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Structural electroneutrality in Onsager-Stefan-Maxwell transport with charged species
Fluid Dynamics · Submitted 24 Nov 2022
abstract compiled · 2026-09-23 · no language-model review
The authors' main claim We present a method to embed local electroneutrality within Onsager-Stefan-Maxwell electrolytic-transport models, circumventing their formulation as differential systems with an algebraic constraint.
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The abstract, sentence by sentence
We present a method to embed local electroneutrality within Onsager-Stefan-Maxwell electrolytic-transport models, circumventing their formulation as differential systems with an algebraic constraint. Flux-explicit transport laws are formulated for general multicomponent electrolytes, in which the conductivity, component diffusivities, and transference numbers relate to Stefan-Maxwell coefficients through invertible matrix calculations. A construction we call a `salt-charge basis' implements Guggenheim's transformation of species electrochemical potentials into combinations describing a minimal set of neutral components, leaving a unique combination associated with electricity. Defining conjugate component concentrations and fluxes that preserve the structures of the Gibbs function and energy dissipation retains symmetric Onsager reciprocal relations. The framework reproduces Newman's constitutive laws for binary electrolytes and the Pollard-Newman laws for molten salts; we also propose laws for salt solutions in two-solvent blends, such as lithium-ion-battery electrolytes. Finally, we simulate a potentiostatic Hull cell containing a non-ideal binary electrolyte with concentration-dependent properties.
background contribution method result interpretation main claim
| # | sentence | role | the authors' own work | states the main conclusion | strength |
|---|---|---|---|---|---|
| s0 | We present a method to embed local electroneutrality within Onsager-Stefan-Maxwell electrolytic-transport models, circumventing their formulation as differential systems with an algebraic constraint. | contribution 0.98 | 0.95 | 0.44 | asserted 1.00 |
| s1 | Flux-explicit transport laws are formulated for general multicomponent electrolytes, in which the conductivity, component diffusivities, and transference numbers relate to Stefan-Maxwell coefficients through invertible matrix calculations. | contribution 0.52 | 0.91 | 0.13 | asserted 1.00 |
| s2 | A construction we call a `salt-charge basis' implements Guggenheim's transformation of species electrochemical potentials into combinations describing a minimal set of neutral components, leaving a unique combination associated with electricity. | method 0.83 | 0.81 | 0.14 | asserted 1.00 |
| s3 | Defining conjugate component concentrations and fluxes that preserve the structures of the Gibbs function and energy dissipation retains symmetric Onsager reciprocal relations. | method 0.35 | 0.85 | 0.11 | asserted 1.00 |
| s4 | The framework reproduces Newman's constitutive laws for binary electrolytes and the Pollard-Newman laws for molten salts; we also propose laws for salt solutions in two-solvent blends, such as lithium-ion-battery electrolytes. | result 0.72 | 0.85 | 0.20 | asserted 1.00 |
| s5 | Finally, we simulate a potentiostatic Hull cell containing a non-ideal binary electrolyte with concentration-dependent properties. | contribution 0.42 | 0.95 | 0.06 | asserted 1.00 |
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Original abstract
We present a method to embed local electroneutrality within Onsager-Stefan-Maxwell electrolytic-transport models, circumventing their formulation as differential systems with an algebraic constraint. Flux-explicit transport laws are formulated for general multicomponent electrolytes, in which the conductivity, component diffusivities, and transference numbers relate to Stefan-Maxwell coefficients through invertible matrix calculations. A construction we call a `salt-charge basis' implements Guggenheim's transformation of species electrochemical potentials into combinations describing a minimal set of neutral components, leaving a unique combination associated with electricity. Defining conjugate component concentrations and fluxes that preserve the structures of the Gibbs function and energy dissipation retains symmetric Onsager reciprocal relations. The framework reproduces Newman's constitutive laws for binary electrolytes and the Pollard-Newman laws for molten salts; we also propose laws for salt solutions in two-solvent blends, such as lithium-ion-battery electrolytes. Finally, we simulate a potentiostatic Hull cell containing a non-ideal binary electrolyte with concentration-dependent properties.
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