3
R. P. Wayne, I. Barnes, P. Biggs, J. P. Burrows, C. E. Canosa-
Mas, J. Hjorth, G. Le Bras, G. K. Moortgat, D. Perner, G.
Poulet, G. Restelli and H. Sidebottom, Atmos. Environ. Part A,
1991, 25, 1.
constants k for the overall reactions of the NO radical with
the primary and secondary alcohols studied.
1
3
Reactions with chloroalkenes
4
5
6
R. Atkinson, J. Phys. Chem. Ref. Data, 1991, 20, 459.
R. Atkinson, J. Phys. Chem. Ref. Data, 1994, monograph 2, 1.
R. Atkinson, Gas-Phase T ropospheric Chemistry of Organic Com-
pounds, in V olatile Organic Compounds in the Atmosphere, Issues
in Environmental Science and T echnology, The Royal Society of
Chemistry, Cambridge, UK, 1995, vol. 4, pp. 65È89.
R. Atkinson, J. Phys. Chem. Ref. Data, 1997, 26, 215.
B. DÏAnna and C. J. Nielsen, J. Chem. Soc., Faraday T rans., 1997,
93, 3479.
The rate constants k obtained here for cis-1,2-dichloroethene,
1
1,1-dichloroethene, trichloroethene, tetrachloroethene and 3-
chloropropene (the latter relative to the rate constants for the
NO radical reactions with 2,3-dimethylbutane and propene)
3
7
8
are given in Table 4. As noted above, the rate constants for
cis-1,2-dichloroethene, trichloroethene and tetrachloroethene
are only of semi-quantitative quality, and only an upper limit
is cited for the tetrachloroethene rate constant. However, as
seen from Table 4, our rate constants for cis-1,2-dichloro-
ethene, trichloroethene and tetrachloroethene are consistent
with the literature data, and our rate constant for 1,1-
dichloroethene is in good agreement with the absolute and
relative rate data of Noremsaune et al.,22 but somewhat
higher than the relative rate constants of Atkinson et al.18 and
Noremsaune et al.20 and the absolute rate constant of
9
S. Langer and E. Ljungstro
1995, 91, 405.
10 S. Langer and E. Ljungstro
11 S. Langer and E. Ljungstro
m, J. Chem. Soc., Faraday T rans.,
m, Int. J. Chem. Kinet., 1994, 26, 367.
m, J. Phys. Chem., 1994, 98, 5906.
12 I. Wangberg, E. Ljungstrom, J, Hjorth and G. Ottobrini, J. Phys.
Chem., 1990, 94, 8036.
13 R. W. S. Aird, C. E. Canosa-Mas, D. J. Cook, G. Marston, P. S.
Monks, R. P. Wayne and E. Ljungstro
T rans., 1992, 88, 1093.
m, J. Chem. Soc., Faraday
14 E. Martinez, B. Cabanas, A. Aranda and R. P. Wayne, J. Chem.
Soc., Faraday T rans., 1996, 92, 53.
Cabanas Galan et al.21 For the reaction of the NO radical
3
15 E. Martinez, B. Cabanas, A. Aranda, P. Martin and R. P. Wayne,
J. Chem. Soc., Faraday T rans., 1996, 92, 4385.
with 3-chloropropene, our rate constants relative to 2,3-
dimethylbutane and propene are in agreement [the rate con-
stant relative to propene has signiÐcant uncertainties because
the rate constant ratio k (3-chloropropene)/k (propene) is
16 T. J. Wallington, R. Atkinson, A. M. Winer and J. N. Pitts, Jr.,
Int. J. Chem. Kinet., 1987, 19, 243.
17 S. Langer, E. Ljungstrom, I. Wangberg, T. J. Wallington, M. D.
Hurley and O. J. Nielsen, Int. J. Chem. Kinet., 1996, 28, 299.
18 R. Atkinson, S. M. Aschmann and M. A. Goodman, Int. J. Chem.
Kinet., 1987, 19, 299.
1
2
\0.1 and only a small fraction of the initial 3-chloropropene
reacted], and agree well with the previous measurement of
Atkinson et al.18 from this laboratory measured relative to the
19 Y. Andersson and E. Ljungstro m, Atmos. Environ., 1989, 23, 1153.
rate constant for the reaction of the NO radical with ethene.
However, our present and previous18 relative rate constants,
3
20 I. W. M. Noremsaune, J. Hjorth and C. J. Nielsen, J. Atmos.
Chem., 1995, 21, 223.
obtained using three di†erent reference compounds, are a
factor of ca. 8È10 lower than the absolute rate constant mea-
sured by Martinez et al.15 There is no obvious reason for this
discrepancy, although a chain reaction initiated by Cl atoms
in the discharge Ñow study15 may account, at least in part, for
this discrepancy. Further absolute measurements of the rate
21 B. Cabanas Galan, G. Marston and R. P. Wayne, J. Chem. Soc.,
Faraday T rans., 1995, 91, 1185.
22 I. W. M. Noremsaune, S. Langer, E. Ljungstrom and C. J.
Nielsen, J. Chem. Soc., Faraday T rans., 1997, 93, 525.
23 S. M. Aschmann and R. Atkinson, Int. J. Chem. Kinet., 1998, in
press.
24 R. Atkinson, C. N. Plum, W. P. L. Carter, A. M. Winer and J. N.
Pitts, Jr., J. Phys. Chem., 1984, 88, 1210.
constants for the reactions of the NO radical with 3-
3
chloropropene, 3-bromopropene and 3-iodopropene are
25 R. Atkinson, S. M. Aschmann and J. N. Pitts, Jr., J. Phys. Chem.,
1988, 92, 3454.
clearly needed.
26 E. S. C. Kwok, S. M. Aschmann, J. Arey and R. Atkinson, Int. J.
Chem. Kinet., 1996, 28, 925.
The authors gratefully thank the US Environmental Protec-
tion Agency, Office of Research and Development (Assistance
Agreement R-825252-01-0) for supporting this research. While
this research has been supported by the US Environmental
Protection Agency, it has not been subjected to Agency review
and, therefore, does not necessarily reÑect the views of the
Agency, and no official endorsement should be inferred.
27 A. A. Boyd, C. E. Canosa-Mas, A. D. King, R. P. Wayne and
M. R. Wilson, J. Chem. Soc., Faraday T rans., 1991, 87, 2913.
28 Y. Rudich, R. K. Talukdar, R. W. Fox and A. R. Ravishankara,
J. Phys. Chem., 1996, 100, 5374.
29 I. Barnes, V. Bastian, K. H. Becker and Z. Tong, J. Phys. Chem.,
1990, 94, 2413.
30 W. Braun, J. T. Herron and D. K. Kahaner, Int. J. Chem. Kinet.,
1988, 20, 51.
31 S. M. Aschmann and R. Atkinson, Atmos. Environ., 1995, 29,
2311.
References
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R. Atkinson, A. M. Winer and J. N. Pitts, Jr., Atmos. Environ.,
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U. Platt and F. Heintz, Isr. J. Chem., 1994, 34, 289.
2
Paper 7/08183I; Received 13th November, 1997
J. Chem. Soc., Faraday T rans., 1998, V ol. 94
1089