Indirect spectrophotometric determination of aqueous ferrate(VI) based on its reaction with iodide in acidic media

Abstract

Ferrate(VI) (Fe(VI)) is utilized as an efficient and environmentally friendly water treatment agent that can be widely used for degradation of (in)organic pollutants in practical applications. However, only a few spectrophotometric methods for Fe(VI) determination were reported. In this study, a novel method for determining trace levels of aqueous Fe(VI) was developed based on the fact that Fe(VI) reacts with iodide at acidic pH to form iodine, which subsequently is treated with starch to yield the blue starch-iodine complex measured spectrophotometrically at 590 nm. The key measurement parameters, including acidic medium, starch dosages, temperature, time, and addition order were optimized to improve the sensitivity of detection. The increase in absorbance at 590 nm was linear with respect to Fe(VI) added (0.022–50 µM). Its sensitivity was determined as (4.61 ± 0.05) × 104 M−1 cm−1, which was higher than that of existing spectrophotometric methods. The principle for Fe(VI) determination was studied by investigating stoichiometry, kinetics, and mechanism of Fe(VI) reaction with iodide. The molar stoichiometry of Fe(VI) with I3− species was determined to be 1:2. The reaction of Fe(VI) with iodide followed a second-order rate law with first order in each reactant and displayed apparent anti-Arrhenius kinetics, then its reaction pathway was proposed as well. Furthermore, the established method was successfully applied to measure Fe(VI) in various environmental water samples. The results show that the proposed approach is simple, convenient, highly reproducible and extremely sensitive, and is also expected to be of use for kinetic studies of Fe(VI) reaction with (in)organic compounds under acidic conditions.