Note on osmotic pressure

Abstract

The vapour pressure theory regards osmotic pressure as the pressure required to produce equilibrium between the pure solvent and the solution. Pressure applied to a solution increases its internal vapour pressure. If the compressed solution be on one aide of a semi-permeable partition and the pure solvent on the other, there is osmotic equilibrium when the com-pression of the solution brings its vapour pressure to equality with that of the solvent. So long ago as 1894 Ramsay* found that with a partition of palladium, permeable to hydrogen but not to nitrogen, the hydrogen pressures on each side tended to equality, notwithstanding the presence of nitrogen under pressure on one side, which it might have been supposed would have resisted tin- transpiration of the hydrogen. The bearing of this experiment on the problem of osmotic pressure was recognised by van’t Hoff, who observes that "it is very instructive as regards the means by which osmotic pressure is produced." But it was not till 1908 that the vapour pressure theory of osmotic pressure was developed on a finu foundation by Calendar. He demonstrated, by the method of the "vapour sieve" piston, the proposition that “any two solutions in equilibrium through any kind of membrane or capillary surface must have the same vapour pressures in respect of each of their constituents which is capable of diffusing through their surface of separation"—a generalisation of great importance for the theory of solutions. Findlay, in his admirable monograph, gives a very complete account of the contending theories of osmotic pressure, a review of which leaves no doubt that at the present moment the vapour pressure theory stands without a serious rival Some confusion of ideas still arises from the want of adherence to a strict definition of osmotic pressure to which numerical data from experimental measurements should he reduced. Tire following definitions appear to be tire outcome of tire vapour pressure theory :— Definition I.—The vapour pressure of a solution is the pressure of the vapour with which it is in equilibrium when under pressure of its own vapour only.