The effect of aqueous complexation on the decarboxylation rate of oxalate

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Understanding the role of carboxylic acid anions in sedimentary basin fluid-rock interactions requires an accurate knowledge of the decarboxylation rates of the anions. In this study, the decarboxylation rate of oxalate was measured in solutions with and without aqueous Al, a strongly complexing cation, at 160, 170, and 180°C. This is the first investigation of the effect of aqueous complexation on decarboxylation rates. Previous studies measured decarboxylation rates of carboxylic acid anions only in solutions free of strongly complexing cations. This study indicates that aqueous aluminum can decrease the decarboxylation rate of oxalate significantly. The magnitude of this effect increases with decreasing temperature. Extrapolation of the experimental results suggests that when oxalate is present in solution as a part of a highly stable aqueous complex, the half-life of oxalate at 80°C may be as much as three orders of magnitude longer than it would be when the oxalate is present as an acid anion only.

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