Application of Tunable Diode Lasers to Laboratory Studies of Atmospheric Chemistry: Kinetics of the Reaction NO3+NO2→NO+NO2+O2
The use of a tunable diode laser spectrometer operated in second harmonic detection mode, in conjunction with a Fourier transform spectrometer, has allowed to obtain the rate constant kD of the reaction (D)NO3+NO2→NO+NO2+O2 as a function of the rate constant kC of the reaction (C) NO3+NO→2NO2. Using literature data of the kDxk±B product where k±B is the equilibrium constant for the reactions (+B, −B), NO3+NO2=M⇄N2O5+M, a value for k has also been determined. The value derived for kD using for kc (3±0.9)× 10−11 cm3 molec−1 s−1 results equal to (5.13±1.80)×l0−16 cm3 molec−1 s−1 and that for k±B equal to (2. 5′6±0.89)×1010 molec cm−3, both at 296 K. Advantages and limitations of the use of the TDL spectrometer in this study are discussed.
KeywordsLaser Emission Line Strength Tunable Diode Laser Steady State Situation Heterogeneous Decomposition
Unable to display preview. Download preview PDF.
- (2).Cox, R.A. and Jenkin, M.E. (1985). Kinetic studies of HO2 reactions using diode laser spectroscopy. Presented at the COST-611 Workshop, Cologne, 12–13 November.Google Scholar
- (3).Finlayson-Pitts, B.J. and Pitts, J.N. Jr. (1986) in Atmospheric Chemistry. Published by J. Wiley & Sons, p. 529.Google Scholar
- (7).Johnston, H.S. and Tao, Y.S. (1951). Thermal decomposition of nitrogen pentoxide at high temperatures, J. Am. Chem. Soc. 73, 2948–2949.Google Scholar
- (10).Chance, E.M., Curtis, A.R., Jones, I.P. and Kirby, C.R. (1977). AERE-report, Harwell, U.K.Google Scholar
- (12).Cappellani, F., Melandrone, G. and Restelli, G. (1987) in Monitoring of Gaseous Pollutants by Tunable Diode Lasers. R. Grisar, H. Preier, G. Schmidtke and G. Restelli Eds. published by Reidel Publishing Co., pp. 51–60.Google Scholar
- (15).Demore, W.B.et al. (1987). Chemical kinetics and photochemical data for use in stratospheric modelling. JPL-Publication 87–8.Google Scholar
- (19).Svensson, R. and Ljungstroem, E. (1988). A kinetic study of the decomposition of HNO3 and its reaction with NO. Int. J. Chem. Kinetics, in press.Google Scholar