Investigation of amine-buffered amide reagents for coulometric Karl Fischer titration

Formamide (FA), N-methylformamide (NMF), and dimethylformamide (DMF), were evaluated as solvents for coulometric Karl Fischer (KF) reagents in combination with several amine bases. Except for the effect of the iodine species (iodine or triiodide), the pH of the reagent and the position of the sulfur dioxide/hydrogen sulfite equilibrium were found to be the main factors explaining the large difference in the observed reaction rates between water and the KF reagent in these solvents. Acid–base titrations showed that hydrogen sulfite is the main sulfur reactant in these media. The results will be of great importance in finding suitable combinations of base and solvent with respect to stoichiometry, side reactions caused by active carbonyl compounds, and reagent stability.