CHAPTER 5

CHAPTER 5
Collection and Analysis of Rate Data

Lecture 1

Failing to plan is planning to fail
Effie Jones

CBB 2074 - Reaction Engineering
Objectives
After completing Chapter 5 the reader will be
able to:
Determine the reaction order and specific reaction
rate from experimental data obtained from either
batch or flow reactors using various techniques of
analysis
Decide the most suitable type of analysis technique
for a particular problem
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
Analysis of Data to find Rate Law
2 common reactors used to obtain rate data:
Batch reactor

Differential reactor
AL
F
A0

F
Ae

Catalyst
Methods used to analyse rate data:
Differential method ( ) (Fogler: page 258-259)
Methods of finding
Graphical
Finite Different Method (Numerical Method)
Polynomial
Integral method (try and error - reaction order)
Half live method
Initial rate method
Linear regression
Non-linear regression

dt
dC
A
dt
dC
A

Consider the following reaction in a batch reactor,
with unknown rate law:
A Products
Mole balance:

Rate Law:

Stoichiometry:

Combine:
V r
dt
dN
A
A
=
o
A A
kC r =
0
V V =
o
A
A
kC
dt
dC
=
Take natural log of :

Plot graph of ln (-dC
A
/dt) vs. ln C
A
gives straight line
graph with:
Slope = o
Intercept = ln k

How to get ?

~Differential method analysis~
o
A
A
kC
dt
dC
=
A
A
C ln k ln
dt
dC
ln o + = |
.
|
\
|
dt
dC
A

Assign 5-1: Differential
method of analysis
The following reaction takes
place in an isothermal constant-
volume batch reaction system.
The initial concentration of B is
0.5 mol/dm
3
.
The concentration of A at
different time was recorded as
shown in Table 1. Determine:
a) Reaction order wrt A
b) If a we assume that the
reaction order wrt to B is first
order, determine the specific
reaction rate constant of the
reaction .

A + B C + D
~Differential method analysis~
Time (min) C
A
(mol/dm
3
)x10
3

0 50
50 38
100 30.6
150 25.6
200 22.2
250 19.5
300 17.4
Table 1
Differential Method
1) Graphical method
work in class

2) Finite Difference method
Initial point:
Interior point:
Last point:

3) Polynomial method
See example in the class
t
C C C
dt
dC
A A A A
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
=
|
.
|
\
|

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

~Integral method analysis~
Zero order reaction:

Integration gives:
k r
dt
dC
A
A
= =
kt C C
0 A A
=
t=C
A0
/ k
Slope = -k
t
C
A

C
A0

First order reaction:

Integration gives:
A
A
A
kC
dt
dC
r = =
kt
C
C
ln
A
0 A
=
t
l
n

C
A
0
/
C
A

Slope = k
Second order reaction:

Integration gives:
2
A
A
kC
dt
dC
=
kt
C
1
C
1
0 A A
=
t
Slope = k

Intercept = 1/C
A0

1/C
A

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.
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
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.
~Method of initial rates~
Half-live, t
1/2
, is define as:

Consider:

Integration gives:

Half live, t
1/2
, occur at C
A
= C
A0

~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
Taking natural log gives:
~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

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.
Design equation similar to CSTR due to gradientless criteria
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

= =
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

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

CHAPTER 5 - Lecture 1

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Collection and Analysis of Rate Data

CBB 2074 - Reaction Engineering

CBB 2074 - Reaction Engineering

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