The present work is part of a research program on the energetics of the linear 4-n-alkoxybenzoic acids, aiming the study of the enthalpic effect of the introduction of an alkoxy chain in the position 4- of the benzoic acid ring. In this work, we present the results of the thermochemical research on 4-n-alkoxybenzoic acids with the alkoxy chain length n = 2, 4, and 8. The standard (p degrees = 0.1 MPa) molar enthalpy of formation of crystalline 4-ethoxybenzoic acid, 4-butoxybenzoic acid, and 4-(octyloxy)benzoic acid was measured, at T = 298.15 K, by static-bomb calorimetry. These values, combined with the values of standard molar enthalpies of sublimation, were used to derive the standard molar enthalpies of formation in the gaseous phase. [GRAPHICS] From those experimental values, the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, are interpreted in terms of structural contributions to the energetics of the substituted benzoic acids and compared with the same parameters estimated from the Benson's Group Method. (C) 2009 Elsevier Ltd. All rights reserved.