Hiroki Ohura

Simultaneous potentiometric determination of ClO3−–ClO2− and ClO3−–HClO by flow injection analysis using Fe(III)–Fe(II) potential buffer

A rapid potentiometric flow injection technique for the simultaneous determination of oxychlorine species such as ClO(3)(-)-ClO(2)(-) and ClO(3)(-)-HClO has been developed, using both a redox electrode detector and a Fe(III)-Fe(II) potential buffer solution containing chloride. The analytical method is based on the detection of a large transient potential change of the redox electrode due to chlorine generated via the reaction of the oxychlorine species with chloride in the potential buffer solution. The sensitivities to HClO and ClO(2)(-) obtained by the transient potential change were enhanced 700-800-fold over that using an equilibrium potential. The detection limit of the present method for HClO and ClO(2)(-) is as low as 5x10(-8) M with use of a 5x10(-4) M Fe(III)-1x10(-3) M Fe(II) buffer containing 0.3 M KCl and 0.5 M H(2)SO(4). On the other hand, sensitivity to ClO(3)(-) was low when a potential buffer solution containing 0.5 M H(2)SO(4) was used, but could be increased largely by increasing the acidity of the potential buffer. The detection limit for ClO(3)(-) was 2x10(-6) M with the use of a 5x10(-4) M Fe(III)-1x10(-3) M Fe(II) buffer containing 0.3 M KCl and 9 M H(2)SO(4). By utilizing the difference in reactivity of oxychlorine species with chloride in the potential buffer, a simultaneous determination method for a mixed solution of ClO(3)(-)-ClO(2)(-) or ClO(3)(-)-HClO was designed to detect, in a timely manner, a transient potential change with the use of two streams of potential buffers which contain different concentrations of sulfuric acid. Analytical concentration ranges of oxychlorine species were 2x10(-5)-2x10(-4) M for ClO(3)(-), and 1x10(-6)-1x10(-5) M for HClO and ClO(2)(-). The reproducibility of the present method was in the range 1.5-2.3%. The reaction mechanism for the transient potential change used in the present method is also discussed, based on the results of batchwise experiments. The simultaneous determination method was applied to the determination of oxychlorine species in a tap water sample, and was found to provide an analytical result for HClO, which was in good agreement with that obtained by the o-tolidine method and to provide a good recovery for ClO(3)(-) added to the sample.

Potentiometric flow-injection determination of trace hydrogen peroxide based on its induced reaction in iron(III)-iron(II) potential buffer containing bromide and molybdenum(VI)

A rapid and highly sensitive potentiometric flow-injection method for the determination of trace hydrogen peroxide was developed by use of an Fe(III)-Fe(II) potential buffer solution containing bromide and Mo(VI). The analytical method was based on a linear relationship between a concentration of hydrogen peroxide and a largely transient potential change of an oxidation-reduction potential electrode due to bromine generated by the reaction of hydrogen peroxide with the potential buffer solution. The oxidation of bromide to bromine by hydrogen peroxide occurred very rapidly with the assistance of Mo(VI) when Fe(II) existed in the potential buffer solution. It was estimated by batchwise experiments that hydroxyl radical, OH., was generated by the reaction of hydrogen peroxide with Fe(II) as an intermediate, and subsequently oxidized bromide to bromine. In a flow system, analytical sensitivities to hydrogen peroxide obtained by the detection of the transient change of potential were enhanced about 75 fold compared with those obtained by using the potential change caused by the reaction of hydrogen peroxide with the potential buffer solution without bromide and Mo(VI). Sensitivities increased with decreasing concentration of the Fe(III)-Fe(II) buffer in the reagent solution. The detection limit (S/N = 3) of 4 x 10(-7) M (13.6 ppb) was achieved by using the 1 x 10(-4) M Fe(III)-Fe(II) buffer containing 0.4 M NaBr, 1.0 M H(2)SO(4) and 0.5% (NH(4))(6)Mo(7)O(24). Analytical throughput was approximately 40 h(-1) and the RSD (n = 6) was 0.6% for measurement of 4 x 10(-6) M hydrogen peroxide. The proposed method was applied to the determination of hydrogen peroxide in real rainwater samples, and was found to provide a good recovery for H(2)O(2) added to rainwater samples.

Potentiometric flow-injection determination of trace chlorine based on its redox reaction with an iron(III)/iron(II) buffer

A very sensitive and rapid potentiometric determination of trace chlorine in water is described. The method is based on the transient potential changes which appears during the reduction of dissolved chlorin with an iron(III)/iron(II) potential buffer containing chloride and sulfuric acid. The sample is injected into a water carrier stream and merged with a stream of this potential buffer solution; chlorine is reduced during passage through a short reaction coil. The potential change from the baseline is measured with a flow-through ORP (oxidation-reduction potential) electrode. Potential changes (peak heights) are proportional to chlorine concentrations from 10−7 M to 10−5 M. The detection limit is 5 × 10−8 M (3.5 μgl−1 as Cl2). The sample throughput is 45 h−1. Reproducibility is in the range 2.5–1.1%. Results for potable water agree with those obtained by the o-tolidine method.

Potentiometric flow injection determination of manganese(II) by using a hexacyanoferrate(III)–hexacyanoferrate(II) potential buffer

A highly sensitive potentiometric flow injection analysis method for the determination of manganese(II), utilizing a redox reaction with hexacyanoferrate(III) in near neutral media containing ammonium citrate is described. The analytical method is based on the detection of the change in potential of a flow-through type redox electrode detector, resulting from the composition change of an [Fe(CN)(6)](3-)-[Fe(CN)(6)](4-) potential buffer solution. A linear relationship between the potential change (peak height) and the concentration of manganese(II) was found. Manganese(II) in a wide concentration range from 10(-4) to 10(-7) M could be determined by appropriately altering the concentration of the potential buffer from 10(-3) to 10(-5) M. The lower detection limit of manganese(II) was determined to be 1x10(-7) M. The sampling rate and relative standard deviation were 20 h(-1) and 1.9% (n=8) for 6x10(-6) M manganese(II), respectively. The proposed method was successfully applied to the determination of manganese(II) in actual soil samples obtained from tea fields. Analytical results obtained by the proposed method were in good agreement with those obtained by an atomic absorption spectrophotometric method.

Potentiometric flow injection analysis of concentrated hydrogen peroxide by using an Fe(II)-Fe(III) redox potential buffer solution.

The flow injection analysis of hydrogen peroxide is proposed, using a redox electrode and an Fe(II)-Fe(III) potential buffer solution. Influencing factors, such as the concentrations of Fe(II)-Fe(III) and sulfuric acid in the potential buffer on sensitivity of the proposed method are examined. The analysis of high concentrations of hydrogen peroxide up to approximately 10 M was conducted successfully with relative standard deviation of 0.7%.

Potentiometric flow injection determination of amylase activity by using hexacyanoferrate(III)-hexacyanoferrate(II) potential buffer

A highly sensitive potentiometric flow injection determination of amylase activity was carried out, utilizing a redox reaction of hexacyanoferrate(III) in alkaline media with reducing sugar as product of the enzymatic hydrolysis reaction of starch with amylase. The analytical method is based on the potential change detection of a flow-through type redox electrode detector due to the composition change of a [Fe(CN)(6)](3-)-[Fe(CN)(6)](4-) potential buffer solution, which is caused by the redox reaction with the product of the enzymatic reaction. A linear relationship exists between the potential change (peak height) and the activity of amylase. Amylase of a wide activity range from 2.5x10(-2) to 1.2x10(-4) U ml(-1) can be determined by the changing the concentrations of the [Fe(CN)(6)](3-)-[Fe(CN)(6)](4-) potential buffer from 10(-3) to 10(-5) M. The lower detection limit of amylase activity is 6.0x10(-5) U ml(-1). The sampling rate and relative standard deviation are 15 h(-1) and 0.9% (n=5) for 3.8x10(-3) U ml(-1) of amylase. The present method was successfully applied to determine amylase activity in real samples (commercial digestive medicines) with an accuracy of 4% compared with analytical results obtained using the present method with those achieved using the conventional titration method.

Sensitivity enchancement by potentiometric flow-injection analysis based on redox reaction with an iron(III)-iron(II) buffer

Abstract Highly sensitive potentiometric flow-injection analysis for oxidative species such as bromate, chlorite, dichromate, hydrogen peroxide and ozone is described, using an Fe(III)-Fe(II) potential buffer continuing bromide. The method is based on detection of large transient potential changes of an oxidation-reduction potential electrode which appear in short period after mixing a sample with the potential buffer. This large transient potential change is due to bromine generated by the reaction of the sample with bromide in the potential buffer. Analytical sensitivities obtained by the transient change of potential are enhanced 25-350-fold compared with that using the change in equilibrium potential. Detection limits of 5 × 10−8 M for bromate, 1 × 10 −7 M for chlorite and 3 × 10−7 M for dichromate were obtained by using a 0.01 M Fe (III)−0.01 M Fe (II) potential buffer containing 0.4 M NaBr and 1.2 M H2SO4. For the determination of hydrogen peroxide, the addition of ammonium molybdate to the potential buffer accelerates the generation of bromine caused by the reaction of hydrogen with bromide and thus enhances the sensitivity.

Rapid and Automated Analytical Methods for Redox Species Based on Potentiometric Flow Injection Analysis Using Potential Buffers

Two analytical methods, which prove the utility of a potentiometric flow injection technique for determining various redox species, based on the use of some redox potential buffers, are reviewed. The first is a potentiometric flow injection method in which a redox couple such as Fe(III)-Fe(II), Fe(CN)6 3−-Fe(CN)(CN)6 4−, and bromide-bromine and a redox electrode or a combined platinum-bromide ion selective electrode are used. The analytical principle and advantages of the method are discussed, and several examples of its application are reported. Another example is a highly sensitive potentiometric flow injection method, in which a large transient potential change due to bromine or chlorine as an intermediate, generated during the reaction of the oxidative species with an Fe(III)-Fe(II) potential buffer containing bromide or chloride, is utilized. The analytical principle and details of the proposed method are described, and examples of several applications are described. The determination of trace amounts of hydrazine, based on the detection of a transient change in potential caused by the reaction with a Ce(IV)-Ce(III) potential buffer, is also described.