Theory of the Heat of Transport of Electrolytic Solutions

Abstract

The limiting concentration dependence of the heat of transport of an ionic component of a dilute solution of electrolyte is determined. The theory is based on recasting the Bearman‐Kirkwood statistical mechanical expression for the heat current into a form linear in the particle diffusion currents and identifying the coefficients with the heat of transport. Ion‐ion interactions are treated exactly to order c^½ by using a nonequilibrium correlation function determined from the Debye‐Hückel radial distribution function by Brownian particle theory. A hydrodynamical model is employed for the analysis of the effect of ion‐solvent interactions. Indications are that the latter contributions are often, but not always, negligible. There is accord between the theory and experimental data.