Numerical A

Techniques

Lake Michigan—unsalted and shark free.

A.1 Useful Integrals in Reactor Design

Also see www.integrals.com.

x 1 -
dx -  ln -----------
 0
-----------
1x 1x
(A-1)

x2
dx 1
1  -------------
 x1
------------------2-  -------------
(1  x )
-
1  x2 1  x1
- (A-2)

x x -
dx -  -----------
 0
------------------
(1  x ) 2 1x
(A-3)

x dx -  1--- ln ( 1  x )
 0
--------------
1  x 
(A-4)

x
(-------------------------
1  x )dx-  ( 1   ) ln -----------
1 -
 0 1x 1x
 x (A-5)

x
( 1  x )dx  (--------------------
1  ) x 1
 0
-------------------------
(1  x )
2
-
1x
  ln ------------
1x
(A-6)

2
x (1  ) x
( 1  x )2dx  2( 1   ) ln ( 1  x )  2x  ---------------------
0
---------------------------
( 1  x )2
-
1x
- (A-7)

897
898 Numerical Techniques Appendix A

x dx 1 B  x
 0
--------------------------------------  ---------------- ln ------------------------
( 1  x ) ( B  x ) B  1 B ( 1  x )
- B  1 (A-8)

W
2

1
2 3
2
( 1  W ) dW  ------ [ 1  ( 1  W ) ] (A-9)
0 3

x dx 2 2
 0
-----------------------------
ax2  bx  c 2ax  b b
 ------------------  --- for b2  4ac (A-10)

x dx 1 ⎛q x  p⎞
 0
-----------------------------  -------------------- ln ⎜ ---  ------------⎟
ax  bx  c a ( p  q ) ⎝ p x  q ⎠
2
for b2  4ac (A-11)

where p and q are the roots of the equation.

 b b2  4ac
ax2  bx  c  0 i.e., p, q  ----------------------------------------
2a

x  bx-
a-------------- bx ag  bc c  gx
0
c  gx
dx  ------  -----------------
g g2
- ln ---------------
c
(A-12)

A.2 Equal-Area Graphical Differentiation

There are many ways of differentiating numerical and graphical data (cf. Chapter 7). We shall confine
our discussions to the technique of equal-area differentiation. In the procedure delineated here, we
want to find the derivative of y with respect to x.
This method finds use in Chapter 5.

1. Tabulate the (y i , xi ) observations as shown in Table A-1.

2. For each interval, calculate xn  xn  xn1 and yn  yn  yn1 .

TABLE A-1

y dy
xi yi x y ------- ------
x dx

⎛ dy ⎞
x1 y1 ⎜ ------⎟
⎝ dx ⎠ 1
⎛ y ⎞
x 2  x1 y 2  y1 ⎜ -------⎟
⎝ x ⎠ 2
⎛ dy ⎞
x2 y2 ⎜ ------⎟
⎝ dx ⎠ 2
⎛ y ⎞
x 3  x2 y 3  y2 ⎜ -------⎟
⎝ x ⎠ 3
⎛ dy ⎞
x3 y3 ⎜ ------⎟
⎝ dx ⎠ 3
x4 y4 etc.
Section A.2 Equal-Area Graphical Differentiation 899

3. Calculate yn /xn as an estimate of the average slope in an interval xn1 to xn .

4. Plot these values as a histogram versus xi . The value between x2 and x3 , for example, is
(y3  y2 )/(x3  x2 ). Refer to Figure A-1.

Figure A-1 Equal-area differentiation.

5. Next, draw in the smooth curve that best approximates the area under the histogram. That
is, attempt in each interval to balance areas such as those labeled A and B, but when this
approximation is not possible, balance out over several intervals (as for the areas labeled C
and D). From our definitions of x and y, we know that

n
y
yn  y1  -------- x i
 x i
(A-13)
i2

The equal-area method attempts to estimate dy/dx so that

xn
d-----y-
yn  y1 
 x1
dx
dx (A-14)

that is, so that the area under y/x is the same as that under dy/dx, everywhere possible.
6. Read estimates of dy/dx from this curve at the data points x1 , x2 , … and complete the table.

An example illustrating the technique is given on the CRE Web site, Appendix A.
Differentiation is, at best, less accurate than integration. This method also clearly indicates bad
data and allows for compensation of such data. Differentiation is only valid, however, when the data
are presumed to differentiate smoothly, as in rate-data analysis and the interpretation of transient dif-
fusion data.
900 Numerical Techniques Appendix A

A.3 Solutions to Differential Equations

A.3.A First-Order Ordinary Differential Equations

See www.ucl.ac.uk/Mathematics/geomath/level2/deqn/de8.html and the CRE Web site, Appendix A.3.

dy  f (t )y  g ( t ) (A-15)
------
dt

Using integrating factor = exp ⎛ f dt⎞ , the solution is


⎝ ⎠


 f dt
 f dt

 f dt
y e  g(t) e dt  K 1e (A-16)

Example A–1 Integrating Factor for Series Reactions

dy  k y  k ek 1t
------ 2 1
dt
k2 t
Integrating factor = exp  k 2dt  e

k 2t
d( ye ) k 2t k 1 t ( k 2  k 1 )t
------------------  e k 1e  k 1e
dt
k 2t ( k 2  k 1 )t k 1 (k 2  k 1)t
e y  k 1 e dt  ---------------
-e  K1
k2  k1
k 1 k 1 t k 2 t
y  ---------------
-e  K 1e
k2  k1

t=0 y=0

k1 k 1 t k 2 t
y  ---------------
- e e
k2  k1

A.3.B Coupled Differential Equations

Techniques to solve coupled first-order linear ODEs such as

dx
------  ax  by
dt
dy
------  cx  dy
dt
are given in Web Appendix A.3 on the CRE Web site.
Section A.4 Numerical Evaluation of Integrals 901

A.3.C Second-Order Ordinary Differential Equations

Methods of solving differential equations of the type

d2y
-------2-  y  0 (A-17)
dx

can be found in such texts as Applied Differential Equations by M. R. Spiegel (Upper Saddle River,
NJ: Prentice Hall, 1958, Chapter 4; a great book even though it’s old) or in Differential Equations by
F. Ayres (New York: Schaum Outline Series, McGraw-Hill, 1952). Solutions of this type are required
in Chapter 15. One method of solution is to determine the characteristic roots of

⎛ d2 ⎞
⎜ -------2-  ⎟ y  (m2  )y
⎝ dx ⎠

which are

m 

The solution to the differential equation is

y  A 1 e x  B
1e
 x (A-18)

where A1 and B1 are arbitrary constants of integration. It can be verified that Equation (A-18) can be
arranged in the form

y  A sinh x  B cosh x (A-19)

Equation (A-19) is the more useful form of the solution when it comes to evaluating the constants A
and B because sinh(0)  0 and cosh(0)  1.0. Also see Appendix A.3.B.

A.4 Numerical Evaluation of Integrals

In this section, we discuss techniques for numerically evaluating integrals for solving first-order dif-
ferential equations.

1. Trapezoidal rule (two-point) (Figure A-2). This method is one of the simplest and most
approximate, as it uses the integrand evaluated at the limits of integration to evaluate the
integral
X1
h
X0
f ( X ) dX  --- [ f ( X 0 )  f ( X 1 ) ]
2
(A-20)

when h  X1  X0 .
902 Numerical Techniques Appendix A

2. Simpson’s one-third rule (three-point) (Figure A-3). A more accurate evaluation of the inte-
gral can be found with the application of Simpson’s rule:
X2
h
 X0
f ( X ) dX  --- [ f ( X 0 )  4f ( X 1 )  f ( X 2 ) ]
3
(A-21)

where
X2X0
h  ------------------
- X1  X0  h
2

Methods to solve
X F
0 ---------
rA
A0
- dX

in Chapters 2, 4, 12,
and

0 X (t )E (t) dt
in Chapter 17

Figure A-2 Trapezoidal rule illustration. Figure A-3 Simpson’s three-point rule
illustration.
3. Simpson’s three-eighths rule (four-point) (Figure A-4). An improved version of Simpson’s
one-third rule can be made by applying Simpson’s three-eighths rule:
X3

X0
f ( X ) dX  --38- h [ f ( X 0 )  3f ( X 1 )  3f ( X 2 )  f ( X 3 ) ] (A-22)

where
X3X0
h  ------------------
- X1  X0  h X2  X0  2h
3

Figure A-4 Simpson’s four-point rule illustration.

4. Five-point quadrature formula.

X4
h
 X0
f ( X ) dX  --- ( f 0  4f 1  2f 2  4f 3  f 4 )
3
(A-23)

X4X0
where h  ------------------
-
4
Section A.6 Software Packages 903

5. For N  1 points, where (N/3) is an integer

XN


X0
f ( X ) dX  3--8- h [f 0  3f 1  3f 2  2f 3

 3f 4  3f 5  2f 6    3f N1  f N ] (A-24)
XNX0
where h  -------------------
-
N
6. For N  1 points, where N is even
XN
h

X0
f ( X ) dX  --- ( f 0  4f 1  2f 2  4f 3  2f 4    4f N1  f N )
3

(A-25)
XNX0
where h  -------------------
-
N
These formulas are useful in illustrating how the reaction engineering integrals and coupled
ODEs (ordinary differential equation(s)) can be solved and also when there is an ODE solver power
failure or some other malfunction.

A.5 Semilog Graphs

Review how to take slopes on semilog graphs on the Web. Also see www.physics.uoguelph.ca/tutorials/
GLP. Also see Web Appendix A.5, Using Semi-Log Plots for Data Analysis.

A.6 Software Packages

Instructions on how to use Polymath, COMSOL, and Aspen can be found on the CRE Web site.
For the ordinary differential equation solver (ODE solver), contact:
Polymath Software Aspen Technology, Inc.
P.O. Box 523 10 Canal Park
Willimantic, CT 06226-0523 Cambridge, MA 02141-2201
Web site: www.polymath- Email: info@aspentech.com
software.com/fogler Web site: www.aspentech.com
MATLAB COMSOL, Inc.
The Math Works, Inc. 1 New England Executive Park
20 North Main Street, Suite 250 Burlington, MA 01803
Sherborn, MA 01770 Tel: +1-781-273-3322
Fax: +1-781-273-6603
Email: info@comsol.com
Web site: www.comsol.com
This page intentionally left blank
 Ideal Gas Constant B
and Conversion
Factors

See www.onlineconversion.com.

Ideal Gas Constant

0.73 ft3  atm 1.987 Btu
R  ------------------------------ R  -------------------------
lb mol  R lb mol  R
8.314 kPa  dm3 8.3144 J
R  ------------------------------------- R  --------------------
mol  K mol  K
dm3  atm 0.082 m3  atm 1.987cal
R  0.082 ----------------------  ---------------------------------- R  --------------------
mol  K kmol  K mol  K
J
Boltzmann’s constant kB  1.381 × 10–23 ------------------------------
-
molecule • K
 1.381 × 10–23 kg m2/s2/molecule/K

Volume of Ideal Gas

1 lb-mol of an ideal gas at 32F and 1 atm occupies 359 ft3 (0.00279 lbmol/ft3).
1 mol of an ideal gas at 0C and 1 atm occupies 22.4 dm3 (0.0446 mol/dm3).
PA y AP
CA  -------  --------
-
RT RT
where CA  concentration of A, mol/dm3 T  temperature, K
P  pressure, kPa yA  mole fraction of A
R  ideal gas constant, 8.314 kPadm3/molK

1M = 1 molar = 1 mol/liter = 1 mol/dm3 = 1 kmol/m3 = 0.062 lb mol/ft3

905
906 Ideal Gas Constant and Conversion Factors Appendix B

Volume Length
1 cm3  0.001 dm3 1 Å  108 cm
1 in3  0.0164 dm3 1 dm  10 cm
1 fluid oz  0.0296 dm3 1 m  104 cm
1 ft3  28.32 dm3 1 in.  2.54 cm
1 m3  1000 dm3 1 ft  30.48 cm
1 U.S. gallon  3.785 dm3 1 m  100 cm
1 liter (L)  1 dm3
⎛ 1 gal ⎞
⎜ 1 ft3  28.32 dm3  -------------------------3  7.482 gal⎟
⎝ 3.785 dm ⎠

Pressure Energy (Work)

1 torr (1 mmHg)  0.13333 kPa 1 kgm2/s2  1J
1 in. H2 O  0.24886 kPa 1 Btu  1055.06 J
1 in. Hg  3.3843 kPa 1 cal  4.1868 J
1 atm  101.33 kPa 1 Latm  101.34 J
1 psia  6.8943 kPa 1 hph  2.6806  106 J
1 megadyne/cm2  100 kPa 1 kWh  3.6  106 J

Temperature Mass
F  1.8  C  32 1 lbm  454 g
R  F  459.69 1 kg  1000 g
K  C  273.16 1 grain  0.0648 g
R  1.8  K 1 oz (avoird.)  28.35 g
Réamur  1.25  C 1 ton  908,000 g

Viscosity
1 poise  1 g/cm/s = 0.1 kg/m/s
1 centipoise = 1 cp = 0.01 poise = 0.1 micro Pascal ⋅ second

Force
1 dyne  1 g ⋅ cm/s2
1 Newton  1 kg ⋅ m/s2

Pressure
1 Pa  1 Newton/m2

Work
A. Work  Force × Distance
1 Joule  1 Newton ⋅ meter  1 kg m2/s2  1 Pa ⋅ m3
B. Pressure × Volume  Work
(1 Newton/ m2) ⋅ m3  1 Newton ⋅ m  1 Joule
Appendix B Ideal Gas Constant and Conversion Factors 907

Time Rate of Change of Energy with Time

1 Watt  1 J/s
1 hp  746 J/s

Gravitational Conversion Factor

Gravitational constant
g  32.2 ft/s2
American Engineering System
( ft )( lbm )
gc  32.174 -------------------
2
-
( s )( lbf )
SI/cgs System
gc  1 (Dimensionless)

TABLE B.1 TYPICAL PROPERTY VALUES

Liquid Gas
(water) (air, 77°C, 101 kPa) Solid
Density 1000 kg/m3 1.0 kg/m3 3000 kg/m3
Concentration 55.5 mol/dm3 0.04 mol/dm3 –
Diffusivity 10–8 m2/s 10–5 m2/s 10–11 m2/s
Viscosity 10–3 kg/m/s 1.82 × 10–5 kg/m/s –
Heat capacity 4.31 J/g/K 40 J/mol/K 0.45 J/g/K
Thermal conductivity 1.0 J/s/m/K 10–2 J/s/m/K 100 J/s/m/K
Kinematic viscosity 10–6 m2/s 1.8 × 10–5 m2/s –
Prandtl number 7 0.7 –
Schmidt number 200 2 –

TABLE B.2 TYPICAL TRANSPORT VALUES

Liquid Gas
Heat transfer coefficient, h 1000 W/m2/K 65 W/m2/K
Mass transfer coefficient, kc 10–2 m/s 3 m/s
This page intentionally left blank
 Thermodynamic C
Relationships
Involving
the Equilibrium
Constant 1

For the gas-phase reaction

b ⎯⎯→ c-- C  d--- D
A  --- B ←⎯⎯ (2-2)
a a a
1. The true (dimensionless) equilibrium constant
RT lnK  G

ca da
aC aD
K  -----------------
ba
aA aB

where ai is the activity of species i

f
ai  ----oi
fi
where fi  fugacity of species i
f io  fugacity of the standard state. For gases, the standard
state is 1 atm
f
ai  ----oi  i Pi
fi

1 For the limitations and for further explanation of these relationships, see, for example,
K. Denbigh, The Principles of Chemical Equilibrium, 3rd ed. (Cambridge: Cambridge
University Press, 1971), p. 138.

909
910 Thermodynamic Relationships Involving the Equilibrium Constant Appendix C

where i is the activity coefficient

K = True equilibrium
constant ca da ca da
C D PC PD
K = Activity K  ------------------
ba ba
-  K Kp
- ------------------
equilibrium constant
Kp = Pressure
A B PA PB

⎧
⎨
⎩

⎧
⎨
⎩
equilibrium constant K Kp
Kc = Concentration
equilibrium constant
⎛ d  ac  a  ---  1⎞
b
⎝ ⎠
K has units of [ atm ] a
 [ atm ]
⎛ d  ac  a  b---  1⎞
⎝ ⎠
Kp has units of [ atm ] a
 [ atm ]
For ideal gases K  1.0 atm –δ

2. For the generic reaction (2-2), the pressure equilibrium constant KP is

ca da
PC PD
K p  -----------------
ba
-
PAPB
(C-1)
Pi  partial pressure of species i, atm, kPa.
Pi  Ci RT
3. For the generic reaction (2-2), the concentration equilibrium constant
KC is
It is important to be CCc  aCDd  a
able to relate K c  -------------------
- (C-2)
K, K, Kc , and Kp. CACBb  a
4. For ideal gases, Kc and Kp are related by
Kp  Kc (RT) (C-3)
Where for the generic reaction (2-2),
c d b
  --  ---  ---  1 (C-4)
a a a
5. KP is a function of temperature only, and the temperature dependence
of KP is given by van’t Hoff’s equation:

Van’t Hoff’s d ln K HRx ( T )

equation -----------------p  --------------------
- (C-5)
dT RT 2

d ln K H
Rx ( TR )  Cp ( T  T R )
-----------------p  --------------------------------------------------------------
- (C-6)
dT RT 2
6. Integrating, we have

K p (T ) H
Rx ( TR )  TR Cp ⎛ 1 ⎞ C
- ⎜ -----  --1-⎟  ---------p- ln -----
T
ln -----------------  ----------------------------------------------- (C-7)
K p (T 1) R ⎝T 1 T⎠ R T1
Kp and Kc are related by
Kp
K c  -------------- (C-8)
( RT )
Appendix C Thermodynamic Relationships Involving the Equilibrium Constant 911

when
⎛d c b ⎞
  ⎜ ---  --  ---  1⎟  0
⎝a a a ⎠
then
KP  KC
7. KP neglecting ΔCP. Given the equilibrium constant at one temperature,
T1, KP (T1), and the heat of reaction, H
Rx , the partial pressure equi-
librium constant at any temperature T is
H Rx
(T R )⎛ 1 1 ⎞
- -----  ---
KP(T) = KP(T1)exp ------------------------- (C-9)
R ⎝T 1 T⎠

8. From Le Châtelier’s principle we know that for exothermic reactions,

the equilibrium shifts to the left (i.e., K and Xe decrease) as the tem-
perature increases. Figures C-1 and C-2 show how the equilibrium
constant varies with temperature for an exothermic reaction and for
an endothermic reaction, respectively.

Variation of
equilibrium
constant with
temperature

Figure C-1 Exothermic reaction. Figure C-2 Endothermic reaction.

9. The equilibrium constant for the reaction (2-2) at temperature T can

be calculated from the change in the Gibbs free energy using
RT ln[K(T)]   G
Rx(T) (C-10)

c d b
G
Rx  -- G
C  --- G
D  --- G
B  G
A (C-11)
a a a
10. Tables that list the standard Gibbs free energy of formation of a given
species Gi
are available in the literature.
1) www/uic.edu:80/~mansoori/Thermodynamic.Data.and.Property_html
2) webbook.nist.gov
11. The relationship between the change in Gibbs free energy and
enthalpy, H, and entropy, S, is
G  H  T S (C-12)
See bilbo.chm.uri.edu/CHM112/lectures/lecture31.htm. An example on how to
calculate the equivalent conversion for ΔG is given on the Web site.
912 Thermodynamic Relationships Involving the Equilibrium Constant Appendix C

Example C–1 Water-Gas Shift Reaction

The water-gas shift reaction to produce hydrogen

H2 O  CO ←⎯⎯⎯⎯→ CO  H
2 2

is to be carried out at 1000 K and 10 atm. For an equimolar mixture of water and
carbon monoxide, calculate the equilibrium conversion and concentration of each
species.
Data: At 1000 K and 10 atm, the Gibbs free energies of formation are G
CO 
47,860 cal/mol; G
CO2  94,630 cal/mol; G
H2O  46,040 cal/mol; and
G
H2  0.

Solution
We first calculate the equilibrium constant. The first step in calculating K is to calculate
the change in Gibbs free energy for the reaction. Applying Equation (C-10) gives us
Calculate G
Rx G
Rx  G
H2  G
CO2  G
CO  G
H2O (EC-1.1)

 0  (94,630)  (47,860)  (46,040)

 730 cal/mol
RT lnK  G
Rx (T) (C-10)

G
Rx ( T ) ( 730 cal  mol )
lnK   ---------------------
-  ------------------------------------------------------------------
- (EC-1.2)
RT 1.987 cal  mol K ( 1000 K )
 0.367
then
Calculate K K  1.44
Expressing the equilibrium constant first in terms of activities and then finally in
terms of concentration, we have

aCO2aH2 f CO2 f H2 CO2 y CO2H2 y H2

K  ------------------
-  ------------------
-  -----------------------------------------
- (EC-1.3)
aCO aH2O f CO f H2O CO y CO H2O y CO2

where ai is the activity, f i is the fugacity, i is the activity coefficient (which we shall
take to be 1.0 owing to high temperature and low pressure), and yi is the mole frac-
tion of species i.2 Substituting for the mole fractions in terms of partial pressures
gives
P Ci RT
yi  -----i  ------------- (EC-1.4)
PT PT

PCO2PH2 CCO2CH2
-  ---------------------
K  -------------------- (EC-1.5)
PCO PH2O CCO CH2O

2 See Chapter 9 in J. M. Smith, Introduction to Chemical Engineering Thermodynam-

ics, 3rd ed. (New York: McGraw-Hill, 1959), and Chapter 9 in S. I. Sandler, Chemical
and Engineering Thermodynamics, 2nd ed. (New York: Wiley, 1989), for a discussion
of chemical equilibrium including nonideal effects.
Appendix C Thermodynamic Relationships Involving the Equilibrium Constant 913

In terms of conversion for an equimolar feed, we have

CCO, 0 X e CCO, 0 X e
K  ---------------------------------------------------------------------
- (EC-1.6)
CCO, 0 ( 1  X e ) CCO, 0 ( 1  X e )
Relate K and Xe
X e2
 ---------------------
-  1.44 (EC-1.7)
( 1  X e )2

Figure EC-1.1 Modell, Michael, and Reid, Robert, Thermodynamics and Its
Applications, 2nd ed., © 1983. Reprinted and electronically reproduced by
permission of Pearson Education, Inc., Upper Saddle River, NJ.
914 Thermodynamic Relationships Involving the Equilibrium Constant Appendix C

From Figure EC-1.1 we read at 1000 K that log KP  0.15; therefore, KP  1.41,
which is close to the calculated value. We note that there is no net change in the
number of moles for this reaction (i.e.,   0); therefore,

K  Kp  Kc (dimensionless)

Taking the square root of Equation (EC-1.7) yields

Calculate Xe, the Xe
equilibrium -  (1.44)1/2  1.2
-------------- (EC-1.8)
conversion 1Xe

Solving for Xe , we obtain

1.2
X e  -------  0.55
2.2
Then
y CO, 0 P0
CCO,0  -----------------
-
RT 0

( 0.5 )( 10 atm )
 ------------------------------------------------------------------------------------
-
( 0.082 dm3 atm  mol K )( 1000 K )
 0.061 mol/dm3
Calculate CCO,e,
the equilibrium CCO,e  CCO,0 (1  Xe )  (0.061)(1  0.55)  0.0275 mol/dm3
conversion of CO
CH2O, e  0.0275 mol/dm3

CCO2,e  CH2, e  CCO,0 Xe  0.0335 mol/dm3

Figure EC-1.1 gives the equilibrium constant as a function of temperature for a

number of reactions. Reactions in which the lines increase from left to right are
exothermic.
The following links give thermochemical data. (Heats of Formation, CP, etc.)
1) www.uic.edu/~mansoori/Thermodynamic.Data.and.Property_html
2) webbook.nist.gov
Also see Chem. Tech., 28 (3) (March), 19 (1998).
 Software Packages D

While Polymath 6.1 is the primary software package for the majority of the
problems requiring numerical solutions, MATLAB and Wolfram are also avail-
able. In addition, one can use COMSOL and Aspen to solve a few selected
problems.

D.1 Polymath

D.1.A About Polymath

Polymath 6.1 is the primary software package used in this textbook. Polymath
is an easy-to-use numerical computation package that allows students and pro-
fessionals to use personal computers to solve the following types of problems:
• Simultaneous linear algebraic equations
• Simultaneous nonlinear algebraic equations
• Simultaneous ordinary differential equations
• Data regressions (including the following)
• Curve fitting by polynomials and splines
• Multiple linear regression with statistics
• Nonlinear regression with statistics
Polymath is unique in that the problems are entered just like their mathemati-
cal equations, and there is a minimal learning curve. Problem solutions are
easily found with robust algorithms. Polymath allows very convenient problem
solving to be used in chemical reaction engineering and other areas of chemi-
cal engineering, leading to an enhanced educational experience for students.
The following special Polymath Web site for software use and updating
will be maintained for users of this textbook:
www.polymath-software.com/fogler

915
916 Software Packages Appendix D

D.1.B Polymath Tutorials

Polymath tutorials (https://www.youtube.com/watch?v=nyJmt6cTiL4) can be

accessed in the Summary Notes by clicking on the purple hot buttons
. Here, screen shots of the various steps are shown for each
of the Polymath programs.

Summary Notes
Chapter 1
A. Ordinary Differential Equation (ODE) Tutorial
B. Nonlinear (NLE) Solver Tutorial
Chapter 7
A. Fitting a Polynomial Tutorial
B. Nonlinear Regression Tutorial
Note: The Living Example Problems (LEPs) need to be copied from the CRE
Web site and pasted into the Polymath software. The Polymath software is
available in most chemical engineering department computer labs in the United
States and in some other countries as well. If you want to have Polymath on
your own laptop or desktop computer, you can purchase special low-priced
educational versions of the software for various time periods. Polymath ver-
sions are compatible with Windows XP, Vista, Windows 7, Windows 8, and
Windows 10. The specially discounted Polymath Software is available ONLY
from the special Web site www.polymath-software.com/fogler. The minimum
educational pricing requires you to refer to your Fogler textbook when you
sign on to the special Web site to order Polymath. Android users can also use
PolyMathLite on phones, tablets, and computers. More information is available
from the Web site www.polymathlite.com

D.2 MATLAB
MATLAB programs for the LEPs are given on the CRE Web site. The dis-
advantage of the MATLAB ODE solver is that it is not particularly
user-friendly when trying to determine the variation of secondary parameter
values. MATLAB can be used for the same four types of programs as Polymath.

D.3 Aspen
Aspen is a process simulator that is used primarily in many senior design courses. It
has the steepest learning curve of the software packages used in this text. It has a
built-in database of the physical properties of reactants and products. Consequently,
one has only to type in the chemicals and the rate law parameters. It is really too pow-
Aspen example on erful to be used for the types of home problems given here. The pyrolysis of benzene
the CRE Web site using Aspen is given as an example on the CRE Web site in Chapter 5, Learning
Resources 4.E, Solved Problem E.5-3 Design . Perhaps one home assignment should be
devoted to using Aspen to solve a problem with heat effects in order to help familiarize
the student with Aspen.
An Aspen tutorial and example problem from Chapters 5, 11, and 12 can
be accessed directly from the CRE Web site home page (under Let’s Get
Started, click on Additional Software and then click Aspen Plus).
Section D.4 COMSOL Multiphysics 917

D.4 COMSOL Multiphysics

COMSOL Multiphysics is a modeling and simulation software available com-
mercially from COMSOL Inc. It solves multiphysics problems in 1D, 1D axi-
symmetry, 2D, 2D axisymmetry, 3D, and at single points (0D). Internally in
the program, these problems are formulated using partial differential equations
(PDEs for 1D to 3D) or ordinary differential equations (ODEs). At www.comsol.
com/ecre, one can download documentation and solve CRE problems, which
are formulated in this book.
A dedicated application, with a tailored user interface, solves problems
for tubular reactors with heat effects involving both radial axial and radial gra-
dients in concentration. A step-by-step COMSOL tutorial with screenshots for
setting up this model and solving the model equations is also given in the CRE
web modules.
In the web modules, the first tutorial is “Heat effects in tubular reactors”
and the second is “Tubular reactors with dispersion.” In the first section, the
four examples focus on the effects of the radial velocity profile and external
cooling on the performances of isothermal and nonisothermal tubular reactors.
In the second section, two examples examine the dispersion effects in a tubular
reactor.

Heat Effects
1. Isothermal reactor. This example concerns an elementary, exother-
mic, second-order reversible liquid-phase reaction in a tubular reactor
with a parabolic velocity distribution. Only the mole, rate law, and
stoichiometric balance in the tubular reactor are required in this
COMSOL exercise.
2. Nonisothermal adiabatic reactor. The isothermal reactor model is
extended to include heat effects whereby the tubular reactor is treated
as an adiabatic reactor. The material and energy balances are solved
simultaneously in the COMSOL exercise.
3. Nonisothermal reactor with isothermal cooling jacket. A cooling
jacket kept at a constant temperature is added to the model described
in the second example above. This is a valid assumption if the cooling
liquid is supplied in such a large amount that the influence of the heat
from the reactor on the coolant’s temperature is negligible. The
boundary condition for the energy balance at the radial boundary is
changed from the thermal insulation boundary condition to a heat flux
boundary condition, where the external temperature corresponding to
the coolant is set to a constant value.
4. Nonisothermal reactor with variable coolant temperature. This
example extends the third example by including the energy balance
on the coolant in the cooling jacket as the temperature of the coolant
varies along the length of the reactor.
918 Software Packages Appendix D

Dispersion and Reaction

1. One-Dimensional model with Danckwerts boundary conditions.
In this example, the mass balance in a tubular reactor with arbitrary
reactions is described by an ordinary differential equation with
dimensionless variables and in terms of the Peclet number and the
Damköhler number.
2. One-Dimensional model with upstream and downstream sections.
This example uses the open-vessel boundary conditions where an
inlet (upstream) section and an outlet (downstream) section are added
to a tubular reactor where dispersion occurs but no reaction.
It is suggested that one first uses and plays with COMSOL Multiphysics
for solutions to examples XX and YY before making any changes. One should
also review the Web Module for Chapter 12 on Axial and radial gradients in
tubular reactors before running the program (www.umich.edu/~elements/5e/
web_mod/radialeffects/index.htm and www.umich.edu/~elements/web_mod/
radialeffects/comsol_ecre.pdf).

Tutorial
Tutorials with step-by-step instructions and screenshots can be found on the
web page www.comsol.com/ecre. Start with the documentation of 1. Isothermal
Reactor and then go to the documentation section for each of the other
exercises. Tutorial material for this exercise is built on but not repeated in the
exercises that follow. Next, go to 2. Nonisothermal adiabatic reactor and
read the additional information there before continuing to exercises 3 and 4.
Again here, the documentation is built on, not repeated, which also holds for
each of the sequential exercises.
 Rate-Law Data E

Reaction-rate laws and data can be obtained from the following Web sites:
1. National Institute of Standards and Technology (NIST)
Chemical Kinetics Database on the Web
Standard Reference Database 17, Version 7.0 (Web Version), Release 1.2
This Web site provides a compilation of kinetics data on gas-phase reactions.
http://kinetics.nist.gov/kinetics/index.jsp
2. International Union of Pure and Applied Chemistry (IUPAC)
This Web site provides kinetic and photochemical data for gas kinetic data evaluation.
http://iupac.pole-ether.fr/
3. NASA/JPL (Jet Propulsion Laboratory: California Institute of Technology)
This Web site provides chemical kinetics and photochemical data for use in atmospheric
studies.
http://jpldataeval.jpl.nasa.gov/download.html
4. BRENDA: University of Cologne
This Web site provides enzyme data and metabolic information. BRENDA is maintained and
developed at the Institute of Biochemistry at the University of Cologne.
http://www.brenda-enzymes.org/
5. NDRL Radiation Chemistry Data Center: Notre Dame Radiation Laboratory
This Web site provides the reaction-rate data for transient radicals, radical ions, and excited
states in solution.
https://www3.nd.edu/~ndrlrcdc/

919
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 Nomenclature F

A Chemical species
Ac Cross-sectional area (m2 )
Ap Total external surface area of particle (m2 )
ap External surface area of catalyst per unit bed volume (m2/m3 )
a Area of heat exchange per unit volume of reactor (m1)
ac External surface area per volume of catalyst pellets (m2/m3 )
B Chemical species
BA Flux of A resulting from bulk flow (mol/m2 s)
Bo Bodenstein number
C Chemical species
Ci Concentration of species i (mol/dm3 )
Cpi Heat capacity of species i at temperature T (cal/gmolK)
C̃pi Mean heat capacity of species i between temperature T0 and temperature T
(cal/molK)
Ĉpi Mean heat capacity of species i between temperature TR and temperature T
(cal/molK)
c Total concentration (mol/dm3 ) (Chapter 14)
D Chemical species
Da Damköhler number (dimensionless)
DAB Binary diffusion coefficient of A in B (dm2/s)
Da Dispersion coefficient (cm2/s)
De Effective diffusivity (dm2/s)
DK Knudsen diffusivity (dm2/s)
D Taylor dispersion coefficient
E Activation energy (cal/gmol)
(E) Concentration of free (unbound) enzyme (mol/dm3 )
Fi Molar flow rate of species i (mol/s)
Fi0 Entering molar flow rate of species i (mol/s)
G Superficial mass velocity (g/dm2 s)

921
922 Nomenclature Appendix F

Gi Rate of generation of species i (mol/s)

Gi ( T ) Gibbs free energy of species i at temperature T (cal/gmolK)
Hi (T) Enthalpy of species i at temperature T (cal/mol i )
Hi0 (T) Enthalpy of species i at temperature T0 (cal/mol i )
Hi Enthalpy of formation of species i at temperature TR (cal/gmol i )
h Heat transfer coefficient (cal/m2 sK)
JA Molecular diffusive flux of species A (mol/m2 s)
KA Adsorption equilibrium constant
Kc Concentration equilibrium constant
Ke Equilibrium constant (dimensionless)
KP Partial pressure equilibrium constant
k Specific reaction rate (constant)
kc Mass transfer coefficient (m/s)
Mi Molecular weight of species i (g/mol)
mi Mass of species i (g)
Ni Number of moles of species i (mol)
n Overall reaction order
Nu Nusselt number (dimensionless)
Pe Peclet number (Chapter 17)
Pi Partial pressure of species i (atm)
Pr Prandtl number (dimensionless)
Q Heat flow from the surroundings to the system (cal/s)
R Ideal gas constant
Re Reynolds number
r Radial distance (m)
rA Rate of generation of species A per unit volume (gmol A/sdm3 )
rA Rate of disappearance of species A per unit volume (mol A/sdm3 )
rA Rate of disappearance of species A per mass of catalyst (mol A/gs)
rA Rate of disappearance of A per unit area of catalytic surface (mol A/m2 s)
S An active site (Chapter 10)
(S) Substrate concentration (gmol/dm3 ) (Chapter 7)
Sa Surface area per unit mass of catalyst (m2/g)
SD/U Instantaneous selectivity (Chapter 8)
~
SD/U Overall selectivity of D to U
Sc Schmidt number (dimensionless) (Chapter 10)
Sh Sherwood number (dimensionless) (Chapter 10)
SV Space velocity (s1 )
T Temperature (K)
t Time (s)
U Overall heat transfer coefficient (cal/m2 sK)
V Volume of reactor (dm3 )
V0 Initial reactor volume (dm3 )
v Volumetric flow rate (dm3/s)
Appendix F Nomenclature 923

v0 Entering volumetric flow rate (dm3/s)

W Weight of catalyst (kg)
WA Molar flux of species A (mol/m2 s)
X Conversion of key reactant, A
Yi Instantaneous yield of species i
Ỹ i Overall yield of species i
y Pressure ratio P/P0
yi Mole fraction of species i
yi0 Initial mole fraction of species i
Z Compressibility factor
z Linear distance (cm)

Subscripts
0 Entering or initial condition
b Bed (bulk)
c Catalyst
e Equilibrium
p Pellet

Greek Symbols
 Reaction order (Chapter 3)
 Pressure drop parameter (Chapter 5)
i Parameter in heat capacity (Chapter 12)
i Parameter in heat capacity
 Reaction order
i Parameter in heat capacity

Change in the total number of moles per mole of A reacted
 Fraction change in volume per mole of A reacted resulting from the change in total
number of moles
 Internal effectiveness factor
i Ratio of the number of moles of species i initially (entering) to the number of moles
of A initially (entering)
 Dimensionless distance (z /L) (Chapter 15)
 Life expectancy (s) (Chapter 17)
 Viscosity (g/cms)
 Density (g/cm3 )
c Density of catalyst pellet (g/cm3 of pellet)
b Bulk density of catalyst (g/cm3 of reactor bed)
τ Space time (s)
 Void fraction (Porosity)
n Thiele modulus
 Dimensionless concentration (CA /CAs )
 External (overall) effectiveness factor
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 Open-Ended Problems G

The following are summaries for open-ended problems that have been used as term problems at the
University of Michigan. The complete problem statement of the problems can be found on the CRE
Web site, Web Appendix G.

G.1 Design of Reaction Engineering Experiment

The experiment is to be used in the undergraduate laboratory and costs less than $500 to build. The
judging criteria are the same as the criteria for the National AIChE Student Chapter Competition.
The design is to be displayed on a poster board and explained to a panel of judges. Guidelines for the
poster-board display are provided by Jack Fishman and are given on the CRE Web site.

G.2 Effective Lubricant Design

Lubricants used in car engines are formulated by blending a base oil with additives to yield a mixture
with the desirable physical attributes. In this problem, students examine the degradation of lubricants
by oxidation and design an improved lubricant system. The design should include the lubricant sys-
tem’s physical and chemical characteristics, as well as an explanation as to how it is applied to auto-
mobiles. Focus: automotive industry, petroleum industry.

G.3 Peach Bottom Nuclear Reactor

The radioactive effluent stream from a newly constructed nuclear power plant must be made to con-
form with Nuclear Regulatory Commission standards. Students use chemical reaction engineering
and creative problem solving to propose solutions for the treatment of the reactor effluent. Focus:
problem analysis, safety, ethics.

925
926 Open-Ended Problems Appendix G

G.4 Underground Wet Oxidation

You work for a specialty chemicals company, which produces large amounts of aqueous waste. Your
chief executive officer (CEO) read in a journal about an emerging technology for reducing hazardous
waste, and you must evaluate the system and its feasibility. Focus: waste processing, environmental
issues, ethics.

G.5 Hydrodesulfurization Reactor Design

Your supervisor at Kleen Petrochemical wishes to use a hydrodesulfurization reaction to produce eth-
ylbenzene from a process waste stream. You have been assigned the task of designing a reactor for
the hydrodesulfurization reaction. Focus: reactor design.

G.6 Continuous Bioprocessing

Most commercial bioreactions are carried out in batch reactors. The design of a continuous bioreactor
is desired since it may prove to be more economically rewarding than batch processes. Most desirable
is a reactor that can sustain cells that are suspended in the reactor while growth medium is fed in,
without allowing the cells to exit the reactor. Focus: mixing modeling, separations, bioprocess kinet-
ics, reactor design.

G.7 Methanol Synthesis

Kinetic models based on experimental data are being used increasingly in the chemical industry for
the design of catalytic reactors. However, the modeling process itself can influence the final reactor
design and its ultimate performance by incorporating different interpretations of experimental design
into the basic kinetic models. In this problem, students are asked to develop kinetic modeling meth-
ods/approaches and apply them in the development of a model for the production of methanol from
experimental data. Focus: kinetic modeling, reactor design.

G.8 Cajun Seafood Gumbo

Most gourmet foods are prepared by batch processes, i.e., a batch reactor. In this problem, students
are challenged to design a continuous process for the production of gourmet-quality Cajun seafood
gumbo from an old family recipe. Some of the most difficult gourmet foods to prepare are Louisiana
specialties, owing to the delicate balance between spices (hotness) and subtle flavors that must be
achieved. In preparing Creole and Cajun food, certain flavors are released only by cooking some of
the ingredients in hot oil for a period of time.
We shall focus on one specialty, Cajun seafood gumbo. Develop a continuous-flow reactor sys-
tem that would produce 5 gal/h of a gourmet-quality seafood gumbo. Prepare a flow sheet of the
entire operation. Outline certain experiments and areas of research that would be needed to ensure the
success of your project. Discuss how you would begin to research these problems. Make a plan for
any experiments to be carried out (see Chapter 7, R7.5, page 273).
Section G.9 Alcohol Metabolism 927

Following is an old family formula for Cajun seafood gumbo for batch operation (10 quarts,
serves 40):
1 cup flour 4 bay leaves, crushed
1 1--2- cups olive oil 1
--- cup chopped parsley
2
1 cup chopped celery 3 large Idaho potatoes (diced)
2 large red onions (diced) 1 tablespoon ground pepper
5 qt fish stock 1 tablespoon tomato paste
6 lb fish (combination of cod, red 5 cloves garlic (diced)
1
snapper, monk fish, and halibut) --- tablespoon Tabasco sauce
2
12 oz crabmeat 1 bottle dry white wine
1 qt medium oysters 1 lb scallops
1 lb medium to large shrimp
1. Make a roux (i.e., add 1 cup flour to 1 cup of boiling olive oil). Cook until dark brown. Add
roux to fish stock.
2. Cook chopped celery and onion in boiling olive oil until onion is translucent. Drain and add
to fish stock.
3. Add 1--3- of the fish (2 lb) and 1--3- of the crabmeat, liquor from oysters, bay leaves, parsley, pota-
toes, black pepper, tomato paste, garlic, Tabasco, and 1--4- cup of the olive oil. Bring to a slow
boil and cook 4 h, stirring intermittently.
4. Add 1 qt cold water, remove from the stove, and refrigerate (at least 12 h) until 2 1--2- h before
serving.
5. Remove from refrigerator, add 1--4- cup of the olive oil, wine, and scallops. Bring to a light
boil, then simmer for 2 h. Add remaining fish (cut to bite size), crabmeat, and water to bring
total volume to 10 qt. Simmer for 2 h, add shrimp, then 10 minutes later, add oysters and
serve immediately.
G.9 Alcohol Metabolism
The purpose of this open-ended problem is for the students to apply their knowledge of reaction
kinetics to the problem of modeling the metabolism of alcohol in humans. In addition, the students
will present their findings in a poster session. The poster presentations will be designed to bring a
greater awareness to the university community of the dangers associated with alcohol consumption.
Students should choose one of the following four major topics to further investigate:
1. Death caused by acute alcohol overdose
2. Long-term effects of alcohol
3. Interactions of alcohol with common medications
4. Factors affecting metabolism of alcohol
General information regarding each of these topics can be found on the CRE Web site.
The metabolism and model equations are given on the CRE Web site. One can load the Living
Example problem for alcohol metabolism directly from the CRE Web site.
928 Open-Ended Problems Appendix G

G.10 Methanol Poisoning

The emergency room treatment for methanol poisoning is to inject ethanol intravenously to tie up the
alcohol dehydrogenase enzyme so that methanol will not be converted to formic acid and formate,
which cause blindness. The goal of this open-ended problem is to build on the physiological-based
model for ethanol metabolism to predict the ethanol injection rate for methanol poisoning. One can
find a start on this problem by the Professional Reference Shelf Material on Physiologically Based
Pharmacokinetic (PBPK) Models in Chapter 9 that is on the Web.
 Use of Computational H
Chemistry Software
Packages

H.1 Computational Chemical Engineering

As a prologue to the future, our profession is evolving to one of molecular
chemical engineering. For chemical reaction engineers, computational chemis-
try and molecular modeling could well be our future.
Thermodynamic properties of molecular species that are used in reactor
design problems can be readily estimated from thermodynamic data tabulated
in standard reference sources such as Perry’s Handbook or the JANAF Tables.
Thermochemical properties of molecular species not tabulated can usually be
estimated using group contribution methods. Estimation of activation energies
is, however, much more difficult owing to the lack of reliable information on
transition-state structures, and the data required to carry out these calculations
is not readily available.
Recent advances in computational chemistry and the advent of powerful,
easy-to-use software tools have made it possible to estimate important
reaction-rate quantities (such as activation energy) with sufficient accuracy to
permit incorporation of these new methods into the reactor design process.
Computational chemistry programs are based on theories and equations from
quantum mechanics, which until recently, could only be solved for the simplest
systems such as the hydrogen atom. With the advent of inexpensive high-speed
desktop computers, the use of these programs in both engineering research and
industrial practice is increasing rapidly. Molecular properties such as bond
length, bond angle, net dipole moment, and electrostatic charge distribution
can be calculated. Additionally, reaction energetics can be accurately deter-
mined by using quantum chemistry to estimate heats of formation of reactants,
products, and also for transition-state structures.
Examples of commercially available computational chemistry programs
include Spartan, developed by Wavefunction, Inc. (www.wavefun.com), and
Cerius2 from Molecular Simulations, Inc. (www.accelrys.com). The Web module
in Chapter 3 on molecular reaction engineering (see www.umich.edu/~elements/
5e/) gives an example of what we can expect in the future.

929
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 How to Use I
the CRE Web Resources

The primary purpose of the CRE Web Resources is to serve as an enrichment resource. The benefits
of using the CRE Web Resources are fivefold:
1. To facilitate different student learning styles:
www.engin.umich.edu/~cre/asyLearn/itresources.htm
2. To provide the student with the option/opportunity for further study or clarification of a par-
ticular concept or topic
3. To provide the opportunity to practice critical thinking, creative thinking, and problem-solving
skills
4. To provide additional technical material for the practicing engineer
5. To provide other tutorial information, such as additional homework problems and instruc-
tions on using computational software in chemical engineering

I.1 CRE Web Resources Components

There are two types of information in the CRE Web Resources: information that is organized by
chapter and information organized by concept. Material in the “by chapter” section of the CRE Web
Resources corresponds to the material found in this book and is further divided into five sections.
• Objectives. The objectives page lists what the students will learn from the chapter. When stu-
dents are finished working on a chapter, they can come back to the objectives to see if they have
covered everything in that chapter. Or if students need additional help on a specific topic, they
can see if that topic is covered in a chapter from the objectives page.
• Learning Resources. These resources give an overview of the material in each chapter and pro-
vide extra explanations, examples, and applications to reinforce the basic concepts of chemical
reaction engineering. Summary Notes serve as an overview of each chapter and contain a logical
flow of derived equations and additional examples. Web Modules and Interactive Computer
Games (ICG) show how the principles from the text can be applied to nonstandard problems.
Solved Problems provide more examples for students to use the knowledge gained from each
chapter.

931
932 How to Use the CRE Web Resources Appendix I

Links to entertaining YouTube videos can be found on the Web site home page.
Chapter 1: Fogler Zone (you’ve got a friend in Fogler).
Chapter 3: The Black Widow murder mystery and Baking a Potato.
Chapter 4: CRF Reactor Video, Crimson Reactor Firm’s video of a “semi batch” reactor with
Diet Coke and Mentos.
Chapter 5: Learn a new dance and song, CSTR to the tune of YMCA, Chemical Good Time
Rhythm rap song, and the University of Michigan students’ Chemical Engineering
Gone Wrong.
• Living Example Problems. These problems are usually the second Home
Problem in each chapter (e.g., P5-2B), most of which require computational
software to solve. Polymath programs are provided on the DVD so students
can download the program to “play” with the problem and ask “what if . . . ?”
questions to practice critical and creative thinking skills. Students can change
parameter values, such as the reaction rate constants, to learn to deduce
trends or predict the behavior of a given reaction system.
• Professional Reference Shelf. The Professional Reference Shelf contains two
types of information. First, it includes material that is important to the practic-
ing engineer but that is typically not included in the majority of chemical
reaction engineering courses. Second, it includes material that gives a more
detailed explanation of derivations that were abbreviated in the text.
• Additional Homework Problems. New problems were developed for this
edition. They provide a greater opportunity to use today’s computing power
to solve realistic problems. Instead of omitting some of the more traditional,
yet excellent problems of previous editions, these problems were placed on
the Web site and can serve as practice problems along with those unassigned
problems in the text.
The materials in Learning Resources are further divided into Summary Notes, Web Modules, Interac-
tive Computer Games, and Solved Problems. Table I-1 shows which enrichment resources can be
found in each chapter.

TABLE I-1 DVD-ROM ENRICHMENT RESOURCES

Chapters
1 2 3 4 5 6 7 8 9 10 11 12 13
Summary Notes
Web Modules
ICGs
Solved Problems
Additional Homework
Problems
LEP
PRS
YouTube video links
Section I.2 How the Web Can Help Your Learning Style 933

Note: The ICGs are high-memory-use programs. Because of the memory intensive nature of the
ICGs, there have been intermittent problems (10–15% of Windows computers) with the games. You
can usually solve the problem by trying the ICG on a different computer. In the Heatfx 2 ICG, only
the first three reactors can be solved, and users cannot continue on to part 2 because of a bug cur-
rently in the program that we cannot find.
The information that can be accessed in the “by concept” sections is not specific to a single
chapter. Although the material can be accessed from the by chapter sections, the “by concept” sec-
tions allow you to access certain material quickly without browsing through chapters.
• Interactive Web Modules. The Web site includes both Web Games and ICGs. Interactive
The Web Games use a Web browser for an interface and give examples of how
chemical reaction engineering principles can be applied to a wide range of sit-
uations, such as modeling cobra bites and cooking a potato.
Computer Games
• Interactive Computer Games (ICGs). The ICGs are games that use a Win-
dows or DOS-based program for an interface. They test knowledge on different
aspects of chemical reaction engineering through a variety of games such as
basketball and jeopardy.
• Problem Solving. Here students can learn different strategies for problem
solving in both closed- and open-ended problems. See the ten different
types of home problems and suggestions for approaching them. Extensive
information on critical and creative thinking can also be found in this sec-
tion. Also see the Strategies for Creative Problem Solving, Third Edition,
by Fogler, LeBlanc, and Rizzo, along with the web site www.engin.umich.edu/scps/.
• Syllabi. Representative syllabi have been included on the Web site: (1) a 4-credit-hour under-
graduate course, Chemical Engineering 344, and (2) a 3-credit-hour graduate course.
• Frequently Asked Questions (FAQs). Over the years that I have taught this course, I have col-
lected a number of questions that the students have asked over and over for years and years. The
questions usually ask for clarification or for a different way of explaining the material or for
another example of the principle being discussed. The FAQs and answers are arranged by chapter.
• Credits. See who was responsible for putting the CRE Web site together.

I.2 How the Web Can Help Your Learning Style

I.2.1 Global vs. Sequential Learners

Global
• Use the summary lecture notes to get an overview of each chapter on the Web site and see the
big picture
• Review real-world examples and pictures on the Web site
• Look at concepts outlined in the ICGs
Sequential
• Use the Derive hot buttons to go through derivations in lecture notes on the Web
• Follow all derivations in the ICGs step by step
• Do all self-tests, audios, and examples in the Web site lecture notes step by step
934 How to Use the CRE Web Resources Appendix I

I.2.2 Active vs. Reflective Learners

Active
• Use all the hot buttons to interact with the material to keep active
• Use self-tests as a good source of practice problems
• Use Living Example Problems to change settings/parameters and see the result
• Review for exams using the ICGs

Reflective
• Self-tests allow you to consider the answer before seeing it
• Use Living Example Problems to think about topics independently

I.2.3 Sensing vs. Intuitive Learners

Sensing
• Use Web Modules (cobra, hippo, nanoparticles) to see how material is applied to real-world
topics
• Relate how Living Example Problems are linked to real-world topics

Intuitive
• Vary parameters in supplied Polymath problems and understand their influence on a problem
• Use the trial-and-error portions of some ICGs to understand “what if . . . ” style questions

I.2.4 Visual vs. Verbal Learners

Visual
• Study the examples and self-tests on the DVD-ROM summary notes that have graphs and
figures showing trends
• Do ICGs to see how each step of a derivation/problem leads to the next
• Use the graphical output from Living Example Problems/Polymath code to obtain a visual
understanding of how various parameters affect a system
• Use the Professional Reference Shelf to view pictures of real reactors

Verbal
• Listen to audios on the Web to hear information in another way
• Work with a partner to answer questions on the ICGs

I.3 Navigation
Students can use the Web site in conjunction with the text in a number of different ways. The Web
site provides enrichment resources. It is up to each student to determine how to use these resources
to generate the greatest benefit. Table I-2 shows some of the clickable buttons found in the Summary
Notes within the Learning Resources and a brief description of what the students will see when they
click on the buttons.
Section I.3 Navigation 935

TABLE I-2 HOT BUTTONS IN SUMMARY NOTES

Clickable Button Where it goes

Solved example problem

General material that may not be related to the chapter

Hints and tips for solving problems

A test on the material in a section, with solutions

Derivations of equations when not shown in the notes

Critical Thinking Question related to the chapter

Web Module related to the chapter

Chapter objectives

Polymath solution of a problem from the Summary

Notes

Biography of the person who developed an equation

or principle

Chapter insert with more information on a topic

Detailed solution of a problem

Plot of an equation or solution

Extra information on a specific topic

Audio clip
This page intentionally left blank
 Index

A Adenosine diphosphate (ADP), 366, 760 isotherms, 410–415

Adenosine triphosphate (ATP), 366, 760 rate constant, 412
Accumulation in bioreactors, 382 ADH (alcohol dehydrogenase), 359 in toluene hydrodemethylation,
Acetaldehyde Adiabatic operations 439–440
decomposition of, 334 acetic anhydride production, Aerobic organism growth, 367
from ethanol, 301 558–559 Aerosol reactors, 236–238
pyrolysis of, 390 batch reactors, 633–639 Affinity constant in Michaelis–Menten
Acetic anhydride butane isomerization, 55–58, equation, 348
cytidine reaction with, 817–820 554–555 Aging in catalyst deactivation, 456–459
production, 556–563 complex reactions with heat effects, Air pollution, 28–29
adiabatic operation, 558–559 594–595 Alcohol dehydrogenase (ADH), 359
co-current heat exchange, CSTRs, 568–572 Alcohol metabolism, 927
561–563 energy balance, 500–502 Algae as alternative energy source,
constant heat exchange fluid batch reactors, 633–639 396–397
temperature, 559–560 equilibrium temperature, Algorithms
countercurrent heat exchange, 521–522 complex reactions, 304
562–563 steady-state nonisothermal CRE problems, 142
Acetylation reactions, 226 design, 508–509 data analysis, 244–245
Activation energies tubular reactors, 510 ethylene glycol production, 150
barrier height, 86 exothermic irreversible gas-phase vs. memorizing, 140
and bond strength, 92–93 reactions, 67 multiple reactions, 282–284
determination, 90–93 interstage heat transfer, 522–526 Aliphatic alcohol, 341
in rate laws, 76 nitroaniline production, 643–644 Alkenes, ozone reactions with, 277
and reaction coordinates, 84 PFRs, 594–595 Alternative energy, 396–397
Active intermediates, 334–335 propylene glycol production in, Alumina-silica catalyst, 483–484
chain reactions in, 343 568–572, 634–639 Amino acids
enzymatic reactions, 343–346 temperature and equilibrium in chymotrypsin enzyme, 344
first-order rate law, 338–339 conversion, 518–522 synthesis, 366
mechanism searches in, 339–342 tubular reactors, 509–518 Ammonia
PSSH in, 336–338 Adjustable parameters for nonideal from hydrogen and nitrogen, 420
summary, 385–386 reactors, 846–847 nitroaniline from, 640–646
Active sites Adsorption, 403 from urea, 355–356
in catalysts, 404, 410–411 of cumene, 421–427 Ammonolysis, 226
in enzymes, 344 in CVD, 449–451 Analytical solution for pressure drop,
Actual rate of reaction in internal dissociative, 270, 412–415, 450 174, 177–188
effectiveness factor, 731, 733 equilibrium constant, 412 Anthracene dimerisation, 103

937
938 Index

Antibiotics, 364–365, 369 B in Langmuir–Hinshelwood kinetics,

Antifreeze 421–422
from ethylene glycol, 157 Back-of-the-envelope calculations, in reversible reactions, 80–82
from ethylene oxide, 185 705 from toluene, 79, 437–446
Antithrombin, 303 Backmix reactors. See Berra, Yogi
Ants running speed, 100 Continuous-stirred tank reactors on destinations, 680
Apparent order in active intermediates, (CSTRs) on observation, 243
338 Bacteria, 364–365. See also Cells on questions, 26
Apparent reactions in batch reactors, 378–381 on termination, 679
in azomethane decomposition, 338 in cell growth, 367–369 Berzelius, J., 400
in falsified kinetics, 737–738 in enzyme production, 344 Best estimates of parameter values in
in kinetic rate law, 77–78 Balance dispersion, 854 nonlinear regression, 261
Approximations in segregation model, Balance in CSTRs, 872–873 Bifurcation problems, 609
815 Balance on heat transfer fluid in tubular Bimodal distributions, 833
Aqueous bromine, photochemical decay reactors, 543–545 Bimolecular reactions, 70
of, 276–277 Balance on hydrogen in membrane Binary diffusion, 684–688
Area balance in CVD, 449 reactors, 219, 222 Biochar gasification, 331
Aris–Taylor analysis for laminar flow, Balance on reactor volume in CSTR Bioconversions, 365
870–871 parameter modeling, 876 Biomass reactions
Aris–Taylor dispersion Bartholomew, C. H., 461, 465 in biosynthesis, 364–365
dispersion model, 852 Basis of calculation in conversions, 32 in reaction rate law, 76
tubular reactors, 859–860 Batch reactors Bioprocessing design problem, 926
Arrhenius, Svante, 83 adiabatic operation, 633–639 Bioreactors, 364–367
Arrhenius equation bacteria growth in, 378–381 cell growth in, 368–369
Arrhenius plots, 90–93 bioreactors, 377 chemostats, 381–383
sintering, 456 catalyst decay, 457–458 mass balances in, 377–381
temperature behavior of reaction rate concentration equations, rate laws in, 369–371
constants, 83–84 109–111 stoichiometry in, 371–377
Arrhenius temperature dependence, 356 cylindrical, 137 summary, 385–386
Arterial blood in capillaries, 275 data analysis methods, 246–247 wash-out in, 383–384
Artificial kidneys, 346 differential, 251–258 Biosynthesis, 365–367
Aspen program, 188 integral, 247–251 Blindness from methanol, 359
acetic anhydride production, 563 nonlinear regression, Blood coagulation, 302–303, 323
explanation of, 916 258–263 Bodenstein number
instructions for, 903 design equations, 32–34, 94 dispersion and T-I-S models, 869
Asymmetric distribution energy balance, 499, 632–639 tubular reactors, 855
maximum mixedness model, 834 enzymatic reaction calculations, Boltzmann’s constant, 905
segregation model, 833 354–356 Bomb calorimeter reactors, 34
Atoms interrupted isothermal operation, Bond distortions in reaction systems,
in diffusion, 681 640–646 86–87
in reactions, 70 isothermal design, 144–151 Bonding for enzyme-substrate complex,
Attainable region analysis (ARA), mean conversion in, 816, 819 344
320–321 mole balances on, 10–12 Boundary conditions
Autocatalytic reactions, 367 in design equations, 33 diffusion, 408–409, 685–688, 690,
Automobile emissions gas phase, 210–212 726, 728
nitrogen oxides, 277, 485–486 integral data analysis, 248 dispersion coefficient determination,
in smog formation, 28–29 liquid phase, 208, 210 863–866
Average molar flux in diffusion, 690 RTDs in, 784–785 dispersion models, 918
Axial concentration profiles, 871 series reactions in, 294–298 mass transfer to single particles, 695,
Axial diffusion, 698 space time in, 59 697
Axial dispersion stoichiometry in, 107–113 maximum mixedness model,
dispersion model, 852 Bed fluidicity in hydrazine 823–824
packed beds, 745–746 decomposition, 704 spherical catalyst pellets, 726, 728
Axial variations in tubular reactors, Beetles, 100 tubular reactors, 600, 855–858
595–596 Benzene Bounded conversions in nonideal
energy balance, 598–603 adsorption of, 426 reactors, 846
energy flux, 597–598 from cumene, 5 Briggs–Haldane Equation, 354
molar flux, 596–597 from cyclohexane, 714 Bromine cyanide in methyl bromide
Azomethane decomposition, 336–338 desorption of, 423, 429–430 production, 230–232
Index 939

Bulk catalyst density in ethylene oxide production, 191 Channels and channeling
packed bed flow, 172 heterogeneous data analysis for, microreactors, 212
pressure drop, 180 436–437 tubular reactors, 797–798
Bulk concentration mechanisms, 439–440 Characteristic reaction times in batch
diffusion and reaction, 742 rate laws, 438–442 operation, 147
mass transfer to single particles, reactor design, 443–446 Chemical reaction engineering (CRE), 1–3
695 in heterogeneous reactions, 79 Chemical species, 4–5
Bulk diffusivity, 721 membrane reactors, 217–219 Chemical vapor deposition (CVD)
Bulk phase, diffusion in, 686–687 in microelectronic fabrication in diffusion, 753
Butadiene from ethanol, 281 chemical vapor deposition in, overview, 448–451
Butane 448–451 professional reference shelf for, 757
butene from, 221 overview, 446–448 Chemisorption, 403–404, 410
isomerization of, 55–56, 512–518, model discrimination in, 451–454 Chemostats, 381–383
548–555 properties of, 401–402 Chesterton, G. K., 399
Butanol dehydration, 483–484 rapid reactions on, 693–697 Chipmunk respiration rate, 713
Butyl alcohol (TBA), 482 rate data, 266–270 Chirping frequency of crickets, 99
Bypassing rate laws, 421–424 Chloral in DDT, 6
in CSTRs, 795–796, 871–873, deducing, 438–439 Chlorination
880–882 derived from PSSH, 435 membrane reactors, 312
in tubular reactors, 797–798 evaluating, 440–442 semibatch reactors, 226
temperature dependence of, 436 Chlorobenzene
rate-limiting, 419–420, 427–430 from benzene diazonium chloride, 91
C reforming, 431–435 in DDT, 6
C curves shell balance on, 723 Churchill, Winston, 895
pulse input experiment, 770–776 steps, 405–420 Chymotrypsin enzyme, 344–345
single-CSTR RTDs, 785 surface reaction, 416–418 Circulating fluidized beds (CFBs),
Cajun seafood gumbo, 926–927 weight 472–476
Calculations ethylene oxide, 185 Classes of cell reactions, 366
back-of-the-envelope, 705 heterogeneous reactions, 7 Clinoptilolite in toluene
enzymatic reactions, 354–356 membrane reactors, 219 hydrodemethylation, 437–446
propylene glycol production, 570 PBR, 37, 172 Closed-closed boundary conditions
Calorimeters, 34 with pressure drop, 178–182 dispersion coefficient determination,
Carbon dioxide from urea, 355–356 Catalytic dehydration of methanol, 863–864
Carbon monoxide 484–485 tubular reactors, 855–858
adsorption, 412–415 Catalytic reactions, isothermal Closed systems, first law of
methane from, 266–270 first-order, 730–733 thermodynamics for, 495
Carbonylation reactions in MCMT Cells Closed vessel dispersion, 855
production, 661 cartilage forming, 763–765 Clotting of blood, 302–303, 323
Cartilage forming cells, 763–765 growth and division CMRs (catalytic membrane reactors),
Catalysts and catalytic reactors, 399 chemostats for, 381–383 217–218
adsorption isotherms, 410–415 and dilution rate, 383 Co-current flow
benzene rate-limiting, 429–430 growth, 368–371 acetic anhydride production, 561–563
catalysis, 400–401 Luedeking–Piret equation, 375 butane isomerization, 550–551
classification, 404–405 mass balances, 377–381 PFR complex reactions with heat
CRE Web site material, 480–481 rate laws, 369–371, 374 effects, 590–591
deactivation. See Deactivation of stoichiometry, 371–377 tubular reactors, 543–544
catalysts wash-out, 383–384 Coagulation of blood, 302–303, 323
definitions, 400–401 reactions in, 365–366 Cobalt-molybdenum catalyst, 483
desorption, 418 Center for Chemical Process Safety Cobra bites, 322
for differential reactors, 264–265 (CCPS), 604 Cocci growth, 367
diffusion in Centers in catalysts, 404 Coking, catalyst decay, 459–461
from bulk to external transport, Cerius program, 335 Colburn J factor
408–409 Certificate programs, 605 hydrazine decomposition, 704
differential equation for, CFBs (circulating fluidized beds), mass transfer correlations, 701
723–725, 729–730 472–476 Collision rate in adsorption, 412
dimensionless form, 726–728 Chain reactions, 343 Collision theory, 74
effective diffusivity in, 721–723 Chain rule for diffusion and reaction, active intermediates in, 335
internal, 409–410 726 professional reference shelf for, 97
for tissue engineering, 763–765 Chain transfer step, 343 in reaction systems, 87–90
940 Index

Combination step overview, 602–603 dead space in, 871–873, 880–882

acetic anhydride production, 557 tubular reactors, 601 design, 14, 152
batch operation, 145–146, 295–296 Concentration-time data design equations, 36, 94
butane isomerization, 513 batch reactors, 246 ethylene glycol, 157–162
catalyst decay, 458 nonlinear regression, 261–262 series, 155–157
CSTRs Concentrations and concentration single, 152–155
with cooling coils, 573 profiles diagnostics and troubleshooting,
parameter modeling, 876 active site balances, 411 794–797
series reactions, 299 batch reactors, 247–248, 296–297 energy balance, 498–499, 565,
single, 153–155 CSTRs, 13, 300 572–574, 585–588, 653
ethylene glycol production, 150, 159 differential reactors, 264–265 in equilibrium equation, 129–130
ethylene oxide production, 187 diffusion, 723, 727, 729 ethylene glycol, 148–151
gas-oil catalytic cracking, 470 dilution, 383 with heat effects, 564–574
gas phase, 211 dispersion model, 852 for liquid-phase reactions, 12–14
glucose-to-ethanol fermentation, 379 enzyme, 346–348 mass balances, 377
laminar flow reactors mean flow systems, 114 modeled as two CSTRs with
conversion, 818 gas-phase, 115–126 interchange, 878–880
membrane reactors key reactants, 118 mole balances, 36, 208–212
flow and reaction, 223 liquid-phase, 114–115 multiple reactions, 585–588
in multiple reactions, 315 species, 115–117 with multiple steady states, 574–581
mole balance design, 209 laminar flow, 871 nonideal reactors using, 882–883
nitroaniline production, 642 mass transfer parallel reactions, 159–160, 288–291
nitrogen oxide production, 215 correlations, 701 propylene glycol production in,
nonisothermal reactor design, to single particles, 695 568–572
494–495 methane production, 268–269 RTDs in, 768–769, 785–786,
PFR reactor volume, 142–144 with pressure drop, 178 794–797
pressure drop rate data analysis, 244–245 in segregation models, 813–814
isothermal reactor design, 170 semibatch reactors, 232 in series, 48–50
tubular reactors, 179 spherical catalyst pellets, 723, 727, design, 155–157, 160–161
propylene glycol production, 729 with PFRs, 53–57
569–570, 635–636 T-I-S model, 851 sequencing, 57–58
semibatch reactors, 230 toluene hydrodemethylation, 440 series reactions, 298–302
tubular reactors tubular reactors, 855 sizing, 42–43, 46–47
adiabatic, 510 Confidence limits in nonlinear space time in, 59
flow in, 163–164, 167 regression, 261 for toluene hydrodemethylation,
urea decomposition, 354 Configuration in chemical species, 4 445–446
Combinations Consecutive reactions, 280 unsteady-state operation
CSTRs and PFRs in, 53–57 Constant heat capacities in enthalpy, 505 energy balance, 499
and species identity, 5 Constant-volume batch systems, startup, 651–656
Competing reactions, 280 110–111, 251 Convection
Competitive inhibition, 357–359 Constant-volume decomposition of in diffusion, 685–686
Complete segregation in nonideal reactor dimethyl ether, 276 mass transfer coefficient in,
modeling, 809–810 Constant volumetric flow for differential 691, 693
Complex reactions, 304 reactors, 265 in tubular reactors, 854, 859
CSTRs, 307–312 Constriction factor in effective Convective-diffusion equation, 859
description, 280–281 diffusivity, 721 Conversion and reactor sizing, 31–32
PBRs, 304–307 Continuous-flow systems, 113–114 batch reactors, 32–34
PFRs with heat effects, 588–595 in mole balance, 12–22 continuous-flow reactors, 38–47
Compressibility factors in flow systems, reactor time, 35 conversion definition, 32
116 RTDs, 768–769 CRE Web site material, 64
Compression of ultrasonic waves, sizing, 38–47 equilibrium. See Equilibrium
340–342 Continuous-stirred tank reactors conversions
Compression ratio and octane number, (CSTRs) flow reactors, 35–38
432 in butane isomerization, 517–518 PBRs, 21
COMSOL program bypassing in, 795–796, 871–873, with pressure drop, 178–180
diffusion, 682, 685–686 880–882 rate laws in, 93–94
dispersion, 870–871, 918 complex reactions, 307–312 reactors in series, 47–58
explanation of, 917–918 conversion in, 868 space time, 58–60
instructions, 903 with cooling coils, 572–574 space velocity, 60–61
Index 941

Conversion bounds in maximum Cyanide as enzyme inhibitor, 357 Decay rate laws
mixedness model, 823–824 Cyclobutane, 335 catalyst deactivation, 456–458,
Conversion factors for units, 906–907 Cyclohexane, benzene and hydrogen 464–465
Conversion using RTDs, 807 from, 714 gas-oil catalytic cracking, 470
nonideal reactor modeling, 807–808 Cyclohexanol, 486–487 moving-bed reactors, 468–469
zero-adjustable-parameter models. Cylindrical pellets, 703 straight-through transport reactors,
See Cytidine, acetic anhydride reaction with, 474–475
Zero-adjustable-parameter 817–820 Decomposition
models Cytoplasm, 365–366 in active intermediates, 338
Cooking Czochralski crystallizers, 447 in reactions, 5
potatoes, 96 Dehydration butanol of alumina, 202
seafood gumbo, 926–927 Dehydration reactions, 483–484
spaghetti, 197 D Dehydrogenation reactions, 220–221
Coolant balance in tubular reactors, Damköhler numbers Denatured enzymes, 344, 356
543–545, 600 in CSTRs Deoxygenation of hemoglobin, 275
Coolant temperature parallel, 160 Deoxyribonucleic acid (DNA) in protein
semibatch reactors, 646–651 series, 156–157, 160 production, 366
steady-state tubular reactors, 544 single, 154–155 Deposition rate laws, 449
Cooling coils in CSTRs, 572–574 in gas-oil catalytic cracking, 471 Design and design equations
Coordinates, reaction, 84 in segregation models, 813, 815, batch reactors, 32–34, 94
Correlations 818 CSTRs, 14, 152
dispersion coefficient, 860–862 in tubular reactors, 854, 858 design equations for, 36, 94
mass transfer coefficients, 690–693, Danckwerts, P. V. ethylene glycol, 157–162
700–704 on boundary conditions in tubular series, 155–157
Corrosion of high-nickel stainless steel reactors, 856–858 single, 152–155
plates, 100 on RTDs, 769, 777 flow reactors, 35–38
Costs in ethylene glycol production, on segregated mixing, 810 propylene glycol production,
191–192 Danckwerts boundary conditions 569
Countercurrent flow in diffusion and reaction, 685 toluene hydrodemethylation reactors,
acetic anhydride production, in dispersion coefficient 443–445
562–563 determination, 863 Desired products
butane isomerization, 551–553 in dispersion models, 918 multiple reactions, 281
PFR complex reactions with heat in tubular reactors, 856–858 parallel reactions, 285–291
effects, 592 Darcy’s Law, 314 series reactions, 294–302
tubular reactors, 544–545 Data acquisition for differential reactors, Desorption, 414, 418
Cracking in moving-bed reactors, 264 of benzene, 425, 429–430
469–472 Data analysis. See Rate data collection in toluene hydrodemethylation,
Creativity in reactor selection, 884 and analysis 439–440
Cricket chirping frequency, 99 DDT (dichlorodiphenyl-trichloroethane) Dichlorodiphenyl-trichloroethane (DDT)
Critiquing journal articles production, 6 production, 6
diffusion, 765 Deactivation of catalysts Diethanolamine formation, 280
mass transfer limitations, 717 by coking and fouling, 459–461 Differential forms and equations
Crystalline aluminosilicates, 401 empirical decay laws, 464–465 batch reactors, 34, 251–258
Crystals in microelectronic fabrication, moving-bed reactors, 467–472 for diffusion in pellets, 723–725,
447 overview, 454–456 729–730
CSTRs. See Continuous-stirred tank by poisoning, 461–464 Ergun equation, 173
reactors (CSTRs) reactors offsetting, 465 ethylene oxide production, 186
Cumene by sintering, 456–459 isothermal reactor design, 169
adsorption, 421–427 straight-through transport reactors, PBRs, 19, 38, 163, 245
decomposition, 5, 430–431 472–476 PFR mole balance, 15–16
in Langmuir–Hinshelwood kinetics, temperature-time trajectories, solutions to, 900
421–422 465–467 triphenyl methyl chloride-methanol
rate law, 429–430 Dead volume reaction, 256–258
Cumulative distribution function, 777 CSTRs, 796–797, 871, 880–882 tubular flow reactor design equations,
Curie, Marie, 767 tubular reactors, 798 37
CVD (chemical vapor deposition), zones, 768 Differential reactors, rate data collection
448–451 Dean, A. R. C., 371 and analysis in, 264–270
in diffusion and reaction, 753 Death phase in cell growth, 369 Differentiation, equal-area graphical,
professional reference shelf for, 757 Death rate in winemaking, 371 255–256, 898–899
942 Index

Diffusion, 679, 719 Dimensionless cumulative distributions, Economic decisions and incentives for
binary, 684–688 788–789 separations systems, 281
boundary conditions in, 408–409, Dimensionless groups in mass transfer Effective diffusivity in spherical catalyst
685–688, 690, 726, 728 coefficient, 691 pellets, 721–723
from bulk to external transport, Dimerize propylene, 53 Effective transport coefficient, 695
408–409 Dimethyl ether (DME) Effectiveness factor
with catalysts, 408–410, 720–721 decomposition, 276 in internal diffusion, 730
differential equation for, from methanol, 484–485 isothermal first-order catalytic
723–725, 729–730 Diphenyl in reversible reactions, 80–82 reactions, 730–733
dimensionless form, 726–728 Dirac delta function isothermal non-first-order
effective diffusivity in, 721–723 in PFR RTD, 784 catalytic reactions,
for tissue engineering, 763–765 in segregation models, 813 733–734
chemical vapor deposition in, 753 in step tracer experiment, 776 overall, 739–743
convection in, 685–686 Disappearance of substrate, 349, 378 Thiele modulus estimates,
definitions, 681–682 Disappearance rate, 5–6 735–737
diffusion- and reaction-limited Disguised kinetics, 738–739 volume change with reaction,
regime estimation in, Disk rupture in nitroaniline production, 733
743–744 645–646 Weisz–Prater criterion,
dispersion model, 852 Dispersion 734–735
falsified kinetics in, 737–739 catalysts, 404 in nitrous oxide reductions,
Fick’s first law in, 683–684 COMSOL for, 870–871, 918 748–750
fundamentals, 680–681 one-parameter models, 847 Efficient parallel reactor schemes, 285
homogeneous systems, 720 in packed beds, 862 Electronics industry, microelectronic
internal, 409–410 vs. T-I-S models, 869 fabrication
internal effectiveness factor, 730 in tubular reactors, 852–854, chemical vapor deposition in,
isothermal first-order catalytic 858–862, 866–868 448–451
reactions, 730–733 Dispersion coefficient overview, 447–448
isothermal non-first-order catalytic experimental determination of, Elementary rate laws, 72–75
reactions, 733–734 862–866 Elementary reactions, 74, 412
Thiele modulus estimates, tubular reactors, 860–862 Eley–Rideal mechanism, 431
735–737 Dissociative adsorption, 270, 412–415, irreversible surface-reaction-limited
volume change with reaction, 733 450 rate laws, 435
Weisz–Prater criterion, 734–735 Distortions in reaction systems, 86–87 in surface reactions in catalysts,
journal article problems, 765 Divide and be conquered case, 418
journal critique problems, 765 705–707 in toluene hydrodemethylation,
limiting situations for, 750–751 Division of cells, 369–371 439–440
mass transfer coefficients, 690 DME (dimethyl ether) Elution, 776
correlations, 690–693 decomposition of, 276 EMCD (equimolar counterdiffusion),
mass transfer-limited reactions, from methanol, 484–485 724
697–700 DNA (deoxyribonucleic acid) in protein Emissions, automobile
mass transfer to single particles, production, 366 nitrogen oxides in, 277, 485–486
693–697 Doubling times in growth rates, 371 in smog formation, 28–29
operating condition changes in, Drinking and driving, 324–325 Empirical decay laws, 464–465
700–704 Drug therapy, 357–359 Endothelium in blood clotting, 302
mass transfer in packed beds, Dual sites Endothermic reactions
744–750 irreversible surface-reaction-limited equilibrium conversion in, 518
Mears criterion for, 743–744 rate laws in, 435 interstage heat transfer, 523–524
modeling with, 687–688 surface reactions in catalysts, Energy
molar flux in, 681–686 416–417 alternative, 396–397
multiphase reactors in, 751–753 conversion factors, 906
overall effectiveness factor in, Energy balances
739–743 E acetic anhydride production,
questions and problems, 757–765 E-curves 557–558
through stagnant film, 688–690 nonideal reactor modeling, 808 adiabatic operations, 500–502
temperature and pressure dependence in normalized RTD function, batch reactors, 633–639
in, 686–687 782–783 equilibrium temperature,
Digital-age problems, 317–318 in pulse input experiment, 770–775 521–522
Dilution rate in RTD moments, 780 in steady-state nonisothermal
bioreactors, 381–382 Eadie–Hofstee plots, 351–353 design, 508–509
chemostats, 381 Early mixing in nonideal reactor tubular reactors, 510
wash-out, 383 modeling, 809 butane isomerization, 513, 550
Index 943

CSTRs, 498–499 Equations Ethylene oxide (EO), 280

with cooling coils, 572–574 batch concentrations, 109–111 CSTRs for, 148–151
heat exchanger in, 565 concentrations in flow systems, 114 in ethylene glycol production, 191
in multiple reactions, 585–588 differential. See Differential forms production of, 185–190
unsteady-state operation, 653 and equations Eukaryotes, doubling times for, 371
enthalpies in, 497, 504–505 Equilibrium Euler method, 825
ethyl acetate saponification, 649 in adiabatic equilibrium temperature, Evaluation
first law of thermodynamics, 519–522 batch operations, 145–146, 297–298
495–496 in CVD, 451 CSTR series reactions, 300–301
heat of reaction in, 505–508 Equilibrium constant ethylene glycol production, 150, 159
MCMT production, 665 in adiabatic equilibrium temperature, gas phase, 211
nitroaniline production, 642 520 nitrogen oxide production, 215
overview of, 498–501 adsorption, 412, 423 PFR reactor volume, 142–143
PBRs, 499 in thermodynamic relationships, propylene glycol production,
PFRs, 499 909–914 651–656
with heat effects, 546–547 Equilibrium conversions, 518 toluene hydrodemethylation, 446
with heat exchange, 540–543 and adiabatic temperature, 518–522 triphenyl methyl chloride-methanol
multiple reactions, 581–588 butane isomerization, 514 reaction, 254
parallel reactions, 583 endothermic reactions, 518–524 tubular reactor design, 167–168
propylene glycol production, 570, exothermic reactions, 518–522 tubular reactor flow, 163–164
636, 653 feed temperature, 526–528 Excel
semibatch reactors, 499 semibatch reactors, 233 activation energy, 91–92
with heat exchangers, 647 stoichiometry, 126–130 CSTR parameter modeling,
multiple reactions, 658 Equimolar counterdiffusion (EMCD), 724 874–876
steady-state molar flow rates, 502–504 Ergun equation, 170–173, 177 trityl-methanol reaction, 250–251
tubular reactors, 540–543, 598–603 Esterification reactions, 226 Excess method in batch reactors, 246
unsteady-state nonisothermal E(t) curves in maximum mixedness Exchange volumes in CSTR parameter
reactors, 630–632 model, 827–828 modeling, 879–880
work term in, 496–498 Ethane Exhaust streams, automobile
Energy barriers, 84–87 from azomethane, 336–338 nitrogen oxides in, 277, 485–486
Energy distribution function, 88, 90 ethylene from, 483 in smog formation, 28–29
Energy economy in ethylene glycol production, 192 Exit-age distribution function, 777
hydrogen-based, 239–240 ethylene hydrogenation to, 452–454 Exit temperature in interstage cooling,
membrane reactors, 220–221 Ethanol 524–525
Energy flux, tubular reactors, 597–598 acetaldehyde from, 301 Exothermic reactions, 507, 518–522
Energy flux vectors, 597 ADH with, 359 equilibrium conversion, 518–522
Energy rate change with time, 907 butadiene from, 281 interstage heat transfer, 523–526
Engine knock, 431–433 in glucose-to-ethanol fermentation, safety issues, 603–605, 640–646
Engineering experiment design problem, 378–381 Experimental observation and
925 Ethoxylation reactions, 312 measurements, 8, 75
Engineering judgment in reactor Ethyl acetate, 204 for dispersion coefficient, 862–866
selection, 884 Ethyl acetate saponification, 647–650 for mass transfer limitations, 712
Enthalpies in energy balance, 497, Ethylbenzene Experimental planning
504–505 hydrogenation to ethylcyclohexane, professional reference shelf for, 273
Enzymatic reactions, 76, 343–344 492 in rate data collection and analysis,
batch reactor calculations, 354–356 styrene from, 220–221 271
Briggs–Haldane Equation, 354 Ethylene Explosions
Eadie–Hofstee plots, 351–352 adsorption of, 403–404 Monsanto plant, 640–646
enzyme-substrate complex, 344–346 epoxydation of, 329 nitrous oxide plant, 613, 673–674
induced fit model, 344 from ethane, 483 T2 Laboratories, 604, 660–668
inhibition of. See Inhibition of ethane from, 452–454 Explosive intermediates, microreactors
enzyme reactions PBRs for, 165–168 for, 212
lock-and-key model, 344 Ethylene chlorohydrin, 240 Exponential cell growth, 368–370
mechanisms, 346–348 Ethylene glycol (EG) Exponential decay rate law in catalyst
Michaelis–Menten equation, 348–354 CSTRs for, 148–151 deactivation, 464
temperature in, 356 from ethylene chlorohydrin and Exponential integrals, 815
Epidemiology, PSSH for, 392 sodium bicarbonate, 240 External diffusion effects. See Diffusion
Epitaxial germanium, 448–449 from ethylene oxide, 185 External mass transfer in nitrous oxide
Epoxydation of ethylene, 329 production of, 157–162 reductions, 749
Equal-area differentiation, 255–256, synthesizing chemical plant design Extinction temperature in multiple
898–899 for, 190–192 steady states, 579
944 Index

F Fixed concentration in mass transfer Formaldehyde

correlations, 701 from methanol, 359
F-curves Fixed coordinate systems in molar flux, oxidation of, 328–329
nonideal reactor modeling, 808 682 Formation enthalpies, 504–505
RTD, 777 Flashing frequency of fireflies, 99 Formation rates in azomethane
Fabrication, microelectronic Flat velocity profiles, 848 decomposition, 336–337
chemical vapor deposition in, Flow Fouling in catalyst decay, 459–461
448–451 in energy balance, 496 Four-point rule in integral evaluation,
overview, 446–448 numerical solutions to, 870–871 902
Facilitated heat transfer, 712 through packed beds, 170–174 Fourier’s law, 683
Falsified kinetics in pipes Fraction of collisions, 88–89
in diffusion and reaction, 737–739 dispersion, 860–861 Fractional area balance in CVD, 449
exercise, 763 pressure drop, 174–177 Free radicals
Fan, L. T. Flow rates as active intermediates, 335
on RTD moments, 778 mass transfer and reaction, 745 in bimolecular reactions, 70
on tracer techniques, 777 mass transfer correlations, 700 Frequency factors in activation energy,
Fanning friction factor, 175 membrane reactors, 314, 316 91
Fast orange formation, 135–136 multiple reactions, 282 Freudlich isotherms, 415
Fed batch reactors. See Semibatch space time, 59 Friction factor in pipe pressure drop, 175
reactors Flow reactors, 113–114. See also specific Frog legs experiments, 683–684
Feed stocks, catalyst poisoning in, 461 flow reactors by name Frossling correlation, 692, 694
Feed temperature in equilibrium concentrations in, 114 F(t) function in integral relationships,
conversion, 526–528 gas-phase, 115–126 777
Femtosecond spectroscopy, 335 liquid-phase, 114–115 Fuel cells, 239–240
Fermentation design equations, 35–38
glucose-to-ethanol, 378–381 CSTR, 36
wine-making, 370–371 PBRs, 37–38 G
Fermi, Enrico, 29–30 tubular, 36–37 Gallium arsenide layers, 448
Fibers, terephthalic acid for, 326–327 with heat exchange, 539–540 Gas-hourly space velocity (GHSV), 61
Fibrinogen, 302 balance on transfer fluid, Gas oil, catalytic cracking of, 469–472
Fick’s law 543–545 Gas phase and gas-phase reactions
in diffusion, 683–684 CRE Web site material, 607–609 adiabatic exothermic irreversible, 67
in dispersion, 852, 859 CSTRs, 564–574 batch systems, 34, 144
Film, diffusion through, 690 multiple steady states, 574–581 complex reactions with heat effects
Finlayson, B. A., 745 nonisothermal reactions, in PFRs, 589
Firefly flashing frequency, 99 581–595 in CVD, 449
First law of thermodynamics, PFR/PBR design algorithm, diffusion in, 686–687
495–496 545–563 elementary and reversible, 80
First-order rate laws, 75, 338–339 questions and problems, 610–626 equilibrium constant, 909–911
First-order reactions, 73 radial and axial variations in flow reactors, 35–36
batch operations, 146 tubular reactors, 595–603 flow reactors with variable
CSTR design safety, 603–605 volumetric flow rate,
series, 155–156 steady-state tubular reactors, 115–126
single, 152–153 540–543 liquid-phase concentrations, 114–115
differential equations for summary, 606–607 microreactors, 213–217
diffusion in spherical catalyst supplementary reading, 626–627 mole balances on, 210–212
pellets, 729–730 with variable volumetric flow rate, packed beds, 140
solutions, 900 115–126 PBRs, 304–307
multiple steady states, 577 Fluid fraction in laminar flow reactors, PFR reactor volume, 142–144
nonideal reactor modeling, 809 787 pressure drop in, 169–170
PFR reactor volume for, 142–144 Fluid Peclet number, 855 tubular reactors, 14, 163–165,
reversible, 518 Fluidized-bed reactors, 79, 753, 756–757 542–543
segregation models, 812 Fluidized continuous-stirred tank Gas-solid heterogeneous reactions, 244
Fitting tail, 801 reactors, 445–446 Gas volumetric flow rate in space
Five-point quadrature formula Flux equation for diffusion in spherical velocity, 61
PFR sizing, 44 catalyst pellets, 724 Gasoline
solutions, 902–903 Force, conversion factors for, 906 catalyst poisoning, 461
Fixed-bed reactors. See Packed-bed Forced convection, mass transfer octane number, 523–524
reactors (PBRs) coefficient in, 691, 693 Gaussian program, 335
Index 945

General mole balance equation, 8–10 Heat of reactions dissociative adsorption of, 450
CSTRs, 13 in energy balance, 505–508 in enzyme-substrate complex, 344
tubular reactors, 15 molar flow rates for, 502–504 in membrane reactors, 219
Generation heat in multiple steady states, Heat terms in multiple steady states, in methane production, 266–270
576–578 575–578 in reversible reactions, 80–82
Generic power law rate laws in gas Heat transfer from water-gas shift reaction,
phase, 210 to CSTRs, 565 912–914
Germanium epitaxial film, 448–449 in diffusion, 683 water splitting, 487–488
GHSV (gas-hourly space velocity), 61 in mass transfer coefficient, 691 Hydrogen-based energy economy,
Gibbs free energy in mass transfer limitations, 712 239–240
in cumene adsorption, 425 in octane number, 523–524 Hydrogen peroxide
in equilibrium constant, 910–911 in pressure drop, 185 decomposition, 392
Globules in segregation models, in tubular reactors, 543–545 sodium thiosulfate reaction, 574
810–812 Height, energy barrier, 85 Hydrogenation reactions
Glow sticks, 342 Helium mixture in monopropellant of ethylene to ethane, 452–454
Glucose in wine-making, 370 thrusters, 702 membrane reactors for, 312
Glucose-to-ethanol fermentation, Hemoglobin, deoxygenation of, 275 Hydrolases enzymes, 346
378–381 Hemostasis process, 302 Hydrolysis
Goals for nonideal reactors, 846 Heptane, 431–432 semibatch reactor operation, 226
Goodness of fit in rate data analysis, 245 Heterogeneous catalytic processes starch, 394
Gradientless differential reactors, 264 in methane production, 269 Hydrophobic forces for
Graphical methods phases in, 401 enzyme-substrate complex, 344
batch reactor data analysis, 252 Heterogeneous data analysis, Hyperbolic decay rate law, 464
equal-area differentiation, 898–899 436–437 Hypothetical stagnant film in diffusion,
triphenyl methyl chloride-methanol mechanisms, 439–440 689
reaction, 255–256 rate laws, 438–442
Gravitational conversion factor, 907 reactor design, 443–446
Greek symbols, 923 Heterogeneous reactions, 7, 70, I
Growth of microorganisms. See 79–80 Ideal gas constant, 905
Bioreactors data for, 244 Ideal gas law, 35
Gumbo, 926–927 external diffusion effects on. See Ideal reactors
Diffusion RTD for, 794–799
mass transfer of reactants in, 720 batch and plug-flow, 784–785
H High-fructose corn syrup (HFCS), 344 laminar flow, 786–789
Hagen–Poiseuille equation, 858 High-nickel stainless steel plates, 100 single-CSTR RTD, 785–786
Hanes–Woolf model High temperature in multiple steady in two-parameter models,
for Michaelis–Menten equation, states, 577 871–873
351–353 Hilder’s approximation, 815 Identity
of Monod equation, 376 Holding time in space time, 59 in chemical species, 4
Heat capacities in enthalpy, 505 Homogeneous reactions, 70, 76–77 in reactions, 5
Heat effects. See also Temperature data for, 244 Ignition-extinction curves, 578–581
COMSOL for, 917 rate law parameters for, 246 Ignition temperature
CSTRs with, 564–574 Homogeneous systems, diffusion and in equilibrium conversion, 527
in semibatch reactors, 647–650 reactions in, 720 in multiple steady states, 579
in steady-state nonisothermal Honeybee flight speed, 100 Imperfect pulse injection in step tracer
reactors. See Steady-state Hot spots in microreactors, 212 experiment, 776
nonisothermal reactors Hydrazine for space flights, 702–704 IMRCFs (inert membrane reactors with
Heat exchangers Hydrocarbons, partial oxidation of, 312 catalyst pellets on the feed side),
acetic anhydride production, Hydrocracking, temperature-time 217–218
559–560 trajectories, 466–467 Independent reactions, 280–281, 581
adiabatic operations, 638–639 Hydrodemethylation of toluene, 79–80, Induced fit model for enzyme-substrate
energy balance, 565 437–446 complex, 344
interstage cooling, 525–526 Hydrodesulfurization reactor design Industrial reactors
microreactors, 212 problem, 926 dimerize propylene into olefins, 53
PFR/PBR with heat effects, 547 Hydrodynamic boundary layer in in mole balance, 22–23
semibatch reactors, 646–651 diffusion, 688 space time in, 59–60
steady-state nonisothermal reactors. Hydrogen Inert membrane reactors with catalyst
See Flow reactors ammonia from, 420 pellets on the feed side
Heat load in interstage cooling, 525–526 from cyclohexane, 714 (IMRCFs), 217–218
946 Index

Inhibition of enzyme reactions, 356–357 Irreversible surface-reaction-limited rate K

competitive, 357–359 laws, 435
noncompetitive, 361–363 Iso-octane, 431–433 Key reactant concentrations, 118
substrate, 363–364 Isobutane production, 512–518, 548–555 Kidneys, artificial, 346
uncompetitive, 359–361 Isomerases enzymes, 346 Kind in chemical species, 4
Inhibitor molecules, 361 Isomerization Kinematic viscosity
Inhibitors, 356–357 batch reactors, 11–12 of helium, 702
Initial conditions in tubular reactors, 600 butane, 55–58, 512–518, 548–555 in mass transfer coefficient, 691
Initial rates for differential reactors, 264 irreversible, 436 Kinetic energy in energy balance, 497
Initiation step in chain reactions, 343 isothermal gas-phase, 39 Kinetic rate law, 72, 77–78
Inlet conditions in reactions, 5 Kinetics in catalyst deactivation, 455,
differential reactors, 266 Isopropyl isocyanate decomposition, 278 463
equilibrium conversion, 527–528 Isotherm equation in adsorption, 415 Knee joint replacements, 763–765
Instantaneous selectivity Isothermal operations Knudsen diffusion, 721
multiple reactions, 281 catalytic reactions Knudsen phase, diffusion in, 686–687
parallel reactions, 285, 291 first-order, 730–733 Kunii–Levenspiel fluidization model,
semibatch reactors, 227 non-first-order, 733–734 753
Instantaneous yield in multiple reactions, flow reactors, 121
282 gas-phase isomerization, 39
Insulin production, 364 interrupted, 640–646
L
Integral data analysis method, 247–251 nitroaniline production, 642–643 Labs-on-a-chip, 212
Integral reactors, 19, 37 sulfur dioxide gas-phase reactions, 121 Lag phase in cell growth, 368
Integral relationships in RTDs, 777–778 sulfur dioxide rate law, 124 Laminar flow
Integrals Isothermal reactors, 139 Aris–Taylor analysis for, 870–871
numerical evaluation of, 901–902 batch, 144–151 dispersion for
in reactor design, 897–898 COMSOL for, 918 pipes, 860–861
Integrated circuit fabrication CRE Web site material, 195–196 tubular reactors, 858–860
CVD in, 448–451 CSTRs, 152 Laminar flow reactors (LFRs)
overview, 446–448 design equations, 94 mean conversion in, 817–820
Interchange in CSTR modeling, 878–880 ethylene glycol, 157–162 RTDs in, 786–789
Interfacial area for catalytic reactions, series, 155–157 in segregation models, 813–815
401 single, 152–155 Langmuir, Irving, 413
Intermediates, active. See Active learning resources for, 195–196 Langmuir–Hinshelwood kinetics
intermediates molar flow rates. See Molar flow in catalyst surface reactions, 418
Internal-age RTDs, 783–784, 801 rates for heterogeneous reactions,
Internal diffusion, 409–410 ODE solver algorithm, 194 79, 244
Internal effectiveness factor pressure drop, 169 nonlinear regression for, 259
in diffusion, 730 analytical solution, 177–188 in rate limiting, 419
isothermal first-order catalytic flow through packed beds, single-site mechanisms, 694
reactions, 730–733 170–174 steps, 421–422
isothermal non-first-order pipes, 174–177 Langmuir isotherm, 413–415
catalytic reactions, rate law, 169–170 Large molecules, synthesis of, 366
733–734 questions and problems, 196–205 Late mixing, nonideal reactor modeling,
Thiele modulus estimates, structure for, 140–144 809
735–737 summary, 193–194 Le Châtelier’s principle, 911
volume change with reaction, 733 supplementary reading, 205 Lead in gasoline, 461
Weisz–Prater criterion, 734–735 synthesizing chemical plant design, Lead titanate, 715
in nitrous oxide reductions, 748–750 190–192 Least-squares analysis
Interrupted isothermal operations, tubular reactors, 162–168 batch reactors, 259
640–646 Isotherms, adsorption, 410–415 multiple reaction analysis, 317
Interstage heating and heat transfer professional reference shelf for,
reactor staging with, 522–526 273
reactor trains with, 536 J LeBlanc, Steve, 629, 807
Ionic forces for enzyme-substrate Januvia, 357 Levenspiel, O.
complex, 344 Johnson, Samuel, 333 on dispersion coefficient
Irreversible reactions, 70 Journal critique problems determination, 864
endothermic, 532–534 diffusion, 765 on dispersion model, 853
exothermic, 67 mass transfer limitations, 717 on reaction combinations, 883
isomerization, 436 Junction balance in CSTR parameter on tubular reactor boundary
order in, 246 modeling, 873, 877 conditions, 858
Index 947

Levenspiel plots Locally stable steady-state values, 580 in packed beds, 697–700, 744–750
adiabatic isomerization, 57 Lock-and-key model, 344 to single particles, 693–697
butane isomerization, 515 Log-log paper Material Safety Data Sheets (MSDS), 162
flow reactors, 41–42, 129–130 batch reactor analysis, 252 Mathematically tractable nonideal
PFRs in series, 52 triphenyl methyl chloride-methanol reactor models, 846
LFRs (laminar flow reactors) reaction, 256 MATLAB program
mean conversion in, 817–820 Logic vs. memorizing, 140, 142 adiabatic tubular reactors, 511
RTDs in, 786–789 Logistic growth law, 395 CSTR parameter modeling, 874–876
in segregation models, 813–815 London van der Waals forces, 344 ethylene oxide production, 188
LHSV space velocity, 61 Los Angeles basin, 28–29 explanation of, 916
Ligases enzymes, 346 Low temperature in multiple steady instructions, 903
Light from ultrasonic waves, 340–342 states, 577 isothermal reactors, 194
Limiting reactants Lubricant design problem, 925 membrane reactors, 223–224
in batch systems, 112–113 Luedeking–Piret equation, 375 non-adiabatic PFR energy balance,
in conversion, 32 Luminescence from ultrasonic waves, 501
Limiting situations for diffusion, 750–751 340–342 nonlinear regression, 261
Linear decay rate law in catalyst Lyases enzymes, 346 Maximum mixedness model, 820–826
deactivation, 464 multiple reactions in, 831–835
Linear least squares, 259 nonideal reactor modeling, 809
Linear plots in batch reactor data M vs. segregation model, 829–830
analysis, 247–249 Macrofluids in nonideal reactor software packages for, 827–829
Lineweaver–Burk plots modeling, 809–810 Maxwell–Boltzmann distribution,
for inhibition Macromixing, 769, 809 87–90
competitive, 359 Maintenance in cell growth, 373 MCMT (methylcyclopentadienyl
noncompetitive, 362–363 Marx, Groucho, 139 manganese tricarbonyl)
uncompetitive, 361 Mass, conversion factors for, 906 production, 660–668
for Michaelis–Menten equation, Mass balances. See also Mole balances Mean conversion
350–351 in cell growth, 377–381 laminar flow reactors, 817–820
Liquid-hourly space velocity (LHSV), 61 in glucose-to-ethanol fermentation, real reactors, 816–817
Liquid phase and liquid-phase reactions 378–381 segregation models, 811–813
batch systems, 34, 110–111, 144 Mass flow rate through packed beds, 171 Mean residence time
butane isomerization, 55–58, 512–518 Mass transfer boundary layers, 688 dispersion coefficient determination,
complex reactions, 307–312 Mass transfer coefficients 865
concentrations, 114–115 in diffusion, 690 RTDs, 778, 788
CSTRs for, 12–14, 307–312 correlations, 690–693 in space time, 59
diffusion in, 686–687 example, 700–704 Mears criterion, 743–744
flow reactors, 35, 114–115 mass transfer-limited reactions, Measured variables
MCMT production, 660 697–700 in rate data analysis, 244
methanol-triphenyl reaction, 276 mass transfer to single particles, in triphenyl methyl chloride-methanol
mole balances, 208, 210 693–697 reaction, 254
pressure drop, 169 in hydrazine decomposition, 703 Mechanism searches, 339–342
selectivity in, 227 in nitrous oxide reductions, 749 Medical applications. See
semibatch reactors, 310–312 in PBRs, 750 Pharmacokinetics
tubular reactors, 163, 543 “what if” conditions for, 705–709 MEK (methyl ethyl ketone) production,
Living example problems (LEPs) Mass transfer limitations, 679–680 486
active intermediates, enzymatic diffusion Membrane reactors
reactions, pharmacokinetic binary, 684–688 design, 217–225
models, and bioreactors, 387 fundamentals, 680–684 mole balances, 208–209
catalysts, 480 mass transfer coefficient, for multiple reactions, 312–316
flow reactors with heat exchange, 608 690–704 packed bed, 172
isothermal reactors, 196 through stagnant film, 688–690 Memorization vs. logic, 140, 142
molar flow rates, 236, 238 on metallic surfaces, 712 Metabolism of alcohol, 927
multiple reactions, 321 in PBRs, 697–700 Metallic surfaces, mass transfer-limited
nonideal reactors, 887 “what if” conditions for, 705–709 reactions on, 712
nonisothermal reactors Mass transfer Metaxylene isomerization, 202
steady-state, 530 in diffusion, 683 Methane
unsteady-state, 670 in heterogeneous reactions, 720 from carbon monoxide and
rate data collection and analysis, 273 mass transfer-limited reactions, hydrogen, 266–270
RTDs, 801 697–700 para-xylene from, 401
zero-adjustable-parameter models, 837 in microreactors, 212 from toluene, 79, 437–446
948 Index

Methanol ethylene glycol production, 191 maximum mixedness model,

ADH with, 359 flow reactors, 35, 115–117, 128 822–823
dimethyl ether from, 484–485 gas phase, 210 MCMT production, 663–664
poisoning by, 359, 928 heat of reaction, 502–504 mean conversion in laminar flow
synthesis problem, 926 learning resources, 236 reactors, 818
in triphenyl methyl chloride reaction, membrane reactors, 217–225, membrane reactors, 219, 221–222,
254–258 313–314 314
in trityl-methanol reaction, 249–251 microreactors, 212–217 moving-bed reactors, 468
Methyl amine, 230–233 mole balances, 208–212 multiple reactions, 283–284, 314,
Methyl bromide production, 230–233 multiple reactions, 282, 313–314, 586, 657
Methyl ethyl ketone (MEK) production, 316 nitroaniline production, 641
486 ODE solver algorithm, 235 nitrogen oxide production, 214
Methylcyclohexane, toluene from, 489 PFR/PBR with heat effects, 546–547 nitrous oxide reductions, 748
Methylcyclopentadienyl manganese PFRs, 16–17 nonisothermal reactor design
tricarbonyl (MCMT) production, semibatch reactors, 227–233 steady-state, 494
660–668 tracer, 852 unsteady-state, 631
Michaelis constant, 348–350, 359 unsteady-state operation of stirred parallel reactions, 289, 583
Michaelis–Menten kinetics and reactors, 225–226 PBRs, 18–19, 208–212, 304
equations, 334 Molar flux in tubular reactors, 596–597 PFRs
in competitive inhibition, 357 Molar rate of mass transfer in diffusion, first-order gas-phase reaction,
in enzymatic reactions, 348–354 739–740, 742 142–143
substrate concentration in, 355 Mole balances, 1–4 with heat effects, 546, 583
in uncompetitive inhibition, 359–361 acetic anhydride production, pressure drop, 169, 178
Microbial growth. See Bioreactors 556–557 professional reference shelf for,
Microelectronic fabrication adiabatic tubular reactors, 510 25–26
chemical vapor deposition in, batch reactors, 10–12, 144–146 propylene glycol production, 569,
448–451 in design equations, 33 635, 652–653
overview, 446–448 enzymatic reactions, 354 rate data analysis, 244
Microfluids in nonideal reactor integral data analysis, 248 reaction rate, 4–8
modeling, 809–810 series reactions, 295–296 semibatch reactors, 227–228, 230,
Micromixing, 769, 809 butane isomerization, 512, 549 310, 657
Microorganism growth. See Bioreactors catalyst decay, 458 straight-through transport reactors,
Microreactors CFRs (continuous flow reactors), 472–474
molar flow rate algorithm, 212–217 12–22 T-I-S model, 851
for phosgene, 203–204 CRE (chemical reaction engineering) toluene hydrodemethylation, 446
Mild reaction conditions in Web site material, 24–26 triphenyl methyl chloride-methanol
bioconversions, 365 CSTRs, 36, 872 reaction, 254
Minimum mixedness, 820 with cooling coils, 573 tubular reactors, 37, 596–597
Mixed inhibition, 361–363 in design, 152, 156 adiabatic, 510
Mixers in microreactors, 212 liquid phase, 308 design, 166
Mixing multiple reactions, 586 with heat exchange, 542
nonideal reactors, 769, 808–809 series reactions, 49, 299–300 Molecular adsorption, 412–415
RTDs, 770 unsteady-state operation, Molecular dynamics, 97–98
segregation models, 810–811 652–653 Molecular sieves, 401
Model discrimination in catalysts, diffusion, 681–682, 724 Molecularity of reactions, 70
451–454 ethyl acetate saponification, 648 Molecules in diffusion, 681
Modeling nonideal reactors ethylene glycol production, 148–149, Moles
using RTDs, 807–808 158 in batch systems, 107–109
zero-adjustable-parameter models. gas-oil catalytic cracking, 470 in reactors in series, 47
See Zero-adjustable- gas phase, 210–212, 304 Moments of RTDs, 778–782
parameter models general mole balance equation, 8–10 Momentum transfer in diffusion, 683
Molar average velocity in diffusion, 683 homogeneous systems, 720 Monod equation, 334
Molar feed rate in flow reactors, 35 industrial reactors, 22–23 bioreactors, 364, 382
Molar flow rates, 114, 207 inert tracer in dispersion model, 853 for exponential growth, 369–370
balance equation, 208 isothermal reactors, 169, 209 Hanes–Woolf form, 376
binary diffusion, 684–687 learning resources for, 24–25 Monoethanolamine formation, 280
CRE Web site material, 236–237 liquid phase, 208, 210, 308, 310 Monolithic catalysts, 401
CSTRs, 14 mass transfer and reaction in packed Monopropellant thrusters, 702–704
diffusion, 681–686 beds, 745 Monsanto plant accident, 640–646
Index 949

Moser growth law, 370–371 Newberger, Tim, 105 dispersion coefficient correlation,
MOSFET devices, 447 Nickel catalysts, 266–270 860–862
Moving-bed reactors, catalyst Nitration reactions, 312 dispersion coefficient
deactivation in, 467–472 Nitroaniline from ammonia and ONCB, determination, 862–866
MSDS (Material Safety Data Sheets), 162 604, 640–642 two-parameter models, 848, 871–873
Multiphase reactors in diffusion, 751–753 adiabatic operation, 643–644 Web site material, 886–887
Multiple reactions, 279 batch operation with heat exchange, zero-adjustable-parameter models.
algorithms, 282–284 644–645 See Zero-adjustable-parameter
analysis for, 317 disk rupture in, 645–646 models
complex. See Complex reactions isothermal operation, 642–643 Nonisothermal reactions, 581
CRE Web site material, 320–322 Nitrogen COMSOL for, 918
CSTRs, 298–302, 585–588 ammonia from, 420 steady-state. See Steady-state
for digital-age problems, 317–318 from azomethane, 336–338 nonisothermal reactors
membrane reactors for, 312–316 from benzene diazonium unsteady-state. See Unsteady-state
nonisothermal, 581 chloride, 91 nonisothermal reactors
energy balance in, 581–588 skin exposure to, 714 Nonlinear least-squares, 317
unsteady-state, 656–668 Nitrogen dioxide Nonlinear regression
packed bed flow, 172 from nitrogen oxide, 390 batch reactor data analysis, 258–263
parallel. See Parallel reactions from reversible gas-phase cell growth, 376
PBRs, 304–307 decompositions, 126–130 ethylene hydrogenation to ethane,
PFRs, 500, 581–582 Nitrogen oxides 452–453
RTD in, 830–835 in automobile emissions, 277, Michaelis–Menten equation, 353
series, 280 485–486 toluene hydrodemethylation, 441–442
batch reactors, 294–298 nitrogen dioxide from, 390 Nonseparable kinetics in catalyst
in blood clotting, 302–303 production of, 213–217 deactivation, 455
CSTR, 298–302 Nitrogen tetroxide decomposition, Normal pentane, octane number of, 433
types, 280–282 126–130 Normalized RTD function, 782–783
Multiple regression techniques, Nitrous oxides Nuclear processes, Fermi work on, 29–30
441–442 in plant effluents, 746–750 Nuclear region in cells, 366
Multiple steady states, 574–575 in plant explosion, 613, 673–674 Number in chemical species, 4
heat of generation in, 576–578 Nomenclature, 921–923 Numerical techniques
heat-removed terms, 575–578 Non-adiabatic energy balance, 501 adiabatic tubular reactors, 511
ignition-extinction curves, 578–581 Noncompetitive inhibition, 361–363 batch reactor data analysis, 252–253
Multiple substrate systems, 388 Nondissociated adsorption, 412 differential equations. See Differential
Multiplication, cell, 367 Nonelementary rate laws, 76–80, 334–335 forms and equations
Mystery Theater module, 198 chain reactions in, 343 equal-area graphical differentiation,
mechanism searches in, 339–342 898–899
PSSH in, 335–338 for flows with dispersion and
N summary, 385–386 reaction, 870–871
N-butyl alcohol, dehydration of, Nonenzymatic lipoprotein, 302 integrals
483–484 Nonflat velocity profiles in dispersion, numerical evaluation of, 901–902
National Oceanic and Atmosphere 858 in reactor design, 897–898
Administration (NOAA), 604 Nongrowth associated product MCMT production, 665–666
Negative steps in step tracer experiment, formation, 372, 374 for membrane reactors, 223
776 Nonideal reactors, 845 semilog graphs, 903
Net rates considerations, 767–770 software packages, 903
batch reactor series reactions, 296 using CSTRs and PFRs, 882–883 Nusselt number, 691–692
CSTRs dispersion flow solutions, 870–871 Nutrients in cell growth, 373–374
liquid phase, 308 guidelines, 846–847
series reactions, 299 modeling using RTDs, 807–810
MCMT production, 664–665 one-parameter models, 847–848 O
membrane reactors, 314 pharmacokinetic modeling, Octane, butyl alcohol for, 482
multiple reactions, 284–285, 296 883–884 Octane number
parallel reactions, 285, 289, 583 T-I-S, 848–852, 869 interstage heat transfer in, 523–524
PBR gas phase reactions, 305 tubular from lead, 461
PFR complex reactions with heat balance equations in, 854 in petroleum refining, 431–433
effects, 589 boundary conditions in, ODE solvers. See Ordinary differential
of reaction, 71 855–858 equation (ODE) solvers
semibatch reactors, 310, 658 dispersion, 852–854, 858–860 Olefins from dimerize propylene, 53
950 Index

One adjustable parameter models, Oxidoreductases enzymes, 346 Pellets, 720–721

nonideal reactor modeling, 808 Oxygen-18 data, 717 differential equation for, 723–725,
One-parameter models for nonideal Oxygen in water splitting, 487–488 729–730
reactors, 846–847 Ozone reactions with alkenes, 277 dimensionless form, 726–728
characteristics, 847–848 effective diffusivity in, 721–723
dispersion, 852–854 in internal diffusion, 409
T-I-S, 848–852 P Penicillium chrysogenum formation, 369
One-third rule, 902 Packed-bed reactors (PBRs), 12, Perfect mixing in CSTRs, 13, 36, 286
Open-ended problems, 925–928 18–22 Perfect operation
Open-open boundary conditions adiabatic, 509–517 in CSTRs, 794–795
in dispersion coefficient catalyst poisoning in, 462–463 in tubular reactors, 797
determination, 864–866 complex reactions, 304–307 PFRs. See Plug-flow reactors (PFRs)
in tubular reactors, 856–857 design equations for, 94 Pharmacokinetics
Open systems, first law of dispersion in, 862 competitive inhibition, 357–359
thermodynamics for, 495 energy balance for, 499 in drinking and driving, 324–325
Open vessel dispersion, 855 flow reactor design equations, 37–38 modeling, 883–884
Operating conditions gas-phase reactions, 140 summary, 385–386
mass transfer coefficients, 700–704 with heat exchange, 499 Tarzlon, 325
parallel reactions, 291–294 acetic anhydride production, Phases
Operating costs in ethylene glycol 556–563 cell growth, 368
production, 191–192 algorithm, 545–548 enthalpy, 504–505
Optimum feed temperature in butane isomerization, 548–555 gas. See Gas phase and gas-phase
equilibrium conversion, 526–528 mass transfer, 697–700, 744–750 reactions
Optimum yield in batch reactor series mole balances, 18–19, 208–212 heterogeneous reactions, 7
reactions, 297 ODE solvers algorithms for, 194 liquid. See Liquid phase and
Orbital distortions, 87 pressure drop, 170–177 liquid-phase reactions
Order, reaction, 72–83 RTDs, 768 Phosgene production, 203–204
Order of magnitude of time in batch for toluene hydrodemethylation, Photochemical decay of aqueous
operation, 147 443–445 bromine, 276–277
Ordinary differential equation (ODE) transfer-limited reactions in, Photos of real reactors, 25
solvers 750–751 Phthalic anhydride, 1–2
adiabatic tubular reactors, 511 Parallel reactions, 280 Physical adsorption, 403
catalyst decay, 479 CSTRs, 159–160, 288–291 Picasso’s reactor, 17
gas phase, 211 desired products in, 285–291 Pipes
isothermal reactors, 194 in mass transfer-limited reactions, dispersion, 860–861
molar flow rates, 235 705 pressure drop, 174–177
multiple reactions, 317 PFRs with heat effects, 582–585 Plant effluents, nitrous oxides in,
Organic reactions, liquid-phase, 110 reactor selection and operating 746–750
Orthonitroaniline from ammonia and conditions, 291–294 Platinum on alumina as reforming
ONCB, 135–136 Partial differentiation (PDE) solvers for catalyst, 432–434
Orthonitrochlorobenzene (ONCB) diffusion, 682, 685 Plug flow
nitroaniline from, 640–642 Partial oxidation, membrane reactors for, in diffusion, 684
orthonitroaniline from, 135–136 312 in tubular reactor design, 163, 166
Oscillating reactions, 323 Partial pressures Plug-flow reactors (PFRs), 12, 14–18
Outlet concentration in nonideal reactors, profiles, 444–445 adiabatic, 509–518
847 in sulfur dioxide rate law, 123–126 butane isomerization, 514–517
Overall effectiveness factor Particle size complex reactions with heat effects,
diffusion and reaction, 739–743, 758 in internal diffusion, 409–410 588–595
nitrous oxide reductions, 748–750 in pressure drop, 182–183 conversion in, 868
Overall mass balance, 228 PBRs. See Packed-bed reactors (PBRs) CSTRs in series as approximation of,
Overall mass transfer coefficient, 220 Peach Bottom nuclear reactor problem, 51–57
Overall selectivity 925 design equations for, 36–37
membrane reactors, 313 Peclet number energy balance, 499
multiple reactions, 282, 313 in dispersion and T-I-S models, 869 with heat exchange, 540–543
Overall yield in multiple reactions, 282 in dispersion coefficient multiple reactions, 581–582
Overenthusiastic engineers, 707–709 determination, 862–864, 866 parallel reactions, 583
Oxidation nonideal reactor modeling, 808 ethylene production, 165–168
of formaldehyde, 328–329 in tubular reactors, 854–855, 858 for gas-phase reactions, 142–144
membrane reactors for, 312 Peclet–Bodenstein number, 869 with heat exchange, 545–548
Index 951

acetic anhydride production, membrane reactors, 223–224, 315 Pressure profiles, 444–445
556–563 methane production, 269–270 Price in ethylene glycol production,
butane isomerization, 548–555 methyl bromide production, 231–232 191–192
mean conversion in, 818 Michaelis-Menten equation, 353 Product-enzyme complex, 353–354
mole balances, 208–212 multiple reactions, 315, 587–588, Product formation in cell growth,
multiple reactions, 581–582 659–660, 833–835 371–377
nonideal reactors using, 882–883 nitroaniline production, 644 Production rate in dilution, 383
parallel reactions, 289–291, 582–585 nitrogen oxide production, 215–216 Products, catalyst poisoning by, 463
reactor volume for, 142–144 nonlinear regression, 261–263, 376 Promoters, 402
RTDs for, 784–785 PBR gas phase reactions, 306–307 Propagation step in chain reactions, 343
runaway in, 608–609 PFRs, 584, 591–595 Propane, dehydrogenation for, 221
in segregation models, 813, 815–816 propylene glycol production, Propylene
in series, 52 571–572, 637–638, 654–655 adsorption of, 422–423
with CSTRs, 53–57 RTD moments, 780–781 from cumene, 5
sequencing, 57–58 segregation models, 816, 824 in Langmuir–Hinshelwood kinetics,
series reactions, 301–302 semibatch reactors, 659–660 421–422
sizing, 43–47 straight-through transport reactors, Propylene glycol production
Point of no return in nitroaniline 475–476 adiabatic reactors, 568–572, 634–639
production, 644 toluene hydrodemethylation, CSTR unsteady-state operation,
Poisoning 441–442, 444 651–656
catalyst decay, 461–464 trityl-methanol reaction, 250–251 Propylene oxide, propylene glycol from,
methanol, 359, 928 tubular reactors, 511, 867 568–572
Polanyi–Semenov equation, 93 variable volumetric flow rate, 127–128 Prostaglandin, inhibiting production of,
Polydisperse solids, mass transfer Polymerization 357
limitations of, 712 batch systems, 111, 147 Protease hydrolyzes, 343–344
Polyesters bioreactors, 366 Prothrombin, 303
ethylene glycol for, 157 professional reference shelf for, Pseudo-steady-state-hypothesis (PSSH),
from ethylene oxide, 185 387–388 333
Polymath programs (Living Example screw extruders in, 777 for active intermediates, 335–338
Problems (LEPs)) Polymers production, 364–365 for epidemiology, 392
acetic anhydride production, 558–563 Polynomial fit for E(t) curves, 827–828 first-order rate law, 338–339
adiabatic reactors, 501, 511 Pore closure in catalyst deactivation, 456 rate laws derived from, 435
blood clotting, 303 Porous catalyst systems, 401 Pulse injection, 770–771
butane isomerization, 516, 550, Potential energy in energy balance, 497 Pulse input experiment for RTDs,
552–553 Power law 770–776
catalyst decay, 458–459 and elementary rate laws, 72–75 Pulse tracer inputs, 772–773, 785, 848,
cell growth, 376 in gas phase, 210 862
CSTRs for homogeneous reactions, 244 Pyridine hydro-chloride, 249
with bypass and dead volume, Practical stability limit
880–882 CSTR unsteady-state operation, 651
with cooling coils, 573–574 propylene glycol production, 654–655 Q
liquid phase, 309 Prandtl number, 691–692
Q term in CSTRs with heat effects,
with multiple reactions, 587–588 Pressure
564–567
parameter modeling, 874–876 conversion factors for, 906
Quarderer, G. C., 271
unsteady-state operation, 654–655 in diffusion, 686–687
energy balance, 501 in energy balance, 496
ethyl acetate saponification, 650 in flow reactors with variable
ethylene hydrogenation to ethane, volumetric flow rate, 116
R
452–453 in sulfur dioxide rate law, 123–126 Radial concentration profiles, 871
ethylene oxide production, 188–190 Pressure drop Radial mixing in tubular reactors, 858
explanation of, 915–916 in ethylene oxide production, 185–190 Radial variations in tubular reactors,
gas-oil catalytic cracking, 470–471 in isothermal reactor design, 169, 209 595–596
glucose-to-ethanol fermentation, 380 analytical solution, 177–188 energy balance, 598–603
heat effects, 584 flow through packed beds, energy flux, 597–598
instructions, 903 170–174 molar flux, 596–597
isothermal reactors, 194 pipes, 174–177 Radioactive decay, 70
maximum mixedness model, 828–829 rate law in, 169–170 Raney nickel, 401
MCMT production, 665–667 tubular reactors with heat exchange, Rapid reactions on catalyst surfaces,
mean conversion, 819 542 693–697
952 Index

Rate constant kinetic, 77–78 cumene adsorption, 424–427

adsorption, 412 mean conversion, 818 surface reactions, 427–428
reaction, 72, 83–93 membrane reactors, 222, 314 Rate of change of energy with time, 907
Rate data collection and analysis, 243 methane production, 267–269 Rate of consumption in spherical catalyst
batch reactor data, 246–247 methyl bromide production, 230 pellets, 727
differential method, 251–258 multiple reactions, 284–285, 314, Rate of desorption, 418
integral method, 247–251 317, 586–587, 658 Rate of detachment in adsorption, 412
nonlinear regression, 258–263 nitroaniline production, 641 Rate of disappearance of substrate, 349
CRE Web site material, 272–273 nitrogen oxide production, 214 Rate of formation
data analysis algorithm, 244–245 nitrous oxide reductions, 748 azomethane decomposition, 336–337
differential reactors, 264–270 nonelementary. See Nonelementary in relative rates of reaction, 70–72
experimental planning in, 271 rate laws for species, 7–9
Rate laws, 69 nonlinear regression for, 262 Rate of generation, 8–9
acetic anhydride production, 557 parallel reactions, 285, 583 Rate of reaction, 4–8
adiabatic equilibrium temperature, PBR gas phase reactions, 304–305, azomethane decomposition, 336
520 546 catalysts in diffusion, 405
adsorption, 412 PFR reactors CSTRs, 13
azomethane decomposition, 336–337 complex reactions, 588–589 diffusion and reaction, 739–742
batch reactors, 145–146, 253–258, 295 with heat effects, 546, 588–589 internal effectiveness factor, 730–733
butane isomerization, 512, 549–550 parallel, 583 methane production, 266–267
catalytic reactions, 421–424 volume for first-order gas-phase multiple reactions, 282
deducing, 438–439 reaction, 142–143 nonlinear regression for, 259–260
derived from PSSH, 435 pressure drop, 169–170, 178 packed bed transfer-limited
evaluating, 440–442 propylene glycol production, 569, reactions, 751
temperature dependence of, 436 635, 653 with pressure drop, 178, 185
cell growth, 369–371, 374, 376–377 from PSSH, 435 relative, 70–72
CRE Web site material for, 96–97 questions and problems, 98–103 Rate of transport in membrane reactors,
CSTRs rate data analysis, 244–245 220
with cooling coils, 573 and reaction order, 72–83 Rate selectivity parameter in parallel
liquid phase, 308 reactor sizing and design, 93–94 reactions, 286
multiple reactions, 586–587 semibatch reactors, 227, 230, 310, Reactants and reactant concentrations
parameter modeling, 876 658 catalyst poisoning by, 463
series reactions, 299–300 spherical catalyst pellets, 724–725 continuous-flow reactors, 39
single, 152 steady-state nonisothermal reactor in conversion, 32
unsteady-state operation, 653 design, 494 desired products for, 285–291
cumene decomposition, 430 straight-through transport reactors, differential reactors, 264
CVD (chemical vapor deposition), 474 energy of formation of, 85
449 sulfur dioxide, 123–126 in heterogeneous reactions, 720
definitions, 70–72 summary, 95–96 mass transfer of, 720
dehydration butanol of alumina, 202 supplementary reading for, 103–104 multiple reactions, 281
elementary, 72–75 surface-reaction-limited irreversible parallel reactions, 285–291
ethyl acetate saponification, 649 isomerization, 436 semibatch reactors, 233
ethylene glycol production, 149, 151, surface reactions in catalysts, 416–417 Reaction coordinates, 84
158 temperature dependence of, 436 Reaction-limited regime estimation,
ethylene hydrogenation to ethane, toluene hydrodemethylation, 438, 743–744
452 440, 443, 446 Reaction mechanisms, searching for,
ethylene oxide production, 186 triphenyl methyl chloride-methanol 339–342
gas-oil catalytic cracking, 470 reaction, 254–258 Reaction order, 72–83
gas phase, 210–211, 304–305 trityl-methanol reaction, 251 Reaction rate constant, 72, 83–93
glucose-to-ethanol fermentation, 379 tubular reactors Reaction rate law
homogeneous reactions, 246 adiabatic, 510 catalyst deactivation, 455–456
inhibition design, 163, 166 catalyst decay, 458
competitive, 357 for urea Reaction steps with catalysts, 405–406
noncompetitive, 361 decomposition, 354 Reaction surface area in heterogeneous
substrate, 363 removal, 346–348 reactions, 7
uncompetitive, 360 variable volumetric flow rate, 129 Reaction time in batch reactors, 145–151
irreversible surface-reaction-limited, Web sites for, 919 Reaction yields in multiple reactions, 282
435 Rate-limiting Reactions
isothermal reactor design, 169–170, benzene, 429–430 heterogeneous, 79–80
209 in catalytic reactions, 419–420 homogeneous, 76–77
Index 953

rates. See Rate of reaction toluene hydrodemethylation, 441–442 Runaway reactions

reversible, 80–83 triphenyl methyl chloride-methanol batch reactors with interrupted
temperature effects on, 92–93 reaction, 258 isothermal operation, 639–646
Reactive distillation, 226 Relative rates of reaction from falsified kinetics, 739
Reactor lab batch reactor series reactions, 295 PFRs, 608–609
isothermal reactor design, 195 CSTR liquid phase, 308 SAChE materials, 604–605
multiple reactions, 321, 331 defined, 70 T2 explosion, 660–668
rate data collection, 273–274 MCMT production, 665
Reactor length in nitrous oxide multiple reactions, 284–285
reductions, 750 parallel reactions, 583 S
Reactor-rate constant in adiabatic PBR gas phase reactions, 305 Saccharomyces cerevisiae, 378–381
operations, 638–639 PFR complex reactions with heat Safety
Reactor staging with interstate cooling or effects, 589 ethylene glycol, 162
heating, 522–526 semibatch reactors, 310, 658 exothermic reactions, 603–605,
Reactor volume stoichiometric coefficients, 71–72 640–646
butane isomerization, 55 Residence time distribution function, Safety and Chemical Engineering
continuous-flow reactors, 39–40 771 Education (SAChE) program,
conversion factors, 906 Residence time distributions (RTDs), 604–605
CSTRs, 36, 49–51, 56–58 212, 767 Santa Ana winds, 28
ideal gases, 905 considerations, 767–770 Saponification, 111–112
membrane reactors, 219 conversion prediction. See Satellite maneuvering, 702–704
PBRs, 18, 20–21 Conversion using RTDs Scale-up of batch reactor data, 144
PFRs, 17–18, 22, 52, 57–58 diagnostics and troubleshooting Scavengers with active intermediaries,
in space time, 59 CSTRs, 794–797 341–342
tubular reactors, 164 tubular reactors, 797–799 Schmidt number
Reactors. See also specific reactor types ideal reactors in diffusion, 692, 696
by name batch and plug-flow, 784–785 in dispersion, 860, 862
in parallel reactions, 291–294 laminar flow reactors, 786–789 Seafood gumbo, 926–927
in rate data analysis, 244 single-CSTR, 785–786 Searching
in series, 47–48 integral relationships in, 777–778 for mechanisms, 339–342
CSTRs, 48–50 internal-age distribution, 783–784 in nonlinear regression, 260–261
CSTRs and PFRs combination, mean residence time in, 778, 788 Second-order ODE solutions, 901
53–57 measurements, 770–777 Second-order rate laws, 76
CSTRs and PFRs comparisons, moments, 778–782 Second-order reactions, 73
57–58 multiple reactions, 830–835 batch reactor data analysis, 248
PFRs, 52 normalized function, 782–783 CSTR design, 153–154
sizing. See Conversion and reactor PBRs, 768 irreversible, 155
sizing pulse input experiment for, 770–776 isothermal, 146–147, 230–233
for toluene hydrodemethylation, step tracer experiment, 775–777 laminar flow reactors, 817–820
443–445 T-I-S model, 850 mean conversion, 817–820
Real reactors two-parameter models, 871–872 multiple steady states, 577
mean conversions in, 816–817 Web site material, 801 PBRs, 178–179
in two-parameter models, 871–873 Respiration rate of chipmunks, 713 Second reactors in interstage cooling,
Realistic models for nonideal reactors, Reversible gas-phase decompositions, 525–526
846 126–130 Secondary nutrients, 374
Reciprocal concentrations, 248 Reversible isomerization, 436 Segregation model
Reciprocal power decay rate law, 464 Reversible reactions, 70 in maximum mixedness model, 820,
Recycle reactors, 196 overview, 80–83 824
Recycle stream in parallel reactions, 291 stoichiometry, 126–130 vs. maximum mixedness model,
Reforming catalysts, 431–435 Reynolds number 829–830
Reforming process, 432 in dispersion, 860–861 multiple reactions in, 830–835
Regression in dispersion coefficient vs. T-I-S model, 852
in activation energy determinations, determination, 862 zero-adjustable-parameter, 810–820
91 in mass transfer coefficient, 691, 693, Selectivity
batch reactor data analysis, 258–263 696 CSTRs, 308
cell growth, 376 in mass transfer correlations, 701 liquid-phase reactions, 227, 308, 310
ethylene hydrogenation to ethane, Ribonucleic acid (RNA), 366 membrane reactors for, 225, 312–316
452–453 Robert the Worrier, 700–704 multiple reactions, 281–282, 285,
methane production, 269–270 RTDs. See Residence time distributions 312–316
Michaelis–Menten equation, 353 (RTDs) parallel reactions, 291
954 Index

Selectivity (continued) Sizing reactors. See Conversion and Stagnant film, diffusion through,
PBR gas phase reactions, 305 reactor sizing 688–690
PFR complex reactions with heat Skewness in RTD moments, 779 Standard deviation, 779
effects, 590 Skin, nitrogen gas exposure to, 714 Standard temperature and pressure (STP)
semibatch reactors, 310 Slow reactions in mass transfer to single in space velocity, 61
temperature effects on, 289 particles, 696–697 Starch, hydrolysis of, 394
Trambouze reactions, 287–291 Slurry reactors, 751–752, 755 Startup of CSTRs, 651–656
Semibatch reactors, 225–226 Small molecule synthesis, 366 Stationary phase
energy balance, 499, 647, 658 Small-scale operations, 10 cell growth, 369, 374–375
with heat exchangers, 646–651 Smog formation, 28–29 substrate balance, 378
liquid phase, 310–312 Soap, saponification for, 111–112 Steady-state bifurcation, 609
multiple reactions in, 656–660 Socrates, 1 Steady state in CSTRs, 13
unsteady-state operation, 227–233 Sodium hydroxide in saponification, 111 Steady-state molar flow rates, 502–504
Semiconductor fabrication Sodium in MCMT production, 661 Steady-state nonisothermal reactors,
chemical vapor deposition in, Sodium thiosulfate, 574 493
448–451 Software packages. See also specific adiabatic operation. See Adiabatic
overview, 447 software packages by name operations
Semilog plots, 92, 903 Aspen, 916 CRE Web site material, 530–531
Separable kinetics in catalyst COMSOL, 917–918 energy balance. See Energy balances
deactivation, 455, 463 instructions, 903 equilibrium conversion. See
Separating variables with pressure drop, MATLAB, 916 Equilibrium conversions
179 Polymath, 915–916 with heat exchange. See Flow
Separation systems, economic incentive Solar energy reactors
for, 281 biochar gasification, 331 information required for, 494–495
Sequencing of reactors, 57–58 chemical storage, 103 questions and problems, 531–536
Series, reactors in, 47–48 field design, 330 summary, 529–530
combinations, 53–57 water splitting, 487–488 supplementary reading, 536–537
CSTRs, 48–50 Solid catalysts in PBRs, 18 Steady-state operation in chemostats,
design, 155–157, 160–161 Solvents from ethylene oxide, 185 382
PFRs, 52 Space satellite maneuvering, 702–704 Step tracer experiment, 775–777
Series reactions, 280 Space time, 58–60 Stern–Volmer equation, 340–342
batch reactors, 294–298 in CSTR modeling, 878 Stirred reactors
blood clotting, 302–303 in dispersion coefficient CSTRs. See Continuous-stirred tank
CSTRs, 298–302, 585–588 determination, 866 reactors (CSTRs)
mass transfer-limited reactions, 705 Space velocity, 60–61 unsteady-state operation
Seveso accidental release, 604 Spartan program, 335 overview, 225–226
Shaft work in energy balance, 496 Specialty chemicals, 212 semibatch reactors, 227–233
Shell balances on catalyst pellets, 723 Species, 4–5 Stoichiometric coefficients
Sherwood numbers mole balances on, 8–9 in conversion, 32
in mass transfer coefficient, 691–692 and variable volumetric flow rate, in relative rates of reaction, 71
in mass transfer correlations, 702 115–117 Stoichiometry, 69, 105–106
Silicon dioxide for microelectronic Specific rate of product formation, 372, acetic anhydride production, 557
devices, 447 374–375 adiabatic equilibrium temperature,
Simplifications Specific reaction rate, 72, 83–93 520
rate data analysis, 244 Spectroscopic measurements, 435 batch systems, 107–113, 145–146
triphenyl methyl chloride-methanol Spheres, mass transfer coefficient for, butane isomerization, 513, 549–550
reaction, 254 694–695 catalyst decay, 458
Simpson’s one-third rule, 902 Spherical bacteria growth, 367 cell growth, 371–377
Simpson’s three-eighths rule, 902 Spherical catalyst pellets, 720–721 CRE Web site material, 133
Simpson’s three-point formula, 56 differential equation for, 723–725, CSTRs
Single particles, mass transfer to, 729–730 with cooling coils, 573
693–697 dimensionless form, 726–728 single, 152
Single-site mechanisms effective diffusivity, 721–723 ethyl acetate saponification, 649
rate-limiting in, 427–428, 435 Spherical reactors, 196 ethylene glycol production, 149,
surface reactions in, 416, 435 Spread of distributions, 779 158–159
Sintering, 456–459 Square of the standard deviation, 779 ethylene oxide production, 186–187
Site balance Stability rates flow systems, 113–126
adsorption isotherms, 411 CSTR unsteady-state operation, 651 gas-oil catalytic cracking, 470
cumene adsorption, 426 propylene glycol production, 654–655 gas phase, 210–211, 306
Index 955

glucose-to-ethanol fermentation, 379 Sulfuric acid one-parameter, 847

isothermal reactors, 209 DDT production, 6 vs. segregation model, 852
liquid phase, 310 ethylene glycol production, 192 Tau, space time, 58–60
MCMT production, 665 professional reference shelf for, 609 Taylor series for energy balance, 565
mean conversion, 818 Sums of squares Temperature, 493. See also Heat effects
membrane reactors, 222–223, 314 ethylene hydrogenation to ethane, 453 and activation energy, 92–93
multiple reactions, 284, 314, 658 multiple reaction analysis, 317 adiabatic operations in batch
nitroaniline production, 642 nonlinear regression, 260, 263 reactors, 638–639
nitrogen oxide production, 215 Superficial mass velocity, 185 in adsorption, 412
parallel reactions, 583–584 Supported catalysts, 402 in cell growth, 371
PBR gas phase, 306 Surface area in collisions, 88–89
PFRs catalyst deactivation, 456–457 conversion factors, 906
with heat effects, 546–547, hydrazine decomposition, 703–704 in CSTRs, 13
583–584, 590 mass transfer-limited reactions, 706 in diffusion, 686–687
reactor volume, 142–143 membrane reactors, 220 in enzymatic reactions, 356
pressure drop, 169–170, 178 microreactors, 212 in flow reactors with variable
propylene glycol production, 569, spherical catalyst pellets, 724 volumetric flow rate, 116
635, 653 Surface-catalyzed reactions, 212 in internal effectiveness factor,
questions and problems, 133–138 Surface-reaction-limited operations 733–734
reversible reactions and equilibrium cumene decomposition, 430 in mass transfer correlations, 700
conversion, 126–130 irreversible isomerization, 436 in mass transfer to single particles,
semibatch reactors, 310, 658 irreversible rate laws, 435 695
steady-state nonisothermal reactors, Surface reactions nonisothermal reactors
494 catalysts, 416–418 steady-state. See Steady-state
straight-through transport reactors, CVD, 449–450 nonisothermal reactors
475 microelectronic fabrication, 447 unsteady-state. See Unsteady-state
summary, 131–133 packed bed transfer-limited nonisothermal reactors
supplementary reading, 138 reactions, 751 in rate laws, 77, 436
toluene hydrodemethylation reactors, rapid, 694–695 selectivity affected by, 289
443–444, 446 rate laws, 422–423, 435 Temperature-concentration phase planes,
triphenyl methyl chloride-methanol rate-limiting, 427–428 651
reaction, 254 toluene hydrodemethylation, Temperature-time trajectories, catalyst
tubular reactors 439–440 deactivation of, 465–467
adiabatic, 510 Surfaces Tenebrionid beetles, 100
design, 163–164, 166–167 catalyst, 693–697 Terephthalic acid (TPA), 326–327
STP (standard temperature and pressure) in effectiveness factor, 739–740 Termination step in chain reactions, 343
in space velocity, 61 in mass transfer to single particles, Termolecular reactions, 70
Straight-through transport reactors 695 Tessier equation, 370–371
(STTRs), 472–476 metallic, 712 Testing new processes, batch reactors for,
Streptomyces aureofaciens, 384 Surfactants from ethylene oxide, 185 10
Stuart Prower factor, 303 Sweetland, Ben, 845 Thermal decomposition of isopropyl
Styrene from ethylbenzene, 220–221 Swimming rate of small organisms, 760 isocyanate, 278
Subscripts, 923 Switch grass, 330 Thermal diffusivity in mass transfer
Substrates Synthesizing chemical plant design, coefficient, 691
in cell growth, 367, 373–376 190–192 Thermodynamic equilibrium constant,
and dilution rate, 383 System volume in mole balance 80, 909–914
disappearance, 349, 378 equation, 8 Thermodynamically limited reactions,
enzyme-substrate complex, Szent–Gyorgyi, Albert, 539, 719 217
344–346 Thermodynamics
inhibition by, 359, 361, 363–364 equilibrium conversion from, 521
mass balances, 378 T first law of, 495–496
in Michaelis–Menten equation, T2 Laboratories explosion, 604, 660–668 in reversible reactions, 83
348–349, 355 Tails Thiele modulus
microelectronic fabrication, 447 fitting, 801 in falsified kinetics, 737
multiple systems, 385 in pulse input experiment, 775 in internal effectiveness factor,
Sulfonation reactions, 312 Tanks-in-series (T-I-S) models 731–737
Sulfur dioxide conversion in, 866–868 in spherical catalyst pellets,
gas-phase reactions, 120–123 vs. dispersion models, 869 726–728
rate law, 123–126 nonideal, 848–852 Third-order reactions, 73
956 Index

Thoenes–Kramers correlation Transition state theory, 97 Uncompetitive inhibition, 359–361

flow through packed beds, 700 Transition states and energy barriers, 85 Underground wet oxidation problem, 926
hydrazine decomposition, 703–704 Transport Undesired products in multiple reactions,
Mears criterion, 744 with catalysts, 405 281
nitrous oxide reductions, 749 in membrane reactors, 220, 222, 314 Uniform surfaces, adsorption in, 415
Three-eighths rule, 902 Trapezoidal rule, 901 Unimolecular reactions, 70
Three-point rule, 902 Trial and error method, 880 Units, conversion factors for, 906–907
Thrombin in blood clotting, 303 Trickle bed reactors, 752, 756 Unstable steady-state temperatures,
Thrusters, monopropellant, 702–704 Triethanolamine formation, 280 579–580
Tic-Tac module, 236 Triphenyl methyl chloride, 254–258 Unsteady-state nonisothermal reactors,
Time Trityl-methanol reaction, 249–251 629
in batch reactors, 146–147 Troubleshooting, 793–794 batch reactors
concentration, 246 corrosion, 100 adiabatic operation, 633–639
reactant, 33–34 CSTRs, 794–797 with interrupted isothermal
in energy rate change, 907 isothermal reactors, 200 operation, 639–646
in growth rates, 371 tubular reactors, 797–799 CRE Web site material, 670–671
Time order of magnitude in batch Truman, Harry S, 493 CSTR operation, 499, 651–656
systems, 147 Tubes energy balance, 499, 630–632
Tissue engineering, 763–765 in microreactors, 212 mole balances, 631
Tissue factor in blood clotting, 302–303 in pressure drop, 185 multiple reactions, 656–668
Titanium dioxide, 488–489 Tubular reactors, 14–18, 202–203 questions and problems, 671–677
TOF (turnover frequency), 404 design equations, 36–37, 94 semibatch reactors, 646–651
Toluene designing, 162–165 summary, 668–669
hydrodemethylation of, 79, 437–446 ethylene production, 165–168 Unsteady-state operation of stirred
from methylcyclohexane, 489 gas-phase reactions, 14, 163–165 reactors, 225–233, 651–656
para-xylene from, 401 hemoglobin deoxygenation in, 275 Unsteady-state tracer balance, 862–863
xylene from, 490–491 nonideal, 847–848 Unsupported catalysts, 402
Tortuosity in effective diffusivity, balance equations, 854 Unwanted products in parallel reactions,
721–723 boundary conditions, 855–858 291–292
Total concentrations in flow reactors, 121 dispersion, 852–854, 858–860 Urea removal, 346–348
Total cycle time in batch systems, 147 dispersion coefficient correlation, batch reactor calculations, 354–356
Total energy in first law of 860–862 Michaelis–Menten equation,
thermodynamics, 495 dispersion coefficient 348–354
Total enzyme concentration, 346–348 determination, 862–866 Urease, 346–348
Total mass, 5 plug-flow. See Plug-flow reactors User-friendly form of energy balance,
Total molar flow rate (PFRs) 633
flow reactors, 115–116 radial and axial variations, 595–596
gas phase, 210, 212 energy balance, 598–603
Total volume energy flux, 597–598 V
CSTRs in series, 51–52 molar flux, 596–597 Vacant sites in cumene adsorption, 426
PFRs in series, 52 RTDs for, 797–799 Van de Vusse kinetics, 321
Toxic intermediates, 212 space time in, 59 Vanadium oxides, 488
TPA (terephthalic acid), 326–327 Turbulent diffusion, 852 Vanadium triisopropoxide (VTIPO), 488
Tracers Turbulent flow van’t Hoff’s equation, 910
CSTR parameter modeling, 873–877, packed bed pressure drop, 176 Vapor-phase reactions, irreversible
879–880 pipes, 860–861 endothermic, 534
dispersion coefficient determination, Turnover frequency (TOF), 404 Variable heat capacities, 530
862–863 Turnover number in Michaelis–Menten Variable temperature in energy balance,
dispersion model, 852–853 equation, 348 500
pulse input experiment, 773 Two parameter models for nonideal Variable volume in gas phase flow
RTDs, 770, 785 reactors, 808, 846, 848, 871–873 systems, 115–126
step tracer experiment, 775–777 Two-point rule, 901 Variable volumetric flow rate, 115–126
T-I-S model, 849 Tyrosinase, 344 Variance
two-parameter models, 871–872 in ethylene hydrogenation to ethane,
Trains of reactors with interstage 453–454
heating, 536 U in RTDs, 779–781, 784
Trambouze reactions, 287–291 Ultraformers, 196 in T-I-S model, 850–851
Transfer. See Mass transfers Ultrasonic waves, light from, 340–342 Vat reactors. See Continuous-stirred tank
Transferases enzymes, 346 Unbound enzyme concentration, 346 reactors (CSTRs)
Index 957

Velocity W Y
fluid in mass transfer to single
particles, 697 Wafer fabrication Yeasts, 393
space, 60–61 chemical vapor deposition in, doubling times, 371
Velocity profiles in tubular reactors, 848, 448–451 growth of, 367
858 overview, 447 Yields
Venkatesan, R., 701 Wash-out in cell growth, 383–384 in bioconversions, 365
Venting in MCMT production, 664 Washington, Booker T., 69 in cell growth, 372, 375–376
Vermont Safety Information Resources, Water in multiple reactions, 282
Inc. (Vermont SERI), 162 light from, 340–342 series reactions in batch reactors, 297
Vessel boundary conditions splitting, 487–488
dispersion coefficient determination, Water-gas shift reaction, equilibrium
864–866 constant in, 912–914 Z
tubular reactors, 855–857 Watson, K. M., 419 Zeolite catalysts, 401
Vessel dispersion number, 855 Web sites for rate law data, 919 Zero-adjustable-parameter models
Vibrational energy, 334 Weber, M., Jr., 769 maximum mixedness model,
Viscosity Weighted least squares analysis, 273 820–826
conversion factors for, 906 Weisz–Prater criterion, 734–735 multiple reactions in, 830–835
of helium, 702 Wen, C. Y. questions and problems, 837–842
in mass transfer coefficient, 691 on RTD moments, 778 segregation models, 810–820
Visual Encyclopedia of Equipment, 26 on tracer techniques, 777 software packages for, 827–830
Volume. See Reactor volume Wet oxidation problem, 926 summary, 835–836
Volume-average particle diameter, 703 Wetlands module, 236, 238 supplementary reading, 842–843
Volume change with reaction, 733 “What if” conditions for mass transfer Web site material, 836–837
Volumetric feed rate in chemostats, 381 coefficients, 705–709 Zero-order reactions, 73, 247–248
Volumetric flow, 114 Wine-making, 370–371 Zewail, Ahmed, 335
differential reactors, 264 Wooden, John, 31 Zwietering, T. N., 810
ethylene oxide production, 188 Work, conversion factors for, 906
methane production, 266–267 Work term in energy balance, 496–498
pulse input experiment, 771
RTDs, 778, 787
T-I-S models, 850
X
tubular reactors, 165 Xylene from toluene, 490–491
variable, 115–126
VTIPO (vanadium triisopropoxide), 488
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