Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System

Michael M. Silaev
Michael M. Silaev * §
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Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System

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Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System Banner

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Abstract

Five reaction schemes are suggested for the initiated nonbranched-chain addition of free radicals to the multiple bonds of the unsaturated compounds. The proposed schemes include the reaction competing with chain propagation reactions through a reactive free radical. The chain evolution stage in these schemes involves three or four types of free radicals. One of them is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the suggested schemes, nine rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. These equations provide good fits for the nonmonotonic (peaking) dependences of the formation rates of the molecular products (1:1 adducts) on the concentration of the unsaturated component in binary systems consisting of a saturated component (hydrocarbon, alcohol, etc.) and an unsaturated component (olefin, allyl alcohol, formaldehyde, or dioxygen).

References

98 Cites in Article
  1. L Gurvich,G Karachevtsev,V Kondrat'ev,Yu Lebedev,V Medvedev,V Potapov,Yu Khodeev (1974). Bond Dissociation Energies, Proton, Hydride, Electron Affinities, and Ionization Potentials of C1 Hydrocarbon Ions.
  2. S Benson (1976). Thermochemical Kinetics: Methods for the Estimation of Thermochemical Data and Rate Parameters.
  3. J Pedley,R Naylor,S Kirby (1986). Thermochemical Data of Organic Compounds.
  4. D Yu,Yu Orlov,I Lebedev,Sh,Saifullin (2001). Termokhimiya organicheskikh svobodnykh radikalov.
  5. Ch,Walling (1956). Free Radicals in Solution.
  6. N Emanuel,E Denisov,Z Maizus (1965). Tsepnye reaktsii okisleniya uglevodorodov v zhidkoi faze.
  7. V Poluektov,E Babkina,I Begishev (1974). On the Dependence of the Rate of a Chain Reaction on the Reactant Ratio.
  8. M Silaev,L Bugaenko (1992). Mathematical simulation of the kinetics of radiation induced hydroxyalkylation of aliphatic saturated alcohols.
  9. M Silaev,L Bugaenko (1994). Kinetics of the Addition of α-Hydroxyalkyl Radicals to 2-Propen-1-ol and Formaldehyde.
  10. M Silaev (1999). ChemInform Abstract: Competition Kinetics of the Free‐Radical Addition, Inhibition of Nonbranched‐Chain Processes by Low‐Reactive Radicals.
  11. M Silaev (2007). Simulation of the nonbranched-chain addition of saturated free radicals to alkenes and their derivatives yielding 1: 1 adducts.
  12. M Silaev (2007). Simulation of nonbranched chain processes for producing 1,2-alkanediols in alcohol-formaldehyde systems.
  13. M Silaev (2001). A New Competitive Kinetic Model of Radical Chain Oxidation: Oxygen as an Autoinhibitor.
  14. M Silaev (2007). Simulation of the Initiated Addition of Hydrocarbon Free Radicals and Hydrogen Atoms to Oxygen via a Nonbranched Chain Mechanism.
  15. Y Bard (1974). Nonlinear Parameter Estimation.
  16. L Bateman (1954). Olefin Oxidation.
  17. W Urry,F Stacey,E Huyser,O Juveland (1954). The Peroxide- and Light-induced Additions of Alcohols to Olefins<sup>1</sup>.
  18. W Urry,O Juveland (1958). Free Radical Additions of Amines to Olefins<sup>1</sup>.
  19. A Shostenko,P Zagorets,A Dodonov,A Greish (1970). γ-Radiation-Induced Addition of Phosphorus Trichloride to Isobutylene.
  20. V Kim,A Shostenko,M Gasparyan (1979). Reactivity of Polychloroalkyl Radicals in the Telomerization of CCl 4 with 1-Propene and 2-Methyl-1-Propene.
  21. V Myshkin,A Shostenko,P Zagorets,K Markova,A Pchelkin (1977). Determination of absolute rate constants of addition of ethyl radicals to olefins.
  22. R Zamyslov,A Shostenko,I Dobrov,N Tarasova (1987). Kinetics of γ-Radiation-Induced Reactions of 2-Propanol with Trifluoropropene and Hexaflu-oropropene.
  23. M Silaev (1990). Dependence of Radiation-chemical γ-Diol Yields on the 2-Propen-1-ol Concentration in the γ-radiolysis of Aliphatic Saturated C 1 -C 3 Alcohol + 2-Propen-1-ol Systems.
  24. M Silaev (1994). Vestnik Moskovskogo universiteta. Seria 16. Biologia.
  25. L Bugaenko,M Kuzmin,L Polak (1993). Ellis Horwood/PTR Prentice-Hall Physical Chemistry Series. High-Energy Chemistry (Bugaenko, L. T.; Kuzmin, M. G.; Polak, L. S.; Kemp, T. J.; Horwood, Ellis).
  26. J Thomas (1967). Pulse γ-radiolysis of Aqueous Solutions of Methyl Iodide and Methyl Bromide. The Reactions of Iodine Atoms and Methyl Radicals in Water.
  27. S Ogorodnikov (1984). Formal'degid (Formaldehyde).
  28. Michael Silaev,A Rudnev,E Kalyazin (1979). Free Unsolvated Formaldehyde in Solutions: Influence of Temperature, Solvent Permittiity, and Total Formaldehyde Concentration.
  29. M Oyama (1965). A Free-Radical Reaction of Primary and Secondary Alcohols with Formaldehyde.
  30. G Nikitin,D Lefor,E Vorob'ev (1966). Free Radical Reaction of Primary Alcohols with Formaldehyde.
  31. M Dzhurinskaya,A Rudnev,E Kalyazin (1984). High Temperature UV Photolysis of Formaldehyde in Liquid Methanol.
  32. E Kalyazin,E Petryaev,O Shadyro (1977). Reaction between Oxyalkyl Radicals and Aldehydes.
  33. A Novoselov,M Silaev,L Bugaenko (2004). Effect of Temperature on the Yields of Final Products in the γ-Radiolysis of Formaldehyde Solutions in C1–C3 Alkanols.
  34. I Novoselov,M Silaev,L Bugaenko (2008). Dependence of Ethanediol Yield on Formaldehyde Concentration in γ-radiolysis of Methanol-Formaldehyde System at 373-473 K.
  35. A Novoselov,M Silaev,L Bugaenko (2010). γ-Induced single-step synthesis of ethylene glycol from methanol-formaldehyde solutions.
  36. I Novoselov,M Silaev,L Bugaenko (2007). Dependence of 1,2-Propanediol Yield on Formaldehyde Concentration in γ-radiolysis of Ethanol-Formaldehyde System at 373473 K.
  37. S Ya,A Pshezhetskii,V Kotov,V Milinchuk,V Roginskii,Tupikov (1972). EPR svobodnykh radikalov v radiatsionnoi khimii.
  38. M Silaev (1993). Estimating the Solvent Concentration in Formaldehyde Solutions at Various Temperatures.
  39. M Silaev (2002). Applied Aspects of the γ-Radiolysis of C1–C4 Alcohols and Binary Mixtures on Their Basis.
  40. M Silaev,L Bugaenko,E Kalyazin (1986). On the Possibility of Adequately Estimating the Rate Constants for the Reaction of Hydroxyalkyl Radicals with Each Other Using the Self-Diffusion Coefficients or Viscosities of the Corresponding Alcohols.
  41. V Sarkisov,A Logvinovich,V Shcherbakova,L Sadovskaуa,Т Sviridova,A Kapariha,D Sviridov (1975). STRUCTURE AND MORPHOLOGY CONTROL OF METAL-MATRIX COMPOSITES BY USING REDOX-ACTIVE NANOPHASES.
  42. M Silaev,; Seki,R Nagai,M Imamura (1968). Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in Which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System 43.
  43. V Ya,Shtern (1960). Mekhanizm okisleniya uglevodorodov v gazovoi faze (Mechanism of the Gas-Phase Oxidation of Hydrocarbons).
  44. H Bäckström (1934). Der Kettenmechanismus bei der Autoxydation von Aldehyden.
  45. A Aliev,V Saraeva (1983). Review for "Ring-opening yields and auto-oxidation rates of the resulting peroxy radicals from OH-oxidation of α-pinene and β-pinene".
  46. E Badin (1948). The Reaction between Atomic Hydrogen and Molecular Oxygen at Low Pressures. Surface Effects.
  47. A Buchachenko (1984). Kompleksy radikalov i molekulyarnogo kisloroda s organicheskimi molekulami.
  48. J Francisco,I Williams (1988). The Thermochemistry of Polyoxides and Polyoxy Radicals.
  49. V Kokorev,N Vyshinskii,V Maslennikov,I Abronin,G Zhidomirov,Yu. Aleksandrov (1981). Electronic structure and chemical trans-formations of peroxides.
  50. A Dmitruk,V Lobanov,L Kholoimova (1986). Role of Tetroxide Conformation in the Mechanism of Peroxy Radical Recombination.
  51. V Belyakov,R Vasil'ev,N Ivanova,B Minaev,O Osyaeva,G Fedorova (1987). Electronic Model of the Excitation of Chemiluminescence in the Oxidation of Organic Compounds.
  52. P Ase,W Bock,A Snelson (1986). Alkylperoxy and alkyl radicals. 1. Infrared spectra of CH3O2 and CH3O4CH3 and the ultraviolet photolysis of CH3O2 in argon + oxygen matrixes.
  53. G Pimentel,A Mcclellan (1960). The Hydrogen Bond.
  54. G Russell (1957). Deuterium-Isotope Effects in the Autooxidation of Aralkyl Hydrocarbons: Mechanism of the Interaction of Peroxy Radicals.
  55. M Silaev (1999). 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.
  56. M Silaev (1999). The Competition Kinetics of Radical-Chain Addition.
  57. Alexandre Darmanyan,Daniel Gregory,Yushen Guo,William Jenks,Laure Burel,Dominique Eloy,Pierre Jardon (1998). Quenching of Singlet Oxygen by Oxygen- and Sulfur-Centered Radicals: Evidence for Energy Transfer to Peroxyl Radicals in Solution.
  58. J Kanofsky (1986). Singlet Oxygen Production from the Reactions of Alkylperoxy Radicals. Evidence from 1268-nm Chemiluminescence.
  59. N Semenov (1934). Gas explosions and the theory of chain reactions.
  60. M Reznikovskii,Z Tarasova,B Dogadkin (1950). Oxygen Solubility in Some Organic Liquids.
  61. J Howard,K Ingold (1967). Absolute rate constants for hydrocarbon autoxidation. VI. Alkyl aromatic and olefinic hydrocarbons.
  62. Nathaniel Barr,Augustine Allen (1959). Hydrogen Atoms in the Radiolysis of Water.
  63. H Smith,A Napravnik (1940). Photochemical Oxidation of Hydrogen.
  64. P Pagsberg,J Eriksen,H Christensen (1979). Pulse radiolysis of gaseous ammonia-oxygen mixtures.
  65. M Silaev (2003). Competitive Mechanism of the Nonbranched Radical Chain Oxidation of Hydrogen Involving the Free Cyclohydrotetraoxyl Radical [OO•••H•••OO]•, which Inhibits the Chain Process.
  66. M Silaev (2008). Simulation of Initiated Nonbranched Chain Oxidation of Hydrogen: Oxygen as an Autoinhibitor.
  67. D Mckay,J Wright (1998). How Long Can You Make an Oxygen Chain?.
  68. N Lipikhin (1975). The Oxygen Dimers, Clusters, and Cluster Ions in the Gas Phase.
  69. S Razumovskii (1979). Kislorod -elementarnye formy i svoistva.
  70. Kevin Dunn,Gustavo Scuseria,Henry Schaefer (1990). The infrared spectrum of cyclotetraoxygen, O4: A theoretical investigation employing the single and double excitation coupled cluster method.
  71. L Brown,V Vaida (1996). Photoreactivity of Oxygen Dimers in the Ultraviolet.
  72. Vincenzo Aquilanti,Daniela Ascenzi,Massimiliano Bartolomei,David Cappelletti,Simonetta Cavalli,Miguel De Castro Vìtores,Fernando Pirani (1999). Molecular Beam Scattering of Aligned Oxygen Molecules. The Nature of the Bond in the O<sub>2</sub>−O<sub>2</sub> Dimer.
  73. Fulvio Cacace,Giulia De Petris,Anna Troiani (2001). Experimental Detection of Tetraoxygen.
  74. H Taylor (1926). Photosensitisation and the Mechanism of Chemical Reactions.
  75. A Nalbandyan,V Voevodskii (1949). Mekhanizm okisleniya i goreniya vodoroda.
  76. S Foner,R Hudson (1962). Mass Spectrometry of the HO2 Free Radical.
  77. J Hochanadel,J Ghormley,P Ogren (1972). Absorption Spectrum and Reaction Kinetics of the HO 2 Radical in the Gas Phase.
  78. J Robertson (1954). A Mass Spectral Search for H 2 O 4 and HO 4 in a Gaseous Mixture Containing HO 2 and O 2.
  79. E Bahnemann,Hart (1982). Rate Constants of the Reaction of the Hydrated Electron and Hydroxyl Radical with Ozone in Aqueous Solution.
  80. Peter Golden (1981). S. L. Tikhvinskii, editor. <i>Tataro-mongoly v Azii i Evrope: Sbornik statei</i> [The Tataro-Mongols in Asia and Europe: A Collection of Articles]. 2d ed., rev. Moscow: Izdatel'stvo “Nauka.” 1977. Pp. 502. 2 r. 49 k.
  81. J Staehelin,R Bühler,J Hoigné (1984). Ozone Decomposition in Water Studied by Pulse γradiolysis. 2. OH and HO 4 as Chain Intermediates.
  82. F Cacace,G De Petris,F Pepi,A Troiani (1999). Experimental Detection of Hydrogen Trioxide.
  83. R Bühler,J Staehelin,J Hoigné (1984). Ozone Decomposition in Water Studied by Pulse γradiolysis. 1. HO 2 /O 2 and HO 3 /O 3 as Intermediates.
  84. I Trushkov,M Silaev,N Chuvylkin (2009). Acyclic and cyclic forms of the radicals HO4⋅ CH3O4⋅ and C2H5O4·: ab initio quantum chemical calculations.
  85. A Mansergas,J Anglada,S Olivella,M Ruiz-López (2007). On the Nature of the Unusually Long OO Bond in HO 3 and HO 4 Radicals.
  86. W Wong,D Davis (1974). A flash photolysis‐resonance fluorescence study of the reaction of atomic hydrogen with molecular oxygen H + O<sub>2</sub> + M → HO<sub>2</sub> + M.
  87. X Xu,R Muller,W Goddard,Iii (2002). The Gas Phase Reaction of Singlet Dioxygen with Water: a Water-Catalyzed Mechanism.
  88. T Seidl,H Schaefer,Iii (1992). Is There a Transition State for the Unimolecular Dissociation of Cyclotetraoxygen (O4)?.
  89. R Hernández-Lamoneda,A Ramírez-Solís,; Varandas,L Zhang (2000). Reactivity and Electronic States of O 4 along Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in Which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System 91.
  90. Terence Armstrong (1991). V.M. Kotlyakov, ed. Glyatsiologicheskiy solver’ [Glaciological dictionary]. Leningrad, Gidrometeoizdat, 1984. 528p..
  91. H Okabe (1978). Photochemistry of Small Molecules.
  92. A Pikaev (1986). Sovremennaya radiatsionnaya khimiya. Radioliz gazov I zhidkostei.
  93. A Boyd,C Willis,O Miller (1971). A Re-examination of the Yields in the High Dose Rate Radiolysis of Gaseous Ammonia.
  94. M Silaev (2000). Competition Mechanism of Substrate-Inhibited Radical Chain Addition to Double Bond.
  95. M Silaev (2003). ChemInform Abstract: Competition Kinetics of the Free‐Radical Addition, Inhibition of Nonbranched‐Chain Processes by Low‐Reactive Radicals.
  96. M Silaev (2005). Low-reactive Free Radicals Inhibiting Nonbranched Chain Processes of Addition.
  97. R Sanderson (1963). Radical Reorganization and Bond Energies in Organic Molecules.
  98. Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in Which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System.
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How to Cite This Article

Michael Silaev. 2013. "Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System". Global Journal of Science Frontier Research, Global Journal of Science Frontier Research - B: Chemistry GJSFR-B Volume 13 (GJSFR Volume 13 Issue B6).

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Journal Specifications

Crossref Journal DOI 10.17406/GJSFR

Print ISSN 0975-5896

e-ISSN 2249-4626

Keywords
autoinhibitorcompetetionenergyhydrogenlow-reactive radical
Classification
GJSFR-B Classification FOR Code: 030601p
  • Submission ReceivedAugust 6, 2013
  • Peer Review Double Blind
    Handling Editor
  • Accepted August 26, 2013
  • Published September 9, 2013
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v1.2

Issue date
September 21, 2013

Language
English
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Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition with Reactions, in which the 1:1 Adduct Radicals Compete for Interaction with Saturated and Unsaturated Components of the Binary Reaction System

Michael Silaev
Michael Silaev Lomonosov Moscow State University
  • Submission ReceivedAugust 6, 2013
  • Peer Review Double Blind
    Handling Editor
  • Accepted August 26, 2013
  • Published September 9, 2013