NUMERICAL DEFINITION OF ORGANOPHOSPHORUS COMPOUNDS DECOMPOSITION PRODUCTS IN THE CHAIN COMBUSTION CONDITIONS
Keywords:
inhibition, quantum-chemical calculation, mechanism of chemical reaction, products of destruction.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.
References
Montreal Protocol on Substances that Deplete the Ozone Layer, with later amendments, http://www.ciesin.org/TG/PI/POLICY/montpro.html.
Tapscott R.E., Mather J.D., Heinonen E.W., Lifke J. L. and Moore T.A., 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, May 1998.
MacDonald M. A., Jayaweera T.M., Fishe E.M, and Gouldin F.C. “Inhibition of Non-Premixed Flames by Dimethyl Methylphosphonate,” Technical Meeting, Central States Section of The Combustion Institute, 27-29 April 1997, Point Clear, Alabama.
Babushok V. Tsang W. Influence of Phosphorus-Containing Fire Suppressants on Flame Propagation / V.Babushok, and – Proceedings, Third International Conference on Fire Research and Engineering. – Chicago, Illinois. – 4–8 October 1999. – PP. 257–267.
Linteris G.T. Suppression of Cup-Burner Diffusion Flames by Super-Effective Chemical Inhibitors and Inert Compounds / Halon Options Technical Working Conference: Int. conf. 24–26 April 2001 – Albuquerque, New Mexico, 2001. – P.178.
Korobeinichev O.P. Bolshova T.A., Shvartsberg V.M. and Chernov A.A. Inhibition and promotion of combustion by organophosphorus compounds added to flames of CH4 or H2 in O2 and Ar // Combustion and Flame. – 2001. – V. 125, 1–2. – PP. 744–751.
Michalkova A.A, Leonid Gorb and Jerzy Leszczynski. Quest for efficient methods of desintegration of organophosphorus compounds: modelling adsorption and decomposition processes // Ch. 16, in “Modeling Adsorption and Decomposition Processes”, in book: Molecular Materials with Specific interactions – Modeling and design,(Ed.) W.A.Sokalski. – 2007. – 598 p.
Кукуєва В.В., Водяницький О.О., Рига Т.М. Екологічні аспекти дослідження фосфорорганічних речовин // Екологія та освіта: актуальні проблеми природокористування в умовах наростаючих ризиків техногенних катастроф: Міжн. наук.-техн. конф., 19–20 квітня 2012 р.: тез. доп. – Черкаси, 2012. – С. 214–216.
Nogueira M.F.M., Fisher E.M. Effect of Dimethyl Methylphosphonate on a Premixed CH4/O2/Ar Flame // presented for the Joint US Section Meeting: The Combustion Institute, Washington, D. C. – March, 1999.
Wainer R.T., McNesby K.L., Daniel R.G., Miziolek A.W., Babushok V.I., Experimental and Mechanistic Investigation of Opposed-Flow Propane/Air Flames by Phosphorus-Containing Compounds. /Halon Options Technical Working Conference HOTWC-2000, 2000, Albuquerque. 11. Семенов Н.Н. О некоторых проблемах химической кинетики и реакционной способности / М.: Изд-во АН СССР. – 1958. – 686 с.
Jayaweera T.M., Milius C.F., Pitz W.J., Westbrook C.K., Korobeinichev O.P., Shvartsberg V.M., Shmakov A.G., Rybitskaya I.V., Curran H.J. Flame inhibition by phosphorus-containing compounds over a range of equivalence ratios. – Combustion and Flame, 140, (2005) 103-115
Westbrook C.K. Inhibition of Hydrocarbon Oxidation in Laminar Flames and Detonations by Halogenated Compounds / Proc. Combust. Inst. – 1982. – V. 19. – P. 127.
Westbrook C.K. Numerical Modeling of Flame Inhibition by CF3Br / C.K.Westbrook. – Combust. Sci. Technol. – 1983. – V. 34. – PP. 201–225. 15. MacDonald, M.A.; Gouldin, F.C.; Fisher, E.M. Temperature dependence of phosphorus- based flame inhibition / Combustion and flame 124(4), 2001, pp. 668-683
Twarowski A. The influence of phosphorus oxides and acids on rate of H+OH recombination // Combust. Flame.-1984.- V. 94. – P. 91-107. 17. Twarowski A. Reduction of a phosphorus oxide and acid reaction set //Combust. Flame.- 1995. – v.102. – P. 41-54.
Twarowski A. The temperature dependence of H+OH recombination in phosphorus oxide containing post- combustion gases // Combust. Flame. – 1996. – V.105. – P.407-413.
Granovsky A.A. URL http: // classic.chem.msu.su/gran/gamess/index.html GAMESS PC.
Werner J.H., Cool T.A. Kinetic Model for the Decomposition of DMMP in a Hydrogen/Oxygen Flame // Combust. Flame. – 1999. – V. 117 – PP. 78–98.
Коробейничев O.П., Шварцберг В.М., Ильин С.Б. Химия деструкции фосфорорганических соединений в водородно-кислородных пламенах // Физика горения и взрыва. – 1997. – T.33, № 3. – C. 32–48.
Korobeinichev O.P. Ilyin S.B., Mokrushin V.V. and Shmakov A.G. Destruction chemistry of dimethyl methylphosphonate in H2/O2 flame studied by molecular beam mass spectrometry // Combust. Sci. Technol. – 1996. – V. 116. – P.51–67.
Korobeinichev O.P., Ilyin S.B., Shvartsberg V.M. and Chernov A.A.. The Destruction Chemistry of Organophosphorus Compounds in Flames – I: Quantitative Determination of Final Phosphorus-containing Combustion Produts Composition in Hydrogen-Oxygen Flame // Combust. Flame. – 1999. – 118. – PP. 718–726.
Пат. №39937 Україна, A62D 1/00. Застосування високодисперсного фосфоровмісного кремнезему к активної основи для вогнегасних порошків багатоцільового призначення / В.В. Кукуєва, В.М. Богатирьов, В.В. Лобанов. – Заявл. 12.06.2008;Опубл.25.03.2009; Бюл. № 6. – 4 с.
