Oklahoma State University

Chemistry 241 - Fall 07

Chem 241 - F07

Chemistry 241
Ye Olde Physical Chemistry
Fall Semester 2007



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

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)

  • 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

  • Exam 1

     
  • 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

  • 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

    •  

  • Exam 2

     
  • 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)

    •  

  • Electrochemistry (11, time permitting)

    •  

  • 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@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 chem241@umr.edu

.

Text:

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

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, 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 9/5 Engel: 1.10, 7.3, 7.15, 1A , 1B any/all of the exercizes
PS #2 9/17 2.17, 2.23, 2.24, 2.28, 2.30
Exam 1 10/5 PS #3 10/1 P3.2, P3.11, P4.5, P4.15, 3A
PS #4 10/22 P5.7, P5.8, P5.18,5A(20 pts, plot required)
PS #5 10/29 P6.2, P6.7, P6.11, P7.23, 6A(20 pts, plot required)
Exam 2 11/14 PS #6 11/7 P6.28, P6.29, 6B, P8.8 (plot data), P8.13, P8.34
PS #7 11/30 9.2, 9.14, 9.23, and 9.27
Exam 3 Monday 10:30 PS #8 11/30 will accept till 12/5 10.2, 10.18, 10.22, 11.2, 11.10, 11.27 10.8
PS #9

Problem 1A. A mixture of hydrogen and ammonia at STP has a volume of 153.2 ml. The ammonia is liquefied by placing the gas in a bath of liquid nitrogen, and the remaining gas drawn off. When the remaining gas is heated back to STP, it had a volume of 98.7 ml. Calculate the mole fraction of ammonia using Amagat's law.

Problem 1B. For the following data for ethane at 700 K, determine the second and third virial coefficients. (hopefully the columns will line up).

P(MPa) 	1.0	2.0	3.0	4.0	6.0	8.0	10.0
z	 0.9998	0.9986	0.9975	0.9962	0.9962	0.9972	0.9993

When you plot the data, label the axes, title the plot, get rid of the gray (default background), do not connect the points, and draw a "best fit" curve to the data.

 

Problem 3A. Calculate the temperature change for nitrogen, originally at 25 bar and 273 K, expanding in a Joule-Thomson apparatus to 1 bar.

Problem 5A. Use the data below to calculate the standard entropy of ammonia at 298 K (units are in cal or cal/K, all for one mol).
T (K) C(p,m,solid)
15 0.175
20 0.368
30 1.033
40 1.841
50 2.663
60 3.474
70 4.232
80 4.954
90 5.612
100 6.246
110 6.877
120 7.497
130 8.120
140 8.699
150 9.272
160 9.846
170 10.42
180 11.03
190 11.71
195.42 11.98
Other Data

melts at 195.42 K

ΔH(fusion) = 1351.6

C(p,m,liq)= 17.89 (ave)

boils at 239.74 K

ΔH(vap) = 5581
T(K) C(p,m,gas)
239.74 8.36
298.15 8.49

Problem 6A. 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 6B.

For the Dang function, D = A - FL where F is the force and L is the length of an elastomer.
i. What are the Maxwell relationships for this function?
ii. What is the change in entropy if the force on an elastomer is doubled at constant temperature in terms of a, b, Lo, and T? The length of the elastomer is given as L = Lo(1 - b/T) where T is the temperature, "b" is a constant, and Lo is the length of the unstretched elastomer. Note - the length of Lo depends on temperature. Let a = (dLo/dT).


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