Problema Sherlock Holmes PDF

1304 323 Chemical Engineering Kinetics
and Reactor Design

By Assist. Prof. Dr. Wipada Sanongraj 1
1
Chapter 2: Design of Ideal Reactors
2 -
and Reactor Design
2
Outline
Analysis of Ideal Reactors
Completely Mixed Batch Reactors
Completely Mixed Flow Reactors
Plug Flow Reactors
2 -
and Reactor Design
3
Elements of Reactor Engineering Elements of Reactor Engineering
2 -
4
Completely Mixed Batch Reactor (CMBR) Completely Mixed Batch Reactor (CMBR)
Analysis of Ideal (Mixing) Reactors
2 -
and Reactor Design
5
Completely Mixed Flow Reactor (CMFR) Completely Mixed Flow Reactor (CMFR)
2 -
6
Plug Flow Reactor (PFR) Plug Flow Reactor (PFR)
2 -
and Reactor Design
7
Mathematical Analysis of Reactor Systems Mathematical Analysis of Reactor Systems - - The mass The mass
balance written in words is given by: balance written in words is given by:
Mass of A entering
the system

Mass of A leaving
the system
Mass of A disappearing or
appearing due to reaction
Mass of A accumulating
within the system
F
H
G
I
K
J
-
F
H
G
I
K
J
+
-
+
F
H
G
I
K
J
=
F
H
G
I
K
J
( )
( )
(2-1)
2 -
8
Completely Mixed Batch Reactor (CMBR) Completely Mixed Batch Reactor (CMBR) - - Step 1 Step 1
Clearly identify the system boundary. Clearly identify the system boundary.
in - out rate = accumulation units:
moles or mass of A.
Completely Mixed Batch Reactors (CMBR)

2 -
and Reactor Design
9
If we choose an accounting period from t to t + If we choose an accounting period from t to t + D Dt t, we , we
may write: may write:
0 0 - + = -
+
D
D
tr V N N
A A t t a t
r V it
N N
t
dN
dt
A t
A t t A t
A
=
-
=
+
lim
D
D
D
0
The general mass balance for a CMBR is: The general mass balance for a CMBR is:
r
V
dC V
dt V
VdC
dt V
C dV
dt
A
A A A
= = +
1 1 1
(2-2)
(2-3)
(2-4)
2 -
10
For constant volume, the mass balance for a For constant volume, the mass balance for a
CMBR becomes CMBR becomes
A
A
r
=
dC
dt
(2-5)
2 -
and Reactor Design
11
The carbonate reaction is actually a The carbonate reaction is actually a
combination of two reactions. combination of two reactions.
Example 2 Example 2- -1 : CMBR 1 : CMBR - - Fast Rate For Acids Fast Rate For Acids
2 2 3
CO H O HCO H
- +
+ +
2( ) 2 2 3( ) aq aq
CO H O H CO +
2 3( ) 3 aq
H CO HCO H
- +
+
The second reaction is very rapid and The second reaction is very rapid and
can be combined to this reaction. can be combined to this reaction.
2 -
12
For this acid base reaction the stoichiometric For this acid base reaction the stoichiometric
equation and elementary reactions are identical equation and elementary reactions are identical
The activity of the solvent is equal to its mole fraction The activity of the solvent is equal to its mole fraction
times its activity coefficient and is equal to one in this case. times its activity coefficient and is equal to one in this case.
{ }{ } { }{ }
2
CO f 2 2 r 3
r k H O CO k HCO H
- +
= - +
2 2 3
CO H O HCO H
- +
+ +
2
CO f 2 r 3
r k [CO ] k [HCO ][H ]
- +
= - +
2 -
and Reactor Design
13
This case is identical to this case. This case is identical to this case.
If we ignore the self ionization of water (H If we ignore the self ionization of water (H
2 2
O O H H
+ +
+ +
OH OH
- -
), the stoichiometric table becomes. ), the stoichiometric table becomes.
A B C +
2
CO f 2 r 3
r k [CO ] k [HCO ][H ]
- +
= - +

Species

Initial

D

Final

A

N
Ao

-X
A
N
Ao

N
Ao
(1-X
A
)

B

0

X
A
N
Ao

X
A
N
Ao

C

0

X
A
N
Ao

X
A
N
Ao

2 -
14
The concentrations of A, B, C in terms of conversion The concentrations of A, B, C in terms of conversion
become. become.
)
Ao
A
A Ao A
N
= (1 X )=C (1 X
C
V
- -
B Ao A
C C X =
C Ao A
C C X =
2 -
and Reactor Design
15
Or we can express them in terms of concentration. Or we can express them in terms of concentration.
A
A
Ao
C
X = 1
C

-

1
A
B Ao A Ao Ao A
Ao
C
C C X C C C
C

= = - = -

1
A
C Ao A Ao Ao A
Ao
C
C C X C C C
C

= = - = -

2 -
16
k k
f f
= 3.0 x 10 = 3.0 x 10
- -2 2
(sec (sec
- -1 1
); ); k k
r r
= 7 x 10 = 7 x 10
4 4
(L/m (L/m- -sec) sec)
The solution in terms of concentration is: The solution in terms of concentration is:
( )
2
( )
A
f A r Ao A
dC
V k C k C C V
dt
= - + -
( )
( )
2
0
A
Ao
C t t
A
C
f A r Ao A
dC
dt
k C k C C
=
- + -

( )
A
Ao
C (t) t
A
2 2
C 0
r Ao f r Ao A r A
dC
dt
k C k k 2C C k C
=
+ - + +

2 -
and Reactor Design
17
( )
A
Ao
C (t) t
A
2 2
C 0
r Ao f r Ao A r A
dC
dt
k C k k 2C C k C
=
+ - + +

dx
ax bx c a p q
q
p
x p
x q
x
2
0
1
+ +
=
-

-
-
F
H
G
I
K
J
z
b g
ln
p q
b b ac
a
, =
- - m
2
4
2
In which p and q are the roots of this equation. In which p and q are the roots of this equation.
2 -
18
The solution in terms of conversion is: The solution in terms of conversion is:
V
dC
dt
k C X k C X V
A
f Ao A r Ao A
= - - + ( ( ) ) 1
2 2
- = - - + C
dX
dt
k C X k C X
Ao
A
f Ao A r Ao A
( ) 1
2 2
dX
k X k C X
dt
A
f A r Ao A
X
X t
A
A
( ) 1
2
0
0
- -
=
=
z z
2 -
and Reactor Design
19
Equilibrium is established in 10 seconds. The rate Equilibrium is established in 10 seconds. The rate
constants are 5 orders smaller than acid base constants are 5 orders smaller than acid base
reactions that involve only a proton transfer [ reactions that involve only a proton transfer [k k
f f
= 3.0 = 3.0
x 10 x 10
- -2 2
(sec (sec
- -1 1
); ); k k
r r
= 7 x 10 = 7 x 10
4 4
(L/m (L/m- -sec)]. Consequently, sec)]. Consequently,
acid base acid base equilibria equilibria are established in microseconds to are established in microseconds to
milliseconds. milliseconds.
How would you determine the free energy as a How would you determine the free energy as a
function of time? How would it look? function of time? How would it look?
2 -
20
Species A, B, and C
0 20 40 60
0
1 10
5
2 10
5
3 10
5
C
A
n
C
B
n
C
C
n
t
num
n
2 -
and Reactor Design
21
A second-order irreversible elementary reaction 2A
Product is carried out in an isothermal batch system of
constant volume. For a certain set of conditions, it is
found that the reaction is 60% complete after 20
minutes. What would be the time required to reach the
same degree of completion if:
Example 2-2 : CMBR
a. the initial concentration of A were doubled?
b thereactionrateconstant weredoubled
2 -
22
Solution
Example 2-2 : CMBR
2A P
r
A
=-kC
A
2
MB for CMBR
A
A
dC
=
r
dt
Af
Ao
C t A A A 2
A
o C 2 2
A A
dC dC dC
=- =dt =k dt
kC
dt - -
kC C
\

\
Af
Ao
C t
o C
A
1
=kt | |
C 2 -
and Reactor Design
23
Af Ao
1 1
- =kt
C C
60% conversion after 20 minutes
So C
Af
=0.4C
Ao
Ao Ao
1 1 1 3
k = - 1 =
20 0.4 40
C C

\

Example 2-2 : CMBR
2 -
24
Example 2-2 : CMBR
(a) If C
Ao, new
becomes 2C
Ao, old
, C
Af
=0.4 (2C
Ao, old
) =
0.8 C
Ao, old
for conversion.

\

Ao.old
Ao,old Ao.old Ao,old
1 1 1 40 1 1 1
C
t = - = - =10 min
k 0.8 2C 3 0.8 2
C C
(b) If k were doubled k =3/20C
Ao
Ao
Ao
20 1 1
C
t = - 1 =10 min
3 0.4
C

2 -
and Reactor Design
25
Example 2-3 : CMBR
Derive the governing equation that describes the fate
of component A, B, C, and D in a gas phase constant
pressure and temperature reactor. An ordinary
differential equation and appropriate initial condition
that could be programmed and solved on a computer
are required.
aA bB cC dD + +
The rate law is given by: r
a
=-k
f
C
a
C
b
+k
r
C
c
The initial conditions are C
ao
, C
bo
, C
co
, and C
do
2 -
26
Example 2-3 : CMBR
aA bB cC dD + +
Rearrange,
A b/aB c/aC d/aD + +
Stoichiometrictable
N
d
=N
do
+d/aX
a
N
ao
+d/aX
a
N
ao
N
do
D
N
c
=N
co
+c/aX
a
N
ao
+c/aX
a
N
ao
N
co
C
N
b
=N
bo
- b/aX
a
N
ao
-b/aX
a
N
ao
N
bo
B
N
a
=N
ao
- X
a
N
ao
-X
a
N
ao
N
ao
A
Final Change Initial Species
2 -
and Reactor Design
27
Example 2-3 : CMBR
Under constant pressure
t
ao a
o to
ao
ao
ao bo co do
N V
(1 Y X )
V N
N
Y
N N N N
b c d
1
a a a
= = + d
=
+ + +
d = - - + +
2 -
28
a ao a ao a
a
o ao a ao a
N N (1 X ) C (1 X )
C mol/L
V V (1 Y X ) (1 Y X )
- -
= = =
+ d + d
Example 2-3 : CMBR
b bo a ao bo a ao
b
o ao a ao a
N N b/aX N C b/aX C
C mol/L
V V (1 Y X ) (1 Y X )
- -
= = =
+ d + d
c co a ao co a ao
c
o ao a ao a
N N c/aX N C c/aX C
C mol/L
V V (1 Y X ) (1 Y X )
+ +
= = =
+ d + d
d do a ao do a ao
d
o ao a ao a
N N d/aX N C d/aX C
C mol/L
V V (1 Y X ) (1 Y X )
+ +
= = =
+ d + d
2 -
and Reactor Design
29
Example 2-3 : CMBR
For a CMBR with a volume change
A mass balance
( )
a a a
t t t
a
a
a
a
a a
In out gen. or loss accum.
0 0 r tV N N
dN
r V
dt
Therefore,
d C V
dC dV
r V C V
dt dt dt
+D
- + =
- + D = -
=
= = +
2 -
30
Example 2-3 : CMBR
a a
a
C dV dC
r
Vdt dt
= +
ao a
ao a ao a o ao a
a
2
o ao a
C (1 X )
d
(1 Y X ) C (1 x ) d[V (1 Y X )]
r
V (1 Y X ) dt dt
-

+ d - + d

= +
+ d
ao a ao a ao a ao a ao a
a
2 2
ao a ao a ao a
C (1 x ) Y dX C dX C (1 X ) Y dX
r
(1 Y X ) dt (1 Y X ) dt (1 Y X ) dt
- d - d
= - -
+d +d +d
ao a
a
ao a
C dX
r
(1 Y X ) dt
= -
+ d
2 -
and Reactor Design
31
Example 2-3 : CMBR
For the rate law,
a f a b r c
r k C C k C = - +
Substitute C
a
, C
b
, and C
c
ao a bo a ao co a ao
a f r
ao a ao a ao a
C (1 X ) C b/aX C C c/aX C
r k k
(1 Y X ) (1 Y X ) (1 Y X )
- - +
= - +

+ d + d + d

2 -
32
Set Equation 1 equal to Equation 2 and rearrange it,
we can get the differential equation for species A:
a ao a ao a bo a ao co a ao
f r
ao ao a ao a ao a
dX (1 Y X ) C (1 X ) C b/aX C C c/aX C
k k
dt C (1 Y X ) (1 Y X ) (1 Y X )
+ d - - +
= - - +

+ d + d + d

Then we use the relationship of the rate law for
other species:
a b c d
r r r r
a b c d
- = - = + = +
Example 2-3 : CMBR
2 -
and Reactor Design
33
Completely Mixed Flow Reactors (CMFR) Completely Mixed Flow Reactors (CMFR)
Mass Balance (Units = Mass) Mass Balance (Units = Mass)
2 -
34
Mass Balance (Units = Mass) Mass Balance (Units = Mass)
Mass of A entering
thesystem

Mass of A leaving
thesystem
Mass of A disappearing( ) or
appearing( ) due toreaction
Mass of A accumulating
withinthesystem
F
H
G
I
K
J
-
F
H
G
I
K
J
+
-
+
F
H
G
I
K
J
=
F
H
G
I
K
J
2 -
and Reactor Design
35
Basis of time interval t to t +Dt
Q C t Q C (t' ) t r (t'' )V t
VC (t t) VC (t)
I Ai E A A
A A
D D D
D
- + =
+ -
A A
A
I E Ai A
(t + t) - (t)
VC VC
- (t) + (t") V = QC Q C
r
t
D

D

If we divide the above equation by Dt.. Note t' and t" is
somewhere in the time interval t and t +Dt and the rate is
evaluated at the effluent concentration because the reactor is
completely mixed
(2-19)
(2-20)
2 -
36
Taking the limit as Dt 0 and the following
expression is obtained.
Ai I A E A
A
Q C - Q C + r V =
dC
V
dt
(2-21)
2 -
and Reactor Design
37
The general equation for the CMFR The general equation for the CMFR
assuming constant V and Q is: assuming constant V and Q is:
V
dC
dt
= Q
C
-
C
+ V
r
A
Ai A A
The mass balance equation for the CMFR assuming The mass balance equation for the CMFR assuming
steady steady- -state and constant volume is: state and constant volume is:
d(
C
V)
dt
=0= Q(
C

C
)+ V
r
A
Ai A A
C
A
-
(2-22)
(2-23)
2 -
38
In many environmental engineering applications, there
is no volumechange upon reaction. In this case, the
hydraulic detention time of the fluid in the reactor, t, is
equal to V divided by Q. If we know t and kinetics then
we can calculate the effluent concentration, or if we
know C
A
and r
A
then we can calculate t.
A
Ai A A
C
0 C C r = - + t
(2-24)
2 -
and Reactor Design
39
Example for First Order: The mass balance equation for Example for First Order: The mass balance equation for
the CMFR assuming steady the CMFR assuming steady- -state and constant volume state and constant volume
for a irreversible first order reaction is: for a irreversible first order reaction is:
L
Li L Li L L
dC
dt
= =
C C
+
r
=
C C
k
C
L
0 - - - t t
L
Li
C
=
C
(1 + k) t
t =
(
C C
)
C k
Li L
L
-
Example 2-4: CMFR
2 -
40
Suppose the influent concentration is 200 mg/L and Suppose the influent concentration is 200 mg/L and
the rate constant is 4(day the rate constant is 4(day
- -1 1
). What would the effluent ). What would the effluent
concentration be if concentration be if t t =12 hr? =12 hr?
t =
200 - 10
(10)(4)
=
19
4
=4.75 days
What What t t would be need for C would be need for C
L L
=10 mg/L? =10 mg/L?
L
C
=
200
1 + 4( )
= 66.6 mg/ L
05 .
Example 2-4: CMFR
2 -
and Reactor Design
41
Example 2 Example 2- -5 : CMFR; Sherlock Holmes Problem 5 : CMFR; Sherlock Holmes Problem
HOLMES: HOLMES: You say he was last seen tending You say he was last seen tending
this vat... this vat...
SIR BOSS: SIR BOSS: You mean You mean completely completely- -mixed flow mixed flow
reactor, reactor, Mr. Holmes. Mr. Holmes.
HOLMES: HOLMES: You must excuse my ignorance of You must excuse my ignorance of
your particular technical jargon, Sir your particular technical jargon, Sir Boss. Boss.
SIR BOSS: SIR BOSS: That That s all right; however, you must s all right; however, you must
find him Mr. Holmes. find him Mr. Holmes. Imbibit Imbibit was a queer chap; was a queer chap;
always staring into the reactor, taking deep always staring into the reactor, taking deep
breaths, and licking his lips, but he was our very breaths, and licking his lips, but he was our very
best operator. Why since he left, our conversion best operator. Why since he left, our conversion
of of googliox googliox has dropped from 80% to 75%. has dropped from 80% to 75%.
(O. Levenspiel, 1999, p. 117-118)
2 -
42
HOLMES: HOLMES: ( (Tapping the side of the vat idly Tapping the side of the vat idly) By ) By
the way, what goes on in the vat? the way, what goes on in the vat?
SIR BOSS: SIR BOSS: J ust an elementary second J ust an elementary second- -order order
reaction, between ethanol and reaction, between ethanol and googliox googliox, if you , if you
know what I mean. Of course, we maintain a know what I mean. Of course, we maintain a
large excess of alcohol, about 100 to 1 and large excess of alcohol, about 100 to 1 and
HOLMES: HOLMES: ( (Interrupting Interrupting) Intriguing, we ) Intriguing, we
checked every possible lead in town and found checked every possible lead in town and found
not a single clue. not a single clue.
SIR BOSS: SIR BOSS: ( (Wiping away the tears Wiping away the tears) We ) We ll give ll give
the old chap a raise the old chap a raise about two pence per about two pence per
week week if only he if only he ll come back. ll come back.
2 -
and Reactor Design
43
DR. WATSON: DR. WATSON: Pardon me, but may I ask a Pardon me, but may I ask a
question? question?
HOLMES: HOLMES: Why certainly, Watson. Why certainly, Watson.
WATSON: WATSON: What is the capacity of this vat, Sir What is the capacity of this vat, Sir
Boss? Boss?
SIR BOSS: SIR BOSS: A hundred Imperial gallons, and we A hundred Imperial gallons, and we
always keep it filled to the brim. That is why we always keep it filled to the brim. That is why we
call it an overflow reactor. You see we are call it an overflow reactor. You see we are
running at full capacity running at full capacity profitable operation profitable operation
you know. you know.
HOLMES: HOLMES: Well, my dear Watson, we must Well, my dear Watson, we must
admit that we admit that we re stumped, for without clues re stumped, for without clues
deductive powers are of no avail. deductive powers are of no avail.
2 -
44
WATSON: WATSON: Ahh Ahh, but that is where you are , but that is where you are
wrong, Holmes. ( wrong, Holmes. (Then turning to the manager Then turning to the manager) )
Imbibit Imbibit was a largish fellow was a largish fellow say about 18 say about 18
stone stone was he not? was he not?
SIR BOSS: SIR BOSS: Why yes, how did you know? Why yes, how did you know?
HOLMES: HOLMES: ( (With awe With awe) Amazing, my dear ) Amazing, my dear
Watson! Watson!
WATSON: WATSON: ( (Modestly Modestly) Why it ) Why it s quite s quite
elementary, Holmes. We have all the clues elementary, Holmes. We have all the clues
necessary to deduce what happened to the happy necessary to deduce what happened to the happy
fellow. But first of all, would someone fetch me fellow. But first of all, would someone fetch me
some dill. some dill.
2 -
and Reactor Design
45
With Sherlock Holmes and Sir Boss impatiently With Sherlock Holmes and Sir Boss impatiently
waiting, Dr. Watson casually leans against the waiting, Dr. Watson casually leans against the
vat, slowly and carefully filled his pipe, and with vat, slowly and carefully filled his pipe, and with
the keen sense of the dramatic lit it. There our the keen sense of the dramatic lit it. There our
story ends. story ends.
What momentous revelation was Dr. Watson What momentous revelation was Dr. Watson
planning to make and how did he arrive at this planning to make and how did he arrive at this
conclusion? conclusion?
Why did he never make it? Why did he never make it?
2 -
46
We were given in the problem statement: We were given in the problem statement: r r
A A
= =- -
kC kC
A A
C C
B B
; ; C C
Bo Bo
= 100 = 100 C C
Ao Ao
; ;
V = 100 imperial gallons V = 100 imperial gallons
Operator Operator Operator Operator
Imbibit Imbibit Present Present Imbibit Imbibit Absent Absent
X X
A A
=0.8 =0.8 X X
A A
=0.75 =0.75
Ao A A B
A
QC
-
QC
-
VkC C
= V
dC
dt
0=
2 -
and Reactor Design
47
Stoichiometric Table Stoichiometric Table
Component Initial Change Final
A N
ao
- X
A
N
Ao
N
Ao
(1 - X
A
)
B N
bo
- X
A
N
Ao
Ao
Bo
Ao
A N

N
N
-
X
F
H
G
I
K
J
A
A
Ao
A Ao A
C
=
N
V
=
N
V
( -
X
) =
C
( - X ) 1 1
B
B Ao
Bo
Ao
A Ao
Bo
Ao
A C
=
N
V
=
N
V

N
N
-
X
=
C

C
C
-
X
F
H
G
I
K
J
F
H
G
I
K
J
2 -
48
C C
B B
= =C C
Ao Ao
(100 (100 - - X X
A A
) and X ) and X
A A
< <1 1
C C
B B
~100 ~100 C C
Ao Ao
and it is pseudo and it is pseudo- -first order. first order.
Ao A A
A
QC
-
QC
- Vk
C
=
VdC
dt
= 0 '
t =
C
- C
k
C
Ao
A
A
2 -
and Reactor Design
49
Imbibit Imbibit present (X present (X
A A
=0.8): =0.8):
C C
A A
= =C C
Ao Ao
(1 (1 - - X X
A A
) )
C C
A A
=0.2 =0.2 C C
Ao Ao
t
B
Ao Ao
Ao
=
C
- 0.2
C
k 0.2C
=
0.8
0.2 k
=
4
k ' ' '
2 -
50
Imbibit Imbibit in the tank (X in the tank (X
A A
=0.75): =0.75):
C C
A A
= =C C
Ao Ao
(1 (1 - - X X
A A
) )
C C
A A
= 0.25 = 0.25 C C
Ao Ao
t
A
Ao Ao
Ao
=
C
- 0.25
C
k 0.25C
=
0.
0.25k
=
k ' ' '
75 3
2 -
and Reactor Design
51
A
B
A
B
= =
V
/ Q
V
/ Q
t
t
3
4
A
B
A B
V
V
=
3
4

V
=
3
4
V
= 75 imp gallons ;
V V
I I
=V =V
B B
- - V V
A A
=100 =100 - - 75 =25 imp gallons. 75 =25 imp gallons.
Volume of Volume of Imbibit Imbibit =(25 Imp gal)(10 lb H =(25 Imp gal)(10 lb H
2 2
O/1 Imp O/1 Imp
gal)(1 ft gal)(1 ft
3 3
/62.4 lb H /62.4 lb H
2 2
O) =4.01 ft O) =4.01 ft
3 3
Assume density is 62.4 lb/ft Assume density is 62.4 lb/ft
3 3
;(14 lb/stone) ;(14 lb/stone)
Weight of Weight of Imbibit Imbibit =(62.4 lb/ft =(62.4 lb/ft
3 3
)(4.01 ft )(4.01 ft
3 3
)(1 stone/14 )(1 stone/14
lb) ~17.9 stone lb) ~17.9 stone .close to 18 stone .close to 18 stone
So So Imbibit Imbibit could well be in the vat!!! could well be in the vat!!!
2 -
52
Suppose we have a CMFR and are given: Suppose we have a CMFR and are given:
C C
Ao Ao
=200 mg/L, k =4 day =200 mg/L, k =4 day
- -1 1
, Q =10,000 m , Q =10,000 m
3 3
/day, V = /day, V =
47,500 m 47,500 m
3 3
. .
(a) What is the steady (a) What is the steady- -state effluent concentration? state effluent concentration?
Example 2 Example 2- -6 : CMFR; Rating Mode or Natural System 6 : CMFR; Rating Mode or Natural System
ass
Ao Ao
C
=
C
+ k
=
C
+ ( . )
= = mg L
1 1 4 475
200
20
10
t
/
2 -
and Reactor Design
53
(b) If at start (b) If at start- -up the tank concentration is 200 mg/L how long up the tank concentration is 200 mg/L how long
would it take for C would it take for C
A A
=12 mg/L? =12 mg/L?
A
Ao A A
dC
= - k
C C C
dt
t - t
dC
C k C
dt
A
Ao A
t
C
C
Ao
A
- +
=
z z
1
0
t t a f
ln
C
- ( + k )
C
C
- ( + k )
C
= - ( + k )
t
Ao A
Ao Ao
1
1
1
t
t
t
t
L
N
M
O
Q
P
2 -
54
C t =
C
(1 + k )
+
k C
e
1 + k
A
Ao Ao
-(1 + k )t/
( )
t
t
t
t t
12 10 190 = +
e
-20t/t
t = (
20
) ln
190
2
=1.08 days
t
L
N
M
O
Q
P
2 -
and Reactor Design
55
Consider the pond given below as a CMFR.
Influent concentration of NH
3
=20 mg/L
Area of lagoon is 1 km
2
Influent flow rate Q =20 MGD
Depth of lagoon is 4 meters
Ammonia is being oxidized to nitrate by autotrophic
bacteria according to this rate law.
( )
3 3
2
NH NH
L
=-k ; k =0.088
C r
mg- day

The initial ammonia concentration in the pond is 20.0 mg/L.
Example 2-7 : CMFR
2 -
56
(a) What is the concentration of ammonia in the effluent
under steady-state conditions?
(b) How long does it take to achieve 99% of X
ss
(where
X
ss
is the steady-state value of the extent of reaction)?
Mathematically, what time corresponds to
i e(t)
i
-
C C
X =
C
such that
i e t
SS
i
-
C C
X =0.99X = 0.99
C
=

e
t
( |
C
=
=steady-state effluent concentration)
Example 2-7 : CMFR
2 -
and Reactor Design
57
Example 2-7 : CMFR
a) What is the concentration of ammonia in the
effluent under steady-state conditions?
Material Balance
in - out - loss =accumulation
2
o
dC
- QC - =V
QC VkC
dt
2
o
dC
- C - =
C kC
dt
t t
At steady-State dC/dt =0 so, tkC
2
+C - C
o
=0
Solution
2 -
58
Example 2-7 : CMFR
2
o
-1+ 1+4k -b + - 4ac
C b
C = =
2a 2 k
t
t
V =A x H =1 x 10
6
x 4 =4 x 10
6
m
3

3
4 3
3
L
m
Q =20 MGD (3.785) =7.57 x /d
10 m
gal L
10
6 3
4 3
V 4 10 m
52.84 d
Q 7.57 x /d
10 m
t = = =
Therefore
o
-1+ 1+4(0.088 L/mg d)(52.84 d)(20 mg/L) -1+ 1+4k
C
C = 1.97 mg/L
2 k 2(0.088 L/mg d)(52.84 d)
t
= =
t
g
g
2 -
and Reactor Design
59
Example 2-7 : CMFR
b) How long does it take to achieve 99% of X
ss
(where
X
ss
is the steady-state value of the extent of reaction)?
From part a,
e
t
C 1.97 mg/L
=
=
Ao e
t
ss
Ao
C C
20 1.97
X 0.9015
C 20
=
-
-
= = =
SS
X =0.99X =0.99 0.9015 0.8925 =
Ao t
Ao
C C
X
C
-
=
2 -
60
Example 2-7 : CMFR
Therefore,
t Ao Ao
C C XC 20 (0.8925)(20) 2.15 mg/L = - = - =
For unsteady state condition,
t t
2 A
Ao A A
dC
- C - = kC C
dt
A
Ao
C t
A
2
Ao A A C 0
dC dt
C C kC
=
- - t t

2 -
and Reactor Design
61
From integral table
( )
x
2
2
0
dx 1 q x p
ln forb 4ac
ax bx c a p q p x q
-
=

+ + - -

where p and q are the roots of the equation

2
2
b b 4ac
ax bx c 0, i.e, p,q
2a
- -
+ + = =
m
In this case, a =-kt, b =-1 and c =C
Ao
.
Substitute k =0.088 L/mg d, C
Ao
=20 mg/L, and t =52.84 d
Example 2-7 : CMFR
2 -
62
Example 2-7 : CMFR
Ao
1 1 4k C 1 1 4(0.088 L/mg d)(52.84 d)(20 mg/L)
p 2.18 mg/L
2k 2(0.088 L/mg d)(52.84 d)
+ + t + +
= = = -
- t -
g
g
Ao
1 1 4k C 1 1 4(0.088 L/mg d)(52.84 d)(20 mg/L)
q 1.97 mg/L
2k 2(0.088 L/mg d)(52.84 d)
- + t - +
= = =
- t -
g
g
t
t
Ao
Ao
C
C
A A
2
Ao A A A C
C
dC 1 1.97 C ( 2.18)
ln
C C kC (0.088)(52.84)(-2.18 - 1.97) 2.18 C (1.97)
- -
=

- - t - - -

2 -
and Reactor Design
63
t
Ao
C 2.15 mg/L
A
2
Ao A A C 20 mg/L
2.15 ( 2.18)
2.15 (1.97) dC 1
ln 0.154
C C kC 19.3 20 ( 2.18)
20 (1.97)
=
=
- -

-

= =
- - t - -

-

t
0.154 =
t
t 0.154 (0.154)(52.84 d) =8.14 d = t =
Substitute C
t
=2.15 mg/L
Example 2-7 : CMFR
2 -
64
How long does it take for Steady State How long does it take for Steady State - - First First
Order Reaction? Order Reaction?
C t =
C
(1 + k )
+
k C
e
1 + k
A
Ao Ao
-(1 + k )t/
( )
t
t
t
t t
Can we obtain a general answer? It depends on Can we obtain a general answer? It depends on
V, Q, K, C V, Q, K, C
ao ao
, , C C
ae ae
. .
C t =
C
| +
k C
e
1 + k
A
A
t=
Ao
-(1 + k )t/
( )

t
t
t t
(2-25)
2 -
and Reactor Design
65
Dimensional analysis shows it only depends on Dimensional analysis shows it only depends on
Damkohler Damkohler number for t/ number for t/t t. So it is possible. . So it is possible.
Da= kt
A A
t=
Ao
-t(1 + k )
C
(t) -
C
|
C
=
k
(1 + k )

e
t
t
t
t
(2-26)
2 -
66
A A
t=
Ao
-t(1 + k )
C
(t) -
C
|
C
=
k
(1 + k )

e
t
t
t
t
.01
(1 + k )
k
=
e
-t(1 + k )
t
t
t
t
Choose the difference as .01 of Cao. Choose the difference as .01 of Cao.
2 -
and Reactor Design
67
Ln
(1 + k )
k
=
-t(1 + k )
.01
t
t
t
t
L
N
M
O
Q
P
1
01 (1 + k )
Ln
k
(1 + k )
=
t
t
t
t t .
L
N
M
O
Q
P
2 -
68 2 -
and Reactor Design
69
In Lake Superior, the open waters of the lake have
DDE (DDT metabolic) concentrations of 10 parts
per 10
15
and yet the fish have concentrations on the
order of 1 part per 10
6
. This is a biomagnification
factor of 10
9
. This would not be troubling except
the eagles that next along the shores of Lake
Superior have total reproductive failure after eating
the fish from Lake Superior.
Example 2-8: CMFR
2 -
70
In order to formulate a dynamic model of Lake In order to formulate a dynamic model of Lake
Superior, we use these parameters ( Superior, we use these parameters (Bierman Biermanand and
Swain, 1982). Swain, 1982).
Depth =145 m Depth =145 m
Detention Time =177 years Detention Time =177 years
Suspended Solid =.75 mg/L Suspended Solid =.75 mg/L
Lake Volume =1.19X10 Lake Volume =1.19X10
16 16
L L
Example 2-8: CMFR
2 -
and Reactor Design
71
dC
dt
=
W
V
-
Q
V
C - (1- f)
v C
z
- K f C
T
T
s T
D T
In which, f is the fraction of the total DDT which is In which, f is the fraction of the total DDT which is
adsorbed to particulate matter. V adsorbed to particulate matter. V
s s
is the settling is the settling
velocity of the particle (151 m/year). C velocity of the particle (151 m/year). C
T T
is the DDT is the DDT
concentration in the water column. W is the concentration in the water column. W is the
atmospheric deposition to the Lake. atmospheric deposition to the Lake. K K
d d
is the rate of is the rate of
destruction of dissolved DDT by various means destruction of dissolved DDT by various means
including photolysis, chemical oxidation, etc (=.069 including photolysis, chemical oxidation, etc (=.069
year year
- -1 1
). ( ). (D D
a a
=49.) =49.)
Example 2-8: CMFR
2 -
72
in which in which K K
p p
is the partition coefficient (=5x10 is the partition coefficient (=5x10
5 5
) )
f =
1
K C +1
p ss
Example 2-8: CMFR
2 -
and Reactor Design
73
0
0.5
1
1.5
2
2.5
1968 1970 1972 1974 1976
Year
D
D
T

C
o
n
c
e
n
t
r
a
t
i
o
n
Series1
Series2
model fit
Example 2-8: CMFR
2 -
(Blerman, V.J. and Swain, W.R., 1982)
74
Plug Flow Reactors
There are two possible points of view that one write There are two possible points of view that one write
mass balances for plug flow reactors: mass balances for plug flow reactors: Eulerian Eulerian and and
Langrangian Langrangian point of view. For the eulerian point of point of view. For the eulerian point of
view, the observer is stationary and fluid flows through view, the observer is stationary and fluid flows through
the system that the observer has chosen. For the the system that the observer has chosen. For the
langrangian point of view, the observer, moves with the langrangian point of view, the observer, moves with the
fluid at its velocity and the system has no flow entering fluid at its velocity and the system has no flow entering
or leaving it. or leaving it.
2 -
and Reactor Design
75
Plug Flow Reactors
Figure 2-1: Notation for a plug flow reactor. (Levenspiel, O., 1999, p. 101)
2 -
76
V+DV
V
Flow Flow
Plug Flow Reactors
2 -
and Reactor Design
77
A mass balance on the small element A mass balance on the small element D DV, can be V, can be
written using the eulerian point of view. written using the eulerian point of view.
in in - - out +rate =accumulation out +rate =accumulation
( ) ( )
( ) ( )
'
A A A
'
A A
tQC V,t tQC V V,t'' r V t
V C t t,V'' C t,V
D -D + D + D D =

D + D -

Plug Flow Reactors
Eulerian Mass Balance
(2-27)
2 -
78
Dividing Equation by Dividing Equation by D Dt and t and D DV yields the following V yields the following
equation. equation.
( ) ( )
( ) ( )
'
A A
A A
a
C t t,V' C t,V
QC V V,t'' QC V,t'
r
V t
+ D -
+ D -
- + =
D D
- +
QC
V

r
=
C
t
A
A
A
For no volume change upon reaction (which occurs For no volume change upon reaction (which occurs
when when D D is 0 or is 0 or Y Y
Ao Ao
is small is small
-

Q C
V
r
=
C
t
A
A
A
Plug Flow Reactors
Eulerian Mass Balance
(2-28)
(2-29)
2 -
and Reactor Design
79
What is the Steady What is the Steady- -State concentration? State concentration?
A A
A
dC QdC
= 0
r
dV dt
- + =
The general equation for describing the fate of reactant The general equation for describing the fate of reactant
A in a PFR assuming steady A in a PFR assuming steady- -state and constant Q is: state and constant Q is:
A
Ao
C
A
C
A
dC
V Q
r
=

AO
A
C
A
C
A
dC
V Q
r
=
-
Or Or
(2-30)
(2-31)
(2-32)
PFR - Steady State Analysis
2 -
80
What is the Steady What is the Steady- -State concentration? State concentration?
V
k
k Q
A Ao Ao
C C e C e
-
- t
= = (2-33)
2 -
and Reactor Design
81
Example 2 Example 2- -9: Compare Volumes for CMFR 9: Compare Volumes for CMFR vs vs PFR PFR
Given: Given: C C
Ao Ao
=200 mg/L, =200 mg/L, C C
Ae Ae
=10 mg/L, k =10 mg/L, k
1 1
=4 day =4 day
- -1 1
; ;
What is the required detention time? What is the required detention time?
-k Ao
Ao
A
A
C 1
= ; = ln =0. 75 days PFR: C
C e
k
C
t
t
Ao Ao
A
A
1
C C
= ; 1 =4.75 days CMFR: C
1+k k
C

t = -

t

CMFR
PFR
4.75
V
= 6.33
0.75
V
=
2 -
82
Let's compare volume requirements for a PFR to a CMFR Let's compare volume requirements for a PFR to a CMFR
for second order reactions. for second order reactions.
A
Ao
C
A
2
C
A Ao
A
dC Q 1 1
PFR: V =Q =
kC k
C C

-

-

( )
Ao A
2
A
Q
C C
CMFR: V =
kC
-
2 -
and Reactor Design
83

C
Ao
- C
A

C
Ao

V
CMFR
/V
PFR

First Order

V
CMFR
/V
PFR

Second Order

99%

21.50

100

95%

6.34

20

90%

3.91

10

50%

1.44

2

10%

1.06

1.11

1%

~1

~1
2 -
84
Why does the PFR require less volume? Compare Why does the PFR require less volume? Compare
expressions. expressions.
( )
Ao Ae
CMFR
A
C C
=Q
V
r
-
-
Ao
Ae
C
A
PFR
C
A
dC
=Q
V
r -

2 -
and Reactor Design
85
-Q/r
A
C
AE
C
AO
2 -
86
-
-Q/r
A
C
AE
C
AO
2 -
and Reactor Design
87
1. Adding baffles
2.Increasing No. of
tanks
How to improve the efficiency of CMFR
2 -
88
-Q/r
A
As the number of CMFRs in series
increases , the detention time
approaches that of a PFR
C
AE
C
AO
2 -
and Reactor Design
89
Special Case when V Special Case when V
PFR PFR
> V > V
CMFR CMFR
Autocatalytic Reaction: A +R Autocatalytic Reaction: A +R R +R; R +R; r r
A A
=k C =k C
A A
C C
R R

mole/L C
A

mole/L C
R

-r = k C
A
C
R

t=0 0.9

0.1

0.09

0.7

0.3

0.21

0.5

0.5

0.25

0.3

0.7

0.21

0.1

0.9

0.09

2 -
90
PFR PFR
> V > V
CMFR CMFR
PFR Area
under the
curve
CMFR Area
of rectangle
-Q/r
A
C
AE
C
Ao
2 -
and Reactor Design
91
PFR PFR
> V > V
CMFR CMFR
; ;
Real World Examples Real World Examples
2
2 2 2
(s)
1
Mn O H O MnO 2H
2
+ +
+ + +
[ ]
2
2 2
0 1 2
Mn
(s) r k Mn k Mn MnO
+
+ +
= - -

Biological Reactions: Substrate Biological Reactions: Substrate - ->Microorganisms. >Microorganisms.
(Caveat: Short times where endogenous respiration is not (Caveat: Short times where endogenous respiration is not
important.) important.)
2 -
92
Plug Flow Reactors -
Langrangian Mass Balance
V+DV
V
Flow Flow
System Moves
with the fluid
velocity.
2 -
and Reactor Design
93
A mass balance on the small element A mass balance on the small element D DV, can be V, can be
written using the written using the Langrangian Langrangian point of view. In this point of view. In this
case, we define a new time as t* which is the time of case, we define a new time as t* which is the time of
travel from a boundary of the reactor or initial travel from a boundary of the reactor or initial
condition. condition.
t t
* *
=time of travel =time of travel
in in - - out +rate =accumulation out +rate =accumulation
0 0 - + = r V
dC
dt
V
A
A
D D
*
(2-34)
2 -
94
A
A
*
r
=
dC
dt
Looks like a CMBR Balance but it is not Looks like a CMBR Balance but it is not
because time is not elapsed time. It is because time is not elapsed time. It is
time that depends on time and position. time that depends on time and position.
(2-35)
2 -
and Reactor Design
95
t
t
0
V
R
C
a
0
V
V
V
R
BC: V =0 BC: V =0
IC: t=0 IC: t=0
2 -
96
Plot the concentration profile one finds in a PFR for no Plot the concentration profile one finds in a PFR for no
initial concentration in the reactor and the influent initial concentration in the reactor and the influent
concentration is 200 mg/L. (boundary condition). concentration is 200 mg/L. (boundary condition).
Given: Given: C C
Ao Ao
=200 mg/L, the irreversible, elementary =200 mg/L, the irreversible, elementary
reaction ; k reaction ; k
1 1
=4 day =4 day
- -1 1
; ; t t =0.750 days. For first order, =0.750 days. For first order,
we may write. we may write.
-
A
A
*
k C =
dC
dt
1
*
kt
A
Ao
C
e
C
-
=
Example 2-10 : Langrangian Mass Balance
2 -
and Reactor Design
97

t
*

C
A
, mg/L

0t

200

.1t

148

.2t

110

.25t

94.5

.30t

81.4

.50t

44.7

.75t

21.1

1.0t

10.0
This is the concentration This is the concentration
as a function of travel as a function of travel
time from either the time from either the
Boundary or Initial Boundary or Initial
Conditions for Conditions for C C
Ao Ao
=200 =200
mg/L. mg/L.
Example 2-10 : Langrangian Mass Balance
2 -
98
A reaction follows the following kinetic expression:
1.5
A A
r kC = -
(a) What is the volume requirement for the PFR and
CMFR at 95% conversion? The feed concentration is 1
mole/L. The reaction rate constant, k, was determined
to be 1.0 (L/mole)
1/2
hr
-1
. The feed flow rate is 100
L/hr.
(b) For unsteady state plot the concentration profile at t*
=0.2t, 0.4t, 0.6t, 0.8t, t, >t. Assume C
Ao
=0 for the
entire reactor at t =0.
Example 2-11: PFR
2 -
and Reactor Design
99
Example 2-11: PFR
C
Ao
=1 mole/L 95% conversion
C
AE
=0.05 mole/L
A 1.5
A A
dC
= =-
kC r
dt*
Solution
2 -
100
Example 2-11: PFR
(a) The volume at a steady state
PFR: mass balance
-
-
- =
-
- =
=
g
AE
Ao
AE
Ao
C
V
A
C
0
A
C
A
C
1.5
A
0.5 0.5
Ao AE
0.5 0.5
0.5 0.5
dC
dV
=
r Q
dC
V
=
kC Q
2 2 kV
C C Q
2 2 (1.0 L /mole hr)V
(1 mole/L) (0.05 mole/L) 100 L/hr
V 694.4 L
2 -
and Reactor Design
101
-
g
Ao AE
A
Ao AE
1.5
AE
0.5 0.5 1.5
- V
C C
=
Q
r
- V
C C
=
kC Q
(1 mole/L) - (0.05 mole/L) V
=
(1.0 L /mole hr)(0.05 mole/L) 100 L/hr
V =8,497 L
Example 2-11: PFR
CMFR: mass balance
2 -
102
Example 2-11: PFR
(b) For PFR unsteady state: mass balance (apply a
Langrangianpoint of view)
D
D
A
A
in - out + gen. - loss = accum.
VdC
0 - 0 + r V =
dt*
dC
r =
dt*
Given: r
A
=-kC
A
1.5
, k =1.0 (L/mole)
0.5
hr
-1
and
C
Ao
=1 mole/L
2 -
and Reactor Design
103
Example 2-11: PFR
= -
= -
- = -
- = -

=

+

A
Ao
1.5 A
A
C t
A
1.5
A C 0
0.5 0.5
Ao A
0.5 0.5
A
2
A
dC
kC
dt*
dC
k dt*
C
2 2
kt*
C C
2 2
(1.0)t*
(1) C
2
C
2 t*
Since
V 694.4 L
6.94 hr
Q 100 L/hr
t = = =
.
2 -
104
Example 2-11: PFR
Table 2-1: The concentration (C
A
) at t = 0.2t, 0.4t, 0.6t, 0.8t and t
0.050 t
0.070 0.8t
0.105 0.6t
0.175 0.4t
0.348 0.2t
1.000 0
C
A
, mole/L time, hr
2 -
and Reactor Design
105
Example 2-11: PFR
2 -

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1304 323 Chemical Engineering Kinetics

and Reactor Design

Completely Mixed Batch Reactors (CMBR)

where p and q are the roots of the equation

PFR - Steady State Analysis

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