NUMERICAL DEFINITION OF ORGANOPHOSPHORUS COMPOUNDS DECOMPOSITION PRODUCTS IN THE CHAIN COMBUSTION CONDITIONS

UDC 544.128.12 • 📖 Issue 27 / 2017 • 157 — 170 pages

https://doi.org/10.15407/znp2017.27.157

V.Kukueva, Ju.Zabulonov

V.Kukueva Ph.D. (Chem.), Postdoctoral Researcher, State Institution «Institute of Environmental Geochemistry of National Academy of Sciences of Ukraine», vitalina.kukueva@gmail.com

 Ju. Zabulonov., D.Sc. (Tech.),Cor. Member NASU State Institution «Institute of Environmental Geochemistry of National Academy of Sciences of Ukraine» zabulonov@mail.ru

Abstract

The research of elementary reactions occurring in the decomposition of organophosphorus compounds (OPC) has been carried out by ab initio quantum-chemical calculation in the 6-31 G basis set. Rapid elementar reactions with the inhibitor molecule, or its thermal decomposition products, bind active centers of flame, and the removal of any of them by recombination, thereby, reduces their overall concentration. The recombination of radicals leads to a smaller number of hydrogen atoms in the reaction zone, which results in the decrease in chain branching and consequently in the combustion rate as a whole. Such a behavior refers to well-known halogen-containing inhibitors such as HBr, CF3Br and OPC such as dimethylmethylphosphonate (DMMP). The performed quantum-chemical calculations made it possible to predict the main thermal decomposition products, as well as probable intermediates. The comparison of the DMMP decomposition energy in the two well-known schemes for the transformation of this substance in the flame showed that in the first stages there is a direct thermal decomposition only at a sufficiently high temperature, therefore, the attack of the inhibitor molecule with active flame radicals should also be taken to account. The results of the quantum-chemical calculations of the Werner-Kool reaction scheme show a significantly greater destruction energy at the first stage of degradation of DMMP, whereas the formation of phosphorus-containing PO2• radicals, which many researchers recognized as possible traps for the active centers of the flame, occur with less energy. The following controversial issue with regard to intermediates: CH3PO2 or (HO)3РО as a result of a quantum chemical study concluded in favor of the formation of orthophosphate acid by the Korobeynichev mechanism. From this, it is possible to propose the use of not all substances as combustion inhibitors, but formed phosphorus-containing radicals, possibly in the composition of other, less harmful chemical combustion inhibitors, as an example phosphorus containing silica.

 

Key words: inhibition, quantum-chemical calculation, mechanism of chemical reaction, products of destruction.

 

Article



Reference

  1. Montreal Protocol on Substances that Deplete the Ozone Layer, with later amendments, available at: http://www.ciesin.org/TG/PI/POLICY/montpro.html.
  2. Tapscott, R., Mather, J., Heinonen, E., LifkeL, J., Moore, T. (1998), Identification and Proof Testing of New Total Flooding Agents: Combustion Suppression Chemistry and Cup Burner Testing, Final Report, NMERI Report No. 97/6/33010, U. S. Department of Defense, Strategic 77 Environmental Research and Development Program and Defense Advance Research Projects Agency, Arlington, Virginia, USA.
  3. MacDonald., T. Jayaweera, E. Fisher and F. Gouldin (1997), Inhibition of Non-Premixed Flames by Dimethyl Methylphosphonate, Technical Meeting, Central States Section of The Combustion Institute, Point Clear, Alabama, USA.
  4. Babushok, V., Tsang, W. (1999), Influence of Phosphorus-Containing Fire Suppressants on Flame Propagation, Proceedings, Third International Conference on Fire Research and Engineering,Chicago, Illinois, USA, pp. 257-267.
  5. Linteris (2001), Suppression of Cup-Burner Diffusion Flames by Super-Effective Chemical Inhibitors and Inert Compounds, Halon Options Technical Working Conference, Albuquerque, New Mexico, USA,178 p.
  6. Korobeinichev, O., Bolshova, T ., Shvartsberg, V., Chernov, A. (2001), Inhibition and promotion of combustion by organophosphorus compounds added to flames of CH4 or H2 in O2 and Ar, Combustion and Flame, 125,(1–2), pp. 744. https://doi.org/10.1016/S0010-2180(00)00232-7
  7. Michalkova, A., Gorb, L., Leszczynski, J.  (2007), Quest for efficient methods of desintegration of organophosphorus compounds: modelling adsorption and decomposition processes, Molecular Materials with Specific interactions, Modeling and design, 598 p.
  8. Kukueva, О. Vodjanizkij, Т. Riga (2012), Ekologichni aspekty doslidgennja phosphor-organichnych rechovyn,  Ecology and education: actual problems using of nature in the increasing risks of technical catastrophes conditions, Int. Conf., Cherkassy, UA, pp.214-216.
  9. Nogueira, M., Fisher, E. (1999), Effect of Dimethyl Methylphosphonate on a Premixed CH4/O2/Ar Flame, The Combustion Institute, Washington, USA.
  10. Wainer, R., McNesby, K., Daniel, R., Miziolek, A., Babushok, V. (2000), Experimental and Mechanistic Investigation of Opposed-Flow Propane, Air Flames by Phosphorus-Containing Compounds, Halon Options Technical Working Conference HOTWC-2000, Albuquerque.
  11. Senemov, N. (1958), O nekotorych problemach chimicheskoj kinetiki I reakzionnoj sposobnosti, АN SSSR, Moscow, RU, 686 p.
  12. Jayaweera, T., Milius, C., Pitz, W., Westbrook, C., Korobeinichev, O., Shvartsberg, V., Shmakov, A., Rybitskaya, I., Curran, H. (2005), Flame inhibition by phosphorus-containing compounds over a range of equivalence ratios, Combustion and Flame, 140, pp. 103-115. https://doi.org/10.1016/j.combustflame.2004.11.001
  13. Westbrook, C. (1982), Inhibition of Hydrocarbon Oxidation in Laminar Flames and Detonations by Halogenated Compounds, Combust. Inst., 19, 127 p. https://doi.org/10.1016/S0082-0784(82)80185-9
  14. Westbrook, C. (1983), Numerical Modeling of Flame Inhibition by CF3Br, Combust. Sci. Technol, 34, pp. 201–225. https://doi.org/10.1080/00102208308923693
  15. MacDonald, M., Gouldin, F., Fisher, E. (2001), Temperature dependence of phosphorus- based flame inhibition, Combustion and flame 124(4), pp. 668-683. https://doi.org/10.1016/S0010-2180(00)00236-4
  16. Twarowski, A. (1984), The influence of phosphorus oxides and acids on rate of H+OH recombination, Combust. Flame, 94, pp. 91-107. https://doi.org/10.1016/0010-2180(93)90022-U
  17. Twarowski, A. (1995), Reduction of a phosphorus oxide and acid reaction set, Combust. Flame, 102, 41 – 54. https://doi.org/10.1016/0010-2180(94)00230-P
  18. Twarowski, A. (1996), The temperature dependence of H+OH recombination in phosphorus oxide containing post – combustion gases, Flame, 105, pp.407-413. https://doi.org/10.1016/0010-2180(95)00208-1
  19. Granovsky, GAMESS PC, available at: http: // classic.chem.msu.su/gran/gamess/index.html.
  20. Werner, J., Cool, T. (1999), Kinetic Model for the Decomposition of DMMP in a Hydrogen, Oxygen Flame, Combust. Flame, 117, pp. 78–98. https://doi.org/10.1016/S0010-2180(98)00101-1
  21. Korobejnichev, O., Shvarcberg, V., Il’in, S. (1997), Himiya destrukcii fosfororganicheskih soedinenij v vodorodno-kislorodnyh plаmenah, Fizika goreniya i vzryva,33, 3, pp. 32–48.
  22. Korobejnichev, O., Il’in, S., Mokrushin, V., Shmakov, A. (1996), Destruction chemistry of dimethyl methylphosphonate in H2/O2 flame studied by molecular beam mass spectrometry, Combust. Sci. Technol., 116, pp. 51–67. https://doi.org/10.1080/00102209608935543
  23. Korobejnichev, O., Il’in, S., Shvartsberg, V.,  Chernov, A. (1999), The Destruction Chemistry of Organophosphorus Compounds in Flames – I: Quantitative Determination of Final Phosphorus-containing Combustion Produts Composition in Hydrogen-Oxygen Flame, Flame, 118, pp. 718–726. https://doi.org/10.1016/S0010-2180(99)00030-9
  24. Kukueva, V., Bogatyrjov, V., Lobanov, V. (2009), Zastosuvannja vysoko dispersnogo phosphorvmisnogo kremnezemu jak aktyvnoi osnovy dlja vognegasnych poroshkiv bagatoziljovogo pryznachannja, №39937, UA.