Advertisement

Combustion, Explosion, and Shock Waves

, Volume 43, Issue 5, pp 530–537 | Cite as

Initiation of chain and thermal explosions by the reactor surface. Criterion for the participation of branching chains in a thermal explosion

  • E. N. Aleksandrov
  • N. M. Kuznetsov
  • S. N. Kozlov
Article

Abstract

The combustion of hydrogen and silane is studied. It is established that the chain initiation reaction on quartz in the zone of hydrogen and silane combustion is manifested as an autocatalytic reaction which is able to initiate a chain explosion and participate in the initiation of a thermal explosion. It is shown that in the case of an oxyhydrogen gas, the assumption of a branching-chain nature of the third limit is inconsistent with Semenov’s law, which includes double exponential dependences of the chain reaction rate on time and temperature. A criterion for the participation of branching chains in complex processes is proposed based on the presence or absence of short delays of a thermal explosion (≈1 sec). According to the criterion, the explosion of an oxyhydrogen gas at atmospheric pressure with delays markedly exceeding 1 sec proceeds without the participation of branching chains and is consistently explained by the joint action of autocatalytic processes on the reactor wall and gas-phase processes.

Key words

chain explosion thermal explosion chain branching atoms radicals third ignition limit criterion for the participation of branching chains in processes 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    N. N. Semenov, Some Problems of Chemical Kinetics and Reactivity [in Russian], Izd. Akad. Nauk SSSR, Moscow (1958).Google Scholar
  2. 2.
    H. N. Alyea and F. Haber, “Ignition of hydrogen-oxygen mixture by quartz rod,” J. Phys. Chem., B-10, 193 (1930).Google Scholar
  3. 3.
    A. V. Nalbandyan and V. V. Voevodskii, Hydrogen Oxidation and Combustion Mechanism [in Russian], Izd. Akad. Nauk SSSR, Moscow (1949).Google Scholar
  4. 4.
    V. V. Azatyan, “New regularities in gas-phase CBPs,” Doct. Dissertation in Chem. Sci., Inst. of Chem. Phys., Moscow (1978).Google Scholar
  5. 5.
    E. N. Aleksandrov, “Some features of hydrogen and carbon oxide combustion near the first ignition limit,” Candidate’s Dissertation in Chem. Sci., Inst. of Chem. Phys., Moscow (1975).Google Scholar
  6. 6.
    E. N. Aleksandrov, “Kinetic resonance fluorescence spectroscopy of low-pressure flames,” Doct. Dissertation in Chem. Sci., Inst. of Chem. Phys., Moscow (1986).Google Scholar
  7. 7.
    E. N. Aleksandrov, S. N. Kozlov, and N. M. Kuznetsov, “Effect of processes on the reactor surface on a low-pressure hydrogen flame,” Izv. Ross. Akad. Nauk, Ser. Khim, No. 8, 1301–1308 (2006).Google Scholar
  8. 8.
    E. N. Aleksandrov, S. N. Kozlov, N. M. Kuznetsov, et al., Promoting catalytic processes on a quartz surface by active combustion products of hydrogen and silane,” Dokl. Ross. Akad. Nauk, 409, No. 3, 345–350 (2006).Google Scholar
  9. 9.
    E. N. Aleksandrov, S. N. Kozlov, and N. M. Kuznetsov, “Heterogeneous chain propagation on a quartz surface,” Combust., Expl., Shock Waves, 42, No. 3, 282–291 (2006).CrossRefGoogle Scholar
  10. 10.
    V. V. Azatyan and N. N. Semenov, “On the role of negative interaction of chains and heterogeneous reactions of active centers of the chains in hydrogen combustion,” in: Combustion and Explosion [in Russian], Moscow (1972).Google Scholar
  11. 11.
    W. C. Gardiner, Combustion Chemistry, Springer-Verlag, New York (1984).Google Scholar
  12. 12.
    V. N. Kondrat’ev and M. I. Ziskin, “OH radicals in hydrogen flame at low pressures,” Zh. Fiz. Khim., 9, 542 (1937).Google Scholar
  13. 13.
    N. M. Chirkov, “Autocatalytic hydrogen oxidation,” Acta Physicochimica, URSS, No. 6, 1915 (1937).Google Scholar
  14. 14.
    V. A. Poltorak and V. V. Voevodskii, “Experimental study of slow hydrogen oxidation and the third ignition limit,” Zh. Fiz. Khim., 24, No. 3, 299–310 (1946).Google Scholar
  15. 15.
    V. V. Azatyan, “Role of the chain mechanism in hydrogen ignition and combustion with oxygen at the third limit,” Kinet. Katal., 37, No. 4, 512–520 (1996).Google Scholar
  16. 16.
    V. V. Azatyan, D. I. Baklanov, L. G. Gvozdeva, et al., “Inhibition of the developed detonation of hydrogen-air mixtures,” Dokl. Ross. Akad. Nauk, 376, No. 1, 55–58 (2001).Google Scholar
  17. 17.
    V. V. Azatyan, I. A. Bolodyan, V. Yu. Navtsenya, et al., “Dominating role of the competition and termination of reaction chains in the formation of the concentration limits of flame propagation,” Zh. Fiz. Khim., 76, No. 5, 775–784 (2002).Google Scholar
  18. 18.
    V. V. Azatyan, G. G. Vagner, and G. K. Vedeshkin, “Effect of reactive additives on detonation in hydrogen-air mixtures,” Zh. Fiz. Khim., 78, No. 6, 1036–1044 (2004).Google Scholar
  19. 19.
    V. V. Azatyan, “Chain nature of the third self-ignition limit of hydrogen-oxygen mixtures and flame propagation at atmospheric pressure,” Zh. Fiz. Khim., 80, No. 1, 1–5 (2006).Google Scholar
  20. 20.
    B. L. Lewis and G. Von Elbe, Combustion, Flames and Explosions of Gases, Academic Press (1961).Google Scholar
  21. 21.
    V. N. Kondrat’ev and E. E. Nikitin, Kinetics and Mechanism of Gas-Phase Reactions [in Russian], Nauka, Moscow (1974).Google Scholar
  22. 22.
    E. N. Aleksandrov, O. N. Davydova, S. N. Kozlov, and N. M. Kuznetsov, “Effect of the reactor surface on a low-pressure hydrogen and silane flame. Initiation of chain and thermal explosions by the surface,” Dokl. Ross. Akad. Nauk, 412, No. 4, 1–4 (2007).Google Scholar
  23. 23.
    V. V. Azatyan and A. A. Shavard, “Chain branching processes at low pressures and some problems of experimental technique,” Kinet. Katal., 25, 1285–1298 (1984).Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • E. N. Aleksandrov
    • 1
  • N. M. Kuznetsov
    • 1
  • S. N. Kozlov
    • 1
  1. 1.Emanuel’ Institute of Biochemical PhysicsRussian Academy of SciencesMoscow

Personalised recommendations