The heat capacity method of DSC measurements, for which sapphire was used as a standard, was applied to determine simultaneously the heat of the transitions and the heat capacity for long-chain compounds. A heat-flux DSC was used because of its relatively high sensitivity at slow scanning rates. The data were analyzed with a computer system. Measurements on indium were performed to obtain information about factors affecting the accuracy. Fairly satisfactory results were obtained for the heat of melting and the heat capacity at heating rates of 0.5 and 2 K min-1. Long-chain symmetrical ketones were also used to test the reliability of the measurement because their thermal behavior is very simple. Solution-grown crystals of henpentacontane and dopentacontane clearly showed high-temperature modifications with a high heat capacity. Analysis by the present method indicates that the heat capacities of these modifications have a relatively large contribution to the overall change in enthalpy from the stable crystal at room temperature to the liquid.