Abstract
The gas-phase thermal decomposition of cyclopentanol, cyclohexanol, and cycloheptanol catalysed by hydrogen chloride in a seasoned Pyrex reaction vessel has been studied in a static system between 693 and 773 K. The reactions are homogeneous. The rate constants (k2) are defined respectively by the Arrhenius equations (i)–(iii)k2= 1013.36 ± 0.12 exp –(36 143 ± 388)/RT cm3 s–1 mol–1(i)k2= 1013.41 ± 0.16 exp –(38 927 ± 529)RT cm3 s–1 mol–1(ii)k2= 1012.31 ± 0.18 exp –(32 254 ± 613)/RT cm3 s–1 mol–1(iii) where R= 1.987 cal mol–1 K–1. The activation energies show a decrease with increasing ring-strain energy changes. The significance of this is discussed.
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