619-3001/02 – Advanced Physical Chemistry (VKFCH)

Gurantor departmentDepartment of Physical Chemistry and Theory of Technological ProcessesCredits7
Subject guarantorprof. Ing. Kamila Kočí, Ph.D.Subject version guarantorprof. Ing. Kamila Kočí, Ph.D.
Study levelundergraduate or graduate
Study languageEnglish
Year of introduction2015/2016Year of cancellation2019/2020
Intended for the facultiesFMTIntended for study typesFollow-up Master
Instruction secured by
LoginNameTuitorTeacher giving lectures
KOC33 prof. Ing. Kamila Kočí, Ph.D.
SME06 prof. Ing. Bedřich Smetana, Ph.D.
Extent of instruction for forms of study
Form of studyWay of compl.Extent
Full-time Credit and Examination 3+3

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 obtained theoretical knowledge in tutorials and laboratory and on selected processes of chemical practice

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. 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.

Compulsory literature:

[1] ATKINS,P.W. Physical Chemistry. Fourth Edition, Oxford: Oxford University Press, 1993. 995 p.

Recommended literature:

[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

Way of continuous check of knowledge in the course of semester

E-learning

Other requirements

No other activities are 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 (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.

Conditions for subject completion

Conditions for completion are defined only for particular subject version and form of study

Occurrence in study plans

Academic yearProgrammeField of studySpec.ZaměřeníFormStudy language Tut. centreYearWSType of duty

Occurrence in special blocks

Block nameAcademic yearForm of studyStudy language YearWSType of blockBlock owner
FMST 2019/2020 Full-time English Compulsory 601 - Study Office stu. block
FMT-new subjects 2019/2020 Full-time English Optional 600 - Faculty of Materials Science and Technology - Dean's Office stu. block
FMMI 2018/2019 Full-time English Compulsory 601 - Study Office stu. block
FMMI 2017/2018 Full-time English Compulsory 601 - Study Office stu. block
FMMI 2016/2017 Full-time English Compulsory 601 - Study Office stu. block
FMMI 2015/2016 Full-time English Compulsory 601 - Study Office stu. block