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The temperature dependence of the rate coefficients for β-hydroxyperoxy radical self reactions

✍ Scribed by Andrew A. Boyd; Robert Lesclaux

Publisher: John Wiley and Sons
Year: 1997
Tongue: English
Weight: 151 KB
Volume: 29
Category: Article
ISSN: 0538-8066
DOI: 10.1002/(sici)1097-4601(1997)29:5<323::aid-kin2>3.0.co;2-w

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✦ Synopsis

A laser-flash photolysis/UV absorption technique has been used to study the temperature dependence (from T ϭ 300 -470 K) of the self-reaction kinetics of representative primary, secondary, and tertiary ␤-hydroxyperoxy radicals:

The following Arrhenius expressions were derived for the rate coefficients of reactions (1) -(3) (in cm 3 molecule Ϫ1 s Ϫ1 ) and for the product branching ratios of reactions ( 1) and ( 2) as a function of temperature (all errors 1):

The calculated rate coefficients for reactions (1) -(3) at 298 K are therefore (in 10 Ϫ13 cm 3 molecule Ϫ1 s Ϫ1 ) 23 Ϯ 2, 6.7 Ϯ 1.3, and 0.040 Ϯ 0.012, respectively, which compare well with the values measured elsewhere at this temperature using a similar technique. The product branching ratios and the Arrhenius parameters are compared with those for other substituted and unsubstituted peroxy radical self reactions.

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