Faradaic electrochemistry at microcylinder,band, and tubular band electrodes

Current-time relationships of faradaic processes at microcylinder, band, and tubular band electrodes have been evaluated. Microcylinder electrodes were fabricated from platinum wires (5 μm radius) sealed in glass capillaries. Band and tubular electrodes were constructed with platinum sheets (～ 20 μm width) or thin pieces of graphite (～ 5 μm width) sealed between insulating mateials. The temporal response of the current at a microcylinder electrode for the reduction of ferricyanide in aqueous potassium chloride solutions is in excellent agreement with that predicted by equations derived for heat flux to a cylinder. An estimation of the magnitude and temporal properties of the measured current at a band electrode can be obtained when a hemicylinder geometry is assumed. The current respone is identical at band and tubular band electrodes even for the smallest tubular radius investigated, 0.54 mm. Cyclic voltammograms at electrodes of all three geometries show significant contributions from radial diffusion at slow scan rates (< 20 mV s^?1). The current at a graphite tubular band electrode was found to be independent of flow of solution through the electrode at flow rates up to 3 ml min^?1.     

管式金电极差分脉冲阳极溶出伏安法测定水中痕量硒

阳极溶出伏安法测定硒已见报导。本文主要介绍了采用管式金电极为流通池,差分脉冲阳极溶出伏安法测定水中痕量硒的方法。管式电极流通池的制作和应用很方便,测定方法具有快速、灵敏、可靠、可用于连续分析的特点。本实验证实了管式电极和差分脉冲法联合应用的理论及其在分析应用中的优越性。本方法可望在现代连续流动分析中推广应用。     

管式电极流体动力催化伏安法的研究

Blaedel等曾证明管式电极在层流条件下的扩散电流方程,随后在管式电极上对极谱催化电流进行了研究,但该理论只适用于化学反应非常快及非常慢的情况。Koichi等运用与Blaedel不同的处理方法,导出了通道电极上更为精确的催化电流方程。     

Linear sweep voltammetry at the tubular graphite electrode: Part II. Totally irreversible processes

The theory of linear sweep voltammetry at the tubular graphite electrode has been developed for irreversible processes. The convective diffusion differential equations have been transformed into an integral equation which is solved numerically. The current-potential curves have been calculated theoretically and verified experimentally. The dependence of the current-potential curves on velocity has been studied. A procedure for the determination of kinetic parameters, i.e. standard rate constant and transfer coefficient, is presented.     

曲率对管状电极电化学行为的影响

利用隐式差分法对管状电极对流扩散方程作了数值解,通过与平板电极电化学行为的比较,分析管状电极特性,讨论了管曲率对管状电极电化学行为的影响,并给出在管状电极中使用Ｌｅｖｉｃｈ近似的条件．     

An electrochemical detector cell for open tubular liquid chromatography and capillary electrophoresis

Summary An electrochemical detector cell has been developed for micro-flow separation systems (OTLC, CE). The cell contains two electrodes, a disk-shaped working electrode made from a carbon fiber bundle, and a tubular Ag/AgCl quasi-reference electrode. The effective cell volume and the coulometric yield have been determined, for different electrode diameters and at different flow rates, in an OTLC system. An effective cell volume of less than 1 nl was observed. The applicability of the cell was demonstrated with the detection of OPA-derivatized amino acids. For use in CE, the cell was equipped with an additional compartment, housing a semi-permeable joint for the decoupling of the high electric field used for the electrophoretic separation. Results are shown on the determination of catecholamines by CE with electrochemical detection. Detection limits with both OTLC and CE were well below 1 fmole.     

Analytical characterisation of a capacitively coupled plasma torch with a central tube electrode

A new type of radiofrequency capacitively coupled plasma torch is presented. The torch electrode geometry is coaxial with a tubular central electrode and one or two outer ring electrodes. The argon plasma is generated at 275 W radiofrequency power and 27.12 MHz and it has a very good stability and a low gas consumption of 0.4 l min(-1). The nebulized sample is introduced through the tubular electrode into the core of the annular shaped plasma thus achieving a better atomisation and a lower background. The limits of detection for 20 elements are in the range of ng ml(-1) and the dynamic range between 2.5 and 3.5. The best results are obtained with the torch with two outer ring electrodes.     

Application of the superposition principle to the study of a charge transfer reaction in cyclic chronopotentiometry. Part II

The general analytical expressions corresponding to the response obtained for a charge transfer process in cyclic chronopotentiometry are presented. The different geometries considered for the mass transport operator are planar, tubular and spherical. In the case of spherical electrodes (such as the dropping mercury electrode and the static mercury dropping electrode), we have analyzed the following two cases: solution soluble product and electrode soluble product or amalgamation. The solutions deduced here are independent of the method used in solving the differential equations system since we have applied the superposition principle for which we have only used the properties of the linear operators.     

Mass transfer enhancement for mesh electrode in a tubular electrochemical reactor using experimental and numerical simulation method

The effect of electrode configuration on mass transfer rate in a tubular electrochemical reactor was investigated with the limiting-current method. The expression of mass transfer enhancement factor was derived from the dimensionless equations for different electrode configurations. Furthermore, the local velocity distribution in the tubular electrochemical reactor was simulated by computational fluid dynamics technology. These simulation results explained the reason of mass transfer enhancement for mesh electrode: the rotation of the solution is induced by high rates of shear, and small eddies are formed. The local velocity distributions in bulk for X-dimension get flatter because of the lateral momentum transfer. Due to the impact and obstruction of electrode holes, the turbulence of the electrolyte gets drastic and the mass transfer performance in the tubular electrochemical reactor is improved.     

Current transients at a channel electrode produced by a potential step

A theory is presented which describes the transient current response to a potential step at a channel (or tubular) electrode for a reversible electrode reaction. Experimental results for a wide range of solution flow velocities are found to be in good agreement with theory.     

Solution nebulization of aqueous samples into the tubular-electrode torch capacitatively-coupled microwave plasma

This work shows the feasibility of using nebulization for introduction of aqueous samples into the tubular-torch capacitatively-coupled microwave plasma (CMP). Previously, solid electrodes were used with this type of plasma, in which analyte carrier and plasma support gases are premixed and swept around the electrode tip. With the new design, the analyte carrier gas passes through the centre of the hollow tubular electrode and mixes with the plasma support gas at the tip of the electrode where the plasma is formed. Sample solutions are nebulized with a Meinhard nebulizer and a laboratory-constructed spray chamber and desolvation system. The tubular torch is made of tantalum. Plasma gases investigated include argon, helium and nitrogen. Typical operating powers are 300-350 W. Elements studied include Ag, Al, Ba, Ca, Cd, Cr, Cs, Cu, K, Li, Na, Pb, Pd, Sr and Zn.     

Adaptation of a commercial ion selective fluoride electrode to a tubular configuration for analysis by flow methodologies

The determination of fluoride ions in water samples is accomplished by using a tubular flow through detector constructed by drilling a channel through a commercially available LaF(3) crystal electrode in such a way that the original contacts of the non-modified unit are maintained. Its performance when incorporated in both FIA and SIA systems was evaluated and the results show that the tubular unit retains the characteristics of the non-modified electrode. In SIA conditions an extended linear range of response and lower detection limit were achieved when compared with the electrode performance in FIA conditions. These aspects together with the additional advantage of low sample and reagent consumptions in SIA when compared to FIA, makes the incorporation of the proposed tubular ISE in a SIA system the preferred approach for on line determination and monitoring of fluoride content in natural water samples.     

Electrospinning P(LLA-CL) Nanofiber: A Tubular Scaffold Fabrication with Circumferential Alignment

In this paper a synthetic Poly(L-lactic-co-ϵ-caprolactone) [P(LLA-CL)] (75:25) copolymer has been fabricated into a nanofibrous structure by electrospinning. The polymer crystal structure has been investigated by DSC and x-ray diffraction method. During electrospinning at room temperature, a crystallization of LLA sequence in the P(LLA-CL) copolymer could not form, while a relatively regular arrangement of CL sequence was observed. In order to obtain a tubular scaffold, a rotating mandrel was designed to collect the fiber, so that the tubular scaffold can be retrieved from the mandrel with an inner diameter same as that of the outer diameter of the mandrel. An auxiliary electrode with a sharp edge and a negative charge was set under the mandrel to guide the fiber deposition on the mandrel. When the sharp edge bar was vertical to the rotating axle of the mandrel and just beneath the spinning nozzle, nanofibers with circumferential alignment were obtained. With this method it is possible to obtain a tubular scaffold with suitable fiber alignment for blood vessel tissue engineering.     

THE THEORY OF CURRENT TRANSIENTS AT TUBULAR ELECTRODES IN A FLOWING FLUID

A theoretical equation is developed which describes theresponse of the current transients to a constant potential at tubularelectrodes for a reversible electrode reaction in the flowing fluid.     

Evaluation of critical parameters for measurement of pH by flow injection analysis determination of pH in soil extracts

A systematic evaluation of the parameters affecting the measurement of pH in a flow injection system incorporating a tubular PVC-based pH-sensitive membrane electrode is presented. In order to obtain reliable results, it is necessary to have a dispersion coefficient D^max ? 1.008 at peak maximum and to adjust the buffering capacity of the carrier stream to be less than that of the sample solution. A suitable design of system to meet these criteria is discussed. The applicability of this approach is demonstrated for the determination of pH in a series of soil extracts; the results are compared with those obtained by conventional glass electrode measurements.     

An amperometric detector with a tubular electrode deposited on the capillary for capillary liquid chromatography

A procedure is described for the preparation of a tubular electrode by chemical deposition of platinum at the end of a fused-silica capillary. The properties of the electrode were tested under liquid chromatographic conditions, demonstrating that both the static and the dynamic behaviour of the detection system satisfy the requirements of capillary chromatographic separations and compare well with a wall-jet amperometric system and with UV photometric detection. The detection system described is easy to prepare and does not require any time-consuming positioning of the electrode system as it is integrated into the separation part of the apparatus.     

Hydrodynamic voltammetry at tubular electrodes-III Determination of traces of bismuth by differential-pulse anodic-stripping voltammetry at a glassy-carbon tubular electrode with in situ mercury plating

An equation for the current in differential-pulse anodic-stripping voltammetry at tubular electrodes is derived. Application of a glassy-carbon tubular electrode to determination of traces of bismuth in environmental water samples by differential-pulse anodic-stripping voltammetry is described. In hydrochloric acid medium, the stripping peak current is proportional to the concentration of bismuth in the range 2-100 ng/ml, with a deposition time of 3-10 min. The detection limit is 0.5 ng/ml.     

Mass transfer to tubular electrodes. Part 2: CE process

The kinetic equations for an electrochemical process consisting of a homogeneous first‐order chemical reaction followed by electron transfer at the electrode surface are solved numerically, for linear sweep voltammetry under hydrodynamical conditions in a tubular electrode. Models for both the cases involving reversible as well as irreversible electrode charge transfer reaction are investigated. The influence on current–potential voltammograms of the experimentally measurable parameters like the potential scan rate, axial flow rate and chemical equilibrium parameter is examined and depicted graphically. This revised version was published online in July 2006 with corrections to the Cover Date.     

Continuous introduction of powdered samples in emission spectroscopy The use of a tube-electrode

A device for the continuous introduction of powdered samples into spark and arc sources is described. The sample is pushed by a motor-driven spindle into the electrode gap through a tubular electrode. The method was found to be simple and versatile.     

化学修饰电极的研究 ⅩⅤⅡ四苯基铁卟啉化学修饰玻碳电极的热处理及其对氧的催化还原

关于金属卟啉、酞菁等化学修饰电极的研究已有大量工作发表.这类电极很不稳定,例如著名的面-面双钴卟啉修饰电报,虽然能直接催化氧还原为水,但经受不住几次电位扫描就失去催化活性.因此,如何提高稳定性就成为研究这类电极的关键.近年来有人报道,吸附在活性碳上的金属卟啉、酞菁类化合物经热处理,可改善其稳定性。热处理后得到的粉状碳催化剂,由于完全不溶于水及有机溶剂,制备电极非常困难。曾有过用这种