Skip to main content
eScholarship
Open Access Publications from the University of California

Transport phenomena in electrolyte solutions: Nonequilibrium thermodynamics and statistical mechanics

  • Author(s): Fong, KD
  • Bergstrom, HK
  • McCloskey, BD
  • Mandadapu, KK
  • et al.

Published Web Location

https://doi.org/10.1002/aic.17091
Abstract

© 2020 American Institute of Chemical Engineers The theory of transport phenomena in multicomponent electrolyte solutions is presented here through the integration of continuum mechanics, electromagnetism, and nonequilibrium thermodynamics. The governing equations of irreversible thermodynamics, including balance laws, Maxwell's equations, internal entropy production, and linear laws relating the thermodynamic forces and fluxes, are derived. Green–Kubo relations for the transport coefficients connecting electrochemical potential gradients and diffusive fluxes are obtained in terms of the flux–flux time correlations. The relationship between the derived transport coefficients and those of the Stefan–Maxwell and infinitely dilute frameworks are presented, and the connection between the transport matrix and experimentally measurable quantities is described. To exemplify the application of the derived Green–Kubo relations in molecular simulations, the matrix of transport coefficients for lithium and chloride ions in dimethyl sulfoxide is computed using classical molecular dynamics and compared with experimental measurements.

Many UC-authored scholarly publications are freely available on this site because of the UC's open access policies. Let us know how this access is important for you.

Main Content
Current View