Isochoric Heat Capacity Measurements for 0.5 H2O + 0.5 D2O Mixture in the Critical Region

Abstract

The isochoric heat capacity C V of an equimolar H2O+D2O mixture was measured in the temperature range from 391 to 655 K, at near-critical liquid and vapor densities between 274.05 and 385.36 kg⋅m−3. A high-temperature, high-pressure, nearly constant-volume adiabatic calorimeter was used. The measurements were performed in the one- and two-phase regions including the coexistence curve. The uncertainty of the heat-capacity measurement is estimated to be ±2%. The liquid and vapor one- and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from the experimental data for each measured isochore. The critical temperature and the critical density for the equimolar H2O+D2O mixture were obtained from isochoric heat capacity measurements using the method of quasi-static thermograms. The measurements were compared with a crossover equation of state for H2O+D2O mixtures. The near-critical isochoric heat capacity behavior for the 0.5 H2O+0.5 D2O mixture was studied using the principle of isomorphism of critical phenomena. The experimental isochoric heat capacity data for the 0.5 H2O+0.5 D2O mixture exhibit a weak singularity, like that of both pure components. The reliability of the experimental method was confirmed with measurements on pure light water, for which the isochoric heat capacity was measured on the critical isochore (321.96 kg⋅m−3) in both the one- and two-phase regions. The result for the phase-transition temperature (the critical temperature, TC, this work=647.104±0.003 K) agreed, within experimental uncertainty, with the critical temperature (TC, IAPWS=647.096 K) adopted by IAPWS.