You are on page 1of 886

Brian Vicente / Max Nori / H.

Scott Fogler


- ..
II!I!!III

..
Soludons Manual for
Elements
of Chemical
Reaction
Engineering
Fourth Edition
Prentice Hallitaternational Series
in the Phys!ptl and Chemical
E.ngineering Sciences
A Complimentary Copy
from

PRENTI CE FT Prentice Hall
HALL
www"pearsoned-asia"com
Enquiries: 3181 0368
, ,


Solutions Manual for
Elements of Chemical
Reaction Engineering
Fourth Edition
Brian Vicente
Max Nori
H. Scott Fogler

PRENTICE
HALL
PTR
Upper Saddle River, NT Boston Indianapolis San Francisco
New York Toronto Montreal London Munich Paris Madrid
Capetown Sydney Tokyo Singapore Mexico City
The authors and publisher have taken care in the preparation of this book but make no expressed
or implied warranty of any kind and assume no responsibility for errors or omissions. No liability
is assumed for incidental or consequential damages in connection with or arising out of the use of
the information or programs contained herein.
Visit us on the Web: www.phptr.com
Copyright 2006 Pearson Education, Inc ..
This work is protected by United States copyright laws and is provided solely for the use of
instructors in teaching their courses and assessing student learning. Dissemination or sale of any
part of this work (including on the World Wide Web) will destroy the integrity of the work and is
not permitted. The work and materials from it should never be made available to students except
by instructors using the accompanying text in their classes. All recipients of this work are
expected to abide by these restrictions and to honor the intended pedagogical purposes and the
needs of other instructors who rely on these materials.
ISBN 0-13-186383-5
Text printed in the United States at OPM in Laflin, Pennsylvania.
First printing, November 2005 ______________ ... ________ . ________ :
**** CONFIDENTIAL ****
UNIVERSITY OF MICHIGAN
INTERACTIVE COMPUTER MODULES FOR CHEMICAL ENGINEERING
CHEMICAL REACTION ENGINEERING MODULES
H. Scott Fogler, Project Director
M .. Nihat GUIllen, Project Manager (2002-2004)
Susan Montgomery, Project Manager (1991-1993)
Department of Chemical Engineering
University of Michigan
Ann Arbor, MI48109-2136
2005
Regents of the University of Michigan
- All Rights Reserved -
INTERPRETATION OF PERFORMANCE NUMBERS
Students should record their Performance Number for each program, along with the
name of the program, and tum it in to the instructor. The Performance Number for
each program is decoded as described in the following pages.
The official site for the distribution of the modules is
http://www.engin.umich.edu/ -cre/icm
Please report problems to icm.support@umich.edu.
PerfOimance NumbeI InteIpIetation: eRE modules
iii
**** CONFIDENTIAL ****
ICMs with Windows interface
Module Format
KINETIC CHALLENGE I
CzBzzAzz
KINETIC CHALLENGE II
CzBzzAzz
MURDER MYSTERY
zzAzz
TIC TAC TOE
zDzCzBzA
Interpretation
Score = 1.5 * AB.C
z = random numbers
Note: 75% constitutes mastery.
Score = 2.0 * ARC
z = random numbers
Note: 75% constitutes mastery.
A even: Killer and victim
correctly identified
A odd: Killer and victim
not identified
z = random numbers
Example
Perf. No. =
Score = 1.5 *( 62.7) = 94 %
Perf.. No. = Q3176.167
Score = 2.0*(47.0) = 94 %
Perf. No. = 50132
Score: No credit
Note: An even number for the middle digit constitutes mastery.
Score = 4.0 * AB.C
z = random numbers
Configurations
Perf. No. = 718Q3281
Score = 4*(15 .. 0) = 60
configuration 7 completed
Note: Student receives 20 points for every square answered correctly.
A score of 60 is needed for mastery of this module.
GREAT RACE
zzzCzABz
PeIformance NumbeI Interpletation: eRE modules
Score = 6.0 * AB .. C
z = random numbers
Perf No. = 777J.8Q18
Score = 6*(07.3) = 44
Note: A score of 40 is needed for mastery of this module.
iv
**** CONFIDENTIAL ****
ECOLOGY
STAGING
AzBCzaaD z = random numbers
a = random characters
A gives info on rl\2 value of the student's linearized plot
A=Y if rl\2 >= 0.9
A=A if 0.9 > rl\2 >= 0.8
A=X if 0..8> rl\2 >= 0.7
A=F if 0..7 > rl\2
A=Q if Wetland Analysis/Simulator portion has not been completed
B gives info on alpha
B=l to 4 => student's alpha < (simulator's alpha 0.5)
B=5 to 9 => student's alpha> (simulator's alpha 0.5)
B=X if Wetland Analysis/Simulator portion has not been completed
C indicates number of data points deactivated during analysis
C=number of deactivated data points if at least 1 point has been deactivated
C=a randomly generated letter from A to Y if 0 points deactivated
C=Z if Wetland Analysis/Simulator portion has not been completed
D gives info on solution method used by student
D=l if polynomial regression was used
D=2 if differential formulas were used
D=3 if graphical differentiation was used
D=4 to 9 if Wetland Analysis/Simulator portion has not been completed
zCBzAFzED z = random numbers
Final conversion = 2*ARC
Final flow rate = 2*DE.F
Perf No .. = A7213DF2
1) A => 0.9 > rl\2 >= 0 .. 8
2) 2 => student's alpha < (simulator's
alpha 0 .. 5)
3) 1 => one data point was
deactivated
4) 2 => differential formulas were
used
Perf. No.. =
conversion = 2*42 . .1 = 84.2
flow rate = 2*31.2 = 62.4
Please make a passlfiil criterion based on these values ..
Performance Number Interpretation: eRE modules
v
**** CONFIDENTIAL ****
ICMs with Dos interface
Module Format
HETCAT
HEATFXl
HEATFX2
Interpretation
zzABzCD A=2,3,5,7: interaction done
B=2,3,5,7: intra done
C=2,3,5,7: review done
D denotes how much they
did in the interaction:
D<2 Not done
2 < D:5 4 Dependences
4 < D:5 6 Parameter values
6<D Mechanism
z = random numbers
Example
Perf. No. = 8027435
A: Worked on interaction
B: Looked at intra
C: Looked at review
D: found parameter values,
didn't find mechanism
Note: Performance number given only if student goes through the
interaction portion of the module
zzAzz A even: score> 85 %
z = random numbers
Perf. No. = 5 3 ~ 7
Score> 85 %
Note: Student told they have achieved mastery if their score is greater than
85%
zzzAzz A even: completed interaction Perf. No. = 407.2.82
z = random numbers Interaction not completed
Note: Performance number given only if student goes through the
interaction portion of the module.
PerfclImance NumbeI InteIpretation: eRE modules vi
Solutions for Chapter 1 - Mole Balances
Synopsis
General: The goal of these problems are to reinforce the definitions and provide an understanding of the
mole balances of the different types of reactors .. It lays the foundation for step 1 of the algorithm in Chapter
4.,
PI-I. This problem helps the student understand the course goals and objectives.
PI-2. Part (d) gives hints on how to solve problems when they get stuck. Encourages
students to get in the habit of writing down what they learned from each chapter.
It also gives tips on problem solving.
PI-3. Helps the student understand critical thinking and creative thinking, which are
two major goals of the course.
PI-4. Requires the student to at least look at the wide and wonderful resources
available on the CD-ROM and the Web.
PI-S. The ICMs have been found to be a great motivation for this material.
PI-6. Uses Example 1-1 to calculate a CSTR volume. It is straight forward and gives
the student an idea of things to come in terms of sizing reactors in chapter 4. An
alternative to PI-IS.
PI-7. Straight forward modification of Example 1-1.
PI-S. Helps the student review and member assumption for each design equation.
PI-9 and PI-IO. The results of these problems will appear in later chapters. Straight
forward application of chapter 1 principles.
PI-II. Straight forward modification of the mole balance. Assigned for those who
emphasize bioreaction problems.,
PI-12. Can be assigned to just be read and not necessarily to be worked, It will give
students a flavor of the top selling chemicals and top chemical companies.
16
PI-13. Will be useful when the table is completed and the students can refer back to it
in later chapters. Answers to this problem can be found on Professor Susan
Montgomery's equipment module on the CD-ROM. See PI-17.
PI-14. Many students like this straight forward problem because they see how CRE
principles can be applied to an everyday example. It is often assigned as an in-
class problem where parts (a) through (0 are printed out from the web. Part (g)
is usually omitted.
PI-IS. Shows a bit of things to come in terms of reactor sizing. Can be rotated from
year to year with PI-6.
PI-16. Open-ended problem.
PI-17. I always assign this problem so that the students will learn how to use
POLYMATHIMaLab before needing it for chemical reaction engineering
problems.
PI-IS. Parts (a) and (b) are open-ended problem.
PI-19 and PI-20. Help develop critical thinking and analysis.
CDPI-A Similar to problems 3, 4, 11, and 12.
CDPI-B Points out difference in rate per unit liquid volume and rate per reactor
volume.
Assigned

PI--l AA
PI-2 I

PI-3 0
PI-4 0
PI-5 AA
PI-6 AA
PI-7 I

PI-8 S
PI-9 S
Pl-IO S
Pl-11 0
Summary
Alternates
1-15
1-7
Difficulty
SF
SF
SF
SF
SF
SF
SF
SF
SF
SF
FSF
Time (min)
60
30
30
30
30
15
15
15
15
15
15
PI-12 I - Read Only SF 30
PI-13 I SF 1
PI-14 0 FSF 30
PI-IS 0 SF 60
PI-16 S SF 15

PI-17 AA SF 60
PI-18 S SF 30
PI-19 0
30
PI-20 0 FSF 15
CDPI-A AA FSF 30
CDPI-B I FSF 30
Assigned
= Always assigned, AA = Always assign one from the group of alternates,
o = Often, I = Infrequently, S = Seldom, G = Graduate level
Alternates
Time
In problems that have a dot in conjunction with AA means that one of the
problem, either the problem with a dot or anyone of the alternates are always
assigned.
Approximate time in minutes it would take a B/B+ student to solve the problem.
Difficulty
*
SF = Straight forward reinforcement of principles (plug and chug)
FSF = Fairly straight forward (requires some manipulation of equations or an
intermediate calculation).
IC = Intermediate calculation required
M = More difficult
OE = Some parts open-ended.
Note the letter problems are found on the CD-ROM. For example A == CDPI-A.
Summary Table Ch-l
---------------,
Review of Definitions and Assumptions 1,5,6,7,8,9
Introduction to the CD-ROM 1,2,3,4
1-8
Make a calculation
Open-ended
PI-I Individualized solution.
PI-2 Individualized solution.
PI-3 Individualized solution.
PI-4 Individualized solution.
6
8,16
PI-5 Solution is in the decoding algorithm given with the modules ..
PI-6
The general equation for a CSTR is:
V = F AO --FA
-r
A
Here rA is the rate of a first order reaction given by:
fA=- kC
A
Given: C
A
= O.lC
AO
, k = 0.23 min-I, Vo = 10dm
3
min-I, FA = 5.0 moVhr
And we know that FA = CAVo andF
Ao
= CAOVo
=> C
AO
= F Aol Vo = 0.5 moVdm
3
Substituting in the above equation we get:
v = CAOV
O
-CAVO = (0.5mol/dm
3
)(lOdm
3
lmin)-0.1(0.5mq!ldm
3
)(lOdm
3
I min)
kC
A
(0.23 min--I)(O. 1(0.5mol I dm
3

V =391.3 dm
3
PI-7
t = INA dNA
-kN
A
NAO
k = 0.23 min-l
From mole balance:
dNA
-- = IA'
V
dt
1-9
Rate law:
Combine:
at T:::: 0, N
Ao
= 100 mol and T:::: T, NA = (O . .01)NAo
1 (N AO J
-+ t= "kIn N A
1
:::: -In(lOO) min t = 20 min
0.23
Pl-8
a) The assumptions made in deriving the design equation of a batch reactor are:
Closed system: no streams carrying mass enter or leave the system.
Well mixed, no spatial variation in system properties
Constant Volume or constant pressure.
b) The assumptions made in deriving the design equation of CSTR, are:
Steady state.
No spatial variation in concentration, temperature, or reaction rate throughout the vesseL
c) The assumptions made in deriving the design equation ofPFR are:
Steady state ..
No radial variation in properties of the system.
d) The assumptions made in deriving the design equation of PBR are:
Steady state ..
No radial variation in properties of the system.
e) For a reaction,
A-7 B
-rA is the number of moles of A reacting (disappearing) per unit time per unit volume [=J moles/
(dm
3
s)
1-10
P 1-9
rA' is the rate of disappearance of species A per unit mass (or area) of catalyst [=] moles/ (time.
mass of catalyst)..
rA' is the rate of formation (generation) of species A per unit mass (or area) of catalyst [=] moles/
(time. mass catalyst)..
-rA is an intensive property, that is, it is a function of concentration, temperature, pressure, and the
type of catalyst (if any), and is defined at any point (location) within the system. It is independent
of amount On the other hand, an extensive property is obtained by summing up the properties of
individual subsystems within the total system; in this sense, -rA is independent of the 'extent' of the
system.
Rate of homogenous reaction rA is defined as the mole of A formed per unit volume of the reactor per
second .. It is an Intensive property and the concentration, temperature and hence the rate varies with spatial
coordinates.
r
A
on the other hand is defined as g mol of A reacted per gm. of the catalyst per second.. Here mass of
catalyst is the basis as this is what is important in catalyst reactions and not the reactor volume.
above:
Applying general mole balance we get:
dN.
--.L=F
o
-F. + fr.dV
dt J ] J
No accumulation and no spatial variation implies
o = F
o
- F. + fr .dV
J ] J
Also Ij = Pb rj' and W = V Pb where Pb is the bulk density of the bed.
=> 0 = (FjO - F) + f r;CPbdV)
Hence the above equation becomes
Fo-F
W=_l __ ,_l
--r
j
We can also just apply the general mole balance as
dN
j
f'
- = (FjO - F
j
) + r/dW)
dt
Assuming no accumulation and no spatial variation in rate, we get the same form as
FO-F
W = ._1_._, _1
-r
j
1-11
PI-IO
Fj
F
,/ i' JO
Mole balance on species j is:
v dN.
Po -P + fr.dV = __ 1
I I I dt
o
Let M j = molecular wt. of species j
Then FjoM j = W jO = mass flow rate of j into reactor:
N jM j = m j = mass cif species j in the reactor
Multiplying the mole balance on species j by M I
v dN
FjOM j - FjM I +M I frjdV = M
j
. __ 1
o dt
Now M I is constant:
F M. -PM. + vfM rdV = d0!
j
N
j
) = d(m1l
1
0
I I I I I dt dt
o
v
w
jO
-- Wj + fM jrjdV =
o
PI-II
Applying mole balance to Penicillin: Penicillin is produced in the cells stationary state (See Chapter 7), so
there is no cell growth and the nutrients are used in making product
Let's do pari c first
1-12
[In flowrate (moles/time)] penicillin + [generation rate (molesltime)]penicillin - [Out flowrate (molesltime)]
penicillin = [rate of accumulation (moles/time)]penicillin
dNp
Fp,in + Gp - Fp,out = dt
Fp,in = 0 """ ''''', ...
v
Gp = f r ~ d V
Therefore,
v dNp
f rp .dV - Fp,out = dt
,., .,(because no penicillin inflow)
Assuming steady state for the rate of production of penicillin in the cells stationary state,
dNp
--=0
dt
And no variations
Or,
Similarly, fOI Corn Steep Liquor with Fe = 0
Assume RNA concentration does not change in the stationary state and no RNA is generated or destroyed.
Pl-12 (a)
Ranking of 10 most produced chemicals in 1995 and 2002 are listed in table below:
.--'
Rank 2002 Rank 1995 Chemical
1 I H
2
SO
4
2 2 N2
3 4 C
2
H
4
4 3 O
2
5 9 C3
H6
6 - H2
1-13
7 6 NH3
8 10 Ch
9 - P20S
10
-
C
2
H
2
Clz
-+ Cherrucals like H
2
, P
2
0
S
, C
2
H
2
Cl
2
has come III top 10 cherrucals and C3H6 has jumped to rank
5 now then rank 9 in 1995 .
Pl-12 (b)
Ranking of top 10 chemical companies in sales in yeru 2003 and 2002:
2003 2002 Company Chemical Sales
I----
($ million 2003)
Dow Chemical 32632 1 1
2 2 DuPont 30249
3 3 ExxonMobil 20190
4 4 General Electric 8371
-
5 8 Chevron Phillips 7018
---
+-.
5 Huntsman Corp. 6990
--
6 PPG Industries 6606
8
9
10
7 Equistar Chemicals 6545
11 Air Products 6029
--
9 Eastman Chemicals 5800
SOllIce: Chemical and Engineering News may 17,2004
-+ We have Chevron Phillips whichjumped to 5 rank in 2003 from 8
th
rank in 2002 and Air
Products coming to 9th rank in 2003 flom 11 th in 2001.
-+Chemical sales of each company has increased compared to year 2002 from 9%(Eastman
Chemical) t028.2%(Chevron Phillips) but Huntsman Corp .. has a decrease by 2 .. 9%.
Pl-12 (C)
Sulfuric acid is prime importance in manufacturing. It is used in some phase of the manufacture of neruly all
industrial products It is used in production of every other strong acid. Because of its lruge number of uses,
it's the most produced chemicaL Sulfuric acid uses are:
-+ It is consumed in production of fertilizers such as ammonium sulphate (NH4hS04 and
superphosphate (Ca(H
2
P0
4
)2) , which is formed when rock phosphate is treated with sulfUric acid ..
-+Used as dehydrating agent.
-+Used in manufacturing of explosives, dyestuffs, other acids, pruchment paper, glue, purification
of petroleum and picking of metals.
-+ Used to remove oxides from iron and steel before galvanizing or electroplating.
-+ Used in non-ferrous metallurgy, in production of rayon and film.
-+as laboratory reagent and etchant and in storage batteries
-+ It is also general purpose food additive.
Pl-12 (d) Annual Production rate of ethylene for year 2002 is 5.21x 1010 lb/yeru
Annual Production rate of benzene for yeru 2002 is 1.58 x 1010 lb/year
1-14
Annual Production rate of ethylene oxide for year 2002 is 7.6 x10
9
lb/year
Pl-12 ( e) Because the basic raw material 'coal and petroleum' for organic chemicals is very limited and
their production is not increasing as production of raw material for inorganic chemicals.
1-15
Pl-13
Type Characteristics Phases Usage Advantage Disadvantage
Batc All the reactants 1. Liquid 1, Small scale L High 1. High
h fed into the phase pdn. Conversion per Operating
reactor. During 2" Gas
2. Used for lab unit volume. cost
reaction nothing phase experimentation. 2. Flexibility of 2. Variable
is added or 3" Liquid 3. using for product
removed .. Easy Solid Pharmaceuticals multiple quality.
heating or
4. Felmentation reactions"
cooling.
3. Easy to clean
CST Continuous flow L Liquid L Used when 1 .. Continuous 1. Lowest
R of reactants and phase agitation required. Operation"
conversion
products .. 2. Gas- 2. Series 2.Good per unit
Uniform liquid Configuration Temperature volume.
composition 3. Solid -, possible for Control 2. By passing
tluoughout liquid different 3 .. Two phase possible with
configuration reactions poor
streams possible. agitation.
4.Good Control 3 High power
5. Simplicity of Input reqd.
construction.
6. Low
operating cost
7. Easy to clean
PFR One long reactor 1. 1. Large Scale 1. High 1. Undesired
or number of Primarily pdn .. conversion per thelmal
CSTR's in gas Phase 2 .. Fast reactions unit volume gradient
series .. 3. Homogenous 2. Easy to 2. Poor
No radial reactions maintain (No temperature
variations .. 4, Heterogeneous moving parts) control
Conc. changes reactions 3 .. low 3" Shutdown
along the length, 5" Continuous operating cost and cleaning
pdn, 4. continuous expensive"
operation
"" -
PBR Tubular reactor L Gas 1. Used plimarily 1. High L Undesired
that is packed Phase in the conversion per thelmal
with solid (Solid heterogeneous gas unit mass of gradient
catalyst Catalyst) phase reaction catalyst 2" Poor
particles" 2.Gas -- with solid catalyst 2" low
temperature
solid e .. g Fischer operating cost control
reactions. tropsch synthesis. 3., Continuous 3.
operation Channeling
4" Cleaning
__
_ .
116
Pl-14
Given
A = 2 * 10
10
ft 2
R = 0.7302 atm ft3
lbmolR
C = 4*10
5
cars
T
STP
= 491.69R
T = 534 .. 7R
H = 2000ft
Po= latm
c S = 2.04 * 10-
10
lbm
3
01
ft
FS = CO in Santa Ana wind FA = CO emission from autos
ft3
V A = 3000-- per car at STP
hr
Pl-14 (a)
Total number of Ib moles gas in the system:
POV
N :=--
R-T
latmx(4xlO
13
ft3)
N = ( 3 J = L025 X 1011 lb mol
0.73 atmft_ x534.69R
lbmol.R
Pl-14 (b)
Molar flowrate of CO into L.A. Basin by cars ..
F - F - VA CPo
A -YA T -YA Rr
STP
F = ~ f t 3 X llbmol x400000 cars
T hr car 359 ft3
FA = 6 .. 685 X 10
4
lb mollhr
Pl-14 (C)
Wind speed through corridor is v = l.5mph
W = 20 miles
The volumetric flowrate in the conidor is
Vo = v.W.H = (l5x5280)(20x5280)(2000) fe/ill
= L673 x lO
l3
fe/ill
(See appendix B)
1-17
Pl-14 (d)
Molar flowrate of CO into basin from Sant Ana wind
FS:= vOC
S
= 1.673 x 10
13
ft
3
fhr x2.04xlO-
1O
Ibmolfft
3
Fs = 3412 x 10
3
lbmolflu
Pl-14 (e)
dN
Rate of emission of CO by cars + Rate of CO by Wind - Rate of removal of CO = - co
dt
Pl-14 (0
t = 0 , Ceo = Ccoo
Pl-14 (g)
Time for concentration to reach 8 ppm,
= V dC
co
dt
C = 2.04 X 10-
8
~ m o l C, = 3..:9
4
X 10-
8
~ ~ m o l
coo ft3 ' co 4 ft3
From (f),
_ V I (FA +Fs--vo.CcooJ
t--- n
VO FA + Fs --VoC
ca
4ft
3
= --In
1.673xlO
13
ft'
hr
t = 6.92 hr
(V =constant, Nco = C co V )
Pl-14 (h)
(1) to 0 tl = 72lus
Ceo = 2.00E-1O IbmoUft
3
a = 3.50E+041bmoUln
v 0 L67E+ 12 fe flu b = 3,OOE+04 IbmoUln
1-18
Fs = 341.231bmol/hr
a + b Sin( JZ" ~ ) + Fs
v = 4.0E+13 ft
3
=
v
dCco
dt
Now solving this equation using POLYMATH we get plot between Ceo vs
See Polymath program Pl-14h-l.pol.
POLYMATH Results
Calculated values of the DEQ variahles
Var'iable initial value minimal value maximal value
t 0 0
C 2.0E-10 2 .. 0E-10
vO 1.67E+12 1 .. 67E+12
a 3.5E+04 3.5E+04
b 3 .. 0E+04 3 .. 0E+04
F 341..23 341 .. 23
V 4.0E+13 4 .. 0E+13
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(C)/d(t) = (a+b*sin(3 .. 14*t/6)+F-vO*C)/V
Explicit equations as entered by the user
[1] vO=1 .. 67*10A12
[2] a = 35000
[3] b = 30000
[4] F = 341 .. 23
[5] V = 4*10
A
13
3.0e-8,---------------
24e8
80
72
2.134E-08
1 .. 67E+12
3.5E+04
3 .. 0E+04
341..23
4.0E+13
(2) tf= 48lus F,=O
a + bSin( Z ~ )
Now solving this equation using POLYMATH we get plot between Ceo vs t
119
final value
72
1.877E-08
1.67E+12
3.5E+04
3.0E+04
341.23
4.0E+13
v
dCco
dt
See Polymath program P 1-14-h--2.pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
C 2 .. 0E-I0 2 .. 0E-I0
vO 1 .. 67E+12 1 .. 67E+12
a 3 .. 5E+04 3 .. 5E+04
b 3 .. 0E+04 3 .. 0E+04
V 4.0E+13 4 .. 0E+13
ODE Report (RKF45)
Differential equations as entered by the user
t 1] d(C)/d(t) = (a+b*sin(3 .. 14 *t/6)-vO*C)/V
Explicit equations as entered by the user
[1] vO = 1.67*10A12
[2] a = 35000
[3] b = 30000
[4] V = 4*10
A
13
2 Oe-8 r-------- .----------,
50
(3)
maximal value final value
48 48
1 .. 904E-08 1 .. 693E-08
1 .. 67E+12 1.67E+12
3 .. 5E+04 3 .. 5E+04
3 .. 0E+04 3.0E+04
4 .. 0E+13 4.0E+13
Changing a -+ Increasing 'a' reduces the amplitude of ripples in graph It reduces the effect of the
sine function by adding to the baseline.
Changing b -+ The amplitude of ripples is directly proportional to 'b' ..
As b decreases amplitude decreases and graph becomes smooth.
Changing Vo -+ As the value of Vo is increased the graph changes to a "shifted
sin-curve" And as Vo is decreased graph changes to a smooth
increasing curve ..
------------------ -----------
PI-IS (a)
- rA = k with k = OD5 mol/h dm
3
CSTR: The general equation is
1-20
v = FAO -FA
-r
A
Here C
A
= D"DIC
Ao
, Vo = 10 dm
3
/min, FA = 5 .. 0. mollhr
Also we know that FA = CAVO and F
Ao
= CAOVo, CAO = FAoI Vo = 0..5 mol/dm
3
Substituting the values in the above equation we get,
V = CAOV
O
-CAvo = (0.5)10-0.01(0.5)10
k 0.05
-7 V=99dm
3
PFR: The general equation is
dF
A
dCAv
O
--=r
A
=k,NowFA=CAvoandFAo=CAovo=> =-k
dV dV
Integrating the above equation we get
V CA V V
- ~ JdC
A
= JdV => V =--.!l(C
AG
,,- C
A
)
k C
AO
0. k
Hence V = 99 dm
3
Volume of PFR is same as the volume for a CSTR since the rate is constant and independent of
concentration.
PI-IS (b)
- rA = kC
A
with k = 0.,,0.0.0.1 s"!
CSTR:
We have already derived that
V = CAOV
O
-CAvo _ v
o
C
Ao
(1-0.01)
-r
A
kC
A
k = D .. DDDls"! = 0. .. 0.0.0.1 x 360.0. hr"!= 0..36 hI'''!
-7 V = (10"dm
3
/ hr )(0.5mal / dny3 O . ~ ? ) => V = 2750 dm3
(0.36hr -1 )(0.01 * 0.5mal / dm
3
)
PFR:
From above we already know that for a PFR
dCAvO - - kC
-rA - A
dV
Integrating
C dC V
_VG f _A =- JdV
k CAO C A 0.
Vo In C
AG
=V
k C
A
Again k = D.DDDls"! = 0..0.0.0.1 x 360.0. hI
o
!= 0..36 ru-!
1-21
Substituing the values in above equation we get
V = 127.9 dm
3
PI-IS (c)
- fA = kC
A
2
with k = 3 dm3/moLhr
CSTR:
-r
A
Substituting all the values we get
PFR:
V = (lOdm
3
/ hr)(O.5mol / dm
3
)(O.99)
(3dm
3
/ hr)(O.Ol * O.5mol / dm
3
)2
dCAvO _ -kC 2
- r
A
- A
dV
Integrating
=> V = 66000 dm
3
V C
A
dC V vII
f _A =- fdV
k CAD C/o k C A C AO
=> V = 10dm
3
I hr ( 1 = 660 dm3
3dm
3
lmol.hr O.OlC
AO
CAO
PI-IS (d)
t
AO dN
t- .
- WA -- r V
A
Constant Volume V=V
o
t = fAO dCA
1A - r
A
Zero order:
1 [ ] .999C
Ao
t = - CAO -O.OOlC
AO
= ---= 9.99h
k 0.05
FiIst Older:
1-22
t =_I_ln(_I_) = 6908s
k C A 0.001 .001
Second order:
1[1 1] 1[ 1 1]
t = k C A - CAD ="3 0.0005 - 0.5 = 666 h
PI-16 Individualized Solution
PI17 (a)
Initial number of rabbits, x(O) = 500
Initial number of foxes, y(O) = 200
Number of days = 500
dx
dt = k
1
x-k
2
xy .................................... (1)
dy
'dt = k3XY _. k
4
y .............. .
Given,
kl = 0.02day--1
k2 = 0.00004/(dayx foxes)
k3 = 0.0004/(dayx rabbits)
k4 = 0.04day-1
. ............... (2)
See Polymath program P 1 .. 17 -a.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value
t 0 0
x SOO 2.9626929
Y
200 1.128S722
kl 0 .. 02 0 .. 02
k2 4 .. 0E-OS 4.0E-OS
k3 4.0E-04 4.0E-04
k4 0 .. 04 0 .. 04
ODE Report (RKF45)
Differential equations as entered by the user
[ 1 J d(x)/d(t) = (k1 *x)-(k2*x*y)
[ 2 J d(y)/d(t) = (k3*x*y)-(k4 *y)
SOO
S19.40024
4099.S17
0 .. 02
4.0E--OS
4.0E-04
0 .. 04
1-23
final value
SOO
4.2199691
117.62928
0.02
4.0E-OS
4.0E-04
0.04
Explicit equations as entered by the user
[1] k1 = 0 .. 02
[2] k2 = 0 .. 00004
[.3] k3 = 0.0004
[4] k4=0 .. 04
5000.------------------
4000
3000
2000
o
400 200 t 300 o
500
When, tfinal= 800 and k
j
= O.00004/(dayxrabbits)
160 320 t 480 640 800
Plotting rabbits Vs .. foxes
1-24
160lli-----------------
o 378
720
1061 rabddPl
1744 2086
PII7 (b)
POL YMATII Results
See Polymath program Pl-17-b.pol.
POL YMA TH Results
NLES Solution
Value f(x)
X-------2.3850387 --'253E-iI"
y 3.7970279 1.72E-12
NLES Report (safenewt)
Nonlinear equations
( 1] f(x) = x
A
3*y-4*yA2+3*x-1 = 0
[ 2 1 f(y) = 6*yJ\2-9*x*y-5 = 0
PI-IS (a)
Ini Guess
2
2
No preheatmg of the benzene feed wtli dlmmlsh the rate of reactIon and thus lesser converSIOns WIll be
achIeved ..
PI-IS (b)
An lDterpolation can be done on the logarithnnc scale to find the desued values from the gIven data.
Now we can lDterpolate to the get the cost at 6000 gallons and 15000 gallons
Cost of 6000 gal reactor = 1 905 x lOS $
Cost of 15000 gal reactor = 5 623 X 10
5
$
PI-IS (c)
We are given C
A
IS 0 .. 1 % of minal concentration
C
A
= OOOlC
AO
1-25
Coat va Volume of reactor (log - log plot)
..
. --
1 -
. ,
"
"--t---

1011 volume (1I8110na)
..

Also from Example 1.3,
Substituting vo= 10 dm
3
/min and
k = 0.23 min-! we get
v = 300dm
3
which is three times the volume of reactor used in Example 1-3.
PI-18 (d) Safety of Plant
PI-19 Enrico Fermi Problem - no definite solution
PI-20 Enrico Fermi Problem -- no definite solution
PI-21 Individualized solution ..
CDPI-A (a)
How many moles of A are in the reactor initially? What is the initial concentration of A?
If we assume ideal gas behavior, then calculating the moles of A initially present in the reactor is quite
simple. We insert our variables into the ideal gas equation:
n = !.V = = 97.5moles
RT (8.3145 kPa.dm
3
)(500) latm
molK
Knowing the mole fraction of A (y Ao) is 75%, we multiply the total number of moles (N
1o
) by the Y A:
molesA = N
Ao
= 0.75x97.5 = 73.1
The initial concentration of A (C
Ao
) is just the moles of A divided by the volume:
C Ao = moles = N Ao = 73 = 0.37 moles / dm
3
volume V 200dm
CDPI-A(b)
Time (t) for a 1 st order reaction to consume 99% of A.
dC
r =_-A
A dt
OUf first order rate law is: -r =kC
A A
1-26
mole balance: dC A =--kC
dt A
-k t
fdt
= CfA dC A
=> C
o CAO A
-kt = In( C
A
), knowing CA=O.OI C
Ao
and our rate constant (k=O.1 min-I), we can solve
CAO
for the time of the reaction: t = -. .!.In(O.OI) = 4.61 1 = 46. 1 min
k O.lmin-
CDPI-A (c)
Time for 2nd order reaction to consume 80% of A and final pressure (P) at T = 127 C.
rate law:
dC
mole balance: :. _2. =
dt
1 1
=>-kt=--+-
C
A
CAo
We can solve for the time in terms of our rate constant (k = 0.7) and our initial
concentration (C
Ao
): -kt = +_1_
CAo CAO
t=_4_= 4 ----=15.4min.Todetermine
kC
Ao
(0.7dm
3
/ mol min)( 0.37moll dm
3
)
the pressure of the reactor following this reaction, we will again use the ideal gas law.
First, we determine the number of moles in the reactor:
NB =Nc =0.8N
Ao
NT = (0.25)N
yo
+ (0.2+0.8+0.8)N
Ao
= 0.25(97.6) + (1.8)(73.2) = 156.1moles
(156. Imole) (0.082 dm
3
atm] (500K)
N RT molK
p = _1_ = _ . ___ ---''---__ = 32atm
V 200dm
3
CDPI-B
Given: Liquid phase reaction in a foam reactor, A
Consider a differential element, V of the reactor:
By material balance
FA -(FA
1-27
Where, (1- V = fraction of reactor element which is liquid.
or: -FA
dF
_A = r (I-e)
dV A
Must relate (-r
A
) to FA '
where, FA is the total (gas +liquid) molar flow rate of A.
-r
A
=rate of reaction (g mol A per cubic cm. of liquid per sec .. ); e = volume fraction of gas; FA = molar
flow rate of A (g mol/sec .. ); V = volume of reactor
1-28
Solutions for Chapter 2 - Conversion and Reactor
Sizing
Synopsis
General: The overall goal of these problems is to help the student realize that if they have -r A=j{X) they
can "design" or size a large number of reaction systems. It sets the stage for the algorithm developed in
Chapter 4"
P2-l. This problem will keep students thinking about writing down what they learned
every chapter.
P2-2. This "forces" the students to determine their learning style so they can better use
the resources in the text and on the CDROM and the web.
P2-3. ICMs have been found to motivate the students learning.
P2-4. Introduces one of the new concepts of the 4th edition whereby the students
"play" with the example problems before going on to other solutions.
P2-S. This is a reasonably challenging problem that reinforces Levenspiels plots.
P2-6. Novel application of Levenspiel plots from an article by Professor Alice Gast at
Massachusetts Institute of Technology in CEE.
P2-7. Straight forward problem alternative to problems 8, 9, and 12.
P2-S. To be used in those courses emphasizing bio reaction engineering.
P2-9. The answer gives ridiculously large reactor volume. The point is to encourage
the student to question their numerical answers.
P2-l0. Helps the students get a feel of real reactor sizes.
P2-ll. Great motivating problem. Students remember this problem long after the
course is over.
P2-l2. Alternative problem to P2-7 and P2-9.
CDP2-A Similar to 2-9
2-1
CDP2-B Good problem to get groups started working together (e.g. cooperative
learning.
CDP2-C Similar to problems 2-8, 2-9, 2-12.
CDP2-D Similar to problems 2-8,2-9,2-12.
Assigned
P2-1 0

P2-2 A

P2-3 A
P2-4 0
P2-.5 0
P2-6 S

P2-7 AA
P2-8 S
P2-9 AA
P2-10 S

P2-11 AA
P2-12 AA
CDP2-A 0
CDP2-B 0
CDP2-C 0
CDP2-D 0
Summary
Alternates
8,9,12
7,9,12
7,8,9
9,B,C,D
9,B,C,D
9,B,C,D
9,B,C,D
Difficulty
M
M
FSF
FSF
SF
SF
SF
SF
FSF
FSF
FSF
FSF
Time (min)
15
30
30
7.5
75
60
4.5
45
45
15
1
60
5
30
30
45
Assigned
= Always assigned, AA = Always assign one from the group of alternates,
o = Often, I = Infrequently, S = Seldom, G = Graduate level
Alternates
In problems that have a dot in conjunction with AA means that one of the
problems, either the problem with a dot or anyone of the alternates are always
assigned.
Approximate time in minutes it would take a B/B+ student to solve the problem.
Difficulty
SF = Straight forward reinforcement of principles (plug and chug)
2-2
FSF = Fairly straight forward (requires some manipulation of equations or an
*
intermediate calculation).
IC = Intermediate calculation required
M = More difficult
OE = Some parts open-ended.
Note the letter problems are found on the CD-ROM. For example A == CDPI-A.
Summary Table Ch-2
Straight forward
Fairly straight forward
More difficult
Open-ended
Comprehensive
Critical thinking
P2-l Individualized solution ..
P2-2 Individualized solution.
-
1,2,3,4,10
7,9,12
5,6,8
6
4,5,6,7,8,9,12
P2-9
P2-3 Solution is in the decoding algorithm given with the modules ..
P2-4 (a) Example 2-1 through 2-3
If flow rate FAD is cut in half.
VI = v/2, F
I
= FAd2 and CAD will remain same ..
Therefore, volume of CSTR in example 2-3,
F;.X 1 FAOX 1
VI =----=---=-6.4=3.2
- r
A
2 -r A 2
If the flow rate is doubled,
F2 = 2F AD and CAD will remain same,
Volume ofCSTR in example 2-3,
V2 = F2X1-rA = 12 .. 8 m
3
P2-4 (b) Example 2-5
2-3
--
Faol2
Levenspiel Plot
45-.-------------------------------------
J--O+X overall
4

'" ';- 25
o
'" 2
LL
15
Faol2
05

o 02 04 06 08
Now, F AO = 0.,4/2 = 0...2 molls,
Conversion
F
New Table: Divide each term in Table 2-3 by 2.
-- 'A
cx:= ---.--/ 0.-10.-1 -.---, 0..2--'--, 0-.4 -.--, 0.-.6
0..445 TI545 0..665 1.0.25 1.77
Reactor 1
VI = 0.. 82m
3
V = (F Aol-IA)X
0.82 = J (Xl)
A XI
By trial and error we get:
Reactor 2
V
2
= 1.2 m
3
XI = 0..546 and X
2
= 0. .. 8
Overall conversion XOver.1I = (l/2)XI + (l/2)X2 = (0..546+0.._8)/2 = 0..673
P2-4 (C) Example 2-6
Now, F
AO
= 0..4/2 = 0..2 molls,
Fao/2
Faol2
X1
.... --+X overall
2-4
_ ,/ 0.---,,-.7
k.-J
F
New Table: Divide each term in Table 2-3 by 2 ..
VI = 0.551m
3
x dX
V; = FAO I--
o -r
A
-r
A
0.1 0.2
0.665
0.4 0.6
1.025 1.77
Plot FAof-rA versus conversion. Estimate outlet conversions by computing the integral of the plotted
function.
Levenspiel Plot
45
4
3.5
3
ca
...
25

"0
2 ca
LL.
1.5
1
0.5
0
0 0 .. 2 0.4 06 0 .. 8
Conversion
[ XI = 0603 f ~ r VI = 0.551m
3
"---X;-=-O .. 89 for V
z
= L614m
3
Overall conversion Xo= (l/2)XI + (1I2)Xz = (0 .. 603+0.89)/2 = 0.746
- . ~ ._----
P2-4 (d) Example 2-7
(1)
ForPFR,
= 0.222m
3
For first CSTR,
~
c5
'"
IL
25
2
15
1
05
0
Levenspiel Plot
0 0.1 02 03 04
Convelsion
2-5
_J
05 06 07
F
AO
_ 3
X
2
= 0..6, _. -1.32m ,
-rA
For second CSTR,
F
AO
3
X3 = 0.65, --= 2.0m ,
-rA
(2)
First CSTR remains unchanged
ForPFR:
05(F }
V= f. _AO X'
02 rA
Using the Levenspiel Plot
V
PPR
= 0..22
ForCSTR,
(3) The worst arrangement is to put the PFR
F (X -X )
V
- AO 3 2 = 01 3
3- . m
. -rA
Levenspiel Plot
25

* 15+----------------------
"0
.f 1
o 5
o +---,---'-'-'---
o 01 02 0.3 04 0.5
Conversion
first, followed by the larger CSTR and finally the smaller CSTR.
-r) -(
06 07
Conversion Original Reactor Volumes
Xl = 0..20 VI = 0.188 (CSTR)
X2 = 0..60 V2 = 0.,38 (PFR)
LX:.::.::..3 _=-=0..:.:.6:.::.5 ________ V.3 = 0.10 (CSTR)
Worst Ana"itgement_,, ___
VI = 0..23 (PFR)
V2 = 0.53 (CSTR)
_____ y3 = 0.10 (CSTR)
ForPFR,
Xl = 0..2
V. = f(
Using trapezoidal rule,
Xo = 0,1, Xl = 0.1
2-6
=
= 0.2 [1.28+0.98]m
3
2
=0.23m
3
ForCSTR,
FAD 3
For X
2
= 0 .. 6, --= 1.32m ,
-rA
FAD () 3
V
2
= -- X
2
- Xl = 1.32(0.6- 0.2) = 0.53 ill
-rA
For 2
nd
CSTR,
FAD 3
For X3 = 0.65, --= 2m ,
-rA
P2-4 (e) Example 2-8
T = 5hrs
Vo = 1dm
3
/min = 60dm
3
/hr C
A
= 2.5 mol/dm
3
X = 0.8
V
For CSTR, T = .-
Vo
V= 300dm
3
(1)
--r A= CAOX = 2.5xO.8 moll dm
3
hr
T 5
= OAmol / dm
3
hr
(2) V = 300dm
3
(3)C
A
= CAO(1-X)
= 0.5 mol/dm
3
P2-5
-
0 0.1
m
3
) 0.8 1.0
9 8
0..2
13
3
-
OA 0.6 0..7 O.
8
2 .. 0 3.5 5.0 8..
5 4 6 0
._.
Levenspiel plot
.............. - .... _ .. _ ... _._ ......_ .. - .... _"
P2-5 (a) Two CSTRs in series
For first CSTR,
V = (F Ad-rAXl) XI
=>Xl =OA4
For second CSTR,
V = (FAd-rAX2) (X
2
- XI)
=> X2 = 0.67

g

01 02 03 04 05 06 07 08 09
x
P2-5 (b)
Two PFRs in series
v 1( +)(
By extrapolating and solving, we get
Xl = 0..50. X
2
= 0.74
P2-5 (C)
4
3 +------------
F"o
-r
A 2
(m')

Two CSTRs in parallel with the feed, F AO,
divided equally between two reactors, FANEW/-
IAXI = o.5FAd-IAXI

.... .-..
----_ .. --_ .. _ ....
V = (o..5F Ad-rAXI) Xl
Solving we get, X
out
= 0.,,60.
o
o 0,2 0,4 0.6
P2-5 (d)
Two PFRs in parallel with the feed equally divided between the two reactors,
FANEW/-rAXI = o.5FAOI-rAXI
By extrapolating and solving as part (b), we get
X
out
= 0..74
P2-5 (e)
A CSTR and a PFR are in parallel with flow equally divided
X
0,,8
Since the flow is divided equally between the two reactors, the overall conversion is the average of the
CSTR conversion (part C) and the PFR conversion (part D)
Xo = (0.,60. + 0.,74) 12 = 0.,67
P2-5 (0
A PFR followed by a CSTR,
X
PFR
= 0...50. (using palt(b
V = (F Ad-rA-XCSTR) (XcSTR - XPFR)
Solving we get, X
CSTR
= 0.,70.
P2-5 (g)
A CSTR followed by a PFR,
X
CS1R
= 0.,44 (using part(a
2-8
1
X pFR F
V = f -.MLdX
-rA
X
CSTR
By extrapolating and solving, we get
P2-5 (h)
A 1 m
3
PFR followed by two 0.5 m
3
CSTRs,
ForPFR,
X
PFR
= 0..50. (using part(b
X
PFR
= 0. .. 72
CSTR
1
: V = (F Ad-rA-XCSTR) (X
CSTR
- X
PFR
) = 0..5 m
3
X
CSTR
= 0..63
CSTR2: V = (F Ad-rA-XCSTR2) (XCSTR2 - XCSTRI) = 0..5 m
3
X
CSTR2
= 0..72
P2-6 (a) Individualized Solution
P2-6 (b)
1) In order to find the age of the baby hippo, we need to know the volume of the stomach.
The metabolic rate,-rA, is the same for mother and baby, so if the baby hippo eats one half of what the
mother eats then Fao (baby) = Y2 Fao (mother).
The Levenspiel Plot is drawn for the baby hippo below ..
Autocatalytic Reaction
5
........................................ __ ... _ ...... -................................. .,


i 3
e
-.l. 2 5
o

1.5
05
02 04
Conversion
06 08
2-9
Since the volume of the stomach is proportional to the age of the baby hippo, and the volume of the baby's
stomach is half of an adult, then the baby hippo is half the age of a full grown hippo.
4 . .5 years 2 25
Age = = . . years
2
2) IfVmax and mao are both one halfofthe mother's then
and since
-r
AM2
bllby
then
1
-vrnaxC
A
1
..=2:....-.. __ = - - r
KM + C
A
. 2 AM2mothef
1
'-m
Catalytic Reaction
2
o
JS= 0.4
Conversion
2 Ao
-----
1
- 2 rAM2
(
mAo J
-r
AM2
baby
(
mAo J
= - rAM mother
mother
m
will be identical for both the baby and mother
-r
AM2
Assuming that like the stomach the intestine volume is proportional to age then the volume of the intestine
would be 0.75 m
3
and the final conversion would be 040
P2-6 (C)
VSlomach = 0.2 m
3
From the web module we see that if a polynomial is fit to the autocatalytic reaction we get:
m
--AO = 127X4 _ 172.J6X
3
+ 100.l8X
2
- 28354X + 4.499
-rAMI
210
r.nAO
And smce Vstomach = ---X,
-rAMI
solve V= 127X
5
- 172.36X
4
+ 1OG.18X
3
- 28..354X
2
+ 4 .. 499X = 0.2 m
3
Xstomach = .. 067.
For the intestine:
The Levenspiel plot for the intestine is shown below. The outlet conversion is 0 .. 178
Since the hippo needs 30% conversion to survive but only achieves 17.8%, the hippo cannot survive ..
Autocatalytic Reaction
5
45 +--------
4+\----

i 3-
n:t
----+---l
!!: 25
fil

E 2
1.5
1-----
05
I
t-------.----...---
o -----,-----r-------.,..------/
o 02
P2-6 (d)
CSTR
PFR:
04
Conversion
Outlet conversion of PFR = 0 .. 111
2
CSTR:
Catalytic Readion
o X= 0.111
Conversion
06 08
2
5
45
4
3.5
,...
:E
ca
..
2.5
-.!.
0
ca
2
E
1.5
05
0
0
2-11
Catalyti c Reaction
o X=0178
Con v ersi on
Autocatalytic Reaction
0.2 0.4
Conversion
0.6 08
We must solve
v = 0..46 = (X-QJ 1l)(127X
4
- 172.36X
3
+ 100. J 8X
2
- 28,354X + 4.499)
X=O,42
Since the hippo gets a conversion over 30.% it will survive"
P2-7
Exothermic reaction: A B + C
r(mol/dm
3
,min
1/-r(dm
3
.min/mol) X )
0. 1 1
0. .. 20. 1.67 0.,,6
0..40. 5 0..2
0..45 5 0.,,2
0..50. 5 0..2
0..60. 5 0..2
0..80. 1 .. 25 0. .. 8
0..90. 0..91 1.1
P2-7 (a)
To solve this problem, first plot 1/-rA vs" X hom the chart above. Second, use mole balance as given below,
CSTR:
Mole balance:
V
CSTR
= FAo ! = (300mollmin)(0.4) =>
- 'A (Smol / dm
3
.min)
=> V CSTR = 24 dm
3
PFR:
x dX
VpFR = F
AO
f--
-r
Mole balance: 0 A
P2-7 (b)
= 3QQ(area under the curve)
V
PFR
= 72 dm
3
2-12
0.4 0.6
X
For a feed stream that enters the reaction with a previous conversion of DAD and leaves at any conversion
up to 0. .. 60., the volumes of the PFR and CSTR will be identical because of the rate is constant over this
conversion range.
P2-' (C)
V CSTR = 105 dm
3
FAOX
Mole balance: V CSlR =--
-r
A
0040
x
._. fA
105dm
3
---. = O.35dm
3
mini mol
300mollmin
Use trial and error to find maximum conversion..
At X= 0..70., 1/-fA = 0..5, and X/-rA = 0..35 dm3 .. minlmol
Maximum conversion = 0..70.
P2-' (d)
..
From part (a) we know that Xl = DAn.
".
Use trial and error to find X
2
.
2-13
CSTR
0.60
1 PFR II
Xl
1
CSTR
--
.....
X2
-
Reananging, we get
X 2 - 0040 = = 0.008
- rAlx2 FAD
X
2
-OAO
At X
2
= 0.64, I = 0.008
-r
A
X
2
Conversion = 0.64
P2-7 (e)
From part (a), we know that Xl = OAO. Use trial and error to find X
2
X
2
dX X
2
dX
Mole balance: V
PFR
= 72 = F
AO
f --. = 300 f--
040 - r A 040 - r
A
At X
2
= 0 .. 908, V = 300 x (area under the curve)
-lIrA
=> V = 300(024) = 72dm
3
Conversion = 0..908 ..
P2-7 ()
See Polymath program P27fpoL
2-14
0.65
052
0.39
0.26
0.13
0.00
0 20
P2-8 (a)
FsoX
V=---
-rs
Fso = 1000 glhr
Q
40
V
60 80 100
1 dm
3
hr
At a conversion of 40% -- = 0.15---
-rs g
Therefore V = (0.15)(1000)(0.40) = 60dm
3
P2-8 (b)
1 dm
3
hr
At a conversion of 80%, -- = 0.8-----
_. rs g
Fso = 1000 glhr
Therefore V = (0.8)(1000)(0.80) = 640dm
3
P2-8 (C)
x dX
VPFR = Fso f--
o -rs
6.0
5 .. 0
to
GJ
3.0
2.0
1.0
0 .. 0
0 17 33 50
V
67 83 100
From the plot of 1/-rs Calculate the area under the curve such that the area is equal to V IPso = 80/ 1000 =
0..08
X= 12%
F X
For the 80 dm
3
CSTR, V = 80 dm
3

-f
s
XI-rs = 0.08.. From guess and check we get X = 55%
2-15
P2-8 (d)
To achieve 80% conversion with a CSTR followed by a CSTR, the optimum arrangement is to have a
CSTR with a volume to achieve a conversion of about 45%, or the conversion that corresponds to the
minimum value of 1I-rs Next is a PFR with the necessary volume to achieve the 80% conversion following
the CSTR. This arrangement has the smallest reactor volume to achieve 80% conversion
For two CSTR's in series, the optimum arrangement would still include a CSTR with the volume to achieve
a conversion of about 45%, or the conversion that cOllesponds to the minimum value of 1I-rs, first. A
second CSTR with a volume sufficient to reach 80% would follow the first CSTR
-r
l
_ kC
s
(O.l[C
so
- C
s
]+ 0.001)
KM + C
s
Let us first consider when C
s
is small
C
so
is a constant and if we group together the constants and simplify
since C
s
< KM
1 KM
- which is consistent with the shape of the graph when X is large (if C
s
is small X is
r, k l ~ + k
2
Cs
large and as C
s
grows X decreases),
Now consider when C
s
is large (X is small)
As C
s
gets larger C
c
appwaches 0:
kCsC
c
1 KM + C
s
If - r = then - - = ---''-'---
l KM + C
s
r, kCsC
c
As C
s
grows large!, C
s
KM
2-16
And since C
c
is becoming very small and approaching 0 at X = 0, 1/-1s should be increasing with C
s
(or
decreasing X)., This is what is observed at small values of X_ At intermediate levels of C
s
and X, these
driving forces are competing and why the curve of 1/-rs has a minimum.
P2-9
Irreversible gas phase reaction
2A+B
See Polymath program P2"-9.poJ.
P2-9 (a)
PFR volume necessary to achieve 50% conversion
Mole Balance
X
2
dX
V=F
AO
f---
Xl (-r
A
)
Volume = Geometric area under the curve of (F AoI-rA)
vsX)
V = GX400000XO.5) + (100000 X 0.5)
V = 150000 m
3
P2-9 (b)
CSTR Volume to achieve 50% conversion
Mole Balance

(-r
A
)
V = 0.5 X 100000
V = 50000m
3
P2-9 (c)
Volume of second CSTR added in series to achieve 80%
conversion
V
__ l!.AO(X2- Xl).
2-
(-r
A
)
V
2
= 500000 X (0.8"- 0.5)
V
2
= 150000m
3
2-17
x
x
x
-I- -+"-
o.s 0 <1 10
P2-9 (d)
Volume of PFR added in series to first CSTR to achieve
80% conversion
1
V
PFR
= (-x 400000 x 0.3) + (100000 X 0.3)
2
V
PFR
= 90000m
3
P2-9 (e)
ForCSTR,
VI = 60000 m
3
(CSTR)
Mole Balance
V= FAOX
(-r
A
)
x == 0.515
ForPFR,
V
2
= 60000 m
3
Mole balance
X2 dX
V=F
AO
f---
Xl (-r
A
)
Eqn .. Of 2
nd
line (sloping upwards)
y -100000 = 1.3 x10
6
(x - 0.5)
X
2
60000 = f (l.3x10
6
(x -- 0.51) + 100000)dX
Xl
=> X
2
= 0 . .746
P2-9 (0
Real rates would not give that shape. The reactor volumes are absurdly large ..
P2-10
x
x
Problem 2-10 involves estimating the volume of three reactors from a picture., The door on the side of the
building was used as a reference., It was assumed to be 8 ft high.
The following estimates were made:
h = 56ft d = 9 ft
V = nr
2
h = 11:(45 fti(56 ft) = 3562 ft' = 100,865 L
218
Length of one segment = 23 ft
Length of entire reactor = (23 ft)(12)(II) = 3036 ft
D=lft
V = m
2
h = n(O.5 ft)2(3036 ft) = 2384 ft3 = 67,507 L
Answers will vary slightly for each individuaL
P2-11 No solution necessary.
P2-12 (a)
The smallest amount of catalyst necessary to achieve 80 % conversion in a CSTR and PBR connected in
series and containing equal amounts of catalyst can be calculated from the figure below.
CSTR
PBR
X
The lightly shaded area on the left denotes the CSTR while the darker shaded area denotes the PBR This
figure shows that the smallest amount of catalyst is used when the CSTR is upstream of the PBR
See Polymath program P2-12.pol.
P2-12 (b)
Calculate the necessary amount of catalyst to reach 80 % conversion using a single CSTR by determining
the area of the shaded region in the figure below ..
2-19
60
2 ,4 6
Conversion, X
8 10
The area of the rectangle is approximately 232 kg of catalyst.
P2-12 (C)
The CSTR catalyst weight necessary to achieve 40 % conversion can be obtained by calculating the area of
the shaded rectangle shown in the figure below.
60
10
_____ __ -LI ____ __ ___
2 4 6 8 10
Conversion, X
The area of the rectangle is approximately 7,6 kg of catalyst
P2-12 (d)
The catalyst weight necessary to achieve 80 % conversion in a PBR is found by calculating the area of the
shaded region in the figure below,
2-20
6
Conversion, X
The necessary catalyst weight is approximately 22 kg ..
P2-12 (e)
The amount of catalyst necessary to achieve 40 % conversion in a single PBR can be found from calculating
the area of the shaded region in the graph below.
60
1;;
f 40
If
<;J,-1... 3
u. I
20
10
2 .4 6
Conversion. X
.8 1.0
The necessary catalyst weight is approximately 13 kg.
P2-12 (1)
2-21
1.0
0 .. 8
0.6
04
0.2
0.0
0 .. 0 6.-1


12..8 \V 19 .. 2
25 .. 6 32.0
P2-12 (g)
For different (-rA) vs .. (X) curves, reactOIs should be arranged so that the smallest amount of catalyst is
needed to give the maximum conversion.. One useful heuristic is that for curves with a negative slope, it is
generally better to use a CSTR Similarly, when a curve has a positive slope, it is generally better to use a
PBR
CDP2-A(a)
Over what range of conversions are the plug-flow reactor and CSTR volumes identical?
We first plot the inverse of the reaction rate versus conversion.
10" 8
r
A
/
/'
/
/
/
o , ..-......... -.. -.---.-,.-..... -... --.-------,--....--.--.-----,-.... -.-...----.. -......,.----.---,-.---..
o 0.2 OA ,)_6 0 .. 8 1.0
Conversion X
Mole balance equations for a CSTR and a PFR:
CSTR: V = FAOX
-- r
A
x dX
PFR: V= S-
0-- r
A
Until the conversion eX) reaches 0.5, the reaction rate is independent of
conversion and the reactor volumes will be identical.
2-22
05 dX F 05 F X
. v f AO fdX - AO - V
1.e. PFR = --=-- - '- CSTR
o - r
A
- r
A
0 - r
A
CDP2-A(b)
What conversion will be achieved in a CSTR that has a volume of 90 L?
For now, we will assume that conversion (X) will be less that 0.5.
CSTR mole balance:
V = !AO
X
= voC AO
X
- r
A
- r
A
V 0.09m3
X =---=. =3xlO-
13
V C 3 l 3
o AO 5 m X 200 mo X 3 X 10
8
!'1 . ~
- r
A
S m
3
mol
CDP2-A (c)
This problem will be divided into two parts, as seen below:
l ) ~ 8
-'A
(m
3
'\
, -----1
! mot 1
,- )
0.2 {I.4 0,6
1.0
Conven,ion X
The PFR volume required in reaching X=O.5 (reaction rate is independent of conversion).
The PFR volume required to go from X=O..5 to X=o.,7 (reaction rate depends on convelsion).,
223
= 8*10
lO
m
3
Finally, we add V
2
to VI and get:
V
tot
= VI + V2 = 2.3 xlO
11
m
3
CDP2-A (d)
What CSTR reactor volume is required if effluent from the plug-flow reactor in part (c) is fed to a CSTR to
raise the conversion to 90 %
10' 1/
r
/\
l
' 1113 ~ ~
ruol f
2
I)
C;onversion X
We notice that the new inverse of the reaction rate (I/-rA) is 7*108. We insert this new
value into our CSTR mole balance equation:
CDP2-A (e)
If the reaction is canied out in a constant-pressure batch reactor in which pure A is fed to
the reactor, what length of time is necessary to achieve 40% conversion?
Since there is no flow into or out of the system, mole balance can be written as:
V
_dNA
Mole Balance: r
A
- --
dt
Stoichiometry: N A = N AD (1 -- X)
2-24
dX
Combine: r
A
V = N AO --
dt
From the stoichiometry of the reaction we know that V = Vo( 1 +eX) and e is 1. We insert
this into our mole balance equation and solve for time (t):
Vo dX
-r
A
-(1+X)=--
N
AO
dt
tSdt - C XS __ d_X __
o - AO 0 - r
A
(1 + X)
After integration, we have:
1
t =--CAoln(l + X)
- r
A
Inserting the values for our variables:
t = 2.02 X 1010 s
That is 640 year'S.
CDP2A (f)
Plot the rate of reaction and conversion as a function of PFR volume.
The following graph plots the reaction rate (-rA) versus the PFR volume:
Ii' "''''''''''' " '" ""''''''''''''''' '"'''''' '
il 4 .. 0*10- Reaction Rate (--r A) ver'sus Reactor' Volume (V)
'I
II-'A

2 .. 0*10-9_
------
.'-..._ ..-...... _,"'_.","", ..
1 .. 0*10-
9
o ----t---___ ----,>----_, --_,
o 1 .. 0*10" 2 .. 0*10" 3 .. 0*10" 4 .. 0*10" 5 .. 0*1011
V (m
3
)
Below is a plot of conversion versus the PFR volume. Notice how the relation is
linear until the conversion exceeds 50%.
225
Conversion (X) versus Reactor Volume (V)
1 .. 0
0 ... 8
x
0 ... 6
0 ... 4
0 .. 2
0--1<----_--;,----..-, -----t,----o,
o 1 .. 0*10" 2.0*10" 3.0*10" 4 .. 0*10" 5 .. 0*1011
V (m
3
)
The volume required for 99% conversion exceeds 4*1011 m
3
.
CDP2-A (g)
Critique the answers to this problem.
The rate of Ieaction for this problem is extremely small, and the flow rate is quite large. To obtain the
desired conversion, it would require a reactm of geological proportions (a CSTR or PFR approximately the
size of the Los Angeles Basin), or as we saw in the case of the batch reactor, a very long time ...
CDP2-B Individualized solution
CDP2-C (a)
o 0.1 O ~ a.3 0.4 ~ e.G 0.1 0.1 o ~
COfivtrll01l. X
!a.}
For an intermediate conversion of 03, Figure below shows that a PFR yields the smallest volume, since fOI
the PFR we use the area under the curve .. A minimum volume is also achieved by following the PFR with a
CSTR In this case the area consideIed would be the rectangle bounded by X =0.3 and X = 0 ... 7 with a height
equal to the CAr/-rA value at X = 0.7, which is less than the area under the curve ...
CDP2-C (b)
2-26
v .... so t/min
o
v ...
Vo I. 'Where
,0 .3
I ,. J_
o
*" <O.l - 0)(10)
"" IS :::c.in
-C
AO
+ <0.1-0.3) -
-%A
X-O.1
1
-+ 2' (0 .3-<D (,50-10) +
<0 .. 1-0.3) (15)
So V .. v .. 1: III (SO l.J:ad.n) (15 lJdn) .. 75,0 1 III 750 =.t.o
CDP2-C (C)
The caa be achieved by ouly Qua CSTR with this systom.
C"I'I
I ... (O.1--{).Ol....u::.;.
-r).
* (0.7-0)(15) - 10.5
'1-0.7
So V - v I .. (SO) Ihniu (10.5) lAiu - 525 1
o
We further roduco the by usin& a PFR at first up to the
CDP2-C (d)
2-27
to t11(1 &::C& of tlu rcctan.;lc up to tho specified c;ouvcr:Jion.
eM
I '" (O.45-0)
-r
A
(0.45-0)(37) - 16.55
:X .. O .1
So V v I. (50 I/min}{16.65 min.) u 832.5 1
o
For thePFR,
f
o. 4S
I ..
o
4(48) ... 2(43) + 31)
..9.....Sli (10 ... 4(1.5 ... 3S ... 43 ... 48) ... 2(20 + 43 ... 50 + 43) ... ]1) ... :1.5. n
.. 3
So V p v I - (50 I/min} {15.12 miu) - 186 1
o
There is also solution at au X>O.1
Tr:r I. .. O.S
For the PFR
+ 4( 15) .... 33)
.!hl. UO ... 4' 20 +- SO +- 3Z .... 1.3) .... .... 43 .... 1.1} ... 33) ... Z3.9
"" 3 \
For tl:a CSU
I (O.19)(30) - 13.7 min
So V ... 'V t ... (SO 1/;:dn)(23.7 min) ... 11S! 1
c
228
For t:.h.a PFR.
I - 23.9 - ~ (O.S-Q.79)(30+33) - 23.9 - 0.315 - 23.58 mi:
...
So V .. v I '" (50 I/mill)(23.SS mal -1179 1
o
o ~ diffc:rcu:u:o
CDP2-C (e)
x 0.0 0.1
C A0/-:r A {J:).inJ 10 20
-;(minJ
0.0 l.O
3CI
1$
20
o 0.1 02
v
7'00 1.
50 If::r.i.a. "" 14
m.in.
"= .-,.
0,,2
43
S .. t)
0.4
X
0.3
SO
15.0
2-29
0.4 0.5 0 .. 6
43 32 11
17.2- 16.0 10,.2
0.7
0.1 0.8
15 33
10 .. 5 2,6.4
CDP2-D
Data taken at WI.;; kPa (10 atrn) and 227"C (500.2 K)
y/\O =0333
y,,(}p (0.333XlO) 00811"-)'d-'
c ;;;;; . __ ... -;;:;; ---------,- ==. J gInO I m
Ao RT (0,082X500.2)
100000 .. -... .. -l
60000
40000
zoooC)
!
I
... ------1
I
I

t
l
() .... -.-......- ... --... ..-----.. -.-.-....-... -.---.-... --.-.
o 0.2
x
0.4 0,6
CDP2-D (a)
30% conversion in PFR:
, 0.3 cLX
-C
pfR
;:;: C
AO
5--....... :;::;: 4,664 .. 84 s
0'-' fA
V
- - (4 84 f
1
min }2 '/ .) 5 - - 3
=? - V
o
" - \' 0 . s, 6.:-.-- m mm = L ).) m
Os
,
CDP2-D (b)
30 to 50% conversion in CSTR:
c (X,-X)
1:CS'IR ;;;:; .... _Au, .. : ............... !...: :;::;: 12,169.2 s =?
.... IAl
"1 (12 169 ') {'
1
min ]2 3/..) 0 - 64 3 Y
CSIR
:::::: ,._S -....... In IIlln =4 3. f m
60s
CDP2-D (C)
2-30
Total Volume:
V
Touu
== 155.5+405.6 == 561.1 m
J
CDP2-D (d)
60% conversion in PFR:
1:PFR ::-:. C At> 20.281.9 s
o ""f
A
80% conversion in PFR:
fA is not known for X>O.60 - can not do.
CDP2-D (e)
50 % in CSTR:
X
't' :::; C Ao :::; 30,422.9 s
- fA.
V:::; v 0"' ;;;; (30,422.9 s {
I
Y. 2 m> Imin)-;;;:: 1014.1 m
3
\ DOS J
CDP2-D (1)
50 to 60% conversion in CSTR:
C.\o(X) -Xl) .
t -;;;:: --.:...--. ....:::."" ..... - :::::: 8112.8
- fAl
V = v.' = (8112.8S{To':-}2 m'/min)= 270.4 m'
CDP2-D (g)
2-31
Rate of Reaction vs. VolUl:oe
IOE,05 ,"-""'.'--"--- ., '--1
7 5E 06 I ... --- "--, -,-- I
? 5 OE 061 .. _, ---, -- I
2 SE 06 -, - -
O.OEtOO ____
o 200 400 600 800
CDP2-D (h)
Critique
Volnme(m
3
)
Answers are Valid:
1. Constant Temperature and Pressure
No heat effects
No pressure drop
Conversion vs. Volurne
06
0.4
0.2
0,
o 200 400 600 800
Volume (m
3
)
2. Single interpolation to X .. :;;; 0.15, 030,0,45, and 0.50 allowable
3. tiuge volume (the size of the LA Basin)! Raise T? Raise P?
CDP2-E
For the CSTR :
F X
VI =: , ..",::'l, .. .L ::;;;; F ...
o
( Area)
.,[' ....
]
Alea == VI == 1200 drri
From the graph we can see thaI Xl :: 0.,60
For the PFR:
F"o(Xl - XI) ( d )
V7. :::: . --,"._, == F Ao Area un .er curve
''''''rA
J
Area under curve == V, == 600 dm
From the graph We can see that X
z
::;;;; 0. .. 80
A ----
poiu:::t
4000
Fio
3000
orA
2000
1000
2-32
CDP2-F (a)
Find the conversion for the CSTR and PFR connected in series
X ,rA lI(-rA)
0 0.2 5
0.1 0.0167 59.9
0.4 0.00488 204.9
0.7 0.00286 349.65
0.9 0.00204 490.19
400 L CSTR and 100 L PFR
Feed is 41 % A, 41 % B, and 18% L
P ;:: 10 attn T :::;:; 227
0
C = 500 K
P 10 atm
C = .. - ;;;:;.--.. ''., ... ----.-...... ,-----... --",.,.".,--- = 0_244 mollL.
' To RT (0.082 I.. . atmfmol " K)( 500 K)
CA. ;;:: OAlC,o;:: 0.41(0.244 maUL)::::: 0.1 mol/I..
F
Ao
:;;; t)OC
AO
::::: 1 Us(O.l moUL)::::: 0.1 molls::: 6 mol/min
There are tv.'o possible arrangements of the system:
1. CSTR followed by the PFR
2. PFR followed by the CSTR
Case 1: CSTR -.,. PFR
CSTR: VI = F .... )Area)
V 400
Area =: """,l". = ' .... , , :;;:;: 66.67
FA., 6
From the graph XI = 0.36
PFR : V 1 :;;:;: FA., (Area under curve)
V, 100
Area under curve:;: ,-- ;;: -""".,.,:;:; 16.667
F: ... ., 6
From the graph .. = 0.445
....... '.' .. ...... .. ........- .. ..
Case 1: CSTR > PFR

400
300

;;::; 200
100
o
0,0 0.2 0.4 0.6 Q,.8 1.0
X
.. "" ... """" -"""'''''-''''''''''''-''''''''-''
2-33
Case 2; PFR --> CSTR

400
,.: :3 00 ,+ . , ... " ... ", ...
.
::::; lQO +." .. "-",,.,
100
o
0.0 0.2 0.4 0.6 0.8 1.0
x:
Case 2: PFR --+ CSTR
PFR: Area under curve:: 1667
From the graph - Xl ::;; 0.259
CSTR. : /\rea::: 66.67
From the grapb . X
2
::;; 0.515
CDP2-F (b)
Two 400 L CSTR's in series.
CSTRl: V;;:;: FAQ(A.rea)
mea;;:;; 66.67
From the graph - XI ::: 0.36
CSTR2 : Area = 66.67
From the graph . X
z
= 0.595
(b) Two CSTR's in Series
5 0 0 ~ r ~
400
~ 300
.
::: 200
100
o
0,0 0.2 0.4 0.6 0.8 LO
X
CDP2-F (C)
Two 400 L CSTR's in parallel.
To each CSTR goes half of the feed
F Ao :::;:; 6/2 ;:::: 3 moUmin
V::: FAo(Area)
V 400
Area ::: .. _,-- :: ------ = 13 3...3
FA" 3
From the graph: X = 0.52
2-34
(c) Two CSTR's in Parallel
500 1"'----------:Jr-.
400
~ 30G
.
::.; 200
100
o
0.0 0 .. 2 0.4 0.6 0 .. 8 1.0
X
CDP2-F (d)
PFR : V ::: F Ao (Area under curve)
From the graph we can find the area under the curve for a conversion of 0.60:
Area == (0 .. 60)(300) :.::: 90
2
V = (2 mol1min)(90) = 180 L
~ - - ~ . - ..-------................... -.-,-----.. . , . - - ~ ............---....... -.-.. ~ .. , .. " .......... .
(d) Single .PFR
500 T - - - - - - - - - - - . - - - . - - - . - - ~ . _ ,
400
.::: 300
.
- 200
1010
o
0.0 0.2 OA 0.6 0.8 1..0
X
CDP2-F (e)
Pressure reduced by a factor of 10.
A decrease in pressure would cause a decrease in the overall concentration which
would in turn cause a decrease in C Ao and F.-\,o" By looking at the design equation:
v::: !.",,,X
"'[A
it is apparent that to compensate for the decrease in F .Aa there would be and increase
in X.
CDP2-F (1)
Use the graph of 1/.,( ... VS. X to find values for all volumes. (Assume a flow rate of
1 mol/min.) Generate the following table and graphs:
X
-r"
V
...... "
0 0.2 0
--;:, ........ -
0.1
""'0.'01'67
-;--
3 .. 494
" ...,,-
0.4
0.0048S-- -"4i984
i----
=+ ... 0.00286
0 .. 7 125.878
0 .. 9 225 .. 088 0.00204
2-35
1"""'"""" .. """'-'----,.,-'"'-'-'-"'- ' - - - ~ - ~ ~ - - - ' - - -------,
t !
! (f) Conversion "'S. ''flolume !
~ i - _ , ~ _____
0&
0.,6
0 .. 4
0,2. I
o .,.,,_,_.,.,_ ... , __ ,-..-J
I 0 100 V 200 300
L-_, _____ , __ , , _ , ~ __ "' ____ ,J
CDP2-F (g) Individualized solution
2-36
(0-1."" 'IS. Volume
DO! - , - - . - - - ' - - - - - - - ~
0.015
.; 0,01
0005
o , .. ___ ,_ .. ,._ .. __ , ___ ..J
Q 100 V ZOO 300
Solutions for Chapter 3 - Rate Law and Stoichiometry
P3-1 Individualized solution.
P3-2 (a) Example 3-1
0 .. 008
0 .. 007 -t-------------
0 .. 006 -t-----------------------#----j
0 .. 005

0 .. 004 +------------------F
.iOi
0 .. 003
0 .. 002
0 .. 001 -t---------= .......
o
310
. T ..... " ..... ,.-++ .... _ ............... .,
315 320
T(K)
For E = 60kJ/moi
k = 1.32 X 10
16
expC-- )
E = 240 kj/mol
35E-22
3E-22 t---+------------i
25E-22
g 2E-22 t----\--------------I
:;; 1 5E'22 t------\-----
1E-22 t-------'b-------
5E-23
325
o 00295 0003 0 00305 0 0031 000315 00032 000325
1fT (11K)
330 335
For E1 = 240kJ/moi
kl = 1.32 X 10
16
exp( -
E=60 kj/mol
6000000 . . ............................... -_ .
5000000
4000000
"'
2. 3000000 t--------"..:::-:--------j
-'"
2000000 t------
1000000
o
000295 0003 0.00305 00031 000315 0.0032 000325
1fT (11K)
P3-2 (b) Example 3-2 Yes, water is alJeady considered inert.
3-1
P3-2 (c) Example 3-3
The solution to the example at a conversion of 20% would remain unchanged. For 90 % conversions of the
caustic soda, the final concentration of glyceryl sterate is 0 instead of a negative concentration. Therefore
90 % of caustic soda is possible.
bed
P3-2 (d) Example 3-4 A + - B ~ -c + - D
a a a
113
So, the minimum value of @B = b/a = -- = 0.33
1
P3-2 (e) Example 3-5
For the concentration of N2 to be constant, the volume of reactor must be constant. V = Vo.
Plot:
180
160
140
120
f"100
::!:-
... 80
60
40
20
1 0.5(1-0.14x)2
-r
A
(I-X)(0.54--0.5X)
1/(-ra) vs X
02 04 06
X
08 12
The rate of reaction decreases drastically with increase in conversion at higher conversions.
P3-2 (0 Example 3-6
For a given conversion, concentration of B is lower in flow reactor than a constant volume batch reactor.
Therefore the reverse reaction decreases ..
C
ro
= constant and inerts are varied.
N
2
0
4
*"72N0
2
A ~ 2B
C 2
Equilibrium rate constant is given by: K c = ~
CA,e
Stoichiometry: = Y A06 = Y AO (2 -1) = Y AO
Constant volume Batch:
3-2
C
- 2N
AO
X -2C X
B - - AO
Vo
Plug flow reactor:
C = X) = C Ao(l- X) and C
B
= 2FAO X = 2CAO X
A v
o
(1 + eX) (l + EX) v
o
(l + eX) (1 + eX)
CAO = Y;o;0 = YAo(O.07176)mol! dm
3
o
Combining: For constant volume batch:
C 2 4C
2
X2
K
Ao .
c- -
CAe C AO (1 - X)
4C
AO
For flow reactor:
C 2 4C
2
X2
K Ao
K C (1 - X e )(1 + eX e)
C CAe C AO (1 - X)(1 + eX)
See Polymath program P32-LpoL
POLYMA TH Results
NLES Report (safenewt)
Nonlinear equations
[1] f(Xeb) = Xeb - (kc*(1-Xeb)/(4*CaoI\() .. 5 = 0
[2] f(Xef) = Xef - (kc*(1-Xef)*(1 +eps*Xef)/(4*CaoA0 .. 5 = 0
Explicit equations
[l) yao = 1
[2] kc = 0.1
[3] Cao = 0 .. 07174*yao
[4] eps = yao
1 ........................
4C
AO
0 .. 9
<: 0 .. 8 ......,-.mIIIJIIl''----------i
0.7
Qi
0 .. 6 ____
o
E 0 .. 5
:::J
04
'3 0 .. 3 1------------------------------
Jr
0 .. 2 +----------------------------1
0 .. 1 -1----------------------------1
o ...... 1 .. ........ ".. ," ... 1 .... ........ , ... .. T .... ................... ..T" ........ '1.'''... .. ... " .. ' ..... "1' ........... " ....... , ........".' ..' " .. .. .. ' .. .. ".... .. T
o 0 .. 1 0 .. 2 0.3 04 0 .. 5 0 .. 6 0 .. 7 0 .. 8 0.,9
y inerts
3-3
-Batchl
-FIOW.J
Y
inert
Yao
0
0.1
0.2
0.3
0.4
0.5
-
0.6
0.7
0.8
0.9
0.95
0.956
P3-2 (g) No solution will be given
P3-2 (h)
1 1
A+-B-7-C
2 2
Xeb
1 0.44
0.9 0.458
0.8 0.4777
0.7 0.5
0.6 0.525
0.5 0.556
0.4 0.5944
0.3 0.6435
0.2 0.71
0.1 0.8112
0.05 0.887
0.044 0.893
Rate law: - r
A
= kAC
A
2C
S
1 dm
3
and kA = 25- --
s mol
(
J
2
~ = ~ = rc
-1 -112 112
1 (dm
3
J2
kc =k
B
=12.5- -
s mol
P3-2 (i)
A+3B -7 2C
Rate law: - r
A
= k A C A C B at low temperatures.
At equilibrium,
C
Ce
K = .. ---- '
C C I12C 3/2
A,e B,e
Xef
0.508
0.5217
0.537
0.5547
0.576
0.601
0.633
0.6743
0.732
0.8212
0.89
0.896
At "Iuil;b,;um, -, A = 0 , so we can sugge" th,t - r A = k A ( C A 1/2 C B 112 - ~ J
But at t = 0, C
c
= 0
So the rate law is not valid at t = 0 ..
3-4
Next guess:
P3-3 Solution is in the decoding algorithm available separately from the author.
P3-4 (a)
Note: This problem can have many solutions as data fitting can be done in many ways.
Using Arrhenius Equation
For Fire flies:
T(in 11T
--- r;:::-_.
Flashes/ In(flash
K) min es/min)
294 0 .. 00340 9
1
298 0.00335 12.16
6
303 0.00330 16.2
0
-
Plotting In(flashes/min) vs lIT,
we get a straight line ..
2.197
2.498
2 .. 785
See Polymath program P3-4-firetlics.pol.
For Crickets:
T(in K) 11T chrips/ In(chirPsi
x10
3
min min)
3.482 80 4 .. 382
293 .. 3 3.409 126 4.836
300 3.333 200 5.298
Plotting In(chups/min) Vs lIT,
we get a straight line ..
-+ Both, Fireflies and Crickets data
follow the Arrhenius Model.
--
In y = A + BIT , and have the same activation energy.
See Polymath program P3-4-crickcts.pol.
3-5
2.66
2.52
2.38
2.24

3.30E-:3 .332E-3 3.34E
1
h 3.36E-3 3.38E-3 3.40E-3
5.3
5.1
49

4..3
3.HE-3 1.36E-3 3.39Eih 1.42E-3 3.45E-3 3.48E-.3
P3-4 (b)
F H b or oney! ee:
T(in K) 1rr
x10
3
298 3.356
303 3.,300
rsoa-
3,,247
V(cm/s) In(V)
0.7 -0.357
1.8 0 .. 588
3 1.098
Plotting In(V) Vs liT, almost straight lme.
In(V) = 44.,6 - 1.33E4/T
At T = 40C(313K) V = 6Acmls
At T = -5C(268K) V = 0,005cmls(But bee
would not be alive at this temperatme)
See Polymath program P3-4-bces.pol.
P3-4 (c)
For ants'
T(in K) 1rr x1Q" V(cm/s) In(V)
-,---
283 3,53 0,,5 -0,,69
293 3,41 2 0 .. 69
303-
3,,30 3,4 1,22
---,,-,------'-
311 3,,21 6,,5 1.,87
~ '------ '------"
Plotting In(V) Vs liT,
almost straight line,
--
See Polymath program P3-4-ants.pol.
So activity of bees, ants, crickets and fireflies follow
Arrhenius modeL So activity increases with an
20 ,----------------,
1.4
o .. s
0.2
-0.4
-1.0 L-__ __ __ __ __ __'
3.25E-3 ,'.2'7E-3 3.29E
1
lr HIE-, 3.3.3E-3 3.36E-3
20 r---------------,
1.4
o.S
0.2
1 0 L ~
3.22E-J .uSE-J J,J,tE1tr 3.41E-J 3.47E-33.53E-3
increase in temperatme, Activation energies fOl fireflies and crickets are almost the same,
---:-c- --
Insect Activation Energy
Cricket 52150
Firefly 54800
---
Ant 95570
Honeybee 141800
P3-4 (d)
There is a limit to temperature for which data for anyone of he insect can be extrapolate, Data which would
be helpful is the maximum and the minimum temperatme that these insects can endme before death.,
Therefore, even if extrapolation gives us a value that looks reasonable, at certain temperatme it could be
useless.,
P3-5
There are two competing effects that bring about the maximum in the corrosion rate: Temperatme and
HCN-H
2
S04 concentration. The corrosion rate increases with increasing temperatme and increasing
concentration of HCN-H
2
S04 complex, The temperatme increases as we go from top to bottom of the
column and consequently the rate of conosion should increase" However, the HCN concentr'ations (and the
3-6
HCN-H2S04 complex) decrease as we go from top to bottom of the column. There is virtually no HCN in
the bottom of the column, These two opposing factors results in the maximum of the cOIrosion rate
somewhere around the middle of the column.,
P3-6 Antidote did not dissolve from glass at low temperatures.
P3-7 (a)
If a reaction rate doubles for an increase in lOoC, at T = T 1 let k = kl and at T = T 2 = T 1+ 10, let k = k2 =
2k
l
Then with k = Ae-
EIRT
in general, kl = Ae-
E1R1i
and k2 = Ae-E'RT2 , or
k2 _ - ~ * - * ) E
--e or
kl R
Therefore:
In (k2 J (T. (T. + 10))
kIll (In 2)(7; (7; +10))
E = R-- = R---,- "
(7;-7;) 10
T. (T. + 10) = lOE
1 1 RIn2
!OED
5
which can be approximated by T = ----
RIn2
P3-7 (b)
E
Equation 3-18 is k = Ae RT
E( 1 I)
Dividing gives ~ 2 , = e -Ii Tz""-"1;" , or
1
3-7
[
1.99 cal ] [ 273 K][ 373 K]
E = mol K In(050) = 7960 cal
lOOK .001 mol
E
A = k e
RT
, = 10-
3
min -I exp
. 1
(
1.99_
Cal
](273K)
molK
P3-7 (c) Individualized solution
P3-8
= 2lO0min-
1
When the components inside air bag are ignited, following reactions take place,
2NaN
3
--7 2Na + 3N
2
... .. .,' , ............. ' .. ' ,,(1)
lONa + 2KN0
3
--> K20 + 5Na20 + N
2
, , ,(2)
K
2
0 + Na20 + Si0
2
--7 alkaline silicate glass" ",.,.,(3)
5x rxn(l) + rxn(2) + rxn(3) = rxn(4)
NaN
3
+ 0.2KN0
3
+ 01Si0
2
-7 04Na20 + 1.6N
2
+ complex/l0., ... , ,(4)
Stoichiometric table:
r--'--- ,--_.
-
Species Symbol Initial Change Final
---
NaN
3
_ A NA -NAX NA(1-X)
KN0
3
B
N ~ B
-O.2XN
A
NA( BB - 02X)
--
Si0
2
C
NABe
OIXN
A
N
A
( Be - 01X)
Na20 D 0 O.4XN
A
O.4XN
A
N2 E 0 1.6XN
A
1.6XN
A
Given weight of NaN
3
= 150g
Therefore, no., of moles of NaN
3
= 2 .. 3
M
wt
of NaN
3
= 65
1 moles of NaN
3
requires 02 mole of KN0
3
=> Moles ofB, KN0
3
= 02(2..3) = 0.46 moles M
wt
ofKN0
3
= lOLl
Therefore, grams ofKN0
3
required = 046 x lOLl = 46..5 g
1 moles ofNaN
3
requires 01 mole of Si0
2
,
Moles of C, Si0
2
= 0.1(2.3) = 023 moles M
wt
of Si0
2
= 60,08
Therefore, grams of Si02 required = 0,23 x 60,,08 = 13,8 g
Following proposals are given to handle all the un-detonated air bags in cars piling up in the junkyards:
Store cars in cool, dry, ventilated areas"
Avoid Physical damage of the bag in cal.
It is stable under ordinary conditions of storage" Decomposes explosively upon heating (over
221 0 For 105
0
C), shock, concussion, or friction,
3-8
Conditions to avoid: heat, flames, ignition sources and incompatibles.
P3-9 (a)
dX
From the web module we know that --= k (1 - .x) and that k is a function of temperature, but not a
dt
linear function. Therefore doubling the temperature will not necessarily double the reaction rate, and
therefore halve the cooking time ..
P3-9 (b)
When you boil the potato in water, the heat transfer coefficient is much larger, but the temperature can only
be 100C.
When you bake the potato, the heat transfer coefficient is smaller, but the temperature can be more than
double that of boiling water.
P3-9 (C) No solution will be given
P3-10 (a)
1) C
2
H
6
~ C
2
H
4
+ H2 Rate law: -fA = kC
C2H6
2) C2H
4
+ 1120
2
-+ C
2
H
4
0 Rate law: -fA = kC
C2H4
C ~ :
3) (CH3)3COOCCCH3)3 ~ C
2
H
6
+ 2CH
3
COCH
3
A ~ B + 2C
Rate law: -fA = k[C
A
- C
B
C
c
2
IKcJ
4) n-C4HIO +-+ 1- C
4
H
lO
Rate law: orA = k[ C C H --C IKe]
n 4 10 iC4 H
lO
5) CH
3
COOC
2
H
s
+ C
4
H
9
0H +-+ CH
3
COOC
4
H
9
+ C
2
H
s
OH
A + B +-+ C + D
P3-10 (b)
2A + B-- C
(1)
(2)
(3)
(4)
P3-10 (C)
orA = kC
A
C
B
2
orA = kC
B
orA = k
orA = kCAC
B
-
1
(1) C
2
H
6
~ C
2
H
4
+ H2
Rate law: -fA = k[CAC
B
- CcCnlKcJ
3-9
(2) H2 + Br2 ----> 2HBr
(3) H2 + 12 ----> 2HI
P3-11 (a)
Liquid phase reaction,
o
/"-
CH
2
--OH
I
CH2 - CH
2
+

CHT-OH
A C
C
AO
= 1 Ibmol/ft
3
C
BO
= 3.47 lbmol/fe
Stoichiometric Table
Species
Ethylene
oxide
Water
f--
Glycol
'----
Rate law:
Therefore,
At 300K
Symbol Initial
A C
Ao
=1Ibmol/ft
3
--
C
BO
= 347lbmol/ft1,
----
B
BB=347
C 0
---- ----_ .. _-----
-rA = kCAC
B
-rA = k (1-X)( BB -X) = k(l-X)(347-X)
E = 12500 cal/mol, X = 0 . .9,
Change Remaining
-CAOX C
A
= CAO(l-X)
= (lX) Ibmol/ft
3
-CAOX
C
B
= C
AO
( BB -X)
=(3.47-X) lbmol/fe
CAOX Cc = CAOX
= X Ibmol/ft3
3 0.1 3 3
k = O . .ldm ImoLs =--x35.315ft Ilbmol.s = 0.0035ft Ilbmol.s
1000
CAOX (1)(0.9) -1
'rCSTR = --- = --2--------- = 1000 . .56 s
-r
A
(0.0035)(1) (1- 0.9)(3.47 - 0.9)
At 350K,
k2 = k expE/R)(lIT-lIT 2= O.0035exp125001l.987)(11T-IIT2= 0.071 dm
3
/moLs
Therefore,
CAOX (1)(0.9) _-1
'rCSTR = --= 2 - 49.3s
-rA (0.071)(1) (1- 0.9)(3.47 - 0.9)
P3-11 (b)
Isothermal, isobaric gas-phase pyrolysis,
C
Z
H
6
C
2
H
4
+ H2
A B + C
Stoichiometric table:
3-10
.... -
e =Yaob= 1(1+1-1)= 1
v = v
o
(1+ eX)
P
C
2
H
4
B
H2 C
=> v = vo(l+X)
CAO = YAO CTQ = YAO -
RT
0 +FAOX FB=FAoX
0 +FAoX Fc=FAOX
FTO=FAO

(I)(6atm)
= = 0..067 kmol/m
3
= 0..067 mol/dm
3
(
0.082 m3atm J(1100K)
K.kmol
C
A
= FA = FAO(l- X) = C (1- X) mol/dm3
v v 0 (l + X) AO (1 + X)
FB FAO(X) X 3
C
B
= -=- =C
AO
--- mol/dm
v vo(l+X) (I+X)
Fe FAO(X) X 3
C
c
= - = = CAO .--- mol/dm
v vo(l+X) (I+X)
Rate law:
(I-X) (I-X)
=kC
AO
--- =o..o.67k---
(I+X) (I+X)
-fA = kC
A
If the reaction is carried out in a constant volume batch reactor, =>( e = 0.)
C
A
= C
AO
(1-X) mol/dm
3
C
B
= CAO X mol/dm
3
C
c
= CAOX mol/dm
3
P3-11 (C)
Isothermal, isobaric, catalytic gas phase oxidation,
1
C
2
H
4
+ - O2
2
1
A + -B C
2
Stoichiometric table:
Species

O
2
C
2
H
4
O
Symbol
A
B
C
---.-::::------,--"------
Entering Change Leaving
F
AO -FAOX FA=FAO(l-X)
F
Bo
-BBFAOX FB=F
AO
( BB -X)
0. +FAOX Fc=FAoX
3-11
_ _ P _ 2 ( 6atm ) _ mol
CAO - YAOCro - YAO-- ( 3) -0.092-- 3
RT 3 0.082 atm.dm (533K) dm
mol.K
FA FAo(1-X) C
AO
(1-X) 0.092(1-X)
C - - - - -
A - V - Vo (1 + eX) - (1-0.33X) - (1-0.33X)
FB 0.046(1-X)
C - - - - --'-----'-
B- V - vo(1+eX) - (1-0.33X)
Fe FAoX 0.092(X)
C = -- = = ---'---"-
e V vo(1+eX) (1-0.33X)
If the reaction follow elementary rate law
_ {0.092(1- X)}{0.046(1- X)}O.5
=> -r -k .
A (1-0.33X) (1-0.33X)
P3-11 (d)
Isothermal, isobaric, catalytic gas phase reaction in a PBR
C6H6 + 2H2 C6HlO
A + 2B C
Stoichiometric table:
Species Symbol Entering Change
Benzene A F
AO
-FAOX
H2 B F
BO
=2F
AO
-2FAOX
----
C6
HlO C 0 FAOX
1 2
e=y J=-(1-2-1)=-,-
, AO 3 3
--------
Leaving
FA=FAO(1-X)
FB=F AO( BB -2X)
Fc=FAOX
-,-
P (1) 6atm ( 1 ) 3
CAO = CroYAO = RT - = ( 3) - = 0.055mol / dm
3 0.082 atm.dm (443.2K) 3
mol.K
_ FA _ FAo(1-X) _ C
Ao
(1-X) _ 0.055(1-X)
C
A
--- - ------
V vo(1+eX)
3-12
C = FB = FAO (BB -2X) = O.l1(I-X)
B v V
o
(1+X)
C = Fe = FAoX __ = CAOX = 0.055X _
c V v
o
(1+X)
If the reaction follow elementary rate law.
Rate law:
-r
A
'= kCAC;
(1 X)3
-r
A
'= 0.0007k-----
3
(1- X)
For a fluidized CSTR:
W = FAoX.
-r '
A
W = FAoX _
(1- X)3
0.0007k--"-3
)
mol
k=53 - "-- at300K
kgcat min atm
3
k = k
j
exp(E(l.. __ !.J) = 1663000 mol
R T 8.314 300 443 kgcatminatm
3
FAO = CAO* Vo
Vo = 5 dm
3
/min
atX= 0.8
W = 0.0024 kg of catalyst
3-13
P3-12
1
A + -B -7 C
2
Stoichiometric table for the given problem will be as follows
A h ssummg gas pl ase
Species Symbol Entering Change
C
2
H
4
A F
AO
-FAOX
O
2
B F
Bo
= eBF
AO
-112 FAOX
-
N2 I FI = elF
AO
-----_.
C
2
H
4
O C 0 FAOX
1
2 F
AO
1
8
B
=---=-
e =_FIO F = 0.79 F
I FAD' 10 0.21 BD
F
AO
2
F
Y AO = -.:iQ.. = 0.30,
F
TO
C = YAO
P
= 0.041!!1
01
AO RT dm
3
(1-X) F
C =_AO =C
A V 'AO (1 + EX)
0.041(1- X)
1-- 0.15X

_ FB _ 2 2 0.020(1---- X)
C
B
---CAO ----------
V 1-----0.15X 1-0.15X
C
c
=J:c = 0.041X
V 1- 0.15X 1- 0.15X
P3-13 (a)
C = Nibroanaline

FAoCI-X)
F AOce
B
- x/2)
FAOel
FAOX
=? e = e 0.79 = 1.88
I B 0.21
Let A=ONCB
B=NH
3
D = Ammonium Chloride
A+2B C+D
3-14
P3-13 (b)
Species
--
A
B
c--:::-------
C
D
---
P3-13 (C)
For batch system,
CA=NAN
P3-13 (d)
-r
A
= kCAC
B
Entering Change Leaving
F
AO -FAOX FAO(1-X)
F
BO
= 0
B
F
AO
-2 FAOX FB=
=6.6/1.8 F
AO
F
AO
C0
B
-2X)
0 FAOX Fc=FAOX
0 FAOX Fo=FAOX
---
FA = = = (1- X) = C AO (1- X) , C A = !A = FA = C AO (1- X)
Vo Vo V Vo
N N N F
FB =-; =-v,B =- T:O(BB-2X)=CAO(BB-2X), C
B
=-1L=C
Ao
(BB- 2X )
o Vo Vo
-r
A
= (1- X)( BB -2X)
BB = = 6.6 = 3.67
CAO 1.8
C
= 1 8i'!!lol
AO . 3
m
FrA
P3-13 (e)
1) At X = 0 and T = 188C = 461 K
2 m
3
( kmOl)( kmOl)
-rAO = kCAoB
B
= kACAOCBO = 0.0017 . 1.8--
3
- 6.6-
3
-
kmolnun m m
E
krnol
-rAO = 0.0202 3 .
In nun
- -
2) At X = 0 and T = 25C = 298K
3-15
k ko ex
p
( !(:o + nJ
[
112735!i 1
m
3
l 1 1
k =0.0017 exp mo -+-
kmol.min 1.987 (461 298)
mol.k
= 2.12xlO-
6
m3
kmol.min
-lAO = kCAOC
BO
= 2.52 X W
5
kmoJ/m
3
min
3)
k !( t-nJ
m
3
k =O.0017---exp
kmolmin
(1 1 J
1.987 cal 461K 561K
molK
m
3
k=0.0152---
kmolmin
-rAO = kCAOC
BO
-r
A
(1.8 kmol)(6.6 kmol)
kmolrmn m
3
m
3
I
kmol
-rA = 0.1806-
3
-.-
m rmn
'---------
P3-13 (f)
lA = kC
AO
\1-X)(e
B
-2X)
At X = 0.90 and T = 188C = 461K
l)att=188C
--_. r
A
= (0.0017 (1- 0.9 )(3 .. 67 - 2(0.9))
kmol.rmn m
2)
= 0.00103 kmol
m
3
min
At X = 0.90 and T = 25C = 298K
3-16
- r
A
= (2.12XlO-
6
(1-0.9)(3.67 - 2(0.9))
kmol.rmn m
3)
= 1.28 X 10-
6
kmol
m
3
min
At X = 0..90 and T = 288C = 561K
- r
A
= (0.0152 m3. J(1.8 (1-- 0.9 )(3.67 - 2(0.9))
kmol.rmn m
= 0.00333 __
kmol
m
3
min
P3-13 (g)
Vo = 2m
3
/min = 0..002m
3
/min
kmol
1)Fof CSTR at 25C -fA = = 1.28 X 10-
6
3 .
mmm
- r
A
:
X
=09
.9.0.02m3 xO.l = 281.25m3
1.28xlO-
6
_ kmol_
m
3
min
kmol
2)At 288C, -rA = 0.00333- 3 .
m rmn
v = v oCAo (I-
- rA:X =O.9
V = 0.002!11
3
= 0.108m3
0.00333 kmol
m
3
min
P3-14
C
6
H120
6
+ a02 + bNH3 ---+ C(C44H7 3N0860L2) + dH
2
0 + eC02
To calculate the yields of biomass, you must first balance the reaction equation by finding the coefficients a,
b, c, d, and e.. This can be done with mass balances on each element involved in the reaction. Once all the
coefficients are found, you can then calculate the yield coefficients by simply assuming the reaction
proceeds to completion and calculating the ending mass of the cells.
P3-14 (a)
3-17
Apply mass balance
For C 6 = 44c + e
For N b = o..86c
ForO
ForH
Also for C, 6(2/3) = 4,4c which gives c = 0.909
Next we solve for e using the other carbon balance
6 = 44 (0.,,90.9) + e
e=2
We can solve for b using the nitrogen balance
b = o..86c = 0..86* (0.,90.9)
b = 0.78
Next we use the hydrogen balance to solve for d
12 + 3b = 7..3c + 2d
12 + 3(0..78) = 7.3(0.,,90.9) + 2d
d = 3.85
Finally we solve for a using the oxygen balance
6 + 2a = 1.2c + d + 2e
6 + 2a = L2(o..9o.9) + 3.85 + 2(2)
a = 1.47
P3-14 (b)
Assume 1 mole of glucose (180. g) reacts:
6 + 2a = L2c + d + 2e
12 + 3b = 7.,3c + 2d
Y
e/s
= mass of cells / mass of glucose = mass of cells /180. g
mass of cells = c*(molecular weight) == 0.,90.9 mol* (9L34g1mol)
mass of cells = 83,.12 g
Y
e1s
= 81.12 g /180. g
Y
els
= 0.46
Y
e/02
= mass of cells / mass of O
2
If we assume 1 mole of glucose reacted, then 1.47 moles of O
2
are needed and 83 .. 12 g of cells are
produced"
mass of O
2
= L47 mol * (32 glmol)
mass of O
2
= 47,0.4 g
Y
e/02
= 83.12 g /47,0.4 g
Y
e/o2
=1.77
3-18
P3-15 (a)
Isothermal gas phase reaction.
1 3
--N +-H ---7NH
2 2 2
23
Making Hz as the basis of calculation:
1 2
H2 +-N
z
-'?- NH3
3 3
1 2
A+-B-'?-C
3 3
Stoichiometric table'
Species Symbol
H2 A
N2 B
'-----1----
NH3 C
P3-15 (b)

e= YAo
6
=0.5X( -
Initial change
F
AO -FAoX
FBO=BBFAO
-F
Ao
Xl3
0 +2FAoXl3
_ (16.4atm) 3
C AO - 0.5 ( J = 0..2 mol/dm
0.082 (500K)
mol.K
C = C = CAO = 0.2(1- X) = O.lmol/ dm
3
H2 A (l+eX) (1- })
2 C
Ao
(l-X) 2 O.2(X) 3
C = C =--x =-x =O.lmol/ dm
NH3 C 3 (l+eX) 3 (1-{)
P3-15 (C)
k
NZ
= 40 dm
3
/mol.s
(1) For Flow system:
3-19
Leaving
FA=FAO(1-X)
FB=F AO( 0B -Xl3)
--
Fc=(2/3)F AOX
(1- X)
(I-X)
(1--})
P3-16 (a)
Liquid phase reaction -? assume constant volume
Rate Law (reversible reaction):
-r =k[C C ~ ]
A A B K
_ c
Stoichiometry:
C
A
=C
AO
(1-X), C
B
=C
AO
(1-X), C
c
=CAOX
To find the equilibrium conversion, set -rA = 0, combine stoichiometry and the rate law, and solve for Xe
CACBK
c
=C
c
C ~ o (1- Xe r Kc = CAOX
e
X: -(2+ 1 JX
e
+1=0
CAoKC
Xe =0.80
To find the equiliblium concentrations, substitute the equilibrium conversion into the stiochiometric
relations.,
3-20
mol mol
C
A
= CAO (I-X) = 2-
3
(1-0.80) =0.4-
3
dm dm
mol ) mol
C
B
=C
Ao
(I-X)=2-
3
(1-0.80 =0.4-
3
dm dm
C
A
= CAOX = 2 mo! *0.80 = 1.6 mo!.
dm dm
P3-16 (b)
Stoichiometry:
e= Y
Ao
t5=(1)(3-1)=2 and Be =0
NAN AO (I- X) (1- X)
C --- -C
A - V - V
o
(1+eX) - AO (1-t-2X)
C = Ne = __ .3NAOX = C 3X
e V Vo (1 +eX) 'AO (1+2X)
Combine and solve for x.,.
K C .Q..-- Xe) =[c 3Xe ]3
C AO (1+
2X
e) AO (1+
2X
e)
Kc (1- Xe)(1 + 2Xe)2 = 7 C ~ o X :
(
7 C ~ o J 3
- 4+--- X +3X +1=0
K e e
e
Xe = 0 . .58
Equilibrium concentrations:
Po lOatm mol
C =--=--------------=0.305---
AO RT (d 3 J d 3
o (400K) 0.082 m atm m
molK
_ (1-0 . .58) _ mol
CA - 0.305 ( ( )) - 0.0.59--
3
1+2 0.58 dm
3(0 . .58)(0.30.5) mol
C = =0246-
e (1+2{0.58)) . dm
3
P3-16 (C)
Same reaction, rate law, and initial concentration as part (b) gas phase, batch reaction.,
3-21
Stoichiometry:
C =N
A
=N
AO
(1-X)=C (I-X)
A V V AO
o
C =Nc =3N
AO
X =3C X
c V V AO
o
Combine and solve for Xe
KCC
AO
(1- Xe) = (3C
Ao
X
e
)3
Xe = 0.39
Equilibrium concentrations
mol
C
A
= (0.30.5)(1-0.39) = 0.19-
3
dm
mol
C
e
= (0.30.5)(0.39) = 0.36--
3
dm
P3-16 (d)
Gas phase reaction in a constant pressure, batch reactor
Rate law (reversible reaction):
-r =k[C ._ ~ ]
A A K
e
Stoichiometry:
= YAoO=(I)(3-1)=2 and Be =0
NAN AO (1- X) (1 - X )
C --- -C
A - V - V
o
(1+X) - AO (1+2X)
C = Nc =_l!'AO
X
--=3C X
c V V
o
(1+X) AO (1+2X)
Combine and solve for Xe:
KCCAO (1- Xe) = [3C
AO
X
e
]3
1+
2X
e 1+
2X
e
Xe = 0.58
Equilibrium concentrations:
3-22
0.305(1-0.58) mol
C = =0.059--
A 1+2(0.58) dm
3
3(0.305)(0.58) mol
C = =0.246-
c 1+2(0.58) dm
3
P3-17
Given: Gas phase reaction A + B -7 8C in a batch reactor fitted with a piston such that
V = O.IP
o
(ft3f
k=l.O---
lbmol
2
sec
-r
A
k C ~ C B
N
AO
= N
Bo
at t = 0
Vo = 0.15 ft
3
T = 140C = 600
0
R = Constant
P3-17 (a)
Y
= N
AO
=0.5
AO
N
AO
+N
BO
8=8-1-1=6
e = YAo8=3
Now
T
and .-.- = 1, Po = lOV
o
' and P = lOV
1'0
Therefore
Therefore
v = lOVo2 (1 + eX)
lOV
or
N = ( Y AOPo ) v:
AO RT 0
3-23
[
1 X]3
-r
A
= 5.03*10-
9
- 3 Ib
3
mol
(1+3X)2 ft sec
P3-17 (b)
V2 =Vo2(1+eX)
0.22 = 0.15
2
(1 + eX)
X = 0.259
-rA = 8.63*10-
10
}b
3
mol
ft sec
P3-18 No solution will be given.
P3-19 No solution will be given.
P3-20 No solution will be given ..
--_ ... _---------
CDP3-A
3-24
w InW r
6.5
13
18
1871802
2.564949
2.890372
300
310
313
1fT'
0.003333
0.003226
0 .. 003195
.... ...... -.--.. .. ---- __ .. 1
3.5 ,..---..- .._ ... -._. ...... _ ...._- I
From the graph:
E= 7120
3
2 . .5
2
e
- 1.S
0.5
y '" -7120.4x + 2:5.593
Fr.O.S8$3
0+-,----.-- '--.--.."' ..__ . .,-.,-----1
o..(XX:I1S 0.0002 0..0032S
1trK
....... .." , .. "" ..... , "".,. ...... ................... -,--"- " ......... .... .......... , .... _ ............... , .... 7"" .............. -. __ ........ .
In W = --7120.4 *(_._ .. -! ..,,,.--) 1- 25.593 == 2.95
41.5+273
W(4L5<>C) = 1 9.2cm I s
I
---------------------------_.-_. __ ._--------
CDP3B
Polanyi equation: E = C - a(-.1HR)
We have to calculate E for the reaction
CH
3
0 + RBI' -7 CH3Br + Ro
Given: dH
R
= - 6 kcaUmol
From the given data table, we get
6.8 = C - a(17.5)
and 6,.0 = C -- a(20)
=> C = 12.4 KJ/mol and a = 0..32
Using these values, and .1HR = - 6 kcaUmol, we get E = 10.48 KJ/mol
CDP3-C (a)
A-7B
Rate law at low temperature: - r
A
= kC A
The rate law t higher temperature must:
1) Satis(y thermodynamics relationships at equilibrium, and
2) Reduce to irleversible rate law when the concentration of one or more of the reaction products is zero.
K
__ CBe
Also, We know, C -
Reauanging, we get
CAe
C - C
Be
=0
Ae K
c
3-25
So, lets assume rate law as
-r
A
=kA( C
A
- ~ J
Also when C
B
= 0, it satisfies the given rate law, Hence the proposed rate law is conect.
CDP3-C (b)
A+2B72D
Rate law at low temperature:
Here,
1/2
-r
A
=kC
A
C
B
But it does not satisfy the irreversible late law at low temperatures"
Hence it is not COlrect
So, taking square root of Kc
fj{ CDe
-V 1\' C = - 112'
CAe C
Be
C 112 C _ C De = 0
Ae Be ~ K c
k
(c
1I2C C
De
J
- r
A
= A Ae Be - ~ K C
Which satisfies the irreversible rate law,
Hence it is the required rate law.,
CDP3-C (C)
A+B-7C+D
. ,kPAP
B
IrreversIble rate law: -, r
A
= . ..::::---
1 + KAP
A
+ KBP
B
PCP
D
PCP
D
We know, K p = or PBP
A
- = 0
PBP
A
Kp
Hence assume rate law as:
k PP -'--.
A B K
p
(
PCPDJ
- r
A
= . ."-----
1 + KAP
A
+ KBP
B
+ KcP
c
+ KDP
D
Which satisfies both the above mentioned conditions,
3-26
CDP3-D
a)
b)
c)
lJ
y - 0.15
NlI
J

O
ideal gas law
C
eo
- ... .. - 8.2 Itra ' .. 0.2 ,mol/l
Va H:ro 0.082 latln
1
OKCSOOK)
. ,:no
C
NH
.. (0.15)(0.2 ,mol/1) .. 0.03 gmol/1
3 ,.0 ........ 3.0 '"""I ..
Compound.
S:r=bol Il1it.i .. l Chan,,,
Find
...
J.
0.15
-O.lS:.t
0.15(1-X)
;)
l
B
0.18
5
- 4<0.151:) 0 .. :18- f<0.15X)
!!O
c 0
+(l.15X
0.151:
H
2
O
3
3
D

+ t'0.151:)
... t' 0 .. lSI:)
N
1
I 0.67
0
0 .. 67
Totill
l' 1.00
+ 1/4(0 .. 15,I,)
1 + I/4( O .. lSl'.)
In.itiol N2 ... 0.19(1-0.15) "'" 0.1.9(0.8S). 0.67
Initial 02 =

Pi ... YiP ... ttr P - 8.2 ;J.t::l (1+(0.151411; )
3-27
1
i ..
P. Catm)
l.
C.
l.
'-------, '''''-'''''''--
A
0.15(1-1.)
1.23 1+{O.15/4]X
0.03 1+(0.15/411
I-I
(0 036 - X) /(1 + .Q...ll I)
4 4
5
0.18 - 4' (O.lSI.)
c O.I5X
1.
::t CO.HI)
0.67
v ... V (l..,O+B I)
o , ....
C
i
d 0 .. 1 1\1
1}
Pi .... CiI::I ... <O.OllHjOO)(O.2)l1
i
Ill! 8.2
OJ131 1+ X
1 'Ill 1 C
i
Pi
II
I
o .:l.,${ 1;-1:)
S .,
0.1.1 - -:; (O .. Ul:)
0.15 X
(0.151:)
0.67
0 .. 03 Ct.-X)
Q n "".I 6 _ o. '15, :x
....... "
0.03 :x
0 .. 1.33
'0 .. 1.99 + 0.0011
1 .. 23 (I-X)
5
1 .. 1(0 .. 11 .... :r {Q .. UX)
1.%3 X
1""," X
... 0 .. 2 (l ... 0 1.5 .x)
3-28
P'tO't'" 1.2 - 0 ... 313 I .. taI.
3) Suu; u (l)
d) 4A+5B-1'4C+6D
Mole balance for a PFR
elF
A
dV
dF
... b
" ... = -r,
dV
dF
...... ,c = -rc
dV
dF
v
dV
Combine with equation 3,,40 and 3-48
3-29
CDP3-E
a.)
b)
A -+ 2B --)
Species
Ben:royl chloride
A.:rom.ooia

Ammonium C1l1oride
CAO
4!'!-
N IV
AO
A
- ... n _)
2. D
D
+""'"
2 :2
C -+- D
Symbol Initi..a1 moles (llange Final moles Conceruration
A NAG --NAoX NAo(l-X) N Ai)( 1-X).fV
B NAoSs -2.'""lAQX NAoC&g-1XW
C N
A
o6
c NAoX
N
A
o(8
c
+X) N Ab(6c.--+X)!V
D N
A
o6
D NAoX
NAQ(8
D
-+-X) N
A
o(6
D
+XW
"'"
2 gma-i/l
3-30
Species
Symbol Entering Olange
Exit Conceruration
Ammooia
B
Fao
-FsoX Fao{1-X) F:ao(l-X)/v
o
Benzo
chloride
A SAFBO
F}3O(S KXI2) F:ao(9
a
.JlY' z,}/v 0
Benzylamide
... C 9
c
FBO
FMXI2 FBO(ec+XI2)

Ammorrlum Chloride
0 eoFBO
Fsr:XJ2 fBO<9
n
+X/2)

1) :Moh.r floy :l:1.tcs considered rll.ther tha.n numb..,r of moles.
2) e. "" F. IF.", , as opposed to N. INA
1 10.;:>0 10 .0
3) Concentration found by dividing the molar floy rate by the
flo. rate 'IT
"
CDP3-F
Given. : A + B -) C taking placo. in .. sqU&xo: duct ..
T
F AO .. loS Ib molel sec.
If B is at equilibrium in the gAS phase throughout the reActor
Since 13 m&int&ins its oquilibriUll'l v&por prouure
throughout the re&ctor. &$ soon as 1 moloculo of B is consumed by the re&ctioll.J
it is replaced by & lIIalccuh of B in tha liquid. Ronco, 0 ... 1 - 1 0, '" TAOQ
3-31
..
.. ..
(1:1) .At 1: ,.. 0.5
CDP3-G
a)
[
-( .25 a'tm) ( .75 3.'t1ll) .......... -1 1 'b.mo 1 e
- {O.S]" .114'; 3
(
.730 .em 2
. % lOOOOR)
11:1 lnole OR
3 5i HC13 .+ 3Hz 15i (S) + 7HCl + 5i H2 Ch
Take Si HC13 as basis
Symtx:!l
Emering ClJani.'C
L&mdDr;
Si HO] (g) A
FAC -FACiX
FA = FAO (I-X)
Hz Cg) B
f=Bo =&s FAo
n =FAo(ea .. X}
H2HCl (g) C
0
+2FAoX Fe :::2FAOX
+}FAoX
3
Si lhC1z (g) D 0 Po =lF
A
oX
3
Si (s) S 0
2.F
A
oX
3
3-32
Assume isothermal and constant pressure. Neglect the vapor pressure of Si(S}
as = 1 Stoichiometric feed
o only involves the changes in gas phase
E = Y AO 0 =:; .1 (1. -+- L - 1 - 1)
233
e=}tt)=t
CAO - Y 0 Po . - 1 ( 2,Q )
. - A R Tn - 2 (O_OR2HI127\
"" "" _. I \ . IJ
c" = := CAO {l- ifL = 0.0088 (1- X)
\) (1 + EX) 1'1- X/3
C
a
:= g. :::: C
A
{Ss-=-X} :::: (1X)
1,) (1 + EX) 1 + X/3
Cc = Fc. == 7 .,.' F AoX _. = 2 CAO __ ,_,X ____ ::: 0 021 X
tl 3 \)0 (1 +. EX) 3 (1 '1- X) (1 + XJ3)
CD == F
D
.::::} ... -=0.OO31 .... -
v 3v
o
(1+c:X)
1he SOlUllon to parts (b) and (c)
and
e)
a...""e similar to Part (a).
CDP3-H
3-33
$0 vc can use the tAble. C's for F's
i
F, C.
,
...
...
.
A
FAO(l-X) CAO{l-X)
B
4F AO(l--X)
4C
AO
{l"-X)
C
4F AO .l.
4C
AO
:!
D
_ F 0
0
:x
eAQ
X
5 F
AC
5 CAO
CAO = 0.0658 aDd FAD - 0.02631 Bruol/s
titer
F
t
V"'v -""'V
o F Q
t.o
at X - 0.5 (beginning of
condensation) C.; c
A 5F
Air
F
A
(}X
B FAO(5-X)
C 4F
AO
X
..... __ "_--1? .. ___ ........ _ ......... _ .. 9:.1F AO( 9.
Total FAO(5-X)+FAO(5-X)/9
3-34
1. i
CAo(l-X)( 4.5)/(5-X)
4C
A0
(1-X)(4.5)/(5-X)
4C,,,oX,( 4.5)J(S ..-X)
C
Ao
(5-X)( 4_5)/(5-X)/9=O.5C
A
{)
._-...,._. .- .... __ .. _-_ .. " ....
C
A
o(5Xt/40.5
P
v
95
.--::w--
u
P 9S0
0.10
Scoich Tl.ble
DoCore Co ndel1s;1I.l:.i on
Spocies Sy:ubol In C1:l&ngo Pp <
P
y
r4111&ining
........, .. _ ....__ ........-._,----_ ....-.
CB:
4
A F
Ae
,,F X
,Ac
FA - FActI-X)
C1
2
13. 4F
AO
-4F
A
cf. Fa
... 4F
AO
(1-X)
liC1
4
C .0
+4FAOl: Fe
-
4F
A
OA
eel.",
D(g) 0
+FAOI Fn
.. FAOX
DO) 0
Fro
SF
AO
Fr ... 5
FAa
.
When conde atioD first begins Fr = 'r
0.50
1) - .0
--} e ,.. 0
AI' "'" AP "" .0 "" .. ,.) Total concentration is consta,llt
p
o
",-""
RL'
o
C.0820S atm lit X 348 K
gmol K
3-35
After COl1dens&tiol1
Pp - Py rem&il1il11
FAOU-IJ
4F
AO
(1-lJ
4FAQ1-
O.10F
T
---" .... "'.","',,"-_ .. ,----
. .
FT-SFAO-FAOX+O.10FT
, F
AO
(S'-X)
FT ... .0.90
CDP3-I
T + 473 K
tl
:;:: "v:: 506,S;:; 0203
10E P 2500
)toich
Species In Change Fi before F'i After condensation PD :::::
condensation PD P
v
remaining
< Pv remaining
'" ....., ..... __ ... .._ ....-.-' ...... _ ....... " ....... " -...... . _.... w'" .......__ , ....... ... -, .. _.,.". ........,_ ....... ,4. ___ ._ ..... _ .. _.oK"
C2H6
BI2,
HBr
C2F14
B1
l
A
B
C
D(g)
FAll
2F
AO
o
o
o
Bafar. coadeas&tioa
,,,FA(;X
-2F
A
oX
2F
A
oX
FAOX
---) e '" 0
FA ::.:.:: F AO( 1 "X) F AO( IX)
Fu ;:::: 2F AO( I-X) 2F AO( IX
Fc == 2F A()..'X 2F AoX
FD = FAaX O.203F'r
3-36
P
-
'Clt _._0
a-I
40
24. 7 ... '/. .. ttti .
= - - 0.673 gcol/l
o .. 0820S &t= lit l: 413 I
1=01 I:.
1 0.673
C
AO
3' <=-rIO :d 3 ,mol/l,. 0,.212 ,moll1
t 'A
'.
Fe
'0 'r
C
4
prAll. pAll.
&IN".
... 11. IM1I.
a-lJ 1
t
.
l'
11 J.&ll ';41 lPA.O <::.40u-%)
0.H16 .0.:1% 0 0 0.11.1 0.111
G.1 a,au Of .Ur.)
0.041 Q.OU Il.ua <LUG
0,4 13.1>44 0.111
0.o"
0.041 0.311 0.U1
0.041 O.Ul (I.U' Q.Q'" o.JU 0.01l
t , .AQ(1.-11
IF>\I.'l'thIl
l'>\I.'l'l
o-n
.u:n
CAl)
IFClIl;l'l
F.w-r:Ti
'J.J::IJ.1;1 O-t) \I
l).fO!!)
a.IML a.ou O.t.1f 0 .,(.5
O.ltl O.OU
t.'
0.011 0.641 0.110 a.aH <f.Ul 0,037
toO 1)
0 Q.lll O.OH Q.l"
\)
3-37
lCjD(l-Xl

Q.llt
Q.134
0.1"
"'PC 1"';-1211: \ l' J
.10 A,Q ll ... X) "
d.l"
0.:110
O.lll
1e ,t"
Ml U-l)
0.1,:$ ,
O.Hl
i).1J'
e (Q .. iq71
J..Q
F AO =< C AO
v
Q
= (0.212) gmal/1 (0.5) lIs n 0.106 gmal/s
F.
F.
F.
C
1-
1.
:l
:0=
-
:::t
...
-
l. V
'If (l+f:l.)
v
0
0
So we first use SUbstituting C's for F's
i F. C
._. __ ... , . ..l.... __ _._:..L __
A F (l.-:n
AO
C
AO
el-I.)
B
2F AO (1-,X)
2C
AO
(1-I.}
c 2F
AO
.! :lC
AO
X
D
___ :.10 1_
ehQ
X
....-
--
.--
Total 3 F
AO
.3
CAO
3-38
C (9710111)
v ..
C
1
i
F '
'C
v -::Ill
o F
to
F.
""
--1.
"Y
2.
F.
1. (2.392...
v C3-IJ
o
OQ 0.1 Q.l as 1),4 os 04 01 04 09 I.Q
,.,. C(A)
.... e(8)
.. C(Cl
0. C(O)
"L
OJ j --.--... ~ ____ ...
". V
o
F ((1no1lS) OJ.
+ FCA}
<>- F(6)
,.. F(C)
<lo F{D)
0.1
O . O ~ ~ : : ____ = : : : : ~ ~
Qj Q.4 V 04 U 1.0
X
CDP3-J
3-39
""'Fm
,13-X)
2.39
Fso
as =,,--=1
F
AO
YAo :::;; 0 .. 5
E == Y ADO = 0.5(1+ 12,.-3--4)= 3
_ - X) _ 6.18*IO-&(1-X)
C
A
-- l+&Y-
C = 1.68 )
8 1+3X
C = X
c 1 +- 3X
. 2.47 * 10-
7
X
C = -.-
D 1+3X
CAO = Y .... O(::1'O = o_i'It)= o.'){. ... ".J= 6.18"" lO-lt
--l 8:314_ * 97.3K
mol*k
_. _ C.-IO (1-, x) _ 6.18" 1 {)8 (1 ' x)
C. A. - -"--"'-"'" ................ -. - ._ ....................... _ ...... _ ...... " ........ -'-'
l+EiX 1+3X
1.68 * 10-$( 1 ...... .. J
('1J = --_ .. _.-........................ .. .....:" .......................... -
1+3X
2.06'" lO-a x-
C c = ............... - ..................... __ .... -
1+ 3X
. 2.47*107X-
c.. = ...................................... _.- ................ .
'0 1+3X
340
CDP3-K
CA)
C QUllZ Q :t\l;;:a. t

bilid
el2
A
1.0
CH4
B
0 .5
CIUel2
c
0
Rel
D
0
l'ot31
T
1.5
(b) 0 "" 1 -I- 2 - 1 - 2 '" 0 Y AO ... 1.0
C '" YAO I) '" 0
Chu,U
-:1
-0.5:1
+{) .5.1
+.1
(c) s,.S1:O': is lao,s ph"'$c Ulltil F -400 m::dl,
c
Q 7(0) .. <400

1-1
O.S(l-X)
0.51.
X
1.S
..... X" =- 1.5189 -} C1I
1
el
z
docs U,Q t !. t 1 a 'bI ..
-r :lI! k C 1
A A
:m CAO (l-l.AJ
.. l.. C (l-ll)
;:I. :2 AO
3-41
(d)
(f)
c. 3E....!...."" .1.
AO 1.5
,mol
= 0.02724 (1-O.6) 0.01090 3
W:zt
-r
A
k - A e::t:.p (- Lz
Rr"
A "" 2 .:t .10
d<e;6
2.
s gm.ol
gJ:llol
E
(-- - (
E. 373.2
Klmpl
.$
3-42
at: 2S"'C
Solutions for Chapter 4 - Isothermal Reactor Design
P4-1 Individualized solution,
P4-2 (a)
Cooking food (effect of temperature), removing of stains with bleach (effect of bleach cone,,), dissolution of
sugar in coffee or tea.
P4-2 (b) Example 4-1
There would be no enur! The initial liquid phase concentration remains the same"
P4-2 (C) Example 4-2
For 50% conversion, X = 0.5 and k = 0.311min-
1
Fe 6.137 12 lb If .
F
AO
=-=--= .27 rna mm
X 0.5
Vo = VAo + VBo = 2VAo and also, VAo = VBo
Vo= 24.52 fe/min
Using Mole Balance,
F
AO
12.27 ft3
Also, VAO =C= min
AO
V = ~ o _ = 24.52xO,5 = 78.93
k(l- X) 0.311(0 . .5)
= 592gal
This is less volume than Example 4-2 because the rate is higher..
P4-2 (d) Example 4-3
For P = 60atm,
C
AO
= 0.0415 lbmol/fe
( C = Y AO Po = 60 )
AO RT 0.73x1980
o
Using equation E-4-3,,6, for X = 0.8
We see that the only thing that changes is C
AO
and it increases by a factor of 10, therby decreasing the
volume by a factor of 10"
1
VOO
P
P4-2 (e) Example 4-4
New Dp = 3DoI4
Because the flow is turbulent
4-1
1)p2 1
fJ2 = A - = 0.0775- = 0.lO33
1)PI 0.75
I
2.0.lO3 atm . 60ft 2
1- ft
10atm
I
= (-0.24)2
2fJ
o
L 0
Now 1 - -- ,so too much pressure drop P = and the flow stops,
Po
P4-2 (0 Example 4-5
For without pressure drop, conversion will remain same as example X = 0,,82.
With Pressure drop,
anew = a
o
= 0.0037 kg-
I
lO
For decrease in diameter,
Po = 2xO.01244[266.,9x2+ 12920.,8]
= 33475lbtlft
3
= 334.75(lbr/ft')xlI144(ft
2
/in
2
)xll147(atml( Ibtlin
2
= 0. 15814atmlft
= 52.71 kPalm
For turbulent flow:
fJ
,_.' _1_ and a-.L => a = a to! 1) pI
2 I
1)p Po Poz Dp2
kCAOW (1 aw)
X - va 2 _ 4,6(0.,949)
- -1 +
Vo 2
X = 0,,8136- virtually the same
(2) Optimum diameter would be larger
a = 0.037x 52.71 = 0.0756kg-
1
25,,8
4-2
Dl
a =a-
P
-=2a
2 1 D 1
p2
aW
1 __ 2 - = 1-a
1
W = 1-(0.037)(27.5) = -0.0175
2
Now l-uW < 0, too much pressure drop due to higher superficial velocity.
P4-2 (g) Example 4-6
For turbulent flow
1 1
a-- and a---
Dp Po
a,
Therefore there is no change.
P4-2 (h) Exmple 4-7
For pressure doubled and temperature decrease
ero = 2*P JRT and T == 688K
See Polymath program P4-2--h.poJ.
POL YMA T!l Results
Calculated values of the DEQ variables
Variable initial value minimal value
----
V 0 0
Fa 2.26E-04 1.363E-05
Fb 0 0
Fe 0 0
E 2 .. 4E+04 2.4E+04
T 688 688
Cto 0.573773 0.573773
Ft 2.26E-04 2.26E-04
Ca 0.573773 0.0236075
k 213.40078 213 .. 40078
ra -70 .. 254837 --70 .. 254837
Fao 2 .. 26E-04 2.26E-04
rb 70 .. 254837 0 .. 1189309
vo 3 .. 939E-04 3 .. 939E-04
re 35 .. 127419 0 .. 0594654
X 0 0
Tau 0 0
rateA 70.254837 0 .. 1189309
ODE Report (RKF45)
maximal value
-1-..
2.26E-04
2.124E-04
1.062E-04
2.4E+04
688
0 .. 573773
3.322E-04
0 .. 573773
213.40078
-0 .. 1189309
2.26E-04
70 .. 254837
3.939E-04
35.127419
0.9395277
0 .. 253044
70.254837
4-3
final value
1. OE-04
1. 363E-05
2 .. 124E-04
1.062E-04
2 .. 4E+04
688
0 .. 573773
3.322E-04
0.0236075
213.40078
-0.1189309
2.26E-04
0.1189309
3.939E-04
0.0594654
0.9395277
0 .. 253044
0.1189309
Differential equations as entered by the user
[1 J d(Fa)/d(V) = ra
[2] d(Fb )/d(V) = rb
[3 J d(Fc)/d(V) = rc
Explicit equations as entered by the user
[1] E = 24000
[2] T=688
[3J Cto = 2*1641/8.314rr
[4] Ft = Fa+Fb+Fc
[ 5] Ca = Cto*FalFt
[6 J k = 0.29*exp(EI1.,987*(1/500-1rr))
[7] ra = -k*Ca"2
[ 8] Fao = 0,,000226
[9 J rb = -ra
[10] vo = Fao/Cto
[11] rc = -ral2
[12] X= 1-FalFao
[13] Tau = Vivo
[14] rateA=-ra
3,Oe-4..-------
.2 .4e-4
O.OHO
............. .., ......... _--" .......... ""..
OOHO 2.0<,-5l.Oe-5
v
60e-5 S,Oe-5 1.0e-4
P4-2 (i) Example 4-8 Individualized solution,
P4-2 (j) Example 4-9
Using trial and error, we get maximum feed rate ofB = O,,0251dm
3
/s to keep concentration ofB
Q.,Olmol/dm
3
,
See Polymath program P42-j.,pol.
POLYMA TH Results
Calculated values of the DEQ variables
Variable
---
t
ca
cb
initial value
o
0,,05
o
minimal value
o
0,0063485
o
maximal value
500
4-4
0.05
0.009981
final value
500
0.0063485
0,,009981
cc 0 0 0 .. 0078965 0.0078965
cd 0 0 0 .. 0078965 0.0078965
k 0.22 0 .. 22 0.22 0.22
vOO 0.0251 0.0251 0.0251 0 .. 0251
cbO 0.025 0.025 0 .. 025 0.025
vO 5 5 5 5
caO 0.05 0.05 0.05 0.05
rate 0 0 3.91E-05 1. 394E-05
v 5 5 17.55 17.55
x 0 0 0 .. 5543321 o .. 5543321 Differential
equations as entered by the user
[1] d(ca)/d(t) :::: -k*ca*cb-vOO*ca/v
[2] d(cb)/d(t) :::: -k*ca*cb+vOO*(cbO-cb)/v
[ 3] d(cc)/d(t) :::: k*ca*cb-vOO*cc/v 0.010
[4] d(cd)/d(t) :::: k*ca*cb-vOO*cd/v
Explicit equations as entered by the user
0.008
[1] k:::: .. 22
GJ [2J vOO:::: 0.0251
0.006
[3J cbO:::: 0 .. 025
[4J vO:::: 5
[5J caO:::: 0.05
0.004
[6 J rate:::: k*ca*cb
[7J v:::: vO+vOO*t
[8] x:::: (caO*vO-ca*v)/(caO*vO)
0.002
If the concentration of A is tripled the
0.000
maximum feed rate becomes
100
200 t
300 400 500
0..064 dm
3
/s
0
P4-2 (k through r) Individualized solution.
P4-3 Solution is in the decoding algorithm given with the modules.
P4-4
We have to find the time required to cook spaghetti in Cuzco, Peru.
Location Elevation (km) Pressure (mm Hg) Boiling Point (0C) Time (min)
Ann Arbor 0.21 739 99.2 15
..
Boulder 1.63 625 94.6 17
-- -
..-
Cuzco 3.416 493 88.3 ?
--
Assume reaction is zero order with respect to spaghetti conversion:
-E de
-r =k=Ae
RT
= ___ A
A dt
so that
4-5
For complete conversion (i.e .. : well cooked) C
A
= 0 at time 1.
Therefore
-E
C
AO
=tAe
RT
C -E

A
In ( C AO ) = In k = In t _ E
A
Now, plot the natural log of the cooking time versus liT b and get a linear relationship .. Extrapolation to T b =
88 . .3C = 36145 K yields t = 21 minutes.
I
2l-L
I
I
I
Ull t}
P4-5 (a)
I
lS-t
I
I
2.69 ::'.72 2.767
4-6
e
Aa
:;:;:; coo;;;; 2: kl!l!i, 0;01 <!:t:n;;hnoilmin
VA;;;; VB =;S E ..... ;;;; ZO .. COO cillmol
TI=:lOOK
'LTsi'll.g the t\lirheniu:s eqUi.lillcl} .!i. tll CSTR rernpeli'il'i.WRof 3,SOK tbe: new sp!l!tifi(:
reactio'll rate.
CSTR tleslf:,";o Btruatilll1::
X = V ( (1_ .. X)2)
10
From the :quadratic
PBR V=800 dm
3
Design Equa.tion:'
dX
F"o'-=-r
A
dV
___
1-- X FAD
X=O,,85
.". rt r'lI ,<,,}('r:: "
\' y\ - r ;"',1' <!r AOJ
T=300K
So, considering the above results, we will choose a CSTR.
4-7
P4-5 (b)
Batch Reactor V=200dm' N
AO
=N
BO
=200 moles X=0.90 Assume Isothermal
Design Equation:
rX dX
t=N
A
O
lJ
--
-rAV
t = (200males) r _dX
(
8.4.5 dm'. J(lmal)2(200dm3) (l-XY
mal * nun dm
3
t = 1.06 min
P4-5 (c)
T=273K
Find the specific Ieaction rate at the new temperature of 273 K using the Anhenius Equation.
k = 2..54 X 10-
3
(200)(9) .
k = -r-( --'-- 3 ~ ) = 3.543 nun = 2 . .5days
2.,.54 x 10- A 200)
P4-5 (d)
1) CSTR and PFR rue connected in seIies:
X . = (200dm
3
)(007dm' / mal.min)(1mall dm
3
)2(1-- X)2
CSJR lOmal / min
Solving the quadratic equation, X
CSIR
= 0 .. 44
ForPFR,
X =0.736
dX = (0.07dm
3
/ mall min)C,40(1- X)(l- X)2 dV
lOmale/min
1. dX = (0.07dm
3
/mallmin)(lmall dm
3
)2(800dm
3
)
044 (1- X)3 lOmale/ min
2) when CSTR and PFR rue connected in parallel,
X = (200dm
3
)(0.07dm
3
/ mal,min)(lmal / dm
3
)\1- X)2
CSTR
.5mal/nun.
X
CSIR
= 0.56
4-8
ForPFR,
1 dX = (0.07dm
3
/ mol.min)(1moll dm
3
)2(800dm
3
)
o (1- X)2 5moll min
X
PFR
= 0.92
0.56+0.92
Hence, final conversion X = =0.74
2
P4-5 (e)
To process the same amount of species A, the batch reactor must handle
2M =
mm hr day day
If the reactants are in the same concentrations as in the flow reactors, then
v = = 14400 dm
3
day mol day
So the batch reactor must be able to process 14400 dm
3
every 24 hours"
Now we find the time required to reach 90% conversion" Assume the reaction temperature is 300K.
N
AO
X . N
Ao
t R = 2 --, and smce --= C AO
VkC I-X V
AO
1 X 1 0.9
tR =-_._--= 3 --=2.14hr
kCAO I-X 4.2 dm_*I(mol) 0.1
molhr dm
3
Assume that it takes three hours to fill, empty, and heat to the reaction temperature.
tf= 3 hours
ttotal = 2. 14hours + 3 hours = 5.14 hours.,
Therefore, we can run 4 batches in a day and the necessary reactor volume is
14400dri = 3600dm
3
4
4-9
Refening to Table 1-1 and noting that 3600 dm
3
is about 1000 gallons, we see that the price would be
approximately $85,000 for the reactor.
P4-S (f)
The points of the problem are:
1) To note the significant differences in processing times at different temperatures (i .. e.
compare part (b) and (c)).
2) That the reaction is so fast at 77C that a batch reactor is not appropriate. One minute to react
and 180 to fill and empty.
3) Not to be confused by irrelevant information. It does not matter if the reactor is red or black.
'rA=kC",CB
":A "" k (F Ai,,) (F NU)
+ butanoi ... "
eiernentary reaction
for liquid systems
volumetric flow u =uo
4-10
+- water
Fe
V - --.------ = -.--.-----.---
CSTR - - .. r kC
2
(l---XXS--X)
A
7\: = 4 A , Fe = 4. x 10
6
Ib / yr , 30d / yr operation
F := 4. x 10
6
It!.. x ..!:x! _1..... x 1 Ib mol
. C yr 30d 24 hr 278 Ib
= 20.0
V
-lOC'fl 1ft" 1 ..
. - I'I.J ga. x. ------:::: j.) J u.
CSIR 7.48 gal "
133.7 h
3
= .. ___ .._._ ..... 20.1bmole/hr_ ..._._ ._._
J 2
12-;--.. fE.--_.-;- ... (1 X) (5-X)
lomol<:::lll f?
Xi. 6X, 1.89 =: 0
X"" 0.33
P4-6 (b)
To increase conversion, use PFR, higher temperature, or use better catalyst.
P4-6 (C)
ME
Rl.
s
c:
E
P4-6 (d)
PFR Design Equation
d)(
dV F
Ac
dX IcC!o (1- X XS"'_ X )
=: W-= ___ __ , - .. ""." ". "...... .. ".-, ___
dV
V = 535dm
3
4-11
P4-6 (e)
MOle baiance.;
The above equation relates the reaction time for a batch and the conversion
achieved during that hatch.. There is a tradeoff bct\vcen high conversion and few
batches and low conversion but many batches per day_ What conversion will
result in the smallest nurllber of reactors?
N
AO
:::;;; 133.7 ft;' * C AO C AO :=: O.2lbmoll ft>
__ __ ... _'!:lQ = = ............ ____ = f{X )
reactor * day t t + 3 1 ( <; ... X \
. bau:h r= In .... '5X J1- 3
=
day 30days 278lb day
480moll
n :::;:.-._--...
f(X)moll dayJ reactor
o 0..2 0.4
x---->
U.O 0.8
The minimum occurs at X = 0.82 and corresponds to 4.192 or 5 reactors
P4-6 (f) Individualized solution
P4-6 (g) Individualized solution
P4-6 (h) Individualized solution
P4-7 (a)
4-12
Elementary gas phase reaction,
A-4B+2C
c ",c (1-X}
r\ ... 0 (1+ X)
P,IQ 10 mol
C
AO
'" RT ::: (0.0$2){400) '" O.3'dml
V;;:967
P4-7 (b)
v", FAcX(l+!!:l
CAJ(l-X)
P4-7 (c)
For a = O .. OOldm-
3
See Polymath program P4, .. 7 .. c.pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal
v 0 0
x 0 0
value maximal value
500
0 .. 656431
Y
1. 0_1721111 1
Co 0.3 0_3 0.3
esp 2 2 2
alfa 0_001 0.001 0_001
4-13
final value
500
0_656431
0 .. 1721111
0_3
2
0_001
C 0.3 0.0077768 0 .. 3 0 .. 0077768
0 .. 044 k 0.044 0.044
r -0" 0132 -0 .. 0132
fo 2 .. 5 2.5
Differential equations as entered by the user
[1 J d(x)/d(v) = -r/fo
[2 J d(y)/d(v) = -alfa*(1 +esp*x)/(2*y)
Explicit equations as entered by the user
[1] Co = 0 .. 3
[2] esp = 2
[3] alfa = 0 .. 001
[4] C = Co*(1-x)*y/(1 +esp*x)
[5] k = 0 .. 044
[6] r = -k*C
[7] fo=2 .. 5
AtV= 500,
x = 0..66, Y = 0..17
P4-7 (d) Individualized solution
P4-7 (e)
A B + 2C
Law:
Stoichiometry:
esc:!
Kc
C"
s ::::;; 2 and C Ao ;;;;; 0 . .3
X
-O-?
"1:1 - .31_
X:::; :::: 0,.47
0 .. 044
-3.422E-04
2 .. 5
-3 .. 422E-04
2 .. 5
1.0 ......:::------------------,
0.8
0.6

LrJ
0.-:1
0.2
0.0 If--__ -'--__ --'-__ -' ___ -'--__ --I
o 100 200 300 400 500
)::: 0
4-14
v
X
1.+ eX
Using these equations in Polymath we get the volume to be 290 dm
3
,
P4-7 (0
A B+2C
Rate Law:
Kc == 0,,025
Stoichiometry: C C =C",,,2S. Cc=2C ...
o
X
.. \ l+eX ,-:a 1 +- ex' l+eX
K - _ (_C,-oX __ ..!,7 ex );; , __ .. __
C - C ... - heX) l+eX C".,(lX) (1+eX}2(1-X)
e::; 2 and CA,o::: 0.3
Xeq::: 0.52
X::: (O.90)Xeq::: 0.47
,E.EB.
,... dX dV F
t" -- ::: - r 0 r -,,, .. ,,.' ;;;; """.ia.
M dV'" dX -r ...
orA = (1- Xl - (1
Using Polymath to solve the differential equation gives a volume of 290 dm
3
See Polymath program P4-7-f.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal
---
X 0 0
V 0 0
Kc 0.025 0,,025
Faa 2,,5 2.5
Caa 0.3 0.,3
k 0.044 0.044
e 2 2
ra -0,0132 -0,,0132
ODE Report (RKF45)
value maximal value
0.47
290,,23883
0.025
2 " 5
0,,3
0.044
2
9" 391E--04
415
final value
0,,47
290.23883
0,,025
2,,5
0.3
0.044
2
-9.391E-04
Differential equations as entered by the user
[1 J d{V)/d{X) = Fao/{-ra)
Explicit equations as entered by the user
[1] KC= .. 025
[2] Fao = 2 .. 5
[3] Gao= .. 3
[4] k = .. 044
[5] e=2
[6] ra = -(k*Gao/{1 +e*X))*{{1-X)-{4*Gao/\2*X/\3)/{{1 +e*X)/\2*Kc))
V:::: 1300 dm)
PFR with pressure drop: Alter the Polymath equations flom part (c)..
See Polymath program P4 .. T .. fpressure.pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value
----"---
v 0 0
x 0 0
Y
1 0 .. 3181585
Kc 0 .. 025 0.025
alfa 0 .. 001 0 .. 001
Cao 0.3 0.3
k 0 .. 044 0 .. 044
esp 2 2
fo 2.5 2.5
r -0.0132 -0.0132
ODE Report (STIFF)
Differential equations as entered by the user
[1] d{x)/d{v) = -r/fo
[2] d{y)/d{v) = -alfa*{1 +esp*x)/{2*y)
Explicit equations as entered by the user
[lJ Kc =.025
[2 J alfa = 0 .. 001
[3] Gao = 0 .. 3
[4J k=0.044
[5J esp = 2
[6J fo = 2 .. 5
maximal value
500
0.5077714
1
0.025
0 .. 001
0 .. 3
0 .. 044
2
2 .. 5
-1.846E-04
4-16
final value
------
500
0 .. 5077714
0.3181585
0.025
0.001
0 .. 3
0.044
2
2 .. 5
-1.846E-04
[7] r = -(k*Cao/(1 +esp*x*(4*Cao"2*xI\3/1+esp*x)1\2*Kc
At V = 500 dm
3
X = 0.507 and y = 0.381
P4-7 (g)
Membrane reactor: A -+ B + 2C
CA = CoFAlFr CB = CoFBIF1 Cc = CoFCIFI
FT = FA + FB + Fe and orA = rB = rel2
Using polymath,
ForPFR,
See Polymath program P47g.pol.
POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value
v 0 0
Fa 2.5 1. 3231889
Fb 0 0
Fc 0 0
Kc 0.025 0.025
Ft 2.5 2 .. 5
Co 0.3 0.3
K 0.044 0 .. 044
kc 0.08 0.08
ra -0.0132 -0.0132
X 0 0
Differential equations as entered by the user
[ 1 J d(Fa)/d(v) = ra
[2] d(Fb)/d(v) = ora - kc*Co*Fb/Ft
[3 J d(Fc)/d(v) = -2*ra
Explicit equations as entered by the user
[1] Kc = 0 .. 025
[2] Ft = Fa+ Fb+ Fc
[3J Co = 0.3
[4J K = 0.044
[5J kc = .. 08
[6 J ra = - (K*Co)*(Fa/Ft CoI\2*Fb*FcI\2/(Kc*FtI\2
['7 J X = 1 - Fa/2 .. 5
Solving for when X = 0 .. 47, we get V = 1040 dm
3
maximal value
1040
2.5
0.3635477
2.3536223
0.025
3 .. 7452437
0.3
0.044
0 .. 08
-3.827E-04
0.4707245
4-17
final value
1040
1.3231889
0.0684325
2.3536223
0.025
3.7452437
0.3
0.044
0.08
-3.827E-04
0 .. 4707245
3.0
-
Fa
2.4
-
Fh
1.8
1.2
0.6
0.0 0
208 416
v
624 832 10-10
P4-8 (a)
The blades makes two equal volumes zones of 500gal each rather than one 'big' mixing zone of IOOOgal.
Si71.g1e B12c:'e
Predicted
F X
'V = ;:;; a __ 7
k
ll _. X)- (1 X)-
AO \., .
rnal
[ aj =:;SL. :.-.----.. -:" -2:
CAok
a = [gal]
X .5 2
1000 gal = a---.. ? .. = a ..-....... :::::. a
(l-Xt .25
a=500 gal
4-18
1 3X
1
+ xf =0
Xl =_ .... -::;:::. .38
2
Reac:or 2
1- 2X-:> + X, 38
:.., "" ./;.,.
., .
X1--3X + 1.38=0
2
Measured
500 gal == 5U{10 L
.!.-.
... '" . .."
P4-8 (b)
A CSTR is been created at the bend due to backmixing, so the effective arrangement is a PFR is in series
with aCSTR.
-c __

A--+B
CSTRzone
created due to
backmixing
k = 5 min-
1
Vo = 5 dm
3
/min ..
x.,xpected = 0.632 X
actual
= 0.586
V = fFAOdX = va In _ 1 =1
In
1 =1.0
x [ ] ( )
o -r
A
k 1- X Expected 5 1- .632
Now,
4-19
ForPFR, Vp = In (_1 J.
I-Xl
. . .1
For CSTR, V
= FAO(Xactual - Xl) = (Xactual - Xl)
c -rA (1- Xactual) ............. .2
Also,
Vp Vc_
-+--}".
V V
Solving I, 2 and 3 by using polymath,
See Polymath program P4-8-b.pol.
POLYMA TH Results
NLES Solution
. .......................... ..3
Variable Value f(x) lni Guess

Xl
Vc
V
X2
Vp
0 .. 350949
0.,567756
1
-3 .. 297E-14 1
0 .. 586
0 .. 432244
NLES Report (safenewt)
Nonlinear equations
[ll f(X1) = In(1/(1-X1))-Vp = 0
[21 f(Vc) = (X2-X1 )/(1-X2) -, Vc = 0
Explicit equations
l11 V = 1
[21 X2 = .586
[3] Vp = V - Vc
Vc = 0..57 dm
3
; Vp = 0.43 dm
3
; Xl = 0.,35
P4-8 (c)
C
AO
= 2 mol/dm
3

Assuming 1st order reaction,
'r"= CAOX
For CSTR,
-r
A
-rA = kC
A
= kCAO(l-X)
=> rk = == = 0.,67
I-X 0.6
ForPFR,
V = F X
f
dX _ rk =
AO kC (I-X)' I-X
o AO 0
=> X PFR = 1-exp( -rk) =1-exp( -0 .. 67) = 0.486
Now assuming 2nd order reaction,
For CSTR, Now, assuming 2nd Older reaction,
4-20
ForCSTR,
ForPFR,
CAOX
1:=--
-r
A
-r
A
= (1- X)2
=> 1:kC
AO
= X 2 = =1.111
(I-X) 0.6
1:=-1-1 dX 2
kC AO 0 (1- X) kC AO 1- X
=> X =1- __ 1_.=1-_1_=.526
1+1:kC
AO
2.111
So, while calculating PFR conversion they considered reaction to be 1st order. But actually it is a second
order reaction.
P4-8 (d)
A graph between conversion and particle size is as follows: Originally we are at point A in graph, when
particle size is decreased by 15%, we move to point B, which have same conversion as particle size at A.
But when we decrease the particle size by 20%, we reach at point C, so a decrease in conversion is noticed"
Also when we increase the particle size from position A, we reach at point D, again there is a decrease in
the conversion,
1
A
x n
dp
P4-9
A<=>B
Kco (300K)= 3.0 V = lOOOgal = 3785.4 dm
3
Mole balance:
V =!.AO
X
-r
A
4-21
Rate law:
StOIchIometry:
Now using: v =(-Z) X =>
Z [(I-X)' _of]
f (X) = 0 = V _ (Z) __ -.! __ _
Z [ X2]
(1-X)2 -'K
c
z =.!. = exp(E[J_ .. _!]) and
ko R To T.
where
K = K
C co R T T
o
Solving usmg polymath to get a table of values of X V s T..
See Polymath program P4-9 po]
POL YMA TH Results
NLE Solution
variable Value
X
To 300
T 305.5
z 2902.2
V 3785.4
E 1.SE+04
R 2
Y 1.5684405
Kco 3
Hrx -2 SE+04
Kc 1 4169064
f(x) Ini Guess
3.638E12 . O.S
NLE Report (safenewt)
Nonlinear equations
043 - ..... --.. ' . '-..
,
( 1 J f(X) = (z/y)*x/1-X)"2 - X"21Kc) .. V = 0
--------, 042+---
i
041
04 ---
x
0.39
038 -------..-----.. -----.-----
4-22 0.37
o 36
Explicit equations
[1] To = 300
[2] T = 305.5
[ 3] z = 2902.2
[4] V = 3785..4
[5] E = 15000
[6] R=2
[7] Y = exp(E/R*(1rro-1rr))
[8] Kco=3
[ 9 ] Hrx = -25000
[10] Kc = Kco*exp(HrxlR*(1rro-1rr))
----
T(in K) X
300 0.40
301 0.4075
-
303 0.4182
304 0.4213
f-- --
305 0.4228
305.5 0.4229
~
305.9 0.4227
307 0.421
310 0..4072
--
315 0.3635
---
--
._--
--
_._------- _._-----_._-
We get maximum X = 0.4229 at T = 305.5 K.
P4-10 (a)
For substrate:
4-23
Fso - Fs + rs V = 0
(C
so
- Cs)vo = rg VY
S1C
= VYSIC[ ,urn.xCS C
c
]
KM +C
S
P4-10 (b)
Cc = YC/s [C
so
- C
s
]
(C
so
- C
s
)Vo - VY
S1C
[,uMAXCS C
c
] =
KM+C
s
=> (C
so
---C
s
)Vo - VY
CIS
[,uMAXCS ]( C
so
- C
s
) =
KM+C
s
(30--C
s
)5_25XO.Sx[O.5XC
s
](30-C
s
) = 0
5+C
s
Solving we get C
s
= 5.0 g1dm
3
or 30 g/dm
3
if C
s
= C
so
no reaction has occurred so the only valid answer is
C
s
= 0.5 g1dm
3

P4-10 (C)
Cc = Y ClS(C
SO
- C
s
)
= 0..8(30 - 5.0)g1dm
3
= 20 g1dm
3
..
P4-10 (d)
V
new
= vJ2 = 25 dm
3
/h
Using equation trom above, we get C
s
= 167 g/dm
3
and Cc = 22 .. 67 g1dm
3
P4-10 (e)
V
new
= V J3 = 25/3 dm
3
Using equation from above, we get C
s
= 1.0 g1dm
3
and Cc = 216 g/dm3
P4-10 (f)
For batch reactor:
C
so
= 30 g/dm3 Ceo = OJ g/dm3
Cc = Cco + Y ClS(CSO - Cs)
V = lOdm
3
See Polymath program P4-1O-f.pol.
POLYMA T!lReults
Calculated values of the DEQ variables
Variable
t
Cs
Cso
Yes
KIn
Umax
Ceo
Ce
initial value
o
30
30
0 .. 8
5
o .. 5
0 .. 1
0 .. 1
minimal value
o
0 .. 0382152
30
0 .. 8
5
0 .. 5
0 .. 1
0.1
maximal value
15
30
30
0 .. 8
5
0.5
0 .. 1
24.069428
4-24
final value
15
0.0382152
30
0.8
5
0.5
o .. 1
24.069428
rg 0.0428571
rs -0.0535714
negative_ 0.0535714
ODE Report (RKF45)
0.0428571
-6.8055436
0.0535714
Differential equations as entered by the user
[1] d(Cs)/d(t) = rs
Explicit equations as entered by the user
[1] Cso = 30
[2] Ycs=0.8
[3] Km=5
[4] Umax = 0.5
[5] Cco = 0.1
[6 J Cc = Cco+Ycs*(Cso-Cs)
[7] rg = (Umax*Cs/(Km+Cs*Cc
[8J rs=-(1IYcs)*rg
[ 9 ] negative_rs = 'rs
30.0r---==:=::;:;;::::::---------1
24.0 .
18.0 .
12.0
6,,0 .
0,,0
0.00 3.00 6.00 t 9.00 12,00 15,,00
P4-10 (g)
5.4444349
-0.0535714
6.8055436
0.0912841
-0.1141052
0.1141052
7.0 ....------------------,
5.6
c::
-]
" tU
4.2
2.8
1.4
0.0 __ ____ ___ .!J
0,00 3.00 6.00 t 9,00 1200 15,00
Graphs should look the same as part (f) since reactor volume is not in the design equations for a constant
volume batch reactor.
P4-11
Gaseous reactant in a tubular reactor: A B
-r
A
=kC
A
k = 0.0015 min-l at 80
0
P
E = 25 X = 0.90
, gmol
lb
MW
A
=MW
B
=58--- D
t
=1 inch (I.D.)
lbmol
P = 132 psig = 146.7 psia T = 260 F = 720 R
4-25
M
B hr
L = 10ft
n
t
= number of tubes
1000!!
FB = hr =17.21Ibmol
58 lb hr
lbmol
For a plug flow reactor:
V = nt1lDt
2
L = F f9 dX
AO
4 -fA
6=1-1=0
1721lbmol
F = FB =' hr = 19 .1
1b
mol
AO X 0.9 hr
c = P
A
~
AO RT RT
(
E( 1 1 )J (25000( 1 1)) . -1
k
2
=k
1
exp - --- =0.0015exp --- ----- =53.6mm
R ~ T2 1.104 540 720
k2 = 53.6min--
1
= 3219hr-
1
(
19.11bmol)(10.73 it3 psia )(720
0
R)
V = FAORT In 10 = . hr lb o ~ ~ _ R _____ In 10
kP (3219hr-
1
)(146.7psia)
V = 0.72ft'
V = !!L,!D
t
2
L
4
4V 4(0.72/t
3
)
n =--=-_. 13.2
t 1D2L (1 J2
t 1 12ft (10ft)
Therefore 14 pipes are necessary..
P4-12
A --4 BI2
4-26
Stoichiometry
Rate Law (elementary reaction)
.... ..... . .,. .. _" ... .... "._._ .. .M._. ____ ................. ............... "._. _ __.
(for the int.egratitJll, refer Appendix A)
from the Idea.l (jus assumption,
(5
!/AO
IE
1
1
1
2 2
F
AU
FAO +Pno+
,-- 11 AO()
_v .. v
1/4
. 1
X
dX
Vp I;' R FAO --
o ---7'11
CAO = YAoCm
1
-
-
2
Substituting X 0.8 (),nd E to Eq. (4)
/ ) 2 (1-1/ 4)20.8
= 2(--1 4 (1-1/ 4) In(1- 0.8) + (-1/ 4) 0.8 + = 2.9, ... " .. .. ,(6)
F
AO
1-0.8
1\1oh\1' flow 1a to of A cut iu haH,
lihHll Eq. (4),
F
i{
AO
-
IF'
,., -'10
2 .
1 !

1
.. Fc;;'; :3
c' -
=1/6
2E/(1 -+ t')ln(l
4-27
V ky
,2 C'2
PFR AD TO_
F'2
AD
2( --'-1/6)(1 - 1/6)ln(l -- X') + ( l/fi)
2
X'
1" I/G)2 X'
I XI
Polymath ='fol1-Liw:cll' Eqnation Solver, X
f
:.::c (}.758
P4-13
Given: The metal catalyzed isomerization A q B , liquid phase reaction
(
CB J .
-r
A
= kl C A --- WIth Keq = 5.8
Keq
For a plug flow reactor with YA = LO, Xl = 0.55
Casel: an identical plug flow reactor connected in series with the original reactor.
Since YA = 10, e
B
= 0 . For a liquid phase reaction e A = e AO (1- X) and e
B
= e AOX
-r, = kCAo((l- X)- i:: J
For the first reactor,
Xl dX Xl dX
~ = F
AO
f-. " = F
AO
f ( . ----"-J" or
o -fA 0 kC (1- X - ~ -
AO K
eq
4-28
\ In[I-(1 +_I_JX
1
] = -0.853In(.355) =0.883
1+- Keq
Keq
Take advantage of the fact that two PFR' s in series is the same as one PFR with the volume of the two
combined.
= X
J
dX
F
AO
0 l-(l+_l_Jx
Keq

Keq ..
kCAOVF = 2 kCAOl-i =
F
AO
F
AO
2
kCAO
l-i =2(0.883)=1.766
F
AO
1.766 =. 11 In[I-(I+_1 .)X
2
]
1+--. 5.8
5.8
X
2
= 0..74
o
Case 2: Products from 1 st reactor are separated and pure A is fed to the second reactor,
The analysis for the fIrst reactor is the same as for case 1 ..
4-29
kC AO v; - 1 [( 1 J ]
F
AO
l+_l_ln 1- 1+ Keq XI
Keq
By performing a material balance on the separator, F
AO
,2 = FAO(l-X
I
)
Since pure A enters both the first and second reactor C
AO
,2 = C
AO
, CBO,2 = 0, 9B = 0
C A = C AO (1 - X) C
B
= C AOX for the second reactor.
X
2
dX F
AO
(1- X) Xl dX
V2 = FAo,2 f- = f X
o -rA kCAO 0 (l-X)--
Keq
and since VI = V
2
kC
AO
V
2
_ _ kCAOV;
F
AO
F
AO
or
---.!-1 In[l--(l +-}-Jx
l
] = - 1- In[l-(l +_1 J X2]
1+- eq 1+- Keq
K K -

Jx, +-(1+ ;Jx,t'
[
(
1 J
X
_
1- 1- l+K.
q
Xl 1
= 1- (0.356)045 = 0.766
2 - 1+_1_ 1.174
Keq
Overall conversion for this scheme:
.- _ F
AO
- F
AO
,2 (1 - X 2) _ F
AO
-- F
AO
(1 _. Xl) (1 - X 2) _ ( ) ( )
X ----F ---- -1- I-Xl I-X2
AO F
AO
X =0.895
P4-14
4-30
Given: Ortho- to meta- and para- isomerization of xylene.
M k
j
>P
M k2 >0
o >P(neglect)
Pressure = 300 psig
T = 750F
V = 1000 fe cat.
Assume that the reactions are irreversible and rust order.
Then:
--r
M
= kjC
M
+ k
2
C
M
= kC
M
k = kl +k2
=0
Check to see what type of reactor is being used ..
Case 1:
Vo = 2500 gal X = 0.37
hr
Case 2:
V =1667 gal
o hr
X =0.50
Assume plug flow reactor conditions:
FMOdX =--rMdV or
x dX
V=FMO J--
o -r
M
Xc d x
V = f MOVO X =vo V
O
In (I-X)
"0 -r
M
0 k(I-X) k
C
MO
, k, and V should be the same for Case 1 and Case 2.
Therefore,
(kV)casel = -( Vo )casel In (1- Xcasej ) = -2500 [1-0.37] = 1155
(kV)case2 = -( vO)caSel
in
(1- Xcase2) = -1667 In [1-0.50] = 1155
The reactor appears to be plug flow since (kVkase 1 = (kV)Case 2
As a check, assume the reactor is a CSTR
FMOX = CMOVOX =-r
M
V
4-31
-r
M
vX
or kV=_o-
I-X
Again kV should be the same for both Case I and Case 2.
gal ( )
(
V ) X 2500- 0.37 1
(
kV) = 0 Casel Casel = hr = 1468 ga
Casel I-X 1-037 hr
Casel
gal ( )
(
V ) X 1667- 0.50 1
(
kV) = 0 Case2 Case2 = hr = 1667 ga
Case2 1- X 1---050 hr
Case 2
k V is not the same for Case 1 and Case 2 using the CSTR assumption, therefore the reactor must be
modeled as a plug flow reactor ..
kV =1155 gal
hr
1155 gal
k = hr _ = 1.55 gal
1000 ft3 cat. hr It
3
cat
For the new plant, with vo = 5500 gal / hr, X
F
= 046, the required catalyst volume is:
-5500 gal_
-v h
V = _0 In (1- X F) = ~ In (1--0.46) = 2931ft3 cat
k 1 . 1 5 5 . K ~
hr ft cat
This assumes that the same hydrodynamic conditions are present in the new reactor as in the old ..
P4-15
A-4 B in a tubular reactor
Tube dimensions: L = 40 ft, D = 0 . .75 in.
n
t
=50
( )
2
(50)n- 0.75
V = n
t
1[D
2
L = 12 40 = 6. 14ft3
4 4
4-32

F
AO
hr =6.861bmol
MW
A
73 lb hr
x dX
V=FAof-
o -r
A
lbmol
-r = kC
Ao
(I-X).=kC (I-X)
A 1+8X AO
V = F
AO
SdX.= F
AO
S dX. = F
AO
In(_I_)
o-r
A
okC
Ao
(I-X) kC
AO
I-X
. P YAOP
wIth CAO =-=--
RT RT
V = FAORT In (_1_) or k = In (_1_)
kyAOP 1- X VYAOP 1- X
Assume An'henius equation applies to the rate constant.
-E
At T J = 600
o
R, kJ = 0.00152 = Ae
R1
;
-E
At T2 = 760
o
R, k2 = 0 .. 0740 = Ae
RT2
-t)]
In = -:(k- n=
E = TrT2 ._
In
k2 =(660)(760) In 0.740 =19,500oR
R Tr - T2 kl 100 0.00152
A = kl exp
RTr
'0 k=k\ex
p
[ - !u -n]
From above we have
k = .FAoRT In (_1_)
Vy P l--X
. AO
so In (_1 ) = kl exp [- E
VYAO
P
I-X R T Tr
Dividing both sides by T gives:
4-33
(
6.S61bmal)(10.73 psiaft3 ) ex [-19500(!- 1 )]
hr lb maze R -In 5 = P T 660
0
R
(
.00152-)(3600 sec)( 6.14ft3 )(114.7 psia) T
sec hr
Evaluating and simplifying gives:
exp [-19500 (! - _1_)]
0.030So R-
1
= T 660
0
R
T
Solving for T gives:
P4-16
Reversible isomerization reaction
m-Xylene -> p-Xylene
Xe is the equilibrium conversion.,
Rate law: -r = k(C _ C
p
)
m m k
e
At equilibrium,
-rm = 0 =>
C
p
C=-
m k
e
K = ~ -
e l--X
e
1 + _1_ = (1 + 1- X e ) = X e + 1- X e = _I_
Ke Xe Xe Xe
-r = kC 1 - ~ - )
m AD X
e
P4-16 (a)
4-34
For batch reactor,
Mole balance: dX = -rm V = kC
AO
(1- X J
dt N
mO
CAO Xe
T=X
e1n
( Xe J
k Xe --X
ForPFR,
V =F
AO
fdX
-rm
= va f dX
k 1-(1+ :JX
1 f dX
TpFR =-;; ( 1 J
1- 1+- X
Ke
T = Xe
PFR k X-X
e
P4-16 (b)
ForCSTR,
V= Fma
X
-rm
X
T CSlR = [;::-1--(-:-1' +-K- 1 e-J-X-=]
Putting the value of Ke,
X( Xe J
TCSIR =k Xe -X
P4-16 (C)
Xe In(. Xe .. )
T, k X -X X --X X -X X

k X --X X -X
e e
4-35
1 - ~ )
1] = Xe In
v X
Xe
1
X
1--
Xe
Following is the plot of volume efficiency as a function of the ratio (x/Xe),
See Polymath program P4-16-c.pol.
1.0 ,;:::--------------,
0.8
Efficiency
0.6
04
0.2
0.0 -----" --
0.010 0 .. 208 OA06v.\.1.604 0.802 1.000
P4-16 (d)
Efficiency = V PFR I V CSTR = 1 from problem statement, which is not possible because conversion will not be
the same for the CSTR' s in series as for the PFR
-------_.
P4-17 (a)
A--7Y2B
E = -1/2, X = 0.3, W = 1 kg, Yexit = 0..25
ForPBR, and
C =C
o
(l-X)y
A (1+ eX)
dX r
A
kC
o
(l- XY y2 kC
Ao
let Z =----
dW F
AO
vJl+eXY Vo
dX (1-x)2l
--=z
dW (1+eX)2
and
dy =-!:'.(l+eX)
dW 2y
Solving for z by trial and error in Polymath to match x and y at exit,
X = 0.3 Yo = 1 and Yf = 5/20 = 0..25
we get: a = 1.043 kg-
l
and z = 0.7 kg'l
See Polymath program P4-I7-al.pol.
POLYMA TH Results
4-36
Calculated values of the DEQ variables
variable initial value minimal value maximal value
W 0 0
x 0 0
Y
1 0 .. 2521521
esp -0.5 -0 .. 5
alfa 1.043 1.043
Z 0.7 0.7
Differential equations as entered by the user
[1] d(x)/d(W) = Z*1-x)*y/(1+esp*x)A2
[2) d(y)/d(W) =alfa*(1+esp*x)/(2*y)
Explicit equations as entered by the user
[1] esp = -0.5
[2] alfa = 1.043
[3] Z=.7
Now for CSTR:
W
_ FoX _ X(l+cXY
-----_._--
-T
A
z(l-XY
Solving we get for W = lkg and z = 0..7 kg'
X=OAO
See Polymath program P417-a2.pol.
POLYMA TH ... Results
NLE Solution
Variable Value
x 0.396566
W 1
esp -0 .. 5
Z 0.7
NLE Report (fastnewt)
Nonlinear equations
fix)
-1.142E-13
[1 J f(x) = W*Z*1-x)/(1 +esp*x)}A2-x = 0
Explicit equations
[1] W = 1
[ 2 J esp = -0 .. 5
[3J Z = 0.7
P4-17 (b)
For turbulent flow:
G
2
a=(constant)-
Dp
1
0.302004
1
-0.5
1.043
0.7
Ini Guess
0.5
4-37
final value
1
0.302004
0 .. 2521521
-0.5
1.043
0 .. 7
a = _a
j
= 0.0326 and
2 32
Now solving using polymath:
See Polymath program P4-17-b.poI.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal
w 0 0
x 0 0
value
Y
1 0,9887079
esp -0 .. 5 -0.5
alfa 0.0326 0 .. 0326
z 2 " 8 2 .. 8
ODE Report (STIFF)
Differential equations as entered by the user
[1 J d(x)/d(w) = Z*((1-x)*y/(1 +esp*x))"2
[2 J d(y)/d(w) = -alfa*(1 +esp*x)/(2*y)
Explicit equations as entered by the user
[ 1] esp = -0,,5
[2] alfa = 0,,0326
[3] Z = 2.8
So, convelsion in PBR, X = 0,,862
P4-17 ( C) Individualized solution
P4-17 (d) Individualized solution
P4-18
Given a Fluidized Bed ('SIR
w = F [ ~ X
'fA
p
0= 0' E =0, thcll P
A
= J'\o(t- X) p
n
No pressure drop ill the CSTR
P
A
== l\o(I ..... X) 'vV =f"AO)l:
kPAO(IX) ,
=>:. Z2 = 4xO.7 = 2.8
maximal value final value
1 1
0.8619056 0.8619056
1 0 .. 9887079
-0.5 -0.5
0.0326 0 .. 0326
2.8 2.8
4-38
k & F
A
(} unknmvl1 .. group into a constant, use values from 1 st case,
= P
A
: \V = ==
a) Put PFR downstream" less \Nasted volume
'IS
P4-18 (b)
b) PBR; == = kPJ\o(l- kPAO(1- X)(l ,,--nW)1l2(since e = 0)
= (I _ X)(l- aW)li2
dW F
AO
J
Xz dX PAOk rW ( . )112
----"=--'JI l-uW dW
xII X F ()
;\0
When X :;:: XI , \V.:::: 0
In } .- __ )[ I .m (I ''', u W) 3/
2
]
.1 ",., X
2
F\o 3a
[
1"",0.
5
1 lO3 '." 2 [ '.' 1 3{2]
In ""'atmkg 20dtm 3("0.oi8)"" 1-,,(I-.O.018kg )Okg)
X
2
= 0.756
k(y
b
4-39
P4-18 (c)
I) ( 1 .')t(Z
C) P == PO(!' (lVV') ito ;= 20 aIm J" 0018kg- (50kg) , = 63 alm
P4-18 (d)
For turbulent flow
a
2
= a
l
(D
Pl
J2 (Ac.l J2 = (0.018kg-
l
) , , ~ ) 2 ~ J 2 = 0.0142kg-l
Dpz Ac2 1 1.5
P
exit
= P
o
(1- UW)05 = (20atm)(1-0.0142kg!(50kg1!2 = 10 . .7 atm
In[1-0.5]= 10-.
3
20atm( ( 2 )][1-(1-0.0142kg-
l
(50kg )t
2
]
1-X2 atmkg 3 0.0142kg-
l
X
2
= 0.,77
P4-19
Production of phosgene in a microreactor ..
CO + Cl
2
-> COCl
2
(Gas phase reaction)
A+B ->C
See Polymath program P419.pol.
.POLX,MA I!lResults
Calculated values of the DEQ variables
Variable initial value minimal value
W 0 0
X 0 0
Y
1 0.3649802
e -0.5 -0,,5
FAO 2"OE-05 2"OE-05
FBO 2,OE-05 2"OE-05
Fa 2.0E-05 4.32E-06
Fb 2"OE-05 4,,32E-06
vO 2,,83E-07 2,83E-07
v 2,,83E-07 2" 444E-07
Fe 0 0
Ca 70,,671378 9,1638708
Cb 70,,671378 9.1638708
a 3.55E+05 3,,55E+05
k 0,,004 0,,004
rA -19.977775 -19,,977775
Ce 0 0
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(X)/d(W) = -rA/FAQ
r 2 J d(y)/d(W) = -a*(1 +e*X)/(2*y)
Explicit equations as entered by the user
maximal value
3,,5E-06
0,,7839904
1
0" 5
2.0E-05
2.0E-05
2,OE-05
2"OE-05
2,,83E-07
4,,714E-07
1,,568E-05
70.671378
70,,671378
3.55E+05
0.004
-0.3359061
53,532416
4-40
final value
3.5E-06
0.7839904
0,,3649802
-0.,5
2"OE-05
2.0E-05
4,32E-06
4 ,. 32E--06
2,.83E-07
4,. 714E-07
1" 568E--05
9,,1638708
9.1638708
3,,55E+05
0.004
-0.3359061
33,,259571
[1] e = -.5
[3] FBO = FAO
[5] Fb = FBO-FAO*X
[7] V = vO*(1 +e*X)/y
[9] Ca = Fa/v
[11] a = 3.55e5
[13] rA = -k*Ca*Cb
P4-19 (a)
0 .. 0 .. --------.---------,
0.0
0.0
[j
Fa.
- Fb
- Fe
0.0
0.0
0.0 IL--_____ __ ____ ___l
OOe+O 7.0(' '7 lAe-6 W 2.1e-6 2.8e-6 .3.5l'-6
P4-19 (b)
The outlet conversion of the reactor is 0 .. 784
[2] FAO = 2e-5
[4] Fa = FAO*(1-X)
[6] vO = 2 .. 83e-7
[8] Fe = FAO*X
[ 10] Cb = Fblv
[12] k=.004
[14] Ce = Fe/v
1.0 ...--------------_=____,
0.8
0.6
0.4
0.2
0.0 L-_____ _
O.Oe+O 7.0l'-7 1.4e-6\V2.1e-6 2.8e-6 3.5e-6
The yield is then MW*F
A
*X = 99 g/mol * 2 e-5 molls * 0 .. 784 = .001.55 g/s = 48 .. 9.5 g/ year.
Therefore 10,000 kg/year / 48 .. 95 kg/ year = 204 reactors are needed.
P4-19 (C)
Assuming laminar flow, a - D
p

2
, therefore
a
z
= a
1
D ~ 1 = (3 . .55x10
5
kg -1) 4 = 14.2x10
5
kg-
1
DP2
4-41
2.0 ... -5.---------------,
16 ... -5
lj
"F:l
. lih
- Fe
1.2\'-5
80\'-6

OOHO ':'()e-':' l..4e-6 W2.1e-6 2.8e-6 3.5('-(;
P4-19 (d)
10 .----------------,
0.8

W
0.6 .
OA
02
0.0 __________ __l
0 .. 01'+0 ':'.Oe-':' 1.41'-6 ",,2 . .1e-6 2.8e-6 3 .. 5e-6
A lower conversion is reached due to equilibrium, Also, the reverse reaction begins to overtake the forward
reaction near' the exit of the reactor"
P4-19 (e) Individualized solution
P4-19 (f) Individualized solution
P4-19 (g) Individualized solution
P4-20 (a)
Mole Balance
Rate Law
=z lA' IF ...
o
dW ...
k' :.:;;; k 11 ;;;; k[!:r( t!> com t!> ""'1)J
<l> ':' c Dp
4-42
k' k'
i1 - 1 k' = Tl k, k = - = - = k" = 3
1.0H;:::::::::::;1..-.._ 11 1
Largen ..
Then
cD p Increasing Particle Size
3 3
11 == :;;:: -_ ..""
<l> cDp
when Dp::: 2 mm, k' ::: 0.06, 11:::;: {,= 0.02
3
0.02=: c(2)
,:=75

2{3
For turbulent flow: a =- "
constant
=>a=------
Dp
aoDpo
a =--"-----.:..:..
Dpl
P4-20 (b)
PoAop(l- fjJ)
See Polymath program P420"b.pol.
4-43
3.0
2.4
1.8
Q
1.2
0.6
0.0
0.0 04 0.8
Dp 12
16 2.0
P4-20 (C)
Gas, =0, C
A
=C"Q(l-X)y
i
y
' whele
Ct, = ki:S2 d;;;'r 708 x 10' kg'
and
?Y
a
;:;;;
dW 2)'
See Polymath program P4 ..20e.pol.
POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
w 0 0 100 100
X 0 0 0 .. 5707526 0 .. 5707526
Y
1 O. 2366432 1 0 .. 2366432
Dp 0 .. 0075 0 .. 0075 0 .. 0075 0 .. 0075
Q
0.5625 0 .. 5625 0 .. 5625 0 .. 5625
Fao 5 5 5 5
4-44
0 .. 00944
0.207
alpha
Cao
kprime
ra
0 .. 00944
0.207
2.9385672
-0.1259147
2 .. 9385672
-0.1259147
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(X)/d(w) = -ra/Fao
[2] d(y)/d(w) = -alpha/21y
Explicit equations as entered by the user
[lJ Dp = .. 0075
[2J Q = 75*Dp
[3J Fao = 5
[ 4 J alpha = .0000708/Dp
[5J Cao = .207
[ 6 J kprime = 3*(3/QA2)*(Q*coth(Q)-1)
[7 J ra = -kprime*(Cao*(1X)*y)A2
P4-20 (d) Individualized solution
P4-20 (e) Individualized solution
P4-20 (1) Individualized solution
P4-20 (g) Individualized solution
P4-20 (h) Individualized solution
P4-21 (a)
Assume constant volume batch reactor
dX
Mole balance: CAD - = -r
A
dt
0 .. 00944
0.207
2 .. 9385672
-0.0012992
0.90
0.72
0.54
036
0.J8
0.00
0.0 0.1
Rate law and stoichiometry: - r
A
= kC A = kC AD (1- X)
Specific reaction rate: k ( 25 C) = 0.0022 weeks-
l
Combine:
x dX --1
t = CAD f----- = --In (1- X)
D kC AD (1- X) k
--}
52.2 weeks =1 In (1- X)
0.0022 weeks-
X =0.108
0.00944
0 .. 207
2.9385672
-0 .. 0012992
0.2 Dp 03
0.4 0.5
C A = CAD (1- X) but since volume and molecular weight are constant the equation can be written as:
m A = mAD (1- X)
4-45
6500IU = mAO (1-0.108)
mAO = 7287IU
%OU = CAO -C
A
*100 = 7287 -6500 *100 = 12.1 %
C
A
6500
P4-21 (b)
10,000,000 lbs/yr = 458 * 10
9
glyr of cereal
Serving size = 30g
Number of servings per year = 458 * 10
9
/30 =1.51 * 10
9
servings/)'1
Each serving uses an excess of787 IU = 4 .. 62 * 10-
4
= 1.02 * 1O-
6
1b
Total excess per year = (L51 * 10
8
servings/yr) * (102 * 1O-
6
Ibs/serving) = 154111b/yr
Total overuse cost = $100/lb * 154.1 Ilb/yr = $15411 /)'1. (trivial cost)
P4-21 (C)
If the nutrients are too expensive, it could be more economical to store the cereal at lower temperatures
where nutrients degrade more slowly, therefore lowering the amount of overuse .. The cost of this storage
could prove to be the more expensive alternative. A cost analysis needs to be done to determine which
situation would be optimaL
P4-21 (d)
k ( 40 C) = 0.0048 weeks -) 6 months = 26 weeks
x dX -1
t = C AO f ( ) = -In (1- X )
o kC
AO
1- X k
-1
26weeks =-- )In(1- X)
0.0048 weeks-
X =0.12
C A = C AO (1 - X) but since volume and molecular weight are constant the equation can be written as:
m
A
=mAo(1-X)
6500IU =mAo(1-0.12)
mAO = 7386IU
%OU = CAO -C
A
*100= 7386-6500_*100=l3.6%
C
A
6500
P4-22 No solution necessary
P4-23
CH
2
0HCH
2
CI + NaHC0
3
-7 (CH
2
0Hh + NaCI + CO
2
4-46
A + B
FAa = 0.1 mol/min = 6 mol/hI'
P4-23 (a)
Mole balance:
dC A = r + Vo (C - C )
dt V AO A
!:!C B = r + V
0
(_ C )
dt V B
Rate law: r
A
= -kCAC
B
V =Vo +Vot
See Polymath program P4-23-a.pol.
POLYMA Results
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
Ca 0 0
Cb 0.75 1. 395E-13
Cc 0 0
Faa 6 6
Caa 1.5 1.5
k 5.1 5.1
Va 1500 1500
va 4 4
V 1500 1500
r 0 -0.0039398
Xb 0 0
Nc 0 0
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Ca)/d(t) = r+(voN)*(Cao-Ca)
[2] d(Cb)/d(t) = r+(voN)*(-Cb)
[3 J d(Cc)/d(t) = -r+(voN)*Cc
Explicit equations as entered by the user
[1] Fao = 6
[2J Cao = 1..5
[3 J k = 5.1
[4] Vo = 1500
[5] vo = Fao/Cao
[6] V=Vo+vo*t
[7] r = -k*Ca*Cb
[8] Xb = 1-Cb*V/(O.75*1500)
[9] Nc = Cc*V
c + D
maximal value
250
0.15
0.75
0.829586
6
1.5
5.1
1500
4
2500
0
1
2073.9649
4-47
+ E
dCc = -r + Vo (-- C )
dt V C
final value
250
0.15
1.395E-13
0.829586
6
1.5
5.1
1500
4
2500
-1.067E-13
1
2073.9649
LO
0 .. 8
0.6
04
0.0
0 50 100 t 150 200 250
0.90....------
- Ca
0.72 '
054'
036
1118

o 50 100 t 150 200 250
P4-23 (b)
O,Oe+O"-j
D /
I
-8.0e-4
I I
-1.6e-3 I I
l /
-2 Ae-31 /
I /
! " .."P,""";'#'/
-3.2e-3 \
1 /
1
1
"
, ,/.i'
_-I.Oe_3l.!s:::..," __ --:'
o 50 100 t 150 200 250
3000.---------------,
2400
600
o
I)
50 100 t 150 200
Taking average time for activities like charging, heating, cleaning = 4..5 hr
So, if there is one batch per day, the time for reaction = 24-4.5 hr = 19.5 hr
Since at the temperature at which we are operating the reactor no side reactions occur, the quickest way to
run the reaction will be at the highest flow rate of A (2 mol/min or 120 mol/hour)
But at 19.5 hours and a flow rate of 120 mol/hr, 1560 dm
3
would be added to the reactor.. Because the
volume of the reactor is 2500 dm
3
, and there is already 1500 dm
3
of B in the reactor, the reaction cannot not
run for 19.5 hours at a flow rate of 120 mol/hr (2 mol/min)
Also, because there is 1500 dm
3
ofB at a concentration of 0.75 M, there are only 1125 moles ofB to react.
This means about 750 dm
3
of 15 M A is all that can be reacted. More A may be added to the reactor to
keep the reaction rate high as the concentration of B drops, but adding twice the necessary volume would be
a waste of time and material (on top of being physically impossible !)..
To add 1125 moles of A at a rate of 120 mol/min takes 9375 hours. Using the Polymath code from part (a)
and changing Fao to 120 and the time to 9375 gives 1107 moles of C. Allowing the reaction to go for 9.5
hours results in 1115 moles of C and a reaction time of 10 hours gives 1124 moles of C.
Now consider multiple batches per day.. If two batches are run, then there will be 9 hours of downtime,
meaning that the time for the reaction will be 15 hours - split between the two batches, with a maximum
4-48
batch time of 10 hours., The following table shows the tluee possible times for reactions and the moles of C
that are formed from the two batches.
Maximum Batch Time Total Moles of C
(hr) Formed
10 1723
9 1790
8 1795
.. -
So the best setup will be to run 2 batches per day. One batch will run for 8 hours and the second batch for 7
hours. Both will be run with a flow rate of 2 mol/min of A.
(If tlu'ee batches are run there will be 135 hows of downtime and only 105 hours for the reaction. A
maximum of 1257 moles of C can be formed if the time is split evenly for each batch (3.5 hows).)
See the Polymath code from part (a) and vary time and flow rate.
P4-23 (C)
F
AO
= 0.15 mol/min = 9 mol flu
vo = FaofCa = 9 molJlu f 1.5 mol/dm
3
= 6 dm
3
flu
1000 dm
3
is needed to fill the reactor. At 6 dm
3
flu it will take 166.67 hows
Now solving using the code from part (a) with the changed equations:
See Polymath program P4-23-e.pol.
1.0 ,-------. ----,
0.8
0.6
0.4
66 t 99 132 165
P4-23 (d) Individualized solution
P4-24
NaOH + CH
3
COOC
2
H
s
------t CH
3
COO- Na+ + C
2
H
s
OH
A B ~ C D
449
Mole balance:
dec =-r+ va (-c)
dt V C
Rate law:
V=Va+Vat
k =koex
p
( !Uo -nJ
To produce 200 moles of D, 200 moles of A and 200 moles of B are needed. Because the concentration of
A must be kept low, it makes sense to add A slowly to a large amount of R Therefore, we will start with
pure B in the reactor. To get 200 moles of B, we need to fill the reactor with at least 800 dm
3
of pure R
Assume it will take 6 hours to fill, heat, etc .. the reactor. That leaves 18 hours to cany out the reaction. We
will need to add 1000 dm
3
of A to get 200 moles in the reactor. We need to check to make sure the reactor
can handle this volume if only 1 batch per day is to be used .. Since we add 1800 dm
3
or 18 m
3
and the
reactor has a volume of 4.42 m
3
we can safely carry out a single batch per day and achieve the necessary
output of ethanol.
Now vary the initial amount of B in the reactor, the flow rate of A, and the temperature to find a solution
that satisfies all the constraints .. The program below shows one possible solution ..
See Polymath program P4--24.pol.
POLY1VIA TH Results
Calculated values of the DEQ variables
Variable
t
Ca
Cb
Cc
Cd
ko
Fao
Cao
Vo
vo
T
k
ra
V
Nc
initial value
o
o
0 .. 25
o
o
5.2E-05
0.04
0 .. 2
1200
0 .. 2
308
1.224E-04
o
1200
o
ODE Report (RKF45)
minimal value
o
o
0 .. 0068364
o
o
5 .. 2E-05
0 .. 04
0.2
1200
0 .. 2
308
1..224E-04
o
1200
o
Differential equations as entered by the user
[11 d(Ca)/d(t) = -ra+(vo/V)*(Cao-Ca)
[2] d(Cb)/d(t) = -ra-(vo/V)*Cb
[3] d(Cc)/d(t) = ra-(vo/V)*Cc
[ 4] d(Cd)/d(t) = ra-(voN)*Cd
Explicit equations as entered by the user
maximal value
6 .. 5E+04
0.1688083
0 .. 25
0 .. 0151725
0 .. 0151725
5.2E-05
0 .. 04
0 .. 2
1200
0 .. 2
308
1 .. 224E-04
1.397E--06
1 .. 42E+04
202 .. 92284
4-50
final value
6.5E+04
0 .. 1688083
0 .. 0068364
0.0142903
0 .. 0142903
5.2E-05
0 .. 04
0 .. 2
1200
0 .. 2
308
1 .. 224E-04
1.. 412E-07
1 .. 42E+04
202 .. 92284
[ 1] ko == 5 .. 2e-5
[2] Fao == .04
[3] Cao ==.2
[4] Vo == 1200
[5] vo == Fao/Cao
[ 6] T == 35+273
[7] k == ko*exp42810/8.3144)*(1/293-1fT))
[8] ra == k*Ca*Cb
[9] V == Vo+vo*t
[10] Nc == Cc*V
P4-25 (a)
A B + 2C
To plot the flow rates down the reactor we need the differential mole balance for the three species, noting
that BOTH A and B diffuse through the membrane
dF
A
=r -R
dV A A
dF
B
=r -R
dV B B
dF
c
--=r.
dV c
Next we express the rate law:
First-order reversible reaction
Transport out the sides of the reactor:
kACroF
A
RA = kAC
A
= -.!.!......!..!!.-!.!..
FI
kBCroF
B
RB = kB C B = --"'--'-""--':::..
Fr
Stoichiometery:
Combine and solve in Polymath code:
See Polymath program P4-25-a.pol.
POLYMA TH Results
Calculated values of the DEQ variables
4-51
Variable initial value minimal value maximal value final value
v 0 0
Fa 100 57 .. 210025
Fb 0 0
Fe 0 0
Ke 0.01 0.01
Ft 100 100
Co 1 1
K 10 10
Kb 40 40
ra -10 -10
Ka 1 1
Ra 1 0 .. 472568
Rb 0 0
Fao 100 100
X 0 0
ODE Rel!ort {RKF4S1
Differential equations as entered by the user
[1 ] d(Fa)/d(v) = ra .. Ra
[2] d(Fb)/d(v) = ra .. Rb
[3 ] d(Fe)/d(v) = -2*ra
Explicit equations as entered by the user
[1] Ke = 0..Q1
[2 J Ft = F a+ Fb+ Fe
Co = 1 [3 ]
[4]
[5]
[6]
[7 ]
[8 ]
[9]
K= 10
Kb = 40
ra = - (K*Co/Ft)*(Fa- CoI\2*Fb*FeI\2/(Ke*FtI\2))
Ka = 1
Ra = Ka*Co*Fa/Ft
Rb = Kb*Co*Fb/Ft
3 r-...,....,---------.----- 100
2
2
1
1
0
0
. .j
8
P4-25 (b)
~
--
~ . ~
12
v
16 20
80
60
40
20
(I
20 20
100 57.210025
9.0599877 1. 935926
61.916043 61.. 916043
0.01 0.01
122.2435 121.06199
1 1
10 10
40 40
-0.542836 -0.542836
1 1
1 0 .. 472568
2.9904791 0.6396478
100 100
0.4278998 0.4278998
...,.......... . ~ ....... ...
o 4 8 12
y
16
The setup is the same as in part (a) except there is no transport out the sides of the reactor ..
See Polymath program P4-25-b.pol.
POL YMAIH Results
4-52
20
Calculated values of the DEQ variables
Variable initial value minimal value
v 0 0
Fa 100 84.652698
Fb 0 0
Fc 0 0
Kc 0.01 0.01
Ft 100 100
Co 1 1
K 10 10
ra -10 -10
Fao 100 100
X 0 0
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Fa)/d(v)::: ra
[2] d(Fb )/d(v) ::: -ra
[3] d(Fc)/d(v) = -2*ra
Explicit equations as entered by the user
[1] Kc = 0.01
[2] Ft = Fa+ Fb+ Fc
[3] Co=1
[4] K=10
[5] ra = - (K*Co/Ft)*(Fa- CoA2*Fb*Fc"'2/(Kc*FtA2
maximal value final value
20 20
100 84.652698
15.347302 15.347302
30 .. 694604 30.694604
0.01 0.01
130.6946 130 .. 6946
1 1
10 10
-3.598E-09 -3.598E--09
100 100
0.153473 0.153473
0.50 -------------------
0 .. 45
0.40
0.35
0.30
0.25
[
--]
- X PFR
... X l\fembmn.
0.20
0 .. 15
-.---.. ----.-............ ............ -.--.-...--.."".....--_ ........_---_ ...
0.10
0 .. 05
0 .. 00
t-________ .. ________ __ _
0 2 4 6 8 10 V 12 14 16
P4-25 (C) Conversion would be greater ifC were diffusing out
P4-25 (d) Individualized solution
4-53
18 20
P4-26
co + H
2
0 ...... CO
2
+ H2
A+B ...... C +D
Assuming catalyst distributed uniformly over the whole volume
dF
A
dF
B
dF
e
Mole balance: ._- = r --= r --= -r
dW dW dW
Rate law: r = r = r = -.y' = -1 = -k [c C _ CeC D]
ABC D AB K
eq
RH2 = KH2 CD
Stoichiometry:
FD
CD=C
ro
-
FT
FT = FA + FB + Fe + FD
Solving in polymath:
See Polymath program P4-26.pol.
POLYMA TH Results
Calculated values of the DEQ variables
variable initial value minimal value maximal value
-----
W 0 0
Fa 2 0,,7750721
Fb 2 0,,7750721
Fe 0 0
Fd 0 0
Keq 1,,44 1.44
Ft 4 3.3287437
Cto 0,,4 0.4
Ca 0,,2 0.0931369
Cb 0.2 0.0931369
Kh 0,,1 0.1
Ce 0 0
Cd

0
Rh

0
k 1.. 37 1.. 37
r -0,,0548 -0,,0548
ODE Report (RKF45)
Differential equations as entered by the user
[ 1 J d{Fa)/d{W) = r
[2 J d{Fb)/d{W) = r
[ 3 J d{Fc)/d{W) = -r
[ 4 J d{Fd)/d{W) = -r -Rh
Explicit equations as entered by the user
[1] Keq = 1..44
[ 2] Ft = Fa+Fb+Fc+Fd
[3] Cto = 0.4
100
2
2
1,,2249279
0.7429617
1,,44
4
0.4
0.2
0.2
0.1
0.147194
0,,0796999
0,,00797
1..37
-0,,002567
4-54
dF
D
--=-r-R
dW H2
final value
100
0.7750721
0,7750721
1.2249279
0,5536716
1. 44
3,,3287437
0,,4
0" 0931369
0,,0931369
" 1
0,,147194
0.0665322
0.0066532
1..37
-0,,002567
[4] Ca = Cto*FalFt
[ 5] Cb = Cto*Fb/Ft
[6] Kh=O,,1
[ 7] Cc = Cto*Fc/Ft
[ 8] Cd = Cto*Fd/Ft
[9] Rh = Kh*Cd
[10] k= 1 .. 37
[11] r = -k*(Ca*Cb-Cc*Cd/Keq)
For 85% conversion, W = weight of catalyst = 430 kg
In a PFR no hydrogen escapes and the equilibrium conversion is reached.
K = CeCD = = _ X_2_ = 1.44
eq CACB __ X)2 (l_X)2
solve this for X,
X= 5454
This is the maximum conversion that can be achieved in a normal PFR.
If feed rate is doubled, then the initial values of Fa and Fb are doubled. This results in a conversion of 459
2 .. 0 r;;----;::====;_
1.6
1.2 _ .. ,,,.,---_ .....--...
0.8
04
20 40 W 60 80 100
P4-27 Individualized solution
P4-28 (a)
Assume isothermal and =0
therefore, P=Po(l-aWl
5
1=10 (1-.01 glW).5
W=99g
P4-28 (b)
4-55
dX -r
A
dW= F
AO
.!..=(l-Wa)-'
Po
-r
A
=kC
A
C
A
==C
A
o(l-X) PlPo
C
A
= C
A
o(1 -X) (1 - 0.01 W).5
Integrate from X=O to X=.9
ax = kC
AO
(1-X) (l-.01W).5
dW F
Ao
W=59.88g
Fust 5% conversion integrate from X=O to X=.OS
W=1.31 g
Last 5% conversion integrate from X==.85 to X=.90
W:alO.85 g
P4-29 Individualized solution
P4-30 (a)
First order gas phase reaction,
C6HjCH(CH3h -7 C 6 ~ + C ~
Y AO = 1, g = 1 [; = 1
P kC
AO
Y=-,a=--
Po F
AO
For aPBR:
dX a(1-X)
dW = (1 + iT y ........................ (1)
dy (I+X)
-= a" ....................... (2)
dW 2y
X = 0.064 and y = 0 .. 123,
Solving (1) and (2) by trial and enOl on polymath we get,
a = 0.000948 (kg of catalystr
1
a = 0.000101 dm-
3
4-56
Now solve for a fluidized bed with 8000 kg of catalyst.
FAOX
Mole balance: W =--
-r
A
Rate law: -fA = kC
A
I-X
Stoichiometry: C A = C AO ---
I+cX
Combine: W = X (I + eX) = 8000 = ___ . X (I + X)
a(1-X) O.OOOlOI(I-X)
X =0.37
P4-30 (b)
ForaPBR:
dX _ a(1-X)
dW - (I+XfY
dy _ (I+X)
---- - '-"--a
dW 2y
where a = kC AO
F
AO
From chapter 12 we see that k will increase as Dp decreases_ We also know that for turbulent flow
I
a- - .. This means that there are competing fOIces on conversion when Dp is changed ..
Dp
I
We also know that alpha is dependant on the cross-sectional area of the pipe: a - ._--
Ac
But alpha is also a function of superficial mass velocity (G). If the entering mass flow rate is held constant,
then increasing pipe diameter (or cross-sectional area) will result in lower superficial mass velocity .. The
relationship is the following for turbulent flow:
I 2
G-- and a-G
Ac
I
therefOIe, a _. -'2 .
~
If we combine both effects on alpha we get the following:
I I
a---
c ~
I
a--
~
So increasing pipe diameter will lower alpha and increase conversion and lower pressure drop ..
457
For Laminar flow:
1
a--
D2
p
so decreasing the particle diameter has a larger effect on alpha and will increase pressure drop resulting in a
lower conversion
1
For Laminar flow a- G and so a .-. -2 .
A;
This means increasing pipe diameter will have the same trends for pressure drop and conversion but will
result in smaller changes.
P4-30 (c) Individualized Solution
P4-31 (a)
I> = 0..33(1-3) =-0..666 P
AO
= 0..333*10 F
Ao
= 13.33 K = 0. .. 0.5
Mole balance: dXldW = -ralFao
Rate law: rA = -KPB
P A = P AO(l - X)/(l - o..666X)
Pc = P AoXl(l - o. .. 666X)
For a = 0., Y = l(no pressure dlOp)
10..---------------#_-
8
6
4
2
o
I)
20 to W 60 80 100
See Polymath program P4-31-a .. pol.
Results
Calculated values of the DEQ variables
Variable
W
X
K
Pao
Pa
Pb
Pc
Fao
ra
initial value
--------
o
o
0.05
3 .. 33
3 .. 33
6 .. 66
o
13 .. 33
-0 ... 333
minimal value
o
o
0 .. 05
3 .. 33
0.0406732
0 .. 0813464
o
13 .. 33
-0.333
0 .. 00 .-----------.--$-.__---:=
-0.08
-0.16
-0.24
1
/
-032/
-040 L-__ _____ ___ ....J
o 20 40 \V 60 80 100
maximal value
100
0.995887
0 .. 05
3.33
3 .. 33
6 .. 66
9.8482838
13 .. 33
-0 .. 0040673
final value
100
0.995887
0 .. 05
3 .. 33
0 .. 0406732
0.0813464
9.8482838
13.33
-0 .. 0040673
458
esp -0.666 -0 .. 666
ODE Report (RKF45)
Differential equations as entered by the user
[1 j d(X)/d(W) = -ra/Fao
Explicit equations as entered by the user
[1] K = 0.05
[2] Pao = 0 .. 333*10
[3] Pa = Pao*(1 - X)/(1 - 0 .. 666*X)
[4] Pb = 2*Pa
[5] Pc = Pao*XI(1 - 0 .. 666*X)
[6] Fao = 13 .. 33
[7] ra = -K*Pb
[8] esp = -0.666
For first 5% conversion weight required = WI = 2 kg
For last 5% conversion weight required = W 2 = 38 kg
Ratio = Wi WI = 19
Polymath solution (4-34 a)
P4-31 (b)
For a = 0 .. 027 kg
l
,
Polymath code with pressure drop equation:
See Polymath program P431-b.pol.
POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value
w 0 0
X 0 0
Y
1 0.1896048
K 0.05 0.05
Pao 3 .. 33 3 .. 33
Pa 3.33 0.4867002
Pb 6 .. 66 0.9734003
Pc 0 0
Pao 13.33 13 .. 33
ra -0.333 -0 .. 333
esp -0.666 -0.666
alfa 0 .. 027 0.027
ODE Report (STIFF)
Differential equations as entered by the user
[1] d(X)/d(w) = ra/Fao
[2] d(y)/d(w) = -alfa*(1 - esp*X)/(2*y)
Explicit equations as entered by the user
[1] K=0 .. 05
[2] Pao = 0.333*10
[3] Pa = Pao*(1 - X)*y/(1 - 0 .. 666*X)
[4] Pb = 2*Pa
[5 J Pc = Pao*X*y/(1 - 0.666*X)
[6] Fao=13.33
-0 .. 666 -0 .. 666
maximal value final value
30

0.4711039 0.4711039
1 0.1896048
0.05 0.05
3.33 3.33
3.33 0.4867002
6 .. 66 0.9734003
1.0583913 0.4335164
13.33 13 .. 33
-0.04867 -0 .. 04867
-0.666 -0 .. 666
0.027 0.027
7.0
5.6
42
2.8
14
4-59 0.0
6 12 W 18 24
[7 ra = -K*Pb
[ 8 esp = -0.666
[9 alfa = 0,,027
0.00,---------------,
0 4 0 ~ ~ ~ ~ ~
o 6 12 W 18 2-t 30
P4-31 (C)
1) For laminar flow:
Diameter of pipe = D and diameter of particle = Dp
Now DIlDo = 3/2 so G
I
= 4/9G
o
a = (constant)(GID/)(lIAc)
So a = ao(G/Go)(Dpof Dpl )2(DofDI)2
= ao(4/9)(2/3)2(2/3)2 = 0 .. 00237 kg
1
1.0 .....,...------.--------,
0.8
0.6
0.4
0.2
0.0 L-_____ _______ --'
o 6 12 W 18 24 30
Less pressure drop and more conversion for same weight of catalyst as in part (b).
2) For turbulent flow:
~ eX) G
2
IDp
a = (constant)(G
2
IDp)(lIAc)
So, a = ao(G
I
/G
o
)2(Dpof Dpl )(DofDl)2
= ao(4/9)2(2/3)(2/3)2 = 0.0016 kg!
Again less pressure drop and more conversion for the same catalyst weight
It is better to have a larger diameter pipe and a shorter reactor, assuming the flow remains the same as
through the smaller pipe.
P4-32 (a)
At equilibrium, r = 0 => cAe B
4-60
1.O,-:::::==========;
0.8
0.6
04
0.2

0081:0 5.181:4 1 0 .. 1:5 t 1 56E5 2.07E5 2591:5
C (l-X(C xJ= (CAOXY
=> AO BO V AO K
o C
VOC
AO
[X2 x]
=> t= +
VOC
BO
,Kc(l'-X)
Now solving In polymath.
See Polymath program P4-32-,a.pol.
P4-32 (b)
See Polymath program P4-32-b.pol.
POLYMATH Results
Calculated values of the DEQ variables
initial value minimal value maximal value final value
0 0
---
1.SE+04
'-L5E+O-4-
t
Ca 7.72 0 2074331 772 0.2074331
Cb 10.93 7.6422086 10.93 9.51217
Cc 0 0 3.2877914 1.41783
Cd 0 0 3.2877914 1. 41783
Kc 1.08 1. 08 1 08 1 08
k 9.0E-Os 9 OE-05 9.0E-OS 9.0E-Os
ra -0.0075942 --0.0075942 1.006E-Os -1.006E-OS
va 0.05 0.05 0.05 0.05
Va 200 200 200 200
V 200 200 950 950
X 0 0 0.9731304 0.9731304
1.0e+o
Differential equations as entered by the user
.. .........
". -.-- .. ... ... ...
..,.'
8.0e--l
../',;',."
[oJ
,
I .. -,
! --_ ..
f
6.0e-l I
I
ODE Report (RKF4S)
40e--l
2.0e--l
4-61
O.Oe+o 0
2976 5952
t
8928 11904 14880
[1 d(Ca)/d(t) = ra - Ca*voN
[2 d(Cb )/d(t) = ra - voN*(Cb- 10 .. 93)
[3 d(Cc)/d(t) = ora - vo*CcN
[4 d(Cd)/d(t) = ora - vo*CdN
Explicit equations as entered by the user
[1 J Kc = 1.08
[2] k = 0,00009
[3] ra = -k*(Ca*Cb - Cc*Cd/Kc)
[4] vo = 0,05
[5] Vo = 200
[ 6] V = Vo + vo*t
[7] X = 1 - Ca/7.72
-1.6e-3
-3.2e-3
-4.8e-3
6 . ..:/e-3 '
D
-8.0e-3 L-
o 2976 5952
t
8928 1190-1 1,4880
Polymath solution
P4-32 (c)
2(le+l ....------------.,
1.6e+1
c;:J<
.. '

ell
L2e+l
8.Ue+O I\'-_--------l

t),Ue+O
o 2976 5952
t
8928 11904 1-1880
Change the value of Vo and C
AO
in the Polymath 1 II ,-------.
program to see the changes
P4-32 (d)
As ethanol evaporates as fast as it forms: CD=O
Now using part (b) remaining equations,
Polymath code:
See Polymath program P432d.po!.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value
maximal value final value
t 0
Ca
Cb
k
ra
va
Va
7.72
10.,93
9.,OE-05
--0" 0075942
0,,05
200
o
0.0519348
6.9932872
9,OE-05
-0,0075942
0,,05
200
08
11,6
04
11.. 2
0.0
I) 1189 2378 t 3567 4756 5945
6000
7 .. 72
10,,93
9"OE-05
-3,,69E-05
0.05
200
6000
0,,0519348
7.8939348
9"OE-05
-3 .. 69E-05
0.05
200
4-62
V 200
X 0
ODE Report (RKF45)
200
o
Differential equations as entered by the user
[1] d(Ca)/d(t) = ra - Ca*voN
[2] d(Cb)/d(t) = ra - voN*(Cb- 10.93)
Explicit equations as entered by the user
[1 J k = 0.00009
[2] ra = -k*Ca*Cb
[3] vo = 0.05
[4J Vo = 200
[5] V = Vo + vo*t
[6] X = 1 - Cal7. 72

-8.0e-.3 0

1189 2378 t .3567 4756 5945
P4-32 (e) Individualized solution
P4-32 (0 Individualized solution
P4-33 (a)
Mole balance on reactor 1:
C
- dN
Al
. _ 1
CAOV
AO
- Alv-rAlV --- with V
AO
--V
o
dt 2
C dN
-.AQ. v -C v-r V=--..A!...
2 0 Ai Al dt
Liquid phase reaction so V and v are constant
CAO CAl _ dCAl
--- - ---- - r - -----
2r r Al dt
Mole balance on reactor 2:
20
16
12
8
4
500
0_9932727
500
0_9932727
------.-------
.....-..." ..-.... --........................ .--.' .........,._ ..... .,..
{I ____ --!
o 1189 2378 t 3567 4756 5945
4-63
CAl C
A2
,_ dC
A2
------r --
T T A2 dt
Mole balance for reactor 3 is similar to reactor 2:
, _ dN
A3
C
A2
V
O
-C
A3
VO -r
A3
V ----
dt
C
A2
C
A3
_ dC
A3
------r ---
T T A3 dt
Rate law:
--r
Ai
= kCAiC
Bi
Stoichiometry
For parts a, b, and c C
Ai
= CBi
so that -r
Ai
= ~ i
See Polymath program P4-33"pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value
t 0 0 100
Cal 0 0 0,8284264
Ca2 0 0 0,,7043757
Ca3 0 0 0.6109587
k
0"
025 0,,025 0.025
Cao 2 2 2
tau 10 10 10
X 1 0,3890413 1
ODE Report (RKF45)
Differential equations as entered by the user
4-64
final value
100
0.8284264
0.7043757
0.6109587
0.025
2
10
0" 3890413
[1] d(Ca1)/d(t) = (Cao/2 -Ca1)/tau -k*Ca1A2
[2] d(Ca2)/d(t) = (Ca1 - Ca2)/tau -k*Ca2A2
[3] d(Ca3)/d(t) = (Ca2 - Ca3)/tau -k*Ca3
A
2
Explicit equations as entered by the user
[1] k = 0,,025
[2] Cao=2
[3] tau = 10
[4] X = 1 - 2*Ca3/Cao
From Polymath, the steady state conversion of A is approximately 0.39
P4-33 (b)
99% of the steady state concentration of A (the concentration of A leaving the third reactor) is:
(0.99)(0.611) = 0.605
This occurs at t =
P4-33 (C)
The plot was generated from the Polymath program given above.
0.90 r------------------,
0.72
0.54
- Cal
0.18
- Ca2
- (:a3
o 00 ~ : . . . . - - ........ - - ~ - - - - - - - - - - - . - - - - - - I
. 0 20 40 60 80 100
t
P4-33 (d)
We must reexamine the mole balance used in parts a-c. The flow rates have changed and so the mole
balance on species A will change slightly. Because species B is added to two different reactors we will also
need a mole balance for species B ..
Mole balance on reactor 1 species A:
dN
AI
. 2 200
CAOV
AO
-CAlv-rAIV =--- wIth VAO =--V
o
and Vo =--
dt 3 15
2C
AO
dN
AI
-_v -C v-r V=---
3 0 Al M ~
Liquid phase reaction so V and v are constant
4-65
CAO CAl dCAI
------r =--
27: 7: Al dt
Mole balance on reactor 1 species B:
, _ dN
BI
CBOV
BO
-CBIV-yBIV --- and
dt
Stoichiometry has not changed so that -rAi = --lBi and it is a liquid phase reaction with V and v constant
CBO C
BI
,_ dC
BI
------Y ---
37: 7: Al dt
Mole balance on reactor 2 species A:
We are adding more of the feed of species B into this reactor such that V2 = Vo + VBO = 20
C
dNA2
CAlVO - A2
V
2 - r
A2
V =--
dt
Mole balance for reactor 3 species A:
dNA 3
C
A2
V
2
-C
A3
V
2
-r
A3
V =dt
C
A2
C
A3
,_ dC
A3
------Y ---
7: 7: A3 dt
2 2
Mole balance for reactor 3 species B:
, _ dN
B3
C
B2
V
2
--C
B3
V
2
--,Y
A3
V-
dt
C
B2
C
B3
,_ dC
B3
------Y
A3
--
7:2 7:2 dt
Rate law:
4-66
See Polymath program P4-J3-d.po1.
POLYMA TH Results
Calculated vaiues of the DEQ variables
Variable
t
Cal
Ca2
Ca3
Cb1
Cb2
Cb3
k
Cao
tau
X
tau2
V
vbo
initial value
o
o
o
o
o
o
o
0 .. 025
2
13.333333
1
10
200
5
ODE Report (RKF45)
minimal value
o
o
o
o
o
o
o
0.025
2
13.333333
0.3721856
10
200
5
Differential equations as entered by the user
[1 J d(Ca1 )/d(t) = (2*Cao/3 -Ca1 )/tau -k*Ca1 *Cb1
[2 J d(Ca2)/d(t) = Ca1/tau - Ca2/tau2 -k*Ca2*Cb2
[3 J d(Ca3)/d(t) = (Ca2 - Ca3)/tau2 -k*Ca3*Cb3
[4] d(Cb1 )/d(t) = (1 *Cao/3-Cb1 )/tau-k*Ca1 *Cb1
maximal value
100
1.1484734
0.7281523
0 .. 6278144
0.4843801
0.7349863
0.6390576
0.025
2
13.333333
1
10
200
5
[5] d(Cb2)/d(t) = Cb1/tau+Cao*vboN-Cb2/tau2-k*Ca2*Cb2
[6 J d(Cb3)/d(t) = (Cb2-Cb3)/tau2-k*Ca3*Cb3
Explicit equations as entered by the user
[1] k=0.025
[2J Cao =2
[ 3 1 tau = 200/15
[ 4 J X = 1 - 2*Ca3/Cao
[5] tau2 = 10
[6] V = 200
[7] vbo = 5
Equilibrium conversion is 0.372 ..
This conversion is reached at t = 85.3 minutes ..
4-67
final value
100
1.1484734
0 .. 7281523
0.6278144
0_4821755
0.7291677
0.6309679
0.025
2
13.333333
0.3721856
10
200
5
2.0 .------------------,
- Cd
1.6
- Cal
1.2
0.8
---,_."._" ...... "" ..".,,---1
0.4
0.0 = - - ~ - - - ' - - - - - ~ - - ~ - - - - '
o 20 40 60 80 100
P4-33 (e) Individualized solution
CDP4-A
CH3I + AgCl0
4
~ CH
3
Cl0
4
+ AgI
0.7 molll CE31 ;= CBO
0.5 moli1 AgCI0
4
~ CAD
V '" 30 dm
3
o
C C
3/2
tCH
3
1 ~ -k ;CH
S
IAgCI0
4
k ~ 0.00042 (dm
3
!mol)3!2(sec)-1 T=298 K
I "" 0.93
v = V
o
CDP4-B
a)
4-68
Integration for! "" 0.98, solved lll!lllerically
1 .
t = ~ - - - . - . (24.18)
0.00042 (O.5)3fb
t " 1.628:t10
5
sec '" 4S.:2 hr
:VIol.! Babnce :
d=". - F' "
-"-'=1:"' - ...-r v
dt <\..1 ,\
= C v- C v kC., V
dt'" 0 ';0...
.. :::5: A. V.e,. _
dt V V
Use POLYMATH: to plot C" vs. t
Eqgal::ions '.
d(ca) Jd (t.) '" (caovo/v) (ca"" (k"v+vo) Iv)
cao=4 .. S
vo=70000
v",15000000
k"O.0025
t.O '" O. I::
f 1000
.... sc:;:
1.
(b) C,a lIS t
,
,

,
I .
':.&.aoC . .. . . ........... .,._.
o"coo :3..'%00 f:I.':X
For steady-state:
t ::.:: 4.6 -...:..... .. ::::: 641 !:us
1 + 1:'k:
C
A
;:;; .CADV. ::::2.930mgldm
3

t
99% of this is 1.905 mg/dm \. which l5 below rhe standard of 3.0 mg/dm) ..
Polymath solution(Ans CDP4-B-a)
b)
Mole Bal::Ulce :
dN
... : ... .i..:= F - F -+ r V
dt .-I" ." ...
Use POLYMATH [0 gener.ate plot of C ... and N" 'IS. L
Em;"-
d(nal/d( cl ..
cao",4.5
yo,,,,70000
vouc=50000
11:=0.0025
"=20000"1::
ca=na/v
t
f '" '150'
Ke.!
.. Na
T
I -
,.=
.

4-69
Na vs t
t
.Ku
Ca
Ca vs t
),000
'T
I
/XX) 1
,
i
I,:)',)(l .1
i
Oc,_ L---' -------+------"-,-';O,,-,,,,-"-+----+-I
D..COO lfPl,Q(:)Q :n.a...:;oo "iC...'C:OO 'tu.coo
Polymath solutionCAns CDP4Bb)
c)
tjsc same equaIio[;s as in pan: (a),
but
60
61
07
0,3
4,9
40
d (ca 1 fd (t:) = - lea (}C"_'.-vo) Iv) 41
vo 7 OfJ-() 0
v'" ,:,5 ,,0 noO()
}<=0_0025
1:
f
.EQlymath solutionCAns CDP4Bc)
37
3,3
29
20
d) This part is almost same as part(b) with minor changes:
V = 15000000 - 10000t
Vo= 80000 and V
out
= 70000
The reason the graph looks so different from(a) is that pure water is evaporated, but water with atrazine is
coming in,
45
Polymath code:
44
d(ca)/dt=cao*vo/v)-
43
(ca (kv+vout) Iv)
ca(O)=4.5 #
42
vo = 80000 #
41
V = 15000000 - 10000*t
k = 0.0025 #
40
cao 4.5 # 39
vout = 70000 #
3,8
t(O)=O #
t(f)=1000
3.7
36
3,5
100 200 300 400 500 600 700 800 900 101
Polymath solutionCAns CDP4-B-d)
CDP4-C
a)Find the number of moles of receptors:
10 cells ;5 receptors 1 mole receptors l000mL -10
I x 10 "'----" * 1 x 1 O-m,--,,_- *,'''---------------''""- '*' '--'-'--'-"-. - == 1.66 x 10 M
mL cell 6.022 x 1023 receptors L.
1_66 XW'lO + .OlL:: 1.66 x 1O-
12
moies
.',. L' " .
Design equation:
Rate Law:
Stoichiometry:
Where:
dX
N ---::-r
AO dt A
C
A
= CAo(l- X)
C
s
=CAO(aB-X)
Total number of moles;
1.56 x 10-
12
+ 1 X 10-9 == 1.002 X 10-9
hence;
Combining and solv41g:
dX k<:;'odt
== ii:
o
'
-_.}:"--, In .. =
8'/1 ,1 aB{l" X) N
AO
t=O.071mm
b) Assume en == egO
Design Equation:
Rate Law:
Stoichiometry:
ax
N -- == "r
,1.0 dt A
C
A
= C;\O(1 X)
C
B
= eRG
4-71
Combine and solve:
1- X N
Ao
1 kCAOCBOt
In .---...--. :::: ...-....----...-.-
A very good approximation ..
c) Design Equation:
RateL1.w:
Stoichiometry:
Combine and solve:
1 -- X N A.O
t==O.069 min
dX
N ---=:.-r
AO dt A
C
A
== C"o(l- X)
Co == CSO
C
c
=:' C"oX
N kjCAo(l X)C
so

dX dt
kjCAOCSO kfCAOCBO -krCIlOX NAO
x dX 5 CAodt
S .... X'-
D k/'BO--X(kjCslJ"f k,) 0
1. kfC
no
_ .sC
AO
-........... ---.. -.-- -........ --- In ... -----...... . .......... _ ...-... --.... -- -.................. -:-. - .----
kfC
SO
+k, kjClJ()--X(kjC
so
+k,) NAo
...L .. --.ln -.--. -- -. = 500
.. 1+ ,1 ,1 XC.l + .. 1)
X =0.5
CDP4-D
Batch reaction: 2A + B -) 2C
kj = L98 feJIbmoLmin, k2 = 9..2 X 10
3
(feJIbmolilmin
V = 5 gal =0. .. 67 fe, x = 0..65 .
C
AO
= 0. .. 0.0.2 IbmollO.67ft
3
= 2 .. 98 x 10-
3
Ibmol/ft
3
CBO = 0..0.0.18 IbmollO.67fe =2.69 x 1O-
3
lbmollft
3
dNA
Mole Balance: --- = -r V
dt A
Rate law: -rA = kjCAC
B
+ k
2
C
A
C
B
2
Stoichiometry: C
A
= C
AO
(1-X)
C
B
= C
Ao
(8
B
-(b/a)X) = C
Ao
(D .. 9 - D5X)
4-72
Combine:
dX 2 r 2]
CAD - = CAD (1- X)lk
l
(0.9 - 0.5X) + k
2
C AD (1- X)(0.9 - 0.5X)
dt
Integrating between X=O to X=O.65 for t = 0 to t = t gives
t =24.1 min
CDP4-E
Ha..--__ -..
e.
io----......... ;>
A,.
"'r
a
= k C!:!A C
n
"'
Liquid feed is a mixture of A and B YAo = 1 - YSo= 0.999
Finally
F
AF
, FH2f
FBF C
BF
(ete)
Y
BF
"" 10-
5
Because of the low concentration of B in the feed, such properties as SG, the specific
gravity, M
w
, the molecular weight, and the solubility of H2 are essentially that of
component A. assume that any H2 depleted via reaction is instantaneously replaced via
absorption of H2 gas over the liquid reacting mixture. Then at 500psig,
4-73
;:(. :r [ __ .x (.L...1l!.ll..J
l 1 l 2& 454 g:tloles g!'.l
.020 81
zal
.UfL.:U!L.aI.

1
v
o
constant .. or
P Jl 0
2.
r.'
!:to' 1.'0
-----
V
.;l
U:.ing ec;,nll.tio:;. for 3. CSTR
(89_3 zallhrHO.:.21L....... __ _
50 .. d (Q .QZQ8 11,r'9U (0.01)
,11.1
k = 0.49 x 10
3
- hr)
C
a
0.G127 IbwoleJgal
2
Let
is:
(
300+14.7)
::: 500+14 * 1
4-74
3 .72
,5
10 Ibmolel;;a.l
314.7 1""'01.,
{.020l0 l'Si'4:71 Ed
~ (SO gal)(S.49x10
3
gal/lbmol-hrHO.0127 Ibmol/g-all
1-1 = 89.3 gal/h.r
2
F = en v = (.0127 Iba
o1e
)(S9.4
g
al) = 1.134 Ibmole/hr
B
2
,F <';2.F 0 gal hr
CDP4-F
(3.72x10-
3
) (1-0.984) = 1.23xlO-S
1-'1.34+3.72
NAo ~ = VpC (.rJ "" VPC kCA
Uqtlid Phase CA "'" CAO OX) "'" ~ ~ (IX)
QX= Pc k {I Xl
de ,
t
X
In--
L
-.
(I-X)
o
o
o
5
.3
.36
10
.5
.69
4-75
20
.73
1.31
30
.85
1.89
40
0.93
2.66
50
.97
3.:5
A. plot In i:; lir:ear v.n rime so we concllmc me reaction is filsi order in 5. 6
benzz:roqumoline with k'=O.o,, th'''':'
f '" .... , ... ".ru ...... '" 6248 oK
___ .30. __ _
(353{383 ))
E ;;; 12,414 .;.:;;i
mol
k (363)
k (36.3) =: 0,63 k (373)
'.:2.,5.. "" (.63) (2) k: :: 126 k'
- kl Pel 1 1
In --L..."" k't
i-X
't
X
CDP4-G
o
o
Develop a design equation
10
057
20
0.82
Mole balance: F ACr) - F ACr + L1r) + rAC2nrMh) = 0
30
0.42
40
0.97
_ FA (r) FA (r + _ (2 h) _ dFA - (2 h)
m m
dr
Rate law:- r
A
= k1C ACB
Assuming 8
B
=1 and E = 0
50
0,,99
Stoichiometry: C A = C AO (1- X) and C B = C AO (e B - X) = C AO (1- X)
dF
A
dX
Also FA = F
AO
(1- X) => --= -F
AO
- = r
A
(2mh)
dr dr
4-76
x
By Integration we get: ---
I-X
b) Now, with the pressure drop,
C
A
= C
B
= CAO(l-X)y
Hence, -r
A
=kC
A0
2
0-X)2y2 =>
dX _ 2mhkC AO
2
0_ - X)
2
Y
2
dr
Where y = (1- aW)1I2 and
2 2 h
W = PbJZ"(r - RO )
Using polymath, following graph is obtained:
Differential equations
d(X)/d(r) = 2*3 .. 1416*h*k*Ca0"2/Fao*(1-X)1\2*yI\2*r
y = (1-alfa*W)"O .. 5
W = density*3_1416*h*(rI\2- 1'0"2)
ro = 0,,1
density = 2
Cao = 0.1
Fao = 10
k=0,,6
h=O.4
alfa = 0 .. 07
variable name: r
initial value: 0.1
= J (21lkC AO
2
)rdr
Ro F
AO
"",,----_._-----------,
1 ~ G"phTItl.
tJ2&3
oro. ' - - ' - - - _ ~ - - - ' - _ ~ ____ .
~ ~ ~ ~ ~ ~ ~ ~ m
,
.. ,. .....
c) Increasing the value of k increases conversion while decreasing it decreases the conversion" Increasing
F AO will decrease the conversion and decreasing it will increase the conversion. Increasing C
AO
causes a
dramatic increase of conversion.. Similarly, decreasing CAoresults in a large decrease in conversion.
Increasing the height will only slightly increase the conversion and decreasing the height causes a real small
decrease in the conversion. Increasing Ro decreases the volume ofthe reactor and hence decreases the
conversion. Increasing RL will increase the conversion as volume increases ..
4-77
CDP4-H
Liquid phase rexrion
A+B--rC
BATCH
L Mole balance on batch reactor
2. Ratelaw
-1'A "'" Ie eACa
3. SroichiCll:!l!'!try
vellmixed
no inflov or outtloll
liquid phase V "" V" (batCh) (if flow u = u",]
4. C.ommne
4-78
Table of reaction imegrals can be found in Appendix A-lO.
a)
I. Niok baIa...,ce on CSTR
2. RateLaw
3. Stoichiometry
liquid phase u ::::: U
o
4, Combine:
5. Parameter evaluation
10 moUmin (0.9)
V=: -------. ..._--
(o,m d:a:J!l/mol min) (2 lllOvd,m3f(1-0.9)2
b) V"", 22500 4m
3
1. Mole bala.'1ce onPFR
F AO JiX.::::: -fA
'dV
if!lQ pressure OJ.' phase change (liquid phase) therefore
V F ~ o r ~
2. Ratelaw
4-79
PFR
C:
A
:;= fM = Cl--A)
U DO
F,,,,,ieR_hX\
C::s :::: :: __ __ .,.....1t., .... (:AD (IX)
'J -UO
(A
V""rAO I
10
.
liX)'-
5, P== evaluation
v = ..... ___ :-QQ.rooVrrrin} ___ ,if1g
(01 cio:r'Jmol min)(2 rnolJdm'J .
d) Solution si::::ni1:at to part (a) ro (e)
e) Arequilibrium ,,,,,=0
t KcJ
Kc - _Cce .... = ,.,.CAolL.= __ .. ,..x._ .. _
- CAe CJl" C'idl-xf CAd)-Xf
x
1 .,. 2X +- X
2
"" _X,.= X.
KCN) 4
X2-2.25X-t 1=0
.dX.",.::!A.""kC rC (1-X'I1.X.j""kC
2
0
[(lXf,:;- .. X .. J
dV FAG AOl AO I Kc A \ KcCAol
V", 250 f6 ....... " ... .,iX",.,", .... _.
- ")-'''' X' o 1 JA, +,
V", 250 15) -+ ,3) + .. i\ 6}]::::
150 Q'j 5 [11 4{ 141)t 2(241). 4{5.26) +100J
V", 250 + +
.:;: 250 llir 1., +-li2Al) + 4{5 26) + 100J
3 c"'\
'" 1656 c:n'
CDP4-I (a)
4-80
Benzene is A
-r =k (C
2
_ CBC
C
)
A A A K
c
for equilibrium - r
A
= 0 :.
4Kc:{1-Xc'f =Xc
2
4Kc - SKcXc: + 4KcXc
2
= Xc
2
0.2X2 - 2.4Xc: + 1.2 = 0
Xc: =0.52
CDP4-I (b)
PFR
Design Equation: V = FAD I dX
-rA
RateLaw: -r =k (C
2
_ CBC
C
)
A A A K
C
Stoichiometry : C C (1 X)
CB
= C Ao
X
C = C ADX
,,= AD - 2 c 2
C Ao = = 5 atm = 0.OO371bmol
RT (0.73 fe atm K1859.67-R) ft3
lbmol- R )
4-81
v= F
Ao
r dX
kC!c, [O-Xy _ X
2
]
4K,
Combine:
V _ (IOlbmoUminXlminl60s) rX dX
- (ISOOfellbmol.sXO.OO37Y Jo [(I-XY -O.S33X
1
]
v - 6 76ft
3
rX dX
-. Jo &-2X+O.167X
z
]
v-
67
1 1
- . \. (O.617X11.45-0.523) 11.45 X-O.523 U
CDP4-I (c)
CSTR
v = 13.5fe
Design Equation: V = FAOX
-rA
RateLaw: -r. =k.( C! _ )
Stoichiometry: C
A
=CAo(l-X) C
a
= C
c
=
Combine: V = FAo
X
!:J
V = (lOXO.51X1l60) . = 147.73ft3
(1800XO.oo37)'[(l-0.51)' -(
CDP4-1 (d)
Amount processed in CSTR ;
(10 IbmoVminX60 minlhr X24 hrlday)= 14,400 IbmoVday
4-82
Batch
t-C J d.X - C
Ao
J d.X
- Ao -::;-- kC
2
[ X
2
]
A Ao (l-xf--
4Kc
t __ I ( 1
- kC
Ao
(O.167Xl1.45-0.523) 11.45 x -0.523 U
t = 0.30s
Taking into account the time it takes to clean the reactor and other down time assume that
the total time per run is 4 hours. Assuming that the reactor can be used twenty-four hours
a day there can be 6 runs per day.
14,400 Ibmollday = 2400 Ibmollrun
6 runs/day
t = N Ao f dX :. V = N Ao J dX
V -rA t -rA
V - N Ao 1 ( 1 In[0.523 (X -11.45 In)
-t kC!o (0.167Xl1.45-0.523) 11.45 X-O.S23 U
v- 2400 ( 1 1
- (4X1800XO.0037Y (O.l67XU.45-0.523) n 11.45 X-O.S23 U
V = 48,690fe
CDP4-1 (e)
E = 30,202 btullbmol
for X =0, -r
A
=kC!o
- rA(800) k800C!o k800 E ( 1 1 )
- r
A
(l400) = k'400
C
!o = k
l400
= exp R T2 - Tl
. -
- rA(800) = ex 30,202 btu/lbmol ( 1 _ 1 )
-tA(I400) P 1.987btullbmol-R 1259..6rR 185?67R
-r
A(800) = 49
- r
A
(1400)
4-83
CDP4-J
PBR
?vfB:
Combine:
ME:
w : : : ; ~ ~ Q > :
-fA
Combine:
b) We know, s = 0, so
f'...o X
W r; ... ---. .... _ ...... _.
kC
llo
(1 ....... X)
1000::;:: ---
1 X
(I- X)
X =.18
P = Po (1- aW)l!2 => 1 = 20(1-- aW)l!2
=> a = 9.98 x 10.
4
c) For conversion to be maximum, a should be minimum
G
2
1
Also, we know that a is proportional to ---- = 6 2 for turbulent flow
AcDp D
pipe
Dp
G 1
And it is proportional to ---2- = 4 2 for laminar flow
AcDp D
pipe
Dp
Hence for minimum a, Dp and D
pipe
should be increased" d) Yes, we can
increase Dp and decrease D
pipe
(or vice versa) according to the above equation to get the same value of a.e)
1
For assumed turbulent flow,a is proportional to .- 6 2
D
pipe
Dp
4-84
6 2
a
l
_ Dpipe2 Dp2 -1
Now, - 6 2-
a2 D pipe! D pI
Dpipel 4
---''---- = -- and D
p1
= 0.5 cm
Dpipe2 6
=>D
p2
= 0.044 em
. 1 Dpl
t) We're gIven, k - => k2 = kl --
Dp Dp2
k2 0.5
Hence - = ---= 11.4
kl 0.044
g) Rate law: - r
A
= kC A
Stoichiometry: C A = C AO (1 -, X) Y
dX -r
Mole balance: - ... = _-A
dW F
AO
dX k C 2(1_ X)(l-a W)1I2
Combining:-- = 2 AO 2 ,- (forE = 0)
dW F
AO
k2 _ CAOk
l
--4 .. ..
- - 11.4 and = 2 X 10 Integratmg WIth hrruts: (X -70 to X; W -7 0 to 1000) => X = 0.78
kl F
AO
CDP4-K
1. Mole Balance:
dz FM
2, Rate Law : lA ;;:;-k'C:\pc (1-- <p)
wherek',pc' and <p are unknown constants 111CY will be groupedimo one unknown
constant, ko '
3 Stoichiometry:
4-85
Pressure Drop:
when neglecting the turbulent contribution to pressure drop, 0 is given by
r< = G[-
Po ' (T '[)"
,Pooe p<i' ,
where all of the bracketed variables are unknown constl.nts,
(
' ill
J =
Ac
The ma.ss flow rate is also and unkrlOwn constant Thus Po can be written as a
E, over cross sectional area.
where
Where E is a fUllction of the mass flow rate, feed properties, and catalyst PIOpclties-'--<llI
of which are constant f6r part (a). Note that all equations up to now apply to a tnbulal
PBR arld spherical PER To find Band k., we must model the tubular PER on
POLYMATH by entering the above equations in addition to
A
It (70' )2 -'14d Z
(
,,;;;;; '_ om :::: J m
- 4
B and leo must be arbitrarily chosen al first Then, depending on wheLher POLTh1ATH
gives high or Imv values of '/ and X, one Cffi1 converge on the true values and B. In
order to do so efficiently. hm.vevcr, \Jue must rnakc usc of the foHm'iing trends: (Note
that tile tollO\vmg taNe IS completely on.1 Y wIlen c > (J.)
a) from POL YMATIi:
B==S43
k==O.21
x=.67
P=yP
o
=973* 1500=1459 .. 5
4-86
qua&.ions .:.
dey) /d(z) ",beta! (po"y)'
d( x1 1.4fzl=ra,Ac/Fao
po,"2500
'eps;O ,.5
l:'ao"'950
Re10
Cao"'O.4
k=O.:21

AC;=3 .1416" (R
H
2)
Ca;Cao"Y* (l x) I (l.+epsx)
beta;B/Ac

220

d (y) Id(z) ""'oeta! (po"y) .. (l+epsx)
d(x} Id(z) ='ra-}l.c!Fao
po=1500
eps=0.5
l:ao==950
R==25
Cao"'O.4.
k=0.21
ll=84.3
L=24
Ac",3 .. 14lli*{R""2(z"'L) ''''2)
Ca"'Cao"y (l"'xJ 1 (1 + eps"x)
:::'a=-k"Ca .. " 2
beta.="B/AC
Zo : 0, zf = 48
fu:.l
-x
... y
!.QCQ
;
i
....
b) From polymath: Maximum flow rate = 1750 molls
aqua cio!!!!:,
dey} Id(zl= .. oota/ (poy) .. n,epsx)
d(xl/d(z) ",ra"Ac/Fao
",0=,,1.500
ep8=0.5
'''ao=>:1750
"",25
cao==(j .. 4
1<;=0.21
3=843
L"24
Ac==3.1.41.6
w
(a""2 .. (z .. L) .";;l)
Ca""Cao"y (l'-x)! (I+eps"x)
ra='"k-Ca*-,2
beta"B/Ac
Zo '" o.
43
a..DC::'
T
;
4-87
x and y vs z
.. ..--..... _ .. " .......... ..... -" .... ".
"',
x and y vs z
(b) Fao ... 1750
....... -1"...-.-. --..
"C.;3CO
."
c) From POLYMATH
Nllnimum pressurc""gO kPa

d (y) Id (zj ",beta! (po
d (Xl Idl z) -Ac/l"'ao
po"'80
e?so:O 5
Fao",SSO
R:=26
Cao",O .. 4..
k'=O .. 21.
13"'843
L::24
he""3 .1.41.6* (R"'2 (z; ..Ll".2)
Ca::Cao"Y" U .. I fl+eps*xl
:::30= .. 'k"'Ca '" '"2
bee ta=:S I AC
,
d) Flom POLYMATI1:
d(y) Id{:d " ..bet.a/
d(x) Id (z)" .... );.a*Ac/23.0
pO=I.5CO
eps"O S
:;;'ao=950
1<.=25
Cao .. O.4
k=0 .. 21
13",843
he=3 141&*CR2 .. (z-L).'Z)
Ca"'Cao*y (1. xl f

De';:a=B/Ac
43
x:
y
Kex
-x
y
4-88
(c) Po;; 80
Cd)
..... -
""" ',.
1:
... ..".
CDP4-L
(a)
C
Kc::: ._l!
C'"
C .... "" C"'o(l- X) , c.
s
== C",oX
Kc =_.C .... oX .. _.::;:
C",.(l .. X) 1 .. X
X"l "" '" _ . "" 0.33
1-+ Kc 1 -+ 0.5
(b) For a conventional PFR:
dX
FAo--;::;:-r
A
dV
"'r" =k(C .... -Ca/K,}=kCAQ{(l-.X) -XlK
c
)
For the IMRCF:
dF
-"'::::::rv
dt "'.,
== "J:'" v. '" v"kcCs
r
A
:= k{C" ... CafKc)
C
A
::: FAN , en
, (1' .... + FrJ
V =:: v ._._-..... __ .
FA"
Use these equations in POLYMATH to generate plots of the conversion profile.
::1.. 3::0
8. lac
0. :20
8.:.JOC
::leo
4-89
",
l::::.CC
!, -===
o .. ooc
(c)
... fb
............ ......

0.000 18.,::)00 2"1.000 3CLOGC
Use the same equations for the IMRCF in POLYATIi to generate the desired
plot.
2. t::c
tL9GG
..;..
_ .....
1 ceo
4-90
(d) By varying one parameter at a time we can see the effect of each:
Increasing the specific reaction rate causes changes in conversion. concentration.
and molar flow rate [0 occur more quickly ..
Lowering the transpon coefficient (k,) causes an increase in both C
a
and Fa. which
causes a decrease in conversion ..
By raising the equilibrium constant (K.,). we cause a decrease in the molar flow rate
of A and an increase in conversion.,
(e) A signitlcant increase in temperature for an exothermic reac1.ion would drive the
reaction in the reverse This would cause a decrease in X and C
s
and an increase in
the CA'
A significant dect-ease in temperarun.': for an exothermic reaction would cause
increase in the rate of the forward reaction. This would drive up X and C
ll
while
lowering C ....
An increase in temperature would drive an endothermic reaction forward, raising X
and Ca. While lowering C"
A decrease in temperature would cause an increase in the reverse reaction for an
endothermic reaction .. This would raise CA' and lower both X and C
II
.
CDP4-M No solution
CDP4-N
4-91
Y F
A3
F .-
,.1,.0
y 1',.1,.3
F A2 FAl (1-X) "nere X is con.version defined with respect to .'1.1.
F
A1
Stoichiometric :able
t"Al
CDP4-0 No solution
Also
v
2
CAl
lDO
v
1
v.
1
t.A1
100
.-----------------------------------_.----------------
492
CDP4-P
(n)
(b)
At equilibtimll
= k"CCe
k
2
C
nO
.'" k
3
C
AO
A
= --k[C" => C
A
== C
AO
e klt
elt
dec '
, cit = +k;2C
llO
... k3C(,
is it constant
U 1 C
k1t
::::. "1 -AO ,.
Problems fwn, I'robjot
From (I)
de
ell
>0 C:::;
for a minima in ell
4-93
(1)
Initial Condition
eno "" CUe
C ;\(Ii vtoto "" cle t 0,' + CCe
'''0
CCe ""Cc\O
CDP4-Q
CDP4-R
CDP4-S
CDP4-T
CDP4-U
CDP4-V
4-94
Solutions for Chapter 5 - Collection and Analysis of
Rate Data
P5-1 (a) Individualized solution
P5-1 (b) Individualized solution
P5-1 (C) Individualized solution
P5-1 (d) Individualized solution
P5-1 ( e) Individualized solution
P5-1 (0 Individualized solution
P5-1 (g) Individualized solution
P5-1 (h) Example 5-1
The graphical method requires estimations of the area under and above curves on a plot as well as in
reading the intersection of lines on the plot. This can lead to small inaccuracies in each data point
The Finite differences method uses mathematical estimates to calculate the rate. It is only possible to use
this when the time interval of each data point is uniform,
The graphical method uses polynomial regression to approximate C
A
as a function of time. The derivative
of the polynomial is then used to calculate the rate,
P5-1 (i) Example 5-2
Assuming zero order reaction:
Rate law: _.4C A = k'
dt
__ __ __ _______ __ __ ___
17 r=J
zero order reaction
dC t(mln .. )
Rate law: ___ A =k'C
A
dt
5-1
4.5
35
25
2
15
05
1st order reaction
50 100 150
t(min,,)
200 250 300
TI27 1 3.49 1 3.66 1 3.81 13.94 14.05
Since none of these plots are straight lines, its is not 1st order reaction or second order reaction.,
P5-1 (j) Example 5-3 Because when a is set equal to 2, the best value of k must be found.
P5-1 (k) Example 5-4
C
HC10
(moVdm'i)
--
1.0 4.0 2.0 0.1 0.5
: 2 7
-rHel,O(mol / em .s)xlO
L2 2.,0 1.36 0..36 0.,74
<--.
See Polymath program P51k.poL
POL YMA TH Results
Nonlinear regression (L-M)
Model: r = k*(Callalfa)
Variable lni guess
k 0.1
alfa 0.5
Precision
R"2
R"2adj
Rmsd
Variance
= 0,,9812838
= 0.9750451
= 0.0341709
= 0 .. 0097304
Value
1.0672503
0.4461986
Rate law: _r
n
= em
2
.s
P5-1 (I) Example 5-5
rate law: r
CH4
=
Regressing the data

5.2e-3
13.2e-3
30e-3
4.95e-3
7.42e-3
5.25e .. 3
Pco(atm)
1
1.8
4.08
1
1
See Polymath program PS .. I-Lpo1.
POL YMA Tn . .&.!!lts
Nonlinear regression (L-M)
Model: r = k*(PCO"alfa)*(PH2
I1
beta)
Variable lni guess Value
k 0 .. 1 0 .. 0060979
alfa 1 1 .. 1381455
beta 1 0.0103839
Precision
R"2 = 0.,9869709
95% confidence
0.0898063
0 .. 076408
-
--
--
-
95% confidence
6.,449E-04
0.0850634
0,1951217
.5-2
P
H2
(atm)
I
1
I
0.1
-
0.5
-
4
--
--
R"2adj = 0.9782849
Rrnsd = 4.17BE-04
Variance = 2 .. 093E-OB
Therefore order of reaction = 1.14
Again regressing the above data putting fJ = 1
POLYMATH Resu1ts
Nonlinear regression (L-M)
Model: r = k*(PCOAO.14)*(PH2)
Variable Ini guess Value 95% confidence
k o.:r-'--- 0-:.0040792 0.0076284
Precision
R"2
R"2adj
Rrnsd
Variance
= -0.8194508
= -0.8194508
= 0.0049354
= 1.754E-04
Therefore, k = 0..0.0.4 (gmoICHJ(gcat.min .. atm
I14

P5-2 Solution is in the decoding algorithm given with the modules.
P5-3 Individualized solution
P5-4 (a)
The kinetics of this deoxygenation of hemoglobin in blood was studied with the aid of a tubular reactor.
Rate law:
Mole balance:
Hb0
2
-7 Hb + O
2

F
AO
dX
dV
dV = Acdz , where Ac is the tube cross sectional area
therefore,
dX = (1 - X r
dz F
Ao
In(
ken A
where, a = __ ....&Q._L
F
Ao
<
Electrode Position 1 2
.5 Position (cm) 0.
!.5
r
I
f
1 .5
,
3
10
.5
! .......... '-' ,. ,......... .. IT
IConversion ofHb02 (X
A
) I 0..0.0.0.0. 0..0.193 I 0..0.382 I 0..0.568
(l-XA) lioOOD 10.980.7 r 0..9618', 0..9432
.ax
"Ii xl Ii z-(cm:
i
)
I
I
I
'f 0. .. 0.193" r 0..0.189 I
I
0. .. 0.0.386 I 0..0.0.378 0..0.0372
5-3
r .5
20.
5
f
I 0..0.748
'r
,
I
I
,
'r
6 .... !"
I
7
3D
5
Electrode Position
dXldz'(cm-
l
)
A plot XIii vs .. z is then of dXldz are
graphical differentiation:
0 .. 00395
0.0039 dX/dz vs. distance
0 . .00385
0 .. 0038
EO 00375
g 0 .. 0037

0 .. 0036
0.00355
0.,0035
0.,00345
0.,0034
o 25 5 75 10 125 15 175 20 225 25 275 30 325 35 375 40
z(cm)
Using the values obtained above, a plot ofln(dXA/dz) vs. In(l-XA) is produced and a line
is fit to the data
In(dXldz) V$, In(1.Xj

. -
y = 1 0577x- 5 5477
In(1-X)
In( = -S.S477 + l.OS77In (1- X)
n=l
In(a) = -5.S
a = exp(-5.S) = 4 .. 1 x 10-
3
em.
Concentration of blood is 150g hemoglobin per liter of blood
Molecular weight of hemoglobin = 64500
Ac=D., 0 196cm
CAO = 2.3x1W
6
mol I em
3
F
Ao
= 45.7 X 10-
6
moles I s
In ( ) = In a + n In (1 - X )
kCn A
where a = Ao c
, F
Ao
k = FAoa = 4S.7x1O-
6
moles Is .. ____ ( 4.1x1O-3 em) = 4.1s-1
C1of\: 2.3 X 10-
6
moles I em
3
xO.0196em
2
Hence rate law is,
mol
-r
A
=4.1C
A
3
dm s
5-4
P5-4 (b)
First we fit a polynomial to the data. Using Polymath we use regression to find an expression for X(z)
See Polymath program P5--4-b.pol.
POLYMATH Results
Polynomial Regression Report
Model: X = aO + a1*z + a2*z"2 + a3*z"3 + a4*z"4 + a5*z"5 + a6*z"6
Variable Value 95% confidence
aO 2.918E-14
a1 0.0040267
a2 -6.14E-05
a3 7.767E-06
a4 -5.0E-07
a5 1. 467E-08
a6 -1.6E-10
General
Order of polynomial = 6
Regression including free parameter
Number of observations = 7
Statistics
R"2 =
Rl\2adj=
Rmsd=
Variance =
1
o
1.669E-10
1 .. 0E+99
0
0
0
0
0
0
0
Next we differentiate our expression of X(z) to find dXldz and knowing that
In ( ~ = In a + n In (1- X)
ken A
where a = Ao r
, F
Ao
Linear regression of In (.:;-) as a function of In (1- X) gives us similar vaules of slope and intercept
as in the finite differences ..
POLYMATH Results
Linear Regression Report
Model: In(dxdz) = aO + a1*ln(1X)
Variable
aO
a1
General
Value
- ~ . 531947
1..2824279
95% confidence
0 .. 0241574
0 .. 3446187
Regression including free parameter
Number of observations = 7
Statistics
R"2 =
R"2adj=
Rmsd=
Variance =
n= 128
0.9482059
0.9378471
0.0044015
1.899E-04
5-5
In a = -5.53, a = 0.00396
k= FAOa = 2 (3.96xlO-
3
em)= 4.0s-
1
2.3xlO- moles / em xO.0196em
Hence rate law is,
_ = 4 0 C
l
28 mol
r
A
A 3
dm s
P5-5 (a)
Liquid phase irreversible reaction:
A -7 B -+- C; c
AO
= 2 mole/dm3
CAO-CA = kc
a
A
T
In ( C AO ; C A ) = In k + a In C A
Space time ( T )min. CA(molldm
j
)
_.

1.5
38 1.25
100 1.0
-
300 0.75
1200 0.5
-
In(CA)
0.40546511
0.22314355
0
-0.28768207
-0.69314718
By using linear regression in polymath:
InCAO-CA)/T)
-3.4011974
-3.9252682
--
-4.6051702
-5.4806389
-6.6846117
See Polymath program P5-Sa.pol.
In((Cao-CaO/tau) vs In{Ca)
POL YMA TH, Results
Linear Regression Report
Model: y = aO + a1*lnCa
In ( C AO ;- C A ) = In k + a In C A
Variable Value 95% confidence
47.-:6:-::0-=8-=-0-=5:79 0 .. 0162119
a1 2.9998151 0.0411145
Statistics
RI\2 =
RI\2adj =
Rmsd=
Variance =
Hence,
a= slope::3
0 .. 9999443
0.9999258
0 .. 003883
1.256E04
In(k) = intercept = -4.6
therefore, k = 0.01 mole-
2
min-
1
.
dC
A
3 3
Rate law: ---= O.OlCAmol / dm mm
dt
P5-5 (b) Individualized solution
P5-5 (C) Individualized solution
-q.s -0.6 -0.4
-1
-2
y = 2 .. 9998x - 4 .. 6081 -3
-4 ....................... ; ....
......... , .. ..,_._"'.-......' ...-.'.' .. ::s ..
...............
-6
-7
8
In(Ca)
5-6
PS-6 (a)
Constant voume batch reactor: A-7B+C
Mole balance:
_ dCA =kC a
dt A
Integrating with initial condition when t = 0 and C
A
= C
AO
for a =t 1.0
1 C(l-a) - C(1-a) 1 (2)(1-a) _ C(l-a)
t = AO A =_ A
k (1- a) k (1- a)
............. ,' ... ,' "substituting for initial concentration C
AO
= 2
t (min.)
0
5
r---"
9
IS
r---.
22
30

-
60
See Polymath program P56a.pol.
POLYMATH Results
Nonlinear regression (L-M)
Model: t = (1/k)*((2A(1-alfa .. (Ca
A
(1"alfa)))/(1alfa)

2
1.6
1.35
1.1
0.87
--
0.70
0.53
0.35
Variable Ini guess Value 95% confidence
k 0.1 0.0329798 3.628E-04
alfa 2 1.5151242 0.0433727
Precision
RA2 = 0.999'7773
RA2adj = 0.9997327
Rmsd = 0" 1007934
Variance = 0,,0995612
K= 0 . .03 (moVdm
3
yo5"s1 and a = 1.5
dC
A
15 3
Hence, rate law is -._- = O.03C
A
mol / dm .s
dt
PS-6 (b) Individualized solution
PS-6 (C) Individualized solution
PS-6 (d) Individualized solution
PS-7 (a)
Liquid phase reaction of methanol and triphenyl in a batch rector ..
CH
3
0H + (C6Hs)3CCI -7 (C6Hs)3COCH3 + HCI
A + B -7 C + D
Using second set of data, when C
AO
= 0 .. 01 mol/dm
3
and C
BO
= 0.1 mol/dm
3
5-7
--
-----
t (h) C
A
(molJdm
3
)
0 0.1
1 0.0847
2 0.0735
5 0.0526
10 0.0357
-'
Rate law:
-r
A

For table 2 data: C
AO
CBO => -Y'A = k I C; where k I = kC;o
1 - cCl-m) 1 (O.01)(l-m) _ C(l-m)
Using eqn 5-21, t = _. A - A
k I (1- m) k I (1 - m)
See Polymath program P57-a-l.poL
POL XMA l]!.!l.esnlts
Nonlinear regression (L-M)
Model: t = (1/k)*((O.1 !\(1-m))(Ca!\(lm)))/(1m)
Variable
k
m
Ini guess
1
2
Nonlinear regression settings
Max # iterations = 64
Precision
R"2 = 1
R"2adj = 0 .. 9999999
Rmsd = 3268E-04
Var iance = 8 .. 902E-07
Therefore, m = 2
Value
------
L 815656
2.0027694
For first set of data, equal molar feed => C
A
= C
B
95% confidence
0.0109025
0 .. 0021115
Hence, rate law becomes -r
A
= =
Observation table 2: for C
AO
=0.01 and CBO = 0..1
t (h) C
A
(molJdm
3
)-
0 1.0
'(J.278 .
0.95.
r-.----
1.389 0.816
2.78 0.707
--
8.33 0.50
--
16.66 0.37
1 C(l-C2+n)) - C(l-C2+n)) __ 1 (O.l)C-l-n) - C
A
C-
1
-
n
)
t = ___ AO A
k (1-(2+n)) k (-I-n))
5-8
See Polymath program P5-7-a--2.pol.
POL YMA TH Results
Nonlinear regression (L-M)
Model: t = (1"(-1-n)Ca"(--1-n))/(k*(--1-n))
Variable
n
k
Ini guess
3
2
Nonlinear regression settings
Max # iterations = 64
Precision
R"2 = 0.9999078
R"2adj = 0.9998848
Rmsd = 0,,0233151
Variance = 0,,0048923
Therefore, n = 0,,8
Value
0.8319298
0.1695108
95% confidence
0.0913065
0.0092096
Hence rate law is:
__ = 0 17 C
2
C
O
.
8
mol
rA A B 3
dmh
P5-7 (b) Individualized solution
P5-8 (a)
At t = 0, theIe is only (CH
3
hO. At t = 00, there is no(CH3hO. Since for every mole of (CH
3
hO consumed
there are 3 moles of gas produced, the final pressure should be 3 times that of the initial pressure"
P(oo) = 3P
o
931 = 3P
o
P
o
:::o31OmmHg
P5-8 (b)
Constant volume reactor at T = .504C = 777 K
(CH
3
hO CH
4
+ H2 + CO
YAO =1
5=3-1=2
e=5y =2
. AO
hase:
"] 1195
562
V = V
o
( ; ) (1- eX) = Va because the volume is constant.
P=Po(1+eX)
at t = 00, X = X
AF
= 1
5-9
1 dNA N
AO
dX
---=-----=r
V dt Vo dt A
Assume -r
A
= kC
A
(i .. e .. 1
st
order)
C A = C AO (1- X) (V is constant)
dX
Then: C
AO
- =kC
AO
(1- X)
dt
po_oR
and X = 0
cPo
dX 1 dP
Therefore: - = ---
dt cPo dt
_1 :!P = k[l- P-Po] -p)
cPo dt cPo cPo
or dP = k ([1 + e] Po - p)
dt
P dP t
f ------= f kdt
R [l+e]Po--P 0
o
[
cPo ] [2Po] [624 ]
Integrating gives: In ( ) - = In = In = kt
1 + e Po --- P 3Pa - P 936 - P _
624
Therefore, if a plot of In vel sus time is linear, the reaction is first order. From the figure below,
936-P
we can see that the plot is linear with a slope of 0.00048.
Therefore the rate law is:
1.6 +-__ ... j
1.2
0.8 +---------7"'''---------------1
0.4
0+-------------------1
I
o 1000 2000 3000 4000
P5-8 (c) Individualized solution
5-10
P5-8 (d) The rate constant would increase with an increase in temperatme, This would result in the
pressure increasing faster and less time would be need to reach the end of the reaction, The opposite is true
fro colder temperatures,
P5-9
Photochemical decay of bromine in bright sunlight:
t (min) 10 20 30 40 50 60
C
A
(ppm) 2..4 1.7 1.2 0.8 0.6 0,,4
5 4 3 8 2 4
P5-9 (a)
Mole balance: constant V
dC
A
=r =-kC
a
dt A A
Differentiation
T (min) 10 20 30 40 50 60
~ t (min) 10 10 10 10 10
C
A
(ppm) 2,45 1.74 1.23 0.88 0,,62 0..44
~ C A (ppm) -071 0.51 -0..35 -0.26 -0.18
.L\C A ( pp.m )
-0,071 -0,,051
L\t mIll
-0,,035 -0.026 -0.018
0,,06
. : : : : ~
.t 0.,1)4
0 .. 01
., .,.. ,---,_._. .._' " __ -.1.-.;),
10
)0
40 50 50
511
10
-}.a
-4.0
Af I' ter pi oUmg an b 1 erentIatmg y equa area
-dCA/dt 0.082
In( -dCA/dt) -2.501
InCA 0.896
Using linear regression: a = 1.0
in k = -3.3864
k = 0 . .0344 min-
l
P5-9 (b)
!!NA=Vr =F
lit A B
0.061
-2.797
0.554
.-
0.042
-3.170
0.207
r
A
= -0.0344 = -0.0344 . at C
A
= 1 ppm
mm lmm
3. 1.0
0.030 0.0215 0.014
3.507 -3.840 -4.269
-0.128 0.478 -0.821
-
FB = (25000 gal) (0.0344 J(60 IlbS_J = 0.426
lbs
lmm hr 1000mg 19a1 453.6g hr
P5-9 (C) Individualized solution
P5-10 (a)
Gas phase decomposition
A7B+2C
Determine the reaction order and specific reaction rate for the reaction
dC
A
n
Assume the rate law as: --= -kC A
dt
Integrating: t = __ 1 - [ 1 - 1 J
k(n-l) C
A
n
-
1
C
AO
n
--
1
5-12
(
2
n
-
1
-lJ
=>In(tl/2) = In + (1- n)In(C AO)
(n -l)k
Run # C
AO
(gmolllt) t (min.)
- ~ 1
1 0.025
_.
2 0.0133
3 0.01
4 0.05
5 0.075
See Polymath program P510a.pol.
POLYMATH Results
Linear Regression Report
Model: Int = aO + a1*lnCaO
7.7
9.8
1.96
1.3
Var'iable Value
a:o-- -2:"'3528748
a1 -1.0128699
95% confidence
0.1831062
0.0492329
General
Regression including free parameter
Number of observations = 5
Statistics
RJ\2 =
RJ\2adj =
Rmsd=
Variance =
0.9993004
0 .. 9990673
0 .. 0091483
6 .. 974E-04
3.0 --.-------------.
24
1.8
1.2
0.6
0 .. 0 L-. _____ __ _
-4 .. 61 -4.20
-3 .. 80 In(dojO
-2 .. 99 -2.59
From linearization, n = 1- slope = 2 . .103;:::;; 2
(2
a
-
1
_l)e-interLePI it
k=- . =10 . .52 ----
a-l gmol.min
5-13
In t InC
Ao
-
1.410987 -3.6888795
2.0412203 -4.3199912
2.2823824 -4.6051702
0.67294447 -2.9957323
0.26236426 -2.5902672
_ dC
A
=1O.5C/gmolllt.rnin
dt
'" .c
See Polymath program P5- lOa,pol.
POL YMA TH Results
Nonlinear regression (L-M)
Model: t = ((2J\(a1 ))1 )/(k*(a1 ))*(1/CaOJ\(a 1))
variable
a
k
Precision
R"2
R
A
2adj
Rrnsd
Variance
Ini guess
2
10.52
= 0 .. 9986943
= 0.9982591
= 0 .. 0531391
= 0.0235313
Value
1. 9772287
8.9909041
C aO
95% confidence
0.093057
3 .. 9974498
Rate law:
dC
A
9 2 11'
----- = .OC
A
gmol t.mm
dt
PS-IO (b)
We know,
(
2
a--l - 1) ( 1 J
k = t1l2 (a- i) C AO a-I
Solving for k at 110 C
k'= (2(2-1) -1)( __ 1_)=20 it
2(2-1) 0.025(2-1) gmol.rnin
i:. \1
Rln k2 (8.314 J )In. 20
From these values, E = kl = mol.K 10.5 = 76 . .5 kJ/mol
U -;J -
5-14
ij
P5-11
0
3
+ wall loss of 0
3
kJ
0
3
+ alkene products k2
Rate law:
dCo C
0
3
= __ 3 =kJ
. dt C
oz
Using polymath nonlinear regression we can find the values of kl and k2
Run ozone rate Ozone concentration
# (mol/s.dm
3
) (mol/s.dm
3
)
Ozra C03
1 1.5e-7 0.01
2 3.2e-7 0.02
3 3.5e-7 0.015
4 5.0e-7 0 .. 005
5 S.Se-7 0.001
6 4.7e-7 O . .oIS
See Polymath program PS 1 l.pol.
POL YMA TH Results
Nonlinear regression (L-M)
Model: Ozra = k1 +k2*Cbu/C03
Variable
k"l--
k2
lni guess
2.0E-07
0.1
Nonlinear regression settings
Max # iterations = 300
Precision
R"2
R"2adj
Rrnsd
Variance
Rate law:
= 0.7572693
= 0.6965866
= 4.531E-08
== 1 .848E-14
Value
3 .. 546E-07
0.0528758
Butene concentration
(mol/s.dm
3
)
Cbu
le-12
le-ll
le-lO
le-09
Ie-OS
le-09
95% confidence
4.872E-ll
1.193E-05
-ro, = (3.5xlO-
7
)+(O.05) mol/dm
3
.s
0
3
P5-12
Given: Plot of percent
decomposition of N0
2
vs V IF AO
X= % Decomposition of N0
2
100
Assume that -r
A
=
5-15
F X
ForaCSTR V
-r
A
v x x
or --=--=--
FAD -r
A

V
withn=O, X =k--
FAD
V
X has a linear relationship with -- as
FAD
shown in the figure ..
Therefore the reaction is zero order ..
P5-13
Si0
2
+ 6HF H
2
SiF
6
+ 2H
2
0
N
s
= moles of Si0
2
= AcPsD
MWs
Ac = crosssectional area
Ps = silicon dioxide density
MW s = molecular weight of silicon dioxide = 60.0
o = depth of Si
N
F
= molesofHF= wpV
lOOMW
F
w = weight percentage of HF in solution
P = density of solution
V = volume of solution
MW
F
= molecular weight ofHF = 20 .. 0
Assume the rate law is -r
s
= kC;
dN
Mole balance: __ S = rs V
dt
_ l\;Ps do _ k( wV ]a V
MWs dt lOOV MW
F
__ do = _ kMWs __ Vwa
dt lOOa !\Ps MW
F
- do = fJwa where fJ = _(--. __ ]a V
dt lOOa !\Ps MW
F
In(- = InfJ + aln w
5-16
In( -
-16,629 -15.425 -1432 -13.816
In w 2.079 2,,996 3.497 3689
where (- dJ) is in
dt rom
FlOm linear regression between In ( - and In w we have:
slope = a = 1.775
intercept = In = -20,462 or = 1.2986 * 10-
9
-13.479
3.871
.,..------:-""'-----------------,
2.5 3 3.5
-
.. 14
-
:g
Il,}
-15 "a
y ;: 1.7746x - 2Q.461
"C
t
-c:
.. 16
-
17
In w
kMWs (p Jl775
fJ = 1001775 AcpsMW:;- V
Ac = (10 * 10-
6
m) (lOm)( 2 sides )( 1000 wafers) = 0.2 m
2
MWs =60-
g
-
gmol
Ps = 2.32
L
= 2.32 *10
6
-.1]
ml m
(Handbook of Chemistry and Physics, 57
th
ed, p"B-155)

ml m
3
MW =20-
g
-
F
gmol
V = 0.5 dm
3
= 0.0005 m
3
fJ = 1.2986 * 10-
9
5-17
1.2986 * 10-
9
=

_--.!!L
20-
g
-
gmol
1.775
k = 3.224*10-'7 min-
I
(
3 J0775
gmol
5-2.316
Final concentration of HF = ( 0.2) = 0.107
5
Initial concentration of HW = 0.2 (given)
dN
F
dN
s
Mole balance for HF: --= 6--
dt dt
weight fraction = 10.7%
weight fraction = 20%
_ pV .dw = 6k( wp Ja V where u = 1.775
100MW
F
dt 100 MW
F
_lO
f
7_ dw t
fdt
WI 775 100MW
20 F
_1_( __ 1_) 10.7 = 6(3.224*10-
7
)( 10
6
J
o
.
775
t
0.775 W0
775
20 20*100
__ 1 _1_) = 2 389*1O-4t
0.775 10.7775 20775 .
t=331 min
P 5-14 (a)
A + 3B -7 C + 2D + E
Observation table for differential reactor
Temperature(K) Cone., Of
rm-
A(molJdm3)
SQ,-- c--.
333 0.10
343 0.05
-,- -
353 0.10
,--
363 0.20
363 0.01
Space time for differential reactor = 2 min
V= F;, = VoC
p
--r
p
-rp
-
Cone, Of
B(molJdm3)
0.10
0.10
0.10

0.01
0.01
5-18
-
--
Cone., Of Rate
C(molJdm3) (mol/dm
3
.min)
-
0.002 0.001
--
0.006 0.003
0.008 0.004
,--
0.02 0.01
0.02 0.01
-,-
0.01 0.005
r, = C
p
= CCzH4
p r 2
Rate law:
rc
Cc =Ae(-BIT)CC
2 A B
Where, A is Arrhenius constant
B = activation energy/R
x is the order of reaction WIt A
Y is order of reaction WIt B
C
A
is the concentration of C
2
H
4
Br
C
B
is the concentration of KI
Now using data for temperature 323K, 333K, and 363K, for finding the approximate value of B because, at
these temperature, the concentration of A and B are the same. Using polymath, the rough value of B =
55o.o.K
While using polymath for solving the rate law apart from guessing the initial values of n, m, and A , we
change the value of B in the model to get the optimum solution .. So after trial and enOf we got B = 65o.o.K
See Polymath program P5-14-a.pol.
POLYMAI!! .. Results
Nonlinear regression (L-M)
Model: r = A*exp(6500/T)*Ga
A
x*Cb
A
y
variable Ini guess Value
A---- 3 .. 6E+05 3 .. 649E+06
x 0.25 0.2508555
Y 0.2 0 .. 2963283
Precision
R"2
R"2adj
Rmsd
Variance
= 0,,9323139
= 0.8871898
= 3 .. 615E-04
= 1.568E-06
Hence, by nonlinear regression using polymath
A = 3649E+o.6(mole/dm3
r
2 6(1/s)
E = 65o.o.R = 54,,0.15 KJ/mol
x = 0..25
y= 0..30.
hence,
95% confidence
2.928E+04
0.0032606
0.0020764
rc = 3.64E + 06e(-54015 / mole/dm
3
.min
P 5-14 (b) Individualized solution
P5-15 (a)
5-19
Modell: Monod equation
dCc JlmaxCsCc
--= r = - - - ' = = ' - - - - - ~
dt g Ks + C
s
See Polymath program P5-15a.pol.
POL YMA TH Results
Nonlinear regression (L-M)
Model: rg = (umax)*Cs*Cc/(Ks+Cs)
variable lni guess Value
umax 1 0 .. 3284383
Ks 1 1.694347
Precision
R"2
R"2adj
Rmsd
Variance
P5-15 (b)
= 0.9999439
= 0.9999327
= 0.0038534
= 1A55E-04
Model 2: Tessier Equation
Tg =tL={I-ex
p
( - ; J]Cc
See Polymath program P515-b.pol.
POLYMATH Results
Nonlinear regression (L-M)
Model: rg = umax*(1exp(-Cs/k))*Cc
Variable
umax
k
Precision
lni guess
0.5
100
R"2 = 0 .. 9999454
RA2adj = 0 .. 9999345
Rmsd = 0 .. 0038004
Variance = 1.415E-04
Value
0.3258202
20.407487
Tg =0.33[I-ex{ ~ ~ J ]CC Wdm'h
P5-15 (C)
Model 3: Moser Equation
r = f.1rruJ.x
C
c
g 1 + kC --Y
S
See Polymath program P51Sc.pol.
POLYMATH Results
Nonlinear regression (L-M)
95% confidence
0 .. 00686
2.2930643
95% confidence
0.0034969
5.7120407
5-20
Model: rg = umax*Cc/(1+k*CsJ\(-y
Variable
umax
k
y
Precision
RA2
RA2adj
Rmsd
Variance
P5-16
Ini guess
0.3
1.6
1
= 0 .. 9999447
= 0 .. 999917
= 0.0038269
= 1.794E-04
Value
0 .. 3265614
162,,599
2,,0892232
95% confidence
6.984E-04
34.273983
0.0461489
O.33C
c
---...:::.....,--- gldm
3
.h
1 + 162.6C s (-2.1)
Thermal decomposition of isopropyl isocynate in a differential reactor ..
--r------ --
Run Rate Concentration Temperatwe
1
2
3
4
5
6
Rate law:
- A (-EIRT)C
n
--r
A
- e A
Where, A is Arrhenius constant
E is the activation energy
n is the order of reaction
(mol/s.dm
3
) (mol/dm3)
4.9 x 10-
4
0.2
1.1 X 10-
4
0.02
2.4 x 10-
3
-
1--------
0.05
2.2 X 10-
2
0.08
1.18 x 10-
1
0.1
1.82 x 10-
2
0.06
C
A
is the concentration of isopropyl isocynate
See Polymath program P516 .. pol..
POLYMATH Results
Nonlinear regression (L-M)
Model: rA = A*exp(-E/(8 .. 314*T*(CA)An
var'iable
A
E
n
Ini guess
100---
1000
1
Nonlinear regression settings
Max # iterations = 64
Precision
RA2
RA2adj
Rmsd
= 0 .. 6690419
= 0.4484032
:::: 0 .. 0097848
Value
1.01E+04
5.805E+04
1.7305416
95% confidence
327.35758
237.32096
0 .. 0134196
5-21
-(K)
700
750
800
850
900
--
950
Variance = 0.,0011489
Hence, by nonlinear regression using polymath
A = 10100 (mole/dm
3
r
2
6(1/S)
E = 58000 J/mol
n = 1.7
therefore,
-YA =lOlOOexp ( mole/dm
3
s
CDP5-A
Given the reaction P + NH;PH -? NHzOHP
where P is Penicillin and NH10HP is hydroxylamine acid (denoted by subscript HA)
Let A """ Absorbency, then CHA, ::; KA where K is some constant.
Cp """ Cp., (1,,, X) (s = 0 for liquid phase reaction.)
KA
C
HA
= Cp"X "'" KA .', X= when X = 1 and A = A..
C
v
"
C
Att=- A =,.......l:2.
- K
Assume reaction is irreversible: - rp' := kC; := kC;" (1- X)*'
1 dN dC?
For a batch. constant volume reactor: = -,-= To
Vdt dt l."
or dA"",.-kC;o(l-X)"=,-kC;"(l-A/A_)"
dt dt A_ dt
or
Try integral analysis first. Assume that reaction is zero Older:
Then K or rdA = A = Kt a plot of A vs. t should be linear if
dt Jo
reaction is zero order. FlOm the plot below, it is evident that the reaction
is not zero order;
06
05
4-
4)
(,,) 0.4 '
c
I
.-
..Q
03" ...
(:)
::L_-
II)
..Q
<
o 10 20 30 40 50
Time
5-22
Next, assume that the reaction is first order;
dA A ciA t (A -A)
- :;:: K( A_ - A) or J . :;:: J Kdt ::: In . - == - Kt
dt 0 (A .. _. A) 0 A ...
. A plot of (A_ - A) VS. t on semi -log paper should be linear .
_ _ ...... __ .. __ . _ _ .................. _ ....... ______ _ _. "W' _ _ ......... __
.. -..-....."-.. ....... -.. -, ....---...-.. -, ..... -..-.-.. .. '-...... . . ~ . . ..............,-
. ~ : ..... w... .......-2C--.. - ..... 30-............. --.40-........... ..
*--_ .. _ ........... _ ................ _ ................... _ ................................................ --..
Time A
A.,.-A
0 0 0.685
10 "'om -0.348
..
t-20"-
0.433 0.252 ..
. -
30 0.495 0.190
40 0.539 0.146
50 0.561 0.124
..
0.685 0
"'"
0.1 ................ - .. - .....- ,-. , .................................................. - . .,..... ..". .......................... _"' ...... -
Time
It is evident from the plot that the reaction is not first order. Try second order:
?A "" K(A_ .. Al _,
dt
or _... . !. .. -.- ::::: ... !_. +- Kt ..
(A_-A) A_
1
A plot of------ vs. t should be linear
(A_-A)
o
--1'0
'-20
30
A A.. .. A
o 1.460
0.33'1" "-'2.967
0.. . . 68--
'"40 0.539
50 0.56 f -8])65
s ........ __ ..-.. -... _ .......................................... .
8
7
2
o


o 10 20 Time 30 4U 50
From the plot, it is evedent that linear relationship exists between (VAx, - A) and time;
Therefore the reaction is second order ..
CDP5-B
Determine the reaction order and specific rate constant for the isomerization reaction:
Rate law:
a dC
A
-rA=kC
A
=-_.-
dt
A7B
5-23
.. --.:r;-... -.. -.-.. ----.--.. -.-...... --.. -..... - ..... - ... -.--.--.---....... -
Iime_(min) .. ___ . CA (mol/dm) . -f,.CA/f,.t .-dCA/dt ........ ____ .. _
o 4 0 .. 39
3 2.89
5 225
8 1.45
to
12 065
15 0.25
17.5 0.07
Plot of log --dCA/dt vs log C
A
shows a. "" 0.5
de.,
kA
CDP5-C
0.37
035
0.32
0..30
0 .. 267
0.25
0.225
0 .. 21
0\75
0.15
0.133
0.1
0.072
0 .. 06
Ethane hydrolysis over a commercial nickel catalyst in a stirred contained solid reactor.
H2 + C
2
H
6
-7 2CH
4
P
A
= CART =CAoRTCl- X) =PAoCl- X)
P
B
=CBRT=CAORTCB
B
-X)=PAoCB
B
-X)
X =!SFTO Y
p
Cl+BB)
2F
AO
2YAO 2
I I FAOX Fp Y pFAO
-r A =-r B=- W--'--2W = 2W
.- r'A = kP
A
a p
B
P
InC-r'A) = Ink + aInP
A
+ fJInPB
y = Ao + Al Xl + A2 X 2
FTo(gmollh) PAO(atm) PBO(atm)
YCH4
X Q PA(atm) PB(atm) -rA(gmollkg .. h)
0.0 0 .. 0
1.7 0 . .5 05 5 5 1 0.475 0.475 1.0625
0.0 0 .. 0
1.2 05 05 7 7 0.465 0465 L05
0.1 01
0.6 0.5 0.5 6 6 1 042 042 L2
01
0.3 04 06 6 0.2 L5 032 0 . .52 0.6
0.75 0 .. 6 0.6 0.1 0.1 1 0.54 0 . .54 0 .. 9375
0.0 0.0 0.6
2.75 0.6 0.4 6 5 7 057 0.37 20625
POLYMATH Results
Nonlinear regression {L.M}
Model: ra = k*(PaAalfa)*(PbAbeta)
Variable lni guess Value 95% confidence
----_.
5-24
k
alfa
beta
Precision
0.1
1
1
R"2 :::: 0.999213
R"2adj :::: 0.9986883
RInsd :::: 0.0051228
Variance :::: 3.149E-04
0.5068635
0.9828027
-1. 9669749
k = 0.5 atm gmollhr kg; a == 1; P == -2
hence, the rate law is: = 0.5 gmol / kg .hr
B
CDP5-D
0 .. 1124446
0.152574
0 .. 1668241
Since oxygen is found in excess, we assume that.-r
1iO
is dependent only on
This gives us a rate law of the form:
- rHO = kC:.o .
From the units of the specific reaction [ate, we assume that ex == 3. Now, using
equation (5-18) from chapter S, we can solve for the desired balf-.Jives.
(a) For == 3000ppm:
t", )= 119.05_
(b) For C"'No<> = 1 ppm:
t", = 2\1.4,,10. )= L071x 10' mID
CDP5-E
Given the data.. postulate a rate law.
r
A
=kc:.
Then write the design equation in tenns of the data given, in this case volume and time.
CA=NAV
NA =N"o(l-X)
V= Yo(l + EX)
V- V.
X= .. ...._J1.
Vue
V-v.
1-_ ........ 2..
C = __ . Yoe
" V
.5-2.5
Plug that into the design equation:
de
--2..=kC:
dt A
5-26
The following grapb is made.
Once that is dorie it is ready to be graphed. The
following graph is the natUral log the derivitive ofthc volunle function against
the natUral 10 . of the volume function.
From the graph we see that ex. is 2. We can also find k:
k
J
== :9
9
=.018
5
N N 85* 303.39*.2 020 1
.. 0 = YAO TO =. 8.314*313 =. rna es
k' .018
k =. -N-
a
-
I
= M!, . 9
.40 .v ...
The following rate law is found:
-r: - 9*c
2
A -. A
Now, to decennine the volume of the CSTR. we must use the design equation and
stoichiometry:
, V;: F,..oX.
-r
A
C
A
:;: CAo(l- X)
C"o =!MJ
RTa
~ ;: Y"ofQ =.6 * 1013.25kPa == 607.95
Combining these with the rate law just determined. the followinl! volume is found.
5-27
CDP5-F
"riP.
Asr't, '" U Z P dZ
0 129 45.3
1.5 70 28,,63
2,5 50 19.4
:l.O 30 9.5
6.5 18 L3
9.0 16 (1.7)
_ de.
AsHi "'" 3.0 Z P dZ
0 129 90
1..5 45 34.0
2.5 22 15.4
4.0 10 2.0
_df.
AsHi = 3.0 Z P dZ
0 129 17.4
1.5 95 15 ..0
PFR
A ... B ::C
-8
I I
,
)
I
1.5 2.0 4 6 9
PM PAl.
Task I, Re\\l'I'ite the design equation (i.e.. mole balance) in. te:rms of me measurement
variables. Recall V ::: Ac Z. then
ax. = :r,,&
dZ FAo
5-28
For iSOthe."!I1ai operation and no pressure drop.
Posrulate
(l .. X)
CA = CAO rr:.. eX)' C
A
'= P,JRT
(1. X)
P
A
= P
A
0(1 +"e;C)
(I + EX) P A = P AO (1 - X)
-tA '= k[PA ~ -~ ~
Now we have the differential. mole balance
in terms of the measured variables P A and
Z.
Task 2. Look for simplifications.
A) Sc:e if volume change can be neglected.
E :: a therefore neglect volume change.
B) \Ve see L1:U forr..:ns 1 and 3 where PAsH} "" 1.5 and 3.0 torr. respectively. [har
most of tht E!;In is consumed. indicating the equilibrium is reasonably fJr to
the ri giu. Conse:quen ely. the reverse reaction is negligible in the fU"St pan of the
reactor. i.e.
C) \'v:: ::lise see i..l-tat for nlnS 1 and 3 that B is in excess and that far excess B
II
5-29
, R
-r, ::::: k pi-' DO- = lK' pet
,,,,\ .. 80 .. A r\
Algorlcnm
Task -' Co1=ul>te (0 Jnd plot vs Z to find (0
. dP
Plod dZ-'\) vs (PA) on log-log paper to find alph3..
Task 4. r:ldo of inidal races at P AsH] =: 3.0 torr and P A1l:1J =: L5 corr
Task 5. k" wd K?
From AjHl of 3,,0 corr we see equilibrium is reached at P Ae :=:.0 {
PC<:::;:; 0.129 0.01 ::::: .119
P:ac <= 3.0 . t 19 = 2.SS1
K == . ! i 2 ::::: J. I] torr
oL
"? (.01)(2.381) .. ..
- :: 90 :< 10-) tg :;.: x;: (.119 torr.l (3.0
k: :::; 0.23 ({or.
5-30
CDP5-G
From given data, find the rate law"
Given: Oxidation of propene to acrolein
Rate law:
r
A
= kPpapo b
2

Using Polymath non linear regression, the following results were obtained:
Nonlinear regression (L-M)
Model: ra = k*Pp
A
a*P02
A
b
Variable lni guess
k 5
a 1
b 1
Precision
RA2
RA2adj
Rmsd
Variance
CDP5-H
1)
= 0.9999969
= 0 .. 9999953
= 5.722E-07
= 4.011E-12
A .. - .. prod
B .. prod
-f
1
= kAC ... +kaCa
Value
0.006609
0.9948724
0,,2034299
95% confidence
2.685E-05
0.0046367
0.001358
-fA =kAC
A
- fa = kaCll
_ =kAC",,(l-X ... )+kBC:ao(l-X
a
)
dt
C1(t) = C
A
(t)t-Ca(t:):= C ... o(l-X ... ) t CaQ(l-Xa)
C1(t) = CAo(l- X ... + 9
g
...... X
B
) = C
Ao
(1.75 - X ... - Xs)
-kAX", +k
a
9
a
-k
a
XB)
dt
= C (k - kAX", + O.75kaea . kaXa)
dt .Ao A
II) tn de II 2 2: 7;
n -) prod - d;- '" -r
II
'" knC
n
'" k
n
e
no
(l-ln)
Crr(t) ... Cn(t)
"" e
no
(I-In)
0
So,
ten.) 0 10 lO 30 40
crt} kal/.
3
0.01,.4 0.0011
0.00'" 0.0074
Xt t. 14
0 O.31J I).SlI 0.700 0 1$
5-31
.50
'0
11 ,00i40
o.ooso
1.00
1.lU
If n. 10
0 0.179 0.301 0.400 0.411 0.571 Q.6.43



-4 -4 -4
Alt}
-:LhlO -1.ldO -ldO -1.4110 -ldO

.. l.hlO-
4
Z.h10'" +1.h10-4 "1.1:tlO-4
-.
+l.ltlO' .. 0,1110 ....
<il:
l.ltlO
If II. cio (1-10,2 1.9hlO
-4
1.3UdO

9.Uhl.O-
3
7.06dO-' 5.41b10-' l.'UtlO-
5

Ln
LJ7S 1.60.1 1.700 1.701 l.lU 3.311 l.lO]
If I! were true .. all kO's should 0(:: the same .._-) II is not true:
rime (s)

CDP5-I
(a) Experimental Plan to tind the rate law for the hydrogenation of cyclopentane on a
PtI All)l catalyst:
1. Since this is a stable catalyst we don't have to worry about catalyst decay and an
Integral React(l" will be used.
2, Perform several different nms, holding C
AO
and W constant while FAG is valied
from run to run.
3., Plot X
A

OUI
V$, WIF;>.o for all IUllS,
4. Fit a curve through all points which passes through the origin,. The slope at any
point is the reaction late Record the slope and COII'cspouding CAl} for many
different X
A
values. 111cse data can be used to determine the rate law.,
(b) Experimental Plan to find the rate law for the liquid-phase production of methyl
bromide from an aqueous solution ofmerhyl amine and bromine cyanide:
L Fot a liquid-phase reaction without a catalyst. use a batch reactor.
2. Vlhile running the reaction record both C
A
and en at equal time intervals
3.. Repeat to ensure a.ccurate data.
CDP5-I (c) No solution
CDP5-J No solution will be given.
5-32
CDP5-KNo solution will be given.
5-33
Solutions for Chapter 6 - Multiple Reactions
P6-1 Individualized solution
P6-2 (a) Example 6-2
ForPFR,
dC
A
Z
- dr = -k
J
- kzC A - k3
C
A
dC
lL
- k
- J
dr
dCB = k C dCy = k C
Z
dr z A dr 3 A
In PFR with V = 1566 dm
3
we get X = LO and SB/XY = 0.394
also at V = 533 dm
3
SBIXY is at its maximum value of 0 .. 625
0.04 .------------.------,
o.J
0..2
0.1
0.,,0.
-0..10.
313
626 tau 940.
1253 1566
See Polymath program P6--2a.poJ.
POL YMATH Result"
Calculated values of the DEQ variables
Variable initial value minimal value
tau 0 0
Ca 0 .. 4 -0 .. 0439962
Cx 1.. OE-07 1 .. OE-07
Cb 0 0
Cy 1.0E-06 1. OE-06
Cao 0,,4 0 .. 4
X 0 0
k1 1.0E-04 1,OE-04
k2 0 .. 0015 0,0015
k3 0.,008 0,,008
Sbxy 0 0
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Ca)/d(tau) = -k1-k2*Ca-k3*CaI\2
[2] d(Cx)/d(tau) = k1
[3] d(Cb )/d(tau) = k2*Ca
[4] d(Cy)/d(tau) = k3*Ca1\2
0'.7r-----
0. .. 6
0..4
0.",3
0.,1
0.",,0. .---"---" - - - - ~ - - - -
0. 313 626 tau 940. 1253 1566
maximal value final value
1566 1566
0,,4
-0 .. 0439962
0,1566001 0 .. 1566001
0.1490534 0 .. 1256308
0 .. 1617665 0,,1617665
0..4 0.4
1.1099906 1 .. 1099906
1 .. OE-04 1,OE-04
0.0015 0 .. 0015
0,,008 0,008
0,,6436717 0.3946104
6-1
Explicit equations as entered by the user
[1] Cao = 0 .. 4
[2] X = 1-Ca/Cao
[3] k1 = 0.0001
[4] k2 = 0 .. 0015
[5] k3=0.008
[ 6] Sbxy = Cb/(Cx+Cy)
(2) Pressure increased by a factor of 100.
Now C
AO
= PIRT = 0.4 x 100 = 40 mol/dm
3
For single CSTR, C
A
' does not change but
v C AO - C A C AO - C A
r - - - - ----'=----=..:...-
- Vo - - r
A
- klA + k
2A
C
A
+ A C ~
T=21217sec
P6-2 (b) Example 6-3
(a) CSTR: intense agitation is needed, good temperature control.
40-0.112
---------sec
0.0001 + 0.00168 + 0.0001
(b) PFR: High conversion attainable, temperature control is hard - non-exothermic reactions, selectivity not
an issue
(c) Batch: High conversion required, expensive products
(d) and (e) Semibatch: Highly exothermic reactions, selectivity i.e. to keep a reactant concentration low, to
control the conversion of a reactant.
(t) and (g) Tubular with side streams: selectivity Le .. to keep a reactant concentration high, to achieve higher
conversion of a reactant
(h) Series of CSTR's: To keep a reactant concentration high, easier temperature control than single CSTR.
(i) PFR with recycle: Low conversion to reuse reactants, gas reactants
(j) CSTR with recycle: Low conversions are achieved to reuse reactants, temperature control, liquid
reactants
(k) Membrane Reactor: yield i.e. series reactions that eliminate a desired product
(1) Reactive Distillation: when one product is volatile and the other is not
P6-2 ( c) Example 6-4
For kl = k2' we get
C
A
=CAoexp(-klT')
6-2
and (
') -1
X
opt
= 1- exp- k(l' = 1- e =0.632
ForaCSTR:
W= FAo-F
A
= vO(CAO-CA)
-r' -r'
A A
, CAO -C
A
CAO -C
A
r = = ---""'---'-"-
-r'A kjC
A
C
A
= C
AO
(r'kj +1)
, C
BO
-C
B
C
B
C
B
r = =-----= .
-r'B -kjC
A
+k
2
C
B
-kjCAO(r'kj +1)+k
2
C
B
1 .. 80..---------------..
to find the maximum concentration of C, differentiate
C
B
with respect to .' and set it equal to 0 ..
See Polymath program P62c.pol.
simplifying we get
Then use the quadratic formula to solve for .'.
(2) Operating temperature = 325 K
6-3
1.64
148
320 340 r 360 380 400
Equation (E6-6.8):
P6-2 (0 Example 67
For equal molar feed in hydrogen and mesitylene.
C
HO
= YHOC
ro
= (0.5)(0.032)lbmollft
3
=0.016Ibmollfe
C
MO
= 0.016lbmollft
3
Using equations from example, solving in Polymath,
we get
T
opt
= 0.38 hr., At1' = 0.5 hr all of the H2 is reacted and only the decomposition oiX takes place .. ,
--
Ex 6-7 This question
X
H
0.50 0.99
--
C
H
0.0105 0.00016
--
C
M
0.0027 0.0042
..
-
C
x
0.00507 0.0077
--!.!-, --_._----
l' 0.2hr 0..38hr
-----
_.
0 .. 596 1.865
SXIT
See Polymath program P6-2-f.pol.
POL YMATH Results
Calculated values of the DEQ variables
Variable
tau
CH
CM
CX
k1
k2
rIM
r2T
rlH
r2H
rlX
r2X
initial value
------
o
0 .. 016
0.016
o
55.2
30.2
-0.1117169
o
-0.1117169
o
0_1117169
o
minimal value
o
1.64E-06
0.0041405
o
55.2
30 .. 2
-0.1117169
o
-0.1117169
-0 .. 0159818
2.927E-04
-0.0159818
._--
maximal value
0.43
6-4
0.016
0 .. 016
0.0077216
55.2
30 .. 2
-2.927E-04
0.0159818
-2.927E-04
o
0.1117169
o
final value
0.43---
1. 64E-06
0.0041405
0.0077207
55.2
30.2
-2.927E-04
2.986E-04
-2.927E-04
-2.986E-04
2.927E-04
-2.986E-04
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(CH)/d(tau) = r1 H+r2H
[2] d(CM)/d(tau) = r1 M
[3] d(CX)/d(tau) = r1 X+r2X
Explicit equations as entered by the user
[1] k1 = 55,.2
[2] k2 = 30.2
[3] r1 M = -k1*CM*(CHI\.5)
[4] r2T = k2*CX*(CHI\ .. 5)
[5] r1 H = r1M
[ 6] r2H = -r2T
[7] r1 X = -r1 M
[8] r2X = -r2T
Increasing 9
H
decreases 'opt and S xrr
P6-2 (g) Example 6-8
Using equation from example 6-8:
Polymath code:
See Polymath program P62g.poL
rOLYMA TUResults
NLES Solution
Variable
CH
CM
CX
tau
K1
K2
CHo
CMo
Value
4.783E-05
0.0134353
0.0023222
0.5
55.,2
30.2
0,,016
0.016
NLES Report (safenewt)
Nonlinear equations
f (x)
-4,,889E-ll
-1. 047E--ll
-9.771E-12
0.020,.-----------------,
0.016
0.012
0.008
0 .. 004
00000.000
Ini Guess
1 .. 0E-04
0 .. 013
0.OQ2
- CH
.. Ci\I
ex
0.086 O.I72
tau
0.258 0.344 0.430
[1] f(CH) = CH-CHo+K1*(CM*CHA.5+K2*CX*CHA.5)*tau = 0
[.'2] f(CM) = CM-CMo-tK1*CM*CHI\,,5*tau = 0
[3] f(CX) = (K1*CM*CHI\.5-K2*CX*CHI\0,,5)*tau-CX = 0
Explicit equations
[1] tau = 0,,5
[2] K1 = 55 .. 2
[3] K2 = 30 .. 2
[4] CHo=0016
[5] CMo=0 .. 016
A plot using different values of T is given ..
For T =0.5, the exit concentration are
C
H
= 4 .. 8 xW
5
lbmoVfe C
M
=00134IbmoVfe
C
x
=0.00232 Ibmollft
3
6-5
0.020,------
0.016
' ........'-..........'".........--......-.,-, .. -'"" ... . - - ........... " ....--., ... '"'"--........ ~ ...
0.012
0.008
0.004
Df]
CH
" Cl\,,1
- ex
0.000 lL:"'-__ - = : : : = = : : : = = = = : d
0.00 0 .. 04 0.08 tau 012 0.16 0.20
The yield of xylene from mesitylene based on molar flow rates exiting the CSTR for T =0..5:
Fx C x 0.00232 0.89mole xylene produced
Y
MX
= --.:..:...-- = ------
F
MO
-FM C
MO
-eM 0.016-0.0134 mole mesitylene . reacted
The overall selectivity of xylene relative to toluene is:
S = .Fx = 8.3mole xylene produced
x IT FI mole toluene produced
Ex 6-8 This Question
C
H
C
M
C
x
T
Y
MX
SXff
P6-2 (h) Example 6-9
(1)
0..0.0.89
0..0.0.29
0..0.0.33
0..5
0..41
0..7
Membrane Reactor
PFR
4.8 x 10-
5
0..0.134
0..0.0.232
0..5
0..89
8.3
-_c--.
SDIU Original Problem
-
2.58
0..666
--
--
SDIU P6-2 h
1.0.1
0..20.8
. .
Doubling the mcommg flow rate of specIes B lowers the selectIvIty .
--
(2) The selectivity becomes 6.52 when the first reaction is changed to A+2B D
P6-2 (i) Example 6-10
Original Case -. Example 6-10
15 --- ---_ ..
12
..
FA
..
FB
9
..
FC
..
FD
6
-
FE
.. If If
3
o 0
2 4
V
6 8
15
12
9
6
3
0
10 0
P6-2 i
- FA
FB
- Fe
- FD
1
2 V 3
5
The reaction does not go as far to completion when the changes are made. The exiting concentration of D,
E, and F are lower, and A, B, and C are higher.
See Polymath program P62i.pol.
P6-2 (j)
6-6
O.Oe+O
O 140 280 t 420 560 700
At the beginning, the reactants that are used to create TF-VIla and TF-VIIaX are in high concentration. As
the two components are created, the reactant concentration drops and equilibrium forces the production to
slow. At the same time the reactions that consume the two components begin to accelerate and the
concentration of TF-VIla and TF-VIlaX decrease .. As those reactions reach equilibrium, the reactions that
are still producing the two components are still going and the concentration rises again .. Finally the reactions
that consume the two components lower the concentration as the products of those reactions are used up in
other reactions.
P6-2 (k)
Base case Equal-molar feed
10 10
-
-
FlU
FlU
-
Fh
Fh
8
Fx
8 Fx
..
FlUe
.. Ii'!
6 6
4 4
2 2
o 0
40 80 V 120
o
160 200 o 40 80 V 120 160 200
Increasing YMO will increase the production of m-xylene and methane, but will result in a large amount of
un-reacted mesitylene ..
P6-2 (I) Individualized solution
P6-3 Solution is in the decoding algorithm given with the modules ( ICM problem)
P6-4 (a)
Assume that all the bites will deliver the standard volume of venom. This means that the initial
concentration increases by 5e-9 M for every bite ..
6-7
After 11 bites. no amount of anttvenom can keep the number of free SIteS above 66 7% of total Sites, ThIs
means that the imttal concentration of venom would be 5 5e-8 M The best result ocelli'S when a dose of
anttvenom sucb that the Iruttal concentration of antivenom In the body IS 5.7e-8 M, wIll result in a mmimum
of 66 48% free sites, wincb IS below the allowable nurumurn.
See Polymath program P6-4-a.pol.
P64 (b)
The VICtim was bitten by a hatmless snake and anttvenom was Injected. ThiS means that the tmttal
concentration of venom 18 O. From the program below. we see that if an amount of antivenom such that the
tmttal concentration in the blood is 7e-9 M, the pattent Will dIe.
See Polymath program P6-4-h.pol.
POLYMA Tn Results
Calculated valges of the DEQ variables
Variable
t
fsv
fs
Cv
Ca
fsa
Cp
kv
ksv
ka
kia
eso
ksa
kp
kov
koa
kop
9
h
m
j
initial value
o .
o
1
o
7 OE-09
o
o
2 OE+OS
6.0E+OS
2.0E+08
1
5.0E-09
6.0E+08
1.2E+09
o
0.3
o 3
o
o
o
-2.1E-09
ODE Report (STIFf)
minimal value
o
o
0.6655661
o
4 503E-09
o
o
2.0E+08
6.0E+08
2 OE+OS
1
S.OE-09
6.0E+08
1.2E+09
o
0.3
0.3
o
o
o
-2.1E09
Differential equations as entered by the user
[ 11 d(fsv)/d(t) = kv * fs * Cv ksv * fsv * Ca
maximal value
o 5
o
1
o
7.0E-09
0.3344339
o
2.0E+08
6.0E+OS
2.0E+08
1
5 OE-09
6 OE+OS
1 2E+09
o
o 3
0,,3
o
o
o
-1 351E-- 09
[2 J d(fs)/d(t) = -kv*fs*Cv - ka * fs Ca + kia * fsa + 9
[3] d(Cv)/d(t) = Cso (-kv * fs Cv - ksa * fsa * Cv) + h
[4 J d(Ca)/d(t) = Cso*(-ka * fs Ca + kia * fsa) + j
[ 5 ] d(fsa)/d(t) = ka * fs * Ca kia fsa - ksa * fsa Cv
[6] d(Cp)/d(t) = Cso (ksv fsv Ca ,+ ksa * fsa * Cv) + m
final value
0.5
o
0.6655661
o
4.503E-09
0.3344339
o
2.0E+08
6.0E+08
2.0E+08
1
5.0E-09
6.0E+08
1. 2E+09
o
0.3
o 3
o
o
o
-1. 3S1E-09
100..--------
ExpliCit equations as entered by the user
[1] kv=2e8
[2J ksv=6e8
[3J ka=2e8
0.92 ---"-- -- - .. -.------.-.-----.-._----- .----- ...--.-.--
[4J kia=1
Q
0.84 '-'--'--'-- --.----.-------..-----.--.. --
rSJ Cso = 5e-9
[6] ksa=6e8
[7J kp=12e9
68
0.76 ------ .--------.-
068 ---------------------.-.-.. ---""'-....::-......
0.60L-----------
0.0 0.1 02 t 03 0.4 0.5
[8] kov= 0
[9] koa=O .. 3
[10] kop=O.3
[11] 9 = ksa * fsa * Cv + ksv * fsv * Ca
[12] h = -kp * Cv * Ca - kov * Cv
[ 1 3 J m = kp * Cv * Ca - kop * Cp
[14 J j = -Cso * ksv fsv * Ca - kp * Cv * Ca - koa * Ca
P6-4 (C)
The latest time after being bitten that anti venom can successfully be administerd is 27.49 minutes. See the
cobra web module on the CDROMlwebsite for a more detailed solution to this problem
I
09
I
'r
:2.-::
I::
<::>
'J:
"
'"
0.8
.;::
...
. :::
'"
g::
l-<
....
Amivcnom Injected at t 2749 min
OJ
o () t-
O 02 04 ()6 OJl t
'!
4 1.4
Time (houri
P6-4 (d) Individualized Solution
P6-5 (a)
Plot of C
A
, CD and C
u
as a function oftime (t):
See Polymath program P6Sa.poJ.
POL YMA Tn Results
Calculated values of the DEQ variables
Variable
t
Ca
Cd
Cu
k1
initial value
o
1
o
o
1
minimal value
o
0 .. 0801802
o
o
1
maximal value
15
1
0.7995475
0 .. 5302179
1
6-9
16
final value
15
0.0801802
0 .. 7995475
0.1202723
1
.1 8 2
k2
K1a
K2a
Cao
X
100
10
1.5
1
o
ODE Report (RKF45)
100
10
1.5
1
o
Differential equations as entered by the user
100
10
1.5
1
0.9198198
100
10
1.5
1
0.9198198
[1] d(Ca)/d(t) = -(k1 *(Ca-Cd/K1 a)+k2*(Ca-Cu/K2a))
[2) d(Cd)/d(t) = k1 *(Ca-Cd/K1 a)
[3] d(Cu)/d(t) = k2*(Ca-Cu/K2a)
Explicit equations as entered by the user
[1] k1 = 1.0
[2] k2 = 100
[3] K1a = 10
[4] K2a = 1.5
[5] Cao = 1
[6) X = 1-CaiCao
1.0
-
0.8 - Cd
0 .. 6
0.4
0.2
0.0 __ ____
o 3 6 9 12 15
1.0
0.8
0 .. 6
0.4
0.2
0.0
o

----'
3 6 9 12 15
To maximize CD stop the reaction after a long time .. The concentration of D only increases with time
P6-5 (b)
Conc. Of U is maximum at t = 0.31 min.(C
A
= 0.53)
P6-5 (C)
Equilibrium concentrations:
CAe = 0.08 mol/dm
3
C
De
= 0 .. 8 mol/dm
3
CUe = 0.12 mol/dm
3
P6-5 (d)
See Polymath program P6-S-d.poL
POLYMATH Results
NLES Solution
Variable Value
Ca 0.0862762
f(x) lni Guess
-3.844E-14 1
6-10
Cd 0 .. 7843289 -2 .. 631E-14 0
Cu 0 .. 1293949 6 .. 478E-14 0
CaO 1
k1 1
k2 100
K1a 10
K2a 1.5
t 100
NLES Report (safenewt)
Nonlinear equations
[1] f(Ca) = CaO-t*(k1 *(Ca-Cd/K1 a)+k2*(Ca-Cu/K2a))-Ca = 0
[2] f(Cd) = t*k1 *(Ca-Cd/K1 a)-Cd = 0
(3] f(Cu) = t*(k2*(Ca-Cu/K2a))-Cu = 0
Explicit equations
[1] CaO = 1
[2] k1 = 1
[3] k2 = 100
[4] K1a=10
[5J K2a = 1 .. 5
[6] t=100
[7] X = 1-Ca/CaO
P6-6 (a)
~ B
Sketch SBX, SBY and SBIXY as a function of C
A
See Polymath program P6 ..6-a.poL
1)
T 1 min 10 min
C
Aexit
0.295 0.133
1----
CDexit
0.2684 0.666
CUexit
0.436 0.199
X 0 . .705 0.867
(
I J1I2
kl = 0.004 ;;3 min
k2 =0.3min-
1
dm
3
k =0.25-----
3 I .
mO.mm
6-11
100min
0..0862
0.784
0.129
0.914

32
24
16
8
o
0.0001 0.0326 0.1301 0.1626
2)
120o.1-----------------------,
960
720
480
240
o
0.0001 0.0326 0 . .1301 lU626
3)
.-1
2
o
0.0001 0.0326 0.1301 01626
P6-6 (b)
Volume of first reactor can be found as follows
6-12
We have to maximize SBIXY
From the graph above, maximum value of SBXY = 10 occurs at CA' = 0 .. 040 mol/dm
3
So, a CSTR should be used with exit concentration C
A
*
Also, C
AO
= P AIRT = 0.162 mol/dm
3
1/2 2
And-rA=YX +rB+ry = (k
1
C
A
+k
2
C
A
+k
3
C
A
)
* *
= = vO(CAO -CA ) = vO(CAO -CA ) = 92.4dm
3
> V * 112 * * 2
-rA (k
1
(C
A
) +k
2
C
A
+k
3
(C
A
) )
P6-6 (C)
Effluent concentrations:
. C
B
C
B
* mol
We know, 't = 9..24 mm => 1: = - = --~ C B = 0.11--
3
rB k
2
C
A
dm
* mol * mol
Similarly: C X = 0.007 -"3 and Cy = 0.0037 --3
dm dm
P6-6 (d)
Conversion of A in the first reactor:
CAO -C
A
= CAOX ~ X =0.74
P6-6 (e)
A CSTR followed by a PFR should be used.
Required conversion = 0.99
dV F
AO
=> For PFR, Mole balance: -- = --
dX -YA
0.99 dX 3
~ V = lOxO.162x f 1/2 2 = 92.8dm
074 (k
1
C
A
+k
2
C
A
+k3CA )
P6-6 (f)
If we notice that E2 is the smallest of the activation energies, we get a higher selectivity at lower
temperatures. However, the tradeoff is that the reaction rate of species B, and therefore production of B,
decrease as temperature drops .. So we have to compromise between high selectivity and production .. To do
this we need expressions for k[, k
2
, and k3 in terms of temperature. From the given data we know:
k
i
= A x p I : ~ ~ ~ )
Since we have the constants given at T = 300 K, we can solve for Ai'
.004
" =-------= 1.4ge12
(
--20000 J
exp 1.98 (300)
~ = ___ .. 3 =5.7ge6
(
-10000 J
exp 1.98 (300)
6-13
A, (.25 )
-30000
exp 1.98(300)
Now we use a mole balance on species A
V= FAO -FA
-r
A
v( CAO -C
A
)
V =---'-----=-::..::.-.-:.:.:...
A mole balance on the other species gives us:
F; =vC
j
=ljV
C
i
=7lj
Using these equations we can make a Polymath program and by varying the temperature, we can find a
maximum value for C
B
at T = 306 K. At this temperature the selectivity is only 5"9,, This may result in too
much of X and Y, but we know that the optimal temperature is not above 306 K. The optimal temperature
will depend on the price ofB and the cost of removing X and Y, but without actual data, we can only state
for certain that the optimal temperature will be equal to or less than 306 K.
See Polymath program P6-6-f.pol.
POL YMA TIl Results
NLE Solution
Variable
Ca
T
R
k1
k2
Cao
Cb
k3
tau
Cx
Cy
Sbxy
Value
0.01.70239
306
1. 987
0.0077215
0.4168076
0.1
0.070957
0,,6707505
10
0,,0100747
0,,0019439
5,,9039386
NLE Report (safenewt)
Nonlinear equations
f(x)
3.663E-10
Ini Guess
0.05
[1] f(Ca} = (Cao-Ca}/(k1 *Ca
A
,,5+k2*Ca+k3*Ca
A
2}-1 0 = 0
Explicit equations
[1] T=306
[2] R= 1.987
[3] k1 = 1.4ge12*exp(-20000/Rff)
[ 4] k2 = 5790000*exp( -1 OOOO/Rff}
[5] Cao =.1
6-14
6] Cb = 10*k2*Ca
71 k3 = 1.798e21*exp(-30000IRfT)
8] tau = 10
9] Cx = tau*k1 *Ca/\5
lO} Cy = tau*k3*Ca"2
11] Sbxy = Cb/(Cx+Cy)
P6-6 (g)
Concenttation is proportional to pressure in a gas-phase system Therefore:
p
S B / XY which would suggest that a low pressure would be ideal. But as before the ttadeoff is
Vp+p2
lower production of B. A moderate pressure would pIObably be best
P6-7
US legal limit: 0 8 gil
Sweden legal limit: 0.5 gil
k2 >C
Where A is alcohol in the gastrointestinal tract and B is alcohol in the blood stteam
dC
A
=-kC
dt ) A
dCB =kC -k
dt ) A 2
k) = lOhr-
1
g
k2 =0.J92--
L hr
Two tall martinis = 80 g of ethanol
Body fluid = 40 L
C = 80g =2 g
AD 40L L
Now we can put the equations into Polymath
See Polymath program P67 .poL

Calculated values of the DEO variables
Vaziable initial value minimal
value maximal value final value
------
tOO
Ca
Cb
kl
k2
2
o
10
0 .. 192
ODE Report (RKF45)
7 .131E-44
o
10
0.192
Differential equations as entered by the user
[1] d(Ca)/d(t) = k1 *Ca
2.0 ----------.-------
16
1.2
0.8
04
0 .. 0 6 8
6-15
10
2
1 .. 8901533
10
0.192
10
7 131E-44
0.08
10
0 .. 192
10
[2] d(Cb)/d(t) = -k2+k1 *Ca
Explicit equations as entered by the user
[1] k1 = 10
[2] k2 = 0 .. 192
P6-7 (a)
In the US the legal limit it 0.8 gIL.
This occurs at t = 6.3 hours ..
P6-7 (b)
In Sweden C
B
= 0.5 gil , t = 7.8 hrs.
P6-7 (C) In Russia C
B
= 0 .. 0 gil, t = 10.5 hrs
P6-7 (d)
For this situation we will use the original Polymath code and change the initial concentration of A to 1 gIL ..
Then run the Program for 0.5 hours. This will give us the concentration of A and B at the time the second
martini is ingested .. This means that 1 gil will be added to the final concentration of A after a half an hour.
At a half an hour C
A
= 0.00674 gIL and C
B
= 0.897 gIL .. The Polymath code for after the second drink is
shown below.
See Polymath program P67d.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable
t
Ca
Cb
k1
k2
initial value
--------
0.5
1.0067379
0.8972621
10
0 .. 192
ODE Report (RKF45)
minimal value
0.5
5 .. 394E-42
0.08
10
0.192
Differential equations as entered by the user
[1] d(Ca)/d(t) = -k1 *Ca
[2] d(Cb)/d(t) = k2+k1*Ca
Explicit equations as entered by the user
[1] k1 = 10
[2] k2 = 0.192
for the US t = 62 hours
Sweden: t = 7 .. 8 hours
Russia: t =10.3 hours ..
P6-7 (e)
maximal value
10
1.0067379
1. 8069769
10
0.192
final value
10
5.394E-42
0 .. 08
10
0.192
The mole balance on A changes if the drinks are consumed at a continuous rate for the first hour.. 80 g of
ethanol are consumed in an hour so the mass flow rate in is 80 glhr. Since volume is not changing the rate of
change in concentration due to the incoming ethanol is 2 gIL/hr.
For the first hour the differential equation for C
A
becomes:
6-16
dC A = -kl C A + 2t after that it reverts back to the original equations ..
dt
See Polymath program P6-7 -e .. pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable
t
Ca
Cb
k1
k2
initial value


10
0.192
ODE Report (RKF45)
minimal value

-1.1120027
10
0 .. 192
Differential equations as entered by the user
[1] d(Ca)/d(t) = if(t<1 )then(-k1 *Ca+2*t)else( -k1 *Ca)
[2] d(Cb )/d(t) = -k2+k1 *Ca
Explicit equations as entered by the user
[1) k1 = 10
[2) k2=O.192
maximal value
11
0.1785514
0 .. 7458176
10
0.192
US: C
B
never rises above 0 .. 8 gIL so the is no time that it would be illegaL
Sweden: t = 26 hours
Russia: t = 5.2 hours
P6-7 (0
60 g of ethanol immediately -7 C A = 1.5 gIL
C
B
= 08 gIL at 0 .. 0785 hours or 4 .. 71 minutes.
final value
11
6.217E-45
-1.1120027
10
0 .. 192
So the person has about 4 minutes and 40 seconds to get to their destination.
P6-7 (g)
A heavy person will have more body fluid and so the initial concentration of C
A
would be lower. This
means a heavier person will reach the legal limit quicker. The opposite is true for a slimmer person. They
will take longer to reach the legal limit, as their initial concentration will be higher.
P6-8 (a)
Let A be the tarzlon in the stolllach and B be the tanion in the blood.
iVlole Balances:
d ~
_ .. __ t_ .. = r
dt A
deB
--=r
dt B
6-17
Rate Laws:
.. r
A
;;;;;; k / ~ A -+- kZC
A
ra = kiC
A
- k, _., k ~ C s
All k values .are given in the proble m statement. It must be noted, however, that
for C
B
< 0, k, must be equal to O.
These equations when entered in POLTh!ATH generate the following results:
See Polymath program P6-8,a.po1.
POLYMATH Results
Calculated values of the DEQ variables
Variable
t
Ca
Cb
k1
k2
k4
k3
initial value
o
6,,25
o
0 .. 15
0.6
0.2
0.1
ODE Report (RKF45)
minimal value
o
0.3111692
o
0.15
0.6
0.2
0.1
Differential equations as entered by the user
[1] d(Ca)/d(t) = -k1 *Ca-k2*Ca
[2] d(Cb)/d(t) = k1 *Ca-k3-k4*Cb
Explicit equations as entered by the user
[1] k1 =0,,15
[2] k2 = 0.6
[3] k4 = 0,,2
[4] k3 = if(Cb<O)then (k1*Ca-k4*Cb) else (0,,1)
P6-8 (b)
maximal value
4
6.25
0.5977495
0.15
0.6
0.2
0.1
6-18
final value
4
0.3111692
0.4057018
0.15
0.6
0.2
0.1
From the following graph generated using the above program in POL Y1v1ATH, We
can see the proper doses of the drug: .
1. First take two doses of the crug.
2, Six hours later take one dose.
), Take one dose every four hours from then on.
Tr\ 68b
i i \

!
I
..........;- __ .. "! .. ____ . +.
2D.CCG '3lJ.,CGG
P6-8 (c)
If one takes initially two doses of Tarzlon, it is not recommended to take another dose within the first six
hours Doing so will result in build up of the drug in the bloodsueam that can cause harmful effects ..
P6-8 (d)
If the drug is taken on a full stomach most of it will not reach the wall at all. The processed food can also
drag the drug to the intestines and may limit its effectiveness .. This effect can be seen in the adsorption
constant kl and elimination constant k2 values If kl decreases this means that the adsorption process is slow
6-19
and if k2 increases means that the rate of elimination of Tarzlon increases. The next graph shows the
concentration profiles for kl = 0.10 h-
I
and k2 = 0.8 h-
I
" Note that the maximum amount of the drug in the
bloodstream is reduced by two.
O:lncentration Profiles
-+- Ca (1l'dm3)

'IiIm(h)
0.6
Concentration profile for Tarzlon in the stomach (A) and bloodstream
(B).. The maximum amount of Tarzlon in the bloodstream is 03 mg/dm
3

P6-9 (a)
Reactor selection

'iA = 1 Oexp( -8000K / T)C A C B

112 31Z
r
ZA
= lOOexp(--lOOOK IT)C
A
C
B
lIZ
exp(-8000K IT)C
A
lOexp(-lOOOK IT)C B 112
r
D
lOexp(--8000K IT)CAC
B
SDU= -= .
ru lOOexp(--lOOOK IT)CAI/2C/IZ
AtT =300K
kl = 2.62 X 10-
11
& k2 = 3.57
At T = 1000K
9.2xlO-
S
C/
IZ
SD/U = IIZ-
C
B
kl = 335 X 10-
3
& k2 =36.78
Hence In order to maximize SDU, use higher concentrations of A and lower concentrations of B .. This can be
achieved using:
1) A semibatch reactor in which B is fed slowly into a large amount of A
2) A tubular reactor with side streams of B continually fed into the reactor
3) A series of small CSTR's with A fed only to the first reactor and small amounts of B fed to each reactor..

-j
___ Pure A
intitially
Semi batch
Tubular reactor
with side streams
6-20
8 '--_._ .... _ ... _ .._. -T ........... __ ..... - "l- _---l
A_ ___
f
T
cLJLll
'- l T i
- l:"' "d--'lll
- T I
::..::0
Series 01 small: CSfRs
Also, since ED> Eu, so the specific reaction rate for D increases much more rapidly with temperature.
Consequently, the reaction system should be operated at highest possible temperature to maximize SDU
(
c )Yz
Note that the selectivity is extremely low, and the only way to increase it is to keep C: < 10-
6
and
add B drop by drop.
P6-9 (b)
and rIA =100exp(-1000KIT)C
A
C
B
A + B U and r
2A
= 10
6
exp( -8000K IT)C A C B
r
D
100exp(-1000K IT)CAC
B
exp(-1000K IT)
SDU= --= =
ru 10
6
exp(-8000KIT)C
A
C
B
10
4
exp(-8000KIT)
AtT= 300K
kl = 3.57 & k2 = 2.623 SDU = 1.14 x10
6
AtT = 1000K
kl = 36.78 & k2 = 3354,.6 SDU = 0.103
Hence we should keep the temperature low to maximize SDU but not so low that the desired reaction doesn't
proceed to a significant extent
P6-9 (C)
and
B+ D -7 U and r
2A
= 10
9
exp(-lO,OOOK IT)CBC
D
S = 'iA = lOexp(-8000K
DU r
2A
10
9
expC-10000K IT)CBC
D
S = exp(-8000IT)C
A
DU 10
8
exp(-10000IT) CD
Therefore the reaction should be run at a low temperature to maximize SDU, but not too low to limit the
production of desired product. The reaction should also take place in high concentration of A and the
concentration of D should be limited by removing through a membrane or reactive distillation
P6-9 (d)
and
and
and
'iA = 4280exp(-12000K IT)C
A
r
2D
= 1O,100exp(--15000K IT)C
D
r
3A
= 26 exp( --10800 KIT)C A
s = = 4280exp(--:12000K IT)C
A
IT)C
D
DIUIU2
r
VI
+ r
V2
1O,100exp(-1.5000K IT)C
D
+ 26exp(-10800K IT)C A
AtT= 300K
kl = 1.18 X 10-
14
& k2 = 194 X 10-
18
& k3 = 6.03 X 10-
15
If we keep C
A
> 1000C
D
S -L94xlO-
18
CD
D/UIU2 1.94 X 10-
18
CD + 6.03x 10-
15
C A .603
6-21
At T= 1000K
kj = 0.026 & k2 = 3.1 X 10-
3
& k3 = 5.3 X 10-4
If we keep C
A
> 1000C
D
S = 0.026CA -3.1xlO-
3
CD "" .026 =49
DIUlUZ 3.1xlO-
3
C
D
+5.3xlO-
4
C
A
.00053
Here, in order to lower Uj use low temperature and high concentration of A
But low temperature and high concentration of A favours U
z
So, well have to optimize the temperature and concentration of A.
Membrane reactor in which D is diffusing out can be used.
P6-9 (e)
A + B D and 'iA = 10
9
exp(-10000K IT)CAC
B
D A + Band rzv = 20 exp( -2000 K IT)C D
A + B U and r3 A = 10 3 exp( -- 3000 KIT) cAe B
r
D
10
9
exp(-10000K IT)CAC
B
-20exp(-2000K IT)C
D
SDIU =-
ru 10
3
exp(-3000K IT)CAC
B
AtT =300K
kj = 3.34 X 10-
6
& k2 = 0.025 & k3 = 0.045
The desired reaction lies very far to the left and CD is probably present at very low concentrations so that:
SDIU ",,0
AtT= 1000K
kj = 4.5399 . .9 & k2 = 2.7 & k3 = 49.7
If we assume that CAC
B
> Q..OOIC
D
then,
S
- 45399.9C
A
C
B
-2.7C
D
_ 45399 -913
DIU - --
49.7C
A
C
B
49.7
Here we need a high temperature for a lower reverse reaction of D and lower formation of U
Also we need to remove D as soon as it is formed so as to avoid the decomposition.
P6-9 (I)
A + B --7 D and -'iA = 10exp(-8000K IT)CAC
B
A ---7 U and -'2A = 26 exp(-IO, 800K IT)C
A
U ---7 A and -r
3U
=1000exp(-1.5,000K IT)C
u
S - r
D
-_____ lOexp(-8000K IT)CAC
B
DIU - ru - 26exp(-'}0,800K IT)C
A
-1000exp( -15,000K IT)C
u
6-22
We want high concentrations ofB and U in the reactor. Also low temperatures will help keep the
selectivity high.
If we use pseudo equilibrium and set -rA = 0 ..
(
-SOOO) (-lOS00) (-15000)
-r
A
=lOexp r- CACB + 26exp T C
A
-1000exp T C
u
=0
C, _ lOexp ( )C
8
+ 26exp(
Cu - lOooex
p
(
C
A
=_1_
exp
(7000)C
C
u
100 T B 1000 T
P6-9 (g)
A+B--7D
A+B---tU
1
D+B--7U
2
(1)
and -liA =SOOexp(-SOOOK
and --r
2B
= 10exp( -300K IT)CAC
B
and -1
3D
= 10
6
exp(-SOOOK IT)CDC
B
SOOexp( -SOOOIT) . SO exp ( -SOOOIT)
SDlU
j
= lOexp(-300IT)C
A
C
B
-= exp(
AtT = 300
2.09S * 10-
10
S =-----
DIU
j

At T = 1000
S = ____ 29.43
DlU
j

To keep this selectivity high, low concentrations of A, and high temperatures should be used.
SOO exp ( -SOOO IT) C B
S = =--
DlU2 10
6
exp(-SOOOIT) CDC
B
10
6
CD
To keep this selectivity high, high concentrations of A and low concentrations of D should be used. Try to
remove D with a membrane reactor or reactive distillation .. The selectivity is not dependant on temperature ..
To keep optimize the reaction, run it at a low temperature to maximized SDiUl in a membrane reactor that
allows only D to diffuse out.
(2)
_
S DIUIU2 - ( ) 6 (._--)
lOexp -3001T CACB + 10 exp -SOOOIT CDC
B
SOO exp ( -SOOO IT)
SDlU1U2 = ( ) 6 ---'--'--( ...:..:........_-)-
lOexp-300lT C
A
+10 exp -BOOOIT CD
At T = 300
6-23
2.09 * 10-
9
COS
S = A::::O
DIV1U2 3.67 C A + 2.62 * 10-
6
CD
At T = 1000 and very low concentrations of D
S = .03617
DIU1U2 7.408C
A
+335C
D

If temperatme is the only parameter that can be varied, then the highest temperatme possible will result in
the highest selectivity. Also removing D will help keep selectivity high.
P6-9 (h) No solution will be given
P6-9 (i)
r
D
exp(-7000K IT)C
A
1I2
-r
v
- 1OC/
2
dF
A
--=r
dV A
dF
v
--=r.
dV v
R = F
AO
B v:
T


r
A
= r
B
= liA + r
2A
FA
C
A
=C
ro
--
FI
mol
C
IO
=0.4--
3
dm
F
Ao
= Crovo
dF
B
_.-=r, +R
dV B B
dF
D
--=r
dV D
s
liA = --1Oexp(-8000K IT)CAC
B
r
2A
= -1OOexp(-1OOOK IT)CA1I2C/12
These equations are entered into Polymath and the plots below are for the membrane reactor .. The code can
be modified to compare with the PFR results.
See Polymath program P69i.poJ.
POL YMA TH Results
Calculated values. of the DEQ variables
Variable
V
Fa
Fb
Fd
Fu
Cto
T
Ft
Cb
Ca
initial value
o
4
o
o
o
0.4
600
4
o
0.4
minimal value
o
0.5141833
o
o
o
0 .. 4
600
4
o
0.0241566
maximal value
10
4
4.5141833
3.034E-06
.3.4858137
0 .. 4
600
8.5141833
0.2120783
0.4
6-24
final value
10
0.5141833
4.51418.33
3 .. 034E-06
3.4858137
0.4
600
8.5141833
0.2120783
0 .. 0241566
rIa 0 -4.S7SE-07
rd 0 0
r2a 0 -0.4461944
ra 0 -0.4461948
rb 0 -0.4461948
ru 0 0
Vt S S
Fao 4 4
Rb o '. 8
0.8
Sdu S .. 423E+OS 2.894E-07
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Fa)/d(V) = ra
[2] d(Fb )/d(V) = rb+Rb
[3] d(Fd)/d(V) = rd
[4) d(Fu)/d(V) = ru
Explicit equations as entered by the user
[1] Cto =..4
[2) T=600
[3) Ft = Fa+Fb+Fd+Fu
[4) Cb = Cto*Fb/Ft
[5) Ca = Cto*FalFt
[ 6] r1 a = -1 O*exp( -8000IT)*Ca*Cb
[7) rd= -r1a
[8) r2a = -1 OO*exp( -1 OOOIT)*Ca
A
5*CbI\1 ,,5
[ 9) ra = r1 a+r2a
[10] rb = ra
[ 11] ru = -r2a
[12] Vt=5
[1.3] Fao = 4
[14] Rb = FaolVt
0 -8 .. 297E-08
4,S7SE-07 8.297E-08
0 -0.2867066
0 -0.2867066
0 -0.2867066
0 ,4461944 0,.2867066
S S
4 4
0.8 0.8
S '. 423E+OS 2.894E-07
[IS] Sdu = exp(-7000IT)*Ca
A
,5/(10*Cbl\,,5+,,00000000001)
5
4
3
2
1
2 .:I
V
6
P6-9 (j) No solution will be given
P6-9 (k) No solution will be given
P6-9 (I) No solution will be given
8
6.0e+5
48e+5
3,6e+5
2 -Ie+5
1.2e+5
O,Oe+O
10 0 2
.:I V 6
.-....... --.. ~ ..---.-.
10 s
6-25
P6-10 (a)
Spect<::5 A:
de
--"-:r
dt -\
-ro. = ktC,-\
Species B:
Species C:
de c _ ..
--c
dt
, , .. fC:::::: klC
B
Pluggmg mto POLYMATH: gets the following,

d(calldP::) "'rat
ci{co) /0.( t) =zo
dice) Id{:::) =rc
k,1-=.4
k2"'.{)1
ra", .. kl"ca
rc"k2"cb
rb"'k:;:'ca .. k2 "cb
key

. Cb
.. Cc
.
0
'"
0,
P6-10 (b)
t"
...
'"
1.00
For CSTR, T = O.Sh
First calculate kJ and k2 :


t 0
ca 1.6
cb ()
cc 0
kl 0.4
k2 0.01
ra 0 64
I'C 0
rb 0.54
6-26
MaximUlll ..
...
1.00 a 100
1.6 5.7898e-18 6' .. 789Be .. 18
1.4556 0 n.6037
0 .. 9963 0 () .9963
0.4 04 0.4
0.01 0.01 0 .. 01
2.'71592et8 -0.54 -2.71.S92e-18
0.014556 0 0.00603'1
-O.OU2417 0.006037
k =O.Olex (20'OOO(_1 __ J
2 P R 373 T
See Polymath program P6-1O-b.pol.
POL YMA)'H Results
NLES Solution
Variable Value
Ca 1 .. 5268515
Cb 0.0319385
Cc 0 .. 04121
tau 0.5
T 760
k1 0 .. 0958161
ra -0.146297
k2 2 .. 580579
rb 0 .. 0638771
rc 0.0824199
NLES Report (safenewt)
Nonlinear equations
f (x)
-6.446E-13
7.28E-14
0
[1] f(Ca) = tau*(ra)-(1 .. 6-Ca) = 0
[2] f(Cb) = tau*(rb)Cb = 0
[ 3] f(Cc) = tau*(rc)-Cc = 0
Explicit equations
[1] tau = .. 5
[2] T = 760
[3] k1 = 72*exp(-10000/(1 .. 987*T))
[4] ra = -k1 *Ca
[5] k2 = 1457152*exp(-20000/(t.987*T))
[6] rb = k1 *Ca-k2*Cb
[7] rc = k2*Cb
Cb vs" temperature
350E-02
3 .. 00E-02 +----.------
2.50E-02
lni Guess
1.5
o
o
I
~ 2.00E02
II
~
tl 1.50E02 - - - f - - - - - - \ - - ~
100E-02
I
5.00E-03 +-_________ -+--_________ .0...._1
o .OOE+OO--------.-----
------.-----------,-----J
o 200 400 600 800 1000 1200
temperature (K)
Therefore, C
B
is maximum at T=760K.
6-27
P6-10 (c)
(e) ?art is similar to part b except for two rate laws:
-k *(' k *('
fA - _II s - I' A
r =k *C-k *C -k, *C
a B 1 -,-\ -1 B ;.
Using those rate laws inPOLYThtlATH produce the following:
Eauations: _ ... __ .......-..,.,
d{ca) /d(t) ;::::r:-a
d(cb)Jd(tl=rb
d(cc) Id(tl ::::e'C
klr=8.33eS
k1"'.OOOl
k2=2.78e-5
rc:::k2"cb
ra=klr""cbklf"ca
var:iable In,itial
2.JC:: -_.
\ . .ti:::: -.
\
!.,2IJC 1
!\
o.oeo
c"cco 0.808
value Maximu.m value
-------.-'"'--- ~
t
ca
cb
cc
k.lr
klf
k2
rc
ra
:r:b
P6-10 (d)
0
1.6
0
(J
8 3.3e"05
0.0001
2.78e06
0
-0.00016
0.00016
350000
1.6
0.833237
0.647'784
S.33e05
0.0001
2.78e06
2 _ 3164e-- 06
6 _ S7168e--07
0.00016
Th isis similar to part d except for one rate law:
r -k' *C -_ok *C
c --"1 .... 8: .. -2 "'c
Using that in POL Th1ATH produces the following:
6-28
l!ti t ~ a 1 .. 1 : : ~
1.6
a
o
J.
Minim1.4'11 value
-_-.-. ....... _ ........... _ ........ _ ...............
0
0.436316
0
0
13. Be-OS
0.0001
2.78e-06
a
0.00016
--1.20632e06
-:inal value
.,. .......... _-, ...... ----.......
350000
0.4.16316
0.5159
0.64'1784
8 .. 33e-OS
0.0001
2.78e-06
1.4342e-06
-6. 57168e-- 07
.. 0' .7703 4e-... 07

d{ca)/d(t)=ra
d(cb)/d(t)=:::b
d(cc)/d(t);r;c
k1:::=8 _ 33E!-'S
k1.f= _, 0001
k2:=2,78e--6
k2r=1.. 3 %-6
ra"k1:r:-cb- kIf'cd
rc'"'k2f*cb-k2:::*cc
2 ce: T
i
5.:lC .!..
r'b=kl f"ca '" klr 'cb-- k2 f "cb+k2.::'cc
to
'"
(), t:l!
350000 .L
'"
Variable
__
----

t 0 150000 0
Cd 1. 6 1 5 a,490306
cb 0 0 833769 0
cc 0 0.525032 0
k1r
8,,33e,05 8 33e-05 8,33e'OS
kif 0.0001
() 0001 00001
kl: 2,788 06 2 730 06 2. ii3e' 06
k2: 1. 3%06 1. 3ge06 1 39806
::::d 0 oootS 4 115738-0'1 '0 ,00016
l:C 0 2 25569806 0
r;b 0, 00Gl6 0 GOO16 -1..124.93806
P6-10 (e)

350000
0 490306
0.583662
0,526032
8.33e05
0.0001
2.,78e-06
L '3%,,1)6
--,4 .11573e .. 0 7
8.91396,0-07
"4,, 79824eO)
(e) Vlhen kl>l00 and k2<O.1 the concentration of B immediately shoots up to 1,6 and
then slO\vly comes back down. while CA drops off irnmediate1y and falls to zero. This is
because the first reaction is so fast and the second reaction is slower with no reverse
reactions.
When k2 ;:;;; 1 then the concentratlon of B spikes again and remains high, while very
little of C is formed.. This is because after R is fonned it will not got to C because the
reverse reaction is faster.
Vlhell k-2 ::::: 0.25, B shoots up, but does not stay as high because the second reverse
reaction is a slightly slower than seen before, but still faster than the forward reaction..
P6-11 (a)
InteImediates (primary K-phthalates) are fOlmed flOm the dissociation of K-benzoate with a CdCh catalyst
reacted with K-terephthalate in an autocatalytic reaction step:
Series
R + S 2S Autocatalytic
C = 1l0kPa =0 02moll dm'
AD RT (8.314 kPa.dm')( 683K) .
mol.K
6-29
Maximum in R occurs at t = 880 sec. See Polymath program P6-11-a. pol,
POLYMATH Results
Variable initial value
t 0
A 0,02
R 0
S 0
k1 0.00108
k2 0.00119
k3 0.00159
ODE Report (RKF45)
minimal value
o
0.003958
o
o
0,,00108
0.00119
0.00159
Differential equations as entered by the user
[1] d(A)/d(t) = -k1 * A
[2] d(R)/d(t) = (k1*A)-(k2*R)-(k3*R*S)
[3) d(S)/d(t) = (k2*R)-(k3*R*S)
Explicit equations as entered by the user
[1] k1 = 108e-3
[2] k2 = 1,1ge-3
(3) k3 = 1 ,,5ge-3
P6-11 (b)
1) T= 703 K
CAO = 0,,019 mol/dm
3
Similarly,
maximal value
1500
0.02
0,0069892
0,0100382
0.00108
0.00119
0.00159
~ =3.3xlO-
3
s-
1
and ~ =3.1xlO-
3
dm
3
Imol.s
final value
1500
0.003958
0.005868
0.0100382
0.00108
0.00119
0.00159
Maxima in R occurs at around t =320 sec" See Polymath program P611b i pol
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value
tOO
A 0,019
R 0
S 0
kl 0 00264
k2 0.0033
k3 0.0031
ODE Report (RKF45)
3,,622E-04
o
o
0,,00264
0.0033
0.0031
Differential equations as entered by the user
[1] d(A)/d(t) = -k1 * A
[2] d(R)/d(t) = (k1 * A)-(k2*R)-(k3*R*S)
[3] d(S)/d(t) = (k2*R)-(k3*R*S)
Explicit equations as entered by the user
[1] k1 = 2,,64e-3
[2) k2 = 3,,3e-3
maximal value
1500
0,,019
0,,0062169
0,0174625
0.00264
0,,0033
0,0031
6-30
final value
1500
3,622E-04
8,856E-04
0,0174625
0.00264
0.0033
0.0031
[ 3 J k3 = 3,1 e-3
2) T = 663 K
CAO = 0,19 moIJdm
3
k; = (1.08xlO-
3
s-l)ex
p
( (42600cal / mol) (_I_-_I_)J = 0.42 X 10-
3
S-1
(1.987callmol.K) 683K 663K
~ =0.4xlO-
3
s-
1
~ = 0.78xlO-
3
dm
3
/ mol.s
See Polymath program P6-11-b2.pol.
POLYMA Tn Results
Calculated values of the DEQ variables
Variable initial value
t 0
A 0.019
R 0
S 0
k1 4.2E-04
k2 4.0E-04
k3 7.8E-04
ODE Report (RKF45)
minimal value
o
2.849E-04
o
o
4.2E-04
4.0E-04
7.8E-04
Differential equations as entered by the user
ll] d(A)/d(t) = -k1 * A
l2] d(R)/d(t) = (k1 * A)-(k2*R)-(k3*R*S)
[3] d(S)/d(t) = (k2*R)-(k3*R*S)
Explicit equations as entered by the user
[1] k1 = OA2e-3
[2] k2 = OAe-3
[3] k3 = 0,,78e-3
Independent variable
variable name: t
initial value: 0
final value: 10000
0.020.------,---------------,
0,004
2000 4000 t 6000 8000 10000
Maxima in R occurs around t = 2500 sec,
P6-11 (C)
maximal value
10000
0.019
0.0071414
0,016889
4.2E-04
4.0E-04
7.8E-04
final value
10000
2.849E-04
0.0012573
0.016889
4.2E-04
4,OE-04
7.8E-04
Use the Polymath program from part Ca) and change the limits of integration to 0 to 1200, We get:
CAexit = 0.0055 moIJdm
3
CRexit = 0.0066 mol/dm
3
6-31
C
Sexit
= 0,0078 mol/dm'
P6-12 (a)
P6-12 (c)
_ -riA _ (,7)(.1) , mol
f
lC
- "-""'- - -,,--- ::: 0,023 "-1"
3 j <inr*s
_-2*r
2D
_,2(3)(50
1
(.I) _ mol
f:c - - ...... -' -_ ... _--,. __ .,_. - == -"Q,O(h2"t--
3 3 dm' *5
lic =r
J
;:-(.2)("049)( .51) =
dm' *5
P6-12 (e)
'" mol
Ii" ::::: 0 liA = O .. ...... -
dm
3
*5
.. mol
'iE ::: liD::: 0,:: -".
dm's
r,E ::: (.2)(.049)(.51):::;: O.OOS .. ..!!!.ol
dm
3
.s
P6-12 (I)
fA ::: --0.07 - 0.0026 :::::: -0.0726 mol
Ie::: 0.023 .... ,0.0052 0.005 = O.0128 ....
dm- .5
fD = 0.0078 0.033 == 0 OOll"""il:..?L ...
dm
1
_s
P6-12 (h)
Mole balance: C
AD
- C A = (_ .. r
A
)r
C
c
= (rc}r
CD = (rD)r
P6-12 (b)
-riA (.7)(.1) .. mol
fIB :;;:: .... - == -_ ..... __ ... _:;;:: 0.023-""--,,,
3.3 dm
3
_$
r"ll = 0 * ro =: 0- m<:t._
... _D dm' _ s
1:,B ::: 0 * fj "" 0 ..
dm' .s
P6-12 (d)
P6-12 (g)
F,F
V=, .. M-, .. ..
.
..
"f
A
_ 100(3 ,0.1) _ 3
- .. ,_ ...._""' .... " ........ ::::: 4000dm
0,0726
Rate law, rA = -[ k"C
A
]
6-32
Solving in polymath:
SBID = I'B/rD = 247
See Polymath program P6-12h. pol.
POL YMATH Results
NLES Solution
var'iable Value
Ca 0.0068715
Cb 0.9620058
Cc 0.5097027
Cd 0.0038925
Ce 0,2380808
kd 3
ka 7
rb 0.0160334
ra -0.0498855
ke 2
rc 0,008495
rd 6,,488E-05
re 0,003968
tau 60
Cao 3
NLES Report (safenewt)
Nonlinear equations
[1] f(Ca) = Cao-Ca+ra*tau = 0
[2] f(Cb) = Cb - rb*tau = 0
[3] f(Cc) = Cc-rc*tau = 0
[4] f(Cd) = Cd-rd*tau = 0
[5] f(Ce) = Ce - re*tau = 0
Explicit equations
[1] kd = 3
[ ~ ] ka=7
[3] rb = ka*Ca/3
fIx)
-2.904E-10
-1 .. 332E-15
--1,67E-08
-2.391E-08
1.728E-08
l4] ra = -(ka*Ca+kd/3*Ca*CcJ\2)
[5] ke = 2
[6] rc = ka*Ca/3 - 2/3*kd*Ca*CcJ\2 ,. ke*Cd*Cc
[7] rd = kd*Ca*CcJ\2 - 4/3*ke*Cd*Cc
[8] re = ke*Cd*Cc
19] tau = 60
[10] Cao = 3
P6-12 (i)
For PFR and gas phase:
dF
A
Mole balance: --- = r
dV A
dF
B
--=r
dV B
lni Guess
3
o
o
o
o
dF
-.i:..=r
dV C
6-33
dF
_D_=r
dV D
dF
__ E =r
dV E
Rate law:
Stoichiometry:
FT =F
A
+FB +Fc +FD +FE
dy = -a FT
dV 2y FTO
Plot of C
B
and C
c
are overlapping.
See Polymath program P612i pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable
V
Fa
Fb
Fe
Fd
Fe
y
Ft
Cta
Ce
ka
kd
ke
Ca
rb
ra
Cd
Fta
re
rd
re
alfa
X
initial value
o
20
o
o
o
o
1
20
0 .. 2
o
7
3
2
0.2
04666667
-1.4
o
20
0.4666667
o
o
1.0E-04
o
ODE Report (RKF45)
minimal value
o
9 .. 147E-04
o
o
o
o
0.9964621
13.330407
0.2
o
7
3
2
1.367E-05
3.191E-05
-1..4
o
20
-1.923E05
-7 .. 012E- 05
o
1.0E-04
o
Differential equations as entered by the user
[1] d(Fa)/d(V) = ra
[2] d(Fb)/d(V) = rb
[3] d(Fc)/d(V) = rc
f 4] d(Fd)/d(V) = cd
[5] d(Fe)/d(V) = re
maximal value
100
20
6 .. 6638171
6 .. 6442656
0 .. 02012S8
0.0043322
1
20
0 .. 2
0 .. 0993605
7
3
2
0.2
o 4666667
-9.S86E-05
3 .. 0E-04
20
0.4666667
8 .. 653E-04
S .. 908E-OS
1.0E-04
0 .. 9999543
6-34
final value
100
9.147E-04
6.6638171
6 .. 6442167
0 .. 0171261
0 .. 0043322
0 .. 9964621
13 .330407
0.2
0.0993325
7
3
2
1 .. 367E-OS
3 .. 191E-OS
-9.S86E-05
2.S6E-04
20
-1 .. 923E-05
-6.742E-OS
5 .. 087E-05
1.OE-04
0.9999S43
[6] d(y)/d(V):::: -alfa*Ft/(2*y*Fto)
Explicit equations as entered by the user
[1] Ft:::: Fa+Fb+Fc+Fd+Fe
[2] Cto:::: 0.2
[3] Cc:::: Cto*Fc/Ft*y
[4] ka:::: 7
[5] kd:::: 3
[6] ke:::: 2
[7] Ca:::: Cto*Fa/Ft*y
[8] rb:::: ka*Ca/3
[9] ra:::: -(ka*Ca+kd/3*Ca*Cc
A
2)
[1. 0 1 Cd:::: Cto*Fd/Ft*y
[Ill Fto::::0 .. 2*100
[12J rc:::: ka*Ca/3 - 2/3*kd*Ca*Cc
A
2' ke*Cd*Cc
[13] rd:::: kd*Ca*Cc
A
2 - 4/3*ke*Cd*Cc
[lA] re:::: ke*Cd*Cc
[15J alfa:::: 0.0001
[16] X::::1-Fa/20
12
!l
>4
\I
0
(I ..!l$(f
#.,1124
(I,out
iJAltZ
1) .IlM
n.IiOO
Il 41l V 6(1
H)O
P6-12 G) Changes in equation from PaIt (i):
dF
c
dV = rc -Rc Rc = kdiffilSeCC
k = 2 . -1
diffilSe nun
See Polymath program P612-j.po1.
6-35
40. 60
. V
..
20r----------------------------,
16
12
8
4
40 V 60 80 100
P6-13 (a)
m-xylene --> benzene + methane
A -->B +M
m-xylene --> p-xylene
A --> P
See Polymath program P613 .. a.pol.
POLYMA TH Results
Calculated values of the DEQ variables
Variable
-'--
V
initial value
o
minimal value
o
Fa
Fb
Fp
Fm
Fi
Ft
k1
k2
Cta
Ca
rl
Cb
r2
Cp
Spb
tau
y
X
75
o
o
o
25
100
0.22
0.71
0.05
0.0375
-0.00825
o
-0.026625
o
o
o
o
o
ODE Report (RKF45)
6.1072984
o
o
o
25
100
0.22
0 .. 71
0.05
0.0026257
-0.00825
o
-0 .. 026625
o
o
o
o
o
Differential equations as entered by the user
[ 1) d(Fa)/d(V) = r1 +r2
[2) d(Fb)/d(V)=-r1
[3) d(Fp)/d(V) = -r2
Explicit equations as entered by the user
[1) Fm = Fb
[2) Fi =25
[3) Ft = Fa+Fb+Fp+Fm+Fi
[4J k1 = ,,22
0,020.--------------------------,
0.016
~
lBJ
40 V 60
maximal value
6000
final value
6000
6.1072984
16 .. 297198
52.595503
16 .. 297198
25
116.2972
0.22
75
16.297198
52.595503
16.297198
25
116.2972
0.22
0.71
0.05
0.0375
-5 .. 777E-04
0.0070067
-0.0018643
0.0226125
3.2272267
3
0,7634409
0.9185694
0.71
0.05
0.0026257
-5.777E-04
0.0070067
-0.0018643
0.0226125
3.2272267
3
0 .. 7634409
0.9185694
80 100
6-36
[5] k2 = .. 71
[6] Cto = .. 05
[7] Ca = Cto*Fa/Ft
[8] r1 = -k1*Ca
[9] Cb = Cto*Fb/Ft
[ 10 ] r2 = -k2*Ca
[11] Cp = Cto*Fp/Ft
[12] Spb = Cp/(Cb+ .. 0000001)
[13] tau = V/2000
[14] Y = Fp/(75 .. 00000001-Fa)
[15] X = (75-Fa)/75
a l' = 2.8 is necessary to achieve 90% conversion
10r--------------------------, 4.0 .-----------------------------,
0.8
3.2 .---.----..... ---.----.. ---. -----
0 .. 6 2t
L6
0 .. 8 r ........ .
2tOO V 3600 4800 6000
0 .. 0
0
P6-13 (b)
CSIB
Mole Balances:
Rate La\vs.
"E r I ')
.,," . 1
k :;:; k. exp. ,,_.d -." - -. " .....
l ,0 R IT 946
\. ./
I ~ ~ P j
1200 2400 V 3600 4800
\
F =1" V
M M
:c == r V
? P
Using these equations and Polymath we find the optimal temperature is 1194 K. The maximum
concentration of p-xylene is 0.013 mol/dm
3
See Polymath program P613b.pol.
pOLYMA THResul!
NLES Solution
Variable
Ca
Cb
Cm
Cp
Cao
tau
k10
E1
R
k20
E2
Value
0 .. 012197
0 .. 0122301
0 .. 0122301
0 .. 0130729
0.0375
0.5
0 .. 22
2 .. 0E+04
1.. 987
0.71
10000
f(x)
7 .. 15E-ll
5 .. 284E-12
5 .. 284E-12
-3 .. 069E-ll
Ini Guess
0.0375
o
o
o
6-37
6000
Yp 0.5166557
T 1194
k1 2.0054175
rb 0.0244601
rm 0.0244601
k2 2.143628
rp 0.0261459
ra -0.050606
NLES Report (safenewt)
Nonlinear equations
[1] f(Ca) = Ca-Cao-ra*tau = 0
[2] f(Cb) = Cb-rb*tau = 0
[3] f(Cm) = Cm-rm*tau = 0
[4] f(Cp) = Cp-rp*tau = 0
Explicit equations
[1] Cao = .0375
[2] tau = ,,5
[3] k1o=,,22
[4] E1 = 20000
[5] R = 1.987
[6] k20 = .71
[ 7] E2 = 10000
[8] Yp = Cp/(.03750000001-Ca)
[9] T= 1194
[10] k1 = k1o*exp((E1/R)*(1/946-1/T
[11] rb = k1*Ca
[12] rm = k1 *Ca
[13] k2 = k2o*exp((E2/R)*(1/946-1/T
[14] rp = k2*Ca
[ 15] ra = -k1 *Cak2*Ca
-_._----------- ---------------------
P6-14(a)
50dm
3
PFn
Mole balance:
dCA
<IV
dCc
dll
[
11(:
=
dV
f';\
Vo
rc
Vo
./ B
Vo
deB f'13
.::::::: ~
dl
T
dev
dV Uo
tlOr Fp
dV' = ~ ~ ;
6-38
Rate laws:
r .'1'1' U 1-- ~ l :;2
Fa 2rVI l'F:"
l'c rlJ 1 I' [::2 . "21'1' 3
tn TO] 2TB2 I TF:)
'IE TE2
Til(} equation for I.he conversion ur A is :
GAU C-"I
)( = ... ----.
C
AO
See Polymath program P6-14a. pol.
POLYMATH Results
No Title 08-01-2005, RevS 1.233
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
------
t 0 0 50 50
Fa 15 0 .. 2090606 15 0.2090606
Fb 20 1. 3440833 20 1.. 3440833
Fe 0 0 1 .. 9655663 0.3535564
Fd 0 0 7 .. 2554436 6 .. 4570707
Fe 0 0 2.5920934 2 .. 5920934
Ff 0 0 4.6265981 4.6265981
va 10 10 10 10
Caa 1..5 1.5 1.5 1.5
Cba 2 2 2 2
Ft 35 15 .. 582463 35 15 .. 582463
Cta 3.5 3.5 3.5 3.5
kd1 0 .. 25 0 .. 25 0 .. 25 0.25
ke2 0.1 0 .. 1 0 .. 1 0 .. 1
kf3 5 5 5 5
Ce 0 0 0 .. 228291 0.0794128
Cd 0 0 1.. 4503322 1 .. 4503322
Cb 2 0 .. 3018965 2 0 .. 3018965
Ca 1.5 0 .. 0469574 1..5 0.0469574
rd1 1.5 0 .. 0010699 1.5 0.0010699
re2 0 0 0.1004639 0.0068104
rf3 0 0 0.3632767 0 .. 0095194
re 0 0 0.1004639 0 .. 0068104
rf 0 0 0.3632767 0 .. 0095194
rd 1..5 -0.042376 1..5 -0 .. 0030314
ra -.1. 5 -1.5 -0 .. 0215011 -0 .. 0215011
rb -3 -3 -0 .. 0116593 -0 .. 0116593
re 1..5 -0 .. 0962952 1..5 -0.0111585
ODE Report (RKF45)
Differential equations as entered by the user
6-39
[1] d(Fa)/d(t) = ra
[2] d(Fb )/d(t) = rb
[3] d(Fc)/d(t) = rc
[ 4 ] d(Fd)/d(t) = rd
[5] d(Fe)/d(t) = re
[ 6 ] d(Ff)/d(t) = rf
Explicit equations as entered by the user
[1] vo= 10
[2] Cao = 1.5
[3] Cbo = 2
[4] Ft = Fa+Fb+Fc+Fd+Fe+Ff
[ 5] Cto = Cao+Cbo
[6] kd1 = 0.25
[7] ke2 =.1
[8] kf3=5
[ 9] Cc = Cto*Fc/Ft
[ 10] Cd = Cto*Fd/Ft
[ 11] Cb = Cto*Fb/Ft
[12] Ca = Cto*Fa/Ft
[13] rd1 = kd1 *Ca*Cb
A
2
[14] re2 = ke2*Ca*Cd
[15] rf3 = kf3*Cb*Cc
A
2
[16] re = re2
[17] rf = rf3
[18] rd = rd1-2*re2+rf3
[19] ra = -rd1-3*re2
[20] rb=-2*rd1-rf3
[21] rc = rd1 +re2-2*rf3
20
16
12
8
-4
()
o 10 20 V 30
P6-14 (b)
- Fa
- Fh
- Fe
- Fd
- Fe
40 50
(b) Det.ermine the effiuellt concentration and eOllversion from a. 50dm:
3
CSfI'll.
IVlo]e Balanee:
} ~ i O f:4 -TA V
F
HO
P
H
~ ~
THV
F
c
' TCV
Fl.) TDV
6-40
F1:; J'E V
FI" 1'FT-l
I == . combining rate law and lllUlc halancc,
- 110' 'J .
fleA)
.t(C
H
)
f(Cd
f"' C )
, \ ... /),
f(C
FJ
)
f(CF)
Polyumth code,
C
A
C.fto rAi
C B -- C'BO-- rBl
--,Cc: + reT
--Co I rvT
--C'B + t ET
--(/p + 'fFT
f (ca)=ca-caO""xa*tau
f(cb)-cb-cbO-rb*tau
f (cc) =r c*tau-cc
f(cd)=rd*tau-cd
f(ce)=tau*re-ce
f(cf)=tau*rfcf
tau""V/vo
V=50
\'0=10
caO=1,5
cbO=2.0
rd1=kdl*ca*cb"2
re2"'ke2*ca*cd
rf3=kf3*cb*cc'2
kdl"'0,25
ke2=O.1
kf3=5
ra=rdl3*re2
rb=2*rdlrf3
rC"'l'd1.+re22*rf3
rd=rdl 2*re2+rf3
re=re2
rf=rf3
ca(O).,;;l
cb(O)=!
cc(O);l
cd(O)=l
ce(O)=l
cf(O)=1
(Ans) C/I = 0,6 t, e
u
= 0 79, C
c
() 11, CD = 045, CEO:; 0 14, Cp = 025
P6-14 (C)
(c) V(J = ilOdlll:; S(,wj,Batch tendor, (l) A is fed to B, (2) B h" fed to A
(Catle 1) A itl fod to 13,
6-41
dCA
+
CAO CA
- rA tiO
elt
deu en
a"
-
t'jj
--voV'
dCC)
C
e
,

= 1'C
....
vo_-
V
de
D CD
. l'J)
..
vov
dt
dCs C
E
= rp;
."yo.
tJoV
dt
deF OF
elt
-- l"f'
.... vo--
V
.t'{
(C80 (:8)
_._ ...._-----
CBO
alld mudifying eorrespondiug ]>OlYlllHt.h code.
d(ca)!d(t)=ravo!V*ca
d(cb)!d(t)"'.rb+vo!V*(cbOcb)
ca(O)=1.5
cb(O)"O
x"'(caOca)!caO
Diffol cntes
(1) Becallse Cs
o
is highel than CAO (i.e ;10% higher molar flow rate), case (2) fenches 1 ill e!ulier time.
(2) \Vitll the snme reason, C(ISC (2) produces D and F mote
(3) With the same reason, e
B
(in tilSC 2) increases more dwstkally(exeessivcly) than GA (ill ease 1)
(<.:) case I concentration vs., lime
"'"
\
G1dl)h litle
''''
1.<10
\
,
\
110
., .
. ",
""
''''
.. .. ! ..
,
6-42
Case
HIO
041}
016
conversion VS, time
0.00 woo 2000
1
case ttl
, __ .",.,_"-____ ... ___ -..< ...... ___ ..... ___ -'-____ '-___ ..1
3j) flO 41} 00 5000 &0 DO 70.00 eliDa 90 on 100 llil
t
Case 2 concentration vs. time
lW
111
!"S2'
lH
IH
:P ~ j
\
\
\
I
\
\
\
;I
" d
6-43
Case 2 conversion vs. time
1.00
--_ .. _._--
090
OSO
Q 70
01>0
050
case (2)
040
0.30
02f1
D.li!
0.00 '---......... ---'---.--'-----'!'--.. -.-...--...... ~ ........ ---'----....... ----' ..... --....
0.00 1000 2DOO 3000 40.00 50.00 60.00 701)0 80.00 gaoa 10000
P6-14 (d)
As a
B
increases the outlet concentration of species D and F increase, while the outlet concentrations of
species A, C, and E decrease .. When a
B
is large, reactions 1 and 3 are favored and when it is small the rate
of reaction 2 will increase ..
P6-14 (e)
When the appropriate changes to the Polymath code from part (a) are made we get the following.
See Polymath program P6-14e.poL
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
V 0 0 500 500
Fa 20 18.946536 20 18.946536
Fb 20 18 .. 145647 20 18.145647
Fe 0 0 0.9342961 0.9342961
Fd 0 0 0.8454829 0.8454829
Fe 0 0 0.0445942 0.0445942
Ff 0 0 0.0149897 0.0149897
vo 100 100 100 100
Ft 40 38.931546 40 38.931546
Cto 0.4 0.4 0 .. 4 0.4
kd1 0.25 0.25 0.25 0 .. 25
ke2 0.1 0.1 0 .. 1 0.1
kf3 5 5 5 5
Ce 0 0 0.0095994 0.0095994
Cd 0 0 0.0086869 0 .. 0086869
Cb 0 .. 2 0.1864364 0.2 0.1864364
Ca 0 .. 2 0.1946651 0.2 0 .. 1946651
rd1 0 .. 002 0.0016916 0.002 0.0016916
re2 0 0 1. 691E-04 1.691E-04
rf3 0 0 8.59E-05 8.59E--05
re 0 0 1 .. 691E-04 1.691E-04
rf 0 0 8 .. 59E-05 8.59E-05
6-44
rd 0 .. 002 0 .. 0014393
ra -0.002 -0.0021989
rb -0 .. 004 -0 .. 004
re 0 .. 002 0 .. 0016889
Sed 1 1
Sef 0 0
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Fa)/d(V) = ra
[2] d(Fb )/d(V) = rb
[3] d(Fc)/d(V) = rc
[ 4] d(Fd)/d(V) = rd
[5] d(Fe)/d(V) = re
[6] d(Ff)/d(V) = rf
Explicit equations as entered by the user
[1] vo = 100
[2] Ft = Fa+Fb+Fc+Fd+Fe+Ff
[3] Cto = A
[4] kd1 = 0..25
[5] ke2 = .. 1
[6J kf3=5
[ 7 J Cc = Cto*Fc/Ft
[8] Cd = Cto*Fd/Ft
[ 9 J Cb = Cto*Fb/Ft
[10] Ca = Cto*Fa/Ft
[11] rd1 = kd1 *Ca*CbJ\2
[12] re2 = ke2*Ca*Cd
[ 13] rf3 = kf3*Cb*CcJ\2
[14] re = re2
[15] rf=rf3
[16] rd=rd1-2*re2+rf3
[ 17] ra = rd1-3*re2
[18] rb = -2*rd1-rf3
[19] rc = rd1+re2-2*rf3
[20] Scd = rc/(rd+..0000000001)
[21] Sef = re/(rf+ .. 00000000001)
0.002 0 .. 0014393
-0 .. 002 -0.0021989
-0.003469 -0.003469
0.002 0 .. 0016889
1.1734311 1 .. 1734311
83 .. 266916 1.9686327
1.20 90 ,--------- - - . - - - ~
~ ~ ~ .... . . . - . ~ ...." ...
_. __ .---------
0.96
0.72
048
0.2-1
(100
o 100
P6-14 (1)
C-SI"
~
200 V 300 400
72
54
36
18
o
500 0
dF
The only change from part (e) is: d ~ - = r
D
- kcDC D
6-45
............................. . - ......
100 21)0 V 300 400 500
See Polymath program P6-14-f.pol.
1.15 125,.--------------,
-----------" . --... .. -
100
0.69
1- Scid J
046
0,23

P6-14 (g)
dF F
The only change from part ( e) is: _---1L = r --1rQ..
dV B V
T
where V r = 500 dm
3
and F
BO
= 20 moVmin
See Polymath program P6--14-g,pol.
1.2 ,.-------------.
1.0
07
0 .. 5
0.2
flO '------.
o 100 200 V 300 400 500
P6-1S (a)
75
50
25
o 0
100 200 V 300 400
700.------
560
420
280
140
o
...... -... -.-..".-"" ...... "--.. -.,, .... -..... ..
I)
100 200 V 300 400
6-46
500
500
(a) Enter the given program into POLY?vlATH Equations for the concentrations
must be added.
The following maximums can be seen in the graph given (More exact values can
be found in (he corresponding table in POLY1VIATH )
CCm.u. == 0 .. 0434 and C
Dtrcu
;:;: 0.0033
i .: ..
0
,*(fd/ft)
d(fal/d(v)=-kl
O
(fa/fcl*lfb/ft)"(1!21-k2*(fa/ftl*W2
d{fbl/dlv'=-kl/2*'fa/ft)-,fb/fcj11/2)
d(fw}!d(v)=k3*lfc/ftl-k4*(fw/fc)*(fd/it)
d(fd)!dlv)=k2IZ*lfa/fc'Z-k4 (fd/ft)* (fwiftl
d(fe) /d{v} ::ok)'" (re/ft)
d(fg) Id{v} ",k4* (fw/ft.) * (Ed/ft)
kl=O .. 04
f t=fa ,fb+ fc+fd+ fetfw+fg
k2=O.007
k3=O 01.4
k4=O 45
vo=lOO
cto",O .. 147
ca"'cto" (fal it)
cb"'cto*(fb/it)
cc,,"cto*(fc/ftl
cci=cto*(fd/ft)
ce=cto*(fe/ft)
cw=cto' (fw/ft)

VI) "" 0,
P6-15 (b)
1000
..
C.2ca
c.aca
;
a.oco
o CDO
6-47
C:.2:::'C :::. :soc
9.8.3
4.91
o
o
o
o
."'., ............. , .....
(b) Overall yield of HCOOH:
Selectivity of HCHO to CO:
- F
S - .. ..
,\E F,
E
Selectivity of HCOOCH
3
to CH.;OH:
Selectivity of BCaOH to HCOOCH
J
:
ell
8 02 =C-
A
Add these equations to the previous program and use it to generate the desired plots ..
o .. acc
1
OSCJ
i
r
"S.tioo f.
t
I
o. "CO
l
O'10C
T
-:--
C ...
?.ne 1.
1
LL __ .. ___ .
P6-15 (c)
6-48

)tp2
(c) Modify the original POLY1-IATH program by adding y to each of the
concentration terms Also add (he followil1g equation:

a ::= 0002 Fro"" 15
The graphs of concentration down the reactor are very similar to those generated
in Palt (a),. The only major difIerence is that with the change in pressure, the
maximum reactor volume is significantly smaller.
, ..
d{ fe)/d (vl =kl* (fa/fe) .. (fb/fe.) "* (1/2 )*y k3" (fe/ft) "'y+k4" (f 0
w/ft)"(fd/ft)"y
d(fa) Id(v) '=-kl* (fa/ft) * (fb/ft) ** O/2)yk2* (fa/ft) 'H2*y 10
d(fb} Id(v) ;;:kL/2* (fa/ft) * (fb/n.) ** (1/2) *y 5
d (fw) Id (v) =k3'" (fel ft) *y .. k4" C fw/ ft) .. (fd! ft) *y 0
d (fd) Id (vl ;k2/2" (fa/ft.) '"*2 *yk4" (f' .... /ft) * (fd/ft) *y a
d(fe)/d(v)=k3*Cfc/ft)*y 0
d(fgl/d(vl=k4*(fw/ft)"(fd/ft)*y 0
d(y)/d(v)=-O.002/2/y*(ft/fto) 1
k2=O,,007
kl",Q,04
ft=fa+fb+tctfd+fe+fw+fg
k3=O.014
k4;;;O.45
vo=1011
ca",fa/vQ
cb=fblvo
cc=fc/vo
cd::;ofd/vo
ce=fe./vo
cg=fg/vo
Vo '" 0,
P6-15 (d)
COlICentralion profile with pre Ul'C .ha:nge
-J.fJCO
c.coo
COlICentIalion profile with pre"Ul'C .hange
6-49
r fJ 1 1 \'\
k" "'" k, eXt11. ~ I ---"-""'. l.)
., ,n \ R\ T 1',.)
Subsdtute this equation in for all of the k values. Vary 'r and find Dut wbat
temperature maximizes the yield of C,
The 'best temperature at \vhich to ron the reactor is 523 K or 250"(;.
P6-16 (a)
(a)
Mole Balances:
Rate Laws:
dF
c
_,"-'-=r
dV C
dF
p
,-=f
dV p
dF
A
--=f
dV A
Ie ::;:: --kl C
c
-- k
2
C
e
fA ;;;;:;k1C
C
+kJCp ,--k,;C" "kJCA
dF
o
--,-=t
dV 0
Stoichiometry:
C
"" ., (FI')
'I' =L!'o F ~
c =: C (.F{.>,,)
o ro F
l'
F =F:+F +F +F
I CPA 0
Use these equations in POLYMATH to generate aplol of the flow rates vs. 't ..
P6-16 (b)
f,e
ip
fa
fo
(b) For a CSTR
;:r:;.,-:::;t; ..
\
15.:::<: . \
'.
\
Mole Balances: Fc = Fco + Ie V
Rate Laws:
6-50
.. -"
.. '
Fo =r
o
V
!'p = ktC
c
-- k3Cp+ k
4
C
A
fo == kSC
A
Swichiometry :
Combine: f(C
c
) =: 0 = CcC
e
" -;- (k
1
+ kzTc'"
fCC?) = 0 = C
p
- (kiC c- K)Cp + k ,eA)r:
f(C
A
) =O=C
A
..... (ktC
c
... kJC
p

f(C
o
)= 0= Co ...... kSCAr
Use these equations in POLYMATH to generate values for the flow lates at different
values of 1: Use these values to generate the desired etHve.
200
!80
Wl
14()
120
100
80
60
:j()
20
()

f (eel "'CC "000+ (kltk2)
(cp) "'cp" (kl *co-kJ"cp+k4"'cal ""tau
(ca} =ca (kl""cc-k3 cpk4ca-kS "'cal' tau
f (co) =co-kS"ca"tau
cco=2
kl",O.12
k2=O .046
k3",O. {)2

vocolO
kS=() .. 04
V",3DOO
fc;:,:vocc
fp=vo*cp
fa-:vo*ca
o;vo"co

0 50 leo
cc
c:p
Cil
co
cco
k 1
k .?

k .,
.J
k4
\/0
k5
U
fc
ip
fa
fa
tau
(b) Flow rates vs. 1;
150 200 250
1; (nJill)
P6-16 ( C) Individualized solution
6-51
350
Sol wt 1 0<1
ll. 039:370 1
0 .. 211711
O. Df.J633865
O. Cl?S0638
2
D.t2
(] 046
C. D2
CU134
10
3COU
C. '393701
2 .. ,171 t
0.(;63:3865
D.76()638
300
. Fe
... FP,
-FA'
Fe) .
I;niS1:a1. vah:e
2
o
o
o
8.54':5e"'7
.- 1. ()78e--16
.. 2 .. :30ge15
'8,518e 18
P6-17 Individualized solution
P6-18 (a)
Blood coagulation living example
See Polymath program P6-18.po[
OLYMA TH Results
Example CD Solved Problems - Blood Coagulation 08-25-2005, Rev51233
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
t 0 0 700 700
TF 2. SE-ll 8.24E-14 2 .. SE-ll 8.24E-14
VII 1. OE-08 3.S13E-10 1. OE--08 3.S13E-10
TFVII 0 0 2.027E-ll S.71E-12
VIla 1. OE--10 1. OE-10 9.724E--09 9.724E-09
TFVIIa 0 0 3.361E-13 1.. 66SE-13
Xa 0 0 1.481E-09 1.481E-09
IIa 0 0 2.487E-07 1. 846E-09
X 1.6E--07 1. 426E-07 1. 6E-07 1.426E-07
TFVIIaX 0 0 1.869E-13 8.423E-14
TFVllaXa 0 0 S.673E-14 2.608E-14
IX 9.0E-08 8.994E-08 9.0E-08 8.994E-08
TFVllaIX 0 0 7.2E-14 3.S68E-14
IXa 0 0 3 .. S79E-ll 3. S79E-ll
II 1.. 4E-06 -3.41E-24 1. 4E-06 -1. OSE-2S
VIII 7 .. 0E-I0 -2.024E-28 7.0E-IO -1.026E-38
VIlla 0 0 S.3S2E-I0 3.366E-ll
IXaVllla 0 0 2.988E-12 2.873E-12
IXaVlllaX 0 0 S.372E-12 4.99SE-12
VIIlalL 0 0 6.S8SE-10 6.S8SE-10
VIIla2 0 0 6.S8SE-10 6.S8SE-10
V 2 .. 0E-08 -1.SSE-S2 2.0E-08 2.793E-90
Va 0 0 1.943E-08 S.077E--09
XaVa 0 0 1 .. 492E-08 1.492E-08
XaVaII 0 -3.938E-26 2.281E--10 -6.977E-27
mIla 0 -8 .. 77E-2S 3.788E-07 1. 663E-2S
TFPI 2.SE-09 2.094E-09 2.SE-09 2.094E-09
XaTFPI 0 0 3.867E-I0 3.867E-IO
TFVIIaXaT 0 0 1 .. 881E-ll 1. 881E-ll
ATIII 3 .. 4E-06 2 .. 001E-06 3.4E--06 2.001E-06
XaATIII 0 0 6.073E-IO 6.073E-10
mllaATIII 0 0 8 .. 247E-07 8.247E-07
IXaATIII 0 0 1.301E-ll 1.301E-ll
TFVlIIaAT 0 0 8.,3S4E-14 8.,3S4E-14
IIaATIII 0 0 S.,734E-07 S.,734E-07
kl 3.2E+06 3.2E+06 .3 .. 2E+06 3 .. 2E+06
k2 0.0031 0.0031 0.0031 0.0031
k3 2 .. 3E+07 2.,3E+07 2.3E+07 2.3E+07
k4 0.0031 0.0031 0.0031 0 .. 0031
kS 4 .. 4E+OS 4 .. 4E+OS 4.4E+OS 4.4E+OS
k6 1. 3E+07 1. 3E+07 1 .. 3E+07 1. 3E+07
k7 2 .. 3E+04 2.3E+04 2 .. 3E+04 2 .. 3E+04
k8 2.SE+07 2.SE+07 2.SE+07 2.SE+07
k9 1. OS 1. OS LOS 1. OS
k10 6 6 6 6
kll 2 .. 2E+07 2.2E+07 2.2E+07 2.2E+07
k12 19 19 19 19
k13 1.0E+07 1.OE+07 1.0E+07 1.0E+07
k14 2.4 2.4 2 .. 4 2.4
6-52
k15 1.8 1..8 1..8 1..8
k16 7500 7500 7500 7500
k17 2.0E+07 2"OE+07 2 "OE+07 2 .. 0E+07
k18 1.0E+07 1 .. 0E+07 1 .. 0E+07 1 .. 0E+07
k19 0.,005 0 .. 005 0.,005 0 .. 005
k20 1 .. 0E+08 1.0E+08 1. OE+08 L OE+08
k21 0.001 0.001 0.001 0.001
k22 8.2 8.,2 8.2 8.2
k23 0.006 0 .. 006 0.006 0.006
k24 2.2E+04 2 .. 2E+04 2.2E+04 2 .. 2E+04
k25 0 .. 001 0 .. 001 0,,001 0 .. 001
k26 2.0E+07 2 .. 0E+07 2 .. 0E+07 2.0E+07
k27 4.0E+08 4.0E+08 4.0E+08 4.0E+08
k28
0,,2 0.,2 0.2 0.2
k29 1.0E+08 1. OE+08 1.0E+08 1 .. 0E+08
k30 103 103 103 103
k31 63 .. 5 63.5 63.5 63.5
k32 1.5E+07 1 .. 5E+07 1 .. 5E+07 1.5E+07
k33 9.0E+05 9 .. 0E+05 9 .. 0E+05 9.0E+05
k34 3.6E-04 3.6E--04 3.6E-04 3.6E-04
k35 3.2E+08 3.2E+08 3 .. 2E+08 3.2E+08
k36 1 .. lE-04 1.1E-04 1.1E-04 1.lE-04
k37 5 .. 0E+07 5 .. 0E+07 5 .. 0E+07 5.0E+07
k38 1500 1500 1500 1500
k39 7100 7100 7100 7100
k40 490 490 490 490
k41 7100 7100 7100 7100
k42 230 230 230 230
r1 8,OE--13 9 .. 728E-17 8 .. 0E-13 9.728E-17
r2 0 0 6.283E-14 1. 782E-14
r3 5 .. 75E-14 L 735E-14 5.75E-14 1. 855E-14
r4 0 0 1 .. 042E-15 5.189E-16
r5 0 0 9 .. 923E-16 2.696E-17
r6 0 0
1_444E-ll 6 .. 953E-12
r7 0 0
4 _ 073E-ll 1_602E-14
r8 0 0
1_318E-12 5 _ 971E-13
r9 0 0 1.962E-13 8.896E-14
r10 0 0 1 .. 121E-12 5.083E-13
r11 0 0 5 .. 381E-15 5 .. 381E-15
r12 0 0 1.078E-12 4 .. 982E-13
r13 0 0 3.024E-13 1_ 506E-13
r14 0 0 1,728E-13 8.609E-14
r15 0 0 1 .. 296E-13 6.456E-14
r16 0 -1. 6E-29 2.883E-13 4 .. 511E-30
r17 0 -9 .. 831E-28 1.159E-ll -4 .. 231E-40
r'18 0 0 4 .. 674E-14 1.217E-14
r19 0 0 1 .. 494E-14 1. 439E-14
r20 0 0 4.406E-ll 4.106E-ll
r21 0 0 5,372E-15 5.006E-15
r'22 0 0 4.405E-ll 4 _105E-ll
r23 0 0 3 .. 211E-12 2 .. 044E-13
r24 0 0 9 .. 527E-15 9 .. 527E-15
r25 0 0 5 .. 372E-15 5.006E-15
r26 0 -2 .. 108E-52 3 .. 312E-10 1 .. 152E-91
r27 0 0 2,999E-09 2 .. 999E-09
r28 0 0 2,,974E-09 2.974E-09
r29 0 -3.763E-24 3 .. 764E-08 6 .. 12E-25
r30 0 -4 .. 056E-24 2,35E-08 1,,105E-24
r31 0 -2.5E-24 1,449E-08 6,81E-25
r32 0 -1 .. 733E--25 7.132E-09 7.062E-26
r33 0 0 2.762E-12 2,762E-12
r34 0 0 1 .. 372E-13 1.372E-13
r35 0 0 4 .. 492E-14 1.762E--14
r36 0 0 2.065E-15 2.065E-15
r37 0 0 3 .. 19E-15 3.19E-15
r38 0 0 4,387E-12 4.387E-12
r39 0 -1,248E-26 7 .. 708E-09 4 .. 499E-27
6-53
r40
r4I
r42
Total
o
o
o
o
ODE Report (STIFF)
o
o
o
o
Differential equations as entered by the user
[1] d(TF)/d(t) = r2-r1-r3+r4
[2] d(VII)/d(t) = r2-r1-r6-r7-r5
[ 3] d(TFVII)/d(t) = r1-r2
[4] d(Vlla)/d(t) = -r3+r4+r5+r6+r7
3 .. S02E-14
4.224E-09
1. 78E-16
S.749E-07
3.S02E-14
2.704E-ll
7 .. 70SE-17
1.903E-09
[5] d(TFVlla)/d(t) = r3-r4+r9-r8-r11 +r12-r13+r14-r42-r37 +r15
[ 6] d(Xa)/d(t) = r11 +r12+r22-r27 +r28-r33+r34-r38
[7] d(lIa)/d(t) = r16+r32-r41
[8] d(X)/d(t) = -r8+r9-r20+r21 +r25
[ 9] d(TFVllaX)/d(t) = r8-r9-r10
[ 10] d(TFVllaXa)/d(t) = r10+r11-r12-r35+r36
[11] d(IX)/d(t) = r14-r13
[12] d(TFVllaIX)/d(t) = r13-r14-r15
[ 13] d(lXa)/d(t) = r15-r18+r19+r25-r40
[14] d(II)/d(t) = r30-r29-r16
[15] d(VIII)/d(t) = -r17
[16] d(Vllla)/d(t) = r17 -r18+r19-r23+r24
[17] d(lXaVllla)/d(t) = -r20+r21 +r22+r18-r19
[18] d(IXaVlllaX)/d(t) = r20-r21-r22-r25
[19] d(Vllla 1 L)/d(t) = r23-r24+r25
[20] d(Vllla2)/d(t) = r23+r25-r24
[21] d(V)/d(t) = -r26
[22] d(Va)/d(t) = r26-r2TH28
[23] d(XaVa)/d(t) = r27-r28-r29+r30+r31
[24] d(XaVall)/d(t) = r29-r30-r31
[25] d(mlla)/d(t) = r31-r32-r39
[26] d(TFPI)/d(t) = r34-r33-r35+r36
[27] d(XaTFPI)/d(t) = r33r34-r37
[28] d(TFVllaXaTFPI)/d(t) = r35r36+r37
[ 29] d(ATIII)/d(t) = -r38-r39-r40-r41-r42
[30] d(XaATIII)/d(t) = r38
r 31] d(mllaATIII)/d(t) = r39
[32] d(IXaATIII)/d(t) = r40
[33] d(TFVlllaATIII)/d(t) = r42
[34] d(lIaATIII)/d(t) = r41
Explicit equations as entered by the user
[1] k1 = 3 .. 2e6
[2] k2 = 3.1 e-3
[3] k3=2.3e7
[4] k4 = 3 .. 1e-3
[ 5] k5 = 4..4e5
[6] k6 = 1 .. 3e7
[7] k7 = 2.3e4
[8] k8=2.5e7
[9] k9 = 1.05
[10] k10=6
[11] k11 = 2 .. 2e7
[12] k12 = 19
[13] k13=1.0e7
[14] k14 = 2 .. 4
[15] k15 = 1.8
[16] k16=7 .. 5e3
3.40E-13 r;:::====:;--r,----,
2.72E-13
2 .. 04E-13
136K13
6.80E-14
O.OOEO 0 .. 00
138.93 2 7 7 8 ~ 416.79 555.72 694.64
6-54
[17] k17=2e7
[18] k18 = 1..0e7
[19] k19 = 5e-3
[20] k20 = 1e8
[21] k21 = 1e-3
[22] k22 = 8,.2
[23] k23 = 6e-3
[24] k24 = 2 .. 2e4
[25] k25 = 1e-3
[26] k26 = 2e7
[27] k27 = 4e8
[28] k28 = 0,.2
[29] k29 = 1e8
[ 30] k30 = 103
[31] k31 = 63 .. 5
[32J k32 = 1 .. 5e7
[33] k33 = ge5
[34J k34 = 3,.6e-4
[35] k35 = 3.2e8
[36] k36 = 11e-4
[37] k37 = 5e7
[38] k38 = 1 .. 5e3
[39J k39 = 7..1e3
[40] k40 = 4 .. ge2
[ 41J k41 = 7.1e3
[42J k42 = 2 .. 3e2
[43J r1 = k1 *TF*VII
[44] r2 = k2*TFVII
[45J r3 = k3*TF*Vlla
[46] r4 = k4*TFVlla
[47] r5 = k5*TFVlla*VII
[ 48J r6 == k6*Xa*VII
[49] r7 = k7*lIa*VII
[50J r8 = k8*TFVlla*X
[51J r9 = k9*TFVllaX
[5'2J r10 = k10*TFVllaX
r 5 3] r11 = k11 *TFVlla*Xa
[54] r12 = k12*TFVllaXa
[55] r13 = k13*TFVlla*IX
[56] r14 = k14*TFVllaIX
[57] r15 = k15*TFVllaIX
[58] r16 = k16*Xa*1I
[59] r17 = k17*lIa*VIIi
[60] r18 = k18*IXa*Vllla
[61] r19 = k19*IXaVllla
[62] r20 = k20*IXaVllla*X
[63 J r21 = k21*IXaVlliaX
[64] r22 = k22*IXaVlliaX
[65J r23 = k23*Vllla
[ 66] r24 = k24*Vllla1L*Vllla2
[67] r25 = k25*IXaVlllaX
[68] r26 = k26*lIa*V
[69] r27 == k27*Xa*Va
[70J r28 = k28*XaVa
[71J r29 = k29*XaVa*1I
[72] r30 = k30*XaVall
[73 J r31 = k31*XaVall
[74] r32 = k32*mlla*XaVa
[75] r33 = k33*Xa*TFPI
[76] r34 = k34*XaTFPI
6-55
[77] r35 = k35*TFVllaXa*TFPI
[78] r36 = k36*TFVllaXaTFPI
[79] r37 = k37*TFVlla*XaTFPI
[80] r38 = k38*Xa*ATIII
[81] r39 = k39*mlla*ATIII
[82] r40 = k40*IXa*ATIII
[83] r41=k41*lIa*ATIII
[84] r42 = k42*TFVlla*ATIII
[85] Total = lIa+1.2*mlla
P6-18 (b) No solution will be given
P6-19
(1) C
2
H
4
+ 1120
2
C
2
H
4
0
E + 1120 D
FlO = 0.82F
m
= 0.007626
P6-19 (a)
(2)
Selectivity of D over CO
2
s= FD
FUl
See Polymath program P619a.po1.
POLYMATH Results
C
2
H
4
+ 30
2
2C0
2
+ 2H
2
0
E + 30 2U
I
+ 2U
2
Variable initial value minimal value maximal value final value
W
-0-----
0
Fe 5 .. 58E-04 1. 752E--I0
Fo 0.001116 4.066E--05
Fd 0 0
Ful 1.. OE-07 1 .. OE--07
Fu2 0 0
Finert 0.007626 0 .. 007626
Ft 0.0093001 0.0091804
Kl 6.5 6.5
K2 4.33 4.33
Pto 2 2
Pe 0_1.199987 3.817E-08
Po 0.2399974 0.008858
kl 0.15 0.15
k2 0.088 0.088
X 0 0
S 0 0
rle -0.0024829 -0.0024829
r2e -0.0029803 -0.0029803
Differential equations as entered by the user
[1] d(Fe )/d(W) = r1 e+r2e
[ 2] d(Fo )/d(W) = 1 /2*r1 e + 3*r2e
[3] d(Fd)/d(W) = -r1 e
[4] d(Fu1 )/d(W) = -2*r2e
[5] d(Fu2)/d(W) = -2*r2e
Explicit equations as entered by the user
[1 J Finert = 0.007626
[2] Ft = Fe+Fo+Fd+Fu1 +Fu2+Finert
[3J K1 = 6 .. 5
2 2
5.58E-04 1. 752E-10
0.001116 4,,066E-05
2.395E-04 2 .. 395E-04
6.372E-04 6.372E-04
6.371E-04 6.371E-04
0.007626 0 .. 007626
0.0093001 0.0091804
6.5 6.5
4.33 4.33
2 2
0.1199987 3.817E-08
0 .. 2399974 0.008858
0.15 0.15
0.088 0.088
0_9999997 0.9999997
0.,4101512 0_3758225
-3.692E-I0 -3.692E-I0
-8.136E-IO -8 _136E-I0
6-56
[4] K2 == 4 .. 33
[5] Pto == 2
[ 6] Pe == Pto*Fe/Ft
[7] Po == (Pto*Fo/Ft)
[8] k1 == 0.15
[9] k2 == 0.088
[10] X == 1 - Fe/0 .. 000558
[11] S == Fd/Fu1
[12] r1e == -k1*Pe*Po"O .. 58/{1+K1*Pe)"2
[13] r2e == -k2*Pe*Po"O.3/{1 +K2*Pe)/\2
x == 0..999 and S == 0.376(mol of ethylene oxide)/(mole of carbon dioxide)
P6-19 (b)
Changes in equation fr'Om part (a):
dFa 1 () 0
--=-r
IE
+3r
2E
+R
a
and Fa a =
dW 2
R = 0.12xO.0093 = 0.001116 mol
a W 2 kg.s
From Polymath program: X == 0..71
S = 0..0.4 (mol of ethylene oxide)/(mole of carbon dioxide)
See Polymath program P6- t9-b .. pol
P6-19 (C)
Changes in equation from pmt (a):
d ~ ()
--= r
lE
+r
2E
+R
E
and FE a = 0
dW
R = .0.06 x . 0 ~ 9 ~ = 0.000558 mol
E W 2 kg.s
From Polymath program: X = 0. .. 96
S == o.Al(mol of ethylene oxide)/(mole of carbon dioxide)
See Polymath program P6-19c .pol
P6-19 (d) No solution will be given ..
P6-20
Solved on web
Go to http://www.wits.ac.zalfac/engineering/procmatiARHomepage/frame.htm
P6-21 (a)
Isothermal gas phase reaction in a membrane reactor packed with catalyst.
A ~ 7 B +C
A-7D
2C+D -7 2E
, [ CBC
c
1
lic = lsc C
A
--_.
K
IC
6-57
CAD = = 24.6atm = O.6mol I dm
3
RT (O.082dm
3
atmlmol.K) (500K)
See Polymath program P621-a.po]
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value
WOO
Fa 10 0.349438
Fb 0 0
Fe 0 0
Fd 0 0
Fe 0 0
y 1 0" 3404952
k2d 0.4 0.4
K1e 0.2 0.2
Ft 10 9.7581913
Cta 0.6 0.6
Cb 0 0
Ca 0.6 0.0073158
Cd 0 0
Ce 0 0
kb 1 1
k1e 2 2
r2d 0.24 0,,0029263
k3e 5 5
rIc 1.2 0,,0051635
ra -1.44 -1,,44
r3e 0 0
rd 0.24 0.0014457
rb 1..2 0,,0051635
re 1.2 -0.0042625
re 0 0
Ce 0 0
alfa 0.008 0.008
Fto 10 10
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Fa)/d(W) = ra
[2] d(Fb)/d(W) = rb(kb*Cb)
(3) d(Fc)/d(W) = rc
[ 4] d(Fd)/d(W) = rd
(5) d(Fe)/d(W) = re
[6) d(y)/d(W) = -alfa*Ft/(2*Fto*y)
Explicit equations as entered by the user
[1J k2d = 0..4
[2J K1c=0 .. 2
[3] Ft = Fa+Fb+Fc+Fd+Fe [4] Cto = 0 .. 6
[5 J Cb = Cto*(Fb/Ft)*y
[6] Ca = Cto*(Fa/Ft)*y
[7] Cd = Cto*(Fd/Ft)*y
[8] Cc = Cto*(Fc/Ft)*y
[9] kb=1
[10] k1c=2
[11] r2d = k2d*Ca
[12) k3e = 5
[13) r1 c = k1 c*(Ca-(Cb*Ce/K1 e
[14] ra = -r1 e-r2d
maximal value
100
10
3,,2375418
4.9873025
2.7304877
1.3722476
1
0.4
0,,2
13.220737
0.6
0.1403618
0.6
0.1019635
0.2117037
1
2
0,,24
5
1.2
-0.0080898
0,,0216828
0.24
1.2
1.2
0,,0216828
0.0398819
0.008
10
10
8
6
4
2
final value
100
0.349438
0,,4443151
4.8617029
2,,7304877
1.3722476
0.3404952
0.4
0.2
9.7581913
0.6
0.0093022
0.0073158
0.057l654
0.1017844
1
2
0.0029263
5
0.0051635
0.0080898
0.0029612
0.0014457
0.0051635
0.0022023
0,,0029612
0.0287293
0.008
10
- Fa
. li'b
.. Fe
- Fd
-"', ....." ........._ .......... .
o "." ..... = = = = ~ . ~ I
o 20 40 \V 60 80 100
6-58
[15] r3e = k3e*(Cc
A
2)*Cd
[16] rd = r2d-(r3e/2)
[17] rb = r1c
[18] rc=r1c-r3e
[19] re = r3e
[20] Ce = Cto*(Fe/Ft)*y
[21] alfa = 0 .. 008
[22] Fto = 10
P6-21 (b)
The interesting concentrations here are species C and D, both of which go through a maximum Species C
goes through a maximum for two reasons: (1) it is an intermediate product which is formed and then
consumed, and (2) there is pressure drop along the length of the reactor and as pressure drops, so does
concentration.
The concentration of species D goes through a maximum because of reason (2) above .. Species D is formed
but then the pressure drops, which causes the concentration to falL
P6-21 (e) Individualized Solution
P6-22 (a) What factors influence the amplitude and frequency of the oscillation reaction?
Ans: k and the initial conditions
P6-22 (b) Oscillations eventually cease because the C
A
is decreasing and becomes the limiting factor.
P6-22 (ae) Observation 1: 'tl and 't2 decreased
Observation 2: 'tpI increased
Observation 3: 'tp2 decreased
Now, Tl = ~ In( L ~ J and T 2 = ~ In(PO* J
JLl JL2
2n 2n
Tpl = (JLl*2- + KU )112 and Tpz = (JL2*2-; K
u
-)l/Z-
_ ko * _[(1-2K
u
)f!=8K
u
]112
--, JL12 -
k' 2
2
From observation 2 and 3, we get
Decreasing III * and increasing 112* => Ku = (ku/k2) will increase
Also, from observation 1, E increased => koIk2 should be increased
Now, P -7 A k = ko ....... (1)
A-7B k=ku. (2)
A+2B -7 3B k = kl ....... (3)
B-7C k=k
2
............ (4)
Hence the reaction (1) and (2) are more temperature sensitive than reaction (4)
P6-22 (d) Individualized solution
6-59
P6-23 Individualized solution
CDP6-24
-u() Ca + ra W = 0
-Uo Cc + rc W ;:: 0

"Uo CD +rD W =0
KEY:
1 - ca
2 - cb
:] .. cc
..... cd
CDP6-25 (a)
PFR:
113' .9'.9'
t) .. :: kl CA - k3 C
A
ra = k1 C
A
.. k2 CB
rc:: k2 CB
6-60
r-,.'lo1e balance:
Rate laws
e
KC
::::: 0 .. 021
C
MO
;;;;; 00105
T ==.5
dC},t
--_._. = r
dr M
Plugging those into POLYMATH gels the following:
6-61
CSTR:
Mole balance:
Rate Law:
Stoichiometry:
F
HO
'" Ffj == (.- r
tB
-. f;H r,H) V
FMO-F
M
=-"I'I:-I
V
Fx =(rtx+f1X)V
F
T
= (r21+ f;r) V
F;-'1< == ('1 + fz ),10 t r.l.\k ) V
Fa =: f'll
FH ::::: 'lOCH
VOCM,
Fx == voCx.
FT == voC
r
F:\1e :::: VOC
Mc
== v
o
(C
l10
... ell)
F
EI
:: \'oC
3
= vo[(C)"m '" eM)" ex' ell
Combining all of these:
C
' C (k CO k '. k c,Q,$c" )
. -HO - H::;;;;.l H 'M + -:: ,tt 'K t ; HI r
C
M
:::: e
HG
-C
H
ell = (C;"iO - eM ) .... C
x
.- C
T
The following i:s the POLTh1.-'\TH program and me summary table showing all of
tIle concemrar,ions.
E:'i'!a;. i 0E!::!!:'
f (en] :eh-eno+ (k1""ch .. 5 c:n-k2 . 5 'cx+kl "ct: . 5) "cau
(c:n) =cm 'crne i kt - 5 .... c:tr'" 'C.a.!l

c:'0=.021
k1.=5S.2
k2",3a.2
ld=l1.2
1;8.u"".51.
erne"', alaS
6 .. 62
Uartaolt?
ch
em
ex
kl
k2
1<:3
erne
cmt?
Solutl.O["'f
Value fO
....... -- ..........." . ..... . ...... .. .. ..- ....."
0.00776519 2.993.-15
0.00301658
0.00:317467
0.00286611
0.021
55.2
"30.2
11.2
0.5l
0 .. 0105
0.01323-;0
0.00114254
I .463", 14-
2 .. 79t? -14
1.495e- i"
The con\.crston of Hydrogen and i'v[esitylene are (hen:
X. = S'.:HQ .. _Sll ::;: 0 . .2:
11
== 0.63
H COO') 1
HO .. -
_ e
MO
" C
SI
0010),0.0030 _
X "'1 - ..... --...... ---. =--........... _._ ................ -..... ----- - . f 1
'C!'-IO O.OW5
C
H
= 0,0078 Ib mol/frl eM:;:; 0.0030 lb molJfr\
C
r
= 0.0029 ib mollft' Crr.::;::;;; 0.Q13 Ib mollft'
CDP6-25 (b)
C
x
= 0.00.32 Ib mol/fr'
::::: 0,,0014 Ib mollfr'
When eM is reduced to 1.5, it now takes a L of 0.24 h to achieve a maximum of xylene, Increasing eM to 10
now requires a L of only 0 .. 08 h
CDP6-25 (C)
To find out the reactor schemes needed, use the attainable region to get these graphs
Using fi PFR wouldmaxirnize C,. If ---'Ie used at rl1ri{) of mesil:ylt!ne to hydrogen of
10, tben we l.vQuld only have to have a t of .08 hours. So our voulme of the reactor
would bt; only 38,08 ft\ So our entering cOl1centraiol'ls would be .0105 Ib mollir'
of Hydrogen and, 105 111 moUff of
CDP6-25 (d)
Ftfst fmd the protJortionality ';;OEst;;;mts of the rate consr.ants usin2 (he
Anheniu$ equation.' 's
A, :::: 12674
Once that is done, by t.rial fu'1d erw[ corne up w;th the temperature where SXT ""STB
and is then 862K or 155 L6R.
6-63

dIem) Id (t);:Dn
d(chl/ci(cl =!h
d(cx)/d (t) =rx
d(eme) Id(t) ;;rme
d(ccl/d(c)=rt:
dlcb}/d(t)=r'b
rm=-55 .. 2 "cm"ch". 5
rb::::l1 .. 2 "ct"chA. S

rt;.=30 ,,2"'c:X:"'ch". 5-rb
rh:::rm-30.2"c:x:"ch".5-rb
rme;::-.t1l\+30 .. 2"cx"'ch" .S+rb
..
t 0
em {}.O!.OS
en o. 021.
ex 0
erne 0
c::. Q
cb a
::m --0 .. 083992
::b 0
::x 0.083992
0
!-h 0.083992
l::me 0.08,3992
Scale: 10
2
2.:::
K&'.;.
,,"" em.
ch
e'X
cme
ct
cb

()
51
0.01.05
0.021
1.:lCC .
O.JCO

() 00506614.
0.0111.815
0.OO4772.U
Q .. 00130452
.. Q.OO:n871S
000.3521.27
(}.08.1992
0 01.46868
.. 0 .. 0126384
0.083992
,
,

(}
(} .. 0001599836
0 . 00381.84"1
0
0
0
0
-Q .083992
0
. 1.1 _. 00523484

-0.083992
0.0126384
The maximum concentration of xylene occurs at I: ;:;;: 0 .. 19 h ..
6-64
0.0105
0.021
o
o
o
o
' ..
..... -"
..
0 .51
a 000699836
0 00381847
0.00372332
0,,017181.5
0.00477233
0.00130452
0.00238715
0,00330298
-0.0045612
0 00364547
-0 .0126384
0.0126384
CDP6-26 (a)
Starr wicb ihe mok balances:
dEl
_ ..... ,,"- ;;;;;: C
dV It
dF,
,"',","'-::: r
dV 9
dF,
-''''''''.- ::: r,
dV '
dF
H
---,-,:;;;: r
dV H
k C
". k k (" " k (' '(" k C'" -,
If.!:::: -ii + -+ -1'fl "'} +- " "}j + 5 "ti
C
?
Finally ,the stoichiometry:
Putting all of (hose together and put it into POLYMAnr and get the following
program and answers
d(cll)/d(V) = rl/vo # cll(O)=0.l37
d(c9)/d(V) = (-r2+r3)/vo
d(clO)/d(V) = (-rl+r2)/vo
d(c8)/d(V)
d(c7)/d(V)
d(c6)/d(V)
(--r3+r4) /vo
(-r4+rS) /vo
-rS/vo
d(ch) Id(V) (rl+r2+r3+r4+rS)/vo
890 c9/(cl0+c8+c7+c6+0.0000001)
887 c8/(c7+0.0000001) #
889 c8/(c9+0.0000001) #
8910= c9/(cl0+0.000000l)#
kl kS*17.6 # k2
k3 kS*4.4 # k4
vo 1 # kS
rl -kl*ch
A
O.S*cl1 #
r2 -k2*ch
A
O.S*cl0 #
r3 -k3*ch
A
O.S*c9 #
r4 -k4*ch
A
O.S*c8 #
rS -kS*ch
A
O.S*c7 #
kS*10
kS*2.7
2.1
X = l-cll/cllo # cll0 = 0.1
V(O)=O # V(f)=0.8
# c9(O)=0
# c10(O)=0
# c8(O)=O
# c7(O)=O
# c6(O)=0
# ch(O)=0.389
#
6-65
006
0.05
0.05
0.04
0.03
0.03
0.02
0.02
0 .. 01
0.01
0.00
0 .. 00 0 .. 03 0 .. 16 0 .. 24 0 ..32 0.40 0.43 0.56 0.64 072 0
V
The ratio of hydrogen to pentamethylbenzene is 2.83 and the volume is 0.8 m
3

polymath solution
CDP6-26 (b)
The polymath program is the same as the first, we see that the value of c11(o)=0.092 and ch(o)=0.434 and
the ratio now becomes 4 .. 8 to 1 and the volume increase to 6.8 m
3
to maximize SS9' To maximize SS7 it
follows that the volume would be smaller because earlier the reaction ends the less C
7
is formed.
67.0
60.3
53 .. 6
46 .. 9
40 .. 2
33 .. 5
26.8
201
13.4
6 . .7
0.0
0.00 0.67 1.35 2 .. 02
CDP6-26 (C) Individualized solution
CDP6-27
2.70 3 .. 37
V
6-66
4.05 4.72 5 .. 40 6.07 674

V"" 10 no
fho=lOOOO
fb=4320
fbo:..;:7200
k::",,2 .. 7
Kl=.0264
k2=:.07
T=40J
Poo""1400
R;:::8.]09
PO;::: I?bo" , 6.
vo=2 .. 41e7/Poo
ph=fh-S.309*Q03,vo
Y"" fc / ( fb}
pc_fc*8.309-T/vQ

rc::-irb) (1+K2".l;>C)
f C:,8
U
: 0
ib
,ba
k 1
Kl
k2
K2
Pbo
Pb
va
Pt,
5:3.5618
82:32.08
l52.1S:
umu
1 Ul)ClO
4:320
72DO
2,,7
O. ':1264
U .. 07
0.04
4U3
:400
8 .. 105
84(]
'.7214.3
2.3541
2.85836
16Ul.31
1]
L8",7\'? 12
28-12"" 14
tftJ
1<=-09
o .. S
The highest yield occurs at pressures: P flO:::: 1400 kPa
P
Ha
:::: 19452 kPa
6-67
Pho
rc
Val UE?
19";5,2
,9. OS-j 26
0 .. 852181
-9.93644
8.232U8
CDP6-28
(a)
Mole Balances:
dF
::: riA + r
2A
dV
dF
D
.. _=r.
dV ZA
Rate Laws:
-riA:: kl(c",Ci -- CcIK
t
)
-I'y. := k1 (c A CD - C1i;C
S
IK
2
)
-f
3C
;;; k)Cc:
Stoichiometry :
C,
Fy == FAt- Fat- Fe + Fo + FE + Fo
p
e'G =R'i'
a
Use these equations in POL ThIATII- Vary Po and To to fmd the optimal
conditions. We determine these to be:
T" =315.8 K
al!.] 6
d (:0) lcl(v) "'4*rla :::-2e ::-3c 14
d( fa) Id(v) "r1a .. ;:2a :5
Q
c.(:gJid(v):.;;-rJc 0
4
1'0:=31.5 a
T"''I:o
P ::;: 160 atm
o
<:;:<1;(:to" (fa/:;;;) (';,'o/'rl
cb$Cto .... {fblf':)(Tol:')
cc=Cto"IEc/!c) "tTo/T)
co.::;C-;,;o'(fd/f-;,;) "(To/T)

:::3c"" .. kJ"cc

r'2a=-k2'"
k1.:=. 9::n"e;<;;i (2.5' (3140011. C./J30 "liT)))
K:,.13J.567" (0. DOl 98 "1:)"" 2 "'e;-cp LHl520.i L 987'" (1/1>1.,1 298) i
k2=. 6J6"t?:xpi 1300011.98'7" (U :'SOD-liT) l
K2 =103943 *el':,;;J 198J4/!. .. 987'" n. iTo, 1/298) )
.. 244 *@.xp (1.5 w 28956 /! . 98 '{,. (1./ 32S-1./T) }
6-68
v
d
it
1;'Q
k1
K1.
X2
kJ
Ct.o
ca
cd
cO:
ria
G
6
J.A
o
3D
315.8
:t60
315.3
0.00428571
2.831.22
40761..5
6 178,,5
1. .. B'573
2,88337

1.23573
200
3.99S't2
1:.3038
"! . .. 13754
30
}lS 3
l50
") 15
g
0.00,128571
279::'12
2.SH122
D.034 . .l899
1 23$73
O.20249.B
0.323821
2.24735
c
",0.0:)22,5647
o
5
1.4.
0.:84792
o
o
[} .. 00:'0827
27 A837
].15.8
1.00
') L5 .. S
O .. 0042857'\.
279:112
2 881.22
4076: .. S
0 .. 0.14]399
6.17366
o 041.5214
2.88337
0.000236652
1.23S73
.. 0.00596389
-{j _
-1.9JJ0'5
9 .. 99558
l) .. lB4792
O.68201H
1.13754
G.00441.766
27,';:933
'H58
0.0042857:.
2791.,12
2,831.22
40761.5
(} .0.HJ899
6 ]:,865
O.I:l4:S214
L 48::'36
n.1S32S6
o 08099:251.5
2.24593
.(1. [HJ527:J54
-0 .. 1)02:564']
4 GOGHeOS
MeChanQl Syncbesig
v ................. _._._
Ij
20
40
60
ao
100
20a
()
0.4<1820445
O.6357();an
0.Si:334782
O .. 8'l()427)
O.90B2S74j
O.sn76642
o .8554.1262
o .. 30470055
(} .. 74650071
o .. 5a:S".l95
(b) Use the same POLYMATH program as aoove and vary the ratio of entering
reactants. The optimal ratio would be :
fs hydrogen gas, TI carbon monoxide, and carbon dioxide
These results are similar to those in paxt (a) in tllat the optimal volume is still
100 dm\ and the cQucentrarion profile is very similar in shape. 'nle primary
difference is that the Fe values are more thar) doubled.
6-69
Mechanol synthesis
equations:



d(Fe) IdCV) =-::2a
d(Fg}/d(V)=-r3c
;1(Fd) Id (V)
1:0=315.8
Po=160
TeTo
J.CCC
r
,
I

t
t
t
1
1_. __ ._ ... ___ .-,---+ __ ,-... .....;._. __ + __ . ___ _

ea a:c I 2:)0::
u
kl=.933-exp(2.S-(31400/l.987-(1/330-1/T}))


3:2::.10] 943"ex;,') (9834/1. 987 (1/T-1129B) I

Cto=?0/(.082-To)


CC=Cto*C?c/ft}(To/T)

Ce=Cto*(Fe/ft}(To/TI
::3c=-kJ Cc

r2a=-k2-(Ca*Cd-Ce*Cb/Kl)
.Kee.h4l>ol.
vsi.able value
.,
0
.f-
a
r.> U
Fe 0
Y. 5
f'1i
I)
N
Q
n. J,
To llS I
Po 15.:1
l' lLS i
kl CI 0041ISU
2191 12
lcl l '41.l2
El S
IeJ o O14lU'
Ct.Q , 178i&
C'""
!.
<:t> 1.29528
Cc: 0
C<! 0
0:.
.:lc: -0
.:l..t.' "0.Q7S07a
6-70
...
200
a
li
2 flU
41
4 00756
o OGOStoln
lO
1.5 a
l60
3l.S
0.004215'11
2791.12
2
40161 5
Q OJ4J."
, nan
. U7i4
J lf528
o 7243"
o Oool.Snn
Sil5l
-0
-".Ol.lUQ8
:tnitl.al value
8
16
o
6
o
o
!!:i.u- v.he ...
0 lOa
1 94105 1
7 IIS7.a 7_aanS
Q
lOU"
5 .. 9''''1
5.""1
\) 4 D07S4I
0 II 0005'JOala
11 lasS :1: ... as
US. ll.Sa
laO 160
US.S 115 .. 8
O .. OO41IS71 o 00421511.
nn 12 2791..1l
2 .. 111.22 2 IBU2
401&1..5 ,0751.S
o 0143899 o OlUU9
, %.7866 , ::raSi
0 .. 5(7917 Q 547'H7
2 :z 11,;a
0 o 57nJ3
0 o OOOUi7a.
I. :U571 1 S93'S!.
-0 Oa.uU -a.Ol".,.
-0 .. 076578 .. 0 .. Qll.l .. oe
Met:hanol Synthesis
v
-.-.--.-.. ....... ..... .. " ..
20
40
60
30
100
120
1'1.0
160
180
2DO
Fc
o
1.2H3568
:: .. 0129151
2.4406221
2 6365715
2.680932
2.6292203
2 .. 5193659
2 376518
2.2171.669
2.0519865
CDP6-29 No solution will be given
CDP6-A
a) A + B-1> C + D

First, find 'r. To do this use the original desigl1 equation for a CSTR:
V ==
-r
A
Then since F ....
a
== CAOV
O
and 1;;::: Vivo then the design equation becomes:
. _ CAQX
1--'
-r
A
Using the rate law and stoichiometry we find:
m-r = k C .(1 .... X)
A i AO
Combining aU these and solving for't when X = .3, CAQ::::: .1 and kl ::::: .412
1: :;::: ..... :;::: -.. .. .. ::::: 1.04b
k\CAQ(l-X) .412*.1*.7
Once that has been calculated, redo all the mole balances:
CAl) -., C
A
::;;; --rA 1:
C
BO
C
B
::;;; -r
B
1:'
C
c
==rc1:'
CD == Io1:'
6-71
Then do the rate laws:
-fA = klC
A
,,r
B
:::: klC A + k
2
C
C
fC ;:;;;;; ktC
A
- k
2
C
C
fD == klC A -1- kzC
c
fg =: k
2
C
C
Combining and rearranging into a function:
fCC
A
);:;:: 0 == C
A
- CAO + k,cA-r
f( C
a
):::: 0 == C
n
..... Coo + (k\C ... + k
2
Cc)-r
f(cd==O=(k,C ... -"kzCc)-r-Cc
feeD) = 0:;;: (k1C ... + CD
f(C
g
)::::. a = k
2
C
C
"f ..... C
E
Plug those into POLyp.,IATII:
6-F
Solution
ESFlations;
f(ca)=ca-cao+klca"cau
Uanab!e U<l!IJE' fO
f (cb) =cb'-cbo";. (kl"'ca..-k2 "cc) .... tau
f(ccJ;(kl*ca-k2cc)*tau-cc


cao=.l
kl=.412
tau=1.04
cbo==.14
k.2=.055
C
c
;::: .028 need Fco == 10
v = Fe ;;::;: = 357 gall h
o C 0"8
c .....
V = 'tVa = 1.04 *' 357 = 371.3gal
b)No solution will be given.
CDP6-B
k
t
D
A---76/'

BatCh Y AO == 1
.,"""'.....,,_. __ ....._-
ca 0.0700015 3.J6le-15
cb 0.10B382 -t.02Je-! I
cc
cd
Cf;'
C.ao
kl
tau
r.be
t2
6-72
0.0283726
Il03i6ia"
O.OO16229i
III
0.112
l.tM
O,ii
o.ffi5
9. 112e--13
"' 9. iOSe- i 3
LSi'S!?! !
(a) k
l
;; O.Ot s.:C-
1
T t == 1..5 ruin::: 90 s
A-7B
NAO!2X = -fA V
dt
kl CA :::: ki CAo(i.X}
in Loo.1 __ );;:;; ktt
\l-Xt
.--1- =: ct,t
I-Xl
CA = C.-...n{l-Xd = CAO e-k\t
.fA. = cook,t ::;; c-{O.Ol}(90) ::: 0.41
CM
rSl=-r",=kIC",
fC =: k:z CB
B--7 D
fC>
:::;;; k3 Cg
XI
X
2
X3
-ra ""'-rsl 'r fC + I'D::::: - k
t
C
A
+ leI CB +- k::3 Cs
.. ::: -ki CA.O e-lc,t .... (k2 + k3) C
B
.. ::::: -{0.01)(O.2) + (0 .. 003 t 0.0(2) CB
d!
== -0.002 (1 - c.o Oll} + 0.005 Cs
Using a Runge.,Kut:u Gill numerical so1.unon. we find that. for t::::: 2 min;: 120 s. CB:::
O. I 36 gmolJdm3..
(c) !!;:. = 'c = x, C. ; = k, C. ; C" =" L c. dl
From the solunon in patt (b). we have values of C:s at intervals as small as 5 sec, so we can
use Simpson's rule to obcain (:'c:
t "" 1 min =: 60 sec.
Cc "" 0.003 Pf)[O + 4(0.0449) + 2(0.0782) + 4{O.102j + 0.1183]
Cc = 0.0129 gmolJdm
3
6-73
t = 2 min == 120 sec
(d)
Cc:= 0.003 (3f)(0 + 4(0.0782)'1- 2{0.1l83) + 4(0.134) + 0.1355]
Cc == 0.0366 gmol/dm3
T I C", CB
0 0.2 0
20 0.164 0.0572
40 0.134 0.0950
60 a.lOK 0.118
KO 0.01:199 0.131
100 0.0736 0.136
120 0.0602 0.135
140 0.0493 0.131
160 0.0404 0.125
lsu 0.0331 O.lib
2()(
I
0.0271 0.107
22! 0.0222 0.0982
24( 0.0181 0.0890
260 0.0149
280 09122 0.0717
JUU 0.00996 --0:00.)(:\
:320 0.0082 0.0566
340 I
0.0067 0.0499
020
o.ts
012
FAo -, FA +fAV =0
,..
1,) CAO - 1.) C
A
- kl C
A
V ::::: 0
CAO - C
A
kl C
A
1: ::; 0
CAO - C
A
(l -+- kl 1:) ;;:: 0
CA ::::: ---1 __ ,, __
CA.O (1 + k
i
t)
Cc Co
0 0

0.()()65 O,t.J(J43
O.OLlY 0.0081)
0.0205 O.Oij{)
0.0285 0.O19()
0.0366 0.0244
0.0447 0.029g
0.0523

U.0392
0.0442
0.0724 0.041:12
0,r}}7,! 0.0520

0.U1:I74

0.U914 O.()bU':/
0.0949 0.0632
0.0979 0.0635'-
FBO - FB + fa V ::::: 0
u CB + (kl C
A
" kl CH - k3 C:a) V::::: 0
,CHi-' kl CA t .. k2 Cg 1: - k3 CB 1: == 0
Cg (1 + kz t + k3 "t) ;;;; kl t C
A
C
A
k2.,'C+ k3 t)
kl t
6-74
__ 1_ z:< CB (1 + \::2 1: + \::3 1:)
CAo 1 + \::1 1: CM \::1 1:
\::11:
CAQ (l + kl "C)(1 + kl1: + kJ 1:)
t(s) 10
Ca/C,Ml 0.08
CDP6-C
50
0.26
find the values for k.
100
0.33
150
0.34
200
0.33
kl :::: = L2
k1, ::;;: 9466e(-l5ll1(OOI9&"7-100}} :::: .18
k
J
= 1 1 127eC'1500(OOI9117100l) :::;; .22
In this problem Isoburylene :::: I
Merhacrolein :::: ,M
CO,::::D
C0
4
::::C
Oxygen:::: 0
The mole balances for these species are as follows:
... FI :::: ('I'll ,.- fu - IJr)V
F.'>i = riM V
Fo =r:m V
Fe = flO V
Oxygen is in excess so we will assume that F" ::: F 00'
The rate laws for these reactions are as follows:
. "IiI :::::--1
10
= riM = kLC1C
OO
1 k (" ('"
-lil::;;: 25 ::;;:4 rm:;;;: 2"1 "'00
6-75
300
0.3
-r = 4rJO = .. == k C C
J! -17 4 3C 3 1. 00
Combine all of these and come up with the following:
Cxo -C
1
= (kIC[C
oo
+. kZC1C
oo
+ k
3
C
r
C
oo
)'r
Coo - Co = (k1C1C
OO

c,1.f == kIC/Cort'
CD =4 * kzC\Coo't
C
c
== 4'" k3CrCoo't
Before plugging into POL YMA TH, evaluate the parameters and derive equations
for conversion.
C . == ...P ... ::;::: __ ........ 3 __ . __ ::;::: 0.034
1 RT .082 * 700
C/O == Y AoCr = .1 *' .034::;::: 0.0034
Ccq ::::; 0.031
X [ ::::: S;lQ:;:5':1
C[O
c
X = ..... :.\':!
u ('
'[0
X ;;;
21 4('
'\.o
X){::;::: XI X
11
X2!
Then plug into POL to get the following:

f (ci.) ""c:i"ci.o+ (kl. -c:i. "c:oo+k2 .:;:oo+1<:.J "ci "coo) cau
f (cmJ =kl *ci. .. cm
f (cd) ='1 "k2 "'ci "coo'"::;au.cd
f(cc)=4,"ci"coo"tau-cc
f {col =cocoo+- (lel. ci."c:oo+25/ 4 "k2*c:i"coo+17/2 "'k:3 "ci "'cool "cau
c:i.o=.0034
kl.=l. .. :2
coo=.03l.
}<2;; .. 1.8
k3== .22
t;.au=lO
xl.=cm/cio
x2"".2S"cd/ci.o
x=={cio'ci)/ci
x.3=x :x1 .... x2
6-76

0 .. OU1
'0,.001
O.Q04.
0.004
0.01
Cl
ern
Cd
Coo
k2
x2
x
xJ
Xl;;; 0.496
CDP6-D
A-tB
C--3<[)+E
F
r
:::: 10 Ibmollsec
dF
., :::::: fA ;;;k
j
C A
dV
CAV
o
valuE'
0.00227273 -1_775e-12
0.Q0084-5"155 1" 0 11 e--12
0.000507273 -! 38:&-12
C.Cl028:818 J.B3::'' i:3
D.CC3"'
1.2

0, L8
C.22
10
D.2"8663
Cl.03?29S5
C .. 495
0.21 DC]?
X2! ::;:: 0.037 ::;:: 0.21
C "" -.. -g:::?---.--. ::: 7,.61 * l{r{i
10 0.73*900
:. Vo = 13140
V == l005ft'
See POLYMATH solution below
d{ fal Jd (VI z;ra
d (fe) /d(V) =rc
d (fb) /d {V) "'ra
d{fd) /d(V)",z:-c
d(fe)/d(V)::="rc
kl"'lQ
k2"" .. OJ
677
5
5
o
o
Q
tfb+fd+ fe
fao=5
cto=S/(900*.73)
fto==1.0
rc::;-k2
X'" f.a) J fao
avo=fto/cto
ca=cto'" (fal ft)
ra=-kl*ca
:nJ:Sial"
V 0
fa. 5
fc 5
fb 0
Ed 0
fa 0
kl 10
1<2 0.03
10 .......
:ao 5

cto 0 .. 00761(}35
ft.o 10
rc 0 03
x 0
avo 1314
ca {) .. 00.3 8051.8
CDP6-E
lie
lOS 0
5 :2.49621
5 1. 65
2.50379 0
3.15 0
3.15 0
10 10
0 .. 03 0.03
13 15 10
5
::;
0 .. 00761035 0.00761035
10 10
0.03 -0.03
0.500758 0
1314 131.4
0.00330518 0.00144464
a) Using the equation for the equilibdum constants:
We can come up with the equations for C
A
, CD, and ex.
C
A
=. D .
KelCH
CD ::::
C
c
ex =
C
y
The test can be found with stoichiometry ..
Cy =C
x
CD:;:: e
RO
_CD,C
y
C
c
=cAOc
A
-ex
6-78
F
lOS
2.49621
l.8S
2.50379
3.15
3.15
10
0.03
13.15
5
O. 00761035
10
-0.03
0.500758
1314
0OOl4444
POLYlv1ATH
6--5 .-:1.

f (ca) "'ca-cc 'cdl nc 'cb)
E (cdl :cd-'K: ca.cb/cc
t -=cx"'K2""cc "cb/cy
Kl=4
K2=1
c.y=cx
cbo=LS
.. :;
cc=cao"'ca--c:x
};;"(ca.o-"c3.1 Jcao
cb"'coo-cd-,cy
C,4, =0_0306
ex =0,71
6--5 d
Sotl".)':lon
Ualue
__ _N.' ____ . __ . " .
C
e
=0,68
C
y
=0.'11
ca
cd
cx
Kl
K2
Cl.J
cbo
CoO
cc
x
cb
Cl.CJ306182
0.109652
0.714386
4
0.714'386
1.5
1.5
0,754995
0.979588
0.675961
iO

!.084 e-,t8
L 1 05e-' 16
We also fmd that X :::: 0.98
b) With the new equatjon we must fmd the new equilibrium equations.
ex =Cy _C
z
C,A = CAli CDC
Z
;,

f (c:yl :=cy--k2 Cc: .. c:b/c.x
flcd)=cd-kLca-cbicc
k;3",5

1<2:..1,,51.
cao=l S
cbo=,L 5
sdz;-;tcdicz
ca=cao'-cd--cz.
cb:;:cbo-c:d-cy
cz
eLJ
cd
cx
CdC
ct:>Q
T
sdz
k3
c"
k2
cb
k 1
x
cc
0 .. 990725
t .07:384
CL 2681 0 1
0.0831 135
! .5
1.5
:300
U.27C6 i 1
1.08389
49.4255
0241174
D .. 480271
0. ; 5806
8.26888
0.839217
: . 17571
1 ...... 1"" ......
1. -r '. '''':;J:;:'
6-79
10
! 09212--13
Lt"''1e-12
2 .s07c'-15
Wefmd that
C
z
=0.65
C/o. = 0.48
X =0.68
Sex =2.8
C
y
=0.91
C
a
=0.22
SDZ =057
CD =0.37
C
c
=0.76
Syz =1.41
ex =0.27
c) When the temperature is raised from 300 K to 500 K, Sex goes down, SDZ goes
up and SyZ goes up.
d) First find the proportionality constants fwm the A ..rrhenius equation.
0.002 ::::: A1e-n()Q(X)/1 911YHX})
== 38603
O 06
- A -(1(,(,'00/1.987' ;(0)
.. - '''"\l
e
A2 == 2..24 x IOu
0.3 ::::: AJe,Pt)()OO/1 987".1(0)
A
J
:::: 2.16 X 10
21
Once those are known, come up with equations for the equations in terms of
space-time 'to
C ..
w
- C
A
'r: :::: .............. , ..... _ ................ _ ...,. .. _ ...
k
j
+ k
2
C,;, +-
rkl + rkJC
A
t - C1{) + C,4 :::: 0
r' ....''' .. ''''''', .... ;... . ...."." ............, .................... .
..(;:/{,+1}+ I(rk, +1)-4(rk )(rkC )

.., \J - J '. 1 AO
.' ,\ = _ ......_ .. _ .. .... .. __ ...... _ .. .. ;;;..i .. .... ...... _ .. ...... .. _ ..-................................ --.-.
- \.. 3
c -.. en ..--c
I"= ., ..... ZL r == ...- 'i =-- ..
.. --k
1
k1C
A
k>C;
ex ;:;; kl r CiJ :::: k:.1.C
A
Cy = k,'t't:1
Use EXCEL solver in order to find the temperature that maximizes C
a
T Ca
312.5336841 0.016513937
k1
0,Q03919233
k2
0.230891512
k3
2.260443602
CDP6-F (a)
Mole balances:
Gx
0.039192325
Cb
0.038129279
Cy
0 ... 006164458
6-80
dF A/dV = -rD-IU
dFn/dV =rD
dFu/dV =IU
Rate laws:
r
D
= l C ~
ru = k
2
C
A
kl = 15 fellbmol.s
k2 = 0.015 SI
Stoichiometry: C
A
= CTo(F A/F
T
), F1 = FA + FD + Fu
Cost = 60F
B
- 15F
c
-lOFAo
Using these equations in polymath to find the necessary volume to maximize Cost:
v = 1425 fe
POLYMATH Results
Calculated values of. the DEQ variables
Variable initial value minimal value
V 0 0
fu 0 0
fa 0.06705 0.0018652
fd 0 0
kl 15 15
k2 0.015 0.015
faa 0.06705 0.06705
ft 0.06705 0.06705
cao 0.00447 0.00447
ca 0.00447 1.243E-04
Cost -0.6705 -0.6705
rd 2.997E-04 2.319E-07
ru 6.705E-05 1.865E-06
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(fu)/d(V) = ru
[ 2] d(fa)/d(V) = -ru-rd
[ 3] d(fd)/d(V) = rd
Explicit equations as entered by the user
[1] k1 = 15
[2] k2=0 .. 015
[ 3] fao = 0 .. 06705
[4] ft = fu+fa+fd
[5] cao = 0 .. 00447
[6] ca = cao*(fa/ft)
[7] Cost = (60*fd-15*fu-1 O*fao)
[8] rd = k1 *(caI\2)
[ 9] ru = k2*ca
Independent variable
variable name: V
initial value: 0
final value: 2000
CDP6-F (b)
Mole balances:
FA =FAo + IAV FD =rDV Fu = IUV
Rate laws: fA = -ID - IU r
D
= k l C ~ ru = k
2
C
A
maximal value
2000
0.0237312
0.06705
0.0414537
15
0.,015
0.06705
0.06705
0.00447
0.00447
1. 46684
2.997E-04
6.705E--05
k
i
= k
io
ex
p
( ~ ) ~ - 91;.67) F; = VOCi
Cost = v
o
(60F
B
-- 15F
c
,lOF
Ao
)
final value
2000
0.0237312
0.0018652
0.0414537
15
0.01.5
0.06705
0.06705
0.00447
1..243E-04
1. 4607519
i.319E-07
1.865E-06
Use these equations in Polymath and vary T from 860
0
R to 1160
0
R and find maximum value of cost.
6--81
Cost steadily rises with temperature and reaches a maximum at 970
0
R(51O.33 0 F).
pOLYMATH Results
NLES Solution
Variable Value
ca 0.0023213
cd 0.0016225
cu 5.262E-04
cao 0.00447
E1 10000
R 1.987
T 970
k20 0.015
E2 2.OE+04
k10 15
vo 15
V 400
tau 26.666667
cost 0.6713603
k1 11.292187
k2 0.0085009
rd 6.085E-05
ru 1.973E-05
ra -8.058E-05
NLES Report (safenewt)
Nonlinear equations
[1] f(ca) = ca-cao-ra*tau = 0
[2] f(cd) = cd-rd*tau = 0
[3] f(cu) = curu*tau = 0
Explicit equations
[1] cao = 0.00447
[2] E1 = 10000
[3] R = 1..987
[4] T= 970
[5] k20 = 0,,015
[6] E2 = 20000
[7 J k10 = 15
[8J vo=15
[9J V = 400
[ 10 J tau = Vivo
f(x)
5.354E-08
-5.354E-08
-2.76E-15
[11] cost = vo*(60*cd-15*cu-1 O*cao)
[12] k1 = k1o*expE1/R)*(11T-1/919.67))
[13] k2 = k2o*expE2/R)*(11T-1/919,,67))
[14] rd = k1*(ca
A
2)
[15] ru = k2*ca
[16] ra = -k1 *(ca
A
2)-k2*ca
Ini Guess
0,,00447
o
o
-----_._----------------------
CDP6-G3
6-82
Mole Balances:
dC,
:= f\
at
de
dt
.... : ..,.::;: I'f
dt
Rate Laws:
wk,C.
C = ... " .., ...

Stoichieme try :
(' -4 k J)'rl '
41
0 1Id 3
'Eo == ;'Y ,me urn' :=) ... mo . m
from Henry's Law:
C ';;:;; 5.9 MPa(O.058 kmol/m J . MPa)= 0,3422 mol/dm!
Use these equations in the following POLYMATH program to generate graphs of CA' C,,_
eL' and C
F
as a fUIlction of time
d(ea) /d(e) "":co.
d(cb) .ld(e) "'1:0
di,ec) Id(:.:.) "':::c
d(ce)/d(t)=.:;e
d(c:::) /d(e)=;::
kl",O .. 000468
Ka=:22 .. 76
k2",O .. 000227
k4=O.00147
k3=;O .00282
rl:w*kl*ca-cb/(l.Xa-ca)
r2=w*k2*ca*cc/ll+Ka*ca)

ro"' r1
20
o 3422
540
o
o
o
6-83
ca
c ~
cc
ce
cf
kl
Ita
k2
k4
k3
r3
r1
1::'2
::'4
rb
re
rf
:::a
~ ~
ca
ec
eEl
cf
~ -;:
:.n:
::Lt-:
;:, ;,,::
:l.,lea
CDP6-H
t
o
o 3422
540
o
o
o
10
0,000468
22.76
0.000227
0 .. 001.4.7
0.00282
o
o 0984025
o
o
0 .. 0984025
o
a
0,0984025
0.0984025
20
ll.3422
540
0,311641
II 136398
6 .. 37928e-05
10
o 000468
22,76
0.000227
O.00H'7
0.00282
o 00873821
0.0984025
1. 621e-05
4.96363e .. 06
"2 .. 31981e-1.9
000878695
2 .. 07778e05
.. 2.32208e .. 19
0 .. 09811025
Ca, Ce. Ce vs t
cf vs
! /""
t /
'r /
j j
t /
1 /
.iL ... .... ~ _ B ...... ____ ............ .
~ ago:: B ::lC::
o
9 l.B51'7e-20
539 658
o
o
o
10
0.000468
22.76
0 .. 00022'1
0.00147
0.00282
o
2.319S1e,,19
o
o
.. 0 09811025
n
o
n .091H025
'0.,00834598
6-84
20
9 1851-7",--20
SJ9 <iSS
0.205615
0116398
6 ,.3 7926e-05
10
0 .. 000468
22,,76
0.000227
0.00147
0.00282
0.00580002
2,31981",-l.9
4.2S838e.;n
1 .. 84167e--22
-231981.", .. 19
0.00560002
2,27051e22
2,32208el'}
-0.00580002
Cb vs t
The equilibrium constant for the reaction
trOL +::. cs--OL
can be csrimaccd as a function of tcmpcratuIe from (he mole fraccion data below t(X)0c.
T
Y:t
Yc'!;
Kp
In Kp
lCooff
_ Yes
K --_.
P Ya:
323 375
.8 .. 75
.2 .. 25
-, -
.,-) 33
,
39 1 11 1
3.09 2.63
}
__ 1000 -:= -683 ""
3_09 - 268 R
6.H '" ... I 3 :51 _.Sl
rool
CDP6-I 2,9-17
CDP6-J
CDP6-K 2, 9-13
CDP6-L
Given: liquid feed to CSTR
L1tttid Peed.
CAll ... 0.4 tm.clJI
Cl'O ... 0 . .4 [ttlOlil
V"", 1201
6-85
With the following re:lCcon s.equence
)::1
A C .. rl :;;: k! C
A
k2
A--,1- B -'z ;: )::2 C
A
k3
B -..,. C r3 ::: );:3 CB
k."
F -..,. B + D i -r4 ::: k...
)::1 ::: 0 .. 0 t min-
1
)::2 =- 0.02 min-
t
k3 = 0.07 min-I
k.. ::: 0 . .50 Vgmol - min
1<2 k3
(a) Since C is an product. formed through intermediate B by either A -...,r B -7 Cor
k.". 1::]
F -...,r B + 0 i -.;. c. or din:ctJ.y from A C. the m.aximum concenmuion of C occurs
when all A and F have b:.:en convened to C: Cm.u;: CAO + CFOr (with E == 0).
(b) Both A and F an: only decomposed by the above scheme:
Bahnee on A: CAO 'U() C
A
",:(.rA) V;: (-rl fZ) V ={kl + c" V
;: (kl + kl)Y.. "" {kt + kt} 1:
CA Uo
or C" ;: __ == 0.4 gmol!! = __ 0.4 gmol/l
1 ... (k! : )::2) 't 1 + (0.01 + 0.02) t -+- (0.03) (60)
C,,;: 0.143 gmat /1
Balance on F: \10 Cr.J Uo C;; ;: (-fF) Y ;: V
. V.:.r. .
wnen:: 1: :::--::; \N" rrun
Uo
Solving we get: C
F
= O.lgmoVI
Balance forB: O-voCB = (-rB)V = (k3CB -k
2
C
A
+k
4
C;)V
(k
2
C A + k
4
C;)T (0.01min"lxO.143gmo1/l + 0.51.mor
l
min-'l 0.lgmo1 /l2)60min
C
B
= 1 + k3T - = 1 + 0.07min-
l
60 min
C B = 0.0907 gmo1 / 1
Balance for C: O-voCe = = (-k3CB -klCA)V
C
c
= (k
3
C
B
+ klCA)T = (O.07min-
l
xO.0907gmoll1 +O.01min-
1
xO.143gmo11l)60min
C
c
= 0.467 gmol/ I
Mole fraction of C =
= 0.467 = = 0.583
CA+CB+CC+C
F
0.143 + 0.09 + 0.467 + 0.1 0.8
6-86
CDP6-M
4A + 5B -:7 4C + 6D
2A +1.5B -:7 E + 3D
2C + B -:7 2F
4A + 6C -:7 5E + 6D
Rate laws:
-fA = fIA + f2A + (2/3)f4C
-fC = -fIA + 2f3B + f4C
-fE = -O.Sf2A - (S/6)f4C
-ljA = k1ACAC;
-r
ZA
= kZACAC
B
-r
3B
= B C ~ C B
-Y4C = k
4C
C
C
C1
13
-fB = 1.2SfIA + O.7Sf2A +f3B
-fD = -l.SfIA - l.Sf2A - f4C
-fp = -2f3B
Using these equations inpolymath to find the exiting molar flow rates.
POLYMATH Results
NLES &.lutioll
NLES Re,Qort {safenewtl
Variable Value f(x)
Nonlinear equations
ca 0.998927 -1. 05 6E-15
[ 1 ) f(ca) ::::; vo*ca-fao-ra*W ::::; 0
cb 0.997227 1. 08 2E-15
[ 2) f(cb) ::::; vo*cb-fbo-rb*W ::::; 0
cc 0.0017849 -1.422E-16
[3) f(cc) ::::; vo*cc-rc*W ::::; 0
cd 0.0037612 -1.041E-16
[4) f(cd) ::::; vo*cd-rd*W ::::; 0
ce 3.613E-04 -1. 73 5E-18
[5) f(ce) ::::; vo*ce-re*W ::::; 0
cf 1. 285E-12 1. 254E-13
[6) f(cf) ::::; vo*cf-rf*W ::::; 0
Explicit equations
vo 10
fao 10
[1) vo::::; 10
W 3
[2) fao::::; 10
[ 3) W::::;3
fbo 10
[4] fbo::::; 10
rho 0.0012
[5) rho::::; 00012
k1 5
[6] k1 ::::; 5
k2 2
[7] k2 ::::;2
k3 10
[8) k3::::; 10
k4 5
[9] k4::::;5
fa 9.98927
[10J fa::::; vo*ca
fb 9.9722697
[ 11] fb::::; vo*cb
fc 0.0178487
[12] fc::::; vo*cc fd 0.0376119
[1.3 J fd::::; vo*cd fe 0.0036129
[ 14] fe::::; vo*ce ff 1. 285E-ll
[ 15] ff::::; vo*cf rl 0.0059604
[16] 1'1 ::::; rho*k1 *ca*(cb"2) r2 0.0023908
[17] r2 ::::; rho*k2*ca*cb r3 3.812E-08
[18J r3::::; rho*k3*cb*(cc"2) r4 1.07E-05
[19J r4::::; rho*k4*cc*(ca"(2/3 rf 7.625E-08
[20] rf::::; 2*r3
re 0.0012043
[21] re ::::; O .. 5*r2+(5/6)*r4
ra -0.0035767
[22J ra ::::; -r1 +r2-(2/3)*r4
rb -0.0092436
[23J rb ::::; -1 .25*r1-0. 75*r2-r3
rc 0.0059496
[24] rc ::::; r1-2*r3-r4
rd 0.0125374
[25] rd ::::; 1 .. 5*r1 + 1 .. 5*r2+r4
6-87
Ini Guess
1
1
0
0
0
0
Y
FE 3.6x10-
3
0336
(b) AE = = = .
FAa -- FA 10-9.989
Y BF = FF _ 2.29xl0-
7
= 8.25xl0-
6
F
Ba
- FB 10-9.973
YAC = Fc _ 0.0178 = 1.663
FAa - FA 10-9.989
CDP6-N 3, 6-21
CDP6-0 3, 6-25
6-88
Solutions for Chapter 7 - Reaction Mechanisms,
Pathways, Bioreactions and Bioreactors
P7-1 (a) Example 7-1
The graph of loll will remain same if CS
2
concentration changes. If concentration of M increases the slope
of line will decrease ..
P7 -1 (b) Example 7-2
For t = 0 to t = 035 sec, PSSH is not valid as steady state not reached ..
And at low temperature PSSH results show greatest disparity.
See Polymath program P7-1-h.pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value
t 0 0 12
C1 0.1 2 .. 109E-04 o .. 1
C2 0 0 L311E-09
C6 0 0 3.602K-09
C4 0 0 2 .. 665E-07
C7 0 0 0.0979179
C3 0 0 0 .. 0012475
C5 0 0 0.0979179
C8 0 0 6 .. 237E-04
CP5 0 0 0 .. 0979123
CP1 o .. 1 2.166E-04 0 .. 1
k5 3.98E+09 3 .. 98E+09 3 .. 98E+09
T 1000 1000 1000
k1 0 .. 0014964 0 .. 0014964 0.0014964
k2 2.283E+06 2 .. 283E+06 2 .. 283E+06
k4 9 .. 53E+08 9.53E+08 9.53E+08
k3 5.71E+04 5 .. 71E+04 5.71E+04
ODE Report (STIFF)
final value
12
2 .. 109E-04
L311E-09
3.602E-09
1.276E-08
0 .. 0979179
0.0012475
0 .. 0979179
6.237E-04
0 .. 0979123
2 .. 166E-04
3 .. 98E+09
1000
0 .. 0014964
2 .. 283E+06
9.53E+08
5 .. 71E+04
Differential equations as entered by the user
[1 J d(C1 )/d(t) = -k1 *C1-k2*C1 *C2-k4*C1 *C6
[2] d(C2)/d(t) = 2*k1 *C1-k2*C1 *C2
.t.Oe-9 ,..----------.--.---,
[3] d(C6)/d(t) = k3*C4-k4*C6*C1
[4] d(C4)/d(t) = k2*C1 *C2-k3*C4+k4*C6*C1
k5*C41\2
[5] d(C7)/d(t) = k4*C1 *C6
[6] d(C3)/d(t) = k2*C1 *C2
[7] d(C5)/d(t) = k3*C4
[8] d(C8)/d(t) = Q..5*k5*C41\2
[9] d(CP5)/d(t) = k3*(2*k1/k5)A05*CP1I\O.5
[ 101 d(CP1 )/d(t) = -k1 *CP1-2*k1 *CP1-
(k3*(2*k1 /k5)1\Q .. 5)*(CP 11\Q .. 5)
P7-1 (C) Example 7-3
The inhibitor sho'NS competitive inhibition ..
See Polymath program PTle.poL
7-1
32e-9
~
(''l
.. ('6
2Ae-9
16e-9
S.lle-HI
OOe+O ' - - - ~ - - - - - -
0.0 24
tS t 72 9.6 120
0.40..--------------..
0.32
0 .. 08
--'
- I'_inhibitor
r
-
_.-

S.Oe-3 6"Oe-3 9.0e-3 LOe-2
P7-1 (d) Example 7-4
l)Now Cure. = 0.001mol/dm3 and t = 10 min = 600 sec.
t =
V
MAX
I-X V
MAX
600
_ 0.0266mol / dm
3
1 ( 1 ) (O.OOlmol / dm
3
)X
sec _ n -- + --L _ _____ ..L-_
0.000266mol / s.dm
3
1- X 0.000266mol / s.dm
3
Solving, we get X = 0,,9974.
2) For CSTR, r = t = 461.7 sec
CureaX
T=-----
_ ... r
urea
VMAXCurea
- = K C
M + urea
CureaX
.- r
urea
=
T
0.000266mol / s.dm
3
xO.lmol / dm
3
(1- X) _ (O.lmol / dm
3
)X
. - --,---._--
O.0266mol/ dm
3
+ O.lmol/ dm
3
(1- X) 461.7 sec
Solving, we get X = 0.,675
See Polymath program PT, Ie.pol.
POLYMA TH Results
NLE Solution
Variable
X
Value fIx) Ini Guess
0.6751896 -8.062E-10 0.5
NLE Report (safenewt)
Nonlinear equations
[1] f(X) = O,,0000266*(1-X)/(O.0266+0.1 *(1-X))-O" 1 *Xl461. 7 = 0
3) ForPFR,
C
f
O dC
urea
T=
Cum - r
and C
urea
= CureaO (1- X)
72
k M I ( 1 ) C urea X
=> r = -- n -- + --"--""--
V
MAX
1- X V
MAX
Same as batch reactor, but t replaced by r x=o . .8
P7-1 (e) Example 7-5
Y = - t,.cs = - (238.7 - 245) = 2 18 /
SIP J'j.C
p
5.03-2.14 . g g
1 1
Y
plS
=--=--=0.46g/g
Y
SIP
2.18
1
YSIC+P =y--
C+PIS
1
= 1.87 g / g
0.075+0.46
Yes there is disparity as substrate is also used in maintenance ..
P7-1 (0 Example 7-6
1) if we go for 24 hIS, fermentation will stop at 13..2 hIS as Cp = Cp' ..
See Polymath program PT-l-f-1.pol.
POLY'!yIATH Results
Calculated values of the DEQ variables
Variable
.---
t
Cc
Cs
Cp
r'd
Ysc
Ypc
Ks
m
urnax
rBm
kobs
rg
initial value
o
1
250
o
0 .. 01
12.5
5.6
1.7
0.03
0.33
0.03
0.33
0.3277712
ODE Report (RKF45)
minimal value
o
1
39 .. 292786
o
0.01
12.5
5.6
1.7
0 .. 03
0.33
0.03
0 .. 0039386
0 .. 0624825
Differential equations as entered by the user
[1] d(Cc)/d(t) = rg-rd
[2] d(Cs)/d(t) = Ysc*(-rg)-rsm
[3] d(Cp)/d(t) = rg*Ypc
Explicit equations as entered by the user
[1] rd = Cc*0 .. 01
[2] Ysc = 1/0.08
[3] Ypc = 5 .. 6
[4] Ks = 1 .. 7
[5] m = 0 .. 03
[6] umax = 0 .. 33
[7] rsm = m*Cc
[8] kobs = (umax*(1-Cp/93)"O.52)
[9] rg = kobs*Cc*Cs/(Ks+Cs)
maximal value
13 .. 2
7-3
16 .. 558613
250
92 .. 981376
0.16559
12.5
5.6
1.7
0 .. 03
0.33
0 .. 4967701
0 .. 33
2.1455962
final value
13 .. 2
16.550651
39 .. 292786
92.981376
0 .. 1655065
12.5
5.6
1.7
0.03
0 .. 33
0.4965195
0.0039386
0.0624825
2)Semi-Batch reactor:
See Polymath program P7-1f-2.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
Cc 1.0E-04 1.0E-04
Cs 1.. OE-04 1. OE-04
Cp 0 0
rd 1. OE-06 1. OE-06
Ysc 12.5 12 .. 5
Ypc 5.6 5 .. 6
Ks 1.7 1.7
m 0.03 0.03
umax 0.33 0.33
rsm 3.0E-06 3.0E-06
kobs 0 .. 33 0.3294925
rg 1.941E-09 1.941E-09
Cso 5 5
vo 0.5 0.5
Vo 1 1
V 1 1
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Cc)/d(t) = rg-rd
[2] d(Cs)/d(t) = vo*CsoN + Ysc*(-rg)-rsm
[3] d(Cp)/d(t) = rg*Ypc
Explicit equations as entered by the user
[1] rd = Cc*0 .. 01
[2] Ysc = 1/0 .. 08
[3] Ypc = 5 .. 6
[4] Ks = 1.,7
[5] m = 0 .. 03
[6] umax = 0.33
[7] rsm = m*Cc
[8] kobs = (umax*(1-Cp/93)1\().52)
(9) rg = kobs*Cc*Cs/(Ks+Cs)
r 10] Gso = 5
[11] vo = 0 .. 5
[12] Vo = 1
[13] V = Vo+vo*t
maximal value
24
0.0474697
12.206266
0.2748298
4.747E-04
12.5
5.6
1.7
0.03
0.33
0.0014241
0.33
0 .. 0137289
5
0.5
1
13
7-4
final value
24
0.0474697
12.206266
0.2748298
4.747E-04
12.5
5.6
1.7
0.03
0.33
0.0014241
0.3294925
0.0137289
5
0.5
1
13
0,30 15
0,24 12
018 9
0.12
~
- C)
6
0.06 3
(100 0
0.0 4.8 96
t
14.4 19,2 140 0,,0 4.8 9.6 t 144 19.2 24.0
3)Changes from part(2)
See Polymath program PT-lf3.po1.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
---
t 0 0
Cc 1 .. 0E-04 1. OE-04
Cs 1.0E-04 1.. OE-04
Cp 0 0
rd 1.0E-06 1.0E-06
Ysc 12 .. 5 12,5
Ypc 5 .. 6 5.6
Ks 1.7 1.7
m 0.03 0.03
umax 0.33 0.33
rsm 3 .. 0E-06 3,OE-06
kobs 0.33 0,,3299991
Ki 0 .. 7 0 .. 7
Cso 5 5
vo 0.5 0 .. 5
Vo 1 1
V 1 1
rg 1,941E-09 1,941E-09
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Cc)/d(t) = rg-rd
[2] d(Cs)/d(t) = vo*CsoN + Ysc*(-rg)-rsm
[3] d(Cp )/d(t) = rg*Ypc
Explicit equations as entered by the user
[1] rd = Cc*Q.,o.1
(2] Ysc=1/o.,o.8
[ 3] Ypc = 5,,6
[4] Ks = 1 .. 7
[5] m=o."o.3
[6] umax = 0.,,33
[ '7 1 rsm = m*Cc
24 24
1.. 514E-04 1.514E-04
12 .. 823709 12.823709
4.669E-04 4.669E-04
1.. 514E-06 1 .. 514E-06
12.5 12.5
5 " 6 5.6
1..7 1..7
0.03 0.03
0,,33 0.33
4.541E-06 4.541E-06
0 .. 33 0.3299991
0.7 0 .. 7
5 5
0.5 0 .. 5
1 1
13 13
8 .. 215E-06 2 .. 568E-06
15
12
9
6
3
0 ~ ~ ~ ~ ~ ~
0,0 48 9,,6 t 14 4 19,2 240
7-5
[8] kobs:;:;: (umax*(1-Cp/93)J\().52)
[9] Ki = 0.7
[10) CSO = 5
[11) vo = 0.5
[12] Vo=1
[13] V = VO+VO*t
[14] rg = kobs*Cc*Cs/(Ks+Cs+CSA2/Ki)
1.00e-4
0.0 9.6 t 14.4 19.2 24.0
4)After 9.67 rus, C
s
= O.
300,--------
240
180
120
60
-
c.s
C)

o 2 4 t 6 8 10
P7 -1 (g) Individualized solution
P7-1 (h) Individualized solution
P7-1 (i) Individualized solution
P7 -1 (j) Individualized solution
P7 -1 (k) Individualized solution
P7 -1 (I) Individualized solution
P7-1 (m) Individualized solution
P7 -1 (n) Individualized solution
O.Oe+O ____
0.0 4 .. 8 9.6 t 14.4 19.2
P7-2 Solution is in the decoding algorithm given with the modules.
7-6
24 .. 0
P7-3
Burning:
GO' ~ O H
then
y ~
-+i,)H
-reI. = 0 = ks(HCl)(H) -- k
6
(CI)(H)
7-7
Cl _ k} (Hell
- k6
fH =: .+kj (o!};. 3k4 (H) (O:d' kz (B- }(02l' 2ks (HCl) (H-)
r'-------............ ,,----,---,'''--....,,,,-----
l r,I_!,:_:, 4k .. :_ ... f: ..:.U
ConstamVoiurne
.btdCH (" *b*"hl- hl
e' -' " e -ae
dt H
Using the integraring f:lctor
d(e-!:l!C
H
)
---" ........ -.. ,-,-:::: a e-,be
dt
C+ =: .. +. KI e
ot
t :: 0 CH :::; 0 therefore K 1 ==
.... ,--'_.,,-:' ' ''' .. ''''-]
t c :. t
If k4 (C'}z) > ks {HCI) ) then "b" is positive
If kj (HCt) > kd02} , then"b" is negative
,,,e"
, . .".
1/
t ......... " .. "" .. ,."."_ .." .....,,'-.. _ ..,,,............ , '"''''''
7-8
=ap(C\-{.)
t "'" 0 Ceo = CCJo
r
.. .. 1
,.. aLt 1
.. CO :::; Cc.O-o - at p _ .. ; c" .... pi'
L .... __..... __ ........... _._J
p( C
H
)= 3k,! (0
2
'[:f{
p::::: 3k
4
(OJ
a::::: 4ls (0
2
)
Reaction Pathway with HGL
Reaction Pathway 'lifo HCL
[ .. J ..................................
... 1
I
J:1 [1_ .. ]
2:, -lH-
..I

P7 -3 (d) Individualized solution
P7 -3 (e) Individualized solution
P7-4
The re::!crion sequence is
--teBO ..
+-CO+CH
4
C'HO CIl
3
-+2CO + H2
7CH .. _ ..
k
,.--4C H
' "2 '6
7-9
[
- ' ..
OR
--T
I
l
]
CO
I"l = k! CAe
!2 = kz CAt: COh-
I) = kl eCHO- CAe
\4 = k4 ('.J;.,
..... 1J"
C (k k (
~ ,(,,2:
= AC !... '2 .. ~ ; + KJ -CHO.i
Active imc:n:ned.iates:
Cfh, CHO
-rc:h;:;:; -r! .... r2 .. r2" r3 +l..r ::: 0
241
k C
2
:=k1C,4C + k2CACC(11) - k
3
C
CHO
C,\C .,' k;.CACCCHl +2' '4 CH}
k
" k C (' k (' ( ~ 1 k (,,2
== .. , leAC +- 2 AC "CH, " . " "C'flO '-'{C+
2
4 'eH,'
"rCHo- :::: -rl + 1'3 :::: .. k! CAe + k3 eCHO. CAe;::: 0
Substituting (3) in (2) gives:
C2Hs
P7 -4 (d) Individualized solution
P7-4 (e) Individualized solution
P7-5 (a)
7-10
(1)
(2)
(3)
Gas phase reaction
with third order kinetics and an apparent negative activation energy .. Consider the
following mechanism, in which NO} is an active intermediate.
fj "'" kll NOJ[02J -k
1
[N0
3
]
T2 ==kzINOlfNOJ]
"" k![NO][ O
2
] k
1
!N0
3
] ls[N0J[NO,]
[N0
3
]
kl
"T == ... k iNO][O,] + (k k
2
[NOJ)
NO 1 . k
1
lk
1
[NO]
== ... 19.21
"_I +.s[NO]
_ 2k
1
k
2
[NOY[Oz]

kl k
2
[NO)
. 2k1k, 41]
r
No
= _.- ... k -"-[NO] .()z
1
For the overall activation energy to be negative,
(E
1
+ EJt == EDt, < 0
=::!;> E < (E+E)
-liZ
A.s long as all energies are positive values.
P7-5 (b)
k3

ks
COCl + Cl
z
-7 COCl
z
+ Cl
7-11
r
COCt
= 0 = k3 (Cl)( CO)-k4 (COCI)-ks (COCI)( CIJ
(COC!) = k3 (Cl)( CO)
k4 + k5 (Cl
2
)
( ) ( )
klk3 ( CO) ( Cl) ( Cl
2
)
rcoCt2 = ks COCI Cl2 = ()
k4 + ks Cl
2
r
ct
= 0 = kl (C1
2
)-k2 (CI)2 -k3 (Cl)( CO)+ k4 (COCI) + ks (COCI)( C1
2
)
add I'COCI to rCI
r
Ct
+ r
eoct
= 0 + 0 = kl ( C1
2
) - k2 ( Cl)2
( Cl)
2
= ( Cl
2
)
k2
(Cl)=
k2
klk3 (CO) :1 (C1
2
t
5
(CI
2
) kl k3 :1 (CO)( CI
2
)%
rCOCt2 = k4 + ( Cl
2
) . - --k-=4
2
'--+-k
s
-(-C-1
2
-)-
k
4
k5 (Cl
2
)
_ k1
2k
3 ( )(
rCOCt2 - -- CO Cl
2
2
k2k4
P7-5 (C) Individualized solution
P7 -5 (d) Individualized solution
P7-6 (a)
K[
N0
2
+ hv NO + 0
K2
O
2
+O+M -7 0
3
+M
K3
0
3
+NO N0
2
+ O
2
UsingPSSH,
P7-6 (b)
7--12
0" M and O} aonear in [he denoI11inacot 2c,;ve Sl,,,,,,,,.r(M1 ;" (')
..... .. ... .... ".;:,.;:::,'-';' ..... ..... ...:> '
fl..pplying rule '3 of t2.b!e 71 to 0::. and 0,:
0] -i- 0.,. 202
(h';- 0;.0
3
0
3
and M appear in the numerator. Applying rule 1 of Table 71 to 0;: 0,.-7 0;: + 0
If the second and third equations are combined, and M is added to each side of the
equation:
A mechanism is proposed which satisfies all the rules of thumb:
r
o
,::::' r
l
t r
2
r
J
::::. . kl [lvll[C?11 j. kz [()JO 1(M] k; [0 ][0
3
]::::' 0
frJ 'i '''2' r
J
::::. k, [lrf][Ol] k2 [0
2
10 ][M j'-k;,lo '10,]= 0
[01 :;:o_ ..
kz[OJM]+'k;,[OJ
P7 -6 (d) Individualized solution
P7 -6 (e) Individualized solution
P7-7(a)
7-13
LOW TEMPERATURES NO ANTIOXIDAm'
= ri = 2ko(I2] - ki[I-J[RH1
== - kpl[ROz-J[RH]
= lep, [R-] [Oil - IcI'1[ROze][RH] - k, (ROz-P
c:{R-]
Cit = ki(RHJ(I-] - kp, [R-] [021 + kpl[ROz-][RH]
dRADlCALS] = 0
PSSA. ... dt
(A) = 0
2ko[h]
rj = 0 [I-] = ki [RH]
c(!.J = 0 = ki [RH][I-] - kpdR-J[021 + kpl(R<h-][RH]
i
= 0 = kp: [R-][Ch] - kp%[R02-][RH] - k
t

Substitute for [R] :
2ko [Iti - kt F = 0
[ROrJ = _!lk
o
[Ill
'V k
t
(A)
(B)
(C)
(D)
Now substitute the expressions for [he radicals into the expression for the degradation of
the oil.
c{RHJ = _k"[2ko[hJl(RH] _ k [2k
o
[hn
llZ
[RHl
cIt I ki [RH]J P:z kl J .
J.
[1-]
= 2ko (I:zJ- r[I:zJ
1n
[RH]
7-14
ODE to be solved- low no antioxidant:
_ c{RH] = .,1,._ "I? 1 + [koJ f'lI ]112 [RHl
[
. lln
cit e.AQ L -.. k
t
J 2 ..
P7-7(b)
Low temperatures with anti-oxidant
= ki[RH](J.]-kp
1
lR.][Oll+kp:(R0
2
.][RH] (same)
dfAe]
dt = kAl [AH][R02-] - k
A
2[A][ROr]
c(RHJ = _ k. [1-1 [RH1- kp .. [Ro,] rRH]
dt l .....
ApplyPSSH:
d[I-]
-=0
cit
d(Rl
----0:. = 0
dt
fIe] = 2
k
o [h]
.. kj [RH]
d(
R
2
2
.] == 0 2ko[h] - kt[ROr]2 .. 2(l<Al
:. - kt [R0:2p- 2kAl [AH] (RO:z] + 2ko [12] = {}
k,[RehP+ (2kAl [AH]) [ROr] - 2ko[h] = 0 Quadradtic in [Reh
e
]
[ROr] = 2kAl [AH] ../(2kAl [AH])2 + 8k
t
ko [h] MUST be positive
2k
t
Now (FINALL let'S substitute into :
7-15
t{RH]
dt
= _ 2ko [12] _ kp [RH] - 2kAl [AM] + ../{2kA 1 [AHJ)2 + 8kt leo (Ill
1 ?k
- t
P7-7(c)
If the radicals are formed at a constant rate, then the differential equation for the concentration of the
radicals becomes:
d e] = ko _ k
i
[ Ie] [RH] = 0
and -
k
i
[RH]
The substitution in the differential equation for R" also changes. Now the equation is:
d = k
i
[Ie][ RH] -kpi [Re][ 02]+ kP2 [R02e][ RH] = 0
. .., ko+kP2[R02e][RH]
and solvmg and substltutmg gIves: [Re] = [ ]
kpi 02
Now we have to look at the balance for R02
d[R0
2
e]. 2
_ .. _-- = kpi [Re][02]--kp [R0
2
e][RH]-k
t
[R02e] = 0
dt
and if we substitute in om expression for [R] we get
0= ko - k
t
[R02 e t which we can solve for [R02]
[R02 e] =
V k
t
Now we are ready to look at the equation for the motor oiL
d = -ki [Ie][RH]-k
P2
[R02e][ RH]
and making the necessary substitutions, the rate law for the degradation of the motor oil is:
d[RHe]
di- = r
RH
= --ko - k
p2VT
[RH]
P7-7(d)
Without antioxidants
With antioxidants
7-16
----------------------------------------------- -- -- -------------------------- ----- -------------- - ----- ---- -- -
P7 -7 (e) Individualized solution
P7 -7 (f) Individualized solution
P7 -7 (g) Individualized solution
P7-8 (a)
Given: Illness mechanism
H -7 r
k:2
r + E-, 21
I t D
I
Ii
H1.
{Healthy person g<:rs
(healthy per;;on cormac:s
from ill oerson i
(Hl person getS v .. cH)
(Ill person dies)
7-17
-'I }
\1(".
it
-+R H
)I-
rD::: k.t [lJ
Applying pseudo steady state hypothesis l:O 1: Ii = fl + f: ~ I:"} . ft=;:C 0
P7-8 (b)
Jt (H]
b+k.&
= --- the demh i.H.e becomes infinite ..
k2
P7-8 (c)
It is enlightening to calculate rtf:
fH "'" -rl - f2 + f3 =:k1 [H) ~ k2 [H] [IJ + kJ [fj ::: k! [H] .. {kz [H] .. kJHI]
rH;;: ----k t k.t (!!4--:-- ;;: _ fl) < 0
(1<3 + k.t ~ k2 tH)}
This expression states rhat for every person who is ill ilnd dies. a healthy person becomes ill For
the population as a whole, "illness is but a 'way station' on [he road to 'death'." Note fur..her that
IR < 0, and therefore the population will die off evenmally_ Initially, the death rate will be slow.
until [H].,,. {k3 + ~ } I k2. I11e model neglects the possibility of birth. In practice, it would appear
to be useful in describing epidemic-like diseases, which occur over a short time so that the birth
:rate can be neglected.
P7-8 (d)
See Polymath program P7-8-d.pol.
1.0\"+9
1 .. 00E9 fi"======::
, ...._.---...._--_.
8 .. 0e+8 8.00E8
CJ
- I
". n
6,OH8 6.00E8
4.0e+8 400E8
2,Oe+8 . 2.00E8
~ ~ . ~ . ~ ~ .....---.....-
O"Oe+O O.OOEO l_"""",===-
0.01'+0 2.0H9 4.01'+f 6.01'+9 8.0e+9 LOe+10 O .. OOEO 2.00E9 4.00Et9 6.00E9 800E9 1.00EIO
Everyone becomes ill rather quickly, and the rate at which an ill person recovers to a healthy person is much
slower than the rate at which a healthy person becomes ilL Eventually everyone is ill and people stru:t dying.
7-18
P7 -8 (e) Individualized solution
P7 -8 (0 Individualized solution
P7-9 (a)
Starting with the design equation for a batch reactor
de
--.. -.. == r
dt P
Tp=kC
c=
de . r C 1
d ....r!: =kfC
so
... C ] 1-- I,'
1.: r __ 1 4.
integrating
Finding k,
y '" 0 C02x + 1. ],697
1
....... ..- "
o 20 40
tlme
------r'- ......, .. .
60
Using the data at 40"F and 45"F the following graphs
o
'5
o
o 20
Finding k
y :O.CG2x t l.l697
40
time
60 80
:::::::::::::::T:.:::.:.::::: .......... _." .... '".........! .." ... .. .. ... " .. , .. ., ... _ .. ....... ""........ , .. _: ...: .. ...........
7-19
from these: k<t):;':: C.\():;.:: 1.1697
8.26*10'" C
45
= 1.1883
The activation energy then is:
(
C -1.5) C
1n ..-- ::;::7.14kt +
C
p
-1.4
E = _ Rln(k.2lkll :::: 108120
lfT1, mol
P7-9 (b)
( -E (1 1)) 1 8 ' 104;
k3& := k4s1 0'" 2.3R "4-9;7 -'- 504 =. 'I'
Using interpolation, C:::: 1.18086
Using the same equation used on the graphs we can solve for t when C
p
:;':: 1.1
t = 49 days.
P7-9 (c)
kn = k4s lO'" ( 516' ,_. ':5'64) ) = .0023
C::::: 1.211
t::::: 2 days
P7-9 (d)
The data appears that it may fit the Monod equation for substrate consumption at the stationary phase.
P7 -9 ( e) Individualized solution
P7 -9 (I) Individualized solution
P7-10 (a)
E+S kJ )E-S E-S k2 )E+S

r
E

S
= k
J
(E)( s) - k2 (E-S) -k3 (E-S) + k4 (p)(s)
since S is not consumed: Sy = S + E-S or S = Sy - E-S
r
E

S
= k
J
(E)[( ST) -( E-S)]-k2 (E-S) -k3 (E-S) + k4 (P)[( Sy ) -( E-S)]
(E-S) = kJ (E) (SrJ+ k4 (P)(ST)
k
J
( E) + k2 + k3 + k 4 ( p)
-r
E
=k
J
(E)(S)-k
2
(E-S)
-r -k E S 1- -
_ ( )()[ kJ(E)+k4(P)] kJ
k
2(E)(Sy)+k2k4(P)(ST)
E J 7 kJ(E)+k2+k3+k4(P) kJ(E)+k2+k3+ k4(P)
7-20
P7-10 (b)
E-S k2 )E+S
E-S k3 )E-P E-P k4 )E-S

r
Eop
= 0 = k3 (E-S)- k4 (E-P) - k5 (E-P)
(E-P) = k3 (E-S)
k4 -+-ks
r
EoS
= (E)(S)-k2 (E-S)-k
3
(E-S)+k4 (E-P)
since E is not consumed: ET = E + E-S + E-P or E = ET - E-S - E-P
(
k3) .( k3)
E = ET - E-S - --- E-S E = E[ - E-S 1+-""-----

Insert this into the equation for rE s and solve for the concentration of the intermediate:
(E-S) = kl (S)(Ey) __ _

(S)+k2 +k3 - k4
k
3
k4 + ks k4 + ks
r = k (E-P) = k3
k
5 (E-S)
P s k +k
4 s
klk3k5 (S)( E[ )
r =
P [k3 +k4 +k5]kl (S)+k2k4 +k3k5
P7-10 (C) No solution will be given
P7-10 (d)
k3
E-S
1
-+- S2 p E-S
1
S
2
k4
k5
E-S
1
S2 --7 P+ E
(1) r
EoS
, = 0 = kl (E)( SI) - k2 (E-S) - k3 (E-S)( S2) + k4 (E-S
1
S
2
)
(2) rEoS,sz = 0 = k3 (E-S) (S2 )_. k4 (E-S
1
S
2
) - k5 (E-S
1
S
2
)
If we add these two rates we get:
(3) r
EoS
, + 'Eos,s2 = 0 = kl (E)( S) - k2 (E-S) - k5 (E-S
1
S
2
)
Plug this into equation 3 and we get:
7-21
P7-10 (e)
kl
E+Sp(E.S)
~ j
k3
(E.S)j p( E.S)2 +
k4
ks
(E.S)2 -7Pz +E
(1) ~ E . S 1 =O=kj(E)(S)-k
2
(E.S)j-k
3
(E.S)j +k
4
(E.S)2(1n
(2) ~ E . S 2 = 0 = k3 (E.S)j - k4 (E.S)2 (p)j - k5 (E.S)2
k
3
(E.S)j
(EoS)2 =" (R)+k
4 j 5
Add (1) and (2) to get ~ E . S 1 + E . S 2 = 0 = k
j
(E)(S)-k2 (E.S)j -k5 (E.S)2
kj(E)(S)
7-22
k kSk3
2 + kS +k
4
(In
(EoS) = k/S(E)(S)
2 k2k4 (Pr) + k2
k
S + kSk3
r =k (EoS) = kr
k
3
k
S(E)(S)
P
2
S 2 k2k4 (Pr) + k2kS + kSk3
(Ey) =(E)+(EoS)r +(EoS)2
P7-10 (0
k, ko

k2
k4

k5
k6
EoS
k,
ks

""
r=k(EoS)
P 3
(1) = 0 = kr (E)(S) - k2 (EoS) - k3 (EoS) + k6 (EoS)( p) + k7 (EoSoP)
(2) =O=k
4
(E)(P)--k
s
(EoP)-k
s
(Eop)(S)+k
9
(EoSoP)
(3) = 0 = k6 (EoS)( p) - k7 (EoSoP) + kg (Eop)( S) - k9 (EoSoP)
(2) + (3): '(EoP) + = 0 = k4 (E)( p) - ks (EoP) + k6 (EoS)( p) - k7 (EoSoP)
now add (1) to this:
7-23
+ + = 0 = kl (E)( S) - k2 (Ee
S
) - k3 (Ee
S
) + k4 (E)( p) - k5 (Ee
p
)
(Ee
S
) = kl (E)(S)+k4 (E)(P)-k5 (Ee
p
)
k2 +k3
(Ee
P
) = k4 (E)(P)+k9 (EaSa
P
)
k5 + kg (S)
(EeSe
p
) = k6 (EeS)(p)+kg (Eep)(S)
k7 +k9
k4 (E)(P)+k9 (k6 (EeS)(p)+k
g
(Eep)(S)]
(Ee
P
) = k7 + k9 ._--"--
k5 + kg (S)
(Ee
P
) = k7k4 (E)(P)+k9k4 (E)(P)+k9k6 (EeS)(P)+k
g
(EeP)(S)
k5 + kg (S)
(Ee
P
) = k7
k
4 (E1( p) +k9
k
4 (E)( p) +k9k6 (Ee
S
)( p).
k5
kl (E)( S) + k4 (E)( p) - k5 (k7
k
4 (E)( p) + k9
k
4 (E)(P) + k9
k
6 (EeS)( P)]
(EeS)= _____ k5
k2 +k3
(EeS) = kl (E)(S)+k4 (E)(P)-k
7
k4 (E)(P)
k2 +k3 -k6k9 (p)
rp = k3 (Ee
S
) = k3 (E) kJ (S) + k4 (p) -. k7
k
4 (p) + (p)
k2 + k3 - k6k9 (p)
(Er )=(E)+(EeS)+(EeP)+(EeSeP)
(E] ) = (E)+ kJ (E)(S)+k4 (E)( p)- k7
k
4 (E)( P)+k9
k
4 (E)(P)
k2 +k3 -k6k9 (p)
k7
k
4 (E)( p) + k9
k
4 (E)( p) + k9
k
6 (kJ (E)(S) + k4 (E)( p) -_ .. k7
k
4 (E)( p) + k9
k
4 (E)( P)J( p)
+__ . _ k2 +k3 (p)
.-'-----
-
k (kJ (E)( S) + k4 (E)(P) - k7
k
4 (E)( p) + k9k4 (E)( P)]
6 k2 +k3 -k6
k
9(P) - (p)
+ -
7-24
k
J
+k9
all of the terms in the numerator have (E) in it and so the (E) can be factored out and an expression for (E)
in terms of (El)' (P), and (S) can be made and plugged back into the equation for rp.
P7-10 (g)
kl k3

k2
k4
E+ppEep
k5
=O=kl(E)(S)-k2(Ee
S
)-k3(Ee
S
)
(Ee
S
) =5lS)(E)
k2 +k3
=O=k
4
(E)(P)-k
5
(Ee
P
)
(Ee
p
)= k4(E)(P)
k5
rp = k3 (EeS) - k4 (E)( p) + k5 (Eep)
rp = __ k4 (E)(P)+k4 (E)(P)
2 3
Isk3 (S)(E)
rp =--'--:"""":
k2 +k3
(ET ) = (E) + (EeS) + (EeP)
(ET )=(E)+ kl(S)(E)+ k4(E)(P)
k2 + k3 k5
(ET )=(E)[1+_
k1
(S) + k
4
(P)]
k2 + k3 k5
klk3 (S)( Er )
r - --- -'--'--c-"-'--__
P - (k2 +k
3
)[1+ kl. (S) + k
4
(P)]
k2 + k3 k5
_ k3 (S)( ET )
r
p (k2 +k3 +(S)+ k4 (k
z
+k3 )(P))
kl klk5
7-25
P7 -10 (h) No solution will be given
P7-10 (i) No solution will be given
P7-10 (j) No solution will be given
P7-10 (k) No solution will be given
P7-11 (a)
The enzyme catalyzed reaction of the decomposition of hydrogen peroxide .. For a batch reactor:
;; = fS "" at t =: 0, Cs "" CS
o
til r LS
Rearranging and integrating:
K I
Cs C C
m n -.... .,.. s So "" V . t
eS
o
max
or J In S"t) '" ':' ..
t \-5 Km t Km
A plot of L I CSt) . Cso - Co;; .'
t n C
s
vs _. -i........c- should be lwear with s:ope .. J ...
Km
10
.01775
20
.0158
50
.0106
100 .0050
00140
0.0135
0.0130
t Cs
0.0125
00120
0.0115
1.1268
.01193
.00225
12654
.01179
.0042
1.8867
OI27()
.0094
4.0000
.01386
.0150
15
1 6 1 7 18 1 9 20 21 22 23
(C{so) - C(S)lt X 1 E5
726
CS!L:CS
t
.000225
.00021
.. 000188
.00015
24 25
F h
013 012 ( min .j
rom t e gnarl, slope "" ... .. -'--.--.--, -,,.-------"1
- , (17.5 ,. 206) x 10
5
,g mol I min; J
Km :::: ,.0310 g mot!l
C C C 1 75 x 10-4
Art In '" ..,,,.2 ::;: """''''''
t Cs rom Imin
mol
V
mu
(01" 5 64 10" 'I O'8
r
-,.\
'K; = , .> +- ,,' . x mlD =, l' 0) mm
( 6
_ - ,,1){031)gmOl\
V m.z:s. :::;:; . .018 J X Hun -. ( --'l""'-j =:;
-78 '0 4 gmol
), X I ---':-"'-
I,nnn
P7-11 (b)
V m= a. (EJ. If the enzyme concentration is incrc:;lscd by a factor of th:ee. then
t/ -'3(-"78*10'4 gmol \-1'" -4 gmol
v rna=< -. .) ) - 7,.>4 * 1
0

r I
k
m
+- C
s
'" C
so
:::;:; '-1734 * 10 __,,_ * 20 min =: ,.-34.7 * 10
4
F.".,!::)1
C
so
L' mm L
-ntis equation shouid be sOlved by ni;),l and error, Rearr;:mging,
in . Cs., :::: CSO,:::,
Cso Km
:. C
s
=: C
so
'"
. L Km 1
,,02 cxo f
"l, .0310 1
Assume a Cs caicut:lte a new (lme from the RHS of the el1!luation.
Assume Cs New Cs % difference
8;----
O.077 O.97
0.0097 O.91
0.0091 O.93 2.2
0.93 0.0092 L 1
Q,.Cl92 0.0092 0
P7 -11 (c) Individualized solution
P7 -11 (d) Individualized solution
P7-12 (a)
7-27
Given me reacrion sequence:
E+S =5
The plat of r$ vs is s.'lown below.
the rnec:banism for the aI:xwe :reaction is:
-r,. ::::; - k Cs lit ; For ('-S I: -rs'" k C Et in qualitative agreement with the graph at
1 + Kl Cs + K, r.;
low values ofCs. fur Cs 1: -rs "" ;2 . This is also in agreement with the gr:aph.
2 I 2I'l'f
s
) _ ..._ .. _ ...... !<-.1 ..... _ .. __ _
or C
s
== -K-widi: -= - - - -
l ( C' ('\2
- -, 1 +- Kl Kl
=0

(1 Kj C
s
+ Kz
2kEt r- Kl - +-:- 11 < 0,,', (-r,) goes through:l maximum.
i K
2

This observation also agrees with (ile above graph
P7-12 (b)
7-28
For a CSTR operatbg with V.::; 1000 I; Uo ;:; 3 1. IJmin
v
Do
with CAD"" 50 m mo\es/l .
f"" = this (linear) equacion is plotted on the accompanying
,) . .)
graph, the equari?n imersects the (.!,) v s C
s
curve from .he rare of renccion at
- 0 mID.Qks. ... (' "" ? 1 ll.rr.ill.e.s. -(
r,; - .;) . --. I .. 5
Il1ID 1
Stability of points: J.Ssume u'1ar a pe:,urbllrion as == c so .. Cs occurs where the overb:;r designarcs
the steady-state condition. balance for any time:
V == rsV + Cso \)0' Cs Uo
dt
c
or 1: :: IS: + eso ... Cs
cit
.'\
}
Combining
at Steady stare
r5 , .. rs
{ d rs \ -
\:-l (Cs" csl ""
\d Cs IC-
.;:,
"1
11 6s + 6s[) :1:. t "" 0 . as -= 0
i
,1
For this solution of the 3.0ove eqtw.rion 10 be stable:
I. \ "L
I, < I or t r
\
C' ('"
.d -s Ie:; d,S les
> 1
At C. = 2 .. 1 m moies/!"f
s
"" O. 111 moles! Imin. rhe of rhe re:lction rare curve is posithe
'Therefore, rhis oper-:J.ring poim is stable. For the other (WO poi:1ts,. the s(;),bi!icy may be exarnined
by estimating the derivative gr;J.phically:
L\CS
'" min
1
2. '
7-29
:. t.'1e point C
s
:::; 9.4. ''is::= 0132 is unsrable ..
At Cs"'" 2.1 m molesll. .= ;:;: Q,-Qfi.12 .. :.D_J218 = - min-I
a Cs fE.s = 2.1 D"Cs 24 - 44 20

1: =: ( .. u,.D!!25. min'1) (3 n min) ::: - 0.775> .,! ; s.abk


a Cs les 2"
At Cs = 5.1 m moleSJ1. -rs :::; 0.154 appears to be sc:!ole. but more accurate calculation
, I-mm
f(
el(orS)). . bl" .. l' d , ... ,
o -_ ..... - IS necessary esra Isn tillS conC,USIon ennmvelV.
(1 Cs'
X = Cso -Cs = 50-2.1 =.958
C
so
50
P7-12 (C)
-rs =--- z
1 + K1C, + KzC
s
!fEr is reduced by 33%, -rs will also decrease by 33%. From the original plot, we see that if the curve -rs is
decreased by 33%, the straight line from the CSTR calculation will cross the curve only once at
approximately C
s
= 40 mmol/L
X=O..2
P7 -12 (d) Individualized solution
P7 -12 ( e) Individualized solution
P7-13 (a)
Data on Ba.ker's Yeast at 13.4 c
no
._L
2C mg
su Ha:1i b.midc. $u[[';mllarnidc!rrH no
adccc to medium $ulfan!l.;mlidc
23.5 17.::t .0425
33.,0 25.6 .0:303
"'!,-7
.. 5 30.8 .02.666
42..0 364- 02.38
43.0 39.6 .02.33
:+3.0
;lOJ) (n,3)
7-30
2 . .0
1.0
.66
AO

..
.200
.0575
.0391
.03246
.02747
.0'2.53
.0250
.
.1.
_K!!!_
___ L __ K (1' 1 _1 _
::;
+
;::;;
___ IIL \ ____ "_) + ______.!-. _____
::
..
fp
Vma.x
S
YmJ.x QC'z V m.;u Po, V ma;x
P
l ~ I 1 '11 hI' Km -!' ---
~ o t ot n : - ~ versus -p ---- wt lave a s ope or ---;.;'... .. , anu an Imercept ot Un
'-<\.h O;l V ron
0.06
.... WItt!
ODS
O/tlln
0.04
(C!5ClI C{:s
OM
om
0.01
0.00
0.0 1..0
1/1){O) (rnm HQ)
From the graph, slope'" JllQJ_:_J1J1. =0165 IlHcrCcpt;;;:: 0.019
1
... V m.:u = 5263, ml
nr rng cells
Km "" 0.0165 Vm:1X ::; (0_,0165)(52.63) ~ 0 mrnHg
P7-13 (b)
Now, with competitive lnhibidon: E + S C;::l E S
Km( 1 +
Rare law becomes:
t5
(1) + f
"S \mu
In this C:lse, (he slope is :
K It +_.L}
111 ~ K"
----"---""--. '.vhile (he imer::epr is the S;;lme as in c;).se fa)
V
ma
;>;
7-31
For the case of uncomperitive inhibition: E + S = E S
E$+1=1-E-5
E'SC;)P+E
Rate law becomes:
1 +-'
In this case, the slope is the same. bur the inrercept is v.JSL
maA
And for the case of non-competitive inhibition: E+I=E-1
E I + S ~ I E S
E + S ~ E S
IES;:)ES+I
E"S;:)P+E
In this case both the slope and intercept change. Plotting the data of t- in mmlig versus r-!:-
~ '<VI;
with sul1anilamide on the same plot as was ploned the data for the case with no sulfanilamide. it is
seen that the slopes are different. but the intercept is the same. 11lerefore the inhibition is
cornparari ve.
P7 -13 ( c) Individualized solution
P7 -13 (d) Individualized solution
P7-14
For No Inhibition, using regression,
Equation model: ---.!- = aO + a1(.l..)
-r S
s
aO = 0 .. 008 al = 0.0266
For Maltose,
Equation model: _1_ = aO + a1(.l..)
-rs S
aO= 0.0098 al = 0.33
For a-dextran,
7-32
Equation model: _1 - = aO + al(!)
-r S
s
aO = 0008 al = 0.0377
=> Maltose show non-competitive inhibition as slope and intercept, both changing compared to no
inhibition case.
=> a-dextran show competitive inhibition as intercept same but slope increases compared to no inhibition
case.
P7-15
rp =k(EHS)
(EHS) = KM (EH)(S)
rp = kK M (EH) ( S)
(EH;) = K2 (H+ )(EH)
( EH) = Kl ( H + ) ( E- )

Kl (H+)
(E] )=(E-)+(EH)+(EH;)
(EH) +
(Er)=-K1(H+) +(EH)+K2(H )(EH)
( EH) = _ (E] ) _
1 + K, + K2 ( H' )
Now plug the value of (EH) into rp
kK M (E] ) Kl ( H + ) ( S )
rp = kKM (EH) (S) = ----------2
1 + Kl (H+) + KIK2 (H+)
At very low concentrations of H+ (high pH) rp approaches 0 and at very high concentrations of H+ (low pH)
rp also approaches 0 .. Only at moderate concentrations ofH+ (and therefore pH) is the rate much greater than
zero.. This explains the shape of the figure ..
P7 -15 ( a) Individualized solution
P7 -15 (b) Individualized solution
P7-16 (a)
For batch reaction,
7-33
dCs
--=r
s
dt
See Polymath program P7-16-a.poI.
POL YMA TH Results
Calculated values of the DEQ variables
r -
s -
&
Variable initial value minimal value maximal value
t 0 0
Cs 20 6.301E-ll
eso 20 20
KIn 0.25 0.25
Yes 0.5 0.5
Ceo 0.1 0.1
Ce 0.1 0.1
umax 1 1
rs -0.0987654 -8,,0781496
re 0.0493827 1.273E-09
ODE Report (RKF4S)
Differential equations as entered by the user
[1) d(Cs)/d(t) = rs
Explicit equations as entered by the user
[1) Cso = 20
[2] Km:::: 0 .. 25
[3] Ycs = 0 .. 5
[4] Cco=O.1
[5] Cc = Cco+Ycs*(Cso-Cs)
[6] umax:::: 1
[7] rs = -umax*Cs*Cc/(Km+Cs)
[8] rc = -Ycs*rs
0.0
1.8
-3.6
c:J
-5.4
-7.2
-9.0
0 2 .:I 6
P7-16 (b)
For logistic growth law:
dCc
---=r
dt g
8 10
10
20
20
0.25
0.5
0.1
10.1
1
-2.546E-09
4.0390748
20
16
12
8
.:I
0
0 2
7-34
final value
10
6.301E-ll
20
0.25
0.5
0.1
10.1
1
-2.546E-09
1.273E-09
.:I 6 8
See Polymath program P7-16--b.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
Cc 0 .. 1 0.1
umax 1 1
Coo 1 1
rg 0 .. 09 0 .. 0080739
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Cc)/d(t) == rg
Explicit equations as entered by the user
[1] umax == 1
[2] Coo == 1
[3] rg == umax*(1-Cc/Coo)*Cc
1.00
0.82
0.64
0.46
0.28
0.10
0 .. 0 1.4 28 t 4_2 5.6
P7-16 (C)
ForCSTR,
7 .. 0
= _Y r = YClSf.imaxCsCC
rg CIS s K + C
M s
maximal value final value
7 7
0 .. 9918599 0.9918599
1 1
1 1
0_2499857 0.0080739
030.---------------
O ..
0.0 1.1 2_8 t 4.2 5.6 7.0
D
-I - h- h h YClSf.imaxCSO
I utlOn rate at W IC was out occurs =
KM +C
so
O.5xlhr-
1
x20g / dm
3
= 0.494hr-1
O.25g / dm
3
+ 20g / dm
3
P7-16 (d)
Dmaxprod = YClsf.imax[l- -J = O.5xlhr-
1
X[l- r / dm
3
]
+20g/dm3
Dmaxprod = 0.44hr-
1
7-35
P7-16 (e)
Ifrd= k.tCc
rh = C c v 0 = (rg - rd )v
Divide by CcV,
D= (r
g
-r
d
) =
C
c
KM +C
s
C

-
Yc/sf.Jmax -- D
Now - rs = Ys/crg
Cc = YC,sD(Cso - Cs )
D+kd
For dilution rate at which wash out occur, C
c
= 0
Cso=Cs
C
- (D+kd )K
M
_.
so-
YC/sf.Jmax - D
DMAX. = YC/S,umaxCSO -- kdKM = X 20g / dm
3
- O.02hr-
1
xO.25g / dm
3
= 0.493hr-1
C
so
+KM 20g/dm
3
+O.25g/dm3
There is not much change in Dilution rate while consideling cell death to one where cell death is neglected.,
DC =YC/SD
2
(c:so-
C
s) C =_(D+kd)KM
C s
D + kd YC/S,umax - D
d(DC
c
)
Now For D max .prod' . = 0
dD
D max prod = 0,446 hI-I
P7-16 (0
Now -rm=mC
c
DCc=rg & D(Cso-Cs)=-rs-rm
rh = Ccvo = (rg)v = f.JCcV
7-36
Divide by C
c
V,
Solving
Now
D = Ji = (YC/sJimaxCs)
KM +C
s
C - DKM
S -
YC/sJi
max
.- D
- r"s = Ys1Cr
g

Cc = [D(Cso - Cs )]
YclsD+m
For dilution rate at which wash out occur, C
c
= 0

C s = DK--=M __
YC/sJimax - D
C = DKM
so
YC/sJimax- D


DMAX YCISJimax Cso O.5xlhr-
1
X 20g / dm
3
= 0.494hr-1
C
so
+KM 20g/dm3 +O.25g/dm
3
d(DC
c
)
For D max prod' ---.- = 0
dD
Now
D max prod = 0.4763 In
l
P7 -16 (g) Individualized solution
P7 -16 (h) Individualized solution
P7-17
Tessier Equation,
. - (1 -Cs I k )c
r g - Jimax - e C
(a) For batch leaction,
dC
__ s =r
dt s'
c c = Ceo + Y
c
I 5 ( C so - C 5 )
See Polymath program P7-17a.poL
POLYMATH Results
Calculated values ofthe DEQ variables
Variable
t
Cs
Ceo
Yes
Cso
Ce
k
umax
Yse
rg
rs
RateS
initial value
o
20
0 .. 1
0 .. 5
20
0.1
8
1
2
0 .. 0917915
-0.183583
0 .. 183583
minimal value
-0-----
0 .. 0852675
o .. 1
0 .. 5
20
0 .. 1
8
1
2
0.0917915
-7 .. 7126957
0 .. 183583
. - (1 -Cslk)c
r g - Jimax - e C
maximal value
7
20
0 .. 1
o .. 5
20
10.057366
8
1
2
3.8563479
-0.183583
7.7126957
final value
7
0 .. 0852675
0.1
0.5
20
10.057366
8
1
2
0.1066265
-0 .. 213253
0.213253
7-37
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Cs)/d(t) = rs
Explicit equations as entered by the user
[1] Cco = 0.1
[2] Ycs = 0.5
[3] Cso = 20
[4] Cc = Cco+Ycs*(Cso-Cs)
[5] k= 8
[6] umax= 1
[7] Ysc=2
[8] rg = umax*(1-exp(-Cs/k))*Cc
[9] rs = -Ysc*rg
[ 10 1 RateS = -rs
16
12
8
4
o
0 .. 0

W
1.4 2.8 4.2 5.6 7.0
(c) DC
c
= rg D(Cso--C
s
)= rs
m = Ccvo = {rg)v = ,uCcV
Divide by C
c
V, D = ,u = ,urnax (1-. e -C
s
I k )
Cs = -kln(l- ,u:-)
Now
For dilution rate at which wash out occur, C
c
= 0
=> Cso = Cs = --k
,urnax
8.0
6.4
4.8
3.2
1.6
0.0 __ __
0 .. 0 14 2.8 t 4.2 5.6
=> DMAJ( = ,urnax (1- e-Csolk)= Ihr-
I
(I- e-20gldm3 ISgldm# )= O.918hr-
1
(d) DCc=DYm(Cso-C
s
) Cs=-kln(l- .u:-)
DC
c
= DY
os
( C
so
+k+- ,u:-)J
7-38
7.0
Now
d(DC
c
)
For Dmaxprod ' ::: 0
dD
Dmax prod = 0,628 hr-!
P7-17 (a) Individualized solution
P7 -17 (b) Individualized solution
P7-18 (a)
rg = JlC
c
Jl::: Jlmax C S
KM +C
s
ForCSTR, DCc:::rg D(Cso-Cs):::-rs -rs:::YsICrg
C
s
:::C
so
(1-X):::lOg/dm3(1-0.9)=lg/dm3 D= v;{
C
c
::: Y
CIS
(c so - C
s
)::: 0.5(10 -l)g / dm
3
::: 4.5g / dm
3
DC ::: r ::: JlmaxCsCc
c g K +C
M s
=>
Vo 4.5g / dm3 = 0.8hr-
1
xlg / dm
3
x4.5g / dm
3
V (4+1)g/dm
3
V ::: 6250dm 1
P7-18 (b)
Flow of cells out = Flow of cells in
Fc ::: VoCc
dC
Cell Balance: Fc + ~ V - Fc ::: V __
c
-
dt
dC
__ c=r
dt g
dC
Substrate Balance: _2_::: voC
so
- voC
s
- Y
s
/ r ~
dt /lC
JlmaxCsCC
r = = - - - - - - - ' -
g KM +C
s
This would result in the Cell concentration growing exponentially., This is not realistic as at some point
there will be too many cells to fit into a finite sized reactor., Either a cell death rate must be included or the
cells cannot be recycled"
P7-18 (C)
TwoCSTR's
For 1 sl CSTR,
V = 5000dm
3
, DC
c
= rg D(C-C )=-r
so s s
7-39
POLYMA TH Results
NLES Solution
Variable Value
Ce 4.3333333
Cs 1. 3333333
urnax 0.8
KIn 4
Csoo 10
Cso 10
Yse 2
rg 0.8666667
r's -1.7333333
V 5000
vo 1000
D 0.2
X 0 .. 8666667
Ceo 4 .. 33
NLES Report (safenewt)
Nonlinear equations
[1) f(Cc) = D*(Cc)-rg = 0
[2) f(Cs) = D*(Cso-Cs)+rs = 0
Explicit equations
[1) umax = 0.8
[2) Km=4
[3) Csoo = 10
(4) Cso = 10
(5) Ysc = 2
(6) rg = umax*Cs*Cc/(Km+Cs)
[7) rs=-Ysc*rg
[8) V = 5000
(9) vo = 1000
[10) D=voN
[ 11) X = 1-Cs/Csoo
[12] Ceo = 4 .. 33
fIx)
9 .. 878E-12
1.976E-ll
x = 0 .. 867
Ini Guess
4
5
Ccl = 4.33 g/dm
3
CSt = 1.33 g/dm
3
CPt = YP/CCCt =0 .. 866 g/dm3
For2
nd
CSTR, D(CC2 -CCI)= rg
See Polymath program P7-18 ..c-2cstr..pol.
POL YMATH Results
NLES Solution
Variable Value
Ce 4.9334151
Cs 0 .. 1261699
urnax O .. B
KIn 4
Csoo 10
Cs1 1.333
fIx)
3 .. 004E-I0
6.00BE-10
Ini Guess
4
5
7-40
Yse 2
rg
0.120683
rs
-0.241366
v
5000
vo
1000
D
0 .. 2
X
0.987383
eel 4.33
NLES Report (safenewt)
Nonlinear equations
[1] f(Cc) = O*(Cc-Cc1 )-rg = 0
[2] f(Cs) = O*(Cs1-Cs)+rs = 0
Explicit equations
[ 1] umax = 0.8
[2] Km=4
[3] Csoo = 10
[4] Cs1=1.333
[51 Ysc=2
[6] rg = umax*Cs*Cc/(Km+Cs)
[7] rs = -Ysc*rg
[8] V = 5000
[9] vo = 1000
[10] 0 = voN
[ 11] X = 1-Cs/Csoo
[121 Cc1 = 4 .. 33
CC2 = 4.933 g/dm
3
C
S2
= 126 g/dm
3
X= 0.987
C
P1
= Y P/CCCl =0 .. 9866 g/dm3
P7-18 (d)
For washout dilution rate, Cc = 0
D = JimaxCso
max KM + C
so
J!.:_8hr-
1
x 109 / dm
3
= O.57hr-1
4g/d
m
3 +lOg/dm3
[

-I[ ._-] -I
DMAXPROD = Jimax 1- -- = O .. 8hr 1-- 3 ------3 = 0.37hr
KM +C
so
4g/dm +lOg/dm
Production rate = Ccvo(24hr) = 4 .. 85 g / dm
3
xlOOOdm
3
Jlnx24hr = 116472.56g/day
P7-18 (e)
For batch reactor,
dCs
---=r
dt s
dC
__ c_=r
dt g
Ceo = 0.5 g/dm3 C
so
= 109/dm}
ro = .J!:max C S C
o K +C C
M S
See Polymath program P7-18e.pol.
POL Y1\1ATH Results
7-41
Calculated values of the DED variables
Variable
t
Cc
Cs
Km
Ysc
umax
rg
rs
initial value
o
0.5
10
4
2
0.8
0.2857143
-0.5714286
ODE Report (RKF45)
minimal value
o
0 .. 5
0.1417155
4
2
0.8
0.1486135
-2.8064061
Differential equations as entered by the user
[1] d(Cc)/d(t) = rg
[2] d(Cs)/d(t) = rs
Explicit equations as entered by the user
[1] Km=4
[2] Ysc=2
[ 3 1 umax = 0.8
[4] rg = umax*Cs*Cc/(Km+Cs)
[5] rs = -Ysc*rg
For t = 6hrs, C
c
= 5.43g1dm
3

maximal value
6
5.4291422
10
4
2
0.8
1. 403203
-0.2972271
final value
6
5.4291422
0.14171.55
4
2
0.8
0.1486135
-0.2972271
So we will have 3 cycle of (6+2)hrs each in 2 batch reactors of V = 500dm
3
.
Product rate = C
c
x no. of cycle x no. of reactors x V = 5.43 gldm
3
x 3 x 2 x 500dm
3
= 16290glday.
P7 -18 (g) Individualized solution
P7 -18 (f) Individualized solution
7-42
Fogler 7 -19 Solution
Problem Statement:
Lactic acid is produced by a Lactobacillus species cultured in a CSTR. To increase the
cell concentration and production rate, most of the cells in the reactor outlet are recycled
to the CSTR, such that the cell concentration in the product stream is 10 % of cell
concentration in the reactor. Find the optimum dilution rate that will maximize the rate
of lactic acid production in the reactor. How does this optimum dilution rate change if
the exit cell concentration fraction is changed? [rp = (a /-l + ~ C c J
/-lmax = 0.5 h-1,
~ = O.lg/g..h,
Solution:
CS,o = 50 IL
Ks = 2.0 giL,
Y
x/s
= 0.2 gig,
CS,Cc
a = 0.2 gig,
Yp/
s
= 0.3 gig
Cs,o= 50 gIL
A steady state material balance on the Bioreactor (including the recycle device) gives:
Accumulation = inlet outlet + generation
Cells: o = o - D*O.l * Cc + /-l*Cc (7 . .19.1)
Substrate: o = D *Cs
o - D * Cs -/-l*Cc/Yx/s -- rp/Y
p
/
s
(7.19.2)
Product: o = o
+
(7..19.3)
7- 43
0.1 Cc
From equation (7.19.1) :
C
s
= 0.1 * D* Ks
/I -0.1 * D
rmax
(7.19.4)
. D*(Cso-C
s
) D*(Cso-C
s
)
Frome
q
uatlOn(7.19.2):C
c
=( I J=( , J'
, J1 aJ1 + fl 0.1 * D a * 0.1 * D + fl
--+ + --------"'-
Y
X1S
Y
PIS
Y
XIS
Y
P1S
(7.19.5)
Rate of production rp = (a Jl + B)Cc =
(a*O.l*D+jJ)*D*(C
s
,o- O.l*D*:s)
J1max -0.1 D
(
9.1 * D + a * 0.1 * D + flJ
Y
XIS
Yp/s
(7.19.6)
Differentiating equation (7.19.6) w.r.t. the dilution rate D, one can determine the optimum
dilution rate that will maximize the rate of production.
For the given parameter values in the problem statement, the substrate and cell
concentrations and the rate of lactic acid production can be calculated from the above
equations and plotted versus the dilution rate. The optimum dilution rate = 3.76.5 In,-I.
-_._-------------------------
Recycle CSTR - Fogler 7-19
80
----------_._--_._--_._----------
70 -----------

60
50
40
30
20
- =EUbstrate cone J
- Cell Cone --------1-
------ -"'- Rate of Production ------
10
.. o --,------,-1 .. --.---'L,
o 1 2 3 4 5
Dilution Rate, 1/h
----------
7-43a
P7-20 (a)
ForCSTR,
XI + S -.-> More XI + PI
X
2
+ XI -> More X
2
+ P
2
dCs _ ( ) .
--- D C 50 - C S - Y
s
I x rgX
dt I I
dC x? ( )
._-- =D-'C +r
dt Xl gX2
r gX, = Jil C XI
See Polymath program P7-20-a.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
tOO 1 1
7-44
Cs 10 1. 2366496
Cx1 25 25
Cx2 7 7
Km1 10 10
Km2 10 10
u1max 0.5 0.5
u2max 0 .. 11 0.11
rgx1 6.25 1 .. 4008218
rgx2 0.55 0.55
Yx1s 0.14 0.14
Ysx1 7.1428571 7.1428571
Yx2x1 0.5 0 .. 5
Yx1x2 2 2
Cso 250 250
D 0.04 0.04
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Cs)/d(t) = D*(Cso-Cs)-Ysx1 *rgx1
[2] d(Cx1 )/d(t) = D*(-Cx1 )+rgx1-Yx1 x2*rgx2
[3] d(Cx2)/d(t) = D*(-Cx2)+rgx2
Explicit equations as entered by the user
[1] Km1=10
[2] Km2 = 10
[3] u1max = 0.5
[ 4] u2max = 0.11
[5] rgx1 = u1 max*Cs*Cx1/(Km1+Cs)
[ 6] rgx2 = u2max*Cx1 *Cx2/(Km2+Cx1)
[7] Yx1s = 0.14
[8] Ysx1=1lYx1s
[9] Yx2x1 = 0 .. 5
[101 Yx1x2 = 11Yx2x1
[11] Cso = 250
[12] D = 0 .. 04
_______ . ___ ...J
0.0 0.2 04 t 0.6 0.8 1 0
10 1.2366496
25.791753 25.456756
7.2791882 7.2791882
10 10
10 1.0
0.5 0 .. 5
0.11 0.11
6.25 1.4008218
0.5748833 0.5748833
0.14 0.14
7.1428571 7.1428571
0 .. 5 0.5
2 2
250 250
0.04 0.04
8.2
6.4
4 .. 6
2 .. 8
10
0.0 0.2 04 t 0.6
7.30,---
7.24
718
712
7.06
7.00 __
0.0 Q2 Q4 t Q6
7-45
0.8 10
0.8 10
0..580 r------------------,
7.0
0.574
0.568 .
0562
0.556
1.0 00
0 .. 2 04 t 0.6 0.8
0.550 t<--__ __ __ __ __ __'
1.0 0.0 02 0.4 t 0 .. 6 0.8 1.0
P7 -20 (b) When we increase D, C
s
increases, C
X
! decreases, and C
X2
has very little decrease.
P7-20 (C) When C
so
decreased, C
s
and C
X
! both decreases, C
X2
has no noticeable change ..
When C
Si
increased, C
X
! increases, C
X2
has no noticeable change for large t
P7 -20 (d) Individualized solution
P7 -20 (e) Individualized solution
P7-21 (a and b)
Run #1
#2
No Yeast Extract
Yeast Extract
TIle percem volume of the gro'W1h product H
2
S collected above [he broth was reponed as a
function of time:
cell t nutrient." more cells + plOducr
(a and b)
ex ;::: Cxo&(t .1<....)
or ex "" CXQ ill e j.l. 1;..
curve fit exponential CHIve;
7-46
1 ......... _ ......... , ........ ,; j ~ . ; . . ' "" ..... _ ...... -._.,.
o ~
.-
o
..
..

..
..
..
..
where A ::::: CXQ e iJ.
Run 1 (between 15, 20, 30 hrs)
!lmu = 0.2125 hrl
A ::: 7492.6
tlog == In ::: 0.21252
tlag ::= 6.0 hr
P7-21 (C)
Stationary
tstationary between
TIme 45 to 55
length of time 10 ill
Run 2 (poims 10, 15,20 ill'S)
!lOla;; :: 0.3124 hr
l
A = 557L7
il
ag
:;: 5.1 hr
25 to 15
20hr
P7-21 (d) Production struts at the end of the exponential (for both runs)
P7-21 (e)
dCc D C' Cc 0
-_. :::: -co' -{;J" jJ. =
dt
D{C'..co Cd + !lee;:;:: 0
-D Cc + jJ.f=<: "" 0
Cc ::: 0 or D ::::: jJ. wash om occurs when D :> gm;u
P7 -21 (0 Individualized solution
P7-21 (g) Individualized solution
P7-22 (a)
dC..-
::: 0 (Cr . ... C .. r) + fg
dt ....... C'......_
d
r
'--
_'-l. __ "" ()
cit
e
so
=: .30
}lma;;, = 1.5 hrl
== CeQ ::: 0.5 g/dm
3
p' f' :;
'.; =) g.,em
Ks == 1 gJdm
3
D == 0.75
YCiS == v.08
7-47
o = .. DC'-c + ---.- .... --.------l
(
!-lrnax Cs Cc \
K
(' (l . CS) I
\ S .,. ,,$ . .,. 1<:-1 J
[-----------------------1
1
/
' Cs 'I'
,D =
I \ ,Ku,
'-.......... w_" ............ _ _ _.-L._w. __ ...... __ ._._._ ,
C:;'Q ..
12_5
D
Cc ::0 YclS (Cso' ('51
pick Cs , caiculate D and
e
so
=:: 30.0 g.!dm->
D =
Cc "" (300, C$)(0.08)
For D = 0 .. 876hr-! (C
s
= 2..5g/dm\ production rate is maximum
P7-22 (C)
Cc
For D = 0.27hr-! , C
e
= 0 if Ceo = 05 g1dm
3
.
For D = 0.J14hr-! , C
e
= 0 if Ceo = 0 g1dm
3
,
And for maximum production rate, D = 0,,876hr-
l
P7-22 (d)
For batch reactor,
"'-'-- Cs
7-48
dC
c
--=r
dt g
See Polymath program P7-22-d.pol.
POLYMA TH Results
Calculated values of the DEQ variables
Variable
t
initial value
o
minimal value
o
Ce
Cs
0.5
30
0.5
2.01E-07
Ki 50 50
umax 1.5 1.5
Ks 1 1
rg
Yes
0.4591837
0.08
8.744E-07
0.08
Yse
rateS
12.5
5.7397959
12 .. 5
1.093E-05
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Cc)/d(t) = rg
[2] d(Cs)/d(t) = -Ysc*rg
Explicit equations as entered by the user
[1] Ki=50
[2] umax= 1.5
(3] Ks= 1
[4] rg = umax*Cs*Cc/(Ks+Cs*(1+Cs/Ki
(5] Ycs=O.08
[6] Ysc=1lYcs
[7] rateS = Ysc*rg
30 ,...;::------ .----
24
c:J
CC
.. (' .
. s
18
12
6
o ~ = = = = = = = = = = : = : : : = l
c..0 04 0.8 t 1.2 1.6 2 .. 0
P7-22 (e)
For semi-batch reactor,
dCc = r _ VaCc_
dt g V
JimaxCsCc
r = - . - - - = ~ ~ . . . : = . . ~ -
g Ks+Cs(I+C
s
/ K/)
See Polymath program P7--22-e.pol.
maximal value
2
40
32
24
16
8
0
2 .. 9
30
50
1.5
1
2 .. 9019168
0.08
12.5
36.27396
~
~ . ~
final value
2
2 .. 9
2.01E-07
50
1.5
1
8.744E-07
0.08
12.5
1.093E--05
..-, .. . ~ ~
0.0 04 0.8 t 1.2 1.6
7-49
2.0
POL YMA TH Results
Calculated values of the DEQ variables
variable initial value minimal value maximal value final value
4 .. 5 t 0 0
Ce o .. 5 0.2329971
Cs 2 0 .. 8327919
Ki 50 50
va 50 50
Va 10 10
V 10 10
Csin 30 30
umax 1.5 1.5
Ks 1 1
rg 0.487013 0.2329022
Yes 0 .. 08 0 .. 08
Yse 12.5 12.5
rateS 6.0876623 2.9112771
VCe 5 5
ODE Report (RKF45)
Differential equations as entered by the user
[1) d(Cc)/d(t) = rg-vo*Cc/V
[2) d(Cs)/d(t) = -Ysc*rg+vo*(Csin-Cs)/V
Explicit equations as entered by the user
[ 1 ) Ki =50
[2] vo= 50
[3] Vo = 10
[4] V = Vo+vo*t
[5] Csin = 30
[6] umax = 1.5
[ 7] Ks = 1
[8] rg = umax*Cs*Cc/(Ks+Cs*(1 +Cs/Ki
[9] Ycs = 0 .. 08
[10 J Ysc = 1IYcs
[11 J rateS = Ysc*rg
[12J VCc = V*Cc
30
24
18
12
6
0
C'?" _,
0.0 09 1.8 t 2.7 36 -1.5
4 .. 5
2 .. 2593341
24 .. 016878
50
50
10
235
30
1.5
1
2 .. 2464622
0.08
12.5
28.080778
530 .. 94351
30
24
18
12
6
0
0.0 119
2 .. 2593341
0.8327919
50
50
10
235
30
1.5
1
1.5283423
0 .. 08
12.5
19 .. 104279
530.94351
-
1 8 t 2.7
~ . c
~ J
600 -------------- ~
480 [vcc]
360
240
120
I)
0 .. 0 0.9 1.8 t 2.7 3.6 4.5
7-50
P7-22 (I) Individualized solution
P7-22 (g) Individualized solution
P7-23 (a)
Fit the data to the equation:
D ; ___ 5:!it:
Ks+C
s
Using POLYMATH, find the values for fi.,rw: and Ks. TIley are L98 and 0.97 respectively.
$29
......."., ._.-._; CS
7.::lC:;J 9 G::JC l i .OOC
P7-23 (b)
Using this equation, solve for Y C,'5:
With the given inf<.umation Yc;s"'" 0.099, therefore, Y
S1C
is equal to the inverse
of that, lOJ)'lS.
P7-24 No solution wiIl be given .
.
P7-25 No solution will be given
P7-26 See Professional Reference Shelf 7..5 on the website for a sample solution.
CDP7-A No solution wiIl be given.
-----------------------------------------------------------
CDP7-B
7-51
Given the following re:rc:lon scr:e::le:
i < + 00 .. _} or +- C! .
with the following f:!te: law:
Active intermediates assumed to be HOCl and HOI
From table I, the: first rule of thumb suggests:
kl
OH' '"< HOCI .,.., oCt < ;. H20. -r\:.::: kl COH CWXI- k.\ Coo' CH:O
kl
kz
OH" + HOI <:..., 01 +- H
2
0 ,<T'Z "" kz COH eHOI k2 Cor CrhO
k .2
The third nlle of thumb suggests that the reverse reactions occur. A chain propagation step.
involving the conversion of one intermediate into the other might tie in both the reactions above.
k3
I +- HOC! ., HOI + Cl< ,r3 "" k1 C! CHOC1
This step makes the overa.ll reaction sequence 1-.;- OCl .... OI + C1 ' possible:
... TO! ;;;;:: r
2
:.:::: k 2COI .. k;;,C[fO C
Hor
[HOI ::= --r2 + ') "" k:,.(-'OfJ C
iJOI
... k.
2
C
or
('H
1
0 .. k
3
C
1
CHOC! =: 0
k)C{ CHOCI :.:::: k2CO[fCHOJ k.
2
C
or
C
fJp
;:;;;;"()f
lllClC .. 1 ::::: -rl - 1.3 :;;: kl COH CH(X.l< k 1 C(Xl CrhO + k
t
C{ . CHCX:J == 0
(
, ., k -1 Ccx::l CH.,Q
or kl (' .. OW .;- k3 Cd CHOCl :;;;; k.! C{Xl CHiJ ; i.e., (HOC1 ::: ;-------< .. - ...
Kl CoB t k3 CI
1
k .1 X3 ('1 CO::
X
Cn,o .
'ben:<fm :::: .-....!_ .._- ........ <-.. IS close; with Xl k3
kl COH .,. \q Ci
KC. COC' k_rkl
r ;;;;;; ...... ,.-_ . ......!-. K :::;----.
Of C k
.. Oll 1
An alternative approach assumes that reaction 1 quickly attains equilibrium, then:
','k3k .. C., .. o "j Ct C,C!
k (-t "' 1 r., 1../ '''',
fhen <. rO! ::;;;:: '3'-- r 'HOCI ;;;;'l -k . .. O-.. __ .
.. , . OR
TIlcse two approaches are basically equivalent
CDP7C
7-52
(a) Assumptions:
Transfer rate from bubble buLle to f1 uid interface is not rate limiting, i.e., Ci is
tneequilibrium oxygen concemration.
System is:ar pseudo steady-state with regard to the particle size, i.e., panicle
growth is slow compar'ed to oxygen transfer.
Rate of oxygen consumption is direcl1y proponional to the cell growth rote:
ro, -= _yl rc where vo, = vield of cells on oxven (.-. g ce1lls
o
)
0, mmoe 1
This implies any oxygen utilization required to maintain the cells is negligible,
and there is no significant metabolic product being synthesized.
Oxygen balance:
where:
kl ilb :: ove.all mass transfer lesiSlance from the bubble to the bulk.
ac = surface area per gra."11 of cells
k :: mass tronsier of cells on 02
yo, ::: yield of cells on 02
Rearrange {'}z balances:
Ro, C' ('
--.-"::; i - 'u
kl ab
(1)
"" Cb - C" (2)
,lo,.Ro.. = c
Tlk C'.c .-$
Add equations 1, 2 and 3
(3)
::; k/ab + J-c (k(;I;c+ (4)
0) When oxygen consumption by the cells is slow, the process is reaction rate limited ..
C I Yo,
Thus 1 and: -1. =: - .......... + . ..:..-.
Ro. k! ab <=<: k
{2} When oxygen consumption is much faster than In3.SS tr.lnsier. the mass transfer
becomes [he limiting factor. ..,9,,, "" .. J.... + -- ........ L._ ..
Ro, kl ab kc ac Cc
7-53
(b) To increase the growth rate, you could:
Ifl(,,-rease kl ab by increasing fem1cntor agitarion,
Increase the concemration of cells (since this is an autoca::alyuc reaction)
Increase clump surface area and the effectiveness factor by decreasing the particle
size (also by increasing fermentor agitation).,
(c) Re "" YOl R(h From equation (4), have:
:=1 Yo., [ ____ L .;. .. L {: __ L, + Yfh.'ll
Ci "'lkl <.tb CC KC 3.(: r;kt
[ + dec " L dl
Cc .,. CeQ {1 _ yo,) Cc
-+ -t-- In Ceo "" Y0
2
Cit
(d) Assumptions:
There is a constant number of particles
Each pellet is roughly spherical and has const::!.nt density.
We do not know which resistances are controlling, so we know theIe are no reaction
limitations. but. may be either internal or external diffusion limitations.
:= Yo. C [ + de' + 1
As particle growth increases, kc. ac and II will change as functions of the particle diameter.
Thus need to fmd particle diameter as a function of Cc
Cc "" npe V c where n "" number concennation of particles (Ill)
Vc "" TI;, d
3
, 6 P Pc ;;::: the density of the parTicles (gil)
Ve :::: particle volume (1)
Intemal diffusional resistance can be modded as:
;, :;::; (Xi do
T)z( .
External diffusional resis::aflce with or 'Withom shear is;
.. _L.
kc 3{:
where cr:! :;;:: at
iCn Pc
Dropping the primes and simplifying:
7-54
+ 3<x, (r 113 .. C I(3) + 21 (C" b!3. C bn) "" C
k[ <lb , ..... c co b'c co Y01 i t
(e) From part (c), we have:
For a vigorously stirred fen-nemor, assume [hac tluid shear is sufficiently high,
that transpOrt to the edge of the floc is negligible(l):
_ ....1. ....... 0
kcac
The mass transfer resistance from air bubble to bulk liquid depends on me fermentor
design, air flow rate, agitation rate and a number of other factors. For a 10 1 laoonuOlY
scale fermentor. kl ab was f()und to 150 mMz. during the growth phase of the
I hI arm
fermentation .. (2)
Dividing through by Hemy's low constant:
k1 ab ;; (ISO ...}(;:;JJl! .... )
1 hr atm mMole ..,600 s
"'" 3.67 x 10.
2
S 1
Effectiveness factor: Microbial growth on multiple substrates (here oxygen and glucose)
is typically modelled using Moncxi type kinetics:
Rc :: ),l.(':c
By representing the reaction as first-order with respect to oxygen, we are essentially
assuming a low oxygen concentration, relative to the intrinsic rate parameter. Ko:
7-55
__ ,.1_ --t 0
kcac
The mass transfer resistance from air bubble to bulk liquid depends on the fermentor
design, air flow rate, agitation rate ::md a number of other factors. For a 10 1 laboratOIY
scale fennemoI', kl ab was found to be -- 150
mJ
,1Qk during the growm phase of the
1 hr atm
fermentation", (2)
Dividing through by Henry's low constant:
kl ab := {1.50
= 3 ..67 x 10.
2
Sl
Effectiveness factor. Microbial growth on multiple substrates (here oxygen and glucose)
is typically moocHed using Monoo type kinetics:
Rc ;;: ).lee
By representing the tt:action as first"order with respect to oxygen, we are essentially
assuming a low oxygen concentration, relative to lbe intrinsic rate parameter, Ku:
For a first order reaction. the effectiveness factor is;
n ($ cosh .. 1)
(
11 ::: OA5
Reaction rate constant:
tI 83 x 10
5
S ,1
k "" ,.-.max "" ..... ,,,_.,, ................ ,, .. ,,,,,,._ .
-K
a
()
3.2 x 10.
4

1
:: 0.26,..1, .. ,.
g0 2 S
Finally, aSSume an initial cell concentration of 0.25 g cell/l, L-'le cell concem:."";;!.tlon equation
now becomes:
(Cc
r -
I 1.5 !
'" I .. . ; In 4Cc
i.{(45)/O.26 0 "J,I
'. \ g. 2 $,
;:;: (1. 5 2. 7:l x 10 ;) t
g02 \ 1
367 x 10.
2
s'
2.7,25 (C-=C; 0.2.5) f 1281n4Cc;:;: 0.012t
Clearly, mass trilllsfer from the gas to lhe liquid phase ond internal diffusion play UnpOItilllt
roles in determining the cell growth rote.
756
Cell mas vs time, Stan ::n 0.25 gil
t {hr) Cc (g/l) 1 thr)
-0--" 0.25 "'---"'8--
1 113 9
2 2.37 10
3 3.74 11
4 S.17 12
5 6.64 05
6 8 .. 13 L5
1 9.63
Cc (g./l) 'm
1 LIS
12.67
14.21
15.74
17.28
0.62
1..72
From the graph it can be seen that growth startS our exponentially and becomes linear as the
fennentation becomes limited by gas liquid mass tmnsfer.
Sensitivity analysis:
TIle mass transfer coefficient is related to the agitation rate to the 0.95
powerO): k! au u NO.95
What is the effect of increasing the agitation by 50%?
kl ti2 "" kJ al (1.595)
::: (3.67 x 10 .2}s -I{ LSO.95}
;; {S.39 x !D,lls1
(see graph)
Since cell growth has an exponential ponion. another way to increase the growth mte
would be to increase the innocuous size. C<:o. What happens when Ceo is quadrupled?
C'-cu =: 1,0 gil (see graph)
From the results shown in the graph. a relatively small increase in the agitation nne leads to
a significant increase in the cell growth rate. while an inCIe:lSe in innoculum size means that
the fennentation leaches a gasliquid ttansfer,limited state more quickly, but the growth rate
remains the same.
cell
mass
(gIl)
18 '"
16 ..
14 ....
12 ..
10 ..
Cell Mass 'IS Time
for a STR P("" ........ fermentation
/
I
I
/
I
I
I
I
lq a 3 .. 67 x 10-
1
5
1
Ceo = O. 25 g/i
kl a = 5 39 x 10.
1
S .;
Ceo " 0 25 g.'1
kl a '" 3 6.7 x 10 Z $:
('':;C '" 1.0 gil
"-j .. -T--r--"'rT'-r-"'T'
2 4 fi 8 10 12 14
t (ttr)
7-57
References:
(I) James E. Bailey and David F. Ollis, FllndamemaIs,
(NY: McGraw-Hilf. 1977), Chapters "1 and 8
(2) (iF. Payne, PhD Thesis, University of Michigan, (1983)..
(3) D.Le Wang, et at, (NY: John Wiley &
Sons, 1979), Chapter 9
CDP7-D No solution will be given.
CDP7-E
Since the deninification f6liow$ Michaelis Memon kinetics, first detemrine V mall;
and Km from Lineweaver BUlk plot.
Initial r-N-;:'ol' __"-J' Time for 50.6 Rate of reaction , I .
[
. .:] t .:2 1f!
_ N ... _. ___ .. .. (min ... __ . ___ ._
25 .04 35 .357 2.800
50 .02 38 .658 1.520
7.5 .013 44
852 1.173
100 .010 50 1000 1.000
100 (given) .005 66 (given) l.515 0660
where the n.He of reaction is fbl."lnd by the r:mo:
.... ._...
rime for 50% reduction
3.0 '.j
2.5 . f
lIr 2.0
1 ..5 .. ..
10
0 ..5
0 ..00
7-58
LineweaveI BUlk:
From the plot, V ma>; :: __ L_ .... "" 2.73 ..
intercept min
:. Km = 165 ppm
Next, need conversion as a function of rime.
Design equation: ;:;: rs V
m
Rate Law:
_ V
max
S
IS - R:+s
Stoichiometry: s == SopX)
Finally, VInax t =- So X Km In (1 .. X)
Know V max Km, t =- 68 hrs :; 4080 min
So "" 0..2.5 (!DOI.) (46.JL.) (!.PP!.::) =: 11,500 ppm
i mol ,. J mgil
Iteration [0 find the conversion obtained after 68 hrs gives: X:;: 0.930
The [N(
2
) level is: (1 0.930) (11.500 ppm) == 805 ppm
Since t, Km. and So are fixed by the system. the change must be made in V nu:x'
Desired conversion:
x = 1 ... 200 _. :::: .. 9565
11.500
... Desired V r;1:U;
11,500 (.9565)- 1651n (l ... 9565)
= =
_ .. _. __ ... _ ........ _ .. __ 40"80 .. '-' ..................... _ .. __ .
2.823
mm
Since V max Ct [E
l
] , increasing the concenoation of whole cells in the emulsion will increase
V mu; (2...8.ll) 50 ... = Sl.7-
mg
... _ .
273 ml emulsion ml emulsion
Therefore, increasing the cell loading to 52 . -- would results in a level of [NOJ <
ml emulslOn
500 ppm after 68 hours ..
CDP7-F No solution will be given ..
7-.59
CDP7-G
>folt bala.nces in a CSTR
the Lite la\-v as given is:
DC
so
.. - LJ(:$ -;- fs =:::; 0
DC
p
' II' C
r
C ,r.
? D
;;;;; "Is
r ( 1 Ee. 1
r 11' (" I (,,)
1.\.5 \ 'p )
Plugging tho$e into POLYMATH and using different values of D and C
t
, come up
with the following;
Using a volume of 200 dm' and a cell concentration of 50, get the best production
of the Lmalic acid.

c50=2
CDP7-H
Michaelisl\fentoll Kinetics:
cs
cp
esc
LJ
cc
vrndx
krn
cpst ar
E=40rng
7-60
Sol ut: Q"
CJ ,35: 657
L 64834
76
C. :.><;8
f ( )
3. 222E''" i 5
<3.2772': 5
Mole Balance:
__ dC.s. == V Wil.CS%
dt K,..
== C
So
%(1-- X) =>
1.4 --0.2
](==- .. -==0.86
14
Where C
S
$ is the percent of fish oil.
For most oils:
., density 0 .. 9 3 0.-
3
m1 3 10
3
11 1
C :;::._---;;;:_._:;:: xl mo1J :;:: x p.mo m
1 MW 300
C
s
::;::; CrC
s
%
{)2 K +C tv t 5.6xlO-
3
=> f .......... m( .. s%:::::: J (';'" dt == f 3 dt
14"S% 0''1 0 .
(
1.4) 5.6xlO3
=> 0.2 +- (1.4- 0.2);;;: -3--
m
- t
=> t:::::: min == 7106 min == 118.4 hrs
5.6x 10
3
/3
CDP7-1 No solution will be given.
CDP7-J
(a) No solution will be given.
(b)
1
X ;;;;: .. _-_.
n 1.- p
For Xn :;:; 5: p :;:: 0 .. 80
X,=dO: p:;::0 . .90
X" == 20 : p ::;;: 0 95
7-61
Use these equations to generate the desired graphs:
Yl YS. j for X. = 5, 10, and 20
o 2
5
.. .. j
020 Il' - -Xn;;;!O I
;:-XneeZO
{I ---.-.-..-----.--... ---.-.--.
o 15 i' I
-,
W J YS. j for X" =: S, 10, and 20
080
070
0,60
0.50
:' !
: t ;:: 040
o 10 " !
1\\
I ;

0,00 ___ "" .. ""''' .. ''''''''''_.
030
o 20 40 j 60 80 100
P
j
;:::: M,,(l .. p)Zpjl =M
o
(1' p)
2
p9
Use the above equation to generate a graph of P
IO
V$, p:

D2 0.1. P 0,6
0,8
{c)
Use these equations to generate graphs of Yj and Wj VS, j.
W j VS. j for p :::;; 0.80, 0.90, 0.95
0,,07 - .. -'-'" ."""'''----,
0,,06 +=---p:::; OSo.
l i\" ;------1'=o,90
0.05 i p =0.95
" ,." ',",."'-'" .. , ----,
004 I \"
i i \
O.oJ t! / "'\,:" "
OO'J-i. \" !
::
o 20 40 60 80 100
7-62
We must find the value of p.
ill = ( -I]; -0.067
wf = 2.803
I2 :::;: 1
2o
cxp( -kat):::;: (O.OOl)exp[( -L4 X 10,3)(14,400)1 == 2.794x 10 ..
9
fJ
.
P == =: --------.... - ..- ...-----.... = 0.99991
kpM + kmM + kee + ksS +
This can then be used to calculate the desired values:
_.- 104 __ . 6
NI ::;:: .-_._--._ ... _ ............... :: l.b) x 10
Jl 1.- 0.99991
(e) Mole fraction of polystyrene of chain length 10 (y 10)'
Use the above equations t.o plot Yo VS.t::
7-63
y 10 VS. t
o

r------'--------------------'.--,.'----------------------l
0.03 I
O.O!) -
I
;'002
\

0.,015
O.Ol
I
0005 1
. ________ .. _,J
2 3 5
t (hr)
CDP7-K
Reaction
R. + I ...", .. &i", P
} J
(a) and (b)
...;;-' r.:;:; r +- R' (k l"l+ k S + k .[')
L} r , m S rt
l l
X
N
tk;h+ + k, + {:}1+ kk:fi
(c) From the above derivation we know that
r
p
Neglecting the solvent term and rearranging yields:
1 i
::::: .\,t
-1M
Substituting in for -'1
M
and Ii and simplifying:
7-64
_ .. [
1 _ 2k,J(I
z
)!?vf(-r
M
) krn knI
= ...... - .......... _ ...._-_ ........ _ ........ _, + .-+ _.,.-
XN' k!(2kof(IzJlkl) kp kpM
1 _ kJ-r;.t) . k
m
, krjI
..;,.,- ..... -:;'."" .."'--...,.... --- ..,.,.. --,_ .....
X
N
k;(lVl) kp kpM
(d) To determine rate law parameters experimentally from a CSTR both the [mal XI'!
value and the final concentrations of wI and I must be recorded. l11ese data can be
used in the above equation to frnd values for the parameters.
(e) An increase in temperature would cause an increase in all three primary steps of
free-radical polymerization (initiation. propagation, and termination). By looking at
the overall rate law:
l2k:(I,W
r . ;;;:;; k M (._-_._.::_.
M
it can be seem that the greatest effect of temperature would be on propagation.
Overall, there would be an increase in monomer disappearance and an increase in
pol ymerization.
CDP7-L
a) PFR:
dlvl
_ .. _-:::::: r
dr ',1

M
12koL,f
riM :::::: .. -
Plug those into POLYMATH to get this graph.

dIm) Id(tau);rm
d(i) /d(cau}=::.
kp=lG
ko""Je- :)
r:i;;-.. ko*i.
=; ..
t:.au
n
:; {)t
t.au
..
0
l
0.0:

0 OUl
0.5
s,,n7
t.e05
,,1 .. i)$
7-65
..

.J 01
14
0.001
{) 5
$e+0 1
. :5
.. < 99lSa,,23
!!i t.
:3
n .01
...

7'99$

2 'S'!J.2"J.
S. %! ::. .. ",8 S .. Ja
tt- 10

-- -
0 .. .')01-
C S O.S
Se,;]."; 5,,01
<)$
-.
::'.1,i>4e-,oS 2 9g:5Bi: n
:: :;c;; -
1 .-,;
: i
J ZOO
0 .. ':00
CSTR:
I
*".
M .- M :::: ..... r I *r I
20
- 2:::: r1: ..
o )<.. POI YM'ATH the followino- !rraphs are
The rate laws are the same so agam usrng . J to to
generated.
Monomer vs space time CS TR
Initiator Concentratlon ..-" Space Tlme CSTR
..1

. .....
'50000 ) OOooc- 1 SO<lQC' 2(101)(10
Tau 1J'::t
S:)O;)O lQOOCO l$COOO 20000-0
:mo=]
t:.du=5el1
io.:=.Ol
kp=:10
ko"'le. 3
1':=.5
k:::=5e"J
b) Fm two CSTRs, the design equations change just a bit
'1"
MM = .. ! *.::-
o 1 lvi, 2
1: T
M .... , .. 1\1, :::: ,. L * 1'1 ."" I, .. , :::: *' "' ....
j .,,: 2 -. 2
Tau, H:,.
2.5

The rate laws are the same with the exception that instead of just 12 or M, 1
2
[> Iw
MI' or M;) are used depending on which reactor they came from and the following
graphs ale generated
7-66
..
.l ... ".,.'" ...., .. ... " ...
I
..
'.
I-
1:_'1!1 i ..
I
I *!:
a ..
2. [
.. .
..
..

Q !loa t
Q,jQl :.
000. r
o ,:)os L
000. [
{) 00"
o{)'c;i:
., .. , .......,
!
> . r 0>01 roC
o ._1. ................... ,._ ... , ........... _ ........ ..
.;2: a ........... . T--., ,,.
Q 'S-IKIQq lOOOQO
.-
c) Making kg bigger causes [2 to decrease rapidly and M does not get formed
as much. Increasing kt> causes M to decrease sl.ightly 1 but not by t.hat much.
Increasing causes M nOt to decrease by very much staying very close to 3.
CDP7-M No solution will be given
CDP7-N
I + iH R
1
R. ti.V!_.!:J:. 7R.
J
a) Balance on I
--'I ::::; k/vlI
L, .. ' I 10 .. I
'f;;;;;; .-...-----:;;;; -..... ..
. (1 k;iYll
10
=> 1;;;;;;",-
l11k,M

;;;:;: kiMI + kp!v(2':Rj
J=l
-
ASLR
j
-== 10 -- I

'-r :::: kMI + k M(I .- I)
1 P 0
7 .. 67
Balance on M:
_ l'tlfo-;lV! A-fo - iYf
r .,,','-----"" == ,----"------,, .-.---.---_ .. _.
r;,! kiA-1f + k/d( If)- !)
=> rk/vll +rkplYf( 1
0
- I) "'" Mo - M
rk"ly[Jo -rk/oM( rk,lvt)
=> ----------'-,-- + ___ c, = 11,11) .- fH
I + 'rk,lv/ 1 + rk 114 i
. ,
=> rkJiJAl +-r2klJoj'yf2 ::;;: (J"1
0
- M)(l+ rk,M)
=> ,k, (1 + )M" + (1 + 'lk'!a -, rk,i'vio )1'.1 ,,',. A10 :::: 0
b) --If<: :::::: --'kiJ\U + kl,;'vlRI
Balance on R1
Similm.!y,
,< ,
R,:::; R21 1
I I +k lv1-'(
\ p )
k If ri< \/j
R j :::; 1 lv/X;'- 1 + rk lrf
! p \ p)
c) Initiation Rate constant < < k" propagation rate constant
Hence, nearly no change in the concentration of Initiator (I).
Mo
10
xi
kp
1
t
0015
1QC()
7-68
0.5
d)
1
tau
......... w._ +-. __ .......w........ ........... w ........ ..
1.5 2
7-69
j x(1+x)
As 2., J.X =
r=l
CDP7-0
a)With the reaction self catalyzed the mole balance and rate law becomes:
dlCOOHl ,
_ .. _J.:_:_.:..:.J = k[COOHY
at
We can then get [COOH 1 as a function of time. The following graph shows both
the given values of p and the calculated value as 11 function of time where
p ::= t CO,Ql!Jn:1 CC!..l?!!J
.... __ 1. ,.,.,. ",.",,'"''
P 'IS time
1
+

..... 'T ...... ".""""""' .. "''',...--, ...... "".. ""."","" .... - .. , .. " .... ".-._,,,.,,., ...,"". """ . " ....,""" .... "" .."""" .... "
0,8 41\
41\
06
0.4
02
o 41\ .."'',.""---- ' t,,,,,,,,"", .. - , ..... t""""
o 500 15(:0 2000
time
It appears to fonow this above 500 min"
7-70
b) The new mole balance and late law is:
== k[COOH][OHJ[lI+]
[OH]=[COOH]
+H+
K
eq [COOH]
[COO" ]= [Bt ]
[Rtf ==
.. kICOOH]12
dt '
Solving for [COOH] as a function of time gives the following graph:
p vs time

0.8

0.6
0.
0,4 '
0,2
o 500
It follows the data above 200 min.
1000
time
1500 2000
e) This mechanism can be made to fit either rate law, depending on whether UA
dissociates before or after the fust reaction.
CDP7-P
CDP7-Q
7-71
I + R
I
R. +M
) 1+1
_. = kOMI = (k M
dt P k
"
dI k
. "'-_._- == .. _S!. I
k/r1.dt k,v'
d8:::::k Mdt
p
dI k ..
--- =. __ ..'2. I => I "'" I e x,
dB k 0
p
dR
--_ .. l=--k MI +k MR
dt 0 p I
dR k
[
);,
. _.J.. == ...... '2.. 1 e ',) ._- R
de k 0 I
p
== e(l
dB k 0
p
dR
-- J. :;;;; R.. .. - R
de ' :!
CDP7-R
7-72
1 -+ R
1
R. -+ lvf R.
) /+1
I - [
r:::: ... 11.._ ... __
ko/vfI
8' ::::. kpi'vFr:
8' :::: .. !.l
koI
k/o
I == -............ _" .. _ ....... -.
k
o
8' +kp
l"tl .. ,lvl
l' :::: .... JL ...... , ... --
k/,;fl
o
A'fo
A1 ;:;; -----.. ---
kl,lor + 1
9';:;; _ .. .. "
k/o'f+ 1
R,
r :::: -----.--... -..... ; ..
kolvlI --- k,)rfR,
k Ie'
R ;::: ... _Q,....
! k (1+ fJ')
1',
1.' == -.. _.-.---.-.. &_ .... , ..,_.-...
k/,fR{- k/V{R
2
R 8
' k k 1 8'2 k I 8
1z
R2 ::: == (j ..
7-73
Fogler 7-24 Solution
Problem Statement:
In biotechnology industry, E. coli is grown aerobically to highest possible concentrations in
batch or fed-batch reactors to maximize production of an intracellular protein product. To
avoid substrate inhibition, glucose concentration in the initial culture medium is restricted to
100 grams/liter in the initial charge of 80 liter culture medium in a 100 liter capacity
bioreactor. After much of this glucose is consumed, a concentrated glucose feed (500 gil)
will be fed into the reactor at a constant volumetric feed rate of 1.0 liter/hour. When the
dissolved oxygen concentration in the culture medium falls below a critical value of 0.5
mg/liter, acetic acid is produced in a growth-associated mode with an a of 0.1 g acetlg
cellmass. The by-product acetic acid inhibits cell growth linearly, with the toxic
concentration (no cell growth) at Cp* oflO g/liter. Find the optimum volumetric flow rate
that will maximize the overall rate of cell mass production when the bioreactor is filled up
and if the feed is turned on after glucose falls below 10 gil. Inoculum concentration is 1 g
cellslliter.
Additional parameters:
f.lmax = 1.2 hr,-I, KG = 1.0 gil, Ko = 1 mg/l, Y
xls
= 0.5 gig, Y
p/s
= 0.3 gig, qo/x = 1000 mglg
Oxygen mass transfer rate kLa = 500 hr-
I
, Saturation oxygen concentration C02*= 7.5 mg/liter
Increase the value of mass transfer rate (up to 1000) or the saturation oxygen
concentration (up to 40 mg/liter) to see if higher cell densities can be obtained in the fed
batch reacator"
(a) list ways you can work this problem inconectiy"
(b) How could you make this problem more difficult?
(Contibuted by Prof. D. S. Kompala, University of Colorado)
Solution:
This problem is solved numerically in three parts, using the following equations on
Berkeley Madonna package:
7-74
The first time period covers the simple batch culture, when glucose and dissolved oxygen
are being consumed for cell growth.
METHOD Stiff
STARTTIME = 0
STOPTIME = 3.4
DT=0.02
INITG =100
INIT X = 1.0
INITO =7.5
INITP=O
mumax = 1.2
KG = 1.0
KO = 1.0
Yxs = 0,,5
Yps = 0.3
q = 1000
kLa = 1000
alpha = 0
SATG = G/(KG+G)
SATO = O/(KO+O)
SATP = 1.0 - (PIlO)
mux = mumax * SATG*SATO*SATP*X
d/dt(X) = mux
d/dt(G) = - muxlYxs
d/dt(O) = kLa*(7.5 - 0) - q*mux
d/dt(P) = alpha*mux
The numerical simulation results shown below identifies the time at which the dissolved
oxygen concentration falls below the critical value of 0.5 mg/liter, triggering the
formation of the by-product acetic acid.
From the simulation results, we find that the dissolved oxygen concentration falls below
the critical values of 0.5 mg/l at the batch culture time of 3.64 hours. At that time, the
glucose concentration has fallen to 67.1 gil and cell mass concentration has growth to
17.45 gil. The by-product acetic acid concentration remains zero through the early batch
culture, as the dissolved oxygen concentration is above the critical level throughout this
time. In the program above, the parameter alpha is set to zero to ensure that no acetic acid
is produced.
7-75
Run 1: 43 steps in 0 seconds
100
18
16
80
14
70
12
60
10
0
.. 50
, .... ... -... 1><

8
40
6
30
4
20
2
10
o
o 0.5 1 1 .. 5 2 2.5 3 3.5 4
TIME
In the second part of the batch culture, acetic acid is getting produced and glucose is still
above its set point of 10 gil, when the concentrated glucose feed is added to the
bioreactor.
7-76
The program equations are given above slightly modified to change the alpha value to the
given value of 0.1 g acetic acidlg g cell mass and integrated from the end of first part of
batch culture.
RlJn 1 2t; steps in 0

..
c.o
20
3.5 4 4 .. 5 5 5 . .5 6 6.5 7 7.5 8
TIME
From the simulation results, we see that glucose concentration reaches the predetermined
value of 10 gil (for turning on the feed) at 7.65 hours of batch culture. At that time, the
cell mass concentration has reached 41.02 gil and the by-product acetic acid
concentration has reached 2.85 gil. Using these values as the initial conditions for the
third part of culture, a glucose feed is added and the balance equations are therefore
modified to include the dilution of all bioreactor contents with the fresh nutrient medium.
The modified program equations are shown below:
7-77
METHOD Stiff
STARTTIME = 7.65
STOPTIME = 209.5
DT=0.02
INIT G =10.0364
INIT X = 41.8957
INIT 0 = 0.1978
INIT P = 2.85834
INIT V = 80
mumax= 1.2
KG = 1.0
KO = 1.0
Yxs = 0 .. 5
Yps = 0.3
q = 1000
kLa= 1000
alpha = 0.1
vin=O.1
SATG = G/(KG+G)
SATO = O/(KO+O)
SATP = 1.0 - (PIlO)
mux = mumax * SATG*SATO*SATP*X
d/dt(X) = mux - X*vin/V
d/dt(G) = - muxlYxs +(vinlV)*(500 - G)
d/dt(O) = kLa*(7.5 - 0) - q*mux
d/dt(P) = alpha*mux - P*viniV
d/dt(V) = Yin
The constant value for yin, the volumetric feed rate can be systematically varied to find
the highest cell mass concentration, when the reactor volume gets filled, i.e. becomes 100
liters. Simulation results for different Yin values ar'e tabulated below:
yin time, hrs Volume X cell con cent
0.,,0.5 40.7.8 10.0. 87,53
0.1 20.8 10.0. 8758
0.,2 10.7.,7 10.0. 87.,6
0.,3 75,,3 10.0. 87.,5
0.4 574 10.0. 87.,3
7-78
0.5
0,6
0.7
47.,7
41
36,2
100
100
100
87,5
87.,6
87,,5
It is clear from these simulation results that volumetric feed rate does not make a strong
difference in the final cell mass concentration. The time for filling up the reactor volume
to 100 liter is of course strong affected by the volumetric feed rate
It is expected if the kLa is smaller, then the acetic acid production will be higher. In that
case, the volumetric feed rate will have a significant effect on the maximum cell mass
concentration achieved in the fed batch reactor.
These simulations nevertheless provide a useful introduction to the concepts of fed-batch
culture.
7-79
Solutions for Chapter 8 - Steady-State Nonisothermal Reactor
Design
P8-1 Individualized solution
P8-2 (a) Example 8-1
ForCSTR
v = FAOX = __ X __
--fA Dok(l-X)
'tk 'tAe -E/RT
X=---=--,
l+'tk 1+ Ae-
E
/
RT
One equation, two unknowns
Adiabatic energy balance
T=To_MIRXX
C
p
A
In two equations and two unknowns
In Polymath form the solution
'tAe-
E
/
RT
f(X)= X -- -E/RT
l+Ae
f(T) = To -
CPA
Enter X, A, E, R, C
p
, To and i1H
Rx
to find '( and from that you can find V.
A
P8-2 (b) Example 8-2
Helium would have no effect on calculation
%Error = (T - TR )

P8-2 ( c) Example 8-3
3
(a) V = 0.8 m
See Polymath program pg-2-c.pol.
1270
= ----- x100 = 5.47%
23,210
8-1
POLYMA TH Results
Calculated values of the DEQ variables
Variable
V
x
Cao
Fao
T
Kc
k
Xe
ra
rate
initial value
o
o
9.3
146.7
340
2.8783812
8.5452686
0.7421605
-79.470998
79.470998
ODE Report (RKF45)
minimal value
o
o
9.3
146 .. 7
340
2.4595708
8.5452686
0.7109468
-110.4184
79.470998
Differential equations as entered by the user
[ 1) d(X)/d(V) = -ralFao
Explicit equations as entered by the user
[1] Cao=9.3
[2] Fao = .. 9*163
[3] T = 340+43.3*X
[4] Kc = 3 .. 03*exp(-830 .. 3*T-333)/(T*333)))
[5] k = 31..1*exp(7906*(T-360)/(T*360
[6] Xe = Kc/(1+Kc)
[7] ra=-k*Cao*(1-(1+1/Kc)*X)
[ 8] rate = ora
PFR
T
X
330
0.26
340
054
0.7
----------_._-
0.6
0.5
0.4
[ ~
0.3
350
0.68
02
330 384 -438 T 492 546 600
P8-2 (d) Example 8-4
maximal value
0.8
0.5403882
9.3
146.7
363.39881
2.8783812
38.191248
0.7421605
-79.470998
110.4184
370
0..66
390
0.65
final value
0 .. 8
0.5403882
9.3
146.7
363 .. 39881
2.4595708
38.191248
0.7109468
-85.208593
85.208593
420
0 .. 62
CSTR has the same trend.
450
0.59
500
0.55
600
0.48
Counter-Current: Guess Ta at V = 0 to be 330 and it will give an entering coolant temperature of 310
K.
See Polymath program P8-2-d.pol.
8-2
POL YMATH Results
No Title 08-17-2005, Rev51 233
Calculated values of the DEQ variables
Variable initial value minimal value
V 0 0
X 0 0
T 310 310
Ta 330,,7 310,16835
Cao 9,,3 9.3
Fao 14.67 14,,67
Kc 3,6518653 2.7812058
k 0.9004084 0,,9004084
Xe 0.7850325 0,7355341
ra -8,,3737978 -27,114595
dHrx -6900 -6900
Ua 5000 5000
Cpo 159 159
rate 8.3737978 0.0460999
m 50 50
Cpc 75 75
ODE Report (RKF45)
Differential equations as entered by the user
[11 d(X)/d(V) = -ralFao
[2] d(T)/d(V) = ra*dHrx)-Ua*(T-Ta))/Cpo/Fao
[3] d(Ta)/d(V) = -Ua*(T-Ta)/m/Cpc
Explicit equations as entered by the user
[1 J Cao = 9.3
[2J Fao = ,,9*163*,,1
[3 J Kc = 3,,03*exp(-830,,3*T-333)/(T*330)))
[4] k = 31,,1 *exp(7906*(T-360)/(T*360))
[5J Xe = Kc/(1+Kc)
[6] ra = -k*Cao*(1-(1+1/Kc)*X)
[ 7 J dHrx = -6900
[8] Ua = 5000
[9J Cpo = 159
[10] rate = ,ra
[11] m = 50
[12] Cpc = 75
P8-2 (e) Example 8-5
maximal value final value
5 5
0,,7797801 0.7797801
344,71423 310.83085
335,79958 310.16835
9,,3 9.3
14.67 14.67
3,6518653 3,,6255777
11.. 763976 0,,9639302
0.7850325 0,7838108
-0.0460999 -0,0460999
-6900 -6900
5000 5000
159 159
27.114595 0.0460999
50 50
75 75
At V = 0, Ta = 995.15 and gives a counter current entering temperature of 1250 K.
See Polymath program P8-2e.poL
POL YMATI{Results
Calculated values of the DEQ variables
variable initial value minimal value maximal value final value
V 0 0 0,,00;1. -----cf:001
X 0 0 0,,3512403 0,,3512403
T 1035 972.39417 1035 1034,,4748
Ta 995,,15 986.00676 1249,,999 1249,,999
Fao 0,,0376 0,,0376 0.0376 0.0376
Cpa 163 163 163 163
delCp -9 -9 -9 -9
Cao 18.8 18.8 18,,8 18.8
To 1035 1035 1035 1035
8-3
dHrx 7 .. 414E+04 7 .. 414E+04
ra -67.304 -67 .. 304
Ua 1 .. 65E+04 1 .. 65E+04
me 0.111 0.111
Cpe 34.5 34 .. 5
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(X)/d(V) = -ra/Fao
7 .. 47E+04
-6.3363798
1.65E+04
0.111
34.5
[2 j d(T)/d(V) = (Ua*(Ta-T)+ra*dHrx)/(Fao*(Cpa+X*deICp
[3 j d(Ta)/d(V) = -Ua*(T-Ta)/mc/Cpc
Explicit equations as entered by the user
[1] Fao = .0376
[2] Cpa = 163
[ 3] delCp = -9
[4] Cao = 18 .. 8
[5] To = 1035
[6] dHrx = 80770+deICp*(T-298)
[7] ra = -Cao*3.58*exp(34222*(1!T0-1/T*(1-X)*(TolT)/(1 +X)
[ 8] Ua = 16500
[9] mc = .. 111
[ 10 1 Cpc = 34.5
(b) P8-2 (f) Example 8-6
Energy balance will remain the same
X
EB
= 2 xlO-
3
(T - 300)
for 2A-"72B
....
,
\
\ 2nd Order
1st Order \
\
\
,
(c) P8-2 (g) Example 8-7
....
....
........
8-4
7.414E+04
-31.792345
1.65E+04
0.111
34.5
Both Xe and XEB will change. The slope of energy balance will decrease by a factor of 3.
x
T
Also Xe will be more temperature sensitive
K =K
e e R T T
1
The dotted line in the plot below shows an increase in -AHRx
x
\
\
\
\
\
\
T
\
,
(d) P8-2 (h) Example 8-8
"
'"
....
(1) CAO will decrease but this will have no effect
(2) 't will decrease
401.1 ft
3
't'=
466.1 ft3 Is
(3) In the energy balance the slope of the energy balance of X vs .. T will be greater
8-.5
l
I
I
I
/
l:8
i
C
PC
= 35 +(18.65X18)+4 x (1.67X19.5)= 35 + 335.7 + 130.2
=501 BTU
I
/
I
I
I
I
I
I
I
I
,-
-- _.
XM
XM,
T
kmoloR
Basecase
I
I
I
I
I
I
I
I
_ _ _ Change QM
8-6
Less Conversions
P8-2 (i) Example 8-9
Change Cp = 29 and ~ H = 38700
POLYMA TH Results
NLES Solution
va:r::iable
x
T
tau
A
E
R
k
Value
0.7109354
593 .. 6885
0 .. 1229
1.696E+13
3.24E+04
1. 987
20.01167
NLES Report (safenewt)
Nonlinear equations
fix)
2 .. 444E-11
1. 2E-09
Ini Guess
0.367
564
[1 J f(X) = X-(397.3*(T-535)+92 .. 9*(T-545))/(38700+7*(T-528)) = 0
[2J f(T) = X-tau*k/(1+tau*k) = 0
Explicit equations
[1] tau = 0 .. 1229
[2J A=16.96*10A12
[3] E = 32400
[4] R = 1.987
[5 J k = A*exp(-E/(R*T))
Vary the heat exchanger area to find the effect on conversion.
P8-2 (j)
a = 1.05 dm
3
See Polymath program P82j.pol.
POL YMA TH Results
Calculated values of the DEQ variables
8-7
Variable initial value minimal value
V 0 0
Fa 100 2.738E-06
Fb 0 0
Fe 0 0
T 423 423
Y
1 0.3120454
kla 482.8247 482.8247
k2a 553.05566 553 .. 05566
Cto 0.1 0 .. 1
Ft 100 77.521631
To 423 423
Ca 0 .. 1 2.069E-09
Cb 0 0
Cc 0 0
rla -48.28247 --373.39077
r2a -5.5305566 -848 .. 11153
Fto 100 100
alpha 1. 05 1. 05
ODE Rel!ort (RKF45}
Differential equations as entered by the user
[1] d(Fa)/d(V) = r1 a+r2a
[2] d(Fb)/d(V) = -r1 a
[3] d(Fc)/d(V) = -r2a/2
maximal value final value
1 1
100 2.738E-06
55.04326 55.04326
22.478369 22.478369
812.19122 722.08816
1 0 .. 3120454
4.484E+04 2.426E+04
1.48E+07 3.716E+06
0.1 0.1
100 77.521631
423 423
0.1 2.069E-09
0.0415941 0.0415941
0 .. 016986 0.016986
-5.019E-05 -5.019E-05
-1.591E-ll -1. 591E-1l
100 100
1. 05 1. 05
[4] d(T)/d(V) = (4000*(373-T)+(-r1 a)*20000+(-r2a)*60000)/(90*Fa+90*Fb+ 180*Fc)
[5] d(y)/d(V) = -alpha/21y*(FVFto)
Explicit equations as entered by the user
[1] k1a = 10*exp(4000*(1/300-1/T
[2 J k2a = 0 .. 09*exp(9000*(1/300-1/T
[3 J Cta = 0.1
[41 Ft = Fa+Fb+Fc
[5J To = 423
[6] Ca = Cto*(Fa/Ft)*(To/T)
['7 J Cb = Cto*(Fb/Ft)*(To/T)
[8] Cc = Cto*(Fc/Ft)*(TolT)
[9] r1 a = -k1 a*Ca
[ 10] r2a = -k2a*Ca"2
[11] Fto = 100
[12] alpha = 1.05
(e) P8-2 (k) Example 8-11
VaryUA
VA= 70,000 J/m
3
-s-K
only the lower steady state exists at T = 318 K SBC = 0.05
VA=60,000 J/m
3
-s-K
only three steady states exist T = 318, 380 (about) and 408 (about) depending how you read the
intersection on the graph.
VA= 700 J/m
3
-s-K
only three steady states T = 300 (about), T = 350 (about) and one are a very high temperature off the
scale of the R (T) and G(T) plot.
In all cases SBC remains low at 0.05, meaning that the reaction has neared completion to form
species C therefore reactor is too large.
8-8
To = 275, very little effect.
Vary l'
't = 0.001 only the lower steady state at T = 316 about and other off scale SBC = 0.05
z = 0.0001 only are steady state at T = 316 and others off scale SBC = 0.05
't = 0.00001, SBC = 5
However, the upper steady state is off the graph and needs to be studied
(f) P8-2 (1) Example PRS P8-4 . .l
1
(J.----
dpPo
U
2
=U
j
:::::
No effect for turbulent flow if both dp and P changed at the same time.
P8-2 (m) Example TS-3
fie = 200 g/s
See Polymath program P82rn.pol.
POLYMATH Results
Calculated values of the DEQ variables
variable initial value minimal value
W 0 0
Ta 320 320
Y
1 0 .. 3044056
T 330 330
X 0 0
alpha 2 .. 0E-04 2.0E-04
To 350 350
Uarho 0.5 0.5
Me 200 200
Cpme 18 18
Hr -2.0E+04 -2 .. 0E+04
Fao 5 5
theta I 1 1
CpI 40 40
CpA 20 20
the taB 1 1
CpB 20 20
Cto 0.3 0.3
Ea 2.5E+04 2.5E+04
Ke 66.01.082 0 .. 8247864
ka 0.046809 0 .. 046809
yao 0.3333333 0.3333333
xe 0 .. 8024634 0 .. 3122841
Cao 0 .. 1 0 .. 1
sumep 80 80
Ca 0.1060606 0 .. 0137198
Cb 0 .. 1060606 0 .. 0137l98
Ce 0 0
ra -5 .. 265E--04 -0 .. 0143957
maximal value final value
4500 4500
334.77131 334 .. 77l31
1 0.3044056
385 .. 31436 338.18498
0.5645069 0.5645069
2 .. 0E-04 2 .. 0E-04
350 350
0 .. 5 0.5
200 200
18 18
-2.0E+04 -2 .. 0E+04
5 5
1 1
40 40
20 20
1 1
20 20
0.3 0.3
2 .. 5E+04 2.5E+04
66.01082 31.. 551036
11 .. 205249 0.1177827
0 .. 3333333 0 .. 3333333
0 .. 8024634 0 .. 7374305
0.1 0 .. 1
80 80
0 .. 1060606 0.0137l98
0.1060606 0 .. 0137l98
0.0724316 0.0355685
-1 .. 745E-05 -1 .. 745E-05
8-9
ODE Report (RKF45)
Differential equations as entered by the user
[Ii d(Ta)/d(W) = Uarho*(T-Ta)/(Mc*Cpmc)
[2] d(y)/d(W) = -alpha/2*(T/To)/y
[3] d(T)/d(W) = (Uarho*(Ta-T)+(-ra)*(-Hr/(Fao*sumcp)
[4 J d(X)/d(W) = -ra/Fao
Explicit equations as entered by the user
[ 1] alpha =.0002
(2) To=350
[3) Uarho = 0.5
[4] Mc = 200
[5] Cpmc = 18
[ 6 J Hr = -20000
[7) Fao=5
[ 8] thetal = 1
[9] Cpl = 40
[10J CpA = 20
[l1J thetaB = 1
[12] CpB=20
[13J Cto = 0.3
[14] Ea = 25000
[15 J Kc = 1000*(exp(Hr/1.987*(1/3031/T)))
[16J ka = .004*exp(Ea/1.987*(1/310-1/T
[17 J yao = 1/(1 +thetaB+thetal)
[18] xe = Kc"O.5/(2+Kc"O.5)
[19] Cao = yao*Cto
[20 J sumcp = (thetal*Cpl+CpA+thetaB*CpB)
[21 J Ca = Cao*(1-X)*y*To/T
[22] Cb = Cao*(1-X)*y*To/T
[2.3] Cc = Cao*2*X*y*Torr
[ 24] ra = -ka * (Ca *Cb-CcJ\2/Kc)
P8-2 (n)
(1) The concentration of A near the wall is lower than in the center because the velocity profile is
parabolic. This means near the walls the velocity is much lower and therefore the time space near
the wall is much larger than in the center. This means the reaction has longer to take place and
conversion will be higher near the wall. Thus the concentration is lower.
Below is the FEMLAB solution.
1. Parameters in simulation on the tubular reactor from Example 8-12 (First Order reaction):
(1) operating parameters
Reactants
Reaction: A + B -7 C
A- propylene oxide; B- water; C- propylene glycol
Feed rate of A F
AO
= 0.1 molls
FAOM A 0.lx58.1xlO-
3
-6 3
Inlet flow rate of A VAO = = =7x10 mls
P
A
830
8-10

Inlet flow rate of B v BO = 2.5 x 2 x V AO = 35 X 10-
6
rrhs

Inlet total flowrate Vo = 2v
AO
+v
BO
= 14xlO-
6
+35xlO-
6
= 49xlO-6 m
3
/s

F
AO
0..1 0. 3
Inlet concentration of A C AO = -- 6 = 20.4 .8 mol/m
Vo 49xlO-

. F v P 35xlO-
6
x1000 3
Inlet concentIatIOn of B C BO = ---.!!.Q.. = - = = 39682.5 mol/rn
Vo MBVO 18xlO-
3
x49xlO-
6




Inlet temperature of the reactant To = 312K
Coolant flowrate, m] = 0.,,01 kg/s
Inlet temperature of the coolant, Tao = 298 K
(2) properties of reactants
Heat of reaction, I1H
Rx
, dHrx = -525676+286098+ 154911.6=-84666.4 J/mol
Activation energy, E = 75362 J/mol
Pre-exponential factor, A = 16.96x1012 13600 lis
Specific reaction rate ko = 1.28/3600 lis @300K
Reaction rate k = ko exp[ E - . ~ - ~ ) ] or k = A exp[- ~ ]
R ~ T RT
Gas constant, R = 8.314 J/molK
Rate law - r
A
= kC A
Thelmal conductivity of the reaction mixture, ke = 0..559 W/mK
Average density of the reaction mixture, p, rho = WOo. kg/m3
Heat capacity of the reaction mixture, Cp = 4180 J/kg"K
Diffusivity of all species, Diff = 10-
9
m%
(3) properties of coolant
Overall heat transfer coefficient, Uk = 1300 J/m
2
"s"K
Heat capacity of the coolant, Cp] = 4180 J/kg-K
2. Size of the Tubular Reactor
Reactor radius, Ra = 0.1 m
Reactor length, L = 1.0 m
2. Femlab screen shots
(1) Domain
(2) Constants and scalar expressions
- Constants
8-11
.314 -+----.---{"
tw .. --------- 12
f-------------- -----------.. -------------.-

............... -.-- ......... - ...... .
fBD __ ._ .. __ .. _. __ .. + _____ . _____ ._. __ .... __ ._... _ ...... __ ... _._ ..... __ ... __ . __ ..
_ .. _{----_._ ... _ .... _ .... __ .... _-_._ .... _----_ ........ -... __ .. _.
----F=-=---------------------+-=
r=-=---_.-.--.-.-.. -f'.---.--.. -----.----------.-------..--.---fc:-::..----.--.. -
- Scalar expressions
(3) Subdomain Settings
- Physics
(mass balance)
Equation
V.( -DVcA+cAu) = R, cA = concentration
Subdomain selection
Library material: . [--; ... - ,
,=' T
Valueil'xpressionDestriptiOI1 .
0'5 [ ... .. coefficient
G) D isotropic .' ..
-. IDiffusion
-I' '
o D anisotropic._ .. --:::l Pilfus!9
n
(;oefficient
R rat!'
u
8-12
(Energy balance)
V*C-kVT + =Q - PCpu.VT, T=temperfrture
(Cooling Jacket)
Equation
v.r = F
c Subdomain selection
[] Select by group
i PhYSics i Init ; Element '
Thermal properties and heat sourcesfsinks
Library material
Quantity Valueibpression Description
1\5 Time-scaling coefficient
o k (isotropic) Thermal conductivity
(':' k (anisotropic) Thermal conductivity
C
p
Heat capacity
Q
hiND.1
!
i Coefficients Element Weak
PDE coefficients
COefficient VilluelExpression Qescription
o .. .. Flux vector
Source term
d
a
Mass coefficient
Active in this domain
(Source Term)
F = Taz-2*pi*Ra*Uk*(T-Ta)/(CpJ*m1)
- Initial values
(Mass balance) cA(tO) = cAO
(Energy Balance) T(tO) = TO
(Cooling Jacket) Ta(tO) = TaO
- Boundary Conditions
@ r = 0, Axial symmetry
@ inlet, cA = cAO (for mass balance)
T = TO (for energy balance)
@ outlet, Convective flux
@ wall, Insulation/Symmetry (for mass balance)
qO = -Uk*(T-TaO) (for energy balance)
8-13
(4) Results

0.6
0,4
0.2
0.6
0.4
0.2
(Concentration, cA)
.." ?,&'
--..----.--.-----------.. .. --".--.. -
'-0.2 ..Ql5 ..01 -0.05 0.05 01 0,,15 0.2 025"
" "
---
-0.2 015 . .0.1" -0.05 0.05
8-14

1782.os5
660222
Second order reaction
[1] Domain
o Axis equal
[2] Constants & Scalar expressions
(1) Constants
, ...
... __ .
uz 2uOC1-CrlRa).A2)
0-- .t-...._.-._-.... " ..--_ ..._ ...
txA (cAO-cA)/cAO
cB
'cC 2'cAO'xA
1-- V",.,_, _".,_"._'"+ ___ .. v""''',.'''" __ _._ .. .. .. " . ,, __ __
rf!: . .rf!: ...... .
J<eq 13031
15--" .......... -...... -.... -........ -.-......... .
8-15
[3] Subdomain Settings
(1) Physics
(Mass balance)
(Energy balance)
(Cooling Jacket)
Equation-' --,,-
V'(-D'lcA+cAu) = R, cA = concentration
i,Subdomain selection--
I filii:! Iii ffl 1111 imll1lllll ,;
[1
II
i 1
!
II
i I
i 1
II
! I
IL
EJ Select by group
G:'.I Active ill Ibis domain
library material:
Quantity ValuelExpressiofi Description;
lh [ ____ Time-s"aling coefficieoi
o D isotropic Diffusion cQefficienl
o D anisotropic ii,ij,Q,:'.".=, _::.c._.J'DiffuSlon coefficient
R Reacti':'Q;/'ate
u
v
]
I Equalion ,
I v.(:kVT ",:" = Q., pCp ..... VT.
I
Subdomain selection ! Element 1
o Select by group
[tJ Acti\ie in
Tl:lermal properties and heat sourcesfsinkS
material; .. L.LOad .... J
Quantity
0kQsolroplC)
Ok (.niSoiropic)
C
p
Q
Value&press;OO De.cription
h' ---- mm:"':::::':':.i.5;t:';-T coefficient


Tberma.l.concWclivilY:-

Heal Cop'CKY
'''''''';;'''''''=c,;''''':::! Healsoi1rce
r ..

hiND ,I
[
;Equation
l vr = F
L
II
I
PDE coefficients-
Coefficient Des"ription
I r
I F term
I d
a
__ :5'
E]Selecl by group
Aclivein this
(Source Term)
F = Taz-2*pi*Ra*Uk*(T-Ta)/(CpJ*m1)
8-16
(2) Initial values
(Mass balance) cA(tO) = cAO
(Energy Balance) T(tO) = TO
(Cooling Jacket) Ta(tO) = TaO
(3) Boundary Values
@ I' = 0, Axial symmetry
@ inlet, cA = cAO (for mass balance)
T = TO (for energy balance)
@ outlet, Convective flux
@ wall, Insulation/Symmetry (for mass balance)
qO = -Uk*(T-TaO) (for energy balance)
[4] Results
_.
2 .Q15 -01 0 os
xA is undefined at (--0 .. 1,0,,6)
0.05
8-17

--0-1 --0-15 ---0-'-2 03
Min: 81735
0.6
0:4
02
0.15 .0,05 0.05 0.1 015
. 02 0.25 .
, .......
P8-2 (0) Individualized solution
P8-3 Solution is in the decoding algorithm available in the beginning of this manual.
P8-4
Find the reactor temperature at steady state (prior to shutdown)
Let M = mass of the NH4N0
3
in reactor.
F AO = lbs/hr of NH4N0
3
fed to the reactor.
Mass balance: FAD - FAD (1- X) = -rAV = kM
Energy Balance:
X = k(T)M
FAD
-FAD LBJH
w
- Hi (T)] + FADXMl Rxn(T) + FAD (1- X)MlVA = 0
Where Hj(T) is the enthalpy of i at the temperature of the reaction, Ml VA is the heat of vaporization
of A, and Ml Rxn (T) is the heat of reaction at the outlet temperature.
8-18
NH
4
NO(l) 2H
2
0(g) + N
2
0(g)

The last term F
AO
(1- X)t:Jl VA accounts for the unreacted N&N03, which exits as vapor rather than
the liquid. Now, we can make some substitutions
BB = .17 ,B
A
=l,Bc =0
.83
Heat capacity of A is given, and the enthalpy change for water 200
0
F (I) 500
0
F (g) is also given.
So, after dividing by F AO, we obtain
CpA (T -200)+ BB[H B(500 F) + C
P1
(T - 500)]+ t:Jl RxnX + (1- X)t:Jl
VA
= 0
The previous equation assumes that the heat capacities are constant over a reasonable temperature
range.
the phase change NH4NO(aq) ----7 NH
4
NO(1) is isenthalpic.
In addition, we must account for the effect of the temperature dependence of Ml Rxn .
44
Ml Rxn(T) = Ml Rxn(T
R
) + (T-- T
R
)[80 C
P1
-CpA] = Ml Rxn(Tr) + (T
Let Ml Rxn = HB (500) -- HB (200), we have
CpA(T -200)+OB(Ml
W
+Cps(T -500)+ X [MlRxIl +i1C
p
(T -500)]+(1- X)Ml
VA
=0
or,T[C
pA
-t0BC
p
> ]+[-C
pA
(200) +OB(Ml
w
--500C
p
,)] + X[Ml Rxll + i1C
p
(T -500)]+ (1-- X)MlVA = 0
Numerical Substitution with
K(560) =:; 5.03 and k(51O) = .53
In(k2) = - E (i __
kj R T2
-::::;.E =44499
R kj
E
Ao = kj exp(-) = 4.51424xlO19

Btu
CpA =.38--;C
p1
=.466
Ih.R
(P = 1 atm over 450 - 500Dp Himmelblau)
C
pc
= .2521_
Btu
(Himmelblau, App E, over 230-265C)
Ih.R
8-19
8 =.:!2. = .205
B .83
Ml = 1034 Btu .03
w lb
F
AO
= 257.3
lb
NH
4
N0
3
hr
AC
p
= 44.02 (.2521)+ 36.03 (.466)-.38=-.0316 Btu
80.05 80.05 Ib.R
MlRxn = C
pA
(41O-T)
Substituting all these into the mass and energy balances:
4 . .51x10
19
ex ( -44499 )M
P T+459.67
Mass balance: X = ---------''----........:..-
257.3
Energy balance:
0= .48T +88.21 + X(-320.20-.03T) + (1- X)(1.55.80"-.38T)
Assume X = .96 and M=500. Then, from mass balance,
T = 5100P
P8-5
F,. ( lb )
Tio(F)
-,
)
-"""-----,--_t__

lbmol
,---+-
p;,(; )
-----------'--
Ml = 20 000 Btu
R ' lb mol A'
Energy balance with work term included is:

A B
10 10
80 80
51 44
128 94
---------
63 67.2
-
8-20
_.-
C
--
0.0
-
-----
47 . .5
-- f------
222
65
F 10
B =1 B X =1
A 'B F 10 ' AF
AO
Q=UA(Ts-T)
Substituting into energy balance,
UA(T
s
- T) - Ws - FAOM-J RX AF = F
AO
[ CpA + C pB ] [T - To]
-T)--Ws -FAOM-J
R
= {FAO [ CpA +CpB]+UA}[T-Yo]
T = T, + UA(T
s
-T)-Ws - FAOM-J
R
o F
AO
[ CpA +CpB]+UA
-W = 63525 Btu
S hr
:. T = 199F
P8-6
Since the feed is equimolar, C
AO
= C
BO
=.1 mols/dm3
Adiabatic:
T =To + {[-_M!R(To)l
rACp; + X8C
p
CA = CAOO-X)
C
B
= C
Bo
(I-X)
8Cp =CpC-CpB-CpA =30-15--15=0

All R(T) = Hc - H B - H A = --41000-(-15000-(-20000) = -6000 cal/mol A
" - cal
L./i;C
i
= CpA +BBCpB =15+15=30--
mol K
T = 300 + X = 300 + 200 X
30
-rA = k X)2 = .0Ik(1- X)2
P8-6 (a)
8-21
For the PFR, F
AO
= CAovo = (.1)(2) =.2 mols/dm
3
See Polymath program P8-6-a.pol.
Calculated values of DEQ variables
,---r-'---" .., ..---t "-""""." "--''''---'1 ....
! IVariable nitial value I Minimal value I Maximal value i Final value I
""-J:;'--'-""'--' ----r-.-.------------.. .. T", -.. , .. __ _-'T---..-----.-. --,
illX 0 10 10.85 0.85 I
. l .,', . ... 1--"., .. , ,-. .. ,,,.,,.,, '-""-' '" ". . ...... ___ .. __ ... _.J
i V 0 10 1308.2917 08.2917 1

151T 1300. 1300. 1470.1470.. I
h 0 ___ ""''01" , ,. "'''" ',f' " ,=, YW ___
16ik 10.01 10.01 14.150375 14.150375 I
f-""'T"'"' ,. w,t" ___ "''_N __ "'W ..." -----, ;
j71ra 1-0.0001 1-0.0018941 1-0.0001 1-0.0009338 I
. .,,, ... ,, .. _ " .. . ... ,... '" ....... 1
Differential equations
:g,: d(V)/d(X) = -FaO / ra
Explicit equations
Cao = .1
FaO = .2
T = 300 + 200 * X
k = .01 *exp((10000 / 2) * (1 / 300 - 1 / T
$ ra = -k * (CaO /\ 2) * ((1 - X) /\ 2)
v = 308.2917dm
3
For the CSTR,
X = .85, T = 300+(200)(85) = 470 K.
k = 4.31 (Using T = 470K in the formula).
-rA = .000971 mol/dm
3
/s
V=_l!AO
X
= .lx2x.85 =175 dm
3
-r
A
9.71xlO-
4
The reason for this difference is that the temperature and hence the rate of reaction remains constant
throughout the entire CSTR (equal to the outlet conditions), while for a PFR, the rate increases
gradually with temperature from the inlet to the outlet, so the rate of increases with length.
P8-6 (b)
X[-Mi
R
]
T=T+---
o
For boiling temp of 550 k,
5.50 = To + 200
To = 3.50K
8-22
P8-6 (c)
0.90
0.72
0.54
0,.36
0.18
O.(lU
(I 62
P8-6 (d)
FAoX
V
CSTR
=--
-r
A
GJ
123
V
185
=> X = V
CS7R
(-r
A
)
F
AO
For V = 500 dm
3
, F Ao=.2
246 3U8
-r
A
= k X)2 = .Olk(l- X)2
T =300+ 200 X
500
460
:120
380
340
300
0
Now use Polymath to solve the non-linear equations.
See Polymath program P86 ..d .. 1. pol.
Calculated values of NlE variables
I'
lvariablejvalue if(x) ;Initial Guess'
liT 1484.4136 :0 1480.
21X !0.9220681j-2.041E-09i o.9
iVariable !Value
> t n
16.072856
2 : ra I (). 0003688
,
Nonlinear equations
1;ci f(T) = 300 + 200 * X - T = 0
f(X) = 500 - .2 * X / ra = 0
Explicit equations
1 k = .01 * exp(10000 / 1.98 * (1/300 - 1/ T))
8-23
[!]
62
123 V
185 246 308
ra = 0.01 * k * (1 - X) A 2
Hence, X = .922 and T = 484.41 K
For the conversion in two CSTR's of 250 dm
3
each,
For the first CSTR, using the earlier program and V = 250 dm
3
,
I Ivalue
11 ]k"" 15.105278

Nonlinear equations
f(T) = 300 + 200 * X - T = 0
f(X) = 250 "" .2 * X / ra = 0
Explicit equations
k = .01 * exp(lOOOO / 1.98 * (1/300 - 1 / T))
ra = 0.01 * k * (1 - X) A 2
T = 476.48 ad X = .8824
Hence, in the second reactor,
V = FAO(X - Xl).
CSTR
-r
A
V
X =_CSTR (-r )+ X
F A I
AO
T = Tou/,CSTRl + 200 (X _. Xl)
See Polymath program P8-6"d2 .. pol.
Calculated values of NlE variables
,.- "'r -
: IVariable;Value if(x) IInitial Guess
;1 IT " 1493.8738 fO" ... 1480. .. . ....
JO.9693688 t -1.359E-09 j 0.8824
; "
t, __ .'''''N._"" T---"
jllk ,7.415252
'16.958E-05
." .(,
8-24
31X1 ;0.8824
Nonlinear equations
f(T) = 476.48 + 200 * (X - Xl) - T = 0
i f(X) = 250 - .2 * (X - Xl) / ra = 0
Explicit equations
ij k = .01 * exp(lOOOO / 1.98 * (1 / 300 .. 1/ T))
ra = 0.01 * k * (1 - X) A 2
Xl = .8824
Hence, final X = .9694
P8-6 (e) Individualized solution
P8-6 (0 Individualized solution
P8-7 (a)
For reversible reaction, the rate law becomes
-or =k(C C - CcJ
A A B K
c
x
e l+K
e
T =300+200X
k = k(300)exp(E (_l ___ .!.)J
R 300 T
K = K (450)ex
p
[Ml Rxn (-.l ___ .!.)]
C C R 450 T
Stoichiometry:
C
c
= CAOX
C
A
= CAo(l- X)
C
B
= CAo(l- X)
See Polymath program P87-a .. pol.
Calculated values of DEQ variables
value Maximal value Final valuel
, l i '" ,., ",... ". i ",. -;
'l1V iOO 110. 10. !
l?Ix. \0 10 10.0050806 0.0050806
8-25
Differential equations
d(X)/ dey) = ora / FaO
Explicit equations
T = 300 + 200 * X
FaO = .2
Kc = 10 * exp(6000 / 2 * (1 / 450 - 1 / T))
k = .01 * exp((10000 / 2) * (1/ 300 - 1/ T))
CaO =.1
i ra = -k * (cao A 2) * ((1 - X) A 2 .. X / Kc)
Xe = Kc / (1 + Kc)
302.0 0.30 ,--------------,
...,.--......., ..-,."., ... ... , ......--..-,----
30L6 0.24
301.2 0 .. 18
300 .. 8 0 . .12
300.4 0.06
300.0
0 2
4 V 6
8 10
{tOO
(I
2 ...
V
P8-7 (b)
When heat exchanger is added, the energy balance can be written as
dT _ Ua(Ta -T) + (-r
A
) [-MIRxn (T)]
dV - F
AO
(I BiC
pi

So with 0, =30, MIRxn= -6000 cal/mol
dT Ua(Ta -T) + (-r
A
) [6000]

dV F
AO
(30)
Where Va = 20 cal/m3/s/K, T a = 450 K
8-26
- x
IT]
-
.,.
6 8 10
See Polymath program P8-7-b.pol.
Calculated values of DEQ variables
""W'"r
IVariable !Initial value l Minimal value: Maximal value I Final value
"'f' ,.
1 Iv:O 10 ;10. 110.
:2 lxJo ... fo _:0.571711210.5717112
3Jr i450. . .. '463.99741452.3087
i4 ICaO !0.1 10.1 10.1
'sIFao iO.2 /0.2 10.2 ]0.2
16T Kc '110. Tio. -T1.2.22765 ! 10.34614
. ..1 i .. .-'
12.586706. 13.616753i2.737647
18 ira f-0.0258671 ;-0.027946 i-0.0035089 T-0.0035089
19 lxe "]0.909090910.9090909 10.9244008 TO.9118643
10 fUfo. j 10. ! 10.! 10. . lio .
. 1450. 1
1
450. [450.
1
1
10
.
Differential equations
J, d(X)/d(V) = -ra / FaO
flO. i 10 ...
d(T)/d(V) = (UA * (Ta - T) + (--ra) * 6000) /30/ FaO
Explicit equations
it CaO = .1
FaO = .2
Kc = 10 * exp(6000 /2 * (1 / 450 - 1/ T))
k = .01 * exp((10000 / 2) * (1/ 300 - 1/ T))
ra = -k * (CaO /\ 2) * ((1 - X) /\ 2 - X / Kc)
Xe = Kc / (1 + Kc)
UA = 10
= 450
;al A = 10
8-27
110 ..
,i
470
466
462
EiJ
458
454
450
0 2 4
V
6 8 10
P8-7 (C)
For a co-current heat exchanger,
Q=mcCpc(Tal-T)[l-.exp( . . UA J]
mcCpc
C
pC
= lcal/glK, T
a1
=450 K, m = 50
L
sec
See Polymath program P87c.pol.
Calculated values of DEQ variables
1.0
0.8
0 .. 6
0.4
0.2
2 4
V
6
Minimal value
11 IV . . 1
0
jo 1
10
. 1
10
. I
12 Ix 10 ]0 [0.575571 ..... 10.575571 j
13 IT 1450. ]450. /465.3828' 1452.51.92" .]
:r"O" T" 1" ..... r "ce,,, ... .0
14 ICaO 10.1 !0.1 10.1 !0.1 I
1'- l' . ".,. r
o
,,,, '1' ! f .<.. . .. 1
1
5
I
FaO
!0.2 1
0
.
2
;0.2 1
0
.
2
I
1611<c .Jl0.JlO. .\12.46524 hO.37812 1
17 kpc 11. 11. 11. /1.1
1 ... ,.: . ' ...8
9
... ... rll., .. k
r
..
a
[2.586706. 13.734633 I2.751.765 J
. 1-0.0281568 1-0.0034309 ]-.0.0034309 J
110jXe 10.9090909 10.9090909 16.9257347 !0.912112 I
11.1 jUA liorio. Tlo. [10. 1
1450. 1450./450. 1450.
1
[131A 110. .... 110. lio. : 10. J.
I
,
1141mc "150. 150. 150. .. 150. . I
[
ls
lq 1-139.420110 J-22.833091
Differential equations
d(X)jd(V) = -ra j FaO
12; d(T)jd(V) = (Q + (-ra) * 6000) j 30 j FaO
8-28
8
Explicit equations
1, CaO = .1
FaO = .2
3. Kc = 10 * exp(6000 /2 * (1/450 - 1/ T))
,fl Cpc = 1
k = .01 * exp((10000 / 2) * (1/ 300 - 1/ T))
6" ra = -k * (CaO /\ 2) * ((1 - X) /\ 2 - X / Kc)
Xe = Kc / (1 + Kc)
8. UA = 10
9. Ta = 450
10 A = 10
.1l mc = 50
12 Q = mc * Cpc * (Ta - T) * (1 - exp(-UA / mc / Cpc))
470 1.0 -------------,
466
462
458
454
450
0 2
" V 6
8
tl8
0 .. 6
0.4
lL2
10 2
4 V 6


8
Next increase the coolant flow rate and run the same program to compare results.
P8-7 (d)
For counter-current flow,
Q = meC,e (I;, -T)[l +ex
p
( -
See Polymath program P8,,:7 d.po!.
Calculated values of DEQ variables
< - .'0'" ';
!Variable'Initial value:Minimal valueiMaximal value Final value
1 iV
!
2 Ix
3 ::r
10
10
{
:450.
io
1"450.
1
, '
,
[10. ilO.
'0.5395082
1451.6471
.. ,
8-29
10.5395082
. ..
.450.2745
10
f4'" . ""TO:1-" ..... ... .. .. .. ..
" ....... '1- ..' .. .. , ........ "Y ............. " ,. ...... .
is !FaO 10.2 10.2 10.2 10.2
l --''''''' , .. ' .. , ,,-, .. , "-, ''''- ,t , .. -, " ....."."""('., ........... " ...... " .."1 ...." ......... ..
6 I Kc 110. ; 10. 110.24606 110.04072
, .... , .... + .... , ..._ ............... ".-1 ....... ,'-, .. , , .............. , , ." ... ," "', 'T' ...... ......, ... , .. , ....... ""'''1'''''''' .. .,,--, .. ..
17 ICpc 11. 11. 11. :1.
18'Tk-''-'''T2:s86706' 1"2.604286
19' .. "" r ,." r
lio
T
Xe ""'10.9090909 10.9090909"'10:91108" 10.9094262
(' A 'Eo.'" "liD."" rio.'Tio.
1"12 !Ta .... t450.145o. 1450. l4S0.
ii3IA"Tio. , .. ,', .. Fo: ... ; 10. flO.
---
Differential equations
d(X)/d(V) = -ra / FaO
d(T)/d(V) = (Q + (-ra) * 6000) / 30/ FaO
Explicit equations
CaO = .1
;2,' FaO = .2
Kc = 10 * exp( 6000 / 2 * (1 / 450 -1 / T
Cpc = 1
k = .01 * exp((lOOOO / 2) * (1 / 300 -1 / T
ra = -k * (CaO /\ 2) * ((1 - X) /\ 2 - X / Kc)
Xe = Kc / (1 + Kc)
UA = 10
Ta = 450
A = 10
j,J, mc = 50
Q = mc * Cpc * (Ta ,. T) * (1 + exp(-UA / mc / Cpc
8 .. 30
452.0,.---------------,
4512
450.8
450.4
2
4 V 6
8 10
P8-7 (e)
10
0.8
0.6
O.j
02
00
0 2 .:j V 6

U;J
8
We see that it is better to use a counter-current coolant flow as in this case we achieve the maximum
equilibrium conversion using a lesser volume of the PFR.
P8-7 (0
If the reaction is irreversible but endothermic, we have
-r
A
= k X)2 = .Olk(1- X)2 as obtained in the earlier problem.
MI Rxn = 6000cal / mol
For co-current flow of coolant,
(7;, -T)[l-ex
p
( -
See Polymath program P8-7fco.pol.
we use 8- 7f cocurrent.pol
Calculated values of DEQ variables
value I Maximal value 1 Final value
, , , , I
, ri '., Y ., f ,. : .
1 IV 10 10 110.10.
, ;
;0 10 fO.5227896 i2
IX
I
13
IT ,
!4 CaO
15 FaO
16 Cpc
7 !k
i
I
8 Ira
, T
9 !UA
10ha
'
"l 1
1450. 1439.9908
10.1 10.1
i
:0.2
1.
10.2
11. .,
12.586706 [2.008972
1-0.0258671 1-0.0258671
110.
,
1450. A50.
,
150. '50.
10.1
10.2
1 '
11.
2.586706
1-0.0053573

110
! I
1450.
SO.
8-31
;0.5227896
:446.1887
;0.1
"io.2
11.
:2.352492
1-0.0053573
llO.
:450.
50.
T' ,,'T' ... .' ....... ---.. ' ... . .. 'c-'- ...... ........ - .. ' .. --...... ,
i
12
iQ 10 10
1 ' .... ,!., .. ......... , .. ', .. , ,. .. " .. .... " " .. ' ' . .,-. ...
Differential equations
d(X)jd(V) = -ra j FaO
d(T)jd(V) = (Q + (-ra) * (-6000)) j 30 j FaO
Explicit equations
Cao = .1
FaO =.2
Cpc = 1
.41 k = .01 * exp10000 j 2) * (1 j 300 - 1 j T))
ra = -k * (CaO A 2) * 1 - X) A 2)
UA = 10
= 450
, ,<
me = 50
fii Q = me * Cpc * (Ta - T) * (1 .. exp(-UA j me j Cpc))
450 -.------ 0.60
OAS
0.36
US
[J]
0.2-4
434 0 .. 12
430
10
For counter-current flow,
Q=rhcCpc(Tal--T)[l+exp(- .UA J]
mcCpC
See Polymath program P8--7 -f-counteLp0l.
POLYMATH program 8-7f countercurrent.pol
Calculated values of DEQ variables

2 4 V 6 8 10
-. -, '-.. - ., "'1 .... ....... ...... , 0
IVariablelInitial value!Minimal value I Maximal valuelFinal value
r' ... r r .. r' ... ...
1 IV 10 10 :10. 110.
2lx '10 fa 10.5594826 fo:s594826
3 IT' ...... }150. f448.4634 ..... 1450. l449.669
8-32
'4 lcao

:6 ICpc
'ill<
,

9juA
101Ta
"
lli
mc
, "
12jQ
iO.1
:0.2
1.
12.586706
1-0.0258671
110.
1450.
o J
i50.
10
Differential equations
. d(X)/d(V) = -ra / FaO
iO.1
0.2
1.
2.4901
-0.0258671
10.
450.
:50.
10
iO.1
11.
i
!2.586706
[ -0.0049788
110.
A50.
50.
139.7022
= (Q + (-ra) * (-6000)) /30/ FaO
Explicit equations
cao = .1
FaO = .2
Cpc = 1
k = .01 * exp((lOOOO / 2) * (1/ 300 _. 1/ T))
:5 ra = -k * (CaO /\ 2) * ((1 - X) /\ 2)
q. UA = 10
") Ta = 450
8 me = 50
Q = me * Cpc * (Ta - T) * (1 + exp(-UA / me / Cpc))
450.0.-------- 0.60
449.6
0,48
449.2 0.36
Q
1),.24
448,4 0,12

000
4
Y
6 8 10
()
448.0
o 2
P8-7 (g)
For a runaway reaction, the following must be true:
RT2
T -T >-'-
, C E
8-33
" [30.09601
2 4
V
6 8 10
and T = Yo + KTa = 300+3*450 = 412.5
c I+K' 1+3
So if we plug this value into the original equation we get:
1.987 T2 -T +450> 0
10000 T 1
Tr= 499 K
P8-8 (a)

Species Balance:
I
dX r
A
--=--
dW F
AO
Vo = 20dm
3
/ s
Po = lOatm
Stoichiometry:
C
A
=C
AO
( I-X )I--,where =1
1+X To
C, = CAO (::
Rate Law is:
--r = kC with k = 0.133 exp [ E !)]
A A' R 450 T
E=31400
!VI Rxn = -20,000 J / mol
Energy Balance:
T
_T X[--M!R(T
o
)]_
-.I
o
+ '" - -
+ XI1Cp
I1C
p
= 15 + 24--40 = 0
T = 450+ X = 450+ 500X
40
See Polymath program P8-8-a.pol.
Calculated values of DEQ variables
lue f ['
i
1
1X 10 10 10.8 10.8 I
....... 10 143.13711'"j43.1371.1 1
8--34
r - ~
'3:T 1450. '450. '850.
~ ~ ~ .. - . ~
~ t ~ ~
:20. :20. 20.
,
.. , ..
,5iTO
1
450
.
1
450. 1450.
A'l
'6.904332
6ik '0.133 '0.133
~
Differential equations
~ d(W)/d(X) = vO * (1 + X) * T / k / (1 - X) / TO
Explicit equations
:lin = 450 + 500 * X
2. vO = 20
3TO = 450
:4 k = .133 * exp(31400 / 8.314 * (1/ TO - 1/ T))
0.8
0.6
0 .. 5
0 .. 3
0 .. 2
0.0
0 9 18 W 27 36
P8-8 (b)
Species Balance for CSTR:
FAOX
WeHR =--,-
'-r
A
T = 450 + 500 X = 450 + 500(.8) = 850 K
k = .133ex
p
[}1400(_1 __ ._1_)] = 6.9
8.314 450 850
W
CSTR
= 39.42 kg
P8-8 (C) Individualized solution
P8-8 (d)
For pressure drop, an extra equation is added
8-35
dP =_
dW 2 1'0 (PlPo)
(
I.-X) T P
C
A
= C
AO
I + X To Po
See Polymath program P8-8-d.pol.
Using POLYMATH program CRE_8_8d.pol
For a=.019
Calculated values of DEQ variables
i valuejFinal
? 10
ji.002E+06 . ,
r41i1450. ... 1450. r850. .. 1850. . .....
151vo "'120:120:" 'fio:120.'1
161To 1450. '1450. 1450. 1450.J
l!Jk, ',"10.133'10.133 16.904332f6.904332 I
,8IpOI1.013E+06 11.013E+06h.013E+06 11.013E+06
r T . r .. T
,9lalpha 10.019 10.019 10.019 10.019
Differential equations
l d(X)jd(W) = k j vO * (1- X) j (1 + X) * TO j T * P j PO
d(P)jd(W) = -alpha j 2 * (T j TO) * PO A 2 j P * (1 + X)
Explicit equations
T = 450 + 500 * W
vO = 20
= 450
iJ k = .133 * exp(31400 / 8.314 * (1 / TO - 1/ T))
PO = 1013250
alpha = .019
8-36
i
.J
0 .. 060 900
0.0-18 800
0.036
Q
700
G
I}, 02-1 600
0 .. 012 500
0.000
000 016 032 W 0.48 0.6-1 0.80
400
0.00 0.16 0.32 W 0 .... 8 0.64 0.80
P8-9 (a)
We use the same equations as problem P8-8, except that the energy balance changes as:
Ua ( ) I
dT - Ta -T +(-rA)(-Mi
Rxn
)
= p ---------
dW FAOC
pA
Where -Mi Rxn = 20,000 J/mol, T a=323 K, C
pA
=40 l/mollK
See Polymath program P8"9"-a.pol.
Calculated values of DEQ variables
i Maximal value 1 Final value
, 3 , ' l
;1 Iw 1010 .. ". :50. 150."
'2jX 10 10 iO.1376181 ;0.1376181
'3 IT i450.
14 ITO 1450.
15 ivO i20.
16 jk iO.133
'{ 1:
10.08 i7 IUarho
is" ITa
, i
19 ipo
1101cAO
1111CA
1121rA
1293.
1.013E+06
1270.8283
f"" ..
1270.8283
1 "
1-36.02017
Differential equations
1381.1888 1450.
i
45O
.
1450.
r
1
20
.
20.
[0.0292331 :0.133
r
l
0.08
1.
08
1293.
i
j293.
11.013E+06
r
i1.013E+06
1270.8283 270.8283
12.42.3648
t
270.8283
I
1-36.02017 '-7.085084
d(X)/d(W) = k * (1 - X) / (1 + X) * TO / T / vO
)381.1888
i450.
I
!20.
,
/0.0292331
,
10.08
"" 1293.
!1.013E+06
!270.8283
i
1242.3648
-7.085084
d(T)/d(W) = (Uarho * (Ta - T) + rA * 20000) / vO / CAO / 40
8-37
Explicit equations
TO = 450
vO = 20
ljl k = 0.133 * exp(31400 /8.314 * (1/ TO - 1/ T))
~ Uarho = 0.08
Ta = 293
PO = 1013250
CAO = PO / 8.314 / TO
1m CA = CAO * (1 - X) / (1 + X) * TO / T
rA = -k * CA
450.----- -----------,
436
422
40S
394
10
20 \V 30
40 50
0.20
0.16
0.12
O.OS
0.1)4
0.00
0 10 20 W 30 40 50
If !!.-!2. was increased by a factor of 3000, we use the same program with the new value. The profiles
Ph
are in the graphs below.
450 ---- 0.20
434 0.16
US
EiJ
0.12
Q
402 0 .. 08
386 0,,04
370
_.
0 10 20
W 30
40 50 10 20
W 30
40 50
P8-9 (b)
8-38
For non-constant jacket temperature, the equation for incorporating the flow needs to be introduced.
co-current:
Tao = 50C
0.20,----------------------------,
436 016
012
408
0,,08
394 0,U4
380 L.-__ ____ _____
o 10 20 W 30 40 50
countercurrent:
dTa =
dW mCCpC
Taf= 50C
guess and check Tao until T a = 323 K at W = 50
Tao = 438.8 K
0.2U
016
422 0,12
.:J08 0,U8
394 n 114
380 L--___
o 10 20 W 30 40 5U
o uo
0
P8-9 (C)
10
10
For a fluidized CSTR with W = 80 kg, VA = 500 J/s/K,
8-39
20 W 30 40 50
20 \V 30
40 50
W
-CAO
Species balance: X MB = = ..:..P-",b__
l+rk F
AO
UA (T-Ta) +C (T-T)
F pA 0
Energy balance: X EB = -------
-MIRxn
X
EB
=X
MB
Solving, X = .95, T = 323 K
P8-9 (d)
For a reversible reaction, we have all the previous equations, but the rate law is modified as:
--rA = kfC
A
-k,CBC
C
C =C =C
B C AO l+X T
Plugging the equation for kl> and solving using POLYMATH program, we get the plots.
Only the cocurrent program and plots are shown.
See Polymath program P8-9-d.pol.
Calculated values of DEQ variables
Minimal valuE!1
j1 IW:O 10 180. 180. ,
_.,,,." f" 1 .. , 1 '{ '" 'v ,1
. 1. . jO.057593 .. J
13 IT \450. 1420.7523 1450. 1420.7523 !
j. .... \... . t'< .. "'" ., j '" ... . J
J4 JTa ,1
4
?6.1627 j42.0.7565. , ,I
.. J450l4?0. ]450. 1
450
. 1
i6 iVO 120. l20. ,20. 120. I
... ]it:.
42131

191po . li.013E+06 li013E+06 h:013E+06 '11.613E+06 1
110'fCAo'127o.82'83 [270.8283 1270.8283'12708283' 'j
f lila!270.8283" "f 258.1071
fi21k'r 102"10.076962 10.2 '10.076962 "'1
(like"10" 10t15.77362 h5.77362'j
r141'c8 ",'.'][0. [0'115.77362 115.77362"'1
j15FA 1-36.02017' 1-36.02017 1-0.0062421 ........ ]-0:0062421]
Differential equations
d(X)jd(W) = -rA j vO j CAO
8-40
2 d(T)/d(W) = (Uarho * (Ta - T) + rA * 20000) / vO / CAO / 40
3 d(Ta)/d(W) = Uarho * (T - Ta) / .2/ 5000
+ sign = cocurrent, -ve sign = countercurrent in RHS of eqn
Explicit equations
1 TO = 450
vO = 20
k = 0.133 * exp(31400 /8.314 * (1 / TO - 1/ T))
4- ~ Uarho == .08 * 3000
S PO = 1013250
6 CAO = PO / 8.314 / TO
"l... CA = CAO * (1 - X) / (1 + X) * TO / T
aE'ili kr = 0.2 * exp(51400 /8.314 * (1/ TO - 1/ T))
CC = CAO * X / (1 + X) * TO / T
~ m : CB = CAO * X / (1 + X) * TO / T
; : ~ i rA = -(k * CA - kr * CB * CC)
450..--------------., OU60
.:14.:1
.:138
432
.:126
16
32 vV.:I8
64
P8-9 (e) Individualized solution
P8-10 (a)
A-7B+C
C =c_
FA
A I F
e = F[
[ F
A
T
C
r
= C
A
+C[
Fr =F
A
+F[
I) U.:l8
0.036
OJ124
U.II12
o.ouo
8U 0
8-41
16 32 W 48 6.:1 80
-------------------
C = CAO +CIO
AOI B + 1
P8-10 (b)
Mole balance:
dX = -r
A
dV F
AO
I
Rate law: -r
A
= kC
A
S
. h C - C 1-- X 1'0
tOlC lOmetry: A - AOI 1+ X T
= YAO
c5
8=1+1-1=1
Y = FAO.= FAO __ 1_
,AO Fro F
AO
+ F;o 1 + B;
1
=--.
1+8.
I
-XMIRX + (CPA +B;C
Pi
)1'o
T=
CpA +B;C
Pi
Enter these equations into Polymath
See Polymath program P8--lO-b.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal
V 0 0
X 0 0
value
Cao 0.0221729 0 .. 0221729
Cio 0.0221729 0.0221729
theta 100 100
Fao 10 1.0
Cao1 4.391E-04 4.391E-04
e 0.009901 0.009901
To 1100 1100
dRrx 8 .. 0E+04 8.0E+04
Cpa 170 170
Cpi 200 200
T 1100 1098.3458
k 25.256686 24.100568
ra 0 .. Oll0894 -0.0110894
ODE Report (RKF45)
Differential equations as entered by the user
[l] d(X)/d(V) = -ra/Fao
maximal value final value
500 500
0.417064 0 .. 417064
0.0221729 0.0221729
0.0221729 0.0221729
100 100
10 10
4.391E-04 4.391E-04
0.009901 0.009901
1100 1100
8.0E+04 8.0E+04
170 170
200 200
1100 1098.3458
25.256686 24.1.00568
-0 .. 0061524 -0,0061524
8-42
Explicit equations as entered by the user
[ 1] Cao = 2/.082/1100
[2] Cio = Cao
[ 3] theta = 100
[4) Fao = 10
[5 J Cao1 = (Cao+Cio)/(theta+ 1)
[6] e = 1/(1 +theta)
[7] To = 1100
[8] dHrx = 80000
[9j Cpa = 170
[10] Cpi = 200
[11] T = (X*(-dHrx)+(Cpa+theta*Cpi)*To)/(Cpa+theta*Cpi)
[12] k = exp(34 .. 34-34222/T)
[13] ra = -k*Cao1 *(1-X)*To/(1 +e*X)/T
1.0
Conversion
1100
0.8 1060
-
No inert
0.6 -
i\fodelate
1020
-
Larae
004 980
0 .. 2 940

--
-
No inert
-
Moderate
-
Larae

0.0
0
900
--_ ..
100 200
V
300 400 500 (}
100 200
V
300 400
LOU
--_.

040
0.20
0..00
3 6

12 15
P8-10 (C)
500
There is a maximum at e = 8. This is because when e is small, adding inerts keeps the temperature
low to favor the endothermic reaction. As e increases beyond 8, there is so much more inert than
reactants that the rate law becomes the limiting factor.
P8-10 (d)
The only change to the Polymath code from part (b) is that the heat of reaction changes sign. The
new code is not shown, but the plots are below.
See Polymath program P81O-d.pol.
8-43
Conversion
1.0 rr------= ....... -------,
0.8
0.6
0.4
0.2
- No inerts
l\Iodcrate
- Larue
Tempel"nture
1600..-------'---------,
1500
- No inerts
1400
- Moderate
- Laroe
1300
1200
0,0 __ _____ . __
o 100 200 V 300 400
1100 .. -. ---'
500 0 100 200 V 300 400 500

0.92
0,,84
0.76
0.68

10 20 TheiN 40 so
The maximum conversion occurs at low values of theta (8 < 8) because the reaction is now
exothermic. This means heat is generated during the reaction and there is no advantage to adding
inerts as there was in the endothermic case.
P8-10 (e)
We need to alter the equations from part (c) such that -rA = and CAo = 1
A plot of conversion versus theta shows a maximum at about 8 = 5.
See Polymath program P81Oe.pol.
8-44
0.90.----------------,
-
050
0
'----2---4 rheIN
8 10
P8-10 (0
We need to alter the equations from part (c) such that -'A = k [ C A _ C c ]
I-X T
We already know that C
A
= C
AO
----......Q.. Now weed need expressions for C
B
and Ce. From
I+EX T
stoichiometry we can see that C
B
= Ce. In terms of C
AO
we find that:
C =C =C X To
Be AO I+EX T
We also need an equation for Ke: Kc = KCl exp [Mi RX ~ - !J] = 2exp 8 0 0 0 ~ (_1_ - !)]
R T.. T 8.314 1100 T
When we enter these inot Polymath we find that the maximumn conversion is achieved at
approximately e = 8.
See Polymath program P8-1 o Lpol.
100
0.30
0
'----:3- -6----9---12
Iheta
P8-10 (g)
See Polymath program P8-1 Og.pol.
15
8--45
10
Fb
8
~
- Part(d)
6
.. Part (e)
4
2
o 0
100 200
V
300 400 500
P8-11 (a)
Start with the complete energy balance:
dE " I I
-=Q_W
s
-"LEiF; in-"LEiF; out
dt
The following simplifications can be made:
It is steady state.
In part a, there is no heat taken away or added
There is no shaft work
That leaves us with
0= -"LEiF; lin -"LEiF; lout
Evaluating energy terms:
In: H AOFAO + H BOFBO + H eoFeo
Out: HA(F
A
+ RAV) + HB(F
B
+RBV)+He(F
e
+ ReV)
Simplifying,
HA(F
A
+RAV)+HB(F
B
+RBV)+He(Fe + ReV)-HAoFAO -HBOF
BO
-HeoFeo = 0
If only C is diffusing out of the reactor we get:
HAFA +HBFB +He (FB +RBV)-HAOFAO -HBOF
BO
-HeoFeo =0
Now we evaluate Fi
FA = F
AO
.- FAOX
FB = F
BO
+ FAOX
Fe = Feo + FAOX - ReV
Inserting these into our equation gives:
HAF
AO
-HAFAOX +HBF
BO
+HBFAOX + HcFeo + HeFAoX -HAOF
AO
-HBOF
BO
-HeoFeo =0
and note that F
Bo
= Feo = 0
H AFAO - H AFAOX + H BFAOX + H eFAoX - H AOFAO = 0 and combining and substituting terms gives:
F
AO
( H A _. H AO ) + F
Ao
X MJ. RX = 0
8-46
Differentiating with respect to V with i1Cp = 0
dT dX
FAoC -+FAo-(LViRx(T))=O
P dV dV
dT (r
A
)[ LVi Rx (T) ]
dV
Combine that with the mole balance and rate law:
dF
A
=r dF
B
=-r dF
e
=-r -k C
dV A
dV
A
dv
Ace
-r
A
=kC
A
C =C FA To
A TO F T
T
C = C FB Yo C = C Fe Yo
B TO FTC TO F T
T I
Forkc = 10
See Polymath program P8-11a.pol.
Calculated values of DEQ variables
.. -- .,-- .-.---.. ,. - _._ ..,- ;
lVariable : Initial value i Minimal value Maximal value Final value
1 IV :0
& "'
i2 Fe
;
0
\3 Fb
10
I
i4 lFa i5.42
,
i5
;T
{
,450.
16 1Ft ,5.42
i7 dHrx '-2.0E+04
i8 lk
iO.133
(
9 ike il0.
1
'loiCto
"r
12.710027
:l1iCa 12.710027
f121Ke 10.0006905
,
,
i
13
I
Ce ,0
114icb 12.710027
l15lra 1-0.3604336
;
i 1
116iCpa
:
Differential equations
d(Fe)jd(V) = -ra - ke * Ce
d(Fb)jd(V) = -ra
:0
;0
:0
15.222116
,
1
450
.
15.42
:-2.0E+04
iO.133
,
'10.
2.710027
;2.610831
10.0002635

10
1
12.610831
1-0.3604336
140.
+
50.
0.0012968
0.1978837
5.42
548.9418
5.421297
-2.0E+04
0.6036997
10.
2.710027
2.710027
10.0006905
;0.0006482
12.710027
1-0.0026249

140.
8-47
50.
0.0005261
10.1978837
15.222116
1
;548.9418
:5.420526
;-2.0E+04
10.6036997
i1O.
12.710027
12.610831
10.0002635
10.000263
12.610831
1-0.0026249
!
140.
~ J d(Fa)/d(V) = ra
~ J d(T)/d(V) = ra * dHrx / Cpa
Explicit equations
Ft = Fa + Fb + Fc
dHrx = -20000
k = .133 * exp31400 / 8.314) * (1 / 450 - 1/ T
kc = 10
Cto = 100 / .082 / 450
Ca = Cto * Fa / Ft
Kc = .01 * expdHrx / 8.314) * (1 / 300 - 1/ T
Cc=Cto*Fc/Ft
Cb = Cto * Fa / Ft
~ I l ra = -k * (Ca - Cb * Cc / Kc)
Cpa = 40
6.0
4.,8
[j
3,,6
~ F ~
Fa
2.-4
1.2
10 20 V 30 40 50
vary kc to see how the concentration profiles change.
P8-11 (b)
Now, the hear balance equation needs to be modified.
dT = Ua(Ta-T) + FAO(r
A
)[ LVIRx (T)]
dV FAO'X-B;C
p
See Polymath program P8,1l-b.pol.
8-48
6.0.----------------,
4.8
[ill
FC
~ Fh
Fa
3 .. 6
2.4
1.2
10 20 V 30 40 50
P8-12(a)
To find the necessary heat removal, we start with the isothermal case of the energy balance
.lL_ Ws --X[Ml +!J.C (T-T, )]="ac .(T-T)
F F RX P R L,.IPI 0
AO AO
Because there is no shaft work W s = O.
!J.C
p
=60--25-35=0
And for isothermal operation T = To
If we simplify the energy balance using this information we get:
Q
----XMl =0
RX
F
AO
or Q = FAOXMl
RX
= CAOvXMl
RX
We now know everything except the heat of reaction to solve for the heat removed term. To find the
heat of reaction consider the adiabatic case:
!J.C
p
= 60- 25-35 = 0
Q =0 and Ws = 0
--XMlRX = IB;CPi(T-T
o
)
Because feed is equal molar in A and B, 8
8
= 1
- X Ml RX = ( CpA + C PB )( T- To )
(25+35)(350-300) kJ
Ml RX = ----.--.------ = -7500-
-0.4 mol
Now go back to the isothermal case:
. (mal) ( m
3
J ( kJ )
Q=CAOvXMlRX = 1000 m
3
.5 min (0.2) 7 5 0 0 ~ o l
8-49
kJ
Q = -750000-.
mm
P8-12(b)
We start with the energy balance for the second CSTR (already simplified):
VA
-(Ta -T)-( X
2
- XI)MI
RX
= (CPA + CpB )(T --To)
F
AO
This equation has two unknowns (T and X
2
) and so we need another equation.
Now wee need the mole balance for the second reactor
F
AO
( X 2 - X I) F
AO
( X 2 - X I)
v: - - ---'-'--'---
2 - --r
A2
- (1- X
2
)2
This equation also brings in another unknown: k. We know that the specific reaction rate is
dependant on temperature and if we have the activation energy, we can make an implicit equation
for k as a function of T. To calculate the activation energy we will use the isothermal and adiabatic
information for reactor 1 and the mole balance for reactor 1.
V. = FAoXI
I 2 ( )2
kC
AO
I-XI
k = FAoX
(1- X)2
vX
--------
VC
AO
(1- X)2
Solving for kat 300 and 350 K gives:
k(300 K) = 0.00015625
k(350 K) = 0.0005555
If we plug these numbers into the Arrhenius equation we get
(
k
2
J E(I IJ In - = -- -- -- - we get EIR = 2664.
kl R 'Fr T2
Which means k(T) = k, ex
p
[ iU - J]
If we use a nonlinear equation solver to solve the energy balance and mole balance for reactor 2 we
find that the exit concentration is 0.423.
See Polymath program P8-12-h.pol.
POLYMATH Results
NLES Solution
Variable Value f (xl Ini Guess
T
X2 0.4214731 -6.666E-12 0.4
UA 4
8-50
Ta 350
vo 0 .. 5
Xl 0 .. 2
dHrx -7500
To 300
V 1
k 3 .. 309E-04
Cao 1000
Fao 500
ra -110.73657
NLES Report (safenewt)
Nonlinear equations
[1] f(T) = (UA)*(Ta-T)/Fao-(X2-X1 )*dHrx60*(T-To) = 0
[2] f(X2) = V-Fao*(X2-X1 )/(-ra) = 0
Explicit equations
[1] UA= 4
[2J Ta == 350
[3] vo=D..5
[4J X1 = 0.2
[5] dHrx = -7500
[6J To = 300
[7J V = 1
[8] k = .. 00015625*exp(2663 . .8*(1/300-1/T
[ 9] Gao = 1 000
[101 Fao = Gao*vo
[11 J ra = -k*GaoJ\2*(1-X2)"2
P8-12(c)
Now we need the differential form of the energy balance
dT Ua(Ta -T)-rAMlRx Ua(Ta -T)-rAMlRx
dV- -- FAO(CPA+CPB)
we also need the mole balance for a PFR. For this case it simplifies to:
dC
A
_ dCB _
-------r
dt dt A
with -rA = kCAC
B
and we can use the same equation for k as in part (b).
When we put these equations into Polymath we get an outlet conversion of X = 0.33
See Polymath program P8--12-c.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
----
V 0 0 1 1
T 300 283 .. 98681 300 283 .. 98681
X 0.2 0.2 0 .. 3281298 0 .. 3281298
Cao 1000 1000 1000 1000
Ua 10 10 10 10
Ta 300 300 300 300
dHrx -7500 -7500 -7500 -7500
Cb 800 671.87016 800 671 .. 87016
8-51
v 0.5 0.5
Fao 500 500
Cpa 25 25
Cpb 35 35
k 1.563E-04 9.47E-05
Ca 800 671. 87016
ra -100 -100
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(T)/d(V) = (Ua*(Ta-T)-ra*dHrx)/(Fao*(Cpa+Cpb))
[2] d(X)/d(V) = -ralFao
Explicit equations as entered by the user
[1] Cao = 1000
[2] Ua = 10
[3] Ta=300
[4] dHrx = -7500
[5] Cb = Cao*(1-X)
[6] v = 0 .. 5
[7] Fao = Cao*v
[8] Cpa = 25
[9] Cpb = 35
[10] k = 0.00015625*exp(2664*(1/300-1/T))
[11] Ca = Cao*(1-X)
[12] ra = k*Ca*Cb
P8-12(d)
0.5
500
25
35
1 .. 563E-04
800
-42 .. 749596
In this case we need to replace the rate law we used in part (c)
-r = k [c C _ Cc ]
A A B K
C
0.5
500
25
35
9.47E-05
671.87016
-42.749596
We also need an equation to calculate Kc at different temperatures.
K = K __
C CI R T.T
1
be careful of the units when entering Kcl into Polymath. Also note that the initial temperature is
different than in part (c)
We get an outlet conversion of X = 0.48
See Polymath program P8-12-d.pol.
POLYMA III Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
V 0 0 1 1
T 350 314.93211 350 314.93211
X 0.2 0.2 0.4804694 0.4804694
R 0.0083144 0.0083144 0.0083144 0.0083144
Ua 10 10 10 10
Ta 300 300 300 300
dHrx -7500 -7500 -7500 -7500
Cao 1000 1000 1000 1000
8-52

0 .. 5 0 .. 5 0 .. 5
Faa 500 500 500
Cpa 25 25 25
Cpb 35 35 35
k 5.556E-04 2.381E-04 5.556E-04
Ca 800 519 .. 53058 800
Cb 800 519.53058 800
Cc 200 200 480.46942
Kc 0.002 0 .. 002 8.63E+121
ra -300 .. 01803 -335.38132 -64 .. 253241
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(T)/d(V) = (Ua*(Ta-T)-ra*dHrx)/(Fao*(Cpa+Cpb
[.2] d(X)/d(V) = -ra/Fao
Explicit equations as entered by the user
[1] R = 8 .. 3144/1000
[2] Ua = 10
[3J Ta = 300
[4] dHrx=-7500
[ 5 j Cao = 1000
[6J v = 0 .. 5
[7] Fao = Cao*v
[8J Cpa = 25
[9] Cpb = 35
[10] k = 0.00015625*exp(2664*(1/300-1/T
[11] Ca = Cao*(1-X)
[12] Cb=Cao*(1-X)
[13] Cc=Cao*X
[14] Kc = .002*expdHrxlR)*(1/350-1/T
[15] ra = -k*(Ca*Cb-Cc/Kc)
P8-12( e) Individualized solution
P8-12(f)
For the gas phase the only the stoichiometry changes.
C = C ~ _ ) T o )
A AO l+EX T
and E= YAoJ=0.5(1-1-1) =-0.5
From Polymath we see the exiting conversion is X = 0.365
See Polymath program P8-12fpol.
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value
V 0 0
T 300 279 .3717
X 0 .. 2 0.2
To 300 300
Ua 10 10
Ta 300 300
maximal value
1
300
0.3650575
300
10
300
8-53
0 .. 5
500
25
35
2 .. 381E-04
519.53058
519.53058
480.46942
8.63E+121
-64 .. 253241
final value
1
279 .. 3717
0.3650575
300
10
300
dHrx -7500 -7500
Cao 1000 1000
vo 0.5 0 .. 5
Fao 500 500
Cpa 25 25
Cpb 35 35
k 1.563E-04 8.ll1E-05
e -0.5 -0.5
Ca 888.88889 834.06666
Cb 888.88889 834 .. 06666
ra -123.45679 -123.45679
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(T)/d(V) = (Ua*(Ta-T)-ra*dHrx)/(Fao*(Cpa+Cpb
[2] d(X)/d(V) = -ra/Fao
Explicit equations as entered by the user
[1] To = 300
[2] Ua = 10
[3] Ta= 300
[4] dHrx = -7500
[5] Cao = 1000
[6] vo = 0 .. 5
[7] Fao = Cao*vo
[8] Cpa = 25
[9] Cpb = 35
[10) k = 0 .. 00015625*exp(2664*(1/300-1/T)
[11) e = -.5
[12) Ca = Cao*(1-X)*To/(1+e*X)/T
[1.3] Cb = Ca
[14] ra = -k*Ca*Cb
P8-13
K = CCCD = X;
C CACB (1-. Xe)2
= .jK;
e 1 +.JK
c
-7500
1000
0.5
500
25
35
1.563E-04
-0.5
888.88889
888.88889
-56 .. 423752
T =To - MIRX =300- (--30000). X = 300 + 600X
CPA + C P
B
( 25 + 25)
See Polymath program pg13.pol.
Calculated values of NLE variables
-I f(x) .. ---- Guess
llxe 6 1. )
,,- T-
i IVariable IValue
,,' .. " 1""0_",,,,.,,,.
!ll! ]300.
8-54
-7500
1000
0.5
500
25
35
8.1llE-05
-0.5
834.06666
834.06666
-56.423752
2 Kc li8E+07'
.J
Nonlinear equations
f(Xe) = Xe - (1 - Xe) * Kc A 0.5 = 0
Explicit equations
1. T = 300
2 Kc = 500000 * exp(-30000 /1.987 * (1/323 - 1/ T))
T X
300 1
320 0 . .999
340 0 .. 995
360 0.984
380 0 . .935
400 0.887
420 0.76
440 0 . .585
460 004
480 0.26
500 0 . .1529
520 0.,091
540 0.035
560 0.035
8-55
Xe
1
0.9
C 0.8
o
'en 0.7
...
0.6
c FxeJ
8 0.5
. 0.4
!:!:!.. 0.3
Q)
>< 0.2
0.1
o -------------T------------,------------,-----------,--------------1---
300 350 400 450
P8-14
For first reactor,
X K
K = el. or X - c
c I-X el I+K
el C
For second reactor
B X K -B
K = C BZ
C I-X eZ I+K
eZ C
For 3
rd
reactor
K =.BB3+
X
e3
or
X _ Kc -BB3
C I-X e3 I+K
e3 C
1 st reactor: in first reaction Xe = 0.3
So, FB = F
A01
(.3)
Temp (K)
500 550
2
nd
reactor: Moles of A entering the 2
nd
reactor: F
A02
= 2F
A01
- F
A01
(.3) = 1.7F
A01
BBZ = .2F
A01
= .12
1.7 F
AO
(T -To) + FAOZX (-/ili R) = 0
X=
(CPA +BBCpB )(T -T 0)
-/ili
R
Slope is now negative
3
rd
reactor:
8-56
X
e2
= 0.3
(}B = (.2F
AOl
) + .3F
A02
= F
AOl
(.2 + .3x1.8)
Say
F
A03
= F
AOl
+ F
A02
(1- XeJ = F
AOl
+ 1.8F
A01
(1- X e2) = 1 + 1.8(1- .3)F
AOl
F
A03
= 2.26F
AOl
Feed to the reactor 3:
(2F
A01
) + .3F
A02
= F
AOl
(.2 + .3x1.8) = 0.7F
Ao1
(} = .74
B3 2.26
Feed Temperature to the reactor 2 is (520+450)12 = 485 K
Feed Temperature to reactor 3 is 480 K
Xfinal = .4
Moles ofB = .2F
A01
+ .3F
Ao
2 + .4F
A03
= F
Aol
(.2 + .54 + (.4)(2.26)) = 1.64 FAol
X = FB/3F AOI = .54
.'f

P8-14 (b)
Xe.
-
, ............ __ - 1-/13
/"
The same setup and equations can be used as in part (a). The entering temperature for reactor 1 is
now 450 K and the outlet is 520 K. When the two streams are joined prior to entering reactor 2 the
temperature is (520+450)12 = 485 K
Say that the outlet temperature for reactor 2 is 510 K. Then the entering temperature for reactor 3
would be (510+510+450)/3 = 490 K
For any reactorj,
(T-To)+ FAOjX (--MI
R
) = 0
X = ( CpA + (}B
C
pB ) (T - To)
-MIR
and 9
B
for reactor 1 = O. For reactor 2, 8
B
> O. This means that the slope of the conversion line from
the energy balance is larger for reactor 2 than reactor 1. And similarly 8
B
for reactor 3> 8
B
for
reactor 2. So the line for conversion in reactor 3 will be steeper than that of reactor 2. The mass
8-57
balance equations are the same as in part (b) and so the plot of equilibrium conversion will decrease
from reactor 1 to reactor 2, and, likewise, from reactor 2 to reactor 3.
x
P8-1S (a)
Substrate -7 More cells + Product
S-7C+P
G(T) =
To solve for G(T) we need X as a function of temperature, which we get by solving the mass balance equation.
V
_ FAOX _ FsoX rg
- --- - -- and since -rs = - then,

C
rg = jiC
c
and ji = ji(T) __ .. _5_
Ks +C
s
O.0038*Texp( 21.6-
where peT) = J4max ------
1+ex
P
(153-
if we combine these equations we get:
v =
ji(T)CcC
s
Ks +C
s
8-58

p(T)CcC
s
V=
XC
so
(1- X)
Canceling and combining gives:
Now solve this expression for X:
Now that we have X as a function ofT, we can plot G(T).
To get R(T) we must calculate the heat removed which is the sum of the heat absorbed by reactants to get to the reaction
temperature and the heat removed from any heat exchangers ..
The heat gained by the reactants = Cpo (T - To )
The heat removed by the heat exchanger = UA(T-Ta)/F
so
VA
R(T) = Cps (T --Yo)+-F-(T -Ta)
so
Now enter the equations into polymath and specify all other constants_ The adiabatic case is shown below_ The non-
adiabatic case would be with explicit equation [12] as A = 11.
See Polymath program P8-15--a.pol.
Differential equations as entered by the user
[ 1] d(T)/d(t) = 1
Explicit equations as entered by the user
[lJ mumax=_5
[2J Ycs = .. 8
[3] vo=1
[4J Ta = 290
[5] mu = mumax*( .. 0038*T*exp(21 .. 6-6700/T))/(1 +exp(153-
48000/T))
[6] Ks=5
[7] V = 6
[8] Cso = 100
[9 J Fso = vo*Cso
[10] Cps = 74
8-59
Adiabatic Case
20000 .---------------,
10000
o
-10000
-20000
-30000 __ __
294 299 303 T 308 312 317
[ 11] dH = -20000
[12] UA = 0*300
[13] kappa = UA/(Cps*Fso)
[14] To = 280
[15] X = 1-Fso*Ks)/mu*V*(Cso"2))-Fso*Cso))
[16] Gt = X*(-dH)*Ycs
[17] Rt = Cps*(T-To)+UA*(T-Ta)/Fso
Independent variable
variable name: t
initial value : 0
final value: 30
P8-1S (b)
To maximize the exiting cell concentration, we want to maximize
Non-Adiabatic Case
20000 ....----------------,
1-4000
8000
2000
-4000
-10000 __ __ __ --l
2 4 299 303 r 308 312 317
the conversion of substrate .. If we look at G(T) from part A, we see that it is at a maximum at about 310 K. This
corresponds to the highest conversion that can be achieved. By changing the values of UA and Il1c we can change the
slope of the R(T). What we are looking to do is get R(T) to intersect with G(T) at 310 K.
Since we now have a limited coolant flow rate we will use a different value for Q.
and so,
R(T) = mcCpc (T -Ta {1-exp( + Cps (T -To)
\ mcCpc
Now we set R(T) equal to the maximum value of G(T) which is 15600 Jlh
G(T) = 15600F
so
= mcC pc (T - Ta f 1- exp(- - J) + FsoC PS (T ._- To)
\ mcCpc
And now plug in the known values .. Assume the maximum coolant flow rate and that will give the minimum heat
exchange area.
15600{(100
L
) =
g hr
860
1560000 ~ . = (88800000 ~ 1-- exp
hr hr
J
VA=70415--
hrK
P8-1S (C)
-UA
[
4440000 _J_)
hr K
+ (162800 ~
hr
There are two steady states for this reaction" There is an unstable steady state at about 294.5 K and a stable steady state
at 316 K.
P8-1S (d)
Increasing To enough will eliminate the lower temperature steady state point. It will also lower the outlet concentration
of cells. Decreasing To will increase the outlet concentration of cells.,
Increasing me increases the slope of R(T) and will increase the exit concentration of cells,
Increasing T a will lower the exit concentration of cells.
P8-16 (a)
G(T) = illi R X
Tk -3 [E[ 1 1)]
X = l+Tk' T=6.6xlO exp Ii 350 - T
R(T) = cpo (1 + K)(T - Tc)
cpo = I. BPp; =BAC
pA
+B1C
pI
=20+30=50
K= VA =_8000_=2
CpoFAO (50)(80)
Tc = ToFAOC
pO
+ U A ~ = KT,,_+To =350
VA+CpoF
AO
l+K
To find the steady state T, we must set G(T) = R(T). This can be done either graphically or solving
the equations. We find that for To = 450 K, steady state temperature 358 K.
P8-16 (b)
First, we must plot G(T) and R(T) for many different To's on the same plot. From this we must
generate data that we use to plot Ts vs To.
8-61
I G('l) \S. R(1)
I 10000
i - 8000
I;
CD


__ ____
Z15 325 375 425
TOO
P8-16 (C)
425
1;,'5. T.
400
375
350
325
300
200 250 300 350 400 450 500 550
T. (X)
-----"
For high conversion, the feed stream must be pre-heated to at least 390 K. At this temperature, X =
.98 and T = 380 K in the CSTR. Any feed temperature above this point will provide for higher
converSIOns.
P8-16 (d)
For a temperature of 375 K, the conversion is .968
P8-16 (e)
The inlet extinction temperature is 375 K.
P8-17
The energy balance for a CSTR:
UA
-F XllH (T) = F ["'.e.c .(T -.r, )+--(T -.r,)]
AO Rx AO I pi 0 F 0
AO
FAOX =-'rAV
Cps isindependentofT.
Cpo (T -- To ) = C p'

F
AO
R(T) = FAOC
pS
+UAT
r
-UAT
D
"f'l' ". dR(T)
1 lerentlatmg: ---- = UA
dT
dG(T) _ -llHRx d(-rA)
dT F
AO
dT
d( -r ) E
where A = --2 ( -r
A
)
dt RT
Setting these two equations equal to each other and manipulating,
8-62
In 1.421 =[E(323-313)]
1.127 R 323 *313
E=19474
FAOC
pS
+ (T _ T ) > RT,2 ,andit will be runaway reaction
UA T a E
At A < 2 . .5 m
2
it will become a runaway.
P8-18 (a)
Mol Balance:
_ FAOX _ voC AO
X
- -r
A
-kT C
A
-C
B
/ Ke1
(:'}[(l-X)-X I K,]
X [1+rk(l+ 11 Ke)] = rk
X = rk
l+rk(I+11 KJ
G(T) = -M/ RxX = 80000X
k=lmin--
1
T=lOmin
Ke =100
X =. 10 =.901
1 + 10(1.01)
G( 400) = 72080 cal/mol
P8-18 (b)
UA = 3600 =9
10*40
R(T) = CpA (1 + K)(T -T
c
) = 400(T - Tc)
T =T
o
+KT
a
.=31O
c I+K
R(T) = 400(T - 310)
The following plot gives us the steady state temperatures of 310,377.5 and 418.5 K
See Polymath program P8-18--b.pol.
8-63
-r-----
-
1_
__ ,_-__o_--+___...:=._
390
P8-18 (C)
3 10K and 418.5 K are locally stable steady-state points
P8-18 (d)
R{418.5) = 400(418.5-310)=43400
G(418.5} = 43400 = 80000 * x
43400
x = 80000 = .54
P8-18 (e)
The plot below shows T a varied.
-
.....
......
t ....
.. '
.."'''''-''''./''.''
100:--__ .... ___ . _____ .c=.. __
m _ _ m m _
GO
-
The next plot shows how to find the ignition and extinction temperatures. The ignition temperature
is 358 K and the extinction temperature is 208 K.
8-64
...
...
1501.-----
150
P8-18 (f)
~ 5 S
. - - - - - - - ~ - - - . - . - - - . - - -
...
-
This plot shows what happens if the heat exchanger quits. The upper steady-state
temperature now becomes 431.5 K.
-
70000
-
_50000
15
,
.l!.
i
4DOOO
..
E
" 30000
20000
1DOOO
351
0
,.0
330 3IiO
TIKI
P8-18 (g)
At the maximum conversion G(t) will also be at its maximal value. This occurs at approximately T
= 404 K. 0(404 K) = 73520 cal. For there top be a steady state at this temperature, R(T) = OCT).
See Polymath program P8-18-g. pol.
8-65
VA
K=---
FAOC
pA
R(T) = CpA (1 + K)(T - TC) = 73520
T +KT
where T = 0 a
C I+K
If we plug in the values and solve for VA, we get:
VA = 7421 cal/miniK
P8-18 (h) Individualized solution
P8-18 (i)
The adiabatic blowout flow rate occurs at T = 0.0041s
V
T = 0.0041s =--
Vo
Vo = TV = 0.0041 *10
dm
3
Vo =0.041- ..
mIll
See Polymath program P8-18-i.pol.
6000
4600
321.11.1
1801.1
1 1 1 0 t l l ~
o 30 60 t 90 120 151.1
P8-18 (j)
Lowing T 1.1 or Ta or increasing VA will help keep the reaction running at the lower steady state.
P8-19
Given the first order, irreversible, liquid phase reaction:
A-7B
VA = l.Ocal! minlC
8-66
Pure A Feed = o...5g mol / mm
C = C == 2eal/ g - mol/DC
0, Po
cal
M1 R = -200 = canst
gmofA
I1C = I1C -- ilC = 0
P pA pB
E V
_ FA oX _ Vo
Designqn -----.----
-rA k(l---X)
RateLaw.. -rA = kC
A
StolchlOmetry C
A
= CAO(l- X)
EnergyBafance -UA(T -T,1)-- FA oX MR = --1'0)
Simplifying,
-rk 1
X=--=--
l+-rk 1+_1
-rk
o =F X(--M ) == F
40
(--M-!.R)_
AO R }
1+-
rk
ThIS IS the curve plotted m the prohlem statement From the equatIOn for heat generatIOn curve, we
get
X == __ = Qg
F
4o
(--MI
R
) 5*200 100
The equatIOn for heat removal curve IS
QR =FAoCp4.(T-To)+UA(T-T4)==5*2*(T--I'u)+1 O*(T-T
j
)
QR = 2T--l;-} 00
Plot thl:' along with the heat generatlon curve for vanous To This I:' shown m the figure
120 140 160 180 200 220
T fe)
The intersectlOn between Qg and QR can be used to
plepme the igmtion - extinctlOn CUlve :.hown m figure
P8-22-:2 The fOl a flJnction of mlet
temperature, To, are tabulated below.
8-67
Qg------1
I I
1- - . - T0=15O I
I 1 160 i
, ..... 0= I
1-' - To=170 I
i-- ... -TO=180 \
l
-
r
0=1901
.- -T0=200
I. - - To=210 I
L ____ ._. ___ ._--"
To (degree C) T s (degree C)
150 132
157 135, 172
160 137, 168,176
170 142.5, 167, 181
190 154.5, 165, 193.5
202 162, 199
210 204.5
P8-19 (a)
To obtain high conversion, the reactor must operate at or beyond point 14 in figure. So the
minimum inlet temperature for high conversion is To 2 202C.
P8-19 (b)
The temperature of the fluid in the reactor corresponding to temperature in part 1 is Ts > 199C
(point 14 in figure).
P8-19 (c)
The inlet temperature of the fluid is To = 202 + 5 = 207C. This will be somewhere between points
14 and 15 in figure. Once the fluid is cooled from this temperature, it will follow the line formed by
points 15, 14, 12,9, etc .. Now To = 207 - 10 = 197C. From figure, Ts = 195.5 C. From equation
(5),
Q
s
= 2*196.5-19-100 = 95 call mol
Q
R
= Q
g
= 96 cal/mol
So X = Q
g
=0.96
, 100
P8-19 (d)
Extinction temperature is the temperature corresponding to point 3 in the figure = 157 c
P8-19 (e) Individualized solution
P8-20 (a)
The following are the explanations for the unexpected conversion and temperature profiles
Case 1: Broken preheater or ineffective catalyst
Case 2: The eqUilibrium conversion was reached due to a problem with the heat exchanger
Case 3: Broken preheater or ineffective catalyst
Case 4: The equilibrium conversion was reached due to a problem with the heat exchanger
Case 5: Ineffective catalyst
Case 6: The equilibrium conversion was reached due to a problem with the heat exchanger
P8-20 (b)
8-68
The following are the explanations for the unexpected conversion and temperature profiles
Case 1: Broken preheater or ineffective heat exchanger
Case 2: Ineffective catalyst
Case 3: Broken pre heater or ineffective heat exchanger
Case 4: Ineffective catalyst
P8-21
Below is the FEMLAB solution.
1. Parameters in simulation on the tubular reactor in Problem 8-6:
Reaction: A + B ~ C
(1) operating parameters
Reactants
Inlet concentration of A C AO = 100 mol/m
3
Inlet concentration of B C BO = 100 moilln'
Inlet total flow rate Vo = 2xlO-
3
m
3
/s
Inlet temperature of the reactant To = 300K
(2) properties of reactants
Heat of reaction, t:.H
Rx
, dHrx = -41+20+15=-6 kcallmol=-25100 J/mol
Activation energy, E = 41840 J/mol
Specific reaction rate ko = 0.0IxlO-
3
m
3
/mol.s @300K
Reaction rate k = ko exp[ E ( ~ - - ) ]
R To T
Gas constant, R = 8..314 J/molK
Rate law - fA = kC A C B
Assumption:
Thermal conductivity of the reaction mixture, ke = 0,,68 W/mK
(needed in the mass halance and the energy balance)
Average density of the reaction mixture, p, rho = 1000 kg/m3
(needed in the enelgy balance)
Heat capacity of the reaction mixture, Cp = 4200 J/kgX
(needed in the energy baJance)
Diffusivity of all species, Diff= 10-
9
m%
2. Size of the Tubular Reactor
(1) Volume of reactor sized by a PFR = 0.317 m'
(2) From FEMLAB
Reactor radius, Ra = 0 .. 1 m
Reactor length, L = 10.0 m
8-69
3. Femlab Screen Shots
(1) Domain
[] Axis equal
(2) Constants and Scalar Expressions
- Constants
- Scalar Expressions
(3) Subdomain Settings
- Physics
:\ ,
[ OK ,,' !I [ cane;] [A;i ___ J
['---'''-J
j OK j Cancel Apply
'" . -, _'_'
8-70
(Mass balance)
rEquation
I Vo(-DVcA+cAu) = R, cA = concentration
I
rSubdomain
'_-13]:1
Species
Library material:
Quantity
ts
ValueJExpression Description
Time-scaling ...
D isotropic
Diffusion coefficient
D anisotropic
Diffusion coefficient
R
u
v
Reaction rate

'=::;;;;;:;;:;;;;;;;;;;;;:;;==":: r-velocity
[J Select by grou!"
z-velocity
Active in this domain
------.---J
[
Artificial Diffusion ...
. __ ._--_._-_._--
(Energy balance) __ "'"___ ._N.____ ._" _____ _____ _ ___ ,, ____ ___ ', _____ _-----.----------.---
;-Equation
i
I V.(kVT + = Q - PCpu.VT, T=temperature
;
Physics Element
Thermal properiies and heat sources/sinks
rsubdomain selection
I
library material: i.
Quantity ValueiEKpression Dllscription
01S [1
(V k (isotropic)
o k (anisotropic)
u
v
1 Time-scaling coefficient
. , Thermal conductiv!y
.........................
Thermal
Dens!y
Heat capac!y
Heat source

z.veloc!y
o Select by group
hj"O,i
Active in this domain
- Initial Values
(Mass balance) cA(tO) = cAO
(Energy Balance) T(tO) = TO
- Boundary Conditions
@ r = 0, Axial symmetry
[ .. :J
@ inlet, cA = cAO (for mass balance)
T = TO (for energy balance)
@ outlet, Convective flux
@ wall, InsulationiSymmetIy (for mass balance)
Thermal Insulation (for energy balance)
(4) Results
(Concentration, cA)
8-71
File Options Draw Physics Mesh SOlve Poslp"ocessing Mulliphyslcs Help
!. ____ _
[!] Contour: Concentration, cA
____________ R_________ _ __________________ . _____ ._
10 --------------- >--,

/

01 02 -------0-.3 -----'-0-_4------ .05"
[SNAP i
.. -'"---------------
4
03
8-72
Max: 97.38
467
378
333.361
331 344.
;.' 329 321
327 31
P8-22 (a)
Liquid Phase: A + B ---7 C
dX = -rA
dV F
AO
-r
A
=kCAC
B
k =.01*exp[- __ l )]
R T 300
C
A
= C
Ao
(l-- X) = C
B
The energy Balance:
dT _ Ua(Ta -T)+(-rA)(-Llli
R
)
dV' - F
Ao
[CPA + CpB ]
4
a=-
D
AssumeD =4
U leal x 1m
2
= .0120 cal
m
2
Ks 4.1841 lOdm
2
dm
2
Ks
Polymath program pg22a.poJ.
Calculated values of DEQ variables
valuelFinal value
i ,,1 ,. " .
i1 IV 10 0 i1000. 11000.
f r
,2 IT 1300. 1434.7779 1348.2031
'3 IX . fo '0 10.9620102 10.9620102
:4 "Ta
SR
16'E
; !
r I
17 leao
'[
;8 lea
19
;300.
11.988
,
110000.
1
1
0
.
1
10.1
:0.1
'0.01
. I .
'-0.0001
iO.
2

.1
300.
:1.988
110000.
,
l'"
1
0
.
1
1'6.003799
;0.003799
,0.01
-0.0010427
15.
15.
0.2
, ..
-6000.
...
-"t'"
;300. i300.
1.988
i
11.988
,
!10000.
1
110000.
iO.1
t .
10.1
,
10.1
", r-
iO.003799
i
101
i
l 10.003799
11.808628 iO.1018746
,-1.47E-06 i-1.47E-06
,
,
i1S. 115.
,
15.
1
15
.
10.2
10.2
1-6000.
-
.1=6000:

8-73
Differential equations
d(T)jd(V) = (U * a * (Ta - T) + (-ra) * (-Dhrl)) j (faa * (cpa + cpb))
2; d(X)jd(V) = -ra j faa
Explicit equations
Ta = 300
R = 1.988
E = 10000
caa = .1
ca = caa * (1 - X)
cb = caa * (1 - X)
k = .01 * exp(-E j R * (1 j T - 1 j 300))
ra = -k * ca * cb
cpb = 15
cpa = 15

faa = .2
Dhrl = -6000

U = .0120
500
460
420
380
340
300
0 200
P8-22 (b)
EiJ
400 V 600 800 1000
1.0
0.8
0.6
0.4
0 .. 2
200 400 V 600 800 1000
8-74
Gas Phase:A f=Z B + C
dX = -r
A
dW FAD
-fA = kjC
A
- krCBC
C
X Yo
C =C =C ---
BeAD 1+ X T
k = .133*exp[- E(J: ___ 1 )]
R T 450
k. =.2exp[E, (_I __ !)],E
r
= 51.4kJ Imol
, R 450 T
The energy Balance:
dT Ua(Ta -T)+(--rA)(-Mi
R
)
=
dW
Mi R = -40 - 50 + 70=-20 kllmol
U=5
See Polymath program P8-22-b.pol.
Calculated values of DEQ variables
.. ", ..... ,. . T ,-, ""T' ,-- - i'
:Variable! Initial value I Minimal value, Maximal value! Final value
,1 jW . :0 ""'10 150.' . " "/50.
12 ,X 10 10 10.0560855' \0.0560855
,3 T [400. /371.902 1400. IJl1.902
, 1 > 1
'4 iTO
is !k
!400. 1400. 1400.[400.
iO.133 10.0651696 ,0.133 :0.0651696
,
1
6 IvO
17 [kr
! 1"
18 IUarho
19
10jPO
llicAO
12ICA
13 Icc
14IC6
15frA
'.
20.
'0.2
:5.
b23.
11.013E+06
T
1304.6819
!
/304.6819
, ;
10
10

'-40.52269
!
Differential equations
i20.
10.0622149
,5.
!323.

11.013E+06
"
1304.6819
'292.8948
0
0
-40.52269
i d(X)jd(W) = -rA j vO j CAO
20. ;20.
,
t -
iO.2 10.0622149
,
15.
1

,
]"323.
:323.
J1.013E+06
1304.6819 1304.6819
,
!304.6819 1292.8948
117.40323 ! 17.40323

;17.40323 117.40323
1-0.2446624 1-0.2446624
8-75
d(T)/d(W) = (Uarho * (Ta - T) + rA * 20000) / vO / CAO / 40
Explicit equations
TO = 400
k = 0.133 * exp(31400 / 8.314 * (1 / TO - 1/ T))
vO = 20
kr = 0.2 * exp(51400 / 8.314 * (1/ TO - 1/ T))
Uarho = 5
;;:Ta = 323
PO = 1013250
CAO = PO /8.314/ TO
CA = CAO * (1 - X) / (1 + X) * TO / T
CC = CAO * X / (1 + X) * TO / T
CB = CAO * X / (1 + X) * TO / T
rA = -(k * CA - kr * CB * CC)
0.060
Q
0012
400
394
388
382
376
... ---.--,
0 .. 000
0

370
10 20
W 30
40 :;0 0 10 20 W 30 40 50
P8-23
First note that = 0 for both reactions. This means that MIRx(T) =
0
for both reactions.
Now strut with the differential energy balance for a PFR;
dT _ Ua(Ta - T)+ ,L lij (-MiRxij) _ Ua(Ta -T)+ 'i.c (-MiRxIC) + r
2D
(_.Mi Rx2D)
dV - ,LFjC
pj
- ,LFjC
pj
If we evaluate this differential equation at its maximum we get
dT
--- = 0 and therefore, - T) -- 'i.cMi RxIC -- r
2D
Mi Rx2D = 0
dV
We can then solve for rIC from this information.
8-76
MI
RxIC
10(325 - 500) - 0.4 (0.2) (0.5) (5000)
'ic = = 0.039
-50000
'ic = 0.039 = klCC
A
C
B
= k
lC
(0.1)( 0.2)
k
lC
= 1.95
= <ro) exp [ ! ( - ) ]
In(k
l
c(500) J
= k
IC
(400) = 7628
R
E = 15,158 cal
mol K
P8-24 (a)
See the additional homework problems in chapter 8 at for the full
solution.
,-----------------,
1
Iso1hermal: T = 321 K
RMAt\. = I, Q = 40
1
: I
I
S4-

.---"" ..
.___'..- i
- I
o -t=----,-.--,.---,---- i -l
o 02 04 06 0.8
x
-.2MIB ._-_ .... -,,2M2B -Me0H --"'TAME
P8-24 (b)
See the additional homework problems in chapter 8 at for the
equations to enter into Polymath. Then vary to see its effect.
8-77
P8-24 (c)
See the additional homework problems in chapter 8 at http://www.engin.umich.edu/-cre for full
solution
Non-Isothermal: To = 353 K, Tw = 298 K
RMIIA = 1.0, Q = 200 Llntin
7 -----------------
-
6
5
$ 4
o
.,5,3
U
2
0. -1"'"'----,.-----.- ---.------,-----1
o 0.2 0..4 X 0.6 08
P8-24 (d) No solution will be given
P8-25
Mole balance:
dF
A
--=r
dW A
dF
B
--=r
dW B
Rate Laws:
r
A
= --r
ZB
+ 'iA + ljA
rc = -r
3A
-'iA = klC
A
-r
ZB
= kBC
B
--r
3A
= k3CC
Stoichiometry:
C = C _FA'Fo
A 1 FT
1
C =C FBTO
B T FT
T
Energy balance:
dF
c
--=r.
dW C
_dT = Ua(Ta -- T) + (---'iA)( -LV! RIA) + (-r
RZB
) + (-ljA)(-LV! R3A)
dW FAC
pA
+ FBC
pB
+ FcCpc
8-78
dT = 16(500 - T) + (-ljA)1800 + (-r
R2B
)1800 + (-'3A)1100
dW 100(F
A
+ FB + Fe)
k
J
=0.5exp[2(l-320IT)]
k
J
k =--
2 K
C
k3 = 0.005 exp [ 4.6(1-460IT)]
Kc =lOexp[4.8(430IT-1.5)]
See Polymath program P8"25.pol.
"alues of variables
" r
Variable I Initial value; Minimal value Maximal value i Final value
, ,< l
""
1 iW
'2 ,fb
13
If a
4
r '
:fc
,5 IT
,6 jua
7 ITa
8 /Dhrla
9 iDhr3a
17!To
i" f
181Kc

19:k2
!201ca
i21
J
cb
'22[rla
f f
231r3a
T'
241rc
j
i25 jr2b
!261rb
i
127lra
o
.
11.
I
i1.
:0
330.
16.
500.
i-1800.
i-llOO.
'100.
,100.
1
100
.
:0.5312401
iO.0008165
12.
:2.
1330.
I

,0.1367403
1.
i1.
1-0.5312401
,
! -0.0008165
;0.0008165
1-0.1367403
I
10.3944998
,
i-0.3953164
1
0
10.9261241
I
iO.6296429
iO
330.
,16.
500.
-1800.
i-llOO.
100.
'100.
'100.
0.5312401
'0.0008165
2.
'" 12.
1
330
.
r
11.062332
10.1367403

)0.7341242
-0.5748799
-0.002138
-0.5770243
-0.0522707
-0.3953164
1.368476
i1.
1
10.2044134
1416.3069
]16.
]500.
,
1-"1800.

i100.
,
I
1
100
.
1
1100.
,
1
:0.7941566
;0.0030853
'2.
2.
;330.
3.885029
0.74756
1.
1.253213
-0.362406
] -0.0007594
;0.002138
,
!-0.1367403
,
10.3944998
, --
10.0510521
8"79
;100.
jO.9261241
10.8694625
j
10.2044134
;416.3069
:1
:16.""
500.
}
)-1800.
:-1100.
100.
<1
1100.
;100.
:0.7941566
:0.0030853
i2.
'2
I .
r """"
""p30.
:1.062332
10.74756
"" 10.6892094
Io.?341242
" ;-0.5473402
! -0.0021264
T'
10.0021264
1-0.5488019
T " --
1-0.0014617
1-0.0006647
Differential equations
d(fb)jd(w) = rb
d(fa)jd(w) = ra
d(fc)jd(w) = rc
d(T)jd(w) = (Ua * (Ta - T) + (-r1a) * (-Dhr1a) + (-r2b) * (Dhr1a) * (-r3a) * (-Dhr3a)) j (fa * cpa + fb *
cpb + fc * cpc)
Explicit equations
Ua = 16
Ta = 500
Dhr1a = -1800
Dhr3a = -1100
cpa = 100
cpb = 100
cpc = 100
k1 = .5 * exp(2 * (1 - 320 j T))
k3 = .005 * exp(4.6 * (1 - (460 j T)))
ct = 2
!U:ift = 2
= 330
Kc = 10 * exp(4.8 * (430 j T - 1.5))
k2 = k1 j Kc
ca = ct * fa j ft * To j T
cb = ct * fb j ft * To j T
r1a = -k1 * ca
[,1,;11 r3a = -k3 * ca
rc = -r3a
r2b = -k2 * cb
rb = -r1a + r2b
ra = -r2b + r1a + r3a
P8-25 (a) As seen in the above table, the lowest concentration of o-xylene (A) = .568 mol/dm
3
P8-25 (b) The maximum concentration of m-xylene (B) = 1253 molldm
3
P8-25 (c) The maximum concentration of o-xylene = 1 molldm
3
P8-25 (d) The same equations are used except that F
BO
= O.
The lowest concentration of o-xylene = 0.638 mol/dm3. The highest concentration of m-xylene =
1.09 mol/dm3. The maximum concentration of o-xylene = 2 mol/dm3.
8-80
P8-25 (e)
Decreasing the heat of reaction of reaction 1 slightly decreases the amount of E formed. Decreasing
the heat of reaction of reaction 3 causes more of C to be formed. Increasing the feed temperature
causes less of A to react and increases formation of C. Increasing the ambient temperature causes a
lot of C to be formed.
P8-25 (0 Individualized solution
P8-26 (a)
AH B+C
A-7D+E
A+C-7F+G
We want the exiting flow rates B, D and F
Start with the mole balance in PFR:
dFA
dF
B
dF
c
--=ra -=r --=r.
dV
dV B dV c
dF
E
dF
dFG
-=r
_F=r
--=r.
dV E dV F dV G
Rate Laws:
dF
D
--=r
dV D
8-81
Fe
P
e
=--Pro
FT

F[ = steamratio x .0034
Energy Balance:
dT - ( 'is /lll RIA + r
2B
/lll R2A + r
3T
/lll R3A )
dV FA *299+ FB *283+ Fe *30+ FD *201 + FE *90+ FF *249+ Fo *68+ F[ *40
Kpi =exp(b
i
+ i +b
3
In(T)+[(b
4
T+b
5
)T+b
6
]T)
See Polymath program P8-26.pol.
For TO = 800K
Calculated values of DEQ variables
value!
"... ..., .. , ...... .,. "... .... J
]2 If a 10.00344 10.002496 10.00344 iO.002,496 j
13 Ifb '10 /0 10.0008974 1o.Q()08974 I
14 IreTa 10 ' jO.0008615 10.000861S' j
15 Ifd 16 10 11.078E-05';l
i
1.078E-05 1
1 ! , . I
16 \0 jO h.078E-05 !1.078E-OSj
17' Iff "'[0 10 i3.588E-05 j3.588E-05j
Is'l1=g 1010 h.588E-05 ]3.588E-05
;9;1
1
-[' ":,i800. T1765.237 """1800'." ',1765.237 I
10TH1al1.18E+05 jl.18E+051
11IH2a .. Ti:052E+05 k052E+05T1.052E+C)sji.oS2E+05!
121 f-5.39E+04' '!-5.39E+04 [-s.39E+041-5.39E+041
nip " 12137. .,". 12137. hBl. 12137. J
,jc):41
a
.4 lO.4 J
lsll<l 10:0459123 ... 10.0196554 10.0459123 10.0196554 1
16:!988 j
., ,10.05332 [0.0542282 f
O
:c)542282 , j
j19
1
Pa 10.154838710.1104652 10.1548387 10.1104652 J
fo 10.039715510.0397155 I
tLE-07
]23 Ed ]i:991E-06 li.991E-06 ]5.16E-07
8-82
i24ire !2.991E-06Is.16E-07
f
2S
F3t--Io 10
10--
271rg 10 10
ig_0002138 -i2.481E-OS
) rb 10.0002138 12.481E-OS
: ..... !3301._ . li .. rr.ac: _ 10.0002138 12.066E-OS
. .. L 1-0.0002167]-0.0002167
Differential equations
J d(fa)jd(v) = ra
7. d(fb)jd(v) = rb
,J d(fc)jd(v) = rc
d(fd)jd(v) = rd
d(fe)jd(v) = re
;p; d(ff)jd(v) = rf
d(fg)jd(v) = rg
2.991E-06
J4.196E-06
!4.196E-06
,
14. 196E-06
!0.0002138
:0.0002138
10.0002138
'0;
1-2.948E-OS
t_.
i2.481E-OS
L
12.066E-OS
'+ ...
j-2.948E-OS
l d(T)jd(v) = -(rls * Hla + r2b * H2a + r3t * H3a) j (fa * 299 + fb * 273 + fc * 30 + fd * 201 + fe * 90 + ff
.... * 68 + fi * 40)
Explicit equations
Hla = 118000
H2a = 105200
H3a = -53900
P = 2137
l5 phi = .4
Jt. KI = exp(-17.34 - 1.302e4 j T + 5.051 * In(T) + -2..314e-1O * T + 1.302e-6) * T + -0.004931) * T)
sr = 14.5
fi = sr * .00344

Pa = fa j ft * 2.4
Pb = fb / ft * 2.4
l
re
pc-l'cjft*24
- II
r2b = p * (1 - phi) * exp(13.2392 ... 25000 j T) * Pa
rd = r2b
it$! re = r2b
r3t = p * (1 - phi) * exp(.2961 .- 11000/ T) * Pa * Pc
ll' rf = r3t
rg = r3t
rls = p * (1 - phi) * exp( -0.08539 - 10925 j T) * (Pa - Pb * Pc j KI)
8-83
rb = rls
rc = rls - r3t
ra = -rls - r2b - r3t
Fstyrene = 0.0008974
Fbenzene = 1.078B-05
Ftoluene = 3.588B-05
SS/BT = 19.2
P8-26 (b)
To= 930K
Fstyrene = 0.0019349
Fbenzene = 0.0002164
Ftoluene = 0.0002034
SS/BT = 4.6
P8-26 (c)
To= 1100K
Fstyrene = 0.0016543
Fbenzene = 0.0016067
Ftoluene = 0.0001275
SS/BT = 0.95
P8-26 (d)
Plotting the production of styrene as a function of To gives the following graph. The temperature
that is ideal is 995K
1. i=b VI. Tol
0.0023 r------:=--------.
0.0022,
C.0021 t .,/
f
0.001'
C.0:U8 i'
0.0018 T
0.001& ,.
C.OO17 i f/ .\
0.0014 -'
lOa
100
tooo
1100 1200
8-84
P8-26 (e)
Plotting the production of styrene as a function of the steam gives the following graph and the ratio
that is the ideal is 25:1
Q.OO2 --..:::=====::-___
0 .. 0019 +-
0001'
!
00017-
o OGIa-
0.0015 .... ----________ ,.j
to 20 40
P8-26 (0
When we add a heat exchanger to the reactor, the energy balance becomes:
dT = Ua(Ta -!)-('isLViRIA +r2BLViR2A +r3TLViR3A)
dV FA *299+ FB *283+ Fe *30+ FD *201 + FE *90+ FF *249+ FG *68+ F, *40
With Ta = 1000 K
Va = 100 kJ/min/K = 1.67 kJ/s/K
The recommended entering temperature would be To = 440 K. This gives the highest outlet flow
rate of styrene.
40e-3
3.2e-3
24e-3
-
fh
-
fe
1.6e-3
-
fd
-
fe
80e-4
tt
2 4
v
6 8
P8-26 (g) Individualized solution
P8-26 (h) Individualized solution
P8-27 (a)
300
241
180
120
60
10
4 v 6
8 10
8-85
Adiabatic exothermic, adiabatic endothermic, exothermic with cooling, endothermic with heating.
All the profiles show the rate of reaction dropping toward the end of the reactor.
PS-27 (b)
The non-adiabatic profiles show an increase and a decrease in temperature profile, and the adiabatic
profiles do go from increasing temperature to decreasing temperature (or decreasing to increasing).
PS-27 (c)
Figure E8-5.3 shows a decrease in temperature while the reaction rate is large because the reaction
is endothermic. Once the reaction rate drops, the heat exchanger increases the temperature profile
because the reaction is no longer removing much heat.
Figure E8-3.1 shows a steady increase in temperature until the reaction rate drops to near zero. The
reaction rate increases at the beginning of the reactor because of the increase in temperature
affecting the specific reaction rate. At too high a temperature the equilibrium constant gets vbery
small and the reverse reaction becomes more prominent and thus the rate decreases as the
temperature rises above 350 K.
PS-27 (d)
In Figure E8-1O.1, the temperature increases quickly until the reactants are used up. Then there is no
more heat generated from the reaction, and the heat exchanger lowers the temperature. Figure E8-
10.2 shows that the flow rate of A drops to about zero at about the same time the temperature
reaches a maximum. Once there is no reactant, the reaction ceases and the flow rates of the products
remains constant.
PS-2S (a)
B
a) Design equation:
Rate law:
Stoichiometry:
Energy balance:
== ,f!q,[!1.-:: T)
dV FAOC
pA
,4: = 5(7OQ.:: T
dV 5*122
Plugging those into POLYMATH gets the following program and the following
graphs. The conversion achieved is 0.36.
8-86
See Polymath program P8-28-a.pol.
POLYMATH Results
Calculated values of the DEQ variables
variable initial value minimal value maximal value final value
V 0 0
T 675 675
X 0 0
Faa 5 5
Ua 5 5
Ta 700 700
dHr -235.524 -236.01067
Cpa 0.1222 0.1222
k 0.0734336 0 .. 0734336
Caa 1 1
Ca 1 0 .. 6419118
ra -0 .. 0734336 -0 .. 3335975
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(T)/d(V) = (Ua*(Ta-T)+(ra*(-dHr)))/(Fao*Cpa)
[2] d(X)/d(V) = -ra/Fao
Explicit equations as entered by the user
[1] Fao=5
[2] Ua = 5
[3] Ta=700
[4] dHr=-231-0 .. 012*(T-298)
[5] Cpa = .. 1222
[6] k = 1A8e11*exp(-19124fT)
[7] Cao = 1
[8] Ca=Cao*(1-X)
[ 9 ] ra = -k*Ca
A
2
700
690
680
670 - - - - ~ - - - - - - - - - - - - - . -
o 2 4 V 6 8 10
P8-28 (b)
0.32
0.24
016
10 10
715 .. 55597 704 .. 76882
0.3580882 0.3580882
5 5
5 5
700 700
-235 .. 524 -235 .. 88123
0 .. 1222 0.1222
0.3658299 0 .. 243008
1 1
1 0.6419118
-0.0734336 -0 .. 1001316
_. _"_. _______ _ - - . l
2 4 V 6 8 10
8-87
Using the same POLYMATH program we were able to change the entering
temperature and come up with this graph.
r
Conversion vs temperature
I
1.2.---------...-;..-----...,
)( 1
5
0
.
8
eO.6

8
0
.
2
___ J

o 200 400 600 800
Temperature, K
1000
P8-28 (c)
Again using the same POLYMATH program, we can vary the ambient
temperature until the reaction runs away. As the following sununary table will
show the maximum temperature is 708 K.
POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
--- -0------
0 10
1()----
V
T 675 675 758 .. 02032 712.2666
X 0 0 0 .. 4862844 0.4862844
Fao 5 5 5 5
Ua 5 5 5 5
Ta 708.2 708.2 708.2 708.2
dHr -235.524 -236 .. 5196 -235.524 -235 .. 9712
Cpa 0.1222 0.1222 0.1222 0.1222
k 0 .. 0734336 0.0734336 1.6320169 0 .. 3233503
Cao 1 1 1 1
Ca 1 0.5137156 1 0.5137156
ra -0.0734336 -1 .. 078707 -0 .. 0734336 -0.0853333
P8-28 (d)
When the reaction becomes adiabatic the energy balance will then
become:
(-r X-All )
T = 1: + _ ... _A_,., __ ..,.L,
o C
pA
However, the heat of reaction is a function of temperature. This is a circular
reference, so we need to find T as a function of just X,
-231X -3.576X
T =._-"'''--_.".,,'''''--_ .. _,.,'-''''', ... -
CpAO.012X
Plugging that into POLYMATH gets the following program and graphs.
8-88
See Polymath program P8-28-d.pol.
POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value
V 0 0
X 0 0
Fao 5 5
Ua 5 5
Ta 708.2 708 .. 2
To 675 675
Cpa 0.1222 0.1222
T 675 618 .. 33416
Cao 1 1
Ca 1 0.9695163
dHr --235 .. 524 -235 .. 524
,< 0 .. 0734336 0.0054738
ra -0.0734336 -0 .. 0734336
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(X)/d(V) = -ra/Fao '
Explicit equations as entered by the user
[1] Fao = 5
[2] Ua = 5
[31 Ta=708.2
[4] To = 675
[ 5] Cpa = .1222
[6] T = (To*Cpa-231*X3 .. 576*X)/(Cpa-0.012*X)
[7] Cao = 1
[8] Ca = Cao*(1'X)
[9] dHr = -231-0012*(T-298)
[10] k= 1.48e11*exp(-19124/T)
[11] ra = -k*CaI\2
0.040 ----
0.032
0.1)24
0 .. 016
Q
0.008
0.000
0 2 4
V
6 8
P8-28 (e)
10
maximal value final value
10 10
0 .. 0304837 0 .. 0304837
5 5
5 5
708 .. 2 708.2
675 675
0 .. 1222 0.1222
675 618.33416
1 1
1 0.9695163
-234 .. 84401 -234.84401
0 .. 0734336 0.0054738
-0.0051452 -0.0051452
680 I
666
652
638
[J
624
610
0 2 4
V
6 S
When it becomes reversible with inerts the two equations that change are the
rate law and the energy balance.
-r.=\c!-; )
8-89
"-
I
10
We can use those equations in POLYMATH and the following graph is made:
Conversion vs. temperature,
reversible
1
__ J
0.8
! 0.6
0.4
8 02

o 500
Temperature
1000
There is no maximum. because the reaction is a runaway at a certain temperature
and the conversion goes to close to one at that point.
P8-28 (I) No solution will be given
P8-29
The elementary, reversible, gas phase teaCIion
Feed: F AO = Fso = 20 moVs = 1200 mol/min.
Po = 580.5 kIno! = 5.74 atm.
To = noc = 3SOOK
YAO=YBO=0.5
CAO = YAO Po = (05) (5.74 atm.) = 0.1 gmo1J1
RTo 10.082 1 attn ) (3SOOK)
\ gtmlOK
Rate conswlt: k = kl exp[f(i
1
- ill
= 0.035 exp (2j3 -i)]
:: 0.035 exp [8419.5 (2i3 -il]
8-90
A+B 2C
(1)
Equilibrium constant:
Mia (T a) = 2Hc - HA - Hs = 2(45.000) + 40,000 + 30.000 = -20.000 J/mole
ac;, = 2C?c - CpA - c;,. = 2(20) - 25 -IS = 0
SO .MiR en = constant = -20,000 l/mole
Kc=Kcl
ICc = 25,000 exp - i)]
Kc = 25,000 exp [-2405.6 i)]
k and Kc can be calc:ulatcd by equation (1) and (3) ifT is given.

CACB
CA=CA)(l-X)f
wheref=]:;}.
T
Cc=2CAQXf
Substitute CA. Ca. and Cc into Kc
Kc = 4cio X2 f2 = 4Xl
cio (1 X)2 f2 (1 - X)2
(3)
(4)
(5)
(2)
Calculate -JKc as a function of temperature from equation substitute in equation (5)
to get Xe.g. as a function ofT_ Energy balance for adiabatic condition-
9A = 9B = 1 9c = 0 To = 3SOK
Substitute: + 20,OOOX = (25 + 15) (T - 350) = T = 500X + 350
or X = 0.002 (T - 350)
Equations (3) = (4):
4X2 = 25000 exp [-2405 6 (....L _ 1
(1 - X)2 298 350 + SOOX
8-91
(6)
(7)
Xeq = 0.8667
0.85Xeq = 0.7366 = 0.7
(a) Plug flow reactor design equation:
(8)
Rate law: orA = Ic[CACa 4 ~ 1
-rA = Ie clAO f2 [(1 -X-y. - ~ ~
(9)
(10)
To evaluate the integral, we need to evaluate fOO as a function of X. This is done in the
table below:
A I!K
Kc
k f.Xl
(eqn.7) (eqn. 3) (eqn. 1) (cqn.9)
0 350 7534.8 30.96 0.0323
0.1 400 3191.1 626 . 1 2.58 x 10-
3
0.2 450 1635.9 6491.5
3.98 x 10-4
0.3 500 958.5
4.216 x 1()4 9.89 x 10-
5
0.4 550 618.9
1.949 x lOS 3.53 x 10-
5
0.5 600 429.9
6.978 x lOS 1.70 x 10-
5
0.6 650 315.8
2.054 x 1()6 1.08 x 10-
5
0.7 700 192.8
1.155 x 10
7
4.98 x 1(}-6
The integral can be evaluated using Simpson's rule for the fust six segmentS and
trapeziodal rule for the last segment.
1=[ f(X) dX '" or- [0.0323 + 4(2.58 x 10-') + 2(3.98 x 10-4) + 4(9.89 x 10.
5
)
+ 2(3.53 x 10 ..
5
) + 4( 1.70 x 10 ..
5
) + 1.08 x 1O.
S
] + DzL[ 1.08 x 1O'
s
+ 4.98 X 10-6]
1- L5x 10-
3
VPFR = (1.2 x HP)(1.5 x 10-
3
)= 180L
8-92
, Exothermic. adiabatic
T

distance down the reactor
(e) CSTR. design equation: V _ F AO XA
-rA
v= FAO
X
kcio
f1
[(l-Xf -ifC]
X 1500L X (0.1)2 (mol]
[
_ = 1 - 001"5
kf2 1200:: - . -
{l-xf = 80...x...
Kc f
2
k
1-2X + X2 4X2 = .8.QX.
Kc f
2
k
(1. ic)X2-{2+ 1 =0
Let bi = 1 - -.!...and i>2 = 2 +...&L
Kc f
2
k (11)
X = - 4b}
2b2 (12)
Nonadiabaric energy balance:
-lO--YL. x 2
m2 K x lkW Ihr 3.6 x 1()6 J
1200 mm. lOOOW x 60min x lKW.hr (T - 290) + 20000X = 40(T - 350)
min
-T + 290 + 20.000X = 40T - 14,000
T = 348.5 + 487.8 X (13)
8-93
So the procedure to calcularc X is as follows:
1. Choose increments in T and calculate X as a function of T from equation (13). This is
the value given by energy balance.
2. Choose increments in T and calculate bl and b2 from equation (11). <Kc and k can be
calculated from equation (3) and cl) rcspcaively.)
3. Calculate X. discarding X > 1 or X < O. This is the value of X given by material
balance.
4. Plot X vs. T given by equation (13) and (11) on the same graph. The intcrSeC1ion'lives
the conversion in the reactor. A typical graph looks like the fonowing: "
x
Operating paint
The aaual calculation gives: X - 0 which is the conversion in CSTR.
d) The same equations can be used except that = 20000 and To = SSOK. The
following graph shows the equilibrium. conversion for this case.
Conversion vs temperature
1
go.s
. :!O.6
!

gO.2
o
o 50 100 150 200 250 '
Temperature
The following POLYMATH program gives the PFR. volume necessary to get a
conversion of .65.
See Polymath program P829.pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
V 0 0 1. OE+08 1.0E+08
X 0 0 0.6495463 0.6495463
Fao 1200 1200 1200 1200
T 550 225.22683 550 225.22683
8-94
Cao 0 .. 064 0 .. 064
To 550 550
k 1 .. 949E+05 5.047E-05
Kc 1 .. 01E+06 1841 .. 4832
f 1 1
Ca 0 .. 064 0 .. 0547713
Cb 0.064 0.0547713
Cc 0 0
ra -798.17344 -798 .. 17344
ODE Report (RKF45)
Differential equations as entered by the user
[ 1 J d(X)/d(V) = -ra/Fao
Explicit equations as entered by the user
[1] Fao = 1200
[2] T = -500*X+550
[3] Cao= .. 064
[4] To = 550
[5] k = .. 035*exp(8419 .. 5*(1/273-1fT
[6] Kc = 25000*exp(2405.6*(1/298-1fT
[7] f = TofT
[ 8 j Ca = Cao*(1-X)*f
[9] Cb=Cao*(1-X)*f
[ 10 1 Cc = 2*Cao*X*f
[11] ra = -k*(Ca*Cb-Ccl\21Kc)
0 .. 064 0 .. 064
550 550
1 .. 949E+05 5 .. 047E-05
1 .. 01E+06 1841 .. 4832
2 .. 4419826 2.4419826
0 .. 064 0.0547713
0 .. 064 0.0547713
0.2030311 0 .. 2030311
-1 .. 503E-07 -1 .. 503E-07
The CSTR conversion can be found similarly to the equilibrium conversion. The
following graph was made to find the conversion.
Conversion vs temperature
0 .. 8f =:j
0 .. 6 r-------------_
:0.4' ~
8 ~ ::==::::_
230 280 330
Temperature
380
The graph shows a conversion of .39 at a temperature of 351.8K
e) If the reaction is left in a large enough volume it will "tuIlaway. If any of the
quantities get bigger. then it will run away even faster.
f) The ambient temperature around the CSTR has little effect on the conversion in
theCSTR.
P8-30 (a)
P8-6 is adiabatic so the radial reactor has no effect on it.
P8-30 (b)
8-95
dX -r
_=--:1..
dW
-r
A
=kC
A
1-- XL
C = C ---.Q V
A ".40
1
+X T.'
dy -a
---=""--
dW 2y
dT
_ - T)+ (-rA)(-M
R
)
- ........ ._- ._.,
dW
Since and p are unknown, we will assume that they are both equal to one.
We wIll also assume that r varies asW
5
varies.
so:
dT _ - T) +
- -
dW F"oC
iM
(
w..s )'S( T)S
U = U{lQ);' To
See Polymath program pgJOb.pol.
POLYMA Til Results
Calculated values of the DEQ variables
Variable initial value minimal value maximal value final value
W 0 0 50 50
Y
1 0.8062258 1 0.8062258
X 0 0 0.7845538 0.7845538
T 450 450 756.08452 756.08452
Fao 5 5 5 5
alpha 0,.007 0.007 0.007 0.007
Ta 300 300 300 300
dHr1 -2.0E+04 -2.0E+04 -2.0E+04 -2.0E+04
WO 0,,01 0.01 0,,01 0.01
To 450 450 450 450
E 3.14E+04 3,,14E+04 3.14E+04 3.14E+04
R 8,,314 8.314 8.314 8.314
Cao 0.2498645 0.2498645 0.2498645 0.2498645
Xl 0 0 784.55376 784.55376
y1 1000 806,,22577 1000 806,,22577
U 5"OE+04 0.9244844 5"OE+04 0.9244844
k 1 1 29.893648 29.893648
8-96
Ca 0 .. 2498645 0 .. 0320395
Cc 0 0
Cb 0 .. 2498645 0 .. 0320395
Kc 1635 .. 8981 187.88715
ra -0 .. 0624323 -0 .. 1234947
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(y)/d(W) = -alphal(2*y)
[2] d(X)/d(W) = -ralFao
[ 3] d(T)/d(W) = (U*(Ta-T)+(-ra)*(-dHr1 /(Fao*40)
Explicit equations as entered by the user
[1] Fao=5
[2] alpha = .007
[3J Ta= 300
[ 4 ] dHr1 = -20000
[5] Wo = .. 01
[6] To=450
[7 J E = 31400
[8] R=8.314
[9] Cao = 9 .. 22/(..082*450)
[10] X1 = 1000*X
[11] y1 = 1000*y
0.2498645 0.0320395
0.2333455 0.2333455
0 .. 2498645 0 .. 0320395
1635 .. 8981 187.88715
-0 .. 0220235 -0 .. 0220235
[12] U = 5*(Wol\.5/(WI\.5+ .. 000000001 1\.5*(TlTo)I\ .. 5*yl\ .. 5*(1 +X)I\.5
[13] k = exp((E/R)*(1/450-1ff)
[14] Ca = Cao*(1-X)*TolT
[15] Cc = 2*Cao*X*TolT
[16] Cb = Ca
[17] Kc = 25000*exp((dHr1/R)*(1/298-11T
[18] ra = -k*(Ca*Cb-CcI\2/Kc)
0.80
0.64
0.48
0.32
Q
20 W 30 to
P8-30 (C)
800
720
64U
560
[2J
400 - - - ~ - . - - ~ - - - - - - - - - - I
o 10 20 W 30 40 50
8-97
W = p v = p7tr
2
h = dW = 2n:prhdr
Material balance:
Taking the limit as tJ.r 0
:: (rA) 21tprh
FA = FAO (l-XA) = ar
A
= -FAO
. dX
A
_ -2milp (rA)
so. dr - FAO
or:
dXA :: _...!A..
. dW FAO
Assuming ptessure drop is negligible. The rate equation is:
-rA = [P(h _{ Pso, )2]
Pso, KpPS(h
The stoichiometry :
A+.LB=C
2
(1)
(2)
o = -0.5, YAO = 0.11 :. = YAOO = -0.055 ; ec = 0 ; Sa = t = 0.91
1- XA XA (O.91-0.5X
A
)
PsQz = PsOu ; Pso, = PsOu ; Paz = Pso,.o
1 +X
A
1 +X
A
1 +XA
Then:.r (O.91-0.SX
A
)_ xl. 1
A X
A
SOu 1-O.05SXA (l.XJ
Equation (3) is aue for X
A
< 0.05
for X
A
0.05
- fA = k(t) (4.3S>lro.22 ( 0.91-9
025
}_ 0,0025 1
1-0.05:>(0.05)
- fA = k{t) [0.848 -
8-98
(3)
(4)
Energy balance:
F AO (l:9i c;,i + X .6.C
p
) Tlr - FAo (Lei Cpi + .6.C
p
X) Tlr+Ar
+ rA W (AHR) -(2) (AA) U (r) (T-T
A
) = 0
or: F AO (rej Cp; + x AC
p
) Tlr - F AO (rej C
Pi
+ ACp x) Tlr+Ar
. + rA 2raIhp (.1HR) 1M - (2) (2xr tu) U(r} (T-T.J = 0
Taking the limit as tu -+ 0:
FAO (rei + x = -U(r) 4m (T-TA) + (-.rA) (-MIR) 2xrhp
Rearranging:
dI. = -U{r) 4m- (T-T
A
) + (-rA) (-AHR) 27trhp
dr FAO(:r9i CPi
-U(r) 1h.(T- T
A
) + (-rAl
or: .dI.. =
dW FAO{:rei CP
i
+ X acp)
Assume that: U(r) = U(ro) (.It.)1f2 ; l) = l)1-
ro
(1 +X)J..

Therefore: U(r) = U(ro} (!f-)l'\f.yn {I - O.055XA)1f2
From example 8-10. we have:
K.p = exp 1 _ 11.24] (Kp in ann-
1f2
T in OR)
[
-176008 ]
k = exp T -110.1 In T + 912.84
MiRm = -42,471 - (1.563)(T - 1260) + (1.36 x 1O-3)(T2 - i26(2)
- (2 459 x lO-7){T3 - 126(3) where AliR in Btu
. 3
8-99
(5)
(6)
(1)
(8)
(9)
l:8i Cy. = 57.23 + 0.014T - 1.788 x 1()-6 T2 (10)
Since equations (1) to (10) must be solved together as two pairs of coupled differential
equations. they must be solved on a computer. employing numerical methods such as
Runge-Kuaa. The results follow:
T
i
I
_--- 1.,0"
,;'- ..
....--- .. ..-/ ... ------..... E:
8 12 16 zo 24 '8 n
y"",.
T
---

.-'
--'
.'
.4
0."
________________
I: " .0.24 %I 12 16 ... 48 U " 60
.,
I AGO
/----------
i
T
t
,-
12110
t
lOGO X
1"0_
---
;
eoo
(J ..: 1I
.,;'
I
r.i.
a
.'
-
. ' 0 ..
I

:go
I
:
0
"
4 a 12 16 :0 44 :t n 16 .a oM 41 U 60
." l. ... j
l71
P8-30 (d)
8-100
=
dr
= J
c = c = C (1'"- X'l_!Q.
A B .'10 'T
TO
C
c
=2C
AO
X-
T
dT _ U(r)47rr(TA -T)+(--rA)(-LlliRJ
dr - F
AO
( CpA + C PB )
u=u(ro)(; )"(;,r
Now put these equations into Polymath to generate the plots.
See Polymath program P8 ..30d.pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value
---
r 0 .. 5 0.5
X 0 0
T 350 350
Ta 373 373
dHrx -2.0E+04 -2.0E+04
Fao 1200 1200
Cpa 25 25
Cpb 15 15
h 0.5 0 .. 5
ro 0.5 0 .. 5
To 350 350
E 7.0E+04 7 .. 0E+04
R 8 .. 314 8 .. 314
Cao 0 .. 1 0.1
U 33.3 0 .. 769425
k 30 .. 955933 30.955933
Ca 0 .. 1 -2 .. 608E-10
ra -3 .. 0955933 -3.0955933
ODE Report (RKF45)
Differential equations as entered by the user
[ 1] d(X)/d(r) = -2*3 .. 1416*h*ra/Fao
maximal value
------
1000
1
493.0235
373
-2 .. 0E+04
1200
25
15
0.5
0 .. 5
350
7 .. 0E+04
8 .. 314
.. 1
33.3
3 .. 398E+04
0 .. 1
2.09E-06
[2] d(T)/d(r) = (U*4*3 .. 1415*r*(Ta-T)+(-ra)*(-dHrx))/(Fao*(Cpa+Cpb))
Explicit equations as entered by the user
[1] Ta = 373
[2] dHrx = 20000
[ 3 ] Fao = 1200
[4] Cpa = 25
[5] Cpb = 15
8-101
final value
1000
1
373
373
-2 .. OE+04
1200
25
15
0 .. 5
0 .. 5
350
7 .. 0E+04
8 .. 314
0.1
0.769425
136.44189
-3 .. 125E-17
4 .. 264E-15
(6) h =.5
(7) ro =.5
(8) To=350
(9) E = 70000
(10) R=8.314
(11) Cao =.1
(12) U = 33.3*(ro/r)I\.5*(TfTo)I\.5
[13] k = .. 035*expE/R)*(1/273-1fT))
[14] Ca = Cao*(1-X)/(1+X)*(TofT)
[15] ra = -k*Ca
P8-31 (a)
Mole balances:
v = F.4.0 - I:..
-r
A
V=Fs=F
c
r
B
re
rate laws:
-r
A
= ","C
A
r
B
=k.C
A
~ C B
rc = k"C
B
Stoichiometry:
c.=F;I..
I Va To
Fa =10F
e
.5 = 0 5 ~
0.5
F;. = .025
11Fe = .025
Fe =.023
FB =.023
From this we can use two of the mole balances to solve for T
8"102
F;
=-

1 0.1
A1e-
E1
KI - KI
T=269F
P8-31 (b)
Knowing the temperature we can then solve for the Volume:
P8-31 (c)
We then need the energy balance:
- T)- - Yo)+ v[(MfR1)('iA) + Mf
R2
('iB)] = 0
Solve for A and we get:
A = 399 ft2
P8-31 (d)
In order to get multiple steady-states, the kappa, tau and feed temperature had to
be changed. l( == 0.1, 't == 0.0005 and To would be changed around.
Tlus first graph is G(T), R(T) vs T at To == 2000 of
20000 " ,--,-,,----"""'-,,---.--..,------.
15000
10000
5000 "
1000 15 0
-5000
-,10000 ..... ---,.--,-"--------.......
As can be seen there are three steady-states.
8-103
Ts vs To
1200 .
1000


800




400 4



200 ....
0
0 5000 10000
P8-32 (a)
Energy balance
To
.!L= Ual PII(r.
dW
tIT _ Ual P.(7;, - T)+(-rAX-MIR(T
R
))
dW I:..oC,..
dX -r
Mole balance: - = -4.
dW
Pressure drop: dy
dW 2y T
Rate law:
Stoichiometry: C
A
= CAo(l- XXI..}
l+X To
Evaluating the parameters:
k = ex] E (-1- _ 1.)1 = ex] 3776.7J' 2... _ 1.)1
450 T J ,. \. 450 T J
Plugging these equations into POL YMAlH we get the following plots.
See Polymath program P832a.pol.
OL YMATH Results
Calculated values of the DEQ variables
8-104
},:ariable initial value minimal value
W 0 0
Y
1 0 .. 6823861
T 450 310 .. 69106
X 0 0
U 5 5
a 0.007 0.007
To 450 450
Ta 300 300
dHrx -2 .. 0E+04 -2 .. 0E+04
Fao 5 5
Cpa 40 40
k 1 0 .. 0232094
Cao 0.25 0.25
Ca 0 .. 25 0 .. 0825702
ra -0 .. 25 -0 .. 25
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(y)/d(W) = -a/(2*y)*(TofT)*(1 +X)
[2 J d(T)/d(W) = (U*(Ta-T)-ra*dHrx)/Fao/Gpa
[3] d(X)/d(W) = -ra/Fao
Explicit equations as entered by the user
[IJ U = 5
[2] a = .. 007
[3J To=450
[4] Ta = 300
[ 5 J dHrx = -20000
[6J Fao = 5
[7J Cpa = 40
[S J k = exp(3776 .. 76*(1/450-1fT))
[9J Cao = .. 25
[101 Ca = Cao*((1-X)/(1-+X))*(T/450)*y
[111 ra = -k*Ca
1.0 ...-.=-------- -----..,
0 .. 8
0.6
IT]
- v
- X
0.4
0.2
.. - - - ~ ............. " ... "'" ... " ......................... .... ~ .................. ... ....."""
10 20 W 30 40 50
P8-32 (b)
maximal value final value
50 50
1 0 .. 6823861
450 310 .. 69106
0 .. 175758 0 .. 175758
5 5
0.007 0.007
450 450
300 300
-2.0E+04 -2.0E+04
5 5
40 40
1 0.0232094
0 .. 25 0 .. 25
0 .. 25 0.0825702
-0.0019164 -0.0019164
50U r------------
460
420
380
340
300
(I
~ - - . - . . , . - - -
10 20 W 30 40 50
From the Polymath summaty table, it is appatent that the maximum value for -rA occurs at the
beginning of the reactor.
P8-32 (c)
8-105
The maximum value for the temperature also occurs at the beginning of the reactor.
P8-32 (d)
Doubling the heat-transfer coefficient causes a decrease in the temperature, the conversion, and the
pressure drop. Halving the heat transfer coefficient casuses all three to increase.
P8-33
Mole balances
Rate laws:
V = vo(CAO -CAl
-rA
-rA =k1C
A
+k
2
C
S
-rs =k1C
A
+k
2
C
S
ru =k
2
C
S
Energy balance:
-FAO[c;,A(T -TAO) +CpB(T - TBO)] + V(rAIX.MiR1(T
R
}+ 6C
p1
(T - T
R
) + V(rA2XllliR2(TR)+6Cp2(T - T
R
})
Evaluating the parameters:
T=400K
kl =1000exp(- k2 =2000exp( -
t..Cp1 =50-20-30=0 t..C
p2
=40-30-20=-10
F
Ao
60 dm
3
vo =-=-=6000- Coo =C
AO
C
AO
.01 min
Simplifying:
CA = 't "rA +C
AO
C
s
= 't "rs +C
so
Co = 't" ro C
u
= 't It ru
171000
V=--------
20190 CA."!" 6660
We can plug those into POLYMATH and find the exit concentrations of U
and D and find the volume of the CSTR.
See Polymath program P833.pol.
POLYMA TH Results
NLES Solution
8-106
variable
Ca
Cb
Cd
Cu
V
Cao
Cbo
vo
k1
k2
tau
rd
ru
ra
rb
Value
0.0016782
0.0016782
0 .. 0071436
0.0011782
3794.94
0 .. 01
0.01
6000
6.73
1.11
0.63249
0.0112944
0.0018628
-0 .. 0131572
-0 .. 0131572
NLES Report (safenewt)
Nonlinear equations
[ 1] f(Ca) = tau*ra+Cao-Ca = 0
[2] f(Cb) = tau*rb+Cbo-Cb = 0
[3] f(Cd) = Cd-tau*rd = 0
[4) f(Cu) = Cutau*ru = 0
f{x)
-1. 472E-16
-1.472E-16
-1.154E-16
-2 .. 017E-17
1. 018E-09
[ 5] f(V) = 171 000/(20190*Ca+6660*Cb)-V = 0
Explicit equations
[1] Cao = .. 01
[2] Cbo = .. 01
[3] vo = 6000
[4J k1 = 6..73
[5] k2=1..11
[6) tau = Vivo
[7J rd=k1*Ca
[ 8] ru = k2*Cb
[9] ra = -k1 *Ca-k2*Cb
[10] rb=ra
P8-33 (a)
C
u
= .0012
C
o
= .0072
P8-33 (b)
V=3794dm
3
P8-33 (c) Individualized solution
Ini Guess
0 .. 0017
0 .. 0017
0.0072
0 .. 0012
3794
8-107
Solutions for Chapter 9 - Unsteady State Nonisothermal
Reactor Design
P9-1 Individualized solution
P9-2 (a) Example 91
The new TO of 20 of (497 OR) gives a new AHRn and T. With T=497+89 .. 8X the polymath program of example 9-1 gives
t= 8920 s for 90 % conversion.
P9-2 (b) Example 92
To show that no explosion occurred without cooling failure ..
Isothermal operation throughout (T = 17S0C)
cooling rate:
Q
r
== UAI448- 298] == 142 * 150
::: 21300 BTU/min
Maximum Q
g
at t == 0 (maximum concentration and reaction rate)
Q := k _liclQ1!!.!.Q. * V(MI )
g V2
== *' 10
6
.. 5J 19 ..
::: 15914.2 BTU/min
For all t:
Qg < Or No explosion
9-1
To show Ll}at no explosion occurs with cooling shllt down for 10 mi after 12 P .. IS
Isothermal operation for 12 hrs (at T:::: 175C)
t ==
e,, ') x
__ iL-=:: __ == 1 276
8
s
(l-x)
3 64--2x == 1276*3.64(1 x)
x:::: 0..38
Qg at t :::; 12 hrs ..
Q
"" .. )
g V &
'-" 0..000 '* 10
6
5..119
" .
= 77844 BTU/min..
Adiabatic operation for 10 min. UA:::: 0.
After 10. minutes
x == 0.385, T == 184"C
Qg :::: 10000 BTU/min.
When we restart the cooling flow rate
Q,I"",. == 21,30.0 BTlJlrnin.
Temperature will dIop to 175"C

P9-2 (c) Example 9-3
Decreasing the electric heating rate (Tedot in polymath program from example 9-3) by a factor of 10 gives a conversion
of 9.72 % at the onset temperature .. For a decrease by a factor 10 the conversion is 2,49 %. The higher conversion of a
lower heating rate is logical since the time it takes to reach the onset temperature is longer and the reactants have a
longer time to react.
P9-2 (d) Example 9-4
Decreasing the coolant rate to 10 kg/s gives a weak cooling effect and the maximum temperature in the reactor becomes
315 K. An increase of the coolant rate to 1000 kg/s gives aT max of 312 K. A big change to the coolant rate has, in this
case, only a small effect on the temperature, and because the temperature does not change significantly the conversion
will be kept about the same ..
P9-2 (e) Example 9-5
Using the same code as seen in Example 9",4, we were able to change the various
parameters. The two graphs we have show To;::: 70 and 120C, T
i
:;;;; 160 and
40C, and Caj =:: .. 1 and ,,2. Each set of parameters had a Temperature time
trajectory and a teIuperature-<:oncentration phase plane. These 31'e the four graphs.
9-2
KEY:
-T
KEY:
-Ca
KEY:
-T

19'5_OOOi

;::I5.oo0.-!-

75.000

..----

0.000
0.1iI'tlO .soo v.Q :l..zou '1 .. oot).

T
\
T
.:), ..!..
T
0.::190
!
;
1 Q.co;a
t

t
Q.ooa
.. '--i
;os-coo tiS;!i.COO 15':>.000
2:2tl.
!
-
Startup of a CSTR
1\
1'---
! .. _. --........--.----...-.................. .......
f
1.0.0CO+ };
t
H,0.::I0011
60.000 -
r
Tl =40)'
zo..,oco -1 ... --------+,-= .. __ ... -.-. ..".,.,.,..-+--.... .. ..
Q.ooo O. !lOa :. q:a::I :2. "\00 ::I. loa ".000
9 .. 3
(L;;60 t
t / ~ y . q.):;!O
_"'_1:._::._
-Ca
1
a CSTR To=120 Tl;40 Cal=.2
T
P9-2 (0 Example 9-6
Using the code flom Example 9-5, we could produce the following graphs either by changing To and finding the steady
state conversion or changing the coolant flow rate and finding the steady state conversion and temperatme. These are the
graphs of those:
0,,9 .....--......................... __ .............
0.8
0.'7
c
o 0.6
f 0.5
(1)
:> 0,4'
c:::
g 0,.3
0.2
0.1
--..
Conversion 'IS To
0""------"'"---,---.,.-----,.,...,,--,---,.- .. -,,-,,,,,,.
66 68 70 72 '74
To
9-4
------,-".,"',"---"--"'-,-
.. ~ .. .... ".... """"'t---- ......T"" ..
76 78 80 82
..... _ ........... _-_ .. _-_._-_ ............ _ ................ _._ .......... __ .... _ .. _--_ .................................................... _._--------
x vs coolant flow
1 ... -.... __ ................ -._ ............... - ..... --. . ~
0.9
0.8 ..
c 0:7
.E
0.6
0.5
co
....
Q,)
>
c
o
o
0.4
0.3 ..
0,2 ..
0.1
--_._-_ .. _ . _ .. __ .. _--
o -!---.----,------......,..., --, ......... -r------r, .. -...........-----1
o 2000
180 ... -_ .... -
u..
160 ..
140
c) 120 .
....
.a 100
a:s
M
~ 80
E 60
Q,)
i- 40
20
4000 6000 8000 10000
Coolant flow, mollh
T vs. coolant flow
---"' ...................._ ............................... __ .,-------------
--_._-_ .... __ .... _---_._--
o .. -.................. .. ...--.,.....--_ .. _ ......... ........ ..r__ .. .. ....---r-_-'--.,.....--- ......._ ....-
o 2000 4000 6000 8000 10000
Coolant flow mol/h
------_ ... __ ._---" ....................... ..
P9-2 (g) Example 9-7
The temperature trajectory changes significantly., Instead of a maximum in temperature, there is now a minimum.
The concentration profiles also change. C
B
no longer goes through a maximum and C
c
does not rise above 0 .. It also
appears that there is no maximum for C
A
..
It appears that because the reactor is kept much cooler with the increase heat transfer and lower coolant temperature the
second reaction does not occur ..
P9-2 (h) Example RE9-1
Using the code from Example RE91 we can determine the value of k. for which
the reacwi""willtall to the lower steadystate and when it becomes unstable. The
following two graphs show those points when ~ ; ; . .2 and 24 respectively. The
third graph shows what happens when To;; 65. It becomes unstable ata much
lower temperature.
9-5
KEY:
--T
t
,
1"" .:J-co-'-
1
i
1
IntE'gr al
(i.90c
P9-2 (i) Example RE9-2
t
T 0=65, 1<:c:=1
t
Using the code from Example RE9-2 ,we can change the values of kc and '1:[ and
find values that produce the lowest oscillations and the quickest return to
state and getting kc =:; 150 and L
J
;;;: L The following graph shows the result.
..... -+--..
3.:1:0(1
t
P9-2 (j) No solution will be given
P9-3
9-6
Find time to explosion
For the we assume the following:
(i) The inlet is closed. but the ourlet is not closed
(ii) Operation is adiabatic, and PV terms are negligible so that H "'" U
Equarion 8-61 reduces to:
(-611R) (-fA V}= NAC'-PA c;J
(-6HR) (kNA)": NACpA
ill. -; AHlhl'1 k(T)
d! Cp".
k ::: .53 exp (44499 (9jO - +)} / 60 min.
See Polymath program P9-3.pol
POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal
t
-0----
0
T 970 970
dH -336 -336
Cpa 0 .. 38 0.38
k 0.53 0 .. 53
ODE Report (RKF45)
Differential equations as entered by the user
[lJ d(T)/d(t) = -dH*k/Cpa
Explicit equations as entered by the user
[1 J dH = -336
[2] Cpa = .38
[3] k = .53*exp(44498*(1/970-1/T
P9-4
Mole balance:
value maximal value final value
------
2.9 2.9
1.119E+23 1.119E+23
-336 -336
0.38 0.38
4.438E+19 4.438E+19
9-7
There is no A leaving the reactor so F" :::; O. 111ere is no Bore entering the reactor
so Fao and F Q) ::: 0.. The amount of B and C leaving is equal to the reaction rate so
Fa::: VIa and Fe::: VIc' Simplifying:
== 0
dt
rf!!c := 0
dt
Rate law:
Stoichiometry:
Simplifying:
Energy balance:
Evaluate the parameteIS:
InCji ) ....
E::: 3467
k = .19 ex
p
[i1i: (4}m ...... -}) 1
tVi(400) ::8kjlmol = LVf(8(X)) = till (1 200) = MI(T)
Assume a heat capacity for A of 20 J/molK and assume there is no A already in the
reactor. We can plug these equations into POLYMATH and get this answer
See Polymath program P94 .pol
POLYMATH Results
No Title 08-11-2005, RevS I 233
Calculated values of the DEQ variables
Variable
---
t
Na
T
Fao
dHr
Cpa
initial value
-0-----
1.0E-09
400
100
-8000
20
minimal value
o
1.. OE-09
400
100
-8000
20
maximal value
100
326,,10947
801.. 376
100
-8000
20
9-8
final value
100
312 .. 51175
800
100
-8000
20
To
k
Vra
400
0.19
-1. 9E-10
ODE Report (STIFF)
400
0.19
-101.76832
Differential equations as entered by the user
[1] d(Na)/d(t) = Fao+Vra
[2] d(T)/d(t) = Vra*dHr)-Fao*Cpa*(T-To/(Na*Cpa)
Explicit equations as entered by the user
[1] Fao = 100
[2] dHr = 8000
[3] Cpa = 20
[4] To= 400
[5] k = .. 19*exp(3467/8 .. 314*(1/400-1/T
[ 6] Vra = -k*Na
NA = 326.125
400
0.3202745
-1.9E-10
400
0.319988
-100
When the flow is turned off, F AO :::: 0 and we get this graph of T and N ....
2000 1.0e9
1600
1200
Q
6.0e-10
800 t.Oe-10
400 2.0e .. l0
0
0 2 4
t
6 8 10
O.Oe+O
(I 2
4 t 6
P9-5 (a)
Mole balance :
dNa dNb
8 10
--_. = ra.V
dt
--- := fa. Vr Fha
dt
dNe
.........---- = -Ta. V
Rate law: -ra:: k(T).Ca.Cb
Stoichiometry :
Ca::: .t:!a
V
IF (t<50) nffiN (V:;;;; Yo + u.t) ELSE (V=V
o
+ 50)
dm
3
1miu
9-9
Nb
Cb :=--....
V
dt
Ne
Cc:: .-... _.
V
where Yo:;;:; 50 dm
3
, '\) = 1
Combining:
Na Nb
-- ra ;:;: k (T) .. ------
V V
k(T);:;:
.. R To T_.
where E::: 10000 cal/mol R == 1.987 callmoLK,
ko ;:;: 0.01 drn
3
/mol.min ,
To= 300 K
Energy balance:
dT _ Q. WS 'LFio.Lpi.(T-Tio)+(--IlHTX(T)).(--ra.V)
- ---------------!Ni .. (;pT--... -... -----
where Q=Ws=O
AHn: (f) == MIrx(fref) + ACp(T-Tref)
ACp = !:." Cp C'pb Cpa = 30 15 ..15"'" 0
a a
Mlrx(273);;:;; [(-41)-(-20}{15)]. lOJ =6000 cal/mol
ilHrx(f) :::: -6000 cal/mol
2:Fio.Cpi.(T-Tio) =: fl)o.(15).(T-323)
LNLCpi:::::: NaCpat f'.c'b.Cpb -+- Nc.Cpc
= 15Na + 15Nh + 30Nc
See Polymath program P9-5-a.pol

08-11-2005, RevS. 1 233
Calculated values of the DEQ variables
Va:r:iable initial value minimal value
---
t 0 0
Na 500 0.1396707
Nb 0 0
Nc 0 0
T 298 298
X 0 0
Fbo 10 0
Nao 500 500
Cbo 10 10
k 0,,0089352 0 .. 0089352
vo 1 0
V 50 50
ra 0 -0.3365379
ODE Report (RKF45)
maximal value
120
500
42.43357
499.86033
510.44411
0.9997207
10
500
10
10 .. 085112
1
100
0
9-10
final value
120
0.1396707
0.1397745
499,,86033
510.44411
0,,9997207
0
500
10
10" 085112
0
100
-1.969E--05
Differential equations as entered by the user
[1] d(Na)/d(t) = ra*V
[2] d(Nb)/d(t) = ra*V+Fbo
[3] d(Nc)/d(t) = -ra*V
[41 d(T)/d(t) = 6000*(-ra*V-(Fbo*1S*(T-323)))/(1S*Na+ 1S*Nb+30*Nc)
[5] d(X)/d(t) = -ra*V/Nao
Explicit equations as entered by the user
[1 J Fbo = if(kSO)then(10)else(0)
[2J Nao = SOO
[3] Cbo = 10
[4 J k = .01 *exp10000/1 .. 987)*(1/300-1/T
[ 5 J vo = Fbo/Cbo
[6 J V = if(kSO)then(SO+(vo*telse(100)
[7 J ra = -k*Na*Nb/(VI\2)
600.------
280
200
o
P9-5 (b)
24
48 t 72
96 120
1.0
0.8
0.6
04
0.2
This is the same as part (a) except the energy balance ..
Energy balance :
24
48 t 72
Q
96 120
dT _ Q_ .. Ws - L Fio. Cpi.(T ... Tio) .+ (--Mirx(T)), (-ra. V)
-;j;" ---." .. -.--.-... ........ ....... ~ ~ - ~ - C --::-.. -.-.-..... -.. -""-..--.. ~ -
...; lVZ. pI.
where Q :::: UA(Ta .. T)
VA;;:: 100, 'fa::::: 323
See Polymath program 1'95 b .pol
9-11
1.0 r----.-____ ......... - ......." ............. - .....--."-......... 500 r--------------,
0 .. 8 -t-t0'
0,6 380
0.0'1 320
0,2 260
72 t 108 I-t4 36 180
200 __ ____ _'___--l
o 36 72 t 108 144 180
P9-5 (C)
This is the same as part (b) except the reaction is now reversible
Rate law: -ra:::: kI(1').Ca.Cb k2(T).Cc
Combining: ''ra:::: k2
C
D.( i-)
k2(T) = koexp[ - )] where E:::: 16(X)(), R::;:; 1.987 ,
ko :::: 10 , To ::;: 300
See Polymath pIOgram P95-cIJol
0.9
P9-6 (a)
Mol balance:
.. --, ...
72 t 108 H-t
dNa
';:;;;;raV
dr
Rate law: .... ra:::: k .. Ca
dNa
-_._-;:;;;; -kNa
dt
180
500
260
200
o 36
9-12
--
72 t 108 14-t 180
But Ca.V:::: Na
Na
In--;;;;-,k.t
Nao
Na:::: Nao.e
kt
Energy balance :
where Nao:::: 0,5 x 50 == 25
dT Q- Ws- LFio.Cpi(T - Tio) + (---Mlrx)(-ra.v)
-, ::;:; "._"""--",-,-.,-,-,,,, .. ,,.,,,,-,,,,,-.,-,--.. - :::: 0
dt LNi.Cpi
Q=Ws=O
constant T
LFi.Cpi(T - Tio):::: (-AHrx)(-ra.V)
FCQ,Cpc.(T- Tio)::;:; (-Mfrx)(k.Na)
:::: )
(-Mlrx).(kNao.e
b
)
Feo =.-.'-...
Cpc.(T - Tio)
::;:; (WOO 2 x x 2 x
0.5. (l 00 - 80)
:::: 3.16 Ibis
P9-6 (b)
Av ;;; l000Btu Ilb
Nao::;:; 25 Ib/mol
Vo = 300 ft3 of which 250 if is solvent
dT
-=0
dt
Fs. Av = ::;:; (-Lllh'x) ( -fa. V)
(-AHrx). (kNao.e-
b
) 25000 x 0.00012 x 25 x exp( -.().OOO12 x 2 x 36{)O)
F s ;;; _.,_.". __ ....... ,_,0""""""" .. ", _",-,,, ::;:; _ .. , .. _--"_,,--'_""""''''''''''''''1000--''--,_ .. ..... _-_."""""""""'-.-".-.'.'.
/I."
Fs ::;:; 0.0316 Ibis
P9-7
9-13
Batch problem
Mol balance:
dX
= ra V
dt
C
' dX
00--':::: '-Ta
dt
Rate law:'
Stoichiometry :
Ca Cao(lX) :::: 0 .. 1 (l-X)
Cb := Cao( l25-X) :::: O.1(1.2S-X)
Cc =: Cao(O+X) :::: 0 IX
.t1(D = -" where E =: 100000 llmoi., R:::: 8.314 J/moLK >
ko ;::;;: 0.002/$ > To;::;;: 373 K
E::= 150000 J/mol., R == 8.314 J/mol.K,
ko :::: O.O<XX)3 Is, To ::::: 373 K
Energy balance:
where INi.Cpi =: Nao(I8iCpi + L\CpX)
L":.C"p =: Cpc Cpb -, Cpa :;: 40 - 25 "". 25 = "'10
a a
Y' Q:""" Cao (' Cbo, b Ceo -
7 01.. Cpt =" .. '-, _pa +-.---. Cpt-- __ , Cpc
Cao Cao Cao
= 25 +- 0 125
/01
25 + 0 = 56..25
L\Hrx(f) = .6Hrx(Tref) + L\Cp(T-Tlef)
::: '." 40000", lO,.(1'298)
Nao
V=="""""",
Cao
subs
(
NaO')
dT [ 40000 + 10" (T .,., 298)] ,,' ra, ,.-:;--..
""'''''''''' :::: '''' ,."",,",,. ,,,._._ ... "., ... _ ... "".... __ ... _. __ ...... ______ " .... , .. Cao.:....
dr Nao(56.25 """ lOX)
9-14
cancelling
l
( -ora)
dT r 40000 + 10. (T -298))...
." .... ,," ... = . ._. __ ."".""" .. "",," .......... ,,_ .. 0.1 __ ..
dt (56.25 lOX)
See Polymath program P9-7.pol
POLYMA Tn Results
Calculated values of the DEQ variables
Variable
t
x
T
k1
Ca
Cb
k2
Cc
ra
initial value


373
0.002
0 .. 1
0.125
3.0E-05
o
-2.236E-04
ODE Report (RKF45)
minimal value
o
o
373
0.002
0.0749517
0 .. 0999517
3.0E-05
o
-0.1344598
Differential equations as entered by the user
[ 1 J d(X)/d(t) = -ral .. 1
maximal value
10
0.2504829
562.91803
106.13627
0.1
0.125
366.75159
0.0250483
8.644E-06
[2 J d(T)/d(t) = 40000+(1 0*(T-298)))*(-ra)*(1/.1 /(56 .. 25-(10*X
Explicit equations as entered by the user
[1] k1 = .002*exp100000/8.314)*(1/373-1/T
[2] Ca = .1*(1-X)
[3] Cb = .1 *(1 .. 25-X)
[4 J k2 = .. 00003*exp150000/8 .. 314)*(1/373-1/T
[5] Cc = .1*X
[ 6] ra = -k1 *(Cal\.5)*(Cbl\.5-(k2*Cc
final value

0 .. 2504829
562.91802
106.13612
0.0749517
0.0999517
366.75083
0.0250483
1.3E-07
600 ----
0.15,..-------- ---
540
[J
0 .. 12 --.-...-.. -----..---
r-----_' ..... -.-... -
480 0.09
420
DD
0.06 - eb
c, ,
-""'- .... -.... -...-"'"
360 0.03
300
0 2 4 6
0.00

_",_',', ..
_J
8 10 0 2 4
t
6 8 10
Cc kl
Check answer: -
Ca JCi; -'ki
0.02504 tOO
'JrE'0"?07""'4:=::9;;:::;;S ';;..JO.09995 == 0.289
9-15
P9-8 (a)
Use Polymath to solve the differential equations developed from the unsteady state heat and mass balances.
See Polymath program P9-8a.pol
POLYMATH Results
No Title 0811-2005. Rev5 1233
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
Ce 0,,1 0,,1
Cs 300 43.080524
T 278 278
Iprime 0.0866522 6.499E-04
KIn 5 5
mu1max 0.5 0.5
Yes 0,,8 0,,8
mu 0.0426159 2" 912E-04
Q 0 0
Cps 74 74
Hrxn -2"OE+04 -2"OE+04
V 25 25
rho 1000 1000
rg 0,,0042616 0.0042616
Cpe 74 74
rs -0.005327 -30 .. 908876
ODE Report (STIFF)
Differential equations as entered by the user
[ 1 J d(Cc)/d(t) = rg
[2 J d(Cs)/d(t) = -rg!Ycs
[ 3] d(T)/d(t) = (O+(-Hrxn)*(rg))/(rho*Cps)
Explicit equations as entered by the user
maximal value
300
205.63558
300
333.55016
0,,3593146
5
0.5
0 .. 8
0" 1725264
0
74
-2"OE+04
25
1000
24.727101
74
-0.005327
[1] Iprime = (0,,0038*T*exp(21.6-6700/T))/(1 +exp(153-48000fT))
[2] Km = 5.0
[3] mu1max= 0,,5
[4] Ycs=0 .. 8
[5 J mu = mu1 max*lprime*(Cs/(Km+Cs))
[6] 0=0
[7J Cps = 74
[8] Hrxn = -20000
[9J V = 25
[10] rho = 1000
[111 rg = mu*Cc
[12] Cpc = 74
[13] rs=-rg!Ycs
9-16
final value
300
205.63558
43.080524
333,,55016
6.499E-04
5
0.5
0.8
2,,912E-04
0
74
-2.0E+04
25
1000
0,,0598648
74
-0 .. 074831
340.--------------------------,
326
312
298
284
60 120 t 180 240 300
0.40..---------------------------,
0 . .32
0.24
0.16
0.08\,..----
0.00 0 ::'t-
I
-
80 240 300
P9-8 (b)
300 ... --_=-----------,
240
180
120
60
o
o

W
60
---'-'-
2-40 300
40 .--------------------------,
32
24
16
8
o
o

LJ
.. -.--.-.......
60 120 t 180 240 300
When we change the initial temperature we find that the outlet concentration of species C has a maximum at To = 300
80 ---------.--
64
48
32
16
o 280
300 To 310
320 330
P9-8 (C)
Cc can be maximized with respect to To (inlet temp), Ta (coolantiheating temperature), and heat exchanger area.
Therefore, if we are to find the optimal heat exchanger area the inlet temperature and coolantiheating temperature needs
to be specified. If we take To = 310 and T a = 290 we find that the optimal heat exchanger area is an infinite amount of
area .. As A increases Cc increase without a maximum in 24 hows. Cc = 118..
9-17
P9-9
First order liquid phase, CSTR
First solve the steady state problem fin the heat exchange area A for notmal operation
T= 358 K.
Mol balance:
Co dCs
.- ......... J:\ V :::::-. __ ... =: 0
1: dt
In(}1)
== .. ---l--.. .. .. -----
...... - ........................... _ ..... _---
R.T2 R.n
8.314(323) 8.314(313)
94852 ::.: JI Inol K
k = Llex
p
[ ....... l)t"l07A Imin for T;;;:.; 358 K
8314 313 T J
Steady state solution:
CAo = 2 M::;: 2*90 "" 180 g/dm'
C
A
:;;;; 180 107.4 (0.4) CA
180
H (0.4* 101.4)
9-18
C
B
:: - ( - 440) 04 = 175 .. 9 gldm
3
Energy balance:
dT Q.- Ws- LFio.Cpi(TTio)+(-AHrx)(-ra.V)
....... -= ----.............. - ......... -.... -.-.-.--............................ _ ........ -......................... __ .... == 0
dt LNi.Cpi
Q == UA(fa - T) = (120*60)A(273-1) J/min
F AOCpA.(f - TAO) = 90000*2*(T - 313) J/min
-180000.(358313) + (250)( 44Ox200) 2
A :::: ........... _ ......... _ ............._ .. --_ ....-...... -.. ----.-.--= 22.7m
7200(273 - 358)
Use the unsteady state equations to detennine what heat exchange area A will give a
l1maway reaction.
where I Ni. Cpi = Cpsol Psol V = 2 x 900 x 200 = 360000 11K
See Polymath program P9-9 .. pol
POLYMATH Results
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
Ca 180 4.1007565
Cb 0 0
T 313 313
tau 0.4 0.4
A 22.696 22.696
k 1..1 1..1
V 200 200
ra -198 -439 .. 75367
Na 0 .. 9 0.0205038
Nb 0 0
ODE Report (RKF45)
Differential equations as entered by the user
[1] d(Ca)/d(t) = 180-Ca)/tau)+ra
[2] d(Cb)/d(t) = -ra-(Cb/tau)
maximal value
10
180
175 .. 89924
357.97719
0.4
22.696
107.23721
200
-198
0.9
0.8794962
final value
10
4.1007565
175.89924
357.97719
0.4
22.696
107 .. 23721
200
-439.75367
0.0205038
0.8794962
[ 3] d(T)/d(t) = 7200* A *(273T-(90000*2*(T -313) )+( (-250)*ra*V) )/(2*900*200)
Explicit equations as entered by the user
[1 j tau =.4
[2] A = 22 .. 696
[3] k=1.1*exp(11409*(1/313-1/T
[4J V = 200
[ 5 1 ra = -k*Ca
[6] Na = Ca/V
[7] Nb = CbN
9-19
360,-----=======1
310
A sensitivity analysis for different values of A show that a new steady state is reached
at every new A but at an increasingly higher T. The required A depends on the
definition of reactor runaway.
P9-10 (a)
X = L 8;CPi [(T - To )/(-Illi Rx)] (1)
X=1 7 T=T
f
gives
P9-10 (b)
C
A
= C
AO
(1- X) (2)
Insert (1) in (2)
(3)
For x= 1, T f = T expression (l) becomes
(4)
Insert the inverse of (4) in (3)
9-20
(5)
Remember that C
BO
is not constant here. Similar to C
A
, use equations (1) and (4)
IeicPi (T-To) _ (T-T
o
) (T-T
o
)_
C B = C BO -- C AO (_ Ml Rx) . (T - To) = C BO - C AO (Tj _ To) - C BO e B (Tj _ To) - C AO (Tj - To) -
C [eB T! -T + (To -eB 'To)]
AO T -T,
f 0
For developing -rA use
[
8 . T - T + (T, - 8 . T, )]
C =C B fOB 0_
B AO T -T,
f 0
Insert (7) and (8) in (9)
P9-10 (C)
The unsteady energy balance for a batch reactor is showed in equation 9-11.
dT Q+Ws + (-Ml
Rx
) (-rA .V)
dt'= INtCPi .
(6)
(7)
(8)
Adiabatic operation ( Q =0), neglecting W, and assuming ~ C p O gives the following using the expression for -rA:
9-21
P9-10 (d)
Put a = 1, P = 1, E>B = 3 in the equation from part (c)
P9-10 (e)
Use the reaction constant expression from the great Swedish chemist Arrhenius and develop expression from 9-lOd.
dT [(--MI
Rx
)] kC
AO
[( ) ( ( ))]
---= --"- 2 T
j
-T . 3T
f
-T+ Yo -3Yo
dt IepPi (T -T,)
. j 0
P9-10 (0
First use a plot ofT vs .. t to get To (329 K) and Tf (439 K).. Checking the concentration of species B gives E>B=3. Make a
table showing t, T, dTldt, left hand side of equation P9-10 . .7 and liT.. Plot left hand side of equation P9-10.7 vs. liT in
Polymath and use linear regression to get E from the slope and kJ from the intercept.
Regression equation as shown in Polymath:
y = aO+ al T _inverse =-8944.2 T _inverse + 17.534
Activation energy and Arrhenius constant from slope and intercept:
slope = -% => E = -8944..28.314 = -74 .. 36 kJ/mol
9-22
aD =17.534 = In( C
AO
2 = In(kl .6.7) => kl = 12100 exp17534 = 1.298.10
11
(
T-T) RYo 12100 6.7
f 0 L-.,..--'
neglect
P9-10 (g)
Follow the procedme from example 9-3 gives heat of reaction.
X=l and T=T
f
gives
-MIRx = I8
j
C
Pi
.(T-To)=(C
PA
+8
B
.CPBXTj-T
o
)
=(189.7+3.75.4. J )(439-329K)=-45.75kJlmO[
mo[K
P9-11 (a)
.
Mol balance:
dNa
' .. ' .... ::;: ra.V
dt
dX
Nao--- ='raV
dt
dNb
. __ .-.. :::;: 2. Ta. V + Fha
dt
Fba::;;: CbO.1)o= 4.1)0
dNc
.... --:::: -raY
dt
V==V
o
+1)o .t
Rate law:
- ra == k.Ca.Cb
2
Stoichiometry:
. ,

V
C
O Ne
.C = " ........_ ..
V
Energy balance:
\\ hc:re Q:= UA.(Ta - T) = 250.(390 - T)
'vis::::: 0 ::::: -55000
2:Fio.Cpi ;;;; Fbo.Cpb :::: Cbo. Do.Cpb = 4*1)0*20:::: SODa
9-23
dT 250.(290 - T) -80uu.{T -- (-55000). (-ra. V)
----- ::: -.. -. -. ---_ .. _.....,..",-_ ........"""""'".
35. Na + 20. Nb +- 75 ,vc
See Polymath program P9-11-a.pol
POLYMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
Na 50 0 .. 3324469
Nb 0 0
Nc 0 0
X 0 0
T 300 283 .. 60209
vb 1.5 1.5
k 5.0E-04 2.3E-04
V 10 10
Fbo 6 6
Ca 5 2.202E-04
Cb 0 0
Cc 0 0
ra 0 -0.0028611
ODE Report (RKF45)
Differential equations as entered by the user
[ 1 j d(Na)/d(t):::; ra*V
[2 J d(Nb)/d(t):::; 2*ra*V+Fbo
[3 J d(Nc)/d(t):::; -ra*V
[ 4 J d(X)/d(t):::; -ra*V/50
maximal value final value
1000 1000
50 0 .. 3324469
5900 .. 6649 5900.6649
49.667553 49.667553
0 .. 9933511 0.9933511
300 298.76383
1.5 1.5
5.0E-04 4.73E-04
1510 1510
6 6
5 2.202E-04
3.9077251 3 .. 9077251
0 .. 0718765 0 .. 0328924
0 -1. 59E-06
[5 J d(T)/d(t):::; ((250*(290-T)) .. (SO*vb*(T325))+(-55000*(-ra*V)))/(35*Na+2O*Nb+75*Nc)
Explicit equations as entered by the user
[1J vb:::; 1.5
[2 J k:::; .. 0005*exp((SOOO/1 .. 9S7)*(1/300-1/T))
[3] V:::; 1 O+(vb*t)
[4] Fbo:::; 4*vb
[5] Ca:::; Na/V
[6] Cb:::; NbN
[7] Cc:::; Nc/V
[8 J ra:::; -k*Ca*CbI\2
5
3
2
1
o 0
200 -ton t 600
-l
[]
800 1000
300 -..----
296
292
288
28-t
281.1
o 200 400 t 600 800 1000
9-24
1.0,------------==""'"
0,8
0.6
0.4
0.2
200 400 t 600 800 1000
T"ble ! Iterating \\ It Uo for X:::O.8 and T <403K and daily Nc " 110 mole
--'''''''-'-1 . f"-"'---__,",",,,,,,_,"-__'-""_,,,,, . -"-", .. _.",,-
~ ) T (X=O.8) t (X:O 8) Nc (X.::::Q 8) Daily Nc
dm'/min ; K 'min mol .. Nc(24*601t+30)
A flowfate of 1.5 mol B/min would produce 120 mol C/ day, with X ;;;;: 80 % and
T< 130C at all times
P9-11 (b)
If the max. coolant rate falls to 200 molimin, then it may not be prudent to assume that
the coolant leaves at the entering arnbient temperature, Ta. It should be assumed that
the coolant temperature varies spatially along the heat exchanger pipes and the
required tenn for the heat exchange would be :
Q =: l'11;:; Cp.:ool (Ta 1 - Tal) where Tal:= ambient T coolant entering
Tal = ambient T coolant leaving
Ta2 = l' - (1" - Tal).exp(-_U:4 )
rTkCpcoJ/
The reduced flowrate and hence heat exchange. may increase the reactor temperature
to approaching 130o.C, the upper limit, at conversions approaching 80 %, and so more
caution is required. The incorporation of temperature control would be prudent.
P9-12
CSTR startup
Need steady-state values at To;::::: 7 5 ~
9-25
dNa
Mol balance: -;;;-;::: F ao ...... Fa + ra.v
dCa (Cao - Ca).vo
--= - +ra
dt V
deb (Cbo - Cb)v.,
-=: +ra
dt V
dCc (Ceo- Cc)u,
--.- ra
dt V
dCM (CMO - CM)U,
--- ...-.". . __ ..... _ ..-
dt V
Fio
Cia=:-
'Va
C:ao == Faq. = 0.18157 Ib moll ft3
1)"
Cbo = .!bo = 2.2696 Ib moll ff
u..
Cco=o
CMO = . : . ~ ? . ;::: 0.22696 Ib moll ftl
v.,
1
V ;::: .... --. ..;. X 500
7.484
Fat) Fba F.tfO 80 1 noo 100. 3
Vo ;::: .-..... _- + .,_ .... - .+ ._._ ....... ;::: ---'-- + --+ ---..- :::: 440 6 ft / hr
pao pbo PMO 0.932 3.45 L54 .
Rate law: - fa;::: k.ea (Co in excess)
k = 16.96eI2.ex
p
(-i9s?1:ir460))
Energy balance:
dT Q- Ws- LFio.Cpi(T.- Tio) + (--t:.Hrx)(-ra_V)
d;- = .---................ _ .. --I)ifi. C;i--------. ...... --
9-26
Ws=o
Q = IDc.Cpcool.(Tal - Ta2) == 1000 x 18 x (60 - Ta2)
l:Fio.CpL(T Tio) == [Fao.Cpa + Fbo.Cpb + FMO.C,PM ].(f - 75)
AHrx == Btullb mol
I,..Ni.Cpi == Na.Cpa + Nb.Cpb + Nc.Cpc + NM'CPM
== 53Ca. V + 18Cb.V + 46Cc.V + 19.5CM.V
Ta2::: T- (T-- Tal).ex
J
_VA J
l1kCpcool
== T -- (T - 60) exp(
. . lOOOx18
Ta2 == T - 0.41111(T - 60)
18000(60- (T - 0.41111(T- 60)- 2275O(T -75) + (36000)(-ra.V)
-- - .. .--........... ...-.-
tIT
35Ca.V + 18Cb.V + 46Cc.V + 195Cv.V
dt
Initial conditions: To::.:; 75, T == 138.5 o:F. Ca:::: 0.03780 Cb :;::: 3.3062
Cc;;: 0.0144, eM:::: O.22691b moll ft
3
If To drops from 75 to 70 OP
P9-12 (a)
P-control only:
manipulated variable:;: lIlc
controlled variable = T
IIlco + kc.(T - Tsp)
See Polymath program 1'9 12a . .pol
POLYMA TH Results
Calculated values of the DEQ variables
where Illco = lOOOlb mollh
Tsp == 138.5 'F
kc= 10
Variable initial value minimal value maximal value final value
tOO 4 4
9-27
Ca 0.03789 0.03789 0 .. 0584442
Cb 2 .. 12 2 .. 12 2 .. 1423214
Ce 0 .. 143 0 .. 1227539 0.143
Cm 0.2265 0.2265 0.226519
T 138.53 125 .. 70694 138 .. 53
I 0 -39 .. 636625 0
FaO 80 80 80
TO 70 70 70
V 66.809193 66 .. 809193 66 .. 809193
Tsp 138 .. 5 138 .. 5 138.5
UA 1.6E+04 1 .. 6E+04 1.6E+04
Tal 60 60 60
ke 10 10 10
k 24.990212 13.770535 24 .. 990212
FbO 1000 1000 1000
FmO 100 100 100
meO 1000 1000 1000
ra -0.9468791 -0.9468791 -0.7913918
NCp 3372 .. 5882 3372.5882 3385 .. 3399
ThetaCp 284.375 284.375 284.375
vO 441 .. 46403 441.46403 441 .. 46403
CaO 0 .. 1812152 0.1812152 0 .. 1812152
CbO 2 .. 2651902 2 .. 2651902 2 .. 2651902
CmO 0.226519 0.226519 0.226519
tau 0 .. 1513355 0 .. 1513355 0 .. 1513355
X 0.7909116 0 .. 6775218 0.7909116
me 1000 .. 3 872 .. 17351 1000.3
Ta2 106 .. 23674 102 .. 00022 106.23674
Q
8.325E+05 6.594E+05 8.325E+05
ODE e ~ o r t {RKF4S}
Differential equations as entered by the user
[1] d(Ca)/d(t) = 1/tau*(CaO-Ca)+ra
[2J d(Cb)/d(t) = 1/tau*(CbO-Cb)+ra
[ 3 J d(Cc)/d(t) = 1/tau*(0-Cc)-ra
[4J d(Cm)/d(t) = 1/tau*(CmO-Cm)
[5] d(T)/d(t) = (Q-FaO*ThetaCp*(T-TO)+(36000)*ra*V)/NCp
[6j d(I)/d(t) = T-Tsp
Explicit equations as entered by the user
[11 FaO = 80
[2] TO = 70
[3] V = (1/7484)*500
[4] Tsp = 138.5
[ 5 ] UA = 16000
[6j Ta1 =60
[7] kc= 10
[8J k = 16 .. 96e12*exp(-32400/1 .. 987/(T +460))
[ 9 1 FbO = 1 000
[10] FmO= 100
[11] mcO = 1000
[ 12] ra =k*Ca
[13] NCp = Ca*V*35+Cb*V*18+Cc*V*46+Cm*V*19 .. 5
[14] ThetaCp = 35+FbO/FaO*18+FmO/FaO*19 .. 5
[15] vO = FaO/0.923+FbO/345+FmO/1 .. 54
[16] CaO = FaOlvO
[ 17] CbO = FbOlvO
[18] CmO = FmO/vO
[19] tau = V/vO
[20] X = (CaO-Ca)/CaO
[21] mc=mcO+kc*(T-Tsp)
[22] Ta2 = T-(TTa1)*exp(-UA/(18*mc))
9-28
0 .. 053671
2.1376461
0.1275442
0 .. 226519
128 .. 49299
-39.636625
80
70
66.809193
138.5
1.6E+04
60
10
15.702753
1000
100
1000
-0.8427832
3383.2355
284.375
441.46403
0 .. 1812152
2 .. 2651902
0.226519
0.1513355
0.703827
899.92991
102.98479
6 .. 963E+05
[23] Q = mc*18*(Ta2-Ta1)
140 1100
136 1040
132
E!J
980
Q
128 -
920
124 860
120
0.0 0.8 1.6
t
2,4 3.2 4.0
800
0.0 0.8 1.6
t
2.4 3.2
P9-12 (b)
I-control only : manipulated variable ::: . ~
controlled variabLe::: T
kc
mc:::mc ... +-]
1.1
dI
-: (T-Tsp)
tit
See Polymath program P912b.pol
where IDeo::: 1000 Ib mollh
kc ::: 10. 'tI::: 1
Tsp= 138_5 ~
4.0
10001,.,...,---------------,
---
940
880
[mJ
820
760
110 - - - ~ - - - ~ -
0.0 0.8 1.6 t 2.4
700
3 .. 2 4 .. 0 0 .. 0 0 .. 8 L6 t 2.4 3.2 4.0
P9-12 (C)
PI-control only: manipulated variable == me
controlled variable = T
kc
rrk == meo + kc(T - Tsp) + .. - I where nlco:;;:;: 1000 Ib molfh
'tl
kc ;;;; 10, 1:1 :;;:;:1
dl
_.,' ... = (T - Tsp)
dt
Tsp ;;;; 138. 5 "F
See Polymath program P9-12c.pol
1-'10,.-------'----, 1100
1020
132 9-'1U
128 860
12-'1 780
120
0.0 0,,8 1.6 t 24 3 .. 2 -'10
700
0,0 0,8
1.6 t 2.4 32
---,------,----
P9-13
Mol balance:
dCa (Cao .... ,. Ca)
-,- ,,_._ .. --+ ra
dt !
Cao ::: 0 . .1 kmollm
3
Cao :::::: 0.1 mol/dm
3
deb (Cbo-- Cb)
--""- = '--'_.'."'''''''''.-'''''''''-' -+ ra
Cbo= Cao
dt 1"
dec _ (0- Cc) "
-. _ .. - -,-----, ...... ra
dt t
1:;;;; 50 s
Rate law: ,',' ra ;;;; k.Ca.Cb
k(T) ;;:;; 0.01 1 __ ..
L 1.987 300 T
930
-'1.0
Energy balance:
dT Q - ....... L Fio, epi(T - Tio) + C,-t:JirxX-ra. V)
'dr" = .------.--...... Cpj---,--------------
V == VI) 't :: 2 x 50 == 100 dm
3
Fao:: Cao . 1)0 = 0.1 x 2 =.:: 0.2 molls:: Fbo (equimolar feed)
LFio.Cpi.(r - Tio) = 2 x 0.2 x (15)(r - 300) = 6(T- 300)
tJfrx(f) = Lllirx(To) + ACp.(T - To) but ACp;;;: 0
= - 41000 - (- 20000) - (-. 15(00)
= .' 6000 cal/mol
f!T 300) + (6000).( -ra. V)
dt 15.Ca.v+ 15.Cb. V +30.Cc. V
No control: See Polymath program P913 .. a.po!
POL YMA Til Results
Calculated values of the DEQ variables
Variable initial value minimal value
t 0 0
Ca 0,,001 1.027E-04
Cb 0,,001 1.027E-04
Cc 0 0
T 300 300
V 100 100
k 0.01 0.01
ra -1" OE-08 -0.0088037
ODE Report (RKF45)
Differential equations as entered by the user
[1 J d(Ca)/d(t) = .1-Ca)/SO)+ra
[2] d(Cb)/d(t) = .1-Cb)/SO)+ra
[3 J d(Cc)/d(t) = (-Cc/SO)-ra
maximal value
400
0.0732572
0.0732572
0.099864
2.574E+05
100
1.893E+05
-1.0E-08
final value
400----
1.027E-04
1.027E-04
0,,099864
2.574E+05
100
1.893E+05
-0.001998
[4 J d(T)/d(t) = 6*(T'300+(6000*(-ra*V)))/(1S*Ca*V+ 15*Cb*V+30*Cc*V)
Explicit equations as entered by the user
[1] V = 100
[2] k = .01*exp10000/1 .. 98'7)*(1/300-1rr
[3] ra = -k*Ca*Cb
9-31
300000
2-40000
rn
.. ell
180000
- Cc
120000 .
60000
0.00
0 80 160
t
240 320 400
0
0 80 160 t 240 320
Tbe results without control, indicate a runaway reaction, as T continues to increase
after the concentrations have approached their steady-state values
Control aspects: assume that the operating T should not exceed 550K, the
boiling point of the liquid.
Without given data for beat exchange:
Try
P-control
manipulated variable::::: Tio (iulet feed T)
conuolled variable::::; T
Tio::;: IF (T<550)'I1IEN (300) ELSE (Tioo +- kc.(f - Tsp))
where Tsp:::: 550 K, Tioo:::: 300 K, kc =-10
Tio rnanipuJation not feasible fc)[ T control for
any kc (requires Tio .. 2000 K)
See Polymath program P913-b.pol
8001'----------------,
700
600
500
400
300 L-_""""'==-__
o 80 160 t 240 320 400
Try
manipulated variable::::: Va (inlet volumetric flowrate)
controlled variable::::: T
9-32
400
P-control
Uo :::: IF (T <550) THEN (2) ELSE ('0
00
+ kc.(f '- Tsp
where Tsp :::: 550 K, U
OO
:::: 2 dm
3
, kc :::: 10
See Polymath program P9-13-c.pol

540
480
420
360
300 __ __
o 80 160 t 240 320 400
P9-14 (a)
CSTR startup
Initial conditions: To:::: 75, T = 138.5 "f. Ca::: 0.03780 , Cb:::; 2.12
Cc::: 0.0144, eM:::: O.22691b mol f ft3
If T drops froIn 138.5 to 133.5 OP
As in P9-12B except:
dCa Fao- Ca. Va
.. ---- = -----. + ra
dt V
Fao 1000 100
Va ::::: ......... , .................. f .. --"' ..._- .+ ... _-
0.932 3.45 1.54
dT 18000(60- (T 0.41111(1'- 60) -(35Fao + 19950).(1'-75) + (36000)(-ra. V)
.--- :::;:;:: "., .. ............................ -...-.. "-.--.. ....----.-....................... '"" ..,-_., ._. __... ,,_._ ...... --_ ..._ .. _. __............. .. ,,- -. ..- .............. _"._--. -----
dE
35Ca. V+ 18Cb. V + 46Cc..1' + V
I-control only:
manipulated variable = Faa
controlled variable = T
Icc
Fao = Faoo+-I where Faoo::::; 80 Ib roollh.
11
say kc = -0.2 ) 'tt ==
9--33
dI
- :::: (T - Tsp)
dt
Tsp = 138.5 OP
See Polymath program P9-14-a pol
POLYMATH Results
Calculated values of the DEO variables
Variable
t
Ca
Cb
Cc
em
T
I
FaOo
TO
V
Tsp
UA
Tal
ke
k
FbO
FInO
meO
ra
NCp
FaD
ThetaCp
vO
CbO
CmO
tau
CaO
me
Ta2
Q
X
initial value
o
0.03789
2.12
0.143
0.2265
138.53
o
80
70
66.809193
138.5
1.6E+04
60
0.2
24.990212
1000
100
1000
-0.9468791
3372.5882
80
284 375
441 .. 46403
2.2651902
0.226519
0.1513355
0.1812152
1000
106.24535
8.324E+'05
0.7909116
ODE Report (STIFF)
minimal value
o
,,27 .. 922973
2.12
' .. 1. 7469378
0.2265
17.999228
-307.34656
80
70
66.809193
1385
1.6E+04
60
0.2
0.0260082
1000
100
1000
-0.9468791
3372.5882
-534.4229
-3993.8255
,,224.21625
-183,_ 76896
-18 376896
-12 277456
--118 36922
938.55771
34 .. 305432
--4.341E+05
-65.857622
Differential equations as entered by the user
(1) d(Ca)/d(t) = 1/tau*(Cao-Ca)+ra
(2) d(Cb)/d(t) = 1/tau*(Cbo-Cb)+ra
[3 J d(Cc)/d(t) = 1/tau*(Q-Cc)-ra
[4] d(Cm)/d(t) = 1/tau*(Cmo-Gm)
maximal value
4
0.0898852
95.168593
0.143
9.3421656
138.53
o
80
70
66.809193
138 5
1.6E+04
60
0.2
24.990212
1000
100
1000
0.723285
5.574E+04
80
9.686E+04
441 46403
364.28299
36.428299
24.337453
61.10206
1000
106.24535
8.324E+05
12.667586
[5] d(T)/d(t) = (-Q-FaO*ThetaCp*(T-TO)+{-36000)*ra*V)/NCp
[6 J d(I)/d(t) = T-Tsp
final value
4
-27 922973
95.168593
-1.7469378
9.3421656
17.999228
-307.34656
80
70
66.809193
138.5
1 6E+04
60
0.2
0.0260082
1000
100
1000
0 .. 723285
5.574E+04
-534.4229
-2.3299873
-224 21625
-4.45998
-0.445998
-0.2979677
2 3835154
938.55771
34.305432
-4.341E+05
12.667586
150 -----.----,-----.--
144
138
132
126
120
0.0 08 1..6 t 2.4
3.2
914
4.0
[10] FmO = 100
[ 11] meO = 1000
[12] ra = -k*Ca
[13] NCp = Ca*V*35+Cb*V*18+Cc*V*46+Cm*V*19,5
[14] FaO = FaOo+(kc/,,1)*J
[15] ThetaCp = 35+FbO/FaO*18+FmO/FaO*19.5
[16] vO = FaO/0.923+FbO/3.45+FmO/1 ,,54
[17] CbO = FbO/vO
[18] CmO = FmO/vO
[19] tau = VivO
[20] CaO = FaOlvO
90
88
86
[21] mc = mcO+kc*J
""""---.--...-----
[22] Ta2 = T-(T-Ta1)*exp(-UA/(18*me))
[23] Q=mc*18*(Ta2-Ta1)
[24] X = (CaO-Ca)/CaO
P9-14 (b)
Tal = 55P
84 .
82
80
0.0 0.8 1.6 t 2.4
I-control onl y :
nUl11ipulated variable ;;::: To
controlled variable::::: T
To;;::: Tooo + - ~ ~ 1
where Too = 75 OP ,
say kc,:;:; ,0.2. 't'I = 0.1
dl
dt ::::: (T - Tsp) Tsp;:: 138.5 OP
See Polymath program P9-14-b.pol
150 85
144 82
138 79
132 76
126 73
120 - - - ~ - - ~
0.0 0.,8 1.6 t 2.4 3.,2 4.,0
70
01) 08 L6 t 2.4
P9-14 (C) No solution will be given
P9-15
9-35
3.2 4.0
3.2 4.0
ammonium nitr'ate
A
nitrous oxide
B
stearn
C
Feed, rno = mao +- meo ;;;;;: 0,,83 mo + 0.17 mo (rnco =:: 17% liquid water in feed)
Mol balance:
dfllfa
.. _-:::;; mao" 0 "I- l'a. V
dt
Ma == Ib A, mao = lblb A
dMb
.. _ .. _. :::: 0- mh, rQ" V
dt
(
b "\
leaving: m};;;::: mao. Gb t,;; X )::::: mao; Sb:::: 0, b/a::;;:: 1
(X;;;;; 1, i.e. all of A entering reacts, but there is some initially inside)
dlvlc
."'-.. :;:;;: mea- me -- 2. ra. V
dt
leaving: me:::: mao. ( 6t + x) :;:;;: mea + 2mao ; e .. .;;t;(}, cia;;;;: 2
assuming all water entering with the ammonium nitrate leaves as steam.
Rate law: -ra. V :;:;:; k.Ca. V ::::: k.Ma
(
0 -''') Ln':))
5.03.
1 1
R,T2 R.n 1.987(560+460) 1.987(510+460)
=:: 88500 Btu Ilb mol
Energy balance :
aT Q- ')' mio .. Cpi(T, Tio) ." .. , meo. Hio)-+- (--Mlrx)( -"'la. V)
d;' = --, .. --"-.. ....... ,-.. ,.--- I. ... " ............. " ... _.
where Ws=o
Q = UA.(Ta - T)
9-36
Imio.Cpi.(T Tio) == mao_CpaCT - Tio)
::::: 0.83 x 310 x 0.38 x (T - 200)
mco.(Hi - Hio) =:: mco.[Hg(T)* HI (Tio)]
=:: 0.17 x 310 x [(1202 + 0.47(f - 500)) - 168J
assumes all liquid water in feed leaves as steam.
Hg(T);;:; Hg(Tref) + Cpc.(T - Tref):::: 1202 + OA7.(T 500)
HI (200);;;:: 168 Btu fIb
2:MLCpi ;::; 0.38 Ma + Cpb.Mb + 0.47 Me
From ChemCAD m physical properties systems:
Cpb (N,O. 516"F) = 1065 J/kg.K. (10
1
55 Btu ). ( 0.454 :J ~ . )
::: 044 Btullb N
2
0, K
P9-15 (a)
att=:O Ca=:5001b, T=516OP
dT 10000.(515- T) ,97..77(1' -, 200) ...... 52.7[(1202 + 0.47(T.,- 500) 1681 +- 336.(-ra V)
"'" .. ., ... .. :;;:;::: .... .... ,., ., .................. , .......... " ......... - ..... " ............ -,-... ~ - , - ......... -...... "' .............. .,..................... , ... , ....... , .. , ...... __ ....... _ ... , ................... _ ..__ .._ ..... _ ..._ ....... _ .. _ ..... _ ................... .
dt OJ8Ma -jOA4.Mb + OA7Mc
See Polymath program P9, IS-a. po]
POLYMATH Results
Calculated values of the DEQ variables
Variable
---
t
Ma
Mb
Mc
T
mco
mao
k
r'aV
rob
mc
initial value
o
500
o
o
516
52.7
257.3
0 .. 7028594
-351..4297
257.3
567.3
ODE Report (RKF45)
minimal value
---
o
399.06704
o
o
514.15817
52.7
257.3
0 .. 6447579
-366.56963
257.3
567.3
Differential equations as entered by the user
[1] d(Ma)/d(t) = 31 0*. 83+raV
[2] d(Mb )/d(t) = -mb-ra V
[3] d(Mc)/d(t) = mco-mc-2*raV
maximal value
10
500
100.93296
201.86591
517.83877
52.7
257.3
0 .. 7677849
-257.30162
257.3
567.3
final value
10
399 .. 06704
100.93296
201.. 86591
514.15817
52.7
257.3
0.6447579
-257 .. 30162
257 .. 3
567.3
[4] d(T)/d(t) = ((1 0000*(515-T))-(99 .. 77*(T200))-(52.,7*(1202+(.47*(T-500)))-168)+(336*(-raV)))/(.,38*Ma+.44'
Mb+.47*Mc)
Explicit equations as entered by the user
[1] mco = 310*.,1]
[2 J mao = 310*.83
[31 k = .,53*exp(44540*(1/970-1/(T +460)))
9-37
[4 raV = -k*Ma
[5 mb = mao
[ 6 me = meo+2*mao

S17
S16
S16
515
514
0
'------. --
2 4
P9-15 (b)
6
t
8
lJA = 10000 Btu lh.ft2
10
soo ,------------------------,


380
340
300
o 2 4 t 6 S 10
P-{:ontrol only: manipulated variable;:: Ta
controlled variable = T
Ta:;;;;; Tao + kc.(T - Tsp)
where Tsp == 516 of, kc = -.5, Tao == 97.5 == 515
See Polymath program P9J5-b pol
SOO
460
420
380
--..._-.._., ........._._ .....................
340
SIS.60
0 2 S
300
10 0 2 4
t
6 4 t 6 8 10
P9-15 (C)
9-38
UA :::: 10000 Btu lh.ft2
PI-control: manipulated variable :::: Ta
controlled variable:::: T
7'0.:::: Tao+kc.(T,-Tsp)+ kr:...I
1J
dI
-' ::::(T-Tsp)
dt
where Tsp;;;: 516 OPt kc;;;: -5, 'tI =:- 1. Tao = 975 ~ = 515 OP
See Polymath program P915c,.po]
516.20.-----------------, 500
516.12 460
516.04 420
515.96 380
51588 340
515.80
0 2
300
10 0 2
- - ~ - - - - - ~
4 t 6 8 4 t 6
8
P9-15 (d)
UA;;;: 10000 Btu lh.ft
2
PI-control1oop 1 : manipulated variable = Ta
controlled variable:::: T
kcl
To. = Tao + kcL(T - Tsp) +--.11
1:11
dll
-=(T-Tsp)
dl
where Tsp = 516 <>p, kcl = -5, crd ;:;;; 1. Tao;:;: 975 oR;:;;; 515 ~
PI-cOIlu'olloop 2 : manipulated variable;:;;;; mao
eontmlled variable == M (= Ma + Mb + Me)
9-39
10
kc2 I"
mao ;;;;; maoo + kc2 .. (1\.1 - Jyfsp) ......
t/2
dI2
= (Ivf - NIsp)
dt
where Msp::::: 500 Ib
1
kc2::;: 25, 't12:::: I, maoa :::: 310 Iblh
See Polymath program P9-15-d.pol
516.20...--------------,
516.12
51604
10
515.80 L-___ __
o 2 4 t 6 8
P9-16 (a)
Plot R(T) vs G(T):
R(T) = U.4(T ,,-1:) + fJVoCp(T ....
G(T) =
500
460
420
380
340
300
0 2
Evaluat.e the parameters in those equations:
k = 2 * 7.08;;: lOti exp( -30{}OOI 1.9871 T)
MI RX ;;;;; -30000 BTU Ilbmol
p ::::: 50lb I .ftJ
[IA:;:: 150'* 250;;;;; 37500
See Polymath program P9-16-a pol
POL YMA TH Results
Calculated values of the DEQ variables
Variable initial value minimal
t 0 0
T 520 520
value
dHr -3 .. 0E+04 -3 .. 0E+04
V 48 48
Caa 0 .. 5 0.5
va 400 400
VA 3.75E+04 3 .. 75E+04
maximal value
140
660
-3.0E+04
48
0 .. 5
400
3 .. 75E+04
9-40
4 t 6
final value
140
660
-3 .. 0E+04
48
0.5
400
3.75E+04
8 10
Ta 530 530
rho 50 50
To 530 530
E 3.0E+04 3.0E+04
k 0.3478362 0.3478362
tau 0.12 0.12
Ca 0.479966 0.0241085
Cp 0.75 0.75
Gt 2.404E+05 2.404E+05
Rt -5.25E+05 -5.25E+05
ODE Report (RKF45)
Differential equations as entered by the user
[ 1] d(T)/d(t) = 1
Explicit equations as entered by the user
[ 1] dHr = -30000
[2] V=48
[3] Cao = ,,5
[4] vo = 400
[5] UA = 250*150
[6] Ta=530
[7] rho = 50
[8] To=530
[9] E = 30000
[10] k=2*7.08e11*exp(-E/1.987/T)
[11] tau = Vivo
[12] Ca = Cao/(1 +tau*k)
[13] Cp = .75
[ 14] Gt = -dHr*V*k*Ca
[15] Rt = UA*(TTa)+rho*vo*Cp*(T-To)
P9-16 (b)
530 530
50 50
530 530
3.0E+04 3.0E+04
164.49672 164.49672
0 .. 12 0.12
0.479966 0.0241085
0.75 0.75
5.711E+06 5.711E+06
6.825E+06 6.825E+06
7.00E6 ,.---------------...,
1- G;T) 1
- Rn
5.40E6
3.80E6
2.20E6
6.00E5
-1.00E6 __ ___
520 548 576 T 604 632 660
From part (a), we find the concentration and temperatures at the points where G(T) and R(T) intersect.
(., - 04'15 T = 547.t<'R
;/\ - .-
C
::: 0.319 T::: 57L3R
A .
CA,= 0.068 T::: 628.6R
The extinction temperature is To = 506R. At this point R(T) is tangent to G(T) at the upper steady state.
P9-16 (C)
Using the unsteady-state equations for a CSTR we get the following
Mole balance:
= CAO ..... <:A} _ kC
A
dt V
Energy balance:
See Polymath program P9-16-c . .pol
9-41
,?Ol:-YI\llp'TH Report
Calculated values of DEQ variables
"" ""'''''r'' """1'''' """'''' ;'i
, ,Variablellnitial valuelMinimal value I Maximal value/Final value
'ifi"-"lo ,,","'," '1'6"'16. "" '16. "
1 <
[21Ca 10.4290427
J638.1791 ,j547.0711
A ICaO '0.5 0.5 10.5
'5 {FaO '200. ,200. '[200.
J
6 ITO
;J JAr
IR
"lu
14iE
15/k
16hau
: 17;rA
i18
J
delH
I
i19lNao
"f' ,
120 lCpa
i530.
11.416E+12
11.987
1
150
.
1250.
1400.
530.
j48.
j3.0E+04
151.27669

;0.12
!-3.491943
j-3.0E+04
124.
175.
Differential equations
1.416E+12
j 1.987
;150.
i250.
I
1400.
1
530
.
148.
i3.0E+04
1.165967
:0.12
-3.971954
-3.0E+04
24.
'75.
d(Ca)jd(t) = rA + CaO j tau - Ca j tau
'530.
! 1.416E+12
i
! 1.987
1150.
,
1250.
1400
i .
'530.
'48.
13.0E+04
!75.24179
.
:0.12
-0.4433316
'-3.0E+04
24.
l530.
11.416E+12
'11.987
t
1
150
.
I "
1
250
.
:400.
:530.
148.
,
r
!3.0E+04
11.463353
10.12
[-0.6223844
i-3.0E+04
24.
;75.
121 d(T)jd(t) = (U * A * (Ta - T) - FaO * Cpa * (T -, TO) + (rA * V) * delH) j (NaO * Cpa)
Explicit equations
CaO = 0.5
2;1 FaO = 200
3/F TO = 530
Ar = 1.416 * 10 A 12
R = 1.987
U = 150
"7 A = 250
vO = 400
Ta = 530
'fijj V = 48
9-42
E = 30000
1'4) k = Ar * exp( -E / R / T)
tau = V / vO
rA = -k * ca
delH = -30000
,16
1
NaO = CaO * V
""""""d
Cpa = 37.5 * 2
0.5
0.'1
0.3
0.2
0.1
IV
0.0 0
O. 1.2 204 t 3.6 48
When the upper steady state is used as the initial conditions, the unsteady-state mole balance shows that this steady state
is actually unstable. The concentration increases and the temperature drops to the lower stable steady state.
P9-16 (d)
When To or Ta is increases slightly, the upper steady state becomes stable .. At these elevated inlet and coolant
temperatures, the lower steady state is no longer stable.
P9-16 (e)
Starting at the lower steady state, if To is increased to 550 OR, the lower steady state is no longer stable, but the upper
steady state is
0.50..--------------------, 800
0040 740
0.30 680
"""""" ........... ---------_._.-
0.20 620
0.10 560
-- 500
.:1.8 6.0 0.0 1.2
0 .. 00 .... --
0.0 1.2 2.4 t 3.6 2.4 t 3.6 48 6 .. 0
If we plot the concentration-temperature phase-plane trajectory, we see that increasing Ta will shift the trajectory to the
left. However, the final steady state is shifted to the right. This means that from the initial conditions, at any temperature
C
A
is lower for the larger Ta until the minimum in C
A
is reached.
9-43
0.5 0.5
0 . .-1 04
03
GJ
n.3
02 0 .. 2
0.1 tlJ
0.0 UO
500 560 620 T 680 740 800 500 560 620 r 680
P9-16 (f) Individualized solution
P9-16 (g)
The following Polymath program gives the linear analysis of the plOblem
A = 1.175, B = 6.03, J = 1600, 1" =12
See Polymath program P9-16g.pol

Calculated values of
''''
lVariable:lnitial value Minimal value Maximal value:Final value
i ;
1 't
1
0 0 6 6
[y 12. 0.0176788 A:159719 iO:0176788
t, l
3 ix 10.2 -0.0225558 0.2 !-0.0001258
:4 jea 0.04847
1
0.4290427,0.4253139
;5 IT 1628. ;542.6046 :638.1791 :547.0711
"6 )cpa 175. 175. 175. )75.
fo.5 10.50.5 :0.5
18 ;Fao .1200. . ' .. 1200. ;200. j200.
9 lTO 1530. 1530. /530. 1530.
15!Ta
.
17lE
;
181k
f
19ltau
L '
i1.416E+12 h.416E+12 :1.416E+12h.416E+12
11.987 1.987 11.987 i 1.987
, f
1150.
:250.
1400.
,
(530.
:48.
i3.0E+04
151:27669
10.12
1
150
. !l50li50 ..
1
250
. : 250. 1250.
1400. :400. 1400.
1530. /530. t530.
J48.
13.0E+04
i
i 1.165967
0.12
t +
148. 148.
J, j
i3.0E+043.0E+04
175.24179 1.463353
!0.12 0.12
9-44
740 800
Differential equations
d(y)jd(t) = (-J * (1 - A) * x + (B - C) * y)
d(x)jd(t) = (-A * x - B * Y j J) j tau
d(Ca)jd(t) = rA + CaO j tau - Ca j tau
:ft d(T)jd(t) = (U * Area * (Ta - T) - FaO * Cpa * (T - TO) + (rA * V) * delH) j (NaO * Cpa)
Explicit equations
Cpa = 37.5 * 2
cao = 0.5
FaO = 200
TO = 530
Ar = 1.416 * 10 /\ 12
R = 1.987
U = 150
Area = 250
vO = 400
= 530
V = 48
E = 30000
k = Ar * exp( -E j R j T)
tau = V j vO
rA =-k * Ca
delH = -30000
NaO = CaO * V
J = -delHjCpa j CaO

B = 6.03

A = 1.175
P9-16 (f)
Only the lower steady state plot of xl and yl will be shown.
9-45
0.50 ,----------------, 0.50 r--------------,
038
0.26
OJ-I

l&J
0.38
0.26
(1.1-1
0.02 . ......... ::;;:=""""' .......
0 .. 02 .
0.10 -
0.0 12 24 t 3 .. 6 .:I S 60 O.Oe+O 1.6e-3 .:I.Se-3 6Ae-3 ROe-3
P9-17
Batch reactor series reaction
Mol balance on A :
Mol balance on B :
Mol balance on C;
dea
-.._.":::: ral
dt
.ral ::: kl.Ca Ca ::::: Cao.exp( k! .t)
deb
.... ;;;:; rbi + rb2
dt
rbl :::;; ... ral = kLCa and l'b2;:::; k2.Cb
deb
""ii = kLCao.exp( k1.t) k2Cb
dCc
dt
,-b2
k2 == ...... }))
Energy balance :
dT Q+ (AHrxal)(-raIY)+ (i.VJrxb2)(rb2.v)
'dt'" == '-'".. ..... ......- ..... 2.. Ni:cpT .. _ .. -__ .. ,,_-,, .. .._
9-46
Q = UA.(ra ... T)
LNi.Cpi = Ca V.Cpa + Cb.V.Cpb +Cc.V.Cpc
dT UA.{330- T)+55000(-ral.V)+ 71500(-rb2.v)
dt 200.v,(Ca+ Cb+ Ge)
P9-17 (a)
UA:;:;O
dT V[55000{-"'raL) + 71500{-rb2.)]
.......... ::::: _._-_._-_ ..... __ .-..... __ ........... _--
dt 200.v.(Ca+ Cb + Ge)
See Polymath program P9-17-a .. pol
POLYMATH Results
Calculated values of the DEQ variables
Va:riable
t
Ca
Cc
Cb
T
UA
v
k1
k2
ra1
:rb2
rb1
initial value
o
0 .. 3
o
o
283
o
10
1.1172964
4.081E-09
-0.3351889
o
0.3351889
ODE Report (STIFF)
minimal value
o
1. 34E-65
o
-2.02E-44
283
o
10
1..1172964
4.081E-09
-35.016552
-27.963241
-6 .. 345E-60
Differential equations as entered by the user
[1] d(Ca)/d(t) = ra1
[2 J d(Cc)/d(t) = -rb2
[3J d(Cb)/d(t) = rb1+rb2
maximal value
---
0.2
0.3
0.3
0.2895784
915.5
o
10
2.141E+05
1.04lE+06
6 .. 345E-60
2.103E-38
35 .. 016552
final value
0.2 .
1. 34E-65
0.3
-1.864E-65
915.5
o
10
2.141E+05
1.041E+06
6.345E-60
-3.974E-59
-6.345E-60
[4] d(T)/d(t) = ((UA*(330-T))+(55000*(-ra1 *V))+(71500*(-rb2*V)))/(200*V*(Ca+Cb+Cc))
Explicit equations as entered by the user
[ll UA= 0
[2] V=10
[3] k1 = 3 .. 03*exp((9900/1 .. 987)*(1/300-1/T))
(4) k2 = 4.58*exp((27000/1.,987)*(1/500-1/T))
[5] ra1 = -k1*Ca
[ 6 ] rb2 = -k2*Cb
[7] rb1 = -ra1
947
0.22
0.14
0.06
-0.02
- Ca
- Cc
Cb
1--==---.-"'----------.--
1000,-------------,
8-10
680
520
360
-0.10 200 ' - - - ~ - - ~ - - - - ~ - - - - '
0.00 0 .. 0-1 0 .. 08 t 0.12 016 020 0 .. 00 0.04 0.08 t 0.12 0.16 0.20
P9-17 (b)
UA: 10000 llmin.K
0.30 '""""'---,--" .....-.--.." ....'--.'--.."" ......" ......... - - ~ ...."' .... 1000,-------------,
0..22 840
0.1-1
0.06
t
-.1D:.
ll
("c
-_ Cb
680
520
0.02 360
-O .. lH 200
000 016 020 0.00 0.04 0.08 t 0.12 fU6 0.20 00-1
008 t
0 .. 12
UA :=: 40000 JJmiu.K V::::::.
10 drn
3
0.30 900
0.22 760
ell
Q
0.1-1 ('c 620
-
CI>
0.06 480
...."."" ... ...--... "' .. ,,"",' .....-..., ....-"--.." ... '"' ...."-..--" .." ......, .......
-002 340
-..
-0.10
0.00 0 .. 04 0 .. 08 t 0.12 0 . .16 0.20
200
000 0.04
008 t
012 016 020
UA: 100000 l/min.K
V;;;;;.
lOdm
3
9-48
030 I,
500
0.24 440
Em
Q
0.18
- Cc 380
- Cb
0.12 320
0.06 ) ,
260
200 . 00
0.00
0
.
00
0.04
0 .. 08 t 0.12 0.16 0.20 o. 0.04 0.08 t 0.12 0.16 0.,20
At UA = 100000 J/min.K the 2nd reaction for C is totally suppressed
P9-17 (c)
UA = 40000 Jhnin.K To =320 K
0040 900 r--;--.-------------,
\
-
Ca
0,,30 780
0.20
.
Cc
660
.
ell
0.10 540
0.,00
lJ
420
-0.100.00 0.04 0.08 t 0.12 0.16 0.20 300 0.00 0.04 0.08 t 0.12 0.16 0,,20
P9-18
Semibatch with parallel reactions
Mol balance;
Rate laws:
dNa
-'"d;'; Fao+(rl+r2).V
dNd .
--=-rl.V
dt
-rl:;:;:kLCa
~ = Foo+ (rl +r2). V
9-49
dNu
-=-r2 V
dt .
- r2:;:;: k2.Cb
Stoichiomeu), :

Energy balance:
dT 20 .. Fao(T
". . :::= _._ .. ... -,-........ ...... ..
dt
P9-18 (a)
Na
Ca::::: .. --
Nd
Cd:;::;-,-
V
V
v:::: Vo + OO.!+ vb.!
Faa
vcz:::;; ..................-
Cao
Ca6 ::::;: 5 molJdm
3
Nb
Cb =_ .. --
Nu
Cu=-
V
V
assume Vo=O
Fho
w == .--......... _-
Cbo
Cbo == 4 mol/dm?
Fao Fba
V =uO.t
where 1)0;;;;;:; -.-.-- + ...... .
Cao Cbo
But Fao == Fba (equimolar feed)
no = GA5.Fao
v == 0.45Fao.t
dT Q" WS "LFio.Cpi.(T - Tio) + (-AHr:x(D).(-ra. V)
'dt' == -.--.-'----.-... "., ....... ':2: Ni:C;;i---'_ .... , .. ..-'--_ .._,-'
where Q==Ws==O
MIrx(T) == .6.Hrx(Tref) + 1.\Cp(T -Tref)
1.\Cp1 == :! .. Cpd'" ,?.,Cpb- Cpa.:::: 50-20--30 = 0
a a
1.\Hrx 1 (T) :=; '., 3000 cal/mol A
1.\Gp2;:::: -Z:.Cpu .. .. Cpb Cpa == 40- 20 -30:::: --10
a a
&Irx2(T) ::: .. , 5000, IOcr ... 3(0)
2.:Fio"Cpi.(rTio):::: 20 FaO.(T-Tao) + 30.Fbo.(T-Tbo)
:L.Ni,Cpi == NaCpa + Nb,.Cpb + Nd,Cpd + Nu.Cpu
Tao) -+ 30. Fba. ., Tbo ..
20. Na. + 30Nbt 50.1Vd + 40" Nu
Selectivity
rl
s= _.-.,
72
9-50
The selectivity is proportional to CAIC
B
and therefore a small concentration of B in the reactor is preferable. To maintain
a low concentration of B it would be beneficial to run a semibatch reactor where B is slowly added to A.
P9-18 (b)
Let the rate laws be :
- r1 == kl.c'''b
Now it would be best to slowly add A to B in a semibatch reactor ..
Let the rate laws be :
-d == kLCaCb
rl == kLCa
- r1 ==k1.Cb
-r2 ==k2.Ca
- 1'2 ;;;;; k2.CaCb
- 1'2;;;;; k2.Ca
-r2= k2.Cb
For these rate law combinations a semibatch reactor will not improve selectivity.
Let the rate laws be : . r1 :::: kl.Ca.Cb
.. 1'1 =kl.Cb
-1'2 =k2.Ca
r2 :::: k:2.CaCb
Now it would be best to slowly add A to B in a semibatch reactor to maintain high concentrations ofB and low
concentrations of A.
Let the rat.e laws be :
- 1'1 == kl.Ca
- 1'2 :::: k:2. CaL"b
- rl ;;:::: lel .Ca.Cb
- r2=k2.0>
Now it would be best to slowly add B to A in a semibatch reactor to maintain high concentrations of A and low
concentrations of B ..
P9-18 (C)
AHrxl callmol A aHlX2(300K) ca1lmol A
Temp. K
3000
If AIh-xl is constant, then if .1.Hrx 1 increases, T increases and S decreases.
If AIm! is constant, then if L1Hrx2(300K) increases, T increases and S decreases.
S is dependent on r1 and 1'2. whicb depend on kl and k2, which depend on the
temperature. The greater the temperature in the reactor the smaller the ratio between
kl and k2, hence reduced S.
P9-19
Plotting the data oft vs. T gives the initial and final temperature of the reaction, To = 52.5 C and T
t
=1668 0c.
9-51

80
-10
o
o s 16 t 24 32 40
Recalling equation (8-29) with LlCp = 0, X = 1 and T == T
f
gives:
cal ( ) cal
!ill R = -18- 166.8 - 52.5 K = -2057.4-
x mol.K mol
Make a table oft (min), T CC), dT/dt, liT (K\ In(dT/dt) and plot In(dT/dt) vs 11K (K) in Polymath. According to
equation (E9 .. 3-14) the slope of the curve is E over R Linear regression gives:
See Polymath program P9-19. pol

Model: InTdot = aO + a1 *T _inverse_kelvin
VariableiValue ;95% confidence
aO 18.88162 . 2.425175
al -6224.846 880.596
Statistics
RA2. 0.9755663;
: R A 2adj 0.9720758
Rmsd 0.0597988
Variance 0.0413783
Remember that T s is the self heating 1 ate, which occur s after the onset temperature is reached.
. --6224
InT, =---+18.88
T
E
6224=-
R
9--52
cal cal
E=6224K 1.987 =-12367-
molK mol
P9-20 No solution will be given
CDP9-A
CDP9-B
CDP9-C
Adiabatic. batch. reversible.
equation :
Rate law:
Stoichiometry :
Combining :
kl 0217
Ln" I.n-----
Parameter evaluation: E =-1' b 1 ::::: .... __ 03_2_4-T- = 8498J I mol
............ " .. _ ............... ,...... , .... , ..... -,."' .......... " ...... ., ............... , .... " ... ...
R.T2 R.TI 8314(340) 8.314(300)
Ke(T) AHr:x (I 1 )
In' ................. -....... ::::: _ ................ _. . ................. -... .
Ke(300) R 300 T
LlCp == 2 Cpa" CPA::::: 20 .. 12 ::::: 8 ]lmol.K
AHrx ::::: LlHIX (300) + LlCp(T 300) == ., 75000 + 8 (1' " 3(0)
9-53
NAO == 0 .. 6667 * 900 '" 254 = 272 127 mol A
Nro = 0..3333 * 900 *454 = 136064 moll
CAO :::= N
AO
I V = 272127 I (50 *28.12) :::= 192 moll dm
3
:::= (1)(12) + 0 + (136064/272027)*(15):::= 195 J/mol
Energy balance:
[.- Lllirx(3OO).X] (.- 75(00). X
T = 10+----------- == 300+ __
CPA + tJ.Cp.X 195+8.X
POLYMATH
t.i ons_,;.,
d {Xl / d ( c) ( ( 1-x) .. {4' cao (x .... 2} I l:(e:} l
TQ",300
cao=192

kl=. 217 "eX? (11322" llT) )
Dhrx=-75000 ... (a w (T-3UO) )
Ke:z7QOaOexp(Dh:::::-x/S.31.4."" /1J300-1,/T))
c:,., 0,
"
9-8
variable
()
o
300
O.04.:j,9S7]
To
;::<:
;,)I. .::.::
300
0_145345
-7SQiJO
70000
JOQ
192
469."731
0.49785
-7364.1 .8
loooa
9-54
o
300
1.92
Joe
a .. 145345
--'75000
1. 62'532
Ini::ial
o
Final value

2
o
JOO
191
'io69.1S1
0 .. 49735
-73641.8
1..62532
9-3

,,,,,'r
"".---i'--"""'--' "',.,"',.+".,-",,-'.",, .. ,,-, .. ,,+"''', .... '''-''' ..,,-,'' .. ''i''
o,.;;)QO :,,200 1.600
:2 COC
Equilibrium conversion. Xe :: 4.5 %
90 % of Xe ::: 0.9 * 4.5 ;:: 4.05 % cOIlversion
Time for this conversion"" 0.11 min:: 6,,6 s
Check:
at equilibrium:
(4.CAo2).Xe
2
+ (Ke.CAo). Xe- Ke.(7Ao:: 0
using the solution to a quadratic:
_. Ke,. Cw
Xe = .--_._. """""""'''''''''''?'''-----''''.'''' .. '''''''-''-
8.CAO-
where at T ;:: Te ::: 470 K, Ke:: 1.625 moll drIl
3
From POLYM.A.."TII, Xe:: 0.045
CDP9-D
9-55
CSTR startup
Part (a)
CSTR startup, gas phase, isobatic - no pressure drop
Mol balance:
Fr T
1)]" :;;;;: 111'0 .-.-. -... ..
Fw To
dFa
._-.- =: (Fao- Fa) + ra . .v
dt
dF'b
'--" = (0- Fb) .. 2.m.V
dE
Fa
Ca =, ...
iJr
Fb
Cb= ..
VI
P
Fro ::::: Cro.vlQ =: -'-:". VIa
R.l0
Fr;:::; Fa + Fb Fro::=: Fao + Tho
V=: lrr.'t 1: = 500 s
Energy balatlce :
UA
--- == 51 I kgcat.s. K
peat
but kg catalyst =: 50 kg
UA = 5 x 50 =: 2.."50 J I s.K
ACp=O
dt 40. Ca. V+ 20 Cb. V
No control:
Ta= 300 K, Tio:::: 450 K.; Fao = 5 moUs
E9.::t,at.ions:

value
Ie-OS
0
c',T) Id{t.};( {250" (Ta-T}} -t40"fao'" (T-Tio)" (20000" (-::::a"V})) / (( 450

':'a=3Qa

1:0.:;450
e,a.u=500
1:au:l;SQQ
k.,.;exp( (31400/8.3U} ,,< !1I450) -(lIt1]}
cao=O.2S
vo<.;fao/cao
Ca""fa/v
Cb;:fb/v
V=v"t:au

9-57
fa
'1'a
'1':.0
taU
Tau
va
Ca
Cb
V
ra
o 30
Ie-OS 0_0106221
o 299.Q98
450 451.548
s s
300 300
450 450
le-OS 299.107
450 450
soo 500
500 500
1 1-0292
0.25 0.25
5 5
20 20
4e-08 1200.55
0,25 0.251187
o 0,250078
la-OS 600273
-0.25 -8.31]]ge-06
,
.
Mininr..:.tn value
a
le-OS
a
445.634
5
300
450
le-08
450
sao
sao
0 . .921054-
0.25
5
20

S .07756e06
a
2e-05
-0.25
final value
30
0.00969749
299.098
451.548
5
300
450
29:9.107
4sa
50{)
500
1.0292
Q.25
5
20
1200.55
f1. Q77S6e-06
-0.249135
600273
-8 .. HJ3ge06
.. ;: \ . 200.i. ..-.... -----. --
I -"..,...=-... .. . -"'" -_.,..,.."---
... ..
..... e.scc.l(-"'
.:..;
""e,:;ooI

j


t
-4H .....
........ 6.000 ::<.::00 19.000 2 ..... 000 30.00e
Part (b)
Mol balance:
dCa (eao Ca)
.................. == .................. ., .._ ......._. + ra
dt 1:
Cao == 0.1 kmollm
3
::::: 0.1 111olldm
3
958
P9-10 cont'd
deb (Cbo'''' Cb)
-_. :;: ---._ .......- + ra
Cbo=Cao
dtz
dCc (OCc)
_. = -_ ... _ ........ Ta
t=50s
dt 1.
Rate law: "ra:: k.Ca.Cb
EneIgy balance:
or Q_ . Ws"LFio.Cpi(T Tio) + (-Mlrx)(ra. V)
:;: -_ ........... __ ......... -.. _- LNi.Cpi---_
m
-
v =:;; t)o 1" = 2 X 50 ::: 100 dm
3
Fao =:;; Cao " 'U
o
= 0.1 x: 2 ::: 0.2 molls::: Fbo (equimolar feed)
IFio.Cpi.(T - Tio) = 2 x 0.2 x (15)(1' - 300) = 6(1' - 3(0)
AIlrxCD;::: .6.H.Ix(To) + .6.Cp.(T - To) but ACp ::: 0
::: - 41000 - (- 20000) - (- 15000)
::: - 6000 cal/mol
dT 6(T - 300) + (6000) .. ( -ra. V)
-- = ------_ ..... _ .. __ .. _-_ ..
dt 15.Ca.v+15.Cb.Vt30.Cc.V
E;g;::ations:
d(ca)/d(cl-O.1-ca)/50)+ra

d(cc}fd(C)={(O-cc)/50}-ra
d(T) Id{c) =( (6" (T-JOO)) +{6000" (-ra*V) 1 } It (IS"ea"''\!)'" (lS"'cb*
V) ... DO"cc"V) )
'\!",100
1<:=0.01 *exp { {1000011. 987) .. ( (lIJ 00 I,, (liT) ) }
raz-k"ca",cb
to
'"
O. t
f 40.0 ==
V<U;'iAble v"alue value
t:- O 400
ca 0.001 0.0732615
cb 0.001 0.0132615
CC
I) Q.0:99$64
T 300 251380
V 100 100
k
0.01 lenSO
:t'a -Ie-OS -ie-OS
959
Mini.mum
0
0.00010274
O. OQ01021'4
{)
300
100
0.01
--O.Oll(HHl
Initial value
0.001
>1),001
a
)00
!ind
400
O. aOOlO::n4
0.00010274
0.099864-
25.7:380
100
la9280
-0.00199796
$c.lf':
10-- 52 ,;>00
-r
T
T
2.\00
"i-
T
t .. 5CO
I
T
o_.seo
T
"I'
0.300
I-
i
...... +--_ ...... _ .............. " .. ..;.-"" ._ ....-.------+ .. ,,-,. __ .. _-_ .. ---\
16ti,cca 320.0CC 400 or;
.:fL!.:o.
9-60
Solutions for Chapter 10 - Catalysis and Catalytic Reactors
PIO-I Individualized solution
PIO-2 (a) Example 10-1
(1) Pentane isomerization nP -pt--7 iP
Assume that Pt is the catalyst used.
Maximum f = 5 molecules/site/sec
Minimum f = 3e-3 molecukes/site/sec
Maximum rate:
--rp = fD(_l __ ) %Pt
MW
pt
100
-rp = = 1.28*10-
4

195 100 s geat
Minimum:
--rp = 3*10-
3
(0.5)(_1 __ = 7.69*10-
7
mol __
195 100 s geat
1
(2) SO +--0 --7 SO
2 2 2 3
No turnover frequency is given so this rate law cannot be determined by this method
(3) H2 + C
2
H
4
C
2
H
6
Assume Cobalt is the catalyst.
--r = fD(_l _)
H2 MW 100
Co
Maximum:
f = 100 molecules/site/sec
( )(
1 ) 1 mol
--r
H
=100 0.5 - ---=0.00849---
2 58.9 100 s geat
Minumum:
f= 0.01
( )
(
1 ) 1 -7 mol
-r
H
=0.01 0.5 - -----=8.49*10
2 58.9 100 s geat
PIO-2 (b) Example 10-2
10-1
(1) C
v
= 1
C
r
1 + KrPr + KBP
B
Ks = 1.39 Kr = 1.038
Pro = YroProtal = 0.3*40 = 12
For 60% conversion
Pr = Pro (1- X) = 12*0.4 = 4.8atm
P
B
=PTOX =12*0.6=7.2atm
C
v
= 1 =_1_=0.063
C
r
1+(1.038)(4.8)+(1.39)(7.2) 15.99
6.3% of the sites are vacant
(2) X = 0.8
Cros = .CvKrPr _ KrPr
C
T
C
r
1 + KrPr + KBP
B
eros = (1.038)(1)(1-0.8) = 0.2076 =0 09
C
T
1+(1.038)(1)(1-0.8)+(1.39)(1)(0.8) 2.3196 .
9% of the sites are covered by toluene
(3) Linearize the rate law to:
PH?Pr 1 KBP
B
KrPr
----=-+--+---
-r
7
k k k
PIO-2 (c) Example 10-3
Increasing the pressure will increase the rate law.
p?
-r---T--R
A 7
l+KrPr
If the flow rate is decreased the conversion will increase for two reasons: (1) smaller pressure drop
and (2) reactants spend more time in the reactor.
From figure ElO-3.1 we see that when X = 0.6, W = 5800 kg.
PIO-2 (d) Example 10-4
With the new data, model (a) best fits the data
(a)
POL YMATH Results
Nonlinear regression (L-M)
Model: ReactionRate = k*Pe*Ph/(1 +Kea*PeatKe*Pe)
10-2
variable
k
Kea
Ke
Precision
RA2
R
A
2adj
Rmsd
variance
(b)
Ini guess
3
0.1
2
= 0,,9969101
= 0 .. 9960273
= 0 .. 0259656
= 0.0096316
POLYMATH Results
Nonlinear regression (L-M)
Value
3.5798145
0.1176376
2.3630934
Model: ReactionRate = k*Pe*Ph/(1+Ke*Pe)
variable
k
Ke
Precision
RA2
RA2adj
Rmsd
Variance
(c)
Ini guess
3
2
= 0 .. 9735965
= 0.9702961
= 0.0759032
= 0.0720163
POL YMATH Results
Nonlinear regression (L-M)
Value
2.9497646
1.9118572
Model: ReactionRate = k*Pe*Ph/((1 +Ke*Pel"'2)
Variable
k
Ke
Precision
RA2
RA2adj
Rmsd
vari.ance
(d)
Ini guess
3
2
= 0.9620735
= 0 .. 9573327
= 0 .. 0909706
= 0 .. 1034455
POL YMATH Results
Nonlinear regression (L-M)
Value
1.9496445
0.3508639
Model: ReactionRate = k*Pel\a*Phl\b
Variable
-k----
a
b
Precision
RA2
R
A
2adj
Rmsd
Variance
Ini guess
3
1
1
= 0 .. 965477
= 0.9556133
= 0 .. 0867928
= 0.107614
Value
0.7574196
0 .. 2874239
1.1747643
95% confidence
0.0026691
0.0014744
0.0024526
95% confidence
0.0058793
0.0054165
95% confidence
0.319098
0 .. 0756992
95% confidence
0 .. 2495415
0.0955031
0.2404971
10-3
Model (e) at first appears to work well but not as well as model (a). However, the 95% confidence
interval is larger than the actual value, which leads to a possible negative value for Ka. This is not
possible and the model should be discarded. Model (f) is the worst model of all. In fact it should be
thrown out as a possible model due to the negative RII2 values.
(e)
POL YMA TH Results
Nonlinear regression (LM)
Model: ReactionRate = k*Pe*Ph/((1 +Ka*Pea+Ke*Pe)ll2)
Variable
k
Ka
Ke
Precision
RA2
RA2adj
Rmsd
Variance
(f)
Ini guess
-3---
1
1
= 0 .. 9787138
= 0.9726321
= 0 .. 0681519
= 0 .. 0663527
POL YMATH Results
Nonlinear regression (LM)
Value
2.113121
0,,0245
0 .. 3713644
Model: ReactionRate = k*Pe*Ph/(1+Ka'Pea)
Variable
k
Ka
Precision
Ini guess
3
1
RA2 = 0 .. 343853
RA2adj = -0 .. 5118346
Rmsd = 0.5415086
Variance = 3 .. 6653942
PIO-2 (e) Example 10-5
1
(l)X =1- klk
(l+kdt ) d
Value
44.117481
101. 99791
As t approaches infinity, X approaches 1.
95% confidence
0 .. 2375775
0.030918
0 .. 0489399
95% confidence
7 .. 1763989
16 .. 763192
10-4
large klta
x
t
(2) Second order reaction with first order decay.
dX ,W
-=-r
A
-
dt NAD
-r '=ak'C
2
A A
a = exp[-kdt]
dX = Wk' C
2
(1- X)2 exp[-k t]
dt N AD d
AD
dX =k(I-X)2 exp[-ki]
dt
X k
1-- X = k(1-ex
p
[ -kd
t
])
d
t... X k
as t -y m Imty -.-- =-
l--X kd
X=J{d
1+ k/
/kd
(3) First order reaction with first order decay
dX Wk'
di- = ""NCAD (1- X)exp[-kd
t
]
AD
dX
- = k(l- X)exp[-kdt]
dt
(I-exp[-kdtj)
t -7 infinity X = l-exp[ - ]
PIO-2 (0 Example 10-6
10--5
Increasing the space time makes the minimum disappear. Decreasing the space time moves the
minimum to the left and the concentration is higher.
Increasing the temperature so that the rate constants are higher will cause the catalyst lifetime to be
shorter.
If tau = 0.005 the minimum C
A
= 0.607
If tau = O.Olthe minimum C
A
= 0.5088
PIO-2 (g) Example 10-7
(1) If the solids and reactants are fed from opposite ends,
da kda
--=- atW=W
e
,a=l
dW Us
C =
1 U
S
This gives the same expression for conversion as in the example.
(2) Second order decay
1
a=-----
kdW
1+---
Us
In(I+'5
dW
J
I-X kdFAO Us
1.24= (0.6)(0.075)2 US_In (1 +
(0.72)(30) Us
Solve for Us by trial and error or a non-linear equation solver.
Us = 0.902
(3) If G = 2
dX 2 (l-x)2
F --- = kC ------a
AO dW AO (1+c
X
r
10-6
(
1+)2 X kC
2
U ( [-k W]J
2 (1 + ) In (1 - X ) + 2 X + = AO S 1 - exp d e
I-X kdFAO Us
9X
12In(I-X)+4X +--=1.24
I-X
X = 0.372
PIO-2 (h) Example 10-8
Uo = 0.25 Uo = 0.025
1 .. 0 -, --------------,
0.8
0.6
0.4
0.2
4 z 6
1.0
Uo =2.5

4 6
z
PIO-2 (i)


8
8
10
10
0.6
0.4
0.2
"-",
0.0
0 2 4
z
6 8 10
Uo=25
1.0
0.8
0.6
0.4
0.2
0.0

I)
2
4 z 6
8 10
For EA = 10 and Ed = 35, for first order decay we rearrange Eq 10-120 to:
In(l- kdotEd J = Ed
EA R T To
Ed ( 1 1 J =- ._---
R I'o T
lO-7
R 1
-In
kdOtEd
Ed
l-
1 1
=---
1'a T
EA
T=
1'a
400

1+0.07948In( 1 )
1-0.00286t
PIO-2 (j) Individualized solution
PIO-3 Solution is in the decoding algorithm given with the modules
PIO-4
W+S,.,.ws
TBA.S,(.,. TBA + S
PIO-4 (a)
Surface Rm Limited
r
".Wl. =0
k
A
C
1
,,.,,C,,. 1

'k, . V {" t l' K


==-'j('-" == \.1B
A
I..'nl.1 L y, SInce K" . ';;;;; 'TBA
D D
10-8
PIO-4 (b)
Adsorption of isobutene limited
r
ADl
;k
Al
[C
r
- ~ ] C
v

Bey Ridea1 Kinetics
PIO-4 (d)
10-9
W .. S
2
+ 19S1HTBA+S2+S1
r -= k [' C C _
S S 'WS2 1.$1 KS
en == C
V1
-+- C
loSl
C =c +C
T2 'V2'W-S2
PIO-4 (e) Individualized solution
PIO-4 (0 Individualized solution
PIO-5 (a)
H..,+ C..,H
.. 4
H +E-4A
Bey Rideal.

E + S E .. S C
E1OS
:::: KE. P E. C
v
"
TS "" k
s
[ C
E
..
S
PH]
CT""'CV+CE"S
=
PIO-5 (b) Individualized solution
PIO-5 (c)
02 +2S p 20S
C3H6 + OS ---) C
3
H
5
0H.S
C
3
H
6
0H.S P C
3
H
5
0H + S
-riJ = r's = k
3
P
B
C
A

S
[
2
rAD =kA PAzCV - KA
Az +2S p 2AS
B + AS ---) CS
CS---)C+S
10-10
r
AD
=0
kA
C
AoS
=
-r
B
= rS =
r
e
.
s
= kD [ C
e

s
- = kD [C
e
.
s
- KePeC
v
1
rcos =0
kD
C
CoS
= KcPcC
v
C
r
= C
v
+ C
AoS
+ C
CoS
= C
v
[1 + KcP
c
]
k
3
C
r
P
B
.JK:P:
-r
B
= rs = + KcP
c
PIO-6 (a)
A (butanol) ;: B (butene) + C (warer)
Possible meChanism:
7 .. :::: K (PC .......
AA ,4 S K
AA.
rs "" ks (CA.s Cs CaoS CcoS Ks)
rDB =: knB (esoS .. PB Cs/Kos)
CS t:! c+s
rDC;: klX {Ccs - Pc Cs/Kr:d
Assume stuface reaction controlling:
( ' - PB Cs - P K ('
a-s --K .. - B AS S
DB
( ' Pc Cs P K
,<:'5 == -K-'" C AC -5
rx:
10-11
'- - ( .,! .. pgpc
C
;._.) _ k K -'Zl'p }!ePc Jl h . K - KKK K
r,J - rs - k
s
! P,tK,Lis -- KKK - S Ais A _. K were eq - S AA DC DE
\ S DB DC eq
site bala:lce: ('T == Cs +- CAS +- CBS + Ccs :;: Cs (l + KAA P A + KAB PB + KAc Pc)
ks KAA cf (P A F1l
:. r A ;:: _....... . . ........._ ...... _ .. __ ._.
{I + P A K.A.A + PB K.A.B + Pc KAc)2
If PBO::: 0 and Pco == 0 , then
.; := Is1 PM _.
AO {I -+ PAn K
AA
)2 1 -+ k2 Pio +- k3 P AO
This is consistent with the observation.
PIO-6 (b)
From r..iJ.c figure.
Point numb::::r 2 3 4 :; 6

AO hr'!b cat
0 0.275 0.5 0.77 0.77 0.5
PAC (arm) 0 4.5 27 54 112 229
.J.p-; ....
405 6 .. 45 8 . .14 L2.06 21.4
"fAO
10-12
At large PAl): = :;; 1... (_l_) ; using point 6: k, = (229) (0.5) ;; 114
k2 K2 PAO k2"
At small P AO: .; AO:= kl P AO ; using point 2: kJ :: 0061 = k2:::: 5.34xlO-4
.. r AO = ..... _... 0.
06
1 .. AO ............... ; so
1 T 5.34x 10-4 PAo + k, P AO
Using point 3: k3 :: 7.05xIO
2
k3 := 3. 19x 10,,2
k3 "" L05x 10.
2
}
= k3 = 3.19xlO-2
Using poim 4;
(The reason for the different
values of k, is from reading
the graph)
Using rJOim 5;
-- y "" 4.3103 + O.073937x R= 099583
20.0 -
J
lntercepb1/k
o
.
5
::: 4.31
k::: 0.054
Slope := KA/kO'! = 0.074
K
A
::: 0.32
o . 0 .. .. "':"':".. "':"."""';.... "1"..""":"...... .... ..
o 50 100 P ISO 200 250
a
PIO-6 (C)
Find the percent of vacant sites
P b and Pc "" 0 so that red llces to:
1 1
%vacant ::::: ._-_ ..... - .. _.:;::: .......... _ .... __ ... __ . =: 0.41
l+K
AA
P
AO
1+0.01596*90
Find the percent of sites occupied by A and B. No B will have occupied any
sites at X ::::: O. So;
0/ _ KAAP
A
_ 0.01595 - 0-9
i''''1:." - .-.......... _ ...._-._. - ...... , .......... , ..... _, ........ , ..................... - . ,J
1 + K,<\,AP A "1 -+- 0.01595" 90
PIO-6 (d) Individualized solution
PIO-6 (e) Individualized solution
----------------------------------------------------------------------
PIO-7
1013
ME --'+ D}(fE + rhO
~ ..
-- ... _-----
100
300
The r.ue o ~ formation ofDME is gream:r inirially. 11ris is a result of IJl(){e vacant siteS being
inirially available for reaction because water is not adsorbed on the sites. As time goes on
the equilibrium concenll:u:ion of Water sites is reached. WaI.C:J: is strongly adsorbed on this
catalyst.
Probable Mech;mism
ME+5 :;= ~ f S
2ME S""""1> W S + DME t S
Assume Surface Reaction Controls
PIO-8
CME-S "" K/.u:. PME Cv
Cw.s == Kw Pv". Cv
Given: Kinetic r.:ue expression for the reduction of NO over :l solid catalyst:
kPNPC
t" ;: """"""'""""---"--------
{I +- Kl PN+- K
z
Per
~ == partial pressue NO
Pe =: partial pressure CO
Assume that overall reaction is of the form
NO +CO "....,.tN2 +COz
PIO-8 (a)
10-14
It is seen that neither Nz or appear in the denominator. This infeIs that neither is
adsortxd on the catalyst, On the other hand. it can be infered that both NO and CO are
adsorbed on the surface. The squared denominaror suggests a dual site surface reaction of
the adsorbates of NO and CO. Therefore the following mechanism is proposed.
kA."i
NO(g) + S <=: NO S
keN
CO(g) + S <=: CO S
ks
P, .. ;;;: P,vo
Pc::::: Pea
'-1"0/ ;;;: k:cN [Pc Cs - Cco.s/KcN]
NO S + CO S -1- N2 + Cth + 25
With the surface reaction controlling
CNQ-S ;;;: KAN' PN Cs
4:o-S :: keN Pc Cs
Tuen CT :: Cs ,. CNQ.S + Cco.s :: Cs (1 +- KAN PN + Kc."'N Pc]
and therefore reaction is -rs:: ks CNo-S Cco-s:;; ks PN Pc KAN Ik"N
or.r$
[1 +- fIN + N.:N PcP
kJ Pc PN'
"'1"s :::: ---,.",,,-,,,--' -'" .. -.
[l + K
t
PN + K2 PcJ2
PIO-8 (b)
with
k\ :: ks ct Km KeN
Kl :;;KAN
K1=KcN
Assume chat Pc flN. Then Pc chattges very little during the course of the reaction
and remai.'1s consu.m,. A maximum in (-rs) rhen occurs. for a fixed value of PN at:
10-15
The rate of n::.action will. increase .. vim an inC're:l.Se in Pc until me: above value is reached.
after which it '..vil.! decrease. It appears tbat there is an excess pressure which will mini:miz.e
reactOr YoiU!l'le .. Operating at excess pressure greater than t..'"tis value will. decrease (-rs), and
hence increase V. This analysis is exact if the catalytic reaCtor is a CSTR. If me reactor is
t:re:ued as PFR. the Cthical value of Pc is only approximarc. but the general observation is
qualitatively the same.
This analysis further assumes that the excess CO can be elimitmcd easily and economically
downstream from the NO converta'.
PIO-8 (C)
The conditions for which the rate law and mechanism are consistent are the
following.. DIe CO S surface reaction must be the rate limiting. P cdP NO must be
small. The mechanism must be a dual site mechanism (which it is).
PIO-9
Methyl ethyl ketone (MEK) is an important industrial solvent that can be plOduced {roll1lhc dehydrogenation
of outall2-ol (Btl) over a zinc oxide catalysl
Bu+MEK+ Hz
/i) 11 t C
The following data giving the reaction rate for MEK were obtained in a difterentialreactO! at 490C,
P
BIt
(atm)
(atm)
PH, (atm)
tIY1f:l!h x cat)
PIO-9 (a)
5
o
0.044
o
o
O(W)
_., --- -, - ., .... _,-
0.5
2
1
0069 0060
Suggest a rate law that is consistent with the experimental data
From data sets 2 and 5
P
BIi
(aim)
(atm) ()
P
II
, (atm) 0
(molf}! x g cat) 0 .. 040 0..043
. __ .:c:= .... _. __ . __ . -... _ .. _ ..... _ ... _ ...... __ ._._ ........ .---.. - .... _ ... .
0
0 10
0.043 0.059
we can say that an increase in BlI partial pressure slightly increases the reaction rate.
10-16
From data sets 1 and 5
Data Set
P
llu
(aIm)
(aIm)
Pit, (aim)
1
5
0
5
o
o
0.043
we can see that the MEK partial pressure has little if no effect 011 the rate law.
From data sets 4 and 6
DataSet
...-.-,.--,-.. .. .. ..",.. .... " ..
P
SlI
(arm)
P.WEK (atm)
(aim)
.( ...
4
1
1
1
0.060
6
1
o
10
0.059
Is seems that the pattial pressure of Hz has no effect on the reaction rate.
If MEK and Hz are weakly adsorbed (or not adsorbed at all) we can proposed initially the following
J , kiP,
.- r ::::: r ::::: ............ ---.:... ...... .
A B ItkP
2 A
But, from the complete data sel
"' .......... __ ............. .
Data Set 2 3 4 6
'" ....... __ . ____ . ._ _ ...................... _-...-_._.'_.' ___ ... __ ........................... _ . ..M.. .. _____ _ ..." , ......... ....... - .. -.-.... .
2 0.1 05 2 1
cat) 0.044 0.040 0.069 0..060 0.043 0.059
We can see that the reaction rate goes through a maximum
008
0 .. 07
006
i
0.05
S
004 0
,5,
003
lii
-...
002
001
0
0 0.5 15 2
P
Uu
(lltm)
10-17
PIO-9 (b)
Suggest a reaction mechanism and rate limiting step consistent with the late law.
One possible mechanism is the following one
(1) A r-S <-> AS
(2) A S + S ,) B . S + C . S
(3) B S' "7 Bt, S
(4)CS<)C+S
If the limiting step is #2 (irreversible surface reaction) and the others me at Pseudo Steady State (# L, 3and 4)
, kC ("
.... fA ;;:: '2 A.) /V
A site's balance wHl yield
TherefOlC,
Solving tm C
v
C" =
1 + P.K + +
" I K K
3 .!
(1
Substituting the expressions for C
v
and CAS into the equation for -r' A
". =.: k
2
C;\ sC" = k, K IPr\C .. .......... -;
(
1 + p. K + J>!L
il I K K)
, 4
which for the case of weak adsorplion of MEK and Hz reduces to
PIO-9 (c) Individualized solution
10-18
PIO-9 (d)
First we need to calculate the rate constants involved in the equation for -r' A in
part (a). We can rearrange the equation to give the following
fE;*+ jtp,
which is a linear equation with slope equal to YJk:' and intercept equal to Y.Jk:' Shown below is the linear
regression we did using the problem data
g
7
6
V1
0 5
<;

..
"'-1
I
------i
I
4

I
I
= 2 7298l>flu + I 3362,
,,': 0 .9991
'"
3
e::.
2
0
0 05
'.H I
I
I
1
I
f
15 2
Thus from the slope and intercept data
mol
kl ::::: 0.56 .--._. and
h gcatcum
Thus,
The design equation for t.he PBR is
F .. cJ?i_. :::::--,'
AO dW II
From stoichiometry (gas phase)
C t1 :::::
2 . .5
I
k 2 ::::: 2.04 ---_.
atm
From the reaction E:= 1 + L 1 _ Assuming isobaric and isothermal operation and using ideal gas law
p,\ =PA{Li-)
Using equations 10 .. 8-13,10-8-14 and 10-8-16 together with Polymath we can solve for W at X::::: 90%..
10-19
See Polymath program P 109-d . .pol.
POL YMA TH Results
Calculated values of the DEQ variables
Variable
W
X
e
Paa
Pa
k1
k2
Faa
ra
rate
initial value
o
o
1
10
10
560
2.04
600
-12.228142
12.228142
ODE Report (RKF45)
minimal value
o
o
1
10
0.0042521
560
2 .. 04
600
-68 .. 5622
2.3403948
Differential equations as entered by the user
[1] d(X)/d(W) = -ralFao
Explicit equations as entered by the user
[1] e=1
[2] Pao = 10
[3] Pa = Pao*(1-X)/(1 +e*X)
[4] k1 = 560
[5] k2 = 2 .. 04
[6J Fao = 600
[7] ra = -k1 *PaI((1 +(k2*Pa))A2)
[8] rate = -ra
maximal value
23
0.9991499
1
10
10
560
2.04
600
-2 .. 3403948
68 .. 5622
~ . mol mol
it should be mentioned that I, . :::: to ... ;;;: 600---
tlU min hr
1.0 --- 70
0.8 56
06
Q
-12
0.4 28
0.2 1-1
final value
23
0.9991499
1
10
0.0042521
560
2.04
600
--2 .. 3403948
2 .. 3403948
.0.0
(I
'---________ " ______ ~ __ .J
0.0 -1.6 9.2
\"
13.8 184
PIO-9 (e) Individualized solution
PIO-9 (0
23.0 0.0 4.6 9.2 W 13.8 18.4 23.0
10-20
Now consider the change in pressure:
Stoichiometry:
(
1-X }P
P =C RT=C ._--, - .. ,RT
AA A" l+iX P
o
Pressure:
dy 'n ( )
.. ""._ ..... = ."." .. - 1 + X
dW 2y
Use these new equations in the Polymath program from part (d).
See Polymath program P 1O-9-f.pol.
POLYMATH Results
Calculated values of the DEQ variables
Variable
W
X
Y
e
Pao
Pa
kl
k2
Fao
ra
rate
alpha
initial value
o
o
1
1
10
10
560
2.04
600
-12.228142
12.228142
0.03
ODE Report (RKF45)
minimal value
o
o
0.0746953
1
10
7.771E-05
560
2.04
600
-68.584462
0.0435044
0.03
Differential equations as entered by the user
[1] d(X)/d(W) = -ra/Fao
[2] d(y)/d(W) = -alpha*(1 +X)/2/y
Explicit equations as entered by the user
[1 J e = 1
[2J Pao=10
[ 3 J Pa = y*Pao*(1-X)/(1 +e*X)
[4] k1 = 560
[5J k2 = 204
[6J Fao = 600
[7 J ra = -k1 *Pa/( (1 +(k2*Pa) )1\2)
[ 8 J rate = ora
[ 9] alpha = ,,03
maximal value
23
0.9997919
1
1
10
10
560
2.04
600
-0.0435044
68.584462
0.03
10-21
final value
23
0.9997919
0.0746953
1
10
7.771E-05
560
2.04
600
-0.0435044
0.0435044
0.03
1.0 70
/,
08 56
/\
42 0 .. 6
[;J ! '
r:f.f{- ./ }
/ I
04 28
/' I
<",,"'
\

\
14
" ... ",
0.2
,,>P' '"
\
(I
"
" 0.0
4.6 9.2 13.8 18.4 23.0 0.0 9.2
W
13.8 1804 23,0 0.0
\V
PIOIO (a)
Iso,ocrene +. Hydro gcn --? isCH)Ctanc
A -t. B
Discrirninarion of mcdds:
Assume 'fA ;: k C1 q q:
For runs 2 and J, 0 < a: < 1 ; 2 and 4, 0 < f) < 1 ; and 2 and 5 , 1 < r < O. From
Perry's handbook, 5th cd". p. 4-8; the reaction is probably surface reaction rate con'Q'"olling.
Mechanism I (H. Alvord):
A+S+!A.S
B2+2S 2BS
AS,2BS;:! CS+2S
CS ;:! C+S
Hence.
Hence,
k fp;.. PB - PcfKuJ
-rA, "'" _._., .. , ... _. '--, .. ,_.,-""-, .... _-,._ ..
[1 +'KAP;..+KfPft+ KcPcP
Mechanism II (S. L Mullick):
A+S +! A.S
B+S B.S
AS+BS f:!: CS+S
CS C+,S
, _ k[PA Ps - Pc/l<.,qJ
"1;.. - ...." ._ ..._, ... " ... _ ... , .. - ." .. _ ...... _ ... , .. , .....
[1 ,. K ... FA t KB Ps -+- Kc PcP
1022
From runs 2. 9 11. 12. P A:::: PB = Pc "" P. a plot of vs. P shows a parabollic
behavior. therefore we Mil drop the second term in the denominator for easy linearization.
Tne readers can calculate value by Gibbs free energy change 4'1 this equation (up to 650
K. the reverse reaction is negligible)
Tne linearized regression model is:
Using given 12 data pointS to solve for these four unknowns:
y :::: 3.0 -+ 1.42 P
A
.;. 0.97 Pa -t. 1.42 Pc
The tinal results are:
0..1113 P
A
Fg
-fA:: ...- ...." .. _._-,,--,,-,,_. -_ ............... _ .... _"
(1 + 0.475 PAt 0322 PB .;. 0 .. 414 Pcr
The comparison of the pen:emage error between the model and the experimental data are:
r
.5
r
Run P
A Pa Pc
(exp.) (calc.) % elmr
expo
1 1 0 0..0362 :'5.26 0.0345 -4.8
2 1 1 1 0..0.239 647 0.0227 -4.7
3 1 :3 1 0..0390 8.77 0..0410 +5.0
4
3 1 1 o. . .Q351 9.25 0.0334 A.a
5 1 1 3 O.D114 9.37 0.0120 +5..7
6 I 10 0 0.0534 13,,69 0 .. 0.505 -5.4
7 10 1 0 0..0310 17.96 0.0302 -2.6
8 1 1 10. 0.0033 lo.Al 0.00315 -4.5
9 2- 2 2 0..0380 10.26 0.0380 0
10. 0.2 0.2 0.2 0.0032 3.54 0.00288 9.8
11 0.1 0.1 0.1 0..0008 3.54 0.00089 +10.7
12 5 5 5 0.0566 21.02 0.0599 .... :.1:2 _
Isuml =59.2
avg. = 4.9
PIO-IO (b)
Discussion: The readers may check the validity of mechanism L To reduce the
accumulation of error in calculations, the readers should have used ail data points and
solved all unblowns simultaneously. To get the maximum informacion of complex kinetics
of a reaction from the least runs, it is advantageous to do planned experiments such as
factOrial design .. (W. G .. Humer. and A. C. Atkinson. Olem1cai p .. 159. June
6. 1966).
A paper discussing chemical reaction rare equations from experimental data is in:
C. n. \Vare 11., Summer Compmer Simulation Conference. Proceedings. 1975, Pa.."t 1. p ..
368.
10-23
PIO-IO (c)
0.2223 (RTr {l-Xr / (l-O.SXY
r A =.-.... ---..--.--.--.-.--................
r 1 + CAOO {(0.475 + 0..322 (I-X)} + OA14x}1-
l 1- .)x .
0 . .1 113 (RT CAot (l.xF I {l-O.5Xr
-r!\ = ----. .. --.--.------..
. r 1 + c.:..o RT fO 797 0383 x'\j2
.. 1-0.SX \. , . '!
FAO::: 2.5 =::: i50
CSTR:
w;;;;;; 21.380 g ::::: 21.4 kg
x
w::; 1501
o 2:
1l13
J1.5J:i!X(LL0.5 x)Z
1 ..,..
11+' _ ...........,..2 ............ {O.797- 0..383
l. 1 - 0 ...5 X 'j
10-24
w= ...- ... 1
x
G (X}dX
0.1113 x 2.25 0
where
[
. 1..5 (0..797' - 0..383 Xl]2
1 + -.-----------. (1 - 0.5 xjZ
G(X):= ... -.. ___ ..__ .. _._ ..... _ ........... _ .....
(1- xf
x G{X)
0. 4.82

0 . .1 5.38

0.2 6.13
:1
0..3 7.16
COO
OA 8.66
05 11.00
0.6 IS.03
0
I) a.l 0':'
0.7 23.15
0 .. 8 44 .. 62
Using Simpson s rule.
area. under the curve i 0
w:;: ... _____ .J2!1 _____ . __ x. 10:;: 6000 g "" 6 kg
0.1113 x. 2.25
PIO-IO (d)
Consider the differential section between L and L + dL
In - Out + Generation"" Accumulation
r)C
4
,L)Ar Pc-H t/J)dL == -.dl{"1 Arv{L)CJL)]
But: A
1
v(L)C
4
(L):= N)L).:::: ... X)
:. FAD f:: TA pdl .. $) rA {Pd
Relating the expression fA to X and L :
;; lFo (lX)
2
:;: }Fo (l-X)
Fc=FAOX == tFox
PA == P
A
... 1:.:X. Pr Pc=-X-Pr
2X 2-X
LetP=Pr,
1
R =-(2 X)
, 2
FIX
P __ ...:1 .. _ ........... _ .
l-P
r
-2 .. X
10-25
c..J
0.4 as
cu. 0:: lUI
"
From th.e Ergun equation. we: have:
All the things on R11S arc: constant. except far p
p=p,((L!x)
. :i = + [75 GJ
df. == 2.:X where 6
0
=.!?Q.Q. ...... .. . .0.,:d 1: +- 1.75 G
dL 2P . Poge D? Q> L Dp
Let L" ",., L..... : p. =..P. . then: dE"", l-X. \3:
L-des Po dL 2p
where
$=04
(
I'sO gmol.) (2 +
G :;:: An fiA + Fso fiB) == hr gmol 4)".6.g,
AT T K. {fr..25:I\2
4 12}
'"'''At: 9 T .......
G == ..,.u.a.ll .
T frZ hr
P :; (3 atm) (14. (144 m:.) = 63487 .lb.
o 1 attn 1 frZ ft2
(57 _Jh.,_.1 (3 ann)
p ;; C
r
m == (5ZJll.\ L := . ____ ___ .Jbmcl.!.. ...... "." ......, ... .:.. ... __ .. __ .. .
0-.' lhmal J RT (0,7301 . .rurrL\1 [(lOO + 273.15)( 1.8 jJ OR
\ IhmoloR,
10-26
IiJ ;:: 0.4
Dp ;: (_1 in) U .... fL} :: _1 ft
16 \12in 192
&<: = 32.174 lli.!IL.JL
Ibr sect
(150 grnol) (2 + 112) ..... 1..-.. { .. -JL-)
G;:: (FAO rnA +- Fae mB) =. hr gmol g
AT T 1L{n..2llj
4 12
J.bm..
T
Po = (3 = 6348.7!i'
__ (57 ,.J.b-:-) (3 atm)
Po:; Cr m (0,,7301 ..fy3 .all oR
Po:: 0.2750 !wt
ft)
IbmoloR,
Ii (3 atID. 200C);: 9.4719 x 10,3 cp (t Cg, He) }
PPROP
:: 8.6211 X 10.
3
cp (all Ca)
(94719 X 1O3j- 8.6211 x 10.
3
) " -4 Ibm
= !J. ;; ................ --.. --......... -----cp 6.7197 x 10 -----
x JQQQ..z..;;.
hI"
Il ""
ft ru"
2 ft sec cp
1027
where
rAT (1 .. 1j K P;
Let: a. "" -.-.....------- = (KA + Ks) Po
FAo
Then: dX:= (1.- _ .....
ell f2-X K' xl1
lP:-+-l'1' 2 J
For a given T. we can solve the twO ODEs to get X(L *)., We need to guess T until X :::; 0,8.
For the rate cOnStaIUS. we use the solution of 6.10 (a)
K :::; 0 .. 1118 - .... ... -.... - ; KA"" 0.475 amr
1
; KB = 0.322 atnl
1
gear'" hr
Kc "" 0.414 atm
l
K
- (0 TAO 4"7- () - 149
2- .. " ..... , .) .... ,.,.- .)-"'1..
a: := 85.958 T
10-28
= (5...5.ll x 1 (J4 f2..hr.) (378.09 + .ll2.Ql) J1'm..
o T ll:xn . T hr
== _ Q 2191 _
A FORTRAN program is written to solve the equations. The results show that any
numbers 6f tubes !oufiicient to allow the given flow rates with a positive pressure provides
more than enough catalyst for the desired conversion The problem as stated, therefore
has no solution. However, we can choose a ditIerent L, and it only changes the
dimensionless parameters.. With L = 20, the problem is still unsolvable
For L ::;: 10 ft , T:::: 2.16 rubes = 1-:::: 0.46
In
Note: Using the modified program with
Dp in II "" 9 .. 05 x 10"3 cp
L""' 10 ft A:; 2.15 il'l2
=> X", 0.80 p. == 0.7531
Using 1 1/2 in schedule 80 pipe (I.D. := 1..5 in) A = 1.76715 in
2
and me length to get
X "" 0 .. 8 is impossible (p( < 0).
With 2 in schedule 80 pipe U.D. "" 1.939 in). A =- 2.952877 in
1
This gives L "" 6.6Jft , X == 080 and p:::: 0.9113
1 1/2 in schedule 40 => A "" 2.03580 in
2
L '" , X = 0 ..8 and P "" 0.6903
PI0-ll (a)
1029
Assume a rate.,ljmiting step; start with surface reaction
AS+S ..... -BS+H S
HS ..... 'H+S
~ ~ ~ ~
Assume a ratelit,wting step; start with surface reaction
. ~ 4 D . ::: 0
kAD
.:fl!2 .. ::;; 0
k
nv
Find the expression for C
y
Combine all of those to get the following rale la\v suggestion.
CheckinO' to see if it fit>;, we see that for high P A' increases in P A cause decreases in
the rate. \Ve see that if P B or PH increase the rate will go down, which is consistent
with the rate law ..
PI0-ll (b)
Now nsing POLYMATH's nonlinear equation regression we can find the values
for the parameters. We find that
k=O . .o0137
K
= 4'16
a I
K
- 0 ")-9
B -._':>
Kc::= 0.424
In the problem it is given that K. ... is 1 or 2 orders of magnitude greater than KB and
~ : which is tme so this is a good auswc{.
1030
T
3.200 J ...
2 .... 00
t.600
0.8CC
0.000
Model: ,. azi<.""Pa ..... ' 1 ... P.aKb.Pbl(h)(Pt')-2
" 0.00137022 ICb .. 0.259382
Ka .. '+.7608'11 1<1'\ '" O. "t2359
o on
:;lAta
[J <i),
vat de
? pOsatlv'@ .. ls. :3 .... 5lC:luals. Sum o! squa
r
-E1'S '"
PIO-ll (C)
The estimates of the rate law parameters were given to simplify the search techniques to make sure
that it converged on a false minimum. In real life, one should make a number of guesses of the rate
lw parameters and they should include a large range of possibilities
PIO-12 (a)
Assume that the second reaction is the rate-limiting step.
Using PSSH, we know that
rS"'H ",= 0 = k1CSu sC
I 4'" . lD4 'V
10-31
Perform a site balance:
Combining all of these we find:
This rate law is consistent with the data. As the concentration gets larger, the
rate change gets srnaller which is consistent with the rate la\v as given.
PIO-12 (b)
No answer is right or wrong, but the points will probably be higher than
the ones given to see that the change in rate becomes even smaller.
PIO-13
Assume the rate law is of the form r
D
=
ep 1 + KP VI1PO
At high temperatures K J,. as T i and therefore KP::rIPO 1
'[Yep = [PO
'[Yep
--=k

0.028
Run 1 ----2 =11.2
( 0.0.5)
Run 2 0.45 = 11.28
(0.2)2
7.2
Run .5 --2 = 11.25
(0.8)
At low temperature and low pressure
'[Yep =
r
--.!l!L = k

Run 1 .2.
004
= 0.4
(0.1)2
10-32
Run 2 0.015 = 0.375
(0.2)2
These fit the low pressure data
At high pressure 1
_ _ k
r
Dep
- KR2 - K
VT1PO
This fits the high pressure data
At PVTIPO = 1.5, r = 0.095 and at P
VTIPO
= 2, r = 0.1
Now find the activation energy
At low pressure and high temperature k = 11.2
At low pressure and low temperature k = 0.4
In(k2) = = E(!2 -7;)
kl R 7; T2 R 7;T2
In(I1.2) _
0.4 - R (473)(393)
E =7738
R
cal
E = 15375----
mol
PIO-14
r1"iD,. :::::
1;;:; Iv + ft.s;::: iv(l+ K,fj)
:: Kp Ii "" Kp Pfnp/PPI
_ ks Pr Kr
I'iiOt----
1 + PI Kr
10-33
ks Pr Kl
;:; 'r::;:: Kr
h-s:::;
==
kPirIP I pp! kP;'TP
r
no
, = 1>;1'"
Low Pnn>: Rxn is second orrier
Since 1 K PfnpfPPl
High PIT!P:
Reac:tion is ze:ro order
High Tempermure Kr very smail such that
PIO-15 (a)
Using Polymath non-linear regression few can find the parameters for all models:
See Polymath program PI 0 1 5. po I.
(1)
POL YMA TH Results
Nonlinear regression (L-M)
Model: rT = k*PMl\a*PH2I\b
Variable
k
a
b
PreciSion
Ini guess
1
0,,1
0 .. 1
RA2 = 0,,7852809
RA2adj = 0,,7375655
Rmsd = 0,,0372861
Variance = 0,,0222441
Value
1 .. 1481487
0 .. 1843053
-0,,0308691
a = 0.184 = -0.031 k = 1.148
(2)
POLYMATH Results
Nonlinear regression (L-M)
95% confidence
0.1078106
0.0873668
0,1311507
10-34
Model: rT = k*PMI(1+KM*PM)
Variable
k
KM
Precision
R"2
R"2adj
Rmsd
variance
k = 12.26
(3)
Ini guess
1
2
= 0,,9800096
= 0.9780106
= 0,,0113769
= 0,,0018638
K
M
= 9.025
OLYMATH Results
Nonlinear regression (L-M)
Value
12.256274
9,,0251862
Model: rT = k*PM*PH2/((1+KM*PM)A2)
Variable
k
KM
Precision
R"2
R"2adj
Rmsd
Vari.ance
k = 8.409
(4)
Ini guess
1
2
= -4.3638352
= -4.9002187
= 0,,1863588
= 0.5001061
KM=2.83
POL YMATH Results
Nonlinear regression (L-M)
Value
8.4090333
2.8306038
Model: rT = k*PM*PH2/(1+KM*PM+KH2*PH2)
Variable
k
KM
KH2
Ini guess
1
2
2
Nonlinear regression settings
Max # iterations = 300
Precision
R"2
R"2adj
Rmsd
variance
= -3,,2021716
= -4 .. 1359875
= 0,,1649487
= 0.4353294
Value
101,,99929
83.608282
67.213622
k = 102 KM = 83.6 KHZ = 67.21
PIO-15 (b)
95% confidence
2.1574162
1.8060287
95% confidence
18.516752
4.2577098
95% confidence
4.614109
7.1561591
5.9343217
10-35
We can see from the precision results from the Polymath regressions that rate law (2) best describes
the data.
PIO-16
Using Polymath non-linear regression few can find the parameters for all models:
See Polymath program P1 0-16.pol.
(1)
POL YMATH Results
Nonlinear regression (LM)
Model: r = k*KNO*PNO*PH2/(1 +KNO*PNO+KH2*PH2)
variable
k--
KNO
KH2
Precision
Ini guess
-1---
1
1
R"2 = 0 .. 9709596
R"2adj = 0 .. 9645062
Rmsd = 5 .. 265E07
Variance = 4 .. 436E-12
Value
0 .. 0030965
57_237884
10l. 9967
k = 0.0031 KNo = 57.23 KH2 = 102
(2)

POL YMATH Results
Nonlinear regression (LM)
95% confidence
3 .. 702E-05
1.0353031
2 .. 2870513
Model: r = k*KNO*PNO*KH2/(1 +KNO*PNO+KH2*PH2)
Variable
k
KNO
KH2
Ini guess
0:1--
10
1
Nonlinear regression settings
Max # iterations = 300
Precision
R"2 = -9 .. 6842898
R"2adj = -12 .. 058576
Rmsd = 1 .. 01E-05
Variance = 1.632E-09
Value
-----
-4.713E-06
-108.42354
1 .. 046E-05
95% confidence
l.297E-05
4.9334604
2 .. 878E-05
k = -0.00000471 KNO = -108.4 KH2 = 0..00001046
(3)
POLYMATH Results
Nonlinear regression (LM)
10-36
Model: r = k*KNO*PNO*KH2*PH2/((1+KNO*PNO+KH2*PH2)"2)
Variable
k
KNO
KH2
Ini guess
0.1
10
1
Nonlinear regression settings
Max # iterations = 300
Precision
R"2
R"2adj
Rmsd
Variance
= 0,,9809761
= 0,,9767486
= 4 .. 262E-07
= 2 .. 906E-12
Value
5.194E-04
13 .187119
18.487727
95% confidence
2 .. 242E-04
7.659298
7.7652667
k = 0.000519 KNO = 13.19 KH2 = 18.49
The third rate law best describes the data.
PIO-17 (a)
Mole balance:
dX
- .... ..... = ,_ ...__ ........ "
dW F
AC
Rate law:
Decay laVor:
.4.': .. =._
dW Us
Stoichiometry:
Evaluate the parameters:
8=.8
POLYMA'I11

d(x) la{w} :::a* (ra) Ifao
d lal/d(w) ",kd*a "ca!Us
kd:::9
fao=4000COO
1037
m
tial
..y!!!!!
o
1
Us=250000
k::::90
cao-= .. 8
eps'" 8
ca=cao* (1. "xl f (l+eps*x)
50000
PIO-17 (b)
Mole balance:
,',4 ==
dlZ
(d; Nov 1:::.g ,. Sed Reac cor
Ca
- x
Everything else is the same and we !Jt:cd to know"
V
r = ,., = 0.004
Ii;)
5 CS'ffi' s in Series
value
1
d (ca) fa (t) ;ca4!t.au ( ( (1*ya4) I (l +'ca/eto) ) t tau'a *k;) 'ca/t.au O. 8
d(ca41/d (t) "ca.,3/tau'" ( ( (1+ya3) I (1+ca4/eto) ) tau a*k) *ca4/t Q 8
d(call/d(tl"cao/tau'" (l'-yao) I {l+callcto ttau*a"k}*caJ./t 0.8
d(ca2) lalt) "'cal.ita\'!- (l+yal) I (lica2/cto +tau*a"k) 'ca2/t 0,8
d (ea}) hilt) "ea2/tau- ( ( (1"'ya2ll (1+ca3/cto) ) +tatl'a"'k) 'ca3/t o. S
ko"'9
10-38
tau=O 004
cto;:l
k"'45
ca,0=0.8
ya4=ca4/cto
yal;cal/cto
ya,2;::ca2/cco
ya3:;ca3/cto
x=Ccao .. ca)/cao
yao=cao/cto
to = 0, t
f
PIO-17 (C)
.... q
Ca
--- x .
0.5
The only change from part (a) is the decay law:
aC
dt d A
WW
r == .._ .. _.llll!L .. _ .
Us
cit =:
Us
da
w ___ = .. _
dW Us
Integrating:
k.CW
In a = .....!L_.:i. ........... + k
Us
W=:WM.AX@a=l
k =:
Us
a =

d(x) Id(w) =a* ( .. :raj Ifao
k=.90
fao=40000DO
kd;;;;S
Us",250000
==50000
cao"" .. 8
eps'='.8
ca=cao*(1.-x)/(l+eps"x)
:ra",-k"ca
a"'e:)Cp (kd*ca/Us" )
PIO-17 (d)
LOOO

a
0"""
Ca
..-- x
Q.6CO
Q,100
T
I
"T"",
t
l
.....
.Ini:::!!::!.
o
tc) 'Moving<Sed Reactor (Count:er:::Ul:re.nt)
10-39
To find the Time-Temperature Trajectory we need to use the following equation
for first,order decay,
r "'d
E r [ E' 1'1 I 'IT]
t
1
300J J.
Since no initial temperamre \vas given, we assumed one of 300K This is the graph
of thar equation,
Temperature- Time
trajectory
1000
iii -800
... ::,;:
..... 600
E f: 400
;:) 200
o
PIO-I7 (e)
o 0,1 0.2
Time (h)
0,3
The two energy of activations are switched and this is {he new graph made,
Temperalure-Time
Trajectory
1000
:::J
iii -..800
i
0. w400 -
E ...
ill 200"
I-
()
. ""., ......... "'-- J
-..- ------------
The graph looks the same just the time is much smaller.
PIO-I8 (a)
10-40
For all of the parts, the mole balances and rate laws are the same, 'They are:
de",
---. = r v
dvV '" 0
'A::::: --kaC",
Find the equation needed f()f a.
da
--::::::kdaC
A
dt
a:::::: exp(-.-kdC",t)
a:::::l when t=O
Assuming values for Vo. k, and come up with the following graphs according to
the cases described,


d{ca) Id{w) =ra*vo
vo=lO
a=l.
ko=l
t=20
k=l
ra=,,k*a*ca
50
1.000
..... Ca
Cb 0 a-oC
_. a
!Ll!\CO
3 .. 200' T
..
o
(a) Cas. I @ t-1000


'-"-'., -.....-.... .. --.--- .... ...... - ... ..... -.-"'"'!
o Q."'OO Q
KJ;;,X.
.......
, Cll
- ill
" . ..., l
"*'"
:
0000 o.aoo
10-41
PIO-IS (b)
Find the new equation for a:
,_!la...;;;:; k a
2
e
dt d i\
1
a:;;;::"'
l+k
d
C
A
t
Using same values come up with these graphs:


dlcal/dlw)=ra*vo
vo",lO
kd"'.OOl
t",lOOO
k"'l
a=11
1
e1;:;
a
(h) Cas,"" II @ t::;:80
Ca
Cb
a
10-42

o
1
(!:Ii Cc.:so I @ 100e
{b) Case IE @ t=lG-
lSU
Ca
Cb
- a
PIO-18 (C)
Find the new equation for a;
__ .da = k aC
ilt d B
a;;;;; expC kd C st)
The following graphs are made:
Eouat.ions: -_. __ .-
d(ca) Id(w) =:r:'a*vo
d(cb) Id(w) '"l:'b*Vo
vo=lO
kd=.OOl
t;;;;1000
k:::l
a=;exp( kd*cb*t)
z:b;;;;:k"a"ca
J:a",k*a*ca
IOO::
..... Ca
. cb
-a

1.
o
Ie) Case I @ :-1000
10-43

ea
en
a
KE'(
Ca
cb
Q.
l.Oc:;
.. ooc
1.0':::
:}"iJ!:n'!
0 ... 600
c,.lIce
d.2{;!:!
J ;)GG
PIO-18 (d)
-----....... ....... ,.
2.0ae ".000 B,.ooe JO .. OQC
(e) Case lXI @
-:-
+
a inlO a differential equation we come up with this:
,,,... 4!!.. == kdCAG
dt
W
t :="
Us
..... . == ..
dW U,
10-44


d(cb)/d(w)=rb*vo

vo",10
kd=.OOl
Us;1.0
k=l
.th::::::k*a*ca
ra.t=:'""k*a
1rr
ca
KEY
Ca
C.b
a
ld} CaSe: II
(d) Case III

Ca
Cn
.....- a
lnitia!
1
Q
1
(d) Case I

1 .00(/

Ca
Cb
a
... - .... --.-.--.-.. .. -.... ' ............ -
T
(j .. QOO
PIO-18 (e)
r -,
t
1 ..
0 .. 000
..,..... .... ... -, ..... ...
.... ::..:.+=:-... ;. .. .. -.-----i-'; ---
::.000 '.oeo .. 000 a.ooo
10-45
=i
lo,ooe
Everything from part (d) is the same except for the decay law. .
. =-k.aC
dt 4'A
_ _. HI
t--_,,
U,
dW
dt= - .....
Us
da kJC, a
... ==:
dW Us
Integrating:
In a =: + k
Us
\'11 =- \V
iv1A
.'.: @ a == 1



vo"d,O
kd"l
k=,001
'..mlOlx;;10
a"'exp(kd.*ca/UsX (W'wmax) )
:t:bmlk'-,a,*ca
"'0 '" 0,
10
10-46
o
......... --- ... " .. _- +-- . .. .. .. --1
... 1> coo G: ace
EEX
_. Ca
", Cb
- a
f;EY
- Ca
... Cb
_. a
'T
t,
I
-'
(:) Case II

a.ooo 'c_ooC
i ., .. ,.,+ ' .... ........ ' .. .. -.'. ... .......
... _ ..... ,..." ... ... . ...-. __ ._.......,
0,000 2 .. CO(; .. boo :i" 10-:; a. 00;]
PIO-19(a)
da =-k
dt D
W-Ut
- s
__ 4..f!.. = =kD a = 1--
dW dt Us Us
kDW h Us 5 k
If 0=1--- t en W =---=-=2.5 g
Us kD .2
!X = -TA (0)) = (l_X)2
dW F
AO
F
AO
F
AO
dX = (1- W J kC AO (1- X)2
dW Us Vo
f dX = kC
AO
fl- kDW dW
(I_X)2 Vo Us
dW=Usdt
Activity is zero for W > 2.5 kg, so the catalyst weight only goes to the effective weight.
10-47
----- W --- - 2.5- -0.25
x _ kCAO [ kDWe
2
]_1(0.2)[ 0.2(2.5)2]_
1- X Vo e 2U
s
1 2 *0.5
X =0.2
PIO-19(b)
1
o ________ ______
o
2.5
PIO-19(c)
For infinite catalyst loading a = 1.
dX = kC
AO
(1- X)2
dW Vo

I-X Vo
X=0.5
PIO-19(d)
kC
AO
[W _ kDW2]
I-X Vo _ 2U,
0 .. 2*25]
1-0.4 2U, _
kg
Us =1.5-
s
PIO-19(e)
kDW
a=I----
Us
0=1- kDW_
Us
5
10-48
Us =k
D
W=0.2*5=I.
kg
s
PIO-19(f)
a = 0 means there is no reaction is taking place. Activity can never be less than o.
PIO-19(g)
U=-U
s
. da = kD
dW Us
kW
a=-D-+C
Us
I
_kDW; C
---+
Us
a = kDWe +1- kDW;
Us Us
Now find We.
0= _kDWe.+ I_.kDW;
Us Us
when W = W;, a = 1
We = Us [kD"i. __ -IJ
kD Us .2.5
We =2.5
dX.=(I_ kDW; +wJkCAo(I-xt
dW Us Vo
1
1
- kDW; +W I-lW
I-X Vo Jl Us r
[(W; -W.)(I- kDW; J+.W;2 --We
2
]
I-X Vo _ Us 2.
= 0.2 [( 5 - 2.5) (1- 0.2 * + 25 - 6.25]
I-X 0.5 2
X
--=1.875
I-X
X =0.65
PIO-19(h)
$ = I60F
Ao
X -lOU
s
10-49
a
\Ve
\\'
\Vt
kDW
a=l---
Us
dX =ka=k(l-!'DW]
dW Us
X =kW _ kk
D
W
2
2U
s
To maximize profit, a maximum in profit is reached and so we set the differential of profit equal to
O .
. d$ =O=160F dX_
lO
dU AO dU
s s
dX kk
D
W
2
dUs -
160F kk
D
W
2
= 10
AO 2U2
S
8F
AO
kk
D
W
2
=
Us
Us =4
mm
PIO-19(i) No solution will be given
PIO-20 (a)
Stan with the mole balance for a balch reactor:
Rare lavv;
Decay law:
da '
.. -._-:z: k a"
i
J
( t
Stoichiomeny:
Plugging those into POLYrvlATH gets the fc)llov,.ing program and the following
graph
10-.50

dlx)/dlc)=-rt"w!cto

w=5
k;:=20
kd"'.l...6
v=l
2.;.082
T=735
:).&00
/,/
r //
T /
-1- /
t I
Tf
II
o
1
....-
p1:=pto (1 x)
rt"'-kcpt"a
lltO=pt.o"v/ (R"T) Tl
-!---..... -- ....." ...............- ...................... f------.--j
::0 = 0,
n.ctio
PIO-20 (b)
For the movingbed reactor the mole balance now becomes:
dX .. /;

dW F
M
)
The decay la\v nOw becomes:
da k"a"
."""'----:"" . ...:::::... ........ .
dW Us
Everything stays the same.. Plug into POL ThIl\ TIl.
The conversion achieved is X:::: 0.266

d(x) Id(w)"'-!:t:./fao
d(a) td (w) ", .. kd"*aA2/0s
kt",,20
ao,,600
l<d"1.. 6
Us=:2

'"
a. ::u;;;:: ..
o
1.
50
50
o 266;6
a loS:.5
pto:2
pt"'pto* (l"x)
xc,,kc"pca
0 0243902 C .024.:130:
20
'NO'" O. We
PIO-20 (C)
50
fao
1<;d
20
500
;;
2
2
-.:10
20 2<';
600 teD
1 6
,
5
2

--0 .7:5i4:
c) Increasing Us \vill get us a higher conversion" Looking at this summary table,
U. = 10 kglh and X :: 0.6
10-51
600
1 Ii
;;:



\01 ()
50 0
50
.,.
::. 1 o. :lllll 0 111111
x 0 O,SS9-i:iSS ()
CL 599686
600 600 600
600
kd 1.6 LoG ]',6
1.6
Us 10 :),0
10
10
kt 20 20
20
20
pta :2 :2 :2 :;:
pC :2
:2 0.e00625
0,800625
t't -40
-l. 77917 -4.0 --1.77917
PIO-20 (d)
For second-order decay:
For s:::: 25 keal/rno! and E
4
::::: 10 kcalimol:
Use tlris equation in Excel to generate the following graph:
Temperarurc .. Time Trajectory
- soo r------- --.------- -, -- ----------1
-----
%500 -- -- -
..
'"
i 'wo t-- --------------
I
"]00 " , .... "' ....... ,." .......,....... .. .. ,.
Q 100 400
'lime (h)
Temper ature-Time Trajectory
,-=10 lInd E;.;2S
1600 , ...... ,.--.-.... --.,----...
bOD
o
tim" (h)
Use this equation in Excel to generate the above graph.
PIO-20 (e)
10-52
In part e, the only thing that changes from (b) is the decay law and the decay
constant:
da krJP/a
2
""-'"-=-..::......:....-
dW Us
ka = 0.2
Plugging into POLYMATH we get the following summary tables for Us:;:: 2 and 10
kglh .. X:;:: 0.50 and 0.88 respectively. X will again increase as Us increases.

d{x)/d(w)=-ra/fao

kd;;;.2
u5=2
fac=600
kt=20
pt.o.:Z
pt"'pto" (l-x)
kd
uS
ao
kt
PI0-21 (a)

\)
o
0 .. 2
1()
600
20
2
2;
.. 40
!.!'!.ili! ....yalue
w a
1.
0,,2
Us
tao &00
20
2
,,40
!ni
o
1
..
so 0
0 502431 0
1. O.lC411J5
02 0.2
:2 2
600 sao
20 20
:2 :2
:2 0.9951.38
2.08253 -40

50 0 SO
08']5709
1
0 2
10
600
20
:2
2
2.75389
(I
0553922
02
10
600
20
Z
0.248581
-40
(I 37$'109
o 553922
0.2
600
20
,/.
o 243581
-2 _ 75389
A -7 B Elementary reaction with 1
st
order decay.
da
-=-k a
dt D
a = exp( -kDt)
PI0-21 (b)
10-53

So
0.502431
0 .. 104635
0 .. 2
2
600
20
:;!
O.99Sl38
2.08253
t
The activity is never zero for first order decay. When a = exp (-kDt) there is no t such that a = O.
PI0-21 (c)
Mole balance:
dX --r' W -r' W -r' W
_= A = __ A _=_A._
dt N
Ao
CAOV
O
CAO Vo
Rate Law:
r
A
' = -a [ --fA' (t = 0) J
-r
A
'(t = 0) = klC
A
Decay:
a = exp( -kDt)
Stoichiometry:
C A = C AO (1- X )
Combine:
dX W
dt- = exp( -kDt )kl (1-- X ~ ~
(
1 ) kW [ J
In -- =_1 - l-exp(-k
D
t)
1-X k v
D 0
X =1-exp(_IsW [1-ex
P
(--k
D
t)JJ
kDVO
PI0-21 (d)
klW (0.2)(1)
-= =2
kDVO (0.1)(1)
X = l-exp( -2[ l-exp( -1)J) = 0.97
10-54
PIO-21 (e)
Decay rate increases more rapidly with temperature than does the specific reaction rate. Therefore,
conversion decreases with increasing temperature.
PIO-21 (1)
kjW (T) = 2ex
P
[-1500(_1 ___ 1_)] = 0.57
kDVO 310 400
k D= __ 1_)] = 0.53
300 400
X = l-exp( -0.57[1-exp( -5.3)J) = 0.43
PIO-22 (a)
In order to get a high conversion the en.tering pressure should be as high as
possible since the rate is a sewnd order function of the pressure. U should be
kept low since the conversion is an indirect function of the flow rate.
PIO-22 (b)
11\e problem with such a low flow rate is that the activity will remain low
PIO-22 (c)
We (an use the same eCluations that are given in example 10,7 with a few
exceptions. For example the rate law, we use the one given in the problem:
I11e activity will be different because the equation given is different:
:;::; k naCcoke
da kDaCcoke
..... , ......., ..... ::;:, .......'""- ..........-. .....---..
dz U
To find the concentration of coke we use stoichiometry:
c , ==
'cot(.e RT
We fmd that the value that gives the best conversion (X;:::: 0.337) and nses the
whole reactor is U :;::; 7. See the following POLYMATH program.
10-55
..:
d(a} Id(z)
d(x)idlz)=-ra/U/Cdo
22-
kc.;;;;1.OO

ao.:;:?

R=.OS2
pao=12
:,;-no=80
U=:Uo*(l"e;:>sxl
pa=pao' (lox) I (l+eps'x)
(I Teps xl
rapr ime=a' ( kpr ime 'p-,a
ccoke=pcoke/R/T
ra:::rho""r:aprirne
PIO-22 (d)
;;;
cao
;Cd
k."1J::;-Z:;ne
tlo
eps
R
T
pao
rho
P"
p-coke
.x:ap;:-i:ne

o
1
o
(} 22
:00
7
o 082
67)
12
80
L2
o
0 0{)12
Inicial ... :alu
1.
.)
15 o
Q 00C2549';8
G 316731
0 .. 22 0.22
100 leo
5e: 05 5e-CS
7 7
1
032 0.082
6"1:! 673
12 12
Be 80
35711 )
12 5.95425
} 0.2288 0
..
-0.0072
0 0547762
3.61547e05 0 51G
To fmd this the only change necessary was the values for the k' s because
they change with temperature.
_ r" ED (1 1 \'1'
kD :;:: lOOeX
p
! --R6ij-i)
LS

a 33673:
:) 22
100
5,,-05
12
BO
9.35712
s. 9S425
) 02"288
-4 S1.934e'O'l
o
..... ....I
The POLYlvlATH program below shows the results. The temperature is 485K
and the conversion is 0 .. 637 __
10-56
Equations:
d (x) !d(z} ;--ra!U/cao

cao;.22
Uo:;;2.5
R=.082
T"'48S
pao"'12
!'ho::30
kd=lOO-e>..'P (15000/1. 987 (1/673-1/T) l
kpri.me::oSe-5*exp(30001l .987* (l/673-l/Tl)
U:;;Uo*{1. ... eps*x}
pa=pao" (I--x) I
pcoke"'pao*x/ (.l+eps*x)
ccoke=pcoke/R/T
J:apr.irne"'a* (-kpri.me"'pa "2)
ra=;rho'raprime
'0 "" O.
:nit:ial_'ya1:!:!.! MaximlmLy!!ue UEill value
cao
Uo
eps
)cd
kprirr.e
pa
pcoke
ecok.
PIO-22 (e)
o 15 (} 15
o 0 6374aS 0 0 637285
1-
()
.22
;J .5
1
o 082
485
12
80
1.29 ..31
2 .. 09558.-05
2.5
12
o
o
-(}. 00J01 763
0.24141
() 605597 (} .605697
o 22
2-5
1
C.22
2.5
1
0 22
2, S
C.082 0 082 Q 082
485 485 4S5
12 12 12
80 80 80
1.29n 1.2932 1.2932
.2 09558. 05 2.09558e-05 2.09558.-05
I 09121 2.5 4.09321
L2 2.65841 2.65841
4.670& (} 4,6708
0.lL7445 0 0.117145
-897021e-05 0.00301763 a 9703le-O!
-0 00711616 0.24141 -0 0071161&
10-57
Initia.l
a
1.
To find the temperature-time trajectory, use equation (10-119) and add C,o\<e
'iNhere necessary:
The following curve is generated from that equation.
o
PIO-23 (a)
0 .. 005
rO-
01
t
Ime,
~ ... ,,- '--'"" .... __ ..... ,,_ ... ,,--_ ................ 'T
() 015
I I
-------l t------------7
~ . ~ . ...,.-"" ..............,.-......",
Design equation:
Assume W=lg
Cumene
(A)
FAD (lX)
r=FAoX
.... '"
Propene
(R)
FAoX
+ Benzene
(S)
FAoX
The amount of cume:le hydroperoxide does not com:ribme SignL.+J.caIldy co the roml number
ofmo!es.
or X =:_:!2.
1 Ys
10-58
X .0204 .0165 ,0133 ,0107 ,00851 .OO563l .00311
a 1 .809 .652 .5145 .410 .276\ .182
t 0 50 100 150 200 3001 400
-
1n a vs. t gives the best fit a "" c-o.
t
'Iberefore. decay is first order with decay constant of 4.27 x 10
3
(sec-I)
PIO-23 (b)
C
A
:; FA"", (I-X)
U u
. 1L F AU (1+X)
Assume no AP. ... "" _ll. := ...... -- = V .::::: ( 1 +X) vo
Vo no FAO
C
A
::: "" CAO l!:X)
, '1,)0(1 tX) (l+X)
P A := C
A
RT =: CAO RT
(l+X)
Mass balance: F AO dX ::;: rdW
10-59
.00241
.118
500
F AO = 2.0 rnol/Il"Jn :: 1/3 mol/sec
CAD '" 0,,06 kmoVm
3
== 0.06 mol/l
R =O ..
K'moi
T "" 273 + 420 :;; 693 K
k ::: 3.8xlO,3 mol/g sec ann
Ct. ;: 4.27x 10--
3
sec,l
W =: 100 kg
Us := 10 kg/min:;; 1/6 kg/sec
Equation (l) becomes:
2ln (lX) -+ X =: ,CAn ..
. .. .. r L .. 3:.:.1.9.0.9 \. 1
2m \ lX) -r X ::::: - - ... I exp \ L J 11
3 .. 6
.. x == LOO
PIO-24 (a)
s .. :;. W +. CO
2
: first order, irreversible..
... da:;:;; k<:J. an C',!1 == k.i an
ill .">
.fA =KaC
A
10-60
- - --- - -- --------------- --------- - ---- - - --- -- - - -- -- -- - -- --- -- - -- ---- -- - - --------------------
For T :::::500K
X%
l!1ntL\
, iI-X!
For T::::: 550 K
o 20
0.,7 0.56
60
0,4.5
80
0,38
120
0..29
99,5 142 178.1 2..2L7 262.6 3443
o 5 to 1.5 20 30 40
X%
1 .,
,.- 0.89 0,,69 0.51 0,42 0.33
, I \
11ln 1 ..... ,1
q .. X!
.!9,,5 87
-.....
111.8 1444 174.9 237.6 302.5
4W,.
I
I
3QQ
I
In(lJ(l-X) I
=1
aJ..I---
G
They axe Straight lines ."" n=2
For TI "" 500 K : slope:: 2.04 }
=('tKh
, =:>
For T 2 ;: 550 K ; siope;:: 6.325 }
{-c K)z ;; 0.02
'-II.
t
z:::> "" 0.02

&::..Jl.QL.: exn {-.!fLf.....L _l_l}
K.s
t
0.1265 8.314 \550 5001
= {- (i
l
)} == K.it exp {- ('s60)} = 0.02
K.i
t
= 1.296 x 10
3
We want to maimain Ka = constant
10-61
+T=500K
OT=550K
K t) := Ko
Ko exp {f t)} Ko (1 + Ki t)
c;cp f E \f ,. l \JL 1 := v -- t
. IR To T I
r E( 1 IJ\']
j ,- 1
t :;;;;; ,---""""-""- ,---------"""""""--""""':,'" --,
Kd
I
""", . .1
l"""",,,
480 485 490 495 500
PIO-24 (b)
Since the equation for the acivation is:
a='""'
1 + lcd'
we cannot find a time for which a:::: 0, because it is mathematically impossible. We can, however,
find a time at wbich the activity is small enough that it can be considered to be zero, The following
graphs show the activation for'the two temperatures given
0 B
> 06
()
Activity of catalyst
500 1000
1500
time (days)
10-62
' ..... a (SaO)

The graphs show that for sao K, the lifetime is about 1100 davs and for 550 K
the lifetime is about 450 days. "
PIO-25
First we need to tlnd C
AO
'
.. l!2_:::: 10
ETB
YTfJ =0.1
C "" !l.tu .. = = 0.065
AO RT (8.309)553
Start by guessing that the decay is fiIst order:
We were told that the reaction is zero order when the conversion is less than 0.75.
This is true at any time after 2 hours. We also need to fmd the denominator
as a function of conversion.
X
C
AO
C
AO
.... C:<t ;:
So we graph this:
This is the graph that we get:
tn (1/cao*x vs
time

o 5 10 15
Time (h)
As can be seen this graph is linear which means that the decay is first OldeL We
also know that the slope will be the decay law constant so kG :: 0.2024.
10-63
PIO-26 (a)
Mass balance:
Rate law:
Decay law:
.9
a
,.
dW Us
Energy balance:
dT
Fa ) { '( , \
.. : .. -. (T A"'" T + "fA )AH Rx )
-_., ....... _ ...".=
Stoichiometry
Evaluate the parameters:
k "'" 0.33 eX
P
[3777(.!- -- 1
450 T J
[' 1 \1
k,. :::: o.,olex
P
!7000( 1 "T""')!J
.) L 450 ,
Plug that into POL ThiA.TH and get the following program and answers U
g
to get
maximum conversion will be 17 kg/g,
10-64

a(al/d[wy=-kd"a/:J
d(x) la(w) ,,ralfao
dlT) fa (w)" (Ua r (Ta"T) ... ! -::al (Dhrl) }! (U"cps+fao*C!;>d)
fao=5 .. 42
U;17
1'a=323
Dr.rl=80000
<;:p5=100
cpa=40
Ed=7QOO
Er=) 777
cao".27
eps=l
U"-"'.8
kd", .. Ol-exp (Ed' (1/450-1/1') )
k:: .. 33 'exp (Er" (1/4501/T} )
Cd"cao" {tx)! U .. epsx)
:;).. 27

a
"
l'
f."
0
1'a
Dhrl
c:ps
cpa.
Ed.
E:::;
cao
eps
,;;""
loa
"
...
,)
.So
5.U
11
n3
.. seooo
100
40
fOCO
J r17
0.21
O.S
0 O!
0.,33
Q


so C
v 2-::-1596
o
.. 61,3 He
5.42 5.42
1J 1'1
321 123
3]oao S()OOC
leo 100
40 40
loon 7000
37Ti 3777
a 21 027
l.
Q B OS
1.:,)4e;. o.n
<I H;:a a B
ca Q,;n 0.27 C Ol61349
:a
,0 069: 0 C:Q;9:2S .. 0 l.4S41
PIO-26 (b)
Using the same program we can see that the maximum conversion is 0.887
PIO-26 (c)
Everything is the same except the energy balance:
dT Uaw ('fa ..... T) + hap(Ts _.- T) + )(llH
Rx
)
........., .. .:.::: .......- ..-..... -...-......- ......... .......-.--.-.. - ...----............... ,.,.... "." ..... -........... .
dW FAOC
pA
1<Ve also need an energy balance on the catalyst particles ..
Choose values ofh and a! .. We fmd that Ts needs to be slightly Ingher
than l' in order to get a large conversion. The maximum conversion will
be different for each T5 that is \1se(i
CDPIO-A
10-65
...
SC
;; 211536
0 887222
6{S 6:3
S <12
17
32}
.. 8;10000
.:CO
40
7000
3';77
0 .. 21
o a
1.:"1401
4>"
0,0161349
".OISJ92S
Given: The catalytic oxidation of ethanol
CH3 CH
2
OH +}' O2 -1- C:FI3 eHO + H:cO
Denote: A[=]CH)CHzOH. B[=]0130IO, W[=] H20 , A'S[=]ethCfhO'S
Mecha111sm is belived to be the following:
A 25

A-S +B-S fA = leA [p A C "' CA-s CH.s!K.J +
t-,
(h
+ 23" f:!
20-5' -ro:= ko(P<4 (:-;, '"
AS
+o-S'
""'T
B +OHS' +$ 'TAO:::; kAo[CA'$ Co.s' PE ({)ii-$" Cs/KAO]

OHS' +HS W+S + S' rw = kw r CoH-$" Cli-S - Pw Cs Cs,!Kwl
L J
It is given also that CH,s = CA,s
'''fa
i..o.;:O
A
:ro,=O
k.:,-
cbs' ::: Ko Po: or Cos,::
" Pw Cs es, .. '0 'r?'-""--
(-{)H-S' LH-S "" -'K.;-" wltn CH-S;::; Y!'.A. .t' A Cs
PwC
S
'
COrV' c;;;;; -.--... ---
.) Kw 'iKA,P
A
CT;:; Cs + eH's + CA'S:::::; Cs [1 + HK;;"P;]
""" ''''' "I.... r . ..-..,. Pw
('I "" eg + C,)-S' .;. (iJH-S':;::: (S\l+ Y Ko P
Ch
-+;:
L Kw yKA,PA
, r", PE c,:'.m.s' Cs 1 ."1' r----..,.------,,, , Ps Pw Cs CS'
--lAO""" k.i\O i CA.S COS' ""--;::::--"1 = kAO 'i KA. P
A
Ko Po:: Cg (S - ---..
!. I\..AO ..: L Kw KAO 'i KA P A
r . 'K"K"'C C - .
_ ?-.AO 'i . A {) SS; .,----- P-a Pw I
"tAO - "" ......... =--_._--. p A, ! Po" .. -_ ... ,,_._-_-._"'-",._-;
'I FA l. " .. K", Kw KA,cdKoi
K""1.::= K;.. Kw K..,o {K;:;
kAO iKAK:(:; Cr C
r
[ P A -{pc}.- . J
r AO _ ... , .... _ ......................................................... :"'''' ..... ''' ... , .. , ...................... - ............... ........ , ............t ..
{P;'l'l + .. 2'1J{";A .. PA. ....] 1 + rKo-- .... Pc-:-
t
----. Pw I
, . -'7. Kwf"KA P ",J
Initially PB =:; Pw ::::; 0
10-66
(b) With reaction 3 irreversible, 'IAO::;;; kAO CA-S (:Os', Since AS. HS, OH-S' are created
(and desrroyed) only at the reaction swface. A stoidriomerric relationship existS between
(a)
The same equilibrium expressions for reactions (1), (2) and (4) exist as before:
(b)
PwCsC
s
'
CoH-S' ::;;; -- ,
Kw
(c)
Expressions for Cr and C;. become
,y> PwCsCs
wIth K A P.4 (, S --K" -""".,-",
IV
CT == Cs (1 + 2fKAPAJ

1
+ +fx'x ]
10-67
Rate expression becomes:
T =- ...... -.... .
A
CDPIO-B
We can first try to come up with a rate law for this data. We can see that as P
E
increases the rate law also increases but slowly the amount by which it
increases becomes smaller this tells us this:
We can then see a similar thing happens as PH increases so:
I Fc!
""!A "" ..., .. , ....., ..... _ .... _ ...... .
1 +KUP
H
Sin,ce both reactants are adsorbed the me(hanism must be a dual site, This
makes the rate law:
o::.,.".,. __ ~ ~ J L _ ....... .
1 +KEP
E
+KBP
H
We can then plug this into POLYMATH. and we then get the follOWing values
for k, KEf and K
H

k= 14.6
Kl) =2 .. 63
K
H
= 1.76
10-68
lO"'8
--,.
t

I
! !
f t
! t
I
I I!
A .... __.... _ J .. ____ L.i .. _ ... _.
c. ace . .J.. .......... ..... ......... --- ............J?-._ ...... _ ... fF. ... .
o.
0.320
C .. 1SC
2 3 e 6
t ....
'" 1 "I .. 53-.... :<" '" 1.75797
;(0/ '" 2.63'17!
... !.atec

1 PQ5t':l\li:" -rE'-SLdr;.;.atsl" 6 neq.,at!;\I(o 1"@$lOU.a!S .. Sum: of squaf9S::::
CDPIOC
(1) NzO + S N20 S
N:zO S -+ SiO S 4 Si0:2 -t. 25 + N2 (Rapid)
rSiOt ;:; Pues PNf?
1 + KPN;;()
(3)
dF -
a
dV A
'Plug Flow Reactor)
10-69
k P'AO (lX) (SB-2X)/O + EX)2
'f
A
= ---------:---{e- -2X}-'---
1 +- KB P
(1 t EX)
k P).o(1 .. X}{SB .. 2X)
:; (1':; eX? -2X) eX)
as
;;::; 1..1.:.2:: 07
. 3 .. 68 -' ..
E:; +- 2 1- 2):; 0.25
11.;) + ).68

1:300
1200
!!l.r 11 00
A

300 .00 500 600 "lOa sao 900 1000
TorT)
Slope =: K. == 0.7465
k'
Inr.erceut ::;:; 1 = 703
k
k::;:; L49xlO-
3
NmTotr'-rr.in
K = Llx10
3
mTorr
1
KB::;:; 1.1 x 10.
3
In Tou
l
KB PAl =(1.1 x 10.
3
)(157) -= .173
k 1.49 x 10 ..
3
(1.57)2::;:; 36.68 Nmin
-r* ;;::; 36.7 Nmin (39.?: .... _._ .... _._
A (1 +- ..25X}2 +-.173 (3.07. 2X)(1 +ZSX)
F AO :::: 3.68 x 10
J
gmok/min
-r* ;;::; {Nrrim}:: 4.4 X lO'-O r- (gmolel
A A (m2min)
a=:; 250 m
2
/rr.in
..Ya.. =:; IX dX Ar-.....a under curve of X YS. L
F 4
AD r r
I) A A
10-70
x . (m
2
/gmolel
...YlI.. .
V{m
3
)
FAO
0 73.6 0.0136 3091 0
0.025 70.3 0 .. 0142 3235 79 .. 1 00012
0.5 67.0 00149 3392 82.8 0.0012
0.1 60.8 0.0165 3739 1783 00026
0.15 549 0.0182 4139 196.9 0.0029
020 494 0.020 4545 217.1 0.0032
0.25 44.2 00226 5145 242.3 0 .. 0036
0.30 39.3 0.0255 5784 273.2 0,,0040
0 .. 35 34.7 0 .. 0288 6547 3083 0 .. 0045
OAO 304 00328 7465 350.3 00052
OA5 26.5 0.0378 8589 40L4 00059
0.50 22.8 0 .. 0439 9983 464.3 0.0068
-0.55 19.3 00517 il746 5431 0.0080
060 16.2 0.0617 14{)29 6444 0.0095
0.65 133 0.0751 17067 7774 0.0114
0.70 10.7 0.0936 21262 958 .. 2 0.0141
0.75 83 001203 27338 1115 0.0179
0.80 6..2 0.01617 36760 1602 0.0236
Reacror Volume per wafer:;;; 9.8 x 10
4
m
3
/wafer
:. Number of wafers, n::::: V!9.& X 10
4
A plot of conversion X. vs. number. of wafers can be obtained
200 --... ------ 80
60
c
ri
;;;
;
100
-0
"2"
40
:

ci
%
....
';"
2Q
o -..,. ... ...,... ....... -+ 0
0.0 0 .. 2 0.4 O.S O.S 1.0
10-71
Tne thickness on mest! wafers C:l.l1 be obtained. from tb,e same plot,
Wafer#l ; X"" 0
or' ;:;:: T3 6 N' !nin
A .
:. After 30 min:
Wafer #50: X '" 0.52
"" 20 Nmin
:. After 30 tnl.'1: @ ..b.
Wafer #110: X:: 0,78
:=; 6 Nmin
A
., .Aite:- 30 min: J 80 ,J.,
CDPIO-D (3/e CDPIO-E)
CDPIO-E
(a) For simDlicitv, letters were substituted for the sDecies in the
. ' .
Droblem sta tement.
"
The late equations for each of the three steps in the m.ecnanism
is given below.
Equation.s 1 and 2. are substituted into equation. 3 because the
third step (the deposition step) is assumed to be the rate
l.imiting step, we want to find the rate law of the deposition, and
we have data for the deposition rate.
10-72
.cuso, remember that we have the relation below:
f
. 1
v= .
1+ KcP
c
Substitute everything into the deposition rate law:
We now have to check if the above rate expression agrees with
experimental observations.
..


The rate of deposition is independent of AI' and 1h. .-YES
At low partial tJressures of TiCI. and NFL, the deposition
, . ,
appears to be first order in TiCl" and second order in

A.t high partial pressures of l'Hi], th.!'! rate varies inversely
with TiCl,.YES
(b) To determine the reaction rate parameters we must
:earrange the rate expression to a linear onn .. f
A plot of the experimental data is shown below.
'TItanium Nitride fUm Deposition
Model Veriiication
:::::i' , ... ,'_ ..... " ....... ". __ ......." ..... _._ ....... _. __ ._ ..
1200000 ..
1
f(x):;;.- ... l.2167%ii .... s:
R,o\l OIl 9 91t98UE.l
200000
Pal'b"2
10-73
1. l
- = Y .... mtcrc:;pt :: 2.2168 x 10
.Jk.!' .
k. ::::: 2.035x 1O-1l_._ .... .. __ '"
. em- min mT'
k.
== slope = 14 42
,J 1\..
. .
:::; :'i .. 505 X 10-
5
rnT3
(c) The experimenrai data, when plotted with the rate law
deri,:ed in this problem, form a straiO'ht line Thor'e''''''''''
. , .... _ . .::; .,.......... ...-...; .. """
ttV2 ;)roposed. Iri.eC.:1arusm may O used to describe ti'..2
depOSition or ru::ride fi.lms.
CDPIOF
Given: Ille dehydrogenation of ethyi benzt;';ne w st:;tTene:
E St +- H2
Quanur.lUve d::ua suggests re.lc:ion rare is of rhe fonn
Pj:;
-r;; a .... .... ,-:-.";::--p"'- where At, lu, A3 are consta..'1ts
1 '!'" "L E"" ."">3 St
T11t that {orE) is independent of Hl suggesLS that me reaction is i.::reversible, and that Ii2
is not adsorbed on the c;:;,ralysr Sth'iace. Also, the aoove expression for (-TE) suggests that
both E and are adsorbed on the su!face.". Try the following reaction scheme.

E "" S H St .. S t 112
Sf S ...;-)- SI t S
-fA::: kAlPECS CE.sf'.r.<.A]
rs == ks fCE-s '. CSt-S PHJKsJ
I'D '" kD [CSt-S - Ps,CslKDl
10-74
To insure that PH
2
does not appear-in the rate expression assume that the surface reaction
controls:
0 CE-S::: KA Cs PE
: == 0 Cst-s =
Then: CT Cs + CE-S + Cst-s :: Cs [ 1 + KA PE +
And rs =: ks [e
E
'
S
- Cst-s PHll ::; ks KA Cs [FE _ PSt PH! J
Ks J KAKS Ko]
Ks > 1, reaction can be considered ineversible, and its dependence on Pm drops ..
out:
kK",PE
rs :::;; ---..-------.. . where k;: ks Cr
1;. K. + EsJ..
.-. e KD
Evaluation for k_ KA and Ko
Rearranging the nue expression: P
e
. "'" _1 -. -+ fs. ....
-rs kKA k KokKA
with PS
l
---1> 0, a oiot of vs .. PE should be linear with slope {1.} and interceot (- ... L .... ).. Since
. "'5 k .kK
A
only two points are given with Ps
l
;::: 0, it is easy [0 solve analytically:
1 I 1.00 L415 x 10
3
- 0.214 x 10
3
._+-_7.:;:..06;;;..;...! .. .J
46.73 _.J

== + l (P-)l and f!:E..\ == .... L_ +.1 (PE'"


rsJl k KA k e \rsh k K." k I ..

from aoove: 1..;: .. 7iliJ."Z :::;; 666 7
k (PEh" {PEIl 0.01 1.0 . gmole
k :;;: 1.50 x 10 .. 3.
gm:;at-mm
10-75
,1 (PlZ \ 1. (P) '706 '7 - - - - 40 a..Wl-g:mcat-min
ana _.-;-.. _ .. == -I - E 1 "" .. bOO.1 "" _ ..--:--_.
k KA -rs h k gmo!e
K
A
::; 16.64 atm
l
Now, taking data points 1 and 3, in which PE is constant. the value ofKo k-K
A
a.ndhence
KD can be dete:n:ni.ned:
Forpoim L:
A '-'-I) A
Forpoim3: (PE) = .. L ... +1.(PEL ....
"IS 3 k KA k JJ Ko k KA
Substracting, and soiving for noring mat (PE); "" (PEn
(PEB (( .. Us),] 1.0 gIn cat .... lin
k K ... ==
KD =: 0.0075.34
.'. Rate expression is
0-
(a) = 106..1 --- ...... .
gmole
. . 1 grnole H..,O
Inen 8) = ._.: .. = 0..2
:;, grnole E
YEo=_L. =0.833 ; P""P
o
=OA15 ; XF=O .. 60 ; 15=21=1 ; T=903"K
1 + 8,
.'. <:: = VE {} (5 = 0. 833 . FSl( = kg m::!)' "" 19.2 kg = eXt'
. . , day 10.4 .. 1 kg day t.
.... F:=RT FE.COX)RT CE.{}RT(1-X} YE...oP,,{l-X)
PE "" CE R 1 = ---"" .... __ . = ...... _ .. _ ...... -.... -.--... "" ........ ............ --............. ::::; .. __ ... _,. .............
1.) 1.>0{ I +EX} 1 +EX 1 +X
F, RT FE-o X RT ., YE.oPo X
PSt"" CstRT "" "" 1)Ji:;.-x)"- '1+X
10-76
Rate expression for a.."lY X is:
0.025
='''''--6 "64" J 1-
1 + 1. - 1 ... eX j + -"," 'r'+ EX
Design expression for a C'.5TR (fluidized bed) is W =
w """ __ + 16.64 + p2.7 XF 1
0,,025 lYE.a Po (I,,,XF) l-XF j
:: _ FStt __ + 16,64 + 132.7]<F.1
0.025 XF lYE.O Po (I-XF) l-XF j
_ 19,2x10
3
gmoi 1 day i 1 +- 0.833 (OA5) , A 132.7 (0.45)1 1 day
- -,- daY-"_'" x 0.025 16,,64 + x
W = 7,,06xl<r g
Cost"" 70.6 kg x "" $T77
::>
(b) Plug flow reac.O!. expression for YE.O. FSr;> PEt and rE are the same as for the
CSTR, Tbe design equation is:
w =- __ .. !-, .... _.L_., (-EX - [l+E]lnO-X]) + 10.64X + 132.7 (-X, in (l"X)Jq;
00.5 X;: \YE.O Po f
__ "I:l_p_(.XF'[l+eJll1[l"XF])' 16.64XF + 132.7[XF+ III (l-XF)]}
,-) F \Y::..O 0
w .. x.."" L"""".",,,,,,
day 0,025 x 0.45 gInol
1-.833(.45) +- 1.833 In (1-A5) _ _ r" _ r _ I ..

11.:l.64(O .... )} b2"J l.o,45 + in (10.4))]1 x 24 *60 .-'


l ':UA .4'), , mm
W = 2.71 x 1()4
Cost:: 27.1 x Sk:
11
"", .5298
g
CDPIO-G
Given: reduction of CO with hydrogen over Ni catalysr:
10-77
Kineric given by:
0.0183 P H ~ Peo (gmOle ClL.)
r ::;; -----" ---- -------,-.. -,-,
1 + 1,5 PH
l
gIn car-min
From the above expression:
1) The appearance orF
2
in the denominator suggest that H2 is adsorbed on the
surface.
2) T.ile fact ll:at CO does not appear in the der.ominator suggests that it. reacr.s as a gas
phase species"
3) 1be square f(x)t. dependence in the numerator suggests that Hz splits.
Therefore, suggested mechanism is:
kl
III + S
-'J< Ih'S
f"
Kl
H2'S
t-
S
_ .. :;
2HS
(0-
k,
IiS +
(X)
;!.
CHO-S
14
CHQ..S + HS .." .. CS + H20 + S
.. --
ks
CS 2Hz
".',"
eXit -+ S
~ -
, f', p>
f5 '" K5 l c.c-s i-h -,- Pen, CsiKsl
Remarks made in Chapter 5 of the text suggest thar reactlon 3 is rare cCEU'oiling:
CT::; C
5
-t, C:H,S+ Ce,g + CCHOS
-, _ -, 'I', ' . - - - 7 ~ PCE." POL PlhO 1
Lr - Cs 1 "1"- Kl p}tz -,. vKr K: Pi', -t "'''''-''-:;'''''>' .,.,--------,-----,
l . Ks Pfh pit Ks iKl K
2
J
10-78
Kinetic expression becomes
Reaction is irreversible .'. let Ks _.+ QQ Then
with K 1 "K 1 Kz Pit, we get
k; fK11G" CT Pre Peo '" _...l_
..,r3 ""., - __ .m __ . This expt-esslon Impbes that. at ml.l'l..\t;l<l.te pressures, most or e
1 + Kl PHl
active sites are occupied by the Hz mole...."Ules.
(a) Design for a plug flow reactOr. Denote A[ =] CO, B [= J Hz; then Y AD = 0,25. YBO ;::
, " .
F .
0.75. as := pE:a!2.;::; =:: 3, XF = 0.80
AU AD
F '0' Xc =; F("ll =: 2000 J1t". x "" 125 lbrnol.
,'>. ."<4 day 16 Ib day
F AO := ill.l.bmQl.;:: 156.25l.1mml.
0.8 day day
DeSiEIl couation F,o dX :; -L' dW or }l{". =: f"U" dx.
_. n
o
___ 0.0183 FA plf
-'A - ----.-'.-.. -.
1+L5PB
P A :;; CART == AU X) ;:;:)1 Ai) PH. (1-X)
1+t:.X 1+E.X
Pa "" CB RT = CAO .. (I"X)
l+s:X I+eX l+eX
0.0183 [YM YAO
.'. -rA;:::: .- " .. "." ..... _._l,_tX.".,,_. t of EX ' __ ;:: _"",,,,,.,,,,,,,,, __ ,,,__ ,,,,-_.J . ..!:.eX
1 + 1.5 f P
o
(l;?C) 1 I + LS[-Y
I+eX . . l+eX 1
f 1 + 1.5 )
____ .... "_ ..... J d.X
\
0.0183 1r[XAO Po (1-
Xl
1312j
1 + E;;X j
10-79
.... == 1[L:LQ
25
l?:J.312 +- 375 r i -0." 5X ]1I2
J
\ dX


FAo 0.0183 {'J(YAO pop!2 0 \t 1 X J L I X .
Tt:: integral can be solved using Si.'11pson's rule
Then f{X) d.X ::; + 6i(O.2) + 2f{OA) + 4f(O .. 6) + f{O.8)]
3
o
X I loX T 1-O.25X + 3.75 fOO
o I 1 I 1 I 1 4.150 1.000 4.750
-.2:2 I 0.8 ," 0.95 I 1.1875 4.974 L090 5.420
'lf4To.6 I 0.9
m
500 5.250 ... -+--::6';:".4";;;3';:'0-+--=-"";'-';';;;;"';';":;'
... .. - 0.85 T}125 ,I ........ 5.875 -r-.... _ .
0.8 0.2 1
0
0.8Q .. _ 4.000 _ .... 7.950 ...... ..1 2.000--1LS.5OO
(0) Design of a CSTR
'. <f F eXt'
Desum cauanan IS W:;:;
.. -fA
l
h. . G'"'l -;J,'. "un -454 p'mol ,.
\F _ 1'1171 .lQl 1;." L , .;:,11 ! \ cav
rv -- .I, _.oJ .... . X x ... X . ..,---. ....,.".;:. ....... __ .. ,.
C.w.V !IIlOi Ibmoi'.AX;::'O
.. L ... v mm
w == 3900 g
CDPIO-H
10-80
(a)
.
I
-r;
/
.
-r

I
0
Fa
'A
Runs 1. 3. 6, 7 Runs 1.2.4 Runs 4 . .5
t P",
... -r s = ..-...-.... ..
1 t KA P A+- ...
t I
..-. r. "" ..............-.-.-.----
1+ KcP
c
+ ....
(b) Numerator: P A and Pa
Denominator: P A and Pc
Power of Denominator: 1
(c) Proposed Rate Law:
(d) To find the rate law parameters., reauange the rate law so
that it can be plotted as a Hne with the rate law parameters
as the slope and intercept of the line.
First, hold Pc constant and plot .. vs .. P i\
r
s
From the plot
K l+K P
Slope:: ." ..... =: 5.2, y.- Intercept =----.!:.-. =: 3..59
k k
10-81
Evaluation v.rith Pa..rameter Evaluation 'W'ith
Pc=const.ant=2 atJ:n P;;t:;const..ant=l atIn
120
25 .-.--.. --.--.-.--------------.-..- ..........--........-
100
20
gO
'"
:::: 60


R .....2 .= '9 -I J
-'i=----.,.------..' ..--T-...... , ..........-, ....---r- .... ,."""",-- .
o "......--1" ........... /" ... '!"T-,-.,-,.- .....
0 1. 4 6 $ 12 14 16 18 20
o 1 2- :.> 4 5 " 7 8 9 10
Pa
Second, hold P", constant and plot VS. Pc
-.{ s
from plot below,
51
K,- 1
ope = .... -'-..
. k
1 +K P
v .. Imerc"'Pt :::: . __.... __ ..... ... _.::. )- '''i)-
J "'. k - .. -".
Using the four equations above to soive for k, K A, and Ke,
we get:
mol
k :;;:: 2.60 ..---------
gear sec" atrn-
(e) A and C are adsorbed on the surface of the catalyst
(f) Proposed Mechanism:
cs=c+s
The irrcver'sible reaction step was assumed to be the limitL'1g
step We check this mechanism and rate limiting step by
rearranging and combining the rate laws for each step. If the
mechanism is correct, we will obtain the rate law proposed in
pane
10-82
Pc
, .
k is much smaller than kA and 1/ -- therefore :::.r A. == .:r = 0
5 ~ / k k.
A C
f b
~ Cr
A ter 511 stltullon, "v:;: ._-""-"---. -
1 + K ... P A + KcP c
Next, substitute the above equations into the reactions step to get
Because this is the same as the rate law in part c, the rate law and
limiting step assumptions have been verified.
(g) Ratio of sites of A to sites of B at 80% conversion:
Conversion at whid\ the Hnmber of sites of A equal the number
of sites oi C:
X=(J76
CDPIO-I
10-83
a) To detemline the mechanism and rate-limiting step we must come up with the
rate law. Looking at the rate dependence of A we See that between runs 1 and
2. P A increases fTom 1 to 1000 attn while the rate law only increases from 1 to
1.5. This tells us that as A gets larger it changes the rate law a good deal less ..
This tells us that A is both in the numerator and the denominator.
' .. . .... f
A
-
l+K
A
PA
Looking at the rate dependence of B we see that between runs 1 and 3, PB
incleases fmm 1 to 4.5. This teUs us that the rate law is directly related to B .
..... r ~ .- P
B
Looking at the rate dependence of C we see that between runs 7 and 9 Pc
increases from () to 4 arm and the rate increases from 4.5 to 4.8. Also in these
luns we see that P A increases from 1 to 4 atm. So one of two things is Due either
Pc is both in the numerator and denominator or just in the denominator. Since C
is a product it will not be in the numerator in an ineversible reactkm.
I ""
r , ................................ .
A 1+ K P:
c c
So the rate law becomes
With that rate law the following mechanisrn exists:
Adsmption
A + S'-1- A S
Snrface reaction
A S+ B(g C S
Dissociation
C ,S"'7 C+S
The surface reaction is the rate limiting step.
10-84
b) In evaluating the parameters we can also see if our rate law is a good one.
Plugging into POLYMATH we can come up with the parameters.
.. aoo
r
r-atellH0
4
n

n

"t.eoc
1
3.200
!
II
r
!
I
2.400
,
I
'r
I I
1 t
II
I'
t
!
LoSee
n
i
lL .
ij I
I
-ltJ
........".u .......... ..,L ...
O.soo
.' , ........ .. ' .. r ..
2 :3 5 0;
Model:
k 2 O .. GOOH'il'ilS7 K" = 0.:;
Ka = 2.9SSaS
We find that the !ate law is a good one. k:::: 0'(>0045
K
A
=3
Kc= ..5


o
d.ata
[J C"I "'" at!>d
I
,I
y.all.u?
I
!

I
i
I,
I
..If ..
7 a
c) The best places to add points would be where Pc is changed, but P
A
and P
B
are
not changed.
d) No solution will be given.
CDPIO-J
:2 C2 Hs OH? C2 H5 0 C2 Us + rhO
(A) (E) (W)
A + S +:! AS
A-S + A-S ES + WS
E-S :;:: E +S
WS w + S
II = kl (p A Cs- C
A
-slKt1
r2 0:::; k2 [ G,.$ - CE'S Cw.slKzl
f3 :::: k3 [CE-S ... PE CsJK3J
I"4 = k4. [Cw.s .. Pw CsJK4]
At steady srat.e r "" - = r == rt =: 2r2 = 2r3 = 21'4
If swface reaction is controlling,
10-85
0 = CA-S:; Kl PA Cs
:'" == 0 C;::.S :::: !'.E Cs.
1<:2 K3
I4 == 0 CWo:) :::;:;!:w,. C;;i.
k4 Kl. r' '1
c == c;. C + (" - C' ,i 1 ' K
r
}, Fe. Pw
'r ., s' . ,{os . 'ws - s, T 1 A + .---;:-.. t --.-.. J
' R]
C:; =---___._c;.r.____.
1 +- Kl P
A
+!I{ + .1.1:.
K, K4
')k I .... z p2 PE pwell r, P- Pwl
- 2L l.\.l AT - K,-K;K:-i -
..... r 2r2, :: .. .. ........ . .::. ;::;: ... ..., "' .........::..,., ....., ........". __ ......._ ... " . .. __ .
111 +- K I P
A
.; JE + II '1 .,- K. P ,PE -+ Pw 12
.. K3 K4J ." ATK3 .
where k :::: 2k
z
Ct Kl
Keq:;; K1 K2 K3 K4
Using points 9 and 13. PE "" 0 , Pw:: 0
... r == __ ......
{l + Kl P,S:
ll = :it i;
r''''''''''
AI' fl 1 (,... K
p at or "V r v'S .. p-;. .... produces a straight line "'1m sione 1 1,. and inteI"Ce')t __ .L
A 1/ k l: k
slope ={f =: 4.945
interCept =: 85.59
Using point H), P "" ()
klleck
... k "" O.04()9
. K
1
:= 17 . .31
.
U sing point 11. PE "" 0 = K4 = 0.0368, dose enough
Using point 6, Pw "'" 0 = K3 "'" 0.659
Finally, using point 12 = K.,q "" 0.0975
r= ..
....... 9._:.0_409 __ .......... _.
) + 17.31 PA t L517 PE ;. 25.05 PwF
Note: Keq may aiS{) be calculated using RT In K.,q "" ClCio.. Interested readers are
encomaged to check the goodness of fit of this rare law with the data ..
--------.---------------
10-86
CDPIO-K
CDPIO-L
Rate law:
kCcoC ACCNaOH
-rAe;:: 2
(l+KAcCAd
Proposed Mechanism:
Pd + COi--'Pd CO

Pd CO + NaOn--Pd CO" NaOH
--'''''''-7
AC+Pd ACPd
AC Pd + Pd ,. CO NaOH""--7C
3
H
s
COOH + NaCl + 2Pd
Neither of the first two reactions can be limiting because they are reversible ..
The rate step must be irreversible because there is no subtraction function in
the numerator.
We will first try the third equation as the ratelimit:ing step:
fA::::: kCYAC
Then
lACO _
""'--0
k
ACO
;:: 0
k
NaOH
Combine to find C"
C
v
;::..__ .. " ... ,_. C{ ... ""."_ .... " ...... , ...
1 +CcoKco + KCOKNa()HCCOCNAOH
This is definitely not what is supposed to be on the bottom of the rate law so
reaction 3 can not be rate-limiting.
Trying reaction 4:
== k4CPdoACCPd<OoNaOH
CpeMe cannot be found so therefore this rate law is also not rate,Umiting so
none of the mechanisms reactions agree with the rate law.
10-87
CDPIO-M
a) Start \!,lith a mole bahmce:
dX
--.::;;;;
Rare law comes next:
r' :::: k a
A r
Then the decay law:
do
.. :;;; ---k,
dt "
-YV'
t ::= .....
Us
da
dVV Us
'We then come up with the equation f()[' the profit:
Vvl1cre:
Then plug into POLThlATH and get the foilo\;villg program. The feed rate of
solids that gives a maximum profit is 4 kg/min .

.
d(a) Id(w) ,;;}Cd/Us 1
d(x)/d(w);'ra/fao 0
fao",1
kd=2
Us=4
10 18 :).
fb=fao'x
.. .. ..
l

x
fao
l<d
:::-:1
1::
?
b) As seen above: X:::: 0.75 and a =.5
-
0 75
c 5
0 i5
4G OiJ
10-88
a '; c ;;
0 73
2 2
1
- "-' ...
"
O. 75
"40 SO
c) The only equation thai changes is the rate law:
--k
dt - d
W,W
I =::_.M:1!. __ .
U
dW
dt =:: -_._-----
U
da kddW
.... " .. == ._.-. ....." ..,.. ...-
dW U
Integrating we get this:
W::::; W
MAX
@ a == 1
k ==
U
a == 1 - ..
U

d(x)/d{w)- ra/fao
kr;;:;5
kd=2
Us=.8
wmax"'l
fbaif{x<11 thenlfaox) eLse(l)
0.",1. (kd/Us* (w-m<Lx'w) <1) ::hen (lMkd/Us" ('HmilXW) ) else (0)
P"'150*iblO"Us
'3
ra -0
o 1)
1
:42

o
G 8
3 142
s
\Ve find U:= 0.8 to ma.xirnize the profit X =:: I and a:: 0 exiting the reactor.
CDPION
10-89
Design Equation:
\V ..
(-J:,\ )a(t)
at t = 0, a(O) "" 1 and X "" I.
Now
FB(t)::::: FAoX(t);::: RON(t)
X(t) == '"
106 RON{D)
For n en order kinetics ..
Second order kinetics and second order decay rate tIt the data very welL
J

l+k .t:::: .........L __
d CAo-,C
A
y == 0003x + 0.0855
Plot of - - A____ vs t:
C.A(J- C
A
-1.lnca; lExp
Data; i
i
() t " .........." .. ....... ................... .. _-....... .., ...". .... """." .. , __ ..... _., __ " .. ,_, ....-.J
o 100 200 300 500
t (h)
F.om the graph: intercept = 1 j k =: 0.0835 k ::::: 11.98
slope = kd J k "" 0003
(b) Activation Energies both for rate constant and decay constant can be estimated from the
temperatu,retime trajectory
CDPIO-O
10-90
Given A -+ R + S
Batch constant volume I"Cactor, P mCI""....ases with time
NAO dX = a fa Wdt
Assume a = e..(lt
'0::;; kP
A
:. PA=CART
C
A
;::: NAG 02.9.;::: (I ;.;.t =: eM (i-X)
V Va
:. NAO <.LX = We..(l' k CAO RT dt
lC J.'
f.
dX.:;:; W k RT J. ea.: dt:;::;; (W.) k RT eat dt
I-X NAo Vo'
o 0 0
L dt wl=e R1
( ,
.In(l.X) == a le'<Xt)
Assume that there is very little deactivation in !he first. 10 sec
-In (i-X) =: .. (at) = (for smail t)
Ct.
( .. lJ :lln{--L-) '" 3 .. T7 X 10.
3
sec
t l-XI 10 1-0 ..037
=
k = 6.63 x 10 5 sec 1
10-91
At t relatively large, e-<ll: = 0

-= -In (I-X)
a
3.37 X 10.
3

a:= == -Ts;J = 5.18 x 10'" sect
" ,1a(1-X) "" 0.128 (i"-e-
S
.
1ax1
o-'1t)
" TIle of a firs;: order :e2.Ction kinetics and a
justified
CDPIO-P
fl pemane
cyc1opem:ane <
coke
Batch mole balam:."e :
AsStL."Ile q :::;;; 2 a = .............. L." ... _
10-92
order decay kinetics is
,
Ifn=O
_I =_I_+5!t
X let k-c
#
Ifn::::l --1._ ;:;;: -L +.5t t
In(l-X) lei kt'
X(%)
o 75 1.33 0.721! 0.333
20 7 .7 1.414 0.815 I OA15
...... ,_. ;,,6
0
7.
5
11 . 0.902 I ..
ou v .., 1.076 I
F
112800 "'1 ---S--4- .)8- . __ . ._-_. __ ._.
_ '- / _ I 1.245. __
1.498 I L053
! 250 I 42 i 2.381 1.836 I ... 1.381
350 I 361 2.778 2.24T--, 1.177
500 I 30 r-' 3.333 I 2.804 ... 2.333 --'
1--';'800-- I 2i ',-"-'4.545 I 3.545 -,
..! 6.3 _ .... L 6.TITI .. .. ___ ?';'O_-_-_-+.;...-_-__5_.1_3_5_:=1---,
f .
",,,l.
I
o L.... .... ..... .."'._ .." ..... .... _ ......... _ . " .. '"M_._ ...... , .' .. ....--. .---...
o tOO ICQ 1=
+lfX
<> -llln(l-X)
II1II (l-X)/X
From the above graph. a111ines are straight lines.. 'lberefore. q = 2 is a good assumption.
We need to ex.amine the data to see which value of n having constant n=:O and n "" 2
At
will have similar behavior of because:
8.= 1.._ 1
X X
At
n == 1 . Av.:;;.1 f.--L--l and.1t;;::"O min
'. l-In( l-X}J ...
:;;; 0.094; 0.087; 0.087; 0.084;
At
0.081 ;
.
........ lit 0.0797
Therefore. ay is deo:easing gradually. It is not a constant.
At
10--93
For n =:; 0, n.:::2: :::: 4 x 10-
3
= constant.
6,
If n::::{) :
_ _ QX, ==
{lX)2 at
(l,Xr "ili.." ::: ... , ..L ........ ;- .. t
. dX KR C AO KR c.-\o
n=2: Slope is negative. It is u.nr:::asonable
n:::{): vs. t is a straight line.
10-94
w = 0.01 kg/m]
C W (0.03 krlifl){ 0'<)1 kg) k
't = 22.-. '" .................. m.. ........:.......... .. _ m
3
... "" 20 _JL min
FAO 1.5 x 10
5
kmol/min {m
3
)2
(b) The order of decay is q;;2
,
k
... Q. "" 4 x 1(},3 =:> k: 3 x 10
3
mini
kA
(c) Moving bed F AO = ; X;;: 0.80
mm
* lia. :;: k' a2
d1: d
In moving bed: t = if where u == =
., . k.:!"
Subsnrure mea equanon (1): .. dW'" = '1:1' a'"
...
a2 u
<> dtldX
10-95
SUDSritllIC n ~ o equation (2), vie have:
(d) If O
- k ~
u =) .---::".-
ttl!.(l
CDPIO-Q
W :::::455 kg
w ==48 .. 6 kg
10-96
a) Mole balance:
Rate law:
Decay law:
Stoichiometry:
C
A
= C
AtI
(1" X)
CD = ~ O e 8 + X)
Evaluate the parameters:
d(x)/d(w)-.-'-ra)/fao
d (ia) Id (w) ",J<d"cb/U
kd,:6,
faOi,:20
:' ~
U;:8
k';350
cao=.l
ca"'cao"(1.x)
, cb:cao * (thet.a +x)
ra" ..k"ca CD
Wo '" o.
1 .. 000
f
10-97
-, .. ,
o
1.
b) The only change is in the stoichiomeuy:
POL '{;v1A TIl
d(xl Id(w) =a* (--ra) Iao
d(a) /d(w) =kd*co/U
kd=6
fao=20
U=S
K=3S0
!
i
T
1 cao::tl:"l,
C "'0..'1 J...
theta::: 1.
alp= .. Q38
ca=cao' (1"",), 5
cb=cao* (theta+x)' (l--alp'w) .. 5
ra="'k*ca*cb
Wo = 0, w
f
= 24
CDPIO-R
Curoene --,
(A)
Propylene
(k)
+- Benz.ene
a:s .I ...
fo
(a) We find a relationshipbetv.tcen a and C
A
.R.ill:Ll.:
t
a
CA
Run 2:
t
a
C
A
F X F
r '" = 2 .. = F"
W W -,
o
1
o
60
07.5
0.01
(W:= 19)
120 180
0,,594 0.491
(LOIS 0.0243
P A ::::: 0.4 aL."'Il
0 100 200
1 0.833 0.733
0 0.0057 0.0106
(S)
300
0.65
0.0148
10-98
Initial
o
1
400
0.583
0.0184
Plot of In a vs. C
A
gives a straight line passing thmugh the origin wirh slope a
(single adsorbed. smface reaction controllingl
I initiai rate are used, P
R
== P
s
= 0 and 1 KAP A (adsolption is small at high temper.rture), then
fo"" kt'KAP A
Using data at time zao from runs 1 and 2 : K.<\ =: 3.2x1O-
3
Hence, overall apparent rare law is
r = KA e<t.c ... P A ; k; KA "" 3.2x1O
3
ex.::; 28.9
::: - k:..:i amf{P A. PR, Ps) == am P"A
Trym::::: -2
Since PAis almost constant. nms 1 and 2 (low conversion)
Run 1: ku PA. :;;; 5.767 x 10-
3
Run 2: k<J P
A
= 1.769 x 10 ..
3
P
A
== i in nm 1 :::) 5.767 x 10.
3
P
A
;;:; OA ill run 2 :::) II "" L29
.
Kl KA "'" 32xlO'
5.767xlO:;
11 ::::; 1.29
t L.'1 minutes
10-99
(c) Overall conversion = 0.60
(2.8 rr.oll:Jec cu...--nene j
\ 4.2 mollsec propene) L. "" 1 1.2 IT'.ol sec
1.4.2 IT'.o.llsec ber-.2ene J
Cu:rnt!ne "'--t Propene -+ Benzene
COllIDosition at reactor oudet
.. YA:
2
& .. =O?S
11.2'--
A ?
VR = Vs "" . .::!.;;.""-." "" 0 315
.. - 11.2 "
(A) (R)
Composition at reactor inlet. Fa :::: 7 + 3 :.= 10 mol/sec
FAo 1 , 3(0.25) "" 1.75
FRO::::: 3(03'15) := Ll25
Fso =:; 3(0375) := LIZ5
Let Xf "" converS1on per pass
YA "'" 0.775
YR ;: 0.112.5
Ys = 0 .. 1115
flovi at outlet before the recycle sc"ea.,s is:
At a.llY point along the reactor:
(S)
Assurne that rate law in (b) is srill good fOr the mO\o'ing tx:d operation (may not be rIue in
practice because of the high conversion)
k, KA PA
I'::::; a k, K.,., P A=:' .. .l. .. " ... _-_ ..
, .. l+k.:!?A,t
Moving bed react()r: t """
F.,odX =rd W

== (1,29+X.\O.Z9 W + _ .... 1 .. .._._( 1.22+X.)
3.2xlO-'x2000 I-X J 3.2xlO-3 I-X
= 6.98 X 10 ..
3
(1.2.2Xj29 W + 2421 (122X.)
I-X IX
With X::O > W=o
If X:: 0.542. using digital computer W :: 3.1 kg
CDPIO-S
a) i'vlole balance:
dX a * -r'
:::::: ................. .::! ..
dW
rate law:
, k'('
::;: ',t
St.oichiometry:
Decay law:
da kd
._ ............ :::::: ._ .. _. a
dW Us
Evaluate the parameters:
?.;:;;; (1 ... o:wt
5
Po
"'" (1--1OOa)05
0::::: 0.0099
rOl da kd dOO
'-'Jl :::: JodW
!:i..;:;;; 0.023
Us
10-101
POLYMATH
EguB!:ions-,.

d(a) Id(wj ;-kd*a
kd" 023
fao:=:4
k=.09
cao::o2
a2.p= 0099
ca=cao*(Ix)*(1-alpw)A.5
:t'a;;;-:t',llca
b) POLYMATH
J J2:) :-
CDPIO-T

w
x
a
kc
tao
!<:
CdO
Cd
ra
Design Equation:
RaleLaw:
FAn a(WX
< ;;;:k'C
A
Decay Law: (for sintering)
Stoichiometry:
Combine:
dX. = _ ... ___ L .... X)
dW l+!'AWu
Us 0
o
I
:.c.':'tial val.l:.f!
..:,elue
l{W
{} 0 .75:;':51
"
D23 0 .023
0 9 0 09
0 0099 0.,0099
{L1S .. 0
004371.1
ceo
dX k' dW
.=.,
l{ tt w J
1 1
From the problem statement a - ::::; ................. :.:::
'e.u, 1+1:< W 4
Us
Plugging in 100 kg fIx W, we can solve fort.:!
$
! ... := 3.43
1 X
10-102
Minirnu:r:. ,ta,l>.!.e

100
C ,57161
0 :00251 C :)0259
0 023 C 023
C 09 C 0'1
2
C 0099 C 0099
0 04.35678 0.04856"18
-0 13 '<Ii 00437:1
CDPIO-U
The heat of activation is given in the problem as a function of the carbon
number so we can just graph that:
c: 80
~ 70
1: 60
o
~ 50 .
nI 40
'030
_ 20
<IS
~ 10
Heat of adsorption vs carbon
number
'r" 0 ............ 'H ...... __ """ ...... ........ ,' ........... ,.,'"'' ... ----".,.--. --_ .. _._ .......... .
o 10 20 30 40
Carbon number
To graph the activation energy we need to find its equation. It is the
Arrhenius equation.
k:;;:Ae-
E/RT
Solving for E we get:
We know that as the temperature increases when n S; 15, the rate increases so
k still gets larger with greater temperature so E is still positive. When the
temperature increases when n > 15, the rate decreases so k decreases making E
negative So we can come up with some equation with the above equation
that fits this criteria and we can corne up with the following graph
>-
0'1
Activation energy vs carbon
number
6 .... _ . _--........ -._.-...... - ... _-_ ........................... _ ......................... ..
5
:;; 4
c
..
3
o ---- . ~ ~ . . .......... .
1 0 20-------3"e- 4
1 . -------.. -----.... -.------.-.... ---.. --...... --... --.... - ..--..---..... -.----
Carbon number
The reason for this unusual temperature dependence is due to the fact that
the higher the carbon number the less it wants to add another carbon
10-103
CDPIO-V
(a) a::: 0 at the end of the reac[Qr:
:;;:? Us = 1 kg/s
(b) For Us::: 0.5 kg/s:
a 1 W 1 {nOoN;;} ;1 (04kg')w
Catalyst Activity vs. Catalyst Weight
W (kg)
When a::: 0, the catalyst is inactive. In theory a can be negative, but in reality, once the
catalyst is inactive there can be no further decrease in activity_
(c) For a catalyst feed rate of Us = 0..5 kgls:
Mole Balance:
Rate Law ;
Decay Law ;
F dX:;;:: a( .... r')
Ao dW A
, k(' (.,
.. r
A
:;;:: '"'A'S
..... .. = .. ... l. = 0.4 kg! :;;:? a == 1 OAW
dW Us 0.5 kgls
Stoichiometry: (Assume T = To, P z Po' and 1) "" 1) Q)
C\ =C
s

Combine:
FAG ..." X)"]

10104
( w w' J
From part (b) we know that the maximum catalyst weight (the point where a:::: 0) is 25 kg
We will find the conversion at this point:
(i? Xr 2.5 2.5' )= 025
X=O.2
(d) To achieve 4()% conversion:
Xl = w .. itt
w
' )
=>
O 66
2.5
. 7 = 1
Us
lJ
s
:= 7.5 kg/s
(e)
W-
2
(!jW') =>
= (0.2)w:::: (0.2X5)= 1 =? X =0".50
CDPIO-W
Design Equation:
RateLaw:
DecayLaw:

So dt
, k'C'z
- fll ;;;; -B
da
.... =k =0.05
dt D
a I
J da =,0.05 J dt a:: I,O.OSt
1 0
From tilL'> we can see that the maximum reaction time is 20 min, We will find the conversion at this point
Stoichiometry :
Combine:
(Assume constant volume)
ell "" ClIo(lX)= x)
V
=: .!t! (1 ""' 0.05t Xl, X l
V-N V2
80
:: (1 ... O.05t}it :: (t _ O.025t
2
)
(1" X Y VI"" X V
= ('20 ... 0,025(20 'f )= 1
I-X (1)
X=050
10-105
CDPIO-X
a) Mole balances:
dF
A
.......... _ .. = r
dW A
dF
___ .l!.:; r
dW B
dF
____ J.:, .. = r
dW C
rate 1a'N5:
stoichiometry:
, F.. F4 (1- aW)Q5
( = ..._ .. "" ... '-., ....... --....._, ......
'-'tt V Vo
, Fa F
s
(1-'aW)QS
C B "'" ."--,, := ..., .... ---.., ........... "-,-,,.
V Vo
decay law:
da k a
"" ,.12"_,,
dw U,
Evaluate the parameteIs:
Plugging all of tllis into POLYMATH we can change values of Us. T, and Vo CP.. ....o)
that will give us the most of product B.
We find that at a tempcratllIe of 396K, a solids velodty of lOkg/s and <I gas volumetric velocity of
o 63'3 dm
3
/s that con esponds to a p3ltial pressure of 5l 3 attn we can the maximum yield CO! B,
d (fa) fd (w) ""a
d(fb) Id (',") =,,10
d(Le) Idlw)=J::'c
d(al/d(w)=kd'a/Us
Us"lO
T=396
alp=9 <lEO",3
Vo= 633
xci", 937* (1/400111')
k2= OJ..*e;<p{20000/1 ,987* (1/40Ql/'.l'I)
kl=, 02 'exp (lOOOOn 987* (1J400 .., 1 IT) )
(J..alp""t..t) ...... 5/vo
(l"alp*w) A ,SIva
xa-;;:'-a*kl *ca

:cb= af!' *ca)

fa
f;;
Ec
Os
41p
VQ
kd
k2
kl
c""
c"
.a
,c
d,
..y;e
0
10
390
o. 009S
n 633
0 0661149
OO,i55S4
Olj6Ln.
1 S'191S
.. 0 0278243
0 02 :82";8
10-106

100 0
Q 3813942
.;) ,.
0 .. 4 n,,71-
1.93102
J,O 11
396 196
0 .CO:iB 0 009'8
0 631 0 633
C.066:':'49 Q .00lil149
o .cp:nSSS4 0 00715554
0,0116131 O,0176i3}
1 579"; S 0.0131646
0 631)42
.. 0 0(10620401 .. 0 .07.::6245
0 00641366
0 02/'S246 "-0.0021742:3

leO
Q.0913942
0 ;4t>631
0 '1l19 i:
1 .. 9Ji02
:0
39G
00093
0 6JJ
0 065::49
0.00775554
;) Ol"l6l.H.
0
0
.;}. ':;OO6:!O403
Q
. 1)

b) Using the same program we can find what it takes to get the most of C possible.
We find that at T:::; 396K, U,:;;;; 10, and vo:;;;; .03 we can get Imol Cis. P AO::::
1082.4 atm

Minimu,tl1 v .. l" .. !:ir..al ..
'"
0 100 0 lOO
fa 1. l 102629 .... 23 1 . G252ge.:n
fb
Q 0 SZ4487 a 135042"",:0
fc
()
1 1
a 1 1 .9370:2 1 1.93702
Us 10 10 1.0 lO
l' 396 396 J96 390'
<>1.;;> 0 0098 0 .. 009S 0.0098 0 .. 0096
vo 0,03 0 0) 0 03 0,03
kd 0.05511.49 o .0651149 00;;61149 0.0661149
k2 0.00775554 0 .. 00715554 0 00175554 0.00775554
kl 0.0116131. 0 0176131. 0 .. 01'76131 {) 0176131
ca 33.33J3 J3 3333 1. 83'798e .. 23 4 .6379Se-23
ch 0 17 .. 26% 6. 36S55e-:.n
ra -0.581104 .. 1 65051" ..24 -0. 5871C4. -1 6505"113 ..14
:c 0 0 .. 13615 9 56332,,-::
rb o .5,s'1104 05971.04 '0. C7!$781 9 55332 .. ":'2
c) To get the Time Temperature trajectory we can use the following equation to
create it:
This will give us the following graph:

Trajectory
1 200 .-........-.......... - ....... -..-----.--...--..-,,-.-............-....... .
1U 1000
...
.;! 800'
lU -
......__ ..................... _ .......__ .......-_._ ...-....
d; ::':::.600
Q. ,-
E 400
1U
I- 200-
o ............... -............ .
o 5
Time {s}
to
d) For this we just add an energy balance We have to assume a heat capacity of the
catalyst since none is given Here it is assumed to be 100 J/kgcat
Plugging this into the POLYIvlATH gives the follow'jng program.
We find that the tempemture is 38SK, D, "" 1 0 kg/s and v 0 ;;::; 051 dmo/s. P AO =
62 .. 4 atIll.
10-107
.Eq:..lationS,l,
d(fa)/d('w)=:r:a
d (fb) /d (w) ,,:tb
d(fc)/d(w)=rc

1
o
o
1
d(1') Id(w) = (-16000) .. rh
T
(--32000 / (cp' (Us+'''cl+fbdc) 1 388
kd= 08*exp(15000/1. S87*(lJ4QG-I/T ...alue
Us=10
c,,=lO()
k2= Ol*exp(20000!1 987*(li400-1/T)}
kl'" 02*exp(lOOOQ/l 987* (1}400,,1/1')}
alp=9,8e" 3
51
ca;:fa* (l-,alp'*w) ..... S/vo
cb"fb*(l"alp'w)A Siva
ta.:::::-.a,'*kl"'ca
t;'c=a "<k2 '"'cb
T
cp
k:::!
kl
dlp
>10
,;;,
:;c
358
C 0446169
10
:,:<)
o 004Sn{)1
':11J553
,0098
o 31
3i5D}S
-Q :3265'44
.,
10-108
100
t
G g 1:,155
o 21532& o
10 to
lce 10;)
{) .C0459207
O,(H085Z:
o 0093 0098
5: 0 S:
96{)'8 -0
o 7;6.3935 :1
'''0,000'15307;5 ,00255;.1\4
0,001'73258
Leo
o 61.1.155
t) ,215328

382 2.:.2
0.0332906
:0
Q :)03}'0577
0,0111477
() .. JOSS
C ,$1
0481:;.54
,':694'1'2
-C.00:)753076
o 00)139124
05
Solutions for Chapter 11 - External Diffusion Effects on
Heterogeneous Reactions
PI I-I Individualized solution
PII-2 (a)
A 2B
1, Z 0,1'=0
W
B
=-2W
A
cD AB dy A (1 + Y A)
W A =----= -cD ABdin ---
(1+ YA) dz dz
Integrating with Y A = 0 at z = ()
W A = .cD AB In(l + YA)
(S-z)
(1)
at z = 0 Y A = Y AO
cDAB ( )
W
A
=-S-l+YAO
(2)
Taking the ratio of Equation (I) to Equation (2) to eliminate W A and solving for YA
~ ( 1 + Y A) = In(1 + Y AO)
S-z 5
( )
1-z/0
YA =1- 1+ YAO
11-1
,
,
" / EIVKD
,
'fA "
"
,
,
,
Pll-2 (b)
(g) Tl = 300K T2 = 350K
kc2 (11-70)
kcl D ABl '\)2 U 1 d
P2
As a first approximation assume
DAB2
DABl 112
AtTl=300Klll ",,0.883cP
At T2 = 3.50K1l2 "" 0.380cP
Assume density doesn't change that much, '\) = Il
p

V
2
112
U
2
_ 1 d
p1
_ 1
U;-2' d
P2
-"2
kl = 4.61xlO-6 mj s
k, 4.61x 10-<> m/ s [2.32 J'" r r
= 4.65xlO-
6
mj s
W
A
= --r; = k
c2
C
Ab
= (4.61XlO-6 mj s )(10
3
mOllm
3
)
-.r; = 0.00465 moll m
2
Is
11-2
Pll-2 (c)
(h) A 50-50 mixture of hydrazine and helium would only affect the kinematic viscosity to a small extent.
Consequently the complete conversion would be achieved. Increase diameter by a factor of 5
k,2 = = 2.9m/tr
=1.3mjs
X = 0.05]
= 1-exp(-4.6)
X=1-0.01=0.99
again virtually complete conversion.
Pll-2 (d)
Liquid phase: e.g.. water
See margin notes on page 786 and 787 for solution,
Pll-2 (e)
= e -4., ;1-;'} -4.000( -
= e-
0
.59 = 0.55
Assume
-
k ( )2/3 ( )1/
6
( )4/6 ( )1/6 ( )5/6 c2 _ DA2 VI _ flJ flJ flJ
-- - -- - - - =-.
kcl D Al V
2
Ji2 Ji
2
Ji
2
k
c2
. = (0.55)5/6 = 0.91
kcl
= (1.059)(0.91) = 0.96
U/s.
In 1 =(0.96)(2)=1.92
1-X2
X
2
=1_e-
192
=0.85
11-3
Pll-2 (f)
CAD
Assume concentration in blood is negligible (C A2 = 0 at ()2). Assume quasi steady state
d(VpC
Ap
)
---=-WA
dt A P
W =.!!ABI [C --C ]
A &. A Al
I
W = DAB2 [C -0]
A J Al
2
adding
W
A DAB 2 DABI A
_ C
A
WA - J &.
_2_+ __ 1_
DAB2 DABI
C
A
= RC
AP
V dCAP = ApRCAP
P dt 8
2
--+--
DABI DAB 2

- DABI DAB 2 P
Flow into the blood
FAB = CpA mol/time, R == [time]
RV
If CpA = constant = C
pAO
F
- CpAO
AB---
R
11-4
FB
If CAD varies
!lCAP =.-1 CpA
dt V R
C
pAO
t
In--=-_
C
A
VR
C = C e-
t
/
VR
A AO
t
C
A
FB = -- 8
1
and 8
2
are given in the side note.
R
FB
t
Pll-3
Mol balance on oxygen: o ~ 0 ... to:! :::: 0 constant liquid composition ..
where n is the reaction order.
. 'd at I l' F P.l)" h talc m1 rt._
AssulIlmg I e gas aw app les: 02 =i?:y' were u,,:::: oxygen up e rate ...ItU
t P ('
Assummg hla.t .. _ .. = cons tan t. "
v R.T .
by correction of 1,)0 to some reference,
Assuming Henry's law applies (low pressures)
where H is Henry's constant and Po:! is the oxygen pa.rtial pressure
115
Substituting into the mol balance:
=-
k.H"
In u" =: nJn +- in ._." ......
C
A plot of in Uo vs In will give n as the gradient.
As the system pressure, P, given in the data is absolute:
if in the reactor. the xylene is at boiling point and dissolved oxygen and
oxidized xylene are at low levels, then P", =' 1 arm (open to the atmosphere)
In order to deduce the correct kinet.ics of the oxidation it is necessary to find the partial
oxygen pressures for rhe conditions where the rate is limited only by the reaction
kinetics and not by diffusional mass transfer.
Plot of stirrer speed, W, vs oxygen uptake rate, 1)", for each run will show the
conditions at which diffusion is negligible.
4QO 900 1400
W, rpm
... ....... ....
.......... 1 " atm-
..... " 1.0 atm.
..,.. .. 20 atm

Ir. can be seen that at stirrer
speeds above 1200 rpm that
OUR is illsensitive to W and
hence the reactor is well mixed
ie. no liquid diffusional
limitations ..
OUR: Oxygen Uptake Rate
Hence using the system pressure dam at 1600 rpm for the plot of in U
o
vs In Po;: will
give n uninfluenced by diffusioIl ..
Po: ;:::: P, PjI{ =: P, I
At 1600 rpm

11-6
,----_._.,-''' ..... , ... _-""' ... " ... "., .. '"'."-'"'''''""'"'--"",-"""'-""",","-"""-"'-"","_.,""'",".,,"""''''"
"l.S -1
y = O.9992x + 4.,6422
.(),,5
LN{(02)
o 0.5
TIle grndient, n"" .999 ::: 1, so the rate law is:
Pll-4
Diffusion in adjacent skin layers
101 kPa
PH,,:::::: 0 kPn
Skin interface

Outer layer
Strotum
comeum
P;>cl
Inner layer
Epidermis
P:-I1:::: 0 kPa
P
H
:::: 81 kPa
0, ::::::0.002 em
em
.,,'--,,-,_._---..
__ ."" . _ . "_. ____ '''. __ " .. " ...... _''_m" '''''''''''''''''''''''''''''''''''' """_""""."""' ____ ,_.
Assnming dilute solution and constant total concentration in both layers gives:
d CA
"""-::::::KI
dz
for each diffusing component in each layer..
: Outer layer: boundary conditions 1.:::: 0 , C
A
:::::: CAO
Z :::: 01 , C,.\ :::::: CAl
c.v-C4.0
KI :::::: -_.--_.-.-
01
11-7
Profile c .. == C,\O - ( C"O .- (AI). :1
Inner layer: boundary conditions z:::; Or ,C ..... ;: CAl
z=b:.,C,-\=O
CAl
K I == .._._._--
02 --Ot
Profiie
Total partial pressure profiles
Outer skin layer:
Cht.:ck:
7 .",
;::; 1010 -. (10 1.0 '" .. -
0.002 0.002
::::: WIO-lOOOz + 5000.;::
=:: 1010 + 4000.;:
Inner skin layer:
p, + Pa :::: .. + Pao'" (PSD ..... Pal) ._.' .... -=:..
(
O' ......
b; -o! \0 :"01
::::; 810 +- 126000(0.01 .. :::) ..... 100000(0.01 ... z)
=;:: SlO+ 26000(0.01 ::)
i\t interface (2 == 0.002 em) :
olllerlaver :::: inner/cryer
p., +- Pa::: p, .-t. Pa
1010 + 4000:; == 810 + 26000(0.0 1 zJ
1018:::: lOl8 conect!
Plot these two profiles across the skin from z :::; 0 to l :::: OO! ern
11-8
He : Inner layer: boundary conditons z = 01 ,e
s
= Cal
z = 0:: Co ::: eso
. C80 - C81
K I :::::: ... _-._- ... _ ..
(
C80' CST \
K z =: C BO -------. _. U51.
o! --01 \ 51"01 )
Profile
(
0' ..... -7')
CB :::::: CIJO'- (C80 -- CSI) -:.-.--":::' ..
0: -"01
Outer layer: boundary couditons z:;::: 01 C
a
::: Cal
z:;::: 0, e
a
:::: 0
Profile
Total concentration profiles:
Outer skin layer:
Inner skin layer:
Evaluation of C,\l and em :
N::: : Outer layer:
Inner layer:
..... "'t.., ..... Z ., Z
CA';' e8 ::::: CAD -.- (CAO'- ell). s; + (8/ ~ f ;
IhNl [.. 0]
W,U ::: --.---- CAl .-. .
02-01' .
Assume that flux in inner layer == flux in outer layer i.e. W AI ::: W A2
w" [C' C"] .. ---- = AO- AI
DIN?' .
-......... ....
lh-Ol
w<{ ; ; ; + ~ , . = c.o
Conversion of kPa to kglCIll*s2
101kPa=101OOOPa==101OOOkg/ms
2
:::101Okg/cms
2
,-.lkPa::::::lOkg/cms
2
11-9
w ::::o ___ ... -.:::: .-.- ......... 0_ ..... ____ :;: 50 * 1
" [ 1 an's'
He: Outer I:lyer :.
DIN, [. _ ]
Wa ::;;:-...... (af --
'"' ..
O.
lrU1ef layer:
Pressure Profile of skin Jayers
1050
'! 1000
E
inner layer

26
950
e
::>
..
..
900
e
0.
]j
850 ..,
I- interface
800
(J 0002 0004 0,006 0008 001
z(cm)
... , .....
6: 61 .
Hence ..
;;:;:;
== lO08kg I em .. s:
a, 0002
= lOkg I em.s:!
1110
The maximum sum of partial occurs at ilie skin layer interface
z == 0002 em PrOIa! :::: 10 18 kg/ems!
Hence the maximum sum of the partial pressures is slightly greater than the saturation
partial pressure and so gas will fonn bubbles at rhe skin layer interface causing
blisters.
Pll-S (a)
Part (a & b)
Mol balance:
Rate law:
Stoichiometry
Combining :.
Packed bed. mass tranfer limited, gas phase
.-.. 1._4.!:!: + ra" . a" := 0
Ac dz
1 FaodX ..
.............. .... _ ... _ _ .. =:;:; ra . a,
Ac dz
U .. Cao.dX ..
::::ra .. a.:
dz
where Fa: U.Ca.Ac
U : const.ant superficial gas velocity
Mass transfer limited boundary condition
fa" :::: kc .. (Ca ... Cas) but Cas:::: 0, rapid reaction
Assume constant T. p. gas phase
Cao.{lX)
Ca;;::: ... _ ...... _ .......... _._ ..... .
(l 'fE.X)
where e:::: yaoo:::: 0.05 x 3:::: 0.15
(j Cao.dX ..
. ........ ---: ra . a.;
dz
Cao.uo .. a.;.kc. Ca
dz
dX a ... kc.(l- X)
..' ... --,,, =- .........._ ...." ........ ",. ,,> --
dz (Jo.(1 '+' O.l5X)
Use Thoenes & Kramers correlation for ke :
11-11
Parameter evaluation:
d = [?v J = = O.238cm
p 1C P n'
. ..
Diffusion of cydohexane in hydrogen (assuming constant T, P)
r 1 I'll'
-
[Jab == ---,-., .. -............. -.... -,----.. -.,,",--""'-
p[(l Va yn "1 (I Vb yny
Fuller, Schettler, Giddings for binalY mixture, low pressure, non
polar (Peny's handbook chem.eng,)
:VIa, Me ::::: molecular masses::::: 84,2 respectively
Va, Vb :::: diffusion volumes;:;:;; 122, 1.07 cmJ/mol respect.ively
4:" 0.4
05: +05tOj)
..... _. 4. _ ._._. _ ..... "" .. __.. "". ::: l.lLi L
Y :::' -" _,0
rr..dp! O
-'7')
..
Uo = 60000 :::: 509cm / s
Ac
4
u :;;;: Uo.( I + EX)::.:: 50.9(1 + O.15X)
11-12
!l =: 0.00017 g/cm.s (Hz. 500 K , 2 atm)
Sc' =: . ..,... - =: 1.044
0.000 19 xO.857
1 [, ( _ ')']112 [ 'Ji/3 III
kc =OJ'8S''' 47.3 1+' OJ)X 1.044J =: 17.98(1 + O.l5X)
a. =: == 6.29cm'l
0.572
!1 =: 0.00017 g/cm.s (H
2
500 K , 2 atm)
50.9(1 + O.l5X)0.572xO ..OO019 .
Re =: ....... _._ ...... _ ............ __ ...... __ ._-- ::= 47.3(1 + O.l5X)
0.00017(1 0.4 )1.146
Sc' =: =: 1.044
0.000 19 xO.857
k
1 r' ( - )'l1/z[ Q44'JiIl .., 8( 5X' liZ
C =: .... _.., .... 47.3 1+ o.])X 1 1. J =: l ... 9 1 + OJ)
0.388 . .
6(10.4) .1
Q, =: ._-_...._ .. =: 6.29cm
0572
dX (1 ... Xl
t1. + O.! .5X-)ili
POLYMATH
.. " ..... .. '=
Pll-5 (b)
11-13



:z;

.. -' x
!: ...........
.2 625
:2 .5875
75
2 8125
;: S'IS
.2 .9375
.3 .. 1.25
3.1875
25
" 3125
j 3'75
.4375
3
J. 5525
Zf '" 5
(.000
a.BOO
Q.600
C.4CO
O.2CD
o
o
o.oeo
"',
(l 9S591419
0,99541018
0.9';)081594
O.99722ilS
Q 39756518
0.99786072
0.993:2039
O.99<l:l4ilS3
O. '33354898
0,9937251
o 99g87983
G 99901579
a 9991:3525
o 99924Q2
O.99'i33242
0.99941344
5
0.99997
o
o
z

o
5
0.99997
-+ ceO os. 000
The results show that only :3 :3 c:c;: of [he mbe is reqllired for conversion of 99.9%,
much tess rhan the fun 10 1:
Pll-S (C)
11-14
kc . dp lj) I U ,dp P !l
[
-11/2 ']113
J);.bh="$ h _;'(1-$). [p Dab
Assuming the porosity remains the same, factors in the correlation affected by the size
of the catalyst pellets are:
d! 0,.25: _ _
2,1t.-, +red.l .- ....... +0.2.)(0..2))
y ::::; -_._._:1._-, _ .. -. ::::; = 1.145
rt.dp- 0.286
;; 1 + ,.J!,.:_:'<l.._
50.9 . (1 + OJ 5X)
dX . (i--X)
-" ... ::::; 6 '8-",-"",,--,,,_ ..,--
dz -- (1 + OJ5X)II:
POLThlATH
Problem Pll-18 parI a/b
l.OoO .".
!
L,
.!Ss.'!'..;". c,acc
I
.. .. x
o .. 6ca
0,,-100
z
As can be seen from the above graph. rhe affect of reducing the dimensions of the
pellets by half results in the conversion reaching 99.9 % U8 em from the entrance.
This seems reasonable because reducing the size of the catalyst particles is one of the
methods for increasing mass transfer and hence kc.
11-15
Pll-5 (d)
rf pure cyclohexane feed were used at the same volumetric flowrar.e 60 dm
3
/min , then
the initial bulk concentration would be greater and there would be a greater
concentration gradient across the sragnant film on the pellets However the mass
transfer coefficient will be reduced as the products must diffuse away fmm the surface
which will be harder in higher concentrations of cydohex<lne.
The equations used In Part (a) do not incorporate Cao, the initial cyclohexane
concentration (Cao is cancelled out), so the only affect this change would have is to
alter [he physical properties of the bulk flow:
(84:<2) . (' _ .1
mm _ == 2647 11m J I == ).0026)8/ em
(t0821x773 ,"
)J.=? g!cm.s (cyclohexam:, 500 K, 2 atm)
Pll-5 (e)
This problem gives an indication as to how changes in parameters may affect a packed
bed.
Pll-6
Given,
Minimum respiration rate of chipmunk,
FAL = L5 /lmol 02/min
Breathing rate of Chipmunk,
Vo= 0.05 dm
3
gas/min
Diameter of hole, D = 3cm
Assuming,
A represents oxygen
B represents nitrogen
Chipmunk has a constant breathing rate of 0.05 dm
3
of gas/min
Minimum flow rate of oxygen to the bottom, FAL
= Minimum respiration rate of chipmunk
= 15 /lmo} of 02/min
11-16
L=O
:-.,-...,.........................
:-........."" ..............., ....,"', ..
:--.....,""', .........,", ..
:-..,"""""", ..
"' ............"".......,""", ..
:-.., ....'s ...........,"", ...,:
;......"' ...,""', ....,', ..
j
" .....x .......,""", ......
" ....,"", ........,"""',.......... ","'!., ........,""', ......
,...."""""""", ...."" ......."" :-..,, ..s ...: ..x ........" ...: ...,', ..
. """.s,,,,,,,,,,,,,,,,"'-:.. """"""", ..
..... """"", .....,s ..." ........-...; :-......" ...,:.......,", ........" ..
-:-.,....""""""""",-..;. :-,....."""""", ..
, ........,"""', .....: ...,"', ....,'" """""""', ..
:-,....."""", ...", ...""' .."" ...,, :-.,....."""""", ..
.....,""""""""",....... :--..: ......."""""" ..
: ..."""""""" ...", ...,,, ........,""""" ...., ..
,'\.,."",s ..."""", ............" .................................................." ......
., ........,', ................,", ....: ......., ............, :-..................................':--......................
, ........, ........................, ............, ........, ...., ........-..;, :.............................................................
, ........, ...., ...................., ........" ........, ........,"-:.. :..............., ............, ...., ....,', ..
" ....,"', ....,"', ....,", ....,'" """", ....,"', ..
" ....,"', ....,"', ............,""....;. : , ............................., ........" ..
, ...." ...., ................" ...., ........,', ................;. ....' L = L " ..................
~ ~ ~ ~ : ~ A L ~ PT ~ ~ ~ ~ ~ _ . . : : . . _ ~ ~ ........, ...., ............ ~ ~ ~ ~ :
Flow rate of A down the hole
= Flux of Ax Cross - sectional Area
C
AO
-CAL
:. F AL = X Ac
L
CAO _. CAL
or xAc
FAL
= 0.18 cm
2
/ s = 0.18x1O-
4
m
2
/ s
Ac= 1'lf)2 = JZ"x(0.03m)2 = 7.069x1O-4m2
4 4
F AL = 1.50x1O-
6
mol /min = 2.5x1O-
8
moll s
Pll-6 ( a) At Pasadena, California
PI
C = - X Y (Ideal gas law)
AO RT . A
where,
----(1)
Py = 1.013 x 10
5
N / m
2
at Pasadena, California ( situated at sea level)
R = 8.314 J / mol.K
T = 25C = 298K
YA =0.21 (Mole fraction of oxygen in air)
C AO = 1.013x10
5
f'.! / m
2
xO.21


mol.K
:.C
AO
=8.59mol/m
3
Now,
Flow rate of A = (Concentration of A at the bottom) x (Volumetric intake of gas)
FAL = CAL xVo
Vo = O.OS dm
3
/ min = 0. OS X 10-
3
m
3
gas/min
. C - F AL _ 2.S X 10-
8
moll s _ 0 03 1/ 3
.. AL --- 3. --. mo m
Vo (0.OSX1O-
3
Imm J
min 60s
Solving for the length from (1),
CAO -CAL xAc
FAL
11-17
L = 0.lSx1O-
4
m
2
I SX((S.59 -0.03
8
0) moll m
3
]X7.069X1O-
4
m
2
2.5x1O- moll s
:. L=4.36m
Pll-6 (b) At Boulder, Colorado
Boulder, Colorado is 5430. feet above sealevel The corresponding atmospheric pressure is 0.,829 x 10-
5
N/m2
P
T
= 0.S29x10
5
N I m
2
at Boulder, Colorado
Py
C =-xy
AO RT ,A
C
AO
= 0.S29x10
5
N 1m
2
xO.21
(
S.314 J X 29SK)
mol.K
:. C AO = 7.03 moll m
3
Solving for the length from (1),
L = -, CAL xAc
FAL
L = 0.lSx1O-
4
m
2
I sx((703 mol 1m
3
]X7.069X1O-
4
m
2
2.5x1O- moll S
:. L =3.56m
Pll-6 (C)
During winter at Ann Arbor, Michigan
T = 0
0
F = -17.7SoC = 255.37 K
Py
C
AO
='RT
xYA
C
AO
= __ N
(
S.314 -J-x255.37 K)
mol.K
.. C
AO
= 10.02 moll m
3
Solving for the length from (1),
L = C AO - CAl X Ac
FAL
11-18
L=0.18xlO-4m21 sx 255 x (10.02 -0.03) mollm x7.069xlO-
4
m
2
( )
175 ( 3 J
298 2.5xlO-
8
mol / s
:. L=3.87m
During winter at Boulder, Colorado
T = 0 F = -17.78C = 255.37 K
C = Pr xy
AO RT . A
CAO = 0.829x10
5
N I m
2
xO.21
(
8.314 K)
mol.K
:. CAO = 8.20 moll m
3
Solving for the length from (1),
L
- V0r C AO - CAl .11
- 4B x''C
FAL
L = 0.18xlO-
4
m
2
1 sX 255 x (8.20 -0.03) moll m x7.069xlO-
4
m
2
( )
L75 ( 3 J
298 2.5xlO-
8
moll s
:.L=3.17m
PII-6 (d) Individualized solution
PII-7 (a)
Given: Py = 510 nun Hg @ 35C (from plot of In Py vs lIT)
B
InP
v
= A - (T + C) Antoine Equation
DAB = 0 .. 120 cm
2
/sec (from equation of Fuller, et aL)
0.00 IT' 75 + _1_
MA MB
DAB =---P(Vl': +VV;;)2 Fuller Equation
where V A and VB are the Fuller molecular diffusion volumes which are calculated by summing the atomic contributions.
This also lists some special diffusion volumes for simple molecules.
Fuller diffusion volumes
Atomic and structural diffusion volume increments
C 15..9 F 14.7
H 2..31 CI 2LO
o 6..11 Br 21.9
N 454 I 29.8
11-19
Ring -18.3 S 22,9
Diffusion volumes of simple molecules
He 267 CO 18.0
Ne 5,.98 C02 26.,9
Ar 16.2 N20 35,.9
Kr 245 NH3 20,,7
Xe 32.7 H20 13.1
H2 6.12 SF6 71.3
D2 6.84 Cl2 382
N2 18..5 Br2 69,,0
02 16.3 S02 4L8
Air 19,,7
PII-7 (b)
By CS
z
molar flow rate balance
-- Z=20cm
t
-- Z=Ocm
CS2
U
R=0,5 cm
dNA =0
dz
And
NA =K
1
Fick's First Law (For NAIR = 0)
dX
A
NA =-CDAB--+XA(N
A
+0)
dz
-CDAB dX
A
1-XA dz
Equating the results of Fick's First Law and molar flow balance, then rearranging and writing in the integral fOIm
Kl1 dz = CD
AB
X
J
dln(l- X
A
)
Xo
Kl = .C;!? AB 1{1 ,- X2]
Z2 1- Xo
Evaluating for Z2 = 20, X
2
= 0
C = ..!..- = _, ____ ....:(l....:)_at_m __ _
RT (82.6) atm.em' (308)oK
gmol.oK
= 3.95 * 10-
5
gmol / em
3
Xo = P
v
-. = 510 = 0.671
PTotal 760
N = K = * 1- 0.0 ]
A 1 (20) 1,- 0.671
= 2.64 * 10 7 gmol / em 2.sec
PII-7 (c)
11-20
Fo, "';f:e;:) between z = 0 and z = 20
z: = I-X, l{ __ l ]
l- Xo
(I-X )=(I-X) [_I_I/Z2 =(1-X) (1-ZIZ
2
)
A OAI_X OA
o A
X
B
= (1- X)A = (X
B
jl-Z/20)
~ ~ C ~ ~ C
M = XAM
A
+ XBM
B
C
B
=XBC
VA =NAIC
A
VB =NBIC
B
=0
V* = NA +N
B
.=7.17*1O-
3
C
n +n
V= A B =nAlp
p
fA = C
A
(VA - V*) = NA - XAN
A
= XBN
A
fB = CB(V
B
.- V*) = -XBNA = -fA
(*10
5
)
Z X
B
X
A
C
B
C
A PB
0 0.329 0.671 1.3 2.65 0.376
5 0.434 0.566 1.71 2.24 0.495
10 0.573 0.427 2.26 1.69 0.655
15 0.757 0.243 2.99 0.96 0.865
18 0.895 0.105 3.54 0.415 1.02
20 1 0 3.95 0 1.14
(*10
3
)
.
Z VB VA V V
0 0 9 .. 9 7.17 8.32
5 0 11.8 7.17 9.05
10 0 15.6 7.17 10 .. 25
15 0 27.5 7.17 12.5
18 0 63.5 7.17 14.9
20 0 1E+06 7.17 17.5
PII-7 (d)
(*10
3
)
PA P ffis
2.02 2.4 0.158
1.71 2.21 0.226
1.29 1.95 0.338
0.73 1.6 0.544
0.316 1.34 0.764
0 1.14 1
(*10
6
) .J:1.1O
jA=-jB JA=-J
B
3.16 8.7
4.52 11.45
6.77 15.15
10.9 20
14.9 23.6
20 26.4
11-21
ooA 00
0.842 60.7
0.774 56
0.661 49.4
0.456 40.5
0.236 34
0 28.97
Mole fraction
0. .. 9
0. .. 8
6
0..,7
~
0..,6
0.,,5
...
Gl o.A
g 0.,3
0.,,2
0.,,1
0.
......... .... T
0. 5 10. 15 20.
Z (cm)
Co ncentraiion
0
E
~ 3,5
~
3
0
~ 2,5
c
0 2
~ 1.5
C
1
2!
c
0..5
0
u
0.
Ill. 1
- - - - - ~
0. 5 10. 15 20.
Z (crn)
Diffusion Flux
30
CiO
<
0
25 ,...

cO 0
20 <
Q)
0 III
,...
cJ,

IiIE 15
. 2 ~
11. III
10 ..
c ra ..
0
E
'iii
5 ::J
...
:!::
'D
0
.................. T .. N .........
0 5 10 15 20
Z (em)
PII-7 (e)
Evaporation Rate of CS
2
(Pliq @ 20C = 126 gm/cc)
11-22
PII-7 (f) No solution will be given
PII-7 (g)
Molecular diffusion of air is taking place
NB = J
B
+ XB(N
B
+ N
A
)
O=J
B
+XB(N
A
)
J
B
=-XB(N
A
) = (l-XA)N
A
=-J
A
PII-8 (a)
Quasi-steady-state - no accumulation in the capillary tube or in either chamber.
Volume 1:
Accumulation = in - out.
dNA
dt=-dt-=O--WAAc
W
A
=-DABC
t
: + YA (WA +W
B
)
EMCD:WA=-W
B
W
- D dC A W IL - D C I
C
A2
A -- AB-- AZo -- AB AC
dt Ai
DAB ( )
W
A
=-- CAl -C
A2
L
Volume 2:

-.- dt = WAAc- 0
dCAI =. AcDAB (c -c )
dt V,L Al A2
I
dC
A2
= AcDAB (c .- C )
dt V L Al A2
2
Subtraction gives us:
d( CAl -C
A2
) = _ AcDAB -c )
dt L V, V Al A2
I 2
Now integrate:
11-23
AcDAB( 1 1 J
- _. - t + Constant
L V; V
2
Pll-8 (b)
(CAl -C
A2
) = kMC
AcDAB(1 IJ
Ink+lnMC= ---- t+Constant
L V; V
2
AcDAB ( 1 1 J
InMC=--- -'-- t+C
2
L V; V
2
InMC = -DAB (O.01025)t+C
2
if we plot I n ~ I C ) as a function of time and find the slope, that would give us -DAB
See Polymath program PIl8b.poL
POL YMA TH Results
Linear Regression Report
Model: InDIC = aO + a1 *t
Variable
aO
a1
General
Value
3 .. 7024708
-0.0107008
95% confidence
0.0078035
9,,83E-05
Regression including free parameter
Number of observations = 9
Statistics
R"2 =
R"2adj=
Rmsd=
Variance =
DAB = 0.0107
Pll-9
0 .. 9998944
0,,9998793
0.0015013
2.608E-05
Dissolution of monodisperse solid particles in exceSs solvent.
Di "'" D +._ .. ! ... --{ Dil ..... [ ) ~ ) = Ct..!
2D*
Define conversion in tenus of volume dissolved:
gives D:: Di (t X) II:;
11-24
Substituting for D :
... lil 1 (D':! [D' (I X 113]2)
D/- Dl (l - X) .. +._........ t .. ,. 1 -) -== fl.. t
2D* .
terIll 1 term 2
Surface reaction controls: D* is large. term 2 is small cf teEm 1
Mass transfer controls:
Borh regimes appare?t :
Pll-lO (a)
Mass transfer limited
Di - Di (1 X)II} ::: fI..t
IIJ fI.,(
1- (l .. X) -== --_.
Di
D* is small. term 1 is small cf term 2
1 2 [. X)lJ)'f)-
... _. ( Dl - D1 (l - - fl.. t
2D* .
Di 2/3 fI. .. t
_. __ ... ( 1- (1- X) ) = ._ ... -
2D* Di
Tenn 1 and term 2 apply
[
. 10] [' Di "13 J fl..!
1 .. (t .. X) + --...... (1- (1. X)- ).' : : : l ' ) ' ~ '
.2D*
A in excess, C,"" :::: C
AO
T he reaction nue is equal to the mass transfer rate
For small particles and negligible shear stress: kc "" 3:pe
D
11-25
;'101 balance on solids:
For t mole A dissolving l mole B then ... c-'./' =. (3," ;;;:; kcC
AO
as e
A
, is undefined
Boundary conditions, t = 0 , D ::: Di
J (D)dD =: de
0, p 0
4.De.Cw.t
......" .. = .. ... ........" .."'"
2 p
Time for dissolution, te , at. D =: 0, and assuming particle density, p:::: 2000 kg/m
3
Di
2
2000 x (lOe - 5)2 ,
tc:::: ='""'""",_ .. _',""0"0::::; 0.1255
8 .. De. CAD 8 x (We, to) x (2000)
ie. vinuully instama..'1eous dissolution
PII-IO (b)
Surface reaction limited
Mass transfer effects are not imporlant when the surface reaction rate is limiring.
balance ()n solids:
For I mole A dissolving L mole B then LA;' = '" la,"
Boundary conditions, t. :::: 0 , D =: Di
D ) k C I
J dD ::::;.:::. ..... J dt
Dr P 0
11-26
D-Di = _ 2.kr.CAo:.!...
p
D::: Dj
p
Time for dissolurion, (C , at D:: 0, and assuming particle density, p:: 2000 kglm
3
tc == . p.pi == .... == 5xlOel2s
2.kT. 2 x (toe -10) x (2000)
a very long time.
PII-IO (C)
At t;;:: 0, total moles A in tan.lc:: 0.1 x 100 == 10 mol A
Le. there is just enough mols of A to completely dissolve all of B in a well mixed tank.
Acid not in excess and dissolution is mass transfer limited (CA:I:;O: 0. and C
A
;: CAo)
,. kr ..
-rAJ ="'-0' C" where
1 + ..
D*
Mol balance on solids:
assume zero order in B
and
D*;:::
kr
2.De
kc = --_.
D
For 1 mole A dissolving 1 mole B then ... lss"
=: dt D
l+ .-_.
" D*
2.kr.Ct
where a. = -_.-
j)
11-27
Boundary conditions. t = 0 , D == Di
DiDt
DP ...... [)J.) :::: eLl
2D'"
As a function of radius:
'">r2 2ri2
:' .... _ .. - 2r + at 2ri ..... -.. _. = 0
D D'
,. [D*.a t .. .,] 0
r- + D* r -+ 1.'."'-'2'-'.' "-' D'" n- rC ""
Using the quadratic solver:
-b
r = ...................... _ ..............................................-
2.a
f
..... ........ .. .. -; ...-... ................. ---.-...-......-.
.. ,. [) I,D .... ........... D n ....... n I
(Of iD at '. 2 '\
r :::; ....................... "'........... ................... ... .... . ..... .................. _ ............................ .1
2
Time for complete dissolution, te, at r:= 0 ;
tc = Vi
.. 2kr. C, 2x(lOe 18)x(OJe3)
assume p == 2000 kg/m.' and 0:;;:;: -. __ ........... = ......... _ ........... _ .... " ...... _. = lOe ..... 19
p 2000
. 2. De 2x(iOe1O) _
D'" ::::=.._. ;;;;;......... ... -.:::: 2xlOe8
kr 10e 18
gives
I r" - (IOe 5)::'1
tc :::: (lOe )) + :2 .. 10e14s
again a very long time ..
PII-I0 (d)
tc ::::: ._._.P ...... [Di +e
i2
'1
2.kr.'C, 2D*
To reduce te, increase C, and lor decrease Di.
To increase tc, decrease C", and I Of increase Di ..
PII-II (a)
Irreversible, gas-phase, adiabatic. no pressure drop. packed bed.
Isorhermal
Mol balance :
moUgcat $
11-28
where FAo = C .. ou" = lOe-3 x lOe4::: 10 mollem'
Rate law:
- to\,':;; k' .C ... , Bur C,,-, is unknown ..
Assume reaction rate is mass transfer limited.
k' .kC.CA cm' mol
::::: ", ........ _-"." ... _ .
kc+k'
"'-1
s.gecu em
where k' = 0,01 at 300 K (constant ... isothermal)
converting: 70.7 x acal;;;:: 70.7 x 60 = 4242 cm
3
/s .. gcat
0 . .0 lx4242xCt
/"A. :::; .................... - ...- ...-.. -.
4242 +0.01
Stoichiometry: gas . phase, constant pressure and temperature
C", = C
AO
(1- X) and CA