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Constant-volume of batch reactor

Integral method of analysis of data


Differential method of analysis of data


TOPIC 2
Determination of Rate Law
Constant volume of batch reactor refer to volume of
reaction mixture, not the volume of the reactor.
It also known as constant-density reaction system.
The measure of reaction rate of component i
becomes

For ideal gas

therefore,
*This means the rate of
reaction of a
component can be
given by the rate of
change of concentration
or partial pressure
[1]
[2]



Say A, converted to something else, or the fraction of A
reacted away. We call this, simply, the conversion of A,
with symbol X
A
.
Suppose that N
A0
is the initial amount of A in the reactor
at time t = 0, and that N
A
is the amount present at time
t. Then the conversion of A in the constant volume
system is given by

The Conversion


and


We will develop the equations in this chapter in terms of
concentration of reaction components and also in terms
of conversions.
Later we will relate X
A
and C
A
for the more general case
where the volume of the system does not stay constant.

[7]
[8]

The integral method of analysis always puts a particular
rate equation to the test by
the with the
.
If the fit is unsatisfactory, another rate equation is
. This procedure is shown and used
in the cases next treated.
It should be noted that the integral method is especially
useful for fitting simple reaction types corresponding to
.
Consider the reaction
Irreversible Unimolecular-Type
First-Order Reactions
[9]
For this reaction. Separating and integrating we obtain
[11]
In terms of conversion (see Eqs. 7 and 8), the rate
equation, Eq. 10, becomes
which on rearranging and integrating gives
[12]
Or
A plot of , as shown in Fig.
below.
If the experimental data seems to be better fitted by a
curve than by a straight line,
because the first-order reaction
.
Integral Method Rate Analysis

We could integrate the combined mole balance
and rate law to plot reaction rate data in terms of
concentration vs. time for 0, 1st, and 2nd order
reactions.
Zero order





First order


For irreversible reaction, the reaction order and
specific rate constant can be determined by
.
It is applicable when the rate is essentially a function
of the concentration of only .
Consider a reaction carried out isothermally in a
constant volume batch reactor and the concentration
is as a function of time.
o
A A
kC r
P A
=

Combine mole balance and rate law:


The reaction order can be found by taking the natural
logarithm of both side



o
A A
A
C k
dt
dC
=
A A
A
C k
dt
dC
ln ln ln o + = |
.
|

\
|

:
Graphical differentiation
Numerical differentiation
Differentiation of a polynomial fit to the data

FAKULTI OF CHEMICAL
ENGINEERING, UiTM CHE584/594
16
Graphical Method
This method accentuates measurement error!


time (s) 0 t
1
t
2
t
3

concentration
(mol/dm
3
)
C
Ao
C
A1
C
A2
C
A3

Numerical Method
Can be used when the data points in the independent
variable are equally spaced.




dC
A
/dt can be calculated by

Initial point

Interior points

Last point

time (s) 0 t
1
t
2
t
3
t
4
t
5

concentration
(mol/dm
3
)
C
Ao
C
A1
C
A2
C
A3
C
A4
C
A5

t t t t t A = =
1 2 0 1
t
C C C
dt
dC
A A A
t
A
A
+
=
|
.
|

\
|
2
4 3
2 1 0
0
( ) ( )
( ) | |
1 1
2
1
+

A
= |
.
|

\
|
i A i A
t
A
C C
t dt
dC
i
| |
5 4 3
5
3 4
2
1
A A A
A
C C C
t dt
dC
+
A
= |
.
|

\
|