* Your assessment is very important for improving the workof artificial intelligence, which forms the content of this project
Download Eötvös Loránd Science University Faculty of Sciences Department of
Stability constants of complexes wikipedia , lookup
Heat transfer physics wikipedia , lookup
Woodward–Hoffmann rules wikipedia , lookup
Thermodynamics wikipedia , lookup
Chemical potential wikipedia , lookup
History of electrochemistry wikipedia , lookup
Detailed balance wikipedia , lookup
Chemical equilibrium wikipedia , lookup
Equilibrium chemistry wikipedia , lookup
Multi-state modeling of biomolecules wikipedia , lookup
Photoredox catalysis wikipedia , lookup
George S. Hammond wikipedia , lookup
Ene reaction wikipedia , lookup
Rate equation wikipedia , lookup
Enzyme catalysis wikipedia , lookup
Reaction progress kinetic analysis wikipedia , lookup
Chemical thermodynamics wikipedia , lookup
Hydrogen-bond catalysis wikipedia , lookup
Physical organic chemistry wikipedia , lookup
Marcus theory wikipedia , lookup
Eötvös Loránd Science University Faculty of Sciences Department of Chemistry Core (required) COURSE OUTLINES and Prerequisites 2013 Course Title: Physical Chemistry (2): Reaction Kinetics + Electrochemistry 1. Course Code Semester Grading kv1c1fzb 3. oral exam Credits / Language Weekly Hours 4/4 English Major Chemistry BSc 2. Course Type: lecture and seminar 3. Course Instructor and Department: Inzelt, György, professor of chemistry, Department of Physical Chemistry 4. Course Instructor: Name: Title: Department, Institution: Inzelt, György prof. of chemistry Dept. of Physical Chemistry 5. Course Requirements: Knowledge of undergraduate general chemistry, mathematics, physics and thermodynamics; elements of quantum mechanics. 6. Course Prerequisites: 6.1. Prerequisites kv1c1fz1, Physical Chemistry (1): Thermodynamics + Statistical Thermodynamics 6.2. Recommended kv1c4fzp, Physical Chemistry Laboratory Course (1) 7. Course Objectives: The course comprises two distinct parts. In the first part, the student is informed about the status and role of reaction kinetics within physical chemistry. S/he understands the molecular and statistical thermodynamical foundations of kinetics basically in gas phase. S/he will be capable to use the basic kinetic formalism derived from these principles to solve general kinetic problems. S/he will learn to apply formal kinetic relationships to practically relevant situations. S/he develops a sound knowledge to treat complex reaction mechanisms, and the way to simplify them to solve practical problems. Based on his/her knowledge in statistical thermodynamics, s/he will be able to derive relevant kinetic parameters – e.g., the rate of elementary reactions – within different conditions. She will get a basic knowledge about homogeneous and heterogeneous catalysis. S/he will analyse observed experimental data, identify the relevant mechanism and calculate its parameters. The sec- ond part covers the thermodynamical description of homogeneous and heterogeneous electrochemical systems, the kinetics of electrode reactions as well as electrochemical technologies, power sources and corrosion. 8. Course Outline: Topics Covered: Historical review of chemical kinetics. The scope of modern kinetics. Definition of the reaction rate and its formulation using different time derivatives. Collision theory in kinetics. Potential energy surfaces in reactive systems. The transition state theory based on quasi-equilibrium approach. Alternative theories of bimolecular reactions. Calculating rate constants for elementary reactions, and the isotope effect. Formal kinetics of chemical reactions. Rate equations of uni- bi- and termolecular reactions. Order of a reaction; solution of rate equations of 0., 1., 2. and 3. order. Half-lifes of reactions. Evaluation of experimental kinetic data in older times (by means of a ruler) and nowadays (using a computer). Elementary reactions and reaction mechanisms. Lindemann and RRKM theories. Dependence of the rate constant on temperature and pressure. Third-order reactions, their two-step equilibrium mechanism. Rate determining steps in different mechanisms. Equilibrium reactions, parallel and consecutive reactions. Methods to solve coupled differential equations. The steady-state approximation of a set of differential equations. Chain reactions, explosions and their kinetic description. Catalysts and inhibitors. Acidbase catalysis. Experimental methods in chemical kinetics. Heterogeneous reactions; twodimensional equations of state and rate equations. Inferring a mechanism from experimental data. Numerical methods used to support eventual mechanisms. The development and importance of electrochemical concepts, investigation methods and technologies. Thermodynamical description of homogeneous and heterogeneous electrochemical systems. Thermodynamic description of phases containing electrically charged particles. The electrochemical potential. Consequences of the electroneutrality principle and the thermodynamic nature of charge carriers. Born theory on hydration. Mean activity, the limiting law of Debye and Hückel. Contact equilibria. Thermodynamic description of a galvanic cell. Potential of the cell reaction. The liquid-liquid junction potential. Measureability of the cell potential. The standard potential of the cell and its relation to the equilibrium constant of the cell reaction. The formal potential. Volta- and Galvani potential differences. Electrodes and their properties. Concentration cells. Electrodes to measure pH and other ionic concentrations. General description of transport: fluxes and forces. Solution of the differential equations of diffusion. The viscous flow. Diffusion in electrolytes. Electric conduction in metals and electrolytes. Theories of electrolytic conduction. Kinetics of electrode reactions. Mechanism of electrode reactions. Rate of the reaction related to the electric current density. Current-potential functions for simple steady state redox-reactions. Polarisation curves. Equilibrium and exchange current. Reversible and irreversible behaviour. Factors determining the rate of charge transfer. The theory of Erdey-Grúz and Volmer for the electron transfer. Interpretation of the transfer coefficient in the framework of the transition state theory and potential energy surfaces. Factors determining the rate of electron transfer and bulk redox reactions. Marcus theory of the electron transfer. Mass transport and the rate of electrode reactions. The Nernst-Planck equation. The role of diffusion, migration and convection. Diffusion current, diffusion layer. Kinetics of complex electrode reactions. Multiple electron transfer. The role of adsorption (chemisorption, eletrosorption). Simultaneous and consecutive charge transfer steps; the role of coupled chemical reactions. Electrocatalysis. Applied electrochemistry. Electrolysis in practice and at an industrial scale. Electrochemical power sources. Mechanism of electrochemical corrosion. Passivity of metal surfaces. Corrosion prevention and its practical applications. 8.1. Course Outline (Weekly) The course comprises three hours of lectures and one hour seminar per week. Lectures typically follow a curriculum based on the relevant chapters of textbooks, where theoretical concepts are discussed in details with some practical examples. The web page of the course always contains the actual material discussed, along with related textbook chapters. The seminar concentrates on solution of practical – mostly real-life – problems related to the theories discussed during the lectures. Students get weekly assignments and write midterm exams during the semester. They also get a microproject and are supposed to write an essay- or publication-like report on the results obtained. Add/Drop courses (Week 1); Subscription to courses (1st week); Lecture 1 Information ont he curriculum and the conditions to get a final grade. Reaction kinetics as part of physical chemistry. Subject and scope of reaction kinetics, its historical development. Molecular vs. macroscopic description of chemical reactions. Recalling statistical thermodynamic calculations in canonical ensembles. Definition of the reaction rate and its formulation using time-derivatives of different quantities; Lecture 2 Collision theory of chemical reactions. Potential energy surfaces, quasi-equilibrium approach, transition state theory (TST). Calculation of the rate constant and isotope effect based on TST. Lecture 3 General description of chemical reactions. Rate equations of unimolecular, bimolecular and termolecular elementary reactions. Rate equations and their solutions for 0th, 1st, 2nd and 3rd order reactions. Half lives of reacting species. Quantitative inference from experimental data in older times (graphically, by means of a ruler) and nowadays (using computer codes). Lecture 4 Elementary reactions, complex reactions, and the mechanism of reactions. Types of coupling elementary reactions; parallel, consecutive and opposing reactions. Writing rate equations for complex reactions, and solving the resulting simultaneous system of differential equations. Chain reactions and their simplified solution using steady-state approximation; Lecture 5 Branching chain reactions and explosions. Pre-equilibrium followed by a bimolecular reaction as an alternative to termolecular elementary reactions. Theories of unimolecular reactions; the Lindemann and the RRKM theory. Lecture 6 Pressure and temperature dependence of the rate reaction. Homogeneous and heterogeneous catalysis. Formal treatment of heterogeneous reactions. Autocatalysis and autoinhibition. Acid-base catalysis; Lecture 7 The development and importance of electrochemical concepts, investigation methods and technologies. Thermodynamical description of homogeneous and heterogeneous electrochemical systems. Thermodynamic description of phases containing electrically charged particles. The electrochemical potential. Thermodynamic description of a galvanic cell. Potential of the cell reaction. The liquid-liquid junction potential. Measureability of the cell potential. The standard potential of the cell and its relation to the equilibrium constant of the cell reaction. The formal potential; Lecture 8 Inner, outer and surface potentials. Volta- and Galvani potential differences. The properties of the electrochemical potentials. Dissociation and solubility equilibria; Lecture 9 The potential of the electrode reaction, the electrode potential. The equilibrium, standard and formal electrode potentials. Nernst equation. The standard potential of the cell and its relation to the equilibrium constant of the cell reaction; Lecture 10 Consequences of the electroneutrality principle and the thermodynamic nature of charge carriers. Born theory on hydration. Mean activity, the limiting law of Debye and Hückel. Diffusion in electrolytes. Electric conduction in metals and electrolytes. Theories of electrolytic conduction. Electrodes and their properties. Concentration cells. Electrodes to measure pH and other ionic concentrations; Lecture 11 Kinetics of electrochemical processes. Kinetics of electrode reactions. Mechanism of electrode reactions. Rate of the reaction related to the electric current density. Currentpotential functions for simple steady state redox-reactions. Polarisation curves. Factors determining the rate of charge transfer; Lecture 12 Equilibrium and exchange current. Reversible and irreversible behaviour. The theory of Erdey-Grúz and Volmer for the electron transfer. Interpretation of the transfer coefficient in the framework of the transition state theory and potential energy surfaces. Factors determining the rate of electron transfer and bulk redox reactions. Marcus theory of the electron transfer; Lecture 13 Mass transport and the rate of electrode reactions. The Nernst-Planck equation. The role of diffusion, migration and convection. Diffusion current, diffusion layer. Kinetics of complex electrode reactions. Multiple electron transfer. The role of adsorption (chemisorption, eletrosorption). Simultaneous and consecutive charge transfer steps; the role of coupled chemical reactions. Electrocatalysis; Lecture 14 Applied electrochemistry. Electrochemical technologies. Electrolysis in practice and at an industrial scale. Electrochemical power sources. Mechanism of electrochemical corrosion. Passivity of metal surfaces. Corrosion prevention and its practical applications. 9. Remarks: 10. Requirements: 10.1. Course Work: Only students registered in the Neptun system can attend the lectures. Prerequisites for completion of course/laboratory (in addition to those listed in „ELTE Organizational and Operational Regulations”) include: During the semester: attendance at the lectures is not compulsory, but the knowledge of the material discussed is necessary to follow the seminars. Attendance at the seminars is compulsory (a record of attendance is kept). Assignments are given and they are corrected and marked on a regular basis. There are 3 to 4 midterm exams and a take-home exam during the semester. Students get an offered final grade based on the marks received for those exams. 10.2. Exam Period In the exam period: if the student does not get or accept an offered final grade, an oral exam is obligatory. If the marks given during the semester for the assignments and the exams are not exceeding a given level, the student has to pass a written pre-exam whose successful completion is the condition to be examined orally. In case of a missing take-home exam, the student should present it as well before the oral exam. 11. Make Up Policy There is a possibility to write an optional midterm exam at the end of the semester whose result replaces the least favourable mark of a previous exam. 12. Office Hours/Consultation: It is possible to have consultative sessions both with the professor giving the lecture and the person leading the seminars, if needed. 13. Lecture Notes, Textbook, Resources, Recommended Reading: E. Keszei: Thermodynamics – an Introduction, Springer, 2012 M.J. Pilling, P.W. Seakins: Reaction Kinetics, Oxford, 1993 P.W. Atkins: Physical Chemistry, 7th edition, London, 1998 Electroanalytical Methods (ed. F. Scholz), Springer, 2010 A.J. Bard, L.R. Faulkner: Electrochemical Methods, Wiley, 2001. Electrochemical Dictionary (eds. A.J. Bard, G. Inzelt, F. Scholz), 2nd edn.,Springer, 2012. 14. Learning Strategy: Knowledge of the material discussed at the lectures and the seminars. Solving assignments and writing midterm exams and the take-home exam. In case the student does not get or accept an offered final grade, an oral exam is necessary. 15. Syllabus Written by (Name, Title, Department/Institution) Keszei, Ernő, professor of chemistry, Department of Physical Chemistry Inzelt, György, professor of chemistry, Department of Physical Chemistry 16. Enforcement Date: September 1, 2014