Abstract
Starting with the continuity and Smoluchowski equations, we write the mass flux for a system out of equilibrium in terms of the physicochemical potential μg. μg is a coarse-grained analog of the chemical potential in the presence of forces that drive the system out of equilibrium. The expression for flux in terms of μg allows for a macroscopic derivation of the Onsager reciprocal relations for the case of transport by diffusion and drift in single or multi-component systems, without recourse to microscopic fluctuations or equations of motion. Transport coefficients for any time reversal-invariant properties now are expressed in terms of only partial molar derivatives and mobilities (diffusion coefficients). The thermodynamic derivation cannot treat time reversal.
Original language | English (US) |
---|---|
Article number | 124502 |
Journal | Journal of Chemical Physics |
Volume | 138 |
Issue number | 12 |
DOIs | |
State | Published - Mar 28 2013 |
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry