Journal of the Chemical Society. Perkin transactions II p. 699 - 704 (1984)
Update date:2022-08-11
Topics:
Schuchmann, Man Nien
Sonntag, Clemens von
In the radiolysis of aqueous solutions of trimethyl phosphate saturated with N2O-O2 the major products (G values in parentheses) are dimethyl hydrogen phosphate (6.4), formic acid (3.4), formaldehyde (1.7), hydrogen peroxyde (2.1), organic peroxide (0.5), and carbon monoxide (1.0).Oxygen is consumed (G 4.1).In the dimethyl phosphate (sodium salt) system the products and their G values are similar to those of the trimethyl phosphate system.Pulse radiolytic studies have shown that in trimethyl phosphate system the first formed peroxyl radicals react with each other to give a short lived tetraoxide (2k = 9 x 1E8 dm3 mol-1 s-1).This intermediate decays either by concerted mechanism or by fragmentation to form O2 and two oxyl radicals.Among other reactions these oxyl radicals undergo a 1,2-hydrogen shift, followed by a complex series of reactions.There are two processes that yield acids at longer reaction times.The faster process has been identified as the hydrolysis of formic dimethylphosphoric anhydride (k = 0.3 + 2.3 x 1E4
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