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Experimental and Computational Investigation of the Energetics of the Three Isomers of Monochloroaniline

2005; American Chemical Society; Volume: 109; Issue: 27 Linguagem: Inglês

10.1021/jp0519565

1520-6106

Manuel A. V. Ribeiro da Silva, José R. B. Gomes, Ana I.M.C. Lobo Ferreira,

Free Radicals and Antioxidants

The standard (p° = 0.1 MPa) molar enthalpies of formation of 2-, 3-, and 4-chloroaniline were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of vaporization or sublimation of the three isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the three isomers of chloroaniline, in the gaseous phase, at T = 298.15 K, as 53.4 ± 3.1 kJ·mol-1 for 2-chloroaniline, 53.0 ± 2.8 kJ·mol-1 for 3-chloroaniline, and 59.7 ± 2.3 kJ·mol-1 for 4-chloroaniline. These values, which correct previously published data, were used to test the computational methodologies used. Therewith, gas-phase acidities, proton affinities, electron donor capacities, and N−H bond dissociation enthalpies were calculated and found to compare well with available experimental data for these parameters.