Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols
Abstract
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.
- Authors:
-
- Technische Univ. Munchen, Garching (Germany); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Technische Univ. Munchen, Garching (Germany)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
- OSTI Identifier:
- 1668765
- Alternate Identifier(s):
- OSTI ID: 1775867
- Report Number(s):
- PNNL-SA-154395
Journal ID: ISSN 0021-9517
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Catalysis
- Additional Journal Information:
- Journal Volume: 390; Journal ID: ISSN 0021-9517
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; entropy enthalpy compensation; chemospecific sensitivity of catalytic rates; alcohol dehydration; confinement effects
Citation Formats
Milakovic, Lara, Hintermeier, Peter H., Liu, Qiang, Shi, Hui, Liu, Yue, Baráth, Eszter, and Lercher, Johannes A. Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols. United States: N. p., 2020.
Web. doi:10.1016/j.jcat.2020.08.009.
Milakovic, Lara, Hintermeier, Peter H., Liu, Qiang, Shi, Hui, Liu, Yue, Baráth, Eszter, & Lercher, Johannes A. Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols. United States. https://doi.org/10.1016/j.jcat.2020.08.009
Milakovic, Lara, Hintermeier, Peter H., Liu, Qiang, Shi, Hui, Liu, Yue, Baráth, Eszter, and Lercher, Johannes A. Sat .
"Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols". United States. https://doi.org/10.1016/j.jcat.2020.08.009. https://www.osti.gov/servlets/purl/1668765.
@article{osti_1668765,
title = {Towards understanding and predicting the hydronium ion catalyzed dehydration of cyclic-primary, secondary and tertiary alcohols},
author = {Milakovic, Lara and Hintermeier, Peter H. and Liu, Qiang and Shi, Hui and Liu, Yue and Baráth, Eszter and Lercher, Johannes A.},
abstractNote = {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.},
doi = {10.1016/j.jcat.2020.08.009},
journal = {Journal of Catalysis},
number = ,
volume = 390,
place = {United States},
year = {Sat Aug 15 00:00:00 EDT 2020},
month = {Sat Aug 15 00:00:00 EDT 2020}
}
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