Liquid-Liquid Equilibria: (Studies in Modern Thermodynamics)

While a satisfactory description of liquid-vapour equilibria in binary and multi-component systems had been developed by the end of the fifties, a similar situation has only been attained for liquid-liquid equilibria in the last ten years. There are several reasons for this, the most important of which is the necessity to employ more complex thermodynamic models for a quantitative description of liquid-liquid equilibria. These models require very sophisticated calculation techniques that cannot be carried out without the assistance of a computer. The authors have attempted to provide a theoretical description of liquid-liquid equilibria at a level permitting routine chemical engineering applications similar to those common for liquid-vapour equilibria. Consequently, a great deal of attention is paid to the calculation of parameters for heterogeneous and homogeneous binary systems, and to the qualitative evaluation of the suitability of the most frequently used thermodynamic models.

Table of Contents:
I. The Basis of the Thermodynamic Description of Non-Electrolyte Solutions. Introduction. Basic thermodynamic relationships. Equilibrium conditions at constant temperature and pressure. Conditions for thermodynamic stability and the critical point. The nonclassical behaviour of systems in the critical region. Empirical and semi-empirical equations for the concentration dependence of the Gibbs energy. The dependence of the excess Gibbs energy on temperature. II. Liquid-Liquid Equilibria in Binary Systems. The shape of the equilibrium curve (liquid-liquid equilibrium) for binary systems. Description of the behaviour of binary systems using the relationship for a strictly regular solution. Calculation of the compositions of coexisting phases in a binary system. Calculation of the parameters of the empirical relationships for the excess Gibbs energy for heterogeneous systems. Parameter calculation in empirical relationships for the Gibbs energy for homogeneous binary systems. III. Liquid-Liquid Equilibria in Ternary and Multi-Component Systems. The shape of the equilibrium curve (envelope) in ternary and quaternary systems. The concentration dependence of the excess Gibbs energy for multi-component systems. Modelling of liquid-liquid equilibria in ternary systems. Calculation of the compositions of coexisting phases in multi-component systems. Calculation of the critical point. Calculation of the parameters in the empirical relationships for the excess Gibbs energy from data on liquid-liquid equilibria in ternary systems. Prediction of liquid-liquid equilibria and empirical relationships used to describe liquid-liquid equilibria in ternary systems. Experimental determination of liquid-liquid equilibria. Appendices. References. Index.