Journal of Catalysis, Vol.390, 237-243, 2020
Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols
The varying steric environment of zeolites subtly influences the rates of hydronium-ion-catalyzed dehydration of alcohols containing a cyclohexyl group in aqueous phase. The investigated primary, secondary, and tertiary alcohols show an increasing stabilization of an ionic transition state in this sequence, i.e., an increasing tendency to move from a concerted (E2 mechanism) to a stepwise dehydration (El mechanism). Hydronium ions confined in the micropores of MFI and BEA zeolites induced much higher catalyzed rates than those in the aqueous phase. Independent of the reaction mechanism and the environment, however, all alcohols investigated follow one compensation correlation between activation enthalpy and entropy for primary, secondary, and tertiary alcohols, respectively. For a given transition enthalpy, the rate of dehydration is the higher the larger the reaction space (translated to the reaction entropy). Surprisingly, all compensation relations intersect in one point. These dependences for the different alcohols are also reflected in the turnover rates, for which all alcohols also intersect in a common point, which appears to mark the highest reaction rate for dehydration catalyzed by hydronium ions at the investigated temperature. (C) 2020 Elsevier Inc. All rights reserved.