跳至主要内容

Vibrational Nonequilibrium in the Hydrogen-Oxygen Reaction at Different Temperatures

Read full paper at:
http://www.scirp.org/journal/PaperInformation.aspx?PaperID=51088#.VFMhOGfHRK0

Author(s)
A theoretical model of chemical and vibrational kinetics of hydrogen oxidation is suggested based on the consistent account for the vibrational nonequilibrium of HO2 radical which forms in result of bimolecular recombination H + O2 = HO2 in the vibrationally excited state. The chain branching H + O2 = O + OH and inhibiting H + O2 + M = HO2 + M formal reactions are considered (in the terms of elementary processes) as a general multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and monomolecular decay of the comparatively long-lived vibrationally excited HO2 radical which is capable to react and exchange of energy with another components of the mixture. The model takes into account the vibrational nonequilibrium for the starting (primary) H2 and O2 molecules, as well as the most important molecular intermediates HO2, OH, O2(1D), and the main reaction product H2O. The calculated results are compared with the shock tube experimental data for strongly diluted H2-O2 mixtures at 1000 < T < 2500 K, 0.5 < p < 4 atm. It is demonstrated that this approach is promising from the standpoint of reconciling the predictions of the theoretical model with experimental data obtained by different authors for various compositions and conditions using different methods. It is shown that the hydrogen-oxygen reaction proceeds in absence of vibrational equilibrium, and the vibrationally excited HO2 radical acts as a key intermediate in the principally important chain branching process. For T < 1500 K, the nature of hydrogen-oxygen reaction is especially nonequilibrium, and the vibrational nonequilibrium of HO2 radical is the essence of this process.<
Cite this paper
Skrebkov, O. (2014) Vibrational Nonequilibrium in the Hydrogen-Oxygen Reaction at Different Temperatures. Journal of Modern Physics, 5, 1806-1829. doi: 10.4236/jmp.2014.516178. 
 

[1] Mallard, W.G., Westley, F., Herron, J.T. and Hampson, R.F. (1994) NIST Chemical Kinetics Database, Ver. 6.0. NIST Standard Reference Data, Gaithersburg.
[2] Skrebkov, O.V. and Karkach, S.P. (2007) Kinetics and Catalysis, 48, 367-375. Original Russian Text in: Kinetika i Kataliz, 48, 388-396.
[3] Bradley, J.N. (1962) Shock Waves in Chemistry and Physics. Methuen & Co LTD-John Wiley & Sons INC, London-New York.
[4] Kondratiev, V.N. and Nikitin, E.E. (1981) Gas-Phase Reactions: Kinetics and Mechanisms. Springer, Berlin.
http://dx.doi.org/10.1007/978-3-642-67608-6
[5] Baulch, D.L., Cobos, C.J., Cox, R.A., Esser, C., Frank, P., Just, Th., Kerr, J.A., Pilling, M.J., Troe, J., Walker, R.W. and Warnatz, J. (1992) Journal of Physical and Chemical Reference Data, 21, 411-429.
http://dx.doi.org/10.1063/1.555908
[6] Li, Z., Zhao, J., Kazakov, A. and Dryer, F.L. (2004) International Journal of Chemical Kinetics, 36, 566-575.
http://dx.doi.org/10.1002/kin.20026
[7] Konnov, A.A. (2008) Combustion and Flame, 152, 507-528.
http://dx.doi.org/10.1016/j.combustflame.2007.10.024
[8] Burke, M.P., Chaos, M., Ju, Y.G., Dryer, F.L. and Klippenstein, S.J. (2012) International Journal of Chemical Kinetics, 44, 444-474.
http://dx.doi.org/10.1002/kin.20603
[9] Kondratyev, V.N. (1979) Rates of Elementary Chemical Processes in Gases on the Works of the Institute of Chemical Physics Akad. Nauk SSSR. In: Kondratyev, V.N., Ed., Problems of Chemical Kinetics. To the Eightieth Anniversary of Academician N.N. Semenov, Nauka, Moscow, 13-21.
[10] Dougerty, E.P. and Rabitz, H. (1980) Journal of Chemical Physics, 72, 6571-6586.
http://dx.doi.org/10.1063/1.439114
[11] Hidaka, Y., Takahashi, S., Kawano, H., Suga, M. and Gardiner Jr., W.C. (1982) Journal of Physical Chemistry, 86, 1429-1433.
http://dx.doi.org/10.1021/j100397a043
[12] Karkach, S.P. and Osherov, V.I. (1999) Journal of Chemical Physics, 110, 11918-11927.
http://dx.doi.org/10.1063/1.479131
[13] Michael, J.V., Suhterland, J.W., Harding, L.B. and Wagner, A.F. (2000) Proceedings of the Combustion Institute, 28, 1471-1478.
http://dx.doi.org/10.1016/S0082-0784(00)80543-3
[14] Skrebkov, O.V., Karkach, S.P., Vasil’ev, V.M. and Smirnov, A.L. (2003) Chemical Physics Letters, 375, 413-418.
http://dx.doi.org/10.1016/S0009-2614(03)00875-3
[15] Belles, E. and Lauver, M.R. (1964) Journal of Chemical Physics, 40, 415-419.
http://dx.doi.org/10.1063/1.1725129
[16] Skrebkov, O.V., Karkach, S.P., Ivanova, A.N. and Kostenko, S.S. (2009) Kinetics and Catalysis, 50, 461-473. Original Russian Text in: Kinetika i Kataliz, 50, 483-495.
http://dx.doi.org/10.1134/S0023158409040016
[17] Jorfi, M., Honvault, P., Bargueno, P., Gonzalez-Lezana, T., Larregaray, P., Bonnet, L. and Halvick, P. (2009) Journal of Chemical Physics, 130, 184301.
http://dx.doi.org/10.1063/1.3128537
[18] Wadlinger, R.L. and deB. Darwent, B. (1967) Journal of Physical Chemistry, 71, 2057-2061.
http://dx.doi.org/10.1021/j100866a013
[19] Pack, R.T., Butcher, E.A. and Parker, G.A. (1995) Journal of Chemical Physics, 102, 5998-6012.
http://dx.doi.org/10.1063/1.469334
[20] Dobbyn, A.J., Stumpf, M., Keller, H.M. and Schinke, R. (1996) Journal of Chemical Physics, 104, 8357-8381.
http://dx.doi.org/10.1063/1.471587
[21] Harding, L.B., Troe, J. and Ushakov, V.G. (2000) Physical Chemistry Chemical Physics, 2, 631-642.
http://dx.doi.org/10.1039/a908929b
[22] Vasil’ev, V.M., Kulikov, S.V. and Skrebkov, O.V. (1977) Zhurnal Prikladnoy Mekhaniki i Tekhnicheskoy Fiziki, 4, 13-21. English Translation in: Plenum Publishing Corporation, 437-444 (1978).
[23] Skrebkov, O.V. and Kulikov, S.V. (1998) Chemical Physics, 227, 349-373.
http://dx.doi.org/10.1016/S0301-0104(97)00296-6
[24] Skrebkov, O.V. (2011) Russian Journal of Physical Chemistry B, 5, 227-234. Original Russian Text in: Khimicheskaya Fizika, 30, 38.
[25] Kuznetsov, N.M. (1972) Doklady Akademii Nauk SSSR, 202, 1367-1370.
[26] Kuznetsov, N.M. (1972) Zhurnal Prikladnoy Mekhaniki i Tekhnicheskoy Fiziki, 3, 46-52.
[27] Marrone, P.V. and Treanor, C.E. (1963) Physics of Fluids, 6, 1215-1221.
http://dx.doi.org/10.1063/1.1706888
[28] Chapman, S. and Cowling, T.G. (1952) The Mathematical Theory of Non-Uniform Gases. Cambridge University Press, Cambridge.
[29] Skrebkov, O.V. (1995) Chemical Physics, 191, 87-99.
http://dx.doi.org/10.1016/0301-0104(94)00303-R
[30] Fernandes-Ramos, A., Miller, J.A., Klippenstein, S.J. and Truhlar, D.G. (2006) Chemical Reviews, 106, 4518-4584.
http://dx.doi.org/10.1021/cr050205w
[31] Nikitin, E.E., Osipov, A.I. and Umanskii, S.Ya. (1989) Vibration-Translational Energy Transfer in Collisions of Homonuclear Diatomic Molecules. In: Smirnov, B.M., Ed., Khimiya Plazmy, Vyp. 15, Energoatomizdat, Moscow, 3-43.
[32] Konovalova, I.A. and Umanskii, S.Ya. (1982) Khimicheskaya Fizika, 1, 901-905.
[33] Skrebkov, O.V. and Smirnov, A.L. (1992) Soviet Journal of Chemical Physics, 10, 1598-1615. Original Russian Text in: Khimicheskaya Fizika, 10, 1036-1046 (1991).
[34] Smirnov, A.L. and Skrebkov, O.V. (1992) Soviet Journal of Chemical Physics, 11, 51-63. Original Russian Text in: Khimicheskaya Fizika, 11, 35-42.
[35] Ryu, S.O., Hwang, S.M. and Rabinovitz, M.J. (1995) Journal of Physical Chemistry, 99, 13984-13991.
http://dx.doi.org/10.1021/j100038a033
[36] Pavlov, V.A. and Shatalov, O.P. (2011) Kinetics and Catalysis, 52, 157-165. Original Russian Text in: Kinetika i Kataliz, 52, 163-172.
http://dx.doi.org/10.1134/S0023158411020157
[37] Herzfeld, K.F. and Litovitz, T.A. (1959) Absorbtion and Dispersion of Ultrasonic Waves. Academic Press, New York-London.
[38] Moore, C.B. (1965) Journal of Chemical Physics, 43, 2979-2986.
http://dx.doi.org/10.1063/1.1697261
[39] Ormonde, S. (1975) Reviews of Modern Physics, 47, 193-258.
http://dx.doi.org/10.1103/RevModPhys.47.193
[40] Sibert, E.L., Reinhardt, W.P. and Hynes, J.T. (1982) Journal of Chemical Physics, 77, 3583-3594.
http://dx.doi.org/10.1063/1.444260
[41] Sibert, E.L., Hynes, J.T. and Reinhardt, W.P. (1982) Journal of Chemical Physics, 77, 3595-3604.
http://dx.doi.org/10.1063/1.444261
[42] Zhang, D.H. and Zhang, J.Z.H. (1994) Journal of Chemical Physics, 101, 3671-3678.
http://dx.doi.org/10.1063/1.467551
[43] Mandelshtam, V.A., Taylor, H.S. and Miller, W.H. (1996) Journal of Chemical Physics, 105, 496-503.
http://dx.doi.org/10.1063/1.471903
[44] Lin, S.Y., Sun, Z., Guo, H., Zhang, D.H., Honvault, P., Xie, D.Q. and Lee, S.Y. (2008) Journal of Physical Chemistry A, 112, 602-611.
http://dx.doi.org/10.1021/jp7098637
[45] Lin, S.Y., Guo, H., Honvault, P., Xu, C.X. and Xie, D.Q. (2008) Journal of Chemical Physics, 128, 014303.
http://dx.doi.org/10.1063/1.2812559
[46] Troe, J. and Ushakov, V.G. (2008) Journal of Chemical Physics, 128, 204307.
http://dx.doi.org/10.1063/1.2917201
[47] Landau, L. and Teller, E. (1936) Physik Zeitschrift der Sowjetunion, 10, 34-38.
[48] Keck, J. and Carrier, G. (1965) Journal of Chemical Physics, 43, 2284-2298.
http://dx.doi.org/10.1063/1.1697125                      eww141031lx
标签：

评论

发表评论

此博客中的热门博文

Electron Spin and Proton Spin in the Hydrogen and Hydrogen-Like Atomic Systems

Read full paper at: http://www.scirp.org/journal/PaperInformation.aspx?PaperID=52202#.VIj7tMnQrzE Author(s) Stanisław Olszewski * Affiliation(s) Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland . ABSTRACT The mechanical angular momentum and magnetic moment of the electron and proton spin have been calculated semiclassically with the aid of the uncertainty principle for energy and time. The spin effects of both kinds of the elementary particles can be expressed in terms of similar formulae. The quantization of the spin motion has been done on the basis of the old quantum theory. It gives a quantum number n = 1/2 as the index of the spin state acceptable for both the electron and proton ...
发表评论
阅读全文

Incorporation of High-Altitude Balloon Experiment in High School Science Classrooms

High-altitude balloon is a balloon, filled usually with helium or hydrogen that ascends into an area called “near space” or stratosphere. The most common type of high-altitude balloons are weather balloons. Other purposes include use as a platform for experiments in the upper atmosphere. Modern balloons generally contain electronic equipment such as radio transmitters, cameras, or satellite navigation systems, such as GPS receivers. The mission of the High-Altitude Balloon Experiment (HABE) is to acquire supporting data, validate enabling technologies, and resolve critical acquisition, tracking, and pointing (ATP) and fire control issues in support of future space-based precision pointing experiments. The use of high-altitude balloons offers a relatively low-cost, low-vibration test platform, a recoverable and reusable payload, worldwide launch capability, and a 'near- space' emulation of the future space systems operational scenarios. More recently, several university...
1 条评论
阅读全文

Fermented Brown Sugar Residue Prolongs the Caenorhabditis elegans Lifespan via DAF-16

Fermented brown sugar residue (FBSR) is generated in the course of purifying biomass ethanol from the yeast fermentation products of brown sugar. It contains abundant nutrition and is used in various industrial applications including as fertilizer and feed. Meanwhile, brown sugar has attracted attention as a health food and is thought to prevent cardiovascular diseases, hypertension, and brain stem diseases. Furthermore, polyphenol, contained in brown sugar, reduces oxidative stress and inhibits glucose absorption. DAF-16 is a transcription factor regulated downstream of the insulin signaling pathway and is one of the main factors contributing to aging and lifespan in C. elegans . Therefore, to determine the precise roles of the DAF-16 transcription factor in stress tolerance and life span, it is necessary to elucidate the signaling pathways involved in DAF-16 activation. This study was designed to elucidate the molecular mechanisms controlling the physiological stress toleran...
发表评论
阅读全文