C7050 Electroanalytical Methods

Faculty of Science
Autumn 2011
Extent and Intensity
2/0/0. 2 credit(s) (fasci plus compl plus > 4). Recommended Type of Completion: zk (examination). Other types of completion: k (colloquium).
Teacher(s)
prof. RNDr. Libuše Trnková, CSc. (lecturer)
Guaranteed by
prof. RNDr. Libuše Trnková, CSc.
Department of Chemistry – Chemistry Section – Faculty of Science
Timetable
Fri 9:00–10:50 C12/311
Prerequisites
Principles of analytical and physical chemistry
Course Enrolment Limitations
The course is also offered to the students of the fields other than those the course is directly associated with.
fields of study / plans the course is directly associated with
Course objectives
Goal of this lecture is the presentation of electroanalytical methods (potentiometry, polarographic and voltammetric methods, chronopotentiometry a chronoamperometry, electrogravimetry, coulometry, stripping techniques, conductometry, dielectrometry), electrode systems (mercury, solid, paste and chemically modified electrodes). The emphasis is placed on physico-chemical principles of these methods and their application in chemical analysis.
Syllabus
  • 1. Introduction - short historical review, bibliography. Definition of electroanalytical methods and their classification. Electrical signals. Basic definition (electrochemical cell, electrodes, electrode process, steady state process, electrochemical potential). Electron transfer. Fermi energetic level.

    2. Potentiometry. Potential, voltage, electromotive force, Nernst equation, standard potential, potential measurements, pH and pX- meters, indication and reference electrodes, potentiometric titrations, titration curves and their evaluation. pH measurements, standard buffer solutions, pH electrodes.

    3. Ion Selective Electrodes - ISE. Definition and classification. Donnan and Nernst equations, membrane potential, construction of ISEs, solid and liquid membranes, ion, gas-sensing and enzyme ISEs, Nicolskij equation, selectivity coefficients and their determination, applications of ISEs.

    4. Electrolysis. Some definitions, two electrode and three electrode setup, indicator, auxiliary and reference electrodes, electrode polarization, depolarizer, overpotential, polarization curves and their registrations. Butler-Volmer, Tafel a Cottrell relations.

    5. Electrogravimetric analysis and its principles. Cells, working electrodes, properties of electro-deposition layers. Accuracy of method and its advantage from analytical point of view. Electrolytical separations. Internal electrolysis.

    6. Coulometry. Principles of coulometry, Faraday`s law. Electrochemical equivalent. Potentiostat, galvanostat. Controlled potential coulometry, constant current coulometry. Determination of number of transferred electrons and methods for determination of the thickness of electrodeposits. Coulometric titration.

    7. Polarography and voltammetry. Introduction, instrumentations and general techniques, current-potential characteristics, Ilkovic equation, diffusion, capacity, kinetic and catalytic and capacity currents. Qualitative and quantitative analysis. Current maxima. Equation of reversible cathodic vawe, logarithmic analysis.Tast-polarography, alternating, square wave polarography or voltammetry. Pulse methods, (normal pulse and differential pulse polarography and voltammetry.

    8. Cyklic voltammetry. Anodic, cathodic and adsorptive stripping voltammetry. Reversible process (Randles-Sevcik equation) and irreversible (Delahay equation). Chronopotentiometry and chronoamperometry.

    9. Hydrodynamic electrodes and microelectrodes. The kinetic study of electrode reactions.Electrochemical catalysis. Mechanisms of electrode processes.Electric double layer and its influence on electrode process at charged interface. Models of electric double layer.

    10. Conductometry and dielectrometry. Basic definitions (absolute rate of mobility, electrolytical mobility, individual ionic conductivity, molar conductivity of electrolytes,Kohlrausch law). Conductometric titratios. High-frequency conductometry. Dielectrometry, principles and applications.

    11. Impedance method. Real and imaginary values of impedance, Nyquist diagram, ekvivalent circuit of electrochemical cell, electrochemical impedance spektrum (EIS), evaluation of EIS data, determination of heterogeneous rate constants.

    12. Electroanalysis using modern electrochemical methods: Quartz Crystal Microbalance QCM, Scanning Tunneling Microscopy STM, Atomic Force Microscopy - AFM), Spectroelectrochemistry (UV-vis, IČ, Raman), Sonoelectrochemistry.
Literature
  • Analytická příručka. Díl I [Zýka, 1988]. Edited by Jaroslav Zýka. 4. upr. vyd. Praha: SNTL - Nakladatelství technické literatury, 1988, 678 s. info
  • ČERMÁKOVÁ, Ludmila and Jaroslav ZÝKA. Analytická chemie méně běžných prvků. 1. vyd. Praha: Státní pedagogické nakladatelství, 1990, 176 s. ISBN 80-7066-050-3. info
  • BRETT, Christopher M. A. and Ana Maria Oliviera BRETT. Electroanalysis. Oxford: Oxford University Press, 1998, 88 s. ISBN 0198548168. info
  • BARD, Allen J. and Larry R. FAULKNER. Electrochemical methods : fundamentals and applications. 2nd ed. New York: John Wiley & Sons, 2001, xxi, 833. ISBN 0471043729. info
  • KLOUDA, Pavel. Moderní analytické metody. 2., upr. a dopl. vyd. Ostrava: Pavel Klouda, 2003, 132 s. ISBN 8086369072. info
  • Bard, A.J., Stratman, M. Encyclopedia of Electrochemistry, Instrumentation and Electroanalytical Chemistry, Vol.3, Wiley-VCH,2001
Teaching methods
Lecture. The emphasis is placed on physico-chemical principles of electroanalytical methods and their application in chemical analysis. Part of the examination or colloquium is the student's presentation with one of the selected topics in the electroanalytical methods.
Assessment methods
Presentation, oral examination
Language of instruction
Czech
Follow-Up Courses
Further comments (probably available only in Czech)
The course can also be completed outside the examination period.
The course is taught annually.
The course is also listed under the following terms Autumn 2007 - for the purpose of the accreditation, Autumn 1999, Autumn 2010 - only for the accreditation, Autumn 2000, Autumn 2001, Autumn 2002, Autumn 2003, Autumn 2004, Autumn 2005, Autumn 2006, Autumn 2007, Autumn 2008, Autumn 2009, Autumn 2010, Autumn 2011 - acreditation, Autumn 2012, Autumn 2013, Autumn 2014, Autumn 2015, Autumn 2016, autumn 2017, Autumn 2018, Autumn 2019, Autumn 2020, autumn 2021, Autumn 2022, Autumn 2023, Autumn 2024.
  • Enrolment Statistics (Autumn 2011, recent)
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