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Chemical Kinetics (Graduate Level Course)

Course description and objectives:

Chemical kinetics is the study of reaction rates. CHEM 6402 combines the essential content of kinetics of chemical reactions and the new developments in molecular and reaction dynamics. The Molecular Collision Theory and the Transition state Theory will be presented and statistical approaches to the reaction dynamics will be discussed. Different modes of catalysis and a theory of catalytic action will be discussed. An overview of experimental methods of studying complex reaction kinetics will be presented. The background assumed is one year of undergraduate Physical Chemistry and enough Mathematics to be able to solve simple differential equations. Students will learn how to apply classical macroscopic methods and molecular chemical dynamics to analyze the chemical kinetic data.

Text:

Chemical Kinetics and Dynamics, by Steinfeld, Francisco and Hase. Prentice 1999. On reserve: “Chemical Kinetics and Catalysis”, by Masel. John Wiley and Sons, 2001.

Examinations and grading:

The grade will be based on one Midterm and a Final Exam (each 100 pts.), Homework Problem Sets from the text and elsewhere to be handed in (two sets by 50 pts. each) and Student’s Presentation (Selected topic from the periodic literature on Chemical kinetics, 50 pts.). The letter grade will be calculated as follows: A>90%; B>75%; C>65%; D-65%-50%; F<50%)

Course Plan / Lecture Sequence:

  1. Introduction. Basic concepts of chemical kinetics.
  2. Reaction rate, reaction order, molecularity, integrated rate laws.
  3. Temperature dependence of rate constants. The Arrhenius equation.
  4. Complex reactions. Reversible, parallel, and consecutive reactions. Steady states, catalysis, oscillations and other complexities.
  5. Kinetic measurements I. Direct and indirect methods. Fitting data to empirical rate laws.
  6. Kinetic measurements II. Relationship between rates and mechanisms. Rate determining step.
  7. Reaction mechanisms I. Mechanisms of gas phase reactions.
  8. Reaction mechanisms II. Reactions in solvents. Surface reactions.
  9. Review of Thermodynamics and Statistical Mechanics.
  10. Calculation of properties using partition functions.
  11. Collision theory. Hard-sphere collision theory. Dynamics of bimolecular collision.
  12. Transition State Theory. The RRKM model.
  13. Activation energies. The Polanyi relationship.
  14. Group discussion of selected topics. Student’s presentations (first group).
Midterm Exam (take home)
  1. Introduction to catalysis. Overview of catalytic action.
  2. Kinetics of catalytic reactions. Langmuir-Hinshelwood, Rideal-Eley and Precursor Mechanisms.
  3. Chemisorption.
  4. Catalysis by Metals. Principles of catalytic action.
  5. Catalytic trends over Periodic Table. Selection of catalysts.
  6. Supported catalysts. Specific surface area, pores, porosity. Types of porous catalysts.
  7. Autocatalysis and oscillating reaction. BZ reaction. Enzyme-catalyzed reactions.
  8. Reactions in solvents. Mechanisms of reactions in a liquid phase. Solvation. Linear free energy relationships.
  9. Transition state theory of solution reactions. Kramer’s theory.
  10. Information-Theoretical approach to state-to-state dynamics. The maximal-entropy postulate. Analysis of energy transfer processes.
  11. Kinetics of Multi-component Systems I: Combustion and Explosions.
  12. Kinetics of Multi-component Systems II: Atmospheric Chemistry.
  13. Overview lecture. Chemical kinetics and catalysis.
  14. Group discussion of selected topics. Student’s presentations (second group).
Final Exam (take home)