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Tous les autres exemplaires originaux sont fiimAs en commen^ant par la premiere page qui comporte une empreinte d'impression ou d'illustration et en terminant par la dernlAre page qui comporte une telle empreinte. Un des symbples suivants apparaitra sur la derniire image de cheque microfiche, salon le cas: le symbole -^ signifie "A SUIVRE", ie symbole V signifie "FIN". Les cartes, planches, tableaux, etc.. peuvent Atre film6s 6 des taux de reduction diffirents. Lorsque le document est trop grand pour itre reproduit en un seul clich6. 11 est film* A partir do Tangle sup^rieur gauche, de geuche k droite. et de haut en bas, en prenant le nombre d'images n6cessalre. Les diagrammes suivants illustrent la mithode. j 1 ' 2 3 ■ * 5 6 -?7f -^Ai ic yi^VC C' M^G ■" ^^^> ^A- "^^ EXTRACTED rROH SILLIMAN'S JOURNAL OF SCIENCE HARCB 4854. ,n J ON THE THEOKBTICAL RELATIONS AND HYDROGEN; by T. Sterrt-Hont , Geological Commission of Canada. OF WATER Chemist to the In carrying out his theory of types, M. Laurent proposed to consider water HaOa, having its equivalent represented by four volumes of vapor, as the type of the oxyds like MsOa, of the hydroxyds (MH) O3, and of the sulphurets correspon- ding to these two classes. By his system of compound radi^-^ '^^ o cals, Liebig had extended to organic chemistry the nom^m . ^'" clature of Lavoisier , and he looked upon spirit of ffiM CUHcOi, as the hydrated oxyd of a radical ethyl (G4Hs4:Cf)^ , while hydric ether GtHsO, was the simple oxyd of the same ' radical. But as ether-vapor contain.s in the same volume; twice as much carbon as the vapor of alcohol, Gerhardt had already proposed to double the formula of ether, and Lau- rent now showed that while alcohol is to be regarded as the hydroxyd of ethyl (Et H)02, or water in which ethyl repla- ces an equivalent of hydrogen, ether is the anhydrous oxyd, in which the second equivalent of hydrogen is replaced, and should be written EtaOa. Hence while ether is neutral, alcohol is monobasic, having an equivalent of hydrogen. is ID — -2 — replaceable by a metal, and is the type of monobasic vinic acids, while water is the typo of bibasic acids. ( Laurent, Recherches sur les Combinaisons asoUes. Ann. de Chim. etdePhys., Nov. 1856.) In a review of that remarkable essay, published in this Journal for Sept., i848 (vol. vi, p. 173), I suggested that this view was ''susceptible of still farther extension, and that we may include in the same type all those saline combi- nations (acids) which contain oxygen." I referred to the hypochlorites CIO, MO, as derivatives of the type HaOa, in which CI replaces H, being (CIH)03, and (CIM)02, while anhydrous hypochlorous acid is Cla Oa, the result of a com- plete substitution. ''In the same manner nitric acid, N HOs, is a monobasic salt (i. e. acid), corresponding to water in which NOa is substituted for H, as in many organic com- pounds; we have then (NOa, H)0 and (NOa, M)0;" or ( NOt, H ) Oa in the notation adopted above. "As an adap- tation of this idea to bibasic compounds, sulphuric acid, SHaO*, is to be regarded as water in which SHOs replaces H;thus (SHOs, H)0. As the replacing elements contain an equivalent of hydrogen which is saline (i. e. replaceable by a metal), the acid is bibasic. When the hydrogen in S HOs is replaced by a metal, we have a class of acid sul- phates like (SKOs, H)0. The complete replacement of hydrogen in the original type yields ($HOs)aO, which is the Nordhausen acid commonly represented by 2SOs, HaO. This latter compound as Gerhardt has shown, corresponds to the anhydrous bisulphate of potash." "The tribasic acids may equally be reduced to the same type, if we conceive the elements which replace one equi- valent of hydrogen, to be bibasic instead of neutral or mono- basic; phosphoric acid, PHsO* is (PHaOs, H)0." "The primitive saline type is then essentially bibasic, and is presented in its most elemental form in water, while the simplest type of the monobasic salt, which is a derivative of — 3 — the lasl, is found in hypocliloroiis acid." p. 174. This view of the derivation of polybasic acids is illustrated by the biba- sic sulphacetic, and the tribasic sulphosiiccinic acid. On page 177 we further remark, that " the binary mole- cule of the metals, hydrogen, chlorine, bromine, etc. will be seen to be the type of an immense number of combinations, embracing the various alloys and amalgams, the hydracids like hydrochloric acid, with their corresponding salts, and such compounds as CI Br and CI I, while ICIs is referable to a triple molecule of these elements, represented by He; to this type belong the perchlorids of antimony, arsenic and phosphorus, while the corresponding trichlorids form a double molecule." In a subsequent Essay on Chemical Classification read before the American Association for the Advancement of Science, at Philadelphia, in September, 1848, and published in this Journal for May and July, 1849, (vols, vii and viii,) we observed that the relation between alcohol and acelene is that which subsists between the two types HaOa, and Ha, acetene being hydrogen in which ethyle replaces H, thus C4H5, H=C4H6, while hydrochloric ether is a chlorinized hydrocarbon corresponding to hydrochloric acid, so that having repeated what has been already cited as to the type Ha, we add, "moreover it follows from the relations of H CI to the chlorinized hydrocarbons, that it ( Ha ) is the type of all the hydrocarbons, as well as of the alkaloids, which may be described as amidized species of them, and are equally susceptible of substitutions by chlorine." It was also remar- ked that "as many neutral oxygenized compounds, which do not possess the saline character, are still derivatives of acids which are referable to the type Ha Oa, we may regard all oxygenized bodies as belonging to this type." "While nitric acid is NHOs, or (NOa, H)aO, the result of the com- plete replacement of H by NOa will he (N0a)3 0, or the unknown dry nitric acid, homologue J the so-called anhy- _ i _ (irons phosphoric and arsenic a(;ids, wliich are equally ( P0«) iO, etc." ( Vol. viii, p. 92 ). One of the ohjects proposed in the essay just quoted, was a comparison of the views of Gerhardt and Liebig with regard to the formation of ethers, amids, and allied bodies. Gerhardt in accordance with the electro-chemical theory of Kerzelius, had considered the acids in these reactions to be electro-negative by their oxygen, while tlie alcohols, ammo- nia, and the hydrocarbons were electro-positive by their hydrogen, so that these bodies minus Ha, replaced Oa in the acid. To this view we objected that it leaves unexplained that change in the basic relations of the acid, which Liebig rightly understood when he compared the ethers to salts, and represented the acid as losing H, which is replaced by the elements of the alcohol minus HOa. This theory, unlike that of Gerhardt, made the ethers of the hydracids enter into the same class with those of the oxacids ; at the same time it did not include those bodies which are produced with the elimination of HaOa, by the action of oxygen acids upon ammonia and hydrocarbons, and which were recognized in Gerhardt's system, as completely analogous to the ethers in the mode of their formation. Here the compound radical theory is found to be defective, although the analogy which forms its point of departure is correct. In concluding, this comparison we remarked that "we are led to recognize the view of Liebig, apart from, his ideas of dualism, and his theory of compound radicals, as the one fundamentally true.'' (Vol. vii,p. 40S.) In this Journal for March, 1848, (vol. v, p. 263,) we ob- served that the relation of wood- spirit to acetonitryl is the same as that of water to hydrocyanic acid, and that water differs from wood-spirit, precisely as this last differs from spirit of wino, so that the relation of homology, recognised by Gerhardt in the compounds of carbon, is extended (O water and liydrogen; fur from the relations which we ^4 linvc assertuil between HaOa, and Hi, it follows that while water is tlie homologiie of the alcohols, hydrogen Hs is the homologue of acetene CUH«, (EtH.) and of formene CaH«, (MeH) which Frankland calls hydrids of ethyl and methyl, as well as of his zinco-methyl GaHs, Zn. The bodies which he regards as the alcohol radicals are still homologues of hydrogen, the result of a complete substitution, and are (CaHs)a etc., like benzile CisHiaOi, which is Uza, while bitter-almond oil is Bz H. In the Journal for January, 1850 (vol. ix, p. 65), this is again referred to, and we remark that as water is to be regar- ded as the homologue of the alcohols, it follows from the principles already laid down "that the ethers are homolo- gous with their parent acids," a point which was illustrated by the action of the cyanic ethers with ammonia ; while the volatile bases of Wurtz "sustain to their corresponding alco- hols, the same relation that ammonia does to water." In volume xiii, p. 206, we repeat, "water is not only the ana- logue, but the strict homologue of the alcohols, so that the molecule Ha is the equivalent (homologue) of GtHe, ant its homologues, and H of ethyl and methyl; (the hypothetical radicals. )" The question whether these homologues of hydrogen Ha are to be regarded as the radicals of the alcohols and ethers, has been discussed by Gerhardt, Hofmann, and others, but resolves itself into this; Frankland's ethyl is to EtCl what Znaisto ZnGI, and Ha toHGl; the metals, hydro^ a and (;hlorine always present a dualism in their reactions, as iiar- ked as ethyl, kakodyl and cyanogen. Williamson ( Philos. Mag., /Vor., I8I1O) has made a beau- tiful application of Laurent's theory of the alcohols; by the action of potassic alcohol (Et K)Oa upon hydriodic ether, Et I, he obtained KI, and EtaOa, and by a similar process mixed ethers, such as (Et Me)02. He at the same time ex- plained the theory of the ordinary ether process, as the reaction MWMU bulweii sulphoviiiic acid, S9(Et H)08, and (Et H)Os, giving SfHsOa, and EtsOa. Meanwhile Chancel, following out the same idea, announced almost simultaneously with Wil- liamson, the production of hydric ether by the distillation of sulphovinato of potash with potassic alcohol ; by the reaction of oxalovinato with sulphomethylate nf potash, he also obtained a mixed oxalic ether G4(Et Me) Os, oxalic acid being aHsOs. Still more recently Gerhtmlt has announced the production of a class of bodies, which he describes us the anhydrids' of the monobasic organic acids. He had formerly regaitled the production of anhydrids as characteristic of polybusic acids, because he would not admit the theoretical derivation of monobasic acids from a bibasic type HaOa, the complete re- placement of whose hydrogen should, as I have long ago shown, yield neutral anhydrids (like the anhydrous nitric acid since discovered), sustaining to the corresponding acids the relation of hydric ether to alcohol. According to the view which I advanced in 1848, acetic acid, G4H4O4, was repre- sented by (C^HsOa, H)Oa, and the anhydrid would be (C4H50a)a02=G8H606, corresponding to four volumes of vapor. This body has been obtained by Gcrhardt as well as the butyric, valeric, benzoic, and cinnamic anhydrids, besides mixed species analogous to the mixed ethers, such as the aceto-benzoic anhydrid, which contains the elements of one equivalent each of acetic and benzoic acids, minus H2O9. These bodies are of course neutral, and regenerate acids by assimilating the elements of water. The process by which these bodies are obtained, is very instructive : when the perchlorid of phosphorus PGI5, or the oxychlorid POaCls acts upon a salt like the acetate of potash, a body represented by GtHsGl Oa is obtained, which bears the same relation to acetic acid that hydrochloric ether does to alcohol; by the action of this acetic chlorid upon acetate of potash, chlorid of potassium and anhydrous acetic acid are J — 7 — pi'udiK'ed. Alcohul CtlltOii being represented as (Et H)Oi, wo may write the furniula of acetic acid (Ac 11)02, (CUHsOa^Ac), while the chlorid is Ac CI. This corresponds to hydrochloric or hydriodic ether, while acetate of potash (Ac K)Os, is ana- logous to potassic alcohol. The process is then similar to that by which Williamson obtained hydric ether; Ac C' + (Ac K)Oa=K CI + AcaOa, or the anhydrous acid. The reaction in all these cases is, as I have pointed out in the paper before quoted (vol. viii, p. 1)3) identical in essence with that between H Cl and (K ll)0s, yielding an alkaline chlorid K CI, and water HaO*, the prototype of all the above acids, ethers, alcohols, and anhydrids. We have there also remarked that HaOa is to be regarded as a derivative of hydro- gen. Ha, and that it is often difficult to distinguish between the types. Thus, for example, the acetic chlorid might be regarded as a chlorinized aldehyde (C4H3, Cl)03, belonging to the second type, while its reactions permit us to compare it whith the hydrochloric ethers of the type Ha. It must be kept in mind that although the apparent dualism deduced from the results of chemical change, is subject to but very simple variations in the (elements, it is exhibited in so many different ways in the higher species, that we cannot assign an absolute value to any hy|x>thcses based upon their changes. I have been particular in again bringing foward these views , because they now belong to the history of chemical theory, and because after having maintained them alone since 18^8, and having insisted upon them in various ways in my communications to this Journal, I now ffnd them brought foward by Williamson, Brodie and Gerhardt. This latter chemist in a paper presented to the French Academy in June 1852, and published in the Annates de Chimie et de Physitfue for March, 1853, abandons those theories to which I bn^ since objected, and brings forward, with a similarity of thought and expression not to be mistaken , the views upon "if iJJ S . ' ■■ ' .W - 8 - which I liavt! hi>rc iiisisltd. (See us above pp. 330 — 3i3. WilliHiiiMii) in a paper read before the British AssiKiatioii ill July, in 1H51, has expressed the same ideas with rogani to the typical relations of water, and is recognized by the English editor of Ginelin's Handbook (vol. vii, pp. 17 and '201 ) as the author of the theory. See also Urodie's lecture tx^forc the Royul Institution in May, 1853 (Chemical Gazette, Aug., 1st) ''On the formation of hydrogen and its homo- logues." , , It is gratifying to And that the views which I have so long maintained, are at last recognized by chemists, and are found productive oflnmutiful and important results; but it would be only just in these chemists, to have admitted the priority, by three or four years, of my own published views, anticipa- ting the brilliant series of discoveries which have served them as the basis of their generalizations. Montreal, ilcc. 90, 1853. ■-■ • ■ ' ' ■ • ' ^ -, .■» . )■ , r» ■ ■■ ..■■■'■■■ ii.jt ».•;••'.;: ' ' ■ ^ -'ol i ,= ;'.V V ^» •' i 1 6ii>. DARIil. — IMPRIHERIE J. CI.AYE , BUF. UINT-BINOIT . 7. ^■v