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Methanol-formic acid esterification equilibrium in sulfuric acid solutions: influence of sodium salts

Molar equilibrium quotients of methanol-formic acid esterification were measured in the concentration range 0-5 M sulfuric acid in the presence and absence of sodium sulfate and sodium nitrate. The sulfuric acid and sodium salts shifts equilibrium in favor of methyl formate. Sulfuric acid appears to catalyze the rate at which the system approaches equilibrium. Temperature had no measureable influence on the measured quotients. All of the data measured at 25°C were correlated with an expression of the form ln(K e ) = A + B[H 2 SO 4 ] + C[Na 2 SO 4 ] + D[NaNO 3 ] with reasonable accuracy. This expression has application in modeling of reactors in commercial chlorine dioxide processes that are based on methanol-chlorate chemistry