Benchmark thermochemistry of methylbenzonitriles: Experimental and theoretical study

Highlights: • Thermochemistry of 2-, 3-, and 4-methylbenzonitriles was studied. • Enthalpies of formation were measured by combustion calorimetry. • Vaporization enthalpies were derived by transpiration method. • Ab initio enthalpies of formation were in excellent agreement with experiment. • Group-additivity terms for cyano substituted benzenes were proposed. - Abstract: The gas-phase enthalpies of formation of 2-, 3-, and 4-methylbenzonitrile at T = 298.15 K were studied by combustion calorimetry, and their vaporization enthalpies were determined using the transpiration method. The composite ab initio methods W1-F12 and G4 were used to calculate the gas-phase enthalpies of formation for these three methylbenzonitriles. These theoretical values were found to be in excellent agreement with the corresponding experimental data. The analysis of these data revealed that the interaction between cyano and methyl groups is slightly stabilizing. Using the experimental data a set of group-additivity terms, which allows to estimate thermochemical properties for methyl and cyano substituted benzenes, was proposed. These terms, together with theoretical data, were subsequently used to reassess the thermochemical properties of 2,6-dimethylbenzonitrile and 2,4,6-trimethylbenzonitrile.