Cyclic voltammetry single electron transfer reactions

Cyclic sulfates of several 1,2-, 1,3-, and 1,4-diols have been reduced by a stepwise single-electron transfer reaction using cyclic voltammetry (84BCJ3160). The interesting mechanism of reduction is outlined in Scheme 79 the cyclic sulfate undergoes disproportionation to give an olefin and a bisulfate ion (83MI2). 

Fig. 8 Reactions of various carbocations with Kuhn s anion [2 ] as compared with their reduction potentials (peak potentials measured vs. Ag/Ag in acetonitrile by cyclic voltammetry cf. Tables 1 and 8 and Okamoto et al., 1983). SALT, salt formation COV, covalent bond formation ET, single-electron transfer. 

Reversibility. The first aspect we analyse with cyclic voltammetry is electrochemical reversibility . Table 6.3 above lists the simplest voltammetrically determined tests of reversibility. A system that fulfills each of these criteria is probably electro-reversible, while a system that does not fulfill one or more of the criteria is certainly not fully electro-reversible. The CV shown in Figure 6.13 is that of a fully electro-reversible couple in a single electron-transfer ( E ) reaction. 

Tetrahydropterins are highly reactive towards oxidation (e.g. 542 — 544) even molecular oxygen can cause hydroxylation. The autoxidation is due to the electron donating groups such as amino and hydroxy, whereas removal of such substituents enhances the stability of the reduced pteridine nucleus tremendously (96CHEC-li(7)70l). The reaction appears to proceed via single electron transfer. The radical cation (543) can be observed by cyclic voltammetry. 

This chapter offers a study of the application of the multipulse and sweep techniques Cyclic Staircase Voltammetry (CSCV) and Cyclic Voltammetry (CV) to the study of more complex electrode processes than single charge transfer reactions (electronic or ionic), which were addressed in Chap. 5. 

The use of a potential-step technique such as cyclic staircase voltammetry represents a simple alternative to Ichise s method (j0 of obtaining information on both adsorption and electron transfer kinetics. The current decay immediately after a step is primarily capacitive while current at later times is almost totally due to electron transfer reactions. Thus, by measuring the current at several times during each step and by changing the scan rate, information on both the kinetics of the electrode process and the differential capacity can be obtained with a single sweep. 

Both single-sweep and cyclic voltammetry can provide information about the approximate number of electrons transferred in each wave or peak. This is done by comparing the plateau or peak height with that of a known one- or two-electron transfer process under identical conditions (as an example, the oxidation of 9,10-diphenylanthracene to the cation radical is a commonly used reference reaction). 

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