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dt
dC
A
\
|
dt
dC
A
\
|
2
4 3
2 1 0
( ) | |
) 1 ( ) 1 (
2
1
+
A
=
|
.
|
\
|
i A i A
ti
A
C C
t dt
dC
( ) | |
f f f
f
A A A
t
A
C C C
t dt
dC
3 4
2
1
1 2
+
A
=
|
.
|
\
|
CBB 2074 - Reaction Engineering
Need to guess reaction order and integrate the
differential form of equation used to model the
reactor used.
If the right reaction order is assume, the plot of
concentration time data should be linear
3 examples will be considered:
Zero order
First order
Second order
Analysis of Data to find Rate Law
~Integral method analysis~
CBB 2074 - Reaction Engineering
Zero order reaction:
Integration gives:
Analysis of Data to find Rate Law
~Integral method analysis~
k r
dt
dC
A
A
= =
kt C C
0 A A
=
t=C
A0
/ k
Slope = -k
t
C
A
C
A0
CBB 2074 - Reaction Engineering
First order reaction:
Integration gives:
Analysis of Data to find Rate Law
~Integral method analysis~
A
A
A
kC
dt
dC
r = =
kt
C
C
ln
A
0 A
=
t
l
n
C
A
0
/
C
A
Slope = k
CBB 2074 - Reaction Engineering
Second order reaction:
Integration gives:
Analysis of Data to find Rate Law
~Integral method analysis~
2
A
A
kC
dt
dC
=
kt
C
1
C
1
0 A A
=
t
Slope = k
Intercept = 1/C
A0
1/C
A
CBB 2074 - Reaction Engineering
Example E5-2: Integral method of analysis
Repeat example E5-1 using integral method.
Confirm that the value of k is the same for
both.
Analysis of Data to find Rate Law
~Integral method analysis~
CBB 2074 - Reaction Engineering
Topics
Lecture 1:
Analysis of data to find rate law:
Differential method of analysis
Integral method of analysis
Lecture 2:
Analysis of data to find rate law
Method of initial rates
Method of half lives
Differential reactors
CBB 2074 - Reaction Engineering
The presence of reverse reaction causes differential
and integral method ineffective in analysing the rate
data
Perform a series of experiment at different initial
concentration, C
A0
, and evaluate the initial rate, -r
A0
for each run.
Analysis of Data to find Rate Law
~Method of initial rates~
CBB 2074 - Reaction Engineering
Half-live, t
1/2
, is define as:
Consider:
Integration gives:
Half live, t
1/2
, occur at C
A
= C
A0
Analysis of Data to find Rate Law
~Method of half-lives~
value initial its half to fall to reactant of ion concentrat for taken time t
2
1
=
o
A A
A
kC r
dt
dC
= =
( )
|
|
.
|
\
|
=
1
0 A
1
A
C
1
C
1
1 k
1
t
o o
o
( )
|
|
.
|
\
|
1
0 A
1
2
1
C
1
1 k
1 2
t
o
o
o
CBB 2074 - Reaction Engineering
Taking natural log gives:
Analysis of Data to find Rate Law
~Method of half-lives~
( )
( )
0 A
1
2
1
C ln 1
k 1
1 2
ln t ln o
o
o
+
=
Slope = 1-o
ln C
A0
ln t
1/2
CBB 2074 - Reaction Engineering
Differential reactors
Normally used to determine rate of reaction as a
function of either concentration or pressure
Criteria of a differential reactor:
Conversion of reactant along catalyst bed is very small
Concentration change of reactant along catalyst bed is very
small
Low conversion means heat release is small therefore
reactor is essentially isothermal.
CBB 2074 - Reaction Engineering
Design equation similar to CSTR due to gradientless criteria
Differential reactors
AL
F
A0
F
Ae
Inert filing
Catalyst
W
F F
r
Ae 0 A '
A
=
( )
W
C C v
W
X F
r
Ae 0 A 0 0 A '
A
= =
CBB 2074 - Reaction Engineering
Example:
The formation of methane form carbon monoxide and hydrogen
using a nickel catalyst was studied by Pursley. The reaction,
3H
2
+COCH
4
+2H
2
O, was carried out at 500 F in a differential
reactor where the effluent concentration of methane was
measured. The exit volumetric flowrate was maintain at 300
dm
3
/min. The weight of catalyst is maintain at 10g. The partial
pressure of H
2
and CO was measured at reactor exit.
1. Relate the rate of reaction to the exit methane concentration
2. Determine the reaction order with respect to CO using data
from Table E5-4.1 assuming the rate law is a function of
r
A
=f(P
CO
)
o
Differential reactors
CBB 2074 - Reaction Engineering
Differential reactors
Run P
CO
(atm) P
H2
(atm) C
CH4
(g
mol/dm
3
)
1 1.0 1.0 2.44 x 10
-4
2 1.8 1.0
3 4.08 1.0
4 1.0 0.1
5 1.0 0.5
6 1.0 4.0
TABLE E5-4.1
CBB 2074 - Reaction Engineering