7
8
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.
C. E. Canosa-Mas, M. D. King, R. Lopez, C. J. Percival, R. P.
Wayne, D. E. Shallcross, J. A. Pyle and V. Daele, J. Chem. Soc.,
Faraday T rans., 1996, 92, 2211.
W. B. DeMore, D. M. Golden, R. F. Hampson, M. J. Kurylo,
C. J. Howard, A. R. Ravishankara, C. E. Kolb and M. J. Molina,
Chemical Kinetics and Photochemical Data for Use in Strato-
spheric Modeling, JPL Publication 97-4, NASA, 1997.
is impacted by urban plumes. One of the conclusions drawn
from the SOS study is that NO reacts with methacrolein, and
3
that substantial amounts of MPAN are formed at night as a
product of this interaction.24
9
Conclusion
Rate coefficients for Ðve structurally similar a,b-unsaturated-
carbonyl compounds have been measured by relative and
absolute methods. The relative-rate measurements are in good
agreement with the results of previous studies where they
exist. However, the kinetic data obtained using the absolute
method are, in some cases, signiÐcantly higher than those
from the relative method. Secondary chemistry, together with
small amounts of reactive impurities, may be the cause of the
discrepancy. Product studies have enabled us to elucidate a
mechanism for the oxidation of methyl vinyl ketone and
10 T. Brauers and B. J. Finlayson-Pitts, Int. J. Chem. Kinet., 1997,
29, 665.
11 C. E. Canosa-Mas, S. J. Smith, S. J. Waygood and R. P. Wayne,
J. Chem. Soc., Faraday T rans. II, 1991, 87, 3473.
12 C. E. Canosa-Mas, S. J. Smith, S. Toby and R. P. Wayne, J.
Chem. Soc., Faraday T rans. II, 1988, 84, 263.
13 C. E. Canosa-Mas, M. D. King, D. E. Shallcross and R. P.
Wayne, Phys. Chem. Chem. Phys., 1999, 1, 2411.
14 E. C. Kwok, S. M. Aschmann, J. Arey and R. Atkinson, Int. J.
Chem. Kinet., 1996, 28, 925.
15 R. Atkinson, J. Phys. Chem. Ref. Data Monograph No. 1, 1989.
16 R. Atkinson, J. Phys. Chem. Ref. Data Monograph No. 2, 1994.
17 Y. Rudich, R. K. Talukdar, R. W. Fox and A. R. Ravishankara,
J. Phys. Chem., 1996, 100, 5374.
methacrolein by NO in the atmosphere. We conclude that
3
NO may be an important oxidant for methacrolein in the
3
urban boundary layer and may also be important where
18 R. Atkinson, J. Phys. Chem. Ref. Data, 1997, 26, 215.
19 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., 1991,
25A, 1.
urban plumes impact on forested areas.
Acknowledgements
20 B. DÏAnna and C. J. Nielsen, Int. J. Chem. Kinet., 1997, 93, 3479.
21 T. Berndt and O. Boge, Int. J. Chem. Kinet., 1997, 29, 755.
22 R. Martin, H. Westberg, E. Allwine, L. Ashman, C. Farmer and
B. Lamb, J. Atmos. Chem., 1991, 13, 1.
23 T. A. Biesenthal and P. B. Shepson, Geophys. Res. L ett., 1997, 24,
1375.
The authors thank NERC for support under grants GST/02/
1259 and GT24/95/LSAC/2. The Centre for Atmospheric
Science is a joint initiative of the Department of Chemistry
and the Department of Applied Mathematics.
24 T. K. Starn, P. B. Shepson, S. B. Bertman, J. S. White, B. G.
Splawn, D. D. Reimer, R. G. Zika and K. Olszyna, J. Geophys.
Res., 1998, 103, 22425.
25 T. K. Starn, P. B. Shepson, S. B. Bertman, D. D. Reimer, R. G.
Zika and K. Olszyna, J. Geophys. Res., 1998, 103, 22437.
26 G. Nouaime, S. B. Bertman, C. Seaver, D. Elyea, H. Huang, P. B.
Shepson, T. K. Starn, D. D. Reimer, R. G. Zika and K. Olszyna,
J. Geophys. Res., 1998, 103, 22463.
27 J. M. Roberts, J. Williams, K. Baumann, M. P. Buhr, P. D.
Goldan, J. Holloway, G. Hubler, W. C. Kuster. A. A. McKeen,
T. B. Ryerson, M. Trainer, E. J. Williams, F. C. Fehsenfeld, S. B.
Bertman, G. Nouaime, C. Seaver, G. Grodzinsky, M. Rogers and
V. L. Young, J. Geophys. Res., 1998, 103, 22473.
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