Abstract — The mechanism and kinetics are developed for the initiated non branched-chain formation of ethanediol 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 insolated 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 ethanediol 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 ethanediol is 139 molecules per 100 eV. The effective activation energy of ethanediol 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 ethanediol 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 the adduct radical HOCH2CH2O•.
Keywords — Methanol, Formaldehyde, Formation, Ethanediol, Radiation-Chemical Yield, Rate Equation.
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