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Kinetics of hydroxyl radical reactions with formaldehyde and 1,3,5-trioxane between 290 and 600 K

✍ Scribed by S. Zabarnick; J. W. Fleming; M. C. Lin

Publisher: John Wiley and Sons
Year: 1988
Tongue: English
Weight: 644 KB
Volume: 20
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550200205

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✦ Synopsis

Absolute rate constants are measured for the reactions: OH + CH20, over the temperature range 296-576 K and for OH + 1,3,5-trioxane over the range 292-597 K. The technique employed is laser photolysis of H,O, or HNO, to produce OH, and laserinduced fluorescence to directly monitor the relative OH concentration. The results f i t t h e f o l l o w i n g A r r h e n i u s e q u a t i o n s : k ( C H 2 0 ) = ( 1 . 6 6 2 0 . 2 0 ) x 10 exp[-(l7O 2 8 0 ) / R T ] cm3 s-' and k(l,3,5-trioxane) = (1.36 t 0.20) X lo-" exp[-(460 t 100)/RT] cm3 s-'. The transition-state theory is employed to model the OH + CH,O reaction and extrapolate into the combustion regime. The calculated result covering 300 to 2500 K can be represented by the equation: k(CH,O) = 1.2 x exp(970/RT) cm3 s-'. An estimate of 91 t 2 kcal/mol is obtained for the first C-H bond in 1,3,5-trioxane by using a correlation of C-H bond strength with measured activation energies. 10 18 ~2 46

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