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Title: 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:
ORCiD logo [1];  [1];  [2]; ORCiD logo [2];  [2];  [2]; ORCiD logo [1]
  1. Technische Univ. Munchen, Garching (Germany); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. 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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