Abstract
Regression of binary vapor—liquid equilibrium (VLE) data is used routinely for the estimation of binary interaction parameters in equations of state. In most cases, least squares or maximum likelihood estimation yields satisfactory results. However, it has been observed that the thermodynamic model may predict erroneous phase separation. Instead of modifying the model, it is often preferable to estimate values for the interaction parameters that ensure prediction of the correct phase behavior. In this paper, the constrained least squares estimation method of Englezos et al. ( Fluid Phase Equil. 53, 81–88, 1989) has been improved to overcome the limitations caused by the lack of adequate and well distributed experimental VLE data. The liquid phase stability criterion is evaluated throughout a user-specified portion of the experimental equilibrium T- P- x surface. The method is illustrated with the estimation of the binary interaction parameters of the diethylamine—water system.
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