Thermodynamic Study of Benzamide, N-Methylbenzamide, and N,N-Dimethylbenzamide: Vapor Pressures, Phase Diagrams, and Hydrogen Bond Enthalpy

A static method was used to measure the vapor pressures of crystalline and liquid phases of benzamide, N-methylbenzamide, and N,N-dimethylbenzamide, in the temperature ranges (344.8 to 438.2) K, (322.9 to 388.4) K, and (297.0 to 361.7) K, respectively. The vapor pressures of the crystalline phase of benzamide were also measured using the Knudsen effusion method in the temperature range (324.1 to 344.2) K. From the experimental results, the standard molar Gibbs energies and enthalpies of sublimation and of vaporization, at T = 298.15 K, and the triple points coordinates (p,T) for the three compounds were derived. The temperatures and molar enthalpies of fusion were also determined using differential scanning calorimetry and were compared with the values derived from the vapor pressure measurements. The results enabled the determination of the hydrogen bond enthalpies in the studied compounds.