A modified clausius equation of state for calculation of multicomponent refrigerant vapor-liquid equilibria

Gow, A.S., 1993. A modified Clausius equation of state for calculation of multicomponent refrigerant vapor-liquid equilibria. Fluid Phase Equilibria, 90: 219-249.

A modified Clausius equation of state with a single temperature dependent energy-volume parameter a(T) in the attractive term was designed to describe the vapor pressure vs. temperature relationship of 39 pure refrigerant fluids including elementary cryogenic materials (e.g. He, Ar, N₂, CO₂, CH₄, etc.), chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), fluorocarbons (FCs), and various other simple cryogenic compounds. The equation developed represents the vapor-liquid coexistence dome, and the superheated vapor compressibility factor and enthalpy for pure refrigerants.

The vapor-liquid equilibrium for refrigerant mixtures is calculated using a “phi-phi” method with “one fluid” van der Waals mixing and combining rules for the equation of state parameters a_M(T), b_M and c_M. A single interaction constant k₁₂ is used to describe non-ideal behavior of each binary. The binary interaction constant, which is a strong function of temperature, and the sign of which signifies the type of deviations from Raoult's law, is obtained by correlating experimental bubble point data for isothermal binary refrigerant mixtures. The proposed equation of state generally describes binary P-x,y data more accurately the higher the temperature for a given system. The method presented is extended to predict vapor-liquid equilibria for the R14-R23-R13 ternary system at 198.75 K using binary interaction constants at this temperature for the three binaries involved.