Oklahoma State University

Chemistry 241 - Fall 05

Chem 241 - F05 Chemistry 241
Ye Olde Physical Chemistry
Fall Semester 2005



Quick Links: Course Outline | Grading | Advice | Schedule/Assignments | Hints, Additional HW Info. |

Class Time/Place:
MWF 10:00-10:50,
126 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. Cp and Cv

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  • Exam 1

     

    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
  • The Second Law and Beyond (4,5)

    •
  • 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

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  • 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)

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  • Exam 2

     

    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
      1. Free Energy
      2. Equilibrium Constants
      3. Estimation of δGr
      1. Temperature
      2. Pressure
      1. Mole Fraction Constant
      2. Mole and Concentration Constants
    2. Free Energy and Equilibrium Constants
      3.
    3. Temperature and Pressure Effects
      4.
    4. Extent of Reaction
      5.
    5. Aqueous Reactions/pH
      1. Thermodynamic Functions
      2. Activity Coefficients
      1. Cell Potentials
      2. Standard Potentials
      3. Electrochemical Series
      4. pH
      5. Temperature Dependence
    2. Ionic Solutions
      3.
    3. Electrochemical Cells
      4.
  • Phase Diagrams (8)

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  • Chemical Equilibria (9)
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  • Ionic Solutions and Electrochemistry (10)
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  • Exam 3 (Final)

     

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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 Personal Home Page

Suggestions for this page should be made to fblum@umr.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 chem241b@umr.edu. 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. Good graphs have the following:
    • Title
    • Labelled axes, tic marks with reasonable divisions, symbols for data points, smooth curves through the fits.
    • Axes in log, not ln
    • sizes that allow the reader to see the quality of the fit/data (not tiny)
    • units when appropriate
  • 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.
  • A Useful website with information about linear least squares fits can be found at:

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 9/7 E1.10b(plots), E1.21b, E1.19b, P1.15, A1.1 any/all of the exercizes
Exam 1 9/26 PS #2 9/21 E2.40b, P2.4, P2.8, E3.12b, E3.13b, E3.16b, P3.21, A2.1 plus any others you may want.
PS #2a The graphing problem
PS #3 10/19 E416b, E4.23b, E4.26b, P4.18(double credit),P4.12
PS #4 10/24 E5.5b(It is isothermal), E5.11b, P5.4 (Calculate φ and f at 100 and 500 atm instead of what the problem calls for), P5.31, P5.32, P23.29b, P23.19
PS #5 10/31 E6.9b, E6.15b, P6.9, P6.22
Exam 2 11/9 PS #6 11/4 E7.13b, P7.9, P7.13, P7.24 Last year's Exam 2
PS #7 11/28 E8.6b, E8.12b, E8.17b, P8.2, P8.5 E8.3b, E8.10b
PS #8 11/30 E9.6b (Why is the pressure not specified?), E9.16b, E9.20b, P9.4, P9.16
Exam 3 CHANGED, Dec. 12, 4-6 PM (MONDAY) PS #9 12/3 E10.12b, E10.19b, E10.26b Last year's Exam 3

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

Problem A1.1 A mixture of hydrogen and ammonia has a volume at STP of 382.5 cm3. The mixture was chilled to liquid nitrogen temperatures and the remaining gas was removed and taken back to STP. It then had a volume of 103.5 cm3. Calculate the mole fraction of ammonia in the mixture based on Amagat's law.

Problem A2.1
The PV data for a real gas was obtained. Fit the data to the van der Waals equation and determine the best fit a and b parameters. (Hint: I did it by putting the formulae in a spreadsheet and changing the a and b till I got a good fit to the data. In the region chosen, one of the parameters may not be very sensitive.) Make two plots (preferably on the same page) using your choice of software. Plot i) P vs Vm and ii) Z vs Vm. On each graph, plot the data as symbols, and the fits for an ideal gas (dashed curve) and van der Waals gas (solid curve).

Vm (m3/mol)     P (Pa)
1.00E-04     3.90E+07
1.25E-04     2.80E+07
1.50E-04     2.20E+07
1.75E-04     1.80E+07
2.00E-04     1.50E+07
2.50E-04     1.15E+07
3.00E-04     9.20E+06
4.00E-04     6.60E+06
5.00E-04     5.20E+06
6.00E-04     4.30E+06

Problem 4.18, Additional instructions.
PART A
Plot C(p) vs T to calculate DeltaH by:
i) Integrating the area under the curve by counting boxes
ii) Integrating using the trapezoid rule
iii) Fitting C(p) = a + b*T + c*T^2 + d*T^3 and integrating this result. (I found this function to work well over the wide range of temperatures used)
Compare the results of all three ways.

PART B
Then for DeltaS:
iv) Plot C(p)/T vs T
v) Plot C(p) vs ln T
Calculate DeltaS for both iv and v using any of the ways (i, ii, or iii) in Part A.
Compare the results from iv and v.

(We did something similar in class, except that i do not like redefining G like the book does. So instead of G, define R = U - TS + PV - fL. Assume P is constant. We use f instead of the books t also. What should we call R? The Rubber Band function, I guess)