On the relationship between principal fluctuations and stability coefficients in multicomponent systems

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Abstract

There is a univocal correspondence between each of the (n+2)! stability coefficients of an n-component system and mean squared fluctuations of Gibbs-space variables (entropy, volume, molecule number) in which the subsystem under study is defined through a single extensive Gibbs-space variable (principal fluctuations). The relationship between principal fluctuations and stability coefficients [Eq. (53)] is derived in this paper starting from the usual expressions involving explicit calculation of the inverse of an(n+1)×(n+1) matrix. A general equation between higher order energy variations in fluctuating subsystems [Eq. (22)] is also derived. The relationship between principal fluctuations and stability coefficients yields, as particular cases, expressions which had been used previously for the limiting case of single-component systems, or extended to solutions through heuristic arguments.

Original languageEnglish (US)
Pages (from-to)1778-1787
Number of pages10
JournalThe Journal of chemical physics
Volume84
Issue number3
DOIs
StatePublished - 1986

All Science Journal Classification (ASJC) codes

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

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