Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Fluoropropane (HFC-281ea)

DeMore, W. B.; Wilson, Edmond W.

doi:10.1021/jp9835521

Cited by 26 publications

(37 citation statements)

References 4 publications

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“…The lower reactivity of cyclopropane is due in part to a lower preexponential factor, following the general dependence of A factors on rate constant that is observed in a large number of OH abstraction reactions. 9 According to our rate constant data, the A factor for cyclopropane is not anomalously low, and fits well with the general trends as discussed in ref 9. However, the data of Clarke et al 7 correspond to an A factor which cannot be accommodated by this general behavior, and would require a different explanation, as put forward in their paper.…”

Section: Discussionsupporting

confidence: 90%

“…The diminished reactivity of methylene groups seen in cyclopropane, due to increased C−H bond energies in that molecule, is largely but not entirely gone in cyclobutane. The lower reactivity of cyclopropane is due in part to a lower preexponential factor, following the general dependence of A factors on rate constant that is observed in a large number of OH abstraction reactions .…”

Section: Discussionmentioning

confidence: 90%

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Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

1999

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Relative rate experiments were used to measure ratios of rate constants as a function of temperature for the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and dimethyl ether. To assure internal consistency, ratios were measured for seventeen reactant pairs among these reactants. All of the derived rate constants are based on an absolute rate constant of the OH + C2H6 reaction using k(ethane) = 1.0 × 10-11 exp(−1094/T) cm3/molecule s. The rate constants obtained are as follows. propane: 1.29 × 10-11 exp(−730/T), k(298 K) = 1.11 × 10-12. n-butane: 1.68 × 10-11 exp(−584/T), k(298 K) = 2.37 × 10-12. n-pentane: 1.94 × 10-11 exp(−494/T), k(298 K) = 3.70 × 10-12. n-hexane: 2.60 × 10-11 exp(−480/T), k(298 K) = 5.19 ×10-12. cyclopropane: 5.15 × 10-12 exp(−1255/T), k(298 K) = 7.64 × 10-14. cyclobutane: 1.62 × 10-11 exp(−611/T), k(298 K) = 2.08 × 10-12. cyclopentane: 2.57 × 10-11 exp(−498/T), k(298 K) = 4.83 × 10-12. cyclohexane: 3.58 × 10-11 exp(−500/T), k(298 K) = 6.69 × 10-12. dimethyl ether: 1.51 × 10-11 exp(−496/T), k(298 K) = 2.86 × 10-12. These results are compared with previous literature data and are discussed in terms of trends in preexponential factors and activation energies. Also, rate constants and Arrhenius parameters are derived for methylene groups in the alkanes and cycloalkanes. In the low temperature regime, the present data illustrate a persistent discrepancy between absolute and relative rate measurements. The relative data show less curvature at low temperatures, and can be adequately fit with two-parameter Arrhenius expressions.

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Section: Discussionsupporting

confidence: 90%

Section: Discussionmentioning

confidence: 90%

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

1999

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“…Unfortunately, to the best of our knowledge, the rate coefficient for the reaction of OH with 1-fluoropropane is unreported. However, we can use the value estimated by DeMore and Wilson, 18 which is given in Table 2. The change in reactivity is almost identical to that seen for ethanol and fluoroethanol.…”

Section: Influence Of F Atom Substitutionmentioning

confidence: 99%

Rate coefficients for the OH + CFH2CH2OH reaction between 238 and 355 K

Rajakumar

Burkholder

Portmann

et al. 2005

Phys. Chem. Chem. Phys.

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The rate coefficient for the reaction OH + CFH2CH2OH --> products (k1) between 238 and 355 K was measured using the pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique to be (5.15 +/- 0.88)x 10(-12) exp[-(330 +/- 45)/T] cm3 molecule(-1) s(-1); k1(298 K)= 1.70 x 10(-12) cm3 molecule(-1) s(-1). The quoted uncertainties are 2sigma(95% confidence level) and include estimated systematic errors. The present results are discussed in relation to the measured rate coefficients for the reaction of OH with other fluorinated alcohols and those calculated using recently reported structure additivity relationships for fluorinated compounds (K. Tokuhashi, H. Nagai, A. Takahashi, M. Kaise, S. Kondo, A. Sekiya, M. Takahashi, Y. Gotoh and A. Suga, J. Phys. Chem. A, 1999, 103, 2664-2672, ). Infrared absorption cross sections for CFH2CH2OH are reported and they are used to calculate the global warming potentials (GWP) for CFH2CH2OH of approximately 8, approximately 2, and approximately 1, respectively, for the 20, 100 and 500 year horizons. A brief discussion of the atmospheric degradation of CFH2CH2OH is provided. It is concluded that CFH2CH2OH is an acceptable substitute for CFCs in terms of its impact on Earth's climate and the composition of the atmosphere. The room temperature rate coefficient for the reaction OH + CFH2CH2OH --> products (k10) was measured to be 3.26 x 10(-12) cm3 molecule(-1) s(-1), in good agreement with recent measurements from this laboratory.

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“…An improvement for this SAR was reported by DeMore and Wilson. 5 We used those equations, and a value of 4.54 × 10 -14 cm 3 molecule -1 s -1 for the global rate constant is obtained. The branching ratios are 45% for the CH 2 group and 55% for the CH 3 group.…”

Section: Resultsmentioning

confidence: 99%

Canonical Variational Transition-State Theory Study of the CF₃CH₂CH₃ + OH Reaction

González‐Lafont¹,

Lluch²,

Varela‐Álvarez³

et al. 2007

J. Phys. Chem. B

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Variational transition-state theory rate constants with multidimensional tunneling contributions using the small curvature method have been calculated for the CF3CH2CH3 (HFC-263fb) + OH reaction over a temperature range from 200 to 373 K. The mPW1B95-41.0 hybrid functional, parametrized by Albu and Swaminathan to generate theoretical rate constants nearly identical to the experimental values for the CH3F + OH reaction, has been used in conjunction with the 6-31+G** basis set to explore the potential energy surface of the title reaction. The good agreement found between theoretical predictions and the experimental data available suggests that the present approach is an excellent option to obtain high-quality results at low computational cost for direct dynamics studies of hydrogen abstraction reactions from complex hydrofluorocarbons. The reliability of the structure activity relationship used to estimate rate constant values for OH reactions with hydrofluorocarbons is also discussed in detail.

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Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Fluoropropane (HFC-281ea)

Cited by 26 publications

References 4 publications

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

Rate coefficients for the OH + CFH2CH2OH reaction between 238 and 355 K

Canonical Variational Transition-State Theory Study of the CF₃CH₂CH₃ + OH Reaction

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Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Fluoropropane (HFC-281ea)

Cited by 26 publications

References 4 publications

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

Rate coefficients for the OH + CFH2CH2OH reaction between 238 and 355 K

Canonical Variational Transition-State Theory Study of the CF3CH2CH3 + OH Reaction

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Canonical Variational Transition-State Theory Study of the CF₃CH₂CH₃ + OH Reaction