The Theory of Solution

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AS some recent viva voce remarks of mine have received an interpretation more wide than I intended, I shall be glad to be allowed to explain that when (now several years ago) I became acquainted with the work of van t' Hoff I was soon convinced of the great importance of the advances due to him and his followers. The subject has been prejudiced by a good deal of careless phraseology, and this is probably the reason why some distinguished physicists and chemists have refused their adhesion. It must be admitted, further, that the arguments of van t' Hoff are often insufficiently set out, and are accordingly difficult to follow. Perhaps this remark applies especially to his treatment of the central theorem, viz. the identification of the osmotic pressure, of a dissolved gas with the pressure which would be exercised by the gas alone if it occupied the same total volume in the absence of the solvent. From this follows the formal extension of Avogadro's law to the osmotic pressure of dissolved gases, and thence by a natural hypothesis to the osmotic pressure of other dissolved substances, even although they may not be capable of existing, in the gaseous condition. If I suggest a somewhat modified treatment, it is not that I see any unsoundness in van t' Hoffs argument, but because of the importance of regarding a matter of this kind from various points of view.

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    "On the Work that may be gained during the Mixing of Gases," Phil. Mag. vol. xlix. p. 311, 1875.

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RAYLEIGH The Theory of Solution. Nature 55, 253–254 (1897) doi:10.1038/055253a0

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