Journal of Chemical Thermodynamics, Vol.135, 155-174, 2019
One- and two-phase isochoric heat capacities and saturated densities of 2-propanol in the critical and supercritical regions
One- (C-V1) and two-phase (C-V2) liquid + vapor equilibrium isochoric heat capacities, densities (rho(S)), and phase-transition temperatures (T-S) of 2-propanol were measured in the critical region. Measurements were made in the immediate vicinity of the liquid-gas phase transition and critical point in order to accurately determine the locus of phase-transition properties (T-S, rho(S), C-V1, and C-V2). Additional measurements were made over an extended temperature range from (317 to 525) K for 9 liquid and 3 vapor isochores between (234 and 697) kg.m(-3) at pressure up to 6.5 MPa. The measurements were performed using a high-temperature, high-pressure, nearly constant-volume adiabatic piezo-calorimeter. The standard uncertainty of the density, temperature, and isochoric heat capacity (C-V) measurements is estimated to be 0.1%, 0.02 K, and 1.5%, respectively. The measured one- (C-V1) and two-phase (C-V2) isochoric heat capacities along the critical isochore and the saturated liquid (rho(S)') and vapor (rho(S)'') densities near the critical point were used to derive theoretically meaningful asymptotic critical amplitudes (A(0)(+/-) and B-0) and related amplitudes for other properties (Gamma(+)(0), D-0, xi(0)) and their universal relations, A(0)(+)/A(0)(-), A(0)(+)Gamma B-+(0)0(2), alpha A(0)(+)Gamma B-+(0)0(-2), D-0 Gamma B-+(0)0(delta-)1, xi(0)(alpha A(0)(+)/upsilon(C))(1/3) and the asymmetric parameters a(3) and b(2) of the coexistence curve singular diameter. Experimental two-phase heat capacities C-V2 as a function of specific volume V , along various isotherms, were used to calculate second temperature derivatives of vapor pressure d(2)P(S)/dT(2) and chemical potential d(2)mu/dT(2) and to estimate the value of the Yang-Yang anomaly strength parameter R-mu for 2-propanol. The relative contributions of the vapor pressure, C-VP = VCT d(2)P(S)/dT(2), and the chemical potential, C-V mu= -Td(2)mu/dT(2), to the measured total two-phase C-V2 were estimated. Published by Elsevier Ltd.
Keywords:Adiabatic calorimeter;Critical amplitude;Critical point;Isochoric heat capacity;Yang-Yang anomaly strength parameter