Kinetics and Mechanism of the Oxidation of Bromide by Periodate in Aqueous Acidic Solution

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 118; no. 45; pp. 10713 - 10719
• Main Authors: Szel, Viktor, Cseko, Gyorgy, Horvath, Attila K
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.11.2014
• Subjects: Bromides; Bromides - chemistry; Bromine; Buffers; Coefficients; Constants; Formations; Hydrogen-Ion Concentration; Kinetics; Models, Chemical; Oxidation-Reduction; Periodic Acid - chemistry; Phosphates; Reaction kinetics; Spectrophotometry; Water - chemistry
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/jp509164e

The periodate–bromide reaction has been studied spectrophotometrically mainly in excess of bromide ion, monitoring the formation of the total amount of bromine at 450 nm at acidic buffered conditions and at a constant ionic strength in the presence of a phosphoric acid/dihydrogen phosphate buffer. The stoichiometry of the reaction was established to be strictly IO4 – + 2Br– + 2H+ → Br2 + IO3 – + H2O. The formal kinetic order of the reactants was found to be perfectly one and two in the cases of periodate and bromide, respectively, but that of the hydrogen ion lies between one and two. We have also provided experimental evidence that dihydrogen phosphate accelerates the formation of bromine, suggesting the appearance of strong buffer assistance. On the basis of the experiments, a simple two-step kinetic model is proposed involving BrIO3 as a key intermediate that perfectly explains all of the experimental findings. Furthermore, we have also shown that in huge excess of bromide, the apparent rate coefficient obtained from the individual curve fitting method of the absorbance–time series is necessarily independent of the initial periodate concentration that may falsely be interpreted as the rate of bromine formation is also independent of the concentration of periodate.