4
12
ORLANDO AND TYNDALL
Barriers to the rearrangement reaction of 8.4 ± 1.5 and
.7 ± 1.5 kcal/mole are estimated for the two radicals.
In considering data for the four structurally similar rad-
14. Ferenac, M. A.; Davis, A. J.; Holloway, A. S.; Dibble,
T. S. J Phys Chem A 2003, 107, 63.
7
1
1
1
5. Tyndall, G. S.; Pimentel, A. S.; Orlando, J. J. J Phys
Chem A 2004, 108, 6850.
6. Wallington, T. J.; Japar, S. M. Environ Sci Technol 1991,
•
ꢁ
ꢁ
icals (this work and [15]), RC(O)OCH(O )R , R, R =
H, CH3, it is seen that the rates of the rearrangement
reaction near 298 K increase by a factor of approxi-
mately 3–4 upon substitution of R = CH3 for R = H
and a factor of approximately 30 upon substitution of
25, 410.
7. Wallington, T. J.; Andino, J. M.; Potts, A. R.; Rudy, S.
J.; Siegl, W. O.; Zhang, Z.; Kurylo, M. J.; Huie, R. E.
Environ Sci Technol 1993, 27, 98.
ꢁ
ꢁ
R = CH3 for R = H, corresponding to a decreases in
the barrier height of approximately 1 and 2 kcal/mole,
respectively.
1
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The National Center for Atmospheric Research is operated by
the University Corporation for Atmospheric Research, under
the sponsorship of the National Science Foundation. The
authors thank Louisa Emmons and Doug Kinnison of NCAR
for their careful reading of the manuscript, G. Arg u¨ ello and F.
Malanca (Universidad Nacional de C o´ rdoba, Argentina) for
helpful conversations and for kindly providing their EoPAN
cross-section data, and two anonymous reviewers for their
helpful comments.
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International Journal of Chemical Kinetics DOI 10.1002/kin