Download Eötvös Loránd Science University Faculty of Sciences Department of

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