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Proceedings of the National Academy of Sciences of the United States of America logoLink to Proceedings of the National Academy of Sciences of the United States of America
. 1980 Apr;77(4):1728–1731. doi: 10.1073/pnas.77.4.1728

Elementary transition state theory of the Soret and Dufour effects

Robert G Mortimer *, Henry Eyring
PMCID: PMC348577  PMID: 16592791

Abstract

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.

Keywords: Onsager reciprocal relationship, ideal mixtures, temperature dependence of thermal diffusion factor

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