Oklahoma State University

Chemistry 241 - Fall 08

Chem 241 - F08

Chemistry 241
Ye Olde Physical Chemistry
Fall Semester 2008



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)

  • 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) and Electrochemistry (11, time permitting)
    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 TBD 1-P1.11, 2-P 1.18, 3-Use the data from P1.18 to calculate the Vm for a pressure of 60 bar, 4-P7.18, 5-Problem FDB1 any/all of the exercizes
PS #2 9/23 P 2.14, P 2.25, FDB2
Exam 1 Oct. 8 (W) PS #3 10/3 P3.9, P3.15, P3.23, P4.12, P4.17 P3.2, Concepts
PS #4 10/20 P5.6, P5.12, P5.18, FDB3
PS #5 11/3 P6.4, P6.9, P6.23, P6.25, P6.28, FDB4
Exam 2
Ag-Mg phase diagram		 Nov. 14 PS #6 P8.9 plot, 8.16, P8.27, P8.32( also do for 30 nm particle and calculate the vapor pressure for a particle of this size).
13/3 PS #7 Dec 3 P9.7, P9.15 (plot the activity coefficients and activities for both species), P9.16, P9.22, P9.29, FDB5
Exam 3 Tuesday
Dec 16
4-6 PM		 PS #8 Dec 5* P10.18, P10.21, P11.4, P11.9, P11.22
PS #9

* May be handed in late with no penalty till Dec 12.

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

 

Problem FDB-1 - Virial Coefficients
The pressure/volume data for Argon is given below for 300 K. (I hope the columns line up ok)
A) Plot the pressure-volume curve for Ar and compare it to that for an ideal gas (curve).
B) Plot the compressibility as a function of 1/Vm and estimate the second (B) and third (C) virial coefficients. Show the virial fit as a continuous curve.

P(MPA)			0.4000	0.5000	0.6000	0.8000	1.000

Vm (dm^3/mol)		6.2208	4.9736	4.1423	3.1031	2.4795	

P(MPA)			1.500	2.000	2.500	3.000	4.000

Vm (dm ^3/mol)		1.6483	1.2328	0.98357	0.81746	0.60998

Problem FDB-2 - Virial Coefficients

For Cl2 gas, calculate ΔU for heating one mole of Cl2 from 400 to 1600 K at constant volume.

T(K)		400	600	800	1000
Cvm(J/k mol)	26.99	28.29	28.89	29.19
T(K)		1200	1400	1600
Cvm(J/k mol)	29.42	29.69	29.78

Problem FDB-3 - Entropy of benzene

Problem FDB-3. (20 pts) Based on a problem from Noggle's book. Use the data below to calculate the standard entropies of benzene.
A. Plot the Cp,m for benzene as a function of temperature from 0 to 400 K. Does the initial part of the curve correspond to the Debye law. Cp prop. to T3.
B. Plot Cp,m/T vs T for benzene for the same range. Calculate the values of S (based on the third law) at 50, 100, 200, 300, 400 K. On your plot of Cp,m/T vs T , note with crosshatching or color (you can do it by hand) the integral corresponding to the increment of S added for each ΔT.
C. Calculate the So for benzene and compare this with that found in your textbook.
T (K) C(p,m,solid, J/K/mol)
13 2.866
14 3.473
15 4.167
20 8.368
25 13.159
30 17.991
35 22.531
40 26.527
50 32.991
60 37.928
70 41.735
80 44.978
90 47.823
100 50.417
120 55.698
140 61.505
160 67.906
180 75.396
200 83.722
220 93.387
240 104.098
260 116.148
278.69 128.700
Other Data (liquid)

melts at 278.69 K

ΔH(fusion) = 127.40 J/g

C(p,liq)= 1.5194 - 1.299x10-3T +6.927x10-6T2 (in kJ/kg/K)

ref: Gorbunova, V. A. et al., Int. J. Thermophysics, 3, 1, 1982. (sorry about the units.)
Other Data (vapor)

boils at 353.2 K

ΔH(vap,m) = 30.8 kJ/mol (at the boiling point)

C(p,vap)= -46.48 + 0.53735T - 3.8303x10-4T2 + 1.0184x10-7T3(in J/(K mol))

ref: Engle and Reed

Problem FDB-4 - Compressibility of toluene

FDB-4. (20 pts) Based on the compressibility of toluene vapor at 600 K. From Atkins text.
A. Plot the compressibility as a function of pressure.
B. Plot the appropriate function which integrates to lnφ (φ = the fugacity coefficient).
C. Calculate φ at 300 and 1000 bar.
P (bar) Z
0.500 0.99415
1.013 0.98896
2.00 0.97942
3.00 0.96995
5.00 0.95133
10.00 0.90569
20.00 0.81227
30.00 0.70177
42.4 0.47198
50.0 0.22376
70.0 0.26520
100.0 0.34920
200 0.62362
300 0.88288
500 1.37109
1000 2.48836

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.