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Reactivity of haloalkanes in their reactions with the chlorine atom

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Abstract

Experimental kinetic data on reactions of the chlorine atom with halogenated derivatives of methane and ethane (37 reactions) have been analyzed by the intersecting-parabolas method. The following five factors have an effect on the activation energy of these reactions: the enthalpy of reaction, triplet repulsion, the electronegativities of the reaction center atoms, the dipole–dipole and multidipole interactions between the reaction center and polar groups, and the effect of π electrons in the vicinity of the reaction center. The increments characterizing the contribution from each factor to the activation energy of the reaction have been calculated. The contribution from the polar interaction, ΔE μ, to the activation energy depends on the dipole moment of the polar group and obeys the following empirical equation: ln(ΔE μ/Σμ) = −0.74 + 0.87(ΔE μ/Σμ) − 0.084(ΔE μ/Σμ)2.

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References

  1. Istoriya ucheniya o khimicheskom protsesse (History of Chemical Process Science), Solov’ev, Yu.I., Ed., Moscow, Nauka, 1981.

  2. Tedder, J.M., Nechvatal, A., and Jubb, A.H., Basic Organic Chemistry, part 5 Industrial Products, London: Wiley, 1975.

    Google Scholar 

  3. Denisov, E.T., Sarkisov, O.M., and Likhtenshtein, G.I., Chemical Kinetics: Fundamentals and New Developments, Amsterdam Elsevier, 2003.

    Google Scholar 

  4. CRC Handbook of Chemistry and Physics, Lide, D.R., Ed., Boca Raton, FL: CRC. 2004–2005, 85th ed.

  5. Kerr, J.A., in Metathetical Reactions of Atoms and Radicals, Comprehensive Chemical Kinetics, vol. 18, Bamford, C.H. and Tipper, C.F.H, Eds., Amsterdam: Elsevier, 1976, p. 39.

    CAS  Google Scholar 

  6. Denisov, E.T., Chem. Phys. Rep., 1992, vol. 11, no. 10, p. 1321.

    Google Scholar 

  7. Denisov, E.T., Russ. Chem. Rev., 1997, vol. 74, no. 9, p. 859.

    Article  Google Scholar 

  8. Luo, Y.-R., Handbook of Bond Dissociation Energies in Organic Compounds, Boca Raton, FL CRC, 2003.

    Google Scholar 

  9. Pauling, L., General Chemistry, San Francisco Freeman, 1970.

    Google Scholar 

  10. NIST Standard Reference Database 19A: Positive Ion Energetics, Ver. 2.02, Gaithersburg, Md. National Inst. of Standards and Technology, 2003.

  11. NIST Standard Reference Database 17: Chemical Kinetics Database, Ver. 6.0, Gaithersburg, MD, National Inst. of Standards and Technology, 1994.

  12. DeMore, W.B., Sander, S.P., Golden, D.M., Hampson, R.F., Kurylo, M.J., Howard, C.J., Ravishankara, F.R., Kolb, C.E., and Molina, M.J., JPL Publication 97-4, 1997.

    Google Scholar 

  13. Maricq, M.M., Shi, J., Szente, J.J., Rimai, L., and Kaiser, E.N., J. Phys. Chem., 1993, vol. 97, p. 9686.

    Article  CAS  Google Scholar 

  14. Senkan, S.V. and Quam, D., J. Phys. Chem., 1992, vol. 96, p. 10837.

    Article  CAS  Google Scholar 

  15. Olsson, B.E.R., Hallquist, M., Ljungstrom, E., and Davidson, I., Int. J. Chem. Kinet., 1997, vol. 29, p. 195.

    Article  CAS  Google Scholar 

  16. Atkinson, R., Baulch, D.L., Cox, R.A., Hampson, R.F., Kerr, J.A., Rossi, M.J., and Troe, J., J. Phys. Chem. Ref. Data, 1997, vol. 26, p. 521.

    Article  CAS  Google Scholar 

  17. Nielsen, O.J., Sidebottom, H.W., O’Farrell, D.J., Donlon, M., and Treacy, J., Chem. Phys. Lett., 1989, vol. 156, p. 312.

    Article  CAS  Google Scholar 

  18. Catoire, V., Lesclaux, R., Schneider, W.F., and Wallington, T.J., J. Phys. Chem., 1996, vol. 100, p. 14356.

    Article  CAS  Google Scholar 

  19. Tschuikov-Roux, E., Faraji, F., Paddington, S., Niedrielski, J., and Miyokawa, K., J. Phys. Chem. A, 1998, vol. 92, p. 1488.

    Article  Google Scholar 

  20. Tschuikov-Roux, E. and Niedrielski, J., J. Photochem., 1984, vol. 27, p. 141.

    Article  Google Scholar 

  21. Mogelberg, T.E., Bilde, M., Sehested, J., Wallington, T.J., and Nielsen, O.J., J. Phys. Chem., 1996, vol. 100, p. 18399.

    Article  CAS  Google Scholar 

  22. Wallington, T.J., Hurley, M.D., and Schneider, W.F., Chem. Phys. Lett., 1996, vol. 251, p. 164.

    Article  CAS  Google Scholar 

  23. NIST Standard Reference Database 17: Chemical Kinetics Database, Ver. 2.01, Gaithersburg, MD, National Inst. of Standards and Technology, 1990.

  24. Talhaoui, A., Louis, F., Devolder, P., Meriaux, B., and Saverysyn, J.P., J. Phys. Chem., 1996, vol. 100, p. 13531.

    Article  CAS  Google Scholar 

  25. Mogelberg, T.E., Sehested, J., Bilde, M., Wallington, T.J., and Nielsen, O.J., J. Phys. Chem., 1996, vol. 100, p. 8882.

    Article  CAS  Google Scholar 

  26. Catoire, V., Ariya, P.A., Niki, H., and Harris, G.W., Int. J. Chem. Kinet., 1997, vol. 29, p. 6995.

    Google Scholar 

  27. Drozdova, T.I., Denisov, E.T., Shestakov, A.F., and Emel’yanova, N.S., Kinet. Catal., 2006, vol. 47, no. 1, p. 106.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432, Russia

    E. T. Denisov & T. G. Denisova

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  1. E. T. Denisov
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  2. T. G. Denisova
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Correspondence to E. T. Denisov.

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Original Russian Text © E.T. Denisov, T.G. Denisova, 2017, published in Kinetika i Kataliz, 2017, Vol. 58, No. 3, pp. 227–234.

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Denisov, E.T., Denisova, T.G. Reactivity of haloalkanes in their reactions with the chlorine atom. Kinet Catal 58, 219–226 (2017). https://doi.org/10.1134/S0023158417030041

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