4. On the Equilibrium of Vapour at a Curved Surface of Liquid

Abstract

In a closed vessel containing only a liquid and its vapour, all at one temperature, the liquid rests, with its free surface raised or depressed in capillary tubes and in the neighbourhood of the solid boundary, in permanent equilibrium according to the same law of relation between curvature and pressure as in vessels open to the air. The permanence of this equilibrium implies physical equilibrium between the liquid and the vapour in contact with it at all parts of its surface. But the pressure of the vapour at different levels differs according to hydrostatic law. Hence the pressure of saturated vapour in contact with a liquid differs according to the curvature of the bounding surface, being less when the liquid is concave, and greater when it is convex.

Studies of nano-structured liquids in confined geometries and at surfaces

“…Thomson employed thermodynamics, generalised dynamics and experimentation to develop a set of equations describing the effects that a range of variables, including geometry, have on basic properties of matter such as vapour pressure and melting point [4,5,6,7,8,9]. In particular there are important behaviours that are closely related to the capillary effect, that reflect the change in bulk free energy caused by the curvature of an interfacial surface under tension [10,11].…”

Nuclear magnetic resonance cryoporometry

“…Thomson, W. Thomson (later Lord Kelvin), and J. J. Thomson were the pioneers of the theory behind phase transitions for confined materials. They employed thermodynamics, generalized dynamics, and experimentation to determine the effects that variables, including geometry, have on basic properties of matter such as vapour pressure and melting point (Gibbs, 1906(Gibbs, reprinted 1961(Gibbs, , 1928Thomson, 1849Thomson, , 1862Thomson, , 1871Thomson, , 1888. In particular, they established that the shift in melting point for a small crystal relative to the bulk melting point varies inversely with crystal size (diameter).…”

“…From this is it possible to obtain, by substitution into eq. (2) under the condition of constant temperature, the Kelvin equation (Thomson, 1871(Thomson, , 1888 RT ln…”

On the Water Retention Behaviour of Shales

“…The chilled-mirror dew point technique is used to measure the relative humidity. The total suction is then obtained by the psychrometric law [7] which relates the relative humidity (RH) and the absolute temperature (T) to the total suction ():…”