A thermodynamic derivation of the reciprocal relations

N. Kocherginsky, M. Gruebele

Research output: Contribution to journalArticlepeer-review


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 languageEnglish (US)
Article number124502
JournalJournal of Chemical Physics
Issue number12
StatePublished - Mar 28 2013

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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