title: Determination of water with a modified Karl Fischer reagent Stability and the mechanism of reaction with water.
abstract: It is shown that the water equivalent of the modified Karl Fischer reagent (standard Karl Fischer reagent in which dimethylformamide is substituted for methanol), depending on pKa and the concentration of the solvent used for preliminary titration, is not dependent on the water concentration being determined. Also discussed are different aspects of the stability of the Karl Fischer reagent and its modifications. On the basis of the literature data and the findings of this work, a mechanism of interaction between water and the modified Karl Fischer reagent is proposed: in the first stage of the reaction pyridine sulphodioxide is solvated with solvents containing active hydrogen (alcohols, organic acids and water). The lower the value of pK(a) of the solvent, the greater the contribution of water to the pyridine sulphodioxide solvation reaction. The results of this work suggest that, especially in particular cases, the water equivalent of the Karl Fischer reagent and its modifications should be determined under the same conditions as the determination of water in the sample.
authors.affiliation: N. D. Zelinsky Institute of Organic Chemistry, Academy of Sciences of the USSR, Leninsky Prospect 47, Moscow B-334, USSR.
authors.forename: F B
authors.initials: FB
authors.lastname: Sherman