Kinetics of Free-Radical Nonbranched-Chain Processes of Formation of 1,2-Alkanediols, Carbonyl Compounds, and Methanol in Alcohol–Formaldehyde Solutions Including Determination of Free Formaldehyde and Solvent Concentrations

Authors

  • Michael M Silaev Chemistry Faculty, Lomonosov Moscow State University, Vorobievy Gory, Moscow 119991, Author

Keywords:

nonbranched-chain process, free formaldehyde, 1-hydroxyalkyl radical, formyl radical, competing reaction, equa tion.

Abstract

A mechanism of the initiated nonbranched-chain process of form ing 1,2-alkanediols, carbonyl compounds, and methanol in alco hol–formaldehyde systems is suggested. The quasi-steady-state  treatment is used to obtain kinetic equations that can describe the  nonmonotonic (with a maximum) dependences of the formation  rates of the products on the concentration of free unsolvated for maldehyde. The experimental concentrations of the free unsol vated form of formaldehyde are given at the different temperatures,  solvent permittivity, and total concentrations of formaldehyde in  water and alcohols. An empirical equation for calculating the free  formaldehyde concentration in alcohol–formaldehyde (including  water/ethanediol –formaldehyde) systems at various temperatures  and total formaldehyde concentrations and an equation for eva luating solvent concentrations in these systems were derived. The  experimental dependence of the ethanediol radiation-chemical  yields on formaldehyde concentration in γ-radiolysis of metha nol–formaldehyde system at 373–473 K is shown. 

Downloads

Download data is not yet available.

References

S. K. Ogorodnikov, Formal'degid (Formaldehyde), Khimiya, Leningrad, 1984.

M. M. Silaev, A. V. Rudnev, and E. P. Kalyazin, “Formal dehyde. III. Concentration of Free Formaldehyde as a Func tion of Temperature, Polarity of Solvents, and Total Concen tration of Formaldehyde in Solution”, Zhurnal Fizicheskoi

Khimii, 1979, vol. 53, no. 7, pp. 1647–1651.

L. V. Gurvich, G. V. Karachevtsev, V. N. Kondrat'ev, Yu. A. Lebedev, V. A. Medvedev, V. K. Potapov, and Yu. S. Kho deev, “Energii razryva khimicheskikh svyazei. Potentsialy ionizatsii i srodstvo k elektronu” (“Bond Dissociation Ener gies, Ionization Potentials, and Electron Affinity”), V. N. Kondrat'ev, Editor, Nauka, Moscow, 1974.

S. W. Benson, “Thermochemical Kinetics: Methods for the Estimation of Thermochemical Data and Rate Parameters”, 2nd Edition, Wiley, New York, 1976.

J. B. Pedley, R. D. Naylor, and S. P. Kirby, “Thermochemical Data of Organic Compounds”, 2nd Edition, Chapman & Hall, London, 1986.

Yu. D. Orlov, Yu. A. Lebedev, and I. Sh. Saifullin, “Ter mokhimiya organicheskikh svobodnykh radikalov” (“Ther mochemistry of Organic Free Radicals”), A. M. Kutepov, Editor, Nauka, Moscow, 2001.

M. M. Silaev and L. T. Bugaenko, “Kinetics of the Addition of α-Hydroxyalkyl Radicals to 2-Propen-1-ol and Formal

dehyde”, Kinetics and Katalysis, 1994, vol. 35, no. 4, pp. 509–513, English Translation in: Kinetics and Katalysis, 1994, vol. 35, no. 4, 1994, pp. 463–467.

M. M. Silaev, “Simulation of Nonbranched Chain Processes for Producing 1,2-Alkanediols in Alcohol–Formaldehyde Systems”, Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2007, vol. 41, no. 4, pp. 379–384, English Translation in: Thoretical Foundations Chemical Engineering, 2007, vol. 41, no. 4, pp. 357–361.

Oyama, M., “A Free-Radical Reaction of Primary and Sec ondary Alcohols with Formaldehyde”, The Journal of Or ganic Chemistry, 1965, vol. 30, no. 7, pp. 2429–2432.

G. I. Nikishin, D. Lefor, and E. D. Vorob’ev, “Free Radical Reaction of Primary Alcohols with Formaldehyde”, Izvestiya Akademii Nauk SSSR, Ser. Khimiya, 1966, no. 7, pp. 1271–1272.

W. H. Urry, F. W. Stacey, E. S. Huyser, and O. O. Juveland, “The Peroxide- and Light-Induced Additions of Alcohols to Olefins”, Journal of the American Chemical Society, 1954, vol. 76, no. 2, pp. 450–455.

M. B. Dzhurinskaya, A. V. Rudnev, and E. P. Kalyazin, “High Temperature UV Photolysis of Formaldehyde in Liq uid Methanol”, Vestnik Moskovskogo Universiteta, Ser. 2: Khimiya, 1984, vol. 25, no. 2, pp. 173–176.

E. P. Kalyazin, E. P. Petryaev, and O. I Shadyro, “Reaction between Oxyalkyl Radicals and Aldehydes”, Zhurnal Orga nicheskoi Khimii, 1977, vol. 13, no. 2, pp. 293–295.

A. I. Novoselov, A.I., Silaev, M.M., and L. T. Bugaenko, “Effect of Temperature on the Yields of Final Products in the γ-Radiolysis of Formaldehyde Solutions in C1–C3 Alkanols”, Khimiya Vysokich Energii, 2004, vol. 38, no. 4, pp. 270–272, English Translation in: High Energy Chemistry, 2004, vol. 38, no. 4, 2004, pp. 236–238.

M. M. Silaev and L. T. Bugaenko, “Mathematical Simulation of the Kinetics of Radiation Induced Hydroxyalkylation of Aliphatic Saturated Alcohols”, Radiation Physics and Che mistry, 1992, vol. 40, no. 1, pp. 1–10.

A. I. Novoselov, M. M. Silaev, and L. T. Bugaenko, “De pendence of Ethanediol Yield on Formaldehyde Concentra tion in γ-Radiolysis of Methanol–Formaldehyde System at 373–473 K”, Khimiya Vysokikh Energii, 2008, vol. 42, no. 1, pp. 74–75, English Translation in: High Energy Chemistry, 2008, vol. 42, no. 1, pp. 69–70.

A. I. Novoselov, M. M. Silaev, and L. T. Bugaenko, “γ-Induced Single-Step Synthesis of Ethylene Glycol from Methanol–Formaldehyde Solution”, Theoreticheskie Osnovy Khimicheskoy Tekhnologii, 2010, vol. 44, no. 4, pp. 450–453,

English Translation in: Theoretical Foundation of Chemical Engineering, 2010, vol. 44, no. 4, pp. 432–435.

A. I. Novoselov, M. M. Silaev, and L. T. Bugaenko, “De pendence of 1,2-Propanediol Yield on Formaldehyde Con centration in γ-Radiolysis of Ethanol–Formaldehyde System at 373–473 K”, Khimiya Vysokikh Energii, 2007, vol. 41, no. 1, p. 58, English Translation in: High Energy Chemistry, 2007, vol. 41, no. 1, p. 53.

S. Ya. Pshezhetskii, A. G. Kotov, V. K. Milinchuk, V. A. Roginskii, and V. I. Tupikov, “EPR svobodnykh radikalov v radiatsionnoi khimii” (“ESR of Free Radicals in Radiation

Chemistry”), Khimiya, Moscow, 1972.

L. Bateman, “Olefin Oxidation”, Quarterly Reviews, 1954, vol. 8, no. 2, pp. 147–167.

M. M. Silaev, “Simulation of the Nonbranched-Chain Addi tion of Saturated Free Radicals to Alkenes and Their Deriva tives Yielding 1:1 Adducts”, Teoreticheskie Osnovy Khimi cheskoi Tekhnologii, 2007, vol. 41, no. 3, pp. 280–295, Eng lish Translation in: Theoretical Foundations of Chemical

Engineering, 2007, vol. 41, no. 3, pp. 273–278.

M. M. Silaev, “Applied Aspects of the γ-Radiolysis of C1–C4 Alcohols and Binary Mixtures on Their Basis”, Khimiya Vysokikh Energii, 2002, vol. 36, no. 2, pp. 97–101, English Translation in: High Energy Chemistry, 2002, vol. 36, no. 2, pp. 70–74.

M. M. Silaev, “Estimating the Solvent Concentration in Formaldehyde Solutions at Various Temperatures”, Zhurnal Fizicheskoy Khimii, 1993, vol. 67, no. 9, p. 1944.

M. M. Silaev, L. T. Bugaenko, and E. P. Kalyazin, “On the Possibility of Adequately Estimating of the Rate Constants for the Reaction of Hydroxyalkyl Radicals with Each Other Using the Self-Diffusion Coefficients or Viscosities of the Corresponding Alcohols”, Vestnik Moskovskogo. Univiver

siteta, Ser. 2: Khimiya, 1986, vol. 27, no. 4, pp. 386–389.

J. F. Walker, Formaldehyde, Reinhold, New York, 1953, English Translation under the title Formal’degid, Goskhi mizdat, Moscow, 1957, p. 106.

O. I. Shadyro, “Radiation-chemical Conversions of Alde hydes in Various Systems”, Ph.D. Thesis (Chemistry), Bela rusian State University, Minsk, 1975.

M. M. Silaev, “Relative Reactivity of α-Hydroxyethyl Radi cals for 2-Propene-1-ol and Formaldehyde Double-Bond Addition”, Vestnik Moskovskogo Universiteta, Ser. 2: Khi miya, 1993, vol. 34, no. 3, p. 311.

H. Seki, R. Nagai, and M. Imamura, “γ-Radiolysis of a Binary Mixture of Methanol and Water. The Formation of Formal dehyde in the Radiolysis of Liquid Methanol”, Bulletin of the Chemical Society of Japan, 1968, vol. 41, no. 12, pp. 2877–2881.

Downloads

Published

2018-09-01

How to Cite

Kinetics of Free-Radical Nonbranched-Chain Processes of Formation of 1,2-Alkanediols, Carbonyl Compounds, and Methanol in Alcohol–Formaldehyde Solutions Including Determination of Free Formaldehyde and Solvent Concentrations . (2018). International Journal of Innovative Research in Computer Science & Technology, 6(5), 102–109. Retrieved from https://acspublisher.com/journals/index.php/ijircst/article/view/13433