Kinetics of the Gas-Phase Reaction of OH + NO2
J. Phys. Chem. A, Vol. 105, No. 46, 2001 10543
form for use in atmospheric models and, as noted by Patrick
and Golden,28 provides a useful method of highlighting uncer-
tainties and ambiguities in experimental data. The exact formal-
ism for this parametrization and the physical significance of
the values of k0 and k∞ are topics of current debate.29 It now
seems reasonable to conclude, based on both the experimental
and theoretical data available, that the peroxynitrous acid
channel plays some role in the recombination reaction, but that
role is extremely uncertain. In our view the parameterization
for atmospheric modeling should be based primarily on the
available experimental data that has been obtained under
atmospheric conditions of gas composition, pressure, and
temperature. In more recent work, Donahue et al.3 have
measured the rate coefficient for the reaction of 18OH with NO2
as a route to the high-pressure limit for reaction 1. They
conclude that their results can reconcile the high-pressure data
with the remainder of the experimental data set. They note that
evaluation of the rate coefficient for reaction 1 has proven
difficult “despite a data set nearly without parallel in either scope
or quality”. We would also note that the database in a pressure
region of critical atmospheric interest between 200 and 760 Torr
is extremely limited. Our results suggest that the formation of
the peroxynitrous acid isomer cannot explain the discrepancies
in the experimental database. Given the importance of reaction
1 in tropospheric chemistry, the resolution of these discrepancies
in the rate coefficient at one atmosphere pressure in air is a
matter of some priority.
our data are fit by the values k1,0 ) [N2] 3.7 × 10-30 (T/300
K)-3.0 cm6 molecule-2 s-1 and k1,∞ ) 3.6 × 10-11 cm3
molecule-1 s-1
.
Acknowledgment. We thank Margaret Williams for assis-
tance with the low [NO2] experiments. We thank Neil Donahue,
David Golden, Horst Hippler, and Jurgen Troe for helpful
conversations and details of unpublished work. This work was
supported by the National Science Foundation through grant
ATM0002242.
References and Notes
(1) Wayne, P. R. Chemistry of Atmospheres, 3rd ed.; Oxford University
Press: New York, 2000.
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(3) Donahue, N. M.; Mohrschladt, R.; Dransfield, T. J.; Anderson, J.
G.; Dubey, M. K. J. Phys. Chem. A 2001, 105, 1515.
(4) Dransfield, T. J.; Donahue, N. M.; Anderson, J. G. J. Phys. Chem.
A 2001, 105, 1507.
(5) Golden, M. D.; Smith, G. P. J. Phys. Chem. A 2000, 104, 3991.
(6) Matheu, D. M.; Green, W. H., Jr. Int. J. Chem. Kinet. 2000, 32,
245.
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1998, 32, 694.
(8) Atkinson, R.; Baulch, D. L.; Cox, R. A.; Hampson, R. F., Jr.; Kerr,
J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data 1997, 26, 1329.
(9) Sander, S. P.; Friedl, R. R; De More, W. B.; Golden, D. M.; Kurylo,
M. J.; Hampson, R. F.; Huie, R. E.; Moortgat, G. K.; Ravishankara, A. R.;
Kolb, C. E.; Molina, M. J. Chemical Kinetics and Photochemical Data for
Use in Stratospheric Modeling, JPL 00-3; Jet Propulsion Laboratory:
Pasadena, Ca, 2000.
(10) De More, W. B.; Sander, S. P.; Golden, D. M.; Hampson, R. F.,
Jr.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.; Kolb, C. E.; Molina,
M. J. Chemical Kinetics and Photochemical Data for Use in Stratospheric
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Ltd.: Chichester, U.K., 1995.
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Conclusion
Our results suggest that the current JPL 2000 recommendation
underestimates the second-order constant for reaction 1 in air
at 298 and 273 K. Our results in air and N2 are in good
agreement with the measurements by Anastasi and Smith and
are well represented by the JPL 1994 recommendation. If the
formation of a weakly bound pernitrous acid intermediate were
significant, it could explain the difference between flow tube
and flash photolysis studies. Our work suggests that the recent
calculations by Golden and Smith on the rates of isomer
formation are not consistent with experimental observations and
cannot explain these discrepancies. Despite their similar mo-
lecular weights, O2 and N2 show measurably different third-
body efficiencies in the range of pressure between 30 and 600
Torr, O2 being less efficient than N2. We find no measurable
enhancement in the rate coefficient in the presence of 20 Torr
of water vapor at room temperature, suggesting that it does not
have an unusually high efficiency as a third body.
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(20) Hippler H., personal communication.
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K. L.; Anderson, J. G. J. Geophys. Res. 1997, 102, 5.
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(25) Davey, C. T.; Richardson, M. D.; Evanseck, J. D., unpublished
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(27) ACUCHEM/ACUPLOT; Braun, W., Herron, J. T., Kahaner, D.
National Bureau of Standards: Gaithersburg, MD, 1986.
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(29) Troe, J. Int. J. Chem. Kinet., accepted for publication.
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Note Added After Review. Since the review of this paper,
we have become aware of other work on this reaction. Hippler
and co-workers have revisited the reaction at ultrahigh pressure
and find that their previous work overestimated these rate
coefficients. In addition, they have observed double exponential
OH behavior at high temperature and pressure that they believe
is direct evidence for formation of both isomers.20 Golden and
Smith are currently revising their RRKM parameters for the
reaction in light of these results. Finally, Troe has reanalyzed
the data set for the forward and reverse reactions (1, -1) over
the temperature range 50-1400 K.29 He suggests that the use
of a temperature independent Fc of 0.4 and values of k1,0
)
)
[N2] 3.0 × 10-30 (T/300 K)-3.0 cm6 molecule-2 s-1 and k1,∞
3.6 × 10-11 cm3 molecule-1 s-1 are consistent with the experi-
mental database over the range 220-400 K. This expression
gives rate coefficients that lie below our data and gives a value
of 9.86 × 10-12 cm3 molecule-1 s-1 at 700 Torr of nitrogen,
9.5% lower than the value reported here. Using an Fc of 0.4,