1

Chapter 2. Mass Balance, Reactor and Flow Models

Materials balance
........ +
(
(
(
(

+
(
(
(
(

(
(
(
(

=
(
(
(
(

vol. control
the within
generation
mass of Rate
volume.
control the
of out mass of
flow of Rate
volume
control the
to in mass of
flow of Rate
vol. control
the within mass
of on accumulati
of Rate
Accumulation = Inflow Outflow + Generation
PART I. REACTION KINETICS AND REACTOR MODELS
2
Accumulation
- Accumulation =
-
- Accumulation =
- Typically V is constant: Accumulation =
- For the steady-state case, mass remains constant (dc/dt = ).
- Note the units of accumulation are mass per time (M T
-1
).
= = M c ;
3
Loading
- Loading = W(t); rate of mass loading, M T
-1
.
- Loading =
Q: volumetric flow rate of all water sources entering the system (L
3
T
-1
, m
3
/hr)
C
in
(t): inflow concentration of these sources (M L
-3
, g/m
3
)
-
= ) (t c
in
4
Outflow
- Outflow =
Q: volumetric flow rate
C
out
: outflow concentration (M L
-3
).
- We assume a well-mixed system, so that C
out
= .
- Outflow = Q C
5
Reaction
- Lets assume first order reaction
- Reaction =
where k: a first order reaction constant (T
-1
).
- Reaction =
6
Settling
- Settling =
where v: apparent settling velocity (L T
-1
), A
s
: surface area of the
sediment or equivalent.
- In our cases for reactor study, this term settling is not considered.
7
Accumulation = Inflow Outflow + Generation
=

t
C
A
For component A:
8
Types of Reactors: (1) Batch, (2) Complete Mix, CFSTR, (3) Plug flow,
(4) Cascade of CFSTR, and (5) Packed Bed
9
Characteristic of each reactor
- Each reaction type has its unique characteristic.
- The mass balance is composed of
- Lets discuss more detail.
10
Batch Reactor
-What is batch reaction or reactor?
11
Batch Reactor:
= V
dt
dC
A
=
dt
dC
A
Accumulation = In Out + Gen
- Batch reactors are never at steady state, unless the reactions
have reached equilibrium:

12
Reactions in Batch Reactor Analytical solution by Integration.
- Zero Order A B, r
A
=
- Accumulation =In Out +Gen
- V drops out, leaving dC
A
/dt = -K
13
Plot C
A
vs. t to get K
14
V r
dt
dC
V
A
A
=
= =
t
t
A
A
A
C or
C
C
0
Batch Reactor
- First order, r
A
=
Using mass balance on batch reactor.

=
dt
dC
A

=
t
C
C A
A
dt K
C
dC
t
A
A
0
-
0

- Accumulation =In Out +Gen

15
Plot
0
t
16

t
0
C
C
2
A
A
dt K -
C
dC
t
A
0
A
Batch Reactor
2
nd
Order, r
A
= (Type 1)
V r V
dt
dC
A
A
=
=
dt
dC
A

17
Plot
18
=
A
r
| |
= =
A
r
dt
A d
Batch Reactor
2
nd
Order Reaction Type 2 Batch Reactor
aA + bB Products
Remember,
Then from Mass Balance
We need to define [B] in terms of [A] and constants
Assume
order ond for r r
a dt
dC
a
r
A
A
sec ,
1 1
= = =
19
b
B B
a
A A
t o t o

=

t
a
b
0
a
b
0 t
A A B B + =
) (
0 0
A A B aKA
dt
dA
a
b
a
b
+ =

=
+
t
A
A a
b
a
b
dt aK
A A B A
dA
t
0 0 0
0
) (
( )

+
+
=
+
C
bx a
x
ln
a
1
bx a x
dx
aKt
A
a
b
A
a
b
B
A
A
a
b
B
t
o
A
A
o o o o
=
|
|
|
|
.
|

\
|
+
ln
1
I am going to stop using [ ]

20
aKt
A
a
b
A
a
b
B
A
A
a
b
A
a
b
B
A
A
a
b
B
o o o
o
t o o
t
o o
=
(
(
(
(

|
|
|
|
.
|

\
|
+

|
|
|
|
.
|

\
|
+
ln ln
1
aKt
A
B
A
a
b
A
a
b
B
A
A
a
b
B
o
o
t o o
t
o o
=
|
|
|
|
.
|

\
|

+
|
|
|
|
.
|

\
|

ln
1
aKt
A B
B A
A
a
b
B
o t
o t
o o
=
|
|
|
|
.
|

\
|

ln
1

t
B
21
aKt
A B
B A
A
a
b
B
o t
o t
o o
=
|
|
|
|
.
|

\
|

ln
1
|
.
|

\
|

o o
A
a
b
B aK
Plot -ln(A
t
B
0
/B
t
A
0
) versus t to get
We can also solve for A
t
If a = b,
t A
a
b
B aK
A B
B A
o t
o t
) ( ln
0 0
=
) (
0
) (
] )[ (
o o
o o
A
a
b
B akt
o
A
a
b
B akt
o o o
t
e bA aB
e A b B a A
A




=
) (
0
) (
] )[ (
o o
o o
A B akt
o
A B akt
o o o
t
e A B
e A B A
A

=
22
=
A
r
=
t
B B
0
= =
A
r
dt
dA
=
dt
dA
( )
(

+
+ =

o
1 1
1
1 1
A
K K
K
A K K
dt
dA
Batch
Reversible 1st Order: K
1
AB
K
-1
Assume B
o
= 0 then B
t
= A
o
-A
t

23
( )

+ =
+

t
o
A
A
t
0
1 1
0
1 1
1
dt K K
A
K K
k
A
dA
( )t K K A
K K
K
A ln
1 1
A
A
0
1 1
1
t
0

+ =
|
|
.
|

\
|
+

( )
(

+
+ =

o
1 1
1
1 1
A
K K
K
A K K
dt
dA
( )t K K
K K
A K
A
A
K K
K
A
t
1 1
1 1
0 1
0
0
1 1
1
ln

+ =
|
|
.
|

\
|
+

|
|
.
|

\
|
+

24
( )t K K
K K
A K
A
A
K K
K
A
t
1 1
1 1
0 1
0
0
1 1
1
ln

+ =
|
|
.
|

\
|
+

|
|
.
|

\
|
+

( )
0 1 1 1 eq
A K K K A 0
dt
dA

+ + = =
1 1
0 1
eq
K K
A K
A

+
=
( )
( )
( )t K K
A A
A A
ln
1 1
eq 0
eq t

+ =

( )t K K
1 1
1
0 0
1 1
1
t
1 1
e
K K
K
1 A A
K K
K
A

+

|
|
.
|

\
|
+
+
|
|
.
|

\
|
+
=
At equilibrium, A
t
= A
eq
Solving for A
t
as a function of constants and time only.

t K K
eq o eq t
e A A A A
) (
1 1
) (

+
+ =
25
=
A
r
Saturation Reaction, e.g., 0 1order
K
s
[A]
26
] A [ K
] A [ K
r
S
A
+

=
| |
| |
= =
dt
A d
K A at
S
Saturation Reaction, e.g., 0 1order
If [A] >> K
S
then ?? order
If [A] << K
S
then ?? order
K
s
= half-velocity constant, substrate concentration at one-half the
maximum rate
The equation is well known as ??????? equation to demonstrate
substrate limited growth of bacteria.
K
s
[A]
27
] A [ K
] A [ K
r
dt
] A [ d
S
A
+

= =
1
A
K
K
dt
] A [ d
S
+

|
.
|

\
|
+
t
0
A
A
S
dt K dA 1
A
K
t
o
Using Mass Balance

= +
t
o
t
o
A
A
A
A
S
Kt dA
A
dA
K

Kt A A
A
A
K
o t
o
t
S
= + ln

Kt A A
A
A
K
t o
t
o
S
= + ln
( )
t
K
K
K
A A
A
A
S S
t o
t
o
=

+ ln
( )
S S
S o t
o
K
K
t K
A A
t
A
A
=

+
ln
28
( )
S
t o
S
t
o
K
K
A A
t K t
A
A
+ =
1
ln
How to plot?
29
| |
=
dt
A d
=
=
2
1
A
A
r
r
=
dt
dA
=
t
A
| |
= =
B
r
dt
B d
( )

+
t
0
t K K
0 1
B
B
dt e A K dB
2 1
t
0
Parallel 1
st
order:
K
1
A B
K
2

30
( )

+
t
0
t K K
0 1
B
B
dt e A K dB
2 1
t
0
) 1 (
1 1 1
0
at
t
at at
e
a a
e
a
dt e

=
|
.
|

\
|
=

( )
( )
t K K
t
e
K K
A K
B B
2 1
1
2 1
0 1
0
+

+
=
( )
( )
t K K
t
e
K K
A K
B B
2 1
1
2 1
0 1
0
+

+
+ =
31
C B A
2 1
K K

| |
| | A K r
dt
A d
1 A
= =
=
t
A
| |
2 1
B B
r r
dt
B d
+ =
| |
=
dt
B d
t K
o 1 2
1
e A K B K
dt
dB

= +
Series Reactions - 1
st
Order

Where, =
1
B
r
=
2
B
r
and

32
C B A
2 1
K K

Series Reactions - 1
st
Order
( ) ( ) t Q Y t P
dt
dY
= +

= Qdt
1
Y
B Y =
t K
o
e A K Q
1
1

=

=
Pdt
e
This is a first order linear differential equation of the form
P( t ) = K
2
, a constant
t K
o 1 2
1
e A K B K
dt
dB

= +
33

=
t
dt K
e
0
2

t K
e
2
=

= dt e A K e
e
Y
t K t K
t K
1 2
2
0 1
1 ( )

= dt e A K e Y
t K K t K
1 2 2
0 1

Boundary Conditions
Possible at t = 0, B = 0
Also possible at t = 0, B = B
0
Lets use this
34
1 1 , , 0
) (
0
1 2 2
= = = =
t K K t K
e and e B B t At
K
K K
A K
B
1 2
0 1
0
+

=
( )
1 2
0 1
0
K K
A K
B K

( )
( ) ( )
(

1 2
0 1
0
1 2
0 1
1 2
2
K K
A K
B
K K
e
A K e B
t K K
t K
t
( )
( ) ( )
(

+ =


1 2
0 1
1 2
0 1
0
1 2
2 2
K K
A K
K K
e A K
e e B B
t K K
t K t K
t
( )

= dt e A K e Y
t K K t K
1 2 2
0 1
( )
| |
t K t K K t K t K
t
e e e
K K
A K
e B B
2 1 2 2 2
1 2
0 1
0

+ =
( )
( )
t K t K t K
t
e e
K K
A K
e B B
2 1 2
1 2
0 1
0

+ =
] ) [(
) (
1 2
0 1
1 2 2
K e
K K
A K
e B
t K K t K
+

=

Need to determine constant of
integration
35
( )
( )
t K t K
1 2
0 1
t
2 1
e e
K K
A K
B

=
| | | | | | | |
0 t t t
A C B A = + +
| | | | | | | | * B A A C
t t 0 t
=
( )
t K t K
1 2
0 1
t K
0 0 t
2 1 1
e e
K K
A K
e A A C

=
Now, in case of B
0
= 0
Lets calculate C
t
for all [C]
0
= 0
[B]
0
= 0
t K
o t
1
e A A

=
36
(

1 2
1
1 2
1
0
2 1
1
1
K K
e K
K K
e K
e A C
t K t K
t K
t
*This can be done for all types of reactions.
Remember we have discussed so far only regarding batch reaction
37
Methods for Determining Reaction Order and Rate Constants
1.Integral Method with Graphical Determination
- It consists of guessing n and integrating the equation to obtain a function
- Graphical methods are then employed to determine whether the model fits the data
adequately.
- The graphical approaches are based on linearized versions of the underlying
models.
n
kC
dt
dc
=
Order Rate units Dependent (y) Independent (x) Intercept Slope
Zero, n=o
First, n=1
Second, n=2
General, n1
38
Methods for Determining Reaction Order and Rate Constants
2. Integration with Tabular Averaging of K
E.g., First Order
t
C
C
ln
K
0
t
A
A

=
t C
A
-ln C
At
/(C
AO
) K
_ _ _ _
_ _ _ _
39
Methods for Determining Reaction Order and Rate Constants
1 1
1 1
+
+

i i
i i i
t t
C C
t
C
dt
dC
3. Differential Method
4. The Method of Initial Rate
5. The Method of Half-Lives
6. The Method of Excess
7. Numerical Method, etc
40
Simple Example of Determination of the Reaction Order and the Reaction Rate
Constant
Batch Reactor Test
Determine the reaction order and reaction rate constant
Time, d Concentration, C
A
, mole/L
0 250
1 70
2 42
3 30
4 23
5 18
6 16
7 13
8 12
A B
41
Batch Reactor Test
V r 0 0 V
dt
dC
A
A
+ =
A
A
r
dt
dC
=
Accumulation = In Out + Gen

k r
dt
dC
A
A
= =
] [A k r
dt
dC
A
A
= =
2
] [A k r
dt
dC
A
A
= =
Time, d Concentration, C, mole/L
0 250
1 70
2 42
3 30
4 23
5 18
6 16
7 13
8 12
42
- First, in case of first order.
- By Computer program (least square)
] [A k r
dt
dC
A
A
= =
Kt
A A
e C C
t
-
0
=
Time, day
0 2 4 6 8
C
A
0
50
100
150
200
250
300
1) By Computer program (least square)
Time, day
0 2 4 6 8
C
A
0
50
100
150
200
250
300
Kt
A
e C
t
-
250 =
K=1.02
R
2
=0.957
- Does not fit-well.
- However, the program gives a good number for R
2
.(this is a problem of
computer program).
43
- In case of second order.
- By Computer program (least square)
2
] [A k r
dt
dC
A
A
= =
Time, day
0 2 4 6 8
C
A
0
50
100
150
200
250
300
1) By Computer program (least square)
- Perfect fit, excellent number for R
2
.
- Now we say the reaction follows second order and k = 0.01
Kt
C
1
C
1
0 t
A A
+ =
K=0.01
R
2
=0.998
kt C
C
C
A
A
A
0
0
1+
=
kt
C
A
250 1
250
+
=
44
- First, in case of first order.
] [A k r
dt
dC
A
A
= =
Kt
A A
e C C
t
-
0
=
Time, day
0 2 4 6 8
C
A
0
50
100
150
200
250
300
2) Graphical Method + Integration Method (no computer program)
- How can you determine k?
45
Kt
A A
e C C
t
-
0
=
2) Graphical Method + Integration Method (no computer program)
- We need linear form of the equation.
Kt
C
C
A
A
t
=
0
ln
Time, d C -Ln (C/Co)
0 250 0
1 70 0.533
2 42 0.775
3 30 0.921
4 23 1.036
5 18 1.143
6 16 1.194
7 13 1.284
8 12 1.319
Time, day
0 2 4 6 8
-
L
n

(
C
/
C
0
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
K?????
Not linear.
So, not first order
46
- In case of second order.
2
] [A k r
dt
dC
A
A
= =
Time, day
0 2 4 6 8
C
A
0
50
100
150
200
250
300
2) Graphical Method + Integration Method (no computer program)
- How can you determine k?
kt C
C
C
A
A
A
0
0
1+
=
47
- In case of second order, we also linear form
2
] [A k r
dt
dC
A
A
= =
2) Graphical Method + Integration Method (no computer program)
kt C
C
C
A
A
A
0
0
1+
=
Kt
C
1
C
1
0 t
A A
+ =
Time, d C 1/C
0 250 0.004
1 70 0.014
2 42 0.024
3 30 0.033
4 23 0.044
5 18 0.056
6 16 0.063
7 13 0.077
8 12 0.083
Time, day
0 2 4 6 8
1
/
C
0.00
0.02
0.04
0.06
0.08
0.10
R
2
=0.998
0.004
01 . 0
2 8
024 . 0 084 . 0
=

=
d d
k
- Reaction follows 2-order or (pseudo 2 order).
48
3) Tabular Average + Integration Method (no computer program)
t C
A
-ln C
At
/(C
AO
) K
_ _ _ _
_ _ _ _
First order
Kt
A A
e C C
t
-
0
=
Kt
C
C
A
A
t
=
0
ln
Second order
t C
A
1/C
A
K
_ _ _ _
_ _ _ _
kt C
C
C
A
A
A
0
0
1+
=
Kt
C
1
C
1
0 t
A A
+ =
49
4) Differential method
N=2.06 (pseudo 2 order)
* If the reaction is more complicated, you need your analytical skills to
solve the problem.
A B * This is a just simple case.
50
Temperature Effect on Reaction Rate
Possible temperature affects:
-The rates of most reactions in natural waters increase with temperature.
- A general rule of thumb is that the rate will approximately double for a
temperature rise of 10 C.
51
- A more rigorous quantification of the temperature dependence is provided by an
empirical equation, Arrhenius equation:
a
RT E
a
Ae T K
/
) (

=
A = Arrhenius constant, a pre-exponential or frequency factor
E = Activation energy for a reaction (J mole
-1
)
R = the gas constant (8.314 J mole
-1
K
-1
)
T
a
= Absolute temperature (K)
-The equation is often used to compare the reaction rate at two different
temperature
1 2
1 2
) (
1
2
) (
) (
a a
a a
T RT
T T E
a
a
e
T K
T K

=
52
- Temperature in most water bodies vary over a rather narrow range, so the
product of T
a1
and T
a2
is relatively constant.
- The difference in temperature (T
a2
T
a1
) is identical whether an absolute or a
centigrade scale is used.
- Consequently, the following can be defined as a constant
1 2
1 2
) (
1
2
) (
) (
a a
a a
T RT
T T E
a
a
e
T K
T K

=
1 2 a a
T RT
E
e
=
) (
) (
1
2
T K
T K
53
- In water quality modeling, many reactions are reported at 20 C.
- The temperature dependency of biologically mediated reactions is often
expressed as the quantity Q
10
, which is defined as the ratio
- Meaning of Q
10
?
- Some typical values of used in water quality modeling
1 2
) (
) (
1
2
T T
T K
T K

=
20
2
) 20 ( ) (

=
T
K T K
10
10
) 10 (
) 20 (
= =
K
K
Q
Q
10
Reaction
1.27 Oxygen reaeration
1.58 BOD decomposition
1.89 Phytoplankton growth
2.16 Sediment oxygen demand (SOD)
54
= HRT
Hydraulic Residence Time in Reactors
HRT =
- This is the theoretical HRT
- Actual HRTs can be less than the theoretical due to dead volume. We can determine
the actual HRT using a tracer.
Input a slug of tracer and
measure the concentration in
the effluent.
55
It is assumed that the average HRT for the tracer molecules is equal to the
average HRT for the water molecules, i.e. the tracer is completely soluble.
Hact

= mass of tracer added

= center of mass time to center of mass
or

=
i i
i i i
act H
t C
t C t
= x axis center of the whole area

=
o Hact
time residence finite mass elemental each added mass total ] [
added mass total
time resisdence finite mass elemental each
Hact

=
0
] [

=
o
out
o
out
dt QC
dt C t Q

=
o
out
o
out
dt QC
dt QC t
56
Steady State Materials Balance for Conservative (Non - reactive) Substances
Assume that two streams meet and completely mix instantaneously
Acc (zero) = In - Out + Generation (zero)
Mass balance on flow
Mass balance on conservative substances.
=
3
C
Mass flux
57
Plug Flow Reactors
58
How to recognize a PFR
Look at the response of the system to the input of a non-reactive tracer.
59
60
Accumulation = In - Out + Generation
=

V
t
C
A
|
.
|

\
|

+ = + =
+
X
X
C
C Q C C Q QC
A
X A A X A X X A
) (
PFR Behavior
61
V r X
X
C
C Q QC V
t
C
A
A
X A X A
A
+ |
.
|

\
|

+ =

X A r X
X
C
Q
t
X A C
A
A A
+

A
A A
r
X
C
A
Q
t
C
+

V r QC QC V
t
C
A X X A X A
A
+ =

+
A X V =
62
A
A A
r
X
C
A
Q
t
C
+

H
V
Q
X A
Q

=

1
A
H
A A
r
C
t
C
+

Taking limit as X 0
63
0
t
C
A
=

H
A
H
A
A
d
dC
or
C
r

=
dt
dC
r
A
A
=
At steady state:
Then
The response of a PFR as a function of
H
at steady state is the same as the
response of a batch reactor, and solutions are exactly the same.
Compare with batch
A
H
A A
r
C
dt
C
+

PFR
What does that mean? Compare reactors in PFR vs. Batch.
64
H
A
H
A
A
d
dC
or
C
r

=
dt
dC
r
A
A
=
PFR
Compare with batch
65
=

H
A
d
dC
0 Order r
A
=
C
Ae
= Effluent value of C
A
C
Ai
= Influent value of C
A
H
A
H
A
A
d
dC
or
C
r

=
PFR
=
Ae
C
66
=

H
A
d
dC
=
Ae
C
1
st
Order r
A
=
=

H
A
d
dC
2
nd
Order r
A
=
*The conversion is the same for all of the reaction rates we covered in batch
reactors. Substitute CAe for CAt, CAi for CA0, and H for t
H
A
H
A
A
d
dC
or
C
r

=
PFR
67
Complete Mix Reactors
1) CFSTR Continuous Flow Stirred Tank Reactor
2) CSTR Continuous(ly) Stirred Tank Reactor
How to recognize a CFSTR
a) Tracer Response- Slug input
Non-reactive
69
Gen Out In Acc + =
= V
dt
dC
T
r
T
= 0 because non reactive tracer (just for this recognition experiment).
T
T
C
V
Q
dt
dC
=

=
t
T
0
T
C
C
t
0 T
T
dt
V
Q
C
dC
70
C
T0
= Concentration in the reactor at t = 0

=
t
T
0
T
C
C
t
0 T
T
dt
V
Q
C
dC
t
t
C
C
C
H T
T
T
t
0
1
ln
0

=
H T
T
t
C
C
t

=
0
ln
H
t
t
T T
e C C

=
0
71
CSTR
PFR
72
= Acc
V r QC QC V
dt
dC
T T T
T
i
+ =
b) Delta Input
= V
dt
dC
T

=

t
C
T T
T
dt
V
Q
C C
dC
t
T
i
0 0
73

=

t
C
T T
T
dt
V
Q
C C
dC
t
T
i
0 0
H T
T T t
0 C
C C
ln
i
t i

( )
H
C
0
T T
t
C C ln
t
T
i

=
H
i
t i
t
T
T T
e
C
C C

H
i i
t
T
t
T T
e C C C

=
=
t
T
C
Here it is assumed C
T0
= 0 in the reactor at t = 0.
74
CSTR
PFR
75
Gen Out In Acc + =
= V
dt
dC
A
KV QC QC 0
e i
A A
=
Q
V
K C C 0
e i
A A
=
=
e
A
C
0 Order, Steady state; r
A
= -K
CSTR Behavior
Now, we finished tracer test just to recognize CSTR
Of course, we do not have C
A
over time.
76
= V
dt
dC
A
=
dt
dC
A
( ) K C C
1
dt
dC
A A
H
A
i

=

=

t
A
0
A
i
C
C
t
0
H
A
H
A
A
dt
C
K
C
dC
( )

+ =
+
bX a
b bX a
dX
ln
1
0 Order Non Steady state; r
A
= -K
t
C
K
C
t
A
A
i
C
C H
A
H
A
H
=
|
|
.
|

\
|

0
ln
Gen Out In Acc + =
77
H
C
C H
A
H
A
t C
K
C
t
A
A
i

=
|
|
.
|

\
|

0
ln
H
H
A
H
A
H
A
H
A
t
C
K
C
C
K
C
i
t
i

=
|
|
|
|
|
.
|

\
|

0
ln
H
i t i
t
H
A
H
A
H
A
H
A
e
C
K
C C
K
C

|
|
.
|

\
|

0
( )
H
i i t
t
H A A H A A
e K C C K C C

=
0
At t , =
t
A
C
At t 0,
=
t
A
C
t
C
K
C
t
A
A
i
C
C H
A
H
A
H
=
|
|
.
|

\
|

0
ln
The same as steady-state
Of course, we have C
A
over time.
78
V KC QC QC V
dt
dC
A A A
A
i
=
Q
V
KC C C 0
e e i
A A A
=
=
i
A
C
=
e
A
C
1st Order steady state, r
A
= -KC
A
Gen Out In Acc + =
Of course, we do not have C
A
over time.
79
=
dt
VdC
A
=
dt
dC
Q
V
A
( )

+
t
0 H
C
C H A A
A
dt
1
K 1 C C
dC
t
A
0
A i
1
st
Order-Non-Steady State CFSTR
( )
( )
H A H A
A H A
H
t
C K 1 C
C K 1 C
ln
1 K
1
0 i
t i

=
(
(

+
+
+

Gen Out In Acc + =

( )

+ =
+
bX a
b bX a
dX
ln
1
80
( )
( )
H A H A
A H A
H
t
C K 1 C
C K 1 C
ln
1 K
1
0 i
t i

=
(
(

+
+
+

( ) ( )
H
H
H
H
i t i
t K
H A
t K
A H A A
e K C e C K C C

+

+ = +
) 1 ( ) 1 (
1 1
0

H
H
H
H
i
t
t
K
A
H
t K
A
A
e C
K
e C
C

+

+
+
|
|
.
|

\
|

=
) 1 (
) 1 (
0
1
1
=
t
A
C
=
t
A
C
At t ,
At t = 0,
Of course, we have C
A
over time.
The same as steady-state
81
= V
dt
dC
A
Q
V
KC C C
e e i
A A A
2
=
0 C C C K
i e e
A A
2
A H
= +
a 2
ac 4 b b
X
2

=
2
nd
Order Steady state r
A
= -KC
A
2
Solve using quadratic formula,
Gen Out In Acc + =
82
V r QC QC 0
A A A
e i
+ =
e
e
e i
A S
A H
A A
C K
C k
C C 0
+

=
e
e
A S
A
A
C K
kC
r
+
=
e i
e
e
A A
A S
A H
C C
C K
C k
=
+

2
e
A S A A A S A A H
C K C C C K C C k
e e i i e
+ =
( ) 0 C K C K k C C
i i e e
A S A S H A
2
A
= + +
Saturation Reaction: 1 0 order, steady state
Solve using quadratic formula,
a 2
ac 4 b b
X
2

=
83
Types of Reactors: (1) Batch, (2) Complete Mix, CFSTR, (3) Plug flow,
(4) Cascade of CFSTR, and (5) Packed Bed
PFR Batch
84
Comparison of PFR vs CFSTR
O Order CFSTR and PFR
1
st
Order CFSTR 1st Order PFR
2
nd
Order CFSTR 2nd Order PFR
Multiple CFSTRs in Series (Cascade)
Instead of this big reactor,
86
=
) ( 1 t
C
Multiple CFSTRs in Series (Cascade)
How to recognize a series of CFSTRs . Look at response to slug input of tracer.
From previous analysis.
=
dt
VdC
2
) t ( 2 ) t ( 1 H
) t ( 2
C C
dt
dC
=
2
t
) 0 ( 1 H
2
C e C
dt
dC
1 H
=

Write Mass Balance for Reactor 2

87
H
2 2
t
) 0 ( 1
H H
2 2
e C
1 C
dt
dC

+
( ) ( ) t Q Y t P
dt
dY
= +

= Qdt
1
Y
2
H
t
0
2
H
t
dt
1
e e

= =

=
Pdt
e
dt e C
1
e e Y
1
H
2
2
H
2
H
t
0
H
t t

=
H
2 2
t
0
H H
2 2
e C
1
) t ( Q ,
C
y ) t ( P ,
dt
dC
dt
dY

= =
Linear First Order D.E.
88
dt
C
e Y
H
t
H

2
2
0
2 1
H H
=
If
|
|
.
|

\
|
+

K t
C
e Y
H
t
H
0
H
t
H
0
e
t C
Y

=
( )
H
t
H
) 0 ( 1
t 2
e
t C
C

=
Do not take constants outside the integral.
At t = 0, Y= C
2( int )
= 0
K = 0
dt e C
1
e e Y
1
H
2
2
H
2
H
t
0
H
t t

=
Need to determine constant of
integration
89
H
t
H H
e
C C
dt
dC

+
0 2 2
dt
dC
' C
2
=
H
1

=
( )
t
t
H
t
e e
C
C C e
H

= +
0
'
( )
t
t
H
t t t t t t
e e
C
C C e C e C e C e C e C e
H

= + = + = + =
0
) ' ( ' ' )' ( '
Other approach to solve the D.E
dt e e
C
C e
H H H
t t
H
t

=
0
Integrate with inserted
90

dt
C
C e
H
t
H
0
K
t C
C e
H
t
H
+

0
H H
t t
H
0
e K e
t C
C

=
( )
H
t
H
0
t 2
e
t C
C C

= =
H
t
2
H
) 0 ( 1
3
e
t
2
C
C

|
|
.
|

\
|

=
( )
H
t
1 n
H
) 0 ( 1
n
e
t
! 1 n
C
C

|
|
.
|

\
|

=
At t = 0, Y = C
2( int )
= 0
K = 0
dt e e
C
C e
H H H
t t
H
t

=
0
H
t
t
e C C

=
0 ) ( 1
91
368 . 0
C
C
) 0 ( 1
max 2
=
271 . 0
C
C
) 0 ( 1
max 3
=
( )
( )
( ) 1 n
1 n
) 0 ( 1
max n
e
! 1 n
1 n
C
C

=
Slug input of nonreactive tracer
For 3 CFSTRs, C
3 max
is at t =
For n CFSTRs, C
n max
is at t =
Note
H
is for 1 CFSTR
For 2 CFSTRs, C
2 max
is at t =
92
One input
Input
CSTR
PFR
93
Input
CSTR
PFR
94
H
0
1
K 1
C
C
+
=
H
e 1
e 2
K 1
C
C
+
=
H
e 2
e 3
K 1
C
C
+
=
Reactions in Cascade of CFSTRs (not tracer test)
1
st
Order, assuming V
1
= V
2
= V
3
, steady state
Reactor 1
Reactor 2
Reactor 3
only for V
1
= V
2
= V
3
( )
n
H
0
ne
K 1
C
C
+
=
nth Reactor
95
3 2 1
V V V
1
H
0
e 1
K 1
C
C
+
=
=
e
C
2
=
e
C
3
1
st
Order
steady state
1 2
2
A A
2
A
H
C C C K 0 + =
CFSTRs 2
nd
Order steady state
solve for C
A1
solve above quadratic for C
A2
97
( )
(
(

|
|
.
|

\
|
=
+
= 1
C
C
K
1
K 1
1
C
C
n
1
An
Ai
H
n
H
Ai
An
(
(

|
|
.
|

\
|
= 1
C
C
K
n
n
1
An
Ai
H
T
H H
n
T
=
Comparison of CFSTR cascade with PFR
1st Order:-
For 90% removal:-
=
PFR T
H
=
CFSTR T H 3
HPFR H
CFSTR T
=

??
1
HPFR H
CFSTR T
=

??
3
Multiple CFSTRs in Series (Cascade)- Model Example
- Incompletely mixed systems such as estuaries, complicated rive..
- This can be represented as a series of coupled completely mixed systems.
Some Useful Tips for PFR vs. CSTR in Environmental Systems
1) Shock charge.
2) Microbial or catalytic activity, in case.
3) Reaction rate, if first order.
4) Treatment time.
5) Effluent quality.
PFR
CSTR
Multiful CSTR
100
Summary through Example Demonstration
PART I. REACTION KINETICS AND REACTOR MODELS
Chapter 2. Mass Balance, Reactor and Flow Models
PFR
CFSTR or CSTR
Vs.
(Similar to Batch)
101
Problem or Question Statement
The elementary, liquid-phase, irreversible reaction below is to be carried out in a
flowreactor.
C B A +
Two reactors are available, a PFR and a CSTR with 200 L volume at 300 K.
The two feed streams to the reactor mix to forma single feed streamthat is equal
molar inAand B, with a total volumetric flowrate of 10 L/min.
Additional information is
K =0.07 L/mol-min
C
A,o
=2 mol/L, Q
A, o
=5 L/min
C
B, o
=2 mol/L, Q
B, o
=5 L/min
Which reactor between CSTR and PFR are you going to use to best perform
the reaction in terms of transformation of chemical A (or B)?
102
Result
CSTR
PFR
300 K
Complete mixing
200 L
C
A,o
=2 mol/L,
Q
A,o
=5 L/min
C
B,o
=2 mol/L,
Q
B,o
=5 L/min
C
A
C
B
C
C
C
A,eff
=0.56mole/L
C
B,eff
=0.56mole/L
C
C,eff
=0.44mole/L
C
A,o
=2 mol/L,
Q
A,o
=5 L/min
C
B,o
=2 mol/L,
Q
B,o
=5 L/min
300 K
200 L
C
A
C
B
C
C
C
A,eff
=0.42mole/L
C
B,eff
=0.42mole/L
C
C,eff
=0.58mole/L
K=0.07
K=0.07
58%Conversion of Chemical A
44%Conversion of Chemical A