Experimental and computational study on the molecular energetics of monobromoanisole isomers

The standard (p° = 0.1 MPa) molar enthalpies of formation in the liquid phase of three isomers of bromoanisole were derived from the standard molar energies of combustion, in oxygen, which yields CO2(g) and HBr · 600H2O(l), at T = 298.15 K, measured by rotating bomb combustion calorimetry. The determination of the standard molar enthalpies of vaporization of these compounds, at T = 298.15 K, was done by Calvet microcalorimetry using the high-temperature vacuum sublimation technique. Combining the former sets of experimental results, the standard molar enthalpies of formation, in the gas-phase, were derived. The gas-phase enthalpies of formation were also estimated by means of the empirical scheme developed by Cox and by density functional theory calculations performed at the B3LYP/6-31+G(d) level of theory.-ΔcUm∘(l)/(kJ·mol-1)-ΔfHm∘(l)/(kJ·mol-1)ΔlgHm∘/(kJ·mol-1)2-Bromoanisole3629.0 ± 1.4101.5 ± 1.761.8 ± 1.33-Bromoanisole3624.0 ± 1.4106.5 ± 1.758.0 ± 1.24-Bromoanisole3623.8 ± 1.5106.7 ± 1.858.3 ± 1.2Full-size tableTable optionsView in workspaceDownload as CSV