Thermo-statistical description of gas mixtures from space partitions

TL;DR

This paper extends a free energy-based mathematical framework to multi-component gas mixtures, providing analytical thermodynamic and structural properties in the low-density limit through space partitioning and statistical geometry.

Contribution

It introduces a novel formalism combining free-energy minimization with space partitions for complex fluids, deriving new thermodynamic variables and identities.

Findings

Analytical thermodynamic functions for hard sphere mixtures.

Agreement with scaled-particle theory and Percus-Yevick approximation at low density.

Derived chemical equilibrium conditions for multi-component systems.

Abstract

The new mathematical framework based on the free energy of pure classical fluids presented in [R. D. Rohrmann, Physica A 347, 221 (2005)] is extended to multi-component systems to determine thermodynamic and structural properties of chemically complex fluids. Presently, the theory focuses on $D$-dimensional mixtures in the low-density limit (packing factor $\eta < 0.01$). The formalism combines the free-energy minimization technique with space partitions that assign an available volume $v$ to each particle. $v$ is related to the closeness of the nearest neighbor and provides an useful tool to evaluate the perturbations experimented by particles in a fluid. The theory shows a close relationship between statistical geometry and statistical mechanics. New, unconventional thermodynamic variables and mathematical identities are derived as a result of the space division. Thermodynamic potentials $\mu_{il}$, conjugate variable of the populations $N_{il}$ of particles class $i$ with the nearest neighbors of class $l$ are defined and their relationships with the usual chemical potentials $\mu_i$ are established. Systems of hard spheres are treated as illustrative examples and their thermodynamics functions are derived analytically. The low-density expressions obtained agree nicely with those of scaled-particle theory and Percus-Yevick approximation. Several pair distribution functions are introduced and evaluated. Analytical expressions are also presented for hard spheres with attractive forces due to K\^ac-tails and square-well potentials. Finally, we derive general chemical equilibrium conditions.