Boon Pin
Boon Pin
Boon Pin
The objective of this experiment is to determine the kinetic parameter of the reaction such
as rate constant, , activation energy, and frequency factor, , and to prove that the
reaction between ethyl acetate and NaOH (saponification) is a second order reaction. The
kinetic parameters are determined by carried out a reaction in batch and continuous
stirred-tanks reactor (CSTR) at 30 oC and 50oC which is being well mixed at constant
agitation speed. The experiment is divided into three parts. In part 1, the relationship
between the conductivity and concentration is determined. And the concentration of
NAOH in the batch and continuous reactor at different time can be observed from the
graph conductivity versus concentration of NAOH which is done in this calibration
process. Part 2 is to determine the kinetic parameter of the reaction by batch reactor.
1
1
Graph
versus time, t, is plotted at temperature 30 oC and 50oC in order to
C A C A0
determine the effect of temperature on the constant rate of reaction. Part 3,for CSTR
reactor,rate constant for continuous reactor are determined by using mole balance
equation. Activation energy, E and frequency factor, A for both reactors can be obtained
by using Arrhenius equation. From the experiment, it is proved saponification of ethyl
acetate and sodium hydroxide is a second order overall reaction For batch reactor, rate
constant, k at 30oC = 1.1229 L/(mol-min), k at 50oC = 1.6852 L/(mol-min), activation
energy, E = 16.53 kJ/mol and frequency factor, A = 792.52 L.mol-1.min-1. For CSTR
reactor, the rate constant k at 30 oC = 2.2513 L/(mol-min), k at 50oC = 3.3407L/(molmin), activation energy, E = 16.07 kJ/mol and frequency factor, A = 1324.02 L.mol-1.min1
. The reasons lead to error is discussed in the discussion.
Keywords: Homogeneous reaction, saponification, Arrhenius equation, Activation Energy
1.0 INTRODUCTION
1.1 Homogeneous Reaction
A reaction is homogenous if it takes place in one
phase alone. All reactants are found within a
single phase, either in gas, liquid, or solid. For
example, the saponification process which is the
NaOH + CH3COOHC2H5
(Liquid)
(Liquid)
(Liquid)
C2H2OH +
CH3COONa
(Liquid)
rA
dC A
dt
1.5 Reactor
Batch Reactor
f ( ) k ' (C o ) 2 k " 2
,which can expand in a Taylor series
about e .Since f ( e ) 0 ,and
2.0 THEORY
2.1 Saponification second order
d
dt
NaOH + CH3COOHC2H5
C2H2OH + CH3COONa
2 k ' C o
k"
1 ;and
k'
ignore terms first order an higher in
d
k ' (C o ) 2 k " 2
dt
extent of reaction
k' rate constant in the forward direction
k" rate constant in the reverse direction
,Eq. (C )become
d
At equilibrium,
d
0
dt
------(B)
Co
e
dt
k ' (C 0 ) 2 (Second
order)
2.2 General Mole Balance Equation
-------(1)
1
2
k"
k '
----(A)
1
2
-----(C)
k ' (C o
k"
k'
F
2
i0 Fi ri dV
dN i
k
dt "
2
e
1
2
k"
1
ri v
1 dN A
V dt
dC
dC
rA A B kC A C B
dt
dt
rA
dX A
rA C A0
dt
k(C A0 C A0 X A )(C B0 C A0 X A )
then,
x
kt
a (a x)
x
versus t, there is a
a (a x)
x
a(a x)
Slope = k
dX A
k (C A0 C A0 X A )(C A0 C A0 X A )
dt
dX A
2
kC A0 (1 X A ) 2
dt
dC A
2
kC A
dt
kt -------(2)
C A C A0
Assumed the initial concentration of reactant of A
and B is same and equal to a, and the
concentration of reactant had been consumed at
time t is x. The balance at time t is
k
A + B
(a x) (a x)
C + D
(x) (x)
k (a x) 2
dt
x
1
0 (a x) 2 dx 0 kdt
dN A
= 0(steady state)
dt
(C A0 C A )
VC A
-----(3)
= pre-exponential factor or
frequency factor
E = activation energy, J/mol or
cal/mol
R = gas constant = 8.314 J/mol.K
T = absolute temperature, K
E 1
R T
----
(5)
A plot of ln kA versus 1/T should be
a straight line whose slope is
proportional to the activation
energy.
The frequency factor A and
the energy of activation E are
usually considered as constants and
independent
of
temperature.
However, it has since been
established that both parameters A
and E are actually not constants at a
wide range of temperature. In this
experiment,
seemingly
the
temperature difference between the
two separate experiments are not
large, therefore it can be assumed
that both the parameters remain
constant throughout the entire
experiment.
At
two
different temperatures,
E
(6)
ln k (T1 ) ln A
RT1
E
(7)
RT2
Solving (6) and (7) simultaneously,
ln k (T2 ) ln A
ln
k1 E 1
1
( ) - - - -(8)
k 2 R T2 T1
3. Procedure
3.1. Description of the experimental set up
Liquid phase chemical reactor is used in this experiment .
Input
Reactor
A
Heater
Output
Tank containing
reactant A & B
(min) k (mS/cm)
c (mole/L)
C A C A0
Vwater(ml)
0.1
0.08
0.06
0.04
0.02
0
20
40
60
80
100
80
60
40
20
0
7.8
0.0345
2
6.6
0.0292
4
6.0
0.0266
6
5.7
0.0252
8
5.5
0.0243
10
5.3
0.0235
12
5.2
0.0230
14
5.1
0.0226
16
5.0
0.0221
18
5.0
0.0221
20
5.0
0.0221
Conductivity Table 2: Concentration of NaOH at Various
Conductivity at 30oC
(mS/cm)
22.5
18.1
13.5
9.1
4.4
0.0000
5.2548
8.6707
10.6483
12.0866
13.6335
14.4515
15.3016
16.1857
16.1857
16.1857
(min) k (mS/cm)
c (mole/L)
C A C A0
0
2
6.7
5.7
0.0297
0.0252
0.0000
5.9029
30oC(303.15K):
At
ln k1 ln A
E
RT1
50oC(323.15K):
At
ln k2 ln A
E
RT2
ln
k1 E 1
1
( )
k 2 R T2 T1
E (8.314)
323.15 303.15
1
1
kt ,
C A C A0
k1
exp( E / RT1 )
1.1229
16532
exp
8.314 303.15
A = 792.52 L/(mol.min)
k A (T ) Ae
1.1229
In
1.6852
E = 16.532 kJ/mol
A
According to equation:
RT
Time,t
(min)
0
Conductivity Concentration, c
, k (mS/cm)
(mole/L)
10.2
0.0452
9.0
8.6
8.4
8.3
8.1
8.1
8.1
8.1
8.1
8.1
0.0399
0.0381
0.0372
0.0368
0.0359
0.0359
0.0359
0.0359
0.0359
0.0359
Time,t
(min)
Conductivity, Concentration, c
k (mS/cm)
(mole/L)
10.4
0.0461
2
4
6
8
10
12
14
16
18
20
8
7.7
7.5
7.5
7.4
7.4
7.3
7.3
7.3
7.3
0.0354
0.0341
0.0332
0.0332
0.0328
0.0328
0.0323
0.0323
0.0323
0.0323
at T = 30C
at T = 50C
v(C A0 C A )
VC A
5. Discussion
Batch reactor
Graph
1
1
VS t is plotted
C A C A0
10
Temperature
(K)
Rate constant,
k (L/mol-min)
Activation
Energy, E
(KJ/mol)
Frequency
factor, A
(L/mol-min)
303.15
323.15
1.1229
1.6852
16.532
792.52
CSTR reactor
From figure 4, both lines for 30C
and 50C are decrease slightly
before it becomes constant. It
maybe cause by taking the value of
conductivity too early during the
experiment before the reactor
achieved steady state. The graph
shows that constant NaOH
concentrations are obtained after
10-14 minutes for both cases. This
means the reactor achieved steady
state after 10-14 minutes.
After that, there is a nearly horizontal
line,
concentrations
sodium
hydroxide remains constant with
time, indicating the reactor was in
steady state and both reactants were
well mixed. There are no spatial
variations
in
concentration,
temperature,
or
reaction
rate
throughout
the
vessel.
The
concentration, CA is equal to the
concentration of NaOH when the
reactor reaches the steady state.
Table 8: Tabulated result for CSTR
reactor
Temperature
(K)
Rate constant,
k (L/mol-min)
Activation
Energy,
E
(KJ/mol)
Frequency
factor,
A
(L/mol-min)
303.15
323.15
2.2513
3.3407
16.07
1324.02
12
System
Batch
Continuous
1.1229
2.2513
k2 at 50oC (L/
(mole-min)
1.6852
3.3407
E (kJ/mole)
16.53
16.07
792.52
1324.02
k1 at 30oC (L/
(mole-min)
A (L/(mole/min)
1.
Octave Levenspiel,
Chemical Reaction
Engineering, 2nd edition, John
Wiley & Sons.
2.
Fogler, H. Scott, Elements
of Chemical Reaction
Engineering, 3rd edition,
Prentice-Hall International
3.
Charles G. Hill, Jr. An
Introduction to Chemical
Engineering Kinetics and Reactor
Design, John Wiley & Sons.
4.Perry, J. H. (2003), Chemical
Engineers Handbook. McGraw-Hill,
Inc.
7. Recommendation
The result obtained in this experiment is not
very accurate, to improve the accuracy of
results, some suggestion are recommended:
The inefficiency pump A used in
experiment to pump the reactants A to
reactor should repair.
A flow meter can be replaced between
the pump and reactor so that the flow
rate of the reactants is determined with
accurate. Although the pump is
inefficiency, the flow meter will show
the actual flow rate of the reactants.
This can eliminate the assumption to
determine the reactants flow rate and
the result getting is more accurate.
The stirrer are located nearly at the
bottom part of the solution, this cause
the solution is not well mixed. The
stirrer should locate at the center of
the solution,
13