The power of electrochemical measurements in respect of thermodynamics, kinetics and analysis is widely recognized but the subject can be unpredictable to the novice even if they have a strong physical and chemical background, especially if they wish to pursue quantitative measurements. Accordingly, some significant experiments are perhaps wisely never attempted while the literature is sadly replete with flawed attempts at rigorous voltammetry.This textbook considers how to go about designing, explaining and interpreting experiments centered around various forms of voltammetry (cyclic, microelectrode, hydrodynamic, and so on). The reader is assumed to have a knowledge to Masters level of physical chemistry but no exposure to electrochemistry in general, or voltammetry in particular. While the book is designed to 'stand alone', references to important research papers are given to provide an entry into the literature.The book gives clear introductions to the theories of electron transfer and of diffusion in its early chapters. These are developed to interpret voltammetric experiments at macro-electrodes before considering microelectrode behavior. A subsequent chapter introduces convection and describes hydrodynamic electrodes. Later chapters describe the voltammetric measurement of homogeneous kinetics, the study of adsorption on electrodes and the use of voltammetry for electroanalysis.
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Cyclic Voltammetry at Macroelectrodes
Voltammetry at Microelectrodes
Voltammetry at Heterogeneous Surfaces
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A]bulk acetonitrile aqueous solution back peak blocks boundary conditions bulk solution cell channel electrode Chapter Chem chemical chemical potential concentration proﬁles convection corresponding current ﬂows curves cyclic voltammetry Cyclic voltammograms deﬁned diffusion coefﬁcient diffusion domain diffusion layer dimensionless electrochemical rate constant electrochemically reversible electrochemistry electrode kinetics electrode potential electrode process electrode surface electrolyte electron transfer equilibrium experimental ferrocene Fick’s Figure ﬁrst ﬂow rate ﬂux follows formal potential Gibbs energy ions irreversible limiting current Marcus theory mass transport measured mechanism microdisc electrode microelectrode molecule Nernst equation overpotential oxidation parameters peak current permission from Elsevier platinum potential step potentiostat pyrolytic graphite radius reactants redox reduction reference electrode reﬂects Reprinted from Ref reversible reduction rotating disc electrode shown in Fig shows signiﬁcant signiﬁcantly simulation solution phase speed channel standard hydrogen electrode steady-state sufﬁciently Tafel transfer coefﬁcient typical voltage scan rate