ChE 414

Kinetics and Industrial Chemistry

Spring 2001

110 Wartik Laboratory, MWF 3:35-4:25

Web site: www.ems.psu.edu/~radovic/kinetics.html

 

 

Instructor and Office Hours

Ljubisa R. Radovic, Professor of Energy and Geo-Environmental Engineering,

205 Hosler Building, 863-0594, LRR3@psu.edu, MWF 8:30-10 am.

 

Teaching Assistant: Kraipat Cheenkachorn (kraipat@yahoo.com or kxc236@psu.edu, 863-4537);

Office hours: MWF 4:30-5:30 pm, 109 Fenske Lab.

Grader: Anthony Kuhar (ajk173@psu.edu)

TA Intern: Michael Zangrilli (mxz138@psu.edu); Office hours, WF 11:30-1:30, Fenske Study Lounge, Sundays 7-9 pm, 201 Thomas Bldg.

 

FINAL EXAM SOLUTION:   p1        p2        p3        p4        p5        p6        p7        p8        p9

 

Grades (updated 5/7): For any remaining discrepancies see me ASAP…

[HW1*0.02 + HW2*0.02 + HW3*0.02 + HW4*0.02 + HW5*0.02 + HW6*0.02 + HW7*0.02 + HW8*0.02 + HW9*0.04 + HW10*0.02 + HW11*0.02 + HW12*0.02 + HW13*0.02 + (Q1+Q2+Q3+Q4+Q5+Q6-Qmin)/5)*0.25 + ((Ex1+Ex2+Ex3)/3)*0.45]*(100/98) + Extra Credit (variable)

A               94-100

A-             90-93

B+             85-89

B                80-84

B-                            75-79

C+             70-74

C               60-69

D               50-59

F                <50

           

Solution to Quiz #4:      p1        p2        p3

Solution to Quiz #5:      p1        p2

Solution to Quiz #6:      p1        p2

 

TextbookS

(1) Required reading:

Octave Levenspiel, “Chemical Reaction Engineering,” 3rd Edition, Wiley, 1999.

This is one of the gems of the chemical engineering literature. It was among the first textbooks of its kind back in 1962; ever since, its pedagogical value has been difficult to surpass. In particular, this textbook introduced the reciprocal rate vs. conversion plots and the residence time distribution analyses as effective diagnostic tools for different reactor types. We shall read it carefully… not everything, but as much as time allows. It literally takes the reader by the hand and does not let go at any point along the way, from the Preface to the Appendix. The instructor’s role will be to motivate, illustrate, attempt to further clarify (if necessary) and, above all, to emphasize problem-solving skills (see below).

(2) Recommended supplementary reading:

H. Scott Fogler, “Elements of Chemical Reaction Engineering,” Third Edition, Prentice- Hall, 1999. See www.engin.umich.edu/~cre.

(3) Additional reading:

-“The Engineering of Chemical Reactions,” by L. D. Schmidt,  Oxford University Press, 1998.

-Sections 7 and 23 in “Perry’s Chemical Engineers’ Handbook,” by S. M. Walas, McGraw-Hill, 1997.

 

It is always good to have a general notion about the historical developments of chemical kinetics and chemical reaction engineering. So take some time to check out these highlights of your profession…

 

Homeworks and Exams

The course will emphasize problem-solving skills. Homework problems will be assigned at the beginning of every week (except spring break); the solutions will be due, and will be discussed, every Monday. Each homework will be worth 2% of the final grade. Teamwork is encouraged, as long as it involves genuine collaboration. Use your favorite math software (e.g., Mathematica, Excel, C++, Polymath, MatLab, MathCad, E-Z Solve, Maple, Basic, Fortran) to set up problems, solve them, construct graphs and perform parametric sensitivity tests. This exercise will bring to life the equations that govern the rates of chemical reactions in their multiple engineering applications.

Many of the problems will be solved using the Mathematica software. It is strongly recommended that you use this powerful math program (if you are not yet committed to an alternative one). You can download the read-only version of Mathematica from Wolfram Research (www.wolfram.com). Mathematica is also available in computer labs on campus. For a quick introduction to Mathematica, also used in Prof. Foley’s ChE 301 class, see http://fenske.che.psu.edu/Faculty/Foley/che301/mathematicaprimer/index.html.

 

There will be three 110-minute evening tests -- scheduled for 2/5, 3/21 and 5/3 -- and six in-class quizzes (1/22, 2/19, 3/16, 3/28, 4/9 and 4/18). Each test will be worth 15% and each quiz 5% of the final grade. The five best quizzes will count toward the final grade. Both the tests and the quizzes will be open-book.

 

Homework #1

Homework #2: 3.2, 3.3, 3.9, 3.11, 3.15, 3.16, 3.20, 3.31.

Extra credit: #3.7 and 3.8 in Fogler (pp. 116-117).

Homework #3: 3.21, 3.30, 4.2, 4.6, 5.1, 5.4, 5.5, 5.8, 5.11, 5.14, 5.25, 5.26, 5.28, 5.29

Homework #4: 5.22, 5.23, 6.1, 6.3, 6.4, 6.6, 6.8, 6.19, 6.20.

Extra credit: #2.5, 2.6 and 4.7 in Fogler.

Homework #5: 2.11, 2.14, 6.2, 6.5, 6.9, 6.10, 6.18, 7.8, 7.9.

Extra credit: #4.8 and 4.16 in Fogler.

Homework #6: 7.14, 7.15, 7.16, 8.2, 8.8, 8.9.

Homework #7: 9.1, 9.2, 9.9, 9.12, 10.6, 10.9, 10.15.

Extra credit 1: Solve Problem 10.20.

Extra credit 2: Construct Figure E9.3 using your favorite math/graphing software.

Extra credit 3 (see handout of 2/23): Construct Figures 5.5 and 5.7 in Schmidt (pp. 223-224, see Additional Reading above; on reserve in Phys. Sci. library).

Extra credit 4: Derive eq. 9.32

Homework #8: 11.1, 11.2, 11.9, 11.10, 12.6, 12.9, 12.11, 13.3, 13.11, 13.12, 14.11.

   Solution:        p1        p2        p3        p4        p5        p6        p7        p8        p9        p10      p11      p12      p13

Homework #9:             Page 1              Page 2

   Solution:        p1        p2        p3        p4        p5        p6        p7        p8        p9        p10      p11

   Summary of results

Homework #10: 17.1, 17.3, 23.1, 23.6, 25.3, 25.7, 25.8

   Extra credit: Construct Figures 25.9 and 25.10

   Solution:        p1        p2        p3        p4        p5        p6        p7        p8

   [Note error on p. 4: in 23.6 the Hatta coefficient should be 100, not 10000… (Thanks, Tony!)]

Homework #11: 18.3, 18.8, 18.9, 18.11, 18.17, 18.24, 18.26

   Extra credit: Construct Figures 18.4 and 18.6

   Solution:        p1        p2        p3        p4        p5        p6        p7        p8        p9

Homework #12: 19.13, 19.15, 19.16, 19.21.

   Figure 19.11 (courtesy of Kelly Caputo)

   Solution:        p1        p2        p3        p4        p5        p6        p7        p8        p9        p10      p11      p12

Homework #13: 26.11, 26.12, 26.14, Construct Fig. 26.4 (see errata sheet below!)

   Solution:        p1        p2

   Extra credit 1: Construct Fig. 26.5 (Compare with Figs. 6.5 and 6.6… Comment!)

   Extra credit 2

  

Practice Exam #3: Solve Problems 18.21, 19.19, 23.3 and 25.11.

Solution:                    p1           p2        p3        p4

 

Example of use of Mathematica: illustration of a key concept (“rate-determining step”)

Use of Mathematica to illustrate the temperature dependence of reaction rates

Chapter 1

Problem 2.14

Reactions of shifting order (Langmuir-Hinshelwood or Michaelis-Menten rate equation)

Trimolecular reaction: constant rxn order but different rxn stoichiometries

Problem 3.15 (Excel)

Problem 3.16 (Mathematica)

Problem 3.16a: Excel-numerical differentiation

Problem 3.16b: Excel-polynomial fit (with contribution from Samir Singh, sps162@psu.edu)

Problem 3.20 (Excel)

Example 3.1 (Mathematica)

Analysis of n-th order rxn (Mathematica)

Differential method (Mathematica)

Solution to Quiz #1

2SO2 + O2 -> 2SO3: a material balance exercise (Excel)

Problem 5.12 (Mathematica)

Problem 5.25 (Mathematica)

Problem 5.28 (Mathematica; with a contribution from Mike Diffendal, mjd262@psu.edu)

Analysis of space time vs. residence time in flow reactors (Mathematica)

Problem 5.21 (Mathematica)

Problem 6.6 (Mathematica)

Illustration of general rule #1 on p. 135 in Levenspiel (Mathematica file)

Illustration of general rule #1 on p. 135 in Levenspiel (annotated file)

Figure 6.5 (partial)

Problem 6.10 (Mathematica)

Problem 7.26 (Mathematica)

Addendum to solution of problem #8.2 (with a key contribution from Kelly Caputo and Hallie Brink)

kt vs. XA: Summary and take-home messages (See Chapter 10)

Chapter 9 (Mathematica)

Example 9.4

Example 9.5

Problem 9.12

Problem 10.6

Problem 10.15

Review of distribution functions

Residence time distributions (Mathematica)

Analysis of tracer pulse response (Excel)

Figure 13.19 (contribution from Kelly Caputo)

Chapter 13: Construction of Figures 13.4 and 13.10 (Mathematica)

A note on voidage in packed bed reactors

Role of mixing (fluid dynamics, mass transfer) in nonideal reactors and heterogeneous reactions

Langmuir isotherm: relationship between fluid-phase and solid-phase concentrations

Analogy between Thiele modulus and Hatta modulus

Heterogeneous catalytic reaction rates: relationship with Figure 1.3

Derivation of Langmuir-Hinshelwood kinetics for heterogeneous catalytic reactions:        p1        p2

 

Textbook Errata Sheet (5th printing)-Provisional (with input from ChE 414 students)

p.8 (Figure P1.2):                     10 m -> 20 m

p.9, line 6 down:                       cracking -> catalytic

p.40, line 12 down:                   say Ain -> say A, in

p.63 (Figure E3.1d):                 ln CA0 -> log CA0

p.73, line 14 down:                   activation using -> activation energy using

p.80, Table P3.21                    T, min -> t, min

p.82, line 6 down:                     pure Aincreases -> pure A, increases

p.88, line 1 down:                     T0p/(t0p0) -> T0p/(Tp0)

p.88, line 1 down:                     z0T0p/(zTp) -> z0T0p/(zTp0)

p.88, line 4 down:                     change pressure -> change in pressure

p.100, line 3 up:                        6 liter/min -> 2 L/min

p.100, line 1 up:                        3 liter/min -> 1 L/min

p.153, eqn. 3:                           k2/k1 -> k1/k2

p.157:                                      (Delete entire paragraph following eqn. 10.)

p.216, last figure:                      0.7 -> 0.8

p.248, Problem 10.6:                Rdesired -> Sdesired

p.259, Figure 11.3 (right):         Here gas us -> Here gas is

p.292, line 2 up:                        Example 12.2 -> Problem 12.11

p.301, eqn. 14:                         (4p(D/uL) -> 4p(D/uL)q

p.316, line 2 down:                   Example 11.3 -> Example 11.4

p.372,  eqn. (i):                         -r”A1 = - (1/S)(dNA/dt) = …

p.372, eqn. (ii):                         -r”A2 = -(1/S)(dNA/dt) = …

p.424, Problem 18.31:              pellets -> spheres

p.424, Problem 18.32:              porous -> diameter

p.424, Problem 18.33:              catalyst -> spherical

p.536, line 3 up:                        5x105 -> 5x103

p.537, rate expression:              .098 -> 0.98

p.578, Eqn. 24:                        kg dp y/D -> kg dp/D

p.595, Eqn. 8a:                         (1-et/tbar) -> (1-e-t/tbar)

p.596, Eqn. 10a:                       (1-et/tbar) -> (1-e-t/tbar)


Course schedule

 

Date       Book Section                                                Topic

 

1/8          Chapter 1                  Introduction to chemical reaction engineering    

                                                (See Ind. Eng. Chem., Vol. 60(4), 1968, pp. 62-64.)

1/10        Chapter 2                  Reaction rate equations: a closer look               

1/12        Chapter 2                  Reaction mechanisms: a closer look                  

1/15        Chapters 1-2             Problem-solving session (HW #1)

1/17        Chapter 3                  Kinetics of reactions in a constant-volume batch reactor           

1/19        Chapter 3                  Kinetics of reactions in a variable-volume batch reactor

1/22        Chapters 1-3             Problem-solving session (HW #2) and quiz #1

1/24        Chapter 4                  Introduction to the design of chemical reactors  

1/26        Chapter 5                  Single reactions in simple ideal reactors (MFR, PFR)

1/29        Chapters 4-5             Problem-solving session (HW #3)

1/31        Chapter 6                  Single reactions in more complex ideal reactors (1)

2/2          Chapter 6                  Single reactions in more complex ideal reactors (2)

2/5          Chapter 6                  Problem-solving session (HW #4) (EXAM 1, Chs. 1-6)

2/7          Chapter 7                  Design for reactions in parallel

2/9          Chapter 8                  Design for reactions in series

2/12        Chapters 7-8             Problem-solving session (HW #5)

2/14        Chapter 9                  Temperature (heat transfer) effects in ideal reactors

2/16        Chapter 9                  Pressure effects in ideal reactors

2/19        Chapters 7-9             Problem-solving session (HW #6) and quiz #2

2/21        Chapter 10                Criteria for reactor selection (1)

2/23        Chapters 6-10           Criteria for reactor selection (2)

2/26        Chapters 9-10           Problem-solving session (HW #7)

2/28        Chapter 11                Introduction to non-ideal flow

3/2          Chapter 12                Diagnosing and curing “misbehaving” reactors

3/12        Chapters 13-14         Brief introduction to modeling of non-ideal reactors                              

3/14        Chapters 11-14         Problem-solving session (HW #8)

3/16        Chapters 9,11,13      Quiz #3

3/19        Chapters 6-14           Design of a non-isothermal non-ideal reactor (HW #9)                         

3/21        Chapters 6-14           Review (HW #9) (EXAM 2, Chs. 6-10)

3/23        Chapters 11-14         Further discussion of nonideal reactors (1)

3/26        Chapters 11-14         Further discussion of nonideal reactors (2)

3/28        Chapters 11-14         Quiz #4 (Chs. 11-14)

3/30        Chapter 17                Introduction to heterogeneous reactions

4/2          Chapters 23,25         Kinetics of fluid/fluid and fluid/solid reactions (HW#10)

4/4          Chapter 18                Kinetics of heterogeneous catalytic reactions (1)

4/6          Chapter 18                Kinetics of heterogeneous catalytic reactions (2)

4/9          Chapter 18                Kinetics of heterogeneous catalytic reactions (3)

4/11        Chapters 23,25         Quiz #5 (Chs. 17,23,25) (HW#11)

4/13        Chapter 19                Heterogeneous chemical reactors

4/16        Chapter 19                Very brief introduction to packed-bed reactors

4/18        Chapter 18                Quiz #6 (Ch. 18)

4/20        Chapter 19                Packed-bed reactors (HW#12)

4/23        Chapters 20,26         Very brief introduction to fluid-particle reactors

4/25        Chapters 1-26           Summary of course highlights (see Chem. Eng. Prog., October 2000, pp. 37-51)

4/27        Chapters 1-26           Review of course highlights (HW#13)

5/3          Chapters 17-26         EXAM 3

 

(LRR3@psu.edu, 05/07/2001)