Transport phenomena in electrolyte solutions: Nonequilibrium thermodynamics and statistical mechanics

Fong, Kara D.; Bergstrom, Helen K.; McCloskey, Bryan D.; Mandadapu, Kranthi K.

doi:10.1002/aic.17091

Transport phenomena in electrolyte solutions: Nonequilibrium thermodynamics and statistical mechanics

Journal Article · Thu Nov 12 00:00:00 EST 2020 · AIChE Journal

DOI:https://doi.org/10.1002/aic.17091· OSTI ID:1762210

^[1]; ^[1]; McCloskey, Bryan D. ^[1]; Mandadapu, Kranthi K. ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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. Furthermore, 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1762210

Alternate ID(s):: OSTI ID: 1786096

Journal Information:: AIChE Journal, Journal Name: AIChE Journal Journal Issue: 12 Vol. 66; ISSN 0001-1541

Publisher:: American Institute of Chemical EngineersCopyright Statement

Country of Publication:: United States

Language:: English

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