Atmospheric chemistry of chloroalkanes: Intramolecular elimination of HCl from chloromethoxy radicals over the temperature range 264-336 K

T. J. Wallington; J. J. Orlando; G. S. Tyndall

doi:10.1021/j100023a021

Atmospheric chemistry of chloroalkanes: Intramolecular elimination of HCl from chloromethoxy radicals over the temperature range 264-336 K

T. J. Wallington, J. J. Orlando, G. S. Tyndall

Experimental Science Section

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Abstract

The Cl atom-initiated oxidation of CH₃Cl was studied over the temperature range 264-336 K. The observed products, measured using Fourier transform infrared (FTIR) spectroscopy, were HC(O)Cl, CO, and HCl. At a given temperature and total pressure, the product ratio HC(O)Cl/CO increased linearly with O₂ partial pressure, reflecting a competition for available CH₂ClO radicals between decomposition and reaction with O₂: CH₂ClO + M → HCO + HCl + M(1); CH₂ClO + O₂ → HC(O)Cl + HO₂ (2). At 700 Torr total pressure the observed rate constant ratio k₂/k₁ was fit by the expression 5.6_-4.9⁺³³ × 10^-23 exp(3300 ± 600/T) cm³ molecule^-1. Assuming an activation energy of 1.5 ± 0.5 kcal mol^-1 for reaction 2, an activation energy of 8.6 ± 1.9 kcal mol^-1 is estimated for the intramolecular elimination of HCl via reaction 1.

Original language	English
Pages (from-to)	9437-9442
Number of pages	6
Journal	Journal of Physical Chemistry
Volume	99
Issue number	23
DOIs	https://doi.org/10.1021/j100023a021
State	Published - 1995

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@article{25149d434b1540518366abba9b51dd0b,

title = "Atmospheric chemistry of chloroalkanes: Intramolecular elimination of HCl from chloromethoxy radicals over the temperature range 264-336 K",

abstract = "The Cl atom-initiated oxidation of CH3Cl was studied over the temperature range 264-336 K. The observed products, measured using Fourier transform infrared (FTIR) spectroscopy, were HC(O)Cl, CO, and HCl. At a given temperature and total pressure, the product ratio HC(O)Cl/CO increased linearly with O2 partial pressure, reflecting a competition for available CH2ClO radicals between decomposition and reaction with O2: CH2ClO + M → HCO + HCl + M(1); CH2ClO + O2 → HC(O)Cl + HO2 (2). At 700 Torr total pressure the observed rate constant ratio k2/k1 was fit by the expression 5.6-4.9+33 × 10-23 exp(3300 ± 600/T) cm3 molecule-1. Assuming an activation energy of 1.5 ± 0.5 kcal mol-1 for reaction 2, an activation energy of 8.6 ± 1.9 kcal mol-1 is estimated for the intramolecular elimination of HCl via reaction 1.",

author = "Wallington, \{T. J.\} and Orlando, \{J. J.\} and Tyndall, \{G. S.\}",

year = "1995",

doi = "10.1021/j100023a021",

language = "English",

volume = "99",

pages = "9437--9442",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Atmospheric chemistry of chloroalkanes

T2 - Intramolecular elimination of HCl from chloromethoxy radicals over the temperature range 264-336 K

AU - Wallington, T. J.

AU - Orlando, J. J.

AU - Tyndall, G. S.

PY - 1995

Y1 - 1995

N2 - The Cl atom-initiated oxidation of CH3Cl was studied over the temperature range 264-336 K. The observed products, measured using Fourier transform infrared (FTIR) spectroscopy, were HC(O)Cl, CO, and HCl. At a given temperature and total pressure, the product ratio HC(O)Cl/CO increased linearly with O2 partial pressure, reflecting a competition for available CH2ClO radicals between decomposition and reaction with O2: CH2ClO + M → HCO + HCl + M(1); CH2ClO + O2 → HC(O)Cl + HO2 (2). At 700 Torr total pressure the observed rate constant ratio k2/k1 was fit by the expression 5.6-4.9+33 × 10-23 exp(3300 ± 600/T) cm3 molecule-1. Assuming an activation energy of 1.5 ± 0.5 kcal mol-1 for reaction 2, an activation energy of 8.6 ± 1.9 kcal mol-1 is estimated for the intramolecular elimination of HCl via reaction 1.

AB - The Cl atom-initiated oxidation of CH3Cl was studied over the temperature range 264-336 K. The observed products, measured using Fourier transform infrared (FTIR) spectroscopy, were HC(O)Cl, CO, and HCl. At a given temperature and total pressure, the product ratio HC(O)Cl/CO increased linearly with O2 partial pressure, reflecting a competition for available CH2ClO radicals between decomposition and reaction with O2: CH2ClO + M → HCO + HCl + M(1); CH2ClO + O2 → HC(O)Cl + HO2 (2). At 700 Torr total pressure the observed rate constant ratio k2/k1 was fit by the expression 5.6-4.9+33 × 10-23 exp(3300 ± 600/T) cm3 molecule-1. Assuming an activation energy of 1.5 ± 0.5 kcal mol-1 for reaction 2, an activation energy of 8.6 ± 1.9 kcal mol-1 is estimated for the intramolecular elimination of HCl via reaction 1.

UR - https://www.scopus.com/pages/publications/0000415657

U2 - 10.1021/j100023a021

DO - 10.1021/j100023a021

M3 - Article

AN - SCOPUS:0000415657

SN - 0022-3654

VL - 99

SP - 9437

EP - 9442

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 23

ER -

Atmospheric chemistry of chloroalkanes: Intramolecular elimination of HCl from chloromethoxy radicals over the temperature range 264-336 K

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