Estimation of the heat capacity of individual substances on the basis of experimental enthalpy increments

A method of determination of the high-temperature (T > 298.15 K) heat capacity function of individual substances by differentiation of enthalpy increment measurements with respect to temperature has been suggested. The approach is based on approximation of enthalpy increment measurements by a polynomial without free term, which makes it possible to strictly meet the boundary conditions of differentiation determined by the properties of the enthalpy increment function. In combination with the Shomate method, the approach enables the optimal choice of the form of temperature dependence of heat capacity that is consistent best of all with the concepts of classical thermodynamics and provides the best reproducibility of enthalpy increment measurements. When low-temperature heat capacity measurements for individual substances are not available, i.e., the Shomate method is inapplicable, the suggested strategy makes it possible to obtain the heat capacity change function in the temperature range of enthalpy increment measurements and to estimate the heat capacity of the substance at standard temperature.