Atmospheric chemistry of 1,1,1,2-tetrachloroethane (CCl3CH2Cl): spectrokinetic investigation of the CCl3CClHO2 radical, its reactions with NO and NO2, and atmospheric fate of the CCl3CClHO radical

Trine E. Møgelberg; Merete Bilde; Jens Sehested; Timothy J. Wallington; Ole J. Nielsen

Atmospheric chemistry of 1,1,1,2-tetrachloroethane (CCl₃CH₂Cl): spectrokinetic investigation of the CCl₃CClHO₂ radical, its reactions with NO and NO₂, and atmospheric fate of the CCl₃CClHO radical

Trine E. Møgelberg, Merete Bilde, Jens Sehested^*, Timothy J. Wallington, Ole J. Nielsen

^*Corresponding author for this work

7 Citations (Scopus)

Abstract

A pulse radiolysis technique was used to study the ultraviolet absorption spectra of CCl₃CClH and CCl₃-CClHO₂ radicals, the kinetics of the self-reaction of CCl₃CClHO₂ radicals, and the kinetics of the reactions of CCl₃CClHO₂ with NO and NO₂ in the gas phase at 296 K. At 240 nm, σ(CCl₃CClH) = (303 ± 35) × 10^-20, and at 250 nm, σ(CCl₃CClHO₂) = (288 ± 48) × 10^-20 cm² molecule^-1. The observed rate constant for the self-reaction of CCl₃CClHO₂ radicals was (5.0 ± 1.2) × 10^-12 cm³ molecule^-1 s^-1. The rate constants for reactions of CCl₃CClHO₂ radicals with NO and NO₂ were k₃ > 9.0 × 10^-12 and k₄ = (8.9 ± 2.6) × 10^-12 cm³ molecule^-1 s^-1, respectively. A long path length Fourier transform infrared technique was used to show that at 295 K in 700 Torr total pressure of air 76 ± 3% of CCl₃CClHO radicals decornpose via C-C bond scission and 24 ± 3% undergo three-center intramolecular HCl elimination. As part of this work rate constants for the reaction of F and Cl atoms with CCl₃CH₂Cl were determined to be (6.4 ± 1.2) × 10^-12 and (5.7 ± 1.0) × 10^-14 cm³ molecule^-1 s^-1, respectively. The results are discussed with respect to the atmospheric chemistry of tetrachloroethane.

Original language	English
Journal	Journal of Physical Chemistry
Volume	100
Issue number	47
Pages (from-to)	18399-18407
Number of pages	9
ISSN	0022-3654
Publication status	Published - 21 Nov 1996

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Atmospheric chemistry of 1,1,1,2-tetrachloroethane (CCl₃CH₂Cl) : spectrokinetic investigation of the CCl₃CClHO₂ radical, its reactions with NO and NO₂, and atmospheric fate of the CCl₃CClHO radical. / Møgelberg, Trine E.; Bilde, Merete; Sehested, Jens et al.

In: Journal of Physical Chemistry, Vol. 100, No. 47, 21.11.1996, p. 18399-18407.

Research output: Contribution to journal › Journal article › Research › peer-review

@article{ff8e7129f74040668f3bb1d83ab90292,

title = "Atmospheric chemistry of 1,1,1,2-tetrachloroethane (CCl3CH2Cl): spectrokinetic investigation of the CCl3CClHO2 radical, its reactions with NO and NO2, and atmospheric fate of the CCl3CClHO radical",

abstract = "A pulse radiolysis technique was used to study the ultraviolet absorption spectra of CCl3CClH and CCl3-CClHO2 radicals, the kinetics of the self-reaction of CCl3CClHO2 radicals, and the kinetics of the reactions of CCl3CClHO2 with NO and NO2 in the gas phase at 296 K. At 240 nm, σ(CCl3CClH) = (303 ± 35) × 10-20, and at 250 nm, σ(CCl3CClHO2) = (288 ± 48) × 10-20 cm2 molecule-1. The observed rate constant for the self-reaction of CCl3CClHO2 radicals was (5.0 ± 1.2) × 10-12 cm3 molecule-1 s-1. The rate constants for reactions of CCl3CClHO2 radicals with NO and NO2 were k3 > 9.0 × 10-12 and k4 = (8.9 ± 2.6) × 10-12 cm3 molecule-1 s-1, respectively. A long path length Fourier transform infrared technique was used to show that at 295 K in 700 Torr total pressure of air 76 ± 3% of CCl3CClHO radicals decornpose via C-C bond scission and 24 ± 3% undergo three-center intramolecular HCl elimination. As part of this work rate constants for the reaction of F and Cl atoms with CCl3CH2Cl were determined to be (6.4 ± 1.2) × 10-12 and (5.7 ± 1.0) × 10-14 cm3 molecule-1 s-1, respectively. The results are discussed with respect to the atmospheric chemistry of tetrachloroethane.",

author = "M{\o}gelberg, {Trine E.} and Merete Bilde and Jens Sehested and Wallington, {Timothy J.} and Nielsen, {Ole J.}",

year = "1996",

month = nov,

day = "21",

language = "English",

volume = "100",

pages = "18399--18407",

journal = "Journal of Physical Chemistry",

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TY - JOUR

T1 - Atmospheric chemistry of 1,1,1,2-tetrachloroethane (CCl3CH2Cl)

T2 - spectrokinetic investigation of the CCl3CClHO2 radical, its reactions with NO and NO2, and atmospheric fate of the CCl3CClHO radical

AU - Møgelberg, Trine E.

AU - Bilde, Merete

AU - Sehested, Jens

AU - Wallington, Timothy J.

AU - Nielsen, Ole J.

PY - 1996/11/21

Y1 - 1996/11/21

N2 - A pulse radiolysis technique was used to study the ultraviolet absorption spectra of CCl3CClH and CCl3-CClHO2 radicals, the kinetics of the self-reaction of CCl3CClHO2 radicals, and the kinetics of the reactions of CCl3CClHO2 with NO and NO2 in the gas phase at 296 K. At 240 nm, σ(CCl3CClH) = (303 ± 35) × 10-20, and at 250 nm, σ(CCl3CClHO2) = (288 ± 48) × 10-20 cm2 molecule-1. The observed rate constant for the self-reaction of CCl3CClHO2 radicals was (5.0 ± 1.2) × 10-12 cm3 molecule-1 s-1. The rate constants for reactions of CCl3CClHO2 radicals with NO and NO2 were k3 > 9.0 × 10-12 and k4 = (8.9 ± 2.6) × 10-12 cm3 molecule-1 s-1, respectively. A long path length Fourier transform infrared technique was used to show that at 295 K in 700 Torr total pressure of air 76 ± 3% of CCl3CClHO radicals decornpose via C-C bond scission and 24 ± 3% undergo three-center intramolecular HCl elimination. As part of this work rate constants for the reaction of F and Cl atoms with CCl3CH2Cl were determined to be (6.4 ± 1.2) × 10-12 and (5.7 ± 1.0) × 10-14 cm3 molecule-1 s-1, respectively. The results are discussed with respect to the atmospheric chemistry of tetrachloroethane.

AB - A pulse radiolysis technique was used to study the ultraviolet absorption spectra of CCl3CClH and CCl3-CClHO2 radicals, the kinetics of the self-reaction of CCl3CClHO2 radicals, and the kinetics of the reactions of CCl3CClHO2 with NO and NO2 in the gas phase at 296 K. At 240 nm, σ(CCl3CClH) = (303 ± 35) × 10-20, and at 250 nm, σ(CCl3CClHO2) = (288 ± 48) × 10-20 cm2 molecule-1. The observed rate constant for the self-reaction of CCl3CClHO2 radicals was (5.0 ± 1.2) × 10-12 cm3 molecule-1 s-1. The rate constants for reactions of CCl3CClHO2 radicals with NO and NO2 were k3 > 9.0 × 10-12 and k4 = (8.9 ± 2.6) × 10-12 cm3 molecule-1 s-1, respectively. A long path length Fourier transform infrared technique was used to show that at 295 K in 700 Torr total pressure of air 76 ± 3% of CCl3CClHO radicals decornpose via C-C bond scission and 24 ± 3% undergo three-center intramolecular HCl elimination. As part of this work rate constants for the reaction of F and Cl atoms with CCl3CH2Cl were determined to be (6.4 ± 1.2) × 10-12 and (5.7 ± 1.0) × 10-14 cm3 molecule-1 s-1, respectively. The results are discussed with respect to the atmospheric chemistry of tetrachloroethane.

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M3 - Journal article

AN - SCOPUS:0003333161

SN - 0022-3654

VL - 100

SP - 18399

EP - 18407

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 47

ER -

Atmospheric chemistry of 1,1,1,2-tetrachloroethane (CCl₃CH₂Cl): spectrokinetic investigation of the CCl₃CClHO₂ radical, its reactions with NO and NO₂, and atmospheric fate of the CCl₃CClHO radical

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