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.
Theoretical exercises:
- Introduction - introduction to exercise timetable, conditions for obtaining
credit and recommended reading. Concentration of solutions, Raoult´s and
Henry´s laws.
- Real solutions of non-electrolytes, different concepts of activities,
thermodynamic functions of solutions, determination of partial molar
quantities.
- Colligative properties of solutions. Miscible, limited miscible and
immiscible binary liquid mixtures.
- Calculation test I.
- Electrolysis, transport numbers of ions. Conductivity of electrolytes.
Strong electrolytes, link between ionic and medium quantities, Debye-
Hückel's law. The product of solubility.
- Chemical equilibriums in solutions of weak electrolytes, buffering capacity.
- Electrode potentials, electromotive force of the galvanic cells and
calculation applications for determination of physico-chemical quantities.
- Calculation test II.
Laboratory exercises:
- Safety in the laboratory, an introduction to laboratory assignments, basic
information on the exercises and the formulation of requirements for
protocol processing.
- Determination of partial molar quantities in liquid systems.
- Viscosity measurement using Höppler viscometer.
- Potentiometric determination of the dissociation constant of weak acids.
- Determination of pH and buffering capacity of buffers, dependence of
buffering capacity on the composition of buffers.
- Electrolysis of aqueous electrolyte solutions.
- Determination of degree of association of benzoic acid in xylene.
- Determination of the product of solubility and dissolving heat of difficult-
to-dissolve electrolytes conductometrically.
- Determination of the mean activity coefficients by measuring the
electromotive force.
- Chinhydrone electrode and determination of its standard potential by
measuring electromotive force.
- Solubility of substances.
- Conductive determination of the thermodynamic dissociation constant of weak
acid.
- Determination of liquid and membrane potential.
- Evaluation of content and formal level protocols, credit.
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MOORE, Walter J. Fyzikální chemie. Praha: SNTL - Nakladatelství technické literatury, 1981.
KELLÖ, Vojtech a Alexander TKÁČ. Fyzikálna chémia. Bratislava: Alfa,1977.
NOVÁK, Josef. Příklady a úlohy z fyzikální chemie. Vyd. 2., přeprac. Praha: Vysoká škola chemicko-technologická [Praha], 2000. ISBN 80-7080-394-0.
Dostupné též z: https://old.vscht.cz/fch/cz/pomucky/sbfch1.pdf
ADAMCOVÁ, Zdenka. Příklady a úlohy z fyzikální chemie. Praha: SNTL - Nakladatelství technické literatury, 1989. ISBN 80-03-00104-8.
LISÝ, Ján Mikuláš a Ladislav VALKO. Príklady a úlohy z fyzikálnej chémie. Bratislava: Alfa, 1979.
LEITNER, Jindřich a Petr VOŇKA. Termodynamika materiálů. Praha: Vysoká škola chemicko-technologická [Praha], 1992. ISBN 80-7080-167-0.
Dostupné též z:http://old.vscht.cz/ipl/termodyn/termmatskr.htm
ATKINS, Peter William a Julio DE PAULA. The elements of physical chemistry. 5thed. Oxford: Oxford University Press, 2009. ISBN 978-0-19-922672-6.
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