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Advanced course on electrochemistry with an emphasis on the principles of electrochemical measurements at the electrode-electrolyte interface. Thermodynamics, kinetics and mechanistic issues are being discussed. Course presents the electrochemical response of real systems emphasizing the effects of adsorption and heterogeneous processes on the measured quantities. Course is focused on the admittance and impedance measurements in addition to basic electrochemical methods, electrochemical instrumentation and mathematical simulation of the electron transfer processes. Finally, spectroelectrochemical techniques, electrochemical atomic force microscopy and scanning tunneling microscopy techniques are presented. Prerequisites include physical chemistry course and knowledge of theories of electrolytes.
Last update: Pátková Vlasta (15.05.2018)
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To understand the principles of charge transfer reactions at the electrode-electrolyte interface. To have cognisance of experimental methods to study charge transfer reactions. Knowledge of the admittance and impedance methods, and special techniques (spectroelectrochemical techniques, electrochemical atomic force microscopy and scanning tunneling microscopy techniques). Last update: Pátková Vlasta (15.05.2018)
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Test the form of short test and interview. Last update: Pátková Vlasta (15.05.2018)
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R: P. Atkins, J. De Paula: Physical Chemistry, Oxford University press, 2014 A: A. J. Bard, L. L. Faulkner: Electrochemical methods. Fundamentals and Applications. Wiley & Sons, N.Y. (2001). A: A. Lasia: Electrochemical Impedance Spectroscopy and its Application. Modern Aspects of Electrochemistry, B. E. Conway, J. Bockris, and R.E. White, Eds., Kluwer Academic/Plenum Publishers, New York, 1999, Vol. 32, p. 143-248. Last update: Macák Jan (12.09.2018)
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Lectures Last update: Macák Jan (12.09.2018)
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1. History of electrochemistry, terms and concepts. Electrode, electrochemical cell, electrolysis and electrochemical equivalent. Faraday‘s law. 2. Electrode polarizability. Potential step, faradaic and nonfaradaic processes, semiempirical solution of the Cottrell equation. 3. Mass transport. Diffusion, Fick’s laws, exact solution of the Cottrell equation. 4. Electrode kinetics, reversibility of electron transfer. Tafel equation, electron transfer coefficient, Butler-Volmer and Marcus theory of charge transfer. 5. Electrode-electrolyte interface. Double-layer structure and Lippmann equations. 6. Adsorption processes and their influence on redox processes. Adsorption isotherms. Inhibitors. 7. Electrochemical methods and their application. Polarography, voltammetry, pulse methods. 8. Charge transfer reaction mechanisms. Heterogeneous electron transfer and coupled homogeneous chemical processes. 9. Electrode impedance. Electrochemical impedance spectroscopy at the electrode-electrolyte interface. 10. Admittance methods, faradaic current and adsorption. 11. Reaction kinetics at rough (real) electrode surfaces, use of fractal geometry. 12. Electrochemical research instrumentation: basics and measurements. 13. Simulation methods for electrochemical data interpretation. 14. Spectroelectrochemistry. Atomic force microscopy and scanning tunneling microscopy methods for studies of the heterogeneous processes. Last update: Pátková Vlasta (15.05.2018)
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Lectures, the recommended literature Last update: Macák Jan (12.09.2018)
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