Abstract
The chemical reactivity of several atmospheric halomethanes CH3Br, CH2Br2, CHBr3, CH3I, and CH2CII was studied in the gas phase, by performing kinetic experiments with chlorine atoms. The absolute rate constants were determined as a function of temperature in the range 273–363 K, using the very low-pressure reactor (VLPR) technique. The primary reactive degradation pathway of most halomethanes is the abstraction of a hydrogen atom leading to the formation of HCl molecules, with the exception of CH2CII where the primary pathway is the abstraction of iodine atom leading to CII molecules. All reactions are rather fast with A factors and activation energies in the ranges (1 – 3) x 10-11 molecule-1 s-1 and 0 – 12 kJ mol-1 respectively.
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References
Class, T. H. and Ballschmiter, K. (1988) J Atm. Chem 6, 35–46.
Reifenhauser, W. and Heumann, K.G. (1992) Atmos. Environ, 26(A), 2905–2915.
Schall, C. and Heumann, K.G. (1993) Fresenius J Anal. Chem 346, 717–722.
Yokouchi, Y., Barrie, L.A., Toom, D. and Akimoto, H. (1996) Atm. Environ 30, 1723–1727.
Moore, R.M. and Tokarczyk, (1992) J. Geophys. Res 19, 1779.
Rattigan, O.V., Shallcross, D.E. and Cox, R.A. (1997) J Chem. Soc. Faraday Trans 93, 2839.
Roel, C.M., Burkholder, J.B., Moortgat, G.K., Ravishankara, A.R. and Crutzen, P.J.(1997)J. Geophys. Res 102, 12819.
Rudolph, J., Koppmann, R. and Plass-Dülmer, C. (1996) Atmos. Environ 30, 1887.
Gierczak, T., Goldfarb, L., Sueper, D. and Ravishankara, A.R. (1994) Int. J. Chem. Kinet 26, 719.
Orlando, J.J., Tyndall, G.S., Wallington, T.J. and Dill, M. (1996) Int. J. Chem. Kinet 28, 433.
Tschuikow-Roux, E., Faraji, F., Paddison, S., Niedzielski, J. and Miyokawa, K. (1988) J. Phys. Chem 92, 1488.
Ayhens, Y. V., Nicovich, J. M., McKee, M. L. and Wine, P. H. (1997) J Phys. Chem A, 101, 9382–9390.
Bilde, M., Sehested, J., Nielsen, O.J., Wallington, T.J., Meagher, R.J., McIntosh, M.E., Piety, C.A., Nicovich, J.M. and Wine, P.H. (1997)J. Phys. Chem 101, 8035.
Kambanis, K.G., Lazarou, Y.G., and Papagiannakopoulos, P. (1997) Chem. Phys. Lett 268, 498–504
Grice, R. (1995) Int. Rev. Phys. Chem 14, 315.
Kambanis, K.G., Lazarou, Y.G., and Papagiannakopoulos, P. (1997) J. Phys. Chem 101, 8496–8502.
Lazarou, Y.G., Kambanis, K.G. and Papagiannakopoulos, P. (1997) Chem.Phys.Lett 271, 280–286.
Kambanis, K.G., Argyris, D.Y., Lazarou, Y.G. and Papagiannakopoulos, P. (1999) J Phys. Chem 103, 3210–3215.
Lazarou, Y.G., Michael, C. and Papagiannakopoulos, P. (1992) J Phys. Chem 96, 1705–1708.
Lazarou, Y.G. and Papagiannakopoulos, P. (1995) Int.JChem.Kinet 27, 343.
Benson, S.W. Thermochemical Kinetics, 2nd ed.; Wiley-Interscience: New York, 1976.
DeMore, W.B., Sander, S.P., Golden, D.M., Hampson, R.F., Kurylo, M.J., Howard, C.J., Ravishankara, A.R., Kolb, C.E. and Molina, M.J., 1997: Chemical Kinetics and Photochemical Data for Use in Stratospheric Modelling, JPL Publication 97–4
Russel, P.B., Lightfoot, P.D., Caralp, F., Calone, V., Lesclaux, R. and Forst, W. (1991) J. Chem. Soc. Faraday Trans 87, 2367.
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Papagiannakopoulos, P. (2000). Kinetics and Mechanism of Homogeneous Reactions of Halomethanes with Chlorine Atoms. In: Zerefos, C.S., Isaksen, I.S.A., Ziomas, I. (eds) Chemistry and Radiation Changes in the Ozone Layer. NATO Science Series, vol 557. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4353-0_25
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DOI: https://doi.org/10.1007/978-94-011-4353-0_25
Publisher Name: Springer, Dordrecht
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