Thermodynamics of Liquid Mixtures

To characterize the thermodynamic behavior of the components in a solution, it is necessary to use the concept of partial molar or partial sped c functions. The partial molar quantities most commonly encountered in the thermodynamics of polymer solutions are partial molar volume V, and partial molar Gibbs free energy Gi. The latter quantity is of special signi cance since it is identical to the quantity called chemical potential, Hi, de ned by 

Since any partial molar property of a pure substance is simply the corresponding molar property, the chemical potential of a component i in pure form, denoted by )U°, is evidently equal to the molar Gibbs free energy G° of pure component i at the same temperature and pressure. 

The chemical potentials are the key partial molar quantities. The )U, s determine reaction and phase equilibrium. Moreover, all other partial molar properties and all thermodynamic properties of the solution can be foimd from the ju, s if we know the chemical potentials as functions of T, P, and composition. 

The free energy of mixing in the formation of a solution, AGmix. is given by 

The partial derivative on the right hand side of Eq. (3.3) is the partial molar Gibbs free energy change, denoted by AG, (Yoimg and Lovell, 1990). 

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A rams, D. S., and J. M. Prausnitz, "Statistical Thermodynamics of Liquid Mixtures A New Expression for the Excess Gibbs Energy of Partly or Completely Miscible Systems," AIChE J., 1975, 21, 116. 

Abrams, D.S. and Prausnitz, J.M., Statistical thermodynamics of liquid mixtures a new expression for the excess Gibbs energy of partly or completely miscible systems, A. I. Chem. E. /., 21 (1975) 116-128. 

Flory PJ (1965) Statistical thermodynamics of liquid mixtures. J Am Chem Soc 87 1833-1838 Flory PJ (1970) Thermodynamics of polymer solutions. Faraday Discuss Soc 49 7-29 Flory PJ (1982) Treatment of disordered and ordered systems of polymer chains by lattice methods. Proc Natl Acad Sci USA 79 4510-4514 Flory PJ, Krigbaum WR (1950) Statistical mechanics of dilute polymer solutions II. J Chem Phys 18 1086-1094... 

We shall now employ the expression for the entropy used by Laar in the thermodynamics of liquid mixtures and obtain... 

The thermodynamics of liquid mixtures is customarily based on the concepts of partial molar properties, such as the partial molar volume. For binary mixtures ... 

Davies, R. H. Duncan, A. G. Saville, G. Staveley, L. A. K. Thermodynamics of liquid mixtures of argon and krypton Trans. 

The NRTL was proposed originally by Renon and Prausnitz [1, 34] for the thermodynamics of liquid mixtures. The NRTL equation has relationship to Wilson s equation. It was established... 

The only possible satisfactory procedure for proper use of activity coefficients of supercritical components is to use Henry s constants as the standard-state fugacity. Henry s constants are not hypothetical but are experimentally accessible also, at least in principle, they can be calculated from an equation of state. Remarkably little attention has been given to the formal thermodynamics of liquid mixtures containing supercritical components. 

Wilhelm, E. Egger, W. Vencour, M. Roux, A. H. Polednicek, M. Grolier, J.-P. E. Thermodynamics of liquid mixtures consisting of a very polar and a non-polar aromatic (benzonitrile -t benzene, or toluene) J. Chem. Thermodyn. 1998,30, 1509-1532... 

Gomes de Azevedo, E. J. S. Calado, J. C. G. Thermodynamics of liquid mixtures of krypton + ethane Fluid Phase Equilib. 1991, 70, 215-225... 

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