Standard molar enthalpies of formation of dimethylbenzophenones

Abstract

AbstractThe standard (p0 = 0.1 MPa) molar enthalpy of formation of 3,4‐dimethylbenzophenone was derived from the standard molar energy of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpy of sublimation of the compound. From these experimental parameters, the standard molar enthalpy of formation of 3,4‐dimethylbenzophenone, in the gaseous phase and at T = 298.15 K, was derived as −(17.1 ± 2.9) kJ mol−1. Density functional theory was used to investigate the gas‐phase molecular energetics of the 12 dimethylbenzophenones. Molecular geometries and vibrational frequencies were computed at the B3LYP/6‐31G(d) level of theory. The larger 6‐311+G(2d,2p) basis set was used to compute the energy of all dimethylbenzophenones and of the other compounds that were considered for the estimation of the standard molar enthalpies of formation at T = 298.15 K. The calculations show that the 2,2′‐ and 4,4′‐dimethylbenzophenones are the least and most stable isomers, respectively. Finally, the calculated enthalpy of formation of the benzophenone that was also studied experimentally, 3,4‐dimethylbenzophenone, is −16.7 kJ mol−1, which is in excellent agreement with the experimental result. Copyright © 2008 John Wiley & Sons, Ltd.