Variational Approach to the Equilibrium Thermodynamic Properties of Simple Fluid Mixtures. III

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Abstract
The variational technique proposed earlier for the calculation of the equilibrium thermodynamic properties of simple pure fluids, melting transitions, and simple pure solids is extended to binary mixtures of simple fluids. The working inequality is introduced and the variational parameters are characterized. For a case study, the present variational approach is applied in predicting the thermodynamic properties of the liquid mixture of argon and krypton at zero pressure and 115.77°K. The thermodynamic and excess properties of this mixture over that of the pure systems (at zero pressure and in liquid state) are calculated and compared with the results of the available Monte Carlo calculations, experimental measurements, and several theories of solutions. Preliminary investigation indicates good agreement between the result of the present variational technique with the experimental and machine‐calculated data. Variations of the thermodynamic properties of the binary mixture, with the variation of the ratios of the force constants of the potential functions of the two components, are calculated at 97°K, zero pressure, and equal mole fractions. These values are compared with the existing values of the Monte Carlo calculations.