✦ LIBER ✦

The Dependence on H2O and on NH3 of the Kinetics of the self-reaction of HO2 in the gas-phase formation of HO2·H2O and HO2·NH3 complexes

✍ Scribed by Edwin J. Hamilton Jr.; Ruey-Rong Lii

Publisher: John Wiley and Sons
Year: 1977
Tongue: English
Weight: 538 KB
Volume: 9
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550090604

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✦ Synopsis

Electron pulse radiolysis a t -298'K of 2 atm Hz containing 5 torr 0 2 produces HOz free radical whose disappearance by reaction (I), HOz + HOz -HzOz + 0 2 , is monitored by kinetic spectrophotometry a t 230.5 nm. Using a literature value for the HOz absorption cross section, the values k = 2.5 X cm3/molec.sec, which is in reasonable agreement with two earlier studies, and G(H) -< G(H02) N 13 are obtained. In the presence of small amounts of added HzO or NH3, the observed second-order decay rate of the HOz signal is found to increase by up to a factor of -2.5. A proposed kinetic model quantitatively explains these data in terms of the formation of previously unpostulated 1:l complexes, HOz + H20 s HOrHzO (4a) and HOz + NH3 F? HOrNH3 (4b), which are more reactive than uncomplexed HOz toward a second uncomplexed HOn radical. The following equilibrium constants, which agree with independent theoretical calculations on these complexes, are derived from the data: 2 X 5 Kqa 5 6.3 X cm3/molec at 295'K and Kqb = 3.4 X cm"/molec a t 298 O K . Several deuterium isotope effects are also reported, including ka/ko = 2.8 for reaction (1). The atmospheric significance of these results is pointed out.

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