Oklahoma State University

Chemistry 241 - Spring 09

Sp09F08

Chemistry 241
Ye Olde Physical Chemistry
Spring 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)

  • 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, 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 1/28 P1.20, P7.6, P7.15, FDB1, FDB2, any/all of the exercizes, P7.21
PS #2 2/16 P2.18, 2.24, 3.16, 3.19, 3.29, FDB3 P3.2
Exam 1 Feb. 20 PS #3 5.8, 5.27, FDB4 (20 pts) Concepts
PS #4 3/16 6.2, 6.6, 6.16, FDB5 (20 pts)
PS #5 4/1 P6.27, P6.29
Exam 2
 April 15 PS #6 4/13 P8.1, P8.10, P8.18, P8.34
PS #7 5/1 P9.9, P9.14, P9.17, P9.27, FDB6 (20 pts) be sure you know how to read vapor pressure/temperature diagrams
Exam 3 Tuesday 4-6 PS #8 5/1 -may be delayed until 5/6 P10.19, P10.28, P11.7, P11.11, P11.23
PS #9


FDB1
The PV data for a real gas at 298 K 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)
1.00E-04
1.25E-04
1.50E-04
1.75E-04
2.00E-04
2.50E-04
3.00E-04
4.00E-04
5.00E-04
6.00E-04
P (Pa)
3.90E+07
2.80E+07
2.20E+07
1.80E+07
1.50E+07
1.15E+07
9.20E+06
6.60E+06
5.20E+06
4.30E+06
 -->
Replacement data. Also plot Z vs P in part 2.		 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. 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 liquified gas is heated back to STP, it had a volume of 80.7 ml. Calculate the mole fraction of ammonia using Amagat's law.

FDB3 (20 pts, after a problem from Noggle)

From the data below, (i) plot the data
(ii) fit the data to C(p) = a + b*T + c*T^2 + d*T^3
(iii) calculate the average Cp
(iv) compare the enthalpy required to heat graphite from 298 to 3000 K at constant pressure via steps i, ii and iii.

T(K) 298, 500, 1000, 1500, 2000, 2500, 3000
Cp(J/Kmol) 8.53, 14.63, 21.54, 23.84, 24.54, 25.00, 25.34

FDB4 (20 pts) The entropy of water.

The following data is for the heat capacity of water from three different sources (hence the different units, so be careful. I suggest that you convert everything to J/K mol). I tried to arrange these in columns so you don't have to retype them.

Part A. Verify the Debye law for the low temperature data (show the appropriate plot). 
T(K)	Cp(cal/K mol)
9.47	0.056
9.88	0.063
10.46	0.075
11.35	0.096
11.55	0.102
12.10	0.118
12.85	0.141
Part B. Plot the heat capacity of water from 0 K to 1000 K.
Part C. Plot either Cp/T vs T or Cp vs lnT.
Part D. Calculate the absolute entropy at 298 K (compare with textbook) and 700 K.
Data for solid water
T(K) Cp(cal/K mol)
10	0.066
20	0.490
30	0.984
40	1.466
50	1.896
60	2.304
70	2.701
80	3.075
90	3.448
100	3.796
110	4.130
120	4.434			
130	4.728
140	4.993
150	5.265
160	5.550
170	5.845
180	6.142
190	6.438
200	6.744
210	7.073
220	7.391
230	7.701
240	8.013
250	8.326
260	8.642
270	8.960
 Data for liquid water
T(°C) Cp(kJ/kg K)
0.01    4.210
5	4.204
10	4.193
20	4.183
30	4.179
40	4.179
50	4.182
60	4.185
70	4.191
80	4.198
90	4.208
100	4.219
 Data for water vapor. 
T(K)	Cp(kJ/kg K)
325	1.871
350	1.88
375	1.89
400	1.901
450	1.926
500	1.954
550	1.984
600	2.015
650	2.047
700	2.08
750	2.113
800	2.147
850	2.182
900	2.217
950	2.252
1000	2.288

FDB5. The data below is for CO2.
Part A. Plot the appropriate function which can be integrated to lnφ.
Note: You can extrapolate the data to P = 0.
Part B. Calculate the fugacity coefficient for P = 500 atm and 1000 atm.		 
P(atm)   Z
   0     -
  50   0.8772
 100   0.7489
 150   0.6384
 200   0.5922
 250   0.6075
 300   0.6471
 400   0.7551
 500   0.8729
 600   0.9928
 700   1.113
 800   1.2280
 900   1.3422
1000   1.4534

FDB6. Problem borrowed from Atkins, Physical Chemistry.

For polychloroprene (ρ = 1.25 g/cm3) in toluene (ρ = 0.858 g/cm3) at 30 °C, the following data were found. Plot the appropriate data, then calculate the molecular mass and second virial coefficient for this polymer-solvent system.

c(mg/cm3)	π(N/m2)
1.33		 30
2.10		 51
4.52		132
7.18		246
9.87		390