Skip to main content
SpringerLink
Log in

The kinetics of radical reactions in the radiolysis of aqueous solutions of organic nitro compounds

  • Physical Chemistry of Solutions
  • Published:
Russian Journal of Physical Chemistry A, Focus on Chemistry Aims and scope Submit manuscript

Abstract

Pulsed radiolysis and computer simulation of gamma radiolytic decomposition of organic nitrates in aqueous solutions were performed to determine the rate constants for reactions with the participation of intermediates determining the mechanism of the process. 2,4,6-Trinitrotoluene, 2,4-dinitrotoluene, and cyclic nitramine, cyclotrimethylene-trinitramine, were used as substrates. The bimolecular rate constants for the reactions of hydrated electrons (e −aq ) and hydroxyl radicals (•OH) with the substrates and constants for the recombination of electron adducts and carbon-centered radicals (the products of the detachment of the H atom from the nitro compound molecule by the OH radical) were determined by direct measurements with the use of high-speed spectrophotometry. Computer simulation of the reaction scheme was used to estimate the rate constant for significant reactions, monomolecular forward and back reactions of electron adducts and electron transfer to molecular oxygen, and refine the rate constant for the reaction of e −aq with tert-butanol.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. C. L. Greenstock, in The Chemistry of Amino, Nitroso, and Nitro Compounds and Their Derivatives (Wiley-Interscience, New York, 1982), Part 1, Ch. 7, p. 291.

    Google Scholar 

  2. P. Neta and D. Behar, J. Am. Chem. Soc. 102(14), 4798 (1980).

    Article  CAS  Google Scholar 

  3. V. G. Plotnikov and A. A. Ovchinnikov, Khim. Fiz. 4(4), 470 (1985).

    CAS  Google Scholar 

  4. D. C. Schmelling, K. A. Gray, and P. V. Kamat, Environ. Sci. Technol. 32(7), 971 (1998).

    Article  CAS  Google Scholar 

  5. E. Yu. Orlova, N. A. Orlova, V. F. Zhilin, et al., Octogene, Thermally Stable Explosive (Nedra, Moscow, 1975), pp. 110–111 [in Russian].

    Google Scholar 

  6. E. L. Protasova and G. I. Khaikin, Khim. Vys. Energ. 35(4), 249 (2001) [High Energy Chem. 35 (4), 219 (2001)].

    Google Scholar 

  7. G. V. Buxton, C. L. Greenstock, W. P. Helman, and A. B. Ross, J. Phys. Chem. Ref. Data 17, 513 (1988).

    CAS  Google Scholar 

  8. G. E. Adams, J. W. Boag, and B. D. Michael, Trans. Faraday Soc. 61, 1417 (1965).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 117071, Russia

    I. E. Makarov, E. L. Protasova & G. I. Khaikin

Authors
  1. I. E. Makarov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. L. Protasova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. I. Khaikin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to I. E. Makarov.

Additional information

Original Russian Text © I.E. Makarov, E.L. Protasova, G.I. Khaikin, 2008, published in Zhurnal Fizicheskoi Khimii, 2008, Vol. 82, No. 11, pp. 2044–2048.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Makarov, I.E., Protasova, E.L. & Khaikin, G.I. The kinetics of radical reactions in the radiolysis of aqueous solutions of organic nitro compounds. Russ. J. Phys. Chem. 82, 1833–1837 (2008). https://doi.org/10.1134/S0036024408110083

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0036024408110083

Keywords

Search

Navigation