Laboratory Kinetics

  • Georges Le Bras
Conference paper
Part of the Nato ASI Series book series (volume 54)

Abstract

The chemical composition of the atmosphere is determined by a combination of chemical reactions, radiation flux, and transport of species. Processes that occur in the gaseous phase in the stratosphere include thermal gas phase reactions and photochemical reactions. Heterogeneous reactions occur between gas phase molecules in/on aerosols and polar stratospheric clouds. Models that attempt to simulate the chemical composition of the stratosphere require a number of parameters that can be measured directly in the laboratory. In the gas phase, these include reaction rate constants, product branching ratios, and photolysis quantum yields. Gas phase reaction rate constants, if determined at stratospheric temperature and pressure, are used directly in models. Photochemical reactions or heterogeneous reactions the data measured in the laboratory require transformation prior to use in model calculations. For example, quantum yield calculations used in models need to account for solar flux. In the case of heterogeneous reactions, the nature, size and distribution of aerosol particles must be considered. Advances in experimental measurements and in the understanding of the measurements themselves, have improved atmospheric models.

Keywords

Combustion Methane Hydrolysis Microwave Sulfide 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Ball SM, G Hancock (1995) The relative quantum yields of O2 (a 1 D g ) from the photolysis of ozone at 227 K. Geophys Res Lett 22:1213–1216CrossRefGoogle Scholar
  2. Brown AC, CE Canosa-Mas, AD Parr, RP Wayne (1990) Laboratory studies of some halogenated ethanes and ethers: measurements of rates of reaction with OH and of infrared absorption cross-sections. Atmos Environ 24A:2499–2511Google Scholar
  3. Burkholder JB, RK Talukdar, AR Ravishankara, S Solomon (1993). Temperature dependence of the HNO3 UV absorption cross sections. J Geophys Res 98:22937 – 22948Google Scholar
  4. Connell PS, CJ Howard (1985) Kinetic study of the OH + HNO3 reaction. Int J Chem Kinet 17:17–31CrossRefGoogle Scholar
  5. DeMore WB, SP Sander, DM Golden, RF Hampson, M J Kurylo, CJ Howard, AR Ravishankara, CE Kolb, MJ Molina (1994) Chemical kinetics and photochemical data for use in stratospheric modeling. JPL Publication 94–26.Google Scholar
  6. Golden DM, LR Williams (1993) In: Low-temperature chemistry of the atmosphere. Moorgat GK, AJ Barnes, G Le Bras, JR Sodeau (eds) 235–262, Spring-Verlag New YorkGoogle Scholar
  7. Hanson DR, AR Ravishankara (1991) The reaction probabilities of ClONO2 and N2O5 on polar stratospheric cloud materials. J Geophys Res 96:5081–5090CrossRefGoogle Scholar
  8. Hanson DR, AR Ravishankara, S Solomon (1994) Heterogeneous reactions in sulfuric acid aerosols: A framework for model calculations. J Geophys Res 99:3615–3629CrossRefGoogle Scholar
  9. Hynes AJ, PH Wine, DH Semmes (1986) Kinetics and mechanism of OH reactions with organic sulfides. J Phys Chem 90:4148–4156CrossRefGoogle Scholar
  10. Hynes AJ, PH Wine, JM Nicovich (1988) Kinetics and mechanism of the reaction of OH with CS2 under atmospheric conditions. J Phys Chem 92:3846–3852CrossRefGoogle Scholar
  11. Jayne JT, P Davidovits, DR Worsnop, MS Zahniser, CE Kolb (1990) Uptake of SO2 by aqueous surface as a function of pH: The effect of chemical reaction at the interface. J Phys Chem 94:6041–6048CrossRefGoogle Scholar
  12. Keyser LK, SB Moore, M-T Leu (1991) Surface reaction and pore diffusion in flow-tube reactors. J Phys Chem 95:5496–5502CrossRefGoogle Scholar
  13. Kircher CK, SP Sander (1984) Kinetic and mechanism of HO2 and DO2 disproportion- ations. J Phys Chem 88:2082–2091CrossRefGoogle Scholar
  14. Larichev M, F Maguin, G Le Bras, G Poulet (1995) Kinetics and mechanism of the BrO + HO2 reaction. J Phys Chem 99:15911–15918CrossRefGoogle Scholar
  15. Rossi M (1995) Compilation of kinetic data on heterogeneous reactions. J Phys Chem Ref Data, in press.Google Scholar
  16. Sander SP, RR Friedl (1989) Kinetics and product studies of the reaction ClO + BrO using flash photolysis-ultraviolet absorption. J Chem Phys 71:5183–5190Google Scholar
  17. Stimpfle RM, RA Perry, CJ Howard (1979) Temperature dependence of the reaction of ClO and HO2 radicals. J Chem Phys 71:5183–5190CrossRefGoogle Scholar
  18. Talukdar RK, A Meelouki, AM Schmoltner, T Watson, S Montzka, AR Ravishankara (1992) Kinetics of the OH reaction with methyl chloroform and its amtospheric implications. Science 257:227–230.CrossRefGoogle Scholar
  19. Toon OB, MA Tolbert (1995) Spectroscopic evidence against nitric acid trihydrate in polar stratospheric clouds. Nature 375: 218–221.CrossRefGoogle Scholar
  20. Vaghjiani GL, AR Ravishankara (1991) New measurements of the rate coefficient for the reaction with methane. Nature 350:406–409CrossRefGoogle Scholar
  21. Wayne RP, G Poulet, P Biggs, JP Burrows, RA Cox, PJ Crutzen, GD Hayman, ME Jenken, G Le Bras, GK Moortgat, U Platt, RN Schindler (1995) Halogen oxides: Radical, sources and reservoirs in the laboratory and in the atmosphere. Atmos Environ 29:2675–2884CrossRefGoogle Scholar
  22. Williams LR, DM Golden (1993) Solubility of HCl in sulfuric acid at stratospheric temperatures. Geophys Res Lett 20:2227–2230CrossRefGoogle Scholar
  23. Zhang Z, RE Huie, MJ Kurylo (1992) Rate constants for the reactions of OH with CH3CFC12, CH3CF2C1, and CH2FCF3. J Phys Chem 96:1533–1535CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1997

Authors and Affiliations

  • Georges Le Bras
    • 1
  1. 1.Laboratoire de Combustion et Sytèmes RéactifsOrléansFrance

Personalised recommendations