Kinetics and mechanism for the oxidation of 1,1,1‐trichloroethane

Linda Nelson; Imelda Shanahan; Howard W. Sidebottom; Jack Treacy; Ole J. Nielsen

doi:10.1002/kin.550220603

Kinetics and mechanism for the oxidation of 1,1,1‐trichloroethane

Linda Nelson^*, Imelda Shanahan, Howard W. Sidebottom, Jack Treacy, Ole J. Nielsen

^*Corresponding author for this work

Department of Chemistry

47 Citations (Scopus)

Abstract

The reaction mechanisms for oxidation of CH₃CCl₂ and CCl₃CH₂ radicals, formed in the atmospheric degradation of CH₃CCl₃ have been elucidated. The primary oxidation products from these radicals are CH₃CClO and CCl₃CHO, respectively. Absolute rate constants for the reaction of hydroxyl radicals with CH₃CCl₃ have been measured in 1 atm of Argon at 359, 376, and 402 K using pulse radiolysis combined with UV kinetic spectroscopy giving 𝓀(OH + CH₃CCl₃) = (5.4 ± 3) 10⁻¹² exp(−3570 ± 890/RT) cm³ molecule⁻¹ s⁻¹. A value of this rate constant of 1.3 × 10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ at 298 K was calculated using this Arrhenius expression. A relative rate technique was utilized to provide rate data for the OH + CH₃ CCl₃ reaction as well as the reaction of OH with the primary oxidation products. Values of the relative rate constants at 298 K are: 𝓀(OH + CH₃CCl₃) = (1.09 ± 0.35) × 10⁻¹⁴, 𝓀(OH + CH₃CClO) = (0.91 ± 0.32) × 10⁻¹⁴, 𝓀(OH + CCl₃CHO) = (178 ± 31) × 10⁻¹⁴, 𝓀(OH + CCl₂O) < 0.1 × 10⁻¹⁴; all in units of cm³ molecule⁻¹ s⁻¹. The effect of chlorine substitution on the reactivity of organic compounds towards OH radicals is discussed.

Original language	English
Journal	International Journal of Chemical Kinetics
Volume	22
Issue number	6
Pages (from-to)	577-590
Number of pages	14
ISSN	0538-8066
DOIs	https://doi.org/10.1002/kin.550220603
Publication status	Published - 1 Jan 1990

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title = "Kinetics and mechanism for the oxidation of 1,1,1‐trichloroethane",

abstract = "The reaction mechanisms for oxidation of CH3CCl2 and CCl3CH2 radicals, formed in the atmospheric degradation of CH3CCl3 have been elucidated. The primary oxidation products from these radicals are CH3CClO and CCl3CHO, respectively. Absolute rate constants for the reaction of hydroxyl radicals with CH3CCl3 have been measured in 1 atm of Argon at 359, 376, and 402 K using pulse radiolysis combined with UV kinetic spectroscopy giving 퓀(OH + CH3CCl3) = (5.4 ± 3) 10−12 exp(−3570 ± 890/RT) cm3 molecule−1 s−1. A value of this rate constant of 1.3 × 10−14 cm3 molecule−1 s−1 at 298 K was calculated using this Arrhenius expression. A relative rate technique was utilized to provide rate data for the OH + CH3 CCl3 reaction as well as the reaction of OH with the primary oxidation products. Values of the relative rate constants at 298 K are: 퓀(OH + CH3CCl3) = (1.09 ± 0.35) × 10−14, 퓀(OH + CH3CClO) = (0.91 ± 0.32) × 10−14, 퓀(OH + CCl3CHO) = (178 ± 31) × 10−14, 퓀(OH + CCl2O) < 0.1 × 10−14; all in units of cm3 molecule−1 s−1. The effect of chlorine substitution on the reactivity of organic compounds towards OH radicals is discussed.",

author = "Linda Nelson and Imelda Shanahan and Sidebottom, {Howard W.} and Jack Treacy and Nielsen, {Ole J.}",

year = "1990",

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T1 - Kinetics and mechanism for the oxidation of 1,1,1‐trichloroethane

AU - Nelson, Linda

AU - Shanahan, Imelda

AU - Sidebottom, Howard W.

AU - Treacy, Jack

AU - Nielsen, Ole J.

PY - 1990/1/1

Y1 - 1990/1/1

N2 - The reaction mechanisms for oxidation of CH3CCl2 and CCl3CH2 radicals, formed in the atmospheric degradation of CH3CCl3 have been elucidated. The primary oxidation products from these radicals are CH3CClO and CCl3CHO, respectively. Absolute rate constants for the reaction of hydroxyl radicals with CH3CCl3 have been measured in 1 atm of Argon at 359, 376, and 402 K using pulse radiolysis combined with UV kinetic spectroscopy giving 퓀(OH + CH3CCl3) = (5.4 ± 3) 10−12 exp(−3570 ± 890/RT) cm3 molecule−1 s−1. A value of this rate constant of 1.3 × 10−14 cm3 molecule−1 s−1 at 298 K was calculated using this Arrhenius expression. A relative rate technique was utilized to provide rate data for the OH + CH3 CCl3 reaction as well as the reaction of OH with the primary oxidation products. Values of the relative rate constants at 298 K are: 퓀(OH + CH3CCl3) = (1.09 ± 0.35) × 10−14, 퓀(OH + CH3CClO) = (0.91 ± 0.32) × 10−14, 퓀(OH + CCl3CHO) = (178 ± 31) × 10−14, 퓀(OH + CCl2O) < 0.1 × 10−14; all in units of cm3 molecule−1 s−1. The effect of chlorine substitution on the reactivity of organic compounds towards OH radicals is discussed.

AB - The reaction mechanisms for oxidation of CH3CCl2 and CCl3CH2 radicals, formed in the atmospheric degradation of CH3CCl3 have been elucidated. The primary oxidation products from these radicals are CH3CClO and CCl3CHO, respectively. Absolute rate constants for the reaction of hydroxyl radicals with CH3CCl3 have been measured in 1 atm of Argon at 359, 376, and 402 K using pulse radiolysis combined with UV kinetic spectroscopy giving 퓀(OH + CH3CCl3) = (5.4 ± 3) 10−12 exp(−3570 ± 890/RT) cm3 molecule−1 s−1. A value of this rate constant of 1.3 × 10−14 cm3 molecule−1 s−1 at 298 K was calculated using this Arrhenius expression. A relative rate technique was utilized to provide rate data for the OH + CH3 CCl3 reaction as well as the reaction of OH with the primary oxidation products. Values of the relative rate constants at 298 K are: 퓀(OH + CH3CCl3) = (1.09 ± 0.35) × 10−14, 퓀(OH + CH3CClO) = (0.91 ± 0.32) × 10−14, 퓀(OH + CCl3CHO) = (178 ± 31) × 10−14, 퓀(OH + CCl2O) < 0.1 × 10−14; all in units of cm3 molecule−1 s−1. The effect of chlorine substitution on the reactivity of organic compounds towards OH radicals is discussed.

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DO - 10.1002/kin.550220603

M3 - Journal article

AN - SCOPUS:0025446476

SN - 0538-8066

VL - 22

SP - 577

EP - 590

JO - International Journal of Chemical Kinetics

JF - International Journal of Chemical Kinetics

IS - 6

ER -

Kinetics and mechanism for the oxidation of 1,1,1‐trichloroethane

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