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 chlo rate and sulfuric acid at several levels of temperature and concentrat ion, ill the presence of mercuric nitrate. The progress of the reactio n was monitored by proton NMR signals corresponding to methanol and fo rmic acid. Chlorine dioxide formation was suppressed by adding mercuri c nitrate, which was shown earlier to catalyze the disproportionation of the intermediate species, chlorous acid, and sequester chloride ion s. The reaction is first order in methanol and chlorate concentration and in the Hammett acidity function. The reaction of formic acid, sodi um chlorate and sulfuric acid was also studied using the same techniqu e. Formic acid was stable and did not react with chlorate at a measura ble rate, even at concentrations and temperatures of a commercial proc ess. This study relates to commercial processes that produce chlorine dioxide by reducing chlorate ions with methanol.