Hydrogen Atom Reactions with Molecular Halogens:  The Rate Constants for H + F<sub>2</sub> and H + Cl<sub>2</sub> at 298 K

Han, Jiande; Manke, Gerald C.

doi:10.1021/jp020293d

Cited by 8 publications

(5 citation statements)

References 43 publications

(65 reference statements)

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“…These reactions are known to generate the vibrationally excited HF molecules. The rate constant for H + F 2 was taken from Baulch et al, as recently recommended, while that for F + H 2 was taken from the data sheet of ref . The nascent vibrational distributions of HF from reactions and were adopted from the review of Manke and Hager, who have summarized the extensive studies conducted for these reactions in the 1970–80s.…”

Section: Kinetic Modelingmentioning

confidence: 99%

Chain Reaction Mechanism in Hydrogen/Fluorine Combustion

Matsugi¹,

Shiina²,

Tsuchiya³

et al. 2013

J. Phys. Chem. A

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Vibrationally excited species have been considered to play significant roles in H2/F2 reaction systems. In the present study, in order to obtain further understanding of the chain reaction mechanism in the combustion of mixtures containing H2 and F2, burning velocities for H2/F2/O2/N2 flames were measured and compared to that obtained from kinetic simulations using a detailed kinetic model, which involves the vibrationally excited species, HF(ν) and H2(ν), and the chain-branching reactions, HF(ν > 2) + F2 = HF + F + F (R1) and H2(ν = 1) + F2 = HF + H + F (R2). The results indicated that reaction R1 is not responsible for chain branching, whereas reaction R2 plays a dominant role in the chain reaction mechanism. The kinetic model reproduced the experimental burning velocities with the presumed rate constant of k2 = 6.6 × 10(-10) exp(-59 kJ mol(-1)/RT) cm(3) s(-1) for R2. The suggested chain-branching reaction was also investigated by quantum chemical calculations at the MRCI-F12+CV+Q/cc-pCVQZ-F12 level of theory.

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Section: Kinetic Modelingmentioning

confidence: 99%

Chain Reaction Mechanism in Hydrogen/Fluorine Combustion

Matsugi¹,

Shiina²,

Tsuchiya³

et al. 2013

J. Phys. Chem. A

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“…The H(D) atoms were generated in a low-power (∼30 W) microwave discharge through a 1% mixture of H 2 (D 2 ) in UHP He. The hydrogen atoms (or D atoms) reacted in the SR either with Cl 2 to give Cl (used for calibration of the acetonyl radical signal) or with NO 2 to give OH(OD) radicals: These reactions are fast [ k 3(H) = (2.52 ± 0.18) × 10 -11 cm 3 molecule -1 s -1 (ref ) and k 3(D) = 1.4 × 10 -11 cm 3 molecule -1 s -1 (ref ); k 4(H&D) = ∼1.3 × 10 -10 cm 3 molecule -1 s -1 (refs and )] and were driven to completion (>99%) in the SR {[NO 2 ] ≈ (2−5) × 10 12 and [Cl 2 ] ≈ (1−4) × 10 13 molecule cm -3 in the SR, reaction time (10−20 ms)}.…”

Section: Apparatusmentioning

confidence: 99%

Reaction of Hydroxyl Radical with Acetone. 2. Products and Reaction Mechanism

et al. 2003

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The products of the reaction of OH with acetone (OH + CH 3 C(O)CH 3 f products) were investigated using a discharge flow tube coupled to a chemical ionization mass spectrometer. It was shown that the yield of acetic acid from the reaction was less than 1% between 237 and 353 K. The yield of acetonyl radical was measured to be (96 ( 11)%, independent of temperature, between 242 and 350 K. The rate coefficients for the reaction were measured with this system to be the same as those reported in part 1 (J. Phys. Chem. A 2003, 107, 5014). The rate coefficients for the removal of OH (V ) 1) by acetone and acetone-d 6 were shown to be (2.67 ( 0.15) × 10 -11 and (3.45 ( 0.24) × 10 -11 cm 3 molecule -1 s -1 , respectively, at 295 K. It was shown that the enthalpy of reaction for the formation of an OH-acetone adduct is more than -8 kcal mol -1 (i.e., the adduct is bound by at most 8 kcal mol -1 ) at 203 K. On the basis of these observations and those from part 1, we deduce that the reaction of OH with acetone occurs through a hydrogen-bonded complex that gives almost exclusively CH 3 C(O)CH 2 and H 2 O. The atmospheric implications of our findings are discussed.

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“…The reactions of hydrogen atoms with halogen gases (F 2 , Cl 2 , and Br 2 ) are the prototypes for light–heavy–heavy atom–diatom reactions and are fundamentally important for understanding the chemical laser mechanism . Over the years, a large number of experimental and theoretical studies have been devoted to these reactions, both for kinetic and dynamical properties. − …”

Section: Introductionmentioning

confidence: 99%

Quantum Wave Packet Study of the H + Br₂ → HBr + Br Reaction on a New Ab Initio Potential Energy Surface

Shang

Shu

et al. 2021

J. Phys. Chem. A

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An accurate global potential energy surface (PES) for the HBr2 system has been constructed using the fundamental invariant neural network fitting method based upon 11 698 ab initio energies at the UCCSD(T)/CBS level of theory, with the spin–orbit coupling of the 2P3/2 orbit of the Br atom properly included. The time-dependent wave packet calculations have been performed to study the H + Br2 → HBr + Br reaction on the new PES. The total reaction probabilities for total angular momentum J = 0 for the ground initial state show no threshold due to the submerged barrier height (−0.351 kcal/mol) of the PES. The total integral cross sections (ICS) for reactant Br2 in ro-vibrational states (v 0 = 0, j 0 = 0, 10, 20, 30; v 0 = 1–5, j 0 = 0) were calculated for collision energy of up to 0.5 eV. It is found that the initial rotational excitation has a negligible effect on the ICS, and the initial vibrational excitation depresses the reactivity to some extent. The thermal rate constants for the title reaction in the temperature range of 100–1000 K were calculated from the Boltzmann averaging of the v 0 = 0–5 rate constants, which overestimated the experimental results to some extent.

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Hydrogen Atom Reactions with Molecular Halogens: The Rate Constants for H + F₂ and H + Cl₂ at 298 K

Cited by 8 publications

References 43 publications

Chain Reaction Mechanism in Hydrogen/Fluorine Combustion

Chain Reaction Mechanism in Hydrogen/Fluorine Combustion

Reaction of Hydroxyl Radical with Acetone. 2. Products and Reaction Mechanism

Quantum Wave Packet Study of the H + Br₂ → HBr + Br Reaction on a New Ab Initio Potential Energy Surface

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Hydrogen Atom Reactions with Molecular Halogens: The Rate Constants for H + F2 and H + Cl2 at 298 K

Cited by 8 publications

References 43 publications

Chain Reaction Mechanism in Hydrogen/Fluorine Combustion

Chain Reaction Mechanism in Hydrogen/Fluorine Combustion

Reaction of Hydroxyl Radical with Acetone. 2. Products and Reaction Mechanism

Quantum Wave Packet Study of the H + Br2 → HBr + Br Reaction on a New Ab Initio Potential Energy Surface

Contact Info

Product

Resources

About

Hydrogen Atom Reactions with Molecular Halogens: The Rate Constants for H + F₂ and H + Cl₂ at 298 K

Quantum Wave Packet Study of the H + Br₂ → HBr + Br Reaction on a New Ab Initio Potential Energy Surface