619-0802/01 – Advanced Physical Chemistry (VKFCH)
| Gurantor department | Department of Physical Chemistry and Theory of Technological Processes | Credits | 8 |
| Subject guarantor | prof. Ing. Kamila Kočí, Ph.D. | Subject version guarantor | prof. Ing. Kamila Kočí, Ph.D. |
| Study level | undergraduate or graduate | Requirement | Compulsory |
| Year | 1 | Semester | winter |
| | Study language | Czech |
| Year of introduction | 2005/2006 | Year of cancellation | 2015/2016 |
| Intended for the faculties | FMT | Intended for study types | Follow-up Master |
Subject aims expressed by acquired skills and competences
- to observe and describe thermodynamic conditions of phase equilibrium in multiphase and multicomponent systems
- to define solutions - experience laws, thermodynamic quantities and models of solutions
- to determine partial molar quantities
- to analyse phase diagrams of binary liquid mixtures
- to apply thermodynamic quantities to electrolyte solutions
- to outline usage possibilities of electrochemical systems - description of electrochemical systems, electrodes, electrolysis, galvanic cells
- to apply gained theoretical knowledge in routine
Teaching methods
Lectures
Individual consultations
Tutorials
Experimental work in labs
Summary
Thermodynamics of solution – non-electrolyte solutions (empirical laws, ideal,
dilute and real solutions, partial molar quantities, thermodynamics functions
and models) colligative properties, phase diagrams - binary liquid miscible
and immiscible mixtures. Propeties of electrolytes (acid, base, salt, buffer)
and electrochemical heterogeneous systems (electrodes, galvanic cells).
Description and application of electrochemical methods.
Thermodynamics of real gas mixtures.
Compulsory literature:
ATKINS,P.W. Physical Chemistry. Fourth Edition, Oxford: Oxford University
Press, 1993. 995 s.
ATKINS,Peter; De Paula,Julio. Elements of Physical chemistry. Fifth Edition. Oxford: University of Oxford, 2009. 578s.
Recommended literature:
Compton,R,G. Electrode potentials, Oxford University Press, Oxford 1996.
Additional study materials
Way of continuous check of knowledge in the course of semester
- two calculation exam
- five laboratory protocols
- active participation in seminars
E-learning
Other requirements
No other activities required.
Prerequisities
Subject has no prerequisities.
Co-requisities
Subject has no co-requisities.
Subject syllabus:
1. Solutions and their classification. Nonelectrolyte solutions, ideal and real solutions. Experience laws - Raoult´s and Henry´s laws. Non-ideal solutions, definition of the standard states for component in binary solutions, deviation from Raoult´s and Henry´s law, activity and activity coefficient.
Multicomponents systems, activities and interaction coefficients.
2. Thermodynamic functions of solutions. Partial molar quantities. Differential and integral quantities. Mixing and excess quantities. Determination of partial molar quantities. Thermodynamic models of solutions – ideal, real, regular and athermal solution. The Gibbs-Duhem equation, applications. The dependence of the activity and the activity coefficient on temperature.
3. Colligative properties of nonelectrolyte solutions. Vapor pressure lowering (decrease in the boiling pressure at constant temperature), boiling point elevation (ebullioscopy), freezing point depression crioscopy), osmotic pressure. Phase diagrams of two-component liquid mixtures (isothermal diagram, isobaric diagram, y-x diagram, miscible liquids, partially miscible liquids, totally immiscible liquids).
4. Distillation, simple distillation, rectification, azeotropic points, azeotropic mixtures, explaining the deviations. Phase diagram of the liquid ternary systems. Three-component system containing two liquid phases, Nernst’s distribution law, extraction.
Electrochemistry, basic terms. Electrolytes and ions, strong electrolyte, weak electrolyte, ion charge number, theory of electrolytic dissociation, dissociation constant, degree of dissociation.
5. Electrolysis and its significance, Faraday’s laws, reactions occurring during electrolysis,concentration changes during electrolysis. Coulometers. Cation and anion transport numbers, cation and anion mobility, Hittorf method of determining transport numbers.
6. Electric conductivity of electrolytes. Specific and molar electric conductivity, concentration dependence Molar conductivity at infinite dilution, theory of ionic conductivity, Kohlrausch’s law of independent migration of ions. Conductivity measurement and its utilization - Ostwald´s dilution law, determination of solubility product, conductometric titrations.
7. Strong electrolyte. Deviation from ideal state. Osmotic coefficient. Mean molality, concentration, activity and activity of electrolyte. Ionic strength of a solution, Debye-Hückel limiting law, activity coefficients at higher concentrations. Conduction coefficient, electrophoretic effect, relaxation effect. Solubility of sparingly soluble salts, solubility product.
8. Equilibrium and dissociation in solutions of weak electrolytes. Ionic product of water. Theory of acids and bases (Brönsted´s, Arrhenius and Lewis theory). Classification of solvents. Determination of pH, acidobasic indicators. Dissociation of week monobasic acids and bases. Hydrolysis of the salt. Buffer solutions, Henderson–Hasselbalch equation, buffer capacity, signification.
9. Electrodes. Electrochemistry potentials - electrode and redox potentials, liquid junction and membrane potentials. Classification of half-cells, decription, function, utilization of electrodes - first-type electrodes, second-type electrodes, reduction-oxidation electrodes, ion-selective electrodes.
10. Galvanic cells, classification, electromotive force of the cell and its measurement. Chemical cells (cells with transference, cells without transference), electrode and electrolyte and concentration cells (cells with transference, cells without transference). Electromotive force and thermodynamic quantities.
11. Theory of liquid junction potential. Electromotive force of galvanic cells with liquid junction potential. Significance of galvanic cells. Electrochemistry power sources.
12. Potentiometry. Direct potentiometry – pH determination, determination of solubility product, activity coefficients and dissociation constants. Potentiometric titrations, equivalence point.
13. Electrode processes. Electrode polarization. Chemical and concentration polarization, elimination, significance. Decomposition voltage, overvoltage. Hydrogen overvoltage, Tafel equation, Butler–Volmer equation, mechanism of hydrogen deposition. Oxygen overvoltage. Basic aspects of polarography and electrochemical corrosion.
14. Real gases. Equations of state, theorem of corresponding states, compressibility factor, compressibility diagram. State behaviour of liquids.
Selected chapters in chemical kinetics:
Terminology in chemical kinetics.
Homogeneous reactions.
Temperature dependence of the rate of a chemical reaction.
Theory of chemical kinetics.
Kinetics of heterogeneous reactions.
Mechanism and mathematical description of diffusion.
Heterogeneous process with consecutive and concurent steps.
Surface phenomena and kinetics of reactions. Physical adsorption and chemisorption. Application of surface processes – examples.
Kinetics of topochemical reactions, desription and analysis of particular periods.
Principles of catalysis, homogeneous and heterogeneous catalysis.
Conditions for subject completion
Occurrence in study plans
Occurrence in special blocks
Assessment of instruction