Free-Radical Nonbranched-Chain Oxidation of Hydrogen
Keywords:
competition, hydrogen, low-reactive hydrotetraoxyl free radical, thermochemical data, etraoxyl free radical, thermochemical data,Abstract
New reaction scheme is suggested for the initiated nonbranched-chain addition of hydrogen atoms to the multiple bond of the molecular oxygen. The scheme includes the addition reaction of the hydroperoxyl free radical to the oxygen molecule to form the hydrotetraoxyl free radical which is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. This reaction competes with chain propagation reactions through a hydrogen atom. Based on the proposed scheme rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. The kinetic description with use the obtained rate equations is applied to the γ-induced nonbranched-chain process of the free-radical oxidation of hydrogen dissolved in water containing different amounts of oxygen at 296 K. The ratio of rate constants of competing reactions and the rate constant of the addition reaction to the molecular oxygen are defined. In this process the oxygen with the increase of its concentration begins to act as an oxidation autoinhibitor (or an antioxidant), and the rate of hydrogen peroxide formation as a function of the dissolved oxygen concentration has a maximum. From the energetic standpoint possible nonchain pathways of the free-radical oxidation of hydrogen and the routes of ozone decay via the reaction with the hydroxyl free radical (including the addition yielding the hydrotetraoxyl free radical) in the Earth’s upper atmosphere were considered.
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M. M. Silaev and L. T. Bugaenko, “Mathematical Simulation of the Kinetics of Radiation Induced Hydroxyalkylation of Aliphatic Saturated Alcohols”, Radiation Physics and Chemistry, 1992, vol. 40, no. 1, pp. 1–10.
M. M. Silaev, “Applied Aspects of the γ-Radiolysis of C1–C4 Alcohols and Binary Mixtures on Their Basis”, Khimiya Vysokikh Energii, Vol. 36, No. 2, 2002, pp. 97–101, English Translation in: High Energy Chemistry, 2002, vol. 36, no. 2, pp. 70–74.
A. K. Pikaev, “Sovremennaya radiatsionnaya khimiya. Radioliz gazov i zhidkostei” (“Modern Radiation Chemistry: Radiolysis of Gases and Liquids”), Nauka, Moscow, 1986.
H. A. Smith and A. Napravnik, “Photochemical Oxidation of Hydrogen”, Journal of the American Chemistry Society, 1940, vol. 62, no. 1, pp. 385–393.
E. J. Badin, “The Reaction between Atomic Hydrogen and Molecular Oxygen at Low Pressures. Surface Effects”, Journal of the American Chemistry Society, 1948, vol. 70, no. 11, pp. 3651–3655.
P. B. Pagsberg, J. Eriksen, and H. C. Christensen, “Pulse Radiolysis of Gaseous Ammonia–Oxygen Mixtures”, The Journal of Physical Chemistry, 1979, vol. 83, no. 5, pp. 582–590.
N. F. Barr and A. O. Allen, “Hydrogen Atoms in the Radiolysis of Water”, The Journal of Physical Chemistry, 1959, vol. 63, no. 6, pp. 928–931.
M. M. Silaev, “A New Competitive Kinetic Model of Radical Chain Oxidation: Oxygen as an Autoinhibitor”, Biofizika, 2001, vol. 46, no. 2, pp. 203–209, English Translation in: Biophysics, 2001, vol. 46, no. 2, pp. 202–207.
M. M. Silaev, “The Competition Kinetics of Nonbranched Chain Processes of Free-Radical Addition to Double Bonds of Molecules with the Formation of 1:1 Adducts and the Inhibition by the Substrate”, Oxidation Communication, 1999, vol. 22, no. 2, pp. 159–170.
M. M. Silaev, “The Competition Kinetics of Radical Chain Addition”, Zhurnal Fizicheskoi Khimii, Vol. 73, No. 7, 1999, pp. 1180–1184, English Translation in: Russian Journal of Physical Chemistry, 1999, vol. 73, no. 7, pp. 1050–1054.
M. M. Silaev, “Competitive Mechanism of the Nonbranched Radical Chain Oxidation of Hydrogen Involving the Free Cyclohydrotetraoxyl Radical [ОО···Н···ОО]•, which Inhibits the Chain Process”, “Khimiya Vysokikh Energii, 2003, vol. 37, no. 1, pp. 27–32, English Translation in: High Energy Chemistry, 2003, vol. 37, no. 1, pp. 24–28.
M. M. Silaev, “Simulation of the Initiated Addition of Hydrocarbon Free Radicals and Hydrogen Atoms to Oxygen via a Nonbranched Chain Mechanism”, Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2007, vol. 41, no. 6, pp. 634–642, English Translation in: Theoretical Foundation of Chemical Engineering, 2007, vol. 41, no. 6, pp. 831–838.
M. M. Silaev, “Simulation of Initiated Nonbranched Chain Oxidation of Hydrogen: Oxygen as an Autoinhibitor”, Khimiya Vysokich Energii, 2008, vol. 42, no. 2, pp. 124–129, English Translation in: High Energy Chemistry, 2008, vol. 42, no. 1, pp. 95–100.
N. N. Semenov, “Tsepnye reaktsii” (“Chain Reactions”), Goskhimtekhizdat, Leningrad, 1934, pp. 241, 203.
J. S. Francisco and I. H. Williams, “The Thermochemistry of Polyoxides and Polyoxy Radicals”, International Journal of Chemical Kinetics, 1988, vol. 20, no. 6, pp. 455–466.
D. J. McKay and J. S. Wright, “How Long Can You Make an Oxygen Chain?”, Journal of the American Chemistry Society, 1998, vol. 120, no. 5, pp. 1003– 1013.
N. P. Lipikhin, “Dimers, Clusters, and Cluster Ions of Oxygen in the Gas Phase”, Uspekhi Khimii, 1975, vol. 44, no. 8, pp. 366–376.
S. D. Razumovskii, “Kislorod – elementarnye formy i svoistva” (“Oxygen: Elementary Forms and Properties”), Khimiya, Moscow, 1979.
K. M. Dunn, G. E. Scuceria, and H. F. Schaefer III, “The infrared spectrum of cyclotetraoxygen, O4: a theoretical investigation employing the single and double excitation coupled cluster method”, The Journal of Chemical Physics, 1990, vol. 92, no. 10, pp. 6077–6080.
L. Brown and V. Vaida, “Photoreactivity of Oxygen Dimers in the Ultraviolet”, The Journal of Physical Chemistry, 1996, vol. 100, no. 19, pp. 7849–7853.
V. Aquilanti, D. Ascenzi, M. Bartolomei, D. Cappelletti, S. Cavalli, M. de Castro-Vitores, and F. Pirani, “Molecular Beam Scattering of Aligned Oxygen Molecules. The Nature of the Bond in the O2– O2 Dimer”, Journal of the American Chemistry Society, 1999, vol. 121, no. 46, pp. 10794–1080.
F. Cacace, G. de Petris, and A. Troiani, “Experimental Detection of Tetraoxygen”, Angewandte Chemie, Internation Edition (in English), 2001, vol. 40, no. 21, pp. 4062–4065.
H. S. Taylor, “Photosensitisation and the Mechanism of Chemical Reactions”, Transactions of the Faraday Society, 1926, vol. 21, no. 63(3), pp. 560–568.
S. N. Foner and R. L. Hudson, “Mass spectrometry of the HO2 free radical”, The Journal of Chemical Physics, 1962, vol. 36, no. 10, p. 2681.
S. N. Foner and R. L. Hudson, “Mass spectrometry of the HO2 free radical”, The Journal of Chemical Physics, 1962, vol. 36, no. 10, p. 2681.
P. D. Lightfoot, B. Veyret, and R. Lesclaux, “Flash Photolysis Study of the CH3O2 + HO2 Reaction between 248 and 573 K”, The Journal of Physical Chemistry, 1990, vol. 94, no. 2, pp. 708–714.
P. Smith, “The HO3 and HO4 Free Radicals”, Chemistry and Industry, 1954, no. 42, pp. 1299–1300. [28] A. J. B. Robertson, “A Mass Spectral Search for H2O4 and HO4 in a Gaseous Mixture Containing HO2 and O2”, Chemistry and Industry, 1954, no. 48, p. 1485.
D. Bahnemann and E. J. Hart, “Rate Constants of the Reaction of the Hydrated Electron and Hydroxyl Radical with Ozone in Aqueous Solution”, The Journal of Physical Chemistry, 1982, vol. 86, no. 2, pp. 252–255.
] G. C. Pimentel and A. L. McClellan, “The Hydrogen Bond”, L. Pauling, Editor, Freeman, San Francisco, 1960, p. 200.
“Vodorodnaya svyaz’: Sbornik statei” (“The Hydrogen Bonding: Collection of Articles”) N. D. Sokolov, Editor, Nauka, Moscow, 1981.
J. Staehelin, R. E. Bühler, and J. Hoigné, “Ozone Decomposition in Water Studied by Pulse Radiolysis. 2. OH and HO4 as Chain Intermediates”, The Journal of Physical Chemistry, 1984, vol. 88, no. 24, pp. 5999–6004.
F. Cacace, G. de Petris, F. Pepi, and A. Troiani, “Experimental Detection of Hydrogen Trioxide”, Science, 1999, vol. 285, no. 5424, pp. 81–82.
R. F. Bühler, J. Staehelin, and J. Hoigné, “Ozone Decomposition in Water Studied by Pulse Radiolysis. 1. HO2/O2–and HO3/O3–as Intermediates”, The Journal of Physical Chemistry, 1984, vol. 88, no. 12, pp. 2560–2564.
I. V. Trushkov, M. M. Silaev, and N. D. Chuvylkin, “Acyclic and Cyclic Forms of the Radicals
∙ HO4,∙
CH3O4, and ∙
C2H5O4: Ab Initio Quantum
Chemical Calculations”, Izvestiya Akademii Nauk, Ser.: Khimiya, 2009, no. 3, pp. 479–482, English Translation in: Russian Chemical Bulletin, International Edition, 2009, vol. 58, no. 3, pp. 489– 492.
. A. Mansergas, J. M. Anglada, S. Olivella, M. F. Ruiz-López, “On the Nature of the Unusually Long OO Bond in HO3 and HO4 Radicals”, Phys. Chem. Chem. Phys., 2007, vol. 9, no. 44, pp. 5865–5873.
W. Wong and D. D. Davis, “A Flash Photolysis Resonance Fluorescence Study of the Reactions of Atomic Hydrogen and Molecular Oxygen: H + O2 + M → HO2 + M”, International Journal of Chemical Kinetics, 1974, vol. 6, no. 3, pp. 401–416.
S. W. Benson, “Thermochemical Kinetics: Methods for the Estimation of Thermochemical Data and Rate Parameters”, 2nd Edition, Wiley, New York, 1976.
Yagodovskaya, T.V. and Nekrasov, L.I., “Use of Infrared Spectroscopy to Study Frozen Hydrogen– Oxygen Systems Containing Hydrogen Polyoxides”,
Zhurnal Fizicheskoi Khimii, 1977, vol. 51, no. 10, pp. 2434–2445.
X. Xu, R. P. Muller, and W. A. Goddard III, “The Gas Phase Reaction of Singlet Dioxygen with Water: a Water-Catalyzed Mechanism”, Proceedings of the National Academy Sciences of the United States of America, 2002, vol. 99, no. 6, pp. 3376–3381.
E. T. Seidl and H. F. Schaefer III, “Is There a Transition State for the Unimolecular Dissociation of Cyclotetraoxygen (O4)?”, The Journal of Chemical Physics, 1992, vol. 96, no. 2, pp. 1176–1182.
R. Hernández-Lamoneda and A. Ramírez-Solís, “Reactivity and Electronic States of O4 along Minimum Energy Paths”, The Journal of Chemical Physics, 2000, vol. 113, no. 10, pp. 4139–4145.
A. J. C. Varandas and L. Zhang, “Test Studies on the Potential Energy Surface and Rate Constant for the OH + O3 Atmospheric Reaction”, Chemical Physics Letters, 2000, vol. 331, nos. 5–6, pp. 474–482.
“Atmosfera. Spravochnik” (“Atmosphere: A Handbook”), Gidrometeoizdat, Leningrad, 1991. [45] H. Okabe, “Photochemistry of Small Molecules”, Wiley, New York, 1978.
A. B. Nalbandyan and V. V. Voevodskii, “Mekhanizm okisleniya i goreniya vodoroda” (“Mechanism of Hydrogen Oxidation and Combustion”), V. N. Kondrat'ev, Editor, Akad. Nauk SSSR, Moscow, 1949.
L. Bateman, “Olefin Oxidation”, Quarterly Reviews, 1954, vol. 8, no. 2, pp. 147–167.
A. W. Boyd, C. Willis, and O. A. Miller, “A Re examiation of the Yields in the High Dose Rate Radiolysis of Gaseous Ammonia”, Canadian Journal of Chemistry, 1971, vol. 49, no. 13, pp. 2283–2289.
M. M. Silaev, “Competition Mechanism of Substre Inhibited Radical Chain Addition to Double Bond”, Neftekhimiya, 2000, vol. 40, no. 1, pp. 33–40, English Translation in: Petroleum Chemistry, 2000, vol. 40, no. 1, pp. 29–35.
. M. Silaev, Mathematical Simulation of Kinetics of Radiation-Induced Free-Radical Oxidation by Nonbranched-Chain Mechanism // Recent Innovations in Chemical Engineering, 2015, vol. 8, no. 2, pp. 112– 124.
M. M. Silaev, “Low-reactive Free Radicals Inhibiting Nonbranched Chain Processes of Addition”, Biofizika, 2005, vol. 50, no. 4, pp. 585– 600, English Translation in: Biophysics, 2005, vol. 50, no. 4, pp. 511–524.
M. M. Silaev, Kinetics of the Free-Radical Nonbranched-Chain Addition // American Journal of Polymer Science and Technology, 2017, vol. 3, no. 3, pp. 29-49.
