be indeed a marvellous thing that so many of 
 them should be perfectly neutral. But when we perceive that these 
 neutral compounds are anhydrides, and reflect that even the sulphuric 
 anhydride is neutral, the wonder ceases ; and w'e perceive that the re- 
 moval from the compounds of the basic hydrogen is the removal of the 
 
394 NITRO-GLYCERINE. 
 
 chemical power, by means of which the acidity of the hydrated acid was 
 made manifest. Hence it is consistent with all analogies, that such 
 compounds as Nos. 15 to 20, each formed by four acids, should, after 
 abandoning }HHO, become perfectly neutral. Let it be remembered, 
 however, that these compounds, though formed by four acids, do not 
 contain four acids. 
 
 NITRO-GLYCERINE. A note by Professor Williamson on this com- 
 pound appears in the Proceedings of the Royal Society for June 15, 
 1854. By acting on glycerine with a mixture of nitric and sulphuric 
 acid, he produced a compound of the following constitution : 
 
 3 NO* = CO 6 + 3 HO. 
 
 He considers that 3 H in glycerine are replaced by 3 NO 4 . On boiling 
 this compound with a concentrated solution of potash, it produced gly- 
 cerine and nitrate of potash. See Railton's Nitroglycerine, No. 43, 
 page 385, with which Williamson's nitroglycerine is identic. 
 
 Hence it appears that Professor Williamson was on the point of dis- 
 covering in 1854 those relations of glycerine to acids, which Berthelot 
 and De Luca have been engaged in determining since that period. 
 
 At Nos. 42 and 43, I have formulated nitroglycerine as if it contained 
 a zotic vice- radical, which is the view that best accords with the com- 
 monly-received opinion of its constitution ; but the recent experiments 
 of MM. Berthelot and De Luca point, I think, to conclusions that are 
 more accurate, and which may be expressed as follows : 
 
 No. 42, De Vrij's Nitroglycerine : 
 
 fC 9 H 5 NO 4 ) 
 = I H 'NO 3 l = Glycyla nitrote cum hydra nitrite. 
 
 No. 43, Williamson and Railton's Nitroglycerine: 
 
 {C 3 H 3 NO 4 ) 
 N 'NO 5 l = ^ty c yl a nifrote cum nitra nitmte. 
 
 Hence No. 42 is, in Berthelot's language, Binitrine, and No. 43 is 
 Ternitrine. We have yet to find Mononitrine, the formula of which will 
 be, H^H'O 2 -f- H,N0 8 . Expressed synoptically, these three salts are : 
 
 Mononitrine = H,H,N ; 
 Binitrine = H,N,N ; 
 Ternitrine = N,N,N; 
 
( 395 ) 
 
 Theory of Polybasic and Conjugated Acids. 
 
 Chemists have divided the salts of organic acids into three classes, 
 which are said to contain one, two, or three equivalents of base combined 
 with one equivalent of acid. This classification is so simple as to seem 
 clear of all difficulties ; but when we examine the facts, we find that the 
 distribution of salts into these three classes is impracticable. Gerhardt 
 and other chemists have, it is true, provided their disciples with abund- 
 ance of rules for discriminating these different classes of acids from one 
 another. But Gmelin that master-spirit among systematic chemists 
 while explaining and illustrating these rules, nullifies them all in one 
 short condemning sentence. " It is difficult," he says, " to decide with 
 any degree of certainty" [with any degree of certainty !~\ " whether the 
 formula of an acid should be so written as to make the acid monobasic, 
 or twice as great so as to make it bibasic, or three times as great, so as 
 to make it terbasic." (Handbook of Chemistry, 1852, vii. 198.) 
 
 The law of simplicity, which nature always obeys, exacts from philo- 
 sophers the simplest possible interpretation of every phenomenon. If a 
 chemical fact can be explained by reference to two chemical atoms, it is a 
 violation of the law of simplicity to explain it by reference to four or to 
 six atoms ; and this violation of a fundamental law ought not to occur 
 unless enforced by overpowering facts. If it is possible to explain the 
 constitution of salts by reference to monobasic acids, it is wrong to 
 resort to bibasic acids or to terbasic acids, or to any other irregular or 
 complex form of combination. The existence of such irregular com- 
 pounds ought only to be admitted when proved by stringent evidence. 
 
 But, according to Gmelin, many of these polybasic acids are sup- 
 ported by no evidence whatever. They are not facts in chemistry, but 
 contrivances in arithmetic. You make a monobasic acid into a bibasic 
 acid by doubling its formula. You make it into a terbasic acid by 
 tripling its formula. And "it is difficult to decide with any degree of 
 certainty" whether the effects produced by this multiplication are right 
 or wrong. 
 
 There can, at any rate, be little difficulty in deciding, whether the 
 practice of such manoeuvres is right or wrong. The law of simplicity 
 forbids it. The doubling and tripling of formula?, when not commanded 
 by facts, and when resorted to for the purpose of bolstering up theories 
 that are supported by no other evidence, is a trick which men of science 
 should scorn. 
 
 If it is " difficult to decide with any degree of certainty" whether an 
 acid with a doubled or tripled formula is really bibasic or terbasic, no 
 benefit can be derived from the acceptance as realities of compounds so 
 purely hypothetical; for, after we have manufactured them, we cannot 
 
396 THEORY OF POLYBAS1C AND CONJUGATED ACIDS. 
 
 safely use them, being placed in the unscientific predicament of floundering 
 amidst uncertainties. If acids are truly polybasic, plain facts will be 
 forthcoming to prove it. If polybasic acids are phantoms, undiscover- 
 able in nature, unsupported by experiment, and resulting only from the 
 duplication or triplication of the formulas of monobasic acids, the recog- 
 nition of such things as scientific facts, is a mockery of scientific 
 exactness. 
 
 Let us examine these so-called polybasic acids with a determination to 
 find out what they really are. We resolve beforehand not to be de- 
 ceived by the masquerading habits in which mobs of atoms may be 
 attired, to play the part of daws in borrowed plumes. When we come 
 upon a terbasic acid whose status seems to depend upon a formula 
 written " three times as great" as that of a monobasic acid, or upon a 
 bibasic acid whose letters of recommendation are " twice as great" as 
 those of a monobasic acid, we will examine, whether these pretentious 
 bodies are actually polybasic acids, or only things that are made to 
 appear like polybasic acids by the force of cumulative symbols ; we will 
 ascertain whether they are objects in nature, or contrivances of art ; 
 whether they have been discovered in the laboratory, or invented at the 
 writing-desk. In other words, we will endeavour to determine whether 
 there really exist such compounds as polybasic acids, or whether all 
 acids are not invariably and absolutely monobasic. The theory of the 
 constitution of salts ought not to remain in the state of dreary doubtful- 
 ness in which Gmelin represents it to be. Chemists must either prove 
 that polybasic acids ARE polybasic absolutely and unquestionably poly- 
 basic, and not polybasic by convention upon the strength of *' trimmed " 
 formulae or they must cease to use a term which, on the failure of such 
 proof, must be held to countenance an illusion. 
 
 For my part, I reject the commonly-received doctrines respecting 
 polybasic acids in toto, and I hope to be able to prove to the reader that 
 those doctrines are unworthy of credit. A salt, as I understand that 
 term, is a compound of two radicals, which may be either simple or 
 compound, oxidised or not oxidised, but each of which radicals must be 
 equivalent to one volume or one atom of hydrogen. I do not admit that 
 one acid radical can combine directly with two or with three basic 
 radicals, nor that one basic radical can combine directly with two or 
 with three acid radicals. The saturating capacity of a radical never 
 changes. It is always equal to the equivalent of one volume of hydrogen. 
 I admit, nevertheless, that salts exist which contain unequal numbers of 
 basic and acid radicals, and I explain that fact by the following hypo- 
 thesis : 
 
 Let B = any Basic radical. 
 A = any Acid radical. 
 
 The formula B -f- A represents most of the salts with which we are 
 
THEORY OF POLYBASIC AND CONJUGATED ACIDS. 397 
 
 acquainted, such as the sulphates, the oxalates, the acetates, the ben- 
 zoates, and other normal salts of monobasic acids. I make it here a 
 question of the combination of two radicals, leaving the oxygen, both as 
 regards its quantity and its distribution, entirely out of consideration. 
 
 The normal salt B + A, I consider to be able to act as a basic radical 
 against A, and as an acid radical against B. Hence B + A can com- 
 bine with the radical B, and produce the compound salt BA + B. In 
 this manner the carbonates are produced. See page 183. These salts 
 are bibasic and monacid. In the same way, the normal salt B + A can 
 combine with the radical A, and produce the compound salt A + BA. 
 In this manner we obtain the hyposulphates. See page 172. These 
 salts are monobasic and biacid. Thus, we have a clear distribution of 
 salts into three classes : 
 
 Bibasic and monacid = B,BA. 
 Normal = BA. 
 
 Monobasic and biacid = BA,A. 
 
 These three classes of salts are distinguishable by analysis, and present 
 no uncertainties. The cloud which everlastingly envelops the com- 
 pounds of " acids and bases," disappears when you look at the salts 
 through the medium of the radical theory. You then perceive the true 
 nature of double salts, not only of those which are biacid and bibasic in 
 the sense which I have just explained, but of these which are at the same 
 time bibasic and biacid, or which are double salts in the ordinary sense 
 of that term ; such as the sulphites, the bisulphates, and the phosphates. 
 In the preceding pages, I have thoroughly investigated the constitution 
 of these several classes of salts ; and in the article on the phosphates, I 
 have especially shown in what manner the acids that are commonly 
 called bibasic and terbasic, may be reconciled with the theory which 
 admits of none but monobasic acids, or, to speak more accurately, with 
 the theory which assumes that every radical has, under all circumstances, 
 the saturating capacity of a single volume of hydrogen a chemical power 
 which nothing can increase nor diminish. 
 
 Undoubtedly, the bibasic phosphates contain two basic radicals, and 
 the terbasic phosphates contain three basic radicals, to each single acid 
 radical, provided you narrow the meaning of the term acid radical so as 
 to make it include only the phosphorus of these salts. But I am for 
 giving to the term acid radical a wider signification. The radicals which 
 occur in the phosphates, exclusive of phosphorus, are hydrogen, metals, 
 and hydrocarbons. None of these radicals are necessarily incompetent to 
 act the part of acid radicals. I have shown that hydrogen, under the 
 force of one set of circumstances, can act as an acid radical just as 
 decidedly as, under the force of another set of circumstances, it can act 
 as a basic radical. In water if the formula H + HO is accepted as its 
 model hydrogen acts both as a basic radical and as an acid radical ; and 
 
398 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 in the consequences which flow from the adoption of this model, we 
 have ample evidence of the fact, that what we call basicity and acidity 
 are qualities that are relative and not absolute ; so that either of them 
 may be justly applied to the same radical placed under the action of dif- 
 ferent chemical forces. Thus, in hydrate of lime = Ca + HO, the cal- 
 cium is a basic radical, while in quicklime = Ca -f- CaO, the oxidised 
 atom of calcium is in the condition of an acid radical. If Ca -f- CaO 
 comes into reaction with H + HO, double decomposition occurs, and the 
 basicity and acidity of the four radicals are so changed, that both the 
 atoms of Ca become basic, and both the atoms of H become acid : 
 
 Ca,CaO -f H,HO = Ca,HO -f- Ca,HO. 
 
 This hypothesis is in accordance with the electro-chemical theory, and 
 commands all the support which that theory can give it. 
 
 According to this method of viewing the relationships of radicals, the 
 salts that are called terbasic phosphates and bibasic phosphates, are not 
 to be considered as compounds respectively of three atoms of base and 
 two atoms of base with one atom of acid, but as double and triple salts 
 in which the number of basic radicals and acid radicals is in all cases the 
 same. Thus : 
 
 KO -{- POO The monobasic phosphate, a single normal salt. 
 
 IKO 4- POO) ^ e ter k as i c phosphate, a double salt, con- 
 KO f Dining a monobasic phosphate and a salt 
 on the model of water. 
 
 -- 
 
 K" ~-L KO f I ^ e bibasic phosphate, a triple salt, containing 
 botn tne above varieties. 
 
 I have entered so fully into details respecting the constitution of the 
 Phosphates, in the article given at page 138, that I need only to refer to 
 that article for farther explanations, and for evidence of the facts. The 
 conclusion to which I wish to bring the reader's attention is, that if, as I 
 assume, the phosphates are multiple salts, built up of normal monobasic 
 salts, they lend no support to the commonly-received doctrines respecting 
 the constitution of polybasic organic acids ; so that, when we come to 
 examine the constitution of organic acids, we are not to be led astray by 
 the intimation that this acid is terbasic, and that that acid is bibasic, 
 because their salts agree in form with the terbasic and the bibasic phos- 
 phates, but we are to insist that every acid which claims to be terbasic 
 or bibasic shall individually supply evidence to justify its particular claim. 
 If we pursue that course, I expect that we shall end our inquiry by prov- 
 ing that the theory of Polybasic Acids is a FALLACY. 
 
BISULPHATES OF ALCOHOL RADICALS. 399 
 
 Before I proceed to the critical analysis of bibasic and terbasic acids, I 
 must trouble the reader with a glance at the theory of conjugated acids ; 
 for I find it to be impossible to keep the details respecting polybasic 
 acids and conjugated acids from intermixture. 
 
 Bisulphates of Alcohol Eadicals. 
 
 The positive or basic radicals of the vinyl series combine with sulphur 
 and oxygen to form a variety of salts, sulphates, sulphites, &c. In each 
 of these salts, that quantity of the compound radical which is equivalent 
 to one volume of hydrogen, replaces one atom of hydrogen of the 
 hydrated acid, and produces a neutral salt ; such as 
 
 CH 3 ,SO* = Sulphate of methyl. 
 
 C 5 H ll ,SO 2 = Sulphate of amyl. 
 C 2 H 5 C 2 H 5 S*0 3 1 
 
 = Sul P hite 
 
 When these salts are gaseous, their atomic measure is the same as that 
 of their positive radicals, because neither sulphur nor oxygen exhibits any 
 measure in gaseous salts. 
 
 These neutral sulphates and sulphites of alcohol radicals have the pro- 
 perty of forming double or acid salts by combining with an equivalent of 
 hydrated acid. Thus we obtain such compounds as the following : 
 
 CH 3 ,SO 2 + H,SO 2 1 , 
 
 = H CH 3 - (SOYl = ^sulphate of methyl. 
 
 C 5 H ll ,S0 2 + H,S0 2 ) . , , . 
 = H C 5 H'*- (SO 2 ) 2 / = Blsul P bate 
 
 H ; C 2 H 5 ; S 2 O 3 1 
 = CW,SO + H,S0 2 | = Bisulphite of ethyl. 
 
 In all of these salts, the atom of H is replaceable by any other basic 
 radical, simple or compound; by which replacement it is possible to 
 produce a great variety of salts, in accordance with the above formula?. 
 
 This is my view of the constitution of this class of double salts ; but 
 the view which is commonly accepted by chemists is entirely different, 
 and it is into the investigation of the propriety of this different view, 
 that I have to request the reader to follow me. 
 
 According to the common opinion, the oxidised sulphur contained in 
 one of these salts is directly combined with its oxidised organic radical, 
 into a "Conjugated" "Copulated" "Coupled" or "Colligated" ACID, 
 which acid produces salts by combining with HO or MO, considered a 
 
400 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 a BASE. Now, I deny that there is any evidence to prove the formation 
 of such Conjugated Acids, or that the organic radical ever acts otherwise 
 in these salts than as a basic radical, neutralising one-half of the oxidised 
 sulphur, or that proportion whose hydrogen it replaces, and leaving free 
 for action the other half of the oxidised sulphur, whose hydrogen it has 
 not replaced, and whose saturating capacity it has not nullified. The 
 problem for determination, therefore, is, whether the alcohol radicals 
 which are present in these salts, act as basic radicals, or as ingredients in 
 conjugated acid radicals. I shall confine the discussion at present to the 
 bisulphates, leaving the investigation of other sulphur salts to other 
 sections. 
 
 The following formula? are written according to my notation and 
 atomic weights : 
 
 C 2 H 5 ,SO 8 + H,SO 2 = H;C 2 H 5 ; (SO 2 ) 2 . 
 C 2 H 5 ,S0 2 + K,SO 2 = K; C 2 H 5 ; (SO 2 ) 2 . 
 
 The first of these salts is the double sulphate of ethyl and hydrogen. It 
 is commonly called the sulphovinic acid. The second salt is the double 
 sulphate of ethyl and potassium. It is commonly called the sulphovinate 
 of potash. Their names according to the new nomenclature are as 
 follow : 
 
 H; C 2 EP; (SO 2 ) 2 = Hydra ethyla bisulphete. 
 
 K; C 2 H 5 ; (SO 2 ) 2 = Potassa ethyla bisulphete. 
 
 In organic chemistry, we find a multitude of sulphates of this descrip- 
 tion, each of which contains ethyl or some other basic radical of the vinyl 
 series, and in all of them the basic H or K, is replaceable by any other 
 metal or basic radical, producing an extensive series of double sulphates, 
 agreeing exactly in composition with the double sulphates of the in- 
 organic kingdom. See page 1 50. But organic chemists are not content 
 to consider the sulphovinates as double sulphates. That would be in 
 effect the accommodation of organic chemistry to the rules of inorganic 
 chemistry, whereas it appears to be an article of faith with the professors 
 of organic chemistry that, before all things, it is necessary to cut an 
 impassable trench between the two departments of the science, and so 
 prevent their intermixture. Hence the " conjugated sulphates " are re- 
 moved from the domain of inorganic chemistry; each of them is assumed 
 to- be something different from an ordinary bisulphate, and is raised to 
 the dignity of a special acid, and made the heading of a new chapter in 
 every book on organic chemistry. From this notion arise the sulphovinic 
 acid, the sulphomethylic acid, the sulphamylic acid, the sulphophenylic 
 acid, the sulphethalic acid, and scores of others ; all of them prolific 
 sources of troublesome, puzzling, worthless synonymes, which encumber 
 the books, load the memory, and hinder the progress of the science which 
 their advocates sarcastically make pretensions to advance. 
 
BISULPHATES OF ALCOHOL RADICALS. 401 
 
 What is gained by the subdivision of chemical compounds into 
 innumerable petty families, founded upon distinctions without differ- 
 ences, and which is so common among these conjugated acids? What 
 is the gain, beyond perplexity and time-wasting? The excuses com- 
 monly made for this practice are scarcely worthy of serious discussion. 
 In regard to the sulphovinates, the excuse is, that a solution of this acid 
 gives no precipitate with a solution of barytes, and therefore it cannot 
 be a solution of a sulphate. The fact does not warrant the conclusion. 
 What the sulphovinic acid could produce by double decomposition with 
 a salt of barytes, is, the double sulphate of barytes and ethyl, which is a 
 soluble salt and consequently not precipitable. To conclude, from the 
 non-precipitation of this salt, that no sulphates are present, is to set all 
 knowledge of the properties of double salts at absolute defiance. This 
 is not reasoning ; this is not chemical science ; it is only a fashion with 
 organic chemists. 
 
 But this excuse is bad for another reason. The action of inorganic 
 reagents upon the radicals of inorganic acids in the presence of organic 
 radicals, is almost always different from the action which they exercise 
 when none but inorganic radicals are present, This is the case not only 
 when the inorganic acids are combined with basic organic radicals, but 
 also when acid organic radicals, and even neutral organic compounds, 
 such as sugar, are present in the solution. The action of the reagents is 
 different, because they are applied under different circumstances. There 
 is a strong tendency in all organic radicals to produce compound soluble 
 salts with one another, and with inorganic radicals. This complicates 
 the action of the reagents, and it is consequently rash in the highest 
 degree to declare that a solution contains no sulphuric acid, merely be- 
 cause it gives no precipitate with a solution of barytes in the known 
 presence of organic radicals. 
 
 The absurdity of setting forth these double sulphates as conjugated 
 acids is best seen if we compare one of them with a double salt of 
 similar constitution, but having an inorganic positive radical : 
 
 C 2 H 5 ,S0 2 + HSO 2 = Bisulphate of ethyl. 
 K,SO 2 + HSO 2 = Bisulphate of potash. 
 
 These two compounds are equivalent, atom for atom. The theory of 
 conjugated acids supposes that, in the bisulphate of ethyl, only the 
 single atom of hydrogen is basic, and that all the other constituents of 
 the compound become conglomerated into an acid radical, which pro- 
 duces the conjugated acid : 
 
 H + C 2 H 5 ,S0 2 ,S0 2 = Ethylo-sulphuric acid. 
 
 The same transformation, performed on the inorganic bisulphate, would 
 produce a similar coniugated acid : 
 
 2 D 
 
402 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 H -f K,SO 2 ,SO 2 = Potassio-sulphuric acid. 
 
 And this conjugated acid, like the former, actually produces a whole 
 series of salts, such as 
 
 Mg -j- K,SO 2 ,SO 2 . Potassio-sulphate of magnesia. 
 
 G + K,SO 2 ,SO 8 . Potassio-sulphate of glucina. 
 C 2 H 5 -f K, SO 2 , SO 8 . Potassio-sulphate of ethyl. 
 
 The potassio-sulphtiric acid is moreover completely justified by M. Ger- 
 hardt's law for determining the basicity of conjugated acids. That 
 law says, that if you add together the basicity of all the elements of a 
 conjugated acid, and deduct i from the sum, the residue is the basicity 
 of the conjugated acid. Now if we add, as he instructs us, 2 for the 
 two atoms of sulphuric acid to o for the potassium, and deduct i, we 
 have a residue of i , which is, true enough, the basicity of the bisulphate 
 of potash. You can, to be sure, by looking at the formula of bisulphate 
 of potash, and observing that it contains just i atom of basic hydrogen, 
 come to the same conclusion without a law and without a reckoning, 
 but that is too empirical a mode of procedure to please organic chemists, 
 whose awful gravity is best pleased with obscure laws and profound 
 complexity. 
 
 I have elsewhere stated, but I may repeat the statement here as 
 apropos to the occasion, that Gerhardt's law for determining the basicity 
 of a conjugated acid is erroneous. If the saturating capacity of each 
 acid radical of the compound be reckoned as unity, or i , it is absurd to 
 reckon the saturating capacity of the basic radical which is presumed to 
 be acting as part of the acid radical as null, or o. It ought to be reck- 
 oned as a minus quantity, viz., i. It is this blunder which makes 
 Gerhardt declare that the basicity of a conjugated acid is always less by 
 unity than the collective basicity of its constituents. But the saturating 
 capacity of a radical can neither be lost nor lessened. The quantity i 
 cannot become o, except by neutralisation with the quantity i. 
 
 Chemists of the old school will perhaps say, that it is absurd to convert 
 bisulphate of potash into an acid, and to make potassium form part of a 
 compound acid radical, and I grant that it is absurd ; but I am showing 
 that the acknowledged laws for constructing conjugated acids and for 
 determining their basicity, require no straining to make them warrant 
 that procedure. If, therefore, chemists of the old school forbid the con- 
 struction of 
 
 C 2 H 5 ; K,S 2 4 = the Potassio-sulphate of ethyl, 
 let them also forbid the construction of 
 
 K; C 2 H 5 ,S 2 4 = the Ethylo-sulphate of potash, 
 for the latter is quite as extravagant as the former, and there is no more 
 
BISULPHATES OF ALCOHOL EADICALS. 403 
 
 reasonable excuse for making a compound acid radical with ethyl than 
 for making one with potassium. 
 
 These conjugated acids and their salts are elaborately described in the 
 chemical systems of Gmelin and Gerhardt, yet the latter, in the conclud- 
 ing part of his work, has declared that the sulphovinic acid is a bibasic 
 sulphate, and that acids of that class are not to be considered as " con- 
 jugated." But the age of knight-errantry has not entirely passed away, 
 and when one doughty champion abandons his lady-love, another 
 appears ready to rescue her from destruction. So, just as Gerhardt 
 retires from the lists, Dr. Guthrie stands forward as the champion 
 of the conjugated acids, and publishes a Paper to prove that the 
 prevalent views respecting them are correct. As I entirely dissent 
 from his conclusions, I shall quote and examine his experiments and 
 arguments. 1 
 
 "With respect to the rational constitution of the sulphovinates, 
 chemists are at present so far agreed as to admit in them the presence of 
 sulphuric acid. An objection was formerly raised to this view, on the 
 ground that the sulphuric acid could not be shown to exist, as such, by 
 means of the usual reagents ; and it was assumed that the salts in ques- 
 tion contained hyposulphuric acid. This position has, however, been 
 overthrown, partly by the discovery of isethionic acid, partly by the 
 observed behaviour of other compounds of ethyl, such as the chloride and 
 sulphide of ethyl, in which the chlorine and sulphur are much more 
 difficult to recognise by means of nitrate of silver, than is the case with 
 the soluble inorganic compounds of these bodies. 
 
 " A question, however, which still has to be answered, is ' In 
 what manner do the sulphovinates contain the sulphuric acid ?' 
 
 " Those chemists who look upon sulphuric acid as a bibasic acid, and 
 express the composition of its hydrate by the formula 2HO,S 2 O 6 , view, 
 for the most part, the salts of sulphovinic acid as basic sulphates, one of 
 whose atoms of base is potash, and the other oxide of ethyl. They 
 accordingly class sulphovinate of potash with the so-called double salts 
 of sulphuric acid, such as the potassio-sulphate of zinc. 
 
 Q >S 2 6 , Sulphate of potash and zinc. 
 S 2 6 , Sulphate of potash and ethyl. 
 
 " Now, in the first place this view is contradicted by the fact that 
 the oxyde of ethyl in the second of these salts cannot be driven out by 
 
 1 On the Sulphovinates, and on Amylophosphoric Acid and the 
 Amylophosphates. By F. Guthrie, B.A, Ph. D., Quarterly Journal of 
 tJie Chemical Society (1856), IX. 131. 
 
 2 D 2 
 
404 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 a more powerful base, as is the case with its analogue, the oxide of zinc, 
 in the inorganic sulphate. Even on continued boiling with potash, the 
 ether is not given off as alcohol. The difficulty of maintaining this 
 view, again, is materially increased when we reflect that in the 
 
 Neutral sulphate of ether, 
 
 the one atom of ether may be eliminated or exchanged for water, or a 
 base, much more easily than the other ; and that the so-called neutral 
 ethers, such as acetic, nitric, or oxalic ether, on being boiled with 
 caustic potash, are transformed under formation of alcohol, into the 
 potash salts of the corresponding acids. 1 
 
 " These considerations render it more than doubtful whether the 
 metallic oxide and the oxide of ethyl be equally basic in function. It 
 seemed desirable, that new facts should be gained for the elucidation of 
 this point. I imagined that such facts might be furnished by the 
 behaviour of an aqueous solution of the sulphovinate towards the gal- 
 vanic current. For if, in the sulphovinate of potash, both the potash 
 and ether be united as base with the sulphuric acid, we should be 
 justified in expecting, on electrolysing a concentrated aqueous solution 
 of this salt, that, at the + pole, sulphuric acid and oxygen would be 
 liberated, and, at the pole, potassium (potash and hydrogen), 
 together with ethyl (or ether or some ethyl compound, possibly 
 hydride of ethyl). 
 
 " Into a cold, concentrated, aqueous solution of sulphovinate of 
 potash, free from sulphate of potash, I accordingly introduced two 
 platinum electrodes, in such manner that they were separated by a 
 porous clay cell. The electric current from four Bunsen's carbo-zinc 
 elements was sufficient to effect a lively disengagement of gas at both 
 poles, accompanied by an evolution of heat which rendered cooling 
 from the exterior necessary. In a short time the liquid surrounding 
 the + pole showed a strong acid reaction. The gas which was here 
 liberated smelt distinctly of aldehyde, and consisted of oxygen and car- 
 bonic acid. The liquid at this pole gave, with chloride of barium, a 
 white precipitate which was insoluble in hydrocloric acid. Sulphuric 
 acid was therefore present in the free state. At the same time, the 
 liquid at the pole assumed an alkaline reaction, and the gas there 
 
 1 These arguments proceed on the unwarranted assumption, that the 
 properties of organic sulphates ought to be the same as the properties 
 of the inorganic sulphates. We might as reasonably argue, that the 
 inorganic sulphates ought all to have uniform properties, and that 
 sulphate of magnesia cannot be a sulphate because it is not insoluble, 
 like sulphate of barytes. J. J. G. 
 
BISULPHATES OF ALCOHOL RADICALS. 405 
 
 liberated proved to be pure hydrogen. I satisfied myself, by careful 
 examination, of the entire absence of all carboniferous gases, nor could 
 I detect at this pole the slightest traces of ether or alcohol. 
 
 " It was imagined that the sulphuric acid and the aldehyde, which 
 appeared at the -f- pole, might be secondary products of decomposition, 
 effected by the oxygen, in statu nascenti. To get rid of this secondary 
 decomposition, I formed the -f pole of amalgamated zinc. On com- 
 pleting the circuit, a lively disengagement of gas took place at the 
 pole, as before, while, on the other hand, at the + pole, no gas at 
 all was liberated, and neither aldehyde nor sulphuric acid were formed. 
 The zinc electrode, however, soon became covered with a pellicle of sul- 
 phovinate of zinc, which, after a time, broke the electric current. Again, 
 a fresh solution being taken, the liquid at the + pole was made strongly 
 alkaline with carbonate of potash. On the introduction of platinum 
 electrodes, carbonic acid was plentifully liberated at the + pole, but as 
 no sulphate of potash could be detected, it followed that this was due to 
 the liberation not of sulphuric, but of sulphovinic acid. 
 
 " In the same manner, making use of platinum electrodes, I electro- 
 lysed an aqueous solution of amylosulphate of potash, and recognised 
 precisely analogous phenomena. At the -f- Pl e > oxygen was liberated, 
 and a distinct smell of valerianic acid noticeable. The solution around 
 this pole became acid, and contained sulphuric acid. At the pole the 
 liquid became distinctly alkaline, and the gas there liberated was, as 
 before, pure hydrogen. The slightest traces of fusel oil or amylic ether 
 would at once have been recognised, by their powerful odour, had they 
 been separated. The liquid at the pole remained inodorous. 
 
 " From these experiments I believe the conclusion may legitimately 
 be drawn, that in amylosulphate and sulphovinate of potash, the oxides 
 of ethyl and amyl have not the same function as the potash, but they 
 are combined with the sulphuric acid in a different, and, as it appears, a 
 more intimate manner. The fact that, on electrolysis, these organic 
 oxides remain with the sulphuric acid, and accompany it to the -f- pole, 
 shows that the potash alone is the electro-positive constituent of these 
 
 KO ) 
 
 salts, and that the formula /-^TTSQ > S 2 O 6 expresses a hypothesis on the 
 
 constitution of sulphovinate of potash which rests upon false assump- 
 tion. 
 
 " It seemed to me of importance to examine in a similar manner the 
 ethylophosphates, and to see whether in these the organic oxide is 
 liberated at the -f- pole, as in the sulphovinates, or whether it goes to 
 the pole. For this purpose, the amylophosphate of potash was 
 chosen, because, if the oxide or hydrated oxide of amyl were liberated, 
 together with the metallic oxide, at the pole, it would be at once re- 
 cognised by the mere odour. On introducing the platinum electrodes 
 into a concentrated aqueous solution of amylophosphate of potash, sepa- 
 
406 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 rated into two portions by a clay cell, hydrogen was liberated at the 
 pole, and oxygen, together with carbonic acid at the -f- pole. The 
 solution at the latter pole assumed an acid reaction, and smelt distinctly 
 of valerianic or butyric acids (evidently secondary products of decom- 
 position), the liquid at the pole became alkaline but remained 
 odourless. 
 
 " From this it would appear that in the amylophosphates, and, gene- 
 rally, in the ethylophosphates, we are not at liberty to assume that the 
 organic oxides are combined in the same manner as the metallic oxides ; 
 that is, as base. Accordingly, we must not understand the ordinary for- 
 mulae for ethylo- and amylophosphate of potash 
 
 2 KO \ prv > , 2 KO \ pr . 5 
 
 o^p ir ^" tf wtfK)r J 
 
 as if the organic oxides played the same part in them as does the basic 
 water in the ordinary tribasic phosphate of potash TT~ I . PO 5 , but we 
 
 must rather assume that the phosphoric acid, together with the oxide of 
 amyl, forms a bibasic amylophosphoric acid." 
 
 With submission to Dr. Guthrie, I hold that the results of his experi- 
 ments are entirely at variance with the conclusions which he is pleased 
 to draw from them. He considers that " on electrolysis, the organic 
 oxides remain with the sulphuric acid, and accompany it to the -}- pole, 
 showing that the potash alone is the electro-positive constituent of the 
 salts." But his experiments prove, that when ETHYL is operated upon, 
 instead of going with the sulphuric acid to the + pole, it suffers decom- 
 position into hydrogen, which goes to the pole, and the acid radical 
 acetyl, which goes in the form of aldehyd to the + 
 
 Ethyl = C^ 5 - H* = CTP Acetyl. 
 
 So also the experiments prove that when amyl is operated upon, it does 
 not go with the sulphuric acid to the -f- pole* but is decomposed into 
 hydrogen, which goes to the pole, and the acid radical valeryl, which 
 goes to the + pole in the form of valerianic acid : 
 
 Amyl = C 5 H U - H* = C 5 H 9 Valeryl. 
 
 The result is the same in the presence both of sulphuric acid and phos- 
 phoric acid. Neither of these acids prevents the reduction of ethyl to 
 acetyl, nor of arnyl to valeryl, and Dr. Guthrie' s assumptions that ethyl 
 and amyl go to the + pole in combination with the strong acids, be- 
 cause he finds then acetyl and valeryl are consequently unwarranted, and 
 at variance with his experiments. I have already drawn attention to the 
 
BISULPHATES OF ALCOHOL EADICALS. 407 
 
 general fact, that compound radicals which contain one atom of hydrogen 
 above the proportion contained in any multiple of the neuter radical 
 vinyl (see page 76) are in most cases basic or positive radicals, but con- 
 vertible into acid or negative radicals by the abstraction of two atoms of 
 hydrogen. Dr. Guthrie's experiments confirm this general fact; they 
 prove that ethyl is reducible to acetyl, and amyl to valeryl, that the 
 abstracted hydrogen goes to the pole, and that the two acid radicals, 
 go, as they ought to go, to the + pole, with the sulphuric and phos- 
 phoric acids ; but this is the very opposite from proving that ethyl and 
 amyl are acid radicals, that they act as such in the sulphovinates and 
 the amylo phosphates, and that, when these salts are electrolysed, the 
 radicals in question accompany the mineral acids to the + pole ; and, 
 therefore, I say that Dr. Guthrie's arguments are at variance with his 
 experiments. 
 
 The electrolysis of the organic radicals, if we may judge from the 
 experiments quoted at page 76, and from these new experiments made 
 by Dr. Guthrie, appears to be subject to the following general con- 
 ditions : 
 
 i). When negative radicals in the state of salts of potash are 
 operated upon, the negative radicals lose carbon and become positive 
 radicals. Thus valeryl becomes butyl, acetyl becomes methyl, caproyl 
 becomes amyl, and cenanthyl becomes hexyl. 
 
 2). When positive radicals in the state of sulphates, phosphates, &c., 
 are operated upon, they lose hydrogen and become negative radicals. 
 Thus, ethyl becomes acetyl, and amyl becomes valeryl. 
 
 Dr. Guthrie's experiments have served to enlarge our knowledge of 
 these particulars, and to strengthen the argument respecting the consti 
 tution of the conjugated sulphates ; only he misunderstood his results, 
 and drew his conclusions in favour of the wrong side of the argument. 
 
 The result of this investigation is to confirm the opinion with which I 
 set out, and with which I trust the reader will now agree, namely, that 
 all the sulphates which contain positive radicals of the vinyl series, in 
 company with metallic radicals, are merely double salts. I find nowhere 
 either experiments more decisive, or arguments more cogent, in support 
 of the doctrine of conjugated acids (as distinct from double salts) than 
 the arguments and experiments of Dr. Guthrie. 
 
 And this conclusion applies, not merely to the sulphates, but to the 
 phosphates, sulphites, hyposulphates, carbonates, oxalates, and all 
 similar " conjugated " salts. The whole of these I take to be double 
 salts, in which simple salts of inorganic positive radicals are combined 
 with simple salts of organic positive radicals ; and I would recommend 
 the dismissal from chemical science of the entire series of denominations 
 of conjugated acids to which misunderstood experiments and fallacious 
 arguments have given origin. 
 
408 THEORY OF POLYEASIC AND CONJUGATED ACIDS. 
 
 Professor Kolbe's Copulated Oxalates. 
 
 Professor Kolbe has advocated the doctrine, that the acid radicals of 
 the vinyl series see page 79 are all compounds of basic radicals with 
 carbon, and, consequently, that all their salts are oxalates copulated with 
 basic radicals, according to the following examples : 
 
 HO.(C 2 H 3 )~C 2 ,0 3 = Acetic acid. 
 
 KO.(C 2 H 3 )~C 2 ,0 3 = Acetate of potash. 
 
 (C 4 H 5 )0.(C 2 H 3 )^C*,0 3 = Acetate of ethyl. 
 
 HO. H -^C 2 ,0 3 = Formic acid. 
 
 HO.(C 8 H 9 )~C 2 ,0 3 = Valeric acid. 
 
 In these formulas C = 6, O = 8, H = i. 
 
 This theory is advocated at great length in the Quarterly Journal of 
 the Chemical Society, vols. iii. and iv. 
 
 According to this doctrine, we are to believe that every neutral salt 
 of an organic acid is an oxalate possessing a sort of appendage or tail, 
 which is copulated with it without affecting its neutrality, although in 
 every instance the tail is a complete basic radical. Thus, a formiate is 
 an oxalate with a tail of hydrogen ; an acetate is an oxalate with a tail 
 of methyl ; a valerianate is an oxalate with a tail of butyl ; and so on 
 Jbhrough the entire vinyl series of acid radicals. The proof of the correct- 
 ness of this doctrine consists of the single fact, that these acids can be 
 decomposed, electrically and otherwise, into carbon and their corre- 
 sponding basic radicals. I admit the fact. See pages 75 and 76. But 
 I consider the doctrine thus based upon the fact to be absurd, and in 
 order to prove its absurdity, I will carry it to its legitimate con- 
 sequences. 
 
 For the sake of the argument, I admit that the acid radicals of the 
 vinyl series are each reducible into an atom of carbon and an atom of a 
 basic radical. I have discussed this matter fully between pages 73 and 
 8 1 . Thus, an acetate can produce methyl and a valerianate can produce 
 butyl. "Right!" says Kolbe, "and therefore the acetates contain 
 methyl, and the valerianates contain butyl." 
 
 Just, however, as every acid radical of the vinyl series can be made 
 to produce a basic radical by abstraction of C 1 , so can every basic 
 radical of that series be made to produce an acid radical by abstraction 
 of H 2 ; and if we are to consider that every acid radical contains a basic 
 radical, we may with equal reason assume that every basic radical con- 
 tains an acid radical, and when we depict the acetate of potash as con- 
 taining an oxalate copulated with methyl, we may depict the sulphate of 
 
PROFESSOR KOLBE'S COPULATED OXALATES. 409 
 
 ethyl, as containing hydrated sulphuric acid copulated with hydride of 
 acetyl. Stated in my notation, these changes would be as follow : 
 
 K,C 2 H 3 O 2 = K,C0 2 + CH 3 
 
 Acetate of potash = Oxalate of potash -f- Methyl. 
 
 C 2 H 5 ,S0 2 H,S0 2 + H,C 8 H 3 
 
 Sulphate of ethyl = Sulphuric acid + Hydride of acetyl. 
 
 The result is, that as, in all salts formed by an acid radical, we have, 
 according to Kolbe, not the nominal acid radical, but practically the cor- 
 responding basic radical, so in all salts formed by a basic radical, we 
 must have, not the nominal basic radical, but its corresponding acid 
 radical. Everything falls out according to the rale of contrary : our acids 
 contain bases, and our bases contain acids. In salts of acetyl we have 
 only methyl. In salts of ethyl, we have only acetyl. And this prin- 
 ciple of regularity extends through the whole series of radicals which are 
 described in the Table on pages 79 and 80. The full force of the prin- 
 ciple is felt, if we ask ourselves the question, What is the actual consti- 
 tution of any given acid in that list ? Take, for example, the valerianic 
 acid, which is near the bottom of the Table. According to Kolbe, this 
 acid contains butyl, not valeryl. If we admit that statement to be true, 
 then we go on as follows founding our conclusions upon facts that are 
 equally true in valeryl is butyl; in butyl is butyryl; in butyryl is 
 propyl ; in propyl is propionyl ; in propionyl is ethyl ; in ethyl is acetyl ; 
 in acetyl is methyl ; in methyl is formyl ; in formyl is hydrogen. All 
 these radicals therefore are contained in the radical of valerianic acid, 
 granting only the truth of the assumption, that a radical CONTAINS what 
 you can make it PRODUCE. 
 
 It is certain, that from the acid radicals you can produce the basic 
 radicals. It is equally certain, that from the basic radicals you can 
 produce the acid radicals : but when you jump from these facts to the 
 inference, that these acid radicals and basic radicals respectively CONTAIN 
 the corresponding basic radicals and acid radicals, ready-formed ; you go 
 astray. What a thing has been, or what a thing may become, is not the 
 same as what a thing is. To confuse these ideas, or to use them indis- 
 criminately, is a breach of scientific exactness. Experiment is our guide 
 in such matters. Experiment shows us the composition of acetyl. It 
 shows us how to convert ethyl into acetyl, and acetyl into methyl. 
 Experiment shows us that acetate of potash contains those proportions 
 of carbon and hydrogen, which constitute neither ethyl nor methyl, but 
 acetyl. Such are the facts. According to these facts, we must judge of 
 the merit of Kolbe's theory, that acetate of potash contains not acetyl, but 
 methyl, a theory which appears to me to be a denial of facts. 
 
 The doctrine which leads chemists astray in matters of this sort is 
 
410 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 due to Gerhardt, who thus expounds it (Introduction to Unitary Che- 
 mistry) : 
 
 " In the dualistic system of chemistry, bodies are represented such as 
 they exist (at the time of examination). This method is incompatible 
 with the unitary system, which bases its definitions upon the metamor- 
 phoses of bodies, j. e., upon their previous state, or upon their future 
 combinations. In this respect it evidently attains the special aim of 
 chemistry, viz., the discovery of the laws which govern the transforma- 
 tions of matter." 
 
 According to this doctrine, the special duty of chemists is to take 
 cognisance of things which once did exist, or which may chance to exist 
 hereafter, but to neglect the things which do exist at the time of 
 examination. The unitary system disdains present existences, and only 
 values the historical and the prophetical. To represent bodies as they 
 exist is left for chemists who follow the despised dualistic system. The 
 special aim of unitary chemists is directed above and beyond the depart- 
 ment of actual existences. It deals only with the past and the future. 
 Lighted by this luminary, we perceive that acetyl is not acetyl but once 
 was ethyl, and may hereafter become methyl ; that valeryl is not 
 valeryl, but in the past was amyl, and in the future may be butyl. The 
 brightness of this theoretical light renders invisible the things that are 
 illuminated only by the dim medium of common sense. But that is 
 evidently desirable. Radicals " such as they exist " are beneath the 
 notice, and incompatible with the objects which unitary chemists spe- 
 cially aim at, under the guidance of this new light. 
 
 By a parity of reasoning, we discover in common life, that bankrupts 
 and heirs-at-law are men of property ; because a man's fortune consists, 
 not in what he possesses, but in what in past times he has squandered 
 away, or in what in the future he may chance to inherit. " The proper 
 definition of a thing," says Gerhardt, " is not what it is, but what it has 
 been, or what it may become" A man, whose fortune is a matter of 
 history or a matter of expectancy, is, therefore, a man of fortune. 
 
 Professor Kolbe's copulated oxalates are the heirs-at-law of the acid 
 radicals. When the acid radicals come to destruction when they die 
 the death their substance is the inheritance of the copulated oxalates. 
 But when the Professor argues, that the heirs-at-law are the present pos- 
 sessors of the estate, he anticipates the fact, and pronounces a judgment 
 which is erroneous. A present acid must be held to contain a present 
 radical. 
 
( 411 ) 
 
 The Malic Grroup of Salts. 
 
 The formula commonly assigned to MALIC ACID is : 
 
 (2HO,C 8 H 4 8 ), in which H = i,C=6, O = 8; 
 
 and as the 2HO are replaceable by two other bases, this compound is an 
 example of what is called a BIBASIC ACID. 
 
 I propose to consider it, not as a bibasic salt, but as a double salt, 
 constituted in agreement with the following formula : 
 
 H,C 2 H 3 O 3 + H,C 2 H0 8 ; in which H = i, C = 12, O = 16. 
 
 This formula contains two assumed acid radicals = C 2 !! 3 and C 2 !!. The 
 former is equivalent in its proportions of elementary atoms to acetyl, and 
 the latter to aconyl, fumaryl, maleyl, and perhaps to several other acid 
 radicals. I do not know whether the radical C 2 H 3 of the malic acid is 
 the same thing as the radical C 2 H 3 of the acetic acid, nor whether the 
 radical C*H is the same as any other radical of the same ultimate com- 
 position. I wish to give in this place no opinion respecting the identifi- 
 cation of these isomeric radicals, and for the purposes of the present dis- 
 cussion, I shall indicate these assumed radicals by temporary names; 
 thus : 
 
 C 2 H 3 will be called Myl. 
 
 C 2 H> Dyl. 
 
 In agreement with these assumptions, crystallised malic acid = 
 H r ,C 2 H 3 3 + H r ,C 2 H0 2 , will be called Hydra mylite cum hydra dylete, 
 The two atoms of H r are both, or either, replaceable by other basic 
 radicals, and the products of that replacement, combined in pairs, pro- 
 duce the salts that are called malates. The mylites and dyletes can 
 separately undergo the various modifications to which all single salts are 
 subject, without suffering separation from one another. As long as they 
 remain conjoined, they constitute the malates. When the conjunction is 
 dissolved, the products of the decomposition receive other names. Yet, 
 while the mylites and dyletes continue in combination, their basic 
 radicals sometimes undergo modifications which cause the compound 
 salts. to receive other names than malates, as will be seen in the descrip- 
 tion of the following examples : 
 
 SALTS BELONGING TO THE MALIC GROUP. 
 
 Group A. Malic Acid, cryst. 
 io H,C 2 H 3 3 + H,C 2 H0 2 . . Hydra mylite cum hydra dylete. 
 
412 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 Group B. Neutral Malates. 
 
 2. Ag,CT[ 8 3 4- Ag,C 2 H0 2 . Argenta mylite cum argenta 
 
 dylete. 
 
 3. Ca,C 2 H 3 O 3 4- Ca,C 2 H0 2 . . Calca mylite cum calca dylete. 
 
 4. Pb,C 3 H 3 3 4- Pb,C 2 H0 2 . Plumba mylite cum plumba 
 
 dylete. 
 
 5. Zn,C 2 H 3 O 3 4- Zn,C 2 H0 2 . . Zinca mylite cum zinca dylete. 
 
 6. ZH 4 ,C*H 3 3 4- ZH 4 ,C 2 H0 2 . Ammona mylite cum ammona 
 
 dylete. 
 
 Group C. Acid Malates. 
 
 . Ca,C 2 H 3 O 3 -f H,C 2 H0 2 . , Calca mylite cum hydra dylete. 
 . Zn,C 2 H 3 O 3 4- H,C*H0 2 . . Zinca mylite cum hydra dylete. 
 9. ZH 4 ,C 2 H 3 3 4- H,C 2 H0 2 . Ammona mylite cum hydra 
 
 dylete. 
 
 Group D. Double and Basic Malates. 
 
 10. ZH 4 ,C 2 H 3 3 4- Zn,C 2 HO 2 . Ammona mylite cum zinca dy- 
 
 lete. 
 
 11. Pb,C 2 H 3 3 4- Pb 8 ,C 2 H0 3 . Plumba mylite cum plumbine 
 
 dylite. 
 
 Group E. Amyl-Malates. 
 
 12. C 5 H ll ,C 2 H 3 3 4-H,C 2 HO 2 . Amyla mylite cum hydra dy- 
 
 lete. 
 
 13. C 5 H ll ,C 2 H 3 3 -f Ca,C 2 HO 2 . Amyla mylite cum calca dylete. 
 
 14. C 5 H U ,C 2 H 3 O 3 4- ZH 4 ,C 2 H0 2 Amyla mylite cum ammona 
 
 dylete. 
 
 Group F. Aspartic Acid. 
 
 15. ZH 2 ,OH 8 8 4- H 5 C 2 HO 2 . Amida mylete cum hydra dy- 
 
 lete. 
 
 Group G. Aspartates, Class a. 
 
 1 6. ZH 2 ,C 2 H 8 2 4- K^HO 2 . Amida mylete cum potassa dy- 
 
 lete. 
 
 17. ZH 2 ,C 2 H 3 2 4- Ba,C 2 H0 2 . Amida mylete cum baryta dy- 
 
 lete. 
 
 1 8. ZH 2 ,C 2 H 3 O 2 4- Ag,C 2 H0 2 . Amida mylete cum argenta 
 
 dylete. 
 
THE MALIC GROUP OF SALTS. 413 
 
 19. ZH 2 ,C 2 H 3 2 -f Pb,C 2 H0 8 . Amida mylete cum plumba dy- 
 
 lete. 
 
 20. ZH 2 ,C 2 H 3 2 4- ZH 4 ,C 2 H0 2 . Amida mylete cum ammona 
 
 dylete. 
 
 Group H. Aspartates, Class 6. 
 
 21. ZHBa,C 2 H 3 2 + Ba,C 2 H0 2 . Barytac mylete cum baryta 
 
 dylete. 
 
 22. ZHPb,C 2 H 3 O 2 + Pb,C 2 HO 2 . Plumbac mylete cum plumba 
 
 dylete. 
 
 23. ZHAg,C 2 H 3 2 4 Ag,C 2 HO 2 Argentac mylete cum argenta 
 
 dylete. 
 
 Group I. Aspartates, Class c. 
 
 JZH 3 Pb,C 2 H 3 O 3 + Pb,C 2 HO 2 ) Plumbam mylite cum plumbac 
 2 4- JZH Pb,C 2 H 3 O 2 4- Pb,C 2 HO 2 J mylete bis" plumba dylete. 
 
 Group K. Aspartic Acid with other Acids. 
 
 JZH 2 ,C 2 H 3 O 2 4- H,C 2 HO 2 ) Amida mylete cum hydra dy- 
 
 2 5'{ HS0 2 + HSO 2 f lete bis hydra sulphete. 
 
 H0 2 1 Amida mylete cum hyd 
 
 HC1 f lete cum hydra chlora. 
 
 ZH 2 ,C 2 H 3 O 2 + H,C 2 H0 2 1 Amida mylete cum hydra dy- 
 f 
 
 Group L. Asparagine. 
 
 27. ZH 2 ,C 2 H 3 2 + ZH 2 ,C 2 HO . Amida mylete cum amida dy- 
 
 late. 
 
 Group M. Asparagine with Bases. 
 
 28. ZH 2 ,C 2 H 3 O 2 + ZHK,C 2 HO . Amida mylete cum potassac 
 
 dylate. 
 
 29. ZH*,C 2 H 3 2 + ZHAg,C 2 HO Amida mylete cum argentac 
 
 dylate. 
 
 30. ZH 2 ,C 2 H 3 2 + ZHCuc,C 2 HO Amida mylete cum cupricac 
 
 dylate. 
 
 Group N. Asparagim with Acids. 
 
 (ZH 2 ,C 2 H 3 O 2 + ZH 2 ,C 2 HO 1 Amida mylete cum amida dy- 
 3T ' I AgNO 3 4- AgNO 3 J late bis argenta nitrite. 
 
 IZH 2 ,C 1! H 3 O 2 4- ZH 2 ,C 2 HO ) Amida mylete cum amida dy- 
 2 f 
 
 ' \ HCO 2 4- HCO 2 f late bis hydra carbete. 
 
 mida mylete cum ami 
 late cum hydra chlora. 
 
 I ZH a ,C 2 H 3 2 4- ZH 2 ,C 2 HO Amida mylete cum amida dy- 
 H,C1 J 
 
414 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 Group 0. Malic Phenyl Amides. 
 
 34. ZH.C'H 5 ; C 2 H 8 O 2 +H,C 2 H0 2 Phenylac mylete cum hydra 
 
 dylete. 
 
 35. ZH,C 6 H 5 ;C 2 H 3 O 2 + ZH 4 ,C 2 H0 2 Phenylac mylete cum ammona 
 
 dylete. 
 
 36. ZH,C 6 H 5 ;C 2 H 3 O a +Ag,C 8 H0 2 PheAylac mylete cum argenta 
 
 dylete. 
 
 37. ZH,C 6 H 5 ;C 2 H 3 2 +ZH,C 6 H';C 2 HO. Phenylac mylete cum 
 
 phenylac dylate. 
 
 38. Z,C*H 3 ,C 6 H 5 ; C 2 H0 3 . . . Mylic-phenylac dylite. 
 
 Group P. Maleic Acid. 
 
 39. H,C 2 HO a Hydra maleylete. 
 
 Group Q. Makates. 
 
 40. K^HO 8 Potassa maleylete. 
 
 41. K,C 2 HO 2 + H^HO 2 . . Potassa hydra bimaleylete. 
 
 42. Ag^'HO 2 Argenta maleylete. 
 
 43. Ag,C*HO 2 -f H,C*HO 2 . . Argenta hydra bimaleylete. 
 
 44. ZH 4 ,C 2 H0 2 Ammona maleylete. 
 
 45. ZH 4 ,C 2 H0 2 + H,C 2 H0 2 . . Ammona hydra bimaleylete. 
 
 46. Pb^HO 2 Plumba maleylete. 
 
 47. Cuc,C 2 HO 2 Cupric maleylete. 
 
 48. ZH 3 Cuc,C 2 HO 8 + Aq. . . Cupricam maleylete aquate. 
 
 Group R. Fumaric Add. 
 
 49. H,C 2 HO 2 Hydra fumarylete. 
 
 Group S. Fumarates. 
 
 50. K,C 2 HO a Potassa fumarylete. 
 
 51. K,C 2 HO 2 + H^HO 2 . . Potassa hydra bifumarylete. 
 
 52. Ag,C 2 HO 2 Argenta fumarylete. 
 
 53. ZH 4 ,C*HO* Ammona fumarylete. 
 
 54. ZH 4 ,C 2 H0 2 + H^HO* . . Ammona hydra bifumarylete. 
 
 55. Pb,C 2 HO 2 Plumba fumarylete. 
 
 56. Pb^HO 2 + Pb,PbO . . Plumbine fumarylite. 
 
 57. (Pb^HO 2 ) 4 + Pb,PbO . Tetrakis plumba fumarylete cum 
 
 plumba plumbate. 
 
 58. (Fec,C 2 HO 2 ) 4 + Fec,FecO . Tetrakis ferric fumarylete cum 
 
 ferric ferrate. 
 
 59. C 2 H 5 ,C 2 H0 8 Ethyla fumarylete. 
 
THE MALIC GROUP OF SALTS. 415 
 
 Group T. Fumaric Amides. 
 
 60. C 2 H,C 2 HO 3 ..... Fumaryla fumarylite. 
 
 61. ZH*,C 2 HO Amida fumarylate. 
 
 62. ZH,C 2 H; C 2 H0 2 . . . . Fumarylac fumarylete. 
 
 63. Z,C 2 H 3 ,C 2 H 3 ; Z^H^HO 5 Mylec dylecute. 
 
 64. ZH^HO+ZIFHgc 2 ; C 2 H0 2 Amida fumarylate cum meric- 
 
 cem fumarylete. 
 
 USUAL NAMES AND FORMULA OF THESE SALTS. 
 
 Group A. Malic acid in crystals: i. H,C 2 H 3 3 + H,C 2 H0 2 . Hydra 
 mylite cum hydra dylete. 
 
 This formula represents, as I have already stated, the crystallised 
 malic acid. Usual formulas : C 8 H 6 0' = C 8 H 6 4 ,0 6 , Gmelm. 2HO, 
 C 8 H 4 8 , Miller. These formulae represent the acid as bibasic, with an 
 acid radical = C 4 H 4 . For an account of the Decompositions of Malic 
 Acid, see the subsequent particulars respecting the reactions of salts of 
 the Malic group, Nos. i and 2. Its production from aspartic acid; see 
 Reactions, No. 6, page 422. 
 
 Group B. Neutral Malates. General formula : C 8 H 4 M 2 O 10 . 2, Ma- 
 late of silver. 3, M. of lime. 4, M. of lead. 5, M. of zinc. 6, M. of 
 ammonia. 
 
 Group C. Acid Malates. General formulae: C 8 H 5 M'0 10 . 7, Bimalate 
 of lime. 8, Bimalate of zinc. 9, Bimalate of ammonia. Decomposition 
 of bimalate of ammonia by heat. See Reactions, No. 3. 
 
 Group D. Double and Basic Malates. 10, Double malate of zinc and 
 ammonium. 1 1, Basic malate of lead. In this salt, the radical Dyl is 
 in the condition of a terbasic salt, according to the usual terbasic formula 
 Pb,C 2 H0 2 + Pb,PbO = Pb 3 ,C 2 HO 3 . A considerable number of the 
 malates contain water, and might have formulas in accordance with 
 No. 1 1 . Thus, the bimalate of ammonia No. 9, in the crystallised state, 
 might have the formula ZH 4 ,C 2 H 3 O 3 + H 3 ,C*HO 3 . 
 
 Group E. Amyl-Malates. 12, Amyl-malic acid = C 18 H 16 O 10 = C 8 H 5 
 (C lo H n )0 10 . 1 3, Amyl-malate of lime = C 18 H 15 CaO l . 14, Amyl-ma- 
 late of ammonia = C 18 H 15 (NH 4 )O 10 . Gerhardt, after Breunlm. 
 
 Here we have a " conjugated acid" and its salts; but according to 
 my notation, No. 12 is a bimalate, precisely equivalent to No. 7, and 
 Nos. 13 and 14 are double salts equivalent to No. 10. It is certain that 
 similar salts could be prepared with other radicals instead of amyl, and 
 there is no necessity to make conjugated acids of any of them. 
 
 Group F. No. 1 5. Aspartic acid, or Malamic acid. Compare this 
 compound with the Bimalate of ammonia No. 9, thus : 
 
416 THEORY OF POLYBASIC AXD CONJUGATED ACIDS. 
 
 No. 9 = ZH 4 ,C 2 H 3 O 3 + H,C 2 HO 2 . Ammona mylite cum hydra 
 
 dylete. 
 No. 1 5 = ZH 2 ,C 2 H 3 O 2 + H,C 2 H0 2 . Amida mylete cum hydra 
 
 dylete. 
 H 2 O 1 = Difference. 
 
 On referring to page 225, it will be 'seen, that the difference between 
 binoxalate of ammonia and oxamic acid is precisely the same as the dif- 
 ference between bimalate of ammonia and aspartic acid. Aspartic acid, 
 like oxamic acid, produces a series of salts, and it is, like oxamic acid, a 
 double salt, with the single difference, that its two acid radicals are not 
 alike. Production of aspartic acid from the hydrochlorate, see Reactions, 
 No. 5, page 422. Its conversion into malic acid, see Reactions, No. 6. 
 Its production from asparagine ; Reactions, Nos. 7 and 8. 
 
 Chemists are not agreed as to the basicity of aspartic acid ; but the 
 investigators have pointed out three varieties of salts, answering to the 
 formula? C 8 NH 6 M0 8 ( = class a), C 8 NH>M 2 O 8 ( = class 6), and MO, 
 C 8 NH 6 MO 8 ( = class c), of each of which I have quoted some examples, 
 Nos. 1 6 to 24. See Gmelin (Handbook of Chemistry, 1856, x. 234). 
 
 Group G. Nos. 16 to 20. The salts of this group are evidently 
 monobasic aspartates, formed in exact accordance with the oxamates ; see 
 page 226, but differing in the quantity of oxygen, and hi having two 
 dissimilar, instead of two similar, acid radicals. Production of aspartate 
 of ammonia, No. 20, from asparagine, No. 27. See Reactions, No. 9, 
 page 422. 
 
 Ghvup H. Nos. 21 to 23. These salts, of which many more might 
 be cited, containing the radicals Ca, Cue, &c., differ from those of 
 group G, by containing metallic vice-amids instead of normal amid ; but 
 they are alike in all other respects. As chemists are not accustomed to 
 admit the existence of these metallic vice-amids, this little group of salts 
 has puzzled them greatly. Gmelin says, "As it is improbable that an 
 amidogen acid should be bibasic, and as Liebig has not given the mode 
 of preparation of the salt which he analysed, Laurent doubts its purity." 
 To which Mr. Watts adds, " Liebig's ' result is, however, confirmed by 
 those of Dessaignes, Pasteur, and Wolff." The analyses are no doubt 
 correct, and they confirm the accuracy of the theory that I have advanced 
 respecting the nature of these metallic vice-radicals. 
 
 Group I. No. 24. Aspartates, class c. Several similar salts occur, in 
 which Pb is replaced by the radicals Ba, Ca, Ag, and Hgc. This salt 
 is evidently intermediate between the malates and the aspartates ; that is 
 to say, it is a combination of a malate with an aspartate, atom to atom. 
 The upper half of the formula No. 24 is equivalent to the bimalate of 
 ammonia No. 9, supposing ammonia ZH 4 to be replaced by plumbam 
 ZH 3 Pb, and H to be replaced by Pb, and the lower half of the formula 
 is the same as that of the aspartate No. 22. 
 
THE MALIC GROUP OF SALTS. 417 
 
 Group K, Nos. 2 5 and 2 6 are examples of salts produced by the com- 
 bination of aspartic acid with mineral acids. No. 2 5 contains one atom 
 of aspartic acid and two atoms of hydrated sulphuric acid. No. 26 con- 
 tains aspartic acid and hydrochloric acid, atom to atom. See Eeactions, 
 Nos. 4 and 5, page 422. 
 
 Group L. No. 27. Asparagine, or Malamide, Gerhardt's Diazoture of 
 malyle and of hydrogen. Formulas: C 8 N 2 H 8 6 = C 8 Ad 2 H 4 O 4 ,O 2 , 
 Gmelin. 
 
 Compare formula 27 with formula 6, which represents the neutral 
 malate of ammonia, from which the double amid is derived. The dif- 
 ference is equal to two atoms of HHO. Thus : 
 
 No. 6. ZH 4 ,C 2 H 3 3 + ZH 4 ,C 2 HO 2 Ammona mylite cum ammona 
 
 dylete. 
 No. 27. ZH 2 ,C 2 H 3 O 2 + ZH 2 ,C 2 HO Amida mylete cum amida dylate. 
 
 H 2 O l + H 2 O l = Difference. 
 
 Again, compare this difference with the difference found to exist 
 between No. 15 and No. 9. From these comparisons it appears that 
 No. 9, the bimalate of ammonia, by losing one equivalent of water, is 
 converted into aspartic acid,' and that No. 6, the neutral malate of 
 ammonia, on losing two equivalents of water, is converted into aspara- 
 gine. The same comparison shows that aspartic acid is a regular 
 amidogen acid, and that asparagine is a double amid. Gerhardt wishes 
 us to consider asparagine as an ammonia, and he represents it by the 
 following formula : 
 
 rC 4 H 4 3 
 N 2 | H 2 
 
 ( H 2 
 
 I have already so fully expressed the reasons why I disapprove of the 
 proposal to formulate oxidised compounds as "ammonias," that I need 
 not take special notice of this formula.' Conversion of asparagine into 
 aspartic acid; see reactions, Nos. 7 and 8, page 422. Conversion into 
 aspartate of ammonia, No. 20; reactions, No. 9. 
 
 The relations which the two ammoniacal salts, No. 6 and No. 9, bear 
 to the amidogen acid No. 1 5 and the double amid No. 27, are, according 
 to the general facts which I have developed in the section on the azotic 
 radicals, such as to show that malic acid acts under all circumstances, 
 as it necessarily must act if it contains TWO acid radicals, instead of only 
 one. This being the case, it is but fair to assume, that, where we have 
 the properties and powers of two radicals, these two radicals are present 
 in substance. 
 
 Group M. Combinations of Asparagine with bases. Nos. 28 to 30. 
 
 2 E 
 
418 THEORY OF FOLYBASIC AND CONJUGATED ACIDS. 
 
 Besides these three salts, other salts of similar structure are formed by 
 the basic radicals Ca, Cd, Pb, Hgc, Zn, &c. 
 
 On comparing the formula of these salts with the formula of aspara- 
 gine, No. 27, we perceive that the amount of the difference between 
 them is, that one of the amids in No. 27 is replaced in the salts by a 
 metallic amidac. Usual names: 28, Asparagine with potash. 29, As- 
 paragine with silver oxide. 30, Asparagine with cupric oxide, Gmelin. 
 Potassic, argentic, and cupric asparagine, Gerhardt. The latter says that 
 ammonic asparagine appears to be unattainable ; for if asparagine is dis- 
 solved in aqueous ammonia, and submitted to spontaneous evaporation, 
 the ammonia flies off, and the solution yields crystals of pure asparagine. 
 He offers no explanation of this difficulty. I suggest that it is due to 
 the fact that ammonium = ZH 4 can never replace hydrogen in a vice- 
 ammon or vice-amid that one ammonium or amidogen cannot involve 
 another. Hence the salt No. 27 can produce such salts as Nos. 28 to 
 30, but the metals K, Ag, and Cue, though replaceable by many other 
 metals, cannot be replaced by the radical ZH 4 . Neither can ZH 2 in 
 No. 27 be replaced by ZH 4 , unless at the same time O 1 becomes O 2 ; 
 but in that case, the ammonic asparagine would become aspartate of 
 ammonia No. 20 ; or, if both atoms of ZH* were replaced by ZH 4 , with 
 O 1 additional for each radical, then the salt No. 27 would be converted 
 into neutral malate of ammonia No. 6. Consequently, the production of 
 ammonic asparagine is impossible. 
 
 Group N. Combinations of Asparagine with hydrated adds and with 
 salts of mineral acids. Nos. 31 to 33. No. 31 is a combination of one 
 atom of asparagine with two atoms of nitrate of silver. No. 32 contains 
 one atom of asparagine with two atoms of oxalic acid ; No. 3 3 is a com- 
 bination of one atom of asparagine with one atom of hydrochloric acid. 
 
 Group O. Malic plienyl amides, or Anilides of malic acid. Nos. 34 to 
 38. These salts have been described by Arppe (Ann. der Chem. u. 
 Phar., 1855, xcvi. 106). I quote from Gerhardt (Traite de Chimie Or- 
 ganique, tome iv., 915). 
 
 34. ZH,C 6 H 5 ; C 2 H 3 2 + H,C 2 HO 2 . This compound is called Phe- 
 nyl-malamic acid, or malanilic acid, and the formula given to it is 
 C*>H 11 NO 8 = C 8 H 6 (C 12 H 5 )NO 8 . Compare it with aspartic acid. No. 15. 
 The only difference between them is the replacement of normal amid by 
 phenylac; thus: 
 
 No. 15 = ZH 2 ; C 2 H 3 O 2 + H,C*H0 2 . 
 No. 34 = ZH,C 6 H 5 ; C 2 H 3 2 + H,C 8 HO 2 . 
 
 Like aspartic (or malamic) acid, this compound, Phenyl-malamic acid, 
 produces salts by exchanging H for basic radicals, of which salts Nos. 
 35 and 36 are examples. This acid is perfectly similar to the anilidogen 
 acids described at letter D, page 228, save only that it has two different 
 acid radicals, instead of two acid radicals of the same kind. 
 
THE MALIC GROUP OF SALTS. 419 
 
 35. Phenyl-malamate of ammonia. 
 
 36. Phenyl-malamate of silver ; formula C 20 H 10 AgN0 8 . 
 
 37. Phenyl-malamide or malanilide ; formula C 32 H I6 N 2 O 6 = C 8 !! 6 
 (C l2 H 5 ) 2 N a 6 . 
 
 38. Phenyl-malimide, or malanile; formula C^H'NO 6 = C 8 H 4 (C 12 H 5 ) 
 NO 6 . 
 
 The reactions of these salts are precisely conformable to what would 
 necessarily be predicted of the reactions of anilidogen salts. 
 
 When the salt No. 38 is boiled with aqueous ammonia, it produces 
 the salt No. 35. Thus: 
 
 Z,C S H 5 ,C 2 H 3 ; C 2 H0 3 \ JZH,C 6 H 5 ; C 2 H 3 O 2 + ZH 4 ,C*HO 2 . 
 H ; ZH 4 O j == \ 
 
 This product is converted by barytic water into the phenyl-malamate of 
 barytes = ZH,C 6 H 5 ; C 2 H 3 2 + Ba,C 2 HO 2 , which can be converted by 
 the action of sulphuric acid into the acid No. 34. 
 
 This acid is evidently the anilidogen acid corresponding to an unknown 
 acid malate of phenylam, thus : 
 
 ZH 3 ,C 6 H 5 ; C 2 H 3 3 + H,C 2 H0 2 = 
 
 The double amid No. 37 is in the same way derived from the unknown 
 neutral malate of phenylam, thus: 
 
 j ZH 3 ,C 6 H 5 ; C 2 H 3 O 3 1 J ZH,C 6 H 5 ; C 2 H 3 2 + ZH,C 6 H 5 ; C 2 HO. 
 \ZH 3 ,C 6 H 5 ;C 2 HO 2 j == [ H 2 O + H 2 O. 
 
 Finally, No. 38 is the "anile" (see page 224, letter b) produced by the 
 abstraction of HHO from the "anilidogen acid" No. 34, thus: 
 
 ZH,C 6 H 5 ; C 2 H 3 2 + H,C 2 HO* 
 
 We perceive all through this set of changes that the acid radical 
 of the malic acid, acts precisely as it must act if it consists of two dif- 
 ferent radicals. There are also, under all circumstances, present in each 
 compound, exactly the number of atoms of oxygen and of basic radicals, 
 which form the complement of two acid radicals, one possessing the 
 power to form normal salts with O 3 , and the other with O 2 . 
 
 Group P. No. 39. Makic Acid. Production of maleic acid. See 
 Reactions, No. I, page 420. 
 
 Group Q. Nos. 40 to 48. Mdeates. Gerhardt terms this a bibasic 
 acid, and gives it the formula C 8 H 4 8 = C 8 H 2 6 ,2HO. But there is not 
 the slightest evidence to prove its possession of bibasic powers, excepting 
 the occurrence of acid salts, such as are represented by Nos. 41, 43, 45. 
 
 2 E2 
 
420 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 I have shown, in respect to the sulphates and oxalates, that such acid 
 salts, or double salts, cannot be accepted as examples of true bibasic 
 salts, and, besides, many organic acids, universally admitted to be mono- 
 basic, exhibit examples of such acid salts. I may instance the acetates, 
 the margarates, the stearates, and the benzoates. Gmelin's formulas for 
 maleic acid and its salts are as follows : C 4 H 2 O 4 = maleic acid ; C 4 HMO* 
 = monomaleate; C 4 HMO 4 ,C 4 H 2 O 4 = bimaleate. His formula for the 
 ammonam salt No. 48 is NH 4 O,C 4 HCuO 4 + Aq. 
 
 Group R. No. 49. Fumaric acid. Production of fumaric acid. See 
 Reactions, No. I, page 420. 
 
 Group S. Nos. 50 to 59. Fumarates. The fumaric acid produces a 
 few acid salts such as Nos. 51 and 54; but most of its salts are neutral, 
 on the model of No. 50. It also produces basic salts, such as are repre- 
 sented by Nos. 56, 57, 58. It has been called a bibasic acid, but with- 
 out necessity, and to no useful end. 59, Fumarate of ethyl. Decom- 
 positions : see Reactions, Nos. 10 and u, page 422. 
 
 Group T. Nos. 60 to 64. Fumaric Amides. 60, Fumaric anhydride ; 
 anhydrous ramaric acid ; anhydrous maleic acid = C 8 H 2 6 . This may 
 be supposed to result from the abstraction of two atoms of HHO from 
 one atom of malic acid, No. I : 
 
 H,C 2 H 3 3 + H,C 2 H0 2 = jjo 2 
 
 It is prepared by heating maleic or fumaric acid. Buchner gives an ac- 
 count of a salt produced by heating the bimaleato of magnesia ( Gmelin's 
 Handbook, viii. 157) which requires the following formula: 2(Mg, 
 C 2 HO 2 ) + C 2 H,C 2 HO 3 . This salt is equivalent in structure to the bi- 
 chromate of potash. See page 126. 
 
 K 2 Cr* O 7 = Bichromate of potash. 
 Mg 2 (C 2 H) 4 O 7 = Bimaleate of magnesia. 
 
 61, Fumaramide = O'NWO 4 . Production ; see Reactions No. 1 1 . De- 
 composition; Reactions, Nos. 12 and 13, page 423. 62, Fumarimide 
 = C 8 NH 3 O 4 . 63, Hydrated fumarimide = C 8 NH 3 O 4 + Aq. Produc- 
 tion ; see Reactions, Nos. 3 and 1 4. 64, Fumaramide with mercuric 
 oxide = C 8 N 2 H 6 O 4 ,2HgO. These names and formulas are quoted from 
 Gmelin's Handbook of Chemistry, vol. x. 
 
 REACTIONS OF SALTS OF THE MALIC GROUP. 
 
 i . When malic acid, No. i , is heated in a retort, it suffers decom- 
 position and produces water, and either maleic acid, No. 39, or fumaric 
 acid, No. 49. It depends upon the regulation of the heat and its dura- 
 tion, whether the chief product is maleic acid or fumaric acid. 
 
 H,C 2 H 3 3 + H,C 2 H0 2 = (H,C 2 H0 2 ) 2 + HHO. 
 
THE MALIC GROUP OF SALTS. 421 
 
 A long-continued heat of about 1 80 C. produces the two acids in about 
 equal quantities. A suddenly-raised heat of 200 C. produces chiefly 
 maleic acid. A long-continued heat of 1 50 C. converts malic acid 
 chiefly into fumaric acid. There is nothing in these results which deter- 
 mines whether the salt H,C 2 HO 2 , which I have assumed to exist ready- 
 formed in the malates, is the maleic or the fumaric acid, nor to show 
 which of these acids is the product of the decomposition of H,C 2 H 3 3 
 into H,C*HO 2 + HHO. Of the two isomeric acids (the maleic and the 
 fumaric), the maleic seems to be most volatile; but it requires a higher 
 degree of heat to volatilize it than that which suffices (if long-continued) 
 to convert the malic acid, and the maleic also, into fumaric acid. 
 
 2. When malic acid is gently heated with oil of vitriol, it produces 
 carbonic oxide gas (Dobereiner) and acetic acid (Liebig) : 
 
 H,C 2 H 3 3 + H,C 2 H0 2 = H,C 2 H 3 2 + (CO) 2 + HHO. 
 
 It is possible that the salt E^OTPO* assumed to be contained in malic 
 acid, may contain the radical of the acetic acid ; but this production of 
 acetic acid from malic acid is not alone sufficient to prove that that sup- 
 position is a fact. The circumstance that the malic-acid radical = C 4 H 4 
 can readily produce the radical = C 8 H l , is another fact that leads to the 
 idea that the malates may contain C 2 H 3 as well as C 2 H' ; it being at the 
 same time pretty certain that C 4 H 4 is NOT C 2 H 2 -f C 2 H 2 , which would 
 make it a multiple of the succinic radical. While assuming that the 
 radical of the malic acid consists of the two radicals C^H 3 and C 2 H l , I do 
 not pretend to be able to identify either of these radicals with other iso- 
 meric radicals. I only wish to demonstrate the probability, at least, of 
 there being, in fact, two radicals and not one radical, present in malic 
 acid, and thereby to explain the cause of the bibasic power of that acid. 
 The identification of the individual radicals is a matter for experimental 
 research. 
 
 3. When the bimalate of ammonia No. 9 is heated to 160 200, 
 it gives off water, and is converted into the salt No. 63 : 
 
 ZH 4 ,C 2 H 3 3 + H,C 2 H0 2 ) j Z,C 2 H 3 ,C 2 H a ; Z,C 2 H,C 2 H0 5 
 ZH 4 ,C 2 H 3 3 -f H,C 2 H0 2 ( := \5(H,HO). 
 
 This is also produced when the hydrochlorate of aspartic acid No. 26 
 is exposed to heat : 
 
 ZH 2 ,C 2 H 3 2 -f- H,C 2 H0 2 + HC1\ J Z,C 2 H 3 ,C 2 H 3 ; Z,C 2 H,C 2 HO 5 
 ZH 2 ,C i H 3 2 + H,C 2 H0 2 -fHClf == | 2 (HC1) + 3 (H,HO). 
 
 Chemists are not agreed respecting the composition of the salt No. 63. 
 It is sometimes called Aspartic acid minus water = C 8 NH 7 O 8 3HO. 
 Sometimes it is said to be hydrated ramarimide = CPNBPO* + Aq. It 
 seems to be a salt in which two amidecs include all the acid radicals of 
 
422 THEORY OF POLYBASIC AXD CONJUGATED ACIDS. 
 
 the two decomposed salts. I Lave given examples of such salts in the 
 indigo series, at page 265. 
 
 4. When the compound No. 63 is boiled with hydrochloric acid, it 
 produces the crystalline hydrochlorate of aspartic acid, No. 26. 
 
 Z,C 2 H 3 ,C 2 H 3 ; Z,C 2 H,C 2 H0 5 ) I ZH 2 ,C 2 H 3 2 + H,C 2 HO 2 -f HC1. 
 2(HC1) -f 3(H,HO) j " |ZH 2 ,C 2 H 3 2 + H,C 2 H0 2 + HC1. 
 
 5. When the hydrochlorate of aspartic acid, No. 26, is dissolved in 
 hot water, the solution divided into two equal parts, the one saturated 
 with ammonia and the other added to it, the mixture thus formed yields 
 on cooling an abundant crystallization of aspartic acid. [The hydro- 
 chloric acid being separated in the state of sal-ammoniac.] 
 
 6. When aspartic acid, No. 15, is acted upon by nitrous acid in the 
 presence of nitric acid, nitrogen is disengaged and malic acid produced : 
 
 ZH 2 ,C 2 H 3 O a + H,C 2 H0 2 ) J H,C 2 H 3 3 + H,C 2 HO 2 
 H,N0 2 f == \ N,N + HHO. 
 
 Here, the reaction seems to be entirely restricted to the amidogen salt. 
 
 7. Diluted sulphuric acid converts asparagine, No. 27, into ammonia 
 and aspartic acid, No. 1 5 : 
 
 ZH 2 ,C 2 H 3 2 + ZH 2 ,C 2 HO 1 j ZH 2 ,C 2 H 3 O 2 + H,C 2 HO 8 
 H,SO a + H,HO f " I ZH 4 ,SO 2 
 
 8. The solution of asparagine, in strong hydrochloric acid evaporated 
 at a gentle heat, leaves sal-ammoniac and aspartic acid : 
 
 ZH 2 ,C 2 H 3 2 + ZH 2 ,C 2 HO 1 J ZH 2 ,C 2 H 3 O 2 + H,C 2 HO 2 
 HC1 + HHO f := I ZH 4 ,C1 
 
 g. When asparagine, No. 27, dissolved in water, is sealed in a glass 
 tube, and heated till the pressure amounts to three or four atmospheres, 
 it is converted into aspartate of ammonia, No. 20, without liberation of 
 any permanent gas : 
 
 ZH (JEW + ZH 2 ,C 2 HO) JZH 2 ,C 2 H 3 O 2 + ZH 4 ,C 2 HO 2 
 H 2 , Of == ( 
 
 10. The fumaric ether or fumarate of ethyl, No. 59, is converted by 
 hydrate of potash into fumarate of potash, No. 50, and alcohol : 
 
 C 2 H 5 ,C 2 H0 2 + KHO = H,C 2 H 5 + K,C 2 H0 2 . 
 
 11. The same ether is converted by aqueous ammonia into alcohol, 
 water, and fumaramide, No. 61 : 
 
 CfH'.C'HO 1 1 JH,C 2 H 5 O + H,HO 
 ZH 4 ,HO j " {ZH 2 ,C 2 HO 
 
THE MALIC GROUP OF SALTS. 423 
 
 12. When fumaramide, No. 61, is heated for some time with water, 
 it is converted into fumarate of ammonia No. 5 3 : 
 
 ZH 2 ,C 2 HO + HHO = ZH 4 ,C*H0 2 . 
 
 13. When fumaramide is heated with aqueous potash, it gives off 
 ammonia, and produces fumarate of potash, No. 50. 
 
 ZH 2 ,C 2 HO -f KHO = K^HO 2 + ZH 2 H. 
 
 14. The hydrated fumarimide, No. 63, see Reactions, No. 3, is de- 
 composed by water, and yields fumarimide, No. 62 : 
 
 fZH,C 2 H; C 2 H0 2 
 = { ZH,C 2 H ; C 2 H0 2 
 1 H;H O. 
 
 Z,C 2 H 3 ,C 2 H 3 ; Z,C 2 H,C 2 H0 5 = 
 
 If we disregard the slight differences in properties which distinguish 
 the maleates from the fumarates, we have good grounds for considering 
 that the formula which I have assigned to malic acid is the true one, and 
 that it is not a bibasic acid, but a compound of two monobasic acids : 
 
 H,C 2 H 3 3 + H,C 2 H0 2 . 
 
 All the chemical reactions among the malates and the products of their 
 decomposition are such as ought to occur if this supposition were true ; 
 and in opposition to it, we have only the bare, vague, unproved notion, 
 that the radical of a bibasic acid possesses all the powers and properties 
 of the radicals of two monobasic acids. I have no faith in that doctrine. 
 It seems to me to be demonstrated by the universal properties of 
 radicals, that every one of them, as long as it continues to be an inde- 
 pendent radical, has, under all circumstances, the saturating capacity of 
 one volume or one atom, a chemical force which nothing can alter. The 
 idea, that one acid radical can neutralise two basic radicals, or, as it is 
 phrased, become bibasic, is in opposition to the essence of a radical. 
 Only when the materials which constitute a radical pass into the form of 
 a different radical, can its saturating capacity change. One radical may 
 be split into two radicals, or several radicals may combine to form one 
 radical, as in the ammoniums. But every radical, so long as it preserves 
 its identity, acts as a unit, as a single volume, a single atom. In strict 
 terms, it cannot be bibasic nor biacid, and the existence of bibasic salts 
 in any other sense than that which has been explained at page 397 is an 
 impossibility. 
 
424 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 The Citric Group of Salts. 
 
 The citric acid is commonly received as the Model " tribasic " acid of 
 the organic series. Its formula is 3HO,C I2 H 5 U , in which 3 HO repre- 
 sent bases replaceable by 3 MO, by 2 HO + MO or by HO + 2 MO. If 
 I double the atomic weights of the carbon and oxygen, and put this 
 formula into the shape commonly adopted in this work, I produce 
 H 3 ,C 6 H 5 O 7 , where C 6 H 5 7 is a constant quantity, and H 3 are replaceable 
 by any three basic radicals. 
 
 The tribasic theory of citric acid is due to Liebig. Several chemists 
 have expressed an opinion that it is a compound acid, Berzelius 
 seems to have considered it to contain two atoms of citric acid of the 
 formula (2C 4 H 2 O 4 ) and one atom of aconitic acid (C 4 H0 3 ). Dumas 
 assumed that it consisted of oxalic acid C 2 O 3 , acetic acid C 4 H 3 O 3 , and 
 oxal-acetic acid C 4 (H 2 ,C 2 2 )0 3 . Pebal thought that it contained one atom 
 of C 4 HO 3 and two atoms of CWO 4 . 
 
 I adopt the idea that tribasic citric acid is a triple salt, containing not 
 only three basic radicals, but also three acid radicals, and I propose to 
 write the formula thus : 
 
 (H,C 2 H 3 3 ] 
 
 2 l , or H,C 2 H 3 8 + 2 (H,C 2 H0 2 ). 
 
 o s j 
 
 I shall apply to the radicals exhibited in this formulas the same pro- 
 visional names that I have used in the section on malic acid ; and I 
 propose to show by examples that all the citrates, and the salts that are 
 derived from them, have the constitution and the chemical characters, 
 which they would necessarily have, if the citrates were triple salts, 
 formed in accordance with the above formula, and having not only three 
 basic radicals, but three acid radicals, each possessing the power of in- 
 dependent chemical action. 
 
 EXAMPLES OF CITRATES. 
 
 H ,C 2 H 3 3 ) 
 
 I. { H ,C 2 H 0*1 Hydra mylite bis hydra dylete. 
 H ,C 2 H 2 J 
 K ,C 2 H 3 8 ) 
 
 K ,C*H O 2 > Potassa mylite bis potassa dylete. 
 K ,C*H 2 J 
 H ,C 2 H 3 8 ) 
 K ,C*H O 2 } Hydra mylite bis potassa dylete. 
 
THE CITRIC GROUP OF SALTS. 425 
 
 K ,C*H 3 3 ) 
 
 H ,C 2 H O 2 1 Potassa my lite bis hydra dylete. 
 
 H ,C 2 H 2 j 
 
 ZH 4 ,C 2 H 3 3 ) 
 
 5. < K ,C 2 H 2 > Ammona mylite bis potassa dylete. 
 
 K ,C 2 H 2 J 
 
 ZH 4 ,C 2 H 3 3 | 
 
 6. < H ,C a H 3 O 2 > Ammona mylite bis hydra dylete. 
 
 ,C 2 H 3 O 2 j 
 
 fZH 4 , 
 
 . < H , 
 
 ( H , 
 
 f H,C 2 H 3 3 ) 
 
 7. < ZH 4 ,C 2 H O 2 1 Hydra mylite bis ammona dylete. 
 (ZH 4 ,C 2 H O 2 J 
 
 (ZH 4 ,C 2 H 3 O 3 H,C 2 H 3 3 ) Ammona mylite bis ammona 
 8. 1 ZH 4 ',C 2 H O 2 + H,C 2 H O 2 1 dylete cum hydra mylite 
 (ZH 4 ,C 2 H O 2 H,C 2 H 2 J bis hydra dylete. 
 
 f K ,C 2 H 3 O 3 Sbc,C 2 H 3 3 ) Potassa mylite bis potassa 
 9 J K,C 2 H0 2 +Sbc,C 2 H0 2 V dylete cum stibic my- 
 [ K ,C 2 H O 2 Sbc,C*H O 2 j lite bis stibic dylete. 
 
 ( Ba ,C 2 H 3 O 3 H ,C 2 H 3 O 3 ) Baryta mylite bis baryta 
 i o. { Ba ,C 2 H O 2 + Ba ,C 2 H O 2 1 dylete cum hydra mylite 
 I Ba ,C 2 H O 2 Ba ,C 2 H O 2 J bis baryta dylete. 
 
 f K ,C 2 H 8 O 3 H ,C 2 H 3 O 3 ) Potassa mylite bis potassa 
 
 ii J K 5 C 2 H0 2 + ZH 4 ,C 2 H0 2 l dylete cum hydra my- 
 
 l K ,C 2 H O 2 ZH 4 ,C 2 H O 2 J lite bis ammona dylete. 
 
 ( Ag,C 2 H 3 3 | ) Argenta mylite bis stibic 
 
 I2c <^Sbc,C 2 H0 2 + AgSbcO > dylete cum argenta sti- 
 Sbc,C 2 H O 2 bicate. 
 
 I Argenta mylite bis argen- 
 P j i i i 
 
 4-o rivlpfp oiiiYi P/lloft 
 VI- 1 J 1 L. 
 
 myhte bis calca dylete 
 cum argenta calcate. 
 
 fCH 3 ,C 2 H 3 3 ] 
 
 14 J C H 3 ,C 2 H 2 > Methyla mylite bis methyla dylete. 
 
 [C H 3 ,C 2 H O 2 ) 
 
 f H ,C 2 H 3 3 ) 
 
 15 JC H 3 ,C 2 H 2 V Hydra mylite bis methyla dylete. 
 
 (C H 3 ,C 2 H 2 J 
 
 'CH 3 ,C 9 H 3 3 | 
 
 1 6. { H ,C 2 H O 2 l Methyla mylite bis hydra dylete. 
 H ,C 2 H0 2 J 
 
426 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 (C 2 H 5 ,C 2 H 3 3 ) 
 
 1 7 .{ C 2 H 5 ,C 2 H 0*1 Ethyla mylite bis ethyla dylete. 
 (C 2 H 5 ,C 2 H 2 j 
 
 fC 5 H u ,C 2 H 3 3 ) 
 1 8. \ H ,C 2 H O 2 V Amyla mylite bis hydra dylete. 
 
 C 5 H u ,C 2 H 3 3 ) 
 
 H ,C 2 H O 2 V 
 
 I H ,CTH 2 j 
 
 19. 
 
 C 5 H U 
 
 H ,C 2 H0 2 J 
 
 1 
 
 l Am y la m y lite cum ethyla dylete 
 
 CUm 
 
 [C 5 H ll ,C 2 H 3 3 ] 
 20. < ZH 4 ,C 2 H O 2 1 Amyla mylite bis ammona dylete. 
 
 r C 5 H 11 C 2 H 3 O 3 1 
 
 J > I Amyla mylite cum potassa dylete 
 
 2 1 \ &- * v> -ti v-' A i i i i j 
 
 TT psTj r^ I cum hydra dylete. 
 Jl ,O H U J 
 
 ^H a ,C 2 H 3 2 ) 
 
 22. { ZH 2 ,C 2 H O \ Amida mylete bis amida dylate. 
 ZH 2 ,C 2 H ) 
 
 fZH 3 ,CH>; 
 1 H, 
 
 Phenlam mlite bis 
 
 r H0 2 
 
 24 bis 
 
 Ag; C 2 H0 8 
 
 f H C^tPO 3 ! 
 
 25 JzH ,C 6 H^' ; C 2 H i H > r f ra f m >" lite bis 
 (ZH,C 6 H 5 ; C 2 HOJ dylate * 
 
 26. IZH ,c e ip c^n'o 3 ! Ar f ^ m r lite bis P hen >* lac 
 
 ,C 6 H 5 ;C 2 HO 
 'Ba;C 8 H 3 O 8 
 
 ' 
 
 21 <(ZH C 6 H 5 - C 2 HO L JUW * 1 J ru * m y^ ite bis phenylac 
 
 ZH,C 6 H 5 ;C 2 HO 
 ZH 3 ,C 6 H 5 ; C^^O 3 ),,, 
 
 ' Phenlai bls 
 
 rZH,C 6 H 5 ; C 2 H 3 O 8 1 
 
 29. ZH cH 5 c 2 H o 
 
 1ZH>H';C 2 HOJ 
 ^ j ZH ,C 6 H 5 ; C 2 H 3 2 ) Phenylac mylete cum dy 
 3 a lZ,C 2 H,C 6 H 5 ; C 2 H O 8 } lic-phenylac dylete. 
 
THE CITRIC GROUP OF SALTS. 427 
 
 I H ; C 2 H 3 3 ) Hydra mylite cum dylic- 
 
 3 1 ' \ Z,C 2 H,C 6 H 5 ; C 2 H O 2 J phenykc dylete. 
 
 )Ag ; C 2 H 3 O 3 1 Argenta mylite cum dylic- 
 Z,C 2 H,C 6 H 5 ; C 2 H O 2 ] phenylac dylete. 
 
 EXAMPLES OF ACONITES. 
 
 33. H ,C 2 HO 2 Hydra aconylete. 
 
 34. Ag ,C 2 H0 2 Argenta aconylete. 
 
 35. C 2 H 5 ,C'HO 2 Ethyla aconylete. 
 
 j K ,C 2 H0 8 1 Potassa aconylete cum hydra aco- 
 3' \ H ,C 2 H0 2 f nylete. 
 
 J K ,C*HO 2 1 Potassa aconylete bis hydra acony- 
 37' J 2 (H,C 2 HO 2 )) lete. 
 
 JZH 4 ,C 2 HO* 1 Ammona aconylete cum hydra 
 3 b ') H,C*H0 2 ( aconylete. 
 
 {ZH 4 ,C i! HO 2 1 Ammona aconylete bis hydra aco- 
 2(H,C 8 H0 8 )j nylete. 
 
 Z,C 2 H,C 6 H 5 ; C 2 H0 8 ) Aeonylic-phenylac acony- 
 H ; C 8 HO 2 1 lete cum hydra aconylete. 
 Z,C 2 H,C 6 H 5 ; C 8 HO 2 ) Aconylic - phenylac acony- 
 Ag ; C 2 H0 2 j lete cum argenta aconylete. 
 J Z,C 2 H,C 6 H 5 ; C 2 H0 2 ) Aeonylic-phenylac aconylete 
 4 2 ' }ZH, C 6 H 5 ; C 2 HO j cum phenylac aconylate. 
 
 43. | :^ ' 
 
 EXAMPLES OF CITRACONATES. 
 
 Hydra tiylete cum hydra dylete. 
 
 44. C 3 H 3 ,C 2 HO 3 Tryladylite. 
 
 ( H C 3 H 8 O 2 \ 
 
 45. -j 7 TT 4 '/-(2tT Q2f Hydra try lete cum ammona dylete. 
 
 I H C 3 H 3 O 2 \ 
 ' 
 
 ' I A c*H O 2 1 
 
 cum argenta dylete. 
 
 4-7. j A ^'f 2 H DM A r enta tr ylete cum argenta dylete. 
 
 j r2tI5 ri3TT3pv21 
 
 48. |c 2 H 5 C 2 H 2 [ Ethyla trylete cum ethyla dylete * 
 
 Pb ,C 3 H 3 O 2 ) Plumba trylete cum plumbine dy- 
 Pb 3 ,C 8 HO 3 f lite. 
 
 ( 
 
 ) 
 
 C 2 H CIO f Tryla chlorate cum d >' la chlorate - 
 
428 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 51. ZH,C 3 H 3 ; C 2 H0 2 Trylac dylete. 
 
 (ZH 2 C*H O ) 
 5 2 ' | H 'csjpQaf Amida dylate cum hydra trylete. 
 
 (ZH 2 ,C 2 HO) . . , , i 
 53* 1 Ba C 3 H 3 O 2 ( Amida dylate cum baryta trylete. 
 
 JZH,C 6 H 5 ; C 3 H 8 1 Phenylac trylate cum phe- 
 54' (ZH,C 6 H 5 ; C 2 H O f nylac dylate. 
 
 JZH,C 6 H 5 ; C 3 H 3 \ Phenylac trylate cum hydra 
 35 '[ H;C 2 H0 8 | dylete. 
 
 ZH,C 6 H 5 ; C 3 H 3 \ Phenylac trylate cum am- 
 
 ZH 4 ; C 2 H0 2 { mona dylete. 
 ZH,C 6 H 5 ; C 3 H 3 O ) Phenylac trylate cum barvta 
 BajC^HO 2 } dylete. 
 
 58. Z^ff^H 5 ; C 2 HO* Trylic-phenylac dylete. 
 
 59. Z^H^H 4 ! ; C 2 H O 2 Trylic - iodic - phenylac 
 
 dylete. 
 
 60. Z,C 3 H 3 ,C 6 H 3 Z 2 ; C^HO 6 Trylic- zotenic- phenylac 
 
 dylaze. 
 
 * JZH,C 6 H 3 Z 2 ; OWO 5 1 Zotenic-phenylac trylute 
 
 \ H ; C 2 H O 8 f cum hydra dylete. 
 
 , (ZH,C 6 H 3 Z 2 ; C 3 H 3 5 \ Zotenic-pheriy lac trylute 
 
 " \ Ag ; C 2 H O 2 j cum argenta dylete. 
 
 INVESTIGATION OF THE CITRATES. 
 i]. H,C 1 H 8 8 + 2(H,C 2 H0 8 ). Hydra mylite bis hydra dylete. 
 
 The hydrated citric acid. In this acid there are three atoms of hydrogen 
 which are all, or one, or two of them, replaceable by other basic radicals, 
 giving rise to the three kinds of salts which characterise the citrates, and 
 which are illustrated by examples in Nos. 2,3, and 4. 
 
 There are three varieties of citric acid obtainable in the solid state, in 
 accordance with the following formulae : 
 
 A). H.CWO 3 + 2(H,C 2 H0 2 ). 
 
 B). H,C 2 H 3 3 + 2 (H,C 2 H0 2 ) + HHO. 
 
 fH,C 8 H'0 3 + 2(H,C 2 HO')l, 
 
 C >' \H,C 2 H 3 3 + 2(H,C 2 H0 8 ) f + l Ia 
 
 A). The acid which corresponds with the normal salts. It is pro- 
 duced by heating the crystallised acids to 2I2F. B). The com- 
 mercial acid, which crystallises when the solution is slowly evaporated. 
 Its ordinary formula is (3HO,C 12 H 5 O U ,2 aq.). C). This acid is pro- 
 duced by saturating the solution at 212, and allowing it to cool and 
 
THE CITRIC GEOUP OF SALTS. 429 
 
 crystallise. Compare the acids B and C with the salts Nos. 12 and 13, 
 which have corresponding formulae. 
 
 2]. K ,C 2 H 3 O 3 + 2(K,C 2 HO 2 ) = Trimetallic citrate. 
 3]. H,C*H 3 3 + 2(K,C 2 H0 2 ) = Bimetallic. 
 4]. K ,C 2 H 3 O 3 + 2(H,C 2 H0 8 ) = Monometallic. 
 
 5]. ZH 4 ,C 2 H 3 3 + 2(K,C 2 H0 2 ). 
 
 This is an example of a neutral, or trimetallic salt, which has different 
 metals as basic radicals. 
 
 6]. ZH 4 ,C 2 H 3 3 + 2(H,C 2 H0 2 ). 
 
 Monometallic or acid salt of ammonium ; of the same order as the 
 potassium salt No. 4.] 
 
 7]. H,C 2 H 3 O 3 + 2(ZH 4 ,C 2 H0 2 ). 
 
 Bimetallic salt of ammonium, corresponding to the potassium salt No. 3]. 
 The trimetallic salt of ammonium = ZH 4 ,C 2 H 3 3 + 2(ZH 4 ,C 2 HO 2 ), 
 can only be prepared in solution; but No. 22 represents the amidogen 
 salt which corresponds to it. 
 
 A great number of citrates are formed according to one or other of 
 these three models. It is useless to quote them, because the fact will 
 not be contested. It is sufficient to say, that these are the common 
 forms of the citrates, and that they may all be represented as triple 
 salts. 
 
 Q1 JZH 4 ,C 2 H 3 O 3 + 2(ZH 4 ,C 2 H0 2 ; 
 ?4' 1 H ,C 2 H 3 3 + 2( H ,C 2 HO ! 
 K,C 2 H 3 3 + 2 ( K,C 8 H0 2 )) 
 Sbc,C 2 H 3 3 + 2(Sbc,C 2 H0 2 )f 
 Ba ,C 2 H 3 O 3 + 2( Ba ,C 2 H0 2 )) 
 H ,C 2 H 3 3 + 2 ( Ba ,C 2 H0 2 )f 
 
 ii 
 
 J K ,C 2 H 3 3 + 2( K ,C 2 H0 2 )1 
 \ H, C 2 H 3 3 + 2(ZH 4 ,C 2 H0 2 )f 
 
 Nos. 8, 9, 10, ii are examples of double citrates, each of which con- 
 tains six monobasic salts, all in the proportions necessary to constitute 
 citrates. The. relation of these salts to the simpler kinds, Nos. i to 7, is 
 so evident on an inspection of the formulae, that comment appears to be 
 needless. 
 
 12]. Ag,C 2 H 3 3 + 2(Sbc,C 2 H0 2 ) + AgSbcO. 
 
 , ( Ag,C 8 H 3 3 + 2( Ag,C 2 H0 2 H 
 1 3J- \Ca ,C 2 H 3 3 + 2 (Ca ,C 2 HO 2 ) f 
 
 In No. 12, one atom of a citrate is combined with a salt on the model 
 
430 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 of water. In No. 13, two atoms of a citrate are combined with a salt 
 on the model of water. These two models are not uncommon among 
 the citrates. If all the radicals of both formulae except C*H 3 and C 2 H 
 were exchanged for hydrogen, the salts would resemble the crystallised 
 acids B and C, No. i. The structure of these salts becomes intelligible, 
 if we assume that the mylite which forms part of them is subject to 
 become terbasic. No. 1 2 would then be represented thus : 
 
 Sbc 3 ,C 2 H 3 O 4 4- 2(Ag,C 2 H0 2 ) = Stibinic mylote bis argenta 
 
 dylete. 
 
 The corresponding crystallised acid (B, No. i) would be : 
 
 IP.CTPO* 4- 2(H,C 2 H0 2 ) = Hydrine mylote bis hydra dylete. 
 
 In these cases, I separate the citrate into three salts which are mono- 
 basic in general, but one of which is, in these examples, terbasic. 
 
 14]. CH 3 ,C 2 H 3 3 + 2(CH 3 ,C 2 H0 2 ). 
 15]. H ,C 2 H 3 3 + 2 (CH 3 ,C 2 H0 2 ). 
 16]. CH 3 ,C 2 H 3 O 3 + 2( H,C 2 H0 2 ). 
 
 These three salts are the citrates of methyl. A comparison of Nos. 14, 
 15, and 1 6, with Nos. 2, 3, and 4, shows that the salts are precisely 
 the same, excepting that the potassium of the latter is replaced in the 
 former by methyl, atom for atom. Yet Gerhardt and other chemists 
 give to the salts Nos. 1 5 and 1 6 the denomination of " conjugated 
 acids." No. 15 is their Methyl-citric acid, and No. 16 is their Dime- 
 thyl-citric acid. The only ground for this assumption is, that salts of 
 lime can be formed with these " acids." In that case, we have 
 
 with No. 1 5, Ca ,C 2 H 3 O 3 + 2(CH 3 ,C 2 HO 2 ). 
 with No. 1 6, CH 3 ,C 2 H 3 3 + 2(Ca, C 2 HO 2 ). 
 
 Both of these salts are citrates equally with Nos. 1 5 and 1 6, and ought 
 not to be removed from that class merely to make imaginary conjugated 
 acids. There is not a particle of evidence to prove that the methyl and 
 the citric radicals are conjugated into a single acid radical. Methyl-citric 
 acid arid Dimethyl-citric acid are phantoms. 
 
 17] 
 
 1 8 
 19 
 
 20 
 
 2 i 
 
 -f C 2 H 5 ,C 2 H0 2 + C 2 H 5 ,C 2 H0 2 . 
 
 + H ,C 2 H0 2 + H ^HO 2 . 
 C 5 H ll ,C 2 H 3 3 4- C 2 H 5 ,C 2 H0 2 + H ,C 2 HO 2 . 
 C 5 H U ,C 2 H 3 O 3 4- ZH*,C 2 HO 2 4. ZH 4 ,C 2 HO 2 . 
 C 5 H U ,C 2 H 3 3 4- K ,C 2 H0 2 4. H,C 2 H0 2 . 
 
 According to my method of looking at these salts they are all citrates, 
 triple salts formed in exact accordance with the constitution of citric 
 
THE CITRIC GROUP OF SALTS. 431 
 
 acid, and with the varieties of metallic citrates described above. But 
 Gerhardt, reporting Breunlin's researches, will have the last four to be 
 salts of "conjugated acids" No. 18 is the Amyl-citric acid, Nos. 20 
 and 21 its salts, and No. 19 is the Ethylamyl-citric acid. In the amyl- 
 citric acid, four radicals out of the six that are present in the salt are 
 assumed to be conjugated into an acid radical, which then of course is 
 bibasic. In the last example, five of the radicals (C 2 H 3 , C 2 H, C 2 H, 
 C 5 H 11 , and C 2 H 5 ,) are conjugated into one acid radical, which has H l to 
 combine with as the corresponding and only remaining basic radical. 
 The formula supplied for the last salt are C 26 H 22 14 = C 12 H 6 (C 4 H 5 ) 
 (C l H ll )O u . There is not the slightest necessity for this conglomerating 
 process, nor has it any beneficial result. Conjugated acids are not 
 merely enemies to the accurate discrimination of facts, and to the precise 
 knowledge of intricate details : they are great high priests of false philo- 
 sophy. In salt No. 1 9, if we consider it as a triple salt, we have an intel- 
 ligible view of its composition; but if we regard it as " ethyl amyl-citric 
 acid," we must suppose that two basic radicals, ethyl and amyl = C^H 5 
 + C 5 H", combine with the three acid radicals = C 2 H 3 + C 2 H + C 2 H, 
 to form a single acid radical = C 13 H 21 , which has then only a saturating 
 capacity equal to H 1 . What has become of the saturating capacities of 
 all the component radicals which are assumed to be condensed into this 
 mammoth radical ? What proof have we that the radical C 13 H. 21 is really 
 formed ? None whatever. 
 
 22]. ZH 2 ,C 2 H 3 2 -f- 2(ZH 2 ,C 2 HO). CITRAMIDE. 
 
 This is the amid which corresponds to the unknown trimetallic or tri- 
 basic citrate of ammonia. That salt can be prepared in solution though 
 it cannot be procured in crystals. I wish to draw attention to the fact, 
 that as every one of the three atoms of ammonium belonging to this salt 
 is converted into amid, every one of the three salts loses simultaneously 
 one atom of oxygen, and the result is the production of an amidogen 
 salt which contains only four atoms of oxygen instead of the seven atoms 
 which belong to the normal citrate. Thus : 
 
 ZH 4 ,C 2 H 3 3 = HHO + ZH 2 ,C 2 H 3 2 . 
 ZH 4 ,C 2 H O 2 = HHO + ZH 2 ,C 2 H O . 
 ZH 4 ,C 2 H O 2 = HHO + ZH 2 ,C 2 H . 
 
 Now, if we knew to a certainty that the citrate of ammonia was a triple 
 salt, consisting of one atom of ZH 4 ,C 2 H 3 O 3 and two atoms of ZH 4 ,C 2 HO*, 
 this result is precisely what we must predicate as certain to occur on the 
 occasion of its conversion into a triple amid. Conversely, therefore, the 
 facts afford excellent evidence in proof of the triple nature of the acid 
 radical of the citrates. Of this conclusion, the following details respect- 
 ing the phenyl amids afford ample corroborative evidence : 
 
432 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 23]. ZH 3 ,C 6 H 5 ; C 2 H 3 3 + 2( H , 
 
 24]. ZH,C 6 H 5 ; C 2 H 3 2 + 2(Ag,C 2 H0 2 ). 
 
 No. 23 is commonly called the Citrate of aniline. The other citrates, 
 containing respectively two and three atoms of phenylara (ZH 8 ,C 6 H 5 ) 
 have not been discovered, though we are acquainted with their amids. 
 
 No. 24 is a salt in which the mylite of phenylam has been converted 
 into an amid, the mylete of phenylac, while the two atoms of hydrated 
 dylic acid have both been converted into dylate of silver. These changes 
 prove unquestionably, that while the three salts which constitute a 
 citrate remain in combination with one another, they yet individually 
 retain their chemical powers unimpaired, and can exhibit the phases of 
 all reactions to which they are respectively competent, as decidedly as if 
 the tripartite union were dissolved. 
 
 No. 24 is described by Pebal as the silver salt of bibasic citro- 
 monanilic acid = 2 AgO,C 24 H ll N0 10 . Here we have another " conjugated 
 acid," which, like all the acids conjugated in this manner, is an unwar- 
 ranted invention and a useless incumbrance. 
 
 26 
 
 *1 
 28 
 
 H, C 2 H 3 3 + 2 (ZH,C 6 H 5 ; C 2 HO). 
 
 Ag, C 2 H 3 O 3 + 2(ZH,C 6 H 5 ; C 2 HO). 
 
 Ba, C 2 H 3 3 4- 2(ZH,C 6 H 5 ; C 2 HO). 
 
 . ZH 3 ,C 6 H 5 ; C 2 H 3 O 3 4- 2(ZH,C 6 H 5 ; C'HO). 
 
 These four salts agree exactly with one another in structure. The only 
 difference among them is, that the basic radical H, in No. 25, is replaced 
 in the other salts by Ag, Ba, and ZH 3 ,C 6 H 5 . In every example, the 
 mylite, or single salt with the radical C 2 H 3 is a normal salt with O 3 , and 
 is accompanied by two atoms of an anile (phenyl-amid) with the acid 
 radical C 2 H. These amids have each, of course, only one atom of 
 oxygen, the total quantity of oxygen in each salt being five atoms. 
 Here, therefore, each of the three acid radicals which constitute the citric 
 acid acts precisely as if it were an independent acid radical. 
 Comparison of No. 28 with No. 23 : 
 
 No. 23]. ZH 3 ,C 6 H 5 ;C 2 H 3 3 
 H; C 2 H0 2 
 H; C 2 H0 2 
 
 No. 28]. ZH 3 ,C 6 H 5 ; C 2 H 3 3 . 
 ZH,C 6 H 5 ; C 2 HO. 
 ZH ,C 6 H 5 ; C 2 H O . 
 
 In No. 28, two atoms of oxygen are deficient because two basic radicals 
 are vice-amids (phenylac). If two atoms of HHO could be combined with 
 No. 28, we should have the tribasic citrate of aniline which has not yet 
 been discovered. If two atoms of HHO could be combined with No. 25, 
 we should have the bibasic citrate of aniline, also at present unknown : 
 
 H ; C 2 H 3 O 3 } (H ; CWO 3 . 
 
 ZH,C 6 H 5 ; C 2 HO + H 2 ()l = ^ZH 3 ,C 6 H 5 ; C 2 H O 8 . 
 ZH,C 6 H 5 ; C*H O + H 2 OJ iZH 3 ,C 6 H 5 ; C 2 H O 2 . 
 
THE CITRIC GROUP OF SALTS. 433 
 
 Usual names of these four salts. No. 25], Citrobianilic acid = 
 C 36 H 18 N 2 10 = HO.C 36 H 17 IS T2 9 , Pebal Phenyl-citrobiamic acid, Ger- 
 hardt. Monobasic-citro-monanilate of aniline = C I2 H 7 N,HO.C 12 H 5 N, 
 C 12 H 5 9 , Fehling. Aniline salt of monobasic citromonanilic acid = 
 C 12 H 7 N.HO.C 24 H'NO 9 , Pebal Hence Pebal giyes two entirely different 
 names and formula?. I do not perceive, from his description, that there 
 is a corresponding difference in the things. 
 
 Nos. 26, 27, and 28 are Citrobianilates. 26] = AgO.C 36 H 17 N 8 9 . 
 27] = BaO,C 36 H 17 N 2 9 . 28] = C 12 H 7 N.HO.C 36 H 17 N 2 9 , Pebal Ac- 
 cording to this chemist, "the composition of these salts shows that the 
 acid is monobasic." (Quarterly Journal of the Chemical Society, v. 287.) 
 I cannot agree that citrobianilic acid is shown to be monobasic, because 
 it appears to me that there is no such thing in existence as citrobianilic 
 acid ; and once again, I say, that these conjugated acids are a nuisance, 
 alike repugnant to truth and to convenience. 
 
 29]. ZH,C 6 H 5 ; C 2 H 3 2 + 2(ZH,C 6 H 5 ; C 2 HO). 
 
 Compare Nos. 22 and 29. The latter is the phenylac compound cor- 
 responding to the amid compound represented by the former. Compare 
 29 with 28. There is simply a difference of HHO in one salt; the 
 phenylam mylite of No. 28 is reduced to phenylac mylete in No. 29; 
 the other two salts in each compound remaining the same. 
 
 Usual names : Citronanilide = C 4S H 23 N 3 8 , Pebal. Phenyl-citramide 
 = C 12 H 8 (C 12 H 5 ) 3 N 3 8 . Also Triazoture of citryle, of triphenyle, and of 
 hydrogen 
 
 1 } Gerliardt. 
 J 
 
 While Pebal is contented with a clump formula, Gerhardt resorts to the 
 ammonia type, and forces three oxidised salts to appear in the garb of 
 a triple atom of ammonia ; a proceeding which is not warranted, and 
 it will be seen, at No. 32, that the ammonia type breaks down when 
 applied to other examples in the citric group. 
 
 3 
 3 1 
 
 ZH,C 6 H 5 ; C 2 H 3 O 2 + Z,C 2 H,C 6 H 5 ; C 2 H0 2 . 
 H ; C 2 H 3 3 + Z,C 2 H,C 6 H 5 ; C 2 H0 2 . 
 Ag; C 2 H 3 3 + Z,C 2 H,C 6 H 3 ; C 2 H0 2 . 
 
 These three salts give important testimony in favour of the theory which 
 I am advocating. Each of the three formulas is divided into two parts. 
 The first part of No. 30] is an amid similar to the first part of No. 29]. 
 The first part of Nos. 31 and 32 resemble the corresponding parts of 
 Nos. 25 and 26. In these parts of the three salts there is, therefore, 
 nothing peculiar. The interest lies in the second part of the formulae, 
 which is the same in all three examples, and which represents the com- 
 
 2 F 
 
434 THEORY OF POL YB ASIC AND CONJUGATED ACIDS. 
 
 pounds that are commonly called Aniles, examples of which are given at 
 
 page 224, and the theory of which has been fully explained in the section 
 
 that commences at page 222. 
 
 The usual names and formula} of tWese three salts are as follow : 
 
 30]. Citrobianil = C^H'WO 8 , Pebal Phenyl-citrimide; Citrobia- 
 
 nile, or diazoture of citryle, of diphenyle, and of hydrogen = C 18 H 16 N 2 O 4 
 
 f (C 6 H 5 ) 2 ) 
 
 = N 2 { C 6 H 5 4 I, Gerhardt. 
 ( H j 
 
 "Citrobianil may be supposed to be formed from bibasic citrate of 
 aniline by separation of 6HO : 
 
 C 18 H 7 N.HCh 
 
 C 12 H 7 N.HO C 12 H 5 U - 6HO = C 36 H 16 N 2 8 ." Pebal 
 HOJ 
 
 31]. "Monobasic citromonanilic acid = CPff'NO 10 . It may be re- 
 garded as monobasic citrate of aniline minus 4HO : 
 
 C 18 H 7 N.HO) 
 
 HO I C 12 H 5 U - 4HO - C^H-'NO 10 ." Pebal. 
 HOJ 
 
 32]. The silver salt of monobasic citromonanilic acid = AgO. 
 C 24 H 10 N0 9 , Pebal. 
 
 I cannot find that Gerhardt has anywhere reduced Nos. 3 1 and 3 2 to 
 " type ammonia." These salts in fact are such as would require an 
 extreme amount of pressure to fit them to that type ; for against one 
 atom of azote we have in 31] the following substitutes for hydrogen: 
 H = i atom, C 6 H 5 phenyl = i atom, C 6 H 5 O 4 citryle = 3 atoms, and O 
 in excess. These atoms will make neither an azoture nor a diazoture, 
 and therefore " type ammonia" breaks down. 
 
 Pebal makes no attempt to explain the constitution of these salts. He 
 shows their mode of derivation from normal salts, but concludes in each 
 case with a clump formula and a name drawn from the store-house of 
 conjugated acids, that much-frequented place of refuge for distracted 
 theorists. 
 
 Tried in any way, these compounds present great difficulties on the 
 theory that the citrates are tribasic but monacid. We have the follow- 
 ing atoms to deal with : 
 
 No. 30]. Z,ZH,C 6 H 5 ,C 6 H 5 ; C 6 H 5 O 4 . 
 No. 3 iJ. ZH,C 6 H 5 ; C 6 H 5 O 5 . 
 No. 32]. ZAg,C a H 5 ; C 6 H 5 O 5 . 
 
 Presented in this light, these basic radicals are unintelligible fragments, 
 and the variations in the quantity of oxygen are difficult to be accounted 
 
THE CITRIC GROUP OF SALTS. 435 
 
 for. The usual theoretical explanation given of salts that contain such 
 fragmentary radicals is, that they are SO-AND-SO minus SO-AND-SO. That 
 explanation tells us how they came to be what they are, but that is not a 
 sufficient explanation. I want to know what they are while they are in 
 the state in which we have them. Gerhardt tries to evade this difficulty 
 by telling us, that the proper definition of a thing is, not what it is, but 
 what it has been, or what it may come to be ; an unsatisfactory argu- 
 ment, which I have discussed at page 410. 
 
 Now, on the theory that the citrates are triple salts, the formulae 30, 
 3 1 , and 3 2 present no difficulties whatever. We can account, not only 
 for the variations in the quantity of the oxygen, but for every separate 
 radical, and show that it is doing its proper duty. Thus : 
 
 ZH 3 ,C 6 H 5 ; C 2 H 3 O 3 ) fH 2 ZH,C 6 H 5 ; C 2 H 3 2 1 
 ZH 3 ,C 6 H 5 ; C 2 H O 2 1 = { H 3 2 + Z ,C 6 H 5 ; C*H I No. 30. 
 H ; C 2 H 3 2 J [H I ; C 2 H 2 j 
 
 A citrate containing two Water, Residue. 
 
 atoms of phenylam 3 atoms. 
 
 The abstraction of HHO from the first salt simply converts it into an 
 amidogen salt. The abstraction of 2 HHO from the other two salts, 
 leaves such a residue as constitutes an imide or an anile, the theory of 
 which I have fully explained in the article on Imidogen compounds at 
 page 222, to which I have already referred. The azotic radical No. 226, 
 page 224, is the exact counterpart of the second half of the formulae of 
 Nos. 30, 31, and 32. Thus: 
 
 Z,C 2 H 2 ,C 6 H 5 ; C 2 H 2 O 2 Succinylic-phenylac succinylete. 
 Z,C 2 H ,C 6 H 5 ; C 2 H O 2 Dylic-phenylac dylete. 
 
 Again, No. 31 requires merely the addition of two atoms of water to be 
 restored to the condition of its normal salt No. 23. 
 
 H ; C 2 H 3 3 } f Zff.OTP ; 
 
 Z,C 6 H 5 ; C 2 H O + H 4 2 \ = J H ; C 2 H O 2 
 
 C 2 HO j ( _ H;C*H0 2 
 
 No. 31 -f- Water = No. 23. 
 
 The same quantity of water applied to No. 32 would produce the fol- 
 lowing salt, which is nearly related to No. 23 : 
 
 ZH 3 ,C 6 H 5 ; C 2 H 3 3 + Ag,C 2 H0 2 + H,C 2 H0 2 . 
 
 These considerations prove, almost with the force of mathematical 
 demonstration, that the citrates ought to be considered to be triple salts, 
 each having, not only three basic radicals, but also three acid radicals. 
 On that supposition you can account fully for all their reactions and 
 
 2 F2 
 
436 THEORY OF POLY BASIC AND CONJUGATED ACIDS. 
 
 transformations, without the necessity of resorting to conjugated acids, 
 type ammonia, or other cumbersome or rickety hypotheses, contrived to 
 make things pleasant, or serving to mix them into a muddle. 
 
 If, on the contrary, you insist that citric acid shall be considered a 
 terbasic acid, I ask you to explain, how it comes to pass, that the citric 
 acid radical C 6 H 5 so thoroughly and effectually holds in the majority of 
 cases, all the chemical powers of three separate radicals, and yet 
 frequently suffers their abnegation to such an extent that you cannot 
 dispose of the positive radicals without a reinforcement of six or eight 
 conjugated acids ? It is easy to declare off hand that a terbasic acid 
 radical has the powers of three monobasic acid radicals ; but when you 
 come to account for the variations in the quantity of oxygen and for 
 the constitution of amides, imides, aniles, conjugated acids, and similar 
 imaginary compounds to which the terbasic doctrine drives you ; the 
 difficulties and contradictions which assail you are so unconquerable, 
 that you are driven, in despair, to take shelter behind that convenient 
 dummy the unitary formula. 
 
 INVESTIGATION OF THE ACONITES. 
 
 When citric acid is exposed to heat, it disengages carbonic oxide 
 and carbonic acid, and yields a residue which is called Aconitic acid, and 
 which is commonly indicated by the following formula : 3HO,C 12 H 3 9 . 
 
 " Aconitic acid is isomeric with fumaric and malaBic acids. Hydratod 
 aconitic acid contains the elements of two equivalents of water less than 
 hydrated citric acid: 3 HO,C 12 H 3 9 + 2HO = 3 HO,C 12 H 5 11 . Meed, 
 aconitic acid derives its principal interest from its close connection 
 with citric acid, and from the light which its composition throws upon 
 some apparent anomalies in relation to the separation of water from the 
 crystallised acid and its salts." Miller (Elem. Chem. iii. 343). 
 
 Doubling the atomic weights of C and O, and re-arranging the for- 
 mula, we produce H 3 ,C 6 H 3 O 6 . These numbers represent a terbasic acid, 
 but this acid is made terbasic without necessity, and I divide the for- 
 mula by 3, which leaves H,C 2 HO 2 . Dr. Miller's remarks respecting the 
 difficulties which depend upon the different degrees of hydration of citric 
 acid, I have disposed of in the Notes to Nos. I and 1 3 of the citrates. 
 The formula to which I have reduced the aconitic acid, H,C 2 HO 2 , agrees 
 exactly with the formula of the acid which I have in the sections on the 
 Malates and the Citrates called Hydra dylete. I cannot undertake to 
 determine whether the radical C 2 !! = DYL is the radical of the aconites, 
 the malseates, or the fumarates. That must remain for special deter- 
 mination. I have hitherto used the term Dyl to signify C' 2 H, in order 
 not to prejudge the question. But I shall use the term aconyl in 
 describing the aconites. 
 
 The Table of Examples, Nos. 33 to 42, afford sufficient specimens of 
 
INVESTIGATION OF THE ACONITES. 437 
 
 the different varieties of aconites. No. 33 is the aconitic acid. Nos. 
 34 and 35 are examples of neutral salts. Nos. 37 and 39 are examples 
 of the triple salts, which probably gave rise to the notion that the 
 aconites were terbasic : 
 
 K,C 2 H0 2 + 2(H,C 2 H0 2 ) = KH 2 ,C 6 H 8 O 6 . 
 
 The salts Nos. 36 and 38 afford examples of double aconites. These 
 were procured by Baup by dividing a quantity of acid into two parts, 
 neutralising one part by a base, and then mixing the whole. The 
 crystals were subsequently analysed, and were found to agree with formulae 
 that lead to Nos. 36 and 38. Gerhardt and Gmelin, prepossessed with 
 the idea that the aconites were undoubtedly terbasic, concluded that 
 Baup's experiments were inexact ; but experiments are not necessarily 
 inexact, because their results disagree with a theory which is itself un- 
 founded. 
 
 !Z,C 2 H,C 6 H 5 ; C 2 H0 2 \ 
 H ; C 2 H0 2 j 
 Z,C 2 H,C 6 H 5 ; C 2 H0 2 ( 
 Ag; C 2 HO 2 j 
 
 These salts are precisely like the salts 3 1 and 3 2 of the citric series, ex- 
 cepting that they contain only one kind of acid radical, instead of two 
 different acid radicals. The theory of the constitution of these salts is 
 the same as that by which I have explained the citric salts. Gerhard t's 
 name for No. 40 is Phenyl-aconitamic, or aconitanilic acid = C 24 H 9 N0 8 
 = C 12 H 6 12 + C 12 H 7 N - 4HO. No. 41 is the silver salt of that hypo- 
 thetical conjugated acid. 
 
 42]. J 
 
 Z,C 2 H,C 6 H 5 ;C 2 H0 2 I 
 ZH ,C 6 H 5 ;C 2 HO[ 
 
 This is evidently the combination of an amidogen salt with an imidogen 
 salt (using the current phraseology of Chemistry). Gerhardt calls it 
 Phenyl-aconitimide ; aconito-bianile ; or diazoture of aconityle, of di- 
 phenyle, and of hydrogen. He gives these formulas : = C 36 H 14 N 2 O 6 
 = C 11 H 4 (C li H) i N 1 0'; also C I8 H M N I O 8 
 
 r(G 6 H 5 ) 2 
 
 = NV C 6 H 3 3 ; 
 I H 
 
 and the following to explain the origin of the compound : 
 
 C l2 H 6 la + 2 C 12 H 7 N - 6HO = C 36 H 14 N 2 6 . 
 
 These three phenylac compounds were discovered by Pebal. 
 
 On the radical theory, No. 42 is accounted for by the following 
 equation : 
 
438 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 ZH 3 ,C 6 H 5 ; C 2 H0 8 ) f HHO + ZH ,C 6 H 5 ; C 2 HO ) 
 
 ZH 3 ,C 6 H*;C*H0 2 = JHHO) I 
 
 H ; C 2 H0 2 J 1 1 HHO ( + Z ' C H ' U j 
 
 These three derivatives from aniline present great difficulties of explana- 
 tion if we treat aconitic acid as terbasic. What these difficulties are, I 
 have explained at the end of the section on the citrates. On the other 
 ha$d, if we treat aconitic acid as monobasic, we can account for the con- 
 stitution of these amids easily and satisfactorily. 
 
 I repeat, then, that the formula of aconitic acid is H r ,C*H0 2 , and that 
 it is monobasic. The assumption of the formula 3HO,C 18 H 3 9 , and the 
 declaration of the terbasicity of this acid are justified only by the doctrine, 
 that it is easy to convert a monobasic acid into a terbasic acid by tripling 
 the formula. See page 395. 
 
 INVESTIGATION OF THE CITRACONATES. 
 
 The common formula of the Citraconic acid is 2HO,C 18 H 4 O 6 , and it is 
 esteemed to be BIBASIC. I propose to show that its reactions and trans- 
 formations are such as indicate that it is a double monobasic salt, having 
 two different acid radicals, and agreeing with the following formula: 
 
 H,C 3 H 3 2 + H,C 2 HO a . 
 
 As this acid can be prepared by heating aconitic acid, it is probable that 
 the radical C 2 H is aconyl; but as the acid is commonly procured by 
 heating citric acid, and as I do not wish to prejudge the question re- 
 specting the identity of these isomeric radicals, I shall, as before, call the 
 radical C'H dyl, while the other radical CT 3 shall be called tryl. This 
 radical agrees in composition with acryl, the radical of acrolein, and 
 with the radical of the pyruvates. All these radicals are produced by 
 heating other hydrocarbons. They may be one and the same thing, but 
 I cannot say that they are so, and therefore I use the term tryl, as a 
 provisional name for the acid radical C 3 H 3 , as it occurs in the Citra- 
 conates. 
 
 Examples of Citraconates are given in the Table, Nos. 43 to 62. As 
 many of these salts present forms of combination which have been 
 already examined minutely, I shall pass over them briefly. 
 
 43]. H,C B H'O i + H,C*HO a Hydra trylete cum hydra dylete. 
 
 This is the hydrated aconitic acid. Being a double acid, it has two re- 
 placeable atoms of hydrogen, and in that sense is truly bibasic ; but, as 
 each of these basic radicals is combined with a separate acid radical, the 
 salts are not bibasic in the ordinary sense of that term, but are biacid as 
 well as bibasic. 44]. This is the citraconic anhydride or anhydrous 
 citraconic acid = C'H^C'HO 3 , which agrees precisely with the compound 
 anhydrides described at page 121. 45] and 46] are examples of acid 
 citraconates. 47] and 48] are examples of neutral citraconates, 49] is 
 
INVESTIGATION OF THE C1TRACONATES. 439 
 
 a compound salt in which one of the constituent salts. is tribasic. 50] 
 is the oxychloride of citraconyl; which Gmelin calls Chloropyrocitryl. 
 A moist air converts it into hydrochloric and hydrated citraconic acid : 
 
 C 3 H 3 ,C10 + H,HO _ H,C B H0 1 + HC1 
 C 2 H ,C10 + H,HO ~ H,C 2 H O 2 + HC1 
 
 The oxychlorides in general have one atom of chlorine and one atom of 
 oxygen with each organic radical. The same proportions occur here. 
 There are two atoms of chlorine and two atoms of oxygen, because there 
 are two organic radicals. 5 1] is the Citraconimide, formed by the action 
 of heat on the citraconate of ammonia, No. 45] : 
 
 45J -1 
 
 _ j H ; C 3 H 3 O 2 ) JZH,C 3 H 3 ; C 2 H0 2 = 51]. 
 ZH 4 ; C 2 H0 2 j == 1 HHO + HHO = water. 
 
 -52] is called Citraconamide, and also Citraconamic acid. The term Ci- 
 traconamide is improper, because it implies the amide of the neutral 
 citraconamate of ammonia, which must have this composition : 
 
 ZH 2 ,C 2 H0 2 + ZH 2 ,C 3 H 3 2 ; 
 
 whereas No. 52] is the amide of the acid citraconate of ammonia, and 
 therefore the term citraconamic acid is preferable. No. 53] is the 
 barytic salt of that acid. There are similar salts with Pb and Ag instead 
 of Ba. These salts belong to the amidogen acids with compound 
 radicals, group C, page 227. Compare 242 (in that page) with 52, and 
 246 with 53. 
 
 54], This is the double amidogen salt, formed from the (unknown) 
 neutral citraconate of aniline. Thus : 
 
 ZH 3 ,C 6 H 5 ; C 3 H 3 O 2 _ ZH,C 6 H 5 ;C 3 H 3 O + HHO 
 ZH 3 ,C 6 H 5 ; C 2 H0 2 * ZH,C 6 H 5 ;C 2 H O + HHO. 
 
 55]. This salt bears the same relation to the acid citraconate of aniline, 
 which 54] bears to the neutral salt, excepting that it is necessarily pro- 
 duced by the abstraction of only one atom of water. Thus : 
 
 ZH 3 ,C 6 H 5 ; C 3 H 3 O 2 _ ZH,C 6 H 5 ; C 3 H 3 O + HHO 
 H ; C 2 H O 8 = H ; C 2 H O 2 
 
 55] belongs to the anilidogen-acids with compound radicals, Group D, 
 page 228. The salts of this class are called acids, only in accordance 
 with Gerhardt's law, that " any substance is an acid which contains 
 hydrogen capable of being replaced by metals by double decomposition." 
 56] and 57]. These are merely examples of salts corresponding to the 
 imaginary "acid" No. 55- 
 
 58]. Z,C 3 H 3 ,C 6 H 5 ; C 2 H0 8 
 
 59], Z,C 3 H 3 ,C 6 H 4 I ? C 2 HO 2 
 
 6oJ. Z^H^H'Z 2 ; C 2 H0 6 
 
440 THEORY OF POLYBAS1C AND CONJUGATED ACIDS. 
 
 No. 58 is an "anile" similar to those described in Group 6), page 224. 
 No. 59 is similar to 58, but contains iodic-phenyl instead of normal 
 phenyl. No. 60 is similar, but contains zotenic-phenyl instead of 
 normal phenyl. The presence of two atoms of azote in this vice-radical 
 causes the salt No. 60 to have four atoms of oxygen more than the cor- 
 responding salts Nos. 58 and 59- See the account of the iodic and 
 zotic vice-radicals at page 132. No. 58 is derived from the acid citra- 
 conate of phenylam by the abstraction of two atoms of HHO. Thus : 
 
 ZH 3 ,C 6 H 5 ; C 3 H 3 O a _ Z,C 3 H 3 ,C 6 H 5 ; C 2 HO 2 
 H ; C'H O 2 ~ HHO + HHO. 
 
 61]. This salt is perfectly equivalent to 55, excepting that it contains 
 zotenic-phenyl instead of normal phenyl, and consequently has four addi- 
 tional atoms of oxygen. 
 
 62]. The silver-salt of the "acid" 61. This salt is equivalent to 
 57, excepting that, like its acid, it contains Z 2 -}- O 4 instead of H 2 in the 
 phenylac. 
 
 Usual names of these aniline compounds. 54]. Diphenyl-itaconamide, 
 or diazoture of diphenyle and of itaconyle = C 17 H 16 N 2 O 2 
 
 [ C 5 H 4 2 
 = N 2 (C'H 5 ) 2 ; 
 I H 2 
 
 also Itaconanilide = C 10 H fl (C 12 H 5 ) 2 N 2 4 , Gerhardt. 55]. Phenyl-itaco- 
 namic, or Itaconanilic acid = OWNO" = C l H 6 (C 12 H 5 N0 6 , Gerhardt. 
 
 6 (C 1 
 Citraconanilic acid = HO.C^H^NO 5 = HO.C 12 H 6 N,C'H 4 O 5 , Fehling. 
 
 58]. Phenyl-citraconimide ; citraconanile = C i2 H 9 NO 4 = C'H 4 (C I2 H 5 ) 
 NO 4 , Gerhardt. 59]. lodophenyl - citraconimide, or Citraconiodanile 
 = C l H 4 (C 18 H 4 I)]S T O 4 , Gerhardt. 60]. Dinitrophenyl- 
 
 ' 
 
 citraconimide = C l H 4 (C' 2 H 3 (NO 4 ) 8 )NO 4 = C 22 H'(NO 4 ) 2 N0 4 = 
 Gerliardt. Citraconbinitranil 
 
 C 12 4 N.C 10 H 4 4 , Fehling. 
 
 acid = 
 
 6il. Dinitrophenyl - citraconamic aci 
 = C l H 6 (C 18 H 3 (NO 4 ) 2 )NO 6 , Gerhardt. 
 
 In 55 and 61, we have, according to Gerhardt, two more conjugated 
 acids ; for which assumptions there is, as usual, neither evidence nor 
 necessity. 
 
 I have treated these complicated compounds (the Citraconates) very 
 briefly, because, as I have mentioned, every form of combination which 
 they exhibit has repeatedly come under our consideration in the preceding 
 pages, and it appears to be useless to repeat explanations and demon- 
 strations with which the r^,der may reasonably be supposed to be by 
 this time sufficiently acquainted. 
 
( 441 ) 
 
 The Succinic Group. 
 
 I have suggested at page 81 the desirableness of classified Tables of 
 compound radicals, which should exhibit all that are known, and indi- 
 cate the place and composition of such as are unknown. And at page 
 79 I have given a Table representing the radicals which constitute the 
 vinyl series. 
 
 In that Table I have pointed out a regular series of Acid radicals, 
 which, beginning with formyl = C'H 1 , proceeds by the addition of 
 atoms of vinyl = C^H 2 , one after the other, to form the series C 2 H 3 , 
 C 3 H 5 , &c., up to Melissyl = C 30 H 59 , at which point we reach the limit 
 of known acid radicals of this series. 
 
 In the same Table I have described a series of Basic radicals, which, 
 beginning with hydrogen H 1 , proceeds by the addition of atoms of 
 vinyl, C 1 H 2 , one after the other, to form the regular series CH 3 , C ? H 5 , 
 &c., up to Myricyl = C 30 H 61 , where the limit of basic radicals of this 
 series hitherto discovered by experiment is again reached. 
 
 In the same manner, I now proceed to describe a regular, though 
 only a short, series of acid radicals, which we may conceive to be formed 
 by commencing with a single atom of carbon = C 1 , and adding to it, 
 one by one, a succession of atoms of vinyl = C 1 !! 2 . We thus produce 
 a series of acid radicals, which are all necessarily distinguished by having 
 an even number of atoms of hydrogen, in which respect they differ 
 essentially from the radicals of the vinyl series, all of which contain an 
 uneven number of atoms of hydrogen : 
 
 C + CH 2 = C 2 H 2 = Succinyl. 
 C + 2CH 2 = C 3 H 4 = Adipyl. 
 C -f- 2CH 2 = C 4 H 6 = Suberyl. 
 C + 4CH 2 = C 5 H 8 = Sebamyl. 
 
 This is the limit of the series as far as it is known at present. These 
 radicals produce the following monobasic acids, each with two atoms of 
 .oxygen : 
 
 Common Names. 
 
 H,C 2 H 2 2 = Hydra succiriylete . . Succinic acid. 
 H,C 3 H 4 O 2 = Hydra adipylete . . Adipic acid. 
 H.CftFO 8 = Hydra suberylete . . Suberic acid. 
 H,C 5 H 8 2 = Hydra sebamylete . . Sebacic acid. 
 These acids, and all their salts, have the faculty of forming interme- 
 diate double salts, and thus produce the following series : 
 
 Common Names. 
 
 (H,C 2 H 2 O 2 (Hydrasuccinyletecum . . ., 
 
 tH,C 3 H 4 2 j hydra adipylete. Pyrotartanc acid. 
 
442 THEORY OF POLYBAS1C AND CONJUGATED ACIDS. 
 
 Common Names. 
 
 |H,C 3 H 4 2 )Hydra adipylete cum ^ v 
 |H,C 4 H 6 2 f hydra suberylete. Pimehc acid ' 
 I H,C 4 H 6 2 1 Hydra suberylete cum A , . 
 tH,C*H 8 2 f hydra sebamylete. Anchoic acid * 
 
 These seven acids are commonly assumed to be Bibasic, but, making a 
 distinction between bibasic salts and double salts, I deny that there is 
 any evidence to sustain this bibasic character. I shall show, that the 
 first four acids are decidedly monobasic, that the last three are double 
 acids, which act precisely as if each contained two separate acid radicals, 
 and that the supposition that they contain special bibasic radicals is 
 erroneous. 
 
 Before I proceed to the examination of these acids individually, I 
 will refer to the relations which they bear to certain acids of the vinyl 
 series : 
 
 H,C 4 H 7 O 2 + O 3 - H,HO = H,C 2 H 2 2 + H,C 2 H 2 2 
 Butyric acid. Succinic acid, 2 atoms. 
 
 H,C 5 H 9 O 2 + O 3 - H,HO = H,C 2 H 2 2 + H,C 3 H 4 O 2 
 Valerianic acid. Pyrotartaric acid, i atom- 
 
 H,C 6 H ll O" + 0* - H,HO = H,C 3 H 4 2 + H.C'H'O" 
 Caproic acid. Adipic acid, 2 atoms. 
 
 H,C 7 H 13 2 + O 3 - H,HO = H.C'H'O 1 + H,C 4 H 6 O 2 
 (Enanthylic acid. Pimelic acid, i atom. 
 
 HjC 8 IPO* + O 3 - H,HO = H,C 4 H 6 O 2 -f H,C 4 H 6 O 2 
 Caprylic acid. Suberic acid, 2 atoms. 
 
 H,C 9 H 17 O 2 + O 3 - H,HO = H^H'O 8 + H,C 5 H 8 O 2 
 Pelargonic acid. Anchoic acid, i atom. 
 
 H,C 10 H 19 O 2 + O 3 - H,HO = H,C 5 H"O 2 -f H,C 5 H 8 O 2 
 Rutic acid. Sebacic acid, 2 atoms. 
 
 According to this Table, when a volatile acid of the vinyl series is 
 decomposed by 3 atoms of oxygen, one atom of water = HHO sepa- 
 rates, and the residue forms two complete acids of the succinic group. 
 Experiment confirms this theoretical view in frequent cases ; the acids 
 with an even number of atoms of hydrogen being often produced when 
 the acids of the vinyl series are heated with nitric acid. So, inversely, 
 when the acids of the succinic group are heated alone, they give off 
 carbonic acid = CO 2 , and produce volatile acids of the vinyl group. 
 
 The succinic group of acids is sometimes called the oxalic acid group, 
 and it is made to commence with the radical C, and the acid H,CO 8 = 
 hydra carbete or hydrated oxalic acid. 
 
 Placing that acid = H,CO 2 , before succinic acid = H,C 2 H 2 2 , we 
 might expect to find the intermediate double acid : 
 
EXAMPLES OF THE SUCCINIC GROUP. 443 
 
 {TT ri O^l 
 r'ri 2 R 2 O 2 i Hydra carbete cum hydra succinylete, 
 
 but no bibasic acid of this composition has hitherto been observed. 
 
 Table of Examples of the Succinic Group. 
 
 A. THE SuccitfATEs. 
 
 1. H ,C 2 H 2 2 Hydra succinylete. 
 
 2. C 2 H 2 ,C 2 H 2 8 Succinyla succinylite. 
 
 j 2(H ,C 2 H 2 O 2 ) ) Bis hydra succinylete cum succinyla 
 *-.VOTP,OTXP f succinylite. 
 4. K ,C 2 H 2 2 Potassa succinylete. 
 
 K ,C 2 H 2 O 2 IPotassa succinylete cum hydra succi- 
 
 H,C 2 H 2 2 f nylete. 
 
 J K ,C 2 H 2 O 2 ) Potassa succinylete tris hydra succi- 
 t 3 (H,C 2 H 2 2 f nylete. 
 
 ZH 4 ,C 2 H 2 O 2 Ammona succinylete. 
 j 
 \ 
 
 ZH 4 ,C 2 H 2 2 ) Ammona succinylete cum hydra 
 
 H ,C 2 H 2 2 } succinylete. 
 
 9. Ag,C 2 H 2 2 Argenta succinylete. 
 
 10. CH 3 ,C 2 H 2 2 Methyla succinylete. 
 
 11. C 2 H 5 ,C 2 H 2 2 Ethy la succinylete. 
 
 j K ,C 2 H 2 O 2 IPotassa succinylete cum magna suc- 
 
 I2 '\ Mg,C 2 H 2 2 f cinylete. 
 
 13. Mg 3 ,C 2 H 2 3 Magnine succinylite. 
 
 Azotic Compounds of Group A. 
 
 14. ZH 2 ,C 2 H 2 . . . . Amida succinylate. 
 
 15. ZH,C 6 H 5 ; C 2 H 2 O . . Phenylac succinylate. 
 
 - IZH 2 ,C 2 H 2 0) , ., . . ., 
 
 1 I H C 2 H 2 2 I ' ' ' -"^y^ ra ami da succmylemte. 
 
 (ZH 2 ic 2 H 2 O| 
 I 7* I A C 2 H 2 2 I * ' ' ^ r g enta ami da succmylemte. 
 
 . JZH,C 6 H 5 ; C 2 H 2 O) 
 I H- C 2 H 2 O 2 I * "ydra pheny lac succmylemte. 
 
 JZH,C 6 H 5 ; C 2 H 2 0) 
 J 9* j Ag- C 2 H 2 O 2 ( ' ^ r g enta ptenylac succmylemte. 
 
 20. ZH,C 2 H 2 ; C 2 H 2 O 2 . Succinylac succinylete. 
 
 21. ZAg,C 2 H 2 ; C 2 H 2 O 2 . Argentic-succiny lac succinylete. 
 
 22. ZC 2 H 2 ,C 6 H 5 ; C 2 H 2 O 2 . Succinylic-phenylac succinylete. 
 IZH 2 ; C 2 H 2 O) Amida succinylate cum ar- 
 
 2 1' jZHAg ; C 2 H 2 Oj gentac succinylate. 
 
444 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 Chlorine Compounds of Group A. 
 
 24. C 2 H 2 ,C1O .... Succinyla chlorate. 
 
 25. H,C 2 C1 2 O 8 .... Hydra chlorenic-succinylete. 
 
 26. K,C 2 C1 2 O 8 .... Potassa chlorenic-succinylete. 
 
 27. C 2 CP,C 2 C1 2 O 8 . . . Chlorunic-ethyla chlorenic-suc- 
 
 cinylete. 
 
 Sulpho-succin ates . 
 
 (H C^ffO 2 1 
 
 28. ^TT'CQS > Hydra succinylete cum hydra sulphete. 
 
 I C 2 H 2 C'H^ 3 ) 
 2 9* I fH'sO 8 "> [Succinyla succinylite bis hydra sulphete. 
 
 ( ZH 4 ',C 2 H 2 2 ) A 
 20 < H QajpAal A mmona succinylete cum hydra succmy- 
 
 I ^/r/m c^a\ I lete bis ammona sulphete. 
 j 
 
 f 
 I 
 
 ' I 
 
 1 
 2 TT82 1 Potassa succinylete cum hydra succinylete 
 
 2 (K SO 9> ) I ^ s Ptassa sulphete. 
 
 { 
 
 I TT '^ajTgQslPlumba succinylete cum hydra succinylete 
 ' J2(Pb',SO 2 ) ) bis P lumba sul P nete - 
 
 (H C 2 H 2 O 2 ) 
 TT- '^Q 2 j-Hydra succinylete cum potassa sulphete. 
 
 Pb'c 2 H 2 2 ) 
 
 Pb'sO 2 [Plumba succinylete cum plumba sulphete. 
 
 ( C 2 H 2 C 2 H 2 O 3 ) 
 ' I 2(C 'sO 2 "i [Succinyla succinylite bis calca sulphete. 
 
 { JC 2 HBa,C 8 H*0 3 )Barytic-succinyla succinylite bis baryta 
 3 't 2(Ba,S0 2 ) f sulphete. 
 
 B. THE ADIPATES. 
 
 37. H,C 3 H 4 2 . . -. Hydra adipylete. 
 
 38. Ca,C 3 H 4 2 . . . Calca adipylete. 
 
 39. Ag jCWO* . . . Argenta adipylete. 
 
 40. C t H B ,C B H 4 1 i . '. Ethyla adipylete. 
 
 C. THE SUBERATES. 
 
 41. H,C 4 H 6 2 . . . Hydra suberylete. 
 
 42. ZH 4 ,C 4 H 6 O 8 . . . Ammona suberylete. 
 
 43. Ag,C*H*O* . . . Argenta suberylete. 
 
 44. Pb,C 4 H 6 O 2 . . . Plumba suberylete. 
 
 J Pb 3 ,C 4 H 6 O 3 ) Plumbine suberylite cum 
 
 45- ] Pb,C 4 H 6 O s ( ' ' ' plumba suberylete. 
 46. CH 3 ,C 4 H 6 2 . . . Methyla suberylete. 
 
EXAMPLES OF THE SUCCIISIIC GROUP. 445 
 
 47. C 2 H 5 ,C 4 H< : 0' 2 . . . Ethyla suberylete. 
 
 48. ZH 2 ,C 4 H C O . . . Amida suberylate. 
 
 49. ZH ,C 6 H 5 : C 4 H 6 O . Phenylac suberylate. 
 
 ( 7TT r^W 5 r* 4 TT 6 O 1 
 
 50. 1 j ; C 4 H 6 O 2 I ' Hydra P hen y lac suberylenite. 
 
 5 1 . ZH ' I g^, . Argenta phenylac suberylenite. 
 
 D. THE SEBATES. 
 
 52. H ,OH 8 O 2 . . . Hydra sebamylete. 
 
 53. K ,C 5 H 8 O 2 . . . Potassa sebamylete. 
 
 54. Ag ,C 5 H*O 2 . . . Argenta sebamylete. 
 
 55. CH 3 ,C 5 H 8 O 2 . . . Methy la sebamylete. 
 
 56. C 2 H 5 ,C 5 H 8 2 . . . Ethyla sebamylete. 
 
 57. ZH*,C 5 H 8 O . . . Amida sebamy late. 
 
 ~ 
 
 H 5 H 8 O 2 ( ' ' ' Hydra amida sebamylenite. 
 59. "H,H,C 3 H 5 ; C 5 H 8 O 4 . Hydren glycyla sebamylote. 
 
 E. THE PYROTARTRATES. 
 
 ( H ,C 3 H 4 2 \Hydra adipylete cum hydra 
 b0 ' \ H ,C 2 H 2 2 ( succinylete. 
 61. C 3 H 4 ,C 2 H 2 3 Adipyla succinylite. 
 
 J ZH 4 ,C 3 H 4 O 8 ) Amniona adipylete cum am- 
 62 ' ^ ZH 4 ,C 2 H 2 O 2 f mona succinylete. 
 
 ZH 4 ,C 3 H 4 2 )Ammona adipylete cum hy- 
 
 H ,C 2 H 2 2 f dra succinylete. 
 , i Ba ,C 3 H 4 O 2 ) Baryta adipylete cum baryta 
 6 4' 1 Ba ,O 2 H 2 O a f succinylete. 
 
 Ba,C 3 H 4 O 2 i Baryta adipylete cum hydra 
 H , C 2 H 2 O 2 f succinylete. 
 Pb ,C 3 H 4 O 2 1 Plumba adipylete cum plum- 
 Pb ,C 2 H 2 O 2 f ba succinylete. 
 Pb 3 ,C 3 H 4 O 3 \Plumbine adipylite cum 
 Pb ,C 2 H 2 O 2 ( plumba succinylete. 
 Pb 3 ,C 3 H 4 3 )Plumbine adipylite cum 
 Pb 3 ,C 2 H 2 O 3 | plumbine succinylite. 
 C H 3 ,C 3 H 4 2 1 Methyla adipylete cum me- 
 C H 3 ,C 2 H 2 O 2 f thyla succinylete. 
 C*H 5 ,C 3 H 4 2 ) Ethyla adipylete cum ethyla 
 70. j c 2 H 5 ,C 2 H 2 2 | succinylete. 
 
 J Alc 3 ,C 3 H 4 3 | Alinic adipylite cum hydrine 
 7 1 ' \ H 3 , C 2 H 2 O 3 j succinylite. 
 
 J 
 
 ' \ 
 
446 THEORY OF POLYBASIC AND COXGUGATED ACIDS. 
 
 (Bic 3 ,C 3 H 4 O 3 )Bisminic adipylite cum bis- 
 i ' (BicH 3 ,C 2 H 2 O 3 ) mic hydren succinylite. 
 
 (Uc 3 ,C 3 H 4 O 3 lUrinic adipylite cum uric 
 73- |UcH 2 ,C 2 H 2 3 / hydren succinylite. 
 
 Azotic Compounds of Group E. 
 
 Adipylac succinylete. 
 
 Adipylic-phenylac succinylete. 
 
 Adipylic-zotic-phenylac suc- 
 cinylote. 
 
 Phenylac adipylate cum hy- 
 dra succinylete. 
 
 Phenylac adipylate cum 
 plumba succinylete. 
 
 Zotic-phenylac adipylite cum 
 hydra succinylete. 
 
 F. THE PIMELATES. 
 
 , Hydra suberylete cum hydra adipylete. 
 . Argenta suberylete cum argenta adipylete. 
 
 G. THE ANCHOATES. 
 
 1 H C 4 H 6 O 2 f * Hyd ra sebamylete cum hydra suberylete. 
 JA r)4ij 6 O 2 l . Argenta sebamylete cum argenta suberylete. 
 
 'puTj6f)2f Baryta sebamylete cum baryta suberylete. 
 
 C 5 H 8 O 2 1 
 'c 4 H 6 O*l ' P Qtassa sebamylete cum hydra suberylete. 
 
 74. ZH,C 3 H 4 ; C 2 H 2 2 . . 
 
 75. Z,C 3 H 4 ,C 6 H 5 ; C 2 H 2 0* 
 
 76. Z,C 3 H 4 ,C 6 H 4 Z ; C' 2 H 2 4 
 
 (ZH,C 6 H 5 
 
 C 3 H 4 O 1 
 
 77' { H 
 
 C 2 H 2 O 2 ) 
 
 7 8 -| ZH) pT 
 
 C 3 H 4 0\ 
 C 2 H 2 2 ( k 
 
 JZH,C 6 H 4 Z 
 
 C 3 H 4 3 ) 
 
 79- 1 H 
 
 C 2 H 2 2 f 
 
 80. 
 
 81 
 82. 
 
 [,C 3 H 4 2 f 
 IAg,C 4 H0 8 i 
 lAg,C 3 H 4 2 | 
 
 Investigation of the Succinic Group of Salts. 
 
 THE SUCCINATES, GROUP A. Nos. i to 36. 
 
 l]. H,C 2 H 2 S Hydra succinylete. 
 
 2\. C 2 H 2 ,C 2 H 2 3 .... Succinyla succinylite. 
 3]. 2(H,C i H 2 O 2 )4-C 2 H 2 ,C 2 H 2 3 Bis hydra succinylete cum 
 
 succinyla succinylite. 
 
 These three salts represent succinic acid. No. i] is the crystallised 
 acid. No. 2] is the anhydrous acid. No. 3] is the sublimed acid, 
 
INVESTIGATION OF THE SUCCINATES. 447 
 
 which contains two atoms of the hydrated acid, and one atom of the 
 anhydride, or in all, four atoms of the radical succinyl. 
 
 Gerhardt doubles the formula of succinic acid, and calls it BIBASIC ; 
 many organic chemists imitate him ; but the practice is unnecessary, and 
 the consequences are more injurious than beneficial. All the salts can 
 be perfectly well accounted for on the supposition that succinyl is mono- 
 basic, and agrees with the formula C 2 H 2 . This radical has no atomic 
 measure in gaseous salts. See page 96. 
 
 4]. K ,C 2 H 2 O 2 
 7]. ZH 4 ,C 2 H 2 2 
 
 sa- 
 il]. 
 
 . CH 3 ,C 2 H 2 2 
 
 C 2 H 5 ,C 2 H 2 2 . 
 9]. Ag,C 2 H 2 2 
 
 These five salts are examples of neutral monobasic succinates. 
 
 , J 
 5>\ 
 
 K,C 2 H 2 O 2 
 H,C 2 H 2 2 
 
 ZH 4 ,C 2 H 2 2 
 H,C 2 H 2 2 
 
 -, 
 I2 > 
 
 J K,C 2 H 2 2 
 }Mg,C 2 H 2 2 
 
 These are examples of double salts, of similar constitution to the double 
 sulphates (page 150) and double oxalates (page 179). 
 
 6], K,C 2 H 2 O 2 + 3 (H,C 2 H 2 2 ). * 
 
 A quadruple salt, equivalent to the quadroxalate of potash (page 179). 
 13], Mg^JTO 3 - Mg,C 2 H 2 2 + Mg,MgO. 
 
 A terbasic succinate, similar in structure to the terbasic phosphates and 
 other salts of this character, which have been frequently explained in the 
 preceding pages. 
 
 Succinates with Azotic Radicals, Nos. 14 to 23. 
 
 The salts of this group present forms of combination which have been 
 so frequently quoted and criticised, that it seems to be scarcely necessary 
 to go through their investigation individually. No. 14] is Succinamide, 
 derived from the neutral ammonium salt No. 7. No. 15] Succinanilide, 
 corresponding to No. 14, but containing phenylac instead of normal 
 amid. 16]. Succinamic acid. See No. 245, page 227. 17]. A salt 
 of the acid No. 16. 18]. Succinanilic acid. See No. 250, page 228. 
 19]. A salt of the acid No. 18. 20]. Succinimide ; see No. 221, page 
 224. 21]. Succinimide, in which H 1 is replaced by Ag l . 22]. Suc- 
 cinanile; No. 226, page 225. 23]. A double atom of succinamide, in 
 which one of the atoms of ZH 2 has been replaced by ZHAg. The salts 
 of this group have been thoroughly investigated in the Theory of the 
 Azotic Radicals, particularly between pages 222 and 228. 
 
 Chlorine Compounds of Group A, Nos. 24 to 27. 
 24]. The oxychloride of succinyl. 25]. Succinic acid, in which all 
 the hydrogen of the acid radical is replaced by chlorine. 26], Potash 
 
448 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 salt of the chlorinated acid No. 25. 27]. Succinate of ethyl, No. 1 1, in 
 which all the hydrogen, both of the succinyl and the ethyl, is replaced 
 by chlorine. 
 
 The Sulpho-succinaies, Nos. 28 to 36. 
 
 It is stated in most chemical works that the sulpho-snccinates contain 
 a compound acid, the sulpho-succinic acid, which is composed of sul- 
 phuric acid and succinic acid, and which is TERBASIC. Gerhardt's for- 
 mula for it are as follow : 
 
 C 8 H 6 S 2 H -f 2 aq. = C 8 H 6 O 8 ,2S0 3 + 2 aq. (Traite de Chimie, ii. 470), 
 and C 4 H 6 S0 7 = O 3 SO'^ ^.^ iy> 6ll< Millei / s formu]a 
 
 is 3 HO, C^IPO 5 , 2 SO 3 , 2 aq. I am unable, however, to find any evidence 
 to prove the existence of this compound or conjugated terbasic acid, and 
 it appears to be far more probable that the salts are compounds of succi- 
 nates with sulphates, sometimes neutral and sometimes with excess of 
 acid. The formulae Nos. 28 to 36, are framed in accordance with this 
 opinion. 
 
 28]. H,C 2 H 2 2 + H,SO*. 
 
 A double salt containing one atom each of hydrated succinic acid and 
 hydrated sulphuric acid. These proportions agree with Miller's formula 
 and with Gerhardt's first formula. It is a double acid, and not a single 
 bibasic acid with a compound radical. 
 
 29]. C'H 2 ,C 2 H 2 3 +2(H,S0 2 ). 
 
 This compound agrees with Gerhardt's second formula. It is the acid 
 which is assumed to be formed by the action of anhydrous sulphuric 
 acid upon hydrated succinic acid ; thus : 
 
 H,C 2 H ? 2 ) (C 2 H 2 ,C 2 H 2 8 
 H,C 2 H 2 2 l = { H,SO 
 S,S0 3 J I H,SO 9 
 
 The acid 29] is equivalent to two atoms of the acid 28], less one equi- 
 valent of HHO. It is half in the hydrated condition, and half in the 
 condition of anhydride. 
 
 H ,C 2 H 2 2 4- ZH 4 ,S0 2 ) 
 [ZH 4 ,C 2 H 2 O 2 4- ZH 4 ,S0 2 ) 
 
 H ,C 2 H 2 2 + K ,S0 2 ) 
 
 K ,C 2 H*O 2 4- K ,SO 2 j 
 
 H ,C 2 H 2 2 4- Pb ,S0 2 i 
 
 Pb ,C 2 H 2 2 4- Pb ,S0 2 j 
 
 These three compounds afford examples of the salts that are commonly 
 called terbasic sulpho-succinates. There are, indeed, three metallic 
 
 -, 
 3J- 
 
INVESTIGATION OF THE SULPHO-SUCCINATES. 419 
 
 radicals in each of these examples, but there is also in each one atom of 
 basic hydrogen, which makes the salts tetrabasic. There is no proof 
 that this atom of hydrogen forms a conjugated acid with the sulphur and 
 the succinyl. On the contrary, the salts are evidently double salts of 
 the form of the hydrated acid No. 28, and are therefore tetra-acid as well 
 as tetra-basic, or, in other words, are quadruple salts. 
 
 33]. H,C 2 H 8 2 + K,S0 2 . 
 
 This salt is produced by mixing a solution of No. 3 1 with a solution of 
 No. 28. This is the simplest form of the acid salt of the series. It 
 resembles one-half of each of the double salts Nos. 30, 31, and 32. 
 
 34]. Pb,C 2 H 2 2 + Pb,S0 2 . 
 
 This is the form of the neutral salt of the series, and it resembles the 
 second half of each salt of the series of double salts, Nos. 30, 31, 32. 
 That is to say, those three double salts result from the combination in 
 pairs of salts of the forms shown by Nos. 33 and 34. 
 
 When the salt No. 34 is dried, it loses water, and falls into the com- 
 pound shown by the following formula : 
 
 C 2 HPb,C*HPb0 3 + 2(Pb,S0 2 ), Fehling. 
 
 In this case the radical succinyl C 2 H 8 is converted into the metallic vice- 
 radical Plumbic-succmyl C 2 HPb. 
 
 35]. C 2 H 2 ,C 2 H 2 3 -f 2 (Ca,S0 2 ). 
 
 This compound represents the semi-anhydride No. 29, with its basic 
 hydrogen replaced by calcium. The formula represents the salt after it 
 is dried at 212 F. When in solution, it has an acid reaction, and pro- 
 bably has then the constitution represented by formula 33, viz.: 
 H^ffO 2 + CaSO 2 ; because 
 
 IC 2 H 2 ,C 2 H 2 3 + 2(Ca,S0 2 ){ JH,C 2 H 2 2 + CaSO 2 ) 
 I -f H , H O \ "- JH,C 2 H 2 2 + CaS0 2 f 
 
 36]. C 2 HBa,C 2 H 2 3 + 2(Ba,S0 2 ). 
 
 This salt contains barytic-succinyl C 2 HBa. The formula represents the 
 composition of the salt dried at 212 F. If dried less, so as to contain 
 HHO more, its composition would be equal to that of the salt 32, namely : 
 
 JH,C 2 H 2 2 -J- Ba,SOM 
 \Ba,C 2 H 2 2 + Ba,S0 2 .f 
 
 No. 36 is the only salt of the series which warrants the common 
 assumption, that the sulpho-succinates contain three atoms of H in the 
 acid, and three atoms of H replaceable by basic radicals. It is, never- 
 theless, an exceptional, and not a normal, form of the sulpho-succinates. 
 There is a remarkable diversity in the constitution of the salts of this 
 
 2 G 
 
450 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 acid, arising from the facility with which it gives off successive quantities 
 of HHO during the process of drying ; but, notwithstanding this di- 
 versity, we perceive nowhere any symptoms of the existence of a con- 
 jugated acid radical composed of succinyl and sulphur. I conclude, 
 therefore, that the sulpho-succinates are double salts composed of sul- 
 phates and succinates, combined together, either in their normal con- 
 dition, or in various states of dehydration. 
 
 THE ADIPATES. GROUP B. Nos. 37 to 40. 
 
 Professor Miller's formula for adipic acid is 2HO,C 12 H 8 6 . Cor- 
 recting the atomic weights of C and O, and dividing the whole formula 
 by 2, we produce HjCPEPO*, which agrees with No. 37. No com- 
 pound of adipic acid is known, which warrants the doubling of the 
 formula to make the monobasic acid appear to be bibasic. 
 
 THE SUBERATES. GROUP C. Nos. 41 to 51. 
 
 The formula commonly given to suberic acid is 2HO,C I6 H I9 O 6 , which 
 represents it to be bibasic. After correcting the weights of C and O, 
 and reducing the formula to the monobasic form, we have H,C 4 H 8 O 2 , 
 which agrees with No. 41. There are no bibasic suberates. No. 45 is 
 a tetrabasic salt of similar structure to the pyrophosphates. The 
 amidogen salts are perfectly regular, and prove this acid to be mono- 
 basic. No. 48 is suberamid, evidently derived, in the usual way, from 
 the neutral ammonium salt No. 42 by the abstraction of HHO. No. 
 49 is the corresponding anilide, differing from No. 48, only by the 
 replacement of amidogen ZH 2 , by phenylac ZH,C 6 H 5 . Gerhardt's names 
 and formula for this salt are as follow : 
 
 Diphenyl-suberamide, or ] 
 
 I = N*H'(C 12 H 5 )*(C 8 H 6 8 ) 2 
 
 * / JT* ' 
 
 Diazoture of diphenyle 
 and of suberyle. 
 
 Tratte, iv. 778. - -^ 
 
 By comparing these four formula? with No. 49 (ZH,C 6 H 5 ; C 4 H 6 O), the 
 reader will perceive how much he gains in knowledge and convenience 
 by doubling the formula to make the acid bibasic, and how much by 
 throwing it into the form of the ammonia type. 
 
 No. 50 is one of the so-called anilidogen acids, Gerhardt's name and 
 formula for which are as follow : 
 
 Phenvl-suberamic or 
 
 suberanilic acid. = NH(C' 2 H 5 )(C 8 H 6 O e ) 2 01 
 
 Traite, ii. 735. ( HQj 
 
INVESTIGATION OF THE SEBATES. 451 
 
 Here we have a formula on the model of water, according to which we 
 are required to believe that the radical nitrogen = N, the radical 
 hydrogen = H, the radical phenyl = C 6 H 5 , two atoms of the radical 
 suberyl, each = C 4 H 6 , and two atoms of oxygen = O 2 , are all com- 
 pressed into a single conjugated radical which is the equivalent of one 
 atom of hydrogen = H l . Gracious goodness, how these organic 
 chemists speculate upon our credulity ! 
 
 Hofmann's formula for No. 50 is H,C 8 H 6 4 ; C 12 H 6 N,C 8 H 6 2 . 
 
 51. This is the silver salt of the "acid " No. 50. 
 
 THE SEBATES. GROUP D. Nos. 52 to 59. 
 
 The common formula of sebacic acid is 2HO,C 20 H 16 6 . After cor- 
 recting the weights of C and 0, and dividing the formula by 2 to bring 
 it down to the monobasic standard, we have H,C 5 H 8 O 2 , which agrees 
 with No. 52. All the salts, Nos. 53 to 59, agree with the assumption 
 that sebacic acid is monobasic. In Nos. 52 to 56, the quantity of 
 oxygen is O 2 . In the rest, it differs. No. 57 is sebamide, and has, 
 therefore, only one atom of oxygen. No. 58 is sebarnic acid, already 
 quoted at page 227. It possesses O 3 . No. 59 is the compound of 
 glycerine and sebacic acid, which Berthelot calls sebacine. I have 
 quoted it at No. n, page 374. In that case, I have represented glycyl, 
 and in this case sebamyl, as the acid radical. That is of little moment, 
 as these radicals are nearly equivalent to each other. The salt No. 59 
 contains 4 atoms of oxygen, namely O*, because the normal glycylates 
 (allylates?) and the normal sebates both require that quantity of 
 oxygen ; O 1 extra because the salt contains an acid radical acting as a 
 basic radical ; and an additional O 1 because the salt is terbasic. Conse- 
 quently the O 4 are essential. Professor Miller gives for this salt, 
 Berthelot's unitary formula of C^EPO 16 , which affords a good example 
 of the utter worthlessness of unitary formulae in organic chemistry. 
 These gentlemen have the help of the theory, that sebacic acid is 
 bibasic. They have the help of the theory, that glycerine is teratomic, 
 and therefore requires three acids, or three atoms of acid, to neutralise 
 it. Yet, with these helps, they cannot get beyond a unitary formula to 
 describe the constitution of the sebate of glycerine, and in that unitary 
 formula they represent as many ultimate atoms as would make nearly 
 three atoms of sebacine instead of one. Even after correcting the 
 atomic weights of C and O, the quantities of every element are clouble 
 what they ought to be. In that way only is it, that the sebates can be 
 made to appear to be bibasic. 
 
 THE PYROTARTRATES. GROUP E. Nos. 60 to 79. 
 
 I consider a pyrotartrate to contain an adipate in combination with a 
 succinate. Thus : 
 
 2G 2 
 
452 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 No. i = H,C 2 H 2 8 ) _ - (H,C 2 H 2 
 No. 37 = H,C 3 H 4 2 ( = So> bo |H,C 3 H 4 
 
 The pyrotartrates are truly bibasic, but they are also biacid. They con- 
 tain two basic radicals ; they also contain two acid radicals ; and these 
 two acid radicals are succinyl C 2 H 2 and adipyl C 3 H 4 . There is no 
 evidence to prove that these salts are bibasic with a single acid radical. 
 All the facts show, that two acid radicals are present in each salt. The 
 azotic compounds, Nos. 74 to 79, are intelligible only on that supposi- 
 tion. I consider it needless to examine the salts individually. A 
 glance at the list of examples instantly supplies abundant evidence of 
 the justness of these assumptions. Every salt contains two atoms of 
 basic hydrogen, which may be replaced together or separately. If both 
 are replaced, we have a neutral salt, Nos. 62, 64, 66, 69, 70. If only 
 one is replaced, we have an acid salt, Nos. 63 and 65. 
 
 In No. 61 we have the pyrotartaric anhydride. Represented as con- 
 sisting of two radicals C 3 H 4 -f- C" 2 H 2 -f O 3 , this salt is intelligible, and 
 the formula agrees with that of all the other anhydrides ; but if we 
 represent it as containing only one radical C 5 H 6 + O 3 , it disagrees with 
 every anhydride that has been spoken of in the preceding pages, and we 
 have, without necessity, and to accomplish no good end, to inaugurate 
 a new class of anhydrous acids. That is a course of proceeding which 
 the law of simplicity forbids. We do not require another class of 
 anhydrides; we can do very well with one class; and the evidence 
 is not in favour of, but strongly against, the existence of the supposed 
 radical C 5 H 6 . I therefore adhere to formula 61. 
 
 TERBASIC PYROTARTRATES. In Nos. 67, 68, 71, 72, and 73, we 
 have examples of terbasic salts. The usual formula? of these salts are 
 very complicated, but, for brevity sake, I forbear to quote them ; parti- 
 cularly as a discussion upon them would not illustrate the particular 
 point which is now under consideration, which is, the biacid nature of 
 the pyrotartaric acid. In each of these terbasic salts, there is an 
 addition of oxygen corresponding to the additional quantity of basic 
 radicals. 
 
 PYROTARTRATES WITH AMIDOGEN BASES. The salts, Nos. 74 to 99, 
 prove decidedly, that pyrotartaric acid contains two acid radicals. Upon 
 that supposition, these six salts are quite regular. Upon the suppo- 
 sition that only one acid radical is present, the formula? of these salts 
 present clumsy improbabilities. In this case I must go a little into 
 detail. 
 
 74]. ZH,C 3 H 4 ; C 2 H 2 O 8 . 
 
 Gerhardt's name and formula for this salt are as follow : Pyrotartrimide, 
 or azoture of pyrotartryl and of hydrogen 
 
 CTTNO 2 = N 
 
INVESTIGATION OF THE PYROTARTRATES. 453 
 
 Of course, Gerhardt considers C 5 H 6 2 to be the equivalent of IP, and 
 so it is; not, however, because H 2 is necessary to complete an am- 
 monia, but because C 3 H 4 is equal to H 1 , and C 2 H 2 is equal to another 
 H 1 . The amidogen salt, No. 74, is derived from the unknown normal 
 ammonium salt ZH 3 ,C 3 H 4 ; C 2 H 2 3 . There is O 3 in this normal salt, 
 because the basic radical contains an acid radical; otherwise the salt 
 produced by the acid radical C 2 H 2 would require only O 2 . Hence the 
 amidogen salt No. 74 contains O 2 , and the pyrotartaric radical is 
 evidently separable into the acid radical C 2 H 2 and the radical C 3 H 4 , 
 which forms part of the vice-amidogen. If we disregard the ammonia 
 type, and write the salt with Gerhardt's radicals, thus : ZH ; C 5 H 6 2 , 
 we have a salt with an imidogen base, the existence of which appears to 
 me to be impossible, for reasons which I have assigned in the article on 
 the imidogens, commencing at page 222. 
 
 7.5], Z,C 3 H 4 ,C 6 H 5 ; C 2 H 2 2 . 
 
 Gerhardt's phenyl-pyrotartrimide, or pyrotartranile = C 10 H 6 (C 12 H 5 ) 
 NO 4 = C'IPNO 4 . 
 
 76]. Z,C 3 H 4 ,C 6 H 4 Z; C 2 H 2 4 . 
 
 Gerhardt's nitrophenyl-pyrotartrimide, or pyrotartronitranile = C'H 6 
 (C 12 H 4 N0 4 )NO 4 = C 2 *H 10 N 2 O 8 . 
 
 77]. ZH,C 6 H 5 ; C 3 H 4 + H; C 2 H 2 2 . 
 
 Gerhardt's phenyl-pyrotartramic acid, or pyrotartranilic acid = C 10 H 8 
 (C 12 H 5 )N0 6 = C 22 H 13 N0 6 . 
 
 78]. This is merely the lead-salt of the " acid," No. 77. 
 79]. ZH,C 6 H 4 Z; C 3 H 4 3 + H; C 2 H 2 2 . 
 
 Gerhardt's nitrophenyl-pyrotartramic acid, or pyrotartronitranilic acid 
 = C l H 8 (C 12 H 4 NO 4 )N0 6 = C 22 H 12 N 8 10 . 
 
 What do Gerhardt's formulae teach us in regard to the proximate 
 constitution of these amidogen salts ? Absolutely nothing. On the 
 other hand, the analysis of these salts on the principles which lead 
 to the formulae Nos. 74 to 79 afford strong proof of two facts ; ist, that 
 these salts contain amidogens; 2ndly, that pyrotartaric acid contains 
 two acid radicals, one of which forms part of the amidogen contained 
 in each salt. It is important to notice the effects that would be pro- 
 duced by the conversion of these amidogen salts into normal ammonium 
 salts : 
 
 74]. ZH 3 ,C 3 H 4 ; C 2 H 2 3 . , ZH 3 ,C 6 H 5 ; C 3 H 4 2 ) 
 
 75J. ZH 2 ,C 3 H 4 ,C 6 H 5 ; C 2 H 2 O 3 . 77 J- H ; C 2 H 8 2 f 
 
 76]. ZH 2 ,C 3 H 4 ,C 6 H 4 Z ; Cm) 5 . Q1 ZH 3 ,C 6 H 4 Z; C 3 H 4 O 4 ) 
 
 7 B > H ; C 2 H 2 2 f 
 
454: THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 The compounds marked 74, 75, and 76, are all succinates. But 
 normal succinates possess only O 2 . In 74 and 75 we find O l extra, 
 because of the presence of the acid radical adipyl in the condition of 
 a basic radical. In 75 to 78 we have phenyl in the basic radical, but 
 phenyl does not carry O l extra into its salts, like acid radicals proper. 
 In 76, we have O 5 , namely O 2 for the normal succinate, O 1 for the 
 adipyl, and O 2 for the nitrogen substituted for hydrogen. In 77 we 
 have an acid pyrotartrate precisely similar to No. 63, and containing the 
 normal quantity of oxygen. In the parallel salt, 78, we have O 8 extra 
 on account of the substituted nitrogen. Thus we can account for every 
 atom, and we find that each has its duty to do, and does it. 
 
 THE PIMELATES. GROUP F. Nos. 80 and 81. 
 
 The Pimelates are composed of suberates and adi pates, combined 
 atom to atom. No. 80 shows the composition of hydrated pimelic 
 acid, and No. 81, that of its neutral salts. 
 
 THE ANCHOATES. GROUP G. Nos. 82 to 85. 
 
 The Anchoates have been recently discovered by Mr. G. B. Buckton 
 (Quarterly Journal Chemical Society, x. 166) among the products 
 obtained by treating Chinese wax with nitric acid. 
 
 According to Professor Brodie, Chinese wax contains two of the 
 superior members of the vinyl series of radicals ; its composition being 
 
 <^H j c? 7 H M O i = Cer J la cerotylete. 
 
 When this salt is heated with strong nitric acid, it splits up into a 
 variety of salts, which contain radicals both of the vinyl series and 
 of the succinic series. Since the radicals of the vinyl series are con- 
 vertible into radicals of the succinic series by oxidation and loss of 
 hydrogen, while the radicals of the succinic series are convertible into 
 those of the vinyl series by loss of carbonic acid, see page 442, it is 
 of course to be expected that, when any salt which contains a complex 
 member of the vinyl series is heated with nitric acid, various members 
 of both series of radicals, all less complex in structure than the radical 
 that is operated upon, will appear amongst the products of the decom- 
 position. 
 
 Accordingly, Mr. Buckton found all the following compounds in the 
 liquor produced by the operation above described : 
 
 Belonging to the Succinic Group. Belonging to the Vinyl Group. 
 Anchoic acid. (Enanthylic acid. 
 
 Suberic acid. Butyric acid. 
 
 Pimelic acid. Caprylic acid. 
 
 The formula? given by Mr. Buckton to the anchoates are as follow : 
 
THE SALICYLIC GROUP. 455 
 
 C 18 H 16 O 8 = Anchoic acid. 
 
 C l8 (H 14 Ag 2 )O 8 = Anchoate of silver. 
 
 He considers the anchoic acid to be a new and peculiar bibasic acid ; 
 but the only evidence produced in support of the bibasic character is 
 the acid potash salt, No, 8 5 ; which, to my mind, is no evidence at all, 
 since this compound may be explained as a double salt composed of 
 neutral sebate of potash and hydrated suberic acid. When the ami- 
 dogen salts of this "acid" come to be examined, they will no doubt be 
 found to be analogous in constitution to those of the pyrotartaric acid. 
 
 In conclusion, I assume it to be proved, that all the salts of the suc- 
 cinic group, like those of the malic and citric groups, can be described 
 with precision as MONOBASIC Salts; and that there is no evidence to 
 justify the assumption that they are BIBASIC. In the absence of proof 
 of the existence of bibasic characters, the law of simplicity demands our 
 stedfast adherence to the Monobasic Theory. 
 
 The Salicylic Group. 
 
 The Salicylates appear to me to be formed on the model of the Car- 
 bonates, and they are consequently BIBASIC in the same definite sense 
 that the carbonates are bibasic. Thus : 
 
 MO + MO + C O .= M,M ; C O 3 = Carbonate. 
 MO + MO + C 7 H 4 O = M,M; C 7 H 4 O 3 = Salicylate. 
 
 There is no known salt which bears to the salicylates the relation that 
 the oxalates bear to the carbonates, namely, a salt of the formula 
 MO -f C 7 H 4 O = M,C 7 H 4 O 2 . The salts that are now called salicylites 
 have the formula M,C 7 H 5 O 2 , which resembles that of the benzoates. 
 They are monobasic, and the radical C 7 H 5 does not belong to the sali- 
 cylic group. I propose to call that radical spiryl. Then, salicylous 
 acid, or the hydride of salicyl, the essential oil prepared from the flowers 
 of the meadow-sweet (Spircea ulmaria), will be H,C 7 H 5 2 = Hydra 
 spirylete. 
 
 It is possible that salicyl = C 7 H 4 , may be hereafter discovered to be 
 a double radical ; but I have at present no evidence of such a discovery, 
 and therefore I admit it to be a single radical, having the power to pro- 
 duce salts with two basic radicals, in the manner of the carbonates. 
 
456 
 
 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 32. 
 73. 
 
 34. 
 
 Examples of Salts that contain Salicyl. 
 
 A. NORMAL SALICYLATES. 
 
 . Hydra hydra salicylite. 
 
 Hydra hydra salicylite cum 
 
 salicylete. 
 . Salicylete. 
 
 . Baryta baryta salicylite. 
 . Plumba plumba salicylite. 
 . Cupric cupric salicylite. 
 
 Hydra baryta salicylite. 
 . Hydra plumba salicylite. 
 
 Hydra cupric salicylite. 
 . Hydra ammona salicylite. 
 
 Hydra amida salicylite. 
 . Potassa cupric salicylite. 
 . Baryta cupric salicylite. 
 . Hydra methyla salicylite. 
 . Baryta methyla salicylite. 
 . Argenta methyla salicylite. 
 . Potassa methyla salicylite. 
 . Methyla methyla salicylite. 
 . Ethyla methyla salicylite. 
 
 Amyla methyla salicylite. 
 . Hydra ethyla salicylite.' 
 . Ethyla ethyla salicylite. 
 . Hydra amyla salicylite. 
 
 ACID RADICALS ACT AS BASIC. 
 
 Hydra acetyla salicvlote. 
 . Methyla cumyla salicylote. 
 
 Methyla succinyla salicylote. 
 . Hydra benzyla salicylote. 
 
 Methyla benzyla salicylote. 
 . Ethyla benzyla salicylote. 
 
 Amyla benzyla salicylote. 
 . Hydra benzylac salicylite. 
 
 C. HIPPURATES. 
 ZH,C 2 H 3 ;C 7 H 4 O 3 . Hydra glycolac salicylite. 
 
 I. H ; 
 
 HrVTlJ4/~l3 
 ; L/ xl v_r . 
 
 (H ; 
 
 H ; C 7 H 4 O 3 ) 
 
 2 '\ 
 
 (7H 4 2 j 
 
 3- 
 
 C 7 H 4 O 2 . 
 
 4. Ba 
 
 Ba ; C 7 H 4 3 . 
 
 5. Pb 
 
 Pb ; C 7 H 4 O 3 . 
 
 6. Cue 
 
 Cue ; C 7 H 4 O 3 . 
 
 7. H 
 
 Ba ; CWO 3 . 
 
 8. H 
 
 Pb ; CWO 3 . 
 
 9. H 
 
 Cue ; C 7 H 4 3 . 
 
 10. H 
 
 ZH 4 ; C 7 H 4 3 . 
 
 ii. H 
 
 ZH 2 ; C r H 4 8 . 
 
 12. K 
 
 Cue ; C 7 H 4 3 . 
 
 13. Ba 
 
 Cue ; GOTO 3 . 
 
 14. H 
 
 C H 3 ; C 7 H 4 3 . 
 
 15. Ba 
 
 C H 3 ; CWO 3 . 
 
 1 6. Ag 
 
 CH 3 ; C 7 H 4 O 3 . 
 
 17. K 
 
 CH 3 ;C 7 H 4 O 3 . 
 
 1 8. CH 3 
 
 CH 3 ; C 7 H 4 3 . 
 
 19. C 2 ^ 
 
 C H d ; C- H 4 3 . 
 
 20. C 5 H 11 
 
 C H 3 ; (7H 4 O 3 . 
 
 21. H 
 
 C 2 H 5 ; OTPO 8 . 
 
 22. C 2 H 5 
 
 C 2 H 5 ; C 7 H 4 O 3 . 
 
 23. H 
 
 C 5 H 11 ; C^O 3 . 
 
 B. SALICYLATES IN WHICH 
 
 24. H 
 
 C 2 H 3 
 
 C 7 H 4 O 4 
 
 25. CH 3 
 
 C io H u 
 
 C 7 H 4 4 
 
 26. CH 3 
 
 C 2 H 2 
 
 C 7 H 4 O 4 
 
 27. H 
 
 (7H 5 
 
 C 7 H 4 4 
 
 28. CH 3 
 
 C 7 H 5 
 
 C 7 H 4 4 
 
 29. C*H 5 
 
 C 7 H 5 
 
 C 7 H 4 O 4 
 
 30. C 5 H 11 , 
 
 C 7 H 5 
 
 C 7 H 4 4 
 
 31. H;ZI 
 
 I,(7H 5 
 
 C 7 H 4 3 
 
 H 
 
 Ag 
 ZH 4 
 
 ZH^H 3 ; (7H 4 O 3 
 
 Argenta glycolac salicylite. 
 Ammona glycolac salicylite. 
 
EXAMPLES OF SALTS THAT CONTAIN SALICYL. 457 
 
 (ZH 4 ; ZH,C 2 H 3 ; C 7 H 4 3 ) Ammona glycolac salicylite 
 
 "{ H ; ZH,C 2 H 3 ; C 7 H 4 3 | * cum hydra glycolac salicylite. 
 
 36. C 2 H 5 ; ZH,C 2 H 3 ; C 7 H 4 O 3 . E thy la glycolac salicylite. 
 
 37. H ; ZH,C 2 H 3 ; C 7 H 3 ZO 5 Hydra glyeolac zotic-salicylute. 
 
 38. Ag ; ZH,C 2 H 3 ; C 7 H 3 Z0 5 Argenta glycolac zotic-salicy- 
 
 lute. 
 
 D. BENZO-GLYCOLLATES. 
 
 39. H ; C*H 3 ; C 7 H 4 O 4 . . . Hydra glycola salicylote. 
 
 40. Ag; C 2 H 3 ; C 7 H 4 O 4 . . . Argenta glycola salicylote. 
 
 41. Ba ; C 2 H 3 ; C 7 H 4 4 . . . Baryta glycola salicylote. 
 
 E. BENZO-LACTATES. 
 
 42. H ; C 3 H 5 ; C 7 H 4 4 . . . Hydra lactyla salicylote. 
 
 43. Ag ; C 3 H 5 ; C 7 H 4 4 . . . Hydra lactyla salicylote. 
 
 F, MANDELATES, OR FORMO-BENZOYLATES. 
 
 44. H ; CH 3 ; C 7 H 4 O 3 . . . Hydra methyla salicylite. 
 
 45. Ba ; CH 3 ; C 7 H 4 O 3 . . . Baryta methyla salicylite. 
 
 46. Ag; CH 3 ; C 7 H 4 3 . . . Argenta methyla salicylite. 
 
 G. SALICYLATES, CONTAINING BROMIC AND CHLORIC-SALICYL. 
 
 47. H;H ;C 7 H 3 C10 3 . . Hydren chloric-salicylite. 
 
 48. H;H ;C 7 H 3 Br0 3 . . Hydren bromic-salicylite. 
 
 49. H ; H ; C 7 H*Br 2 3 . . Hydren bromenic-salicylite. 
 
 50. H;H ;C 7 HBr 3 O 3 . . Hydren brominic-salicylite. 
 
 51. H; CH 3 ; C 7 H 3 C1 O 3 . . Hydra methyla chloric-sali- 
 
 cylite. 
 
 5 2 . H ; C 2 H 5 ; C 7 H 2 Br 2 3 . . Hydra ethyla bromenic-sali- 
 cylite. 
 
 H. SALICYLATES, CONTAINING AZOTIC-SALICYL. 
 
 53. H;H jCWZO 5 . . Hydren zotic-salicylute. 
 
 54. H ; H ; C 7 H 2 Z 2 O 7 . . Hydren zotenic-salicyleze. 
 
 55. H;H ;C 7 HZ 3 O 9 . . Hydren zotinic-salicyloze. 
 
 56. H ; ZH 4 ; CWZO 5 . . Hydra ammona zotic-salicvlute. 
 
 57. H ; Z H 2 ; C 7 H 3 Z O 4 . . Hydra amida zotic-salicylote. 
 
 58. H;Pb ;C 7 H 3 Z0 5 . . Hydra plumba zotic-salicylute. 
 
 59. Pb; Pb ; C 7 H 3 Z O 5 . . Plumba plumba zotic-salicylute. 
 , (H;Pb ;C 7 H 3 Z0 5 ) Hydra plumbine bis zotic-sali- 
 Da tPb;Pb ;C 7 H 3 Z0 5 f ' ' cylute. 
 
 61. H ; C 2 H 5 ; C 7 H 3 Z O 5 . . Hydra ethyla zotic-salicylute. 
 
 62. H ; Ba ; Cm^O 7 . . Hydra baryta zotenic-salicyleze. 
 
 63. Ba ; Ba ; C 7 H 2 Z 2 O 7 . . Baryta baryta zotenic-salicyleze. 
 
458 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 64. H ; CH 3 ; C 7 H 2 Z 2 O 7 . . Hydra methyla zotenic-salicv- 
 
 leze. 
 
 65. ZH 4 ; CH 3 ; C 7 H 2 Z 2 Cy . . Ammona methyla zotenic- 
 
 salicyleze. 
 
 66. H ;CH 3 ;C 7 HZ 3 9 . . Hydra 'methyla zotinic-sali- 
 
 cyloze. 
 
 Investigation of the Salts of Salicyl. 
 
 GROUP A. NORMAL SALICYLATES. 
 i]. H; H; C 7 H 4 3 . 2].| H; H; tfH^j. 3]. C 7 H 4 2 . 
 
 No. i is the hydrated salicylic acid, No. 2 the anhydrous salicylic acid, 
 and No. 3 is salicylid. The two latter are produced by acting on sali- 
 cylate of soda by oxy chloride of phosphorus. Thus : 
 
 H; Na;C 7 H 4 3 
 
 H; Na; C 7 H 4 3 
 
 H; Na; C 7 H 4 3 
 
 + CPPO 
 
 NaPO 3 
 
 NaCl + NaCl + HC1 
 
 H ; H ; C 7 H 4 3 + C 7 H 4 2 = No. 2. 
 
 C 7 H 4 2 = No. 3. 
 
 The term " anhydrous " acid was given to No. 2 by Gerhardt, on the 
 presumption that the radical salicyl was C 7 H 5 , a constitution which is 
 incompatible with the fact that the salicylates are bibasic. No. 3 is the 
 true anhydrous salicylic acid, just as CO 2 is the anhydrous carbonic acid. 
 Nos. 4] to 23], with the exception of No. n], present examples of 
 normal salicylates, neutral and acid, the whole of which are so regular 
 that they scarcely demand explanation. A very few words will suffice. 
 No. II is the salicylamid derived from the ammonium salt No. 10. 
 No 14 is the oil of winter-green, gaultheric acid, hydrate of methyl- 
 salicyle, salicylate of methyl, methyl-salicylic acid, or methyl-spiroylic 
 acid, for it has all these names, and more. Nos. 15 to 20 are salts of 
 the methylsalicylic acid. No. 21 is ethylsalicylic acid, and No. 23 is 
 amylsalicylic acid. There is, of course, not the least necessity to treat 
 these salts as conjugated acids. An inspection of the Table shows that 
 they are all regular bibasic salicylates, and that the salts from No. 4 to 
 1 3 have the same right to be elevated to the rank of conjugated acids as 
 the salts from Nos. 14 to 23. 
 
 GROUP B. SALICYLATES WHICH CONTAIN ACID RADICALS IN THEIR 
 
 BASES. 
 
 The salts from No. 24 to 30, all contain an acid radical acting as one 
 of their basic radicals, and consequently every one of them possesses an 
 
INVESTIGATION OF THE SALTS OF SALICYL. 459 
 
 additional atom of oxygen, in accordance with the observation which I 
 have recorded at page 376. In other respects, these salts resemble 
 normal salicylates. In No. 3 1 , the amidogen salt is deficient of O l , be- 
 cause it is an amidogen salt. If it were completed to an ammonium salt, 
 the O 3 would have O 4 like the other salts in Group B. Gerhardt's 
 names for this group of salts are as follows : 24, Anhydrous aceto- 
 salicylic acid, acetate of salicyl, or salicylate of acetyl. 25, Cuminate of 
 methylo-salicyl, or oxide of cumyl and methylo-salicyl ; formula 
 
 C 7 H 4 (CH 3 )0 2 \ n 
 C'H U I 
 
 26, Succinate of methylo-salicyl, or oxide of succinyl and methylo- 
 salicyl 
 
 C^CCH^CA n 
 = C 7 H 4 (CH 3 )0 2 J U * 
 C 4 H 4 2 ,O 
 
 In this formula everything is doubled, in order to make succinyl appear 
 to be a bibasic radical. 
 
 27, Anhydrous benzosalicylic acid, benzoate of salicyl, or salicylate of 
 benzoile. 28, Benzoate of methylo-salicyl, or oxide of benzoyl and 
 methylo-salicyl. 29, Benzoate of ethylo-salicyl, or oxide of benzoyl and 
 ethylo-salicyl. 30, Benzoate of amylo-salicyl. 3 1 , Benzoylsalicylamid. 
 
 Gerhardt's formulae show that he considered the salicyl radical to be 
 C 7 H 5 , and that he assumed that it had the power of exchanging H 1 for a 
 complete hydrocarbon. It appears to me, that that assumption is erro- 
 neous and hazardous. The hydrogen in amidogens and ammoniums can 
 be exchanged for complete radicals, bui I do not believe that, in any 
 case, the hydrogen of a hydrocarbon can be replaced by another complete 
 hydrocarbon. If such substitutions could occur, the individuality of all 
 compound radicals, and consequently the power to identify them, would 
 speedily be lost. In Gerhardt's formulae for No. 26, we perceive that 
 he places oxygen in five different situations, a pretty wide scattering of 
 one element in one salt, to be advocated by the great champion of 
 unitary formulae. 
 
 THE CONJUGATED BENZOATES. GROUPS C to F. 
 
 The salts constituting Groups C to F, Nos. 32 to 46, are usually re- 
 presented as salts of conjugated acids, containing benzyl as one of their 
 negative elements. I refer them in preference to the salicylic group, for 
 the following reasons : 
 
 1 . They are not conjugated salts, but merely bibasic salts, and their 
 quantum of hydrogen agrees with that of salicyl and not with that of 
 benzyl. 
 
 2. The quantity of oxygen contained in each salt agrees with that 
 
460 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 which is necessary to constitute a salicylate, and not with that which is 
 required to complete a benzoate. 
 
 3. In so far as regards the properties of the salts, and the products of 
 their decomposition, they may be as properly referred to the salicylic as 
 to the benzoic group. 
 
 A glance over the relationship of the radicals which are depicted in 
 the Tables, will satisfy the reader that these reasons are forcible. 
 
 Usual Names of the Salts. 
 
 C. HIPPFJEATES. 32, Hippuric acid. 33, Hippurate of silver. 34, 
 Hippurate of ammonia. 35, Acid hippurate of ammonia. 36, Hippuric 
 ether. 37, Nitrohippuric acid. 38, the silver salt of the acid No. 37. 
 
 I refrain from quoting the common formula?, because I have so fre- 
 quently discussed the merits and demerits of all kinds of formulae, that 
 farther repetitions are needless, unless peculiar points require elucidation. 
 
 D. BENZOGLYCOLLATES. 39, the benzoglycollic acids. 40, its silver 
 salt. 41, its barium salt. 
 
 E. BENZOLACTATES. 42, the benzolactic acid. 43, its silver salt. 
 
 F. MANDELATES. 44, the mandelic acid. 45, its barium salt. 46, 
 its silver salt. The mandelates, 44, 45, 46, are isomeric with the gaul- 
 theriates, 14, 15, 16 just as the hydride of salicyl is isomeric with 
 benzoic acid, both = H,C 7 H 5 2 . I do not know whether they are 
 identic as w r ell as isomeric. 
 
 I might fill a long chapter with an inquiry into the merits of the dif- 
 ferent theories that have been suggested to explain the constitution of 
 these four classes of salts. But if the reader will kindly look into the 
 systematic works of Gerhardt, Gmelin, &c., and compare the various 
 hypotheses he finds there with that which is now presented to him, he 
 will have no difficulty in determining on which side there is simplicity 
 and probability of truth. 
 
 Group G. CONJUGATED SALICYLATES, CONTAINING BEOMIC AND 
 CHLORIC-SALICYL. 
 
 There is nothing in these salts that requires particular explanation. 
 The quantity of oxygen is the same as that which is required to com- 
 plete normal salicylates, because the bromic and chloric vice-radicals take 
 the same quantity of oxygen to form salts as do the corresponding 
 normal radicals. 
 
 Group H. CONJUGATED SALICYLATES, CONTAINING AZOTIC-SALICYL. 
 
 These salts differ from normal salicylates only by containing zotic- 
 salicyl instead of normal salicyl, and an increase in the quantity of oxygen 
 in each salt, at the rate of O 2 for every Z l which goes into the acid 
 radical. 
 
( 461 
 
 The Tartrates. 
 
 The atomic weights represented by the symbols given in the follow- 
 ing Table are stated at page 28. 
 
 GEOUP A. TARTARIC ACID. 
 
 1. H,C 2 H 2 3 
 
 2. C 2 H 2 , C 2 H 2 5 
 H,C 2 H 2 3 + H,C 2 H 2 3 
 
 C 2 H 2 , C 2 H 2 5 
 
 GROUP B. NORMAL, NEUTRAL, OR MONOBASIC TARTRATES. 
 
 4. K ,C 2 H 2 3 8. Ag,C 2 H 2 3 12. Fee ,C 2 H 2 3 
 
 5. Na ,C 2 H 2 3 9. Pb,C 2 H 2 3 13. ZHHgc 3 ,C 2 H 2 3 
 
 6. ZH 4 ,C*H 2 O 3 10. Cuc,C 8 H 2 3 14. CH 3 ^KPO 3 
 
 7. Ca ,C 2 H 2 3 ii. Sn ,C 2 H S 3 15. C 2 H 5 ,C*H 2 3 
 
 1 8. H 2 Bic,C 2 H 2 4 
 
 19, H 2 Na,C 2 H 2 4 
 
 20. K,C 2 H 2 3 
 
 GROUP C. TERBASIC TARTRATES. 
 
 16. Sbc 3 ,C 2 H 9 4 
 
 17. Uc 3 ,C 2 H*0 4 
 
 ACID TARTRATES. 
 ] 21. ZH 4 ,C 2 H 2 3 
 
 AMIDOGEN SALTS. 
 
 Amida tartrylete. 
 
 )TJ -, , . , 
 
 [Hydra amida tartrylenute. 
 
 ^ 
 
 **W amida tartrylenute. 
 
 GROUP D. 
 
 H,C 2 H 9 3 ] 21. ZH 4 ,C 2 H 2 3 + H,C 2 H 2 3 
 
 GROUP E. 
 22. ZH 2 ,C 2 H 9 2 . . 
 
 2 3'{ = H; ZH 2 ; (C 2 H 2 ) 2 O 5 
 
 !zH 2 ,C 2 H 2 2 + f" 
 
 GROUP F. DOUBLE TARTRATES. 
 
 28. Na,C 8 H 2 3 + Ba ,&&& 
 
 29. Na,C 2 H 2 3 + ZH 4 ,C 3 H 2 3 
 
 30. Na,C 2 H 2 3 4- Mg ,C 2 H 8 O 8 
 
 GROUP G. CONJUGATED TARTRATES. 
 
 35. C*W ,C 2 H S 3 + Ba ,C 8 H 2 3 
 
 36. C 2 H 5 ,C 2 H 9 O 3 4- Ag,C 2 PI 2 O 3 
 
 37. C 5 H ll ,C 2 H*0 3 + H .C^HPO 8 
 K,C 2 H 2 3 38. C 5 H U ,C 2 H 2 3 4- Ag,C 2 H 2 3 
 
 25. K,C 2 H 2 3 + Na ,C 2 H 2 3 
 
 26. K,C 2 H 2 3 + ZH 4 ,C 2 H 2 3 
 
 27. 
 
 H 3 ,C 2 H 2 O 8 + H,C 2 H 9 O 3 
 C H 3 ,C 2 H 2 3 + K,C*H 2 3 
 
 31 
 22 
 33 
 34. C 2 H 5 ,C 2 H 2 3 
 
462 
 
 THEORY OF POLY BASIC AND CONJUGATED ACIDS. 
 
 GROUP H. TETRABASIC TARTRATES. 
 
 39. Na ,C 8 H 2 8 4- H 3 ,C 2 H 2 O 4 
 
 40. H ,C 2 H 2 3 + Sbc 3 ,C 2 H 2 4 
 
 41. Na ,C 2 H 2 O 3 4- Sbc s ,C 2 H 2 4 
 ZH 4 ,C 2 H 8 8 4. Sbc 3 ,C 2 H 2 4 
 K ,C 2 H 2 3 4- Sbc 3 ,C 2 H 2 4 
 
 44. Ba .C'EPO 8 4- Sbc 3 ,C 2 H 2 4 
 
 45. Ag ,C 2 H 2 3 + Sbc 3 ,C 2 H 2 4 
 
 46. Pb ,C 2 H 2 O 3 4- Sbc 3 ,C 2 H 2 4 
 
 47. ZH 4 ,C 2 H 2 O 8 4.Asc 3 ,C 2 H 8 O 4 
 
 42. 
 43. 
 
 48. 
 49. 
 50. 
 
 5 1 - 
 52. 
 
 53- 
 
 54- 
 
 K ,C 8 H 2 3 4- 
 ZH 4 ,C 2 H 2 3 + 
 H ,C 8 H 8 O 3 -j- 
 H ,C 8 H ? 3 + 
 K ,C 8 H 2 O 3 4- 
 
 Na ,C 2 H 2 3 4- 
 
 KptgTTsr^ 3 i 
 jV-f il \J -f- 
 
 H ,C 2 H 2 O 3 4- 
 K ,C 2 H 2 3 + 
 
 Fec 3 ,C 2 H 2 () 4 
 
 Fec 3 ,C 2 H i> O 4 
 
 HFec 2 ,C 2 H 2 (3 4 
 
 Crc 8 ,CH a 4 
 
 Crc 3 ,C 2 H 8 () 4 
 
 Cuc 3 ,C 2 H 2 4 
 
 B 3 ,C 2 H 2 O 4 
 
 U 3 ,C 2 H 2 4 
 
 U 3 ,C 2 H 8 O 4 
 
 GROUP I. DOUBLE TARTRATES, CONTAINING VICE-TARTRYLS. 
 
 57. H .CTffSbcO* + Sbc ,C 2 HSbc0 3 
 
 58. K ,C 2 HSbc0 3 + Sbc,C 2 HSbc0 3 
 
 59. Ba ,C 2 HSbc0 3 + Sbc . 
 
 60. Ag,C 2 HSbcO 3 + Sbc 
 
 61. Pb,C 8 HSbc0 3 + Sbc ,C 2 HSbc0 3 
 
 62. K ,C 2 HBicO 3 + Bic ,C 2 HBicO 3 
 
 63. K ,C 2 HB 8 + B ,C 2 HB O 3 
 
 GROUP K. COMPLEX TARTRATES. 
 
 ( H 3 ,C*H 2 
 
 O 4 
 
 4- 
 
 Sbc 3 ,C 2 H 2 
 
 O 4 } 
 
 64. | H 3 ',C 2 H 8 
 
 
 
 H 3 ,C 2 H 2 
 
 4 f 
 
 ^ j Sbc^H 2 
 
 O 3 
 
 -f 
 
 Sbc 3 ,C 2 H 8 
 
 O 4 
 
 5 '] Sbc,C 8 H 8 
 
 O 3 
 
 4- 
 
 Sbc ,C'H 2 
 
 
 
 K ,C 2 H 2 
 
 O 3 
 
 -h 
 
 Sbc 3 ,C 2 H 8 
 
 O 4 ) 
 
 
 H ,C 2 H 8 
 
 O 3 
 
 4. 
 
 H ,C 2 H a 
 
 O 3 ) 
 
 66.- 
 
 or else 
 
 
 
 
 
 
 H ,C 2 H 2 
 
 O 3 
 
 4_ 
 
 Sbc 3 ,C 2 H 2 
 
 O 4 ) 
 
 
 K ,C"H 2 
 
 O 3 
 
 -f 
 
 H ,C 2 H 8 
 
 O 3 ) 
 
 
 K ,C 8 H a 
 
 O 3 
 
 _l_ 
 
 Sbc 3 ,C 2 H 2 
 
 O 4 , 
 
 /r_ 
 
 K,C*H 2 
 
 O 3 
 
 4- 
 
 H ,C 2 H 2 
 
 O 3 
 
 67.' 
 
 K ,C 2 H 8 
 
 O 3 
 
 -f 
 
 H ,C 2 H 8 
 
 O 3 
 
 
 K ,C 4 H 8 
 
 O 3 
 
 -f 
 
 H ,C 2 H 8 
 
 O 3 
 
 , Q j KH*,C 2 H 2 
 
 O 4 
 
 
 Sbc 8 ,C 2 H 2 
 
 O 4 ) 
 
 tb '| K ,C 2 H a 
 
 O 8 
 
 4. 
 
 Sbc 3 ,C 8 H 2 
 
 4 f 
 
 69. Sbc ,C'H SbcO 3 4- 
 
 Sbc 8 ,C 2 H SbcO 4 
 
 70. Sbc 8 ,C 2 H 2 
 
 O 4 
 
 4- 
 
 Uc 3 ,C'H 2 
 
 O 4 
 
 7 r. Sbc ,C 2 H SbcO 3 4- 
 
 Uc 3 ,C 2 H SbcO 4 
 
 72. BaH 2 ,C 2 H 8 
 
 O 4 
 
 -f 
 
 Sbc 3 ,C'H 2 
 
 O 4 
 
 73. Sbc 3 H 2 ,C 2 H 4 
 
 O 5 
 
 
 Sbc 3 ,C 2 H 8 
 
 O 4 
 
INVESTIGATION OF THE TARTRATES. 463 
 
 GROUP L. ANILIDES OF TARTARIC ACID. 
 
 74. ZH ,C 6 H 5 ;C 2 H 2 O 2 . . Phenylac tartrylete. 
 
 ZH ,C 6 H 5 ; C 2 H 2 O 2 ( Phenylac tartrylete cum 
 
 H ; C 2 H 2 O 3 j ' ' hydra tartrylite. 
 
 ZH ,C 6 H 5 ; C 2 H 2 O 2 ) Phenylac tartrylete cum 
 
 Ba ; OTP0 8 f ' * baryta tartrylite. 
 
 J ZH ,C 6 H 5 ; C 2 H 2 2 \ Phenylac tartrylete cum 
 
 7 7 ' \ Ag ; C 2 H 2 3 j ' ' argenta tartrylite. 
 
 78. Z,C 2 H 2 ,C 6 H 5 ;C 2 H 2 4 . . Tartrylic-phenylac tar- 
 try lote. 
 
 The constitution of TARTRYL, the radical of Tartaric Acid, is C 2 H 8 . 
 Its salts are monobasic, but they combine with one another in endless 
 variety. The classification in the Table is intended to show the prin- 
 cipal forms of the compound salts which are thus produced. 
 
 A peculiarity of tartaric acid is, that it not only gives origin to salts 
 which resemble the salts of monobasic acids, usually so-called, such as 
 the acetates ; but also to the acid salts and double salts which charac- 
 terise the acids that are commonly called bibasic, such as the sulphates 
 and oxalates; and, finally, to a third series, which includes the three 
 different forms of salts that so remarkably distinguish the phosphates. 
 
 Thus, in Group B, we have a series of monobasic salts ; in Group D, 
 acid double salts ; in Group F, neutral double salts ; in Group C, we 
 perceive terbasic salts, formed like the terbasic phosphates; and in 
 Group H, we find combinations of monobasic salts with terbasic salts, 
 affording compounds that are precisely similar in constitution to the 
 bibasic pyrophosphates. 
 
 The variety which exists among the tartrates is still further increased 
 by the circumstance that, under the action of heat, the radical tartryl 
 can exchange one atom (the half) of its hydrogen, for a metalloid or an 
 acidifiable metal, and thus produce a vice-radical, which retains the 
 power of forming salts. Among the vice-tartryls thus produced, I 
 may cite stibic-tartryl, arsanic-tartryl, ferric-tartryl, chromic-tartryl, 
 bismic-tartryl, uranic-tartryl, and boric-tartryl. Examples of the salts 
 of these vice-radicals are quoted in Groups I and K. 
 
 A knowledge of these particulars enables us to comprehend the con- 
 stitution of the tartrates, which would otherwise appear to be not a 
 little perplexing. I shall briefly run over the list of examples, and 
 quote the common names of the leading salts. A particular account of 
 the whole of them may be seen in the Tratte de Chimie of Gerhardt, 
 and the Handbook of Chemistry of Gmelin. 
 
 GROUP A. Tartaric Acid. i]. Crystallised tartaric acid. The 
 formula given by Gerhardt is C 8 H 6 O 12 . Gmelin's formulae are C 8 H 6 O 12 
 and C 8 H 6 6 ,O 8 . These formula? represent the acid as bibasic, and they 
 
464 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 assume the atomic weight of C to be 6, and that of O to be 8. As 
 these formulae of the acid are so much more complicated than that 
 which is given in No. i, it may be inferred that the formula?, that are 
 given by the same chemists to the various tartrates, are also more com- 
 plicated and cumbersome than those that are given in the above Table. 
 That is actually the case ; but I shall forbear the quotation of them, 
 because they present no particularly novel points, and I have already 
 sufficiently discussed the ordinary characters of organic formula?. 
 2]. The tartaric acid anhydride. 3]. A combination of the anhydride 
 with two atoms of the hydrated acid. This compound is usually called 
 tartrelic acid. A similar compound, containing one atom of the anhy- 
 dride with six atoms of the hydrated acid, has been called tartralic acid. 
 I mention these particulars to show that various combinations are 
 formed by hydrated and anhydrous tartaric acid, and that chemists are 
 in the habit of describing such compounds as new acids. It may be 
 doubted whether that practice is judicious. If you apply heat to a 
 number of atoms of hydrated tartaric acid, or of any tartrate, you can, 
 according to the degree of heat applied, and to the duration of its appli- 
 cation, drive off more or less HHO, and consequently more or less 
 change the constitution of the substance so exposed to heat. When the 
 crystallised acid is so treated, the product may be a mere mixture of 
 
 and is not necessarily a new acid. When a salt is so treated, it passes 
 from one class to another class of the salts described in the foregoing 
 Table, and seems to become a new salt, yet when the dried salt is ex- 
 posed to the action of water, it recovers ts original condition. 
 
 Group B. Normal, Neutral, or Monobasic Tartrates, 
 of potash. 8 
 
 of soda. 
 
 of ammonia. 10 
 
 of lime. 1 1 
 
 of silver. 1 2 
 
 of lead. 1 3 
 
 of copper. 1 4 
 
 of tin. 15 
 
 of iron. 
 
 of mercury-ammonium. 
 
 of methyl. 
 
 of ethyl. 
 
 The characteristics of the salts of this group are, that one basic radical is 
 combined in them with one atom of normal tartryl and with O 3 . These 
 monobasic salts can be converted into apparently-bibasic salts, by the 
 easy process, described at page 395, of doubling the formula?. Thus, 
 
 4 O 6 , 
 
 X 2 becomes KKC 4 H 4 O 6 , to which formula it would be 
 judicious to add in all cases cui bono ? 
 
 GROUP C. Terbasic Tartrates. These salts agree in composition with 
 the terbasic phosphates see page 138 ; thus, No. 16 is Sbc,C 2 H 2 3 -f 
 Sbc,SbcO, namely, it is a monobasic tartrate of Group B, combined with 
 a salt formed on the model of water. 16], Neutral tartrate of anti- 
 mony. 17]. Tartrate of sesquioxide of uranium. 18]. Tartrate of bis- 
 
INVESTIGATION OF THE TARTRATES. 465 
 
 muth. 19]. Neutral tartrate of soda. The acid tartrate of soda is 
 No. 39. As commonly represented in chemical books, the salts 16 and 
 1 7 contain (-5 aq) in addition to the constituents represented in these 
 formulae. Thus No. 16 is represented as 2Sb0 3 ,C 8 H 6 O 12 , and No. 17 as 
 2U 2 O 3 ,C 8 H 6 12 , which formulas are expressed by No. 73. This differ- 
 ence may be due to the presence of a little extra water, or it may arise 
 from error in analysis. The tartrates lose water gradually while in 
 course of drying, and there is no fixed temperature at which standards 
 can be taken, while they suffer from the disadvantage that, being fre- 
 quently decomposable by pure water, they cannot be washed clean 
 previous to analysis. However, the presence of additional water in these 
 salts does not invalidate the terbasic formulas, any more than the presence of 
 water of crystallisation invalidates the formulae of the terbasic phosphates. 
 No. 1 9 represents a neutral crystallised salt which has been frequently 
 analysed, and the composition of which appears to be free from doubt. 
 
 These salts are of course all changed in composition when heated. 
 No. 1 6 represents a salt dried at iooC. If heated to i9OC, it is 
 changed into No. 69. This is explained by the following equation : 
 
 Sbc 3 ,C 2 H 2 4 1 j Sbc,C 2 HSbcO 3 + Sbc 3 ,C 2 HSbcO 4 
 Sbc 3 ,C 2 H 2 4 f : j H O + H 
 
 There being in No. 1 6 no ready-formed water separable by the increased 
 heat, the tartryl undergoes substitution of Sbc for H, to the extent of 
 half its hydrogen, but never more without entire destruction to the acid. 
 In like manner, No. 17 produces a salt equivalent to No. 69, but having 
 6Uc instead of 6 Sbc. The salts Nos. 16 and 17 combine together, to 
 produce the compound ^No. 70, and when this compound is dried at 
 200 C, it is reduced to the condition of No. 71. The salt No. 16 com- 
 bines with three atoms of hydrated acid and three atoms of water to 
 form the quadrotartrate No. 64. It combines with three atoms of mono- 
 basic tartrate (not known in the separate state) to form the quadruple 
 salt commonly called acid tartrate of antimony No. 65. It combines 
 with one atom of the monobasic acid No. i , to form the tetrabasic salt 
 No. 40, and when No. 40 is dried at i6oC, it produces the double 
 vice- tar try late No. 57. It is evident, from these examples, that if 
 C 2 H 2 , the acid radical of tartaric acid, was as indestructible by heat as P, 
 the acid radical of phosphoric acid, it would be easy to produce among 
 the tartrates, with any given positive radical, every variety of salt which 
 is producible among the phosphates. 
 
 When No. 19 is heated, it loses HHO and becomes No. 5. No. 18 
 probably undergoes a similar reduction to Bic,C 2 H 2 3 . 
 
 GROUP D. Acid Tartrates. 20]. This is the fundamental salt of the 
 tartaric series cream of tartar or bitartrate of potash. 21]. The acid 
 tartrate of ammonia. Soda forms a similar salt, namely, Na,C 2 H 2 O 3 -4- 
 H,C 2 H 2 3 . 
 
 2n 
 
466 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 GROUP E. Amidogen Salts. 22]. Tartramide, derived, as usual, from 
 the normal tartrate of ammonium No. 6, by abstraction of H,HO. 23]. 
 Tartramic acid, derived from the acid tartrate of ammonia No. 21, by 
 abstraction of H,HO. 24]. Tartramate of ethyl, or tartramethane. 
 No. 22, tartramide, is quoted at No. 172, page 21 1, in the list of amids. 
 No. 23, tartramic acid, belongs to the amidogen acids with compound 
 radicals, which are described in Group C, page 227. The evidence from 
 analogy offered by these compounds is in favour of the theory that tar- 
 taric acid is monobasic. 
 
 GROUP F. Double Tartrates. These salts are of the same rank as the 
 double sulphates, page 150, and the double oxalates, page 179. The 
 arguments which I have employed to prove the monobasic nature of 
 sulphuric and oxalic acids apply equally to tartaric acid, and need no 
 repetition. 25]. Tartrate of potash and soda. Salt of Seignette. 
 Rochelle salt. 26]. Tartrate of potash and ammonia. Tartarus solu- 
 bilis ammoniacalis. 27]. Tartrate of potash and copper. 28]. Tartrate 
 of soda and barytes. 29]. Tartrate of soda and ammonia. 30]. Tar- 
 trate of soda and magnesia. 
 
 GROUP G. Conjugated Tartrates. The conjugated tartrates contain 
 imaginary acids formed in accordance with the fallacious doctrine which I 
 have examined in the chapter on the Bisulphates of the Alcohol Radicals, 
 page 399. All the conjugated tartrates, as is shown by the formulae 
 Nos. 31 to 38, consist of double tartrates, each containing one positive 
 radical of the vinyl series, and one positive radical of the inorganic series. 
 
 31]. Tartaromethylic acid, or methyltartaric acid. 32]. Tartaro- 
 methylate of potash. 33]. Tartarovinic acid. 34]- Tartarovinate of 
 potash. 35]. Tartarovinate of barytes. 36]. Tartarovinate of silver. 37], 
 Amylotartaric acid, or tartramylic acid. 38]. Tartramylate of silver. 
 
 Trusting that the reader will examine the arguments which I have 
 urged in the chapter on the Bisulphates of the Alcohol Radicals, and 
 will apply them to the corresponding bi tartrates, it is only necessary for 
 me to make here the remark, that the so-called " conjugated " tartrates 
 afford no evidence in favour of the bibasic nature of tartaric acid, but, on 
 the contrary, tend to prove it to be monobasic. 
 
 GROUP H. Tetrabasic Tartrates. These salts are tetrabasic and biacid, 
 and agree exactly in constitution with the bibasic phosphates, which are 
 also tetrabasic and biacid, and cannot be divided into salts that are 
 bibasic and monacid, because of the uneven number of their atoms of 
 oxygen. These salts are produced by the combination of salts of 
 Group B with those of Group C, atom to atom. It is the same with 
 the phosphates. A monobasic salt and a terbasic salt make together the 
 intermediate wrongly-called bibasic salt. 
 
 All the salts of Group H suffer loss of water when heated, and they 
 are thus changed into salts belonging to other groups. No. 39 minus 
 HHO, produces a salt equivalent to No. 20 in Group D. 
 
INVESTIGATION OF THE TARTRATES. 467 
 
 No. 40 HHO becomes No. 57. 
 43 HHO 58. 
 
 44 HHO 59. 
 
 45 HHO becomes No. 60. 
 
 46 HHO 61. 
 54 HHO 63. 
 
 In this change, the tetrabasic and biacid salts are transformed into 
 double monobasic salts, with a conversion of normal tartryl into vice- 
 tartryl. There is, however, no permanent alteration of the acid radical ; 
 for if the salts of Group I are treated with water, the normal radical 
 C 2 H 2 is again formed, and the salts resume their original constitution. 
 Many of the salts of Group H take up, when crystallised, or when newly 
 precipitated and undried, more water than I have represented in the 
 formula. In particular, tartar emetic No. 43, and several equivalent 
 salts, take up half an atom more water, and assume the constitution that 
 is exhibited by No. 68. With still more water, they acquire the form 
 of No. 72, and with still more, that of No. 73. 
 
 39]. Acid tartrate of soda. 40]. See note to 16. 41]. Tartrate of 
 antimony and soda. 42]. Tartrate of antimony and ammonia. 43]. 
 Neutral tartrate of antimony and potash dried at 1 00 C. Tartar emetic. 
 Tartarised antimony. When this salt is crystallised, it has the com- 
 position shown by No. 68. When it is dried at 200 C, it becomes 
 No. 58. When ^8 is dissolved in water, it again becomes equal to 43. 
 44]. Tartrate of antimony and barytes dried at 100 C. When dried 
 at 25OC, it changes to No. 59. When in crystals its composition is 
 epresented by No. 72. 45]. Tartrate of antimony and silver, air-dried. 
 When dried at i6oC, it changes to No. 60. 46]. Tartrate of anti- 
 mony and lead. When dried at 230 C, it becomes No. 61. 47]. 
 Tartrate of arsenious acid and ammonia. 48]. Tartrate of potash and 
 peroxide of iron dried at 100 C. 49]. Tartrate of ammonia and per- 
 oxide of iron. 50]. Tartrate of peroxide of iron, according to Gmelin's 
 formula = 2Fe 2 O 3 ,3C 8 H 6 O 12 . If No. 50 were deprived of Aq 1 , it would 
 be reduced to the condition of two atoms of No. 12. 51], Tartrate of 
 sesquioxide of chromium. 52]. Tartrate of potash and sesquioxide of 
 chromium. 53. Tartrate of soda and cupric oxide. 54]. Tartrate of 
 potash and boron. Borotartrate of potash. Soluble tartar. Dried at 
 iooC. When it is heated to 28oC, it is changed into No. 63. 
 55]. Tartrate of uranous oxide dried at 100 C. 56]. Tartrate of potash 
 and uranous oxide. 
 
 GROUP I. Double Tartrates containing Vice-Tartryls. These salts have 
 been so frequently referred to, that farther detail seems needless. The 
 only salt that has not been specially alluded to, is No. 62, which is com- 
 monly called the tartrate of potash and bismuth, dried at 200 C. 
 When the salts of this section are dissolved in water, they must be con- 
 sidered to be again restored to the condition of the salts contained in 
 Group H. 
 
 GROUP K. Complex Tartrates. This list might be extended to a 
 
 2 H 2 
 
468 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 great length, the habits of tartaric acid being such as tend to the in- 
 definite production of such multiple salts. It is sufficient to give a few 
 examples. Nos. 64, 65, 69, 70, and 71, have been already explained 
 in the article on No. 16, Group C. 64]. Supertartrate of antimony. 
 65]. Acid tartrate of antimony. 66]. Acid cream of tartar, dried at 
 iooC. This may be considered as a compound of tartar emetic, No. 
 43 , with two atoms of hydrated tartaric acid, No. i ; or as a compound 
 of tartrate of antimony No. 40, with bitartrate of potash, No. 20. 67]. 
 A compound of one atom of tartar emetic, No. 43, with three atoms of 
 cream of tartar, No. 20. 68]. Crystallised tartar emetic; see No. 43. 
 69, 70, and 71]. See note to No. 16. 72]. See note to No. 44. It 
 is the crystallised tartrate of antimony and barytes. 73]. The freshly- 
 precipitated neutral tartrate of antimony; see No. 16. 
 
 GROUP L. Anilides of Tartaric Acid. The compounds formed by tar- 
 taric acid with aniline have been described by Arppe ( Quarterly Journal 
 Chemical Society, viii. 179), from whom I copy the following names and 
 formula : 
 
 74]. Tartanilide = C 32 H 16 N 2 8 = 2C 12 H 7 N.C 8 H 6 O 12 - 4HO. 75]. 
 Tartanilic acid = C^IFNO 10 . 76]. Tartanilate of barytes = BaO. 
 C 20 H 10 N0 9 . 77]. Tartanilate of silver = AgO.C 20 H 10 NO 9 . 78]. Tar- 
 tanil = CTEPNO 1 = C 18 H 7 N.C 8 H 6 O 12 - 4HO. 
 
 So long as chemists confine themselves to unitary formulae, or to the 
 equally-enlightening formula of " so-and-so minus so-and so," they must 
 be puzzled to account for the variations in the quantity of oxygen pre- 
 sented by such salts as the above. But on the radical theory, and 
 assuming the propriety of the amidogen theory which I have advanced, 
 every atom described in these formula? can be rationally accounted for. 
 In 74, we have O 2 , because the normal tartrate of phenylam must have 
 O 3 (viz. ZH 3 ,C 6 H 5 ; C 2 H*O 3 ). In 75, 76, 77, we have O\ because there 
 is present one amidogen tartrate with O 2 , and one normal tartrate with 
 O 3 . In 78,- we have O 4 , because tartryl, when acting as a basic radical, 
 carries O* extra into its salts, and in this salt C 2 H 2 replaces H 1 . In 
 other respects 78 agrees exactly with 74. These anilides prove that 
 tartryl is C 2 H 2 , and monobasic. 
 
 In the foregoing explanation of the constitution of the Tartrates, I have 
 made use of the radicals which, at page 33, I denominated BASYLIC. 
 They effect a decided simplification in the formulae, by displacing some 
 commonly -received extravagancies. 
 
 For example, No. 50, the Tartrate of the peroxide of iron = 
 H,C 8 H 2 O 3 + HFec 2 ,C 2 H 2 4 , is described by Gmelin as follows : 
 
 2Fe 2 3 ,3C 8 H 6 12 . 
 
 The symbol C 8 H 6 12 contained in the above formula, is Gmelin's 
 aormula for hydrated tartaric acid ; that of his anhydrous acid being 
 
INVESTIGATION OF THE TARTRATES. 469 
 
 C 8 H 4 10 . We have consequently in this salt, according to this formula, 
 two atoms of base and three double or bibasic atoms of acid. The 
 reason that there are present these proportions of base and acid is, that 
 there are six atoms of oxygen in the given quantity of base, and there 
 must consequently be six atoms of monobasic acid ; for it is a law, ob- 
 servable by those who profess to believe in the existence of acids and 
 bases, that a salt must have an atom of acid for every atom of oxygen 
 that is contained in its base. 
 
 Turn now to the consideration of the constitution of the double 
 tartrate of potash and peroxide of iron, No. 48 in the above list = 
 K,C*H 2 3 + Fec 3 ,C 2 H 2 O 4 . Gmelin's formula for this salt is C 8 H 4 K 
 (Fe 2 2 )0 12 , and Professor Miller's formula is KO,Fe 2 8 ,C 8 H 4 10 . In 
 these formulae, the law that enjoins a certain correspondence between the 
 quantities of the acid and the base, is set at defiance. Why so ? We 
 have four atoms of oxygen in the bases, and we ought therefore to have 
 two atoms of bibasic acid; but we have only one atom. Why so? 
 How comes it that the usual law is observed in the tartrate of iron, but 
 not in the tartrate of potash and iron? Why, in the latter case, is 
 Nature a rebel against the law of the philosophers ? Simply because the 
 law is absurd, and Nature cannot observe it. 
 
 Take the formula KO,Fe 2 3 ,C 8 H 4 O 10 , and ask yourselves the question, 
 which of these components of the salt is the acid and which is the base ? 
 Is Fe 2 3 a base ? If so, the salt ought to have twice its present 
 quantity of acid. Is Fe 2 3 an acid ? If so, we want a base for it, for 
 KO only suffices to saturate half the quantity of acid which is expressed 
 by the symbols C 8 H 4 O 10 . In short, whether you treat the sesquioxide 
 of iron as acid or as base, you are equally unable to give a rational 
 account of the composition of this salt. So it always is, when you trust 
 to the theory of the sesquioxides to explain a critical case. Your guide 
 betrays you, and down you sink into inextricable muddle. That is 
 surely sufficient reason to induce you to doubt the trustworthiness of 
 your guide, and to look for assistance upon which you can depend. 
 Examine, then, the value of the help offered by the basylic radicals. See 
 how the radical theory applies to these two tartrates. 
 
 Gmelin's first formula = 2Fe 2 O 3 ,3C 8 H 6 O 12 , corrected for water be- 
 comes 2Fe 2 O 3 ,3C 8 H 4 O'. Correcting the atomic weights of the carbon 
 and oxygen, this becomes Fe 4 O 3 ,C l2 H 12 O 15 . Exchanging the four ferrous 
 atoms for six ferric atoms, and putting the oxygen together, the product 
 is Fec 6 ,C I2 H l2 18 . Dividing this formula by 6, we have Fec,C 2 H 2 O 3 , 
 which corresponds with No. 1 2, and in fact shows that the salt expressed 
 by Gmelin's immense formula, which comprehends 88 ultimate atoms, 
 can, on the radical theory, be clearly expressed by a formula that con- 
 tains only 8 ultimate atoms, or the eleventh part of Gmelin's quan- 
 tities. Including the water of Gmelin's formula, the reduced formula 
 becomes No. 5? which contains 19 ultimate atoms. 
 
470 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 The formulae for the double salt is KO,Fe 2 O 3 ,C 8 H 4 O 10 . Correcting the 
 atomic weights of the iron, the carbon, and the oxygen, and collecting 
 the oxygen together, this formula becomes K,Fec 3 ,C 4 H 4 O 7 , and this 
 thrown into the analytical form becomes 
 
 K,C 2 H 8 3 + (Fec,C 2 H 2 3 + Fec,FecO), 
 
 which is equal to No. 48, a formula that exhibits no difficulties, and 
 excites no doubts respecting the functions performed by the atoms of 
 iron. 
 
 How simple this explanation appears ! How the radical theory 
 scatters the mists that are produced by the hypotheses of " acids " and 
 " bases," and " sesquioxides " scientific shams, which nominally serve 
 to explain the constitution of the tartrates, but actually to puzzle and 
 bewilder you ! 
 
 
 
 The Xanthates. 
 
 A. SULPHOCARBONATES, OR SULPHOXANTHATES. 
 
 1. H ,H ,CS 4 ,S 2 . . Hydren xantha sulphene. 
 
 2. ZH 4 ,ZH 4 ,CS 4 ,S a . . Ammonen xantha sulphene. 
 
 3. K ,K ,CS 4 ,S 8 . . Potassen xantha sulphene. 
 
 4. Fe ,Fe ,CS 4 ,S 2 . . Ferrenous xantha sulphene. 
 
 5. Fee ,Fec ,CS 4 ,S 2 . . Ferrenic xantha sulphene. 
 
 6. C H 3 ,C H 3 ,CS 4 ,S 2 . . Methylen xantha sulphene. 
 
 7. C 2 H 5 ,C 2 H 5 ,CS 4 ,S 2 . . Ethylen xantha sulphene. 
 
 8. K ,C 2 H 5 ,CS 4 ,S 2 . . Potassa ethyla xantha sulphene. 
 
 B. XANTHATES. 
 
 a). Xanth&twthylates. 
 
 9. CH 3 ,CH 8 ,CS 4 O . . . Methyla methyla xanthate. 
 
 10. K ,CH 3 ,CS 4 O . . . Potassa methyla xanthate. 
 
 1 1 . Pb ,GH 3 ,CS 4 O . . . Pltimba methyla xanthate. 
 
 b). Xanthates. 
 
 12. H ,C 2 H 5 ,CS 4 O . . Hydra ethyla xanthate. 
 
 13. C 2 H 5 ,C*H 5 ,CS 4 O . . Ethyla ethyla xanthate. 
 
 14. C H 3 ,C 2 H 5 ,CS 4 O . . Methyla ethyla xanthate. 
 
 1 5. ZH 4 ,C 2 H 5 ,CS 4 O . . Ammona ethyla xanthate. 
 
 1 6. K ,C 2 H 5 ,CS 4 O . . Potassa ethyla xanthate. 
 
 17. Na ,C 2 H a ,CS 4 O . . Natra ethyla xanthate. 
 
 1 8. Ba ,C 2 H 5 ,CS 4 O . . Baryta ethyla xanthate. 
 
 1 9. Pb ,C 2 H 5 ,CS 4 O . . Plumba ethyla xanthate. 
 
 20. Cu ,C*H*,CS 4 . . Cuprous ethyla xanthate. 
 
THE XANTHATES. 471 
 
 c). Xanthamylates. 
 
 21. H ,C 5 H U ,CS 4 O . . Hydra amyla xanthate. 
 
 22. C 5 H ll ,C 5 H ll ,CS 4 . . Amyla amyla xanthate. 
 
 23. CH 3 ,C 5 H ll ,CS 4 . . Methyla amyla xanthate. 
 
 24. C*H 5 ,C 5 H ll ,CS 4 O . . Ethyla amyla xanthate. 
 
 25. ZH 4 ,C 5 H U ,CS 4 . . Ammona amyla xanthate. 
 
 26. K ,C 5 H ll ,CS 4 O . . Potassa amyla xanthate. 
 
 27. Pb ,C 5 H ll ,CS 4 O . . Plmnba amyla xanthate. 
 
 d~). XantJwpropylates and Xantlwcetylates. 
 
 28. K,C 3 H 7 ,CS 4 O . . . Potassa propyla xanthate. 
 
 29. K,C 16 H 33 ,CS 4 . . . Potassa cetyla xanthate. 
 
 <?). Sulpho-carbamates. 
 
 30. H ,ZH 2 ,CS 4 . . . Hydra amida xantha. 
 
 31. ZH 4 ,ZH 2 ,CS 4 . . . Ammona amida xantha. 
 
 32. Pb ,ZH 2 ,CS 4 . . . Plumba amida xantha. 
 
 33. Zn ,ZH 2 ,CS 4 . . . Zinca amida xantha. 
 
 34. Cu ,ZH 2 ,CS 4 . . . Cuprous amida xantha. 
 
 C. BlNOXYSULPHOCARBONATES. 
 
 35. CH 3 ,CS 4 .... Methyla xanthate. 
 
 36. C 2 H 5 ,CS 4 .... Ethyla xanthate. 
 
 37. C 5 H ll ,CS 4 O .... Amyla xanthate. 
 
 38. ZH 2 ,CS 4 .... Amida xantha. 
 
 D. OXYXANTHATES. 
 
 JC 2 H 5 ,C 2 H 5 ,CS 4 0) Ethylen xanthate cum ethylen 
 
 39'|C 2 H 5 ,C 2 H 5 ,C0 3 | * ' carbite. 
 
 j C 2 H 5 ,C 2 H 5 ,CS 4 i Ethylen xanthate cum potassen 
 
 4 -{K ,K ,C0 3 f ' ' carbite. 
 
 j C 2 H 5 ,C 2 H 5 ,C S 4 ) Ethylen xanthate cum argenten 
 
 41 ' }Ag ,Ag ,CO 3 j * ' carbite. 
 t j C 2 H 5 ,C 2 H 5 ,C S 4 O ) Ethylen xanthate cum plumben 
 
 " \Pb ,Pb ,C0 3 j carbite. 
 
 E. XANTHAMIDES. 
 
 j C 2 H 5 ^H 5 ,CS 4 1 Ethylen xanthate cum ammona 
 
 43-|zH 4 ,CNOf ' cyanate. 
 
 lC 5 H ll ,C 5 H 11 ,CS 4 Oi Amylen xanthate cum ammona 
 
 44-jZH 4 , ,CNOf cyanate. 
 
 The compounds that are exhibited in the above Table are those 
 which are produced by the combination of sulphide of carbon with posi- 
 
472 THEORY OF POLYBA.SIC AND CONJUGATED ACIDS. 
 
 live radicals, with or without oxygen. The formula which is usually 
 given to sulphide of carbon is CS 2 , but in consequence of my having 
 doubled the atomic weight of carbon, I am forced to give to this com- 
 pound the formula CS 4 , and this alteration produces so great a change in 
 the apparent composition of its salts, that I have considered it proper to 
 give a comprehensive series of examples. 
 
 Sulphide of carbon appears in this list in the character of an acid 
 radical, and to act in that character, sometimes with bibasic power, and 
 sometimes with monobasic power. The results are convenient for pur- 
 poses of classification and nomenclature ; but I think it right to add, in 
 order to prevent misapprehension, that, in my opinion, the sulphide of 
 carbon is not a radical, but the sulphide of a radical, and ought to be 
 denoted by the formulae CS 3 ,S ; from which it follows, that the formula 
 for the salt No. i ought in strict accuracy to be that of a triple sulphide 
 = CS 3 S + HS -f- HS, while the formula for No. 9 ought to represent 
 a double salt = CH 3 ,CH 3 O -f CS 3 ,S. This opinion is founded upon the 
 notion, that there exists a series of sulphic vice-radicals which cor- 
 respond to the vinyl series of hydrogen and chlorine radicals. Thus : 
 
 CH, CH 2 , CH 3 ; CH 3 ,H 
 
 CC1, CC1 2 , CC1 3 ; CC1 3 ,C1 
 CS, CS 8 , CS 3 ; CS 3 ,S. 
 
 But the subject of sulphic radicals is one of such importance and extent 
 that I shall not press it upon the attention of chemists in this article. 
 The formula? given in the above Table may pass as convenient synoptical 
 formula for the respective salts, while their closer examination is de- 
 ferred. 
 
 I have denoted the sulphide of carbon, CS 4 , in these Tables by the 
 term xanth. At pages 53, 98, and 109, 1 wrote xanfhyl. Upon recon- 
 sideration, I think it expedient to leave the terminal yl in the exclusive 
 possession of the hydrocarbons. 
 
 Xanth, in the state of gas, measures two volumes (see page 53) ; but 
 the bibasic xanthates also measure two volumes ; see three examples at 
 page 60; hence xanth, like sulphur and carbon, measures nothing in 
 its gaseous salts; and I have so described it at page 109. The measure 
 of two volumes which xanth possesses per se, is adverse to the notion 
 that it is a radical. 
 
 In the following notes, I must quote many of the names that have 
 been applied by chemists to the different kinds of xanthates ; but the 
 number of synonymes for these salts to which rival hypotheses respecting 
 their composition have given rise, is so enormous, that I can only give 
 space to a selection from them, and to only a brief notice of the theories 
 upon which they depend. The reader will find ample details respecting 
 the different compounds on consulting the following works : Gmelin's 
 Handbook of Chemistry, vols. vii, viii, and ix. Gerhardt, Traite de 
 
THE XANTHATES. 
 
 473 
 
 Chimie, tome i. Liebig's Handworterbuch der Chemie, Band iv, article 
 Kohlensulfidsalz ; Band v, article Methyloxydsulfokohlensaure ; Sup- 
 plemente, articles Aethersulfokohlensaures Salze, and Amyloxydsulfo- 
 kohlensaure. 
 
 GROUP A. Sulphocarlonates. 
 
 The salt No. 2 is prepared by dissolving bisulphide of carbon in a 
 solution of sulphide of ammonium. ZH 4 ,8 + ZH 4 ,S + CS 4 . The acid 
 No. i is prepared by acting upon the salt No. 2 with hydrochloric acid : 
 
 ZH 4 ,ZH 4 ,CS 4 ,S 2 + HC1,HC1 = H,H,CS 4 ,S 2 + ZH 4 C1,ZH 4 C1. 
 
 Diluted solutions of these salts when exposed to the air are rapidly de- 
 composed, carbonates being formed and sulphur precipitated : 
 
 K,K,CS 4 ,S 2 + O 3 = KK,C0 3 + S 6 . 
 
 Concentrated solutions, when mixed with strong acids, are decomposed, 
 producing the acid No. I : 
 
 K,K,CS 4 S 2 -f HC1,HC1 = H,H,CS 4 ,S 2 + KC1,KC1. 
 
 Besides the salts that are named in the Table from Nos. i to 8, similar 
 compounds have been formed with Na 2 , Ba 2 , Sr 2 , Ca 2 , Li 2 , Crc 2 , Uc 8 , 
 Auc 2 , Sn 2 , Snc 2 , Hg 2 , Hgc 2 . Consequently, the basylous and basylic 
 atoms are acted upon by CS 4 equally. 
 
 Usual names. i]. Hydrosulphocarbonic acid. Trisulphocarbonic 
 acid. Hydrothiocarbonsaure. 2}. Hydrosulphocarbonate of ammonia. 
 Kohlensulfid-ammonium. 3]. Sulphocarbonate of potassium. Kohlen- 
 sulfid - kalium. Kalium -sulfocarbonat. Hydrothiocarbonsaures kali. 
 The names of No. 3 may serve as patterns of those of all the salts which 
 have M,M as radicals. I shall point out the formulae which distinguish 
 the salts that contain basylic atoms. 
 
 Common Formulae. Proposed Formulae. 
 
 Ferrous atoms . . FeS . CS 2 Fe ,Fe ,CS 4 ,S 2 . 
 
 Ferric atoms . . Fe 2 S 3 .3CS 2 Fee ,Fec ,CS 4 ,S a . 
 
 Chromic atoms . . Cr 2 S 3 ^CS 2 Crc ,Crc ,CS 4 ,S 2 . 
 
 Auric atoms . . Au 2 S 3 .3CS 2 Auc,Auc,CS 4 ,S 2 
 
 Mercurous atoms . Hg 2 S . CS 2 Hg ,Hg ,CS 4 ,S a 
 
 Mercuric atoms . . HgS . CS 2 Hgc,Hgc,CS 4 ,S 2 
 
 Uric atoms . . . IPS 8 . CS 2 Uc ,Uc ,CS 4 ,S 2 
 
 Stannous atoms . . SnS . CS 2 Sn ,Sn ,CS 4 ,S 2 
 
 Stannic atoms . . SnS 2 .2CS 2 Snc ,Snc ,CS 4 ,S 2 
 
 There is here a striking contrast between the regularity of the proposed 
 formula?, and the irregularity of the common formula?. There can be no 
 pretension here, any more than among the cyanides, that the difference 
 is attributable to the presence of protoxides and peroxides, and therefore 
 these examples show the absurdity of the commonly-received atomic 
 
474 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 weights, and justify the adoption of basylic as well as basylous atoms. 
 See page 32. 
 
 6]. Sulphocarbonate of methyl. Tristtlphocarbonate of methyl. Sul- 
 focarbonate de sulfure de methyle. Schwefelkohlenstoff-Schwefel-For- 
 mafer. Kohlensulfid-methyl. Methylic sulphocarbonate. 7]. Similar 
 to No. 6. 8j. Sulphoxanthate of potassium. Trisulphuretted carbovi- 
 nate of potash. Ethyl-trisulphocarbonate of potash. A conjugated acid 
 corresponding to No. 8 is described in the books = H,C 2 H 5 ,CS 4 ,S 2 , but 
 no such acid exists. The salt No. 6 produces a gas, the measure of 
 which is two volumes. See page 60. 
 
 GROUP B. Xanthates. 
 
 a). Xantliomefhylates. According to organic chemists, the foundation 
 of this group of salts is an acid of the following constitution H,CH 3 , 
 CS 4 0, and which has received the following very fine names : Holz- 
 Xanthonsaure. Holz-xanthogensaure. Methyl - schwefelkohlensaure. 
 Methyloxydsulfokohlensaure. Methyl-xanthonsaure. Acide methyl- 
 xanthique. Acide methyl-disulfocarbonique. Acide sulfocarbome- 
 thylique. Xanthomethylic acid. Methyl-disulphocarbonic acid. Sul- 
 phocarbomethylic acid. Methylxanthic acid. Unluckily, this many- 
 named acid does not exist. What a pity it is, that so much excellent 
 nomenclature should be wasted! The salts Nos. 10 and n have names 
 that correspond in euphony and explicitness with the names of the un- 
 known " acid." No. 9] has some special names. Methyl-xanthic 
 ether. Schwefelkohlenstoff- Formester. Sulphocarbonate of methyl- 
 oxide. Disulphocarbonate of methyl. Kohlensulfid-methyloxyd. Me- 
 thyl-oxysulfocarbonat. Gmelin's formula for it is C 2 H 3 0,CS 2 . Ger- 
 
 hardt's formula is C*S 4 1 ^0' Duraas ' s formula is C 2 H 3 0,CS 2 -f 
 
 HO,CS 2 . Berzelius's formula is C 2 H 3 O.C0 2 + 2(C 2 H 3 S.CS 2 ). The last 
 formula arranged on the plan of my Table, after correcting the atomic 
 weights of C and 0, becomes 
 
 fCH 3 ,CH 3 ,CS 4 ,S 2 ] 
 ^CH 3 ,CH 3 ,CS 4 ,S 2 ' 
 (CH 3 ,CH 3 ,C O 3 ! 
 
 But if all the substances here represented are divided by 3, this great 
 formula is reduced to No. 9. The proof that it ought to be so reduced 
 lies in the fact, that the salt is gaseous, and has an atomic measure of 
 two volumes, which is the bulk of two atoms of CH 3 , the xanth and 
 oxygen measuring nothing. See page 60. 
 
 b). Xanthates. The salts of this group, Nos. 12 to 20, differ from 
 those of the preceding group merely by containing ethyl instead of 
 methyl. They constitute the xanthates proper, and were discovered 
 earlier, and are better known, than the salts in groups a), c), d\ and e). 
 
THE XANTHATES. 475 
 
 Nomenclature : 12]. Xanthic acid. Sulphocarbonic acid. Sulphocar- 
 bovinic acid. Sulphocarbethenic acid. Aetherschwefelkohlensaure. 
 Xanthogensaure. Xanthonsaure. Xanthinsaure. Hydroxanthinsaure. 
 Aethyloxyd-Bisulfocarbonat. Saures Aethyloxysulfocarbonat, Berzelius. 
 Kohlenschwefelsaures Aethyloxydhydrat, LieUg. Acide ethyl-disulfo 
 carbonique, Gerhardt. Formula: C 4 H 6 O 2 ,2CS 2 , Gmelin. C 2 S 4 (C 4 H S O 
 + HO), Gerhardt. C 4 H 5 O.CS 2 + HO.CS 2 , Zeise. (C 4 H 5 O.C0 2 + 
 HO.CO 2 ) + 2(C 4 H 5 S.CS 2 -f HS.CS 2 , Berzelius. 
 
 tfKPO.C + HS.CS 2 , KdEbe. 
 
 The variety of the names and the intricacy of the formulae of this " acid " 
 sufficiently indicate the diversity of opinions that have prevailed among 
 chemists respecting the constitution of the salts to which it belongs. 
 Absolute certainty on the subject is unattainable, and conjectures can be 
 multiplied indefinitely. If xanth was certainly an acid radical, there 
 would be little difficulty, for then we might say in H,M,CS 4 O, we have 
 clearly a bibasic salt. But I do not believe that CS 4 is a radical. Its 
 atomic measure of two volumes is adverse to that supposition. Taking 
 xanth to be a sulphide = CS 3 ,S, we are still in doubts respecting the 
 composition of the xanthates, for we may formulate No. 1 2 
 
 |H,C 2 H 5 OI f H,CS 3 0) JC 2 H 5 ,CS 3 ) ]C 2 H 5 ,CS 3 O 
 88 JCS 3 ,S } or |C 2 H*,S }' or { H ,SO f ' r i H , S 
 
 The accuracy of these formulas admits neither of proof nor disproof, and 
 therefore I have rested, at present, upon the formula No. 12, which 
 serves, at any rate, to form a central point around which the different 
 varieties of xanthates can be grouped, while we wait for more exact in- 
 formation respecting their intimate nature. 
 
 13]. Kohlensulfid-Aethyloxyd. Schwefelkohlenstoffaether. Aethyl- 
 oxysulfocarbonat. Ether xanthique. Disulfocarbonate d'ethyle. Oxy- 
 sulphocarbonate of ethyl. Xanthic ether. Aethyloxydschwefelkohlen- 
 stoff. Schwefelkohlenstoffvinester. Xanthonsaures Aethyloxyd. Ether 
 sulfocarbonique. 
 
 14]. Vinomethylic Oxysulphocarbonate. Carbomethylovinide bisul- 
 fure. Zweifach-geschwefeltes Carbomethylovinid. Disulfocarbonate 
 d'ethyle et de me"thyle. Vinomethylic carbonate. Xanthate of methyl. 
 Xanthomethylate of ethyl. No. 1 4 is a gas, having an atomic measure 
 of two volumes. See page 60. 
 
 I will not trouble the reader with the synonymes of the salts Nos. 15 
 to 2O, but in regard to the names of the entire group, I wish him to 
 observe the simplicity and perfect regularity in the composition of the 
 salts as exhibited by the formula from Nos. 12 to 20, and then to com- 
 pare these qualities with the strange complexity and irregularity of the 
 names that I have quoted as employed by eminent chemists to designate 
 
476 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 the salts Nos. 12, 13, and 14. Surely, there is evidence here of the 
 want of a PRINCIPLE in chemical nomenclature by which chemists might 
 be guided in forming names for the salts which they discover. 
 
 The potash salt No. 1 6, is formed by the direct action of sulphide of 
 carbon upon a solution of hydrate of potash in absolute alcohol. This 
 reaction agrees extremely well with the formula : 
 
 K,C 2 H 5 O + CS 4 = K,C*H 5 ,CS 4 O. 
 
 Potash in alcohol -j- xanth = xanthate of potash. 
 
 c). Xanthamylates. As the salts Nos. 21 to 27 differ from the pre- 
 ceding groups only by the replacement of CH 3 , or C 2 H 5 , by C 5 H U , it is 
 needless to go into details respecting them. I will however quote a 
 single set of names and formulas for three examples, as given by a 
 chemist who has investigated them, (Johnson, Quarterly Journal of the 
 Chemical Society (1852), v. 142). 
 
 - /C 2 H 3 \ p,^ Sulphocarbonate of methyl 
 
 23]. 
 
 and 
 
 -, /C 10 H U .CS 2 0\ Sulphocarbonate of amyl 
 
 2 4J- \fa H 5 .CS 2 0/* and ethyl. 
 
 25]. H 4 N.C 10 H U ,2CS 2 O. Amyloxanthate of ammonia. 
 
 Here, in describing three equivalent salts, we have three changes in for- 
 mula? and two changes in nomenclature. Why ? 
 
 d]. Xanthopropylates and Xanthocetylates. 28]. Propyloxanthate of 
 potash, Chancel. 29]. Potash salt of Acide cetyl-disulfocarbonique, 
 Desains. There are, in chemical books, descriptions of imaginary con- 
 jugated acids corresponding to both these salts. 
 
 e). Sulphocarbamates. Nos. 30 to 34. The fundamental salt of this 
 series is No. 31 = ZH 4 ,ZH 2 ,CS 4 . Gerhard t calls this salt the sulpho 
 carbamate of ammonia, and gives it the formula C 2 H 2 (NH 4 )NS 4 . 
 Kolbe's name and formula are Sulfocarbamidsaures Ammoniumsulfuret 
 NH 4 S.C(SNH 2 ),CS 2 . The salt is produced from the ammonium salt 
 No. 2] by the abstraction of two atoms of HS. We may also consider 
 the series 30 to 34, as amidogen salts of the xanthic series ; for if HHO 
 was added to each salt, we should have, for example, 
 
 No. 30 raised to H ,ZH 4 ,CS 4 O. 
 32 Pb,ZH 4 ,CS 4 O. 
 
 We have indeed no knowledge of ammonium salts that are constituted 
 in agreement with these formula? ; but they may probably be found if 
 looked for. 
 
 C. BlNOXYSULPHOCARBONATES. 
 
 35]. Binoxysulphocarbonate of methyl. Persulfure methyl-disulfo 
 carbonique 
 
THE XANTHATES. 477 
 
 36], Binoxysulphocarbonate of ethyl, Desains. Persulfure ethyl-di- 
 sulfocarbonique 
 
 C 2 4 ( C 4 H 5 S 2 Q 
 
 C 2 S 4 { C 4 H 5 S 2 ' 
 
 37]. Binoxysulphocarbonate of amyl = C 10 H U .2CS 2 0, Johnson. Persul- 
 fure amyl-disulfocarbonique 
 
 C 2 4 ( C 10 H U S 2 
 
 No. 36 is produced by the action of iodine upon the salt No. 16. 
 Thus': 
 
 K,C 2 H 5 ,CS 4 O + I = KI + C 2 H 5 ,CS 4 O. 
 
 The group of salts C, as compared with those of Group B, present the 
 peculiarity, that the same acid radical with the same quantity of oxygen 
 is in one case monobasic, and in the other bibasic. I have pointed out 
 several examples of this peculiarity in treating of the polythionates ; 
 where I have shown that this effect, though apparent, is unreal. See 
 page 173. A similar interpretation is probably due in this case; so 
 that methyloxanthate, instead of being a simple salt, as represented by 
 formula 35, may be, in fact, a double salt, or compound of two salts, 
 whereof one may be oxidised, and the other not oxidised. For example, 
 CH 8 ,SO +CS 2 ,S. 
 
 This explanation implies the existence of a vice-radical of the form 
 CS 2 , namely, one that is equal to vinyl CH 2 , but having the hydrogen 
 replaced by sulphur. There is no argument to urge against the pro- 
 bability of the existence of such a vice-radical, but I can adduce no facts 
 to support it. In the meantime, I represent the binoxysulphocarbonates 
 as monobasic xanthates. 
 
 38]. This is the amidogen salt of this series, derived from the un- 
 known ammonium salt ZH 4 ,CS 4 O. The ordinary names of this amidogen 
 salt are Hydranzothine, Bihydrosulphuretted sulphocyanogen, Bisulphide 
 of sulphocarbammonium, Poppelt-Schwefelwasserstoff-Schwefelcyan, all 
 of which conceal the nature of the substance as much as they can. 
 
 D. OXYXANTHATES. 
 
 39]. Carbonate of sulphethyl, or carbonate of ethylic sulphide 
 = C 4 H 5 S,C0 2 , Gmelin. Sulphocarbonate of ethyle, or carbonate of 
 
 {C 4 H 5 S 
 n*H 5 S" 4]- Oxyxanthate of potassium 
 
 = C*H 5 KS S ,2C0 2 , Gmelin. Kohlensaures Aethyl - Kaliumsulfuret, 
 
478 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 (r<4TJ5a 
 K S ' GerhardL 
 
 41] and 42]. Similar names to those of Nos. 39 and 40. 
 
 The formulas in the Table Nos. 39 to 42 appear to be justified by the 
 following reaction : 
 
 Xanthic ether No. 13, dissolved in alcohol, and mixed with an 
 alcoholic solution of hydrate of potash, produces oxyxanthate of potash 
 No. 40, and mercaptan. 
 
 C 2 H 5 ,C 2 H 5 ,CS 4 
 C 2 H 5 ,C 2 H 5 ,CS 4 
 K,HO 
 K,HO 
 
 C 2 H 5 ,C 2 H 5 ,CS 4 1 
 K, K,C O a 
 H ,C 2 H 5 ,S 2 
 H ,C 2 H 5 ,S 2 
 
 } = 40]. 
 
 Nevertheless, it will be observed, that the formula No. 40 is divisible 
 into two equal parts, thus : 
 
 C 2 H 5 ,C 2 H 5 ,CS 4 1 I K,C 2 H 5 ,CS 2 2 
 
 KTT- rt r\3 f \ -ir niTT5 r i Q*H2 
 , J\. )\s \J J [1V,1^ XI ,V-<O \J 
 
 And, secondly, that this formula agrees equally well with the reaction 
 just described. Thus : 
 
 C 8 H 5 ,C 2 H 5 ,CS 4 K,C 2 H 5 ,CS'O* 
 K,H O == H,C 2 H 5 , S 2 
 
 In the formula K,C 2 H 5 ,CS 2 O 2 , we have again the radical CS 2 to which I 
 have before referred, and here it appears to act as a bibasic acid radical 
 with two atoms of oxygen. Though I am inclined to admit the com- 
 pound CS 2 to be a radical, yet I am not of opinion that it can be bibasic, 
 and therefore I adhere to the formulae quoted in the Table, which repre- 
 sent each salt as consisting of a carbonate combined with a xanthate, as 
 being probable though complicated. 
 
 Group E. XANTHAMIDES. Nos. 43 and 44. If we suppose a salt 
 of Group D to contain ammonium, and that salt to be deprived of two 
 atoms of water, we should have the residue expressed in the following 
 equation : 
 
 CIP,CIP,CSO i JOT 'S* c^ol Residue - 
 
 7tr4 7tT4 n f == <&n. ,^n ,^ <J| 
 
 1 ' ( H 2 , H 8 , O 2 = Aq 2 . 
 
 That portion of the compound amidogen salt which is represented by 
 ZH 2 ,ZH 2 ,CO is carbamide, of which I have treated fully at pages 221, 
 338, and 359, where I have advanced arguments that I imagine will 
 justify the formulae which I have now given to the Xanthamides. 
 
 Usual names. 43]. Xanthamide. Xanthogenamid. C C NH 7 S 2 O* 
 
 = C 4 AdH 5 * . = Xd. Gmdin. = C 4 H fi S 2 ,C s HNO* 
 
THE XANTHATES. 479 
 
 = 3 C 4 H 6 S 8 ,C 6 H 3 N 3 6 = C 4 H 5 0,C 9 NH'O.CS 2 
 = C 4 H 5 O,C*NH ? O,C0 2 + C 4 H 5 S,C 2 NH 2 S,CS 2 , 
 
 Debus (in Gmelms Handbook of Chemistry, ix. 277). Sulphocarbamate 
 of ethle. Ure'thane sulfuree = ^ ^i Gerhardt. 
 
 It would be difficult to determine what particular meaning, if any, the 
 various authors attached to these singular groups of symbols. 
 
 Preparation of Xanthamide. " Dry ammoniacal gas is passed into an 
 alcoholic solution of bioxysulphocarbonate of ethyl" [No. 36], "where- 
 upon the liquid becomes hot, and yields a precipitate of sulphur. As 
 soon as this precipitation is at an end, the passage of the gas is inter- 
 rupted, the liquid filtered, and the filtrate evaporated to dryness in 
 vacuo. The residue effloresces almost completely, forming small aggre- 
 gated crystals of xanthate of ammonia" [No. 15] " saturated with an 
 oily liquid which is xanthamide," Gmelin. 
 
 C 2 H 5 ,CS 4 O ZH 2 ,H] (ZH 4 ,C"H 5 ,CS 4 O = No. 15. 
 C 2 H 5 ,CS 4 + ZH 2 ,Hl = {C J H 5 ,C 2 H 5 ,CS 4 Ot _ 
 C 2 H 5 ,CS 4 O ZH 2 ,HJ (Z H 4 , CN Oj = 
 
 No. 36. Ammonia. 
 44]. Sulphocarbamate of amyle = ^ pw}Jua}> Gerhardt. Xan- 
 
 thamylamide = C 12 H 13 NO 8 S 2 , Johnson. Obtained by the action of am- 
 monia on the salt No. 37. The explanation is the same as that just 
 given of the process for preparing No. 43. 
 
 The only thing that prevents the formation of simple and exact 
 formulae for the different orders oi xanthates, is the want of a precise 
 knowledge of the proximate constitution of the sulphide of carbon. 
 Until that knowledge is obtained, all possible formulae for its salts must 
 be subject to uncertainty. Yet the salts are so simple, so regular, and 
 so evidently related to one another in groups, that there is no excuse for 
 the wild extravagance of the names by which they all are commonly 
 designated. In the construction of these names there has been a total 
 disregard, not only of scientific order but of common intelligence. In 
 only one particular can they be considered to be successful, which is, in 
 effectually concealing the information which they profess to carry. It 
 would be scarcely possible to pick out from among them a single name 
 after which an impartial student of chemistry could undertake to write 
 a formula of the salt to which it refers. That result infers the arrival 
 at a degree of perfection in the art of concealing knowledge which I 
 reckon to be the ne plus extra of non-scientific nomenclature. 
 
( 480 ) 
 
 The Conjugated Sulpho- Acids. 
 
 Under the head of Conjugated Sulpho-Acids, I propose to give some 
 account of the salts that are produced by the action of sulphuric acid 
 upon compound organic radicals. Many of these salts have already 
 passed incidentally under our notice in the review of other groups of 
 salts; but it is still necessary to give them a formal and systematic 
 examination, partly that I may place the subject before the reader in a 
 complete state, and partly that I may be able to supply corrections 
 which recent discoveries have rendered it necessary to make in preceding 
 statements. 
 
 I propose, now, when interpreting the proximate constitution of the 
 conjugated sulpho-acids, to avail myself of the fact which I first pointed 
 out at page 376, namely, that when a radical which, under ordinary cir- 
 cumstances, acts the part of an ACID radical, goes into a salt in the cha- 
 racter of a BASIC radical, it carries with it an additional quantity of 
 Oxygen. I have said at page 376, that it takes with it one additional 
 atom of oxygen ; but I must correct that expression. When the radical 
 belongs to the vinyl series, or to any series which produces normal salts 
 with O 2 , then the transferable quantity of oxygen is indeed O l ; but when 
 the radical belongs to those which produce normal salts with O 3 , then 
 the transferable quantity of oxygen is O 2 . Hence it is, that the com- 
 position of the nitric acid anhydride is N,NO 5 , that of the phosphoric 
 acid anhydride P,PO 3 , and that of the tartaric acid anhydride C 2 H 2 , 
 C 2 H 2 O 5 . 
 
 I regret to have to repeat here, what I have stated at page 377, that 
 I cannot point out which are the radicals that act as transporters of 
 oxygen into salts, and which do not so act. I am unable to draw a clear 
 line of distinction between them. Generally speaking, all the acid 
 radicals of the vinyl series, and many of those which belong to the series 
 TiCH 2 H 9 , take up O 1 additional when they act as basic radicals. On 
 the other hand, phenyl and most of the radicals of the series riCH 2 H 7 , 
 act as basic radicals without taking up additional oxygen. A few 
 radicals of frequent occurrence, such as benzyl, sometimes take up addi- 
 tional oxygen, and sometimes, in circumstances apparently similar, dis- 
 pense with it. These anomalies may hereafter disappear. In the mean- 
 time, the main fact, that certain acid radicals take up O 1 or O 2 extra, 
 when they pass into salts to act as basic radicals, is so certain, and leads 
 to such remarkable elucidations of difficult theoretical points, that the 
 nature and extent of the action demand a thorough investigation. 
 
THE CONJUGATED SULPHO-ACIDS. 481 
 
 BISULPHATES OF BASIC RADICALS. 
 
 Group A. Bisulphates with Radicals of the Vinyl Series. 
 
 {C* T_T3 C/^2 \ 
 r 'cQg? Methyla sulphete cum hydra sulphete. 
 
 {C 2 H 5 SO 2 ) 
 j *gQ[ Ethyla sulphete cum hydra sulphete. 
 
 3. C 2 H 5 ,SO 2 -f Pb ,S0 2 Ethyla sulphete cum plumba sulphete. 
 
 (C 2 H 5 ,S0 2 + H,S0 2 ) Ethyla sulphete cum hydra sulphete plus 
 r |C 5! H 5 ,SO 2 + Pb ,S0 2 | ethyla sulphete cum plumba sulphete. 
 
 I C 2 H 5 ,SO a + Pb ,SO 2 ) Ethyla sulphete cum plumba sulphete plus 
 5 ' (C 2 H 5 ,SO 2 + Pb 3 ,SO 3 | ethyla sulphete cum plumbine sulphite. 
 
 ( C 3 H7 SO 2 ) 
 6. < j> 'cQaf Propyla sulphete cum baryta sulphete. 
 
 7 
 
 8. < TT 'gQ2f Amyla sulphete cum hydra sulphete. 
 
 {C 8 H 17 SO 2 ) 
 ^ H 'so 2 1 O ct yl a sulphete cum hydra sulphete. 
 
 I (} 4 H 9 gQ2 ] 
 
 . < TT- '<>Butyla sulphete cum potassa sulphete. 
 
 {rn6TT33 CQ2 . 
 'sO 2 ( ^ et . v ^ a sulphete cum hydra sulphete. 
 
 Group B. Bisulphates with Radicals not of the Vinyl Series. 
 
 {C 6 H 5 SO 2 ) 
 TT 'OQS[ Phenyla sulphete cum hydra sulphete. 
 
 I C 6 H 5 SO 2 ) 
 I2 * 1C H 3 'sO 2 1 -^henyla sulphete cum methyla sulphete. 
 
 (C 8 H 5 SO 2 ) 
 
 '| Piien y la sul phete cum barytic-methyla sulphete. 
 
 (C 10 !! 13 SO 2 ) 
 14. -j jj 'sO a I T % m 7 la sulphete cum hydra sulphete. 
 
 )C 10 H 13 SO 2 ) 
 ^ Ba 's0 2 ( Th 7 m J la sulphete cum baryta sulphete. 
 
 BISULPHATES OF ACID RADICALS. 
 Group A. Bisulphates containing Radicals of the Vinyl Seiies, 
 
 {H C 2 H 3 O 2 ) 
 m'sO 2 ) 2 I H y^ ra acet 7 lete bis hydra sulphete. 
 
 {C 2 H 3 SO 3 ) 
 ^ H 'SO 2 | -^ cet y^ a sulphite cum hydra sulphete. 
 
 2 i 
 
482 THEORY OF POLY BASIC AND CONJUGATED ACIDS. 
 
 1 8. <g a 'so 2 ! Baiytic-acetyla sulphite cum baryta sulphete. 
 
 {H C 2 H 3 O 2 ) 
 / Ba ' gQayj- Hydra acetylete bis baryta sulphete. 
 
 {Q2TT3 SO 3 ) 
 
 HBa 2 'SO 3 ^ cet yl a su lp^te cum hydra baryten sulphite. 
 
 ( C 2 H 2 A0 i SO 3 ) 
 
 20. < A L ^'gQ 2 > Argentic-acetyla sulphite cum argenta sulphete. 
 
 (C 3 H 4 Ba SO 3 ) 
 
 21. -jg 's0 2 f Barytic-propionyla sulphite cum baryta sulphete. 
 
 {C 3 !! 5 SO 3 ) 
 H 'SO 2 ( P r P ion yl a sulphite cum hydra sulphete. 
 
 ( ZH 3 C 3 H 5 SO 3 ) 
 
 2 3* |ZH 4 ' ' gQ > Propionylam sulphite cum ammona sulphete. 
 
 I r^4TJ6T3 tJO 3 \ 
 
 24. \ -g a '^Qij j> Barytic-butyryla sulphite cum baryta sulphete. 
 
 I C 4 H 7 SO 3 ) 
 
 2 5. \ jj ' gQ 2 > Butyryla sulphite cum hydra sulphete. 
 
 Group B. Bisulphates containing Benzyl. 
 
 f Q7JT5 SO 3 ) 
 
 26. < jj 'g O2 > Benzyla sulphite cum hydra sulphete. 
 
 (C 7 H 5 SO 3 ) 
 
 2 7* I Ba 'SO 2 ( ^ enz y la sulphite cum baryta sulphete. 
 
 28. <g 'so 2 ! ^ ai T t i c ~' :)eriz yl a sulphite cum baryta sulphete. 
 
 ( P7JT 5 SO 3 1 
 
 29. < * 'gQ 2 > Benzyla sulphite cum argenta sulphete. 
 
 30. < . 'gQ 8 > Argentic-benzyla sulphite cum argenta sulphete. 
 
 ( C7H 5 SO 3 1 
 
 3 *' I C 2 H 5 'SO 2 f ^ enz y^ a su lphi te cum ethyla sulphete. 
 
 32. Z y 3 Q-2jj5 .'go 2 ! ^ enz y^ a su lphite cum ethylam sulphete. 
 
 t Q7JJ5 gQ3 J 
 
 33. )r*H 3 "N" 'SO 2 1 ^ enz yl a sulphite cum natric-ethyla sulphete. 
 
 ( C 7 !! 5 SO 3 ) 
 
 34' ] C 2 R 4 B- 'SO 2 ! ^ enz yl a sulphite cum barytic-ethyla sulphete. 
 
 G-roup C. Bisulphates containing Anisyl, Cinnamyl, or Spiryl. 
 
 ( TT C^H'O 3 1 
 35. < /TT ' SO 2 V -^y^ ra ams ylite bis hydra sulphete. 
 
THE CONJUGATED SULPHO-ACIDS. 48o 
 
 TT r* 8 TT 7 o 3 \ 
 
 CBa SO 2 } 2 ! H y dra anis 7 lite bis baryta sulphete. 
 I TT f^TT^O 3 ) 
 
 37. {/pu ' goT I ^ dra anis y lite k is P lumba sulphete. 
 
 38. j j_j- ' gQ 2 > Anisyla sulphote cum hydra sulphete. 
 
 I C 8 H 6 Ba SO 4 ) 
 
 39. <- SO 2 I Barytic-anisyla sulphote cum baryta sulphete. 
 
 ( C^JrPPb SO 4 1 
 
 40. < p, < f Plumbic-anisyla sulphote cum plumba sulphete. 
 
 (C 9 H 7 SO 3 ) 
 
 41. <TT SO 2 ! ^ mnam y^ a sulphite cum hydra sulphete. 
 
 42. < * ^' ^Q 2 [ Argentic-cinnamyla sulphite cum argenta sulphete. 
 
 ( C 7 H 5 SO 4 ) 
 43 *^T-T ' cr)2 ! Spiryla sulphote cum hydra sulphete. 
 
 DOUBLE HYPOSULPHATES. 
 Group A. Hyposulphites containing Radicals of the Vinyl Series. 
 
 {/"<T-J3 S 2 O 3 1 
 
 TJ- ' os'o 3 ( -^ e ^y' a sulphenite cum hydra sulphenite. 
 
 / /-^TT2r> Q*O 3 1 
 
 * m ' S 2 O 3 f ^ ar y t i c ' met hyl a sulphenite cum baryta sulphenite. 
 
 \ CH 2 Ag , S*0 3 1 Argentic-methyla sulphenite cum argenta sul- 
 *1A ,S 2 3 f phenite. 
 
 ( 7TT 3 
 47. < ^pT4' ' o 8 Q3 - Methylam sulphenite cum ammona sulphenite. 
 
 I Q*pp S 2 O 3 I 
 
 48. <|TT 's 2 O 8 ( ^ tu y^ a sulphenite cum hydra sulphenite. 
 
 lC 2 H 4 Ba ',S 2 3 U 
 
 49. < g $ 8 O 3 ( ^ ar y tlc ~ etn } T * a sulphenite cum baryta sulphenite. 
 
 !ZH 3 C 2 H 5 S 2 O a i 
 
 /pi*' ' c*o 8 Ethylam sulphenite cum ammona sulphenite. 
 
 JC 3 H 7 ^O 3 )^ 
 
 51. <TT cans i "ropy la sulphenite cum hydra sulphenite. 
 
 I.H. ,o u i 
 
 I C 3 H 6 Ba S ? O 8 ) 
 
 5 2 . < o 's^ 3 1 ^ ar y ^ c 'P r Py^ a sulphenite cum baryta sulphenite. 
 
 GROUP B. Hyposulphates containing Phenyl. 
 
 I C 6 H 5 S 2 O 3 ) 
 
 53. JJT 's*0 3 l ^ nen }^ a sulphenite cum hydra sulphenite 
 
 2 I 
 
484 
 
 THEORY OF POLYBASIG AND CONJUGATED ACIDS. 
 
 I C 6 H 4 Ba S 2 O 3 ) 
 54. | p> 's 8 O 3 l Barytic-phenyla sulphenite cum baryta sulphenite. 
 
 s 8 O 3 
 GROUP C. ffyposulphates containing Naphtyl. 
 
 f/^10TT7 O2pv8 1 
 
 55- <TT " 's*O 3 l ^ a P n tyl a sulphenite cum hydra sulphenite. 
 
 f C l H 6 Ba S 2 O 3 \ 
 56. < r> ' g2Q3 [ Barytic-naphtyla sulphenite cum baryta sulphenite. 
 
 GROUP D. ffyposulphates containing Anisol. (Toluenyl?) 
 
 J C 7 H 7 ,S O 2 -f Ba,SO 2 ) Toluenyla sulphete cum hydra sulphete 
 57- \ H ,S O* + Ba,S0 2 f bis baryta sulphete. 
 
 R (C 7 H 6 Ba,S 2 O 4 | Barytic - toluenyla sulphenote cum baryta sul- 
 5 8 '\Ba ,S 2 O 3 ( phenite. 
 
 ( C* 7 H 7 S 2 O 4 1 
 59* I H 's 2 O 3 l Toluenyla sulphenote cum hydra sulphenite. 
 
 jk} \J J 
 
 Group E. Amidogen Hyposulphates. 
 
 S 2 O 3 | 
 
 C2Q3 [ Phenylac sulphenite cum hydra sulphenite. 
 
 S 2 3 jBary tic-phenylac sulphenite cum baryta sill- 
 s' 3 ! phenite. 
 
 S 2 O 3 | Argentic phenylac sulphenite cum argenta sul- 
 S 2 O 3 ( phenite. 
 
 S 2 O 3 ) 
 
 qn*f Phenylac sulphenite cum amida sulphenite. 
 
 S 2 O 3 1 
 
 > Phenylac sulphenite cum barytec sulphenite. 
 
 60. 
 
 ZH,C 6 H 5 
 H 
 
 , f ZBa,C 6 H 5 
 
 r '| Ba, 
 62. JZA&CW 
 
 6 3 . { V H5 
 
 6 r ZH,C 6 H 5 
 6 4' j ZBa 2 
 
 SULPHITES. 
 Group A. Sulphites containing Radicals of the Vinyl Series. 
 
 C H 3 ; S 2 8 Hydra methyla sulphenite. 
 C H 3 ; S 2 O 3 Baryta methyla sulphenite. 
 C H 3 ; S 2 O 3 Argenta methyla sulphenite. 
 C H 3 ; S*O 3 Plumba methyla sulphenite. 
 C H 3 ; S 2 O 4 Plumbine methyla sulphenote 
 = CH 3 ,SO+Pb 3 ,SO 3 Methyla sulphate cum plumbine sulphite. 
 C H 3 ; S 2 O 3 Potassa methyla sulphenite. 
 C H 3 ; S 2 O 3 ) Potassa methyla sulphenite cum hydra me- 
 C H 3 ; S 2 3 f thyla sulphenite. 
 C 2 H 5 ; S ? O 3 Hydra ethyla sulphenite. 
 C 2 H 5 ; S 2 3 Ethyla ethyla sulphenite. 
 C 2 H 5 ; S 2 8 Potassa ethyla sulphenite. 
 
 65. 
 
 H 
 
 66. 
 
 Ba 
 
 67. 
 
 Ag 
 
 68. 
 
 Pb 
 
 69. 
 
 / Pb 3 
 
 i r^i 
 
 70. 
 
 ( = OJ 
 K 
 
 
 f K 
 
 7 1 - 
 
 I H 
 
 12. 
 
 H 
 
 73- 
 
 C 2 H 5 
 
 74- 
 
 K 
 
THE CONJUGATED SULPHO-ACIDS. .485 
 
 75. Ag; C 2 H 5 ; S 2 O 2 Argenta ethyla sulphenite. 
 
 76. Ba; C'H 5 ; S*O 3 Baryta ethyla sulphenite. 
 
 77. H ; C 5 H 11 ; S 2 O 3 Hydra amyla sulphenite. 
 
 78. Ba; C 5 H 11 ; S 2 O 3 Baryta amyla sulphenite. 
 
 Group B. Sulphites of the Radicals rcCH 2 H 7 and rcCH 2 H' 3 . 
 
 79. H;C 6 H 5 
 
 80. Cue; C 6 H 5 
 
 81. H;C 7 H 7 
 
 82. Ba;C 7 H 7 
 Ba; C 8 H 9 
 
 H ; C 9 H 11 
 H; C'H 7 
 K; C l H 7 
 
 87. Ag;C 10 H 7 
 
 88. H;C 10 H 13 
 
 89. Ba;C 10 H 13 
 
 83. 
 84. 
 85. 
 
 86. 
 
 S 2 3 Hydra phenyla sulphenite. 
 
 S 8 3 Cupric phenyla sulphenite. 
 
 S 2 O 3 Hydra toluenyla sulphenite. 
 
 S*O 3 Baryta toluenyla sulphenite. 
 
 S 2 3 Baryta xylenyla sulphenite. 
 
 S S O 3 Hydra cumenyla sulphenite. 
 
 S 8 O 3 Hydra naphtyla sulphenite. 
 
 S*O 3 Potassa naphtyla sulphenite. 
 
 S 2 O 3 Argenta naphtyla sulphenite. 
 
 S 2 O 3 Hydra thy my la sulphenite. 
 
 S 2 O 3 Baryta thymyla sulphenite. 
 
 90. 
 91. 
 92. 
 
 93- 
 
 94. 
 
 95- 
 
 96. 
 
 97- 
 
 H; 
 H; 
 H; 
 K; 
 
 If: 
 
 .Del ? 
 
 H: 
 H; 
 
 C 
 
 C 
 C 
 C 
 
 C 
 C 
 
 C 
 C 
 
 H'Cl 
 HC1 2 
 Cl 3 
 H 2 C1 
 HC1 2 
 Cl 3 
 H 4 C1 3 
 10 H 5 Br 2 
 
 Group C. S'dphites containing Chloric Vice-radicals. 
 
 S 2 3 Hydra chloric-methyla sulphenite. 
 
 S 2 O 3 Hydra chlorenic-methyla sulphenite. 
 
 S 2 O 3 Hydra chloririic-methyla sulphenite. 
 
 S 2 O 3 Potassa chloric-methyla sulphenite. 
 
 S 2 O 3 Argenta chlorenic-methyla sulphenite. 
 
 S 2 O 3 Baryta chlorinic-methyla sulphenite. 
 
 S 2 O 3 Hydra chlorinic-naphtyla sulphenite. 
 
 S 2 O 3 Hydra bromenic-naphtyla sulphenite. 
 
 Group D. Amidogen Sulphites. 
 
 {ZH 2 SO ) 
 j J CQ[ Amida sulphate cum hydra sulphete. 
 
 I ZH 2 SO ) 
 99. I ^T'C:O* f Amida sulphate cum methyla sulphete. 
 
 I jOw J 
 
 I Phenylac sulphate cum hydra sulphete. 
 I Phenylac sulphate cum baryta sulphete. 
 
 > Phenylac sulphate cum argenta sulphete. 
 
 SO ) 
 
 -iQf Toluenylac sulphate cum ammona sulphete. 
 
 (ZH,C 6 H 
 100. < H 
 
 IZH,C 6 H 5 
 Ba 
 
 101. 
 
 103. | 
 104 
 
 ZH,C 7 H 7 
 ZH 4 
 
 SO 
 
 SO 
 
 so 
 so 
 
 
 [ Toluenylac sulphate cum potassa sulphete. 
 
486 
 
 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 {ZH C 10 H 7 SO ] 
 H SO 2 1 Na P^ t y lac sulphate cum hydra sulphete. 
 
 1 06. 
 107. 
 108. 
 109. 
 
 ( 
 
 j = 
 
 Zn ; C H 3 
 Ba ; C H 3 
 Mg; CH 3 
 Ca; C H 3 
 H;CH 3 
 
 j 
 
 ill. Zn;C 2 H 5 
 
 (SO) 8 
 
 112. Ba;C 2 H 5 
 
 (SO) 3 
 
 113. Ag;C*H 5 
 
 (SO) 3 
 
 114. Cuc;C 2 H 5 
 
 (SO) 3 
 
 115. Na;C 2 H 5 
 
 (SO) 3 
 
 1 1 6. C 2 H 5 ;C 2 H 5 
 
 (SO) 3 
 
 f H ; C 2 H 5 
 ll jA JC 2 H 5 , 
 1 = 1 H, 
 
 (SO) 3 
 SO 1 
 3 2 2 ( 
 
 METHYLODITHIONATES. 
 
 (SO) 2 Zinca methyla bisulphate. 
 (SO) 8 Baryta methyla bisulphate. 
 SO 2 Magna methyla bisulphate. 
 
 Calca methyla bisulphate. 
 
 Hydra methyla bisulphate. 
 
 Methyla sulphate cum hydra sulphate. 
 ETHYLOTRITHIONATES. 
 
 Zinca ethyla trisulphate. 
 Baryta ethyla trisulphate. 
 Argenta ethyla trisulphate. 
 Cupric ethyla trisulphate. 
 Natra ethyla trisulphate. 
 Ethyla ethyla trisulphate. 
 Hydra ethyla trisulphate. 
 
 Ethyla sulphate cum hydra sulphenete. 
 
 INVESTIGATION OF BISULPHATES OF BASIC RADICALS. 
 
 According to many chemists, the salts of this section, Groups A and 
 B, Nos. I to I 5, are conjugated sulphates, a class of salts in which the 
 organic radicals are supposed to be combined with the sulphur and 
 oxygen into monobasic conjugated acids. I have examined that theory 
 in the Article which commences at page 399, and shown that it is not 
 tenable, and that these salts ought to be described, as I have described 
 them in this Table, as double sulphates. 
 
 Each salt in these two groups has four atoms of oxygen. In Group A, 
 the organic radicals are all such as belong to the vinyl basic series. In 
 Group B, they are such as belong to other series, but none of them have 
 assumed the extra atom of oxygen which distinguishes certain acid 
 radicals when they act as basic radicals. 
 
 Usual Names of these Bisulphates of Basic Radicals. GROUP A, i]. 
 Sulphomethylic acid. The atom of basic hydrogen is replaceable by 
 any other basic radical. 2]. Ethylosulphuric acid, or sulphovinic 
 acid. The basic hydrogen, H 1 , is replaceable by any other basic radical, 
 and produces a great variety of double sulphates. 3]. An example of 
 a normal sulphovinate, which is commonly said to be monobasic. 4], A 
 biacid sulphovinate. 5]. A bibasic sulphovinate. In this case one of 
 the four sulphates contained in the salt has O 3 , in consequence of 
 
THE CONJUGATED SULPHO-ACIDS. 487 
 
 the presence of two extra basic radicals, the analytical formula being 
 Pb,S0 2 + Pb,PbO. Salts equivalent to No. 3, are produced by ex- 
 changing Pb for ZH 4 , Na, K, Ba, L, Sr, Ca, Mg, Mn, Zn, &c. 
 6]. The barytic salt of trityl-sulphuric acid = C 6 H 7 BaS 2 O 8 , Gerhardt. 
 7]. Sulphobutylate of potash. 8]. Sulphamylic acid. 9]. Octylsul- 
 phuric acid. 10]. Cetyl-sulphuric acid. All these acids exchange H l 
 for any other basic radical. 
 
 GROUP B. n], Sulpho-phenic acid. The H 1 is replaceable by a 
 basic radical. 12] and 13] seem to me to be salts of precisely the same 
 character as No. 1 1 , the hydrogen in that salt being replaced by CH 3 to 
 produce 12, and by CH 2 Ba, to produce 13. Gerhardt, however, con- 
 siders No. 1 2 to be a " conjugated acid." He calls it Methyl-sulpho- 
 phenic acid, and gives it this formula 
 
 The single atom of hydrogen represented in this formula he represents 
 to be replaceable by barium, and so accounts for the production of the 
 salt No. 13. In this theory, Gerhardt assumes that the radical methyl 
 replaces one atom of hydrogen in the radical phenyl. Most of the 
 modern French chemists, following Gerhardt, frequently resort to this 
 practice of representing the hydrogen of hydro-carbons as replaceable by 
 other complete hydro-carbons, atom for atom. To me, this practice ap- 
 pears to be highly pernicious, and one that, if carried out, would 
 destroy the power of identifying radicals. But it is as unnecessary as 
 it is dangerous. In the present instance, it is done merely to accommo- 
 date the formula to the barytic radical in No. 13, but surely it is better 
 to adopt the theory of " metallic vice-radicals," page 137, which cannot 
 possibly produce the muddle that must necessarily ensue from admit- 
 ting the notion that hydro-carbons can replace hydrogen in other hydro- 
 carbons, and produce compound intermediate hydrocarbons. According 
 to Gerhardt, the organic radical which is present in methyl-sulphophenic 
 acid is a hydro-carbon = C 7 H 7 . This agrees in composition with 
 toluenyl, or with the radical which is commonly assumed to be present 
 in anisole, and in fact Gerhardt calls the acid, not only methyl-sulpho- 
 phenic acid, but also sulphanisolic acid. The question naturally arises, 
 what radical is actually present in the salt? Is it anisol, or toluenyl, or 
 methyl plus phenyl, or any other combination of radicals which can 
 together amount to C 7 H 7 ? Why, without the slightest necessity, 
 should we adopt a practice which evidently opens a door to such inter- 
 minable confusion ? 
 
 14]. Thymylsulphuric acid, or sulphothymic acid. 15], The baryta 
 salt of that " conjugated acid." 
 
488 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 INVESTIGATION OF BISDLPHATES OF ACID RADICALS. 
 Examples Nos. 1 6 to 42. 
 
 These salts are either double sulphates or triple salts. The hydro- 
 carbon that is present in each of them, is an acid radical. Consequently, 
 there is in each salt an addition to that quantity of oxygen, which is 
 required to complete a normal sulphate, when its hydrocarbon is basic. 
 
 I will introduce the explanation of these salts by an account of some 
 recent researches by MM. Buckton and Hofmann (Proceedings of the 
 Royal Society, vii. 544, and viii. 158; also Quarterly Journal of the 
 Chemical Society. 1856, ix. 241). 
 
 When acetamide is acted upon by fuming' oil of vitriol, the results 
 are such as may be represented as follows : 
 
 
 JZH 4 ,SO 2 
 
 ZH 2 ,C 2 H 3 0] 
 ZH 2 ,C 2 H 3 Oy = 
 (H^O 2 ) 8 ] 
 
 f H',C*H 3 
 \ H,S0 2 
 I H,S0 2 
 JCH 3 ,S 8 3 
 
 
 1 H,S*0 3 
 
 
 I ,C0 2 
 
 u* 
 
 = d. 
 
 Two atoms of acetamide and eight atoms of sulphuric acid produce in 
 the main (for the products vary according to the manner of conducting 
 the process) as follows : 
 
 a. Two atoms of sulphate of ammonia. These carry off the 
 
 nitrogen. 
 
 b. A combination of one atom of hydrated acetic acid with two 
 
 atoms of hydrated sulphuric acid = No. 16]. 
 
 c. A double or acid hyposulphate of methyl = No. 44. 
 
 d. An atom of carbonic acid, set free. 
 
 The methods of separating the three salts, a, b, c, are described by 
 MM. Buckton and Hofmann, but need not be repeated here. By 
 operating upon other am ids in this manner, similar results were ob- 
 tained. Each decomposition affording a salt belonging to the Bisul- 
 phates of Acid Radicals in company with another salt belonging to the 
 Double Hyposulphates with basic radicals. The production of the salt 
 c depends, of course, upon the reduction of the acid radical to the cor- 
 responding basic radical by the expulsion of C 1 . That is effected by 
 using a sufficient excess of acid, and a suitable high temperature: CO 8 
 then flies off, and the nascent basic radical combines with the sulphuric 
 acid. 
 
 GROUP A. Bisulphates of Radicals of tJie Vinyl Series, Nos. 16 
 to 25. 
 
THE CONJUGATED SULPHO-ACIDS. 48 9 
 
 1 6]. H,C 2 H 3 2 -f 2(H,S0 2 ) 
 
 This triple acid can be obtained in the state of dehydrated crystals that 
 have the composition represented by the formula. The usual crystals 
 contain aq. in addition to what is represented in the formula. This 
 compound is the sulphacetic acid of organic chemists : Melsen's formula 
 for it is C 4 (H 2 S0 2 )O 3 ,SO 3 2HO -f 2Aq. By an abstraction of HHO, 
 the compound No. 16 is reduced to No. 17. 
 
 17]. C 2 H 3 ,S0 3 + H,SO*. 
 
 Miller's formula for sulphacetic acid is 2HO,C 4 H 2 S 2 8 , and Hofmann's 
 formula is C 4 H 4 S 2 10 , both of which represent it as a bibasic conjugated 
 acid. I have not, however, met with any analysis of an acid of this 
 composition, although the form agrees with that of many of the normal 
 salts. 
 
 1 8]. C 2 H 2 Ba,S0 3 + Ba,S0 2 . 
 
 The sulphacetate of barytes. Hofmann's formula = C 4 (H 2 Ba 2 )S 2 O 10 . 
 Gmelin's formula = C 4 H 2 Ba 2 4 , 2 SO 3 . Miller's formula = 2BaO, 
 C 4 H 2 S 2 O 8 . These formulas all intimate the presence of a bibasic conju- 
 gated acid. 
 
 Now, let us examine this point, whether the evidence is sufficient to 
 prove the existence in these salts of an acid radical which is conjugated 
 of acetyl and sulphur. 
 
 Suppose the acid No. 1 6 to be deprived of an atom of HHO. The 
 residues would be C 2 H 3 ,H,S,S,O 5 , and the question to be solved is, 
 in what order do these atoms combine with one another to form a com- 
 pound salt ? 
 
 T . H.CPH'SO* C 2 H 3 ,S0 3 
 
 Is it so: H | s()2 ;orso: ^0* ? 
 
 According to the first supposition, we have a double salt, containing a 
 sulphic vice-radical, such as I have described at page 136, which radical, 
 in this case, is sulphacetyl = C 2 H 2 S, where H l is replaced by S 1 , sub- 
 ject to the addition of O l to the oxygen of every salt into which the 
 conjugated radical enters. This supposition, as I have shown at page 
 137, agrees with the composition of the salts; and according to it, the 
 salt, No. 1 8], cited above, would be represented by the formula : 
 
 Ba,C 2 H 2 S0 3 + Ba,S0 2 . 
 
 But this supposition leaves out of consideration the important fact, to 
 which I have adverted in the beginning of this Section, namely, that an 
 acid radical can act the part of a basic radical, provided an addition 
 of oxygen is made to its salts. On that principle the formula No. 17 
 is founded ; for in the salt which that formula represents, we have a 
 sulphate with acetyl for its basic radical, and consequently with O 3 as 
 its quantum of oxygen. 
 
490 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 The objection that applies to this formula is, that sulphacetic acid 
 (like all the acids of this category) is bibasic, while the double acid, 
 represented by formula 1 7, contains but one atom of basic hydrogen. To 
 meet that objection, another fact comes into play, namely, the fact that 
 hydrocarbons, when acting as basic radicals, can exchange an atom of 
 hydrogen for a metal, and produce a metallic vice-radical. I have 
 proved this to be the case in so many instances, that I do not hesitate 
 to cite it as a fact that is incontestable. 
 
 These considerations drive the argument into a corner. We have to 
 choose between these two probabilities : does acetyl in the sulphacetates 
 exist as an acid radical in combination with sulphur = C 2 H 2 S, or as a basic 
 radical in combination with a metal = C 8 H 2 M ? I am decidedly in 
 favour of the latter opinion, and I do not now, as I once did, consider 
 the existing evidence to be in favour of the occurrence of sulphic radicals. 
 When I wrote the Article on sulphic radicals at page 136, and those on 
 the sulphur salts of indigo between pages 269 and 274, I was favour- 
 able to the theory of sulphic radicals ; but the facts developed during 
 the investigation into the polyatomic alcohols respecting the power of 
 acid radicals to act as basic radicals under certain conditions of suroxida- 
 tion, together with the ever-increasing proof of the existence of basic 
 hydrocarbons containing metals by substitution for hydrogen, have com- 
 pletely changed my opinion; and I now consider that the evidence 
 which tends to prove the existence of sulphic radicals is outweighed 
 by that which tends to prove the contrary, and consequently that 
 flre have no right to assume that such things as conjugated sulpho-acids 
 exist. I shall show that all the salts that are collected under this head 
 are subject to an interpretation which is independent of the theory of 
 conjugated acids. 
 
 I conclude, therefore, that the salt No. 1 8 is properly represented as 
 a double sulphate, one of the salts being in its normal state, and the 
 other containing barytic-acetyl, and, therefore, an additional atom of 
 oxygen. 
 
 C 2 H 3 .SO 3 H ,C 2 H 3 2 -, 
 = HBa 2 ,S0 3 or (Ba,SOy. = W 
 
 The barytic salt No. 19 is procurable in crystals, which may be ex- 
 plained by either of these two formulae. According to the first formula, 
 we have a sulphate of acetyl combined with a terbasic sulphate. Both 
 salts contain O 3 , the first because of the presence of an acid radical, the 
 second because of the presence of three basic radicals. According to the 
 second form we have hydrated acetic acid, in combination with two atoms 
 of sulphate of barytes. This form agrees with the hydrated acid No. 16, 
 and is, I think, the most probable. When this salt is heated, HHO 
 goes away, and a new arrangement of atoms occurs, which produces the 
 salt No. 1 8. 
 
THE CONJUGATED SULPHO-ACIDS. 491 
 
 20]. C 2 H 2 Ag,S0 3 + Ag,S0 2 , 
 
 the silver salt of the same acid. Numerous other salts might be 
 quoted, but none which afford additional evidence on the point now 
 discussed. In matters of this sort, cumulative concurrent evidence adds 
 to the probability of the truth of a theory, but does not make it 
 certain. 
 
 21]. C 3 H 4 'a ,SO 3 + Ba ,SO 2 . 
 
 22]. C 3 H f ,SO 3 + H ,SO 2 . 
 
 23]. ZH 3 ,C 3 H 5 ,S0 3 + ZH 4 ,S0 2 . 
 
 24]. C 4 H 6 Ba ,S0 3 + Ba ,SO 2 . 
 
 25]. C 4 H 7 ,S0 3 + H ,S0 2 - 
 
 Usual Names: -21]. Sulphopropionate of barium = C 6 (H 4 Ba 2 )S 2 10 , 
 Buckton and Hofmann. 22]. Sulphopropionic acid. 23]. Sulphopro- 
 pionate of ammonium : (the relation of this salt to the acid No. 22, 
 plus two atoms of ammonia = ZH 2 H + ZEPH, is seen at a glance). 
 24]. Sulphobutyrate of barium = C 8 (H 6 Ba 8 )S 2 O', Buckton and Hof- 
 mann. 25]. Sulphobutyric acid. 
 
 These salts differ from the sulphacetates only by the substitution of 
 propionyl = C 3 H 5 , and butyryl = C 4 H 7 , for acetyl = C 8 H 3 . The theory 
 which applies to sulphacetic acid applies to every acid of this description. 
 It is, I think, wrong to call them " acids." They are simply double 
 sulphates modified by the quantity of oxygen which is governed by the 
 organic radicals and metallic vice-radicals. 
 
 Group B. Bisulphates containing Benzyl, Nos. 26 to 34. 
 
 No. 26 in this series is sulphobenzoic acid, and the other salts, from 
 27 to 34, are sulphobenzoates. The theory of these salts is precisely 
 similar to that of the preceding group, and it is useless to cite them 
 individually for discussion. One or two points may be noticed. No. 27, 
 the monobarytic salt, is a form that has not yet been found among the 
 salts of the preceding group. The salts Nos. 31 to 34 have been recently 
 described by Limpricht, who is of opinion that; the acid of No. 3 1 con- 
 tains not only sulphur and benzyl but ethyl. He calls it ethyl-sulpho- 
 benzoicacid. The ammonia salt, No. 32, he calls ethyl-sulphobenzoate 
 
 C 14 H 4 S 8 O 6 ) 
 of ammonia, and the formula which he gives for it is /~ 4 TTSX-NTT \ O 4 . 
 
 My interpretation of these salts is entirely different. I consider No. 31 
 to be a double sulphate, but having O l extra, because of the presence of 
 benzyl in the condition of its basic radical : the ethy], of course, demands 
 no additional oxygen. When a metal acts upon this double salt, the 
 odd atom of hydrogen in the ethyl is exchanged for it, and thus the salts 
 33 and 34 are produced. When ammonia acts upon No. 31 it simply 
 converts the ethyl into ethy lam, which, being a normal ammonam, de- 
 mands no additional oxygen, as is seen in No. 32. 
 
492 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 Group C. Bisulphates containing Anisyl, Cinnamyl, and Spiryl. 
 Nos. 35 to 43. 
 
 The bisulphates that contain anisyl have been recently investigated 
 by Zervas, under the guidance of Hofmann (Proceedings of the Royal 
 Society, 1857, viii. 494; Quarterly Journal Chemical Society, 1857, 
 x. 211). The compounds were prepared by the action of fuming 
 sulphuric acid on anisic acid. 
 
 35]. H,C 8 H 7 3 + 2(H ,S0 2 ). 
 
 36]. H^IFO 3 + 2(Ba,SO*). 
 37]. H,C"H 7 3 + 2(Pb,S0 2 ). 
 
 These were crystallised salts, for which the discoverer gives the following 
 formulae : 
 
 for 35, C 16 H 8 S 2 18 + 2aq. 
 
 for 36, C 16 (H 6 Ba 2 )S 8 12 + 2 aq. 
 
 for 37, C le (H 6 Pb 2 )S 2 O 12 + 2 aq. 
 
 No. 35 is called sulphanisic acid, and the others are sulphanisates. 
 38]. C 8 H 7 ,S0 4 + H ,S0 8 . 
 39]. C 8 H 6 Ba,SO 4 + Ba,SO 2 . 
 40]. C 8 H 6 Pb,S0 4 + Pb,S0 8 . 
 
 No. 38 is produced by heating the crystals of 35 at 100 C. No. 39, 
 by heating the crystals of 36 at 170 C. JN"o. 40, by heating the 
 crystals of 37 at 176 C. 
 
 Theory. There is here no evidence of the formation of the "conju- 
 gated" sulphanisic acid. The first three salts are combinations of sulphates 
 with hydrated anisic acid. The others differ from these in consequence 
 of having each undergone an abstraction of HHO. The effect of this 
 abstraction of HHO is, to throw the anisyl into the condition of a basic 
 radical, and as this acid radical requires O 3 for its normal salts, on be- 
 coming basic, it carries with it O 2 , and consequently raises the oxygen 
 of the sulphate into which it enters from O 2 to 0*. In this respect only 
 do the sulphanisates differ in principle from the sulphacetates and sul- 
 phobenzoates. 
 
 41]. cm 7 so 3 + H, so 2 . 
 
 42]. C 9 H 6 Ag,S0 3 + Ag,S0 2 . 
 
 No. 41 is the sulphocinnamic acid, and 42 its silver salt. There are 
 many other salts similar to No. 42. It is evident at a glance that these 
 salts resemble those which contain benzyl, group B, and that they require 
 no other theoretical explanation. 
 
 43]. C 7 H 5 ,S0 4 + H,S0 8 . 
 
 Hofmann quotes this formula (or rather he quotes C U H 6 S 8 O 12 ) as that of 
 another new conjugated acid, the sulpho-salicylic acid, recently dis- 
 
THE CONJUGATED SULPHO- ACIDS. 493 
 
 covered by Mr. Baldwin Duppa. No particulars are given respecting 
 the salt. The correctness of this formula is doubtful. C 7 H 5 represents 
 spiryl, not salicyl, but spiryl could scarcely require O 4 in its sulphate, 
 
 INVESTIGATION OF DOUBLE HYPOSULPHATES. 
 
 A Hyposulphate contains two atoms of sulphur, three atoms of 
 oxygen, and one positive radical (see page 172). There is no a priori 
 argument against the possibility of the formation of double hypo- 
 sulphates. I conclude thence, that the salts in the Table, from No. 44 to 
 59, are all double hyposulphates, and that they contain no conjugated 
 acids of any description whatever. It may be urged in opposition to this 
 opinion, that the properties arid reactions of these salts are not in accord- 
 ance with the properties and reactions of hyposulphates ; but it does not 
 appear to me that the properties and reactions of hyposulphates are, at 
 present, known with such perfection that much reliance can be placed 
 on arguments which depend solely upon that knowledge. 
 
 The process by which these salts are produced has been described in 
 general terms at page 488. 
 
 All the basic radicals that are contained in the salts that form groups 
 A, B, C, are truly basic, and therefore they bring no additioanl oxygen 
 into the salts. In group D, we perceive the radical (7H 7 , the nature of 
 which I do not understand, but which has evidently the power of an 
 acid radical of the benzyl series, and consequently adds O 1 to its salts. 
 
 All the other particulars that are exhibited by the formulae, from 
 Nos. 44 to 59, have been so fully discussed, that the reader will imme- 
 diately comprehend the meanings that these formula? are intended to 
 convey. But as the discovery of these salts is but recent, and as their 
 discoverers are impressed with the conviction that they have discovered 
 five or six NEW ACIDS, I will quote some of their names and formulae. 
 My impression is, that the salts are hyposulphates, and nothing else. 
 If this impression is correct, I apprehend that little favour is due to mere 
 names which imply the existence of conjectural conjugated acids. Not 
 one such acid ought to be recognised as existent without conclusive 
 evidence in its favour. The law of simplicity commands us to admit in 
 chemistry of the existence of no greater variety of substances than nature 
 actually produces : they are numerous enough in all conscience. Every 
 new conjugated acid, and every new polyatomic base, which speculative 
 chemists adopt inconsiderately and without necessity, is an injury to the 
 exactness and an obstacle to the progress of true science. 
 
 Groups A and B. Names and Formula given by Messrs. Euckton 
 and Hofmann. 
 
 44]. Disulphometholic acid = C 2 H 4 S 4 18 . 
 
 45]. Disulphometholate of barium = C 2 (H 2 Ba 8 )S 4 12 . 
 
494 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 46]. Disulphometholate of silver = C 2 (H 2 Ag 2 )S 4 12 . 
 
 Disulphometholate of Ammonium = C 2 [H 2 (NH 4 ) 2 ]S 4 12 . 
 Disulphetholic acid = C 4 H 6 S 4 O r 
 
 n 
 
 48] 
 49 
 
 5 2 . 
 53. 
 
 54] 
 
 Disulphetholate of barium = C 4 (H 4 Ba*)S 4 O 12 . 
 
 Disulphetholate of ammonium = C 4 [H 4 (NH 4 ) 2 ]S 4 O 12 . 
 
 Disulphopropiolic acid = C C (H 8 )S 4 O 12 . 
 
 Disulphopropiolate of barium = C 6 (H 6 Ba a )S 4 O 18 . 
 
 Disulphobenzolic acid = C 12 H 6 S 4 O 12 . 
 
 Disulphobenzolate of barium = C 12 (H 4 Ba 2 )S 4 O 12 . 
 
 Group C. Names quoted by Gerhardt. 
 
 55]. Disulphonaphtalic acid; thionaphtic acid; hyposulphonaphtic 
 acid = C io H 8 S 4 O 12 = C 20 H 8 + 4(SO 3 ,HO) - 4HO. 
 56. Disulphonaphtalate of barytes = C 20 H 6 Ba 2 S 4 12 . 
 
 Group D. Names of Zervas and Hofmann. 
 
 57]. Disulphanisolate of barium = C 14 (H 6 Ba 2 )S 4 O u -f- 2 aq. This 
 salt is evidently a quadra-sulphate, the four basic radicals of which 
 areBa, Ba, C 7 H 7 , and H. The salts Nos. 58 and 59 were inferred to 
 exist, rather than proved to exist, by these chemists. 
 
 Looking over these salts, there seems to be no evidence to favour the 
 assumption of the existence of a series of conjugated sulpho-acids, but 
 much to prove the accuracy of the formulae which are given in the Table, 
 and according to which these salts are all hyposulphates. 
 
 The radical marked C 7 H 7 is derived from anisyl C 8 H 7 by abstraction 
 of C 1 . Hofmann calls it anisol. Is it toluenyl = C 7 H 7 , or some other 
 isomeric radical ? It acts here as an acid radical, whereas toluenyl acts 
 as a basic radical (see No. 81). 
 
 Group E. Amidogen Hyposulphates. 
 
 Usual Names. -60]. Disulphanilic acid = C 12 H 7 NS 4 12 , Euckton and 
 Hofmann. 61]. Distil phanilate of barium = C 12 (HW)NS 4 O 12 , B. and H. 
 62]. Disulphanilate of silver = C 12 (H 5 Ag 2 )NS 4 12 , B.andH. 63]. Di- 
 thiobenzolic acid = C 12 H 8 N 2 S 4 O 12 , Hilhenkamp. Phenyldisulphodiamic 
 acid, Hofmann. 64]. The barium salt of that acid. The salts of this 
 group have been described at page 240. There is a peculiarity in their 
 composition which I do not understand. If HHO is added to the 
 
 Z H 8 C 6 H 5 * S 2 O 4 ) 
 amidogen salt No. 60 we produce r \ g ? Q 3 \ . The upper member 
 
 of this salt represents twice as much sulphur and oxygen as belongs to 
 a sulphate in combination with only one basic radical. 
 
 If 2 (HHO) is added to the double amidogen salt No. 64 we produce 
 
 ZH 8 C 6 H 5 S 2 O* 1 
 
 ZH 2 'B 2 S 2 O 4 I ' ^ s * s a d u ble salt, with a similar disproportion of 
 
THE CONJUGATED SULPHO-ACIDS. 495 
 
 acid radicals to basic radicals. Other examples occur, see page 241, 
 in which amidogens seem to be equally competent with ammoniums to 
 act as basic radicals in hyposulphates. 
 
 INVESTIGATION OF THE SULPHITES. 
 
 A sulphite contains two atoms of sulphur, three atoms of oxygen, and 
 two positive radicals. See pages 171 and 237. 
 
 The salts described in the Table, from Nos. 65 to 97, are all formed 
 in accordance with these particulars, and consequently are entitled to be 
 called sulphites. The common practice of organic chemists is, however, 
 to represent them as salts of conjugated acids, chiefly under the sup- 
 position, that the organic radical which is present in each salt is not 
 present in the character of a basic radical, but is conjugated with the 
 sulphur into a compound acid radical. The arguments by which that 
 supposition is supported have been examined in the article which com- 
 mences at page 399, in which I have shown that the evidence adduced, 
 instead of proving the existence of conjugated acids, proves exactly the 
 reverse. Referring the reader to those arguments and facts, I assume 
 here, that all the compound radicals which appear in this Table are 
 present in the salts in the condition of basic radicals, that the salts are 
 sulphites, and that the theory of conjugated acids is totally inapplicable 
 to every one of them. 
 
 Even the chloric- and bromic-vice-radicals, some of them containing 
 two or three atoms of chlorine or of bromine, with no hydrogen, still act 
 in these salts as basic radicals, and have no effect on the quantum of 
 oxygen which is demanded by the sulphur for the formation of normal 
 sulphites. 
 
 GROUP A. Sulphites with Alcohol Radicals. Nos. 65 to 78. 
 
 65} H; CH 3 ; S 2 3 = CH 3 ,SO + H,S0 2 . The H being replaceable, 
 this acid gives rise to the salts that are formulated in Nos. 66 to 7 1 , and 
 to many others. This acid has been called Sulphosomethylic acid. 
 Hyposulphomethylic acid, Gmetin. Acide methyl -sulfureux ; acide 
 methyl-dithionique, or sulfomethyl-sulfurique 
 
 = C 2 H 4 S 2 6 = 'S 2 6 , Gerhardt. 
 
 Acide sulfoformique, Laurent. Methylunterschwefelsaure, or Hydrated 
 hyposulphate of methyl = C 2 H 3 ,S 2 O\HO, Kolbe. In applying the term 
 hyposulphate to a salt of this formula, Kolbe seems to have considered 
 only the relations of the sulphur and oxygen, and to have forgotten that 
 with these proportions of S and O, the presence of two basic radicals 
 makes a sulphite, while a hyposulphate requires only one basic radical. 
 But probably Kolbe was guided in his opinion by the notion that in this 
 case the hydrogen alone acted as the basic radical, and that the methyl 
 
496 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 = C 2 H 3 acted merely as a neutral, indifferent, powerless, hanger-on, like 
 the basic radicals in his copulated oxalates, which I have described at 
 page 408. However, the mistaking of sulphites for hyposulphates is 
 not peculiar to Kolbe, but is a common practice among organic 
 chemists. 
 
 66] to 71]. These are salts of the "acid" No. 65, and therefore 
 demand no particular explanation. No. 71 is a double or acid salt. 
 No. 69 is a salt one half of which is terbasic. In this example we have 
 the proportions of S and O which are proper to a normal sulphate, but 
 with twice the ordinary number of basic radicals. 
 
 72]. H ; C 2 H 5 ; S 2 ^ = C 2 H 5 ,SO -f H,SO 2 . This is commonly called 
 the Ethylosulphurous acid. Nos. 73 to 76 are examples of its salts, of 
 which many more might be quoted. No. 73 is also called the sulphite 
 of ethyl, and affords an instance of an organic salt, which, for a wonder, 
 organic chemists have omitted to convert into a conjugated acid. 
 
 77]. The hyposulphamylic acid. 78]. Its barium salt. 
 
 GROUP B. Sulphites containing Radicals of the Series nCH 2 H 7 , 
 and rcCH 2 - H 13 . 
 
 79]. H ; C 6 H 5 ; S 2 O 3 = C 6 H 5 ,SO -f H,S0 2 . All the salts of Group B 
 have this constitution. The H, of course, is replaceable by a basic 
 radical, and gives rise in each case to a series of salts. 
 
 Usual names. 79]. Funeschwefelsaure, Gmelin. Acide phenyl-sul- 
 fureux or acide sulfobenzidic 
 
 Hyposulphobenzidic acid, Gregory. Sulphobenzolic acid = HO,C 12 H 5 S 2 5 , 
 Miller. 8oJ. The copper salt of the acid 79. 81]. Sulphotoluy lie acid. 
 Thiotoluic acid. Acide sulfobenzoenique. Toluolschwefelsaure. 82]. 
 Its barium salt. 83]. The barium salt of xylenyl-sulphurous acid, or 
 Sulpho-xyloic acid. 84]. Cumenyl-sulphurous acid. Sulphocumenic 
 acid. 85]. Sulphonaphtalic acid. Naphtyl-sulphurous acid. Hypo- 
 sulphonaphtalic acid. Naphtyl-dithionic acid. 86 and 87]. Salts of the 
 acid No. 85. 88]. Thymyl-sulphurous acid, Sulphocymenic acid, or 
 sulphocamphic acid, Gerhardt. 89]. Its barium salt. 
 
 GROUP C. Sulphites containing Chloric Vice-Radicals. 
 
 The salts Nos. 90, 91, 92, differ from the salt No. 65, only by the 
 substitution of chloric-, chlorenic-, and chlorinic-methyl, in the place of 
 normal methyl. The resulting salts retain the usual form and the usual 
 quantity of oxygen. The salts Nos. 93, 94, and 95, differ to the same 
 extent from the normal salts Nos. 70, 67, and 66. The salts Nos. 96 
 and 97, differ from the salt No. 85, only by the replacement of naphtyl 
 by chlorinic- and bromenic-naphtyl. 
 
THE CONJUGATED SULPHO-ACIDS. 497 
 
 Nevertheless, these simple relations have been overlooked, and 
 chemists have given to these salts a variety of very complex names and 
 formula?, depending upon equally complicated and diversified theories ; 
 for a full account of which I refer the reader to Gmelin's Handbook of 
 Chemistry, vii., 295 to 303, and 351. 
 
 Usual names. 90]. Chloro-sulphosomethylic acid, Gmelin. Chlor- 
 elayl - Unterschwefelsaure, chlorelaylhyposulphuric acid, or chloro- 
 methylodithionic acid 
 
 = HO . /C 2 j^TpS 2 ^ 5 , Kolbe. 
 
 Acide sulfoformique chlore, Laurent. Acide metholique chlorosulfure, 
 Gerhardt. 93]. One of its salts. 91]. Bichlorosulphosomethylic acid, 
 Gmelin. Chlorformyl - Unterschwefelsaure, Dichloromethylodithionic 
 acid, or chloroformylohyposulphuric acid 
 
 = HO.C 2 ", 2 PS 2 ,0 5 , Kolbe. 
 
 Acide sulfoformique bichlore, Laurent. Acide metholique bichlorosul- 
 fure, Gerhardt. 94]. Its silver salt. 92], Terchloro-sulphosomethylic 
 acid, Gmelin. Terchlorinated Sulphosomethylic acid, Gmelin. Chlor- 
 kohlen-Unterschwefelsaure, chlorocarbohyposulphuric acid, or trichloro- 
 methylodithionic acid = HO . (C 2 C1 3 )^S 2 ,O 5 , Kolbe. Acide sulfofor- 
 mique triehlore, Laurent. Acide metholique trichlorosulfure, Gerhardt. 
 95]. Its barium salt. According to Kolbe, the chloric vice-radical which 
 forms part of each salt, is copulated with the two atoms of sulphur into 
 a single acid radical. That process apparently converts the salts from 
 sulphites into hyposulphates. But there is no evidence that this copula- 
 tion takes place ; the salts can be described with simplicity as sulphites ; 
 and the existence of the copulated hyposulphates is highly improbable. 
 96]. Trichloro-sulphonaphtalic acid 
 
 97]. Bibromo-sulphonaphtalic acid 
 
 ! Gerhard , 
 
 In these last two formulae, chlorinic-naphtyl, or bromenic-naphtyl, in 
 company with two atoms of sulphur and two atoms of oxygen, are made 
 to -be collectively equal to H 1 . This arbitrary ascription of the model of 
 water to compounds which are evidently double salts is not to be justi- 
 fied. The manufacture of conjugated acids in this easy way is a farce. 
 
 GROUP D. Amidogen Sulphites. Nos. 98 to 105. 
 
 The salts of this group have all been described in former sections 
 and it is consequently needless to dwell upon them again in detail. The 
 
 2 K 
 
498 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 amidogen sulphites are all to be considered as double sulphates minus 
 HHO ; for if we suppose an addition of HHO to be made to each of the 
 salts in this Table, they immediately become converted into normal 
 bisulphates or double sulphates. Thus : 
 
 ZH 2 ,S04-HHO JZH 4 ,SO* 
 
 H ,SO 2 = t H ,S0 2 
 
 -, ZH,C'H 7 ; SO + HHO _ JZH 3 ,C 10 H 7 ; SO 2 
 H ; SO 2 = I H ; SO 2 
 
 Usual Names. 98]. See 312, page 233. 99]. Sulphomethylane ; 
 see 320, page 237. 100]. Sulphanilic acid; see 321, page 237, and 
 28, page 285. 101] and 102]. Salts of sulphanilic acid; see Nos. 324 
 and 323, page 237, and No. 29, page 285. 103] and 104]. Thiotol- 
 nates; see Nos. 331 and 332, page 240. 105]. Thionaphtamic acid; 
 see No. 329, page 240. 
 
 IJTVESTIGATION OF THE METHYLODITHIONATES. The Methylodithio- 
 nates have recently been described by Dr. J. T. Hobson ( Quarterly 
 Journal of the Chemical Society, 1857, x. 248,) as part of a " New Series 
 of Organo-Thionic Acids." The name mettiylodithionates was not well 
 chosen, because Gerhardt has already applied it to another series of salts, 
 the acid sulphites of methyl, forming Group A of this Table ; see note 
 to No. 65. Dr. Hobson's methylodithionates were prepared by acting 
 upon zinc-methyl with sulphurous acid. The formulae which he gives, 
 as representing the results of the analyses, are as follow : 
 
 f r* 2 H 3 1 
 
 1 06]. Methylodithionate of Zinc ZnO,S 2 I Q3 \ 
 
 (r 2 H 3 l 
 107]. Methylodithionate of Baryta BaO,S 2 .j ^ j- 
 
 i/~12TT3l 
 O 3 j 
 )C 2 H 3 ) 
 O 3 I 
 
 1 10]. The " acid" was found to be very unstable, and could not be 
 procured in a condition fit for analysis. Its composition was calculated 
 from that of the salts. 
 
 It appears to me, that this " methylodithionic acid" has no existence, 
 and that these salts are hyposulphites, constituted in accordance with the 
 formula which I have explained in the article commencing at page 160. 
 The salt No. 106, for example, is 
 
 CH 3 ,SO 4- Zn,SO Methyla sulphate cum zinca sulphate. 
 The other salts are constituted in a similar manner. 
 
THE CONJUGATED SULPHO-ACIDS. 499 
 
 INVESTIGATION OP THE ETHYLOTRITHIONATES. 
 
 The Ethylotrithionates have been described by Dr. J. T. Hobson 
 ( Quarterly Journal of the Chemical Society, 1857, x. 55). They were 
 produced by acting on zinc-ethyl with sulphurous acid. They are, like 
 the methylodithionates, stated by Dr. Hobson to be part of a "New 
 Series of Organo-Thionic Acids." The formulas which he assigns to the 
 salts are as follow (I omit water of crystallisation) : 
 
 ZnO ,S 8 (C 4 H 5 )O 5 . Ethylotdthionate of zinc. 
 
 BaO ,S 3 (C 4 H S )0 5 . Ethylotrithionate of baryta. 
 
 AgO ,S 3 (C 4 H 5 )O 5 . Ethylotrithionate of silver. 
 
 CuO ,S 3 (C 4 H 5 )0 5 . Ethylotrithionate of copper. 
 
 NaO ,S 3 (C 4 H 5 )O 5 . Ethylotrithionate of soda. 
 
 C 4 H 5 O,S 3 (C 4 H 5 )O 5 , Ethylotrithionate of oxide of ethyl. 
 
 HO, S 3 (C 4 H 3 )O 5 . Ethylotrithionic acid. 
 
 Dr. Hobson's theory is expressed thus : " The compound [No. in] 
 is the zinc salt of a new acid, formed by the substitution of one equiva- 
 lent of oxygen in three equivalents of sulphurous acid by ethyl." This 
 supposition is by no means sufficient to prove the existence of a con- 
 jugated acid. I do not believe that the ethyl goes thus into the acid 
 radical. That assumption is negatived by the evidence given in the 
 section which commences at page 399. I therefore consider ethyl as 
 sustaining in these salts its normal character of a basic radical. 
 
 If we could consider zinc-ethyl to be a radical, (and its atomic measure 
 of one volume might tend to lead us to that opinion,) then, these salts 
 might at once be described as trithionates, using that term in the sense 
 in which it is used in the Article at page 168. Thus, the salt called 
 ethylotrithionate of zinc, No. in, would be rendered ZnC'H^O 3 . 
 
 But I am of opinion, that zinc-ethyl is not a radical, but a salt. The 
 grounds of that opinion are stated at page 106. Hence, these salts cannot 
 be trithionates. If we throw the synoptical formula No. 1 1 1 into an 
 analytical formula, we produce : 
 
 C 2 H 5 ,SO 
 
 Zn,SO,SO 
 
 and comparing this formula with that of the different polythionic salts, 
 which I have described in the Article commencing at page 1 56, I con- 
 clude that the ethylotrithionates are compounds of a sulphate = C 2 H 5 ,SO 
 (page 159) with a sulphenete = Zn,SO,SO (page 170). The circum- 
 stance that salts of this constitution are at present nearly unknown, 
 is no obstacle to their acknowledgment when they are made known. 
 Hitherto, in fact, they have not been looked for, and, as I have shown 
 in the investigation into the constitution of the polythionates, many 
 varieties of oxy sulphur salts have been disregarded, because the minds of 
 
 2 K 2 
 
500 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 chemists were preoccupied by erroneous notions respecting their consti- 
 tution. The sulphenetes are salts in which sulphurous acid = SO, is 
 combined with a salt of the form MSO, just as the hyposulphates consist 
 of SO combined with a salt of the form MSO 2 . In such a supposition 
 there is nothing improbable, and by accepting it we are provided with 
 satisfactory formulae for the salts now in question, and freed from the 
 necessity of admitting without proof the existence of a conjugated acid. 
 
 I have gone somewhat into detail respecting the " Conjugated Sulpho- 
 acids," because chemists are in the common practice of taking for 
 granted that such compounds actually exist; for which reason I have 
 thought it proper to show them, that we have no evidence to prove the 
 existence of even a single acid of this description. Our Books, indeed, are 
 crammed with their Names, but Nature objects to make the Things. 
 
 The Silicates. 
 
 Much controversy has taken place respecting the composition of silica 
 and the silicates. Different chemists have ascribed to silica the follow- 
 ing formulae : 
 
 SiO 3 , SiO 2 , and SiO. 
 
 Berzelius. Gmelin. Thomson. 
 
 In the year 1834 ^ suggested that silica ought to be denoted by 
 Si^, and the neutral silicates by MSiO. These formulae seem now, 
 after twenty-four years of research and reflection, to be more probable 
 exponents of the truth than any of the other formula?. 
 
 The most recent " researches on silica " have been made by Colonel 
 Philip Yorke (Proceedings of the Itoyal Society, April 1857, viii. 440). 
 His method of operating was that of " determining the quantity of car- 
 bonic acid which is displaced from excess of an alkaline carbonate in fusion, 
 by a given weight of silica." The results were as follows : When car- 
 bonate of potash was used, the experiments indicated the formula SiO 8 . 
 When carbonate of soda was used, the formula indicated was SiO 3 . 
 When carbonate of lithia was used, the formula became SiO. These 
 experimental results gave, therefore, no satisfactory theoretical result. 
 The process led to nothing, because silicates of fixed alkalies, whatever 
 their composition, fuse with indefinite quantities of silica, and produce 
 a variety of silicates, which differ in composition, according to the pro- 
 portions of the ingredients in the mixtures, the degree of heat employed, 
 and the time of its duration. To this principle it is that glasses and 
 glazes owe their variety. 
 
THE SILICATES. 501 
 
 Colonel Yorke's conclusions were as follow. " After guarding him- 
 self from drawing any decided inference from the experiments recorded, 
 the Author concludes by observing that at present he can see no alterna- 
 tive but to admit of more than one equivalent for silicic acid (that is to 
 say, of more than one acid), the value of which is determined by circum- 
 stances, such as the presence of water and the nature of the base to 
 which it is presented. The existence of such different silicic acids has 
 been already suggested by chemists at different periods, particularly by 
 Ebelmen and Laurent, and lately by M. Fremy." 
 
 I think we may come to a more satisfactory result respecting the 
 atomic weight of silicon, if we examine the constitution of its gaseous 
 compounds, and proceed, as I have done in the investigation of the 
 compound radicals, from gases to solids, with the single view to make 
 out, if we can, how much of the element which is under investigation is 
 ths chemical equivalent of a single volume of hydrogen. That quantity of 
 the element must be accepted as its atom. Silicon must submit, like 
 other elements, to this rule. Its atom, or Radical, is that quantity which 
 replaces a volume of hydrogen. 
 
 In the Table of Gases, printed between pages 50 and 63, we have the 
 following examples of gases that contain silicon : 
 
 Atomic measure. 
 
 Silicate of amyl, or amyla silate . . C 5 H u ,SiO . . . ^-volume. 
 
 Silicate of ethyl, or ethyla silate . . C 2 H 5 ,SiO . . . ^volume. 
 
 Chloride of silicon, or sila chlora . Si,Cl . . volume. 
 
 Fluoride of silicon, or sila fluora . . Si,F % volume. 
 
 Chlorosulphide of silicon, or sila J Si,S 1 A 1 
 
 sulpha bis sila chlora . . . . { (Si,Cl) 2 f ' 
 
 If we suppose the radical Si which appears in these formulae to be, 
 in all the examples, replaced by H, we should have the following series 
 of well-known salts : 
 
 C 5 H U ,HO = amylic alcohol. 
 C 2 H 5 ,HO = common alcohol. 
 H ,C1 = hydrochloric acid. 
 H ,F = hydrofluoric acid. 
 
 2(HC1) -j- HS = a mixture of two atoms of hydrochloric acid 
 with one atom of hydrosulphuric acid. 
 
 Here then is evidence clear and convincing, as far as it goes, that the 
 quantity of silicon, which is the equivalent of H 1 , is that which is 
 marked in the Table by Si 1 . An examination of the constitution and 
 specific gravities of the respective gases fully explains the weight of this 
 radical. 
 
502 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 The composition of Silicate of Amyl = Amyla silate, is : 
 
 Amyl = (m 11 = 71 
 Silicon = Si = 7*5 
 Oxygen = O = 16 
 
 94'5 
 
 If this is doubled, it becomes 189, which represents its theoretical spe- 
 cific gravity, whereas Ebelmen's experiments showed it to be 1 69 3 ; 
 which, though not a very accurate number, is sufficient to prove that 
 the atomic measure of this gas is half a volume. Now, the correspond- 
 ing gas, with H l instead of Si 1 , amylic alcohol = C 5 H U ,HO measures 
 two volumes. The cause of this differerence is explained at page ic8, 
 where I have shown that H l , when it forms part of a salt, measures 
 i volume, and does not alter the measure of the radical with which 
 it combines to produce that salt, whereas the measure of silicon in a 
 salt is o volume, while it diminishes the measure of the radical with 
 which it combines to form that salt from i volume to half a volume. 
 Hence it is, that all the siliceous gases measure half a volume for each 
 atom of silicon which they contain. 
 
 This explanation applies to all the five gases which are quoted 
 above. The chloride of silicon, or sila chlora = SiCl, has the following 
 composition : 
 
 Silicon = Si = 7*5 
 Chlorine = = 35-5 
 
 43-0 
 
 The theoretical specific gravity is 86, while Pierre found it experi- 
 mentally to be 85*94. In the same way, the atomic weight of 
 the silicate of ethyl, or ethyla silate = C*H 5 ,SiO is shown in the 
 Table, at page 58, to be 52*5; its theoretical specific gravity to be 
 105 ; and its experimental specific gravity, as determined by Ebelman, 
 to be 105 '92. The fluoride of silicon, or sila fluora = SiF, has an 
 atomic weight of 26*5, and a theoretical specific gravity of 53, which 
 Dumas found experimentally to be 52 '09. Finally, the triple salt, the 
 chlorosulphide of silicon = 2 SiCl + SiS has the atomic weight of 
 109*5, wmcn corresponds to the theoretical specific gravity of 73, its 
 measure being ! volume, and this specific gravity is corroborated by 
 the experimental weighings of Pierre, which gave 73*51. 
 
 These facts afford strong evidence in favour of the statement, that the 
 atomic weight of silicon is 7 5. I adopt that conclusion as true, and I 
 proceed to show how exactly it accords, not only with the composition 
 of the siliceous gases and the chief artificial salts, but with the infinite 
 variety of complex mineral silicates. 
 
THE SILICATES. 503 
 
 The composition of anhydrous silica, on this theory, is as follows : 
 
 Per Cent. By Expt. 
 
 Silicon, 2 atoms =7-54-2 = 15 =48*39 48*275 
 Oxygen, i atom = 16+1 16 = 51*61 51*725 
 
 = Si,SiO = Sila silate. 
 
 The Chloride of Silicon is decomposed by water, and produces hydro- 
 chloric acid and hydrated silica ; thus : 
 
 SiCl 4- H,HO = H,SiO 4- HC1. 
 
 This hydrated silica H,SiO is the model of the neutral silicates. The 
 basic radical H is replaceable by any other basic radical. There are 
 other varieties of hydrated silicic acid besides this normal hydrate. 
 Doveri has shown that when it is air-dried at 60 F., its composition is : 
 
 H 2 ,Si 4 3 = 2(H,SiO) 4- Si,SiO; 
 and that when it is dried at 212 F., it becomes : 
 
 H 2 ,Si 8 5 = 2(H,SiO) 4- 3(Si,SiO). 
 
 We have consequently three, probably more, forms of hydrated silicic 
 acid ; 
 
 H,SiO, H 2 ,Si<0 3 , H 2 ,Si"0 5 , 
 
 all of which forms agree with many kinds of salts, both natural and 
 factitious. Thus, there are three precisely similar varieties of silicate of 
 ethyl, which are described in the following page. 
 
 Fluoride of Silicon = SiF = Sila fluora. When this gas acts upon 
 water, one-third of the silicon separates as hydrated silica, and the solu- 
 tion contains hydrofluosilicic acid : 
 
 SiF 4- SiF 4- SiF \ ]H,SiO 
 
 4-HHOf : \HF + 2(SiF). 
 
 This product HF 4- 2 (SiF) = HSi 2 F 3 is the hydrofluosilicic acid. 
 The H 1 is replaceable by many other basic radicals, which replacement 
 produces a variety of triple salts, called Silico-fluorides. 
 
 According to Berzelius's atomic weights, the preceding reaction is 
 commonly represented as follows : 
 
 3 SiF 3 4- 3 HO = 3 HF. 2 SiF 3 4- SiO 3 . 
 
 In this equation O = 8, and Si signifies 3 times 7 * 5 of silicon, and 
 this triple atom necessarily causes a triplication of all the other elements 
 that are concerned in the reaction. But even with this triplication, the 
 representation is not accurate, for SiO 3 represents anhydrous silica, 
 whereas the experiment produces hydrated silica, which demands 3 HO 
 in addition to what is scored in the above equation. 
 
504 
 
 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 Usual Formula;. 
 
 Proposed 
 Formula?. 
 
 3 NH 4 F . 
 
 2 SiF 3 
 
 ZH 4 Si 2 F 3 
 
 Al* F 3 . 
 
 2 SiF 3 
 
 Ale Si 2 F 3 
 
 3 Ba F . 
 
 2SiF 3 
 
 Ba Si 2 F 3 
 
 3Fe F . 
 
 2 SiF 3 
 
 Fe Si 2 F 3 
 
 Fe 2 F 3 . 
 
 2SiF 3 
 
 Fee Si 2 F 3 
 
 3Cu 2 F . 
 
 2SiF 3 
 
 Cu Si 2 F 3 
 
 3Cu F . 
 
 2SiF 3 
 
 Cue Si 2 F 3 
 
 3 Hg 2 F . 
 
 2SiF 3 
 
 Hg Si 2 F 3 
 
 3 Hg F . 
 
 2 SiF 3 
 
 HgcSi 2 F 3 
 
 3 H F . 
 
 2SiF 3 
 
 H Si 2 F 3 
 
 A comparison of these two equations shows that a great simplifi- 
 cation of formulae is produced by adopting the small atomic weight for 
 silicon = 7 ' 5. I may add a few examples to show this difference : 
 
 SILICO-FLUORIDES, 
 
 Of Ammonium . . 
 Aluminum . . 
 Barium 
 Iron (ferrous) 
 Iron (ferric) . . 
 Copper (cuprous) 
 Copper (cupric) . 
 Mercurous 
 Mercuric . . . 
 Hydrogen . . . 
 
 The analytical form of the proposed formulas is H r F + 2(SiF) where 
 H r is the replaceable atom. The names of such salts may be chosen 
 to suit either the synoptical or the analytical formulas ; thus : 
 
 HSi 2 F 3 = Hydra silen fluorine. 
 
 HF -f (SiF) 2 = Hydra fluora bis sila fluora. 
 FeSi 2 F 3 = Ferrous silen fluorine. 
 
 FecF + (SiF) 2 = Ferric fluora bis sila fluora. 
 
 Silicates of Ethyl. I have quoted the composition of one silicate of 
 ethyl; but Ebelmen has described three varieties (Gmelin's Handbook of 
 Chemistry, viii. 478-81). 
 
 Gmelin's Formulae. Proposed Formulae. 
 
 Disilicate of ethyl = 2C 4 H 5 O, SiO 8 C 2 H 5 ,Si O 
 
 Monosilicate of ethyl = OHK), SiO 2 (C 2 H 5 ) 2 ,Si 4 O 3 
 Bisilicate of ethyl = C 4 H 5 O,2SiO 2 (C 2 H 5 ) 2 ,Si 8 O 5 
 
 These three varieties of silicate of ethyl correspond with the three 
 descriptions of hydrated silicic acid referred to at page 503. I do not 
 however admit these salts to be, as Colonel Yorke suggests, salts of 
 different acids, but simply different kinds of multiple silicates : 
 
 The Monosilicate, being The Bisilicate, being 
 a triple salt : a fivefold salt . 
 
 C 2 H 5 ,SiO C 2 H 5 ,SiO 
 
 C 2 H 5 ,SiO C 2 H 5 ,SiO 
 
 Si ,SiO Si ,SiO 
 
 Si ,SiO 
 Si ,SiO 
 
 Bis ethyla si late Bis ethyla silate 
 
 cum sila silate. tris sila silate. 
 
 The Disilicate, being 
 
 the normal salt : 
 
 C 2 H 5 ,SiO 
 
 Ethyla silate. 
 
THE SILICATES. 505 
 
 For if we consider a difference in the proportion between the basic 
 radicals and the silicon, or between the silicon and the oxygen, to be, 
 in each case, the indication, or the proof, of the existence of a different 
 silicic acid, we must prepare ourselves to accept of at least a HUNDKED 
 Silicic Acids, for it would be easy to point out that number of varieties 
 in the formulae of well-known natural or artificial silicates. 
 
 Silicate of Amyl. I have described this salt by the formula C 5 H u ,SiO : 
 Varrentrap describes it as 3C 10 H u O.Si0 3 ; Gmelin as 2C 10 H 1I O,Si0 2 
 = C a) H 22 SiO 4 ; Gerhardt as C 40 H 44 8 Si 4 = 4(C 10 H"0,SiO). These high 
 numbers result solely from the false estimate taken of the weight of the 
 atom of silicon. Gmelin's Si = 7 5 -f 2 ; the others = 7*5 + 3. One 
 of these numbers causes duplication, and the other triplication of all the 
 elements associated with the silicon. 
 
 I pass now to the consideration of MINERAL SILICATES, the compo- 
 sition of which I propose to explain in accordance with the notion that 
 MSiO expresses a neutral or normal silicate, the M or basic radical in 
 which is replaceable by hydrogen, or by any metal, either of the basylous 
 order or basylic order, the difference between which I have explained at 
 page 33. 
 
 The normal silicates thus formed, of all the different orders = H,SiO, 
 R,SiO, and Kc,SiO, can combine with one another, and also with an- 
 hydrous silica = Si,SiO, and with salts formed on the model of water 
 = H,HO, H,MO, and M, MO. Thence arise all the varieties of natural 
 and factitious silicates neutral, acid, and basic. 
 
 It follows from these premises, that every silicate contains twice as 
 many radicals as it contains atoms of oxygen. Thus every simple 
 silicate is MSiO, and every complex silicate is 
 
 in which R signifies any basylous atoms, such as H, K, Na, Ba, Fe, 
 Mn, &c., and Re signifies any basylic atoms, such as Ale, Fee, Mnc, &c., 
 while x, y, z, are collectively equal to two atoms, the quantity of oxygen 
 being one atom. 
 
 There does not seem to me to be the slightest probability that, in the 
 formation of the complex silicates, there is first produced a complex 
 silicic acid, containing a multiple number of atoms of silicon, and that 
 this complex acid then combines with an equally complex base containing 
 a multiple number of basic radicals. On the contrary, I consider the 
 complex silicates to be formed by simple silicates combined with one 
 another, atom after atom, and that each step in this additive process 
 produces a special silicate. I hope to make this notion clear by means 
 of the formulae that are given in TABLE I. 
 
506 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 TABLE I. THEORETICAL CONSTITUTION OF SILICATES. 
 A. B. C. D. E. 
 
 MMO+ SiSiO-f 4MSiO+ 2MSIO+ MSiO-f 
 nMSiO nMSiO nSiSiO wSiSiO nSiSiO 
 
 M M 
 
 Si Si 
 
 
 
 
 M 
 
 Si k 
 
 M 3 Si O 2 k 
 
 M Si 3 O 8 k 
 
 
 
 
 M 
 
 Si 3 2 k 
 
 M* Si 2 O 3 k 
 
 M 2 Si 4 O 3 k 
 
 
 
 M 2 Si 4 O 3 d 
 
 M 
 
 Si 5 O 3 k 
 
 M 5 Si 3 O* 
 
 M 3 Si 5 O 4 k 
 
 
 
 M 2 Si 6 O 4 d 
 
 M 
 
 Si 7 O 4 
 
 M 6 Si 4 O 5 k 
 
 M 4 Si 6 O 5 k 
 
 M 4 
 
 Si 6 O 5 d 
 
 M 2 Si 8 O 5 k 
 
 M 
 
 Si 9 O 5 k 
 
 M 7 Si 5 O 6 k 
 
 M 5 Si 7 O 6 
 
 M 4 
 
 Si 8 O 6 d 
 
 M 2 Si 10 6 d 
 
 M 
 
 Si"0 6 
 
 M 8 Si 6 O 7 k 
 
 M 6 Si 8 7 k 
 
 M 4 
 
 Si 10 O 7 k 
 
 M 2 Si 12 7 k 
 
 M 
 
 Si ,3 7 
 
 M 9 Si 7 O 8 
 
 M 7 Si 9 O 8 
 
 M 4 
 
 Si l2 8 d 
 
 M 2 Si u 8 d 
 
 M 
 
 Si 15 8 
 
 M 10 Si 8 9 k 
 
 M 8 Si 10 9 k 
 
 M 4 
 
 Si l4 O 9 
 
 M 2 Si I6 O 9 k 
 
 M 
 
 Si lr O 9 
 
 M ll Si 9 QIC 
 
 M 9 Si^O 10 
 
 M 4 
 
 Si 16 10 d 
 
 M 2 Si 18 lo d 
 
 M 
 
 Si 19 10 
 
 M l8 Si lp O u k 
 
 M l Si 1? O n k 
 
 M 4 
 
 SWk 
 
 M 2 Si 20 O u 
 
 M 
 
 Si 2 '0 u 
 
 M 13 Si I 1() 12 
 
 M"Si l3 12 
 
 M 4 
 
 Si 20 12 d 
 
 M 2 Si s? 0' 2 d 
 
 M 
 
 Si^O 12 
 
 M u Si 12 O 18 k 
 
 M l2 Si u 13 
 
 M 4 
 
 Si 22 O 13 
 
 M 2 Si^CPk 
 
 M 
 
 Si^O 13 
 
 M l5 Si 13 14 
 
 M 13 Si I5 14 
 
 M 4 
 
 Si 24 14 d 
 
 M 2 Si 26 14 d 
 
 M 
 
 Si 27 u 
 
 M I Si U ,5 
 
 M 14 Si 16 O l5 k 
 
 M 4 
 
 Si 26 O 15 
 
 M 2 Si^O^k 
 
 M 
 
 Si 29 O 15 
 
 In this Table, Si = 7- 5 . O = 16. 
 
 Column A. It is supposed that a salt formed on the model of water 
 = M,MO combines with a normal silicate = M,SiO, atom after atom, 
 to produce the series of silicates that are here represented, and perhaps 
 others that are beyond the limits of the Table. 
 
 Column B. In this case it is supposed that an atom of anhydrous 
 silica = Si,SiO combines with a normal silicate = M,SiO, atom after 
 atom, to produce another series of silicates, necessarily differing in con- 
 stitution from the former. The salts represented in Column A. all 
 contain a small excess of base. Those of column B., an equal excess of 
 acid. 
 
 Column C. This column begins with the salt M 4 Si 6 O 5 , which is sup- 
 posed to be transferred from column B., and to have been formed by 
 the addition of 4MSiO to SiSiO. The operation is now considered to 
 be reversed, and the anhydrous acid SiSiO is added instead of the salt 
 MSiO, atom by atom, to the salt M 4 Si 6 O 5 , so as to produce the series 
 of superacid salts given in this column. 
 
 Column D. In this case the salt M 8 Si 4 O 3 , transferred from column B., 
 is increased by successive additions of SiSiO, till it forms the series of 
 salts represented in the Table. Nearly all the varieties of "Glass" 
 belong to the silicates that are inscribed in this column. 
 
 Column E. The salts depicted in this column are produced by the 
 combination of the neutral silicate = MSiO with successive atoms of 
 anhydrous silica = SiSiO. The salts are consequently all acid salts. 
 
THE SILICATES. 
 
 507 
 
 ' The letter R frequently inserted in this Table intimates that the 
 silicates so marked are known and of frequent occurrence. The letter d 
 signifies that the salts are duplicates, and that similar, and more generally 
 simpler, formulae will be found in other columns of the Table. 
 
 The foregoing theory is now to be applied to the investigation of 
 mineral silicates. 
 
 TABLE II. CONSTITUTION OF THE CHIEF VARIETIES OF KNOWN 
 MINERAL SILICATES. 
 
 
 RAMMELSBERG'S FORMULA. 
 
 GRIFFIN'S 
 
 . 
 
 B. 
 
 C. 
 
 FORMULA. 
 
 Oxygen of the 
 
 Silicates of 
 
 Silicates of 
 
 D. 
 
 Base. Acid. 
 
 Protoxides. 
 
 Sesquioxides. 
 
 
 I. I 12 
 
 RO,4Si0 3 
 
 R 2 O 3 ,i2SiO 3 
 
 R 2 Si 24 13 
 
 2. 
 
 9 
 
 RO, 3 SiO 3 
 
 R 2 3 , 9 Si0 3 
 
 R Si 9 O 5 
 
 3- 
 
 6 
 
 RO,2Si0 3 
 
 R 2 3 , 6Si0 3 
 
 R 2 Si 12 7 
 
 4- 
 
 41 
 
 2RO, 3 SiO 3 
 
 2 R 2 3 , 9 Si0 3 
 
 R 4 Si w O" 
 
 5- 
 
 4 
 
 3 RO,4Si0 3 
 
 R 2 3 , 4S10 3 
 
 R 2 Si 8 O 5 
 
 6. 
 
 3 
 
 RO, SiO 3 
 
 R 2 3 , 3 Si0 3 
 
 R Si 3 O 8 
 
 7- 
 
 2 
 
 3 RO,2SiO 3 
 
 R 8 3 , 2Si0 3 
 
 R 8 Si 4 O 3 
 
 8. 
 
 
 ~s 
 
 2RO, SiO 3 
 
 2R 2 3 , 3 Si0 3 
 
 R 4 Si 6 O 5 
 
 9- 
 
 
 
 3 RO, SiO 3 
 
 R 2 3 , SiO 3 
 
 RSi O 
 
 10. 
 
 3 
 
 
 4RO, SiO 3 
 
 4R 2 O 3 , 3 Si0 3 
 
 R 8 Si 6 O 7 
 
 u. 
 
 1 
 
 
 9 RO,2Si0 3 
 
 3 R 2 3 , 2Si0 3 
 
 R 6 Si 4 O 5 
 
 12. 2 
 
 
 6RO, SiO 3 
 
 2R 2 3 , SiO 3 
 
 R 4 Si O 3 
 
 I 3- 3 3 
 
 
 9 RO, SiO 3 
 
 3 R 2 3 , SiO 3 
 
 R 3 Si O 2 
 
 Rammelsberg's Nomenclature of the above Salts. 
 
 i, Fourfold silicates. 2, Threefold silicates. 3, Twofold silicates. 
 4, One-and-a-half fold, or sesquisilicates. 5, Four-thirds silicates. 
 6, Neutral or normal silicates. 7, Two-thirds, or half basic silicates. 
 8, Half or basic silicates. 9, One-third, or twofold basic silicates. 
 10, One- fourth, or threefold basic silicates, n, Two-ninths, or three- 
 and-a-half-fold basic silicates. 12, Sixth, or five-fold basic silicates. 
 13, Ninth, or eight-fold basic silicates. 
 
 In Rammelsberg's formula, S = 22*5, O = 8, 
 In column D., S = 7 5, O = 16. 
 
 TABLE II. is extracted from the "Einleitung" to Rammelsberg's 
 Handworterbuch des chemischen Theils der Miner alogie, Berlin, 1841, a 
 work of great utility to all who study the chemistry of mineralogy. 
 
 According to Rammelsberg, who follows closely the system of 
 Berzelius and the Berlin school of chemists and mineralogists, the 
 silicates are divided into two categories the silicates of protoxides, and 
 
508 THEORY OF POLYBAS1C AND CONJUGATED ACIDS. 
 
 the silicates of sesquioxides. These require the formulae exhibited in the 
 Table, in columns B. and C. 
 
 Innovations suggested, i]. The atomic weight of silicon is to be 
 reduced from 22*5 to 7 * 5. 2]. The atomic weight of oxygen is to be 
 raised from 8 to 16. 3]. Every sesquioxide is to be considered to 
 contain not R 2 but Re 3 , that is to say, not two combined basylous atoms, 
 but three separable basylic atoms. 
 
 Effect of these Innovations, i]. All the formulae in column B. are 
 transformed into those represented in column D. 2]. All the formula 
 in column C. are transformed into those represented by column D., 
 excepting that, instead of R., it is necessary to write Re. By these trans- 
 formations, the formulae that represent basylic silicates are made to agree 
 in atomic quantities with those that represent basylous silicates ; whereas 
 the formulae of column C. are atomically three times as great as those of 
 column B. These changes are of importance when considered in 
 relation to what the chemical mineralogists, by a peculiar figure of 
 speech, call rational formulae ; for it appears to me that the formulas 
 which commonly bear this title are singularly irrational. 
 
 TABLE III. (except the last column) is an extract from a larger Table 
 of the same kind which is given in Rammelsberg's Drittes Supplement 
 zu dem Handworterbuch des chemischen Theils der Mineralogie, Berlin, 
 1847. The object of this Table is to show the relation that exists 
 between the oxygen of the water, of the protoxides, of the sesquioxides, 
 and of the anhydrous silicic acid contained in various classes of silicates. 
 I have added the last column to show my view of the constitution of the 
 same salts. 
 
 The alterations which I have made in the atomic weights of oxygen, 
 silica, alumina, &c., necessarily affect the formulas of the silicates to a 
 great extent ; but there is one consequence which is extremely remark- 
 able, and, which, though it follows as a mathematical necessity, I had 
 not foreseen, and first noticed with surprise. 
 
 Rammelsberg gives in this Table simple numbers to intimate the 
 relations which the oxygen of the different radicals of the silicates bear 
 to one another. These are stated in column B. of the Table. 
 
 Now, according to my atomic weights, these numbers, just as they 
 stand, (and the observation applies to the whole of Rammelsberg's 
 Table as well as to the short extract from it which is given as a specimen 
 in Table III.) these numbers express the numbers of the radicals that 
 are present in each silicate, and are collectively twice as great as the total 
 number of the atoms of oxygen. Consequently, the formation of formula? 
 in accordance with the radical theory is simple in the highest degree, as 
 will be seen on comparing the formulae in the last column of Table III. 
 with the formulae in the preceding columns. 
 
 Rammelsberg's formulae as given in this Table are intended to show 
 
THE SILICATES. 
 
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 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
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THE SILICATES. 
 
 511 
 
 only the relative quantities of acids and bases contained in the respective 
 salts, namely, the number of atoms of protoxides, of alumina, of silica, of 
 water, &c. The formulae which chemical mineralogists are pleased to 
 call Rational, are given in the second column of Table IV. 
 
 TABLE IV. RATIONAL FORMULAE OF THE SILICATES. 
 
 Anhydrous Silicates with one Protoxide. 
 RAMMELSBERG'S FORMULAE. GRIFFIN'S FORMULAE. 
 Trisilicate of lime CaO ,SiO 3 CaSi 3 2 
 
 Wollastonite . . 3 CaO ,2Si0 3 Ca 2 Si 4 3 
 
 Gadolinite . . 3YO ,SiO 3 YSiO 
 
 Williamite . . 3ZnO ,SiO 3 ZnSiO 
 
 Augite(rnangan.) 3MnO ,2SiO 3 Mn 2 Si 4 3 
 
 Phenakite . . 3BeO ,2SiO 3 G 2 Si 4 3 
 
 Hydrous Silicates with one Protoxide. 
 
 Meerschaum . MgO ,SiO 8 + HO 
 Dioptase . . 3CuO ,2SiO 3 + 3HO 
 Silicate of manga- 3MnO ,Si0 3 + 3HO 
 
 nese. 
 Okenite . . . 3 CaO ,4Si0 3 +6HO 
 
 Anhydrous Silicates with one 
 
 Cyanite . . . 3APO 3 ,2Si0 3 
 Zircon . . . Zi^O 3 ,Si0 3 
 Agalmatolite . A1 2 O 3 ,3Si0 3 
 Bamlite . 
 Bucholzite 
 
 H 2 Mg 2 Si 6 5 
 
 HCucSi'O 2 
 
 H 2 Mn 2 Si 2 3 
 
 H 4 Ca 2 Si 2 7 
 
 Alc 6 Si 4 O 5 
 
 ZrSiO 
 
 AlcSi 3 2 
 
 Alc 4 Si 6 O 5 
 
 AlcSiO 
 
 Worthite 
 Erenite , 
 Cimolite 
 
 Augite . 
 OH vine . 
 Bustamite 
 Troostite . 
 Knebelite 
 
 Beryl 
 Ditto . 
 Euclase 
 
 APO 3 ,Si0 3 
 
 Hydrous Silicates with one 
 (5AP0 3 ,Si0 3 )+(AP0 3 +3HO)HAlc 6 Si 5 O 6 
 
 A1 2 3 ,2Si0 3 
 A1 2 3 
 
 6HO 
 
 H 4 Alc 2 Si 4 5 
 
 H 2 Alc 2 Si 6 5 
 
 Anhydrous Silicates with several Protoxides. 
 
 . (Ca,Mg,Fe,Mn) 3 O 3 ,2Si0 3 (Ca,Mg,Fe,Mn) 2 Si 4 O 3 
 
 . (Mg,Fe) a 3 ,Si0 3 (Mg,Fe)SiO 
 
 . 3CaO,2SiO 3 + 2(3MnO,2SiO 3 )Ca*Mn 4 Si 12 O 9 
 
 . 3 FeO,2Si0 3 + 3( 3 MnO,Si0 3 ) Fe 2 Mn 6 Si IO O 9 
 
 . 3FeO,SiO 3 + 3MnO,SiO 3 FeMnSi 2 O 2 ' 
 
 Anhydrous Silicates with several Sesquioocides. 
 
 , . Be0 3 ,4SiO 3 4. 2(AFO 3 ,2SiO 3 ) G 2 Alc 4 Si 16 O u 
 , Be0 3 , 3 Si0 3 + 2(^Al s 3 , 3 Si0 3 ) GAlc 2 Si 9 O 6 
 . BeO } Si0 3 + 2(AP0 3 ,Si0 3 ) GAlc 2 Si 3 3 
 
512 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 Anhydrous Silicates with both Protoxides and Sesquioxides. 
 
 Felspar . . . KO ,SiO 3 +Al ? O 3 ,3Si0 3 KAlc 3 Si ly O 8 
 
 Albite . . . NaO,SiO 3 + APC^SiO 3 NaAlc 3 S 12 8 
 
 Leucite . . . 3KO,2SiO 3 + 3(Al 2 O 3 ,2SiO 8 ) KAlc 3 Si 8 6 
 
 Vesuvian. . . 3RO,SiO 3 + R'O 3 ,SiO 3 RRcSi 2 O* 
 
 Garnet . . . 3RO,SiO 8 + R 2 O 3 ,SiO 3 RRcSi 2 O 2 
 
 Hydrous Silicates with loth Protoxides and Sesquioxides. 
 
 f CaO,SiO s + Al 2 3 , 3 SiO 3 + 6HO. Rammelslerg. 
 ' ' \ H 6 Ca 1 Alc 3 Si l8 11 . Griffin. 
 
 r , , . .. j (Ca,Na,K)0,Si0 3 + Al s 3 , 2 Si0 3 +6HO? Xammelsberg. 
 
 ' ] H*(K,Na,Ca) l Ald > Si 9 0? -Griffin. 
 
 , .. j CaO,Si0 3 + Al 2 3 ,Si0 3 + 3HO. Rammelsberg. 
 
 Scolezite. . H . Ca . Alc . sw g^* 
 
 NaO,SiO 8 + Al*0 3 ,Si0 3 + 2 HO. Xammelsberg. 
 H < Na l Alc 3 Si 6 6 . Griffin. 
 
 A ,. j ^NaO,2Si0 3 + 3(Al 2 3 ,2Si0 3 )+6HO. Xammelsberg. 
 
 Analcime . ^ 
 
 J 
 ' \ 
 
 3CaO,2Si0 3 + 3 (AFO 3 ,2Si0 3 ) + i2HO. Rammelsberg. 
 ' \ H 4 Ca l Alc 3 Si 8 8 . Griffin. 
 
 TABLE IV. is an extract from a Table, comprehending all known 
 silicates, which is given in the second volume of Rammelsberg's ffand- 
 wdrterbuch, already quoted. In the second column of this Table we 
 have the so-called " rational formulae " of the different silicates. This 
 term is used to signify that we have here an account of what is com- 
 monly considered to be the proximate constitution of the substances. 
 
 In this Table, the rational formulas are tolerably simple, excepting a 
 few near the lower end ; but the rational formula?, constructed for many 
 other minerals, are excessively complicated, as I shall presently show. 
 
 Let us endeavour to ascertain what is the actual value of these rational 
 formulas. Take the last in the list, that of Laumonite, as an example. 
 This mineral, according to the information supplied in Table III., con- 
 tains 3CaO, 3A1 2 3 , SSiO 3 , I2HO; and, in Table IV., these substances 
 are put into the form of the following rational formulaB : 
 
 3 CaO, 2Si0 3 + 3 (A1 2 3 , 2Si0 3 ) + I2HO. 
 
 For this classification of the elements of the salt there is no evidence 
 whatever. First, we have a salt in which three atoms of lime are 
 assumed to be combined directly with two atoms of silicic acid, a mode 
 of combination which agrees, indeed, with the law respecting what is 
 called " combination in multiple proportions," but not with the laws of 
 nature, which preside only over binarv combinations ; nor even with the 
 
THE SILICATES. 513 
 
 law of Berzelius, that a salt must contain an atom of acid for every atom 
 of oxygen which is present in the base. Then, one atom of this irregular 
 salt is assumed to be combined directly with three atoms of another 
 irregular salt in which one atom of alumina A1 2 3 is stated to be com- 
 bined with two atoms of silicic acid. Finally, there are twelve atoms of 
 hydrogen set aside as water, without any attempt to prove that none of 
 it exists in the salt in any other condition. The formula, therefore, is 
 crammed with assumptions that are taken, without evidence, for facts, 
 and its use is to make difficult of comprehension what otherwise is 
 simple and clear for 
 
 Take, on the contrary, the formula which is supplied for the same 
 mineral by the radical theory, and which is 
 
 We can trust this formula, because the quantities are the result of 
 analysis, and because every radical which it represents is known to be 
 the equivalent of a volume of hydrogen. The compound contains eight 
 simple silicates, which the formula makes known at a glance. Nothing 
 would be gained by converting this unitary formula into a rational 
 formula : 
 
 Thus, Or thus, Or thus, 
 
 Ca ,SiO Ca SiO + HSiO Ca ,SiO 
 
 Alc,SiO AlcSiO + HSiO 3Alc,SiO 
 
 Alc,SiO AlcSiO + HSiO /j.H ,SiO. 
 
 Alc,SiO AlcSiO + HSiO. 
 
 H ,SiO 
 H ,SiO 
 H ,SiO 
 H ,SiO. 
 
 These formulas are useless, because all the information which they give 
 is given at a glance by the unitary formula without needless display. 
 And that great advantage results from giving to all the elements of the 
 silicates such equivalents or atomic weights as level the whole to uni- 
 form simplicity. I do not admit of the existence of sesquioxides in sili- 
 cates. I recognise therein the presence of salts formed on the model of 
 water = H,HO ; M,SiO, &c., and these alone. 
 
 Before I conclude the description of Laumonite, I may point out the 
 difference that exists between the number of atoms which are demanded 
 by Berzelius's notation, as employed by Rammelsberg, to represent the 
 composition of that mineral and the number which is demanded by the 
 radical theorv. 
 
 2 L 
 
No. of Atoms 
 
 No. of Atoms 
 
 No. of Atoms 
 
 in 
 
 when corrected 
 
 after 
 
 Rammelsberg's 
 
 for new 
 
 Division 
 
 Formulae. 
 
 Atomic Weights. 
 
 by 3. 
 
 3 
 
 3 
 
 I 
 
 12 
 
 12 
 
 4 
 
 6 
 
 9 
 
 3 
 
 8 
 
 24 
 
 8 
 
 . 48 
 
 24 
 
 8 
 
 514 THEORY OF POLYBASIC AND CONJUGATED ACIDS. 
 
 ELEMENTS. 
 
 Ca. . 
 
 H . . 
 
 Al. . 
 
 Si . . 
 
 o . . 
 
 77 72 24 
 
 A glance over the preceding Tables will show that this great reduction 
 in the number of atoms takes place generally when the formulae are 
 recast to suit the radical theory ; and it affords a powerful argument 
 against those absurd and troublesome marplots the sesquioxides, to 
 the imagined presence of which the formulae of the natural silicates are 
 indebted for most of their extravagance. So long as chemical mineralo- 
 gists persist in introducing sesquioxides into their formulae of silicates'; 
 so long as they continue to patronize the doctrine of combination in 
 multiple proportions ; so long as they exclude from their comprehension 
 the facts, that a silicate is a very simple salt, and that simple silicates 
 combine with one another to make complex silicates ; just so long must 
 their "rational" formulae be models of irrational modes of thought ; just 
 so long must they be fancy sketches, based upon guesses, incapable of 
 proof, unworthy of credit puzzling, useless, obstructive. 
 
 COMPLEX SILICATES. 
 
 I will quote a few examples of complicated silicates, to show in what 
 manner the new method of notation is qualified to meet the difficulties 
 which they present. 
 
 AUGITE. In the foregoing Tables I have quoted the manganese 
 augite = 
 
 3MnO,2SiO 3 Rammelsberg. 
 Mn 2 Si 4 Griffin. 
 
 The manganese of this mineral is subject to be replaced by Ca, Mg, 
 Fe, in various proportions, without any other change taking place in the 
 composition of the mineral. Consequently these varieties are obtained : 
 
 a. Mn 2 Si 4 O 3 
 
 b. Ca'Mg 1 Si 4 O 3 
 
 (Ca 1 Mn 2 ) 2 Si 4 3 
 (Ca'MgW) 2 Si 4 3 
 (Ca,Mg,Fe,Mn) 2 Si 4 O 3 
 
 c. Ca'Fe 1 Si 4 3 
 
 a. 
 
 Examples of Rammelsberg's formulae for these minerals : 
 
 For 6. 3MgO,2Si0 3 + 3CaO,2SiO 3 . 
 For/. 2 (3MgO,2Si0 3 ) -f 3( 3 CaO,2Si0 8 ) 
 
THE SILICATES. 515 
 
 The condensed, or synoptical formula/, can be easily expanded to an 
 analytical formula representing whole atoms, as follows : 
 3Ca ,SiO. 
 
 R 6 Si 12 O 9 = 2 p I e g 'g)o' In makin g this change of formula it is to be 
 
 3 Si JSKX 
 
 observed that the basic portion of formula /, namely (Ca^g^e 1 ) 2 , sig- 
 nifies Ca|,Mg|,Fe| , of two atoms. If these fractions are made into 
 whole numbers, the two atoms become six atoms, or are multiplied by 
 three, in which case the silicon and the oxygen of the salt must also be 
 multiplied by three. 
 
 CHABASITE. Among many formulae for this mineral, Rammelsberg 
 gives the following : 
 
 [ 3 CaO,2Si0 3 + 3 (Al 2 3 ,2SiO 3 ) + i8HO] 
 + 2 [ 3 NaO,2Si0 3 + 3(AP0 3 ,2Si0 3 ) + iSHOJ. 
 
 This formula contains the following ultimate atoms: 3Ca,6Na,54H, 
 i8Al,24Si,i62O, in all 267. When the atomic weights are corrected, 
 they become 3Ca,6Na,54H,27Alc,72Si,8iO; in all 243. When these 
 corrected numbers are uniformly divided by 9, they produce the following 
 formula : 
 
 H 6 (Na 2 Ca I ) 1 Alc 3 Si 8 9 . 
 
 Gmelin's formula for this soda chabasite (which is also called Gmelinite) 
 is = 2NaO,iCaO,3Al 2 3 ,i2SiO 2 ,i8HO. This formula is equivalent to 
 the above. His formula for lime chabasite is iNaO,3CaO,4Al 2 3 ,i6SiO 8 , 
 24HO, which produces the formula 
 
 H 6 (Na 1 Ca 3 ) 1 Alc 3 Si 8 9 . 
 
 It is remarkable that Gmelin's two formulae differ considerably in the 
 proportions of silica, alumina, and water. Yet, when they are recast to 
 suit the radical theory, they harmonize exactly, and prove that the actual 
 differences between the two salts exist only in the quantities of sodium 
 and calcium, all other elements remaining the same. The new formulae 
 show this fact significantly : the others conceal it. 
 
 p H 6 (Na 2 Ca 1 ) 1 Alc 3 Si 8 9 , 
 
 Compare- H 6 (Na 1 Ca 3 yAlc 3 Si 8 O 9 , 
 
 2NaO, i CaO,3 Al 2 3 ,i 2SiO 2 , 1 8HO. 
 
 iNaO,3CaO,4A! 2 3 , i6SiO 2 ,24HO. 
 
 Upon first looking at the last two formulae, it seems impossible that the 
 minerals can agree precisely with one another in their proportions of 
 hydrogen, aluminum, silicon, and oxygen ; yet they do so, and by doing 
 so they show how faulty is the existing theory which succeeds in 
 smothering facts of such importance. 
 
 2 L 2 
 
516 THEORY OF POLYBAS1C AND CONJUGATED ACIDS. 
 
 VESUVIAX. Idocrase. Gmelin gives the general formula 3CaO, 
 2SiO 8 + AP0 8 ,SiO 2 . This becomes reduced to CaAlcSi 2 O 2 . 
 
 Rammelsberg's formula is 3RO,SiO 3 +R 2 O 8 ,SiO 3 ; which yields the 
 same result. 
 
 Gmelin gives the following formula, which exhibits the vicarious 
 elements of this mineral. 
 
 49CaO, 5MgO, 2Fe 2 O 3 , i6APO 3 , 54SiO 2 , with an atomic weight of 
 4125 "2. This formula permits the following reduction : 
 
 Ca Mg Fe Al Si O 
 
 49 5 4 32 54 216 = Gmelin's atoms. 
 
 49 5 6 48 1 08 1 08 = After correcting the atomic weights. 
 
 54 54 108 108 
 
 i 122= Division by 54. 
 
 Hence the formula? of this complicated salt is in round numbers 
 Ca l Alc 1 Si 2 2 , or, with almost perfect accuracy : 
 
 8Ca SiO 
 
 Ca 8 Mg 1 Fec 1 Alc 8 Si 18 18 = 
 
 iMgSiO 
 SAlcSiO 
 iFecSiO. 
 
 FUCHSITE. Dr. Schafhautl supplies the following formula for 
 Fuchsite (Gmelin 1 s Chemistry, iii. 450). 
 
 38 ( 3 KO,Si0 3 )-f 2 ( 3 NaO, Si0 3 ) + 
 
 360 (Al 2 3 ,Si0 3 ) -f 24 (Cr 3 3 , 3 SiG 3 ) + 
 
 1 8 (MgO,Si0 3 )-f 12 (Fe 2 3 , 3SiO 3 ) + 
 
 9 CaF 2 . 
 
 Bravo ! This is the ne plus ultra of chemical accuracy ! So charming 
 a performance deserves an attentive examination. The ultimate atoms 
 here represented are U4K, 6Na, i8Mg, 24Fe, 480, 72oAl, 5268!, 
 29040, gCa, i8F; in all 4387. When the atomic weights are cor- 
 rected, the number of atoms becomes 4383, and they permit of arrange- 
 ment into simple silicates in accordance with the radical theory as follows : 
 1080 Alc,SiO) 
 
 72 Crc,SiOU 1 188 = 9 (Alc 30 Crc'Fec 1 ) 1 ,SiO 
 36 Fec,SiOJ 
 1 8 Mg,SiO) 
 114 K ,SiOU i38 = i( K^VMg 1 V,SiO 
 
 6 Na ,SiOJ 
 126 Si ,SiO =126 = 1 Si ,SiO 
 
 1452 Neutral silicates. 
 
 = (KNaMg) l (AlcCrcFec) 9 Si 19 O ll + T VCaF; 
 nearly equal to KAlc 9 Si' 2 O n + T VCaF, and not very far from AlcSiO. 
 
THE SILICATES. 517 
 
 These details show that Dr. SchafhautTs giant formula is of no more- 
 use than the shortest possible formula. The affectation of marvellous 
 accuracy in analysis which this formula displays, goes for nothing, 
 because we know that such a degree of accuracy is beyond the power 
 of human manipulation. The short formula gives us an idea of the 
 composition of this mineral. The comprehension of Dr. Schafh'autl's 
 formula is about as easy as the comprehension of the distances of the 
 fixed stars, expressed in lines or millimetres. 
 
 These examples are sufficient to show in what manner I propose to 
 formulate the natural silicates. I double the atomic weight of the 
 oxygen ; reduce the atom of silicon to one-third of Berzelius's number or 
 to one-half of Gmelin's number ; and dismiss the sesquioxides in a body. 
 The formulae, written on the model of (R*Rc y Si*) 2 O', then become simple 
 and uniform. 
 
 It may perhaps be objected that the formulae which I recommend for 
 the designation of the silicates are unitary, whilst I have in other sections 
 of the work strongly objected to the use of unitary formulae. I reply to 
 that objection, that the formulae of the silicates are unitary by necessity, 
 and that nevertheless they differ entirely in nature from the unitary 
 formulae which are often applied to the hydrocarbon salts. In the 
 next section I shall show that the unitary formulae C 16 H 32 O* exhibit the 
 composition of sixteen different salts, which contain sixteen different 
 basic radicals, and sixteen different acid radicals ; the presence and 
 composition of not one of which can be inferred from the inspection 
 of the formula C 16 H 32 O 8 . No such difficulty can possibly occur from 
 the use of the formulas which I have recommended for the silicates. 
 
 I do not enter upon the consideration of the Classification and 
 Nomenclature of the Silicates. The number of vicarious atoms which 
 they contain renders the construction of a convenient System and the 
 application of a correct Nomenclature a matter of difficulty, for the dis- 
 cussion of which no space is left in this volume. 
 
 With this section I conclude my investigation into the constitution of 
 the polybasic and conjugated acids; not because the subject is ex- 
 hausted, but because the figure at the top of this page warns me of the 
 necessity of bringing the discussion to a conclusion. I set out with the 
 expression of the opinion, that every normal salt is a binary compound, 
 consisting of one basic radical and one acid radical. I hope that the 
 facts and arguments which I have advanced in the course of the 
 discussion will have satisfied the reader that this opinion was advanced 
 with reason. It is a point of considerable importance in chemical 
 philosophy. Conjugated and polybasic acids, like complicated organic 
 bases, are obstacles to the progress of chemical science. I have 
 
518 THE ALUMINOUS AND ALUMIX1C RADICALS. 
 
 endeavoured to expose the fallacies upon which they are founded, and I 
 shall rejoiee if that exposure helps to destroy their credit. 
 
 The Aluminous and Aluminic Eadicals. 
 
 In the Table of Atomic Weights, I have ascribed two equivalents to 
 Aluminum: the aluminous equivalent, Al = 15.65, and the alum in it- 
 equivalent, Ale = 9.1 ; the latter corresponding to the ferric atom, 
 and the former to the ferrous atom. 
 
 I have been induced to suggest two equivalents of aluminum, in con- 
 sequence of the results of the recent experiments of Mr. Crum, one of 
 which is represented in the following diagram : 
 
 AlcSO 2 
 
 AlcSO 2 + 
 
 AlcSO* 
 
 Pb,C 2 H 3 8 
 
 Pb,C 2 H 3 O 2 
 
 Pb,C 2 H 3 2 
 
 Produce 
 
 Pb,S0 2 ) 
 Pb,SO 2 l 
 Pb,SO 2 ) 
 A1,C 2 H 3 O 3 
 A1,C 2 H 3 8 
 C*H 3 2 
 
 Kamely, an atom of the compound commonly called Tersulphate of 
 alumina, mixed with 3 atoms of acetate of lead, produce 3 atoms of sul- 
 phate of lead, i atom of binacetate of alumina, and I atom of free acetic 
 acid. That is to say, as much alumina as saturates 3 atoms of sulphuric 
 acid, can saturate only 2 atoms of acetic acid. 
 
 I am inclined to explain this result, by supposing that the 3 aluminic 
 atoms in the sulphate are converted during the' process of double decom- 
 position, into two aluminous atoms, which take up two atoms of acetic 
 acid, and leave the third atom free. The free acid is left, however, 
 without a base. If it takes H from the water of the solution to supply 
 that want, either oxygen must be liberated, or peroxide of hydrogen be 
 dissolved in the mixture. Thus : 
 
 C 2 H 3 2 + HHO = H,C 2 H 3 2 + 
 
 , CWO 2 . WTTn H,C 2 H 3 O 2 . 
 or else, 2 3 2 + HHO = * + 
 
 This assumption of two different radicals of aluminum is countenanced 
 by other facts detected by Mr. Crum, namely, that there are two 
 hydrates of alumina possessed of very different properties, and that the 
 acetate of alumina can be so altered by heat as to lose its powor of 
 acting as a mordant. I am not able to say, that the aluminous atom, as 
 distinct from the aluminic atom, certainly exists ; but Mr. Cram's 
 researches certainly point towards such a conclusion, and are difficult of 
 explanation on the ordinary theory of salts. 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 519 
 
 My friend, Mr. W. D. Clark, has communicated to me another fact 
 which seems also to point to the conclusion, that there are two different 
 oxides of aluminum. If a quantity of calico, mordanted with alumina, 
 is boiled with a quantity of madder a little too small to dye the cloth of 
 a desired colour, the operation entirely fails. The cloth does not obtain 
 a faint shade of the desired colour, corresponding with the insufficient 
 quantity of madder, but there is produced an entirely different compound 
 by which the cloth is sometimes spoiled. This result seems to show it 
 to be possible to convert the Mordanting oxide of aluminum into the 
 Non-mordanting oxide even after its combination with vegetable fibre. 
 These facts are quite in accordance with the theory which I have 
 advanced respecting the transmutability of basylous and basylic radicals. 
 
 Thoughts on the Origin and Metamorphoses of 
 Organic Eadicals. 
 
 A great proportion of the solid mass of plants consists of compounds 
 which contain carbon united to those proportions of oxygen and hydrogen 
 that are necessary to compose water. C + HHO. We can account for 
 the production of such compounds by assuming that water and carbonic 
 acid combine together, under separation of the quantity of oxygen which 
 is not required for these organic compounds. The separation of the 
 oxygen, and the combination of the residues appear to take place, under 
 circumstances which I shall state more explicitly hereafter, in the cells 
 upon the leaves of the plants which are exposed to sunshine. 
 COO + HHO give off OO and produce CHHO. This product appears 
 to me to be the oxide of the important neutral radical which I have 
 called VINYL = CH 2 . Accordingly, I propose to give to this compound 
 the formula CH 2 O, and to call it Vinylate. 
 
 The relation borne by vinylate to certain important neutral vegetable 
 substances may be expressed as follows : 
 
 CH 2 O. Vinylate. This is the composition of Fructose, sugar of 
 
 fruits, or grape sugar. 
 C + (CH 2 0) 4 . Dried milk sugar. 
 C + (CH*0) 4 -f HHO. Milk sugar, nndried = CH 2 O. 
 C + (CH 2 0) 5 . Starch. Cellulose. Woody fibre (flax, cotton, paper). 
 C -f (CH 2 0) 5 + HHO,HHO. Glucose. Starch sugar = (CH 2 0) 6 
 
 f Aq. 
 
 C -f- (CH 2 0) 2 . Lignin, but which is of variable composition. 
 C + (CH 2 O) 7 . Inulin. 
 C 4- (CH 2 O) U . Cane sugar. Arabin (gum arabic). 
 
520 ORIGIN" AND METAMORPHOSES OF ORGANIC RADICALS. 
 
 The above important compounds, comprehending woody fibre, the 
 gums, starches, and sugars the solid structure of trees, and the sweet 
 juices of fruits, seem to be all reducible to compounds of vinylate united, 
 atom after atom, to a single atom of carbon = C + CH 2 + ^H 2 + 
 CH 2 , &c. 
 
 When these compounds lose their single atom of carbon, they are all 
 reduced to the condition of vinylate or grape sugar. Thus, when cane 
 sugar is acted on by an alkali or an acid, the atom of carbon is removed 
 and grape sugar remains. So also when starch or woody fibre is acted 
 on by an acid, the atom of carbon is removed, and grape sugar or 
 vinylate remains. It would be an important discovery in the chemical 
 arts, could we find a method of combining with a multiple of grape 
 sugar this odd atom of carbon which converts it into starch or into cane 
 sugar. But at present our chemical power is limited to the decomposition 
 of the higher orders of organic compounds. We cannot recompose them. 
 
 It appears, from these considerations, that vinylate, or the simplest 
 form of sugar, is the nutritive principle of plants, the material which is 
 employed to form the various radicals which the different orders of 
 plants, and the different organs of each plant, demand for their support. 
 The metamorphoses of the sugar probably takes place in the cells of the 
 green leaves, of the blossoms, or of the fruit ; in those parts, namely, 
 where it is acted upon by the light and heat of the sun, and where it is 
 able to disengage its superfluous oxygen. It is difficult to form a precise 
 idea of the processes by which this change of sugar into radicals, or into 
 salts composed of radicals, is effected. Probably the walls of the cells in 
 which the operations occur consist of azotic substances, which give them 
 the power of galvanic batteries. It is possible that the azotes of those 
 cells may be endowed with very active powers, and may, according to 
 certain conditions of osmose, regulated by light, heat, air, and water, 
 run incessantly backwards and forwards through its various characters of 
 amidogen-, ammonium-, and cyanogen-former, and thus repeat in each 
 particular cell those processes of construction and transformation of 
 radicals which I have endeavoured to describe and classify in treating of 
 the theory of azotic radicals. Millions of such cells exist in a tuft of 
 grass or the twig of a plant. It is known that they are azotic ; it is 
 known that azotic cells have a powerful action even on dead vegetable 
 matter (as in fermentation) ; it is known that plants grow vigorously 
 after a thunder-storm ; and these conditions are all favourable to the idea 
 that the conversion of sugar into compound radicals is the work of azote, 
 acting with intense electrical force in the cells of plants exposed to air 
 and light. 
 
 When the oxygen is disengaged, the residue of the components of 
 sugar can produce an astonishing variety of radicals which differ accord- 
 ing to the wants of the plants, or to other special circumstances which 
 lead to their production. I will quote a few instances. 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 521 
 
 a). When jargonelle pears are in course of ripening, the compound 
 which gives them their odour and flavour is produced by the metamor- 
 phosis of 7 atoms of CH 2 O minus O 5 . The product is C 5 H U ,C 2 H 3 O 2 , 
 which I may call amyla acetylete, or the acetate of amyl, a compound 
 which is now made artificially, and sold under the name of pear-oil or 
 essence of jargonelles. In the production of this essence, one atom of 
 sugar is divided into H -f- CH. 5 atoms of CH 2 then become attached 
 to the odd atom of H, producing amyl = C 5 H U , and I atom of CH 2 to 
 the atom of CH, producing acetyl = C' 2 H 3 . For this salt, and for all 
 the salts of the vinyl series, only two atoms of oxygen are required, so 
 that all the rest of the oxygen belonging to the atoms of vinylate which 
 are required to produce the salt must be disengaged. 
 
 All the ethereal essences which give fragrance and flavour to ripen- 
 ing fruits appear to be produced in the same manner. Thus : 
 
 C 3 H IO O 2 , the residue left by the expulsion of O 3 from five atoms of 
 sugar, produces CH 3 ,C 4 H 7 2 = methyla butyrylete, or the butyrate of 
 methyl, which is the essence of the apples called rennets. 
 
 C IO H W O* produces C 5 H U ,C 5 H 9 2 = amyla valerylete, or valerianate of 
 amyl, the essence of other varieties of apples. 
 
 C 6 H 12 O 2 produces C 2 H 5 ,C 4 H 7 O 2 = ethyla butyrylete, or the butyrate 
 of ethyl, the oil which yields the flavour of the pine-apple. 
 
 C l 'H 22 O 2 produces C 2 H 5 ,C 9 H' 7 O 2 = ethyla pelargylete, or the pelargo- 
 nate of ethyl, which is the essence of quinces. 
 
 C 9 H i8Q 2 pr(X i uces C 2 H 5 ,C 7 H 13 2 = ethyla cenanthylete, or cenanthylate 
 of ethyl, an oil which gives flavour to Hungarian wine. It is probable 
 that the flavour of many wines may thus be imitated. 
 
 The metamorphoses of sugar into these fragrant essences is only a 
 single example selected from a multitude of possible changes. The Table 
 of Examples on the following page exhibits a more enlarged view of these 
 interesting metamorphoses. 
 
522 ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 PRODUCTS OF THE METAMORPHOSES OF SUGAR. 
 
 From C 4 H80 
 
 From C 8 H'60* 
 
 From C 12 H* 4 2 
 
 From C^H^O 2 
 
 = 4 atoms of Sugar 
 
 = 8 atoms of Sugar 
 
 = 12 atoms of Sugar 
 
 = 1 6 atoms of Sugar 
 
 minus O 2 . 
 
 minus O 6 . 
 
 minus O 1 ". 
 
 minus O' 4 . 
 
 H ,C 4 H 7 2 
 
 H ,CH 15 2 
 
 H ,C 12 H S3 2 
 
 H ,C 16 H 31 2 
 
 C 1 H 3 ,C 3 H 5 2 
 
 C 1 H 3 ,C 7 H I3 2 
 
 C 1 H 3 ^"ITO 2 
 
 C 1 H 3 ,C 15 H ?9 O 2 
 
 C 2 H 3 ,C 2 H 3 2 
 
 C 2 H 5 ,C 6 H II 2 
 
 C 2 H 5 ,C 10 H 19 2 
 
 C 2 H 5 ,C 14 H 87 2 
 
 C'H^C'ITO 2 
 
 C 3 H 7 ,C 5 H 9 O 2 
 
 C 3 H 7 ,C 9 H 17 O 2 
 
 C 3 H 7 ,C 13 H 85 2 
 
 
 C 4 H 9 ,C 4 H 7 2 
 
 C 4 H 9 ,C 8 H 15 O 2 
 
 C 4 H 9 ,C lf H iB 1 
 
 
 C 5 H ll ,C 3 H 5 O 2 
 
 C 5 H U ,C 7 H 13 2 
 
 C 5 H",C 11 H 8I O 8 
 
 
 C 6 H 13 ,C 2 H 3 O 2 
 
 C 6 H 18 ,C 6 H U 2 
 
 C 6 H 13 ,C'H I9 2 
 
 
 (TH^C'H 1 O 2 
 
 C 7 H 15 ,C 5 H 9 O 2 
 
 (7H I ,C 9 H I7 > 
 
 
 
 C 8 H 17 ,C 4 H 7 O 2 
 
 C 8 H' 7 ,C 8 H 15 2 
 
 
 
 C 9 H^C 3 H 5 O 2 
 
 C 9 H 19 ,C 7 H I3 2 
 
 
 
 C l H 2l ,C 2 H 3 2 
 
 C IO H 21 ,C 6 H 11 O 2 
 
 
 
 C U W,C 1 H 1 O 2 
 
 C 11 H 23 ,C 5 H 9 2 
 
 
 
 
 C 12 H* 5 ,C 4 H 7 O 2 
 
 
 
 
 W*H,<? H 5 O 2 
 
 
 
 
 C t4 H 29 ,C 2 H 3 2 
 
 
 
 
 C 15 H 31 ,C 1 H 1 s 
 
 From C^H^O 2 = 30 atoms of Sugar minus O 28 . 
 
 H ^H^O 2 Hydra melissylete. 
 C l H 3 ,C 29 H 57 2 Methyla ? 
 C 2 H 5 ,C 88 H 55 2 Ethyla ? 
 
 C 3 H 7 ,C 27 H 53 2 Propyla cerotylete. 
 C 4 H 9 ,C 26 H 51 O 2 Butyla ? 
 
 C 5 H ll ,C 25 H 49 2 Amyla ? 
 
 C 6 H l3 ,C 24 H 47 2 Hexyla ? 
 
 C 7 H 15 ,C 23 H 45 2 Heptyla 
 
 C 9 H 19 ',C 21 H 41 O 2 Nonyla behenylete. 
 C 10 H 21 ,C 20 H S9 O 2 Decatyla arachylete. 
 C ll H 23 ,C 19 H 37 O 2 Endecatylabalenylete 
 118JJ35Q2 Dodecatyla stearylete 
 ? margarylete 
 
 C 16 H 33 ,C 14 H 27 O 2 Cetyla myristylete. 
 
 C 17 H 35 ,C 13 H 25 2 
 C 18 H 37 ,C 12 H 23 O 2 
 &*H*,C"H n & 
 C 20 H 4l ,C 10 H 19 O 2 
 C 21 H 43 ,C 9 H 17 2 
 
 cocinylete. 
 
 laurylete. 
 
 margaritylete. 
 
 rutylete. 
 
 pelargylete. 
 
 C 23 H 47 ,C 7 H 13 2 ? oenanthyleto. 
 
 C 24 H 49 ,C 6 H n 2 ? caproylete. 
 
 C^H 51 ^ 5 H 9 O 2 ? valerylete. 
 
 C 26 H M ,C 4 H 7 2 ? butyrylete. 
 C 27 H 55 ?C 3 H s Q2 Ceryla propionylete. 
 
 C 28 H 57 ,C 2 H 3 2 ? acetylete. 
 
 C^H 59 ^ 1 H 1 2 ? formylete. 
 
 The sign ? indicates that the radicals are undiscovered or unnamed. 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 523 
 
 According to this Table, the metamorphoses of 4 atoms of sugar can 
 produce 4 different complete salts, each with a different acid radical and 
 a different basic radical. Which of these four compounds is producible 
 on any given occasion, depends upon the wants of the plant, upon its 
 power of metamorphoses, or upon other causes which it is impossible to 
 specify. 
 
 In the same manner, 8 atoms of sugar produce 8 different salts. 
 1 2 atoms of sugar produce 1 2 different salts. 1 6 atoms produce 1 6 
 salts. 30 atoms produce 30 salts. Hence it appears, that any number 
 of atoms of sugar can produce by metamorphoses an equal number of 
 different salts. 
 
 Several particulars resulting from these observations require notice. 
 
 a). In all the groups of this Table, every acid radical is combined 
 with a different basic radical. This fact proves that these radicals are 
 exchangeable or equivalent, and that, whatever their composition, how- 
 ever high or however low they stand in the scale, their power of neu- 
 tralisation is the same. Every radical in the series is chemically equiva- 
 lent to every other radical, and the replacement of the most complex by 
 the most simple is attended by no change in neutrality. In the year 
 1845, Professor Hofmann expressed opinions that were antagonistic to 
 these facts. " By organic base, in the strict sense of the word, I under- 
 stand, with Liebig, that class of compound, azotised bodies, which pos- 
 sess all the properties of basic metallic oxides. The oxides of ethyle, 
 methyle, &c. are not included, as the most common character of salts is 
 wanting in their compounds, viz., the replacement of their acids by 
 other acids, and their bases by other bases." Memoirs of the Chemical 
 Society, ii. 268. In the year 1857, Professor Hofmann may probably 
 be induced to abandon these opinions, opposed as they are to innumerable 
 facts which prove that ethyl, methyl, &c., are true radicals, each pre- 
 cisely equivalent in basic power to the most complicated ammoniums. 
 
 I). We perceive the utter worthlessness of unitary formulae as applied 
 to organic salts. The formula C 16 H 32 O 2 applied to a compound of the 
 vinyl series, signifies SIXTEEN DIFFERENT SALTS, and every similar 
 unitary formula signifies as many different salts as it contains atoms of 
 carbon ; of which fact, the unitary formula gives no intimation. 
 
 c). We have a complete exposition of Berzelius's doctrine of meta- 
 merism, a term by which he indicated " the case in which the compound 
 atoms of two chemical compounds containing the same elementary 
 atoms, and for the most part in the same proportions, are nevertheless 
 made up of different proximate elements." We see in the opposite Table 
 5 complete metameric groups, and we perceive both the cause and the 
 extent of the metamerism, and can therefore complete other groups at 
 our pleasure. 
 
 d). The note of interrogation in Group 5 of the Table, shows the 
 position and composition of the radicals of the vinyl group which have 
 
524 ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 
 not yet been recognised. Of course, these radicals are unnamed, which 
 accounts for the blanks in the names of the salts of this group. 
 
 I take this opportunity of suggesting, that as known radicals are be- 
 coming numerous, it will soon be found expedient to have some kind 
 of Systematic Names, to identify them and to intimate their composition. 
 In this work I have used the names of radicals as I found them, though 
 many are objectionable, and the series must soon be greatly enlarged. 
 This point may therefore be recommended to chemists as one that 
 requires early consideration. It is quite possible to designate the precise 
 composition of all possible hydrocarbons, the composition of which does 
 not exceed C' 00 !! 100 , by names of two syllables, easy to distinguish and 
 to recollect, and not liable to run into confusion with those terminal 
 numerals, which I have recommended to be used as enumerators of 
 radicals and of oxygen when combined into salts. 
 
 I proceed now to direct the reader's attention to the relations which 
 the organic radicals bear to one another. I have thrown the most im- 
 portant of them into the Table which is printed on the opposite page, 
 and which, though imperfect, may serve as the first rough sketch of that 
 chart of organic radicals which I have described at page 81, as being so 
 desirable an acquisition. 
 
 CLASSIFICATION OF RADICALS. If this Table were correct and 
 complete, it would present a classification of radicals. The radicals 
 placed in the vertical columns of this Table are far more closely connected 
 together than those which occur in the horizontal lines. The latter, 
 indeed, present a uniform quantity of carbon, and this uniformity induced 
 Gmelin to plan the arrangement of organic bodies in his great system, 
 in accordance with the quantity of carbon alone. It has proved to be 
 very disadvantageous to his book ; for the relations of the radicals that 
 are similar only in the number of atoms of carbon, are far less important 
 than those which characterise the radicals of each vertical group in this 
 Table. Had he taken such groups for his standards, and had he 
 arranged the salts of each radical on the plan of his inorganic chemistry, 
 the organic chemistry would have been as easy of reference as the 
 inorganic part, whereas it is now extremely complicated and trouble- 
 some. 
 
 TOTAL NUMBER OF ORGANIC RADICALS. It is a remarkable circum- 
 stance, that the number of well-known Organic Radicals does not 
 greatly exceed the number of Inorganic Radicals, page 28. 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 RELATIONS OF THE ORGANIC RADICALS. 
 
 525 
 
 A. 
 
 B. 
 
 C. 
 
 D. 
 
 E. 
 
 rcCH 2 + H' 
 
 wCH 2 -H l 
 
 nCH 2 -H 2 
 
 nCH 2 -H 3 
 
 wCH 2 H 4 
 
 nCH*-CH 
 
 wCH 2 + CH 
 
 wCH 2 + C 1 
 
 
 
 C 1 H 3 k 
 
 C'H'k 
 
 C l Hk 
 
 
 
 C 2 H 3 k 
 
 C 2 H 3 k 
 
 C 2 H 2 k 
 
 C 2 H l k 
 
 C 2 Hk 
 
 C 3 H 7 k 
 
 C 3 H 5 k 
 
 C 3 H 4 k 
 
 C 3 H 3 k 
 
 C 3 H 2 
 
 C 4 H 9 k 
 
 C 4 H 7 k 
 
 C 4 H 6 k 
 
 C 4 H 5 k 
 
 C 4 H 4 kB 
 
 C 3 H u k 
 
 C 5 H 9 k 
 
 C 3 H 8 k 
 
 C 5 H 7 k 
 
 C^H 6 kB 
 
 C 6 H 13 k 
 
 C 6 H ll k 
 
 
 Q6JJ9 
 
 C 6 H 8 
 
 C 7 H 15 k 
 
 C 7 H 13 k 
 
 
 C 7 H U 
 
 C 7 H 10 kB 
 
 C'HWk 
 
 C 8 H 15 k 
 
 
 C 8 H 13 k 
 
 C 8 H 12 
 
 C 9 H 19 
 
 C 9 H 17 k 
 
 
 C 9 H 15 
 
 C 9 H 14 kB 
 
 Q10JJ21 
 
 C 10 H 19 k 
 
 
 C l H 17 k 
 
 
 QHJJ23 k 
 
 C u H 21 k 
 
 
 C 11 H 19 
 
 
 C 12 !! 25 !^ 
 
 C l2 H 23 k 
 
 
 C 12 H 21 
 
 
 C^H^k 
 
 C 13 H 25 k 
 
 
 C 13 H 23 
 
 
 C 14 H 29 
 
 C 14 H 27 k 
 
 
 C 14 H 25 
 
 
 C 15 H 3l k 
 
 C 15 H 29 k 
 
 
 C l5 H 27 k 
 
 
 C 16 H 33 k 
 
 C 16 H 31 k 
 
 
 C 16 H 29 k 
 
 
 C 17 H 35 
 
 C l7 H 33 k 
 
 
 C 17 H 31 
 
 
 C 18 H 37 
 
 C 18 H 35 k 
 
 
 C l8 H 33 k 
 
 
 C^H 39 
 
 C 19 H 37 k 
 
 
 C 19 H 35 k 
 
 
 C 20 H 41 
 
 C 20 H 39 k 
 
 
 C 20 H 37 
 
 
 C 21 H 43 
 
 C 21 H 4I k 
 
 
 C 21 H 39 
 
 
 C 82 H 45 
 
 C 22 H 43 
 
 
 C 22 H 41 k 
 
 
 C 23 H 47 
 
 C 23 H 45 
 
 
 
 
 C 24 H 49 
 
 C 24 H 47 
 
 
 
 
 C 25 H 51 
 
 C 25 H 49 
 
 
 
 
 C 26 H 53 
 
 C 2G H 51 
 
 
 
 
 C 27 H 55 k 
 
 C 27 H 53 k 
 
 
 
 
 C 28 H 57 
 
 C 28 H 53 
 
 
 
 
 C*H"k 
 
 C 29 H 57 
 
 
 
 
 (Continued on the next page.) 
 
526 ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 
 RELATIONS OF THE 
 
 F. 
 
 G. 
 
 H. 
 
 I. 
 
 K. 
 
 
 nCH*-H 5 
 
 nCH 2 -H 6 
 
 nCH 2 -H7 
 
 nCH 8 -H 8 
 
 wCH 2 -H 9 
 
 
 C 3 H l 
 
 C 3 HkB 
 
 
 
 
 
 
 C 4 H 2 k 
 
 C 4 H l 
 
 era 
 
 
 
 
 C 5 H 4 kB 
 
 C 5 H 3 k 
 
 
 C 5 IT 
 
 
 
 
 C 6 H 5 k 
 
 
 C 6 H 3 
 
 
 
 
 C 7 H 7 k 
 
 
 C 7 H 5 k 
 
 
 
 
 (fHk 
 
 
 C 8 H 7 k 
 
 
 
 
 C 9 H ll k 
 
 
 C 9 H 9 k 
 
 
 
 
 C 10 H l3 k 
 
 
 C l H"k 
 
 
 
 
 
 
 C u H is 
 
 
 EXPLANATION OF THE TABLE EXHIBITING THE RELATIONS WHICH THE 
 ORGANIC RADICALS BEAR TO ONE ANOTHER. 
 
 I have arranged the radicals in vertical columns according to the 
 method of grouping them which is most in use among organic chemists ; 
 that is to say, in agreement with the formulae nCH 2 -}-!! 1 , nCH 2 H 2 , 
 7iCH 2 -H 3 , &c. 
 
 I wish it, however, to be understood, that these headings do not 
 represent my opinion of the Constitution of the radicals that are placed 
 below them. If these formulae represent the result, they certainly do 
 not represent the order, of Nature's proceedings. If Nature has to 
 produce a Hill, she certainly does not in the first instance produce a 
 Mountain and then cut it down. The early crystallographers supposed 
 that if Nature wanted to produce an octahedron, she first produced 
 a cube and then cut off' all its corners till nothing remained of its 
 original faces, but a mathematical point in the centre of each. In like 
 manner, these organic formulae appear to assume, that if Nature desires 
 to produce a radical, such as cumyl for example, she first combines 
 together ten atoms of vinyl into the compound C l H 20 , and then takes 
 away H 9 , and leaves the desired result C'H 11 . I renounce that method 
 of explanation, believing Nature's process to be, in all cases, that of 
 adding atom to atom one by one till she reaches the desired point. She 
 never overworks herself, in order to be forced to undo what she has done 
 umiss. 
 
 The horizontal lines in the Table represent the radicals which agree in 
 possessing the same quantity of carbon. 
 
 Throughout the Table, proceeding from above downwards, every 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 ORGANIC RADICALS. 
 
 527 
 
 
 L. 
 
 M. 
 
 N. 
 
 0. 
 
 P. 
 
 
 wCH*-H 10 
 
 nCH a -H" 
 
 nCH*-H 12 
 
 wCH 8 =H 13 
 
 nC + H 
 wC-j-CH 
 
 
 
 
 
 
 cm 1 
 
 
 
 
 
 
 CPH'k 
 
 
 
 
 
 
 C 3 H l 
 
 
 
 
 
 
 C 4 H l 
 
 
 C 5 H 
 
 
 
 
 C'H 1 
 
 
 C 6 H 2 kB 
 
 C 6 R l 
 
 C 6 H 
 
 
 C 6 H l 
 
 
 C 7 H 4 kB 
 
 C 7 H 3 k 
 
 
 ffWk 
 
 C 7 H'k 
 
 
 
 C 8 H 5 
 
 
 C 8 H 3 k 
 
 
 
 
 C 9 H 7 k 
 
 C 9 H 6 kB 
 
 C 9 H 5 
 
 
 
 
 
 C 10 H 8 
 
 C 10 H 7 k 
 
 
 
 
 
 C ll H"kB 
 
 
 
 radical exceeds the one above it by the addition of CH 2 , proving that the 
 same relation which holds true among the radicals of the vinyl series, 
 quoted in columns A. and B., holds equally true in all the other series ; 
 the differences being confined to the constitution of the first radical, or 
 starting point of each group. This principle of a common difference 
 among a series of radicals is what Gerhardt calls HOMOLOGY. Every 
 column in the Table is, in his terms, an Homologous series. 
 
 The radicals which are marked k in the Table are known to chemists, 
 if not in an isolated state, at least in some form of combination. Those 
 marked B. are the radicals of bibasic acids : strictly speaking many of these 
 should be rejected from this Table, because they are actually double 
 radicals, and appear again in their single form in other groups in the 
 Table. See columns C. and E., and the article on the succinic group of 
 salts, page 441. 
 
 Most of the radicals in the Table have an uneven number of atoms of 
 hydrogen, and only those which have that composition seem to possess 
 an atomic measure when they form part of gaseous salts. The salts of 
 vinyl CH 2 , of succinyl C 2 H 2 , of salicyl C 7 H 4 , when in the gaseous state 
 measure only as much as is due to the radicals with which they are in 
 combination. See page 96. 
 
 GROUP A. Basic Radicals of the Vinyl Group ; and 
 
 GROUP B. Acid Radicals of the Vinyl Group. 
 
 These two groups have undergone so complete an investigation in the 
 preceding pages, particularly in the articles between pages 49 and 8 1 , and 
 just now in the note on the metamorphoses of sugar, that I need not go 
 into farther details. The radicals of this series which are known to 
 
528 ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 
 chemists are marked k. The others will probably soon be found. I 
 have pointed out (pages 73 to 77, page 407, &c.) several processes by 
 which the radicals of this series can be successively reduced from basic 
 to acid, and from acid to basic, by the alternate removal of H* and C 1 ; 
 and there is no doubt that a continuation of researches of this character 
 will soon produce the radicals that are now unknown, among the 
 products of the decomposition of the radicals which are placed higher in 
 the series. 
 
 Buckton's recently published interesting researches respecting the 
 acids of the succinic group (see page 454), prove that much can be suc- 
 cessfully accomplished by acting on the higher members of the organic 
 compounds. But the energy of Buckton's agent hot nitric acid is 
 such as to shatter the complex radicals too readily into fragments. It is 
 desirable to employ milder processes, and thus to reduce the complex 
 radicals, step by step, down the scales of basic to acid, and acid to basic, 
 until those intermediate radicals which have hitherto escaped detection, 
 but the places and composition of which are indicated in the Table, are 
 produced and converted into characterising salts. All the compound 
 radicals which are lower in composition than C 30 H 61 will certainly be 
 discovered if they are carefully sought for. 
 
 GROUP C. Radicals of the Sucdnic Group. Monobasic. They are 
 described at page 441. It is assumed of the radicals of this group, that 
 they are formed by the successive addition of atoms of vinyl to one 
 atom of carbon ; every step in that additive process producing a new 
 radical. The primary radical C 1 and its first compound C 2 H 2 , both have 
 the peculiarity of losing their atomic measure when they form gaseous 
 salts. The other members of the series do not produce gaseous salts. 
 
 GROUP D. The salts of this group differ among themselves by the 
 common difference of CH 2 , and they contain as an invariable element, or 
 common ingredient, the radical C 2 H which stands at the head of the 
 list. This radical is equivalent to CH + C, which are the characteristics 
 of the salts of Groups B and C, and therefore the radicals of Group D 
 are each equal to a radical belonging to Group B combined with another 
 belonging to Group C. Yet they are all monobasic, and we must 
 consequently consider them to be single radicals. The known radicals 
 of this series are as follows : C*H. Maleyl ; fumaryl ; dyl ; see the 
 article on the Malic Group, page 411, and the Citric Group, page 424. 
 C 3 H 3 . Acryl ; pyruvyl ; tryl ; see the article on the Citraconates, 
 page 438. C 4 H 5 , the radical of isotartaric acid. C 5 H 7 , the radical of 
 camphoric acid and angelic acid. C 8 H 13 , conyl, probably the radical 
 contained in conia. C 10 H 17 , the radical of campholic acid. C 15 H 27 , the 
 radical of moringic acid, procured from the oil of ben. C 16 H 89 , the 
 radical of hypogeic acid, a compound produced during the saponification 
 of arachidic acid, which is formed by the radical arachyl = C 20 H 39 of the 
 vinyl series. C 18 !! 33 , oleyl, the radical of oleic acid. C 19 H 35 , the radical 
 
ORIGIN AND METAMORFHOSES OF ORGANIC RADICALS. 529 
 
 of doeglinic acid, which is procured from a species of sperm whale ; it is 
 remarkable for being an oil which contains no glycerine. C 22 H 41 , the 
 radical of erucic or brassic acid, derived from the oil of mustard. 
 
 The radicals of this series appear to be nearly all produced by the 
 application of heat to substances that belong to the vinyl series, and their 
 relation to the radicals of that series is easily perceived. Thus 
 
 Glycyl (or allyl) = C 3 H 5 - H 2 = acryl C 3 H 3 . 
 
 Stearyl = C^H 35 - H 2 = oleyl C^H 33 . 
 
 Oleyl = C^H 38 - C 1 = margaryl C !7 H 33 . 
 
 Acetyl = C 2 H 3 - H 2 = fumaryl C 2 H l . 
 
 In short, all the radicals of this group may be considered to be converti- 
 ble into acid radicals of the vinyl series, Group B, by the addition 
 of H 2 , or the subtraction of C 1 . Probably they all existed in the living 
 plant or animal as members of the vinyl series, and owe the forms in 
 which they are shown in Group D, to the metamorphoses effected by 
 the chemical reactions that were employed to effect their separation from 
 other substances. The whole of the series D, except C 2 H may also be 
 considered as compounds of CH 2 , repeated n times, with one atom of 
 pyruvyl C 3 H 3 constant in all, and it is remarkable that this last atom is 
 that which is frequently produced when other more complex radicals 
 are subjected to heat. Pyruvic acid = H,C 3 H 3 O 3 is equal to a com- 
 pound of formic acid = H,*CHO 2 with pyrogallic acid = CH,CHO, all 
 of which are nearly allied in their chemical characters. 
 
 GROUP E. With the exception of the starting radical C a , which 
 represents the acid radical of the mellates, all the radicals of this group 
 are double radicals of Group C. They form double salts, and appear to 
 have no title to be called simple radicals. See page 441. 
 
 GROUP F. I find no radicals which can with any certainty be ascribed 
 to this group. 
 
 GROUP G. C 3 is the acid radical of the mesoxalic acid, which has the 
 formula H i ,C 3 3 , and is therefore apparently bibasic; but this acid belongs 
 to an important series of compounds, the products of the decomposition 
 of cyanyl, which I have not examined in this volume. I consider this 
 formula to represent a double salt. C 4 H 2 is phtalyl, the radical of phtalic 
 acid, which is commonly said to be bibasic, but which is actually mono- 
 basic ; its salts corresponding to the formula M,C 4 H 9 2 . This fact is 
 completely confirmed by the constitution of thephtalamides, phtalimides, 
 and phtalanil'es of the series. C 5 H 4 is the assumed radical of the citraconic 
 acid, which I have shown to be a double acid ; see page 438. 
 
 GROUP H. The known radicals of this series, except the first two on the 
 list, are so important that they have undergone repeated discussions in the 
 preceding pages. C 5 H 3 is the radical of the pyromeconic acid. C 6 IP is 
 phenyl. The same composition is commonly ascribed to citryl, but the 
 arguments which I have used in the article on the citrates at page 424, 
 
 2 M 
 
530 ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 
 prove that citryl is not a radical. (7H 7 is toluenyl (and anisol?) 
 C 8 H 9 is xylenyl. C 9 H 11 is cumenyl. C l H 13 is thymyl. These radicals 
 are all of the basic order, and act in salts as basic radicals without 
 requiring any oxygen beyond that which is proper to the normal salts of 
 the acid radicals with which they combine. 
 
 In tracing the homology of this group of radicals from below upwards, 
 we come to the radical OH 1 , which does not belong to the vinyl series. 
 I have endeavoured to account for the origin of this radical in Group P, 
 where I suppose that a series of radicals are produced by the successive 
 addition of atoms of C l to one atom of H, taken as the primary nucleus. 
 The radicals of Group H belong to the series of essential oils, which are 
 produced by nature in fruits and seeds under circumstances where not 
 only oxygen but water itself could be given off during the conversion of 
 sugar into the oils demanded by the wants of the living plant. In that 
 way atoms of carbon could be added to salts of the vinyl series till the 
 composition demanded by the plant was completed, though it is 
 impossible to form a clear idea of the manner in which this operation 
 takes place. 
 
 The artificial formation of some of these radicals takes place in 
 accordance with facts that have been frequently referred to. Thus, 
 indyl = C 8 H 3 the basis of indigo, can by chemical means be deprived of 
 C 2 and be made to receive an addition of H 2 , producing C 6 H 5 phenyl. 
 These two operations, viz., the abstraction of C 2 , or the addition of H 2 , 
 frequently take place among radicals. Here the two actions occur 
 simultaneously and render the process more complicated yet not more 
 mysterious. 
 
 GROUP I. I can find no well-ascertained Examples in agreement with 
 this formula. 
 
 GROUP K. The known radicals of this group are C 7 H 5 = benzyl, and 
 perhaps spiryl; see page 455; C 8 H 7 = toluyl and anisyl; C 9 H 9 = 
 styryl; C l H 11 = cumyl. These radicals belong to the resinous or 
 aromatic series, and are nearly related to those of Group H, both in 
 properties and in composition, and their origin is probably liable to a 
 similar method of explanation. On comparing the radicals of the two 
 groups as they stand m the same horizontal lines of the Table, we perceive 
 that they bear to one another, in pairs, precisely the relations of basic 
 radicals to acid radicals, the common difference, like that between 
 the two orders of vinyl radicals, situated on the same horizontal lines in 
 the Table being H 2 . 
 
 Thus, Toluenyl C 7 H 7 - H 2 = C 7 H 5 , benzyl. 
 
 Xylenyl C 8 H 9 - H 2 = C 8 H 7 , toluyl. 
 
 Cumenyl C 7 H 11 - H 2 = C 9 H 9 , styryl. 
 
 Thymyl C 10 H 13 - H 2 = C 10 H U , cumyl. 
 
 or, changing the operation in terms, though not in essence, we have 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 531 
 
 Phenyl C 6 H 5 + C l = C 7 H 5 , benzyl. 
 
 Toluenyl C 7 H 7 + C 1 = C 3 H 7 , toluyl. 
 
 Xylenyl C 8 H 9 + C 1 = C 9 H 9 , styryl. 
 
 Cumenyl C 9 H 11 + C 1 = C 10 H U , cumyl. 
 
 Thymyl C l H 13 + C 1 = C U H 13 , ? 
 
 And in effect these figures accurately express the corresponding chemical 
 powers of the respective radicals ; for those of Group H are basic while 
 those of Group K are acid. Those of Group H go into salts as basic 
 radicals without carrying additional oxygen with them ; but those of 
 Group K, when they act as basic radicals demand an additional supply 
 of oxygen, and that quantity differing according to the acid properties of 
 each special radical : thus, benzyl, which forms benzoates with O 2 takes 
 with it O l extra when it acts as a basic radical ; while anisyl, which 
 forms anisates with O s , takes with it O 2 extra when it acts the part of a 
 basic radical. These details afford interesting illustrations of the truth 
 of the general principle which I have advanced, namely, that the 
 difference which exists between basic radicals and acid radicals is 
 expressed either by C 1 or H 2 , since these proportions of carbon or of 
 hydrogen are sufficient to change the class of any radical, whatever may 
 be its ultimate composition. The question of basicity or acidity never 
 depends upon the absolute quantity of carbon or hydrogen that happens 
 to be present in any radical, but entirely upon the relative proportions of 
 those elements. 
 
 GROUP L. The known radicals of this group are only two in number, 
 C 6 H 2 , the radical of the bibasic comenic acid, respecting the composition 
 of which I have great doubts, and C 7 H 4 , which is salicyl, a bibasic 
 radical, the salts of which I have investigated at page 455. It is by no 
 means improbable that C 7 H 4 represents two radicals instead of one, and 
 that the salicylic acid is a double acid and not a bibasic acid ; but the 
 reactions of the salts do not afford any clue to the unravelment of this 
 mystery. 
 
 GROUP M. The formula C 7 H 3 represents the radical of gallic acid, 
 which, in accordance with this formula is tribasic. I do not believe that 
 that is the true account of the gallates, but I am unable to give a better 
 account of them. The recorded experiments are not sufficient to give 
 clear and satisfactory ideas respecting their composition. When gallic 
 acid is heated, it produces a compound which is called pyrogallic acid. 
 The formula of this compound appears to me to be CH, CHO, according 
 to which it is not an acid at all, but a suboxide of formyl. In the new 
 nomenclature this salt would be called formyla formylate. It acts as a 
 powerful reducing agent, because one atom of it requires four atoms of 
 oxygen for the decomposition. Thus : 
 
 CH, CHO + O 4 = HHO + CO 2 + CO 2 . 
 
 The other known radical of this group, C 9 H 7 , is cinnamyl, the radical 
 
 2 M 2 
 
532 ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 
 of the cinnamic acid H,C 9 H 7 2 . It takes O l extra when it acts as a basic 
 radical. 
 
 GROUP N. The formula C 9 H 6 represents the radical of Hofmann's 
 recently discovered bibasic insolinic acid = HH,C 9 H 6 O 4 . When this acid 
 is distilled, it yields benzoic acid. This reaction, with the composition 
 of the formula, its bibasic nature, its large quantity of oxygen, and the 
 even number of its atoms of hydrogen, all concur to induce me to 
 consider the insolinic acid to be a double acid, probably composed of 
 
 = benzoic acid. 
 
 = dylic acid? See page 411. 
 
 The other formula of this group C M H' represents the radical of sinapic 
 acid, H 2 C U H |0 O 5 , a bibasic acid, the existence of which is rather suppo- 
 sitional than proved. 
 
 GROUP O. The known radicals of this group are as follow : 
 C 7 H l is the radical of the rneconic acid, which is assumed to be tribasic, 
 but I cannot say that this tribasic character rests upon satisfactory 
 grounds. The meconates are HHH, C 7 H'O 7 . When heated, they give 
 off CO 2 and become comenates = HH, C 6 H 2 O 5 , when the comenates 
 are heated, they give off CO 2 , and become pyromeconates = H,C 5 H 3 3 . 
 Thus, throughout the series the acid radical contains in all 8 atoms. 
 When C l goes off, H l comes to replace it. This proceeding is repeated. 
 The H l which thus replaces the disengaged C l is a basic radical ; and as 
 the change proceeds in the acid radical, the acid radical of the salt, which 
 first is tribasic, changes to bibasic, and then to monobasic; I expect 
 that we .shall by-and-by have a very different account of these meta- 
 morphoses. 
 
 C 8 H 3 is the formula of indyl, which I have fully discussed in the 
 article on indigo, page 257. It is worthy of remark, that this radical is, 
 like meconyl, liable to undergo two remarkable changes, without diminu- 
 tion of the collective number of its ultimate atoms. Thus : 
 
 Indyl, C 8 H 3 - C 1 + H* = C 7 H, salicyl. 
 Indyl, C 8 H 3 - C 2 + H 2 = C 6 H 5 , phenyl. 
 
 I wish I could understand or explain the nature of these changes. 
 
 The last formula of this group is C l H 7 = naphtyl, a radical which has 
 so often come under our notice, that I need scarcely enter upon any 
 discussion respecting it. Like phenyl, it is singularly addicted to form 
 part of amidogens and ammoniums, in which it acts exactly in the same 
 manner as phenyl. Hofmann has recently made a "new base" by 
 means of this radical, which however is merely a framework upon which 
 to hang a new set of hard names. 
 
 Menaphthalamine (for so he calls it) has the following constitution : 
 C 42 H' 7 N 3 , which, as I take it, means that it is a double amidogen salt : 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 533 
 
 I 7"LT pUOTT/ . TJ 1 
 
 ^" I 7HV 10 H 7 CN I = ^ a phtyl ac hydra cum naphtylac cyana. 
 The salts of this " base " are as follows : 
 
 ( ZH 3 C l H 7 Cl ) 
 
 B. < ^TT nioTT7 .' fi>j \ - Naphtylam chlora cum naphtylac cyana. 
 
 (ZH,'c i H 7 ; CN] 
 
 C. < ZH,C 10 H 7 ; CN I = Bis naphtvlac cyana cum hydra cyana. 
 I H; CNJ 
 
 [ C'H ? ; CNO 
 
 D. { G l H'; CNOl= Bis naphtvla cyanate cum hydra cyana. 
 I H ; CN j 
 
 Hofmann's names for these salts are as follow : B. Hydrochlorate 
 of menaphthalamine = C 42 H 17 N 3 HC1. C. Dicymenaphthalamine = 
 C 46 H 17 N 5 = CWN 3 + Cy 2 . D. Menaphthoximide = C 46 H 15 N 3 O 4 . 
 He tells us that " menaphthoximide may be viewed as binoxalate of 
 menaphthalamine minus 4 equivalents of water 
 
 C 4g H' 7 N 3 HC*0 4 ,HC 2 4 - 4HO = CFHPWj 
 
 Binoxalate of menaphthalamine. Menaphthoximide. 
 
 and this view is corroborated by the deportment of the substance with 
 
 potassa, which reproduces menaphthalamine and oxalic acid." Proceed- 
 
 ings of the Royal Society, 1856, viii. 12. 
 
 I see nothing to prove that binoxalate of menaphthalamine ever had 
 any existence, and I account for the last-mentioned reaction thus : 
 
 C l H 7 ,CNO } f ZH,C 10 H 7 ; H 1 _ A 
 D.{C 10 H 7 ,CNO |ZH,C'H 7 ; CNj 
 H,CN 
 
 According to this view, menaphthalamine is a "new base," but not a 
 new radical. It is only a new double salt, of the same nature as 
 melaniline, which I have investigated at page 291. The introduction of 
 what chemists call a " new base " is by no means to be considered as the 
 discovery of a new radical. Lest the reader should at any time feel a 
 difficulty in distinguishing a " base " from a " radical," let me remind 
 him, that a radical is the equivalent of one volume of hydrogen or of 
 chlorine, and possesses the saturating capacity proper to one volume 
 of either ; whereas a base is a heterogeneous mixture of atoms, which 
 have no specific chemical duty to do, and which, as to number, are with- 
 out limit, and, as to collocation, are without order. A radical may be 
 compared to a thorough- trained soldier, who forms part of a system, is 
 accustomed to discipline, and acts according to order. A base is a 
 Bashi Bazouk, who is thoroughly untrained, who despises system, 
 is unaccustomed to discipline, and is obedient only to the dictates 
 
534 ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 
 
 of caprice. Any harum-scarum fellow answers for a Bashi Bazouk. 
 Any conglomeration of atoms serves as a base. But a soldier must be 
 a man who knows his duty and does it. A radical is a collection 
 of atoms determinate as to quantity, orderly as to system, and always 
 prepared to fulfil the functions which its position in the system it 
 pertains to imposes upon it. In short, the difference between a radical 
 and an organic base is like the difference between order and disorder. 
 
 GROUP P. This group, purely hypothetical, is inserted to account for the 
 starting radicals in the columns D, F,H, K,M,0. I suppose that originally 
 C 1 combines with H 1 or with C'H 1 , and that C 1 is then added atom after 
 atom, till the several products which are exhibited in this column 
 are produced ; after which these radicals, acting as units, combine with 
 successive atoms of CH* to produce the radicals which form the groups 
 given in the different columns of the Table. 
 
 It is however just as easy to imagine that the radicals are first formed 
 in accordance with the methods of production explained in reference to 
 the vinyl radicals, and that these radicals then become subject to the 
 successive additions of atoms of C 1 . Or, on the other hand, some of 
 them may be explained as being derived from radicals actually belonging 
 to the vinyl series, by the artificial expulsion of a limited quantity 
 of hydrogen. Thus terbasic glycerine = H,H,H,C 3 H 5 3 when deprived 
 of HHO produces monobasic allylic acid = H,C 3 H 5 2 , and when de- 
 prived of a second atom of HHO, it produces acrolein = H,C 3 H 3 0, in 
 which we have an acid radical belonging to Group D. This last reaction 
 differs in no respect, or degree, as respects the change in the radicals, 
 from that which converts alcohol into aldehyde. 
 
 H,C 2 H 5 - H 2 = H,C 2 H 3 0. 
 
 It is unquestionably a fact that the basic radicals are reducible to acid 
 radicals by the abstraction of H 2 , and it does not seem unreasonable to 
 assume that the acid radicals themselves may be capable of snstaining 
 successive abstractions of H*, by artificial means, so as to produce the 
 more highly carbonised radicals. Thus C 5 H U may become in succession 
 C 5 H 9 ,C 5 H 7 ,C 5 H 5 ,C 5 H 3 ; and in like manner C 9 H 19 , may become C 9 H 17 , 
 C 9 H 15 ,C 9 H 13 ,C 9 H 11 ,C 9 H 9 ,C 9 H 7 ,C 9 H 5 . These are points that are capable of 
 experimental investigation, and are not likely to pass unheeded. 
 
 Besides these groups of radicals, I have endeavoured to trace the 
 existence of others, but without useful results. For example, the Group 
 wC+CH 2 produces C 4 H 2 and C 6 H 2 , but no other known radicals; and 
 the Group C-j-nH produces CH,CH 2 ,CH 3 , and then stops, as there 
 is no known hydrocarbon radical- with a greater proportion of H to C 
 than is found in methyl. 
 
 On looking over these homologous groups of radicals, the remarkable 
 fact strikes us, that the greater proportion of them are produced 
 by a very direct process from sugar or vinylate, and that most of 
 
ORIGIN AND METAMORPHOSES OF ORGANIC RADICALS. 535 
 
 the others seem to be derived by processes, which, though indirect, are 
 short and obvious, from the same substance. Sugar in the form of 
 CH 2 is the raw material which life in plants works up into the in- 
 numerable finished manufactures which vegetables expose to the admi- 
 ration of mankind and among which animal life finds sustenance. 
 
 The METAMORPHOSES of Organic Radicals have been so often dis- 
 cussed in the preceding pages, that I need only refer to the main facts. 
 
 Acid radicals can be transformed into basic radicals by the abstraction 
 ofC 1 . Thus: 
 
 Formyl = C'H 1 - C 1 = H = hydrogen. 
 
 Acetyl = C 2 H 3 - C 1 = C'H 3 = methyl. 
 
 Allyl = C 3 H 5 - C 1 = C 2 H 5 = ethyl. 
 
 Benzyl = (7H 5 - C 1 = C 6 H 5 = phenyl. 
 
 On the other hand, basic radicals can be reduced to acid radicals by the 
 abstraction of H 2 . These matters have been so fully discussed at page 
 74, in the article at page 399, and incidentally on several other occasions, 
 that I need enter now into no details. 
 
 When hydrides of acid radicals are sealed up in glass tubes with a 
 saturated solution of hydracids in water, and heated to 212 F., they are 
 changed into chlorides of the corresponding basic radicals. In this 
 way acid radicals are converted into basic radicals by the addition of H 2 , 
 instead of the abstraction of C 1 . Berthelot thus produced the following 
 metamorphoses : 
 
 Propionyla hydra . C 3 H 5 ,H -f HC1 = C 3 H 7 ,01 Propyla chlora. 
 
 Valeryla hydra . C 5 H 9 ,H + HC1 = C 5 H ll ,Cl Amyla chlora. 
 
 Capryla hydra. . C 8 H 15 ,H + HOI = C 8 H' 7 ,C1 Octyla chlora. 
 
 Palmityla hydra . C l6 H 3l ,H + HC1 = C 16 H 33 ,C1 Cetyla chlora. 
 
 And, by acting in the same manner on what he calls Ethylene by 
 hydrobromic acid, he produced bromide of ethyl : 
 
 CH 2 + CH 2 + HBr = C 2 H 5 ,Br 
 
 Vinyl, 2 atoms. Ethyla broma. 
 
 By a process quite equivalent to this, the hydrides of amidogens are 
 converted into chlorides of ammoniums. Thus : 
 
 ZH 2 H + HC1 = ZH 4 ,C1. 
 
 Many transformations of this description will be seen under the head of 
 Aniline, page 274. 
 
 Akin to this process is also that by which the amids of oxygen acids 
 are converted into normal ammonium salts. Thus : 
 
 ZH 2 ,CO + HHO = ZH 4 ,C0 2 . 
 
536 ORIGIN AND METAMORPHOSES OF ORGANIC RADICAL. 
 
 These transformations have been illustrated by innumerable examples 
 during the investigation of the azotic radicals. 
 
 Another method of metamorphoses consists in converting complex 
 radicals which contain many times CH 2 , into radicals of a simpler kind, 
 by the action of nitric acid. An example of this mode of procedure is 
 referred to in the article on the Anchoates at page 454. 
 
 The doctrine of Vice-Radicals has been fully explained and illustrated 
 in the preceding pages. A vice-radical is a hydrocarbon in which the 
 hydrogen has been more or less replaced by Cl, Br, I, N, S, or a metal, 
 and which, notwithstanding that replacement, still acts the part of a 
 radical. 
 
 Many acid radicals can be made to act as basic radicals, provided 
 they are supplied with a certain excess of oxygen. This excess of 
 oxygen is demanded by such radicals even when they form part of an 
 ammonium. 
 
 Many other processes of metamorphoses might be noticed, and have 
 been already described in this work; but they are reducible to three 
 classes : 
 
 a). They change a basic radical into the acid radical next below it by 
 the abstraction of H 2 , or into the acid radical next above it by the 
 addition of C l . 
 
 b). They change an acid radical into the basic radical next below it by 
 the abstraction of C l , or into the basic radical next above it by the addi- 
 tion of H 2 . 
 
 c). They reduce a complex radical to one or more radicals of a sim- 
 pler constitution. 
 
 What chemists have need of at present, are processes which will 
 enable them to imitate the operation of nature, in forming complex 
 radicals from simpler kinds by the addition of atoms of CH 2 to a nucleus, 
 or by combining together ready-formed atoms of the simpler kind to 
 produce those of the complex kind. That power is, however, more to 
 be desired than expected. 
 
 The metamorphoses of organic radicals which depend upon the trans- 
 mutations of azote, and those which take place in living animals, I must 
 decline to touch upon. They are too important to be slighted, and I 
 have not considered them sufficiently to be warranted in pronouncing 
 clear opinions upon them. The theories which I have advanced in this 
 work respecting the existence, the nature, the properties, the origin, and 
 the transformations of hydrocarbon radicals must, if they represent what 
 is true, have a great effect in changing the commonly-received formulae 
 of azotic and animal substances, which are extremely unsatisfactory. 
 The " unitary" formula which I have quoted in page 167 are, con- 
 fessedly, declarations of ignorance of anything beyond the knowledge 
 afforded by destructive analyses; while the "rational" formulas gene- 
 rally met with are in the highest degree fanciful such as 
 
DALTONISM THE ATOMIC THEORY. 537 
 
 2o(C 36 ff 5 N 4 10 . 2HO) + 8EPNS + H 2 NP = albumen of eggs. 
 (C 36 H 25 N 4 O U . 2HO) + H 2 NS + H 2 NP = fibrin of ox-blood. 
 6(C 36 H 25 N 4 O n . 2 HO) + S 2 O 2 = fibrin-protein. 
 
 I copy these formulas from Lehmann's Physiological Chemistry, 1851, 
 vol. i., where they are attributed to Mulder. The application of the 
 radical theory to these compounds would no doubt produce formulae of 
 a much simpler character ; but the investigation is one for which I can- 
 not afford time. 
 
 Daltonism. The Atomic Theory. The Law of Com- 
 bination in Multiple Proportions. 
 
 The " LAWS OF CHEMICAL COMBINATION " at present recognised by 
 chemists are explained by Professor Miller as follows : 
 
 "The relative proportion in which the different elements unite is 
 regulated by fixed laws. These important laws, which are three in 
 number, regulate the mode of combination of every known chemical 
 compound. These are usually termed the laws of chemical combination. 
 
 1 . " The first of these laws is the law of Definite Proportions, which, 
 although of great simplicity, is one of fundamental importance to the 
 science of chemistry. This law may be stated in very few words ; it is 
 as follows : In every chemical compound* the nature and the proportions 
 of its constituent elements are fixed, definite, and invariable" 
 
 2. " The second law of combination is usually termed the law of 
 Multiple Proportions. It frequently happens that a pair of elementary 
 bodies unite together in more than one proportion. The compounds so 
 obtained are very different from each other ; but there is still a uniformity 
 in the plan upon which these compounds are formed, and the propor- 
 tions of the two elements in each are very simply related. The law of 
 multiple proportion may be thus stated : If two elements, A and JJ, 
 unite together in more proportions than one, on comparing together quan- 
 tities of the different compounds, each of which contains the same amount 
 of A, the quantities of B will bear a very simple relation to each other ; 
 such as 
 
 A + B, A -f 2 B, A + 3 B, A + 4 B, &c.; 
 or, 2A + 3B, 2A -f 56, 2A -{- 78, &c.; 
 or, A + B, A -f- 36, A -f 58, &c. 
 
 Water, for instance, is a compound of oxygen and hydrogen ; in I oo 
 parts, by weight, there are, as already mentioned, 88*9 of oxygen and 
 1 1*1 of hydrogen. But there is another compound of oxygen and 
 hydrogen known to chemists, termed the peroxide of hydrogen. By 
 
538 DALTONISM THE ATOMIC THEORY. 
 
 analysis it has been found that 100 parts of this body contain 94/1 of 
 oxygen, and 5-9 of hydrogen. Now, on comparing together the quan- 
 tities of oxygen which in these two compounds are united with an equal 
 quantity, say I part of hydrogen, it is evident that in water, for i of 
 hydrogen there are 8 of oxygen : 
 
 Since ii'i : 88-9 : : i : 8. 
 
 And by a similar process it is seen that in the peroxide of hydrogen, for 
 I part of hydrogen 1 6 of oxygen are present : 
 
 5-9 : 94-1 :: i : 16. 
 
 The quantity of oxygen combined with the hydrogen in the peroxide, 
 being just double what it was when combined with the same quantity 
 of hydrogen in water. 
 
 " A similar simple proportion between the quantities of the com- 
 bining elements is found to hold good in every series of compounds 
 formed by the union of two elements with each other. A certain 
 quantity of one of the elements combines with a certain quantity of the 
 other ; in the next compound with twice as much as in the first ; in the 
 next with three times ; in the next with four times that quantity, and so 
 on. Sometimes the proportion is rather less simple, two proportions of 
 one element combining with 3, 5, 7, or 9 of the other. 
 
 " This important law, which was first clearly established by Dalton, 
 was explained by him by means of his Atomic Theory. Upon this 
 hypothesis, the ultimate particles of each element are considered to be 
 uniform in size and in weight for that element, and moreover to be in- 
 capable of farther subdivision. When bodies unite chemically, as the 
 particles of the same element have all the same size and relative weight, 
 the proportions in which they combine must be definite ; and farther, if 
 they unite in several different proportions, those proportions must be 
 simply related to each other. Thus, water may be conceived to be a 
 compound in which each separate particle of hydrogen is united with a 
 single particle of oxygen ; and peroxide of hydrogen would be repre- 
 sented as consisting of a combination of two particles of oxygen with 
 each particle of hydrogen. 
 
 3. " This explanation will simplify the consideration of the third law, 
 which is usually known as the Law of Equivalent Proportions. It may 
 be stated as follows : An elementary substance, in combining with other 
 elements, does so in a fixed proportion, which may be represented numeri- 
 cally. 
 
 " If a certain proportion of an element, A, unites with certain other 
 fixed quantities of different elements, B, C, D, &c., to form compounds 
 AB, AC, AD, &c., the quantities of B, C, and D, which so unite with 
 A will also be the quantities, in which B and C, C and D, combine 
 
LAW OF COMBINATION IN MULTIPLE PKOPORTIONS. 539 
 
 to form compound BC, BD, CD, &c." Elements of Chemistry, 1855, 
 i. 12. 
 
 I devote the following pages to the exposition of facts, which show that 
 the " law of combination in multiple proportions" the main-spring of the 
 atomic theory, is unsound ; that it is founded on a fallacy, and that, 
 being fallacious, it necessarily leads to practices which are injurious to 
 chemical philosophy. 
 
 The particular fallacy to which I allude is this : 
 
 a). IT is a. fact, that compounds exist which contain uneven numbers 
 of the elements of which they are composed; such as 
 
 A + A+B;A-fB-fB; A-f-A + B-fB + B. 
 
 b). It MAY BE a fact, that these compounds are constituted by the 
 direct combination of all the atoms of one kind with all the atoms of the 
 other kind. Thus : 
 
 AA + B; A + BB; AA + BBB. 
 
 c). It MAY BE & fact, that chemical combination never takes place 
 except between single atoms of elements, or single equivalents of com- 
 pounds, in which case the compounds which contain the number of 
 atoms of A and B specified above, must make certain intermediate com- 
 pounds. Thus : 
 
 A + AB; AB + B; AB + (AB + B). 
 
 The supposition marked c is in accordance with the electro-chemical 
 theory. The supposition marked b, sets the electro-chemical theory at 
 defiance ; for as it is against all experience in electrolytic researches, that 
 a compound represented by the formula A 2 B 3 , should be separated into 
 A A, going off at one electrode, and BBB going off at the other ; so I 
 conceive it to be equally opposed to electro-chemical probability, that 
 combination should take place directly between such clumps of atoms as 
 AA and BBB. 
 
 But, the law of combination in multiple proportions is founded upon 
 the supposition which is marked b. It takes for granted, but never pre- 
 tends to offer the slightest proof, that combination actually occurs 
 between multiple proportions of atoms. Now, if the supposition which 
 is marked c should prove to be true, that which is marked b must neces- 
 sarily be false, and in that case the law of combination in multiple pro- 
 portions is false ; while so long as it remains uncertain, whether sup- 
 position b or supposition c is true, it is a fallacy to reason as if 
 supposition b was absolutely known to be true. The Jaw of combination 
 in multiple proportions is therefore unsound and not to be trusted. 
 
 We are indebted for this law to Dalton, and we have only to look 
 into the writings of that philosopher to find how feeble and uncertain is 
 the evidence upon which the law is founded. Indeed, while Dalton laid 
 
540 DALTONISM THE ATOMIC THEORY. 
 
 down this law respecting the combination of elements in multiple pro- 
 portions, he confessed that he was totally unable to determine how much 
 of any single element constituted a single proportion. If he was unable to 
 determine how much constituted a single proportion, surely he was in- 
 competent to determine how much constituted a multiple proportion, 
 and if, while in this state of ignorance respecting the very premises of 
 his argument, he made laws which implied the possession of accurate 
 knowledge, though, by accident, the laws might prove to be true, there 
 was far greater chance of their proving to be false. 
 
 I copy the following statement from the Memoirs of John Dalton, by 
 Dr. W. C. Henry, published by the Cavendish Society in 1854. 
 
 " It must be conceded, in limine, that the great atomic generalisation 
 does not stand on the solid basis of induction, which is here, in its first 
 announcement, claimed for it, by its illustrious Author. Even assuming 
 the existence of elementary atoms of different weights (itself obviously 
 hypothetical), we are not in possession of the mathematical elements 
 necessary to infer ' from the relative weights in the mass, the relative 
 weights of the ultimate particles or atoms of the bodies.' All that is 
 certainly established, is, the proportions by weight in which bodies com- 
 bine, in Dalton's words, ' the relative weights of the simples, which 
 constitute a compound.' Now these relative or equivalent weights are, 
 on the atomic hypothesis, the products of the atomic weights into the 
 number of atoms. Consequently, to infer the unknown atomic weights 
 from the known equivalents, we require the number of atoms. But 
 these numbers cannot be ascertained in the case of a single chemical 
 compound. They can only be gathered, according to grounds of proba- 
 bility, from various relations and arguments, to be hereafter enumerated. 
 This general statement may be made clear by a single example. It is 
 established by experiment, that 8 parts by weight of oxygen combine 
 with i part by weight of hydrogen. Let W and w represent the un- 
 known atomic weights of oxygen and hydrogen, and N and n the 
 numbers of atoms present in each mass respectively, 
 
 Then N W = 8 and nw = I 
 8 i 
 
 And W = -r r and w = 
 N n 
 
 Wand w cannot be inferred without knowing ^Vand n. 
 
 "Mr. Dal ton derived the numerical value of N and n from a suppo- 
 sition, which, though highly probable, is still nothing more than an 
 hypothesis. He maintained, that the most stable combinations must be 
 binary, and that when only a single combination of two elements was 
 known, it was probably binary. Water was the only compound of 
 oxygen and hydrogen then known to exist. He therefore regarded it 
 as constituted of one atom of oxygen and one atom of hydrogen. Hence 
 
LAW OF COMBINATION IN MULTIPLE PROPORTIONS. 541 
 
 .A' and n being identical, the atomic weights will be represented by the 
 equivalents 8 and i. 
 
 For W : w :: ~ - :: 8 : i. 
 
 N n 
 
 To bring out more distinctly the hypothetical character of this reasoning, 
 it may be observed, that Berzelius never admitted water to be a 
 ' binary compound ;' but inferred from its being constituted of i part 
 by volume of oxygen and 2 parts of hydrogen by volume, that it consists 
 of i atom of oxygen united with 2 atoms of hydrogen. Substituting i 
 and 2 for N and n in the above formula, we obtain 1 6 as the weight of 
 the atom of oxygen, hydrogen being unity. 
 
 " Mathematical certainty is, therefore, not attainable (even if we 
 admit the existence of atoms of different weights) in any single atomic 
 determination. It is in vain to contend for a higher degree of evidence 
 than that of probabilities, in support of the atomic hypothesis itself; or 
 still less of special calculations of the weights of elementary and com- 
 pound atoms. 
 
 " After this distinct avowal, it will be more satisfactory to recal 
 Dalton's mode of estimating the number of atoms in compounds, in his 
 own words, as expressed in the Appendix to his second volume, 1827, 
 and as therefore conveying his matured views and final teaching. 
 
 " ' The second object of the atomic theory, namely, that of investi- 
 gating the number of atoms in the respective compounds, appears to me 
 to have been little understood, even by some who have undertaken to 
 expound the principles of the theory. When two bodies, A and B, 
 combine in multiple proportions; for instance, 10 parts of A combined 
 with 7 of B to form one compound, and with 14 to form another, we 
 are directed by some authors to take the smallest combining proportion 
 of one body as representative of the elementary particle or atom of that 
 body. Now it must be obvious to any one of common reflection, that 
 such a rule will be more frequently wrong than right. For, by the 
 same rule, we must consider the first of the combinations as containing 
 I atom of B, and the second as containing 2 atoms of B, with i aton 
 or more of A ; whereas it is equally probable by the same rule, that 
 the compounds may be 2 atoms of A to i of B, and i atom of A to i 
 of B respectively ; for, the proportions being 10 A to 7 B (or, which i$ 
 the same ratio, 20 A to 14 B), and 10 A to 146, it is clear by the 
 rule, that when the numbers are thus stated, we must consider the 
 former combination as composed of 2 atoms of A and the latter of i 
 atom of A, united to i or more of B. Thus there would be an equal 
 chance for right or wrong. But it is possible, that 10 of A, and 7 of B 
 may correspond to i atom A, and 2 atoms B; and then jo of A, and 
 14 of B, must represent i atom A, and 4 atoms B. Thus it appears 
 the rule will be more frequently wrong than right. It is necessary not 
 
542 DALTONISM THE ATOMIC THEORY. 
 
 only to consider the combinations of A with B, but also those of A 
 with C, D, E, &c., as well as those of B with C, D, E, &c., before we 
 can have good reason to be satisfied with our determinations as to the 
 number of atoms which enter into the various compounds. Elements 
 formed of azote and oxygen appear to contain portions of oxygen, as the 
 numbers i, 2, 3, 4, 5, successively, so as to make it highly improbable 
 that the combinations can be effected in any other than one of two 
 ways. But in deciding which of these two we ought to adopt, we have 
 to examine not only the compositions and decompositions of the several 
 compounds of these two elements, but also compounds which each of 
 them forms with other bodies. I have spent much time and labour upon 
 these compounds, and upon others of the primary elements, carbon, 
 hydrogen, oxygen, and azote, which appear to me to be of the greatest 
 importance in the atomic system ; but it will be seen that I am not satis- 
 fied on this head, either by my own labour or that of others, chiefly 
 through the want of an accurate knowledge of combining proportions.' " 
 This extract proves that Dalton, at the time of his " matured views 
 and final teaching," in the year 1827, was unable to determine, by the 
 help of his atomic theory, how much of any single element constituted 
 a single combining proportion. Thirty years, fruitful in chemical dis- 
 coveries, have since elapsed. But the disciples of Dalton are, at this 
 time, as unable as was the philosopher himself, from the beginning to 
 the end of his career, to determine the atomic weight of any single 
 element by the help of the atomic theory. The defect is a radical one ; 
 and a " fixed law," affecting " to regulate combination in multiple pro- 
 portions/' instituted in virtue of a theory which cannot distinguish 
 multiple proportions from single proportions, can only be regarded as a 
 house built upon shifting sands, liable to be moved hither and thither 
 with every wave of adverse doctrine. 
 
 RELATION OF THE ATOMIC WEIGHTS OF ELEMENTS TO THE SPECIFIC 
 GRAVITIES OF THEIR GASES. 
 
 Among the methods that have been suggested for determining how 
 much of an element constitutes a combining proportion, the one which is" 
 apparently least liable to error, is that which considers the specific 
 gravities of elementary gases to be the expression of their combining 
 proportions. Upon that idea, 
 
 the atomic weight of oxygen is = 1 6 
 that of hydrogen is = I 
 chlorine is = 35*5 
 nitrogen is = 14 
 
 It was pointed out by Gay-Lussac in the year 1809, that the combining 
 weights of the elements which produced gases, bore a relation to 
 the weights of single volumes of gases, so that combination actually 
 
LAW OF COMBINATION IN MULTIPLE PROPORTIONS. 543 
 
 took place either between even volumes of gases or between simple 
 multiples of even volumes. 
 
 Thus nearly at the same time that Dalton invented the atomic theory, 
 Gay-Lussac discovered this law of nature. Of these two things, Gay- 
 Lussac's has proved to be by far the most beneficial. 
 
 The difference in value between the two systems is easily shown 
 by a few examples. One volume of hydrogen and one volume of 
 chlorine produce two volumes, or one atom, of hydrochloric acid. This 
 would agree with either theory. 
 
 Two volumes of hydrogen and one volume of oxygen form one atom 
 of water, which in the state of gas measures two volumes. 
 
 Equal volumes of hydrogen and oxygen produce peroxide of hydrogen. 
 Of course, equal volumes may signify O l + H 1 , or O 2 -f- H 2 . This 
 compound is unknown in the state of gas. 
 
 We have seen that in the interpretation of the constitution of water 5 
 Dalton went upon no fixed ground. He considered it to be composed 
 of one atom of each element, because it was the only compound of oxygen 
 and hydrogen with which he was acquainted. Professor Miller's argument 
 is scarcely more cogent. " Water," he says, " may be conceived to be 
 a- compound in which each separate particle of hydrogen is united with 
 a single particle of oxygen ; and peroxide of hydrogen would be repre- 
 sented as consisting of a combination of two particles of oxygen with 
 each particle of hydrogen." 
 
 But if, as Berzelius originally suggested, we take a single volume of 
 each of the four gases above named to represent a single combining pro- 
 portion, we are freed at once from doubt and difficulty, at least as far as 
 respects these four elements and their compounds. Thus : 
 
 One vol. of chlorine = Cl 1 _ TT _ Hydrochloric acid. 
 
 One vol. of hydrogen = H J 2 volumes. 
 
 One vol. of hydrogen = H ) _ TTQ _ Peroxide of hydrogen. 
 
 One vol. of oxygen = O f volume unknown. 
 
 Two vols. of hydrogen = HH ) _ TTTTQ _ Water. 
 
 One vol. of oxygen = O f 2 volumes. 
 
 Two vols. of nitrogen = NN 1 _ -VT^/^ _ Protoxide of nitrogen. 
 
 One vol. of oxygen = O j 2 volumes. 
 
 One vol. of nitrogen = N j _ -^Q _ Deutoxide of nitrogen. 
 
 One vol. of oxygen = O j ~ 2 volumes. 
 
 One vol. of nitrogen = N 1 _ -\rr\r\ _ Peroxide of nitrogen. 
 
 Two vols. of oxygen = 00 f 2 volumes. 
 
 The point to be observed here the great point, the useful point, the 
 deciding point, is, that we not only WEIGH the combining proportions, 
 but we also MEASURE them, and we acquire by that means a security 
 which Dalton's atomic theory can never afford us. If the resulting 
 volumes of the compounds produced by the combination of these gases 
 
544 DALTONISM THP] ATOMIC THEORY. 
 
 had been marked by regularity, the security afforded by this method of 
 reasoning would no doubt have been perceived by chemists long ago ; 
 but the irregularity of the atomic measures of these compound gases 
 obscured the view which chemists ought to have taken of their compo- 
 sition and components. 
 
 Consult the " Inquiry into the Causes which modify the Atomic 
 Measure of Compound Gases," page 94. 
 
 Let us follow out the argument derived from the constitution of gases. 
 
 Only a few of the elements produce gases at the ordinary tempera- 
 ture of the air, and we must derive the atomic weights of the fixed or 
 non-volatile elements by indirect processes. Yet the reference to the 
 densities of the four gases, as fundamental authorities, is of the greatest 
 importance. I frame upon it the observation that 
 
 The combining proportion of any element is the quantity which is chemi- 
 cally equivalent to a single volume of hydrogen or of chlorine. 
 
 I take hydrochloric acid as the model of a chemical compound, or as 
 I have called it, for shortness, a SALT. The formula is HC1, in which 
 H and Cl represent two elements, each of which is separately replace- 
 able by other elements. To these two replaceable halves of a salt, 
 whether simple or compound, I apply the term RADICAL : in this 
 example, H is the basic radical and Cl is the acid radical. If Cl is 
 replaced by Br, we procure the salt HBr; if replaced by I, we pro- 
 cure the salt HI. The quantity of Br which replaces 35-5 parts of 
 Cl weighs 80; the quantity of I weighs 127. If these quantities of 
 Br and I are raised by heat into vapour until they measure as much 
 as one volume of chlorine, the specific gravities of the vapours become 
 as follow : 
 
 Cl = 35-5; Br = 80; I = 127. 
 
 Consequently, these replacements confirm the accuracy of the rule, and 
 fix the atomic weights of Br and I. On the other hand, if we replace 
 the basic H in HC1 by a metal, as by potassium, barium, silver, &c., 
 we produce KC1, BaCl, AgCl, &c., and these quantities of metals com- 
 bine equally well with the equivalent quantities of Br and I, to produce 
 the neutral salts KBr, KI, BaBr, Bal, and AgBr,AgI ; consequently, 
 the quantities K, Ba, and Ag are the equivalents of H. 
 
 Proceeding in this manner, we gradually discover how much of each 
 known element is the equivalent either of H 1 or Cl 1 . The quantities 
 thus determined are quoted in the Table which is printed at page 28, 
 and which I take the liberty to call here, a Table of Simple Radicals. In 
 the course of this proceeding, experiment develops the peculiarity, that 
 certain metals possess the power to form two simple radicals which differ 
 from one another in weight, but not in their chemical equivalency, each 
 being able to replace H 1 and to neutralise Cl 1 , Br 1 , or I 1 , and to prpduce 
 a series of neutral salts, equivalent to one another in chemical power, 
 
LAW OF COMBINATION IN MULTIPLE PROPORTIONS. 545 
 
 but possessed of entirely different physical properties. Thus iron can 
 produce a radical the weight of which is 28, and another, the weight of 
 which is 1 8-f , and these two radicals produce two extensive series of 
 salts, which differ greatly in their properties, but only in their compo- 
 sition to the extent that 28 by weight of iron in one salt is replaced by 
 i8| of iron in the other, all other elements in the salts remaining the 
 same. From the fact that these radicals produce salts that are perfectly 
 and characteristically distinct from one another, I assume that the 
 radicals themselves, though both produced by iron only, are perfectly 
 different radicals. This argument is pursued at page 32, and I need 
 not repeat it. 
 
 On the Daltonian theory, this parallelism in the sets of salts is not 
 acknowledged to exist. Instead of it, a triplication is made of all the 
 ingredients of one of the sets of salts, and the triple atoms are in each 
 salt divided into an imaginary conglomeration of three atoms of " acid " 
 and a "base" consisting of two atoms of metal and three atoms of 
 oxygen, with which base the three atoms of acid are assumed to be 
 combined. I have given an example of such salts at page 37. These 
 complex salts are taken under the especial patronage of the law of com- 
 bination in multiple proportions. They are commonly called salts of the 
 sesquioxides, and their assumed composition is, without exception, ima- 
 ginary and unreal. 
 
 The formula which I have adopted as the model of a salt, namely, 
 HC1, is of great importance as regards organic compounds. I have 
 shown that a vast number of organic compounds may be arranged in 
 three groups : 
 
 A, Basic Radicals. B, Acid Radicals. C, Salts. 
 
 The basic radicals are equivalent to H, or a single volume of hydrogen ; 
 the acid radicals are equivalent to Cl, or a single volume of chlorine ; 
 the salts are equivalent to HC1, or to two volumes of hydrochloric acid : 
 the evidence in support of these facts is given in the Table of Gases at 
 page 49, and in the commentary which follows it. This evidence is 
 abundant and conclusive. It proves that a radical measures one volume, 
 and that it is of no importance as respects its measure whether a radical 
 is simple or compound, whether it is oxidised or not oxidised. In 
 short, it proves that one volume is the measure of a chemical equiva- 
 lent, an acting quantity, a combining proportion, or an atom, give it 
 what name you please, and therefore that one volume of an elementary 
 gas is the quantity with which we may begin to construct our Table 
 of Atomic Weights. The entire set of laws which are founded on 
 the "atomic theory" are utterly insignificant, when compared with 
 the results which thus naturally flow from Gay-Lussac's discovery re- 
 specting the combination of gases, and Berzelius's perception of its 
 utility. 
 
 * 2N 
 
546 DALTONISM THE ATOMIC THEORY. 
 
 The discovery of the fact that radicals of every description are the 
 equivalents of H 1 and Cl 1 , and that two radicals complete a salt, whether 
 oxygen is present or not, reduces the theory of salts to great simplicity, 
 and goes far to obliterate the needless and absurd distinction which is 
 usually made between inorganic chemistry and organic chemistry. 
 
 I need scarcely refer in this summary to matters of detail that have 
 been amply developed in the article on the gases, such as the fact, that 
 oxygen, carbon, sulphur, and radicals with an even number of atoms 
 of hydrogen, measure nothing in gaseous salts; nor to any other 
 of the peculiarities of the elements of gases, the elimination of which 
 has enabled me to give to the theory of gases a useful degree of 
 exactness. See page 108. 
 
 If the law of combination in multiple proportions was well founded, 
 and could explain anything, it might be useful in organic chemistry to 
 explain the production of complex organic radicals. Let us see how it 
 helps us there. Turn to page 525, and look down Group A. What 
 does the law of combination in multiple proportions teach us in reference 
 to the radicals which are formulated in that column? Reading the 
 Table, in accordance with this law, we may say " One atom of carbon 
 combines with three atoms of hydrogen to form one atom of methyl. 
 Twenty-seven atoms of carbon combine with fifty-five atoms of hydrogen 
 to form one atom of ceryl. Thirty atoms of carbon combine with sixty- 
 one atoms of hydrogen to form one atom of myricyl." That is the 
 teaching of the law of combination in multiple proportions ! Can any 
 human being believe such statements to be true? What kind of 
 " affinity " is it which induces 30 atoms, all alike, to combine with one 
 another into a clump, which induces 61 other atoms, also all alike, and 
 in the presence of 30 different atoms, to combine with one another into 
 another clump, and which then induces the two clumps to combine into 
 one compound ? 
 
 I confess, that this doctrine of combination in multiple proportions is 
 beyond my powers of comprehension, and I cast it aside as a useless 
 incumbrance. I do not believe that the radicals of Group A, page 525, 
 are in any case formed by the direct combination of all their carbon with 
 all their hydrogen. On the contrary, I believe that the radicals of this 
 group, like those of all other groups, are built up progressively by the 
 method which I have described in the last section. The evidence in 
 favour of this supposition is the fact, that at each step of the progression, 
 a definite radical is produced which possesses an ascertainable in- 
 dividuality. 
 
 Thus, H is a radical = Hydrogen. 
 
 C-f H is a radical = CH, Formyl. 
 CH+H is a radical = CH 2 , Vinyl. 
 CH 2 +H is a radical = CH 8 , Methyl. 
 
EVIDENCE OF ELECTROLYSIS IN FAVOUR OF THE RADICAL THEORY. 547 
 
 Then, in another series we have 
 
 H + CH 2 = CH 3 , methyl. 
 CH 8 -f-CH 2 = C'H 5 , ethyl, 
 C*H 5 + CH 2 = C 3 H 7 , propyl, and so on to 
 C 29 H 59 -f CH 2 = C 30 H 61 , myricyl. 
 
 In this process of construction, everything goes on step by step, and 
 every step is of use. There is no evidence of the occurrence of those 
 monstrous jumps of one mighty block of atoms to join another mighty 
 block, which the law of combination in multiple proportions calls upon 
 its votaries to credit. 
 
 When a galvanic circuit shall be found to require 30 zincodes and 
 6 1 platinodes, and shall be able to decompose an atom of myricyl in such 
 a manner as to throw off 30 atoms of carbon at the zincodes and 61 
 atoms of hydrogen at the platinodes, and shall thereby give us some 
 reason to believe in the possibility of " decomposition in multiple propor- 
 tions," it will be time to begin to believe in the assumed fact of 
 "combination in multiple proportions;" but there is no necessity to 
 adopt this belief, till we have witnessed the performance of that 
 experiment. 
 
 The Evidence of Electrolysis in favour of the Eadical 
 
 Theory. 
 
 As the terms employed by writers on electro-chemistry differ greatly, 
 I take the liberty to prefix a list of synonyms. 
 
 Negative Pole ; pole ; cathode ; platinode ; negative electrode. 
 To this pole go Hydrogen, Metals, Alkalies. 
 
 Positive Pole ; -f- pole ; anode ; zincode ; positive electrode. 
 To this pole go Oxygen, Chlorine, Acids. 
 
 A. MAGNUS'S RESULTS. 
 
 An interesting series of u electrolytic researches " has just been pub- 
 lished by Professor G. Magnus (Poggendorf s Annalen der Physik und 
 Chemie, No. 9, i857 Band cii.), from which I extract the following 
 1 2 results ; referring to the original essay for details. 
 
 1. For i equivalent of oxygen disengaged [in the voltameter], when 
 cuprous chloride is acted on, 2 equivalents of copper are deposited. 
 
 2. From stannous chloride, Sn-f-Cl, for i equivalent of oxygen, 
 I equivalent of tin. 
 
 2N2 
 
548 EVIDENCE OF ELECTROLYSIS 
 
 2. From stannic chloride, Sn-{-2Cl, for I equivalent of oxygen, half 
 an equivalent of tin. 
 
 Hence, an atom of stannous chloride requires for its decomposition 
 half as much electrical power as an atom of stannic chloride. 
 
 4. When the current went from the voltameter first through cupric 
 sulphate and then through cuprous chloride, twice as much copper was 
 deposited in the latter as in the former. 
 
 5. There is no evidence in favour of Darnell's supposition of the 
 decora posability of CuO-f SO 3 into Cu+SO 4 . 
 
 6. When an aqueous solution of pure crystallised iodic acid is acted 
 upon, i equivalent of iodine is deposited on the negative electrode and 
 5 equivalents of oxygen are set free on the positive electrode. 
 
 7. It requires five times the electric power to decompose an atom of 
 iodic acid = I -f- O 5 , that it requires to decompose an atom of water 
 
 = H+O. 
 
 8. The same electric power is required to separate the same quantity 
 of oxygen from iodic acid and sulphuric acid, while for H l disengaged 
 by the sulphuric acid only I-i- is deposited by the iodic acid. 
 
 9. To decompose an atom of ferric sulphate = Fe 2 3 + 3 SO 3 + Aq 
 into ferrous sulphate 2(FeO -f- SO 3 ) and into oxygen 0, and sulphuric 
 acid SO 3 , it requires the same power as to decompose an atom of water 
 H + O, and also the same power as to decompose FeO + SO 3 into iron 
 on the one side, and oxygen and sulphuric acid on the other. 
 
 I o. The same power is required to separate a simple substance from 
 a binary compound as is required to separate it from a complex saline 
 compound. 
 
 1 1 . This result may present a difficulty to chemists, who can only 
 conceive the decomposition of a salt to be into an acid and a base ; for, 
 according to this view, the power which is required to decompose the 
 oxide must also be strong enough first to separate the oxide from the 
 acid, and then to decompose the oxide. But this difficulty falls away 
 if we consider the galvanic decomposition to be a distributive action of 
 the electricity (eine vertheilende Wirkung der Electricitat). 
 
 12. How greatly the atoms which are equivalents in galvanic action 
 differ from chemical atoms is shown by the following examples : 
 
 Chemical Atoms. Galvanic Equivalents. 
 
 H + H + 
 
 1 + 50 ii + o 
 
 CuO -|- SO 3 + 5Aq CuO + SO 3 + 5Aq 
 
 Cu + Cl Cu + Ci 
 
 2 Cu + Cl 2Cu -f- Cl 
 
 Sn + Cl *Sn -f Cl 
 
 2Sn + Cl Sn + Ci 
 
IX FAVOUR OF THE KADICAL THEORY. 549- 
 
 B. FARADAY'S RESULTS. 
 
 13. " Electrolytes must consist of two ions." 
 
 14. " There is but one electrolyte, composed of the same elementary 
 ions, at least such appears to be the fact, dependent upon a law, that 
 only single electro-chemical equivalents of elementary ions, can go to the 
 electrodes and not multiples." 
 
 15. "Electro-chemical equivalents coincide, and are the same with 
 ordinary chemical equivalents." 
 
 1 6. "A very valuable use of electro-chemical equivalents will be 
 to decide, in cases of doubt, what is the true chemical equivalent, 
 or definite proportional or atomic number of a body ; for I have such a 
 conviction that the power which governs electro-decomposition and 
 ordinary chemical attraction is the same, and such confidence in the 
 overruling influence of those natural laws which render the former 
 definite, as to feel no hesitation in believing that the latter must submit 
 to them also. Such being the case, I can have no doubt, that assuming 
 hydrogen as i, and dismissing small fractions for the simplicity of 
 expression, the equivalent number or atomic weight of oxygen is 8, of 
 chlorine 36, of bromine 78*4, of lead 103*5, ^ * m 59' & c ' notwith- 
 standing that a very high authority doubles several of the numbers." 
 
 17. " The equivalent weights of bodies are simply those quantities of 
 
 them which contain equal quantities of electricity or, if we 
 
 adopt the atomic theory or phraseology, then the atoms of bodies have 
 equal quantities of electricity naturally associated with them. But I 
 must confess I am jealous of the term atom ; for though it is very easy 
 to talk of atoms, it is very difficult to form a clear idea of their nature, 
 especially when compound bodies are under consideration." Henry's 
 Memoirs of JDalton, page 1 06. 
 
 C. GMELTN'S SUMMARY. 
 
 1 8. An electric current decomposes an atom of an oxygen salt in the 
 same time as it decomposes an atom of water or chloride of lead. 
 
 19. When sulphate of soda is decomposed it is found that the 
 volume of detonating gas collected in the voltameter is equal to the 
 volume of hydrogen obtained in the negative division of the decomposing 
 apparatus together with that of the oxygen evolved in the positive 
 division, and that for every 9 parts (one atom) of water decomposed 
 in the voltameter, 32 parts (one atom) of soda are set free in the 
 negative, and 40 parts (one atom) of sulphuric acid in the positive 
 division. 
 
 20. If the voltameter consists of fused chloride of lead, then an atom 
 of lead is deposited for every atom of sulphate of soda, or sal-ammoniac, 
 or chloride of sodium, which is decomposed in the cells. 
 
550 EVIDENCE OF ELECTROLYSIS 
 
 21. These experiments are favourable to the supposition that the 
 oxygen-salts should be regarded as compounds of metals with the 
 so-called salt-radicals, e.g., sulphate of soda not as NaOjSO 3 , but as 
 Na,S0 4 ; and that the same quantity of electricity which serves to sepa- 
 rate an atom of oxygen, chlorine, or iodine, from an atom of hydrogen, 
 or a metal, is likewise exactly sufficient to separate an atom of SO 4 , 
 or any other compound salt-radical from an atom of metal. Daniell. 
 
 22. Matteucci obtained the same results by subjecting other salts to 
 similar treatment. For every atom of water decomposed in the 
 voltameter he obtained from the saline solution i atom of hydrogen gas, 
 I atom of oxygen, i atom of base, and i atom of acid. 
 
 23. The theory which regards sulphate of soda as Na,S0 4 certainly 
 affords the simplest explanation of its electrolysis. Since, however, 
 many weighty reasons may be urged against the adoption of this hypo- 
 thesis, the following explanation may for the present be admitted. 
 Sulphate of soda is NaO,S0 3 ; decomposition by the electric current is 
 exerted only on the soda (since, by Faraday's law, SO 3 is incapable 
 of direct decomposition). Sodium separates at the negative pole, where 
 it decomposes water and yields soda and hydrogen gas. The oxygen 
 which was combined with the sodium is transferred, together with the 
 sulphuric acid, to the adjacent atom of sodium. An atom of oxygen is 
 set free at the positive pole, and since the sodium which was combined 
 with it goes towards the negative pole, the sulphuric acid is set free by 
 secondary action, or rather it passes from its state of combination with 
 soda into that of combination with w r ater. 
 
 24. In the case of sulphate of copper, &c., similar actions take place, ex- 
 cepting that the metal liberated by the current does not decompose water. 
 
 25. The decomposition of oxygen-salts of ammonia is most satisfac- 
 torily explained by adopting the ammonium theory of Berzehus, 
 according to which, sulphate of ammonia, for example, which always 
 contains water, is to be regarded as sulphate of oxide of ammonium 
 (NH 4 O,SO 3 ). The electric current decomposes the oxide of ammonium, 
 just as it does a metallic oxide, into oxygen and ammonium, and the 
 latter is resolved into hydrogen gas which escapes, and ammonia which 
 remains in solution. According to this view, the direct action of the 
 electric current is confined to the decomposition of metallic oxides, and 
 the transference of the acid from the decomposing oxide to the water is 
 merely a consequence of this action. (Hess's Observations on Daniell's 
 Theory, in Pogg. Ann., 53, 505). Gmelin's Handbook of Chemistry, 
 i. 460. 
 
 D. PARTICULAR FACTS. 
 
 26. It is clearly proved by experiment that for every 32 grains of 
 zinc which is dissolved in any one cell of the battery, 9 grains of water 
 are decomposed in the voltameter. Miller. 
 
IN FAVOUR OF THE RADICAL THEORY. 551 
 
 27. If the current is made to pass first through fused iodide of lead, 
 and then through fused chloride of tin, for each 32 grains of zinc 
 dissolved in any one cell of the battery, 104 grains of lead, and 59 
 grains of tin will be separated on the respective platinodes, whilst 126 
 grains of iodine, and 36 grains of chlorine will be evolved on the 
 respective zincodes. Miller. 
 
 28. When starch which contains both iodine and bromine is subjected 
 to the action of the current, the mixture becomes blue at the negative 
 pole and orange-coloured at the positive pole, showing that iodine is 
 transferred to the former and bromine to the latter. De la Rive. 
 
 29. When dilute phosphoric acid is acted upon, and the oxygen and 
 hydrogen are collected apart, it is found that while one atom of water is 
 decomposed, only from one-fifth to one-fourth of an atom of phosphoric 
 acid is carried over to the positive pole. Daniell. 
 
 30. When hydriodic acid is electrolysed, hydrogen goes to the 
 negative pole, and iodine and oxygen to the positive pole. Matteucci. 
 
 3 1 . Aqueous solution of iodide of potassium yields iodine at the 
 anode, potash and hydrogen gas at the cathode. Faraday. 
 
 32. Fused protochloride of tin is resolved into metallic tin and 
 bichloride of tin, the latter escaping in vapour. Faraday. 
 
 33. Aqueous solution of sal-ammoniac is resolved into chlorine at the 
 positive pole and hydrogen and ammonia at the negative pole. Hisinger 
 and Berzelius. 
 
 34. Solution of common salt gives chlorine at the positive pole, 
 hydrogen gas and soda at the negative pole. Higgins and Draper. 
 
 35. Hydrate of potash yields oxygen gas at the anode, and at the 
 cathode hydrogen gas and potassium. Davy. 
 
 APPLICATION OF ELECTROLYTIC FACTS TO THE SUPPORT OF THE 
 RADICAL THEORY. 
 
 I proceed to show that these electrolytic facts are in accordance with 
 the radical theory, and in particular with the following axioms : 
 
 1. A salt is a compound of two radicals, simple or compound, with or 
 without oxygen. 
 
 2. Water is a salt, whose constitution is represented by the formula 
 H-fHO. 
 
 3. All combination is binary. One basic radical combines with one 
 acid radical. 
 
 4. Combination in multiple proportions never takes place. 
 
 5. Chemical radicals are the same as galvanic equivalents. 
 
 In the following explanations, I take the facts in the order of the fore- 
 going list. The symbols have now the values given at page 28. 
 
 i . Cuprous chloride, CuCl, gives Cu, with ^ O in the voltameter. 
 
552 EVIDENCE OF ELECTROLYSIS 
 
 Because Cu is the basylous atom = 64 combined with Cl. Both Cu 
 and Cl are equivalent to H. Consequently ^(HHO) is decomposed 
 in the voltameter. If HHO were set free in the voltameter, that is to 
 say, 2 parts or 2 volumes of hydrogen, and 16 parts or I volume of 
 oxygen, the equivalents of HH, namely, C1C1 and CuCu, must be set 
 free in the cells. Magnus's " I equivalent of oxygen," signifies 8 by 
 weight, or % volume of gas, so that if the equivalent of is doubled, 
 the equivalent of the deposited metals must also be doubled. On this 
 point, consult No. 16, page 556. 
 
 2. Stannons chloride, SnCl, gives Sn for^O. Because Sn is the 
 basylous atom =59, combined with Cl. Both atoms = H. Hence 
 (HHO) is decomposed. 
 
 3. Stannic chloride, SncCl, gives Snc or Sn, for O. Because Snc 
 is the basylic atom = 29*5, combined with Cl. Both atoms = H. 
 Hence ^(HHO) is decomposed. 
 
 Magnus's idea that the atom of stannous chloride requires for its de- 
 composition half as much electrical power as the atom of stannic 
 chloride is a fallacy. If Cl is put as the standard, the same power sepa- 
 rates it from each salt, but with the deposition of Cu in one case, and 
 Cue in the other, the former radical being twice as heavy as the latter. 
 
 4. When cupric sulphate = CucSO 2 and cuprous chloride = CuCl 
 are acted on by the same current, the first gives Cue = 32, and the 
 second gives Cu = 64, because both of these are radicals of the same 
 chemical and voltaic equivalence. 
 
 5. Read Gmelin's summary of facts and opinions as to Daniell's 
 Theory, Nos. 1 8 to 25. 
 
 I do not know in what manner the oxygen of a salt is divided between 
 the basic radical and the acid radical, and the whole series of electro- 
 lytic researches gives no conclusive results on this point. 
 
 When sulphate of copper = Cuc,SOO, which consists of two radicals 
 with two atoms of oxygen, is decomposed in the presence of water, I 
 apprehend that hydrated sulphuric acid is instantly constituted at the 
 cost of an atom of water; thus : 
 
 jCuc,SOO] [Cue + H,SOO 
 (Cuc,SOO \ = { Cue -f H,SOO 
 Water HHOJ [ O 
 
 According to this equation, 64 parts of copper are deposited while 
 1 6 parts of oxygen are disengaged, which agrees with the statical re- 
 sults. The reason that two atoms of the copper salt are decomposed 
 is, that water contains two atoms of hydrogen, and demands two atoms 
 of sulphur with which to combine. See No. 16, page 556. 
 
 The passage of the electric current through a solution of sulphate of 
 copper, may be represented thus : 
 
IX FAVOUR OF THE RADICAL THEORY. 
 
 553 
 
 A. Before the current passes. 
 
 - Pole 
 
 CucSOO 
 CucSOO 
 
 CucSOO 
 CucSOO 
 
 CucSOO 
 CucSOO 
 HHO 
 
 B. After the current passes. 
 
 Cue 
 Pole Cue 
 
 SOOCuc 
 SOOCuc 
 
 SOOCuc 
 SOOCuc 
 
 SOO 
 
 soo 
 
 HH 
 
 Pole. 
 
 Pole. 
 
 o 
 
 Before the current passes, (A.), the atoms of sulphate are supposed to be 
 in contact with water, ready to act in case of need, which I take it we 
 must admit to be the constant duty of the water of a solution. After 
 the current passes (B.), an atom of oxygen is given off at the positive 
 pole, two atoms of hydrated sulphuric acid are deposited there, and 
 simultaneously two cupric atoms are deposited at the negative pole. 
 The electric power is transferred through the solution in the manner 
 shown by the diagram. 
 
 In this explanation, I have supposed that the cupric sulphate is 
 Cue -f- SOO; let us see how it would act if its composition were 
 CucO -f SO. 
 
 A. Before the current passes. 
 
 - Pole 
 
 Cue 
 
 - Pole Cue 
 
 CucOSO 
 CucOSO 
 HHO 
 
 B. After the current passes. 
 
 CucOSO 
 CucOSO 
 
 CucOSO 
 CucOSO 
 
 OSOCuc 
 
 OSOCuc 
 
 OSO 
 
 OSOCuc 
 
 OSOCuc 
 
 oso 
 
 1 
 
 
 HH 
 
 Pole. 
 
 Pole. 
 
 O 
 
 There is no effect represented here which helps to decide the question 
 whether the oxygen of a sulphate is entirely combined with the sulphur, 
 or divided equally or unequally between the sulphur and the metal. The 
 movements of oxygen are too subtle for detection either by chemical re- 
 actions or electrolysis. 
 
 6. When a salt which contains iodine as its negative radical without 
 oxygen, is electrolysed, the iodine is deposited on the positive pole ; see 
 iodide of potassium (27 and 31) and hydriodic acid (30); but when 
 iodic acid (H,IO 3 ) is electrolysed, the iodine is deposited on the negative 
 pole, and the oxygen is given off on the positive pole. 
 
 7, 8. The disengagement of O 5 from diluted sulphuric acid leaves the 
 sulphuric acid in its original condition, so that the O 5 come entirely from 
 
554 EVIDENCE OF ELECTROLYSIS 
 
 water, and must liberate H 10 . The disengagement of O 5 from iodic acid 
 leaves nothing but iodine, its hydrogen and oxygen being all disengaged ; 
 but since HIO 3 does not contain O 3 , we must examine more closely what 
 this reaction signifies : 
 
 When this compound is exposed to electrolysis, I imagine that it gives 
 off its oxygen atom by atom, producing a series of acids which may be 
 represented by the following formulae : 
 
 JHIOOO , ni 
 
 l - IHIOO ' 
 
 IHIOO 2 
 
 2< IHIOO " 
 
 IHIOO 3 
 
 j' 1 TTTO ~i 
 
 , IHIO 04 
 
 4- {mo +c 
 
 I"-** 
 
 6. 1 J +HHO 
 
 By five successive operations, each equivalent to the decomposition of an 
 atom of water, and each therefore yielding O 1 , it gives oft' in all O 5 . 
 Arrived at this point, the last O and the two atoms of H combine 
 together, and the iodine is finally isolated. It is easy to understand, that 
 as the iodine is deposited on the negative pole, the liberated oxygen 
 must act there upon the water, and cause a corresponding reaction at the 
 positive pole. Every O 1 lost by the iodic acid takes H 2 from the water 
 at the negative pole, and therefore throws off O 1 at the positive pole. 
 The correspondence of the decomposition of one atom of iodic acid with 
 the disengagement of O 5 from sulphuric acid is clear enough, but it 
 remains equally clear that the acid radicals of iodic and sulphuric acid 
 are each one radical, and that each effects the decomposition of 5HHO. 
 9. I conceive this reaction to take place as follows : 
 
 (FecSO 2 ) (FeSO 2 ) 
 
 ^ FecSO 2 1 \ FeSO 2 1 
 
 (FecSO 2 ) (HSO 2 ) 
 
 f FecSO 2 I FeSO 2 ) 
 
 4 FecSO 2 1 {FeSOH 
 
 [FecSO 8 ] IH SO 2 ] 
 H,HO O 
 
 Under the action of the electric current, which decomposes an atom of 
 water and sets free H 2 , the ferric atoms of these sulphates become con- 
 verted into ferrous atoms. Six ferric atoms produce four ferrous atoms, 
 and set free SO 2 -|- SO 2 to take up the free H 2 and produce two atoms 
 of hydrated sulphuric acid. The separation of H 2 from water sets O 1 
 free. Extensive as this reaction appears in the diagram, the electrolytic 
 action takes place only upon one atom of HHO, and therefore corre- 
 sponds with , HHO in the voltameter. The presence of the basic 
 hydrogen thus set free, is the predisposing cause of the reduction of 
 
IX FAVOUR OF THE RADICAL THEORY. 555 
 
 the ferric atoms to ferrous atoms. I have fully explained the nature of 
 this operation at pages 34 and 310 in this work. 
 
 The reduction of ferrous sulphate to iron, oxygen, and sulphuric acid, 
 referred to in 9 as being effected by the same amount of electric power 
 as the decomposition of H + HO, may be explained as follows : 
 
 FeSO 2 + H Fe + HSO 2 
 
 FeSO 2 + H = Fe + HSO 2 
 
 O O 
 
 Here again the effect is practically produced by the electro-decomposition 
 of one atom of water. 
 
 10. The statement made at this number is true within certain limits, 
 but not in an absolute sense. One unit of electric power decomposes one 
 equivalent of an iodide and liberates one atom of iodine, see 27, 31 
 whereas five units of electric power are demanded to decompose one 
 equivalent of hydrated iodic acid, and liberate one atom of iodine, see 
 6, 7, 8. 
 
 The statement is probably true of all salts that contain TWO RADICALS 
 with no oxygen, or with O 1 , or with O 2 , but not with O 3 ; for the salts of 
 iodine with O 3 , just referred to, and those of phosphorus with O 3 , see 
 29 both require additional force. The uniformity of the action upon 
 salts that contain 0, O 1 , O 2 , depends upon the contemporaneous reaction 
 on one atom of water H -f- HO ; the special results in each case varying 
 according to the individual properties of the radicals submitted to elec- 
 trolysis ; such as the power of the separated metal to remain metallic, as 
 copper, or to form a hydrated alkali, as potassium, or that of the acid 
 radical to fly off in gas as chlorine, or to remain in the liquid as 
 hydrated acid, like sulphuric acid. 
 
 1 1 . The difficulty which Magnus alludes to in this number, is for me 
 non-existent. Every lase and every acid is for me a SALT. All these 
 three classes of compounds contain on the radical theory two radicals, 
 and are subject to decomposition by the same amount of electric power, 
 provided their quantum of oxygen presents no hindrance. But if I felt 
 a difficulty on this point, and required an explanation, I should be dis- 
 satisfied with that which is given by Magnus ; because I am unable to 
 comprehend how "the same power" can perform distributively twice 
 the work that it can perform collectively. 
 
 12. Magnus's conclusion, that ''galvanic equivalents are not the same 
 as chemical atoms" is a fallacy, which arises from the reasonings 
 prompted by his atomic weights (viz., O = 8, water = H + O, &c.) 
 and which disappears when the equivalents are adjusted to suit the 
 atomic weights of the radical theory. Thus 
 
 Water should be = H,HO. 
 Hydrated iodic acid ~ H,I0 3 
 
556 EVIDENCE OF ELECTROLYSIS 
 
 Ciipric sulphate = CucSO 2 
 
 Cuprous chloride = CuCl 
 
 Cupric chloride = CucCl 
 
 Stannous chloride = SnCl 
 
 Stannic chloride = SncCl. 
 
 The explanations which I have given prove that the chemical and gal- 
 vanic atoms are perfectly equivalent. Be it remarked, however, that 
 the chemical equivalents are not atoms according to the common scale of 
 atomic weights, but radicals in accordance with the radical theory, 
 which acknowledges that both tin and copper make two different 
 radicals, each of which is the equivalent of an atom of hydrogen, even 
 in the electric current. 
 
 13. This first law of electrolysis, as laid down by Faraday, seems to 
 be true, arid to be destructive of the law of combination in multiple pro- 
 portions ; for if chemical and electrical action is the same, how can we 
 logically admit that chemistry can combine together multiple propor- 
 tions which electricity cannot separate? 
 
 14. This result must be compared with the results obtained by 
 Magnus, such as the electrolysis of the compounds 
 
 Cu Cl Sn Cl 
 
 CucCl SncCl 
 
 These results seem to be in opposition to the law which is here laid 
 down by Faraday, but they agree perfectly well with the theory that 
 the basylous and basylic atoms are different radicals produced by the 
 same element, and act severally as elementary ions. 
 
 I 5. Electro-chemical equivalents agree with radicals. 
 
 1 6. I agree with Faraday's general principle, but not with all the 
 atomic numbers which he has deduced by means of it. Those of 
 chlorine, bromine, and lead I agree to. That of tin represents the 
 stannous radical, and must be coupled with another to represent the 
 stannic radical. Faraday's experiment (32) is not adverse to this 
 proposal. He found that SnCl was resolved by electrolysis into SncCl 
 4- Snc, namely, the combined action of heat and electricity splits Sn 
 into Snc -}- Snc, half the metal remains behind and the volatile SncCl 
 flies oft' in vapour. My chief objection lies to Faraday's number for 
 oxygen = 8, which is only half what it ought to be. It is no doubt 
 true that half a volume of oxygen gas is separable in electrolysis, with 
 one volume of hydrogen gas ; but it is equally true, that one volume of 
 oxygen gas is separable with two volumes of hydrogen ; and the law of 
 galvanic equivalency is sufficiently obeyed, if it is shown, that for every 
 volume of oxygen which is disengaged, there is a simultaneous disen- 
 gagement of two volumes of hydrogen ; for the electrolysis of water 
 into HH -}- O, that is to say, into two volumes of hydrogen and one 
 
IX FAVOUR OF THE RADICAL THEORY. 
 
 557 
 
 volume of oxygen, is the product of TWO electrolytic operations ; the first 
 of which separates H -f- HO into H and HO, while the second separates 
 HO into H and O. It is a consequence of this twofold electrolysis, that 
 the same current which decomposes 18 parts of water in the voltameter, 
 decomposes two atoms of any normal salt upon which it is made to 
 act, and sets free four radicals, two of them basic and two acid : thus, 
 the decomposition of 1 8 parts of HHO in the voltameter is accompanied 
 by the simultaneous 
 
 Deposition of 
 Cu 4- Cu 128 parts. 
 Cue 4- Cue = 64 parts. 
 Sn -f- & n = 1 1 8 parts. 
 Snc 4- >Snc = 59 parts. 
 Na + Na = 46 parts. 
 
 and Separation of 
 Cl 4- Cl 
 SO 2 4- SO 8 
 Cl 4. Cl 
 Cl -f- Cl 
 SO 8 + SO 2 
 
 From 
 2Cu Cl = No. i. 
 2CucSO 2 = No. 4. 
 2Sn Cl = No. 2. 
 2SncCl = No. 3. 
 2NaS0 2 = No. 19. 
 
 Thus, when the voltameter, or standard of electrolytic power, is the 
 quantity of water that undergoes decomposition, there is, in all cases, 
 for each HHO that is decomposed, or each O that is set free, a decom- 
 position effected of two atoms of a normal salt, which sets free two 
 positive radicals and two negative radicals, it being perfectly indifferent, 
 as respects the electrolytic power, whether the positive radicals are of 
 the basylous or the basylic description. If the reader prefers to have 
 this result stated in the usual cabalistic language of chemists, I may say, 
 that the same current can separate a greater quantity of metal from a 
 "protofsctft*' than it can from a "persalt." 
 
 When the voltameter of a circuit contains a binary compound free 
 from water, such as rased chloride of lead, then the current which decom- 
 poses one atom of the standard and liberates its two radicals, will also 
 decompose one atom of any normal salt through which it passes ; 
 thus : 
 
 Pb 4- Cl 
 Pb + I 
 
 Na,SO 2 
 ZH 4 ,C1 
 Na,Cl 
 Sn,Cl 
 
 = No. 20. 
 
 = No. 27. 
 
 Hence it follows, that Faraday's laws of electrolysis agree precisely in 
 sense with the radical theory, and differ only in the form of expression 
 which was accommodated by him to the current views of chemists. If 
 water is taken to be constituted of H 4- HO, and oxygen is fixed at 
 1 6, we still agree with Faraday's results. 
 
 17. Here, again, we have a law which is opposed, and justly op- 
 posed, to the law of combination in multiple proportions. If the 
 equivalent radicals A. and B. contain equal quantities of electricity, that 
 is to say, equal powers of chemical combination, it is impossible for 
 
558 
 
 EVIDENCE OF ELECTROLYSIS 
 
 them to neutralise one another when presented for combination in such 
 assortments as 
 
 A + 2B, A + }B, A + 46 
 2A + 38, 2A + 56, 2A + 76. 
 
 See the quotation from Professor Miller, at page 537. So also the 
 formation of the organic radicals C 30 + H 61 , C 30 + H 39 , &c., page 525, 
 must be impossible. If we consider the nature of these examples, 
 we must conclude that if the law of combination in multiple propor- 
 tions is true, those of electro-chemistry must be false ; for they are 
 perfectly incompatible. 
 
 1 8. This observation agrees with No. 10 of Magnus's results, and 
 needs no further remark. 
 
 19. The decomposition of sulphate of soda here described may be 
 represented as occurring in a circuit, thus : 
 
 A. Before the current passes. 
 
 -Pole 
 
 H HO 
 H HO 
 
 Na, SO 2 
 Na, SO 8 
 
 Na, SO 8 
 Na, SO 8 
 
 Na, SO 8 
 Na, SO 2 
 HHO 
 
 B. After the current passes. 
 
 H 
 - Pole H 
 
 HO Na 
 HO Na 
 
 SO 8 Na 
 
 SO 3 Na 
 
 SO 8 Na 
 SO* Na 
 
 SO 8 
 SO 8 
 HH 
 
 Pole. 
 
 Pole. 
 
 
 
 This scheme shows distinctly how it happens that one volume of 
 oxygen is given off at the + pole, and two volumes of hydrogen at the 
 pole, and how, corresponding with these proportions of the two 
 gases, we have two equivalents of hydrated sulphuric acid at the -f- 
 pole, and two equivalents of hydrated soda at the pole. 
 
 20. This agrees precisely with Faraday's proportions: 2 atoms of 
 sulphate of soda = 2 atoms of lead = 2 atoms of chlorine = 1 8 parts 
 by weight of water. See No. 1 6. 
 
 21. What Daniell and Gmelin call NaSO*'is what I call NaSO 8 . 
 Daniell's experiment proves nothing respecting the distribution of the 
 oxygen between Na and S. That puzzle still awaits a solution. 
 
 22. Numbers which corroborate those given in 19. 
 23 and 24. Already sufficiently explained at No. 5. 
 
 25. The first effect produced on an oxidised salt of ammonia would 
 probably resemble that produced on a salt of soda. See ?9. Hydrogen 
 would escape, and \ve should have in solution the hydrate ZH* + HO. 
 If the electrolytic action proceeded, the next decomposition would be 
 into ZH 2 ,H + H,HO ; namely, water would be separated, and ammonia 
 produced. This may go off as gas, or finally be resolved into N -J- H 3 . 
 
IN FAVOUR OF THE RADICAL THEORY. 559 
 
 26. The reaction Zn -f- H,SO* = H + Zn,S0 2 is equal to HHO ; 
 or if we double the figures we have 
 
 = HHO in the 
 
 27. These quantities represent the weights of radicals, as already- 
 explained. 
 
 28. Another example of the separation of iodine at the negative pole. 
 In 27 and in 30 it is separated at the positive pole. Hence, even ener- 
 getic elements can act either as basic or as acid radicals, according to the 
 force impressed upon them by other radicals with which they are in 
 contact. 
 
 29. Compare this experiment with the note to No. 8. 
 
 30. Electrolysis of hydriodic acid = HI. The oxygen gas is, of 
 course, derived from water, which is decomposed simultaneously. The 
 quantity of oxygen increases with the dilution of the acid and the strength 
 of the current. The quantity of hydrogen which is disengaged at the 
 negative pole is always equal to that which is disengaged in the water 
 voltameter ; because HI is equal to H,HO, and so far as water is con- 
 cerned, H,HO in the solution is equal to H,HO in the voltameter. 
 
 3 1 . Electrolysis of an aqueous solution of iodide of potassium : 
 
 A. Before the current passes. 
 
 - Pole | H HO |K I | K I|K I|K I | + Pole. 
 
 B. After the current passes. 
 
 - Pole HI HO K | I K | I K|I K ] I + Pole. 
 
 32. See No. 16. 
 
 33. Decomposition of sal-ammoniac : 
 
 Cl at the + pole. 
 
 ZffCl yields 
 
 34. Electrolysis of common salt : 
 
 N c Cl at the + pole. 
 
 H,HO 
 
 35. Decomposition of hydrate of potash (Davy) : 
 ( O at the + pole. 
 
 K,HO yields |K J^.^, 
 
 SUMMARY. I consider the evidence that is afforded by these electro- 
 lytic experiments to be entirely in favour of the radical theory. Magnus's 
 
560 CATALYSIS. 
 
 results prove that radicals, and not atoms, are the galvanic equivalents. 
 The tendency of the whole of the experiments is to show, that H -f- HO 
 is the true formula for water. With the aid of this formula every 
 electrolytic experiment is easily and clearly explained. Without it, you 
 must adopt Magnus's conclusion, that " galvanic equivalents differ from 
 chemical atoms," and thus unsettle the electro-chemical theory, and settle 
 nothing. The experiments of Faraday and Daniell distinctly agree with 
 the radical theory. Those of Magnus are identified with it, and incom- 
 patible with any previous theory. The only ground upon which 
 English chemists can persist in ascribing to water the formula HO, is, 
 that they have been accustomed to do so for fifty years. That water is 
 a binary compound of oxygen and hydrogen, was the first deduction 
 from the Atomic Theory, and it has been a fruitful source of fallacies 
 and difficulties during the entire period of its supremacy. There will 
 be no simplicity in chemical formula, and no logic in chemical theories, 
 until this Idol of Daltonism is overthrown. 
 
 Catalysis. 
 
 Chemical combinations and decompositions sometimes occur in the 
 presence of substances which seem to cause these reactions, but which 
 are not changed by them. 
 
 Some facts described in these pages may help to explain this mys- 
 tery. I . The element azote by producing an amidogen converts three 
 radicals into one ; by producing an ammonium, it converts five radicals 
 into one. It can let free these radicals by combining with C l to produce 
 an acid radical ; and these changes can be reversed. 2. Certain metals 
 produce two radicals. Thus Cu can become Cue 2 , and Cue 2 can become 
 Cu. Sn can become Snc 2 , and Snc 2 can become Sn. Fe 2 can become 
 Fee 8 , and Fee 8 can become Fe 2 . All these changes take place according 
 to the amount of basic or acid power that is brought to bear upon the 
 materials; such changes in the number of radicals, produce an enor- 
 mous alteration in the saturating capacity of a given quantity of matter; 
 and as it is possible that the acting substances may end as they began, 
 a great effect is produced by a hidden cause. 
 
[ 561 ] 
 
 INDEX. 
 
 ACETAL, constitution of, 371 
 Acetates, atomic measure of, 112 
 Acetin, varieties of, 379, 389 
 Acetochlorhydrin, 388 
 Acetochlorhydrobromhydrin, 388, 391 
 Acetodichlorhydrin, 388 
 Acetone, 50 
 Acetonia, 216 
 Acetonitrile, 60, 218 
 Acetyl, bromide, 50 
 
 chloride, 50 
 
 iodide, 50 
 
 oxychloride, 50 
 
 perchloride, 56 
 
 Acetyla acetylite, 120 
 Acetylam, 191 
 Acetylamine, 50, 201 
 Acetylate, 123 
 Acetyl-urea, 361 
 Acid, acetic, 50 
 
 1 anhydrous, 50, 120 
 
 aconitic, 438 
 
 adipio, 450 
 
 allophanic, 362 
 
 amyl-citric, 431 
 
 amyl-malic, 415 
 
 amyl-salicylic, 458 
 
 anchoic, 454 
 
 anilocyanic, 304 
 
 anthranilic, 349 
 
 aspartic, 412, 415 
 
 benzamic, 349 
 
 benzoic, 52 
 
 biamidobenzoic, 254, 362 
 
 bibromo-sulphonaphtalic, 497 
 
 bichloro-sulphosomethylic, 497 
 
 bromhydric, 52 
 
 butyric, 52 
 
 anhydrous, 53 
 
 campholic, 53 
 
 camphoramic, 227 
 
 caproic, 53 
 
 Acid, carbamic, 359 
 carbanilic, 349 
 
 carbonic, 53 
 
 cetyl-sulphuric, 487 
 
 chloracetic, 55 
 
 chlorhydric, 54 
 
 chlorous, 54 
 
 chloro-sulphosomethylic, 497 
 
 chrysammic, 252 
 
 citraconamic, 439 
 
 citric, 424 
 
 its varieties, 428 
 
 argument that it is not a 
 
 tribasic acid, but a triple 
 
 acid, 424 
 
 citrobianilic, 433 
 
 citromonanilic, 434 
 
 co3rulin-sulphuric, 270 
 
 cuminamic, 354 
 
 cyanhydric, 56, 245 
 
 cyanic, 250 
 
 dimethyl-citric, 430 
 
 disulphanilic, 241, 494 
 
 disulphanisolic, 494 
 
 disulphetholic, 494 
 
 disulphobenzolic, 494 
 
 disulphometholic, 493 
 i disulphonaphtalic, 494 
 
 disulphopropiolic, 494 
 
 dithiobenzolic, 494 
 
 dithionic, 157 
 
 dithionous, 157 
 
 ethylamyl-citric, 431 
 
 ethylosulphurous, 496 
 
 ethylsalicylic, 458 
 
 ethylsulphobenzoic, 491 
 
 ethylotrithionic, 499 
 
 formic, 59 
 
 fumaric, 414, 420 
 
 gallic, 531 
 
 gaultheric, 458 
 
 glycollic, 44 
 
 2 o 
 
562 
 
 INDEX. 
 
 Acid, glycylic, 374, 382 
 
 hydrobromic, 52 
 
 hydrochloric, 54 
 
 hydrocyanic, 56, 245 
 
 hydrofluosilicic, 503 
 
 hydroiodic, 59, 551 
 
 hydrosulphuric, 62 
 
 hypochlorous, 54 
 
 hyponitric, 61, 253 
 
 hyponitrous, 253 
 
 hypophosphorous, 144 
 
 hyposulphamylic, 496 
 
 hyposulphuric, 157 
 
 hyposulphurous, 157 
 
 insolinic, 532 
 
 iodic, 548, 554 
 
 iodohydric, 59, 551 
 
 isamic, 268 
 
 isatic, 261 
 
 isatinamic, 268 
 
 isatinic, 261 
 
 malamic, 415 
 
 malanilic, 418 
 
 maleic, 414, 419 
 
 malic, 411 
 
 argument that it is a double 
 
 acid, not a bibasic acid, 411 
 
 methyl-citric, 430 
 
 methylodithionic, 498 
 
 methyl-salicylic, 458 
 
 methyl-spiroylic, 458 
 
 methyl-xanthic, 474 
 
 nitric, 61, 251, 256 
 
 anhydrous, 61, 253 
 
 nitrous, 61, 253 
 
 octyl-sulphuric, 487 
 
 oenanthylic, 61 
 
 organic, defined, 81 
 
 oxamic, 195, 226 
 
 oxanilic, 227, 287 
 
 pentathionic, 157 
 
 phenic, 45 
 
 phosphoglyceric, 385 
 
 phosphoric, 138, 551 
 
 phosphorous, 143 
 
 potassio-sulphuric, 402 
 
 pyrogallic, 531 
 
 pyrotartranilic, 453 
 
 radicals, conversion into basic ra- 
 dicals, 75, 535 
 
 radicals act as basic radicals with 
 
 additional oxygen, 376, 480 
 
 salicylic, 62, 458 
 
 salicylous, 62, 455 
 
 sebacic, 451 
 
 Acid, sebamic, 451 
 
 selenious, 62 
 
 silicic, 501 
 
 hydrates of, 503 
 
 suberic, 450 
 
 suberanilic, 450 
 
 succinic, 446 
 
 succinamic, 447 
 
 succinanilic, 288, 447 
 
 sulphacetic, 489 
 
 sulphamic, 235 
 
 sulphamylic, 487 
 
 sulphanilic, 238, 285, 498 
 
 sulphanisic, 492 
 
 sulphindigotic, 270 
 
 sulphobenzidic, 496 
 
 sulphobenzoic, 491 
 
 sulphobenzolic, 496 
 
 sulphobutylic, 487 
 
 sulphobutyric, 491 
 
 sulphocarbonic, 473 
 
 sulphocinnamic, 492 
 
 sulphocumenic, 496 
 
 sulphocymenic, 496 
 
 sulphocyanic, 247 
 
 sulphoglyceric, 385 
 
 sulphomethylic, 486 
 
 sulphonaphtalic, 496 
 
 sulphophenic, 487 
 
 sulphopropionic, 491 
 
 sulphopurpuric, 274 
 
 sulphosalicylic, 492 
 
 sulphosomethylic, 495 
 
 sulphosuccinic, 448 
 
 sulphothymic, 487 
 
 sulphotoluylic, 496 
 
 sulphovinic, 400, 486 
 
 sulphoxyloic. 496 
 
 sulphuric, 62 
 
 anhydrous, 62, 119 
 
 sulphurous, 62 
 
 tartanilic, 468 
 
 tartaric, 461, 463 
 
 tartaromethylic, 466 
 
 tartarovinic, 466 
 
 tartramic, 466 
 
 tartramylic, 466 
 
 terchloro-sulphosomethylic, 497 
 
 tetrathionic, 157 
 
 thionaphtamic, 498 
 
 toluamic, 354 
 
 trichloro-sulphonaphtalic, 497 
 
 trithionic, 157 
 
 valerianic, 63 
 xanthic, 475 
 
INDEX. 
 
 563 
 
 Acidification, 75 
 
 Acidity, its relation to basicity, 73. 
 
 Acids, anhydrous, 118 
 
 and bases, theory of, 18 
 
 consequences to which that theory 
 
 leads, 311, 358 
 
 amidogen, 208, 225 
 
 amidogen, with compound radicals, 
 
 227 
 
 anilidogen, 228 
 
 constitution of, 3 
 
 conjugated, theory of, 395 
 
 copulated, 399 
 
 coupled, 399 
 
 colligated, 399 
 
 monobasic, how convertible into 
 polybasic, 395 
 
 organic, their atomic measure, 66 
 
 nomenclature of, 89 
 
 polybasic, theory of, 395 
 
 polythionic, 156 
 
 peculiarities in their saturat- 
 ing capacity, 173 
 
 tri basic, atomic measure of, 112 
 
 Aconites, 427, 436 
 
 Acrolein, 50 
 
 Acryl, 50 
 
 Acrylic alcohol, 50 
 
 Adipates, 444, 450 
 
 Agalmatolite, 511 
 
 Air, atmospheric, 50 
 
 Albite, 512 
 
 Alcohol, 56, 65, 81, 88 
 
 acrylic, 50, 65 
 
 amylic, 51, 65 
 
 butylic, 52, 65 
 
 caproic, 53, 65 
 
 caprylic, 53, 65 
 
 castor-oil, 53, 65 
 
 methylic, 59, 65, 88 
 
 propylic, 62, 65 
 
 Alcohols, nomenclature of, 88 
 
 polyatomic, 366 
 
 Aldehyde, 50 
 
 Aldehydes. See Aldides 
 
 Aldides defined, 81 
 
 examples of, 65 
 
 nature of, 124 
 
 nomenclature of, 88 
 
 preparation of, 78 
 
 Alkarsin, 53 
 
 Allophanates, 362 
 
 Allophanic ether, 363 
 
 Allyl, sulphocyanide, 50 
 
 versus aery], 378 
 
 Alumina, binacetate, 518 
 
 tersulphate, 518 
 
 Aluminic radical, 518 
 Aluminous radical, 518 
 Amethanes, 226 
 Amid, defined, 193 
 Amida carbate, 194 
 
 indylate, 258 
 
 Amidac, defined, 193 
 Amidacs, hydrides of, 199 
 
 salts, 224 
 
 Amidated acids, 225 
 Amidec, defined, 193 
 Amided acids, 225 
 Amides, 208 
 Amidogen theory, 190 
 
 gaseous salts of, 196 
 
 acids, 208, 225 
 
 with compound radicals, 227 
 
 hyposulphates, 484 
 
 sulphites, 485, 497 
 
 Amidogens, nature of, 99 
 Amids, conjugated, 299, 301 
 
 hydrides of, 199 
 
 conversion into ammons, 194 
 
 non-oxidised, salts of, 215 
 
 production of various classes of 
 
 salts of, 209, 211, 213 
 
 relation to ammons, 193 
 
 table of, 211 
 
 Amines, 201 
 Ammon, defined, 193 
 
 carbonate of, 356 
 
 Ammon chlorplatammonium, 313 
 
 Ammon oxyplatammonium, 313 
 
 Ammonam, defined, 193 
 
 Ammonams, salts of, 202 
 
 Ammonem, defined, 193 
 
 Ammonems, salts of, 203 
 
 Ammonia, anhydrous, oxysulphur salts 
 
 of, 233 
 
 alums, 230 
 
 atomic measure, 50, 99 
 
 bicarbonate, 356 
 
 . carbamate, 50, 359 
 
 carbonate, 355, 359 
 
 compounds of, 100 
 
 constitution of, 99 
 
 cyanate, permanent ,338 
 
 non-permanent, 338 
 
 hydrochlorate, 50 
 
 hydrocyariate, 50 
 
 hydrosulphate, 50 
 
 hydrotellurate, 50 
 
 is a salt, not a radical, 196 
 
 2 o 2 
 
564 
 
 INDEX. 
 
 Ammonia, its salts are of two classes, 
 those of amidogen and those of ammo- 
 nium, 197 
 
 polythionates, 233 
 
 sulphate, electrolysed, 550 
 
 type, 210, 232, 297 
 
 Ammonias, compound, 201 
 
 classified table of, 199 
 
 Ammoniated salts, 198, 229 
 Ainmonim, denned, 193 
 Aramonims, salts of, 204 
 Ammonium theory, 190 
 
 salts of, 198 
 
 cannot exchange H for Cy, N,0, or 
 
 NO 2 , 288, 289, 297 
 Ammoniums, formulae of, 202, 207 
 
 compound salts of, 205 
 
 of impossible constitution, 311,323, 
 
 337, 346 
 
 Ammonom, defined, 193 
 Ammonoms, salts of, 204 
 Ammons and amids double salts of, 195 
 Ammons combined with amids, 215 
 Ammons converted into amids, 194 
 Amyl, 50 
 
 acetate, 51 
 
 borate, 51 
 
 chloride, 51 
 
 cyanide, 51 
 
 hydride, 50 
 
 hydrosulphide, 51 
 
 iodide, 51 
 
 nitrite, 51 
 
 oxalate, 51 
 
 silicate, 51, 501, 505 
 
 sulphide, 51 
 
 valerianate, 51 
 
 Amylamine, 201 
 
 Amylaniline, 282 
 
 Amylec, 193 
 
 Amylen, 63, 373 
 
 Amylic alcohol, 51 
 
 Amylic glycol, 372 
 
 Amyl-malates, 412, 415 
 
 Amylom, 193 
 
 Arnylosulphates electrolysed, 405 
 
 Amylo-urethane, 353 
 
 Analcime, 512 
 
 Analytical and synoptical formulas dis- 
 tinguished, 127 
 
 Anchoates, 446, 454 
 
 Angelyl, 51 
 
 Anhydrides, 118 
 
 amended theory, 377, 480 
 
 double, 121 
 
 Anhydrides, nomenclature of the, 90, 
 120 
 
 Gerhardt's, 120 
 
 Anhydrous acids, 118 
 Aniles, 222, 224 
 Anilides of tartaric acid, 468 
 Anilin-ammeline, 295 
 Aniline, 51, 274 
 
 bases, general view of, 307 
 
 salts, critical notes on, 280 
 
 table of its salts, 276 
 
 theory, 275 
 
 Anilo-urea, 298 
 Anis, essence of, 51 
 Anthranilates, 305, 349 
 Antimoniuretted hydrogen, 51 
 Antimony, salts of, 104. 
 Antimony, terchloride, 51 
 Apple-oil, 521 
 Arabin, 519 
 Argentac, 191 
 
 Argentam, 191 
 Arsen-ethyl, 58 
 
 Arsenic, 51 
 
 chloride, 51 
 
 iodide, 51 
 
 oxide, 51 
 
 atomic measure, in gases, 103 
 
 Arseniuretted hydrogen, 51 
 
 Arsen-triethyl, 52 
 
 Asparagine, 413, 4 '7 
 
 with acids, 413, 418 
 
 with bases, 413,417 
 
 Aspartates, 412, 416 
 
 Atomic measure of gases, simple and 
 compound, tabular view of, 49 63 
 
 measure of gases, question whether 
 
 all, simple and compound, have the 
 same measure, 116 
 
 measure of compound gases, causes 
 
 which modify the, 94, 107 
 
 measure of the vapours of poly- 
 basic acids, 111 
 
 . theory, inquiry into the, 537 
 
 theory, unable to determine what 
 
 constitutes an atom, 542 
 
 theory, of no use in explaining the 
 
 constitution of organic radicals, 546 
 
 weights, table of, 28 
 
 weights of gases, 49 
 
 Augite, 511, 514 
 
 Auric radical, 34 
 
 Aurous radical, 34 
 
 Azote, the constructor of basic radicals. 
 306 
 
INDEX. 
 
 565 
 
 Azote, its transmigration from ammo- 
 niums into cyanogen, 217 ; and back 
 from cyanogen into ammoniums, 220, 
 306 
 
 Azotic bases, their nature, 274 
 
 radicals, examples of, 199 
 
 theory of, 189 
 
 in series, 256 
 
 Bamlite, 511 
 
 Bases, constitution of, 3 
 
 their relation to acids, 311 
 
 their relation to basic radicals, 275, 
 
 282, 285, 295, 533 
 
 Basic and acid radicals discriminated, 73 
 
 radicals reduced to acid radicals, 
 
 74, 406 
 
 Basicity of radicals, 70 
 
 of conjugated acids, 402 
 
 Basylic atoms or radicals, 33 
 
 radicals in salts, i. e. : 
 
 . in alums, 230 
 
 in chlorides, 33, 187 
 
 in cyanides, 39 
 
 in oxalates, 37, 181 
 
 in phosphates, 140 
 
 in silicates, 507, 514 
 
 in sulphates, 150, 554 
 
 in tartrates, 465, 468 
 
 in xanthates, 473 
 
 Basylous atoms or radicals, 33 
 
 and basylic atoms, their relation to 
 
 xanthates, 473 
 
 relation in silicates, 507 
 
 Benzoates, atomic measure, 112 
 
 Benzoicin, 379 
 
 Benzoile, chloride, 52 
 
 chlorohydride, 52 
 
 Benzo-glycollates, 457, 460 
 
 Benzo-lactates, 457, 460 
 
 Benzole, 61 
 
 Benzonitrile, 61 
 
 Benzoyl-urea, 361 
 
 Beryl, 511 
 
 Biatomic, the term defined, 146 
 
 alcohol, 366 
 
 Bibasic acids, atomic measure of their 
 gases, 112 
 
 Binary theory of salts, 18 
 
 Binoxysulphocarbonates, 471, 476 
 
 Bismuth, chloride, 52 
 
 atomic measure in gases, 104 
 
 Bisulphates of alcohol radicals, 399, 481 
 
 containing acid radicals, 481, 488, 
 
 489 
 
 Biuret, 363 
 
 Boron, chloride, 52 
 
 fluoride, 52 
 
 its measure in gases, 104 
 
 Bromine, 52 
 Bromaniline, 281 
 Bromhydrine, 389 
 Bromic-indyl, 262 
 Bromic-phenyl, 275 
 Bromic-phenylac, 281 
 Bromic-radicals, 132 
 Bromic-salicylates, 457 
 Bromides, organic, 67 
 Bromisatine, 262 
 Bucholzite, 511 
 Bustamite, 511 
 Butyl, 52 
 
 acetate, 52 
 
 bromide, 52 
 
 chloride, 52 
 
 cyanide, 52 
 
 hydride, 52 
 
 iodide, 52 
 
 Butyl-amyl, 52 
 Butyl-hexyl, 52 
 Butylene, 52 
 
 chloride, 52 
 
 Butylic alcohol, 52 
 
 mercaptan, 52 
 
 Butyral, 52 
 
 Butyrin, 379 
 
 Butyrone, 53, 62 
 
 Butyryl-urea, 361 
 
 Cacodyl, 53 
 
 its measure in gases, 104 
 
 chloride, 53 
 
 cyanide, 53 
 
 oxide, 53 
 
 oxychloride, 53 
 
 sulphide, 53 
 
 Camphogene, 53 
 Campholene, 53 
 Camphor, 53 
 Camphorimide, 224 
 Cane-sugar, 519 
 Caproic alcohol, 53 
 Caproiline, 59 
 Caproyl, 59 
 Caprylene, 53 
 Caprylic alcohol, 53 
 Carbamide, theory, 221 
 
 Hofmann's arguments, 298 
 
 objections to them, 300 
 
 theory compared with the 
 
 theory, 298, 341 
 
 Carbamates, 359 
 
566 
 
 INDEX. 
 
 Carbamide-carbanilide, 298 
 Carbamide-nitrocarbanilide, 289 
 Carbanilates, 305, 349 
 Carbanilide, 298, 306 
 Carbon, an acid radical, 73 
 
 its measure in gases and salts, 95 
 
 protochloride, 54 
 
 bichloride, 54 
 
 sesquichloride, 54 
 
 sulphide, 53, 472 
 
 Carbonates, constitution of, 183 
 
 essentially bibasic, 183 
 
 acid, 184 
 
 basic, 184 
 
 double, 184 
 
 neutral, 184 
 
 with organic radicals, 185 
 
 Carbonic acid, 53 
 
 oxide, 53 
 
 Carbonyle, 114 
 Castor-oil alcohol, 53 
 Catalysis, 560 
 Cedrene, 53 
 Cedrole, 53 
 Cellulose, 519 
 Cetene, 54 
 Chabasite, 512, 515 
 Chemical types, 91 
 Chinese wax, 454 
 Chloral, 55 
 Chloraldehyd, 55 
 Chloral, hydrate, 55 
 
 Chloraniline, 281 
 
 Chlorbenzid, 56 
 
 Chlorcyanilid, 295 
 
 Chlorenic-methyl, 54 
 
 Chlorenic-ethyl,' 94 
 
 Chlorenic-vinyl, 54 
 
 Chloretherose, hydrochlorate, 56 
 
 Chlorhydrin, 384, 389 
 
 Chloric radicals, nature of, 93, 131 
 
 their measure in gases, 101 
 
 nomenclature, 94 
 
 Chloric-ethyl, 55, 94 
 
 Chloric-indyl, 262 
 
 Chloric-methyl, 54, 94 
 
 Chloric-oxide, 54 
 
 Chloric-phenyl, 275 
 
 Chloric-phenylac, 280 
 
 Chloric-salicylates, 457 
 
 Chlorides, constitution of, 186 
 
 if polybasic or not ? 186 
 
 multiple, 188 
 
 their atomic measure, 101 
 
 of organic radicals, 67 
 
 Chlorides of bibasic acid radicals, 112 
 
 of tribasic acid radicals, 112 
 
 electrolysis of, 551 
 
 Chlorine, 54 
 
 substitutions for H, 93 
 
 gases containing it, 54 
 
 oxides of, their measure, 102 
 
 vice-radicals, 93, 131 
 
 Chlorinic-radicals, 94-, 132 
 
 Chlorinic-methyl, 54 
 
 Chlorisatates, 263 
 
 Chlorisathyde, 264 
 
 Chlorisatin, 262, 281 
 
 Chloroform, 54 
 
 Chloro-hydrated sulphuric acid, 153 
 
 Chloro-nitrous gas, 56 
 
 Chlorplatammonium, 313 
 
 Chloro-sulphuric acid, 56, 114, 145, 155 
 
 Chlorovinic formiate, 55 
 
 Chromates, 125 
 
 Chromium, its atomic measure in gaseous 
 
 salts, 102 
 
 oxychloride. 56 
 Chromous chromite, 120 
 Cimolite, 511 
 Cinnamol, 63 
 Citraconamide, 439 
 Citraconates, table of, 427 
 
 double salts of monobasic acids, 438 
 
 Citrates, table of, 424 
 shown to be triple salts of mono- 
 basic acids, 424, 435 
 Citric group of salts, 424 
 Citrobianilates, 433 
 Citrobianile, 434 
 Citronanilide, 433 
 
 Classification of organic radicals, 525 
 Combining proportion of an element, 
 
 defined, 544 
 Comenates, 532 
 Compound radicals, tables of, 44, 70, 79, 
 
 525 
 Compounds produced by the abstraction 
 
 of water from the salts of ammonium, 
 
 208 
 
 Composition of gases, table of, 49 
 Conjugated acids, theory of, 395 
 
 of the benzoic group, 4 59 
 
 citric group, 430 
 
 salicylic group, 458, 460 
 
 sulphuric group, 399, 480, 
 
 486, 495 
 
 of the tartaric group, 461 
 
 xanthic group, 470 
 
 cyanides, 246 
 
INDEX. 
 
 567 
 
 Copper, electrolysis of its salts, 552 554 
 
 Copulated oxalates, 408 
 
 Cream of tartar, 463 
 
 Cumenyl hydride, 56 
 
 Cumyl, hydrate, 56 
 
 Cupric atom, 34 
 
 sulphate, electrolysed, 548, 552 
 
 Cuprous atom, 34 
 
 chloride, electrolysed, 548 
 
 Cuprousam, 191 
 Cyananilide, 290 
 Cyanates, 250 
 
 their measure as gases, 100 
 
 terbasic, 305, 348 
 
 tetrabasic, 362 
 
 Cyanides, constitution of, 38, 43, 217 
 
 221, 243246 
 
 single, 39, 243 
 
 double, 40, 244 
 
 triple, 39, 244 
 
 fourfold, 42, 244 
 
 decomposition of, 41, 220 
 
 their atomic measure, 108 
 
 organic, 67 
 
 are not nitriles, 217 
 
 Cyanilide, 291 
 Cyaniline, 297 
 
 Hofmann's theory, 297 
 
 its insufficiency, 298 
 
 Cyanite, 511 
 Cyanogen, 38, 56 
 
 bromide, 56 
 
 chloride, 56 
 
 consideration of the proposal to 
 
 abolish free cyanogen, 38 
 conjugated, a needless hypothesis, 
 
 246 
 Cyanurates, their atomic measure as 
 
 gases, 100 
 Cymen, 63 
 Daltonism, 537 
 
 Davy, on the composition of salts, 21, 128 
 Definite proportions, 537 
 Definition of compounds,Gerhardt's theory 
 
 of, and its consequences, 410 
 Diacetochlorhydrin, 388 
 Dibromaniline, 281 
 Dibutyrosulphurin, 390 
 Dicyanomelaniline, 294 
 
 metamorphoses of, 302 
 
 Dicymenaphthalamine, 533 
 Dinitromelaniline, 290 
 Dioptase, 511 
 Diplatinamine, 313 
 Diplatosamine, 313 
 
 Disulphanilates, 494 
 Disulphanisolates, 494 
 Disulphetholates, 494 
 Disulphobenzolates, 494 
 Disulphometholates, 493 
 Disulphonaphtalates, 494 
 Disulphopropiolates, 494 
 Dutch liquid, 54 
 Elayl, 73, 
 Electrolysis gives evidence in favour of 
 
 the radical theory, 548, 560 
 its laws are incompatible with those 
 
 of combination in multiple proportions, 
 
 547, 557 
 
 applied to conjugated acids, 404 
 
 Electrolytes, 549 
 Electrolytic researches, 547 
 Elements, table of, 28 
 
 atomic weights of, 30 
 
 names of, 28 
 
 symbols of, 28 
 
 proposal to abolish them, 38 
 
 relation of their atomic weights to 
 
 the densities of their gases, 542 
 Equivalent proportions, law of, 538 
 Equivalency of radicals not affected by 
 
 oxygen, 69 
 Equivalents are sometimes assumed to be 
 
 different from atoms, 148 
 
 are the same as radicals, 34 
 
 Erenite, 511 
 Ethel ene bibromide, 54 
 Ether, 56, 66, 81 
 Ethers, compound, 66, 8.1 
 
 nomenclature, 89 
 
 necessity of, 73 
 
 chlorinated, 55 
 
 Ethyl, 56 
 
 acetate, 57 
 
 benzoate, 57 
 
 borate, 57 
 
 bromide, 57 
 
 butyrates, 57 
 
 caproate, 57 
 
 caprylate, 57 
 
 carbamate, 57 
 
 carbonate, 57 
 
 chloride, 55, 57 
 
 chlorocarbonate, 55 
 
 cinnamate, 57 
 
 cuminate, 57 
 
 cyanate, 57 
 
 cyanurate, 57 
 
 cyanylate, 57 
 
 formiate, 57 
 
568 
 
 INDEX. 
 
 Ethyl, formiate tribasic, 57 
 
 hydride, 57 
 
 iodide, 57 
 
 laurate, 58 
 
 nitrite, 58 
 
 oxalate, 58 
 
 phosphite, tribasic, 58 
 
 pyromucate, 58 
 
 succinate, 58 
 
 silicate, 58 
 
 non- volatile, 501, 504 
 
 sulphide, 58 
 
 bisulphide, 58 
 
 hydrosulphide, 58 
 
 sulphite, 58 
 
 sulphocyanide, 58 
 
 valerianate, 58 
 
 Ethyl-amyl, 58 
 
 oxide, 58 
 
 Ethyl-butyl, 58 
 
 Ethyl and methyl, oxide, 58 
 
 Ethyl and methyl, oxalate, 58 
 
 Ethylamine, 58 
 
 Ethylaniline, 282 
 
 Ethylin, 379 
 
 Ethyl-oenanthyl ether, 58 
 
 Ethylophosphates, electrolysis, 405 
 
 Ethylopiperidine, 63 
 
 Ethylotrithionates, 486, 499 
 
 Ethyl-urethane, 57, 352 
 
 Euclase, 511 
 
 Fats, relation to glycerin, 384 
 
 Felspar, 512 
 
 Ferric atom, or radical, 33 
 
 Ferric salts, 33, 35 
 
 Ferric sulphate, electrolysed, 548, 554 
 
 Ferrous atom, or radical, 33 
 
 Ferrous salts, 33, 35 
 
 Ferrous sulphate, electrolysis, 548, 554 
 
 Fluorides, organic, 67 
 
 their measure in gases, 101, 108 
 
 Formanilides, 286 
 Formo-benzoylates, 457, 460 
 Formomethylal, 60 
 Formulas, construction of, 84 
 
 consequences that result from their 
 
 duplication and triplication, 366, 395 
 Formyl, 58 
 
 chloride, 54 
 
 perchloride, 54 
 
 suboxide, 531 
 
 Fructose, 519 
 
 Fruit essences, nature of, 521 
 Fuchsite, 516 
 Fumaramide, 420 
 
 Fumarates, 414, 420 
 
 Fumaric amides, 415, 420 
 
 Furfurol, 59 
 
 Gadolinite, 511 
 
 Galvanic equivalents, 548, 555 
 
 Garnet, 512 
 
 Gases and vapours, tabular view of their 
 composition, &c., 49 
 
 inquiry into the causes which mo- 
 dify their atomic measure, 94 
 tabular view of these causes, 108 
 
 measure of the condensation effected 
 
 by special radicals, 108 
 
 atomic measure, rule to calculate, 
 110 
 
 specific gravity,rule to calculate,! 10 
 
 such as have irregular atomic mea- 
 sure, 96, 109 
 
 of polybasic acids, examination 
 
 of Gerhardt's theory, 111 
 
 Clark's table of, 5 
 
 Glucose, 519 
 
 Glyceramine, 377 
 
 Glyceric ether, 377 
 
 Glycerides, 376 
 
 Glycerin, 374, 376 
 
 wonderful account of its basic 
 
 power, 386 
 
 fallacies in that account, 391 
 
 Glycocoll, 352 
 Glycol, 366 
 Glycyl, 376 
 
 salts of, 374, 392 
 
 Glycylites, 376 
 Grape-sugar, 519 
 Gross's platinum base, 312 
 Guajacene, 51 
 Gum-arabic, 519 
 Hexyl, 59 
 Hexyline, 59 
 Hippurates, 456, 460 
 Homologous series, 527 
 Homology, 527 
 Hydra acetylete, 50, 89 
 
 aconylete, 427, 438 
 
 adipylete, 444, 450 
 
 broma =z HBr, 52 
 
 butyrylete, 52 
 
 cWora=HCl, 54 
 
 cyana = HCy, 243 
 
 cyanate = HCyO, 250 
 
 formylete, 59, 189 
 
 fumarylete, 414 
 
 ioda =HI, 59, 551 
 
 iodite, 548, 553 
 
INDEX. 
 
 569 
 
 Hydra maleylete, 414, 419 
 
 nitrate = HNO, 255 
 
 nitrete^HNO 2 , 255 
 
 nitrite, = HNO 3 , 251, 255 
 
 cenanthylete, 61 
 
 phenylate, 45 
 
 sebamylete, 445, 451 
 
 silate, 503 
 
 suberylete, 444 
 
 succinylete, 446 
 
 sulphate, 120, 160 
 
 sulphete, 118, 156 
 
 tartrylite, 461 
 
 " valerylete, 63 
 
 Hydramides, 228 
 
 Hydranzo thine, 477 
 
 Hydrated alkalies, theory of, 9, 14 
 
 acids, theory of, 4 
 
 Hydrides of radicals, 65 
 
 nomenclature of, 88 
 
 Hydrocarbons, with an even number of 
 atoms of hydrogen, discussion respect- 
 ing, 368 
 
 cannot displace hydrogen in other 
 
 hydrocarbons, 459, 487 
 
 Hydrocyanic acid, 42 
 
 Hydrogen, as a gas, 59 
 
 acts as a basic radical, 73 
 
 its atomic measure in salts, 69, 108 
 
 Hypophosphites, 144 
 
 Hyposulphates, constitution of, 172 
 . double, 493 
 
 containing vice-ammons and vice- 
 
 amids, 240 
 
 various, 483, 484 
 
 Hyposulphites, with vice-amids and vice- 
 ammons, 242 
 
 constitution of, 160 
 
 complex, 165 
 
 Idocrase, 516 
 
 Imasatine, 267 
 
 Imesatine, 266 
 
 Imides, 222, 224 
 
 Imidogen compounds, 208, 222 
 
 Indigo, 257 
 
 blue, 258 
 
 multiple salts of, 264 
 
 oxidised, 260 
 
 oxysulphur salts of, described, 269- 
 
 274 ; theory corrected, 490 
 
 reduced, 259 
 
 sulphate of, 270 
 
 white, 258 
 
 Indigogen, 258 
 
 Indigotine, 258 
 
 Indyl, 257 
 
 conversion into phenyl, 280, 532 
 
 conversion into salicyl, 532 
 
 Indylac, 264 
 
 salts in which it is the positive ra- 
 dical, 269 
 
 salts in which it is the negative ra- 
 dical, 264 
 
 Indylam, 269 
 
 Inulin, 519 
 
 lodaniline, 281 
 
 lodic-phenylac, 275, 281 
 
 lodic -radicals, 132 
 
 Iodides, their measure in gases, 101 
 
 metallic, their electrolysis, 551 
 
 organic, 67 
 
 Iodine, 59 
 
 Iron, its ferrous radical, 33 
 
 its ferric radical, 33 
 
 essential difference between the fer- 
 rous and ferric radicals, 35 
 
 circumstances under which the fer- 
 rous and ferric radicals are respectively 
 produced, 36, 310 
 
 electrolysis of its salts, 554 
 
 the peroxidation and protoxidation 
 
 of its salts explained, 37. 
 
 cyanides containing, 38 
 
 double salts of, 37 
 
 Isathyde, 262 
 
 Isatides, 261 
 
 Isatimide, 267 
 
 Isatine, 260, 280 
 
 Isatinides, 261 
 
 Isatites, 261 
 
 Jargonelles, essence of, 521 
 
 Ketones, atomic measure, 66 
 
 defined, 81 
 
 how prepared, 76 
 
 nomenclature of, 89 
 
 Klumene gas, 58 
 
 Knebelite, 511 
 
 Kolbe's copulated oxalates, 408 
 
 Laumonite, 512 
 
 Leucite,512 
 
 Lignin, 519 
 
 Lignone, 60 
 
 Likene, 59 
 
 Lime, trisilicate, 511 
 
 Magnus's platinum salt, 318 
 
 Malamide, 417 
 
 Malates, acid, 412,415 
 
 basic, 412, 415 
 
 double, 412, 415 
 
 neutral, 412, 415 
 
570 
 
 INDEX. 
 
 Malates, shown to be double salts of mono- 
 basic acids, 411-423 
 Maleates, 414, 419 
 Malic group of salts, 411 
 < summary of their chemical reac- 
 tions, 420 
 
 Malic-phenyl amides, 414, 418 
 Mandelates, 457, 460 
 Manganese, silicate, 511 
 Manganic radical, 34 
 Manganous radical, 34 
 Marsh gas, 59 
 Meconates, 532 
 Meerschaum, 511 
 Melaniline, 291 
 
 Hofmann's diversified theories, 293 
 
 salts of, 292 
 
 Melanoximide, 302 
 
 its decomposition by heat, 307 
 
 Menaphthalamine, 532 
 Menaphthoximide, 533 
 Mesitylol, 59 
 Metallic oxides, Intel-mediate, 123 
 
 vice radicals, 137 
 
 evidence of their occurrence, 304, 
 
 416, 467, 490 
 Metamerism, 17 
 
 traced to its cause, 523 
 
 Metamorphoses of organic radicals, 519 
 Metaphosphates, 138 
 Menthene, 59 
 
 Mercaptan, 58 
 
 Mercuric radical, 34, 59 
 
 bromide, 59 
 
 chloride, 59 
 
 iodide, 59 
 
 sulphide, 59 
 
 Mercurous radical, 34 
 
 bromide, 59 
 
 chloride, 59 
 
 Mercury, 59 
 
 its measure in gases, 107 
 
 Mericac, 191 
 
 Merousac, 191 
 
 Mesitylene, 59 
 
 Methyl, 59, 66 
 
 acetate, 59 
 
 benzoate, 59 
 
 borate, 59 
 
 bromide, 60 
 
 butyrate, 60 
 
 caprylate, 60 
 
 chloride, 54, 60 
 
 chloric, 54 
 
 caproate, 60 
 
 Methyl, cyanide, 60 
 
 cyanurate, 60 
 
 cyanylate, 60 
 
 fluoride, 60 
 
 formiate, 60 
 
 tribasic, 60 
 
 hydride, 59 
 
 iodide, 60 
 
 nitrate, 60 
 
 salicylate, 60 
 
 succinate, 60 
 
 sulphide, 60 
 
 bisulphide, 60 
 
 sulphate, 60 
 
 sulphocyanide, 60 
 
 sulphocarbonate, 60 
 
 xanthate, 60 
 
 Methylal, 61 
 
 Methylam, 192 
 
 Methylamine, 61 
 
 Methyl and amyl oxide, 60 
 
 Methylem, 192 
 
 Methylene, bichloride, 55 
 
 Methyl-hexyl, 60 
 
 Methylic alcohol, 59 
 
 Methylic-amylac, 191 
 
 Methylic ether, 59 
 
 monochlorinated, 55 
 
 bichlorinated, 55 
 
 terchlorinated, 55 
 
 Methylim, 192 
 
 Methylodithionates, 486, 498 
 
 Methylopiperidine, 63 
 
 Methylom, 192 
 
 Methyl-urea, 345 
 
 Milk-sugar, 519 
 
 Mineral silicates, 505 
 
 Model of water, 82 
 
 Monatomic, defined, 146 
 
 Multiple combining proportions, laws of, 
 537 
 
 they are fallacious, 539 
 
 improbable if not impossible, 546 
 
 incompatible with the facts of 
 
 electrolysis, 547, 556, 557 
 
 Mutability of simple radicals, 310 
 
 of azotic radicals, 217221 
 
 Naphtha, 61 
 
 Naphthaline, 61 
 
 Natrolite, 512 
 
 Nicotine, 61 
 
 Nitra nitrate = N,NO, 255 
 
 Nitra nitrite = N,N0 8 , 255 
 
 nitrute = N,N0 5 , 120, 255 
 
 Nitraniline, 288 
 
INDEX. 
 
 571 
 
 Nitrate =NO, 255 
 Nitrates =M,N0 3 , 251 
 Nitrete = N0 2 , 255 
 Nitriles, 208, 217 
 Nitrites = M,N0 2 , 253 
 
 gaseous, 67 
 
 Nitrobenzide, 61 
 Nitrogen, 61 
 
 protoxide, 61 
 
 deutoxide, 61 
 
 peroxide, 61 
 
 atomic measure of, 99 
 
 Nitroglycerine, 385, 394 
 Nitrotoluine, 61 
 Nomenclature, systematic, 86 
 
 numeration of radicals, 86 
 
 numeration of oxygen, 86 
 
 numeration of water, 88 
 
 examples of, 87 
 
 of amidoo-ens and ammoniums, 
 
 190 
 of multiple salts. See malates, 
 
 citrates, tartrates, aniline, platinum. 
 
 &c. 
 
 (Enanthol, 61 
 Okenite, 511 
 Oleene, 59 
 Olefiant gas, 63, 73, 96 
 
 oil of, 54- 
 
 Olein, 379 
 
 Olivine, 511 
 
 Origin of organic radicals, 519 
 
 Othyl, 122 
 
 Oxalates, 177 
 
 complex, 182 
 
 copulated, 408 
 
 their measure as gases, 95, 112 
 
 Oxamates, 226 
 Oxamelanile, 302 
 Oxamide, 194 
 
 Dumas's strange theory, 209 
 
 Oxanilamide, 286 
 
 Oxanilates, 227, 287 
 
 Oxanilide, 210, 286 
 
 Oxidation, nature of the process so called 
 
 260 
 
 Oxychlorides, 68, 90 
 Oxygen, 61 
 has no measure when in gaseous 
 
 salts, 68, 95 
 no quantity of it increases the 
 
 measure of its gaseous salts, 69 
 is not a radical, not the equivalent 
 
 of any radical, nor a constituent of 
 
 radicals, 69 
 
 Oxygen not the acid-former ; not the sole 
 
 cause of acidity, 70 
 
 salts, classification of, 26 
 
 Oxyplatammonium, 313 
 Oxyxanthates, 471, 477 
 Palmitin, 379 
 Paraffine, 61 
 Pear-oil, 521 
 Pentathionates, 157, 158 
 Peppermint camphor, 51 
 Perchlorovinic formiate, 55 
 Petrolene, 61 
 Phenakite, 511 
 Phenyl, cyanide, 61 
 
 .hydride, 61 
 
 nitrite, 61 
 
 relation to aniline, 275 
 
 Phenyla cyanate, 304 
 Phenylac, 190, 193, 275 
 Phenylam, 193, 275 
 
 cyanate, 298 
 
 Phenylec, 191 
 Phenylem, 275 
 
 cyanate, 298 
 
 Phosgene gas, 55, 114 
 
 Phospha phosphute, 120 
 
 Phosphates, constitution of, 138 
 
 considered in reference to the theory 
 
 of poly basic acids, 138 
 
 nomenclature of, 141 
 
 Phosphites, 143 
 Phosphoglycerates, 385 
 Phosphorus, 61 
 
 terchloride, 61 
 
 pentachloride, 62 
 
 oxychloride, 62 
 
 its measure in gases, 102 
 Phosphuretted hydrogen, 62 
 
 hydriodate of, 62 
 
 hydrobromate of, 62 
 
 Phtalimide, 223, 529 
 Pimelates, 446, 454 
 Pine-apple oil, 521 
 Piperidine, 63 
 Platammonium, 313 
 Platic atom or radical, 309 ,3 14 
 
 salts, 316 
 
 Platicam, 191, 309, 314 
 
 salts of, 328 
 
 Platiccem, 333 
 
 Platinamine, 313 
 
 Platinum bases, 308 
 
 Platinum bases, theoretical, 312 
 
 discussion respecting the platous 
 
 and platic radicals, 308 
 
572 
 
 INDEX. 
 
 Platinum salts, 314 
 
 the transformations of the platous 
 
 aud platic radicals, 309, 321 
 
 Platosamine, 312 
 
 Platous atom or radical, 309, 314 
 
 salts, 314 
 
 Platousam, 309, 314 
 
 salts of, 317 
 
 Platousem, 319 
 
 Polyatomic alcohols, 366 
 
 are fallacies, 385 
 
 Polybasic acids, theory of, 395 
 
 fallacies in Gerhardt's laws re- 
 specting the measure of their gases, 
 111 
 
 insufficiency of Gerhardt's argu- 
 ments in support of, 148 
 
 Polybasic properties of oxy-sulphur acids 
 explained, 173 
 
 Polythionates, 157 
 
 nomenclature of, 175 
 
 of ammonia, 233 
 
 Potassac, 191 
 
 Potassec, 191 
 
 Propionic aldide, 62 
 
 Propyl, butyrate, 62 
 
 Propylene, 62, 373 
 
 bromide, 62 
 
 Propylic alcohol, 62 
 
 glycol, 372 
 
 Protoxides, 14 
 
 Proximate and ultimate constitution of 
 salts discriminated, 10 
 
 Prussian blue, two kinds, 40 
 
 Pyromeconates, 532 
 
 Pyrophosphates, 138 
 
 Pyrotartranile, 453 
 
 Pyrotartrates, 445, 451 
 
 terbasic, 452 
 
 aniline salts, 463 
 
 Quinces, essence of, 521 
 
 Radical, what constitutes a, 501, 544 
 
 atomic measure of a, 94 
 
 theory, principles of the, 25 
 
 applications of the, 117 
 
 supported by the evidence of 
 
 electrolytic facts, 548 
 
 Radicals, elementary, table of, 28 
 
 compound organic are equivalent to 
 
 elementary radicals, or atoms, 48 
 
 all of them measure one volume as 
 
 gas, 64, 68 
 
 < those which contain an even num- 
 ber of atoms of hydrogen have no mea- 
 sure in their gaseous salts, 96 
 
 Radicals, classification to show their rela- 
 tions, 525 
 
 their origin and metamorphoses, 
 
 519 
 
 their behaviour in voltaic current, 
 407 
 
 table of, in the order of their pro- 
 portions of carbon, 44 
 
 table of, in the order of their basi- 
 city, in which the carbon is taken at 
 unity, 70 
 
 table of the vinyl series, 79 
 
 necessity of a more accurate discri' 
 
 mination of radicals, 379 
 
 their multitudinous names, 379 
 
 reduction of acid radicals to basic 
 
 radicals, 75, 407 
 
 reduction of basic radicals to acid 
 
 radicals, 74, 407 
 
 acid from basic, how distinguished, 
 
 73, 545 
 
 metamorphoses, various modes of, 
 
 535 
 
 azotic, theory of, 189 
 
 degrees of oxidation, 122 
 
 Radicals, (Vice-): 
 
 containing Cl instead of H, 93, 131 
 
 Z instead of H, 132 
 
 S instead of H, 136, 472 
 
 Metals instead of H, 137 
 
 Raewsky's platinum base, 312 
 
 Reduction, nature of the process so called, 
 260 
 
 Reiset's platinum base, 312 
 
 Rennets, essence of, 521 
 
 Retinnaptha, 63 
 
 Retinole, 56 
 
 Retinyl, 56 
 
 Rochelle salt, 466 
 
 Salts, constitution of, 3, 18 
 
 binary, theory of, 1 8 
 
 are composed of two radicals, 69, 
 
 544 
 
 in which the number of acid and 
 
 basic radicals is uneven, how explained, 
 397 
 
 Clark's table of (1826), 5 
 
 Griffin's classification of (1834), 15 
 
 Ditto (1857), 26, 397 
 
 their atomic measure is two vo- 
 lumes, 68, 95 
 
 their electrolysis, 552 
 
 with one atom of oxygen, 89 
 
 organic, nomenclature of, 90 
 
 normal , 397 
 
INDEX. 
 
 573 
 
 Salts, bibasic and monacid, 397 
 
 monobasic and biacid, 397 
 
 tetrabasic and biacid, 397 
 
 ' peculiarities in their saturating ca- 
 pacities, 173, 423 
 
 Salicyl, 455 
 
 its atomic measure in salts, 96 
 
 salts containing, 456 
 
 Salicylamide, 458 
 
 Salicylates, 455, 458 
 
 with acid radicals, 456 
 
 Salicylic conjugated acids, 458 
 
 group of salts, 455 
 
 Salicylid, 458 
 
 Scolezite, 512 
 
 Sebacin, 379,451 
 
 Sebamide, 451 
 
 Sebates, 445, 451 
 
 Selenium, its atomic measure in gaseous 
 salts, 105 
 
 Seleniuretted hydrogen, 62 
 
 Sesquioxides, the theory pernicious. See 
 basylic radicals. 
 
 the chief obstacle to the simplifica- 
 tion of the silicates, 514 
 
 Silica, 500 
 
 Silicates, on the, 500 
 
 normal, 505 
 
 general formula, 505 
 
 theoretical constitution of, 506 
 
 constitution of chief varieties of 
 
 known mineral silicates, 507 
 
 relation of the oxygen of their radi- 
 cals, 509 
 
 rational formulae of, 511 
 
 inquiry into the worth of their ra- 
 tional formulae, 512 
 
 easy transformation of the formulae 
 
 of Berzelius into those of the radical 
 theory, 508 
 
 simplification of the formulae of sili- 
 cates, 514 
 
 classified tables of, 506-512 
 
 Siliceous gases, peculiarities of their atomic 
 measure, 501 
 
 Silico-fluorides, 503 
 
 Silicon, determination of its equivalent, 
 502 
 
 its measure in gases, 105, 501 
 
 chloride, 62, 501, 503 
 
 fluoride, 62, 501, 503 
 
 chlorosulphide, 62, 501 
 
 Soda, sulphate, electrolysis of, 550, 558 
 
 Specific gravities of gases, 49 
 
 Spiryl, 455 
 
 Stannic chloride, electrolysis of, 548, 552 
 
 Stannous chloride, electrolysis of, 548, 
 552 
 
 Starch sugar, 519 
 
 Stearin, 379 
 
 Stib-ethyl, 58 
 
 Stilbite, 512 
 
 Styrol, 63 
 
 Suberamide, 450 
 
 Suberates, 444, 450 
 
 Suberone, 62 
 
 Substitution, 91 
 
 Sucdnamide, 447 
 
 Succinanile, 447 
 
 Succinanilide, 447 
 
 Snccinates, 443, 446 
 
 Succinic group of salts, 441 
 
 series of radicals, 441 
 
 Succinimide, 447 
 
 Succinyl, its measure in gases, 96 
 
 oxy chloride, 447 
 
 Sugar, varieties of, 519 
 
 metamorphoses of, 522 
 
 Sulpha sulphate =S, SO, 120 
 
 Sulpha sulphite = S, SO 3 , 119 
 
 Sulphacetates, 489 
 
 Sulphacetyl, 489 
 
 Sulphamethylane, 237 
 
 Sulphamide, 234 
 
 Sulphanilates, 285, 498 
 
 Sulphanisates, 492 
 
 Sulphasatyde, 271 
 
 Sulphates, on the, 144 
 
 atomic measure in gases, 112 
 
 inquiry respecting their assumed 
 
 bibasic character, 145 
 
 Davy's theory, 128 
 
 multiple salts, 150 
 
 nomenclature of, 156 
 
 double, of alcohol radicals (conju- 
 gated), theory, 400 
 
 of vice-ammons, 229 
 
 of vice-umids, 231 
 
 Sulphenetes, 170 
 
 of vice-amids, 243 
 
 Sulphic-indyl, 272, 490 
 
 vice-radicals, 136, 472, 490 
 
 Sulphide of carbon, 53, 471 
 
 Sulphindigotates, 270 
 
 Sulphindylates, 270 
 
 Sulphites, on the, 171 
 
 essentially bibasic, 171 
 
 acid, 171 
 
 neutral, 171 
 
 organic, 484 
 
574 
 
 INDEX. 
 
 Sulphites, with amidogens, 237, 485 
 conjugated, 495 
 
 with chloric radicals, 496 
 
 often miscalled hyposulphates, 495 
 
 Sulphobenzoates, 491 
 Sulphobutyrates, 491 
 Sulphocarbamates 471, 476 
 Sulphocarbanilide, 301 
 Sulphocarbonates, 470, 473 
 Sulphocyanides, 247 
 Sulphocyanogen, 247 
 Sulphogly cerates, 385 
 Sulphomethylane, 498 
 Sulphopropionates, 491 
 Sulphosuccinates, 444, 448 
 Sulphovinates, theory of, 400 
 
 biacid, 486 
 
 bibasic, 486 
 
 monobasic, 486 
 
 Guthrie's attempt to prove their 
 
 existence by electrolysis, 403 
 
 causes of its failure, 406 
 
 Sulphoxanthates, 470, 473 
 Sulphur, as a gas, 62 
 
 its measure in gaseous salts, 97 
 chloride, 63 
 
 dichloride, 63 
 
 terchloride, pentasulphate of, 63 
 
 Sulphuretted hydrogen, 62 
 Sulphuryl, 146 
 Synoptical formulae, 127 
 Systematic nomenclature, 86 
 Tartanilates, 468 
 Tartanilide, 468 
 Tartramide, 466 
 Tartrates, table of, 461 
 
 great variety of forms of, 463 
 
 acid, 461, 465 
 
 neutral, 461, 464 
 
 terbasic, 461, 464 
 
 amidogen salts, 461, 466 
 
 double, 461, 4tf6 
 
 conjugated, 461, 466 
 
 with sesquioxides, 468 
 
 tetrabasic, 461, 466 
 
 with vice-tartryls, 461, 467 
 
 complex, 461, 467 
 
 Tartryl, 463 
 
 Tellurium, its measure in gases, 105 
 
 Telluretted hydrogen, 63 
 
 Tephroite, 509 
 
 Teratomic alcohols, 366, 374 
 
 Tetrathionates, 157, 168 
 
 Thiotoluates, 498 
 
 Thymyl, hydride, 63 
 
 Titanium, its measure in gases, 105 
 
 chloride, 63 
 
 Tin, its measure in gases, 105 
 
 chloride, 63 
 
 electrolysis of its chlorides, 548 
 
 its stannic radical, 556 
 
 its staunous radical, 556 
 
 Toluine, 63 
 
 Toluol, 63 
 
 Trithionates, 157, 168 
 
 Troostite, 511 
 
 Turpentine, essence, 63 
 
 Type ammonia, 210, 232, 297 
 
 Types, chemicals, theory of, 91 
 
 Unitary formulae, origin of, 16 
 
 unsuited to organic compounds, 17 
 
 . why they should be dissected, 167 
 
 demonstration of their worthless- 
 
 ness, 523 
 
 Urea and carbamide theories compared, 
 298, 339 
 
 theory, summary of evidence re- 
 specting it, 341 
 
 chemical reactions of, 339 
 
 salts of, 343 
 
 Ureas, compound, 343 
 
 theory of, 344 
 
 Ureides, 360 
 
 are merely ureas with acid radicals, 
 
 and O 1 extra for that reason, 480 
 
 Ureo-carbonates, 363 
 
 Urethane, 57, 352 
 
 Ure thy lane, 351 
 
 Valeral, 63 
 
 Valerin, 379 
 
 Valerine, 63 
 
 Valeronitrile, 52 
 
 Valeryl, 63 
 
 Valeryl-urea, 361 
 
 Vapours, table of, 49 
 
 Vesuvian, 512, 516 
 
 Vice-amids, theory of, 190 
 
 discrimination of, 1 90 
 
 nomenclature of, 190 
 
 sulphates of, 231 
 
 sulphites of, 237 
 
 hyposulphates of, 240 
 
 hyposulphites of, 242 
 
 Vice-ammons, theory of, 190 
 
 discrimination of, 191 
 
 nomenclature of, 190 
 
 salts of, 202 
 
 . inorganic, sulphates, 229 
 
 organic, sulphates, 231 
 
 sulphites of, 237 
 
INDEX. 
 
 575 
 
 Vice-ammons, hyposulphates of, 240 
 
 hyposulphites of, 242 
 
 Vice-indyls, 258 
 Vice-phenylac, 275 
 Vice-phenylam, 275 
 Vice-radicals, theory of, 131 
 
 atomic measure of, 101 
 
 their saturating capacity equal to 
 
 that of normal radicals, 131, 281 
 Vice-tartryls, 463 
 Vinyl, the neutral radical, its importance 
 
 as the substratum of organic radicals, 
 
 63, 73, 78, 96, 519, 520 
 its measure in gases, 96 
 
 its series of radicals, 79, 527 
 
 doubled, to produce the imaginary 
 
 glycol, 367 
 
 Voltaic equivalents, 549, 556 
 Water, constitution of, 31, 82, 557 
 
 electrolysis of, 549, 557 
 
 model of, 82 
 
 model of, grotesque caricatures of, 
 
 84, 381 
 
 White indigo, 258 
 
 Williamite, 511 
 
 Wine-oil, 521 
 
 Wollastonite, 511 
 
 Woody fibre, 519 
 
 Worthite, 511 
 
 Xanth, 53, 472 
 
 Xanthamide, 471, 478 
 
 Xanthamylates, 471, 476 
 
 Xanthates, 470, 474 
 
 Xanthic ether, 60, 475 
 
 Xanthocetylates, 471, 476 
 
 Xanthomethylates, 470, 474 
 
 Xanthopropylates, 471, 476 
 
 Xanthyl, 53, 472 
 
 Z, value of symbol, 94 
 
 Zinc, its measure in gases, 106 
 
 Zinc-ethyl, 58, 63 
 
 its measure as a gas, 106 
 
 Zircon, 511 
 
 Zot, signification of, 94 
 
 Zotic radicals, 132 
 
 -dF 
 
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