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Author(s):   Johnson, D.; Cassanelli, P.; Cox, R.A.
Title:   Correlation-type structure activity relationships for the kinetics of the decomposition of simple and beta-substituted alkoxyl radicals
Journal:   Atmos. Environ.
Volume:   38
Page(s):   1755 - 1765
Year:   2004
Reference type:   Journal article
Squib:   2004JOH/CAS1755-1765

Reaction:   n-C5H11O· → CH2O + n-C4H9
Reaction order:   1
Temperature:   190 - 330 K
Pressure:  1.01 bar
Rate expression:   1.0x1013 [s-1] e-55600 [J/mole]/RT
Category:  Theory
Data type:   Estimated: thermochemical, kinetic, or other
Comments:   The authors developed a structure activity relationship (SARs) for the estimation of rate data for the decomposition of RO to alkyl radical and carbonyl fragments. The SARs are based upon strong, non-linear, correlations between the logarithm of measured room temperature rate coefficients and the average measured ionisation potential (IP) of the reaction products,. The considered compounds include simple unsubstituted, beta-chlorinated and beta-hydroxylated alkoxylradicals. Chemical activation processes in the decomposition chemistry are briefly discussed.

The temperature range over which the estimates are intended to be useful is not given, but the results are derived for atmospheric chemistry occurring in the troposphere through lower stratosphere. This is assumed by us to approimately cover 190 K to 330 K.

For the 10 simple and 11 heteroatom-substituted RO: species used to construct the correlations, 18(85%) of the room temperature rate coefficients predicted using the present method are within a factor of two of their measured (or theoretically calculated) values, and 100% are within a factor of three. The average ratio of measured to calculated rate coefficients is 0.9.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [s-1]
190 5.19E-3
200 3.01E-2
225 1.24E0
250 2.42E1
275 2.75E2
300 2.09E3
325 1.16E4
330 1.58E4