Cyclic voltammetry applications

C. P. Andrieux, P. Hapiot, J. Pinson, J.-M. Saveant. Determination of Formal Potentials of Chemically Unstable Redox Couples by Second-Harmonic Alternating Current Voltammetry and Cyclic Voltammetry. Application to the Oxidation of Thiophenoxide Ions. J.Am. Chem. Soc. 1993,115, 7783-7788. 

M. Tilset. Derivative Cyclic Voltammetry Applications in the Investigation of the Energetics of Organometallic Electrode Reactions. In Energetics of Organometallic Species, J. A. Martinho Simoes, Ed. NATO ASI Series C, Kluwer Dordrecht, 1991 chapter 8. 

Richardson DE, Taube H (1981) Determination of E -E in multistep chaige transfer by stationary-electrode pulse and cyclic voltammetry application to binuclear amines. Inoig Chem 20 1278-1285... 

E., and Taube, H. (1981). Determination of E20-E10 in Multistep Charge Transfer by Stationary-Electrode Pulse and Cyclic Voltammetry Application to Binuclear Ruthenium Ammines. Inorg. Chem., 20, 1278-1285. (c) Cotton, F. A. Donohue, J. P., and Murillo, C. A. (2003). Polyunsaturated Dicarboxylate Tethers Connecting Dimolybdenum Redox and Chromophoric Centers Syntheses, Structures, and Electrochemistry. J. Am. Chem. Soc., 125, 5436-5450. (d) Berry, J. F. Cotton, F. A., and Murillo, C. A. (2004). A Trinuclear EMAC-Type Molecular Wire with Redox-Active Ferroeenylaeetylide "Alligator Clips" Attaehed. Organometallics, 23, 2503-2506. (e) Sheng, T. Appelt, R. Comte, V., and Vahrenkamp, H. (2003). Chain-Like... 

Cyclic Voltammetry measurement of the current or current density as a function of the electrode potential by application of one or more potential sweep cycles. 

Cyclic voltammetry can also be useful for quantitative purposes, based on measurements of the peak current (equation 2-1). Such quantitative applications require the establishment of the proper baseline. For neighboring peaks (of a mixture), the baseline for the second peak is obtained by extrapolating the current decay of the... 

Explain clearly why effective compensation of the ohmic drop is essential for diagnostic applications of cyclic voltammetry (e.g., estimating n from AEp). 

According to experimental data,208,209 the SNIFTIR technique can be used to probe the electrical properties of the electrical double layer even in more concentrated solutions where cyclic voltammetry (cv), impedance, chronocoulometry, and other techniques are not applicable. Iwasita and Xia210 have used FTIR reflection-adsorption spectra to identify the potential at which the orientation of water molecules changes from hydrogen down to oxygen down. 

In practical terms, large-scale cracking in the produced films, detrimental to photoelectric applications, was the main drawback of the above method. In order to prevent the appearance of cracks, propylene carbonate (PC) has been used as a solvent, with encouraging results [51]. The mechanism of electrodeposition of CdS in PC solutions containing Cd(II) ions and elemental sulfur has been studied by performing cyclic voltammetry at stationary Pt and Au electrodes [52]. 

Cyclic voltammetry is perhaps the most important and widely used technique within the field of analytical electrochemistry. With a theoretical standard hydrogen electrode at hand, one of the first interesting and challenging applications may be to try to use it to make theoretical cyclic voltammograms (CVs). In following, we set out to do this by attempting to calculate the CV for hydrogen adsorption on two different facets of platinum the (111) and the (100) facets. 

In this chapter, the voltammetric study of local anesthetics (procaine and related compounds) [14—16], antihistamines (doxylamine and related compounds) [17,22], and uncouplers (2,4-dinitrophenol and related compounds) [18] at nitrobenzene (NB]Uwater (W) and 1,2-dichloroethane (DCE)-water (W) interfaces is discussed. Potential step voltammetry (chronoamperometry) or normal pulse voltammetry (NPV) and potential sweep voltammetry or cyclic voltammetry (CV) have been employed. Theoretical equations of the half-wave potential vs. pH diagram are derived and applied to interpret the midpoint potential or half-wave potential vs. pH plots to evaluate physicochemical properties, including the partition coefficients and dissociation constants of the drugs. Voltammetric study of the kinetics of protonation of base (procaine) in aqueous solution is also discussed. Finally, application to structure-activity relationship and mode of action study will be discussed briefly. 

By varying the scan rate, this equation allows then the evaluation of the diffusion coefficient of the transferring ion. With the determination of the formal transfer potential of an ion and thus of its Gibbs energy of transfer by application of Eq. (10), this is the most important application of cyclic voltammetry. 

The application of this technique (even in its various modes such as cyclic voltammetry) to other electrodes has already been mentioned in the description of LSV at the dme [Section 3.3.1.2.1(5)]. Especially with stationary electrodes LSV becomes fairly simple, under the conditions of sufficient solubility of ox and red, because of the constant and undisturbed electrode surface at an inert electrode the residual faraday current can be adequately eliminated by means of "J compensation (cf., Fig. 3.23) or by subtractive [cf., Section 3.3.1.2.1(3)] and derivative59 [cf., Section 3.3.1.2.1(4)] voltammetry at a stationary mercury electrode (e.g., HMDE), in addition to the residual faradaic current,... 

Electrochemical techniques have been utilized for many years to study metal corrosion. Two of these techniques, linear polarization (LP) and cyclic voltammetry (CV), complement each other, LP providing corrosion rates under conditions where the surface is minimally altered and CV furnishing information about the corrosion mechanism. With the advent of impedance spectroscopy (IS), both kinds of information can be gleaned simultaneously and more rapidly, while leaving the surface almost intact. In this paper, we discuss the application of IS to the study of rapid steel corrosion and describe a study we undertook to elucidate the roles played by adsorption and film formation in the inhibition mechanisms of the above-named compounds. For comparison, we also investigated two quaternary nitrogen salts, which appear to adsorb electrostatically and presumably do not form macroscopic films (8). 

Another important bioanalytical application of voltammetric ISEs is the detection of polyions (see also above). A technique using cyclic voltammetry on micropipette electrodes filled with the organic electrolyte solutions in 1,2-dichloroethane was successfully applied for the detection of protamine [65] in saline solution and heparin in undiluted sheep plasma samples [66]. Protamine transport was facilitated with dino-nylnaphthalenesulfonic acid (DNNS). As a heparin-selective component the tetrakis-(4-chlorophenyl)borate salt of trimethyloctadecyl ammonium was used. 

Wang et al240 reported the electrooxidation of MeOH in H2S04 solution using Pd well-dispersed on Ti nanotubes. A similar reaction was studied by Schmuki et al.232 (see above), but using Pt/Ru supported on titania nanotube which appear a preferable catalyst. Only indirect tests (cyclic voltammetry) have been reported and therefore it is difficult to understand the real applicability to direct methanol fuel cell, because several other aspects (three phase boundary to methanol diffusivity, etc.) determines the performance. 

There are cases where application of nondestructive techniques such as cyclic voltammetry is not sufficient to establish the reaction mechanism unambiguously. Analyzing the distribution of products at the preparative-... 

Application of these curves may have as other objective to uncover the kinetic characteristics of the electrode electron transfer. This cannot be done in the absence of catalysis since the RDEV response is nil insofar as the steady-state response of an attached species is nil. Cyclic voltammetry could be used instead. The response is not nil, but the signal is in general small, often hardly emerging from the baseline current. Determining the standard potential under these conditions is generally feasible, but an accurate... 

What benefits and drawbacks to these problems can one expect from the use of cyclic voltammetry instead of RDEV They are related. In a general case, the application of cyclic voltammetry will be more complicated, because playing with the scan rate, one can make the diffusion layer penetrate the film or remain outside, as is the case with RDEV. We have already seen a fruitful application of the first of these possibilities in the use of cyclic voltammetry to the characterization of electron hopping transport within the redox films (Section 4.3.4). In the second situation, cyclic voltammetry may replace RDEV in a manner similar to what has been seen in Section 4.3.2 Each time a term (1 — ///a) is encountered in the analysis, it suffices to replace it by... 

Several electrochemical techniques may yield the reduction or oxidation potentials displayed in figure 16.1 [332-334], In this chapter, we examine and illustrate the application of two of those techniques cyclic voltammetry and photomodulation voltammetry. Both (particularly the former) have provided significant contributions to the thermochemical database. But before we do that, let us recall some basic ideas that link electrochemistry with thermodynamics. More in-depth views of this relationship are presented in some general physical-chemistry and thermodynamics textbooks [180,316]. A detailed discussion of theory and applications of electrochemistry may be found in more specialized works [332-334],... 

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