Asymmetric primitive-model electrolytes: Debye-Hückel theory, criticality, and energy bounds

Daniel Zuckerman, Michael E. Fisher, Stefan Bekiranov

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1 Citation (Scopus)

Abstract

Debye-Hückel (DH) theory is extended to treat two-component size- and charge-asymmetric primitive models, focusing primarily on the 1:1 additive hard-sphere electrolyte with, say, negative ion diameters (Formula presented) larger than the positive ion diameters (Formula presented) The treatment highlights the crucial importance of the charge-unbalanced “border zones” around each ion into which other ions of only one species may penetrate. Extensions of the DH approach that describe the border zones in a physically reasonable way are exact at high T and low density ρ and, furthermore, are also in substantial agreement with recent simulation predictions for trends in the critical parameters, (Formula presented) and (Formula presented) with increasing size asymmetry. Conversely, the simplest linear asymmetric DH description, which fails to account for physically expected behavior in the border zones at low T, can violate a new lower bound on the energy (which applies generally to models asymmetric in both charge and size). Other theories, including those based on the mean spherical approximation, predict trends in the critical parameters quite opposite to those established by the simulations.

Original languageEnglish (US)
Number of pages1
JournalPhysical Review E - Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics
Volume64
Issue number1
DOIs
StatePublished - Jan 1 2001
Externally publishedYes

Fingerprint

Electrolyte
Criticality
borders
electrolytes
Charge
Energy
Mean Spherical Approximation
trends
energy
Hard Spheres
Violate
positive ions
Model
negative ions
Asymmetry
ions
Simulation
simulation
asymmetry
Lower bound

ASJC Scopus subject areas

  • Statistical and Nonlinear Physics
  • Mathematical Physics
  • Condensed Matter Physics
  • Physics and Astronomy(all)

Cite this

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abstract = "Debye-H{\"u}ckel (DH) theory is extended to treat two-component size- and charge-asymmetric primitive models, focusing primarily on the 1:1 additive hard-sphere electrolyte with, say, negative ion diameters (Formula presented) larger than the positive ion diameters (Formula presented) The treatment highlights the crucial importance of the charge-unbalanced “border zones” around each ion into which other ions of only one species may penetrate. Extensions of the DH approach that describe the border zones in a physically reasonable way are exact at high T and low density ρ and, furthermore, are also in substantial agreement with recent simulation predictions for trends in the critical parameters, (Formula presented) and (Formula presented) with increasing size asymmetry. Conversely, the simplest linear asymmetric DH description, which fails to account for physically expected behavior in the border zones at low T, can violate a new lower bound on the energy (which applies generally to models asymmetric in both charge and size). Other theories, including those based on the mean spherical approximation, predict trends in the critical parameters quite opposite to those established by the simulations.",
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N2 - Debye-Hückel (DH) theory is extended to treat two-component size- and charge-asymmetric primitive models, focusing primarily on the 1:1 additive hard-sphere electrolyte with, say, negative ion diameters (Formula presented) larger than the positive ion diameters (Formula presented) The treatment highlights the crucial importance of the charge-unbalanced “border zones” around each ion into which other ions of only one species may penetrate. Extensions of the DH approach that describe the border zones in a physically reasonable way are exact at high T and low density ρ and, furthermore, are also in substantial agreement with recent simulation predictions for trends in the critical parameters, (Formula presented) and (Formula presented) with increasing size asymmetry. Conversely, the simplest linear asymmetric DH description, which fails to account for physically expected behavior in the border zones at low T, can violate a new lower bound on the energy (which applies generally to models asymmetric in both charge and size). Other theories, including those based on the mean spherical approximation, predict trends in the critical parameters quite opposite to those established by the simulations.

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