Critique of primitive model electrolyte theories

Daniel Zuckerman, Michael E. Fisher, Benjamin P. Lee

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Approximate theories for the restricted primitive model electrolyte are compared in the light of Totsuji’s lower bound for the energy (an improvement over Onsager’s), Gillan’s upper bound for the free energy, and thermal stability requirements. Theories based on the Debye-Hückel (DH) approach and the mean spherical approximation (MSA), including extensions due to Bjerrum, Ebeling, Fisher, and Levin, and Stell, Zhou, and Yeh (PMSA1, 2, 3) are tested. In the range [Formula Presented] all DH-based theories satisfy Totsuji’s bound, while the MSA possesses a significant region of violation. Both DH and MSA theories violate Gillan’s bound in the critical region and below unless ion pairing and the consequent free-ion depletion are incorporated. However, the PMSA theories, which recognize pairing but not depletion, fail to meet the bound. The inclusion of excluded-volume terms has only small effects in this respect. Finally, all the pairing theories exhibit negative constant-volume specific heats when [Formula Presented] this is attributable to the treatment of the association constant.

Original languageEnglish (US)
Pages (from-to)6569-6580
Number of pages12
JournalPhysical Review E - Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics
Volume56
Issue number6
DOIs
StatePublished - Jan 1 1997
Externally publishedYes

Fingerprint

Electrolyte
Mean Spherical Approximation
electrolytes
Pairing
depletion
approximation
Depletion
ions
thermal stability
free energy
Critical region
specific heat
Model
inclusions
Thermal Stability
Approximation Theory
Specific Heat
Violate
requirements
Free Energy

ASJC Scopus subject areas

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

Cite this

Critique of primitive model electrolyte theories. / Zuckerman, Daniel; Fisher, Michael E.; Lee, Benjamin P.

In: Physical Review E - Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics, Vol. 56, No. 6, 01.01.1997, p. 6569-6580.

Research output: Contribution to journalArticle

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