The Catalytic Cycle of Oxidation of Iodide Ion in the Oxygen/Nitrous Acid/Nitric Oxide System and Its Potential for Analytical Applications

Abstract The oxidation of iodide to iodine by nitrous acid in aqueous acidic medium takes place catalytically in the presence of dissolved oxygen and can be followed spectrophotometrically at 288 and 352 nm. An indirect molar absorptivity for nitrite on the basis of I3 − formation can be as high as 8.5×105 L mol−1 cm−1 at 288 nm. Analytical curves were established. The iodine released in the catalytic cycle can also be titrated with thiosulfate. The reaction is pseudo–second‐order in oxygen consumed, with t1/2=15.7 min at 25°C. A rate determining step could be the NO · O2 as the activated species. Measurements of the iodine formed at catalytic conditions was used to determine nitrite in meat extracts and NOx in car exhausts.