Chemical association via exact thermodynamic formulations

Michael E. Fisher, Daniel M. Zuckerman

Research output: Contribution to journalArticlepeer-review

5 Scopus citations


It can be fruitful to view two-component physical systems of attractive monomers, A and B, "chemically" in terms of a reaction A+B⇌C, where C = AB is an associated pair or complex. We show how to construct free energies in the three-component or chemical picture which, under mass-action equilibration, exactly reproduce any given two-component or "physical" thermodynamics. Order-by-order matching conditions and closed-form chemical representations reveal the freedom available to modify the A-C, B-C, and C-C interactions and to adjust the association constant. The theory (in the simpler one-component, i.e., A ≡ B, case) is illustrated by treating a van der Waals fluid.

Original languageEnglish (US)
Pages (from-to)461-468
Number of pages8
JournalChemical Physics Letters
Issue number5-6
StatePublished - Sep 4 1998
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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