Lecture Outlines

Introduction to Chemical Kinetics and Reaction Mechanisms

  1. Utility of Chemical Kinetics
    1. Practical Aspects of Reaction Rates
    2. Specific Applied Research Areas
    3. Fundamental Studies of Chemical Reactivity
  2. Short Review of Selected Reaction Mechanisms
    1. Basic Ester Hydrolysis (Tetrahedral Intermediate)
    2. SN1 Solvolysis (Carbocation Intermediate)
    3. Aldol Reaction (Carbanion Intermediate)
    4. Allylic Oxidation (Radical Intermediate)
    5. Wolff Reaction (Carbene Intermediate)

Practical Chemical Kinetics

  1. Basic Concepts
    1. Extent of Reaction
    2. Dynamic Equilibrium
    3. Reaction Order and Rate Laws
  2. Integration of Simple Rate Laws
  3. Experimental Methods
    1. Determining Reaction Order
    2. Common Kinetics Experiments
    3. Instrumentation and Special Techniques
  4. Least-squares Fitting of Experimental Data

Approximations for Complex Systems

  1. Reaction Schemes with More than One Step
    1. Elementary Steps and Mass-Action Kinetics
    2. Derivation of Rate Equations
    3. Building Mechanistic Models based on Rate Experiments
  2. Steady-State Approximation
  3. Rapid Equilibrium Approximation

Numerical Integration of Complex Rate Laws

  1. Overview of a Kinetics and Mechanism Problem
  2. Illustration using Euler's Method
  3. Programs: ODE Solvers

Introduction to Reaction Rate Theory

  1. Potential Energy Surfaces
  2. Issues for Theoretical Calculations of Rate Constants
  3. Transition State Theory
  4. Free-Energy Diagrams for Reaction Mechanisms
  5. The Rate-Limiting Step Concept

Kinetic Isotope Effects

  1. Classification of Isotope Effects
    1. Primary Isotope Effects
    2. Secondary Isotope Effects
    3. Solvent Isotope Effects
  2. Interpretation of Kinetic Isotope Effects
    1. Primary Kinetic Isotope Effects (H/D)
      1. H/D Example: Streitweiser Model
      2. Proton Transfer Case: Westheimer Effect
      3. Tunneling Contributions
      4. Guidelines
    2. Secondary Isotope Effects (H/D)
      1. SN1 Example
      2. Interpretation
      3. Acyl Transfer Example
      4. Guidelines

Structure-Activity Relationships

  1. Basis for Linear Free-Energy Relationships (LFERs)
    1. Background
    2. General Equation for LFERs
  2. Bronsted Relationships
    1. Acid Dissociation Model Reaction
    2. Base Protonation Model Reaction
  3. The Hammett Equation
    1. Model Process: Benzoic Acid Ionization
    2. General Interpretation
    3. Example
  4. Nonlinear Free-Energy Relationships
    1. Scatter
    2. Systematic Curvature
      1. Parallel Change in Mechanism
      2. Serial Change in Mechanism
      3. Change in Transition State Structure

Electron Transfer Reactions

  1. Inner Sphere
  2. Outer Sphere
  3. Marcus Equation
    1. Derivation of Simple Form
    2. Organic Example and the Inverted Region
    3. More Advanced Considerations

Proton Transfer Reactions

  1. Proton Transfer Between Electronegative Atoms
    1. Eigen Model
    2. Intramolecular Examples
    3. Theoretical Approaches to the Transfer Step
  2. Proton Transfers At Carbon Atoms
    1. Role of Electron Delocalization
    2. Marcus Theory Applied to Proton Transfers
  3. Marcus Curvature and LFERs

Enzyme Kinetics

  1. Overview of Protein Structure
    1. Primary, Secondary, Tertiary, and Quaternary Structure
    2. Active Sites of Enzymes
  2. Steady-State Enzyme Kinetics (One-Substrate Cases)
    1. Used of Rapid-Equilibrium and Steady-State Approximations
    2. Determination of V, Km, and V/Km
    3. Interpretation of V, Km, and V/Km
    4. More Complex Examples
  3. Transient Enzyme Kinetics (Pre-Steady State Emphasis)
    1. Types of Observations
    2. Qualitative View of Bursts and Lags
    3. Derivation of a Burst Equation
    4. Burst Example: Glutathione Transferase

Polymerization Kinetics

  1. Step-Growth Polymerization Kinetics
    1. Issues and Examples
    2. Derivation of a Rate Equation
    3. Degree of Polymerization
    4. Example with Rate Data
  2. Chain-Growth Polymerization Kinetics
    1. Mechanistic Issues and Reaction Steps
    2. Model for Kinetics
    3. Kinetic Chain Length and Degree of Polymerization
    4. Example

Introduction to Photochemical Kinetics

  1. Principles and Definitions
  2. Photophysical Terms / Energy Diagram
  3. Excited-State Lifetimes
  4. Stern-Volmer Studies
  5. Examples

Nonlinear Chemical Dynamics

  1. Introduction
  2. Belousov-Zhabotinsky Reaction
    1. History
    2. The Field-Koros-Noyes Mechanism (FKN)
    3. The Oregonator
    4. The Brusselator
  3. Linear Stability Analysis
  4. Continuous Stirred-Flow Tank Reactor (CSTR) Studies
    1. Reactor Design
    2. Special Types of Dynamic Behavior