Functional constraints on phenomenological coefficients

Václav Klika, Michal Pavelka, Jay Burton Benziger

Research output: Contribution to journalArticlepeer-review

13 Scopus citations


Thermodynamic fluxes (diffusion fluxes, heat flux, etc.) are often proportional to thermodynamic forces (gradients of chemical potentials, temperature, etc.) via the matrix of phenomenological coefficients. Onsager's relations imply that the matrix is symmetric, which reduces the number of unknown coefficients is reduced. In this article we demonstrate that for a class of nonequilibrium thermodynamic models in addition to Onsager's relations the phenomenological coefficients must share the same functional dependence on the local thermodynamic state variables. Thermodynamic models and experimental data should be validated through consistency with the functional constraint. We present examples of coupled heat and mass transport (thermodiffusion) and coupled charge and mass transport (electro-osmotic drag). Additionally, these newly identified constraints further reduce the number of experiments needed to describe the phenomenological coefficient.

Original languageEnglish (US)
Article number022125
JournalPhysical Review E
Issue number2
StatePublished - Feb 21 2017

All Science Journal Classification (ASJC) codes

  • Statistical and Nonlinear Physics
  • Statistics and Probability
  • Condensed Matter Physics


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