Determination of iron(II) and iron(III) by flow injection and amperometric detection with a glassy carbon electrode

Flow injection analysis can be used for the determination of both iron(II) and iron(III) with an amperometric detector. The flow-through cell contains a glassy carbon electrode. Selection of the appropriate voltammetric technique, choice of the indication potentials, sample size, composition of the carrier stream, etc., are discussed. The limit of determination is about 10^-6 M; the calibration curves are linear in the concentration ranges 10^-3–10^-5 M for iron(III) and 5 × 10^-4–10^-5 M for iron(II). To illustrate the potentialities of the proposed method, standard rocks have been analysed.     

Chelate adsorption for trace voltammetric measurements of iron(III)

Summary A very sensitive electrochemical stripping procedure for trace measurements of iron(III) is described. The chelate of iron with Solochrome Violet RS is adsorbed on the hanging mercury drop electrode, and the reduction current of the accumulated chelate is measured by voltammetry. The adsorption and redox behaviours are explored by cyclic voltammetry. The height of the chelate peak, which is about 0.28 V more negative than the peak of the free dye, is shown to be proportional to the iron concentration. Optimal experimental conditions include a preconcentration potential of –0.40 V, solution pH of 5.1 and a linear scan mode. The sharp chelate peak, associated with the effective interfacial accumulation, coupled with the flat baseline, facilitates measurements at the nanomolar and submicromolar concentration levels using short preconcentration times. The limit of detection after 1 min preconcentration is 0.04 gl^–1 (7 × 10^–10 M), and the relative standard deviation at the 10^–7 M level is 4.7%. The effects of possible interferences, due to coexisting metal ions or organic surfactants, are evaluated. The ability of measuring iron(III) in the presence of iron(II) is illustrated. Actual analyses of sea and tap waters are reported.

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Chelat-Adsorption für voltammetrische Spurenanalyse von Eisen(III)

     

The spectrophotometric determination of anions by solvent extraction with metal chelate cations. part XX : Trichloroacetic acid with tris(1,10-phenanthroline)iron(ii) chelate

Trichloroacetic acid can be extracted from an aqueous solution by nitrobenzene with tris(1,10-phenanthroline)iron(II) chelate, and can be determined spectrophotometrically by measuring the extract at 516 nm. The extracted species is probably [Fe(phen)₃].(CCl₃COO)₂. Beer's law is obeyed over the concentration range 1.0·10^-5–1.0·10^-4M trichloroacetic acid in aqueous solution. Large amounts of phosphate and sulfate and moderate amounts of chloride, acetic acid, and monochloroacetic acid do not interfere, equal amounts of dichloroacetic acid give a slight positive error     

Spectrofluorimetric quantification of bromazepam using a highly selective optical probe based on Eu–bromazepam complex in pharmaceutical and serum samples

A rapid, simple and sensitive spectrofluorimetric method for determination of trace amount of bromazepam is developed. In phosphate buffer of pH 7.4. The bromazepam enhance the luminescence intensity of the Eu³⁺ ion in Eu³⁺–bromazepam complex at λ_ex = 390 nm. The produced luminescence intensity of Eu³⁺–bromazepam complex is in proportion to the concentration of bromazepam. The working range for the determination of bromazepam is 2.3 × 10⁻⁸ to 6.2 × 10⁻⁷ M with detection limit (LoD) and quantitative detection limit (LoQ) of 3 × 10⁻⁹ and 1.2 × 10⁻⁸ M, respectively. While, the working range, detection limit (LoD) and quantitative detection limit (LoQ) in case of the quantum yield calculations are 3.7 × 10⁻⁸ to 3.4 × 10⁻⁷ M with of 3.4 × 10⁻⁹ and 9.2 × 10⁻⁸ M, respectively. The enhancement mechanism of the luminescence intensity in the Eu³⁺–bromazepam system has been also explained.     

Extraction—spectrophotometric determination of palladium(ii) with 2-nitroso-5-diethylaminophenol

An extraction—spectrophotometric determination of palladium(II) with 2-nitroso-5-diethylaminophenol is described. Complex formation and extraction of the complex with chloroform are possible with aqueous phases of about 2.5 M sulfuric acid. The molar absorptivity of the complex is 4.38 X 10⁴ l mol^-1 cm^-1 at 486 nm. Few of the common ions interfere at concentrations of 10^-4–10^-3 M; more than 10^-5 M Ir(IV), 10^-5 M W(VI), 5 × 10^-6 M Au(III) and 10^-6 M iodide cause negative errors. The method can be applied to the determination of palladium in catalysts for automobile exhaust purifiers.     

Construction of a New Perbromate-Selective Electrode. Kinetic Study of the Iron(II)- Perbromate Reaction and Microdetermination of Iron

Abstract

A perbromate- selective membrane electrode with a liquid membrane of crystal violet-perbromate dissolved in chlorobenzene is described, The liquid membrane electrode exhibits rapid and near Nernstian response to perbromate activity from 10^?5 to 10^?2 M. The response is unaffected by pH in the range 2–10, Major interferences are periodate and perchlorate. A kinetic study of the iron(II)- perbromate reaction was carried out with the perbromate electrode, A potentiometric method is described for the determination of 50–500 μg of iron (II) with relative errors and standard deviations of 1–2%.     

Application of reducing column for metal speciation by flow injection analysis : Spectrophotometric Determination of Iron(III) and Simultaneous Determination of Iron(II) and Total Iron

Iron(III) (3 × 10^?4-5 × 10^?4 M) is determined in a flow-injection system by passage through a Jones reductor mini-column before spectrophotometric detection with 1,10-phenathroline in citrate buffer, pH 5.0. The mid-range precision is < 1.4%, at a sampling rate of 60 h^?1. Iron(II) and total iron are determined by splitting the injected sample so that a portion passes through the reductor column and a delay coil before both streams are recombined with the unreduced portion preceding the remainder of the sample to mix with the reagent for spectrophotometric detection. Two peaks are produced for each sample, the first being measure of iron(II), the second of total iron.     

Differential pulse anodic stripping voltammetry of copper(II) at the glassy carbon electrode

Optimum conditions for the use of the bare glassy carbon electrode (GCE) are reported. Linear calibration graphs are obtained in the range 5 × 10^-7–3.5 × 10^-5 M copper(II). The detection limit for copper(II) is 5.9 × 10^-9 M at pH 4.5 and 3.3 × 10^-8 M at pH 6.5.     

Organic solvent-soluble membrane filters for the preconcentration and spectrophotometric determination of iron(II) traces in water with Ferrozine

An organic solvent-soluble membrane filter (MF) is proposed for the simple and rapid reconcentration with subsequent spectrophotometric determination of trace levels of iron (II) in water. Iron (II) is collected on a nitrocellulose membrane filter as ion associate of an anionic complex, which is formed by iron (II) and Ferrozine and a cation-surfactant. The ion-pair compound and the MF can be dissolved in small volumes of 2-ethoxyethanol and the absorbance of the resulting solution is measured at 560 nm against a reagent blank with molar absorptivity of 4.01 × 10⁴ L mol^–1 cm^–1. Beer’s law is obeyed over the concentration range 0–10 μg L^–1 of iron (II) in water and the detection limit is 0.03 μg L^–1 with a 50-fold enrichment factor. The proposed method can satisfactorily be applied to the determination of iron (II) in natural water and sea water.     

Thermal lens studies of the reaction of iron(II) with 1,10-phenanthroline at the nanogram level

The determination of iron(II) with 1,10-phenanthroline in aqueous solutions was carried out exemplarily by thermal lens spectrometry. The peculiarities of analytical reactions at the nanogram level of reactants can be studied using this method. Under the conditions of the competing reaction of ligand protonation, the overall stability constant for iron(II) chelate with 1,10-phenanthroline was determined at a level of n × 10^–7 mol L^–1, logβ ₃ = 21.3 ± 0.1. The rates of formation and dissociation of iron(II) tris-(1,10-phenanthrolinate) at a level of n × 10^–8 mol L^–1 were found to be (2.05 ± 0.05) × 10^–2 min^–1 and (3.0 ± 0.1) × 10^–3 min^–1, respectively. The conditions for the determination of iron(II) with 1,10-phenanthroline by thermal lensing were reconsidered, and ascorbic acid was shown to be the best reducing agent, which provided minimum and reproducible sample pretreatment. Changes in the conditions at the nanogram level improved both the selectivity and sensitivity of determination. The optimum measurement conditions for thermal lensing were determined not only by the absorption of the analyte and reagents, but also by the background absorption of the solvent. The limits of detection and quantification of iron(II) at 488.0 nm (excitation beam power 140 mW) are 1 × 10^–9 and 6 × 10^–9 mol L^–1, respectively; the reproducibility RSD for the range n × 10^–8–n × 10^–6 mol L^–1 is 2–5%.     

Highly Selective and Sensitive Perchlorate Sensors Based on Some Recently Synthesized Ni(II)‐Hexaazacyclotetradecane Complexes

Three nickel(II)‐hexaazacyclotetradecane complexes were studied to characterize their abilities as perchlorate ion carrier in PVC membrane electrodes. The electrodes based on these complexes exhibit Nernstian responses for ClO over very wide concentration ranges (1.0×10^?1 ?5.0×10^?7 M) with detection limits of 2.0×10^?7 ?5.0×10^?7 M (20–50 ng/mL). The sensors show very good selectivity for ClO ion in comparison with the most common organic and inorganic anions. The responses of the proposed electrodes are independent of pH in the range of 3.5–11.0. The perchlorate selective membranes show fast response time (<10 s) and can be used for 4–12 weeks without any major deviation. The sensors were successfully used to determine the perchlorate ion in water, wastewater and human urine samples.     

Hexacyanoferrate(III) as a mediator in the determination of total iron in potable waters as iron(II)-1,10-phenanthroline at a single-use screen-printed carbon sensor device

Hexacyanoferrate(III) was used as a mediator in the determination of total iron, as iron(II)-1,10-phenanthroline, at a screen-printed carbon sensor device. Pre-reduction of iron(III) at −0.2 V versus Ag/AgCl (1 M KCl) in the presence of hexacyanoferrate(II) and 1,10-phenanthroline (pH 3.5-4.5), to iron(II)-1,10-phenanthroline, was complete at the unmodified carbon electrode surface. Total iron was then determined voltammetrically by oxidation of the iron(II)-1,10-phenanthroline at +0.82 V, with a detection limit of 10 μg l⁻¹.In potable waters, iron is present in hydrolysed form, and it was found necessary to change the pH to 2.5-2.7 in order to reduce the iron(III) within 30 s. A voltammetric response was not found at lower pH values owing to the non-formation of the iron(II)-1,10-phenanthroline complex below pH 2.5.Attempts to incorporate all the relevant reagents (1,10-phenanthroline, potassium hexacyanoferrate(III), potassium hydrogen sulphate, sodium acetate, and potassium chloride) into a modifying coated PVA film were partially successful. The coated electrode behaved very satisfactorily with freshly-prepared iron(II) and iron(III) solutions but with hydrolysed iron, the iron(III) signal was only 85% that of iron(II).     

1‐Pyrrolidine Dicarbodithioate Based Electrodes for Determination of Iron(III) in Lubrication Oil

The lipophillic ammonium salt of 1‐pyrrolidine dicarbodithioic acid (PCDT) (I) was introduced as a new selective ionophore for an iron selective electrode. In addition, the effect of immobilization of 18‐crown‐6 (18CE6) (membrane type‐II), on the electrode performance was discussed. The slope of the PCDT‐based (I) electrode was (20 mV/decade). The linear concentration range was (10^?5–10^?1 M) after one day doping. The detection limit for electrode type‐(II) was (1.3×10^?6 M). For membrane with only 18CE6 (type‐III) the linear range and the detection limit were improved (10^?5–10^?1 M and 3.2×10^?6 M, respectively). The pH‐range was between 5–11 for type‐II, and III electrodes, while it was 7–11 for type‐I electrode. Most of the common cations were tested for the evaluation of the electrode selectivity with correlation to the ionic radii of the tested cations. Among them only Ag⁺ and Pb²⁺ were the real interference for type‐III electrode. Application of using the electrode for the determination of iron in lubrication oil samples was performed with RSD (1.77–2.7%) and (1.01–2.3%) for type‐II and III electrodes, respectively. The corresponding recovery ranges were (93.0–99.9%) and (96.3–100%). The obtained results were compared to those of an atomic absorption spectrophotometric method.     

Application of the thermal lens effect for determination of iron(II) with 4,7-diphenyl-1,10-phenanthroline disulfonic acid

A heat-induced refractive index change is used to increase the sensitivity of the spectrophotometric determination of iron(II) in a dual-beam system. An argon ion laser (514.5 nm) is used as the heating source and the intensity variation of a helium—neon laser (632.8 nm) is measured. The sensitivity is increased 7.3 times compared with spectrophotometry; the detection limit is 3 × 10^-7 M.     

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 1×10⁻⁷ M. The sampling rate and relative standard deviation were 20 h⁻¹ and 1.9% (n=8) for 6×10⁻⁶ 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.     

Organic solvent-soluble membrane filters for the preconcentration and spectrophotometric determination of iron(II) traces in water with Ferrozine

An organic solvent-soluble membrane filter (MF) is proposed for the simple and rapid reconcentration with subsequent spectrophotometric determination of trace levels of iron (II) in water. Iron (II) is collected on a nitrocellulose membrane filter as ion associate of an anionic complex, which is formed by iron (II) and Ferrozine and a cation-surfactant. The ion-pair compound and the MF can be dissolved in small volumes of 2-ethoxyethanol and the absorbance of the resulting solution is measured at 560 nm against a reagent blank with molar absorptivity of 4.01 × 10⁴ L mol^–1 cm^–1. Beer’s law is obeyed over the concentration range 0–10 μg L^–1 of iron (II) in water and the detection limit is 0.03 μg L^–1 with a 50-fold enrichment factor. The proposed method can satisfactorily be applied to the determination of iron (II) in natural water and sea water. Received: 23 June 1998 / Revised: 21 July 1998 / Accepted: 25 August 1998     

Liquid-state mercury(II) ion-selective electrode based on N-(O,O-diisopropylthiophosphoryl)thiobenzamide

A liquid ion-exchange electrode containing a complex of mercury(II) with N-(O,O-diisopropylthiophosphoryl)thiobenzamide in carbon tetrachloride is described. The electrode shows excellent sensitivity and good selectivity. The slope of the calibration graph is 29.0 mV/pHg²⁺ in the pHg²⁺ in the pHg²⁺ range 2–15.2 in mercury(II) ion buffers. The electrode can be used for determination of 5 × 10^?5–10^?2 M Hg(II) in the presence of 10^?2 M Cu(II), Ni(II), Co(II), Zn(II), Pb(II), Cd(II), Mn(II), Fe(III), Cr(III), Bi(III) or Al(III) ions and in the presence of 10^?3 M Ag(I) ions. It can bealso used for end-point detection in titrations with EDTA of 10^?3–10^?4 M mercury(II) at pH 2.     

Indirect determination of mercury(ii) with an air-gap cyanide sensor

The method is based on the stability of the dicyanomercurate(II) complex at pH 0.5–1, where most other cyanide complexes decompose. The selectivity is much better than that in the direct application of mercury-selective electrodes. The method is useful in the range 5 × 10^-5–5 × 10^-3 M mercury(II).     

Application of electrogenerated chemiluminescence of luminol to determination of traces of cobalt(II) in aqueous alkaline solution

A selective method for determination of traces of cobalt(II) in aqueous alkaline solution has been developed, based on the electrochemical generation of luminescence from luminol at a rotating ring—disc electrode. The detection limit is 10^-8 M, and the linear calibration range extends up to 3 × 10^-6 M; the r.s.d. for 2.0 × 10^-7 M cobalt is 6%. Of 21 metal ions, only chromium(III) and copper(II) interfere seriously; EDTA also interferes.     

Speciation of Fe(III) and Fe(II) in water samples by liquid–liquid extraction combined with low-temperature electrothermal vaporization (ETV) ICP-AES

The use of 1-phenyl-3-methyl-4-benzoylpyrazolone (PMBP) as extractant for separation of Fe(III) and Fe(II) and low-temperature vaporization of the Fe(III)–PMBP chelate into ICP-AES for their speciation analysis was investigated. The factors affecting the formation of Fe(PMBP)₃ chelate and its vaporization behavior were investigated in detail. PMBP was used not only as the extractant for the separation of Fe(III) and Fe(II) but also as the chemical modifier for the low-temperature ETV-ICP-AES determination of iron. Under the optimized conditions, the detection limit for iron(III) and iron(II) are both 3.2?ng/mL, with relative standard deviations of 3.9 and 4.5%, respectively. The proposed method was applied to the determination of trace iron in biological standard reference materials and the species in East Lake water samples, and the results obtained were satisfactory.