Quantum Cluster Equilibrium Theory for Multicomponent Liquids

In this work, we present a new theory to treat multicomponent liquids based on quantum-chemically calculated clusters. The starting point is the binary quantum cluster equilibrium theory, which is able to treat binary systems. The theory provides one equation with two unknowns. In order to obtain another linearly independent equation, the conservation of mass is used. However, increasing the number of components leads to more unknowns, and this requires linearly independent equations. We address this challenge by introducing a generalization of the conservation of arbitrary quantities accompanied by a comprehensive mathematical proof. Furthermore, a case study for the application of the new theory to ternary mixtures of chloroform, methanol, and water is presented. Calculated enthalpies of vaporization for the whole composition range are given, and the populations or weights of the different clusters are visualized.