CHAPTER III

INTERPRETATION OF
BATCH REACTOR DATA

1
Type of
Reactors
1) Batch reactor

2
 2) Flow reactor

Krishnan, A. T. and A. L. Boehman. Selective Catalytic Reduction of Nitric

Oxide with Ammonia at Low Temperatures. Applied Catalysis B:Environmental,
3
18, 189-198 (1998).
Batch  Simple to scale up
 Homogeneous reactions

Flow  Heterogeneous reactions

 Suitable for reactions which are
difficult to follow, yield variety of
products, very rapid reactions and
gas-phase reactions.

4
Method for Analyzing Data
1. Integral
Step 1. Set up reaction rate
1 dN dC
 rA   A
  A  kCA
V dt dt
Step 2. Integrate (linearize)
 dCA  kCAdt
1
  dCA   kdt
CA
 lnC
A  kt c
5
 Step 3. Check the result by plotting the
corresponding data from experiment
plot ln CA vs. t
if straight line  right kinetics
if not  repeat step 1 to 3

2. Differential
1 dN
A dC
plot or A vs.CA
V dt dt

6
Irreversible Unimolecular – Type 1st
Order Reaction
A  product
Test : 1st order equation
dCA
 rA    kCA
dt
CA dC t
  A  k dt

C CA
A0 0
 (lnC
A  lnCA0)  kt
CA
 ln  kt
CA0
7
fraction conversion, xXAA  NA0 NA
NA0
 C A0 1  x A 
NA
CA 
V

Therefore, -ln(1-xA) = kt

plot ln (1-xA) or ln (CA/CA0) vs. t

Caution: Can’t apply to -rA =

kCA0.6CB0.4
8
Irreversible Bimolecular – Type 2nd
Order
Case I
Reaction
A + B  products
dC A
 rA    kCACB
dt

at time t, CA,reacted =CB,reacted

CA,reacted  CAo  CA  CAo X A

CB,reacted  CBo  CB  CBo X B

From CA = CAo(1-XA)

9
 d [C Ao (1  X A )]
 rA    k [C Ao (1  X A )][CBo (1  X B )]
dt
dX A
C Ao  k (C Ao  C Ao X A )(CBo  CBo X B )
dt
dX A
C Ao  k (C Ao  C Ao X A )(CBo  C Ao X A )
dt
CBo
M
C Ao
2
dX A kC Ao  CBo 
 (1  X A )(  X A )
dt C Ao  C Ao 
 kC Ao (1  X A )(M  X A )
XA 1 t
 dX A   kC Ao dt
0 (1  X A )(M  X A ) 0
10
 XA
1  M  XA  t
ln   C Aokt 0
M  1  1 X A  0
1  M  XA  1
ln   ln M  C Aokt
M  1  1 X A  M  1
1  (M  X A ) 
ln   C Aokt
M  1  M (1 X A ) 
 (M  X A ) 
ln   C Ao (M  1)kt
 M (1 X A ) 
11
  (M  X A )  1  X B 
Prove: lnM (1 X )   ln1  X 
 A   A

CBo XA
M  XA   XA   XA
C Ao XB
XA
 1  X B 
XB
CBo XA
M (1  X A )  (1  X A )  (1  X A )
C Ao XB
 XA 
X 1  X 
B 
 (M  X A )   (1  X B ) 
ln   ln B   ln 
 M (1  X A 
) X
 A (1  X A )   (1  X A 
)
 X B 
12
an
d  1 XB   1  (CBo  CB ) / CBo 
ln   ln 
 1  X A  1  (C Ao  C A ) / C Ao 
 CAoCB 
 ln 
 CBoCA 
 M  XA   CAoCB   1 X B 
ln    ln   ln 
M (1 X A )   CBoCA   1 X A 
(CBo  CAo )
 CAo (M  1)kt  CAo kt
CAo
 (CBo  CAo )kt; M  1

Plot ln(CB/CA) vs t  slope = (CBo - CAo)k

y-intercept = ln(CBo/CAo)
13
14
Case II 2A  products
dC A 2
 rA    kCA
dt
CA 1 t
  dC A   kdt
2
CAo C A 0
CA
 1  t

  
  kt 0
 C A  CAo
1 1
  kt
C A C Ao

Plot 1/CA vs t  slope = k

 1 1
  kt
C Ao (1  X A ) C Ao
1  1 
  1  kt
C Ao  (1  X A ) 
1  XA 
   kt
C Ao  (1  X A ) 

Plot XA/(1- XA) vs t  slope = kCAo

16
Case III A + 2B  products
If from experiment it is found that this reactio
dC A
 rA    kCACB
dt

at time t, CA,reacted = 0.5CB,reacted

1
C Ao  C A  (CBo  CB )
2
1
C Ao X A  CBo X B
2
2C Ao X A
XB 
CBo
dC A
 rA    k [C Ao (1  X A )][CBo (1  X B )]
dt
17
 dC A 2C Ao X A
  kC Ao (1  X A )CBo (1  )
dt CBo
 kC Ao (1  X A )(CBo  2C Ao X A )
2 CBo
 kC Ao (1  X A )(  2X A )
C Ao
2
 kC Ao (1  X A )(M  2 X A )
dC A dX A 2
  C Ao  kC Ao (1  X A )(M  2 X A )
dt dt

18
XA 1 t
 dX A   kC Aodt
0 (1  X A )(M  2 X A ) 0
XA
1  M  2X A  t
ln   C kt
M 2   Ao
 1  X A 0
0

 (M  2 X A ) 
ln
 M (1  X )    C Ao (M  2)kt, M  2
 A 

CBo 2X A 2X A
M  2X A   2X A   2X A  (1  X B )
C Ao XB XB
C 2X A
M (1  X A )  Bo (1  X A )  (1  X A )
C Ao XB
(M  2 X A ) (1  X B )

M (1  X A ) (1  X A )
 (M  2 X A )   (1  X B )   C AoCB 
ln   ln   ln 
 M (1  X A )   (1  X A )   CBoC A  19
If M = 2
dC A 2
  2kC Ao (1  X A )2  2kC A
2
dt
CA 1 t
  dC A  2k  dt
2
CAo C A 0
1 1
  2kt
C A C Ao
XA
 2kt
C Ao (1  X A )

20
 Irreversible Trimolecular-Type 3rd
Order Reaction
1. A  B  D  Product
dC A
- rA    kC A CBCD
dt

Change this eq. in term of x A . Using separation

variable and integratio n, we obtain
1 C A0 1 CB0
ln  ln
(C A0  CB0 )(C A0  CD0 ) C A (CB0  CD0 )(CB0  C A0 ) CB
1 C
 ln D0  kt
(CD0 - C A0 )(CD0 - CB0 ) CD
If CD0  C A0 and CB0, the reaction becomes 2nd order : - rA  k C ACB

21
2. A 2B R
dC A 2
- rA    kC A CB
dt
M  CB0 /C A0 , CB0 XB  2C A0 X A

(2CA0  CB0 )(CB0  CB ) CA0CB

 ln( )
CB0CB C A CB0
 (2CA0  CB0 )2 kt, M  2

1 1
If M  2,   8kt
C2A C2A0
22
3. A B R
dC A 2
- rA    kC A CB
dt

(C A0  CB0 )(CB0  CB ) C A0CB

 ln( )
CB0CB CB0C A
 (C A0  CB0 )2 kt, M  1
1 1
If M  1,   2kt
C2A C2A0

23
Empirical Rate Equation of nth Order
dCA n
-rA    kCA
dt
1n 1n
CA  CA0  (n 1)kt, n 1
1n
CA0
timeat CA  0, t  , forn 1
(1 n)k
From this equation we can find n by
trial-and-error by
1. select value of n, calculate k
24
Overall Order of Irreversible Reaction
from the Half-life, t1/2
Half-life, t1/2 = the time required for the
of reactants to drop to one-half
original value.
For irreversib le reaction
A  B  ...  products
dC A
 rA    kC AaCBb...
dt

25
 at any time CB /C A   / 
dC A a   b
 rA    kC A ( C A ) ...  k( ) ...CaAb ...
b
dt  
dC A 
or   k' CnA ; k'  k( )b ...
dt 

n  1, C1An  C1A0
n
 k' (n  1)t

2n1  1 1n
t1/2  C A0
k' (n  1)

We can determine the order of the reaction, n

by varying CA0 ,obtaining t1/2 from the
experiment, and then plotting log(t1/2) vs. 26
Example Find the order of the reaction that agr
Time, s CA, mol/m3
0 4.83
1800 3.68
3600 3.38
5400 2.91
7200 2.46
9000 2.18

Solution: Use half-life method:

27
Plot CA vs. t
5

4
CA, mol/m3

1 8650 9200

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t, s
28
From graph find t1/2
vs. CA0
t1/2, s CA0, mol/m3 logt1/2, s logCA0, mol/m3

8000 4.83 3.90 0.68

8550 4.60 3.93 0.66

8980 4.40 3.95 0.64

29
Plot logt1/2 vs. logCA0
log t1/2 vs log CAo

3.96
3.95
3.94
log t1/2

3.93
3.92
y = -1.25x + 4.7517
3.91
R2 = 0.9868
3.9
3.89
0.63 0.64 0.65 0.66 0.67 0.68 0.69
log CA0

From graph
1-n = -1.25
n = 2.25 30
31
Fail to match

32
Fail to match

33
34
35
36
Irreversible Reaction in Parallel
Consider the simplest case. Both paths
Reactions: k1
A R
k2
A S
Rate of change rA =  dCA/dt
= k1CA+k2CA
= (k1+k2)CA
rR = dCR/dt =
rkS1CA= dCS/dt =
CA + CR + CS =k2CCA0
A 37
  ln (CA/CA0) = ( k1 + k2)t
plot -ln (CA/CA0) vs. t, slope
= k1 + k2
rR/rS = dCR/dCS = k1/k2
(CR-CR0)/(CS-CS0) = k1/k2
plot (CR-CR0) vs. (CS-CS0), slope =
k1/k2
38
39
Irreversible Reaction in Series
k1 k2
1st order A R  S
dC A
rA   k1C A (44)
dt
dCR
rR   k1C A  k 2CR (45)
dt
dC S
rS   k 2CR (46)
dt

Start with CA0 of A and no R or S.

Integrate eq. 44:
 k1t or CA  CA0ek1t
CA
 ln (47)
CA0
40
 Substitute of CA in eq. 45;
dCR
 k 2CR  k1CA0 e k1t (48)
dt

which is a 1st order linear differenti al eq. Integrate with

integratin g factor ek 2t and the initial condition CR0  0 at t  0
e k1t e k 2 t
CR  C A0k1(  ) (49)
k 2  k1 k1  k 2
C A0  C A  CR  CS

41
Therefore;
k2 k1t k1
CS  C A0 (1  e  e k 2t ) (50)
k1  k 2 k 2  k1
if k 2  k1 CS  C A0 (1  e k1t )
if k1  k 2 CS  C A0 (1  e k 2t )

Find CR,max by setting dCR /dt  0

1 ln(k 2 /k1)
tmax   (51)
k log mean k 2  k1
k1 k 2/(k 2 k1)
and CR,max  C A0 ( ) (52)
k2

42
CR,max

t@CR,max

43
Complex Reaction: Consecutive
reactions
Simultaneous and consecutive
reactions of the form
k1 M + H
B + C 

k2 D + H
M + C 

k3
D + C  T + H

Based on C  simultaneous reaction

Based on B, M, and D  consecutive re

44
Example Manufacturing of
Chlorobenzene
(Use FeCl3 as a catalyst)
k1
C6H6 + Cl2   C6H5Cl + HCl (1)
k2
C6H5Cl + Cl2   C6H4Cl2 + HCl (2)
k3
C6H4Cl2 + Cl2   C6H3Cl3 + HCl (3)

(C6H6 = B, Cl2 = C, C6H5Cl = M, C6H4Cl2

= D, C6H3Cl3 = T)

45
umption: 1. Isothermal batch reactor
2. Irreversible 2nd order reactions
1 dNB k
 rB  
V dt
 1 NB NC
V2 (4)

1 dNM k1 k2
rM 
V dt

2
NB NC 
2
NM NC (5)
V V

(6)
1 dND k 2 k3
rD   NM NC  NDNC
V dt 2 2
V V

1 dNT k3
rT 
V dt

2
ND NC (7)
V
rB is defined in terms of the disappearance of B
rM, rD, and rT are defined in terms of the appearance o
46
Suppose at t = N0,B  NBo
with the presence Mof Cl
N o
 N o

D2 T 0
N o

Thus, o
NB  NB  NM  ND  NT (7a)
moles of C consumed  NM  2ND  3NT (7b)
 k2  NM
(5)/(4) 
dNM
 1   
dNB  k1  NB
dNM     k2 
  NM  1 ;    
dNB  NB 
(8)
 k1 
Eq. 8 is a 1st order linear differential equation with va
which are of the form:
47
 dy
 P ( x )y  Q( x )
dx
where y = NM, x = NB, P(x) = -/NB, and
Q(x) = -1. A general solution of this
differential equation is
ye  P ( x )dx   Q( x )e  P ( x )dxdx  K
where K is the constant of integration. For
eq. (8) the following result is obtained on
the basis of the initial
o condition
o when
NB  NB , NM  NM  0

   1
NM  1    NB  

  1 
NB    1   N o   (9)
  B  
48
 dND k2 NM k3 ND
(6)/(4)   
dNB k1 NB k1 NB
(10)

dND    NM

 

dNB  NB 
ND  
NB
(11)
where
k3 NM
 , from eq. (9)
k1 NB

Again, eq. (11) is a linear 1st order differential

initial condition
o
N D  0 when N B  N B
 N o   N / N o (N / N o )  N o (N / N o ) 
ND   B   (12)
B B  B B  B B B
 1    1       (1   )(   )
  

49
NT can be expressed in terms of NB by use of e
For a given amount of B reacted, the
corresponding amount of C consumed is
determined by use of eq. (7a), (7b), (9),
and (12). If Cl2 amount is constant
throughout the reaction, then eq. (4) may
be solved too give
 k1NC 
NB  NB exp ( )t  (13)
 V 

The expression for NM and ND are solved from

50
Example The chlorination is to be carried
out isothermally at 55C in a perfectly
mixed semibatch reactor. MacMullin has
reported that the following values at 55C
k1 k
 8, 2  30
k2 k3
Initial feed contains pure benzene. Find the
moles of chlorine required to maximize the
production of monochlorobenzene. Also,
find the corresponding product
distribution. Cl2

C6H6
51
Solution:
Since monochlorobenzene is produced by
the first reaction and consumed by the
second reaction, there exists the possibility
for a maximum concentration of
monochlorobenzene 2, N
M  0 and k1 ( kto
of benzene reacted M increases
occur. initially
This as
In particular,
) increase.
o
N

since
process continues
NB  NB until the concentration
o

of monochlorobenzene builds up to value

such that rM = 0. At the point where rM =
0, it can be shown by use of eq. (2) and (8)
that dNM
0
dNB

52
Differentiate eq. (9) with respect to NB and set

 1  1 1 
NM   NB  NB
   1 (  1) o 1
(N B)

dNM 
1
dNB 
1 1  1dN
( )NB B
 1 (  1) o 1
(NB )
dNM 1 1   1  0
  NB
dNB   1 o 1 (  1)
(NB )
o 1
 1 NB
NB 

1 /( 1)
o 1
NB  NB  
 
53
 and  = k2/k1 = 1/8, hence
o
NB  NB (8)8 / 7  0.09287NB
o

Substitue back in eq. (9)

1  (0.09287)7 / 8 
o
0.09287NB
NM,max 
 7/8
o
 0.743NB
The moles of D formed when when NM =
NM,max can be found by use of eq. (12) and
k3 k2 k3 1
   
k1 k1 k2 240
54
 NBo
(1/ 8)  0.09287 (0.09287)1/ 8  NB (1/ 8)(0.09287)
o 1/ 240
ND    
(7 / 8)  (1  1/ 240) (1/ 8  1/ 240)  (1  1/ 240)(1/ 8  1/ 240)
o
 0.1635NB
o
NT  NB  NB  NM  ND
o o o o
 NB  0.09287NB  0.743NB  0.1635NB
o
 0.0006NB

Finally, the moles of chlorine reacted when N

NC  NM  2ND  3NT
o o o
 0.743NB  2(0.1635NB )  3(0.0006NB )
o
 1.0718NB
55
First-Order Reversible Reactions
A  R, k1, k2

dC A dX A
 rA    C Ao  k1C A  k 2CR
dt dt
 k1C Ao (1  X A )  k 2 (CRo  C Ao X A )
CRo
Let M 
C Ao
dX A
C Ao  k1(C Ao  C Ao X A )  k 2 (C AoM  C Ao X A )
dt

56
 dX A
At equilibrium, 0
dt

0  k1(C Ao  C Ao X Ae )  k 2 (C Ao M  C Ao X Ae )
k1 M  X Ae
 KC 
k2 1  X Ae
k1(1  X Ae )
k2 
M  X Ae

57
 dX A k1(1  X Ae )(M  X A )
 k1(1  X A ) 
dt M  X Ae
k1[M ( X Ae  X A )  ( X Ae  X A )]

M  X Ae
k1( X Ae  X A )(M  1)

M  X Ae
XA 1 k1(M  1) t
 dX A   dt
0 X Ae  X A M  X Ae 0
Let z  X Ae  X A  dz  dX A

58
 XAe XA 1 k1(M 1) t
  dz  dt
XAe z M XAe0
t
XAe XA k1(M 1)
 lnz XAe  t
M XAe 0
 XAe XA   CA CAe  k1(M 1)
 ln    ln   t
 XAe   CAo CAe M XAe

59
Second-Order Reversible Reactions
k1 k1
A B  R S 2A  R  S
k2 k2

k1 k1
2A  2R A  B  2R
k2 k2

CA0 = CB0, CR0 = CS0 = 0

x Ae - (2x Ae - 1)x A 1
ln( )  2k1( - 1)CA0t
x Ae - x A x Ae
60
Differential Method of Analysis of
Data
Analysis of the Complete Rate Equation
1. Hypothesis the mechanism and from i
rate equation.
dC A
 rA    f(k,C )
dt
or
dC A
 rA    f(C)
dt

61
 2. From experiment we obtain conce
and plot them
3. Draw a smooth curve through
these data
4. Determine slope at selected
concentration values.
(slopes = dCA/dt = rate of reaction at
5. Evaluate
selected CA) f(C) for each
composition
6. Plot –dCA/dt vs. f(C)
If straight line  the rate
eq. is valid.
62
63
Guess nth order:  rA  kCAn
log( rA )  n log CA  log k

logk

64
65
66
67
Volume Change with Reaction
For a reaction in general form

aA  bB  cC  dD
b c d
or A B C D
a a a

68
 NT  NT0  (ND,formed  NC,formed NA,reacted
 NB,reacted
)
From EOS (Equation of State)
d c b
 NT0  ( N
a
PV =  ZN
A,reacted
a
RT  NA,reacted
NA,reacted
T a
 NA,reacted
)
Where  N  N d c b
(    1)
T0 A,reacted
V = volume a a of a system
 NT0  NA0xA
NT = total number of moles
= NTo+ NAox,  = d/a + c/a - b/
T = absolute temperature, K
P = total pressure, atm
Z = compressibility factor
R = gas constant
= 0.08206 dm3 atm/moleK
69
at t = 0
P0V0  Z0NT0RT
0

P0 T Z NT
V  V0( ) ( )
P T0 Z0 NT0
NT  NT0  δNA0xA

NT NA0
 1 δxA  1 δyA0xA
NT0 NT0
NA0
yA0   mole fraction
of Ainitailly
NT0

70
Defin change on total number of moles when rxn. completed
e   total number of moles fed to the reactor
d c b N
 (  - - 1) A0  δy A0
a a a NT0

Hence  = yA0
P0 T Z
V  V0( ) ( )(1 εxA)
P T0 Z0
Most of gas-phase system the compressibility
constant, hence Z0=Z
P0 T
V  V0( )( )(1 εxA)
P T0
71
For isothermal and isobaric system (constant
V = V0(1+xA)
Rate change of A
NA
d V
1 dN A 1 V 1 dC AV
 rA     
V dt v dt v dt
1 dC A dV
  (V  CA )
V dt dt
dC A C A dV dC A d lnV
 rA       CA
dt V dt dt dt

72
 NA
CA  , NA  NA0 (1 - x A )
V
NA0 (1  x A ) 1 x A
CA   CA0 ( )
V0 (1  εx A ) 1  εx A
CA
1- ( )
CA 1- x A C A0
 or x A 
C A0 1  εx A εC A
1 ( )
C A0
CA0 dx A
- rA  const. T and P
1  εx A dt
dxA
const. ε  0, - rA  CA0
density,
dt 73
Differenta
ilMethod
Analysis
Forisothermal
variable
- volume
dCA dCA dlnV CA0 dxA
replace by  CA or-
dt dt dt 1 εxA dt

74
Integral Method
Substitute V = V0(1+ xA)
then, 1 dNA CA0 dxA
- rA  - 
V dt 1 εxA dt
xA
dxA
CA0 t
0
(1 εxA)(-rA)

75
Zero-Order Reaction
1 dN A CA0 dx A
- rA  -   k
V dt 1  εx A dt

CA0 CA0 V V  V0
ln(1  εx A )  ln  kt XA 
ε ε V0 V0

V kε
plotln vs.t, 
slope
V0 CAo
76
First-Order Reaction
1 dN A
 rA    kC A
V dt
C A0 dx A kC A0( 1-x A )
 rA  
1  εx A dt ( 1  εx A )

V
ln(1 - x A )  - ln(1 - )  kt
V0

(V V- V0)

77
Second-Order Reaction
2A products
A+B products, CA0 = CB0

(1  ε )x A
 ln(1 - x A )  kC A0t
1- x A

78
nth-Order Reaction
1- xA n
- rA  kC  kC (
n n
)
1 εxA
A A0

(1 εxA)
xA n-1

0 (1- xA)n dxA  CA0kt

n-1

79
Example I. Use of a graphic integral
method to determine a rate expression for
a gas phase chemical reaction monitored
by recording the total pressure of the
system (Hinshelwood and Askey)

CH3OCH3  CH4 + CO + H2
(dimethylether)
E  B+C+D

The reaction occurred in an isothermal

(552C) constant volume reactor. Find the
order of the reaction and the reaction rate
constant. 80
Solution: Guess 1st order reaction
 CE 
ln   kt (A)
 CEo 
Assume ideal gas behavior
PE y E 
CE 
RT

RT (B)
where  = total pressure
yE = mole fraction of E
Combining eq. (A) and (B)
 yE  
ln   kt (C)
 o 
81
Prepare a mole Table

Species/Time, t 0 t 

CH3OCH3 CEo CEo(1-XE) 0

CH4 0 CEoXE CEo

H2 0 CEoXE CEo

CO 0 CEoXE CEo

Total moles CEo CEo+2CEoXE 3CEo

Pressure o  =3o

82
 o
 o  CEo RT  CEo 
RT
  CEo (1  2X E )RT   o (1  2 X E )

1  
X E    1 (D)
2  o 
The mole fraction of ether at time t is given b
CE CEo  CEo X E 1 X E
yE   
Ctotal CEo  2CEo X E 1  2 X E (E)
1  1 (   1)
2 o 3 o  
yE  
1  2[ 1 (   1)] 2
2 o
83
    3 o   
Thus, ln    kt
 o  2  
 3 o   
ln   kt
 2 o 
ln(3 o   )  ln 2 o  kt
Data:
Time, t (sec)  (mmHg) 3o-
0 420 840
57 584 676
85 662 598
114 743 517
145 815 445
182 891 369
219 954 306
261 1013 247
299 1054 206 84
 Plot ln(3o-) vs t

 straight line Slope = -k  k = 4.94X10-3 s-

 This is a 1st order reaction. 85