Chemistry 3434
Fall, 1996
Instructor: Lionel M. Raff
Office: P.S. I - Room 107
Office Hours: By appointment.
Homework Grading: Dr. Lowell Mathews
Office: PS I - Room 206
Office Hours:1330-1520, Wed and Th
plus whenever he has time.
Course Grading:
Three hour examinations (100 points each) 300 points
Homework (approximately 10 or 11 sets) 200
Final examination (comprehensive) 167
Total Possible Points 667
Grading Scale (absolute) 500 - 667 = A
400 - 499 = B
320 - 399 = C
265 - 319 = D
0 - 264 = F
Homework Grading:
All homework is due at the start of class on the day designated.
No late homework will be accepted.
Usually 1-4 problems of each set will be graded. The grade on the
set will depend upon the score received on the problems graded.
Course Outline
I. Properties of Gases --- Barrow: Chapter 1, Chapter 2.12 to 2.16
Castellan: Chapters 2 and 3
Atkins: Chapter 1
A. Equations-of-State -- General Comments
B. Ideal Gases
1. Boyle's Approximation
2. Charles' Approximation
3. Combined Approximations
4. Avagadro's Approximation
5. Dalton's Approximation
C. Non-Ideal Gases
1. Virial Equation-of-State
2. van der Waals Equation-of-State
3. "Law" of Corresponding States
4. The Residual Volume
5. Linear Least-Squares Analysis
II. The First Law of Thermodynamics-- Levine: Chapter 2
Castellan: Chapters 6 and 7
Atkins: Chapters 2 and 3
A. Total Differentials
B. Exact and Inexact Differentials
C. Work-Heat
D. First Law of Thermodynamics
E. Heat Capacity
F. Joule-Thomson Coefficient
G. Proof of Inexactness of dq
H. Adiabatic Processes
III. Thermochemistry --- Levine: Chapter 5
Castellan: Chapter 7
Atkins: Chapter 2
A. Heats of Reaction
1. Standard Molar Heats of Formation
2. Summation of Thermochemical Equations
3. Variation with T
4. Variation with P
B. Solution Reactions
C. Bond Energies
IV. Entropy and the Second Law of Thermodynamics
Levine: Chapters 3 and 5
Castellan: Chapters 8 and 9
Atkins: Chapters 4 and 5
A. The Carnot Cycle
B. The Second Law of Thermodynamics
C. Reversible and Irreversible Processes
D. Energy and Enthalpy Differentials in Terms of Entropy
E. Temperature Dependence of S
F. Volume and Pressure Dependence of S at Constant T
G. The Joule-Thompson Coefficient- Expressions for Enthalpy
and Energy Differentials with Respect to P and V
H. The Third Law of Thermodynamics
V. The Gibbs and Helmholtz Free Energies--Chemical Equilibrium
Levine: Chapters 4 and 6
Castellan: Chapters 10 and 11
Atkins: Chapters 5 and 9
A. The Helmholtz Free Energy
B. The Gibbs Free Energy
C. The G and A Differentials
D. Maxwell's Relationships
E. Open Systems - The Chemical Potential
F. Variation of G with P at Constant T
1. Standard Gibbs Free Energies
2. Equilibrium Constants - Ideal Systems
G. Variation of G with T at Constant P - Gibbs-Helmholtz Equations
1. Variation of Equilibrium Constant with T
2. Variation of Equilibrium Constant with P
H. Non-ideal Gases - Equilibrium Constants - Fugacity
VI. Liquids and Phase Equilibrium---Daniels-Alberty: Chapter 3
Castellan: Chapters 5 and 12
Levine: Chapter 7
Atkins: Chapter 6
A. The Condition for Phase Equilibrium
B. Clasius-Clapeyron Equation
1. Application to Liquid-Vapor Equilibrium
a. Effect of T upon Vapor Pressure
b. Effect of Total Pressure upon Vapor Pressure
2. Application to Solid-Liquid Equilibrium
VII. Crystals and Solids -- Castellan: Chapters 26 and 27
Levine: Chapter 24
Daniels-Alberty: Chapter 19
Atkins: Chapters 2.7, 21
A. Thermodynamics of Solids
1. Types of Crystal Forces - Qualitative Treatment
2. Measurement of Crystal Energies
3. Calculation of Crystal Energies
4. Heat Capacity of Crystals
a. Einstein Formulation
b. Debye Formulation
B. Structure of Crystals
1. Crystal Forms
2. Crystal Indices
a. Weiss Indices
b. Miller Indices
3. The Unit Cell - The Bragg Method
4. X-Ray Analyis
VIII. Liquid Solutions - Non-Electrolytes---
Castellan: Chapters 13,14,and 16
Levine: Chapters 9,10, and 12
Atkins: Chapter 7
A. Ideal Solutions
1. Raoult's Law - Vapor Pressures
2. Thermodynamics of Mixing
3. Solubility
a. Solids in Liquids
b. Gases in Liquids
4. Henry's Law
5. Colligative Properties
a. Freezing Point Lowering
b. Boiling Point Elevation
c. Osmotic Pressure
B. Non-Ideal Solutions
1. General Considerations
2. Activities
a. Reference Function
b. Reference State
c. Activity Coefficients
d. Measurement of Activities
IX. Chemical Kinetics----- Barrow: Chapters 16 and 17
Castellan: Chapters 31 and 32
Atkins: Chapters 26, 27, and 28
A. General Considerations and Definitions --Law of Mass Action
B. Simple Systems
1. Zero-Order Reactions
2. First-Order Reactions
a. Half-Life
b. Relaxation Time
3. Second-Order Reactions
C. Determination of Reaction Order and Rate Coefficients
D. Complex Systems
1. Equilibrium Systems
2. Consecutive Reactions
3. Stationary-State Hypothesis
4. Rate-Determining Step
E. Theoretical Kinetics
1. Relationship of Rate Coefficient to T
2. Lindemann Theory of First-Order Gas-Phase Reactions
3. Transition-State Theory
4. Collision Theory
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Department of Chemistry at OSU
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Regents Professor and Chairman
Department of Chemistry
Oklahoma State University
Stillwater, OK74075
Telephone: (405)744-9047
Fax: (405)744-6007
© Lionel M. Raff --- raff@okway.okstate.edu
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