Reaction of methanol with chlorate ions in acid solution containing Hg+2 by NMR

The reaction rate of methanol was measured in solutions of sodium chlorate and sulfuric acid at several levels of temperature and concentration, ill the presence of mercuric nitrate. The progress of the reaction was monitored by proton NMR signals corresponding to methanol and formic acid. Chlorine dioxide formation was suppressed by adding mercuric nitrate, which was shown earlier to catalyze the disproportionation of the intermediate species, chlorous acid, and sequester chloride ions. The reaction is first order in methanol and chlorate concentration and in the Hammett acidity function. The reaction of formic acid, sodium chlorate and sulfuric acid was also studied using the same technique. Formic acid was stable and did not react with chlorate at a measurable rate, even at concentrations and temperatures of a commercial process. This study relates to commercial processes that produce chlorine dioxide by reducing chlorate ions with methanol.