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A relative rate study of the reaction of chlorine atoms (Cl) and hydroxyl radicals (OH) with a series of ethers

✍ Scribed by Peter McLoughlin; Rosaleen Kane; Imelda Shanahan

Publisher: John Wiley and Sons
Year: 1993
Tongue: English
Weight: 754 KB
Volume: 25
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550250302

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✦ Synopsis

Rate constants for the gas phase reactions of hydroxyl radicals and chlorine atoms with a number of ethers have been determined at 300 2 3 K and at a total pressure of 1 atmosphere. Both OH radical and chlorine atom rate constants were determined using a relative rate technique. Values for the rate constants obtained are as follows.

Compound

Hexane 5.53 2 1.55 _ _ _ . 2-Chloro ethyl methyl ether 4.92 ? 1.09 14.4 2 5.0 2,2-Dichloro ethyl methyl ether 2.37 2 0.50 4.4 2 1.6 2-Bromo ethyl methyl ether 6.94 2 1.38 16.3 2 5.4 2-Chloro,l,l,l-trifluoro ethyl ethyl ether <0.3 0.30 2 0.10 Isoflurane <0.3 <0.1 Enflurane <0.3 CO.1 Di-i-propyl ether 11.08 2 2.26 16.3 2 5.4 Diethyl ether __..

25.8 2 4.4

The above relative rate constants are based on the values of k(OH + pentane) = [3.94 2 0.981 X lo-'' and k(OH + diethyl ether) = [13.6 2 2.263 X lo-'' cm3 molecule-' s-l in the case of the hydroxyl reactions. In the case of the chlorine atom reactions, the above rate constants are based on values of k(C1 + ethane) = f5.84 2 0.881 X lo-" and k(C1 + diethyl ether) = L25.4 2 8.053 X lo-" cm3 molecule-' s-'. The quoted errors include 2 2 u from a least squares analysis of our slopes plus the uncertainty associated with the reference rate constants.

Atmospheric lifetimes calculated with respect to reaction with OH radicals are based on a tropospheric OH radical concentration of (7.7 2 1.4) x lo5 radicals ~m -~, and lifetimes with respect to reaction with C1 atoms are based on a tropospheric C1 atom concentration of 1 x lo3 atoms ~m -~.

Observed trends in the relative rates of reaction of hydroxyl radicals and chlorine atoms with the ethers studied is discussed. The significance of the calculated tropospheric lifetimes is also reviewed. 0 1993 John Wiley & Sons, Inc.

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