Abstract
The reaction with the OH radical constitutes the singlemost important removal process for most organiccompounds found in the atmosphere. Efforts to measurethe OH radical rate constants of all troposphericconstituents remain incomplete due to the largevariety of primary emitted compounds and theirtropospheric degradation products.Based on the measured rate constants of ≈250molecules with the OH radical, a structure-activityrelationship (SAR) for OH reactions has beendeveloped. The molecules used in the dataset includemost classes of tropospheric compounds (includingalkanes, alkenes, and oxygenated hydrocarbons), withthe exception of aromatic and halogen-containingcompounds. Using a new parameterization of themolecular structure, the overall agreement betweenmeasured values and those estimated using the SARdeveloped in this study is usually very good, with10% of the molecules showing deviations larger than50%. In particular, the estimated rate constants ofethers and ketones are in better agreement withexperimental data than with previous SARs (Kwok andAtkinson, Atmos. Environ. 29, 1685–1695,1995). Rate constants of organic nitrates werenot well described by the SAR used in thisstudy. The basic assumption that the additive rateconstant for a chemical group is only influenced byneighbouring functional groups did not allow a goodparameterization for the rate constants of organicnitrates. The use of a second parameter to alter thereactivity of C-H bonds in β-position to thefunctional group resulted in markedly better agreementbetween calculated and measured rate constants, butwas not extended due to the limited set of data. This indicates that strong electron withdrawing groups(e.g., nitrate groups) might influence the reactivityof C-H bonds that are not directly adjacent.
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Alvarado, A., Arey, J., and Atkinson, R., 1999: Kinetics of the gas-phase reactions of OH and NO3 radicals and O3 with the monoterpene oxidations products pinonaldehyde, caronaldehyde, and sabinaketone, J. Atmos. Chem. 31, 281-297.
Aschmann, S. M. and Atkinson, R., 1998: Rate constants for the gas-phase reactions of selected dibasic esters with the OH radical, Int. J. Chem. Kin. 30, 471-474.
Atkinson, R., 1986: Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with organic compounds under atmospheric conditions, Chem. Rev. 86, 69-201.
Atkinson, R., 1988: A structure-activity relationship for the estimation of rate constants for the gas phase reactions of OH radicals with organic compounds, Int. J. Chem. Kin. 19, 799-828.
Atkinson, R., 1994: Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data 2, 1-216.
Atkinson, R., 1997: Gas-phase tropospheric chemistry of organic compounds: 1. Alkanes and alkenes, J. Phys. Chem. Ref. Data 26, 215-290.
Atkinson, R., Aschmann, S. M., and Arey, J., 1990: Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296 ± 2 K, Atmos. Environ. 24, 2647-2654.
Atkinson, R., Aschmann, S. M., and Carter, W. P. L., 1983: Rate constants for the gas-phase reactions of OH radicals with a series of bi-and tricycloalkanes at 299±2 K, Int. J. Chem. Kin. 15, 37-50.
Atkinson, R., Aschmann, S. M., and Carter, W. P. L., 1984: Kinetics of the reactions of O3 and OH radicals with a series of dialkenes and trialkenes at 294 ± 2 K, J. Atmos. Chem. 16, 967-976.
Atkinson, R., Aschmann, S. M., and Pitts, J. N. J., 1986: Rate constants for the gas-phase reactions of the OH radical with a series of monoterpenes at 294 ± 1 K, Int. J. Chem. Kin. 18, 287-299.
Bennett, P. J. and Kerr, J. A., 1989: Kinetics of the reactions of hydroxyl radicals with aliphatic ethers studied under simulated atmospheric conditions, J. Atmos. Chem. 8, 87-94.
Benson, S. W., 1976: Thermochemical Kinetics, Wiley, New York.
Bevington, P. R. and Robinson, D. K., 1992: Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill, Inc., New York.
Bierbach, A., Barnes, I., and Becker, K. H., 1992: Rate coefficients for the gas-phase reactions of hydroxyl radicals with furan, 2-methylfuran, 2-ethylfuran and 2,5-dimethylfuran at 300 ± 2 K, Atmos. Environ. 26, 813-817.
Cohen, N. and Benson, S. W., 1987: Empirical correlations for rate coefficients for reactions of OH with haloalkanes, J. Phys. Chem. 91, 171-175.
Dagaut, P., Liu, R., Wallington, T. J., and Kurylo, M. J., 1989a: The gas phase reactivity of aliphatic polyethers towards OH radicals: Measurements and predictions, Int. J. Chem. Kin. 21, 1173-1180.
Dagaut, P., Liu, R., Wallington, T. J., and Kurylo, M. J., 1989b: Kinetic measurements of the gasphase reactions of OH radicals with hydroxy ethers, hydroxy ketones and keto ethers, J. Phys. Chem. 93, 7838-7840.
Dagaut, P., Liu, R., Wallington, T. J., and Kurylo, M. J., 1990: Flash photolysis resonance fluorescence investigation of the gas-phase reactions of hydroxyl radicals with cyclic ethers, J. Phys. Chem. 94, 1881-1883.
El Boudali, A., Le Calvé, S., Le Bras, G., and Mellouki, A., 1996: Kinetic studies of OH reactions with a series of acetates, J. Phys. Chem. 100, 12364-12368.
Frank, I., Parrinello, M., and Klamt, A., 1998: Insight into chemical reactions from first-principles simulations-the mechanism of the gas-phase reaction of OH radicals with ketones, J. Phys. Chem. 102, 3614-3617.
Gaffney, J. S. and Levine, S. Z., 1979: Predicting gas phase organic molecule reactions rates using linear free-energy correlations. I. O(3P) and OH addition and abstraction reactions, Int. J. Chem. Kin. 11, 1179-1209.
Glasius, M., Calogirou, A., Jensen, N. R., Hjorth, J., and Nielsen, C. J., 1997: Kinetic study of gas-phase reactions of pinonaldehyde and structurally related compounds, Int. J. Chem. Kin. 29, 527-533.
Güsten, H., Klasinc, L., and Maric, D., 1984: Predictions of the abiotic degradability of organic compounds in the troposphere, J. Atmos. Chem. 2, 83-93.
Hallquist, M., Wängberg, I., and Ljungstrom, E., 1997: Atmospheric fate of carbonyl oxidation products originating from alpha-pinene and Δ3-carene: Determination of rate of reaction with OH and NO3-radicals, UV absorption cross-sections and vapor pressures, Environ. Sci. Technol. 31, 3166-3172.
Heicklen, J., 1981: The correlation of rate coefficients for H-atom abstraction by HO radicals with C-H bond dissociation enthalpies, Int. J. Chem. Kin. 13, 651-665.
Jenkin, M. E., Saunders, S. M., and Pilling, M. J., 1997: The tropospheric degradation of volatile organic compounds: A protocol for mechanism development, Atmos. Environ. 31, 81-104.
Jolly, G. S., Paraskevopoulos, G., and Singleton, D. L., 1985: Rates of OH radical reactions. XII. The reactions of OH with c-C3H6, c-C5H10, and c-C7H14. Correlation of hydroxyl rate constants with bond dissociation energies, Int. J. Chem. Kin. 17, 1-10.
Kwok, E. S. C. and Atkinson, R., 1995: Estimation of hydroxyl radical reaction rate constants for gasphase organic compounds using a structure-reactivity relationship: an update, Atmos. Environ. 29, 1685-1695.
Le Calvé, S., Hitier, D., Le Bras, G., and Mellouki, A., 1998: Kinetic studies of OH reactions with a series of ketones, J. Phys. Chem. 102, 4579-4584.
Le Calvé, S., Le Bras, G., and Mellouki, A., 1997: Kinetic studies of OH reactions with a series of methyl esters, J. Phys. Chem. 101, 9137-9141.
Mallard, W. G., Westley, F., Herron, J. T., and Hampson, R. F., 1994: NIST chemical kinetics database-version 6.0, in W. G. Mallard (ed.), Chemical Kinetics and Thermodynamic Division-NIST, Gaithersburg, U.S.A.
Nelson, L., Rattigan, O., Neavyn, R., and Sidebottom, H., 1990: Absolute and relative rate constants for the reactions of hydroxyl radicals and chlorine atoms with a series of aliphatic alcohols and ethers at 298 K, Int. J. Chem. Kin. 22, 1111-1126.
Peeters, J., Boullart, W., Pultau, V., and Van Hoeymissen, J., 1996: Laboratory studies on the tropospheric degradation mechanism of biogenic VOCs: Isoprene and DMS, EV5V-CT91-0038, European Community.
Percival, C. J., Marston, G., and Wayne, R. P., 1995: Correlations between rate parameters and calculated molecular properties in the reactions of the hydroxyl radical with hydrofluorocarbons, Atmos. Environ. 29, 301-311.
Porter, E., Wenger, J., Treacy, J., Sidebottom, H., Mellouki, A., Teton, S., and Le Bras, G., 1997: Kinetic studies on the reactions of hydroxyl radicals with diethers and hydroxyethers, J. Phys. Chem. 101, 5770-5775.
Vaghjiani, G. L., and Ravishankara, A. R., 1989: Kinetics and mechanism of OH reaction with CH3OOH, J. Phys. Chem. 93, 1948-1959.
Walker, R.W., 1985: Temperature coefficients for reactions of OH radicals with alkanes between 300 and 1000K, Int. J. Chem. Kin. 17, 573-582.
Wallington, T. J. and Kurylo, M. J., 1987: Flash photolysis resonance fluorescence investigation of the gas-phase reactions of OH radicals with a series of aliphatic ketones over the temperature range 240–440 K, J. Phys. Chem. 91, 5050-5054.
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Neeb, P. Structure-Reactivity Based Estimation of the Rate Constants for Hydroxyl Radical Reactions with Hydrocarbons. Journal of Atmospheric Chemistry 35, 295–315 (2000). https://doi.org/10.1023/A:1006278410328
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DOI: https://doi.org/10.1023/A:1006278410328