CHE 646

THE UNIVERSITY OF KENTUCKY

DEPARTMENT OF CHEMISTRY

Chemistry 646 - Chemical Kinetics


Course Description:A through study of modern chemical kinetics and reaction dynamics. Topics will include atomic spectroscopy, microwave, infrared and UV-visible spectroscopy of diatomic and polyatomic molecules, lasers, creation and detection of excited states, fluorescence, phosphorescence, radiationless processes and photochemical transformations.

Prerequisites: CHE547 or CHE548 or permission of instructor.

CHEMICAL KINETICS AND REACTION DYNAMICS

Syllabus 2006

Professor: Dennis J. Clouthier

Office:  CP-235

Office Hours:  Tuesday and Thursday Mornings  9:30-11:00 A. M.

Text:  There is no required textbook for this class.  My notes have been prepared from a large selection of recent books.  Most of the topics are covered in "Chemical Kinetics and Dynamics" by Jeffrey I. Steinfeld, Joseph S. Francisco and William L. Hase.  The second (1998) edition is available new or used from Amazon.com and would be a good reference book to have.

Course Content:

I. Review of Basic Undergraduate Concepts in Chemical Kinetics

Elementary Reactions with Simple Rate Laws

1. Zero-Order Reactions

2. First-Order Reactions

3.  Second-Order Reactions

4.  Equilibrium

Temperature Dependence of Rate Constants

II.  Experimental Methods in Chemical Kinetics

General Features

1.  Classical Methods

i.  Sampling

ii.  In Situ Measurements

iii.  Relative Rate Methods

2.  Relaxation Techniques

3.  Flash Photolysis

4.  Laser Flash Photolysis

5.  Laser-Induced Fluorescence

6.  Pump-Probe Laser Techniques

7.  Femtochemistry

III.  Analysis of Kinetic Data

Experimental or Measurement Errors

Propagation of error

Least-squares analysis of data

IV.  More Complex Kinetic Schemes

A. Single Step Reactions

1.  Pseudo-First Order Kinetics

2. Third Order Kinetics

3. Van'T Hoff  and Half-Life Plots for Determining Reaction Order

B. Multistep Reactions

1. Equilibrium

2.  The Principles of Detailed Balance and Microscopic Reversibility

3. Parallel Reactions

4.  Consecutive Reactions and The Steady State Approximation

5.  Catalysis

6.  Autocatalysis and Oscillating Reactions

7. Chain Reactions

8.  Determining Mechanisms from Rate Laws

V. Numerical Analysis of Complex Reaction Systems

Numerical Differentiation - Euler and Runge-Kutta Methods

The Stochastic Method

Sensitivity Analysis

VI.  Phase Influences on Chemical Reactions

1.  Solution Phase

2.  Surface Reactions

3.  The Gas Phase

VII.  Theories of Bimolecular Chemical Reactions

1. Simple Collision Theory

2. A Simple Introduction to Statistical Thermodynamics

3. Activated Complex Theory (ACT) or Transition State Theory

4. Thermodynamics and ACT

5.  Applications of Transition State Theory

VIII. Unimolecular Reactions

1. The Lindemann Mechanism

2. RRKM Theory

IX. Molecular Reaction Dynamics

1. State-to-State Reaction Dynamics

2. Molecular Beam Experiments and Measurement of the Reaction Cross-Sections

3. Cross-Sections

Class meetings: TR, 11:00-12:15 AM, Room CP-208

I have developed a comprehensive set of notes for this class, taken from a wide variety of reference books.  Portions of these notes will be given to you at the beginning of each class.  You will be responsible for studying them diligently before the next class, and coming to class prepared to ask questions and discuss the notes.  The remainder of the class time will be taken up with students doing problems at the blackboard in small groups.  For examination purposes, you will be responsible for all the material in the notes and in the classroom and homework problems.

There will be three examinations:

1. A written in-class hour exam on or about Mar. 2, 2006.

2. A written 2 hour exam in the evening on or about  Apr.  5, 2006.

3.  A comprehensive 2 hour final exam Tuesday May 2, 2004 at 10:30 AM in CP-208.

There will also be approximately 12 sets of problems which will be distributed in class, to be handed in during class one week from the day of distribution. These problems will be graded on a scale from 0 !10 and will count at total of 20% of your final grade.  The exams will be based largely on material similar to that in the problems.  It will be mandatory that all students hand in worked solutions to all the problems. Failure to submit all the problem sets, on time, will result in the loss of one letter grade. In order to obtain high marks on the problems it is essential to show all the details of your calculations and reasoning in a clear and understandable fashion.  The right answer without the details will not be acceptable.  My solutions to the problems will be put on reserve in the library after you receive your graded problems.

Computer Software and Hardware:

Many of the problem sets will involve the use of computer software to do least squares analysis of kinetic data, modeling of reaction rates etc.  Two computers are available for this purpose in room 150H of the Chemistry-Physics library.  SigmaPlot, a general purpose graphing and plotting program, is recommended for most applications - the manual is available on reserve in the Chem. Phys. library.  Other specialized programs are also available on these computers and will be introduced in the lectures.  There are also programs (TableCurve, Excel) available in the Chem-Phys computer labs.  Hand drawn graphs and estimates of lines through data will not be acceptable in this course.  It is up to you to learn a suitable software package and use it for the homework.

Grading:

Mid-term exam #1 .....................20%

Mid-term exam #2 .....................25%

Final exam .................................35%

Problems.....................................20%

                                                 

The cut points for letter grades in this course will be:

A  100 - 90%

B  89.9 - 80%

C  79.9 - 70%

E        <70%

These represent guaranteed minima, meaning that if you score within the quoted range, you are assured that you will receive at least that letter grade. Undergraduate students will be graded on an A, B, C, D, E scale.  The instructor reserves the right to lower the minimum grade cut points to account for variations in the difficulty of examinations.

Important Dates:  Last day to drop any course without a grade appearing on record - Feb. 8, 2006.

Last day to drop with a W on record - March 10, 2006.

Plagiarism:  “When students submit work that they represent as their own, but which in any way borrows ideas, organization or wording from another source without appropriate acknowledgment,  the students are guilty of plagiarism.”[1]  Appropriate acknowledgment means enclosing all writing that is taken from other sources in quotation marks and giving a complete reference, as shown in the previous sentence.  My advice is that you simply do not use material from any source other than your own inspiration.  For this course, this specifically means that copying off of old homework solutions, or submitting writing in the homework that is taken from the literature, off of a web page, or from the work of other students will be treated as plagiarism.  Plagiarism is an academic offense.

[1] Students Rights and Responsibilities handbook, University of Kentucky, Section 6.3.1, pg 84.

The minimum penalty for cheating in this course will be a grade of "E".

The minimum penalty for academic offenses such as plagiarism or cheating in this course will be a grade of "E".


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