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Zeitschrift für Naturforschung A

A Journal of Physical Sciences

Editor-in-Chief: Holthaus, Martin

Editorial Board: Fetecau, Corina / Kiefer, Claus

IMPACT FACTOR 2016: 1.432

CiteScore 2017: 1.30

SCImago Journal Rank (SJR) 2017: 0.403
Source Normalized Impact per Paper (SNIP) 2017: 0.632

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Volume 31, Issue 12


Thermodynamic Excess Functions of Binary Liquid Mixtures with Chain Association of One Component*. Part I: The Excess Gibbs Free Energy GE/RT

F. Becker / M. Kiefer / P. Rhensius / H. D. Schäfer
Published Online: 2014-06-02 | DOI: https://doi.org/10.1515/zna-1976-1229


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.

About the article

Received: 1976-11-06

Published Online: 2014-06-02

Published in Print: 1976-12-01

Citation Information: Zeitschrift für Naturforschung A, Volume 31, Issue 12, Pages 1651–1660, ISSN (Online) 1865-7109, ISSN (Print) 0932-0784, DOI: https://doi.org/10.1515/zna-1976-1229.

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© 1946 – 2014: Verlag der Zeitschrift für Naturforschung. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License. BY-NC-ND 3.0

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