Conformality in the KirkwoodBuff solution theory of statistical mechanics
Abstract
The KirkwoodBuff solution theory of statistical mechanics is examined in the light of the conformal solution approximation of the mixture radial distribution functions. By joining the mixture compressibility equation of the KirkwoodBuff solution theory with the mixture energy and virial equations of statistical mechanics, a set of density and temperature dependent mixing rules has been developed which are used here to calculate properties of molecular fluids with varying size and interaction energy differences. It is demonstrated that the conformality approximation in the compressibility equation produces mixture results with a deviation, from the exact mixture data, on the opposite side of the predictions of the van der Waals theory of mixtures. The KirkwoodBuff relation for the composition derivative of the chemical potential is also integrated by combining it with the conformal solution approximation and compared with the simulation data.
 Publication:

Journal of Chemical Physics
 Pub Date:
 February 1987
 DOI:
 10.1063/1.452743
 Bibcode:
 1987JChPh..86.1478H
 Keywords:

 Gas Mixtures;
 Problem Solving;
 Statistical Mechanics;
 Binary Mixtures;
 Compressibility;
 Computerized Simulation;
 LennardJones Gas;
 Spheres;
 Thermodynamics and Statistical Physics