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^OM THE TRAHSACnONSOFTHE ROYAL SOCIETY OF CAHADA 
 SECOND SBRIBS-igos-igos- 
 
 VOLUMBTII SBCTIOMIII^ 
 
 aCATMBMATICAI., PHYSICAL AND CHSMICAL SCIBNCU 
 
 V 
 
 i 
 
 NOTE ON THE 
 
 Identification of Basic Salts 
 
 By W. LASH MILLER and PRANK KBNRICK 
 
 k 
 
 \. MOPK * •OMt, OTTAWA ; TMB COPP-CLARK COn TORONTO 
 BBRMARD QUARITCH, LONDON, BNOLAND 
 
 igoi 
 
 
i 
 
8BL.TIOM III., 1901 
 
 [88] 
 
 Ta^iw. K. 8. C. 
 
 VI. — Note on the Identification of BaMc iSalts. 
 By W. Lasu Miller and Frank B. Kenrick. 
 
 (Retul May 22, 1901.) 
 
 Basic Salts are prepared by the action ol water or of bases — potash, 
 ammonia, etc. — on the " normal " salts of most of the metals ; in 
 composition they stand in lermediate between the normal salts and the 
 oxides (bases), hence the name " Basic Salt." Some arc well defined 
 crystalline compounds, but the fjicater nunibor are knuwn only as amor- 
 phous, muddy precipitates, whose composition varies with the concen- 
 tration and temperature of tlie solutions and even with the order of 
 mixing the ingredients from, which they arc prepared. 
 
 When the basic salt, besides being amorphous, is insoluble, non- 
 volatile, and infusible — and this is the rule rather than the exception 
 — it is quite impossible to purify it by any of the usual means ; and 
 as the removal of the mother-liquors by washing with water can be 
 ■<'«uried to only when special experiments have shown that the compo- 
 sition of the precipitate i- not affected by such treatment, even the 
 ultimate analysis of th crude precipitate is not unattended with 
 difficulties. 
 
 In the article "Ai .unoine" in the Encyclopedie Chimique, M. 
 Guntz quotes analyses of an oxychloride of antimony by four different 
 'hemibts; the percentage of chlorine varies from 11-25% to 7 8%. As 
 exP'Timonts carried out by Mr. Good (referred to below) show that the 
 Kib»i .iws a alysed with such descrepant results were in all probability 
 •ftp ani th( sijme chemical compound, M. Guntz's conjecture that the 
 ^ rrial for analysis was washed too much by some of the analysts, and 
 'f^f •■ otli< rs, may be accepted as correct. 
 
 M^t the alloration of foriiinlae is apt to be somewhat 
 
 luthors -istributc them with a lavish hand, and 
 
 in endow i-ig "amorphous finely-divided precipitates" 
 
 f chemica. individuality; while the more conservative 
 
 ; 'Bp -inribe the same precipitates as "impure modifi- 
 
 ,, \ -ijjouiuis" vhich have already found their way into the 
 
 k- Olaiir le took a cautious course; after analysing the 
 
 • som«» jiroduced when cupric chloride is dissolved in 
 
 «atei. say.'': — ' longh the ilt is evidently somewhat irr"!jular 
 
 ta compusition, i ?»pma^he8 nearer [within 2-3%] to the oxychloride 
 
 •^Kmmm 
 
 ■iMgg^ 
 
8(5 
 
 ROYAL SOCTKTY 1 
 
 CuCl,.2CuO than to any other of th .^ht or nine that have bet-n 
 described by previous investigators." 
 
 In the absence of any tk-arly defined principle ol selection much 
 must of necessity be left to individual taste, and as there is wide room 
 for difference of oi uion, Hat contradictions are not uncommon in the 
 literature of the abject. In Danimer'a "Hundbuih tier annganisrh n 
 Chemie," for instance, after detailed descriptions of seven compuundi 
 of lead chloride with ammonium chloride, comes the announcement 
 that " according to Kandall, none of Andre's compounds exist" ; liile 
 with reference to Cross and Suguira"* basic oxychlorides of lead, 
 Pb,jCl2iO„ Pb,(;l„0, and Pb«Cl,0, the editor himself ventures on the 
 criticism, " I'hese were obviously impure, and probably badly analysed." 
 r t neither Aiidr nor Ikndall, Cross nor Dammcr adduces inclusive 
 eviv nee in eup of his contentions. Mere comple.Xi^y in the 
 
 formula ]•■ in itse o bar to the genuineness of a chemical compound 
 — Mr AlliiiiV jcperinients, referred t« below, establish bjyond qiustion 
 the e.xirt.itL' of a basic nitrate of bismuth with the formula 
 
 Even lu the case of so important an article of commerce as white 
 lead, it is still wholly uncertain whether the different varieties arc to be 
 regarded ps distinct chemical species, as mixtures of a few individuals, 
 or as more or less saturated (solid) solutions of carbon dioxide in lead 
 oxide or in some basic carbonate. It is consequently hardly surprising 
 that success in the manufacture of such substances is conditioned by 
 strict adherence to empirical recipes, any deviation from which may 
 seriously affect the pro[)ertics — and the value — of the product. 
 
 Application of the Phase Rule. 
 
 
 •,ii* 
 
 Difficult though it might appear to find any rational basis of 
 classification for these precipitates, there is one large group— viz., all 
 eases where equilibrinm is attained between precipitate and mother- 
 liquor — for which the problem is completely solved by two theorems 
 due to Professor Willard Gibbs, which form part of what is commonly 
 known as his "Phase Rule." 
 
 These theorems may beetated as follows: — Assuming that thesyth 
 tem has arrived at rqiiilibiiuvi, at "arbitrary" temperature and pr.^isrrp, 
 (i) The system can in general consist of no more phases than it has 
 compon( 1 =, (ii) A solution can form one of a group of n phases (« is 
 the number of the components) only if it has attained a certain compo- 
 sition dependent on the temperature and pressure, and on the chemical 
 and physical nature of the other phases present. 
 
[niLL«R « KKNEicK] IDENTIFICATION OF BASK" SALTS 37 
 
 The first thcorcn; docs not exihule thf i.iB^li'.ity it tho ».iM*i»t- 
 ciKC of H-4- i or I'vcn n+J phases '.huUt CTtuin loiiditidus of i.iniHr itun; 
 ana pressure; but if Ue expcriiiu iiu^ bo uarri.' 1 oui ui almo-phcric 
 pressure iu a thermostat eet for some temiKrature below the lM)iling- 
 point of the solution, the . iance of meeting with such special conditioaa 
 
 is negligible. 
 
 These theorems, which were reached by (jihba lU 1876, -n the 
 course of an abstract thcrmodynamical study of the condition of 
 equilibrium in heterogeneous systems, Imve often been verified; their 
 impoi-tance, however, as funiishing a means— ofU-n the only i.ieans— 
 of discovering tho chemical individuals in ill-defined mud ly pivcipi- 
 tates, ii= only now beginning to !'e geni.rally rciilized. 
 
 Applied to a particnlnr cise. fi r ins'.an.r the foinwtioi of ba-ic 
 PiiUs by tlicnctioii nf water on thf ihl.iri.ic of a:itimony or ><n the nitrate 
 of itismiith (temiMrature and pressuiv lixid as al. Vi), tlie th' orenH 
 
 aftiriu: 
 
 (i) That if the system, which consists of three com(Hine;it£ (see 
 below), has arrived at equilibrium, not more than three ph.ises can 
 coexist. Of these tlie solution forms one, the precipitate consequently 
 must bo cither one sinj^le hoinogeneuus substan-e (one p,.asc). or a 
 mixture of two phases— for instance, of two l^isic salts, or of one basic 
 salt ^vith the oxide. 
 
 . i That i le observed difTerei^ in composition between two 
 precipitates, formed by the action of dilTen'tit <|uanti<ies of water on 
 the same salt, is due to 'heir being mixtures of the same [)air of basic 
 salts in different proportions, tlie composition of the mothr-liquurs 
 will be the same in the two cases. 
 
 The possible cases are thus divided into three groups: — 
 
 1. The solutions are identical in composition in different experi- 
 
 ments, while the composition of the preeipitato varies.— The 
 precipitate is a mixture of two piiases. 
 
 2. The solutions differ in composition, but the precimtates havo 
 
 the samo composition. — The precipitate i- a sir.-cu chemical 
 compound. 
 
 3. Both solnuons and precipitates vary.— The picipitjtte is a 
 
 single phase of variable con ^sition, a "solid solution." 
 If it were possible to represent tin- conipc«iti(ms of the solutions 
 by abscissae, and those of the precipitates l«v ordinates. <!;■• results of a 
 series of experiments could be represented by a curve perpendicular 
 lines would then correspond to case 1 above, horizon' li linos io case 
 2, and slanting lines to case 3. In a three-component s'riem this is in 
 general not possible. In many eases, however, a pair or pairs of com- 
 
88 
 
 ROYAL SOCIETY OF CANADA 
 
 ponents may be found whose ratio in the solution, or precipitate, 
 changes whenever the composition of the solution, or precipitate, 
 changes, and only then; and since for the interpretation of the results it 
 is only necessary to know whether the composition of solutions and 
 precipitates remains constant or changes from experiment to experi- 
 ment, it is sufficient to plot these ratios instead of the compositions 
 themselves. An illustration is afforded by the following curve taken 
 
 ^A 
 
 ■ 
 
 
 
 NxOs 
 
 ZB,.O^-IV^0, -hH^O 
 
 
 8 
 
 • 
 
 1 
 
 
 6 
 
 ■ 
 
 
 6Bi^Ot-5KOs*9H^O 
 
 4 
 
 ■ 
 
 
 2 
 
 ■ 
 
 
 
 
 
 
 ■oos 
 
 ■010 
 
 ots 
 
 ■ozo 
 
 ■ozs 
 
 03O 
 
 
 from Mr. Allan's paper on the basic nitrates of bismuth. Tlie abscissae 
 give the ratios between NjOj and HjO in the solutions, and the 
 ordinates those between BijOj and NjOj in the precijiitateB. 
 
 The Mechanism. 
 
 Although a great deal of use has been made of the Phase Rule in 
 classifying chemical reactions, and in the study of solutions and alloys, 
 and more recently of such compounds as steel and the various commer- 
 cial varieties of iron, comparatively little attention has been paid to 
 the mechanism by means of which the results foretold by it are arrived 
 at in the system. The subject is not only interesting in itself, but 
 leads to an extension of the method of identifying chemical individuals 
 among the basic salts, to the case where the precipitation is carried out 
 by means of potash, ammonia, etc., although here the system no longer 
 consists of three components only, and consequently the direct applica- 
 tion of the Phase Rule in the manner just illustrated is not possible. 
 
[miLiR A KKWRicK] IDENTIFICATION OF BASIC SALTS 
 
 89 
 
 <■* 
 
 The ^' 'pitates produced by the action of water on the nitrate of 
 Bismutu axe all of the general formula BijOj, mNjOj, nH,0; the com- 
 position of the solutions al-o may be expressed in terms of the same 
 Bubstances, BijO,, NjO,, and HjO, which are lieiu eforwurd termed the 
 " components'' of the System. The compositions of the precipitates and 
 Bolutionfl might be expressed in terms of other groups of three, — 
 elements, compounds, or mixtures — but three at least are necessary, aud 
 more than three are superfluoiis; if for example the elements Bi, N, H, 
 and 0, be selected, and the quantities of three of them in the solution 
 be known, that of the fourth lan be calculated from the stochiometric 
 relations. 
 
 The condition sine qua non for the application of the Phase Rule 
 is that' equilibrium be reached with respect to all reactions that occur 
 Idi the system. There is only one sure sign of the attainment of equi- 
 liFrium, namely, that the compositions of precipitates and solution 
 are found to be independent of the order in which the eomiioneiits were 
 mixed, — the composition of the precipitate must be the same whether 
 Bi(NOj)a be mixed with water, or Bi,0, with dilute nitric acid, provided 
 only that the samo quantities of the three components be employed in 
 each case. In other words, the quantities of the thr o components 
 (together with the temperatun- and the pressure) ar»> suflioient to 
 define the state of the system. 
 
 Now, it can be shown by a simple algebraical argument' that if 
 A, B, C, and D, be any four phases whatever, formed from the same 
 three components, it is possible either 
 
 (i) to mix three of these, e.g., A, B, and C, in such proportions 
 that the components are present in the mixture in tlie same propor- 
 tions as they are in D, or 
 
 (ii) to prepare a mixture of A and B, and another of C and D in 
 Buch proportions that the quantities of the three components are the 
 same in both mixtures. 
 
 In other words, it is possible with these four phases to build up two 
 systems identical with respect to the amounts of eaeh of the three com- 
 ponents, but differing in the nature and composition of the phases 
 composing them, and the condition that the state of the system should 
 be completely defined hy the nmounfs of the components (and tempera- 
 ture and preflBure) can be fulfilled only if one of these alt rnative 
 systems changes spontaneously into tlie other ; that is, if reactions 
 between the phases 
 
 A+B=C-LD 
 
 A+B-fC=D 
 
 ' Van der WaalB, quoted by Rooieboom, Rec. Trav. Chlm. Pays-Bas 6 
 286. (1887.) 
 
40 
 
 KOYAL SOCIETY OF CANADA 
 
 take place whenever possible, and proceed until one at least of the react- 
 ing pliasee totally disappears. Which of the four will be the firsb to 
 disappear, depends obviously on the direction of the reaction and on 
 the relative amounts of the diiferent phases present. When the number 
 of phases has been reduced to three, the possibility of a reaction of this 
 nature has vanished. 
 
 The occurrence of reactions of this type, then, is the mechanism by 
 means of which the number of phases in a three-component system is 
 kept down to three. If it fails, the state of the system is no longer 
 defined solely by temperature, pressure, and the masses nf the compo- 
 nents. Experimental evidence of such definition, must therefore 
 be reganled as proof that not more than three phases are present in the 
 (three-component) system. 
 
 Tiie result predicted by the second theorem is effected by means 
 of reactions of a second type, which can take place in a three-component 
 system of three phases only if one of the three is capable of continuous 
 varir.tion in compo.sition (a solution). 
 
 By dissolving more or less of the solid phases in the solution it 
 would be possible to construct a whole series of systems— formed of 
 tlie same amounts of the same components— but differing in the com- 
 position of the solutions and in the relative quantities of the solid 
 phases. If only one of these is found to exist in fact, the disappearance 
 of the others must be ascribed to the occurrence of reactions of this 
 second type, which fix the composition of the solution irrespective of 
 the relative quantities of the three phages of which the system is com- 
 
 Extension of the Method. 
 
 The two theorems which serve to interpret the experimental results 
 distinguishing between mixtures and single substances, and identifying 
 the chemical individuals in the precipitates, are thus dependent on the 
 occurrence of reactions of two types :-the first (which does not involve 
 change of composition of any of the phases) resulting in the disappear- 
 ance of all phases in excess of three; the second (which involves change 
 of composition of the solution) keeping the composition of the solution 
 constant so long as it is in contact with che same pair of basic salts. 
 
 The possibility of applying the same method to the study of preci- 
 pitates formed by j.otash in solutions of metallic salts, depends on the 
 discovery of conditions under which a fourth component may be added 
 to the system without interfering with the occurrence of these tiro 
 classes of reactions. 
 
[MlLLW * MXKICK] IDENTIFICATION OF BASIC SALTS 4, 
 
 ments there mu.t be a constant ratio between the amounts o7the fourth 
 component and of the water in the system. 
 
 If the water is present in large excess, (condition a) the mass of the 
 solution wdl be much greater than that of the precipitate, nrd no reac! 
 |o„ oceurnng in the system can have more than a vvry slight "on 
 
 ,n,lf .^^^K ^ "°^ .^^''^'^ ^''^ composition of the solution re. ain 
 mialtered), the quantiti^ of the other components eat.ring or leav n" 
 the solution must be still smaller than that of the water; so t at "^ 
 ^Zed " '''' '"^"^ '"^ '''"' '"^^^ "^ '"^^ sol„tion'(p,.a:ti:lli;) 
 If now a fourth component be added, the total amount of which 
 m the solution is unafTectod by the reaction (conduion b), this slight 
 variation m the quantities of the other components in the olut on vil 
 
 Tct oft ' r ''' ?':'' "' "" '=°"P"'''°" °^'*"« '"»- thatlh 
 effect of the change m checking the progress of the reaction may safely 
 
 be neglected; so that the prince of the fourth component, under tl«e 
 
 cond ions, will not interfere with the efficiency o'f re..etions o t"e 
 
 first type m kee,„ng down the number of phases to three 
 
 of thoTnf r\°' '^T'""^ *yP« ('°^'«l^^i"g changes in the compositi..,> 
 of the solut.on) are of course just as posslMe when the solution contains 
 
 soluTons""''^"''^* " "'^^ '' ""^ ""'• ^° °^^-' '— -, th^ 
 solutions over a given pair of basic salts should roach exactly the same 
 
 composition in diilorent experiments, it is obviously nccessan- tha the 
 
 concentration of the fourth component in the solution should be h 
 
 same from case to case. This is provided for by condition c. In exp ri 
 
 ments on the action of caustic pota.h on solutions of bichloride of 
 
 copper, for example, H,0, CuO, and CuCl, may be selected a ompo 
 
 nents with KCl as the "fourth component" of the pre e,l ng pTra 
 
 graphs; and condition c requires that if the quantity of pota ladlTd 
 
 nonrKri : f ''IT'' "^"^'^^" ^'^""'"^ vary-from'case to ca!., 
 enongh KCl must 1^ added to keep the total amount of potne.ium per 
 cubic centimetre of water the same in each experiment. ^ 
 
42 
 
 ROYAL SOCIETY OF CANADA 
 
 }-M 
 
 ?#, 
 
 Experiments. 
 
 In the spring and summer of 1899 the writers carried out a lengthy 
 series of experiments on the action of potash and ammonia on the 
 chloride of lead. The less basic of the oxychlorides are formed with 
 remarkable tlowness ; the reaction between n/3 ammonia and lead 
 chloride not coming to a standstill in ten days shaking at 100° C. 
 PbCljSPbO, however, was formed in a few hours in the cold. 
 
 In the winter of 1900-1901, Mr. Good took up the study of the 
 action of water on antimony tri-chloride, presenting his results as a 
 thesis in competition for the 1851 Exhibition scholarship. His observa- 
 tions may be rejrarded as confirming the individuality of the oxychloridc 
 SSbCl.nSb.Oj ui the powder of Alfiuroth : allliough in this case also 
 equilibrium is often not attained i'Util days after the precipitation. 
 
 Mr. F. B. Allan, Lecturer on Chemistry in the University of 
 Toronto, has just completed a series of experiments on the action of 
 water (111 the nitrate of bismuth,' which lie has presented as a thesis 
 for the degree of Ph.D. His results, some of which are represented in 
 llic <urv(' on pajro 38, establish the existence ot basic nitrates of the 
 fomiute Bi,0,.X,0,.2H„0, 3Bi„0,.X„0,.H,0, GBi,03..5X,0,.9H,0 ; 
 while although precipitates were obtained intermediate in composition 
 between the two last named, they were obviously mixtures. Two of 
 these latter have found their way into the literature as "compounds" 
 5Bi,03.4N„0,.9H„0, and llBi„03.9X„0,.21H,0. 
 
 "Mr. Wilson has been engaged during the past Kaster term with 
 experiments on the precipitation ot cupric chloride by potash. With 
 n/5 solutions at 85°C. the precipitate consists altogetner of CuCU.SCuO. 
 2H,0 until all the copper is removed from the solution; on further 
 addition of potash the precipitate turns black, no potash remaining in 
 the solution until the precipitate is totally converted into the oxide. 
 
 Amer. Chem. Jour. 25 307. (1901.) 
 
•tfj'— :iii:..^'^..ii'