Novel general linear concentration rules and their theoretical aspects for multicomponent systems at constant chemical potentials — Ideal‐Like Solution Model and Dilute‐Like Solution Model

Abstract

AbstractGeneral simple rules have been established both for binary and higher‐order systems related to their pure components and for ternary and higher‐order systems related to their binary subsystems. In this paper we present two new general linear concentration rules, together with their strict thermodynamic aspects and main statistical explanations, for the real systems {A1+A2+…+Aq+B+C+…+Z} related to their subsystems {A1+A2+…+Aq+i} (i∈{B,C,…,Z}) at constant chemical potentials of A1, A2,…,Aq. One of the linear rules holds good for the real system having zero interchange energy among B, C,…,Z, while the other linear rule, for the real system, having nonzero interchange energies among them. In the simplest case of q=1, they are identical with Zdanovskii's rule for mixed electrolyte aqueous solutions, semi‐ideal hydration model for mixed nonelectrolyte aqueous solutions, linear solubility equation for carbon in ternary alloys, and Wang's general linear concentration rules and corresponding solution models for the real systems {A+B+C+…+Z} related to their binary subsystems {A+i} at constant chemical potential of A, respectively, which quantitatively fit the literature experiments for organic and organic‐inorganic mixtures, aqueous and nonaqueous solutions, alloys, molten salt mixtures, slags and nonstoichiometric solid compounds under normal and supercritical conditions. In order to verify their applicabilities at q≥2, isopiestic measurements for fifteen quaternary and quinary aqueous solutions, each containing two unsaturated solutes and one or two saturated solutes, and joint solubility measurements for four quaternary systems, each containing two saturated solutes and two organic solvents, are reported at T=298.15 K. The experimental results are in excellent agreement with the new linear rules.