The statistical mechanical theory of thermal diffusion in binary solutions is developed from the point of view of the pair space linear relations which have been used previously to derive theories of the heat of transport and thermal conductivity. The thermal diffusion factor is obtained in terms of statistical mechanical averages over the equilibrium radial distribution functions, and when assumptions of the theory of regular solutions are introduced into the general expression, we find that it is related to the molar volumes, thermal expansion coefficients and compressibility coefficients of the pure components and to the self‐diffusion coefficients in the mixture.

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7.
The use of the symbol α to designate the thermal diffusion factor should not be confused with its use as a running index.
8.
In a two‐component system there are three independent gradients, which may be temperature and the two concentrations or alternatively temperature, pressure, and a mole fraction.e(b) In the present instance it is more convenient to choose the first set initially, and therefore the operator Vr1T differs from Tr defined in the phenomenological theory.
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