Exact thermodynamic formulation of chemical association

Michael E. Fisher, Daniel Zuckerman

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The thermodynamics of interacting systems of two species of particles, A and B, may be specified in "physical" terms using only the two densities ρa and ρb or, alternatively, in a "chemical picture" using three densities ρa, ρb, and ρc related by a mass-action law corresponding to the "reaction" A+B⇌C, where C denotes a "compound," "complex," "cluster," or "associated pair." We present exact methods for generating associative or "chemical" thermodynamics from an arbitrary physical specification. Both explicit order-by-order matching conditions and a variety of thermodynamically stable, closed-form solutions are derived. The analysis elucidates precisely the freedom available to choose the association constant, the definition of a cluster, and the interactions of a cluster (or "pair") with other clusters and with unpaired (i.e., dissociated, or "free") species. A single-species system of, say, X particles described chemically by 2X⇌Y is analyzed similarly. Various examples, including purely hard-core liquids and the van der Waals fluid, demonstrate applications of the theory, which should aid in improving approximate treatments for electrolytes and other systems. The precautions necessary in selecting a physically acceptable association constant are discussed.

Original languageEnglish (US)
Pages (from-to)7961-7981
Number of pages21
JournalJournal of Chemical Physics
Volume109
Issue number18
DOIs
StatePublished - Dec 1 1998
Externally publishedYes

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Thermodynamics
formulations
thermodynamics
Electrolytes
Specifications
complex compounds
accident prevention
Fluids
Liquids
specifications
electrolytes
fluids
liquids
interactions

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Exact thermodynamic formulation of chemical association. / Fisher, Michael E.; Zuckerman, Daniel.

In: Journal of Chemical Physics, Vol. 109, No. 18, 01.12.1998, p. 7961-7981.

Research output: Contribution to journalArticle

Fisher, Michael E. ; Zuckerman, Daniel. / Exact thermodynamic formulation of chemical association. In: Journal of Chemical Physics. 1998 ; Vol. 109, No. 18. pp. 7961-7981.
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