Indirect flow-injection determination of ascorbic acid by flame atomic absorption spectrometry

A continuous-flow procedure is proposed for the indirect determination of ascorbic acid, based on its reducing properties because of the oxidation of its 1,2-enediol group. Iron(III) was injected into a 1,10-phenanthroline stream, which was mixed with a sample carrier and then with a sodium picrate solution stream. In these conditions the iron(III) was reduced to iron(II) by the ascorbic acid. Thus, the iron(II) formed reacts with 1,10-phenanthroline to form a charged red complex, which with picrate ion forms a stable red-orange uncharged ion-association complex that is adsorbed on-line on a non-ionic polymeric adsorbent (Amberlite XAD-4), proportionally to the ascorbic acid in the sample. The unadsorbed iron was determined by flame atomic absorption spectrometry. The proposed method allows the determination of ascorbic acid in the range 0.5–25 g ml^–1 with a relative standard deviation of 2.9% at a rate of ca. 90 samples h^–1. This method has been applied to the determination of ascorbic acid in pharmaceutical preparations, fruit juices and sweets. The results obtained in the analysis are compared with those provided by the 2,6-dichloroindophenol method.     

Sequential potentiometric complexometric redox determination of iron(III) and cobalt(II) with application to alloys

A simple potentiometric method is presented for successive determination of iron(III) and cobalt(II) by complexometric titration of the iron(III) with EDTA at pH 2 and 40 degrees , followed by redox titration of the cobalt(II) complex with 1,10-phenanthroline or 2,2'-bipyridyl at pH 4-5 and 40 degrees , with gold(III). There is no interference in either determination from common metal ions other than copper(II), which severely affects the cobalt determination but can be removed by electrolysis. The method has been successfully applied to determination of iron and cobalt in Kovar and Alnico magnet alloys.     

Preconcentration of metal ions on aluminum oxide modified with tiron

It is found that iron(III), titanium(IV), vanadium(V), copper(II), lead(II), and zinc(II) ions are adsorbed on aluminum oxide modified with Tiron. The adsorption of iron(III) is accompanied by the violet coloration of the adsorbent (560 nm), which indicates the formation of a 1: 2 complex on the adsorbent surface; copper forms a 1: 1 yellowish green complex (430 nm). The group preconcentration of metal ions on this adsorbent in a dynamic mode is possible; the preconcentration rate is 2.5 × 10³. The method for the determination of metal ions is proposed based on the adsorption recovery of the elements followed by the direct determination by X-ray fluorescence spectroscopy on the adsorbent surface.     

Potentiometric redox determination of gold(III) and its application to alloys

The simple potentiometric method proposed for the indirect determination of 1–10 mg of gold(III) is based on reduction to the metal with excess of cobalt(II) in the presence of 1,10-phenanthroline or 2,2'-bipyridine at pH 3 and 50°C, and titration of the unused cobalt(II) complex with iron(III) chloride solution. Many metal ions can be tolerated; Ag(I) and Pd(II) are eliminated by precipitation with sodium chloride and 1,10-phenanthroline or 2,2'-bipyridine, respectively, but Hg(II), Fe(III) and Pt(IV) interfere. The method is applied to the determination of gold in alloys.     

Use of acetohydroxamic acid in the direct spectrophotometric determination of iron(III) and iron(II) by flow injection analysis

The direct spectrophotometric determination of iron(III) and iron(II) by flow injection analysis with acetohydroxamic acid and 1,10-phenanthroline as reagents is reported. The working ranges are 0.5–10 and 10–60 mg l^?1, respectively. Results obtained for synthetic mixtures of Fe(III) and Fe(II) and for acid extracts of haematite samples were accurate. Interference studies indicate that the method is highly selective.     

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).     

Simultaneous kinetic determination of Fe(III) and Fe(II) by H-point standard addition method

The H-point standard addition method (HPSAM) was applied to kinetic data for simultaneous determination of Fe(III) and Fe(II) or selective determination of Fe(III) in the presence of Fe(II). The method is based on the difference in the rate of two processes; reduction of Fe(III) with Co(II) and subsequent complex formation of resulted Fe(II) with 1,10-phenanthroline, and direct complex formation between Fe(II) and 1,10-phenanthroline in pH 3 and cetyl trimethyl ammonium bromide, CTAB, micellar media. Fe(III) can be determined in the range of 0.75-5.13 mug ml(-1)with satisfactory accuracy and precision in the presence of excess Fe(II) under working conditions. The proposed method was successfully applied to the simultaneous determination of Fe(III) and Fe(II) and also to the selective determination of Fe(III) in the presence of Fe(II) in several synthetic mixtures containing different concentration ratios of Fe(III) to Fe(II).     

Flow injection determination of iron by its catalytic effect on the oxidation of 3,3',5,5'-tetramethylbenzidine by hydrogen peroxide

A flow injection-photometric method has been developed for the determination of iron(II+III). The method is based on the catalytic effect of iron(III) on the hydrogen peroxide oxidation of 3,3',5,5'-tetramethylbenzidine to form a blue compound (lambda(max)=650 nm). In this catalyzed reaction, 1,10-phenanthroline acted as an effective activator. Iron(II) is also determined, being oxidized by hydrogen peroxide. Calibration graphs for iron(II) and iron(III) obtained under the optimized conditions were identical with each other and linear in the range 0.2-200 ng ml(-1) with a detection limit of 0.05 ng ml(-1) iron. The reproducibility was satisfactory with a relative S.D. of 1.0% for ten determinations of 5 ng ml(-1) iron(III). The proposed method was successfully applied to the determination of iron in river and lake water samples and can be determined free iron species.     

Selective determination of trace iron in different oxidation states in natural water by flow injection-solid phase spectrometry

A novel method for the selective determination of Fe(II) and Fe(III) in water using 2-nitroso-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (PSAP) was developed. QAE-Sephadex anion exchanger packed in a flow-through cell was used as a medium not only for both the concentration and the spectrophotometric measurements of the Fe-PSAP complex, but also for reduction of the Fe(III)-PSAP complex. The PSAP complex of Fe(II) or Fe(III) was strongly adsorbed on the anion exchanger in a weakly acidic to weakly basic region, but the Fe(III) complex was readily and completely reduced to the Fe(II) complex only in a neutral to weakly alkaline region in the solid phase. These properties were utilized to determine the Fe(II) and total Fe concentration without the addition of any reducing agent. The detection limits (3σ) were 0.18 ng for Fe(II) and 0.18 ng for total Fe using a 3.2-cm(3) sample solution. The present method is applicable to the determination of dissolved iron species present at μg dm(-3) levels in natural water samples.     

Application of the H-point standard addition method to the speciation of Fe(II) and Fe(III) with chromogenic mixed reagents

Simultaneous determination of Fe(II) and Fe(III) or selective determination of each oxidation state of iron in the presence of the other one by H-point standard addition method (HPSAM) is described. Mixed reagents of 1,10-phenanthroline and salicylic acid was used as a selective chromogenic system for speciation of Fe(II) and Fe(III). It was shown that with appropriate selection of wavelength pairs, both Fe(II) and Fe(III) can be considered as analyte. The results showed that Fe(II) and Fe(III) can be determined simultaneously with the concentration ratios of Fe(II) to Fe(III) varying from 10:1 to 1:20 in the mixed sample. The accuracy and precision of the method are all satisfactory.     

Spectrophotometric determination of tannins in tea and beer samples with iron(III) and 1,10-phenanthroline as reagents

A simple and accurate spectrophotometric method is proposed for the determination of tannins in tea and beer samples based on the reduction of iron(III) to iron(II) by tannins at 80 degrees C for 20 min. The iron(II) was then reacted with 1,10-phenanthroline at pH 4.4 to form a coloured complex. Background correction could be effected by precipitating the tannins in the sample solution twice with gelatin and kaolin. Absorbance measurements were made at 540 nm and the calibration graph was linear from 0 to 5.5 micrograms ml-1 of tannic acid with a slope of 0.213 A p.p.m.-1. The precision for the determination of tannins in a tea sample containing 9.45% of tannins was 1.8%. Most of the ingredients commonly found in tea and beer samples do not interfere with the determination. Several tea and beer samples were analysed for their tannin content using the proposed method.     

A potentiometric study of the oxidation of cobalt(II) with gold(III) chloride in presence of 1,10 phenanthroline or 2,2'-bipyridine : A new titration of cobalt (II) and its application to nickel-base alloys

The redox reaction between cobalt(II) and gold(III) chloride in the presence of 1.10-phenanthroline or 2,2'-bipyridine was studied, and a titration of the cobalt(II) complex with a gold(III) chloride solution was developed. A 4-fold amount of 1,10-phenanthroline or 2,2'-bipyridine was necessary for rapid quantitative reaction; the permissible pH range was 1.5–5. The oxidation of the cobalt(II) complex proceeds rapidly at 40–50°C, and a direct potentiometric titration was possible. The following maximum errors were obtained: 3.3% for 0.2–1.0 mg Co, 2.0% for 1–5 mg Co, and 0.70% for 10–40 mg Co. The following ions did not interfere: Ni(II), Zn(II), Pb(II), Cd(II), Mn(II), Fe(II), Cr(III), Al(III), Th(IV), Se(IV), Ti(IV), U(VI), Mo(VI), SO^2-₄ and PO^3-₄. Even small quantities of silver(I), copper(II), palladium(II), mercury(II)and iron(III) interfered. The method was applied to the determination of high cobalt contents in high-temperature nickel-base alloys.     

Ion-exchanger colorimetry-I Micro determination of chromium, iron, copper and cobalt in water

A new sensitive, colorimetric method based on the direct measurement of light-absorption by an ion-exchange resin phase, which has sorbed the sample complex species, has been developed. Determinations ofchromium(VI) with diphenylearbazide, iron(II) with 1,10-phenanthroline, copper with Zincon and cobalt with thiocyanate have more than ten times the sensitivity obtainable with conventional solution colorimetry. The present method can be applied to natural water samples containing very low levels of these metals.     

Ion paired chromatography of iron (II,III), nickel (II) and copper (II) as their 4,7-Diphenyl-1,10-phenanthroline chelates

A reversed phase ion-paired chromatographic method that can be used to determine trace amounts of iron (II,III), nickel (II) and copper (II) was developed and applied to the determination of iron (II) and iron (III) levels in natural water. The separation of these metal ions as their 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline) chelates on an Inertsil ODS column was investigated by using acetonitrile-water (80/20, v/v) containing 0.06 M perchloric acid as mobile phase and diode array spectrophotometric detection at 250-650 nm. Chromatographic parameters such as composition of mobile phase and concentration of perchloric acid in mobile phase were optimized. The calibration graphs of iron (II), nickel (II) and copper (II) ions were linear (r > 0.991) in the concentration range 0-0.5, 0-2.0 and 0-4.0 mug ml(-1), respectively. The detection limit of iron (II), nickel (II) and copper (II) were 2.67, 5.42 and 18.2 ng ml(-1) with relative standard deviation (n = 5) of 3.11, 5.81 and 7.16% at a concentration level of 10 ng ml(-1) for iron (II) and nickel (II) and 25 ng ml(-1) for copper (II), respectively. The proposed method was applied to the determination of iron(II) and iron(III) in tap water and sea water samples without any interference from other common metal ions.     

Preconcentration of Nickel(II) in White Wine Using Quinoxaline-2,3-dithiol and a Finely Divided Anion-Exchange Resin for the Determination by Solid-Phase Spectrophotometry

A simple and sensitive method for the determination of trace amounts of nickel(II) is described. The method is based on the adsorptive enrichment of nickel(II) as the complex with quinoxaline-2,3-dithiol using a finely divided anion-exchange resin, collection of the resin on a membrane filter by filtration, and direct measurement of the absorbance of the resultant circular thin layer by reflective spectrophotometry at 605 nm. In the presence of interfering cations such as copper(II) and cobalt(II) a sample solution is first filtered, after the addition of ammonium thiocyanate and Zephiramine, to extract these cations onto a membrane filter as the ion-pair precipitate formed between the metal-thiocyanate complex anions and Zephiramine cations, then nickel(II) in the filtrate is determined. Interferences from iron(III), silver(I), bismuth(III), cadmium(II), mercury(II), indium(III), palladium(II), platinum(IV), tin(IV), and zinc(II) can also be eliminated. The proposed method was applied to the determination of nickel in white wine. The concentrations of nickel found in 5-ml aliquots of 10 different wine samples were in the range 16.1-68.0 ng ml⁻¹.     

Sequential flow-injection spectrophotometric determination of iron(II) and iron(III) by copper(II)-catalyzed reaction with Tiron

A flow injection method for the sequential determination of iron(II) and iron(III) was developed. It is based on the differential reaction kinetics of iron(II) and iron(III) with Tiron in a double-injection FI system. The proposed method employs the accelerating action of copper(II) for the oxidation of iron(II) in the presence of Tiron. A linear calibration graph is obtained for iron (II) and iron(III) in the concentration range 1.8 × 10^–5– 1.8 × 10^–4 mol/L; the throughput of samples is 30 injections/h. Received: 22 October 1996 / Revised: 4 December 1996 / Accepted: 10 December 1996     

Solid-phase spectrophotometric microdetermination of iron with ascorbic acid and ferrozine

 A very sensitive and selective method for the determination of trace amounts of iron has been developed, based on the reduction of Fe(III) to Fe(II) by ascorbic acid, followed by chromogenic chelation of Fe(II) with ferrozine. The complex Fe(II)-ferrozine is easily sorbed on a dextran-type anion-exchange gel packed in a 1 mm cell, and the absorbance of the gel is measured directly at 569 and 800 nm. The extended linear range of the determination is 0.5–10 ng ml^-1 of iron (apparent molar absorptivity=4.4×10⁷ l mol^-1 cm^-1) and the precision (RSD) 1.3% for a concentration of 5 ng ml^-1 of iron (n=10). The detection limit for a sample volume of 1000 ml, using 0.040 g of anion-exchanger, corresponds to 0.12 ng ml^-1. The method has been successfully applied to the determination of iron in natural and waste waters, wine, soil extract and previously digested vegetal tissues, drugs and human hair. Received: 20 November 1995/Revised: 23 January 1996/Accepted: 26 January 1996     

Spectrophotometric determination of Rauwolfia alkaloids: estimation of reserpine in pharmaceuticals.

A simple, sensitive and economically viable spectrophotometric method for the determination of some Rauwolfia alkaloids (ajmaline, ajmalicine, reserpine and yohimbine-HCl) has been developed. The method involves the oxidation of Rauwolfia alkaloids by iron(III) and subsequent complexation of iron(II) with 1,10-phenanthroline, forming a red-colored complex having the maximum absorbance at 510 nm. The method is applied to the determination of reserpine in tablets of pharmaceutical formulations. The common excipients do not interfere with the proposed method. A statistical comparison of these results with those of a reported method shows good agreement and indicates no significant difference in the precision.     

Sensitive spectrophotometric determination of ascorbic acid in fruit juices and pharmaceutical formulations using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP)

A simple and very sensitive method has been developed for the determination of ascorbic acid based on the oxidation of ascorbic acid to dehydroascorbic acid by iron(III), followed by a complexation of iron(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol(Br-PADAP). The iron(II) complex is formed immediately, with absorption maxima at 560 and 748 nm and a molar absorptivity of 1.31 × 10⁵ l mole^–1cm^–1 and 5.69 × 10⁴ l mole^–1cm^–1, respectively. The ascorbic acid determination is possible with a linear range up to 2.4 μg ml^–1, a calibration sensitivity of 0.744 ml μg^–1 at 560 nm and 0.323 ml μg^–1 at 748 nm, and a detection limit of 15 ng ml^–1 and 44 ng ml^–1, respectively. The procedure was used for the ascorbic acid determination in several fruit juices and pharmaceutical formulations. The results demonstrated a good precision (R.S.D. < 1%) and are in agreement with those obtained with others methods. The Br-PADAP method proposed is six times more sensitive than the method using the iron(II)-1,10-phenanthroline system. Received: 7 May 1996 / Revised: 1 July 1996 / Accepted: 8 August 1996     

Potentials of thermal lens spectroscopy for polymethacrylate optical sensors

The sensitivity of the earlier proposed procedures for the determination of iron(II, III) with 1,10-phenanthroline, silver(I) with dithizone, mercury with copper(II) dithizonate, copper(II) with lead diethyldithiocarbamate, and ascorbic acid with 2,6-dichlorophenolindophenol using polymethacrylate optical sensitive elements for solid phase spectrophotometry is enhanced through the use of thermal lens spectrometry as the most sensitive method of molecular absorption spectroscopy. The limits of detection for all photometric reactions in the polymethacrylate matrix are reduced by an order of magnitude (to 10 nM) without substantial changes in the experimental conditions.