Measurement of the isobar heat capacity of fluids in the critical area by the method of flowing adiabatic calorimeter

Abstract

With regard to the problem of refining the fundamental equations of state of hydrocarbons, the methodological and design features of the experimental measurement of the isobaric heat capacity in the critical region by the method of a flow adiabatic calorimeter are considered. The pressure measurement system has been improved by introducing a differential manometer into the measuring circuit, which made it possible not only to increase the accuracy of pressure determination, but also to implement a universal scheme of calorimetric experiment. The use of a universal scheme of the calorimetric experiment allows one to determine two values of the isobaric heat capacity at pressures that differ by the value of the pressure loss in the calorimeter. Such an approach in the critical region is relevant, since it makes it possible to quite simply and reliably determine the value of the derivative of the heat capacity with respect to pressure, which is used to estimate not only the error in assigning the value of heat capacity to pressure, but also the equilibrium conditions of the experiment in a flow-through calorimeter. The technique of determining and making a correction for the inhomogeneity of the supply wires of the differential thermocouple, for the throttling of the flow of matter in the calorimeter is considered. Correct relations are obtained for determining the average temperature of the measurement experiment for various methods of measuring the temperature and temperature difference in a flow-through calorimeter. The results of experimental measurements of the isobaric heat capacity of n-pentane in the critical region, obtained using the universal scheme of the calorimetric experiment, for n-pentane were measured on an isobar of 3.400 MPa (critical pressure 3.355 MPa), which is the closest to the critical point at practice of flow calorimetry.