Abstract
Formyl chloride has been generated in aqueous solution (i) by stopped-flow ozonation of vinyl chloride and (ii) by reacting dichloromethyl radicals with OH radicals using the pulse radiolysis technique. Vinyl chloride reacts in water with ozone (k = 1.7 × 104 dm3 mol-1 s-1, as determined by stopped-flow) yielding as final products (mol per mol of ozone) chloride ions (1.05), CO (1.01), and formate ions (0.06). Hydroxymethyl hydroperoxide (formaldehyde plus H2O2; 1.08) is also formed. HCl and formic acid are formed in less than 2 ms (the detection limit of the stopped-flow setup). At high pH the CO yield decreases (at pH 13.6 by 50%). It is concluded that the precursor of CO, HCl, and formic acid is formyl chloride. It predominantly decays into CO and HCl, and only at very high pH can hydrolysis to formic acid and HCl compete successfully. Using the pulse radiolysis technique dichloromethyl radicals are generated in Ar-saturated solutions from chloroform by reacting it with the solvated electron (originati...
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