The present work is part of a broader research program on the energetics of formation of heterocycles, aiming the study of
the enthalpic effects of the introduction of different substituents into heterocycles. In this work we present the results
of the thermochemical research on sulphur heterocycles of the type substituted thiophenes with different kind of substituents,
mainly alkyl, ester, acetyl, carboxamide, acetamide, carbonitrile and carboxaldehyde.
The standard (po=0.1 MPa) molar enthalpies of formation, in the condensed phase, at T=298.15 K, of a large number of substituted thiophenes, were derived from their standard massic energies of combustion, measured
by rotating-bomb combustion calorimetry, while the standard molar enthalpies of vaporization or sublimation of those compounds
were obtained either by high temperature Calvet Microcalorimetry, or by the temperature dependence of their vapour pressures
determined by the Knudsen effusion technique. The standard molar enthalpies of formation, of the studied sulphur heterocycles
in the gaseous phase, were then derived. The results are interpreted in terms of structural contributions to the energetics
of the substituted thiophenes, the internal consistency of the results is discussed and, whenever appropriate and possible,
empirical correlations are suggested for the estimation of standard molar enthalpies of formation, at T=298.15 K, of substituted thiophenes. A Table of enthalpic increments for different group substituents in positions 2 or 3
of the thiophene ring has been established.