Amperometric determination of hydrogen peroxide in pickling baths for copper and copper alloys by flow injection analysis

The hydrogen peroxide is oxidized at + 1.5 V vs. SCE at a glassy carbon electrode of the wall-jet type. The samples are diluted about 100 times in a dispersion coil before entering the amperometric detector. The calibration curve is linear from 10^?4 to 1 M H₂O₂, when 5-μl samples are used. With 50-μl samples the detection limit decreases to 10^?6 M H₂O₂. Neither metal ions (Cu²⁺, Zn²⁺, Ni²⁺, Al³⁺) up to 0.5 M nor changes in the sulfuric acid concentration of the samples between 0.1 and 1 M interfere with the hydrogen peroxide determination. About 75 samples can be analyzed per hour.     

Ultrasound-enhanced flow injection chemiluminescence for determination of hydrogen peroxide

A novel ultrasonic flow injection chemiluminescence (FI-CL) manifold for determining hydrogen peroxide (H2O2) has been designed and evaluated. Chemiluminescence obtained from the luminol-H2O2-cobalt(II) reaction was enhanced by applying 120 W of ultrasound for a period of 4 s to the reaction coil in the FI-CL system and this enhancement was verified by comparison with an identical manifold without ultrasound. The system was developed for determining ultra-trace levels of H2O2 and a calibration curve was obtained with a linear portion over the range of 10-200 nmol L(-1) H2O2 (correlation coefficient 0.9945). The detection limit (3sigma) and the quantification limit (LOQ) were found to be 1 x 10(-9) and 3.3 x 10(-9) mol L(-1) respectively and the relative standard deviation was 1.37% for 2 x 10(-7) mol L(-1) H2O2 (n = 10). The method was applied to the determination of trace amounts of H2O2 in purified water and natural water samples without any special pre-treatments.     

Fluorimetric determination of trace hydrogen peroxide in water with a flow injection system

A fluorimetric flow-injection procedure with a single reagent solution containing p-hydroxyphenylacetic acid, peroxidase and ammonia permits the determination of aqueous hydrogen peroxide in the range 10^?8?10^?4 M; 30–60 samples can be processed per hour. The method exhibits a wide linear range and is insensitive to sample pH within the range 2–6.     

Amperometric sensor for hydrogen peroxide based on poly(aniline-co-p-aminophenol)

It was found that the poly(aniline-co-p-aminophenol) film can effectively catalyze the oxidation of hydrogen peroxide in a sodium citrate buffer solution with pH 5.0. Here, we applied the copolymer to the construction of an efficient electrochemical sensor to determine the concentration of hydrogen peroxide. The sensor exhibited an excellent electrocatalytic activity toward the oxidation of H₂O₂, and the interferences of ascorbic acid and phenol were completely avoided. Unlike the inherent instability of enzyme, the poly(aniline-co-p-aminophenol) film-based sensor showed an outstanding stability.     

Test method for the determination of hydrogen peroxide in atmospheric precipitation and water using indicator papers

A test method is proposed for the determination of hydrogen peroxide based on the oxidation of 4-chloro-1 -naphthol oro-tolidine catalyzed with horseradish peroxidase on cellulose or aldehydecellulose papers. The concentration of H₂O₂ is determined by the length of the colored zone on a test strip (3 x 80 mm) sealed into adhesive polymer film after its contact with the test solution. The analytical range of H₂O₂ is 0.1–300 mg/L. For the determination of H₂O₂ by the color intensity of indicator paper after passing 20 mL of a test solution, the analytical range is 0.005-1 mg/L. Rapid test procedures for the determination of hydrogen peroxide in atmospheric precipitation and in waste and natural waters are developed and tested (RSD ≤ 30%).     

New method for simultaneous determination of Fe(II) and Fe(III) in water using flow injection technique

The method exploits the possibilities of flow injection gradient titration in a system of reversed flow with spectrophotometric detection. In the developed approach a small amount of titrant (EDTA) is injected into a stream of sample containing a mixture of indicators (sulfosalicylic acid and 1,10-phenanthroline). In acid environment sulfosalicylic acid forms a complex with Fe(III), whereas 1,10-phenanthroline forms a complex with Fe(II). Measurements are performed at wavelength λ = 530 nm when radiation is absorbed by both complexes. After injection EDTA replaces sulfosalicylic acid and forms with Fe(III) more stable colourless complex. As a result, a characteristic “cut off” peak is registered with a width corresponding to the Fe(III) concentration and with a height corresponding to the Fe(II) concentration. Calibration was performed by titration of four two-component standard solutions of the Fe(II)/Fe(III) concentrations established in accordance with 2² factorial plan. The method was tested with the use of synthetic samples and then it was applied to the analysis of water samples taken from artesian wells. Under optimized experimental conditions Fe(II) and Fe(III) were determined with precision less than 0.8 and 2.5% (RSD) and accuracy less than 3.2 and 5.1% (relative error) within the concentration ranges of 0.1-3.0 and 0.9-3.5 mg L⁻¹ of both analytes, respectively.     

Amperometric sensing of hydrogen peroxide vapor for security screening

Rapid detection of the hydrogen peroxide precursor of peroxide explosives is required in numerous security screening applications. We describe a highly sensitive and selective amperometric detection of hydrogen peroxide vapor at an agarose-coated Prussian-blue (PB) modified thick-film carbon transducer. The sensor responds rapidly and reversibly to dynamic changes in the level of the peroxide vapor, with no apparent carry over and with a detection limit of 6 ppbv. The remarkable selectivity of the PB-based screen-printed electrode towards hydrogen peroxide leads to effective discrimination against common beverage samples. For example, blind tests have demonstrated the ability to selectively and non-invasively identify concealed hydrogen peroxide in drinking cups and bottles. The attractive performance of the new microfabricated PB-based amperometric peroxide vapor sensor indicates great potential for addressing a wide range of security screening and surveillance applications. Figure Experimental setup (left) with three electrode electrochemical Hydrogen Peroxide sensor hanging above container of “unknown” liquid. Schematic (right) demonstrating fundamental principles of operation of the sensor.     

Individual and sequential flow injection spectrophotometric determination of vanadium(V) and titanium(IV)

Summary Methods for the individual and sequential flow injection spectrophotometric determination of vanadium(V) and titanium(IV) are proposed, based on the formation of peroxo complexes. The detection limits are 1.0 × 10^–5 mol/l V (120 l) and 2.5 × 10^–6 mol/l Ti (80 l). A cation exchange resin mini-column is incorporated on-line into the vanadium manifold to remove the titanium complex and allow the vanadium to be determined selectively. A normal injection valve is used for the individual determinations, but it is modified for determination of V(V)/–Ti(IV) mixtures in order to introduce two samples sequentially into the reagent stream. One passes through a cation exchanger minicolumn, the other through an empty column, before reaching the detector. The former allows V alone to be measured, the latter V+Ti.

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Individuelle und sequentielle spektralphotometrische Fließinjektionsbestimmung von Vanadium(V) und Titan(IV)

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Fluorimetric determination of hydrogen peroxide in water using acetaminophen

A fluorimetric procedure for the determination of hydrogen peroxide, based on the oxidation of acetaminophen with hydrogen peroxide in acidic medium, is described. The calibration graph was linear in the range 5.0 x 10(-8) - 2.4 x 10(-5) M hydrogen peroxide at an emission wavelength of 333 nm with excitation at 298 nm. The method has been applied to the determination of hydrogen peroxide in rain water, and the recoveries in milk samples were good.     

Simultaneous spectrofluorimetric determination of cerium(III) and cerium(IV) by flow injection analysis

Cerium(III) (1–100 μg l^?1) is determined by injection into a carrier stream of hydrochloric, perchloric or sulphuric acid, and monitoring its native fluorescence. Cerium(IV) can be determined similarly by incorporating a zinc reductor minicolumn into the system. Splitting the injection sample so that only part passes through the reductor, and the remainder by-passes it, allows total cerium and cerium(III) to be detected from the two sequential fluorescence peaks obtained.     

Spectrophotometric determination of traces of hydrogen peroxide with the Ti(IV)-xylenol orange and the Ti(IV)-chromazurol S reagents

The formation of mixed ligand complexes in Ti(IV)-xylenol orange (XO)-H₂O₂ and Ti(IV)-chromazurol S (CAS)-H₂O₂ systems was studied by spectrophotometry. The former system gave constant absorbance (λ_max = 562 nm) under the condition of [XO]/[Ti(IV)] = 1 in the pH 2–4 region. In the latter system, a distinct maximum at 557 nm was observed when [CAS]/[Ti(IV)] = 4 in the pH range of 4.5–5.2. In both cases, the absorbance at λ_max was stable for a long time and proportional to the concentration of hydrogen peroxide. From those facts, the usefulness of the mixtures of Ti(IV)-XO and Ti(IV)-CAS as the colorimetric reagents for the determination of hydrogen peroxide can be expected. The conditions for the use of the Ti(IV)-XO and the Ti(IV)-CAS reagents were examined in detail, and both reagents were found to be available for trace analysis of hydrogen peroxide with high sensitivity.     

Flow injection determination of hydrogen peroxide using diperiodatoargentate- and diperiodatonickelate-luminol chemiluminescence

A novel chemiluminescence (CL) method for the determination of hydrogen peroxide is described. Method is based on the transition metals in highest oxidation state complex, which include diperiodatoargentate (DPA) and diperiodatonickelate (DPN) and show excellent sensitisation on the luminol-H₂O₂ CL reaction with low luminol concentration in alkaline medium. In particular, the sensitiser which was previously reported (such as Co²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Fe³⁺, Cr³⁺, KIO₄, K₃Fe(CN)₆ etc.) to be unobserved CL due to poor sensitisation with such low concentration of luminol which makes the method hold high selectivity. Based on this observation, the detection limits were 6.5?×?10^?9?mol?L^?1 and 1.1?×?10^?8?mol?L^?1 hydrogen peroxide for the DPN- and DPA-luminol CL systems, respectively. The relative CL intensity was linear with the hydrogen peroxide concentration in the range of 2.0?×?10^?8–6.0?×?10^?6?mol?L^?1 and 4.0?×?10^?8–4.0?×?10^?6?mol?L^?1 for the DPN- and DPA-luminol CL systems, respectively. The proposed method had good reproducibility with a relative standard deviation of 3.4% (8.0?×?10^?7?mol?L^?1, n?=?7) and 1.0% (2.0?×?10^?6?mol?L^?1, n?=?7) for the DPN- and DPA-luminol CL systems, respectively. A satisfactory result has been gained for the determination of H₂O₂ in rainwater and artificial lake water by use of the proposed method.     

Amperometric determination of hydrogen peroxide with a manganese dioxide film-modified screen printed carbon electrode

A carbon thick film electrode modified with an MnO₂-film is investigated as an amperometric detector for hydrogen peroxide in flow-injection analysis (FIA). At an operating potential of +0.48 V vs. Ag/AgCl catalytic oxidation of the analyte is exploited for amperometric monitoring. Experimental parameters, such as pH of the carrier, working potential, flow rate and injection volume, are optimized. The amperometric signals are linearly proportional to the concentration of H₂O₂ in the range from 0.005 to 10 mg/L, showing a detection limit (3σ) of 2.3 μg/L. The method is applied to the determination of H₂O₂ in rain water and to a simple assay to quantify glucose in human plasma. Received: 29 January 1998 / Revised: 4 May 1998 / Accepted: 13 May 1998     

Fluorescent quenching method for determination of trace hydrogen peroxide in rain water

A simple and sensitive fluorescent quenching method for the determination of trace hydrogen peroxide (H(2)O(2)) has been proposed to determine hydrogen peroxide in rain water sample. The method is based on the reaction of H(2)O(2) with 3,3'-diethyloxadicarbocyanine iodide (DI) to form a compound which has no fluorescence in acetate buffer solution (pH 3.09). The maximum emission wavelength of the system is located at 604 nm with excitation at 570 nm. Under the optimal conditions, the calibration graph was obtained between the quenched fluorescence intensity and hydrogen peroxide concentration in the range of 5.0 x 10(-7) to 9.0 x 10(-4) mol L(-1). The proposed method was applied to determine H(2)O(2) in rain water samples, and the result was satisfactory. The mechanism involved in the reaction was also studied.     

Amperometric determination of hydrogen peroxide with a manganese dioxide film-modified screen printed carbon electrode

A carbon thick film electrode modified with an MnO₂-film is investigated as an amperometric detector for hydrogen peroxide in flow-injection analysis (FIA). At an operating potential of +0.48 V vs. Ag/AgCl catalytic oxidation of the analyte is exploited for amperometric monitoring. Experimental parameters, such as pH of the carrier, working potential, flow rate and injection volume, are optimized. The amperometric signals are linearly proportional to the concentration of H₂O₂ in the range from 0.005 to 10 mg/L, showing a detection limit (3σ) of 2.3 μg/L. The method is applied to the determination of H₂O₂ in rain water and to a simple assay to quantify glucose in human plasma.     

Application of Doehlert matrix to the study of flow injection procedure for selenium (IV) determination

A method for the rapid determination of selenium is reported. It is based on the injection of selenium sample into a stream of KI and subsequent measurement of the increase of the absorption at 290 nm due to the formation of I₃⁻. A Doehlert matrix was applied for the determination of the optimal working conditions. With the developed method, a linear calibration curve from 1 to 10 ppm was obtained. For the analysis of semiconducting thin layers of CuInSe₂ (CIS), a cationic resin was added to the sample solution in order to eliminate the effect of copper and indium on the absorbance values. With the developed procedure a sample throughput of 36 samples per hour and a relative standard deviation 1.1% was achieved.     

Selective determination of hydrogen peroxide by adduct formation with a dinuclear iron(III) complex and flow injection analysis/tandem mass spectrometry

A highly selective method for the determination of hydrogen peroxide is presented. In a flow injection analysis (FIA) instrument, the analyte is brought into contact with a dinuclear heptadentate iron(III) complex. The formation of the peroxide adduct is quantified using electrospray tandem mass spectrometry (ESI-MS/MS). Selected reaction monitoring (SRM) based on the transition from the triply charged peroxide adduct with m/z = 251.2 to the triply charged fragment ion of m/z = 240.5 is performed. The limit of detection for hydrogen peroxide is 10(-7) mol dm(-3), limit of quantification is 3 x 10(-7) mol dm(-3), and a linear range of 2.5 decades starting at the limit of quantification is observed.     

Automation of the determination of hydrogen peroxide, dichromate, formaldehyde and bicarbonate in milk by flow injection analysis

Summary Automatic flow injection methods for the determination of hydrogen peroxide, dichromate, formaldehyde and bicarbonate in dairy products are proposed. They are based on reaction with vanadium pentoxide, diphenyl-carbazide, fuchsine-sulphur dioxide and alizarin, respectively. Sample pre-treatment (paper and membrane filtration, dialysis) is widely discussed for on-line incorporation. The usefulness of these methods was tested by applying them to different commercial samples, satisfactory results being obtained in all instances.