Section: 5 | Chemical Reaction Rate Constants for Atmospheric Studies |
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John R. Rumble, ed., CRC Handbook of Chemistry and Physics, 102nd Edition (Internet Version 2021), CRC Press/Taylor & Francis, Boca Raton, FL.
If a specific table is cited, use the format: "Physical Constants of Organic Compounds," in CRC Handbook of Chemistry and Physics, 102nd Edition (Internet Version 2021), John R. Rumble, ed., CRC Press/Taylor & Francis, Boca Raton, FL.

CHEMICAL REACTION RATE CONSTANTS FOR ATMOSPHERIC STUDIES

James B. Burkholder and Michael J. Kurylo

These tables present evaluated rate constants and equilibrium constants for bimolecular and termolecular reactions of a wide variety of species important in understanding and modeling the chemistry of the different components of the Earth's atmosphere. The data in these tables are taken from the latest data tables produced by the NASA Panel for Data Evaluation (Ref. 20). For a complete history of the Panel and its predecessors, please see the Introduction to this document in the Online Edition of the CRC Handbook available at <http://www.hbcponline.com/> or Refs. 1-20 below.

Bimolecular reaction rate constants

In Tables 1a through 1l, rate constants for bimolecular reactions are grouped into the following classes, with reaction constants for each class given in a separate table as follows. 

Table No.  Contents
1a Ox
1b O(1D)
1c Singlet O2
1d HOx
1e NOx
1f Organic compounds
1g FOx
1h ClOx
1i BrOx
1j IOx
1k SOx
1l Metals

The tables contain recommended bimolecular reaction rate constants k(T) at temperature in Arrhenius form,

k(T) = A × exp(–E/RT)   (1)

The parameters for equation 1 given in Tables 1a to 1l are defined as follows. 

Column heading Definition
Reaction Molecular formulas of chemical reactants and products; tables are divided into reactant families; for O(1D), branching ratios are given for each reaction pathway
A Arrhenius pre-exponential factor, in units of cm3 molecule-1 s-1
E/R Recommended temperature dependence (“activation temperature”), in K
k298 Recommended rate constant at 298 K, in of units cm3 molecule-1 s-1
f298 Rate constant uncertainty factor at 298 K
g Parameter used to calculate the rate constant uncertainty at temperatures other than 298 K

The temperature ranges shown for each reaction indicate the range for the available experimental data. This is not necessarily the range of temperature over which the recommended Arrhenius parameters are applicable. See the corresponding note in Ref. 20 for each reaction for such information.

The parameters f298 and g can be used to calculate the estimated rate constant uncertainty over the recommended temperature range from the following expression:

f(T) = f298 × exp│g × {1/T – 1/298}│    (2)

where the exponent is an absolute value.

Note that f298 and g have been defined to correspond to approximately one standard deviation. Hence, f(T) yields a similar uncertainty interval. The more commonly used 95% confidence limits at a given temperature can be obtained by multiplying and dividing the recommended value of the rate constant at that temperature by the factor f2(T). It should be emphasized that the parameter g has been defined for use with f298 in the above expression and should not be interpreted as the uncertainty in the Arrhenius activation temperature (E/R).

The uncertainty represented by f(T) is normally symmetric; i.e., the rate constant may be greater than or less than the recommended value, k(T) by the factor f(T). In a few cases, asymmetric uncertainties are given in the temperature coefficient. For these cases, the factors by which a rate constant is to be multiplied or divided to obtain, respectively, the upper and lower limits are not equal, except at 298 K where the factor is simply f298.

Termolecular reaction rate constants

Table 2.1 gives rate constants for the termolecular reactions, which have a more complicated dependence on temperature and pressure. Hence, recommendations are made for the low-pressure limiting rate constant k0(T) at temperature and for the high-pressure limiting rate constant  k(T), also at temperature T,  as well as the parameters required to obtain the effective second-order rate constant for a given temperature and pressure.

For the low-pressure limit, the following equation holds:

k0(T) = k0298 (T/298)-n    (3)

Similarly, for the high-pressure limit, the equation is as follows:

k(T) = k298 (T/298)-m    (4)

The parameters for equations 3 and 4 are given in Table 2.1 and are defined as follows.

Column heading Definition
Reaction Molecular formulas of chemical reactants and products; the table is divided into reactant families
k0298
Low-pressure rate constant for the termolecular reaction at 298 K, in units of cm6 molecule-2 s-2
n Exponent for low-pressure temperature dependence
k298 High-pressure rate constant for the termolecular reaction at 298 K, in units of cm6 molecule-2 s-2
m Exponent for high-pressure temperature dependence
k(T,[M]) (298 K, 1 Atm) Bimolecular rate coefficient calculated at 298 K and 1 Atm using the coefficients given in the other columns, in units cm3 molecule-1 s-1
f298 Rate constant uncertainty factor at 298 K
g Parameter used to calculate the rate constant uncertainty at temperatures other than 298 K

More complete details on the equations in which these parameters are used are available in Ref. 20.

Rate constants for chemical activation reactions

Table 2.2 contains rate constants for chemical activation reactions. 

For the low-pressure limit, the following equation holds:

k0(T) = k0298 (298/T)n (5)

Similarly, for the high-pressure limit, the equation is as follows.

k(T) = k298 (298/T)m (6)

Some association reactions produce not only recombination product(s) but also additional products that appear to originate from a simple bimolecular reaction. In these cases, the total rate constant kTotal is equal to the sum of the rate constant for the association reaction kf(T,[M]) and the rate constant for the formation of products resulting from chemical activation kfCA(T,[M]). More details on this model are given in Ref. 20. kf(T,[M]) is a function of k0(T) and k(T) (Ref. 20). kfCA(T,[M]) is dependent on the second order rate constant at [M] = 0 (i.e., the zero-pressure intercept), given by the Arrhenius expression as follows.

kint(T) = Ae-BT (7)

The parameters for equations 5, 6, and 7 are given in Table 2.2 and are defined as follows.

Column heading Definition
Reactants, reaction type, and products Molecular formulas of chemical reactants; second line has products for association pathway; third line has products for dissociation pathway
k0298 Low-pressure rate constant for the termolecular reaction at 298 K, in units of cm6 molecule-2 s-2
n Exponent for low-pressure temperature dependence
k298 High-pressure rate constant for the termolecular reaction at 298 K, in units of cm6 molecule-2 s-2
m Exponent for high-pressure temperature dependence
A Arrhenius pre-exponential parameter for the rate coefficient in the zero-pressure limit, in units cm3 molecule-1 s-1
B Arrhenius temperature dependence parameter for the rate coefficient in the zero-pressure limit, in units K
kTotal (298 K, 1 Atm) Total rate constant at 298 K and 1 Atm, calculated with data in the other columns, in units cm3 molecule-1 s-1
f298 Rate constant uncertainty factor at 298 K
g A parameter used to calculate the rate constant uncertainty at temperatures other than 298 K

Equilibrium constants

Some three-body reactions form products that are thermally unstable at atmospheric temperatures. In such cases, the thermal decomposition reaction may compete with other loss processes, such as photodissociation or radical attack. Table 3 contains recommended equilibrium constants Keq(T) for several reactions that may fall into this category. Each recommended equilibrium constant is given in Arrhenius form and contains the information shown below.

Keq(T) = A exp(B/T) for temperatures 200 K <T< 300 K   (8)

The parameters for equation 8 are given in Table 3 and are defined as follows.

Column heading Definition
Reaction Molecular formulas of chemical reactants and products
A Arrhenius pre-exponential factor, in units of cm3 molecule-1
B Recommended temperature dependence (“activation temperature”), in K
Keq(298) Recommended equilibrium constant at 298 K, in units of cm3 molecule-1
f298 Equilibrium constant uncertainty factor at 298 K
g Parameter used to calculate the rate constant uncertainty (corresponding to approximately one standard deviation) at temperatures other than 298 K

As for bimolecular reactions, f298 is the approximate one standard deviation uncertainty factor in the equilibrium constant at 298 K, and g is the parameter to be used to calculate the equilibrium constant uncertainty at temperatures other than 298 K.

The process of evaluating chemical kinetic data does not conform to a simple set of mathematical rules. There is no “one-size-fits-all” algorithm that can be applied and each reaction must be examined on a case-by-case basis. Consideration of uncertainties in the kinetic and photochemical parameters used in atmospheric models plays a key role in determining the reliability of and uncertainty in the model results. Quite often the cause(s) of differences in experimental results from various laboratories cannot be determined with confidence and making recommendations for the uncertainties of the rate constant is often more difficult than making recommendations for the Arrhenius parameters themselves. In many cases, investigators suggest possible qualitative reasons for disagreements among data sets. Thus, data evaluators necessarily must consider a variety of factors in assigning a recommendation, including such aspects as the chemical complexity of the system, sensitivities and shortcomings of the experimental techniques employed, similarities or trends in reactivity, and the level of agreement among studies using different techniques.

These data are the recommendations that appear in the most current NASA JPL document (JPL 19-5) (Ref. 20). Readers should consult the Online Edition of the CRC Handbook (see footnotes) for the descriptive notes and bibliography associated with each line entry. In particular, the notes contain important details about the latest revision date, changes from previous evaluations, data formats, units, and the actual use of the recommendations and their indicated uncertainties.

  1. Hudson, R. D., Ed., Chlorofluoromethanes and the Stratosphere, NASA Reference Publication 1010, NASA, Washington, DC, 1977.
  2. Hudson, R. D., Reed, E. I., Eds., The Stratosphere: Present and Future, NASA Reference Publication 1049, NASA, Washington, DC, 1979.
  3. DeMore, W. B., Golden, D. M., Hampson, R. F., Howard, C. J., Kurylo, M. J., Margitan, J. J., Molina, M. J., Ravishankara, A. R., Watson, R. T., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation, Number 7, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 85-37, 1985. [https://doi.org/10.1002/kin.550171010]
  4. DeMore, W. B., Golden, D. M., Hampson, R. F., Howard, C. J., Kurylo, M. J., Molina, M. J., Ravishankara, A. R., Sander, S. P., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 8, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 87-41, 1987.
  5. DeMore, W. B., Golden, D. M., Hampson, R. F., Howard, C. J., Kurylo, M. J., Molina, M. J., Ravishankara, A. R., Sander, S. P., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 9, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 90-1, 1990.
  6. DeMore, W. B., Golden, D. M., Hampson, R. F., Howard, C. J., Kurylo, M. J., Molina, M. J., Ravishankara, A. R., Sander, S. P., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 10, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 92-20, 1992.
  7. DeMore, W. B., Golden, D. M., Hampson, R. F., Howard, C. J., Kurylo, M. J., Molina, M. J., Ravishankara, A. R., Sander, S. P., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 11, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 94-26, 1994.
  8. DeMore, W. B., Golden, D. M., Hampson, R. F., Howard, C. J., Kurylo, M. J., Molina, M. J., Ravishankara, A. R., Watson, R. T., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 5, Jet Propulsion Laboratory, California Institute of Technology, Pasadena CA, JPL Publication 82-57, 1982.
  9. DeMore, W. B., Golden, D. M., Hampson, R. F., Howard, C. J., Kurylo, M. J., Molina, M. J., Ravishankara, A. R., Watson, R. T., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 6, Jet Propulsion Laboratory, California Institute of Technology, Pasadena CA, JPL Publication 83-62, 1983.
  10. DeMore, W. B., Golden, D. M., Hampson, R. F., Kurylo, M. J., Margitan, J. J., Molina, M. J., Stief, L. J., Watson, R. T., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 4, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 81-3, 1981.
  11. DeMore, W. B., Sander, S. P., Golden, D. M., Hampson, R. F., Kurylo, M. J., Howard, C. J., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 12, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 97-4, 1997.
  12. DeMore, W. B., Stief, L. J., Kaufman, F., Golden, D. M., Hampson, R. F., Kurylo, M. J., Margitan, J. J., Molina, M. J., Watson, R. T., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation Number 2, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 79-27, 1979.
  13. Ko, M. K. W., Newman, P. A., Reimann, S., Strahan, S. E., Plumb, R. A., Stolarski, R. S., Burkholder, J. B., Mellouki, W., Engel, A., Atlas, E. L., Chipperfield, M., Liang, Q., Lifetimes of Stratospheric Ozone-Depleting Substances, Their Replacements, and Related Species, SPARC Report No. 6, WCRP-15/2013, 2013.
  14. Sander, S. P., Abbatt, J., Barker, J. R., Burkholder, J. B., Friedl, R. R., Golden, D. M., Huie, R. E., Kolb, C. E., Kurylo, M. J., Moortgat, G. K., Orkin, V. L., Wine, P. H., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 16, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 09-24, 2009.
  15. Sander, S. P., Abbatt, J., Barker, J. R., Burkholder, J. B., Friedl, R. R., Golden, D. M., Huie, R. E., Kolb, C. E., Kurylo, M. J., Moortgat, G. K., Orkin, V. L., Wine, P. H., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 17, Jet Propulsion Laboratory, California Institute of Technology,  Pasadena, CA, JPL Publication 10-6, 2011.
  16. Sander, S. P., Finlayson-Pitts, B. J., Friedl, R. R., Golden, D. M., Huie, R. E., Keller-Rudek, H., Kolb, C. E., Kurylo, M. J., Molina, M. J., Moortgat, G. K., Orkin, V. L., Ravishankara, A. R., Wine, P. H., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 06-2, 2006.
  17. Sander, S. P., Finlayson-Pitts, B. J., Friedl, R. R., Golden, D. M., Huie, R. E., Kolb, C. E., Kurylo, M. J., Molina, M. J., Moortgat, G. K., Orkin, V. L., Ravishankara, A. R., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 14, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 02-25, 2002.
  18. Sander, S. P., Friedl, R. R., DeMore, 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, Evaluation Number 13, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, JPL Publication 00-3, 2000.
  19. Burkholder, J. B., Sander, S. P., Barker, J. R., Huie, R. E., Kolb, C. E., Kurylo, M. J., Orkin, V. L., Wilmouth, D. M., and Wine, P. H., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 18, JPL Publication 15-10, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, 2015.
  20. Burkholder, J. B., Sander, S. P., Abbatt, J., Cappa, C., Crounse, J. D., Dibble, T. S., Huie, R. E., Kolb, C. E., Kurylo, M. J., Orkin, V. L., Percival, C. J., Wilmouth, D. M., and Wine, P. H., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 19, JPL Publication 19-5, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, 2019. <http://jpldataeval.jpl.nasa.gov/>

  • Refs. 3-12 and 14-20 are available at http://jpldataeval.jpl.nasa.gov.
  • Ref. 13 is available at http://www.sparc-climate.org/publications/sparc-reports/sparc-report-no6/.

TABLE 1a. Ox Bimolecular Reaction Rates of Atmospheric Importance



ReactionT/KA/cm3 molecule-1 s-1E/R/Kk298/cm3 molecule-1 s-1f298g
O + O3 → O2 + O2220–4098.0 × 10–1220608.0 × 10–151.1200


TABLE 1b. O(1D) Bimolecular Reaction Rates of Atmospheric Importance



ReactionBranching ratio*T/KA*/cm3 molecule-1 s-1E/R/K*k298*/cm3 molecule-1 s-1f298g
Continued on next page...
O(1D) + O2104–4243.3 × 10-11-553.95 × 10-111.110
→ O(3P) + O20
→ O(3P) + O2(1Σ)0.80 ± 0.20
→ O(3P) + O2(1Δ)0.20 (0.40–0)
O(1D) + O3103–3932.4 × 10-1002.4 × 10-101.250
→ O(3P) + O30
→ O2 + O20.50 ± 0.03
→ O2 + O(3P) + O(3P)0.50 ± 0.03
O(1D) + H2204–4201.2 × 10-1001.2 × 10-101.1550
→ O(3P) + H2<0.01
→ OH + H1.0 (+0/-0.01)
O(1D) + H2O217–4531.63 × 10-10-602.0 × 10-101.0820
→ O(3P) + H2O<0.003
→ O2 + H20.006 ± 0.006
→ OH + OH1.0 (+0/-0.015)
O(1D) + N2104–6732.15 × 10-11-1103.1 × 10-111.120
→ O(3P) + N21
O(1D) + N2O195–7191.19 × 10-10-201.27 × 10-101.125
→ O(3P) + N2O<0.01

  • *Italicized values are estimated.


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