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The K-values are calculated from the composition data, Ki = Yi/Xi. The fugacities and fugacity coefficients, fi L , φ Vi , are calculated from the compositions, temperature, and pressure, using, for instance, an equation of state and liquid density data as described earlier. 30 is then used to correlate, or fit, the experimentally determined activity coefficients. Normally, the binary VLE data are correlated, generating binary interaction coefficients. These coefficients may then be used to reproduce the binary VLE data and also to predict multi-component VLE behavior as described in the discussion of some of the activity coefficient equations later in this section.
These parameters must be determined from binary phase equilibrium data. The modified van Laar equation reduces to the van Laar equation if Cij = 0. Refer to the source (Black, 1959) for detailed mathematical formulation of the equation. Other activity coefficient equations have been proposed since the earlier equations of Margules and van Laar. It is outside the scope of this book to present the detailed development of these equations, which may be found in the indicated references. The objective here is to present the basis for each of the more commonly used equations, their features, and applicability.
5 term in the Redlich– Kwong equation with a more general temperature-dependent parameter, a(T): P= RT a(T ) − V − b V (V + b) The development of the equation was targeted primarily at improving the accuracy of VLE calculations. The underlying reasoning in developing the equations was that a necessary condition for an equation of state to predict mixture VLE properties was that it accurately predict pure component VLE properties, namely pure component vapor pressures. The Soave equation uses an additional parameter, the acentric factor, to correlate vapor pressure data.