Modeling derivative properties and binary mixtures with CO2 using the CPA and the quadrupolar CPA equations of state

The cubic plus association (CPA) equation of state (EoS) is extended to include quadrupolar interactions. The quadrupolar term is based on a modification of the perturbation terms by Larsen et al. (1977) [5] for a hard sphere fluid with a symmetric point quadrupole moment. The new quadrupolar CPA (qCPA) can be used without introducing any additional pure compound parameters. Alternatively a single additional adjustable parameter can be employed. To evaluate qCPA several pure compound properties are predicted. The model is furthermore evaluated for its ability to predict and correlate binary vapor-liquid equilibria (VLE) and liquid-liquid equilibria (LLE) of mixtures containing CO2 and hydrocarbons, water, alcohols, or selected quadrupolar compounds. The results indicate that most pure compound property predictions are satisfactory but similar to other CPA approaches. When binary mixtures are considered, qCPA appear to offer a systematic improvement as compared to the cases where quadrupolar interactions are ignored. This improvement is particularly pronounced when mixtures of CO2 and hydrocarbons are considered, where the model is almost fully predictive. Using the same modeling approach qCPA can accurately correlate both the phase behaviour of CO2 + hydrocarbon mixtures as well as mixtures of CO2 + a self-associating compound. (C) 2015 Elsevier B.V. All rights reserved.