Measurement of heat capacity by fitting the whole temperature response of a heat-pulse calorimeter

A new method that fits the whole temperature response of a heat-pulse calorimeter for heat capacity is developed. Analyzing the thermal response of a heat-pulse calorimeter on a model that was used by the relaxation method, the authors derived some useful relations and further utilized the numeric method of the general linear least squares to determine the heat capacity of a sample. Absolute accuracy of the proposed method was verified by determining the heat capacity of a 0.249 76 g copper sample (purity 99.999%) on a self-designed and fully automated calorimetric system from 4.5 to 80 K. Comparing the result with the literature, the deviation in average was 1.2% from 4.5 to 20 K and 2.0% from 20 to 80 K. It is found that the proposed method is capable of measuring heat capacity regardless if the sample is adiabatically or nonadiabatically isolated. The size of the specimen is not critical for the application of the method and the temperature range of measurement can be expanded. It also deals with the τ2 effect. Details of the employed calorimetric system are described. Stability, inherent limitations, and further improvement of the system are also discussed.