Stereoisomeric effects on dynamic viscosity versus pressure and temperature for the system cis-Â +Â trans-decalin

In order to study the influence of stereoisomeric effects on the dynamic viscosity, an extensive experimental study of the viscosity of the binary system composed of the two stereoisomeric molecular forms of decalin - cis and trans - has been carried out for five different mixtures at three temperatures (303.15, 323.15 and 343.15) K and six isobars up to 100 MPa with a falling-body viscometer (a total of 90 points). The experimental relative uncertainty is estimated to be 2%. The variations of dynamic viscosity versus composition are discussed with respect to their behavior due to stereoisomerism. Four different models with a physical and theoretical background are studied in order to investigate how they take the stereoisomeric effect into account through their required model parameters. The evaluated models are based on the hard-sphere scheme, the concepts of the free-volume and the friction theory, and a model derived from molecular dynamics. Overall, a satisfactory representation of the viscosity of this binary system is found for the different models within the considered (T, p) range taken into account their simplicity. All the models are able to distinguish between the two stereoisomeric decalin compounds. Further, based on the analysis of the model parameters performed on the pure compounds, it has been found that the use of simple mixing rules without introducing any binary interaction parameters are sufficient in order to predict the viscosity of cis + trans-decalin mixtures with the same accuracy in comparison with the experimental values as obtained for the pure compounds. In addition to these models, a semi-empirical self-referencing model and the simple mixing laws of Grunberg-Nissan and Katti-Chaudhri are also applied in the representation of the viscosity behavior of these systems.