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Evaluated kinetic and
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for atmospheric
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Atmos. Chem. Phys. Discuss., 7, 16349–17067, 2007
www.atmos-chem-phys-discuss.net/7/16349/2007/
© Author(s) 2007. This work is licensed
under a Creative Commons License.
Atmospheric
Chemistry
and Physics
Discussions
Evaluated kinetic and photochemical data
for atmospheric chemistry: Volume IV –
gas phase reactions of organic halogen
species
R. Atkinson
1
, D. L. Baulch
2
, R. A. Cox
3
, J. N. Crowley
4
, R. F. Hampson
5
,
R. G. Hynes
6
, M. E. Jenkin
7
, M. J. Rossi
8
, J. Troe
9
, and T. J. Wallington
10
1
Air Pollution Research Center, University of California, Riverside, California 92521, USA
2
School of Chemistry, University of Leeds, Leeds LS2 9JT, UK
3
Centre for Atmospheric Science, Dept. of Chemistry, University of Cambridge, Lensfield
Road Cambridge CB2 1EP, UK
4
Max-Planck-Institut f
¨
ur Chemie, Division of Atmospheric Chemistry, Postfach 3060, 55020
Mainz, Germany
5
U.S. Dept. of Commerce, National Institute of Standards and Technology, Bldg. 221, Rm
A111, Gaithersburg, MD 20899, USA
6
CSIRO Energy Technology, Lucas Heights Science and Technology Centre, Building 2,
PMB7, Bangor, NSW 2234, Australia
16349
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Evaluated kinetic and
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R. Atkinson et al.
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7
Centre for Environmental Policy, Imperial College London, Silwood Park, Ascot, Berkshire,
SL5 7PY, UK
8
Laboratoire Pollution Atmospherique et Sol LPAS/ ENAC, CH-H5 Station 6 EPFL,CH 1015
Lausanne, Switzerland
9
Institute of Physical Chemistry, University of G
¨
ottingen, Tammannstr. 6, 37077 G
¨
ottingen,
Germany
10
Ford Motor Company, Research and Advanced Engineering, Mail Drop RIC-2122, Dearborn,
Michigan 48121-2053, USA
∗
(The IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry)
Received: 12 June 2007 – Accepted: 9 July 2007 – Published: 23 November 2007
Correspondence to: R. A. Cox (rac26@cam.ac.uk)
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Abstract
This article, the fourth in the series, presents kinetic and photochemical data sheets
evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric
Chemistry. It covers the gas phase and photochemical reactions of organic halogen
species, which were last published in 1997, and were updated on the IUPAC website5
in 2006. The article consists of a summary sheet, containing the recommended ki-
netic parameters for the evaluated reactions, and four appendices containing the data
sheets, which provide information upon which the recommendations are made.
1 Introduction
In the mid 1970s it was appreciated that there was a need for the establishment of an10
international panel to produce a set of critically evaluated rate parameters for reactions
of interest for atmospheric chemistry. To this end the CODATA Task Group on Chemical
Kinetics, under the auspices of the Inter national Council of Scientific Unions (ICSU),
was constituted in 1977 and tasked to produce an evaluation of relevant, available
kinetic and photochemical data. The first evaluation by this international committee15
was published in J. Phys. Chem. Ref. Data in 1980 (Baulch et al., 1980), followed by
Supplements in 1982 (Baulch et al., 1982) and 1984 (Baulch et al., 1984). In 1986 the
IUPAC Subcommittee on Data Evaluation superseded the original CODATA Task Group
for Atmospheric Chemistry, and the Subcommittee has continued its data evaluation
program with Supplements published in 1989 (Atkinson et al., 1989), 1992 (Atkinson et20
al., 1992), 1997 (Atkinson et al., 1997a), 1997 (Atkinson et al., 1997b), 1999 (Atkinson
et al., 1999) and 2000 (Atkinson et al., 2000). Following the last of these reports,
Supplement VIII (Atkinson et al., 2000), the evaluation has continued to be updated and
published on the worldwide web (http://www.iupac-kinetic.ch.cam.ac.uk/). The IUPAC
website hosts an interactive database with a search facility and implemented hyperlinks25
between the summary table and the data sheets, both of which can be downloaded
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as individual PDF or word files. In order to further enhance the accessibility of this
updated material to the scientific community, the evaluation is being published as a
series of articles in Atmospheric Chemistr y and Physics. This article is the fourth of
the series, Volume IV.
Summary of recommended rate coefficients for organic halogen reactions5
The ordering of families in the Summary Table is: FO
x
(Appendix 1), ClO
x
(Appendix 2),
BrO
x
(Appendix 3) and IO
x
(Appendix 4). The reactions are numbered sequentially for
the whole Volume. Within each family, reactions are listed in the order : O(
3
P), O(
1
D),
halogen atom, HO radical, NO
3
radical, halogen oxide reactions and photochemical
processes. Chemical reactions are listed as first reactant (usually an atom or radi-10
cal)+second reactant (usually a molecule). Each datasheet has a unique identifier:
“Volume: Appendix: reaction number”. For example, the first reaction in the summary
sheet below refers to Datasheet “IV.A1.1”. Photochemical reactions are listed at the
end of each family section.
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R. Atkinson et al.
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Table 1. Summary of recommended rate coefficients for organic halogen reac-
tions
Reaction k
298
Temp. dependence of Temp.
number Reaction cm
3
molecule
−1
s
−1
∆log k
a
298
k/cm
3
molecule
−1
s
−1
range/K ∆(E/R)/K
a
FO
x
Reactions - based on data sheets in Appendix 1, and on the IUPAC website updated in 2005.
1 O(
1
D)+COF
2
→ O(
3
P)+COF
2
5.2×10
−11
→ other products 2.2×10
−11
overall 7.4×10
−11
±0.3
2 O(
1
D)+CH
3
F → O(
3
P)+CH
3
F 2.7×10
−11
→ other products 1.2×10
−10
overall 1.5×10
−10
±0.15
3 O(
1
D)+CH
2
F
2
→ O(
3
P)+CH
2
F
2
3.6×10
−11
→ other products 1.5×10
−11
overall 5.1×10
−11
±0.3
4 O(
1
D)+CHF
3
→ O(
3
P)+CHF
3
8.2×10
−12
→ other products 9.1×10
−13
overall 9.1×10
−12
±0.15
5 O(
1
D)+CH
3
CH
2
F → O(
3
P)+CH
3
CH
2
F 4.7×10
−11
→ other products 2.1×10
−10
overall 2.6×10
−10
±0.3
6 O(
1
D)+CH
3
CHF
2
→ O(
3
P)+CH
3
CHF
2
1.1×10
−10
→ other products 9.2×10
−11
overall 2.0×10
−10
±0.3
7 O(
1
D)+CH
3
CF
3
→ O(
3
P)+CH
3
CF
3
→ other products 5.8×10
−11
±0.5
8 O(
1
D)+CH
2
FCF
3
→ O(
3
P)+CH
2
FCF
3
4.6×10
−11
→ other products 3.0×10
−12
overall 4.9×10
−11
±0.3
16353