Effects of isotopic substitution and vibrational excitation on reaction rates. Kinetics of OH(ν= 0, 1) and OD(ν= 0, 1) with HCl and DCl

Smith, Ian W. M.; Williams, Martin D.

doi:10.1039/f29868201043

Cited by 42 publications

(45 citation statements)

References 3 publications

(4 reference statements)

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Section: Reactions With Brci and Icimentioning

confidence: 89%

“…However, Smith and Williams [227] recently reported a value at 298K which is only one third that of References 32 and 226. The validity of Smith and Williams [227] data is reinforced by their rate constant value for OH+HC1 at 300K which is in agreement with previous studies. They attribute the discrepancy in the results for OH+DC1 to decreased isotopic purity of DC1 due to significant isotopic scrambling between DCI and the OH radical precursors in the earlier studies [32,226].…”

Section: Reactions With Brci and Icimentioning

confidence: 89%

“…These rate constants for removal of the v=l radicals for OH+HC1, OH+DC1 and OD+DCI were found to be faster, by factors of 1.4, 1.1 and 2.3 respectively, than the corresponding reactions of the v=0 radicals. Smith and Williams [227] concluded that the observed small enhancement of the total rate constant is probably due entirely to vibrational relaxation v/a near resonant vibrational energy exchange with the reagent molecules.…”

Section: Reactions With Brci and Icimentioning

confidence: 97%

“…The primary kinetic isotope effect at 300K, kH/kD, is ~2 [32,226] or ~6 [227] depending on which value of the rate constant for OH+DCI is correct. Calculations of the isotope effect based on transition state theory using semiempirical potential functions (Bond-Energy-Bond-Order, London-Eyring-PolanyiSato) by Smith and coworkers [32,227] gave a value ki-l/kD ~ 2, which is smaller than the recent experimental value of --~6 [227] discussed above.…”

Section: Reactions With Brci and Icimentioning

confidence: 99%

“…Two values of the total (reaction plus deactivation) rate constant for the reaction OH(v--1)+HC1, determined by Glass et al [228] and Smith and Williams [227] (Table XVI), vary by a factor of ~2. The latter authors also determined total rate constants for OH(v--l) and OD(v--1) with DC1 (Table XVI).…”

Section: Reactions With Brci and Icimentioning

confidence: 99%

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Reactions of OH radicals with inorganic compounds in the gas phase

Paraskevopoulos

Singleton

1988

Reviews of Chemical Intermediates

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Section: Reactions With Brci and Icimentioning

confidence: 89%

Section: Reactions With Brci and Icimentioning

confidence: 89%

Section: Reactions With Brci and Icimentioning

confidence: 97%

Section: Reactions With Brci and Icimentioning

confidence: 99%

Section: Reactions With Brci and Icimentioning

confidence: 99%

See 3 more Smart Citations

Reactions of OH radicals with inorganic compounds in the gas phase

Paraskevopoulos

Singleton

1988

Reviews of Chemical Intermediates

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Kinetics of the OH+HCl→H₂O+Cl reaction: Rate determining roles of stereodynamics and roaming and of quantum tunneling

et al. 2018

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The OH + HCl → H2O + Cl reaction is one of the most studied four‐body systems, extensively investigated by both experimental and theoretical approaches. Here, as a continuation of our previous work on the OH + HBr and OH + HI reactions, which manifest an anti‐Arrhenius behavior that was explained by stereodynamic and roaming effects, we extend the strategy to understand the transition to the sub‐Arrhenius behavior occurring for the HCl case. As previously, we perform first‐principles on‐the‐fly Born–Oppenheimer molecular dynamics calculations, thermalized at four temperatures (50, 200, 350, and 500 K), but this time we also apply a high‐level transition‐state‐theory, modified to account for tunneling conditions. We find that the theoretical rate constants calculated with Bell tunneling corrections are in good agreement with extensive experimental data available for this reaction in the ample temperature range: (i) simulations show that the roles of molecular orientation in promoting this reaction and of roaming in finding the favorable path are minor than in the HBr and HI cases, and (ii) dominating is the effect of quantum mechanical penetration through the energy barrier along the reaction path on the potential energy surface. The discussion of these results provides clarification of the origin on different non‐Arrhenius mechanisms observed along this series of reactions. © 2018 Wiley Periodicals, Inc.

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Study of the reactions of OH with HCl, HBr, and HI between 298 K and 460 K

Khamaganov

Orkin

Larin

2020

Int J of Chemical Kinetics

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The reactions between OH radicals and hydrogen halides (HCl, HBr, HI) have been studied between 298 and 460 K by using a discharge flow-electron paramagnetic resonance technique. The rate constants were found to be k HCl (298 K) = (7.9 ± 1.3) × 10 −13 cm 3 molecule −1 s −1 with a weak positive temperature dependence, k HBr (298-460 K) = (1.04 ± 0.2) × 10 −11 cm 3 molecule −1 s −1 , and k HI (298 K) = (3.0 ± 0.3) × 10 −11 cm 3 molecule −1 s −1 , respectively. The homogeneous nature of these reactions has been experimentally tested.

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Effects of isotopic substitution and vibrational excitation on reaction rates. Kinetics of OH(ν= 0, 1) and OD(ν= 0, 1) with HCl and DCl

Cited by 42 publications

References 3 publications

Reactions of OH radicals with inorganic compounds in the gas phase

Reactions of OH radicals with inorganic compounds in the gas phase

Kinetics of the OH+HCl→H₂O+Cl reaction: Rate determining roles of stereodynamics and roaming and of quantum tunneling

Study of the reactions of OH with HCl, HBr, and HI between 298 K and 460 K

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Effects of isotopic substitution and vibrational excitation on reaction rates. Kinetics of OH(ν= 0, 1) and OD(ν= 0, 1) with HCl and DCl

Cited by 42 publications

References 3 publications

Reactions of OH radicals with inorganic compounds in the gas phase

Reactions of OH radicals with inorganic compounds in the gas phase

Kinetics of the OH+HCl→H2O+Cl reaction: Rate determining roles of stereodynamics and roaming and of quantum tunneling

Study of the reactions of OH with HCl, HBr, and HI between 298 K and 460 K

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Kinetics of the OH+HCl→H₂O+Cl reaction: Rate determining roles of stereodynamics and roaming and of quantum tunneling