The Free-Radical Nonbranched-Chain Initiated Formation of Ethylene Glycol from Methanol–Formaldehyde Solutions
DOI:
https://doi.org/10.6000/1929-5030.2020.09.01Keywords:
Methanol, Formaldehyde, Formation, Ethylene Glycol, Radiation-Chemical Yield, Rate Equation.Abstract
The mechanism and kinetics are developed for the free-radical nonbranched-chain initiated formation of ethylene glycol in methanol–formaldehyde solutions at formaldehyde concentrations of 0.1-3.1 mol dm-3 and temperatures of 373-473 K. The experimental concentrations of the free unsolvated form of formaldehyde are given at the different temperatures and total concentrations of formaldehyde in methanol. The experimental dependence of the radiation-chemical yields of ethylene glycol on formaldehyde concentration in γ-radiolysis of methanol-formaldehyde solutions at 373-473 K is shown. At a formaldehyde concentration of 1.4 mol dm-3 and T = 473 K, the radiation-chemical yield of ethylene glycol is 139 molecules per 100 eV. The effective activation energy of ethylene glycol formation is 25 ± 3 kJ mol-1. The quasi-steady-state treatment of the reaction network suggested here led to a rate equation accounting for the non-monotonic dependence of the ethylene glycol formation rate on the concentration of the free (unsolvated) form of dissolved formaldehyde. It is demonstrated that the peak in this dependence is due to the competition between methanol and CH2=O for reacting with adduct radical HOCH2CH2O-¢.
References
[1] Novoselov AI, Silaev MM, Bugaenko LT. Effect of Temperature on the Yields of Final Products in the ?- Radiolysis of Formaldehyde Solutions in ?1–?3 Alkanols. Khim Vys Energ 2004; 38(4): 270
[High Energy Chem (Engl Transl), 38(4): 236]. https://doi.org/10.1023/B:HIEC.0000035410.87205.09
[2] Silaev MM, Bugaenko LT. Mathematical Simulation of the Kinetics of Radiation Induced Hydroxyalkylation of Aliphatic Saturated Alcohols. Radiat Phys Chem 1992; 40(1): 1. https://doi.org/10.1016/1359-0197(92)90131-X
[3] Ogorodnikov SK. Formal’degid (Formaldehyde), Leningrad: Khimiya 1984.
[4] Silaev MM, Rudnev AV, Kalyazin EP. Formaldehyde. III. The Concentration of Free Formaldehyde as a Function of Temperature, Solvent Polarity, and the Total Formaldehyde Concentration in the Solution. Zh Fiz Khim 1979; 53(7): 1647.
[5] Silaev MM. Estimating the Solvent Concentration in Formaldehyde Solutions at Various Temperatures. Zh Fiz Khim 1993; 67(9): 1944.
[6] Novoselov AI, Silaev MM, Bugaenko LT. Dependence of Ethanediol Yield on Formaldehyde Concentration in ?- Radiolysis of Methanol–Formaldehyde System at 373–473 K. Khim Vys Energ 2008; 42(1): 74-75
[High Energy Chem (Engl Transl), 42(1): 69-70]. https://doi.org/10.1134/S0018143908010141
[7] Yanovskaya LA, Yufit SS, Kucherov VF. Khimiya atsetalei (Chemistry of Acetals), Moscow: Nauka 1975.
[8] Silaev MM. Simulation of nonbranched chain processes for producing 1,2-alkanediols in alcohol-formaldehyde systems. Teor Osn Khim Tekhnol 2007; 41(4): 379
[Theor Found Chem Eng (Engl Transl), 41(4): 357]. https://doi.org/10.1134/S0040579507040045
[9] Oyama M. A Free-Radical Reaction of Primary and Secondary Alcohols with Formaldehyde. J Org Chem 1965; 30(7): 2429. https://doi.org/10.1021/jo01018a079
[10] Dzhurinskaya MB, Rudnev AV, Kalyazin EP. High Temperature UV Photolysis of Formaldehyde in Liquid Methanol. Vestn Mosk Univ Ser 2: Khim 1984; 25(2): 173.
[11] Seki H, Nagai R, Imamura M. ?-Radiolysis of a Binary Mixture of Methanol and Water. The Formation of Formaldehyde in the Radiolysis of Liquid Methanol. Bull Chem Soc Jpn 1968; 41(12): 2877. https://doi.org/10.1246/bcsj.41.2877
[12] Orlov YuD, Lebedev YuA, Saifullin ISh. Termokhimiya organicheskikh svobodnykh radikalov (Thermochemistry of Organic Free Radicals), Kutepov, A.M., Ed., Moscow: Nauka 2001.
[13] Benson SW. Thermochemical Kinetics: Methods for the Estimation of Thermochemical Data and Rate Parameters, New York: Wiley 1968.
[14] Gurvich LV, Karachevtsev GV, Kondrat’ev VN, Lebedev YuA. Medvedev VA, Potapov VK, Khodeev YuS. Energii razryva khimicheskikh svyazei. Potentsialy ionizatsii I srodstvo k elektronu (Bond Dissociation Energies, Ionization Potentials, and Electron Affinity), Kondrat’ev, V.N., Ed., Moscow: Nauka 1974.
[15] Pshezhetskii SYa, Kotov AG, Milinchuk VK, Roginskii VA, Tupikov VI. EPR svobodnykh radikalov v radiatsionnoi khimii (ESR of Free Radicals in Radiation Chemistry), Moscow: Khimiya 1972; p. 212.
[16] Sanderson RT. Radical Reorganization and Bond Energies in Organic Molecules. J Org Chem 1982; 47(20): 3835. https://doi.org/10.1021/jo00141a006
[17] Silaev MM. Applied Aspects of the ?-Radiolysis of C1-C4 Alcohols and Binary Mixtures on Their Basis. Khimiya Vysokikh Energii 2002; 36(2): 97-101
[High Energy Chem (Engl Transl), 36(2): pp. 70-74].
[18] Vereshchinskii IV, Pikaev AK. Vvedenie v radiatsionnuyu khimiyu (Introduction to Radiation Chemistry), Spitsyn, V.I., Ed., Moscow: Akad. Nauk SSSR 1963; p. 190.
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