Chronocoulometry electron transfer

The general electrochemical behavior of surface-bound molecules is treated in Sect. 6.4. The response of a simple electron transfer reaction in Multipulse Chronoamperometry and Chronocoulometry, CSCV, CV, and Cyclic Staircase Voltcoulometry and Cyclic Voltcoulometry is also presented. Multielectronic processes and first- and second-order electrocatalytic reactions at modified electrodes are also discussed extensively. 

The chronocoulometry and chronoamperometry methods are most useful for the study of adsorption phenomena associated with electroactive species. Although less popular than cyclic voltammetry for the study of chemical reactions that are coupled with electrode reactions, these chrono- methods have merit for some situations. In all cases each step (diffusion, electron transfer, and chemical reactions) must be considered. For the simplification of the data analysis, conditions are chosen such that the electron-transfer process is controlled by the diffusion of an electroactive species. However, to obtain the kinetic parameters of chemical reactions, a reasonable mechanism must be available (often ascertained from cyclic voltammetry). A series of recent monographs provides details of useful applications for these methods.13,37,57... 

Majda and co-workers provided an elegant demonstration of through-bond and chain-chain hopping processes as parallel mechanisms for electron transfer across SAMs [46, 133]. In n-alkanethiol monolayers formed on hanging drop mercury electrodes, the adsorbate coverage T is measured by chronocoulometry of the mercuric thiolate formed upon adsorption. For the as-adsorbed films, geometric con-... 

Double potential-step chronocoulometry [1,2,221] may be used similarly to DPSCA. The working curves now include the charge ratio —Qb/Qf, which takes the value 0.414 for a simple electron transfer reaction. The reductive cyclization of ethyl cinnamate (see Chapter 21) illustrates the use of the technique [226,227]. 

A number of studies have been made of the reduction of model enones in buffered aqueous or buffered ethanolic solutions in order to elucidate the sequence of electron transfer, proton transfer, and coupling steps as a function of pH [39-42,91-95]. The experimental methods applied include polarography, CV, LSV, and chronocoulometry. 

In suitable cases, pulse techniques such as chronocoulometry or rapid linear-sweep voltammetry also can be employed to monitor the electrode kinetics within the precursor state "i.e., to evaluate directly the first-order rate constant, k, [Eq. (a) in 12.3.7.2] rather than k. Such measurements are analogous to the determination of rate parameters for intramolecular electron transfer within homeogeneous binuclear complexes ( 12.2.2.3.2). Evaluation of k is of particular fundamental interest because it yields direct information on the energetics of the elementary electron-transfer step (also see 12.3.7.5). 

Andrieux, C.P, Hapiot, P, and Saveant, J.-M. 1984. Electron-transfer coupling of diffusional pathways Theory for potential step chronoamperometry and chronocoulometry. Journal of Electroanaytical Chemistry 1172, 49-65. 

In a potential-step experiment, the potential of the working electrode is instantaneously stepped from a value where no reaction occurs to a value where the electrode reaction under investigation takes place and the current versus time (chronoamperometry) or the charge versus time (chronocoulometry) response is recorded. The transient obtained depends upon the potential applied and whether it is stepped into a diffusion control, in an electron transfer control or in a mixed control region. Under diffusion control the transient may be described by the Cottrell equation obtained by solving Tick s second law with the appropriate initial and boimdary conditions [1, 2, 3, 4, 5 and 6] ... 

The various terms in the equation are as follows i is the current, n is the number of electrons transferred, F is the Faraday, A is the electrode area, C is the concentration, D is the diffusion coefficient, and t is the time. Thus the technique may be used to estimate, among other things, the charge transport parameter. The reader interested in the solution of the Fick s law equation using the Laplace transformation should consult Ref. 6. A closely related technique is chronocoulometry, in which the excitation function is still the potential pulse, but instead of monitoring the current, the integrated charge is monitored as a function of time. This entails less error as a cumulative measurement is made. The equation for chronocoulometry is... 

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