Relation of Wertheim association constants to concentration-based equilibrium constants for mixtures with chain-forming components

Aseel M. Bala, Carl T. Lira

    Research output: Contribution to journalArticle

    Abstract

    Several association modeling approaches have been developed to accurately describe the properties of polar solutions. Chemical theory and Wertheim's perturbation theory are among the most popular of these and they have been shown to yield similar functional forms for the contributions of association to Helmholtz energy and activity coefficients. In this paper, we study Flory polymerization theory through the work of Campbell and elucidate its correlation to Wertheim's theory. A simple key relationship between the concentration-based equilibrium constant and Wertheim's association constant is developed for systems in which all associating components have one acceptor and one donor site. Algebraic and numerical proofs are given for the equivalence of Flory's polymerization theory and Wertheim's perturbation theory for pure fluids and mixtures. Additionally, a new generalized activity expression is developed for Wertheim's theory.

    Original languageEnglish (US)
    Pages (from-to)47-56
    Number of pages10
    JournalFluid Phase Equilibria
    Volume430
    DOIs
    StatePublished - Dec 25 2016

    Profile

    Hexosaminidase A
    Association reactions
    Common Hepatic Duct
    Agglutination Tests
    Polymerization
    Equilibrium constants
    polymerization
    perturbation theory
    Agglutination
    Amoxicillin
    Activity coefficients
    Fluids
    equivalence
    fluids
    coefficients
    energy

    Keywords

    • Association
    • Chemical theory
    • Perturbation theory
    • Wertheim theory

    ASJC Scopus subject areas

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

    Cite this

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    abstract = "Several association modeling approaches have been developed to accurately describe the properties of polar solutions. Chemical theory and Wertheim's perturbation theory are among the most popular of these and they have been shown to yield similar functional forms for the contributions of association to Helmholtz energy and activity coefficients. In this paper, we study Flory polymerization theory through the work of Campbell and elucidate its correlation to Wertheim's theory. A simple key relationship between the concentration-based equilibrium constant and Wertheim's association constant is developed for systems in which all associating components have one acceptor and one donor site. Algebraic and numerical proofs are given for the equivalence of Flory's polymerization theory and Wertheim's perturbation theory for pure fluids and mixtures. Additionally, a new generalized activity expression is developed for Wertheim's theory.",
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