Peak potential in cyclic voltammetry

Mid-peak potential in cyclic voltammetry - potential, subentry -> mid-peak potential in cyclic voltammetry... 

The relative abilities of the leaving groups in the cathodic cleavage of //-methoxy-carbonylbenzyl carboxylates have been measured in a DMF acetate buffer. There seemed to be no recognizable correlation between the relative rate of cleavage and either the of the conjugate acid of the leaving anion or the peak potential in cyclic voltammetry [61]. 

Each electroanalytical technique has certain characteristic potentials, which can be derived from the measured curves. These are the half-wave potential in direct current polarography (DCP), the peak potentials in cyclic voltammetry (CV), the mid-peak potential in cyclic voltammetry, and the peak potential in differential pulse voltammetry (DPV) and square-wave voltammetry. In the case of electrochemical reversibility (see Chap. 1.3) all these characteristic potentials are interrelated and it is important to know their relationship to the standard and formal potential of the redox system. Here follows a brief summary of the most important characteristic potentials. 

Ferrocenyl-modified dendrimers were found to be able to recognize small inorganic anions [105, 106]. From shifts of the ferrocene-based peak potentials in cyclic voltammetry in CH2CI2 solution and shifts of 5nh in NMR, resulting from the titration of the dendrimers with the tetrabutylammonium salts of anions such as H2P04 , HS04 , C1 , and NO3 , changes in the apparent association constant of the anion with the ferrocenyl dendrimer were monitored. 

Unlike the table of the Electrochemical Series, which lists standard potentials, values for radicals are experimental values with experimental conditions given in the second column. Since the measurements leading to potentials for ion radicals are very dependent on conditions, an attempt to report standard potentials for radicals would serve no useful purpose. For the same reason, the potentials are also reported as experimental values, usually a half-wave potential in polarography) or a peak potential in cyclic voltammetry). Unless otherwise stated, the values are reported vs. SCE (saturated calomel electrode). To obtain a value vs. 

Anodic peak potentials for cyclic voltammetry of amines in acetonitrile, NaC104, scan rate 6 V s . Ref. [74],... 

Peak potentials from cyclic voltammetry measurements at mercury-plated platinum, in MeCN-TEAB at 10 V s sweep rate. Values in parentheses relate to peak potentials obtained when the potential was cycled in the positive direction after observation of the reduction. 

Figure II.8.3 gives two examples, one for the dependence of a voltammetric peak potential of copper reduction on the composition of copper sulfide-selenide solid solutions, and one for the dependence of the formal potentials (mid-peak potentials from cyclic voltammetry) of mixed iron-copper hexacyanoferrates on the composition of these compounds. The copper sulfide-selenides behave in very nonideal fashion, whereas the solid solution hexacyanoferrates give, within the limit of experimental errors, an almost linear dependence. These and other examples [18-21] are well suited to show that by voltammetric measurements of immobilized microparticles it is extremely facile to answer the two questions, is it a solid solution or not, and what is its composition.

Abstract. The characterization of cyclodextrin(CD) systems by electrochemical methods, mainly by cyclic voltammetry is discussed. The addition of CD to the electrolyte solution causes a decrease in the peak current and also a shift in the apparent half-wave potential in cyclic voltammetry. Quantitative analysis in the both phenomena affords the formation constants of CD complexes. The formation or dissociation rate constants can be evaluated from the cyclic voltammetric data at high scan rates. Adsorption of CD on the electrode surface is also mentioned. 

Useful experimental parameters in cyclic voltammetry are (i) the value of the separation of the potentials at which the anodic and cathodic peak currents occur, A = Pia — PiC, and (ii) the half wave potential, 1/2, the potential mid-way between the peak potentials. A value of AE of c. 0.057 V at 25°C is diagnostic of a Nernstian response, such as that shown in Figure 2.87. More generally, if n electrons are transferred from R, then the separation will be 0.057/n V. It should be noted that the expected value for AE of 0.57/nV has no relationship to the usual Nernstian slope of RT/nF = 0.059/n V at 25UC. 

Since the values of for many organic acceptors are generally unobtainable (in organic solvents), an alternative measure of the electron-acceptor property is often based on the irreversible cathodic peak potential F (in cyclic voltammetry). Thus for a series of related compounds, Fig. 6 shows that the values of Fred are linearly related to gas-phase electron affinities (EA).70... 

FIGURE 1.25. Successive reversible electron transfers in cyclic voltammetry of attached reactants. Normalized charge (a) and current (b) as a function of the separation between the standard potentials, at 25°C, from right to left A ° — E — E = 0.4, 0.1, 0.0356, —0.2 V. The middle of each curve corresponds to — )/2. (c) Variation of the normalized peak current with AE° in the range where a single wave is observed. 

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