Physical Chemistry

6.

Chemical Kinetics

6.1.

Empirical Chemical Kinetics

6.1.1.

6.1.1.1.

Definition and Units

6.1.1.2.

Rate of Consumption and Formation

6.1.1.3.

Measurement Techniques

6.1.2.

6.1.2.1.

Differential Rate Laws

6.1.2.2.

6.1.2.3.

6.1.2.3.1.

6.1.2.3.2.

Order with Respect to Individual Reactants

6.1.3.

Integrated Rate Laws

6.1.3.1.

Zero-Order Reactions

6.1.3.2.

First-Order Reactions

6.1.3.3.

Second-Order Reactions

6.1.3.4.

Pseudo-Order Reactions

6.1.4.

Determination of Rate Laws

6.1.4.1.

Method of Initial Rates

6.1.4.2.

Isolation Method

6.1.4.3.

Graphical Methods

6.1.5.

Half-Life and Reaction Kinetics

6.1.5.1.

Definition of Half-Life

6.1.5.2.

Half-Life for Different Reaction Orders

6.1.6.

Temperature Dependence of Rate Constants

6.1.6.1.

The Arrhenius Equation

6.1.6.2.

Activation Energy

6.1.6.3.

Pre-exponential Factor

6.1.6.4.

Determination from Experimental Data

6.2.

Reaction Mechanisms

6.2.1.

Elementary Reactions

6.2.1.1.

6.2.1.1.1.

Unimolecular Reactions

6.2.1.1.2.

Bimolecular Reactions

6.2.1.1.3.

Termolecular Reactions

6.2.2.

Complex Reactions

6.2.2.1.

Multi-step Mechanisms

6.2.2.2.

Reversible Reactions

6.2.2.3.

Parallel Reactions

6.2.2.4.

Consecutive Reactions

6.2.3.

Approximation Methods

6.2.3.1.

The Steady-State Approximation

6.2.3.2.

The Pre-Equilibrium Approximation

6.2.3.3.

Rate-Determining Step

6.2.4.

Chain Reactions

6.2.4.1.

Initiation Steps

6.2.4.2.

Propagation Steps

6.2.4.3.

Termination Steps

6.2.4.4.

6.3.

Theories of Reaction Rates

6.3.1.

Collision Theory

6.3.1.1.

Kinetic Theory of Gases

6.3.1.2.

Collision Frequency

6.3.1.3.

Activation Energy

6.3.1.4.

6.3.1.5.

Temperature Dependence

6.3.2.

Transition State Theory

6.3.2.1.

Activated Complex

6.3.2.2.

Potential Energy Surfaces

6.3.2.3.

The Eyring Equation

6.3.2.4.

Thermodynamic Formulation

6.3.2.5.

Comparison with Arrhenius Equation

6.3.3.

6.3.3.1.

Electron Transfer Reactions

6.3.3.2.

Reorganization Energy

6.3.3.3.

Driving Force Effects

6.4.

Reactions in Solution

6.4.1.

Solvent Effects on Reaction Rates

6.4.1.1.

Polarity Effects

6.4.1.2.

Hydrogen Bonding

6.4.1.3.

6.4.2.

Diffusion-Controlled Reactions

6.4.2.1.

Encounter-Controlled Limit

6.4.2.2.

Smoluchowski Equation

6.4.3.

Activation-Controlled Reactions

6.4.3.1.

Transition State in Solution

6.4.4.

Ionic Strength Effects

6.4.4.1.

Primary Salt Effects

6.4.4.2.

Debye-Hückel Theory Applications

6.5.

6.5.1.

Homogeneous Catalysis

6.5.1.1.

Mechanism of Catalytic Action

6.5.1.2.

Catalyst Regeneration

6.5.1.3.

Acid-Base Catalysis

6.5.2.

Heterogeneous Catalysis

6.5.2.1.

Surface Adsorption

6.5.2.2.

Langmuir-Hinshelwood Mechanism

6.5.2.3.

Eley-Rideal Mechanism

6.5.3.

Enzyme Kinetics

6.5.3.1.

Michaelis-Menten Mechanism

6.5.3.2.

Michaelis Constant (Km)

6.5.3.3.

Maximum Velocity (Vmax)

6.5.3.4.

Turnover Number (kcat)

6.5.3.5.

Enzyme Inhibition

6.5.3.5.1.

Competitive Inhibition

6.5.3.5.2.

Noncompetitive Inhibition

6.5.3.5.3.

Uncompetitive Inhibition

6.6.

Advanced Topics in Kinetics

6.6.1.

Molecular Reaction Dynamics

6.6.1.1.

Potential Energy Surfaces

6.6.1.2.

Reaction Coordinates

6.6.1.3.

Molecular Beam Experiments

6.6.2.

6.6.2.1.

Ultrafast Spectroscopy

6.6.2.2.

Transition State Spectroscopy

6.6.3.

Single Molecule Kinetics

6.6.3.1.

Stochastic Processes

6.6.3.2.

Fluctuation Theorems

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