Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

ABSTRACT

The fusion enthalpies of the series butanedioic acid through to tetradecanedioic acid and hexadecanedioic acids have been measured by DSC. In addition to fusion, a number of solid solid phase transitions have also been detected in these diacids. The vaporization enthalpies of these compounds have been measured by correlation gas chromatography using the vaporization enthalpies of butanedioic, hexanedioic and decanedioic acids as standards. The vaporization enthalpies of the diacids from C4 to C10 correlated linearly with the number of methylene groups present. Above C10, the vaporization enthalpies of C11 C14 and C16 begin to deviate from linearity. The vaporization enthalpies for these compounds are dependent on the temperature of the GC column used. Similar departure from linearity has also been observed previously in the sublimation enthalpies for these compounds. The results are discussed in terms of formation of a cyclic intramolecular hydrogen bonded network in the gas phase similar to the bimolecular association observed in smaller mono-carboxylic acids at ambient temperatures.