A treatise on the theory of solution including the phenomena of electrolysis . iedbefore the liquid will rise in the tubes, and, by making thetubes of the right diameter, we can arrange that the curvatureof the surface of the solution in them is just enough to increasethe vapour pressure to an equality with that of the flat surfaceof the pure solvent. There will then be equilibrium betweenthe flat surface of the solvent and the solution held in thecapillaries, and FitzGerald has pointed out that such anarrangement furnishes a perfect semi-permeable membrane fora non-volatile solute in a volati
A treatise on the theory of solution including the phenomena of electrolysis . iedbefore the liquid will rise in the tubes, and, by making thetubes of the right diameter, we can arrange that the curvatureof the surface of the solution in them is just enough to increasethe vapour pressure to an equality with that of the flat surfaceof the pure solvent. There will then be equilibrium betweenthe flat surface of the solvent and the solution held in thecapillaries, and FitzGerald has pointed out that such anarrangement furnishes a perfect semi-permeable membrane fora non-volatile solute in a volatile solvent\ Van t Hoff showed that the application of thermodynamicsenables us to deduce from the observed exist- Theoretical Laws of osmotic pres- euce of osmotic pressure its absolute valueand the laws which describe its variation withvolume and temperature-. We shall here treat this problemby an application of the principle of available energy. 1 Helmholtz Lecture, Trans. Chern. Soc. Lon. Jau. 1896.* Phil. Mag. vol. xxvi. p. 88, 1888. 104 SOLUTION AND ELECTROLYSIS [CH. V. A B C Fig. 38. Let a volume of the solution of a volatile gas in a nonvolatile solvent be confined between two semi-permeable pistons in an engine cylinder. Ofthese pistons, the upper BB is permeable tothe gas but not to the solvent, the lower GCis permeable to the solvent but not to thedissolved gas. Two non-permeable pistonsA A and DD are placed beyond the regionoccupied by the solution and confine a volumeof gas above and a volume of pure solventbelow. Let us at first confine ourselves to theconsideration of solutions so dilute thatthe volume and thermal changes on furtherdilution are negligible. The piston BB,which defines the top of the solution, can then be fixed, as thetotal volume of the solution and solvent together is constant. First, let the pistons AA, DD also be fixed, so that thewhole system is at constant volume, and let the moveablepartition CC have taken up such a position that there isequi
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