Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols

Milakovic, Lara; Hintermeier, Peter H.; Liu, Qiang; Shi, Hui; Liu, Yue; Baráth, Eszter; Lercher, Johannes A.

doi:10.1016/j.jcat.2020.08.009

Title: Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols

Journal Article · Sat Aug 15 00:00:00 EDT 2020 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2020.08.009· OSTI ID:1668765

^[1]; Hintermeier, Peter H. ^[1]; Liu, Qiang ^[2];

^[2]; Liu, Yue ^[2]; Baráth, Eszter ^[2];

^[1]

Technische Univ. Munchen, Garching (Germany); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Technische Univ. Munchen, Garching (Germany)

The varying steric environment of zeolites subtly influences the rates of hydronium-ion-catalyzed dehydration of alcohols containing a cyclohexyl group in aqueous phase. Here, 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 (E1 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.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1668765

Alternate ID(s):: OSTI ID: 1775867

Report Number(s):: PNNL-SA-154395

Journal Information:: Journal of Catalysis, Vol. 390; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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