Oklahoma State University

Chemistry 241 - Fall 09

FDB-Chem 241

Chemistry 241
Ye Olde Physical Chemistry
Fall Semester 2009



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@mst.edu
Office Hours: 3:00 - 4:00 M, T, Th, (usually, please check with me if you know for sure you are coming by) or by appointment.

Tentative Outline
Topic (Engel and Reid)

  • Properties of Gases (1, 7.1-7.4)
    1. Equations of State
      1. Thermal Equilibrium and Temperature
      2. Gas Laws
    2. Gas Laws
      1. Models
      2. Critical Behavior
      3. Other Factors
    3. Intermolecular Forces
      1. Hard Sphere
      2. Square Well
      3. Others
    4. Mixed Gases
      1. Dalton's Law
      2. Amagat's Law
      3. Virial Coeficients


  • First Law of Thermodynamics and Related Quantities (2)
    1. Basic Concepts
      1. Definitions
      2. Heat, Work and Energy
      3. Heat Capacity
      4. First Law
    2. Changes
      1. State and Path Functions
      2. Work
    3. Enthalpy and Internal Energy
      1. Enthalpy
      2. Calulations for Ideal Gases

    •  

  • Enthalpy and Internal Energy Calculations (3)
    1. Some Formalism
      1. Changes
      2. Some Tricks
      3. Application
    2. Dependence of U and H on ...
      1. U(T,V)
      2. H(T,P)

  • Exam 1

     
  • Thermochemistry (4)
    1. Standard Enthalpy Changes
      1. Physical Changes
      2. Chemical Changes
    2. Standard Enthalpies of Formation
      1. From Reaction
      2. Temperature Dependence
      3. Measurement

  • The Second Law of and Beyond (5)
    1. Heat Engines
      1. Engines
      2. Carnot Cycle
      3. Other Engines
    2. Entropy
      1. Cyclic Path
      2. Entropy Changes
      3. Second Law
    3. Third Law
      1. Entropy at Low Temperatures
      2. Low Temperature Behavior
      3. Third Law Entropies

  • Chemical Equilibria (6, 7.5)
    1. Free Energy
      1. Helmholts Free Energy
      2. Gibbs Free Energy
      3. Work and Free Energy
    2. Some Useful Relationships
      1. Basic Definitions
      2. Basic Differentials
      3. Maxwell Relationsips
      4. Working Equations
    3. More Gibbs Energy
      1. General
      2. Temperature Variation
      3. Pressure Variation
    4. Deformation of Soilds
      1. Basic Concepts
      2. Reversible Extension
      3. Calculations
    5. Mixtures
      1. Chemical Potential
      2. Mixtures
      3. Mixing of Ideal Gases

  • More Chemical Equilibria (6)
    1. Free Energy and Eq. Consts.
      1. Free Energy
      2. Equilibrium Constants
      3. Estimation from ΔGr
    2. Temp. and Pressure Effects
      1. Temperature
      2. Pressure
    3. Extent of Reaction
      1. Mole Fraction Constant
      2. Mole and Concentration Constants
      3. More Examples

  • Exam 2

     
  • Phase Behavior (8)
    1. Phase Stability
      1. Phase
      2. Chemical Potential, μ
      3. Phase Boundaries
      4. Order of Transitions
    2. Surface Tension Some Additional Information
      1. Relationships
      2. Young-Laplace Equation
      3. Capillary Rise
      4. Liquid Droplets on Solids

    •  

  • Solutions (9)
    1. Important Quantities
      1. Comparison
      2. Partial Molar Quantities
    2. II. Two-Comp. Sys. (T-Fixed)
      1. Vapor Pressure Diagrams
      2. Liquid-Vapor Diagrams
    3. III. Two-Comp. Sys. (P-Fixed)
      1. Distillation
      2. Liquid-Liquid Diagrams
    4. IV. Colligative Properties
      1. Gibbs-Duhem Eq.
      2. Boiling Point Elevation
      3. Freezing Point Depression
      4. Osmotic Pressure
    5. V. Activity
      1. Solvent Activity
      2. Solute Behavior
      3. Equilibrium

    •  

  • Electrolyte Solutions (10) and Electrochemistry (11, part)
    1. I. Ionic Solutions
      1. Thermodynamic Functions
      2. Measurement/Estimation
      3. Activity Coefficients
      4. Equilibria
    2. II. Electrochemical Cells
      1. General
      2. Electrical Work
      3. Nernst Equation
    3. III. Cell Potentials
      1. Standard Potentials
      2. Electrochemical Series
      3. Temperature Dependence
      4. Batteries

    •  

  • 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 Personal Home Page

Suggestions for this page should be made to fblum@mst.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 chem241@lists.mst.edu.

Text:

Primary: Physical Chemistry, Engel and Reid, Pearson, 2006.

Grading/Exams (Tentative):

Grades will be based on 3 - 100 pt. exams, homework sets/quizze(s) worth 100 pts total. Exams will be announced prior to being given. You will be allowed to bring a calculator, one notecard (w/ equations, etc.), and a ruler (optional) 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 9/11 P1.10, P7.5, P7.11 (1/RT in middle equation should be eliminated), FDB1, FDB2 any/all of the exercizes,
Exam 1 9/23 PS #2 9/17 P2.9, P2.29, P2.40, FDB3, P3.11, P3.37 (you may use an underived formula in the chapter) P3.15
PS #3 10/12 P4.12, P4.22, P5.6, P5.21, P5.39, P5.46
PS #4 P6.5, P6.21, P6.33, P6.38, FDB4 (plot)
Exam 2
 10/4 PS #5 2 Dec P8.1, P8.15, P8.17, P8.34, P9.1(also plot like Fig 9.13, and calc ai's), P9.5, P9.26, FDB5 (plot)
PS #6 7 Dec. (will accept later) P10.10, P10.22, P10.25, P11.16, P11.24, P11.27
PS #7
Exam 3 Wednesday 1:30 - 3:30 PS #8
PS #9


FDB1 (20 pts)
The PV data for a real gas at 298 K was obtained as shown below. a) Fit the data to the van der Waals equation by determining the best fit, a and b parameters. Two significant figures are satisfactory for a and b. (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.)
b) Estimate the second virial coefficient from a plot of Z vs. 1/Vm.
Make two plots (preferably on the same page) using your choice of software. Plot i) P vs Vm. Plot the van der Waals best fit and also show the curve for an ideal gas. ii) Plot Z vs 1/Vm and show the fit to the virial equation.
c) How do the estimates of the virial coefficient compare from the two different ways?
Remember, 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)
1.00E-03
1.25E-03
1.50E-03
1.75E-03
2.00E-03
2.50E-03
3.00E-03
4.00E-03
5.00E-03
6.00E-03
 P (Pa)
2.22E+06
1.82E+06
1.54E+06
1.33E+06
1.17E+06
9.49E+05
7.97E+05
6.03E+05
4.85E+05
4.06E+05

FDB2
This is trickier than it sounds ar first. One mole of CO2 and one mole of N2 at 298 K and 50 bar, were held in two different containers, with a valve between them. The valve was opened and the gases allowed to mix at constant temperature and constant total volume. Assuming that these are both van der Walls gases, calculate the total pressure after mixing at at 298 K if a) Dalton's Law and b) Amagats's Law holds. (Hint: Calculate the volumes of each first.)

FDB3
For the reversible processes for an ideal gas with CV = (3/2)R (as discussed in class):
Step A - A gas at P1, V1 and T1 is expanded to V2 at constant pressure. Then
Step B - The gas is heated/cooled back to T1 at constant volume. Then
Step C - The gas is isthermally compressed back to the original conditions.

Calculate ΔU, q, w, and ΔH for Step C.
Calculate ΔU, q, w, and ΔH for the entire process (I did them for steps A and B in class).
Please do your answers in l•atm. Then they can match up with mine.

FDB4. Calculalate the fugacity coefficients of methane at 100, 500, and 1000 atm (plot the appropriate plot) at T=203K for which the data below are given.
P (atm) Z
1 0.9940
10 0.9370
20 0.8683
30 0.7928
40 0.7034
50 0.5936
60 0.3429
100 0.3767
120 0.4259
140 0.4753
160 0.5252
180 0.5752
200 0.6246
250 0.7468
300 0.8663
400 1.0980
500 1.3236
600 1.5409
800 1.9626
1000 2.3684

Problem FDB-5 - Osmometry of Polystyrene
The osmotic pressure of polystyrene in cyclohexane was measured at 34oC.

c(g/cm3)		0.0081	0.0201	0.0964	0.180	0.257
 π (kPa)		0.275	0.728	3.49	8.59	17.2


Evaluate the molecular mass and second (and if needed third) virial coefficient from this data.