Fluctuation theory of supercritical solutions

Lloyd L. Lee, Pablo Gaston Debenedetti, Henry D. Cochran

Research output: Chapter in Book/Report/Conference proceedingChapter

2 Scopus citations


One of the most significant developments in the theory of solutions occurred in 1951, when Kirkwood and Buff 1 published their paper entitled “The Statistical Mechanical Theory of Solutions”. The Kirkwood-Buff (KB) formalism yields rigorous expressions for key thermodynamic derivatives (such as isothermal compressibility, partial molar volumes, and chemical potential compositional derivatives) in terms of microscopic quantities (correlations between pairwise concentration fluctuations, or, equivalently, integrals of pair correlation functions). Because of its theoretical foundation in the statistics of concentration fluctuations in the grand canonical ensemble, the formalism is also frequently referred to as the fluctuation theory of mixtures.

Original languageEnglish (US)
Title of host publicationSupercritical Fluid Technology (1991)
Subtitle of host publicationReviews in Modern Theory and Applications
PublisherCRC Press
Number of pages34
ISBN (Electronic)9781351357517
ISBN (Print)9781138507005
StatePublished - Jan 1 2017

All Science Journal Classification (ASJC) codes

  • General Chemistry


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