PURPOSE
Within the framework of this course the students will get acquainted with the application of fundamental laws of thermodynamics as well as mathematical methods for solving the chemical engineering problems of: estimation of thermodynamic functions of pure substances, mixtures and solutions, phase equilibria calculation, chemical equilibria calculation.
THE CONTENTS OF THE COURSE:
1. Introduction to thermodynamics of real systems - what is thermodynamics, what does it deal with, classification of thermodynamics, course contents, prerequisites, basic definitions: thermodynamic systems, functions, parameters, phases, states, processes, laws of thermodynamics,
Volumetric properties of real fluids - pT-diagram, Gibbs phase rule, ideal gas equation, deviations from ideality, compressibility coefficient, Joule-Thomson coefficient, liquefaction of real fluid
Seminar: getting acquainted with the seminar numeric problems programme, (Cepanec)
2. Volumetric properties of real fluids - gas particles interaction, Lennard-Jones potential, virial equation, Boyle temperature, BWR equation
Volumetric properties of real fluids - van der Waals equation, parameters, liquefaction work, equilibrium pressure, corresponding states principle, thermodynamic similarity principle, critical compressibility coefficient, Pitzer acentric coefficient, Lee-Kesler correlation
Seminar - numeric problems: Volumetric properties of real fluids (Cepanec)
3. Volumetric properties of real fluids - third order polynomial equation of states, Redlich-Kwong, Soave-Redlich-Kwong, Peng-Robinson, calculation of pvT-properties, comparison of equations, gas mixtures
Thermodynamic properties of real fluids - steam (heat) tables and diagrams, construction of ph and sT-diagrams, departure functions, corresponding states principle, thermodynamic similarity principle, Yen-Alexander and Lee-Kesler correlation for enthalpy and entropy
Seminar - numeric problems: Volumetric properties of real fluids (Cepanec)
4. Thermodynamic properties of real fluids - fugacity and fugacity coefficient, fugacity as a departure function, calculating Gibbs energy using fugacity, fugacity vs. pressure and fugacity vs. temperature correlations, fugacity and the corresponding states principle, fugacity and the thermodynamic similarity principle
Thermodynamics of real solutions - ideal solution definition, volume, enthalpy and entropy of mixing, the causes of non-ideality of real solutions
Seminar - Equations of state of real fluids (Cepanec)
5. Thermodynamics of real solutions - partial molar functions in two- and multicomponent real systems, Gibbs-Duhem equation, partial fugacity and partial fugacity coefficient, mixing functions, excess functions
Thermodynamics of real solutions - activity and activity coefficient, standard states of pure gas, liquid and solid as well as of gas and liquid mixture components, Poynting factor, Lewis-Randall rule, infinitely dilute solution, Henry law for real solutions
Seminar - numeric problems: Thermodynamic properties of real fluids (Cepanec)
6. Thermodynamics of real solutions - determination of partial molar functions using the methods of intercept, tangent, apparent molar functions, as well as by the Gibbs-Duhem equation, Gibbs energy vs. activity and activity coefficient correlation
Activity coefficient models - activity coefficient models: Margules, power series, Van Laar, Wohl, regular and athermal solutions, Scatchard-Hildebrand; Flory-Huggins interaction parameter, solubility parametar, determination of model parameters
Seminar - numeric problems: Thermodynamics of real solutions (Cepanec)
7. Activity coefficient models - activity coefficient models: Wilson, Tsuboka-Katayama, Hiranuma, NRTL, UNIQUAC; structural group contribution models: ASOG, UNIFAC
Recapitulation - thermodynamics of real solutions and activity coefficient models, preparation for partial exam
Seminar - Preparation for partial exam 1 (Cepanec)
8. Partial exam 1 - volumetric properties of real fluids, thermodynamic properties of real fluids, thermodynamics of real solutions, activity coefficient models
Thermodynamic equilibrium - equilibrium criteria in isolated and closed systems, system stability criteria, reacting systems, thermodynamic interpretation of Le Chatelier principle
Seminar - numeric problems: Thermodynamics of real solutions (Cepanec)
9. Vapour-liquid equilibria - equilibrium criteria using chemical potentials and partial fugacities, phase non-ideality description using equation of states and activity coefficient models, equilibrium criteria for ideal vapour and liquid phase, respectively
Vapour-liquid equilibria - phase diagrams, Txy-diagram, pxy-diagram, xy-diagram, systems of regular behaviour, azeotropic systems, bubble point, dew point, flash, numerical methods in vapour-liquid equilibrium calculations
Seminar - numeric problems: Thermodynamics of real solutions (Cepanec)
10. Liquid-liquid equilibria - equilibrium criteria using chemical potentials, phase diagrams, vapour pressure vs. composition, Gibbs energy of mixing vs. composition, miscibility as influenced by temperature and pressure, determination of model parameters using experimental data, ternary diagrams, lever rule
Solid-liquid equilibria - equilibrium criteria using chemical potentials and partial fugacities, phase diagrams, eutectics, intermolecular compounds, peritectics, calculation of solubility of a solid in a liquid, Schroeder equations, ternary eutectics, eutectic troughs
Seminar - numeric problems: Vapour-liquid equilibria (Cepanec)
11. Solid-gas equilibria - equilibrium criteria using chemical potentials and partial fugacities, supercritical fluids as solvents, calculation of solubility of a solid in a fluid (gas)
Chemical equilibria - chemical equilibrium criterion: minimum Gibbs energy, stoichiometric sum of chemical potentials, homogeneous chemical reactions, standard Gibbs energy of reaction, standard Gibbs energy of reaction vs. temperature correlation
Seminar - numeric problems: Solid-liquid equilibria (Cepanec)
12. Chemical equilibria - examples of solving homogeneous chemical equilibria problems, chemical equilibria at multireaction systems, determination of minimum number of reaction, Denbigh method, matrix elimination method
Chemical equilibria - determination of global minimum Gibbs energy of a systems, heterogeneous chemical equilibria
Seminar - Preparation for partial exam 2 (Cepanec)
13. Partial exam 2 - thermodynamic equilibrium, vapour-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria, chemical equilibria, thermodynamics of irreversible processes
Recapitulation - discussion on the course content, lectures, seminars, questions and answers, preparation of final written and oral exam
Seminar - numeric problems: Repetition (Cepanec)
GENERAL AND SPECIFIC COMPETENCE:
General competences:
Application of fundamental laws of thermodynamics in combination with literature or own experimental data for solving the chemical engineering problems of: 1. estimation of thermodynamic functions of gases and liquids depending on the given pressure, temperature and composition, 2. characterisation of vapour-liquid and liquid-liquid equilibria and 3. characterisation of chemical equilibria
Special competences:
Calculation of thermodynamic functions of real fluids using equations of state: virial, vdW, RK, SRK, PR, Lee-Kesler
Calculation of thermodynamic functions of real solutions using activity coefficient models: Margules, Van Laar, Wilson, NRTL, UNIQUAC, UNIFAC, ASOG
Calculation of activity coefficient model parameters using experimental data
Calculation of equilibrium temperature, pressure and phase composition for the vapour-liquid equilibria: bubble point, dew point, flash calculations
Calculation of equilibrium phase composition for the liquid-liquid equilibria
Calculation of equilibrium composition in reacting systems as dependent on pressure and temperature: gas phase reactions, multiple gas phase reactions, heterogeneous reactions
STUDENT RESPONSIBILITIES
Obligatory lectures and seminars
Obligatory attendance to partial and final exams
FORMAT OF INSTRUCTION
lectures (ex cathedra)
seminars (ex cathedra)
MONITORING STUDENT WORK
Two partial exams during the semester (60% at each exam required to replace the oral exam)
Written exam (three calculation problems, 50% needed for passing the exam, 100% needed for one of the three problems for passing the exam)
Oral exam
MONITORING TEACHER WORK
Student survey
LEARNING OUTCOMES AT THE COURSE LEVEL
1. To interpret ways of extending and correcting basic physical and chemical laws for the application in real gases and solutions
2. To select literature data and theoretical models to describe the dependence of thermodynamic properties of real gases and solutions on temperature and pressure
3. To set up a system of equations to describe the vapour-liquid or liquid-liquid phase equilibria, as well as chemical equilibria
4. To propose a way of solving the system of equations for the description of the vapour-liquid or liquid-liquid phase equilibria
LEARNING OUTCOMES AT THE STUDY PROGRAMME LEVEL
1. to solve qualitative and quantitative problems using the appropriate chemical principles and theories
2. to evaluate chemical information and data
3. to analyse chemical information and data using a computer
4. toretrieve information through on-line computer searches
COMPULSORY LITERATURE
M.Rogošić, Nastavni tekstovi na mrežnim stranicama FKIT-a, 2013.
S.I.Sandler, Chemical, Biochemical and Engineering Thermodynamics, 5th Ed., Wiley, New York, 2017.
ADDITIONAL LITERATURE:
J.M.Smith, H.C.Van Ness, M.M.Abbott, M.Swihart, Introduction to Chemical Engineering Thermodynamics, 9th Ed., McGraw-Hill, New York, 2022.
J.M.Prausnitz, R.N.Lichtenthaler, E.G.de Azevedo, Molecular Thermodynamics of Fluid Phase Equilibria, 3rd Ed., Prentice Hall, Englewood Cliffs, 1999.
J.R.Elliott, V.Diky, T.A.Knotts IV, W.V.Wilding, The Properties of Gases and Liquids, 6th Ed., McGraw-Hill, New York, 2023.
|
Pristupačnost
