The standard (p degrees = 0.1 MPa) molar enthalpies of formation of the liquid 2-bromophenol and crystalline 4-bromophenol, respectively, Delta H-f(m)degrees(l) = -(133.5 +/- 1.4) kJ . mol(-1) and Delta H-f(m)degrees(cr) = -(152.4 +/- 1.4) kJ . mol(-1), were derived from the standard molar energies of combustion, in oxygen, to yield CO2(g) and HBr center dot 600H(2)O(l), at T = 298.15 K, measured by rotating-bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpy of vaporization or sublimation of the compounds, Delta H-g(l)m degrees = (55.5 +/- 1.3) kJ . mol(-1) and Delta H-g(cr)m degrees = (83.1 +/- 1.6) kJ . mol(-1). These two thermodynamic parameters yielded the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, of 2- and 4-bromophenol, respectively, Delta H-f(m)degrees(g) = -(78.0 +/- 1.9) kJ . mol(-1) and Delta H-f(m)degrees(g) = -(69.3 +/- 2.1) kJ . mol(-1). The experimental values of the gas-phase enthalpies of formation of each compound were compared with estimates using the empirical scheme developed by Cox and with the calculated values based on high-level density functional theory calculations using the B3LYP hybrid exchange-correlation energy functional at the 6-311++G(d,p) basis set. (C) 2009 Elsevier Ltd. All rights reserved.