Extended Group Contribution Model for Polyfunctional Phase Equilibria

Material and energy balances and equilibrium data form the basis of most design calculations. While material and energy balances may be stated without much difficulty, the design engineer is left with a choice between a wide variety of models for describing phase equilibria in the design of physical separation processes. In a thermodynamic sense, design requires detailed knowledge of activity coefficients in the phases at equilibrium. The prediction of these quantities from a minimum of experimental data is the broad scope of this thesis. Adequate equations exist for predicting vapor-liquid equilibria from data on binary mixtures, composed of structurally simple molecules with a single functional group. More complex is the situation with mixtures composed of structurally more complicated molecules or molecules with more than one functional group. The UNIFAC method is extended to handle polyfunctional group situations, based on additional information on molecular structure. The extension involves the addition of second-order correction terms to the existing equation. In this way the current first-order formulation is retained. The second-order concept is developed for mixture properties based on ideas applied to modelling of pure component properties. Chapter 2 describes the conceptual background of the approach. Three extensions of the present first-order UNIFAC model are formulated in chapter 3. These obey the Gibbs-Duhem restriction, and satisfy other traditional consistency requirements. In chapter 4 parameters are estimated for the first-order UNIFAC model, based on which parameters are estimated for one of the second-order models described in chapter 3. The parameter estimation is based on measured binary data on around 4000 systems, covering 11 C-, H- and O-containing functional groups. While the results are good in most cases, the main limitations of the second-order ap