Voltammetry electrodes

HYDRODYNAMIC STATIONARY- LARGE AMPLITUDE VOLTAMMETRY ELECTRODE PULSE... 

Carbon ring electrodes with structurally ultrasmall tip diameters were fabricated as described elsewhere. Electrodes with 3-5 pm tip diameters were used for intracellular voltammetry. Electrodes used for characterization ranged from 3 to 15 im in tip diameter. 

Cyclic voltammetry provides a simple method for investigating the reversibility of an electrode reaction (table Bl.28.1). The reversibility of a reaction closely depends upon the rate of electron transfer being sufficiently high to maintain the surface concentrations close to those demanded by the electrode potential through the Nemst equation. Therefore, when the scan rate is increased, a reversible reaction may be transfomied to an irreversible one if the rate of electron transfer is slow. For a reversible reaction at a planar electrode, the peak current density, fp, is given by... 

Stripping voltammetry involves the pre-concentration of the analyte species at the electrode surface prior to the voltannnetric scan. The pre-concentration step is carried out under fixed potential control for a predetennined time, where the species of interest is accumulated at the surface of the working electrode at a rate dependent on the applied potential. The detemiination step leads to a current peak, the height and area of which is proportional to the concentration of the accumulated species and hence to the concentration in the bulk solution. The stripping step can involve a variety of potential wavefomis, from linear-potential scan to differential pulse or square-wave scan. Different types of stripping voltaimnetries exist, all of which coimnonly use mercury electrodes (dropping mercury electrodes (DMEs) or mercury film electrodes) [7, 17]. 

Osteryoung J and Murphy M M 1991 Normal and reverse pulse voltammetry at small electrodes Microelectrodes Theory and Applications (Nate ASI Series E vol 197) ed M I Montenegro, M A Queiros and J L Daschbach (Dordrecht Kluwer)... 

O Dea J, Wo]ciechowski M and Osteryoung J 1985 Square wave voltammetry at electrodes having a small dimension... 

Albery W J and Brett C M A 1983 The wall-]et ring disc electrode. 2. Collection efficiency, titration curves and anodic stripping voltammetry J. Electroanal. Chem. 148 201... 

Ekiund J C, Markem F, Waller D N and Compton R G 1996 Voltammetry in the presence of ultrasound, a novel sono-electrode geometry E/eofrooh/m. Aofa 41 1541... 

Modestov A D, Zhou G-D, Ge FI-FI and Loo B FI 1995 A study by voltammetry and the photocurrent response method of copper electrode behavior in acidic and alkaline solutions containing chloride ions J. Electroanal. Chem. 380 63-8... 

In voltammetry the working electrode s surface area is significantly smaller than that used in coulometry. Consequently, very little analyte undergoes electrolysis, and the analyte s concentration in bulk solution remains essentially unchanged. 

A form of voltammetry using a dropping mercury electrode or a static mercury drop electrode. 

A form of voltammetry in which the analyte is first deposited on the electrode and then removed, or stripped, electrochemically while monitoring the current as a function of the applied potential. 

In hydrodynamic voltammetry current is measured as a function of the potential applied to a solid working electrode. The same potential profiles used for polarography, such as a linear scan or a differential pulse, are used in hydrodynamic voltammetry. The resulting voltammograms are identical to those for polarography, except for the lack of current oscillations resulting from the growth of the mercury drops. Because hydrodynamic voltammetry is not limited to Hg electrodes, it is useful for the analysis of analytes that are reduced or oxidized at more positive potentials. 

Anodic stripping voltammetry consists of two steps (Figure 11.37). The first is a controlled potential electrolysis in which the working electrode, usually a hanging mercury drop or mercury film, is held at a cathodic potential sufficient to deposit the metal ion on the electrode. For example, with Cu + the deposition reaction is... 

Potential-excitation signal and voltammogram for anodic stripping voltammetry at a hanging mercury drop electrode. 

In adsorptive stripping voltammetry the deposition step occurs without electrolysis. Instead, the analyte adsorbs to the electrode s surface. During deposition the electrode is maintained at a potential that enhances adsorption. For example, adsorption of a neutral molecule on a Hg drop is enhanced if the electrode is held at -0.4 V versus the SCE, a potential at which the surface charge of mercury is approximately zero. When deposition is complete the potential is scanned in an anodic or cathodic direction depending on whether we wish to oxidize or reduce the analyte. Examples of compounds that have been analyzed by absorptive stripping voltammetry also are listed in Table 11.11. 

Determining Equilibrium Constants for Coupled Chemical Reactions Another important application of voltammetry is the determination of equilibrium constants for solution reactions that are coupled to a redox reaction occurring at the electrode. The presence of the solution reaction affects the ease of electron transfer, shifting the potential to more negative or more positive potentials. Consider, for example, the reduction of O to R... 

Scale of Operation Voltammetry is routinely used to analyze samples at the parts-per-million level and, in some cases, can be used to detect analytes at the parts-per-billion or parts-per-trillion level. Most analyses are carried out in conventional electrochemical cells using macro samples however, microcells are available that require as little as 50 pL of sample. Microelectrodes, with diameters as small as 2 pm, allow voltammetric measurements to be made on even smaller samples. For example, the concentration of glucose in 200-pm pond snail neurons has been successfully monitored using a 2-pm amperometric glucose electrode. ... 

Faraday s law (p. 496) galvanostat (p. 464) glass electrode (p. 477) hanging mercury drop electrode (p. 509) hydrodynamic voltammetry (p. 513) indicator electrode (p. 462) ionophore (p. 482) ion-selective electrode (p. 475) liquid-based ion-selective electrode (p. 482) liquid junction potential (p. 470) mass transport (p. 511) mediator (p. 500) membrane potential (p. 475) migration (p. 512) nonfaradaic current (p. 512)... 

In voltammetry we measure the current in an electrochemical cell as a function of the applied potential. Individual voltammetric methods differ in terms of the type of electrode used, how the applied potential is changed, and whether the transport of material to the electrode s surface is enhanced by stirring. 

In hydrodynamic voltammetry the solution is stirred either by using a magnetic stir bar or by rotating the electrode. Because the solution is stirred, a dropping mercury electrode cannot be used and is replaced with a solid electrode. Both linear potential scans or potential pulses can be applied. 

In stripping voltammetry the analyte is first deposited on the electrode, usually as the result of an oxidation or reduction reaction. The potential is then scanned, either linearly or by using potential pulses, in a direction that removes the analyte by a reduction or oxidation reaction. 

This experiment introduces hydrodynamic voltammetry using a rotating working electrode. Its application for the quantitative analysis of K4Fe(CN)6 is demonstrated. 

The purity of a sample of K3Fe(CN)6 was determined using linear-potential scan hydrodynamic voltammetry at a glassy carbon electrode using the method of external standards. The following data were obtained for a set of calibration standards. 

Anodic stripping voltammetry at a mercury film electrode can be used to determine whether an individual has recently fired a gun by looking for traces of antimony in residue collected from the individual s hands, fn a typical analysis a sample is collected with a cotton-tipped swab that had been wetted with 5% v/v HNO3. When returned to the lab, the swab is placed in a vial containing 5.00 mb of 4 M HCl that is 0.02 M in hydrazine sulfate. After allowing the swab to soak overnight,... 

Electrochemical Detectors Another common group of HPLC detectors are those based on electrochemical measurements such as amperometry, voltammetry, coulometry, and conductivity. Figure 12.29b, for example, shows an amperometric flow cell. Effluent from the column passes over the working electrode, which is held at a potential favorable for oxidizing or reducing the analytes. The potential is held constant relative to a downstream reference electrode, and the current flowing between the working and auxiliary electrodes is measured. Detection limits for amperometric electrochemical detection are 10 pg-1 ng of injected analyte. 

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