TY  - JOUR
A1  - Becker, Friedrich
A1  - Kiefer, Michael
A1  - Rhensius, Peter
A1  - Schäfer, Hans-Dieter
T1  - Thermodynamic excess functions of binary liquid mixtures with chain association of one component. Part I: The excess Gibbs free energy GE/RT
T2  - Zeitschrift für Naturforschung, A
N2  - 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.
Y1  - 2014
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/74214
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-742144
SN  - 1865-7109
VL  - 31
IS  - 12
SP  - 1651
EP  - 1660
PB  - Verlag der Zeitschrift für Naturforschung
CY  - Tübingen
ER  -