Isochoric Heat-Capacity Measurements for Pure Methanol in the Near-Critical and Supercritical Regions

Isochoric heat-capacity measurements for pure methanol are presented as a function of temperature at fixed densities between 136 and 750 kg·m⁻³. The measurements cover a range of temperatures from 300 to 556 K. The coverage includes the one- and two-phase regions, the coexistence curve, the near-critical, and the supercritical regions. A high-temperature, high-pressure, adiabatic, and nearly constant-volume calorimeter was used for the measurements. Uncertainties of the heat-capacity measurements are estimated to be 2–3% depending on the experimental density and temperature. Temperatures at saturation, T _S(ρ), for each measured density (isochore) were measured using a quasi-static thermogram technique. The uncertainty of the phase-transition temperature measurements is 0.02 K. The critical temperature and the critical density for pure methanol were extracted from the saturated data (T _S,ρ_S) near the critical point. For one near-critical isochore (398.92 kg·m⁻³), the measurements were performed in both cooling and heating regimes to estimate the effect of thermal decomposition (chemical reaction) on the heat capacity and phase-transition properties of methanol. The measured values of C _V and saturated densities (T _S,ρ_S) for methanol were compared with values calculated from various multiparametric equations of state (EOS) (IUPAC, Bender-type, polynomial-type, and nonanalytical-type), scaling-type (crossover) EOS, and various correlations. The measured C _V data have been analyzed and interpreted in terms of extended scaling equations for the selected thermodynamic paths (critical isochore and coexistence curve) to accurately calculate the values of the asymptotical critical amplitudes ( and B ₀).