Determination of O2(1Sigma g +) and O2(1Delta g) yields in Cl + O2 and Cl + O3 reactions

The electronically excited oxygen molecules O2( /sub g/ ) and O2( /sub g/) were detected in the Cl + O2 reaction system by observing the 0-0 transitions at 762 nm and 1.27 m, respectively. The kinetics for the formation of O2( /sub g ) and O2( /sub g/ were studied by the flow-discharge/chemiluminescence detection method. From the dependence of O2( /sub g/ ) and O2( /sub g/) concentrations on (Cl.), (O2), pressures, and reaction times, the authors estimated the rate constants for the following reactions: Cl + ClO2 Cl2 + O2( /sub g/ ), k = 8.0 x 10 T cmT/(molecule.s); Cl + ClO2 Cl2 + O2( /sub g/), k = 2.0 x 10 S cmT/(molecule.s). The overall error limit is about a factor of 2. A failure to detect any O2( /sub g/ ) and O2( /sub g/) signals in the Cl + O3 reaction system led the authors to estimate the upper limits of the rate constants for the following reactions: Cl + O3 ClO + O2( /sub g/ ), k < 6.0 x 10 V cm3/(molecule.s); Cl + O3 dClO +d O2( /sub g/), k < 3.0 X 10 T cmT/molecule.s); ClO + ClO Cl2 + O2( /sub g/ ), k < 7.5 X 10 W cm3/(molecule.s). 30 references, 10 figures, 2 tables.