Rate constants deduced by ab-initio calculations for decomposition reactions of CH3OCH2, C4H9OCH2 and C4H8OCH3 radicals
(2001) Zeitschrift fuer Physikalische Chemie — Vol. 215, p. 1055-1068 (2001)
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- Abstract
- The importance of thermal decompositions during the oxidation of methyl tertbutyl ether (MTBE) has motivated a theoretical investigation of reactions: C4H9OCH2-->t-C4H9 + CH2O Eq. (r. 1), C4H8OCH3 --> i-C4H8 + CH3O Eq. (r.2) in comparison with reaction CH3OCH2 --> CH3 + CH2O Eq. (r.3). The conventional ab-initio molecular orbital procedures have been used to calculate the potential energy surface of the corresponding reactions and the thermodynamic properties of the reactants and the activated complex. The transition state theory (TST) has allowed to deduce the unimolecular rate constants: k(1) = 4.0 x 10(14) exp (-23 800/RT) s(-1), k(2) = 1.5 x 10(13) exp (-21 800/RT) s(-1), k(3) = 2.32 x 10(14) exp (-28 190/RT) s(-1) (E-a : cal mol(-1)). The rate constant obtained for reaction (r.3) from our calculations is in good agreement with the literature data. No experimental data are available for reactions (r.1) and (r.2). Use of Tree's formalism allows to evaluate the influence of pressure on the rate constants below 1200 K.
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van der Loos, A., Vandooren, J., Van Tiggelen, P., & Peeters, D. (2001). Rate constants deduced by ab-initio calculations for decomposition reactions of CH3OCH2, C4H9OCH2 and C4H8OCH3 radicals. Zeitschrift fuer Physikalische Chemie, 215, 1055-1068. https://hdl.handle.net/2078.5/138625 (Original work published 2001)