Temperature dependence of the rate constant and product channels for the BrO + ClO reaction

Alan J. Hills; Ralph J. Cicerone; Jack G. Calvert; John W. Birks

doi:10.1021/j100318a032

Temperature dependence of the rate constant and product channels for the BrO + ClO reaction

Alan J. Hills, Ralph J. Cicerone, Jack G. Calvert, John W. Birks

Experimental Science Section

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12 Scopus citations

Abstract

We have measured the rate constant for the reactions BrO + ClO → Br + OClO (6a), BrO + ClO → Br + Cl + O₂ (6b), and BrO + ClO → BrCl + O₂ (6c) over the temperature range 241-408 K and found k₆ = (8.2 ± 1.0) × 10^-12 cm³ molecule^-1 s independent of temperature. Measurement of the individual product branching ratios yielded values for channels 6a, 6b, and 6c equal to 0.55 ± 0.10, 0.45 ± 0.10, and < 0.02, respectively. Measurements of ozone in the stratosphere over Antarctica have shown that the springtime ozone column has fallen 40% from 1960 to 1985. The reaction above could account for a large fraction of the springtime "ozone hole" reported recently, provided that at least 20 ppt of total inorganic bromine is present, and it may provide a source of chlorine dioxide of sufficient magnitude to explain the recent measurements of this species in the Antarctic stratosphere.

Original language	English
Pages (from-to)	1853-1858
Number of pages	6
Journal	Journal of Physical Chemistry
Volume	92
Issue number	7
DOIs	https://doi.org/10.1021/j100318a032
State	Published - 1988

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@article{8b2d551dabaf4047b6b084513a02b4be,

title = "Temperature dependence of the rate constant and product channels for the BrO + ClO reaction",

abstract = "We have measured the rate constant for the reactions BrO + ClO → Br + OClO (6a), BrO + ClO → Br + Cl + O2 (6b), and BrO + ClO → BrCl + O2 (6c) over the temperature range 241-408 K and found k6 = (8.2 ± 1.0) × 10-12 cm3 molecule-1 s independent of temperature. Measurement of the individual product branching ratios yielded values for channels 6a, 6b, and 6c equal to 0.55 ± 0.10, 0.45 ± 0.10, and < 0.02, respectively. Measurements of ozone in the stratosphere over Antarctica have shown that the springtime ozone column has fallen 40\% from 1960 to 1985. The reaction above could account for a large fraction of the springtime {"}ozone hole{"} reported recently, provided that at least 20 ppt of total inorganic bromine is present, and it may provide a source of chlorine dioxide of sufficient magnitude to explain the recent measurements of this species in the Antarctic stratosphere.",

author = "Hills, \{Alan J.\} and Cicerone, \{Ralph J.\} and Calvert, \{Jack G.\} and Birks, \{John W.\}",

year = "1988",

doi = "10.1021/j100318a032",

language = "English",

volume = "92",

pages = "1853--1858",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - Temperature dependence of the rate constant and product channels for the BrO + ClO reaction

AU - Hills, Alan J.

AU - Cicerone, Ralph J.

AU - Calvert, Jack G.

AU - Birks, John W.

PY - 1988

Y1 - 1988

N2 - We have measured the rate constant for the reactions BrO + ClO → Br + OClO (6a), BrO + ClO → Br + Cl + O2 (6b), and BrO + ClO → BrCl + O2 (6c) over the temperature range 241-408 K and found k6 = (8.2 ± 1.0) × 10-12 cm3 molecule-1 s independent of temperature. Measurement of the individual product branching ratios yielded values for channels 6a, 6b, and 6c equal to 0.55 ± 0.10, 0.45 ± 0.10, and < 0.02, respectively. Measurements of ozone in the stratosphere over Antarctica have shown that the springtime ozone column has fallen 40% from 1960 to 1985. The reaction above could account for a large fraction of the springtime "ozone hole" reported recently, provided that at least 20 ppt of total inorganic bromine is present, and it may provide a source of chlorine dioxide of sufficient magnitude to explain the recent measurements of this species in the Antarctic stratosphere.

AB - We have measured the rate constant for the reactions BrO + ClO → Br + OClO (6a), BrO + ClO → Br + Cl + O2 (6b), and BrO + ClO → BrCl + O2 (6c) over the temperature range 241-408 K and found k6 = (8.2 ± 1.0) × 10-12 cm3 molecule-1 s independent of temperature. Measurement of the individual product branching ratios yielded values for channels 6a, 6b, and 6c equal to 0.55 ± 0.10, 0.45 ± 0.10, and < 0.02, respectively. Measurements of ozone in the stratosphere over Antarctica have shown that the springtime ozone column has fallen 40% from 1960 to 1985. The reaction above could account for a large fraction of the springtime "ozone hole" reported recently, provided that at least 20 ppt of total inorganic bromine is present, and it may provide a source of chlorine dioxide of sufficient magnitude to explain the recent measurements of this species in the Antarctic stratosphere.

UR - https://www.scopus.com/pages/publications/0001109218

U2 - 10.1021/j100318a032

DO - 10.1021/j100318a032

M3 - Article

AN - SCOPUS:0001109218

SN - 0022-3654

VL - 92

SP - 1853

EP - 1858

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 7

ER -

Temperature dependence of the rate constant and product channels for the BrO + ClO reaction

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