ChE421

Chemical Engineering Thermodynamics, Fall, 2009

I. COURSE OBJECTIVES

At the end of the semester, students are expected to

be able to apply the theory of the first and second law of thermodynamics to engineering applications, especially the chemical engineering processes involving the exchanges of energy and work of fluids.
be able to estimate the thermodynamic properties under various process conditions, such as enthalpies, entropies, fugacity coefficients, activity coefficients, and Gibbs energies of individual components in a multicomponent vapor/liquid mixture, and,
be able to predict the equilibrium compositions of mixtures under phase and chemical-reaction equilibria.

II. INSTRUCTOR AND MEETING TIMES

Instructor: Professor Wei-Yin Chen

Office: Room 140, Anderson Hall
Telephone: 915-5651
E-mail: cmchengs@olemiss.edu
Class: 4:15 pm - 5:30 pm, Tuesdays and Thursdays
Recitation Sessions: 1:30 p.m. - 2:30 p.m. Monday
Office Hour: 2:30 - 4:00 pm Tuesdays and Thursdays, or by appointment

III. TEXTBOOKS:

Smith, J.M., H.C. Van Ness, and M.M. Abbott, "Introduction to Chemical Engineering Thermodynamics," 7^th ed., McGraw-Hill, New York (2005).
Chen, W.Y., "Study Guide for Chemical Engineering Thermodynamics," University of Mississippi, revised, 2005.

IV. REFERENCES:

Reid, R.C., J.M. Prausnitz, and T.K. Sherwood, "The Properties of Gases and Liquids," 5th edition, McGraw-Hill Book Company (2000).
Sandler, S., "Chemical and Engineering Thermodynamics," 3rd edition, Wiley, New York (1999).
Elliott, J.R., and C.T. Lira, "Introductory Chemical Engineering Thermodynamics," Prentice Hall, Englewood Cliffs, New Jersey (1999).
Prausnitz, J.M., R.N. Lichtenthaler, and E.G. de Azevedo, "Molecular Thermodynamics of Fluid-Phase Equilibria," 3nd Edition, Prentice Hall, Englewood Cliffs, New Jersey (1999).
Tester, J.W., and M. Modell, "Thermodynamics and Its Applications," 3rd edition, Prentice Hall, New Jersey (1996).
Kyle, B.G., "Chemical and Process Thermodynamics," 3rd Ed., Prentice Hall, Englewood Cliffs, New Jersey (1999).
Walas, S.M., "Phase Equilibria in Chemical Engineering," Butterworth-Heinmann, Boston, MA (1985).
Denbigh, K., "The Principles of Chemical Equilibrium," 4th Edition, Cambridge University Press, London, England (1981).
Winnick, J., "Chemical Engineering Thermodynamics," Wiley, New York (1997).

V. Exams/Tests/Homework:

There will be two hourly exams, and one final exam. Homework will also be assigned every week, and the exam problems will be in similar nature of, but not be verbatim from, the homework assignments.

VI. Grading:

Homework 200 points
Hourly Exams 200 points
Final Examination 200 points
___________________________________________
Total 600 points

Total grade will be given according to a scale similar to the following:
600 < A < 480
479 < B < 420
419 < C < 360
359 < D < 300
299 < F
Depending on examination difficulty, this scale may be relaxed.

Because the level of difficulties of the materials, attendance is very important for the course. In accordance with Departmental policy, students missing more than 9 class periods are subject to direct grade penalties. Penalties may be assessed without regard to the student's performance.

Students are expected to keep up with the material as it is presented and submit assignments on time; most students find this difficult without regular class attendance. Successful learning involves the following important steps

    1. Attend all classes and listen carefully
    2. Do not fall sleep
    3. Do not hesitate to ask questions in or out of the classroom
    4. Do not play crosswords
    5. Practice, practice and practice

VII. TENTATIVE COURSE SCHEDULE

Number
of Week
Week of Topics Reading Assignments

1 August 23 Introduction & review of first law of thermodynamics Chapter 1 and 2

2 August 30 Volumetric properties of pure fluids Chapter 3

3 September 6 Volumetric properties of pure fluids Chapter 3

4 September 13 Heat effects Chapter 4

5 September 20 Second law of thermodynamics Chapter 5

6 September 27 Thermodynamic properties of fluids, Exam I Chapter 6

7 October 4 Thermodynamic properties of fluids Chapter 6

8 October 11 VLE: introduction Chapter 10

9 October 18 Solution thermodynamics: theory Chapter 11

10 October 25 Solution thermodynamics: theory Chapter 11

11 November 1 Solution thermodynamics: applications Chapter 12

12 November 8 Solution thermodynamics: applications; Exam II
(teacher away at AIChE annual meeting) Chapter 12

13 November 15 Solution thermodynamics: applications and chemical-reaction equilibria Chapters 12 & 13

14 November 22 :) Fall Break and Thanksgiving :)

15 November 29 Chemical-reaction equilibria Chapter 13

16 December 6 Final Exam, 4:00 p.m., Monday, December 9

VIII. MATHCAD PROGRAMS

Download MathCad programs: MCPH, ICPH, MCPS, ICPS, MDCPH, IDCPH, MDCPS, IDCPS, HRB, SRB, and PHIB: (v.2001i format)
http://home.olemiss.edu/~cmchengs/CHE421/programs.mcd

IX. HOMEWORK ASSIGNMENTS

Chapter 2: #2(a), #4, #13, #29, #31, and the problem below:
"Cylinders of compressed gas are being filled from a supply system where the pressure and temperature are 13.6 bar and 294 K. The cylinders are originally evacuated and then connected to the supply system and filled rapidly until the cylinder pressure is equal to the supply pressure. The cylinder is then disconnected and stored in a room where the temperature is 294 K. Assuming the filling occurs at adiabatically, what will be the cylinder pressure when the cylinder and the contents have reached 294 K? Assume ideal gas behavior and constant heat capacity, Cp, of 30 kJ / (kmol K)."
Ans:
    #2   (a) 1.715 kJ, (b) 1.429 kJ, (c) 20.014 deg C, (d) -1.715 kJ
    #4   134.875 W
    #13   27.78 degC
    #29   578.36 m/s, 1.493 cm
    #31    (a) 4200 BTU, 10920 BTU (b) -7000 BTU
    Extra problem: 9.831 bar

Chapter 3: #1, #9, #17, #33, #40(for system "a" of #38), #45, #48, #49, #53
Ans:
    #1   226.2 bar
    #9   (b) State 1: 600 K, 10 bar; State 2: 600 K, 3 bar; State 3: 400 K, 2 bar; State 4: 378.831 K, 2 bar
           (c) Step 41 (state 4 to state 1): deltaU = 4.597*10^3 J/mol, delatH = 6.436*10^3 J/mol, Q = 0, W = 4.597*10^3 J/mol;
                Step 12 (state 1 to state 2): deltaU = 0, delatH = 0, Q = 6.006*10^3 J/mol, W = -6.006*10^3 J/mol;
                Step 23 (state 2 to state 3): deltaU = -4.157*10^3 J/mol, delatH = -5.82*10^3 J/mol, Q = -4.157*10^3 J/mol, W = 0 J/mol;
                Step 34 (state 3 to state 4): deltaU = -439.997 J/mol, delatH = -615.996 J/mol, Q = -615.996 J/mol, W = 175.999 J/mol;
    #17 (b) W = 878.9 kJ
    #33 (a) V = 1625 cm^3/mol, Z=0.907,
            (b) V = 1634 cm^3/mol, Z=0.912,
            (c) V = 1622.7 cm^3/mol, Z=0.906
            (d) V = 1624.8 cm^3/mol, Z=0.907,
            (e) V = 1605.5 cm^3/mol, Z=0.896.
    #40 PR EOS: V_liquid=92.2 cm^3/mol, V_vapor=1454.5 cm^/mol;
            Rackett:: V_liquid=94.2 cm^3/mol;
            Pitzer/Virial: V_vapor=1537.8 cm^/mol; Note we can use Lee/Kesler to estimate V_liquid that requires extrapolation.
    #45 98.213 kg
    #48 9920 kPa
    #49 42.68 bar
    #53 0.532 g/cm^3

Chapter 4: #2(b), #3, #11(for chloroform), #21(e, f), #22(f), #26, #28, #32
Ans:
    #2   (b) 1413.8K
    #3   3.469*10^3 BTU
    #11 (a) 245 J/gm,   (b) 247.7 J/gm
    #21 (e) -367,582 J, (f) -2,732,016 J
    #22 (f) -2,716,381 J
    #26   -333.509 kJ
    #28   -6748436 J
    #32 54881 J

Chapter 5: #3, #8, #9, #29, #43
Ans:
    #3 (a) Q_H=1.583*10^5 kW, Q_C=6.333*10^4 kW
          (b) Q_H=2.714*10^5 kW, Q_C=1.764*10^5 kW
    #8   entropy change of water = 1.305 kJ/(kg K), entropy change of reservoir = -1.121 kJ/(kg K), total entropy change = 0.184 kJ/(kg K).
    #9   (a) 20.794 J/K   (b) deltaS_total=20.794 J/K
    #29 0.5 (equal numbers of moles), 12.97 J/(K mol)
    #43 S_G=0.27 kJ/K, W_lost=81.039 kJ

Chapter 6: #2, #3, #8, #11, #14(a), #18, #21, #28, #33, #50, #60, #61, #82, #87(g)
Ans:
    #8     delatS=0.733 J/(mol K),   deltaT = -0.768 K
    #21   deltaH=377.1 BTU/lbm,   deltaS=0.266 BTU/(lbm R)
              ideal gas: delatH=372.536 BTU/lbm,   deltaS=0.259 BTU/(lbm R)
    #28   1.268 J/(gm K)    ideal gas: 1.302 J/(gm K)
    #33   -869.9 kJ
    #50   184.2 cm^3/mol, deltaH=6734.9 J/mol, deltaS=-15.9 J/(mol K)
    #60   302.71 K, deltaS=22.36 J/(mol K)
    #61   (a) 308.19 K, -11852 J/mol
             (b) 303.11 K, -11567 J/mol
    #82   1.961 kg/s, S_G=4.194 kJ/(s K)
    #87   (g) VR = -92.045 cm^3/mol, HR = -554.403 J/mol, SR = -2.469 J/(mol K)

Chapter 10: #1, #2(b), #17, #25, #30
Ans:
#1    (a) y1=0.545, P=109.303 kPa   (b) x1=0.169, P=92.156 kPa   (c) y1=0.542, T=103.307 C
        (d) x1=0.173, T=109.131C   (e) x1=282, y1=484    (f) V=0.238
#2    (b) Please see the graphical results at the end of this section.
#17 (a) P_bubble=47.971 kPa, y1=0.196 (b) P=42.191 kPa, x1=0.0104 (c) azeotrope: x1=y1=0.857, P=81.366 kPa
#25 and #30 Similar to Examples 10.4 through 10.6 in the textbook. Please use spreadsheet for your calculations.

Chapter 11: #2, #3, #13, #16, #18, #23(b), #24(a), #27, #28
Ans:
    #2   deltaS=38.27 J/K
    #3   deltaS=1411 J/(s K)
    #16    See the graphical results at the end of this section.
    #18    (a) 18.76 bar (b) 73.169 bar
    #23    (b) 2.zzz bar
    #24    (a) See the graphical results at the end of this section.
    #27    (a) phi1 = 1.019, phi2 = 0.881, phi3 = 775, f1 = 7.491 bar, f2 = 13.254 bar, f3 = 9.764 bar
              (b) phi1 = 0.977, phi2 = 0.88, phi3 = 759, f1 = 7.182 bar, f2 = 13.251 bar, f3 = 9.569 bar
    #28    See the graphical results at the end of this section.

Chapter 12: #1, #12, #14, #16, #27, #32, #39, #46, #52
For #12, #14 and #16, calculations should be conducted for the 1-propanol (1) / water (2) system; please also note the statement before Problem 12.12 (in the middle of p.473 of textbook) for these problems.
Ans:
   #1    a) root-mean-square (RMS) error = 0.399 kPa, b) 0.454 kPa, c) 0.48 kPa,
           d) 0.167 kPa, e) 0.286 kPa, f) 0.305 kPa. Draw the figures for comparison.
   #12 See the graphical results at the end of this section.
   #14 See the graphical results at the end of this section.
   #16 (a) P_bubble = 31.33 kPa, y1 = 0.413
           (b) P_dew = 27.79 kPa, x1 = 0.042
           (c) V = 0.813, x1 = 0.08, y1 = 0.351
           (d) P_azeotrope = 31.511 kPa, x1 = 0.4386
   #27 V = 2243 cm^3 / mol, V = 2250 cm^3 / mol
   #32 -646.905 J
   #39 16.298 C
   #46 20880 BTU/s
   #52 131.2 BTU/lbm, 155 F.

Chapter 13: #2, #5(a), #9, #11, #18, #34
Ans:
#2 See the results shown at the end of this section.
#5 (a) See the graphical results at the end of this section.
#11 yHCl = 0.3508, yO2 = 0.0397, yH2O = 0.3048, yCl2 = 0.3048.
#18 (a) y1=0.0186, y_H2O=0.7814 (b) y_steam=0.8682
#34 (d) 3.638 (f) 0.924

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Number of Week	Week of	Topics	Reading Assignments
1	August 23	Introduction & review of first law of thermodynamics	Chapter 1 and 2
2	August 30	Volumetric properties of pure fluids	Chapter 3
3	September 6	Volumetric properties of pure fluids	Chapter 3
4	September 13	Heat effects	Chapter 4
5	September 20	Second law of thermodynamics	Chapter 5
6	September 27	Thermodynamic properties of fluids, Exam I	Chapter 6
7	October 4	Thermodynamic properties of fluids	Chapter 6
8	October 11	VLE: introduction	Chapter 10
9	October 18	Solution thermodynamics: theory	Chapter 11
10	October 25	Solution thermodynamics: theory	Chapter 11
11	November 1	Solution thermodynamics: applications	Chapter 12
12	November 8	Solution thermodynamics: applications; Exam II (teacher away at AIChE annual meeting)	Chapter 12
13	November 15	Solution thermodynamics: applications and chemical-reaction equilibria	Chapters 12 & 13
14	November 22	:) Fall Break and Thanksgiving :)
15	November 29	Chemical-reaction equilibria	Chapter 13
16	December 6	Final Exam, 4:00 p.m., Monday, December 9