A modified UNIQUAC equation for mixtures containing self-associating compounds

Abstract

-The UNIQUAC model for the excess Gibbs energy is modified using chemical theory to account for chain-like association occurring in self-associating compounds such as alcohols. The equation considers the alcohol to be a mixture of clusters in chemical equilibrium. The UNIQUAC equation is used to model the behavior of the mixture of clusters, with size and surface parameters related to the number of alcohol molecules involved in their formation. The values of association enthalpy and entropy were obtained through fitting vapor pressure data. The model is used to correlate phase behavior of alcohol-hydrocarbon mixtures at low pressures, presenting excellent results in bubble point calculations. A further extension was made to allow for cross-association, the formation of a hydrogen bond between the molecules of an alcohol and an active solute. This extension was used to model alcohol-aromatic mixtures with equally good results.