Local order around tungsten atoms in tungstate fluorophosphate glasses by X-ray absorption spectroscopy

X-ray absorption spectroscopy was used to study the local environment of tungsten atoms in NaPO3-BaF2,-WO3 glasses and the results were compared with crystalline references Na2WO4 and WO3. XANES measurements at the W-L-1 edge allowed to determine a distorted octahedral environment of tungsten atoms in these glasses similar to the local order of tungsten in monoclinic WO3. Extended X-ray absorption fine structure (EXAFS) has been used as a local probe to monitor the effect of WO3 concentration on the tungsten environment. Based on an analysis of the EXAFS data, we proposed a three-shell model of oxygen atoms around tungsten as in monoclinic WO3. With increasing WO3 concentration, it was found that R-2 decreases from 1.96 to 1.92 angstrom whereas R-3 increases from 2.07 to 2.12 angstrom. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis and electrical characterization of tungsten doped Pb(Zr0.53Ti0.47)O-3 ceramics obtained from a hybrid process

Pure and W-doped PZT ceramics (PZT and PZTW) were prepared by a hybrid process consisting in the association of polymeric precursor and partial oxalate methods. The phase formation was investigated by simultaneous thermal analysis (TG/DSC) and X-ray diffraction (XRD). The effect of W doping PZT and their electrical properties was evaluated. Substitution of W by Ti leads to an increase of Curie temperature and broadening of dielectric constant. A typical hysteresis loop was observed at room temperature and the remnant polarization was increased with the content of W. (c) 2007 Elsevier B.V. All rights reserved.

Application of a glassy carbon electrode modified with poly(glutamic acid) in caffeic acid determination

Glassy carbon electrodes were coated with films of poly( glutamic acid) ( PG), and the modified electrode proved to be very effective in the oxidation of caffeic acid. The performance of the film was also tested with ascorbic acid, coumaric acid, ferulic acid, sinapic acid and chlorogenic acid. At pH 5.6, all the hydroxycinnamic acids yield a higher peak current intensity when oxidized after incorporation in the PG-modified electrode, and only the oxidation of ascorbic acid exhibits overpotential reduction. At pH 3.5 only caffeic and chlorogenic acid are incorporated in the modified electrode and exhibit a well-defined oxidation wave at +0.51 V and +0.48 V, which is the base for their determination. Linear calibration graphs were obtained from 9 x 10(-6) mol L-1 to 4 x 10(-5) mol L-1 caffeic acid by linear voltammetric scan and from 4 x 10(-6) mol L-1 to 3 x 10(-5) mol L-1 by square wave voltammetric scan. The method was successfully applied to the determination of caffeic acid in red wine samples without interference from other hydroxycinnamic acids or ascorbic acid.

Evaluation of a highly sensitive amperometric biosensor with low cholinesterase charge immobilized on a chemically modified carbon paste electrode for trace determination of carbamates in fruit, vegetable and water samples

A highly sensitive amperometric biosensor for determination of carbamate pesticides directly in water, fruit and vegetable samples has been evaluated, electrochemically characterized and optimized. The biosensor strip was fabricated in screen printed technique on a ceramic support using silver-based paste for reference electrode, and platinum-based paste for working and auxiliary electrodes. The working electrode was modified by a layer of carbon paste mixed with cobalt(II) phthalocyanine and acetylcellulose. Cholinesterase (ChE) enzymes with low enzymatic charge were immobilized on this layer. The operational simplicity of the biosensor consists in that a small drop (similar to 50 mu l) of substrate or sample is deposited on a horizontally positioned biosensor strip representing the microelectrochemical cell. The working potential of the biosensor was 370 mV versus Ag/AgI on a ship reference electrode preventing the interference of electroactive species which are oxidable at more positive potentials. The biosensor was applied to investigate the degradation of two reference ChE inhibitors in freeze dried water under different storage conditions and for direct determination of some N-methylcarbamates (NMCs) in fruit and vegetable samples at ppb concentration levels without any sample pretreatment. A comparison of the obtained results for the total carbamate concentration was done against those obtained using HPLC measurements. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Flow injection amperometric detection of ascorbic acid using a Prussian Blue film-modified electrode

The PB film-modified electrode was used as an amperometric detector for flow injection analysis of ascorbic acid. The modified electrode detector showed good sensitivity, stability and reproducibility. The calibration curve for ascorbic acid was linear over the concentration range from 5.0 x 10(-6) to 1.0 x 10(-3) mol l(-1) with a slope of 19.9 mA mol(-1) per litre and a correlation coefficient of 0.999. The detection limit of this method was 2.49 x 10(-6) mol l(-1). The relative standard deviation of six replicate injections of 2.5 x 10(-4) mol l(-1) ascorbic acid was 2.5%. The results obtained for ascorbic acid determination in pharmaceutical products are in good agreement with those obtained by using the procedure involving the reaction between triiodide and ascorbic acid. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Electrode surface modifications improve cathode hydrogen production and anode capacity in Ni-MH batteries

This paper reports results from electrochemical evaluations of electrodes used as cathodes for a hydrogen evolution reaction and anodes in Ni-MH batteries that had been surface-modified by micro-encapsulation, co-deposition and sol-gel methods. The surface modifications produced actual improvements in the corresponding electrochemical reactions by enhancing the performance and/or the mechanical stability of the electrode material. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

An electrode of the second kind for aspirin determination in tablet formulations

This paper describes the construction of an electrode of the second kind, Pt\Hg\Hg-2(Salic)(2)\Graphite, sensitive to salicylate. This electrode responds to the salicylate ion with a sensivity of 58.66 mV/decade over the range 6.0x10(-4) - 1.0x10(-1) mol/l at pH 6.0 and an ionic strength of 0.500 - 3.00 mol/l, adjusted with NaClO4. The electrode is easily constructed, shows a fast response time, is low in cost, has excellent response stability, and has a lifetime greater than 18 months, which is much longer than those reported earlier for other systems. The influence of 10 different carboxylate and inorganic anions on the electrode response showed that there was negligible interference by most of these ions. It was used to determine aspirin in tablets (after hydrolysis of acetylsalicylic acid to salicylate) by means of the standard additions method. The results obtained using this electrode for aspirin determination, in three different samples of antithermic drugs, compared favorably with the results given by the British Pharmacopoeia method.

Thermal analysis and electrochemical study of Hg reactions on Pt-30% Ir alloy electrode

Thermogravimetry (TG), cyclic voltammetry (CV) and other analytical techniques were used to study the reactions of mercury with Pt-30% Ir alloy. The results allowed to suggest that an electrodeposited mercury film interacts with the substrate and when subjected to heat or electrochemical removal at least four mass loss steps or five peaks appeared during the mercury desorption process. The first two steps were attributed to Hg(0) removal probably from the bulk and from the adsorbed monolayer which wets the electrode surface. These two processes are responsible for peaks D and F in the cyclic voltammograms. The last two peaks (G, H) in CV were ascribed to the intermetallic compound decomposition. In TG curves, the last two steps were attributed to the PtHg4 (third step), and PtHg2 decomposition followed by Hg removal from the subsurface. The PtHg2 was formed by an eutectoide reaction: PtHg -> PtHg2+Hg(Pt-Ir). The Hg diffused to the subsurface was not detectable by cyclic voltammetry.

Determination of nickel in fuel ethanol using a carbon paste modified electrode containing dimethylglyoxime

A mercury-free electrode chemically modified with carbon paste containing dimethylglyoxime was used for determination of nickel in fuel ethanol. The instrumental parameters and composition of the modified paste were optimized. The analytical curve for nickel determination from 5.0 x 10(-9) to 5.0 x10(-7) mol(-1) was obtained using 25 min of accumulation time. The detection limit and amperometric sensitivity obtained for this method were 2.7 x 10 mol(-1) and 5.2 x 10(8) mu A mol(-1) L, respectively. The values for nickel concentration in four commercial samples of fuel ethanol were obtained in the range of 1.1 x 10(-8) to 6.9 x 10(-8) mol(-1). A comparison to graphite furnace atomic absorption spectrometry (GFAAS) was performed for nickel determination in commercial samples of ethanol.

Studies of the voltammetric behavior and determination of diazo reactive dyes at mercury electrode

The electrochemical reduction of two reactive dyes: Procion Red HE-3B 9 (RR120) and Procion Green HE-4BD (RG19) was investigated using cyclic voltammetry, differential pulse and DC, polarography, chronoamperometry and controlled potential electrolysis at mercury electrodes. The bis-azo groups of the RR120 dye are reduced together in one single step of four electrons, the bis-azo groups of the RG19 dye are reduced in two steps owing to the difference in the electron densities promoted by the different substituents in the benzene rings adjacent to the azo groups. The bis-monochlorotriazine reactive groups in both dyes are reduced only in acidic medium in their protonated form, leading to the reduction of the triazine groups. The reduction mechanism of both reactive dyes is discussed. Both dyes can be quantified in aqueous medium by differential pulse polarography in the concentration range of 1 x 10(-7) mol L-1 to 1 x 10(-5) mol L-1 by monitoring the reduction of the chromophore group or the reactive group.

An electrode of the second kind for benzoate determination in medicinal syrups

This paper describes the construction of an electrode of the second kind, Pt\Hg\Hg-2(Bzt)(2)\graphite, sensitive to benzoate ion (Bzt). The electrode provides a near-Nernstian response (-58.19 mV/decade at 25 degrees C) to benzoate ion in the concentration range 1.11 x 10(-1) to 5.00 x 10(-4) M at pH 7.0 and ionic strength 0.500-3.00M, adjusted with NaClO4. The electrode is easily constructed, shows a fast response time, is low in cost, has excellent response stability, and has a lifetime greater than 24 months. which is much longer than those earlier reported for other systems. A further salient feature of the electrode is that perchlorate does not interfere in its response, which may be advantageous in the analysis of perchloric acid-treated samples. It was applied to the determination of sodium benzoate in some commercial expectorating medicinal syrups using the standard additions method. The results obtained by the proposed procedure compare very favorably with those obtained through the reference method recommended by the United States Pharmacopeia. (C) 1998 Academic Press.

Determination of iodide and idoxuridine at a glutaraldehyde-cross-linked poly-L-lysine modified glassy carbon electrode

The detection limit (about 0.017 mu g mL(-1)) for voltammetric determination of iodide (peak at +0.87 V vs. Ag/AgCl at pH 2) at a glutaraldehyde-cross-linked poly-L-lysine modified glassy carbon electrode involving oxidation to iodine was found to be several orders of magnitude lower than that for the voltammetric determination on a bare glassy carbon electrode. This method was applied successfully to the determination of iodide in two medicinal formulations. Idoxuridine was determined indirectly at the same electrode by accumulating it first at -0.8 V vs. Ag/AgCl. At this potential the C-I bond in the adsorbed idoxuridine is reduced giving iodide, which is then determined at the modified electrode. The method was successfully applied to the determination of idoxuridine in a urine sample.

Non-isothermal kinetic of oxidation of tungsten carbide

Tungsten carbide, WC, has shown dissimilar thermal behavior when it is heated on changeable heating rate and flow of oxidant atmosphere. The oxidation of WC to WO3 tends to be in a single and slow kinetic step on slow heating rate and/or low flux of air. Kinetic parameters, on non-isothermal condition, could be evaluated to the oxidation of WC to heating rate below 15 degrees C min(-1) or low flow of air (10 mL min(-1)). The reaction is governed by nucleation and growth at 5 to 10 degrees C min(-1) then the tendency is to be autocatalytic, JMA and SB, respectively.

Adsorptive potentiometric stripping analysis of trace tamoxifen at a glassy carbon electrode

A highly sensitive adsorptive stripping procedure for trace measurement of the anticancer drug tamoxifen is described. The method is based on controlled adsorptive accumulation of the drug at an electrochemically treated glassy carbon electrode, followed by chronopotentiometric measurement of the surface species. The chronopotentiometric operation effectively addresses the large background contribution inherent to the glassy carbon electrode to yield a detection limit of 4 x 10(-10) M after 4 min preconcentration. The adsorptive stripping response is evaluated with respect to electrode type and conditioning, accumulation potential and lime, stripping current, pH, drug concentration, potential interferences, and other variables. Applicability to urine samples is illustrated. (C) 1997 Elsevier B.V. B.V.

Potentiometric determination of saccharin in commercial artificial sweeteners using a silver electrode

A simple, precise, rapid and low-cost potentiometric method for saccharin determination in commercial artificial sweeteners is proposed. Saccharin present in several samples of artificial sweeteners is potentiometrically titrated with silver nitrate solution using a silver wire as the indicator electrode, coupled to a titroprocessor. The best pH range was from 3.0 to 3.5 and the detection limit of sodium saccharin was 2.5 mg/ml. Substances normally found along with saccharin in several commercial artificial sweeteners such as maltodextrin, glucose, sucrose, fructose, aspartame, cyclamate, caffeine, sorbitol, lactose, nitrate, methyl- and n-propyl-p-hydroxybenzoate, benzoic, citric and ascorbic acids do not interfere even in significant amounts (e.g. 20 excess relative to saccharin). Chloride ion interferes when present in concentrations larger than 10 mg l(-1); this interference is eliminated with previous extraction of the sweetener from the aqueous medium with ethyl acetate. The results obtained by applying the proposed method compared very favorably with those given by the HPLC method recommended by the FDA. (C) 2003 Elsevier Ltd. All rights reserved.