Ab initio calculation on the rate constants of the reaction H2O2+Cl

Marouani, S.; Koussa, H.; Bahri, Mohamed; Hochlaf, M.; Batis, H.

doi:10.1016/j.theochem.2009.03.011

Cited by 5 publications

(4 citation statements)

References 39 publications

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“…Leu and DeMore 4 and Poulet et al 5 studied the kinetics of the reaction by discharge flow mass spectrometry at 295 and 298 K, respectively. Keyser 6 determined by the discharge flow resonance fluorescence technique the rate constant at 298 K and the Arrhenius expression over the temperature range 298− 424 K. Marouani et al 7 reported for the first time ab initio calculations of the Cl + H 2 O 2 → HCl + HO 2 and Cl + H 2 O 2 → HOCl + OH reactions using the post Hartree−Fock MCQDPT2//CASSCF approach and the aug-cc-pVTZ basis set. The kinetics of both reactions was investigated using transition state theory over a wide temperature range (200− 2500 K).…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of Hydrogen Peroxide with Br and I Atoms

et al. 2018

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The reaction mechanisms of Br and I atoms with HO have been investigated using DFT and high-level ab initio calculations. The H-abstraction and OH-abstraction channels were highlighted. The geometries of the stationary points were optimized at the B3LYP/aug-cc-pVTZ level of theory, and the energetics were recalculated with the coupled cluster theory. Spin-orbit coupling for each halogenated species was also explicitly computed by employing the MRCI level of theory. Thermochemistry for HOBr and HOI has been revised and updated standard enthalpies of formation at 298 K for HOBr and HOI are the following: ΔH°(HOBr) = (-66.2 ± 4.6) kJ mol and ΔH°(HOI) = (-66.8 ± 4.7) kJ mol. The rate constants have been estimated using transition state theory (TST), canonical variational transition state theory (CVT), and CVT with small curvature tunneling (CVT/SCT) over a wide temperature range (250-2500 K). For the direct abstraction mechanism, the overall rate constant at 300 K was predicted to be 2.58 × 10 and 7.42 × 10 cm molecules for the Br + HO and I + HO reactions, respectively. The modified Arrhenius parameters have been estimated for the overall reactions: k(T) = 4.80 × 10 T exp(-5.51 (kJ mol)/RT) and k(T) = 3.41 × 10 T exp(-56.32 (kJ mol)/RT).

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Section: Introductionmentioning

confidence: 99%

“…Because of their possible implications in the destruction of the stratospheric ozone layer, attention has been paid to the reactions of Cl and Br with H 2 O 2 − (Table ). Hydrogen peroxide is of atmospheric and combustion interests as it acts as a precursor for key species such as HO 2 and OH radicals.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Hydrogen Peroxide with Br and I Atoms

et al. 2018

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“…CH 3 is an important radical in various atmospheric processes and low‐temperature oxidation and its reactions with H, [28] OH, [29] F, [30] NO 2 [31] and CH 3 OH [32] have been investigated. The species of CH 3 , HOOH, CH 3 OOH and CH 3 CH 2 OOH have been found to coexist in the low temperature combustion of CH 4 and C 2 H 6 .…”

Section: Introductionmentioning

confidence: 99%

Kinetics of the Reactions of Methyl Radical with Hydrogen, Methyl and Ethyl Peroxides

et al. 2021

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The HOOH+CH3, CH3OOH+CH3 and CH3CH2OOH+CH3 reactions were characterized using accurate ab initio methods with reliable basis sets. The reaction rate constants were calculated by canonical variational transition state theory as applied to a complex mechanism involving the formation of reactant complexes. The formation of aldehyde or formaldehyde was observed when the CH3 radical attacks on the CH2 group in CH3CH2OOH or on the CH3 group in CH3OOH. The results showed that the channels of H‐abstraction from OH group are dominant channels at low temperature, while the channels of OH‐transfer to CH3 become predominant with increasing temperature. For the CH3OOH+CH3 reaction, the channel producing CH2O+OH and the OH‐transfer channel have a similar rate coefficient.

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“…此外, 在 298 K 时通道 R1 的速率常数 kR1为 1.60×10 -13 cm 3 •molecule -1 •s -1 , 与前人所报道的实验和理论值均较接近 3,4,6 , 证实本文所选用的 CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ 量子化学双水平方法描述 H2O2+Cl 气相反应是合适的. 由表 5 可知, 在计算温度范围内通道 RW1 和 RW2 的速率常数分别为 3.76×10 -18 -3.46×10 -17 cm 3 • molecule -1 • s -1 和 7.88 × 10 -19 -1.56 × 10 -16 cm 3 • molecule -1 •s -1 , 比相同温度下无水分子参与通道 R1 的速率常数 kR1小了 4.62×10 3 -7.79×10 3 和 9.75×10 4 -2.69× 10 5 倍, 说明经由通道 RW1 和 RW2 水分子对 H2O2+ Cl 反应的发生起负催化作用, 这与水分子在通道 RW1 和 RW2 中对产物 HO2+HCl 生成能垒的降低起 Keq(IM) is the equilibrium constant for the process of H2O2+Cl→ IM; k2(TS) is the rate constant for the process of IM→TS→IMF;kR1 is the rate constant of Channel R1; a ,b denote the values obtained from reference 3 and reference6 , respectively.…”

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Theoretical Study on the effect of a Single Water Molecule on the H<sub>2</sub>O<sub>2</sub>+Cl Gas Reaction

Xu¹,

Zhang²,

Wen-Bin³

et al. 2014

Acta Physico-Chimica Sinica

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The reaction mechanism and rate constant of the H2O2+Cl reaction, with and without a single water molecule, was investigated theoretically at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory. The calculated results show that there is only one channel for the formation of HO2 + HCl in the naked H2O2+Cl reaction with an apparent activation energy of 10.21 kJ•mol-1. When one water molecule is added, the product of the reaction does not change, but the potential energy surface of the reaction becomes complex, yielding three different channels RW1, RW2, and RW3. The single water molecule in the RW1 and RW2 reaction channels has a negative influence on reducing the reaction barrier for the formation of HO2 + HCl, whereas it has a positive influence in Channel RW3. Additionally, to estimate the importance of these processes in the atmosphere, their rate constants were evaluated using conventional

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Ab initio calculation on the rate constants of the reaction H2O2+Cl

Cited by 5 publications

References 39 publications

Reactivity of Hydrogen Peroxide with Br and I Atoms

Reactivity of Hydrogen Peroxide with Br and I Atoms

Kinetics of the Reactions of Methyl Radical with Hydrogen, Methyl and Ethyl Peroxides

Theoretical Study on the effect of a Single Water Molecule on the H<sub>2</sub>O<sub>2</sub>+Cl Gas Reaction

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