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• W2023100334 abstract "Intermolecular and intramolecular 13C kinetic isotope effects in the pyrolysis of dimethyl ether were measured at temperatures between 451 and 550 °C; initial pressures were between 14 and 1000 torr. A few experiments on the NO-inhibited reaction were carried out at 501 °C. Both isotope effects are of the order of 1% and decrease with increasing temperature; the temperature dependence of the intermolecular effect is the greater. No significant pressure effects were observed. The isotope effects arise in the destruction of the symmetry of the reactant in hydrogen transfer reactions of the form R+C2H3OC1H3→RH+⋅C2H2OC1H3, where R=CH3, H, or NO. The method of three-element reaction coordinates was used to model the hydrogen transfer, the elements being displacements in the stretching coordinates R⋅⋅⋅H, H⋅⋅⋅C2, and C2-O. With adjustments of the transition state diagonal force field which are physically and chemically reasonable, the best simultaneous fit to the experimental results is obtained for reaction coordinates in which displacements in R⋅⋅⋅H and H⋅⋅⋅C2 are large but that in C2-O is small. The fit is not critically sensitive to the degree of transfer of H from C2 to R in the range 25%–75%, and in that range is essentially the same for R=H, CH3, or NO. Predictions are made of kH/kD for comparative pyrolyses of CH3OCH3 and CD3OCD3." @default.
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• W2023100334 date "1976-04-01" @default.
• W2023100334 modified "2023-10-16" @default.
• W2023100334 title "13C kinetic isotope effects in the pyrolysis of dimethyl ether" @default.
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• W2023100334 doi "https://doi.org/10.1063/1.432588" @default.
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