Analytical Sciences

Abstract − Analytical Sciences, 20(3), 513 (2004).

Potentiometric Determination of Bromate Using an Fe(III)-Fe(II) Potential Buffer by Circulatory Flow-Injection Analysis
Hiroki OHURA,* Toshihiko IMATO,** Kiminori KAMEDA,* and Sumio YAMASAKI*
*Department of Industrial Chemistry, Faculty of Engineering, Kyushu Sangyo University, Fukuoka 813-8503, Japan
**Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, Fukuoka 812-8501, Japan
A method for the potentiometric determination of bromate by circulatory flow injection analysis (CFIA) is described. The procedure involves the use of an Fe(III)-Fe(II) potential buffer solution, which is recycled via a reservoir. The analytical method is based on a linear relationship between the concentration of bromate and a very transient potential change in the electrode potential due to the generation of intermediate bromine during the reaction of bromate with the Fe(III)-Fe(II) potential buffer solution, which also contains NaBr, (NH4)6Mo7O24 and H2SO4. An aliquot (5 µl) of a bromate sample solution was injected into the stream of the potential buffer solution, 100 ml of which was circulated at a flow rate of 1 ml/min; the potential buffer solution stream was then returned to the reservoir after passing through a flowthrough redox electrode detector. A potential change due to the reaction of the injected sample with the potential buffer in a reaction coil was measured with the detector in the form of a peak signal. The effects of the bromide, sulfuric acid and Fe(III)-Fe(II) concentrations in the potential buffer, and length of the reaction coil on the peak heights were examined in order to optimize the proposed CFIA method. The analytical sensitivities to bromate were 5.6 mV/µM for 1 × 10-2 M and 30.9 mV/µM for 1 × 10-3 M in the concentration of Fe(III)-Fe(II) in a potential buffer solution containing 0.35 M NaBr, 0.2% (NH4)6Mo7O24 and 1 M H2SO4. The detection limit of bromate obtained by a 1 × 10-3 M Fe(III)-Fe(II) potential buffer solution was 0.02 µM (2.5 ppb). The numbers of repetitive determinations in which the relative sensitivities within 5% were regarded as being tolerated were ca. 4000 and 2000 for the use of only 100 ml of 1 × 10-2 M and 1 × 10-3 M Fe(III)-Fe(II) potential buffer solution, respectively.