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

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

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;** **

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**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.

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

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 H_{2} + O_{2}
à
H_{2}O; 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 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.

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

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**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)