Helmholtz-Type Equations of State for Hydrocarbon Refrigerant Mixtures of Propane/n-Butane, Propane/Isobutane, n-Butane/Isobutane, and Propane/n-Butane/Isobutane

Abstract

Highly accurate thermodynamic property models for binary and ternary hydrocarbon mixtures containing propane, n-butane, and isobutane have been developed. In the present model, reliable equations of state explicit in Helmholtz free energy for these three hydrocarbons that have already been developed by the present authors have been adapted. The excess term used to represent the contribution of mixing was optimized for each binary mixture by using the available experimental thermodynamic property data including PρTx, isochoric heat capacity, and saturation properties (bubble-point pressures, mole fractions in the vapor phase, and saturated vapor- and liquid-densities) as input data. A generalized correction for the three binary mixtures, besides the ideal mixing, consists of only four terms in its functional form, the structure of which was determined by simultaneous optimization to the input data for the three binary mixtures by employing a stepwise regression analysis. The “bank of terms,” that is a matrix of candidate terms applied for the regression, was carefully prepared through detailed observation of the nonideal mixing representation of the experimental data of the three binary mixtures. No additional adjustable parameters were used in the present model for the ternary propane/n-butane/isobutane mixture. Based on comparisons with the available experimental data and values from the developed equations of state, the present models for the three binary and the ternary hydrocarbon mixtures accurately represent most of the reliable experimental data. In addition, the graphical tests of the derived thermodynamic properties show that the models, including that for the ternary mixture, provide a physically sound representation of all the thermodynamic properties over the entire fluid phase.