Journal of Chemical and Engineering Data, Vol.59, No.4, 968-974, 2014
Isobaric Heat Capacity Measurements of Liquid Methane plus Propane, Methane plus Butane, and a Mixed Refrigerant by Differential Scanning Calorimetry at High Pressures and Low Temperatures
Isobaric heat capacity c(p) measurements are reported at temperatures between (108 and 168) K for liquid mixtures of CH4 (1) + C3H8 (3) at x(1) approximate to 0.8 and p approximate to 5 MPa; CH4 (1) + C4H10 (4) at x(1) = 0.96, 0.88, and 0.60 and p approximate to 5 MPa; and a five-component mixture that is similar in composition to a commercial mixed refrigerant at p = (1.0 and 5.0) MPa. Measurements were made, with an estimated uncertainty of about 0.02.c(p), using a specialized calorimeter further modified to prevent preferential condensation of the less volatile component and minimize possible stratification of the mixture during sample loading. Our results for CH4 + C3H8 agreed within 0.02.c(p) of the values predicted using the GERG 2008 equation of state (EOS), whereas literature c(p) data over the same temperature range agree within 0.03.c(p). In contrast the c(p) predicted for this mixture with the Peng-Robinson EOS (PR-HYSYS) shows an offset of about 0.02.c(p) from the average of the literature data at 165 K, which increases to 0.045.c(p) at 120 K. For CH4 (1) + C4H10 (4) our data for x(1) = 0.96 and 0.88 are within 0.05.c(p) of the GERG 2008 predictions; however, at x(1) = 0.6, the deviations increase from 0.02.c(p) at 168 K to nearly 1.1.c(p) at 118 K. The PR-HYSYS predictions for this binary mixture deviate from the measured c(p) data by 0.11.c(p) at 168 K, which increases to 0.21.c(p) at 118 K. For the mixed refrigerant (mole fraction composition 0.247 CH4 + 0.333 C2H6 + 0.258 C3H8 + 0.076 C4H10 + 0.059 N-2), the deviations of the measured c(p) from GERG 2008 are less than 0.02.c(p) in the range (168 to 148) K, increasing to 0.19.c(p) at 108 K. The deviations from the predictions of PR-HYSYS range from 0.07.c(p) at 168 K to 0.15.c(p) at 108 K. Similar differences from the various EOS are observed for the data of Furtado, who measured the c(p) of a mixture with a mole fraction composition of 0.359 CH4 + 0.314 C2H6 + 0.327 C3H8 at similar temperatures.