The Role of Computer Simulation in Studying Fluid Phase Equilibria

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Abstract
Computer simulations provide a method for studying mixtures in which the intermolecular forces are precisely defined. They can be used to study specific systems, where laboratory experiments may be too costly, time consuming, or difficult, or to develop better theoretical equations of state. In this paper we first review some of the most promising methods for studying phase equilibria in fluid mixtures. These can be divided into direct methods, which simulate the two-phase system itself, and indirect methods in which the chemical potential of a homogeneous phase is determined. Examples of the use of each of these approaches given, including the determination of vapour-liquid equilibria for binary mixtures and of the properties of dilute solutions. This is followed by an application in which the objective is to develop a better equation of state for polar and associated fluids. Here, computer simulation is used to develop a more suitable reference term in the equation of state for such fluids.