Prediction of the thermodynamic properties of {ammonia + water} using cubic equations of state with the SOF cohesion function

The SOF cohesion function for cubic equations of state is based on the behavior of the residual energy of pure fluids. It contains two adjustable parameters for each component, which have been obtained for over 800 substances by regression of pure-fluid saturation pressures, and correlated in terms of a four-parameter corresponding states principle. In the present work, we compare the performance of this function and of the original Soave cohesion function with the Redlich–Kwong and Peng–Robinson equations of state in the prediction of vapor–liquid equilibria and enthalpy–composition diagrams for the polar system {ammonia + water}. We use simple van der Waals one-fluid mixing rules, linear for the covolume and quadratic for the cohesion parameter with one (symmetric) and two (asymmetric) binary interaction parameters. The non-linear least squares minimization algorithm lsqnonlin, in Matlab®, is used to adjust the interaction parameters to phase equilibrium and enthalpy data taken from the IAPWS fundamental formulation. Upper and lower bounds of the optimized interaction parameters are obtained using Matlab®bootstrap with 95% confidence of a normal distribution sampling. The validity of the parameters as functions of temperature is between the triple point of water and the critical point of ammonia. At lower temperatures, a rapid increase of statistical uncertainties is observed that can be attributed to the scarcity of phase equilibrium data.The two-parameter SOF cohesion function and the cubic equations of state are shown to give accurate predictions of the VLE and enthalpies of {ammonia + water}. Both equations of state give very similar results. Statistical analysis of the interaction parameters shows that their values (within the range of validity mentioned above) are effectively the same for both cohesion functions. At higher temperatures, however, extrapolation of the two cohesion functions gives different results, and correspondingly requires different interaction parameters.

Research highlights
► We obtained the binary interaction parameters for NH3/H2O as function of T and x.
► VLE and enthalpy optimization provide BIP that represent accurately the VLE data.
► The binary interaction parameters can be considered to be true system properties.
► Bootstrap shows that asymmetry of Margules mixing rule is statistically significant.
► CEOS with SOF cohesion function and BIP represent accurately VLE and enthalpies.