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Reaction of methanol with chlorate ions in acid solution containing Hg +2 by NMR
Author(s) -
Ernst William R.,
Indu Bhart,
Crump Brian,
Gelbaum Leslie T.
Publication year - 1996
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690420518
Subject(s) - chemistry , chlorate , methanol , ion , inorganic chemistry , nuclear chemistry , organic chemistry
Abstract The reaction rate of methanol was measured in solutions of sodium chlorate and sulfuric acid at several levels of temperature and concentration, in 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 commerical processes that produce chlorine dioxide by reducing chlorate ions with methanol.