Note 12 — Chapter II · OSMOTIC PRESSURE AND THE THEORY OF SOLUTION I

When appreciable heat of dilution is shown by a solution, some chemical change, resulting from dilution, is indicated (such as, dissociation of the solute, hydration, hydrolysis, etc.). In such a case, the Avogadro-van 't Hoff principle holds for each concentration for its actual composition, and the principle may often be used to determine the extent of the chemical change produced by dilution. But then the osmotic pressure will not obey Boyle's and Gay-Lussac's laws. The same exception applies also to gases which undergo chemical changes, as the result of dilution or change of temperature. In the case, for instance, of nitrogen tetroxide, which dissociates according to N2O4 ⇄ 2 NO2, the extent of the dissociation varies with changes of concentration (pressure) and of temperature, and the gas does not obey the laws of Gay-Lussac and of Boyle. In regard to the rôle of heat of dilution in connection with osmotic pressure, see Bancroft, J. Phys. Chem., 10, 319 (1906).