Includes a historical perspective of chemical kinetics and basic physical-chemistry information (Boltzmann distribution law, harmonic oscillator, equilibrium constants, etc).
2. Reaction rate laws
Definition. Factors that influence the rates (nature of the reactants, concentration of the reactants, temperature, light, catalysts, medium).
3. Experimental methods
Conventional analytical techniques, including procedures for their application in examples of first and second order reactions, complex reactions, and enzyme catalysis. Fast reaction methods, including relaxation techniques, stopped flow, NMR, flash photolysis, single photon counting, time-resolved photoacoustic calorimetry, femtochemistry. Most of these techniques are illustrated with data collected in the authors’ labs.
4. Rate constants and reaction orders
First, second and zero-order reactions, complex reaction mechanisms (parallel, consecutive and reversible reactions), methods to solve kinetic equations (Laplace transforms, matrix, Runge-Kutta, Markov chain, Monte Carlo), simplification of reaction mechanisms (isolation method, pre-equilibrium approximation, steady-state hypothesis).
5. Collisions and molecular dynamics
Simple collisions theory, reaction cross-sections, classical trajectories, avoided crossings in potential energy surfaces, molecular dynamics.
6. Reactivity in thermalized systems
Transition-state theory, including semi-classical treatments of zero-point energy and tunnelling. Intersecting-state model.
7. Structure-Reactivity Relationships
Linear and quadratic free-energy relationships, Brönsted, Hammett and Taft relationships. Hammond postulate, reactivity-selectivity principle, Ritchi