Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship: An update

doi:10.1016/1352-2310(95)00069-B

Atmospheric Environment

Volume 29, Issue 14, 1995, Pages 1685-1695

https://doi.org/10.1016/1352-2310(95)00069-B Get rights and content

Abstract

The structure-reactivity approach proposed by Atkinson (1986, Chem. Rev. 86, 69-201) and extended by Atkinson (1987, Int. J. Chem. Kinet. 19, 799-828) for the calculation of rate constants for the gas-phase reactions of the OH radical with organic compounds has been re-investigated using the presently available database. Substituent group factors for several new groups are derived, including those for fluorinated eithers. Using a large fraction of the available database to derive the parameters needed to calculate the OH radical reaction rate constants, the 298 K rate constants of ∼90% of approximately 485 organic compounds are predicted to within a factor of 2 of the experimental values. Disagreements between calculated and experimental rate constants most commonly occur for halogen-containing compounds, and in particular for haloalkanes, haloalkenes and halogenated ethers. Disagreements also arise for ethers, especially for polyethers and cycloethers. The present estimation technique is reasonably reliable when used within the database used in its derivation, but extrapolation to organic compounds outside of this database results in a lack of assurance of its reliability, and its use for organic compounds which belong to classes other than those used in its development is discouraged.

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^†: Also at Department of Soil and Environmental Sciences.

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Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship: An update

Abstract

Kinetics and mechanisms of the gasphase reactions of the hydroxyl radical with organic compounds under atmospheric conditions

Chem. Rev.

A structure-activity relationship for the estimation of rate constants for the gas-phase reactions of OH radicals with organic compounds

Int. J. Chem. Kinet.

Atmospheric transformations of automotive emissions

Estimation of gas-phase hydroxyl radical rate constants for organic chemicals

Envir. Toxicol. Chem.

Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with organic compounds

J. phys. chem. Ref. Data

Atmospheric lifetimes of dibenzo-pdioxins and dibenzofurans

Sci. Total Envir.

Gas-phase tropospheric chemistry of organic compounds

J. phys. chem. Ref. Data

OH radical reaction rate constants for polycyclic alkanes: effects of ring strain and consequences for estimation methods

Int. J. Chem. Kinet.

Atmospheric processes

Envir. Sci. Technol.

The long-range transport of organic compounds

Kinetics of the gas-phase reactions of the hydroxyl radical with naphthalene, phenanthrene, and anthracene

Envir. Sci. Technol.

Transition-state-theory calculations for reactions of OH with haloalkanes

J. phys. Chem.

Empirical correlations for rate coefficients for reactions of OH with haloalkanes

J. phys. Chem.

Reactions of hydrofluorocarbons and hydrochlorofluorocarbons with the hydroxyl radical

Atmospheric Environment

The gas phase reactivity of aliphatic polyethers towards OH radicals: measurements and predictions

Int. J. Chem. Kinet.

Flash photolysis resonance fluorescence investigation of the gas-phase reactions of hydroxyl radicals with cyclic ethers

J. phys. Chem.

Organic photochemistry. 20. A method for estimating gas-phase rate constants for reactions of hydroxyl radicals with organic compounds from their relative rates of reaction with hydrogen peroxide under photolysis in 1,1,2-trichlorotrifluoroethane solution

Envir. Sci. Technol.

Predicting gas-phase organic molecule reaction rates using linear free-energy correlations. I. O(3P) and OH addition and abstraction reactions

Int. J. Chem. Kinet.

Kinetics of the atmospherically important gas-phase reactions of a series of trimethyl phosphorothioates

Archs. Envir. Contam. Toxicol.

Atmospheric reactions of a series of dimethyl phosphoroamidates and dimethyl phosphorothioamidates

Envir. Sci. Technol.

Atmospheric Chemical Compounds: Sources, Occurrence, and Bioassay

Environmental persistance of organic compounds estimated from structure-reactivity and linear free-energy relationshipsun—saturated aliphatics

Atmospheric Environment

Predicting gas-phase organic molecule reaction rates using linear free-energy correlations. I. O(³P) and OH addition and abstraction reactions