Étude thermodynamique des trois isomères du dihydroxybenzène

Abstract

The present work is concerned with a thermodynamic study of the three isomers of dihydroxybenzene. By combustion calorimetry of small amounts of substance, sublimation calorimetry, differential thermal analysis, and heat capacity measurements, it was possible to determine the enthalpies of formation of 1,2-, 1,3-, and 1,4-dihydroxybenzene in the condensed and gaseous phases, their enthalpies of fusion and transition, and the temperature of their triple point and transition. The experimental results are used to discuss the relative stability and determine the conjugation energy of the three compounds. The values are in good agreement with the theoretical values obtained from a quantum chemical calculation. The enthalpies of atomization enabled us to determine an energy value for the intramolecular Cb—OH bond in dihydroxybenzenes and to correlate it with previous results obtained from a study of alkane-diols. The enthalpies of sublimation were discussed. An intramolecular hydrogen bond was displayed in the ortho isomer. Intermolecular hydrogen bonds associated with van der Waals interactions exist in dihydroxybenzenes. Their energy contributions were determined. Key words: thermodynamics, calorimetry, differential thermal analysis, 1,2-benzenediol or 1,2-dihydroxybenzene or catechol; 1,3-benzenediol or 1,3-dihydroxybenzeneorresorcinol; 1,4-benzenediol or 1,4-dihydroxybenzene or hydroquinone or quinol; enthalpies of combustion, of sublimation, of fusion, of transition, energy of conjugation, enthalpies of atomization, of inter- and intramolecular bonds; triple point and transition temperatures.