| Course Unit Code | 619-3001/02 |
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| Number of ECTS Credits Allocated | 7 ECTS credits |
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| Type of Course Unit * | Compulsory |
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| Level of Course Unit * | Second Cycle |
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| Year of Study * | |
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| Semester when the Course Unit is delivered | Summer Semester |
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| Mode of Delivery | Face-to-face |
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| Language of Instruction | English |
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| Prerequisites and Co-Requisites | Course succeeds to compulsory courses of previous semester |
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| Name of Lecturer(s) | Personal ID | Name |
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| SME06 | prof. Ing. Bedřich Smetana, Ph.D. |
| KOC33 | prof. Ing. Kamila Kočí, Ph.D. |
| Summary |
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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. Properties of electrolytes (acid, base, salt, buffer) and electrochemical heterogeneous systems (electrodes, galvanic cells). Description and application of electrochemical methods.
Thermodynamics of real gas mixtures.
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| Learning Outcomes of the Course Unit |
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- 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 obtained theoretical knowledge in tutorials and laboratory and on
selected processes of chemical practice
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| Course Contents |
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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 (cryoscopy), 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, description, 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. Thermodynamics of liquids.
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| Recommended or Required Reading |
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| Required Reading: |
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[1] ATKINS,P.W. Physical Chemistry. Fourth Edition, Oxford: Oxford University
Press, 1993. 995 p. |
[1] NOVÁK,J. a kol. Fyzikální chemie: bakalářský a magisterský kurz. Praha:
VŠCHT, 2011. 490 s. Elektronická verze:
http://www.vscht.cz/fch/cz/pomucky/FCH4Mgr.pdf
[2] KELLÖ,V., TKÁČ,A. Fyzikálna chemia. Bratislava: Alfa, 1977. 778 s.
[3] BUREŠ, M., ČERNÝ, Č., CHUCHVALEC, P. Fyzikální chemie II. Praha: VŠCHT,
1994. 335 s.
[4] DUDEK,Rostislav; PEŘINOVÁ, Kristina; KALOUSEK Jaroslav. Teorie
technologických procesů [online] 2012. Dostupné z WWW:
<http://www.person.vsb.cz/archivcd/FMMI/TTP/index.htm>.
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| Recommended Reading: |
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[1] ATKINS,Peter; De Paula,Julio. Elements of Physical chemistry. Fifth
Edition. Oxford: University of Oxford, 2009. 578s.
[2] BAGOTSKY, V. S. Fundamentals of Electrochemistry, Second Edition.
Hoboken, N.J: John Wiley, 2006. 722 p.
Elektronická verze: http://onlinelibrary.wiley.com/book/10.1002/047174199X
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[1] ATKINS,P.W. Fyzikálna chémia. Bratislava: STU, 1999.
[2] MOORE,W.J. Fyzikální chemie. Praha: SNTL. 1979. 974 s.
[3] ADAMCOVÁ,Z. a kol. Příklady a úlohy z fyzikální chemie. Praha: SNTL,
1989. 666 s.
[4] LISÝ, M., VALKO, L.Príklady a úlohy z fyzikálnej chémie. Bratislava:
Alfa, 1979. 813 s.
[5] DVOŘÁK,J., KORYTA,J. Elektrochemie. Praha: SNTL. 1983. 410 s.
[6] LEITNER, J., VOŇKA, P. Termodynamika materiálů. Praha:VŠCHT, 1997.
211 s.
Elektronická verze: http://www.vscht.cz/ipl/termodyn/termmatskr.htm
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| Planned learning activities and teaching methods |
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| Lectures, Individual consultations, Tutorials, Experimental work in labs |
| Assesment methods and criteria |
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| Tasks are not Defined |