Coupled homogeneous chemical reaction surface

The popularity of the cychc voltammetry (CV) technique has led to its extensive study and numerous simple criteria are available for immediate anal-j sis of electrochemical systems from the shape, position and time-behaviour of the experimental voltammograms [1, 2], For example, a quick inspection of the cyclic voltammograms offers information about the diffusive or adsorptive nature of the electrode process, its kinetic and thermodynamic parameters, as well as the existence and characteristics of coupled homogeneous chemical reactions [2]. This electrochemical method is also very useful for the evaluation of the magnitude of imdesirable effects such as those derived from ohmic drop or double-layer capacitance. Accordingly, cyclic voltammetry is frequently used for the analysis of electroactive species and surfaces, and for the determination of reaction mechanisms and rate constants. 

Precise and detailed kinetic and mechanistic studies of surface changes, electron transfer processes and of coupled homogeneous chemical reactions. 

This book was initially prepared as lecture notes for an electrochemistry course which has been presented regularly in Southampton and elsewhere during the past fifteen years. The course seeks to develop an understanding of electrochemical experiments and to illustrate the applications of electrochemical methods to, for example, the study of redox couples, homogeneous chemical reactions, and surface science. In many studies, several of the techniques will be equally applicable, but there are situations where one technique has a unique advantage and hence the course also seeks to discuss the selection of method and the design of experiments to aid the solution of both chemical and technological problems. 

As will now be clear from the first Chapter, electrochemical processes can be rather complex. In addition to the electron transfer step, coupled homogeneous chemical reactions are frequently involved and surface processes such as adsorption must often be considered. Also, since electrode reactions are heterogeneous by nature, mass transport always plays an important and frequently dominant role. A complete analysis of any electrochemical process therefore requires the identification of all the individual steps and, where possible, their quantification. Such a description requires at least the determination of the standard rate constant, k, and the transfer coefficients, and ac, for the electron transfer step, or steps, the determination of the number of electrons involved and of the diffusion coefficients of the oxidised and reduced species (if they are soluble in either the solution or the electrode). It may also require the determination of the rate constants of coupled chemical reactions and of nucleation and growth processes, as well as the elucidation of adsorption isotherms. A complete description of this type is, however, only ever achieved for very simple systems, as it is generally only possible to obtain reliable quantitative data about the slowest step in the overall reaction scheme (or of two such steps if their rates are comparable). 

Proton-coupled electron transfer is a prominent theme in biological redox systems. There are three basic mechanisms for these processes (Figure 18). In the first mechanism (path A), electron transfer occurs prior to proton transfer. This mechanism is commonly observed for the electrochemical reduction and oxidation of quinones and flavins in protic media [52], In this interfacial environment, proton transfer is manifested as an ECE (E represents an electron transfer at the electrode surface and C represents a homogeneous chemical reaction) two-electron reduction of these systems to their fully reduced states (Figure 19). As electron transfer occurs prior to the proton transfer event, proton transfer does not affect either the redox potential or the electron transfer rate to or from the cofactor. 

This section concerns heterogeneous electron transfer reactions coupled with homogeneous chemical reactions in which either the electroactive species A or the product of the electron transfer B participate as reactants. Perturbations of electrochemical responses of different techniques evoked by these reactions enable the elucidation of the mechaism and the evaluation of the kinetic parameters of the chemical steps. Chemical reactions that are indicated in the electrochemical way occur in the thin layer reaction layer) adjacent to the electrode surface only. This is illustrated in Fig. 1 where the concentration dependence of the product B on the distance from the electrode plane (with and without follow-up chemical reaction) is plotted. It must be stressed that the kinetics and the electrode mechanism are affected not only by the nature of the electroactive as well as electroinactive species including the type of the solvent, but also by the electrode material and substances adsorbed on the electrode surface. 

Fig. 7 Micropatteming. a Direct mode where the microelectrode acts as counter electrode, b Local generation of reagents which corrode locally the sample surface, c coupling of homogenous and heterogeneous reactions in which the species generated at the tip undergoes a homogenous chemical reaction locally enabling a heterogeneous electrochemical reaction at the sample surface. Adapted from [2] with permission of Wiley...

Cyclic and square wave voltammograms showed that an ECjrrev mechanism appears as the most probable to describe the surface electrochemical reaction, where E represent a reversible electron transfer reaction, and Cinev an irreversible homogeneous chemical reaction (Laviron, 1972). The dependence between /pn and Epn on the logarithm of acid bulk concentration would indicate that a deprotonation reaction should be the fast follow-up chemical reaction coupled to the initial electron transfer reaction (Laviron, 1972 Mirceski Lovric, 2000). 

The novelty in the aforementioned studies is the use of a comprehensive numerical model for the investigation of catalytic microscale reactors which includes, for the first time in the literature, detailed heterogeneous and homogeneous chemical reaction mechanisms, two-dimensional treatment for both the gas and solid wall phases and surface radiation heat transfer, under both steady and transient (quasisteady) conditions. Moreover, a validated chemical kinetics model for the coupled catalytic and gas-phase combustion of propane (a fuel of particular interest for portable applications) is presented for the first time. 

During the time dt, the thickness of the ArBs layer increases by dyA3 at interface 3 as a result of diffusion of the A atoms from interface 2 to interface 3 and their subsequent partial chemical reaction (4.2) with the surface B atoms. In the ApBq-B reaction couple the ApBq phase acts as a source of diffusing A atoms. It must be clear, however, that the content of component A in this phase cannot be less than the lower limit of its homogeneity range. Hence, as reaction (4.2) proceeds, the ApBq compound becomes unstable and therefore should undergo a partial transformation into another compound of the A-B multiphase binary system. To reveal the essence of this transformation, let us consider one of the simplest cases, in... 

It is well known that experimental CVs for species in solution phase frequently diverge from theoretical ones for -electron reversible couples. The divergence can be caused by a variety of factors deviations from reversibility, occurrence of coupled chemical reactions and/or surface effects, and resistive and capacitive effects (Nicholson and Shain, 1964 Nicholson, 1965a). These last effects will be briefly treated here because of their potential significance when microheterogenous deposits or more or less homogeneous coatings of microporous materials cover the electrode surface. 

A systematic description of all possible combinations of homogeneous chemical processes coupled to electron transfer at an electrode surface is impossible because an infinite range of theoretically possible reaction schemes can be constructed. Unfortunately, a consistent form of nomenclature for defining the possible web of reaction pathways has not yet been invented. However, the lUPAC nomenclature [89] is of assistance with respect to simple reaction schemes. In this article, the commonly employed descriptors for electron transfer (E) and chemical (C) sequences of reaction steps, e.g. ECEC, will be used for a sequence of reactions involving electron transfer-chemical process-electron transfer-chemical process. Reaction schemes involving branching of a reaction pathway will be considered later. 

This chapter is concerned with measurements of kinetic parameters of heterogeneous electron transfer (ET) processes (i.e., standard heterogeneous rate constant k° and transfer coefficient a) and homogeneous rate constants of coupled chemical reactions. A typical electrochemical process comprises at least three consecutive steps diffusion of the reactant to the electrode surface, heterogeneous ET, and diffusion of the product into the bulk solution. The overall kinetics of such a multi-step process is determined by its slow step whose rate can be measured experimentally. The principles of such measurements can be seen from the simplified equivalence circuit of an electrochemical cell (Figure 15.1). 

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