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The Principles of Chemistry, Volume I

Note 45 — Chapter I · ON WATER AND ITS COMPOUNDS

George Kamensky translation

All the different forms of chemical reaction may be said to take place in the process of solution. (1) Combinations between the solvent and the substance dissolved, which are more or less stable (more or less dissociated). This form of reaction is the most probable, and is that most often observed. (2) Reactions of substitution or of double decomposition between the molecules. Thus it may be supposed that in the solution of sal ammoniac, NH4Cl, the action of water produces ammonia, NH4HO, and hydrochloric acid, HCl, which are dissolved in the water and simultaneously attract each other. As these solutions and many others do indeed exhibit signs, which are sometimes indisputable, of similar double decompositions (thus solutions of sal-ammoniac yield a certain amount of ammonia), it is probable that this form of reaction is more often met with than is generally thought. (3) Reactions of isomerism or replacement are also probably met with in solution, all the more as here molecules of different kinds come into intimate contact, and it is very likely that the configuration of the atoms in the molecules under these influences is somewhat different from what it was in its original and isolated state. One is led to this supposition especially from observations made on solutions of substances which rotate the plane of polarisation (and observations of this kind are very sensitive with respect to the atomic structure of molecules), because they show, for example (according to Schneider, 1881), that strong solutions of malic acid rotate the plane of polarisation to the right, whilst its ammonium salts in all degrees of concentration rotate the plane of polarisation to the left. (4) Reactions of decomposition under the influences of solution are not only rational in themselves, but have in recent years been recognised by Arrhenius, Ostwald, and others, particularly on the basis of electrolytic determinations. If a portion of the molecules of a solution occur in a condition of decomposition, the other portion may occur in a yet more complex state of combination, just as the velocity of the motion of different gaseous molecules may be far from being the same (see Note 34, p. 81).

It is, therefore, very probable that the reactions taking place in solution vary both quantitatively and qualitatively with the mass of water in the solution, and the great difficulty in arriving at a definite conclusion as to the nature of the chemical relations which take place in the process of solution will be understood, and if besides this the existence of a physical process, like the sliding between and interpenetration of two homogeneous liquids, be also recognised in solution, then the complexity of the problem as to the actual nature of solutions, which is now to the fore, appears in its true light. However, the efforts which are now being applied to the solution of this problem are so numerous and of such varied aspect that they will afford future investigators a vast mass of material towards the construction of a complete theory of solution.

For my part, I am of opinion that the study of the physical properties of solutions (and especially of weak ones) which now obtains, cannot give any fundamental and complete solution of the problem whatever (although it should add much to both the provinces of physics and chemistry), but that, parallel with it, should be undertaken the study of the influence of temperature, and especially of low temperatures, the application to solutions of the mechanical theory of heat, and the comparative study of the chemical properties of solutions. The beginning of all this is already established, but it is impossible to consider in so short an exposition of chemistry the further efforts of this kind which have been made up to the present date.

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