Potential square-wave

Troise Frank et al. (83) reported the use of potentiometric tips to probe ion fluxes near surfaces. Ten and 50 yam diameter silver microdisk electrodes were used to probe the concentration profile due to the diffusion of Ag+ to and from a planar Ag electrode. A similar experiment was carried out with a 50 yam diameter micro-cylinder substrate electrode. The tip response was recorded at various locations above the substrate while simultaneously applying a potential square wave to the substrate to induce the dissolution and plating of silver. These experiments demonstrated the principle of the tech-... 

Catalyst stability can also be measured with a half-cell by using either a potential square wave scan or CV cycling. In a typical experiment, before durability testing, the EPS A and ORR mass activity are measured using the same procedure described above. Then, potential square wave scans are performed,... 

Figure Bl.28.5. Applied potential-time wavefonns for (a) nomial pulse voltannnetry (NPV), (b) differential pulse voltannnetry (DPV), and (e) square-wave voltammetry (SWV), along with typieal voltannnograms obtained for eaeh method.

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]. 

Anodic-stripping voltaimnetry (ASV) is used for the analysis of cations in solution, particularly to detemiine trace heavy metals. It involves pre-concentrating the metals at the electrode surface by reducmg the dissolved metal species in the sample to the zero oxidation state, where they tend to fomi amalgams with Hg. Subsequently, the potential is swept anodically resulting in the dissolution of tire metal species back into solution at their respective fomial potential values. The detemiination step often utilizes a square-wave scan (SWASV), since it increases the rapidity of tlie analysis, avoiding interference from oxygen in solution, and improves the sensitivity. This teclmique has been shown to enable the simultaneous detemiination of four to six trace metals at concentrations down to fractional parts per billion and has found widespread use in seawater analysis. 

One aspect that reflects the electronic configuration of fullerenes relates to the electrochemically induced reduction and oxidation processes in solution. In good agreement with the tlireefold degenerate LUMO, the redox chemistry of [60]fullerene, investigated primarily with cyclic voltammetry and Osteryoung square wave voltammetry, unravels six reversible, one-electron reduction steps with potentials that are equally separated from each other. The separation between any two successive reduction steps is -450 50 mV. The low reduction potential (only -0.44 V versus SCE) of the process, that corresponds to the generation of the rt-radical anion 131,109,110,111 and 1121, deserves special attention. 

Potential-excitation signals and voltammograms for (a) normal pulse polarography, (b) differential pulse polarography, (c) staircase polarography, and (d) square-wave polarography. See text for an explanation of the symbols. Current is sampled at the time intervals indicated by the solid circles ( ). 

Electrically insulating materials can be analyzed in HF-plasma SNMS by applying a square-wave HF in the 100 kHz range to the sample (Fig. 3.34). Dielectric charge transfer at the start of a period shifts the surface potential to the amplitude Uhfm applied. Ar" ions are attracted from the plasma and sputter the surface until the end of At . The potential increase AU = 1-100 V caused by their charge is then converted to a positive absolute AU which is reduced to less than 1 V within <0.1 ps by the... 

Neufeld, P. and Queenan, E. D., Frequency Dependence of Polarisation Resistance Measured with Square Wave Alternating Potential , Br. Corros. J., 5, 72-75, March (1970) Fontana, M. G., Corrosion Engineering, 3rd edn., McGraw-Hill, pp 194-8 (1986) Dawson, J. L., Callow, L. M., Hlady, K. and Richardson, J. A., Corrosion Rate Determination By Electrochemical Impedance Measurement , Conf. On-Line Surveillance and Monitoring of Process Plant, London, Society of Chemical Industry (1977)... 

Sodium-silicate glass, 151 Sol-gel films, 120, 173 Solid electrodes, 110 Solid state devices, 160 Solvents, 102 Speciation, 84 Spectroelectrochenristry, 40 Spherical electrode, 6, 8, 9, 61 Square-wave voltammetry, 72, 92 Staircase voltammetry, 74 Standard potential, 3 Standard rate constant, 12, 18 Stripping analysis, 75, 79, 110 Supporting electrolyte, 102 Surface-active agents, 79... 

In such a synthesis the lengths of the pulses are variable as well as the potentials of the square wave. Recently a potential-time profile has been used to maintain the activity of an electrode during the oxidation of organic compounds (Clark et al., 1972) at a steady potential the current for the oxidation process was observed to fall, but a periodic short pulse to cathodic potentials was sufficient to prevent this decrease in electrode activity. 

The redox properties of a series of heterometal clusters were assessed by electrochemical and FPR measurements. The redox potentials of derivatives formed in D. gigas Fdll were measured by direct square wave voltammetry promoted by Mg(II) at a vitreous carbon electrode, and the following values were determined 495, 420,... 

FIG. 30 Top Square voltage waveform applied to the tip. Bottom. Corresponding changes in tip deflection (converted to force after multiplying by the lever spring constant). There is a net attractive force for both the positive and the negative cycles, but it takes time to reach the final force value. Note that the square-wave voltage is not symmetrical around zero. An offset is applied to compensate for the contact potential difference between the tip and the surface. This offset is dependent on humidity and is equal to the potential difference between the tip and the sample. (From Ref. 78.)... 

The most commonly used waveform for in vivo voltammetric measurements is square-wave. This involves the application of a potential pulse to the working electrode for a fixed time at fixed intervals. The current is measurai at the end of the potential pulse to minimize capacitive charging current contributions. This waveform is shown in Fig. 15 A. 

Fig. 3.46. Alternating square-wave potential, (a) rigid wave, (b) tilted wave.

In connection with the square-wave technique, mention can be made of high-frequency polarography, also called radiofrequency polarography and developed by Barker53, in which a sinusoidal radio-frequency cu, (100kHz to 6.4 MHz) square-wave modulated at co2 (225 Hz) is superimposed on to the dc potential ramp as the wave form includes (apart from additional higher... 

Electrochemically Modulated Infra-Red Spectroscopy (EMIRS) [23] consists of applying a square-wave potential modulation to the working electrode and analyzing the modulated part of the IR detector response using a dispersive instrument. 

Cyclic voltammetry, square-wave voltammetry, and controlled potential electrolysis were used to study the electrochemical oxidation behavior of niclosamide at a glassy carbon electrode. The number of electrons transferred, the wave characteristics, the diffusion coefficient and reversibility of the reactions were investigated. Following optimization of voltammetric parameters, pH, and reproducibility, a linear calibration curve over the range 1 x 10 6 to 1 x 10 4 mol/dm3 niclosamide was achieved. The detection limit was found to be 8 x 10 7 mol/dm3. This voltammetric method was applied for the determination of niclosamide in tablets [33]. 

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