PURPOSE
Within the framework of this course the students will master 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. In addition, the student will get acquainted with the fundamentals of the non-equilibrium and irreversible thermodynamics.
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
Volumetric properties of real fluids - gas particles interaction, Lennard-Jones potential, virial equation, Boyle temperature, BWR equation
Seminar: getting acquainted with the seminar numeric problems program, laboratory program as well as with the seminar individual problems program (Rogošić, Cepanec)
Seminar - numeric problems: Volumetric properties of real fluids (Cepanec)
2. 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
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)
Seminar - numeric problems: Volumetric properties of real fluids, preparation for the seminar individual problem 1 (Rogošić, Cepanec)
3. 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
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
Seminar - numeric problems: Thermodynamic properties of real fluids (Cepanec)
Seminar - individual problems: equation of states of real gases (Rogošić, Cepanec)
4. 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
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 parameter, determination of model parameters
Seminar - numeric problems: Thermodynamic properties of real fluids (Cepanec)
Seminar - individual problems: equation of states of real gases (Rogošić, Cepanec)
5. 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 - numeric problems: Thermodynamics of real solutions (Cepanec)
Seminar - individual problems: equation of states of real gases (Rogošić)
6. 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
Vapor-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 vapor and liquid phase, respectively
Laboratory: partial molar volumes (Cepanec)
Laboratory: partial molar volumes (Cepanec)
7. Vapor-liquid equilibria - phase diagrams, Txy-diagram, pxy-diagram, xy-diagram, systems of regular behavior, azeotropic systems, consistency tests
Vapor-liquid equilibria - phase equilibrium calculations in chemical engineering: bubble point, dew point, flash, numerical methods in vapor-liquid equilibrium calculations
Vapor-liquid equilibria - high pressure range: retrograde condensation, equilibrium calculations; solubility of gases in liquids, Prausnitz and Shair procedure
Laboratory: Vapor-liquid equilibria (Cepanec)
Laboratory: Vapor-liquid equilibria (Cepanec)
8. Liquid-liquid equilibria - equilibrium criteria using chemical potentials, phase diagrams, vapor 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, calculation of equilibrium composition in two- and three-component systems
Liquid-liquid equilibria - breaking azeotropes by changing pressure or by adding the third component, Liquid-liquid-vapor equilibria, phase diagrams, phase equilibrium calculations
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
Laboratory: Liquid-liquid equilibria (Cepanec)
Laboratory: Liquid-liquid equilibria (Cepanec)
9. 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)
Recapitulation - thermodynamic equilibrium, vapor-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria, solid-gas equilibria
Seminar - numeric problems: Thermodynamics of real solutions (Cepanec)
Seminar: laboratory data analysis (Cepanec)
10. Partial exam 2 - thermodynamic equilibrium, vapor-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria
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
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
Seminar - numeric problems: Vapor-liquid equilibria (Cepanec)
Seminar: preparation for the seminar individual problem 2 (Rogošić, Cepanec)
11. Chemical equilibria - determination of global minimum Gibbs energy of a systems, heterogeneous chemical equilibria
Thermodynamics of irreversible processes - external and internal entropy change, example of irreversible processes, heat and mass transfer, thermodynamic potentials and flows, entropy production, examples: thermal and mass diffusion
Thermodynamics of irreversible processes - examples: simultaneous thermal and mass diffusion, irreversible expansion of ideal gas, chemical reaction, affinity
Seminar - numeric problems: Liquid-liquid equilibria (Cepanec)
Seminar - individual problems: Vapor-liquid equilibria (Rogošić, Cepanec)
12. Thermodynamics of irreversible processes - phenomenological equations, flow vs. potential relationship, Onsager phenomenological coefficients, examples: electric current in electrolytes and metals, Ohm law, mass diffusion, Fick law, simultaneous diffusion of two substances
Thermodynamics of irreversible processes - examples: thermal diffusion, Fourier law, thermoelectric effects, cross phenomenological coefficients, chemical reactions, simple and complex
Thermodynamics of irreversible processes - stationary and non-stationary states examples, thermal diffusion, Prigogine principle and its consequences: chemical potential gradient, sequential chemical reactions, stability of a stationary state, Lyapunov stability theory
Seminar - numeric problems: Liquid-liquid equilibria (Cepanec)
Seminar - individual problems: Vapor-liquid equilibria (Rogošić, Cepanec)
13. Partial exam 3 - chemical equilibria, thermodynamics of irreversible processes
Recapitulation - discussion on the course content, lectures, seminars, laboratory and individual seminar problems, questions and answers, preparation of final written and oral exam
Seminar - numeric problems: Solid-liquid equilibria (Cepanec)
Seminar - individual problems: Vapor-liquid equilibria (Rogošić, 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. characterization of vapor-liquid and liquid-liquid equilibria and 3. characterization of chemical equilibria
Understanding of the basic principles of irreversible thermodynamics
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 vapor-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 3 lab exercises
Obligatory 2 numerical exercises
Obligatory attendance to partial and final exams
FORMAT OF INSTRUCTION
lectures (ex cathedra)
seminars (ex cathedra)
laboratory (practiced in groups supervised by an assistant and demonstrators)
numerical exercises (independent computing assignments supervised by an assistant and demonstrators)
consultations if necessary
MONITORING STUDENT WORK
Entry exam for laboratory
Written exit exam for laboratory
Written exam for numerical exercises
Three 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
5. To identify thermodynamic potentials and flows in the system (to describe phenomena of mass and energy transfer in thermodynamic terms)
LEARNING OUTCOMES AT THE STUDY PROGRAMME LEVEL
1. to explain the basic principles of chemical engineering in the fields of modelling and simulation of chemical reactions, the processes of transfer of momentum, mass and energy and separation processes
2. to define chemical engineering problems, including their analysis and formulation to solve them by the application of the basic principles
3. to select appropriate methods of analysis, modelling, simulation and optimization
4. to use literature in printed and electronic form to collect the information needed to solve chemical engineering problems
5. to apply techniques and methods with an awareness of their limitations
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.
D.Kondepudi, I.Prigogine, Modern Thermodynamics, Wiley, New York, 1998.
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.
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