Elementary transition state theory of the Soret and Dufour effects.

The elementary transition state approach has been used to obtain a simple model theory for the Soret effect (thermal diffusion) and the Dufour effect. The flow of heat in the Dufour effect is identified as the transport of the enthalpy change of activation as molecules diffuse. The theory as now formulated applies only to thermodynamically ideal mixtures of substances with molecules of nearly equal size. The results of the theory conform to the Onsager reciprocal relationship. When the results were fit to data on thermal diffusion for two liquid systems, a close fit was obtained and yielded reasonable values of between 2 and 3 kcal mol(-1) for enthalpy changes of activation and differences between the entropy changes of activation for the two components of between 0 and 1 cal K(-1) mol(-1).