Chemistry 241 - Fall 04

Chem 241 - F04

Chemistry 241
Ye Olde Physical Chemistry
Fall Semester 2004

Class Time/Place:
MWF 10:00-10:50
125 Schrenk Hall

Instructor Information:
Frank D. Blum, 138 Schrenk, fblum@okstate.edu

Office Hours: 3:00 - 4:00 M, T, Th, or by appointment.

Tentative Outline
Topic (Atkins and de Paula Chapters)

Properties of Gases (1)
1. Equations of State
  1. Ideal Gas Law
  2. Thermal Equilibrium
  3. Gas Laws
  4. Non-ideality Exposed
2. Intermolecular Forces
  1. Simple Potential Funcitions
  2. Virial Coefficients
3. Mixed Gases
  1. Dalton's Law
  2. Amagat's Law

First Law of Thermodynamics (2, 3)
1. Basic Concepts
  1. Definitions
  2. Heat, Work and Energy
  3. First Law
2. Heat and Work
  1. Internal Energy
  2. Work
  3. Heat and Heat Capacity
  4. Enthalpy
  5. Adibatic Changes
3. Thermochemistry
  1. Standard Enthalpy Changes
  2. Standard Enthalpies of Formation
  3. Temperature Dependence
4. Some Formalism
  1. State and Path Functions
  2. Exact and Inexact Differentials
  3. Internal Energy Changes
  4. Some Tricks
5. Joule et al.
  1. Joule Experiment
  2. Internal Energy Changes
  3. Enthalpy Changes
  4. Joule-Thomson Experiment
  5. C_p and C_v

Exam 1
The Second Law and Beyond (4,5)
1. Heat Engines
  1. Engine
  2. Carnot Cycle
  3. Other Engines/Cycles
  4. Perpetual motion (optional)
2. Entropy
  1. Cyclic Paths
  2. Second Law
  3. Entropy Changes (An example of spontaneity)
3. Third Law of Thermodynamics
  1. Entropy at Low Temperatures
  2. Low temperature behavior
  3. Third Law Entropies
4. Some Useful Relationships
  1. Basic Definitions
  2. Basic Differentials
  3. Maxwell Relationships
  4. "Working" Equations
5. Gibbs Free Energy Revisited
  1. General
  2. Temperature Variation
  3. Pressure Variation
6. Deformations of Solids
  1. Basic Concepts
  2. Reversible Extensions

Phase Behavior I (6)
1. Phase Diagrams
2. Stability and transitions
  1. Chemical Potential
  2. Phase Boundaries
  3. "Order" of Transitions
3. Surface Tension
  1. Relationships
  2. Young-Laplace Equation
  3. Capillary Rise
  4. Droplets

Solutions (7)
1. Important Quantities
  1. Composition
  2. Partial Molar Quantities
  3. Mixing
  4. Chemical Potential
  5. More Mixing
2. Colligative Properties
  1. Boiling Point Elevation
  2. Freezing Point Depression
  3. Osmotic Pressure
3. Activity
  1. Solvent (Raoult's Law)
  2. Solute Behavior (Henry's Law)

Exam 2
Phase Diagrams (8)
1. Gibbs Phase Rule
  1. Number of Phases, P
  2. Number of Components, C
  3. Degrees of Freedon, F
  4. Phase Rule
  5. One-Component System
2. Two-Component Systems T-Fixed
  1. Vapor pressure Diagrams
  2. Liquid Vapor Diagrams
3. 2-Component Systems, P-Fixed
  1. Distillation
  2. Liquid-Liquid Diagrams
  3. Regular Solutions
  4. Liquid-Solid Diagrams
4. and a little something extra to help with Phase Diagrams

Chemical Equilibria (9)
1. Free Energy and Equilibrium Constants
  1. Free Energy
  2. Equilibrium Constants
  3. Estimation of δG_r
2. Temperature and Pressure Effects
  1. Temperature
  2. Pressure
3. Extent of Reaction
  1. Mole Fraction Constant
  2. Mole and Concentration Constants
4. Aqueous Reactions/pH

Ionic Solutions and Electrochemistry (10)
1. Ionic Solutions
  1. Thermodynamic Functions
  2. Activity Coefficients
2. Electrochemical Cells
  1. Cell Potentials
  2. Standard Potentials
  3. Electrochemical Series
  4. pH
  5. Temperature Dependence

Exam 3 (Final)

Disclaimer: I will attempt to keep this information current and accurate. However, changes will need to be made in class from time-to-time and these may not necessarily be reflected in this page.

Frank's Chem. Dept. Home Page

Frank's Personal Home Page

Suggestions for this page should be made to fblum@okstate.edu .

E-mail List: If you would like to send e-mail to the entire class, you can do so by sending the mail to[List address given in class]. Text: Primary: Physical Chemistry, 6th ed., Peter Atkins, Freeman & Co..

Grading/Exams (Tentative): Grades will be based on 3 - 100 pt. exams, homework sets worth 100 pts total. . Exams will be announced prior to being given. You will be allowed to bring a calculator and one notecard (w/ equations, etc.) to class for the exam. The material covered by the exam will include the text and lecture material. Quizzes may require a calculator, but no notes may be used.

Advice and Homework:

Try to work the problems assigned by yourself. If you don't get the right answer discuss the approaches with your classmates at that point.
Please try to be neat.
Do not wait for the last minute to do the problem sets. Look at the problems assigned after each lecture. Solve the ones that we have covered material for then.
Graphs are really useful in understanding how functions and physical phenomena behave. Resist the temptation to blindly use fits without graphing the problem to see if the appropriate functions fit.
There is a lot of software on campus that both graphs and fits the data to functions.
Think about your answers. Are they physically reasonable? If not then comment on why they might be unreasonable.

Homework Hints and Additional Questions:

Schedule of Events: Note: The E identifies exercises and the P problems.

Event	Date	Prob. Set	Due	Hand-in Problems	Other Problems
		PS #1	9/8	P1.2, P1.6, P1.18, P1.23
Exam 1	Wed. Oct. 6	PS #2	9/22	E2.9b, E2.22b, P2.7, P2.19, P2.27	E2.16, P2.1, P2.3
		PS #3	9/27	P3.4 (dont believe everything you read), P3.14(trust your sign), P3.29, E3.17b, E2.37b	E3.4, E3.6, E3.8
		PS #4	10/18	E4.7b, E4.7b', E4.19b, E4.23b, P4.17
		PS #5	11/1	E5.7b, E5.11b, P 5.4, P5.15, Rubber band	E5.4, E5.6, P5.5
Exam 2	11/12	PS #6		E6.8b, E6.12b, E6.14b, P6.3, E7.4b, E7.10b, P7.9, P7.25	any/all E's
		PS #7	11/29	E8.7b, E8.8b, E8.13b, E8.17b	any/all E's
		PS #8	11/31	E9.8b, E9.13b(for part B, calc. ΔG at both temperatures), E9.19b(calc K and ΔG for both temps.), P9.22	any/all E's
Exam 3	Tues. 10:30-12:30	PS #9	12/3	E10.5b, E10.12b, E10.18b, P10.27(part b only)	any/all E's

Please check out the "other problems", plus any others you may want. Most of them are good practice.

E4.7b' - Repeat the calculation above for nitrogen (a real gas, use same C(V), assume it is described by a van der Walls gas).

P4.17
A: Calculate (and plot) the enthalpy and entropy at each temperature relative to the value at T=0 K. (do the integrals by calculating the area under the curves.
B. Compare the values of S at 200 k from that done by plotting (i) C(p)/T vs T and (ii) C(p) vs ln(T).
(you may either plot it by hand or using software, but please calculate the integral manually.)

Rubber Band:

Suppose a rubber band of 10 x 2 x 2 cm was stretched to 30 cm adibatically (q = 0). Calculate the temperature increase on stretching. Assume that C_p = 1.3 J/K g, density = 1.00 g/ml, σ = 2 x 10^6 x ε Pa. Here ε is the strain and σ is the modulus. C_p is approximately C_V. Hint: calculate Δ U which should be related to the temperature increase.