화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.106, No.36, 8378-8385, 2002
Bromine nitrate photochemistry: Quantum yields for O, Br, and BrO over the wavelength range 248-355 nm
A laser flash photolysis-resonance fluorescence technique has been employed to investigate the production of Br, O, and BrO from photodissociation of bromine nitrate (BrONO2) at wavelengths in the range 248355 run. The values obtained for the Br atom quantum yields are 0.35 +/- 0.08, 0.65 +/- 0.14, >0.62 +/- 0.11, and 0.77 +/- 0.19 at 248, 266, 308 and 355 nm, respectively. The values obtained for the 0 atom quantum yields are 0.66 +/- 0.15, 0.18 +/- 0.04, <0.13 +/- 0.03, and <0.02 at 248, 266, 308, and 355 nm, respectively. Quantum yields for BrO production were investigated at some of the above wavelengths by converting photolytically generated BrO to Br via the reaction BrO + NO --> Br + NO2. Measured BrO quantum yields are 0.37 +/- 0.12 at 266 nm and 0.23 +/- 0.08 at 355 nm. Uncertainties in the above quantum yields are estimates of absolute accuracy at the 95% confidence limit. No evidence for pressure-dependent quantum yields was observed over the range 20-200 Torr in N-2 bath gas. No evidence for temperature-dependent quantum yields was observed either, although only a few experiments were done at temperatures other than room temperature. The above results are considered in conjunction with recently reported NO3 quantum yields [Harwood; et al. J. Phys. Chem. A 1998, 102, 1309] in order to examine the role of BrONO2 photochemistry in the catalytic destruction of stratospheric ozone.