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.

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.

Electrochemical measurements of oligonucleotides in the presence of chromosomal DNA using membrane-covered carbon electrodes

Substantial improvements in the selectivity of electrochemical measurements of trace nucleic adds are obtained by using membrane-covered carbon disk electrodes. Access to the electrode surface can be manipulated via a judicious choice of the membrane molecular weight cutoff (MWCO). The resulting separation step, performed in situ at the electrode surface, adds a new dimension of selectivity based on molecular size to electroanalysis of nucleic acids, Transport properties are evaluated with respect to the oligonucleotide length and membrane MWCO. A highly selective response is observed for synthetic oligonucleotides in the presence of otherwise interfering chromosomal DNAs. Discrimination among oligonucleotides of different lengths is also possible, Short accumulation periods (1-5 min) are sufficient for convenient measurements of low milligram per liter concentrations.

Development and Evaluation of a Nanoporous Iron (Hydr)oxide Electrode for Phosphate Sensing

Nanoporous iron (hydr) oxide electrodes are evaluated as phosphate sensors using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The intensity of the reduction peak current (I-cp) of the ferrihydrite working electrode is tied to phosphate concentration at low pH; however, a hematite electrode combined with the use of EIS provided reliable sensing data at multiple pH values. Nanoporous hematite working electrodes produced an impedance phase component (theta) that shifts with increasing phosphate, and, at chosen frequencies, theta values were fitted for the range 1 nM to 0.1 mM phosphate at pH 4 and pH 7 in 5 mM NaClO4.

Stepping-motor-driven constant-shear-rate rotating viscometer

Despite the frequent use of stepping motors in robotics, automation, and a variety of precision instruments, they can hardly be found in rotational viscometers. This paper proposes the use of a stepping motor to drive a conventional constant-shear-rate laboratory rotational viscometer to avoid the use of velocity sensor and gearbox and, thus, simplify the instrument design. To investigate this driving technique, a commercial rotating viscometer has been adapted to be driven by a bipolar stepping motor, which is controlled via a personal computer. Special circuitry has been added to microstep the stepping motor at selectable step sizes and to condition the torque signal. Tests have been carried out using the prototype to produce flow curves for two standard Newtonian fluids (920 and 12 560 mPa (.) s, both at 25 degrees C). The flow curves have been obtained by employing several distinct microstep sizes within the shear rate range of 50-500 s(-1). The results indicate the feasibility of the proposed driving technique.

Electrocatalytic study of an electrode modified with Reactive Blue 4 dye covalently immobilized on amine-functionalized silica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The influence of hydrogen plasma pre-treatment on the structure of BDND electrode surface applied for phenol detection

The surface properties of boron-doped nanocrystalline diamond films treated with H(2) plasma was investigated in regard to their electrochemical response for phenol oxidation. The surface of these films is relatively flat formed by crystallites with sizes of about 40 nm. X-ray photoelectron spectroscopy analyses showed that electrode surface has a high amount of C-H bonds. This behavior is in agreement with Mott-Schottky plot measurements concerning the flat band potential that presented a value as expected for hydrogenated diamond surface. This electrode presented the phenol detection limit of 0.08 mg L(-1) for low phenol concentrations from 40 to 250 mu mol L(-1).