Thermodynamic Properties of Methanol in the Critical and Supercritical Regions

The isochoric heat capacity of pure methanol in the temperature range from 482 to 533 K, at near-critical densities between 274.87 and 331.59 kg ·m−3, has been measured by using a high-temperature and high-pressure nearly constant volume adiabatic calorimeter. The measurements were performed in the singleand two-phase regions including along the coexistence curve. Uncertainties of the isochoric heat capacity measurements are estimated to be within 2%. The single- and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from experimental data for each measured isochore. The critical temperature (Tc =512.78±0.02 K) and the critical density (ρc =277.49± 2kg·m−3) for pure methanol were derived from the isochoric heat-capacity measurements by using the well-established method of quasi-static thermograms. The results of the CV VT measurements together with recent new experimental PVT data for pure methanol were used to develop a thermodynamically self-consistent Helmholtz free-energy parametric crossover model, CREOS97-04. The accuracy of the crossover model was confirmed by a comprehensive comparison with available experimental data for pure methanol and values calculated with various multiparameter equations of state and correlations. In the critical and supercritical regions at 0.98Tc T 1.5Tc and in the density range 0.35ρc ρ 1.65ρc, CREOS97-04 represents all available experimental thermodynamic data for pure methanol to within their experimental uncertainties.