Thermodynamic excess functions of binary liquid mixtures with chain association of one component. Part I: The excess Gibbs free energy GE/RT

  • In this paper equilibrium models for the calculation of the excess Gibbs free energy of binary liquid mixtures are developed, the component A of which undergoes chain-forming self-association whilst the component B acts as an 'inert' solvent. It is shown that the extension of the well-known chain-association model of Mecke and Kempter, in which the probability of chain prolongation is assumed to be independent of chain length, is unable to establish satisfactory results because it does not exhibit sufficient unsymmetry. Reduction of the probability of chain growth with in-creasing chain length leads to an improved model with the geometric series replaced by the exponential series. This model, in which only two parameters are used, i. e. the equilibrium constants K for mutual solvation of A and B, and ρ for self-association of A, allows fitting of isothermal experimental GE /R T literature data on cycloalkanol-cycloalkane, alkanol-alkane, and NMF -CCl4 systems within the limits of experimental error. Compared with the two-parameter Wilson equation which gives equally small standard deviations, our equilibrium model has the advantage of allowing passage from GE to HE data and of being applicable to liquid-liquid equilibria.

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Metadaten
Author:Friedrich BeckerGND, Michael Kiefer, Peter RhensiusGND, Hans-Dieter Schäfer
URN:urn:nbn:de:hebis:30:3-742144
DOI:https://doi.org/10.1515/zna-1976-1229
ISSN:1865-7109
Parent Title (German):Zeitschrift für Naturforschung, A
Publisher:Verlag der Zeitschrift für Naturforschung
Place of publication:Tübingen
Document Type:Article
Language:English
Date of Publication (online):2014/06/02
Year of first Publication:1976
Publishing Institution:Universitätsbibliothek Johann Christian Senckenberg
Release Date:2023/06/26
Volume:31
Issue:12
Page Number:10
First Page:1651
Last Page:1660
HeBIS-PPN:510578683
Institutes:Biochemie, Chemie und Pharmazie / Biochemie und Chemie
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Sammlungen:Universitätspublikationen
Licence (German):License LogoCreative Commons - Namensnennung-Nicht kommerziell-Keine Bearbeitung 3.0