Exam Two Review, Chemistry 331W, Spring 2004, Dr. Mahler

Review Topics for Exam Two                                   Physical Chemistry II 331W            

Spring 2004                             Lycoming College                                       Dr. Mahler


Please note that almost all of the ‘discussion questions’ are useful (i.e. the first several exercises for each chapter);


Chapter 24, Sections 24.1, 2, 3, 4, 5, and 6.

Kinetic Theory of ideal gases; Molecular motion in gases; Various speeds (mean, rms, etc.); Mean free path, collision flux and frequency; Effusion and Graham’s Law; Flux and the three transport properties of ideal gases – diffusion, thermal conductivity, viscosity (and their coefficients); Conductance and (molar) conductivity, limiting molar conductivity, strong and weak electrolytes; Kohlrausch’s Law, degree of deprotonation, and Ostwald’s Law.

Chapter 24: Exercises 5, 8, 9, 11, 12, 14, 16, 17, 28;



Chapter 25, all sections (1-8)

Kinetics - some lab techniques for measuring it; rate, stoichiometric number and rate of formation/consumption; rate laws, rate constant (and units), order (overall and of individual species); differential and integrated rate laws (0th, 1st, 2nd order); half-lives and k; Reactions approaching equilibrium; Arrhenius equation and parameters (activation energy and frequency factor), temperature dependence of rate; Temperature jump method. Reaction Mechanisms; Elementary reactions – molecularity; observed vs. predicted (theoretical) rate laws; Consecutive elementary reactions; Three assumptions used to determine rate laws from mechanisms: rate determining step, steady state approximation, pre-equilibrium (plus uses, conditions of each); Kinetic isotope effect (primary and secondary) and causes; Unimolecular reactions and the Lindemann-Hinshelwood mechanism, assumptions needed to make it first and second order; Activation energy of a composite reaction – positive and negative activation energies.


Chapter 25: Exercises 6 - 12, 14 - 16, Problems 1, 12, 18;


Chapter 26, Sections 1, 2, 3, 4, 5, 6, 7, 11, 12.

Use of the three assumptions to determine rate laws from mechanisms (rate determining step, steady state approximation, pre-equilibrium); Chain reactions; chain carriers; steps in a chain mechanism initiation, propagation, retardation, inhibition, termination); rate laws for chain mechanisms; explosions (thermal and chain-branching); explosion limits in H2 + O2 à H2O; Polymerization kinetics; Stepwise and Chain polymerization and mechanisms; kinetic chain length; Homogenous catalysis and Enzyme kinetics, Michaelis-Menten mechanism, maximum velocity and turnover number; Autocatalysis (brief); Photochemical processes and mechanisms; Quantum yield (primary and overall); Photochemical rate laws; Photosensitization; brief quenching.


Chapter 26: Exercises 5, 6, 8 -12, Prob. 6, 12;


Chapter 27, Sections 1, 2, 6, 7, 8

Molecular reaction dynamics;  Collision theory and using collision frequency to get collision density; Limitations on collision theory - steric requirements and activation energy; steric factor p and harpoon theory; Diffusion controlled reactions (diffusion controlled limit and activation-controlled limit); Reactive collisions and potential energy surfaces, translational and vibrational motion, attractive and repulsive surfaces.


Chapter 27: Exercises 4, 5, 7, (15, 17);


Chapter 11, Sections 1, 2,

Quantum Mechanics; failures of classical physics (black body radiation, heat capacities of solids, line spectra, photoelectric effect); Quantum mechanical explanations for each of these; Planck distribution, constant and quantization; Particle-wave duality and the de Broglie relation; Photoelectric effect.


Chapter 11: Exercises 5 – 11, 15, 16, 18 – 20; (all but 19 are fair game for exam)