Reaction of hydroxyl with fluoroethane. The extent of hydrogen abstraction from the .alpha. and .beta. positions

Singleton, D. L.; Paraskevopoulos, G.; Irwin, R. S.

doi:10.1021/j100456a001

Cited by 9 publications

(8 citation statements)

References 3 publications

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“…Singleton et al 34 found an ␣ abstraction percentage of 85%Ϯ3% at 297 K ͑see Table VI͒. Although the SCFFAF result ͑90.6%͒ is slightly outside the error bars of the experiment, it shows a dominance of the ␣ abstraction that is close to what has been observed.…”

Section: Resultssupporting

confidence: 65%

The calculation of thermal rate constants for gas phase reactions: A semiclassical flux–flux autocorrelation function (SCFFAF) approach

Runge

Cory

Bartlett

2001

The Journal of Chemical Physics

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A semiclassical approach to the calculation of thermal rate constants, based on the flux-flux autocorrelation function method, is presented with its applications. The autocorrelation function is generated along classical trajectories using a classical interpretation of the Boltzmannized flux operator. The activation energies for considered reactions are calculated using the G2/MP2 procedure. The forces are generated using a new parametrization of the PM3 NDDO Hamiltonian optimized for accurate gradients. Thermal rate constants for hydrogen abstraction from ethane and haloethanes by hydroxyl radical serve as a first test of this approach. Calculated results are in good agreement with cumulative rate constants for all systems considered over a range of temperature including room temperature. The approach is able to distinguish between ␣ and ␤ abstraction with a result for fluoroethane at room temperature that is consistent with the available experiment and trends that are in line with those expected.

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Section: Resultssupporting

confidence: 65%

The calculation of thermal rate constants for gas phase reactions: A semiclassical flux–flux autocorrelation function (SCFFAF) approach

Runge

Cory

Bartlett

2001

The Journal of Chemical Physics

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“…In the case of CH3CH2F, with non-equivalent C-H bonds, the correlation indicated that hydrogen abstraction occurred mainly from the CY position of CH3CH2F. This was later confirmed by product analysis (4).…”

Section: Introductionmentioning

confidence: 69%

“…The D(CH3CHF-H) = 96.3 kcal mol-' was kstimated using the rate constant of hydrogen abstraction from (28). the a position of CH3CH2F which is 85% of the overall rate constant (3,4).…”

Section: Correlation Of Log (K/n) With Average Stretching Frequenciesmentioning

confidence: 99%

A kinetic study of the reactions of OH radicals with fluoroethanes. Estimates of C—H bond strengths in fluoroalkanes

Martin¹,

Paraskevopoulos²

1983

Can. J. Chem.

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PARASKEVOPOULOS. Can. J. Chem. 61, 861 (1983). A kinetic study of the reactions of OH radicals with a series of fluoroethanes in the gas phase is prcsented. OH radicals were generated by flash photolysis of H 2 0 vapor in the vacuum uv (A > 165 nm) and were monitored in absorption by timc-rcsolved attenuation of resonance radiation at 308.15 nm [OH(A'C' + X'n)]. The following absolute rate constants (in units of 10%m3 mol-' s-I at the 95% confidence limit) were determined at 298 K: kcli2rcli,r = 67.7 + 7.2, kC~2FClIF2 = 11.0 + 1.1, ~C H~C F~ = 1.03 20.26, kCHZFCFl = 3.10 2 0.35. kCHF2CF3 = 1.50 I+--0.17. From a linear correlation of the present and previously published rate constants with bond dissociation energies, the following quantities (in kcal mol-' at 298 K) were estimated to be: D(CH,CHF-H) = 96.3 5 .1.5, D(CH,FCHF-H = 98.8 5 .

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“…Curvature in the Arrhenius plot is evident from the study by Kozlov et al [738], which was conducted over an 1-65 extended temperature range above and below room temperature. Singleton et al [1202] determined that 85 ± 3% of the abstraction by OH is from the fluorine substituted methyl group at room temperature. Hence this curvature is quite possibly due to the increasing importance of hydrogen abstraction from the unsubstituted methyl group with increasing temperature.…”

Section: -41mentioning

confidence: 99%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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Reaction of hydroxyl with fluoroethane. The extent of hydrogen abstraction from the .alpha. and .beta. positions

Cited by 9 publications

References 3 publications

The calculation of thermal rate constants for gas phase reactions: A semiclassical flux–flux autocorrelation function (SCFFAF) approach

The calculation of thermal rate constants for gas phase reactions: A semiclassical flux–flux autocorrelation function (SCFFAF) approach

A kinetic study of the reactions of OH radicals with fluoroethanes. Estimates of C—H bond strengths in fluoroalkanes

Environmental effects of large igneous province magmatism: a Siberian perspective

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