Electrochemistry and Theory of Solutions 1

Course guarantor:

Lecturer:

Tutor:

Supervisor:

Department of Nuclear Chemistry

Synopsis:

Introduction to electrochemistry and theory of solvents. Basic electrochemical laws, electrolytic conduction, electrochemical equilibria and kinetics. Fundamentals of solvent theory, chemical potentials, activity and activity coefficients, thermodynamics of electrolytes solutions, theory of ion interaction.

Requirements:

The lecture follows the course of general chemistry and thermodynamics.

Syllabus of lectures:

1. Introduction to solvent theory: partial molar state functions, chemical potentials, Gibbs - Duhem equation, activity and activity coefficients.

2. Diluted liquid solutions of non-volatile substances: decrease of solvent vapour pressure, ebulioscopy, cryoscopy, osmotic pressure, osmotic phenomena in the solutions of electrolytes, diffusion in solutions.

3. Introduction to electrochemistry: electrochemical processes, electrochemistry landmarks, the Faraday`s laws, coulometry, solvation of ions, ion pairs.

4. Electrolytic transfer: transference numbers, Hittorf`s method, moving boundary method, influence of solvation and complexation on the transference numbers of cations.

5. Electrolytic conduction: measurement of conductance, molar and equivalent conductance, Kohlrausch law of independent ion migration, classical electrolyte dissociation theory, Ostwald dilution law, conductivity and ion mobility, applications of conductance measurements.

6.-7. Ion interaction theory: theory of solutions of strong electrolytes, ion atmosphere, limiting law of electrolytic conductivity, viscous, electrophoretic and relaxation effects, Debye - Hückel - Onsager equation, Wiener effect, Debye - Falkenhagen effect.

8. Thermodynamics of electrolytes solutions: activity and activity coefficients of ions, mean chemical potential, mean activity and activity coefficients, determination of activity coefficients, ionic strength, Lewis` empirical relation, theory of ion interaction and activity coefficients of ions.

9. Galvanic cells: electric tension and its measurement, dependence of the electric tension on state functions, Nernst equation, electrode potentials (IUPAC conventions, standard electrode potentials), basic types of electrodes and galvanic cells, applications of potentiometric measurements.

10. Potentials on liquid interfaces: phase potential and electrochemical potential, difussion potential, Donnan potential, ion exchange membranes, ion selective electrodes.

11. Kinetics of electrode processes (basics): kinetic theory of electrode potential, electrode reactions, concentration polarization and chemical polarization, overvoltage, decomposition voltage, dependence of current-flow density on the overvoltage.

12. Influence of transport phenomena on the electrode processes: basics of polarography, Ilkovic`s equation and equation of polarographic wave, half-wave electric tension.

13. Equilibria in weak electrolytes solutions: Broensted conception of acids and bases, protolytic reactions, neutralization and hydrolytic reactions, buffers, indicators in titrimetric analysis.

Syllabus of tutorials:

Study Objective:

Students learn first the thermodynamics of the nonelectrolytic solutions and then extend their knowledge to the behavior of the solutions containing charged particles.

Study materials:

Key literature:

1. Koryta J., Dvořák J., Kavan L.: Principles of Electrochemistry, 2nd edition, Wiley, Chichester, 1993

Recommended literature:

1. Hamman C.H., Hamnett A., Viestich W.: Electrochemistry, Wiley, Weiheim, 1998

Note:

Further information:

No time-table has been prepared for this course

The course is a part of the following study plans: