Abstract
A flow system was used to study gas-phase equilibria of the cyclohexanol dehydrogenation: ▪ in the temperature range from 467.5 to 533.8 K over a catalyst consisting of copper and zinc oxides, and of hydrogen redistribution during ▪ in the temperature range 453.1 to 533.1 K over a magnesium oxide catalyst. The values of Δ r H m o and Δ r S m o obtained from the temperature dependences of the equilibrium constants were (63.4 ± 2.3) kJ · mol −1 and (119.9 ± 4.6) J · K −1 · mol −1 for reaction (1) and −(9.9 ± 1.9) kJ · mol −1 and −(5.8 ± 3.9) J · K −1 · mol −1 for reaction (2). Based on molecular and spectroscopic information, statistical calculations of the thermodynamic properties of cyclohexanol and cyclohexanone were made over the range 298.15 to 1000 K for the ideal-gas state, taking into account the conformations of the compounds. The calculations agree with all experimental thermodynamic properties. An original technique is suggested for calculation of the contributions of conformers to the heat capacity.
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