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Abstract: We report new experimental data of heat capacity of two primary amines, namely 1-pentylamine and 1-hexylamine over wide ranges of pressure [0.1–60(MPa)] and temperature [303.15–403.15(K)]. The experimental behaviour of the heat capacity versus temperature and pressure is analyzed. An attempt to rationalize this behaviour is performed through a two-state association model (TSAM), which allows expressing the specific effect due to association at molecular level. It appears that the heat capacity trend versus temperature is clearly governed by auto-association between amines molecules. The physical meaningful of the (TSAM) model parameters highlights the capability of this approach to capture the heat capacity behavior of the amines. [Copyright &y& Elsevier]