Fluid phase equilibrium activity coefficient models

Thermodynamic models are widely used for the calculation of equilibrium and thermophysical properties of fluid mixtures. Two types of such models will be examined cubic equations of state and activity coefficient models. In this chapter cubic equations of state models are used. Volumetric equations of state (EoS) are employed for the calculation of fluid phase equilibrium and thermophysical properties required in the design of processes involving non-ideal fluid mixtures in the oil and gas and chemical industries. It is well known that the introduction of empirical parameters in equation of state mixing rules enhances the ability of a given EoS as a tool for process design although the number of interaction parameters should be as small as possible. In general, the phase equilibrium calculations with an EoS are very sensitive to the values of the binary interaction parameters. 

The calculations reported in this paper and a related series of publications indicate that it is now quite feasible to obtain reasonably accurate results for phase equilibria in simple fluid mixtures directly from molecular simulation. What is the possible value of such results Clearly, because of the lack of accurate intermolecular potentials optimized for phase equilibrium calculations for most systems of practical interest, the immediate application of molecular simulation techniques as a replacement of the established modelling methods is not possible (or even desirable). For obtaining accurate results, the intermolecular potential parameters must be fitted to experimental results, in much the same way as parameters for equation-of-state or activity coefficient models. This conclusion is supported by other molecular-simulation based predictions of phase equilibria in similar systems (6). However, there is an important difference between the potential parameters in molecular simulation methods and fitted parameters of thermodynamic models. Molecular simulation calculations, such as the ones reported here, involve no approximations beyond those inherent in the potential models. The calculated behavior of a system with assumed intermolecular potentials is exact for any conditions of pressure, temperature or composition. Thus, if a good potential model for a component can be developed, it can be reliably used for predictions in the absence of experimental information. 

The discussion of the previous section was concerned with low-pressure vapor-liquid equilibria and involved the use of activity coefficient models. Here we are interested in high-pressure phase equilibrium in fluids in which both phases are describable by equations of state, that is, the cj -4> method. One example of the type of data we are interested in describing (or predicting) is shown in Fig. 10.3-1 for the ethane-propylene system. There we see the liquid (bubble point) and vapor (dew point) curves for this system at three different isotherms. At each temperature the coexisting vapor and liquid. phases have the same pressure and thus are joined by horizontal tie lines, only one of... 

The fugacities in the vapor and liquid phases may be obtained from an EOS. Alternatively, an activity-coefficient model can be used to describe the liquid phase to estimate > f. However, as discussed in Chapter 1, activity coefficient models, in general, may not be suitable for reservoir fluids because they are based on the assumption of no change in volume due to mixing. At equilibrium, when liquid and solid phases are present. 

The difficulties encountered in the Chao-Seader correlation can, at least in part, be overcome by the somewhat different formulation recently developed by Chueh (C2, C3). In Chueh s equations, the partial molar volumes in the liquid phase are functions of composition and temperature, as indicated in Section IV further, the unsymmetric convention is used for the normalization of activity coefficients, thereby avoiding all arbitrary extrapolations to find the properties of hypothetical states finally, a flexible two-parameter model is used for describing the effect of composition and temperature on liquid-phase activity coefficients. The flexibility of the model necessarily requires some binary data over a range of composition and temperature to obtain the desired accuracy, especially in the critical region, more binary data are required for Chueh s method than for that of Chao and Seader (Cl). Fortunately, reliable data for high-pressure equilibria are now available for a variety of binary mixtures of nonpolar fluids, mostly hydrocarbons. Chueh s method, therefore, is primarily applicable to equilibrium problems encountered in the petroleum, natural-gas, and related industries. 

BEN 10] Ben Gaida L., Dussap C.G., Gros J.B., Activity coefficients of concentrated strong and weak electrolytes by a hydration equilibrium and group contribution model . Fluid Phase Equilibria, vol. 289, no. 1, pp. 40-48, 2010. 

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