P4E2: Kinetics Of Homogeneous Reaction In Batch And Continuous StirredTank Reactor At Two Different Temperature

Goh Chen Liew and Goh Ai Chin

Department of Chemical Engineering
University of Malaya
50603 Kuala Lumpur
Email: chenliew@hotmail.com

The objective of this experiment is to prove that the reaction between ethyl acetate and
NaOH (saponification) is a second order reaction and determine the kinetic parameter
of the reaction. The kinetic parameter likes rate constant, k, activation energy, E,
frequency factor are determined by carried out a reaction in batch and continuous
stirred-tanks reactor (CSTR) at 25 oC and 30oC with well mixed. The apparatus that we
use in this experiment is a liquid phase chemical reactor which can operate as a batch
reactor or continuous reactor. The concentration of NaOH in the sample is determined
at every interval of time by using titration. For batch reactor, a plot of x/[a(a-x)] versus
t is plotted at T=25C and 30C. The rate constant, k can be determined from the slope
of the plot whereas for CSTR reactor, a plot of C NaOH versus time is plotted at T=25C
and 30C. 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 that the reaction
between ethyl acetate and NaOH is a second order reaction. For batch reactor, rate
constant, k at 25oC = 0.1668 L/(mol-min), k at 30 oC = 0.1815 L/(mol-min) at 30 oC,
activation energy, E = 12.694 kJ/mol and frequency factor, A = 27.94 L.mol-1.min-1. For
CSTR reactor, the rate constant k at 25 oC = 0.1974 L/(mol-min), k at 30oC = 0.2263 L/
(mol-min), activation energy, E = 20.534 kJ/mol and frequency factor, A = 781.5 L.mol1
.min-1. The results that we take from the experiment are deviate from the theory. This
may be due to the error occurring during the experiment.
Keywords: Homogeneous reaction, rate constant, Arrhenius equation, reaction order , Activation Energy
1.0 INTRODUCTION

The rate of reaction of any reaction component A

is defined as

1.1 Homogeneous Reaction

A homogeneous reaction is one that involves only
one phase. All reacting materials are found within
a single phase, in gas, liquid, or solid. If the
reaction is catalytic, the catalyst must also be
present within the same phase as the reactants and
products.
1.2 The Reaction Rate Constant
The variables that affect the process of reaction
are the composition of the materials within the
phase, temperature and the pressure of the system.
Thus we may write for the reaction rate of
component A as
rA = f ( composition, temperature, pressure)

rA

1 dN A 1 d(C A V)

V dt
V dt

E1.2
The rate of disappearance of A is -rA. If A appears
as product, the rate of reaction, rA is positive.
1.3 Reaction Order
rA = KcACBCD,

E1.3

and
+++=
The exponent of the concentrations in E1.3 led to
the concept of reaction order. The order of
reaction refers to the power to which the
concentration is raised in the kinetic rate law. In
E1.3, the reaction is order with respect to
reactant A, and order with respect to reactant B.
The overall order of reaction is .
1

3.0 THEORY
1.4 Elementary Rate Law

The reaction in saponification is an irreversible

and elementary reaction and it is shown as below:

Consider a single reaction with stoichiometric

equation
A+BC
A reaction follows an elementary rate law if the
reaction order of each species is identical with the
stoichiometric coefficient of that species.
The rate law for the above reaction:
-rA = k CA CB
where k is the specific reaction rate constant.
When a reaction has an elementary rate law, it is
referring to as an elementary reaction.

NaOH + CH3COOHC2H5 C2H2OH + CH3COONa

(A)
(B)
(C)
(D)

1.5 Batch Reactor

For batch reaction, there are no input and output,

then E3.1 become

The feed is charge into a vessel at the beginning of

the process and the vessel content are removed
sometime later. No masses across the system
boundaries between the time the feed is charge
and the time product is removed. Usually, batch
reactor is operated isothermally and at constant
volume. In constant-volume batch reactor, the
reactor is perfectly mixed so that the concentration
of the reacting species is spatially uniform. It is in
a form of tank with or without agitation and is
used primarily in a small-scale production.
1.6 Continuous-Stirred Tank Reactor (CSTR)
The input and output flow continuously
throughout the duration of the process. CSTR is
normally run at steady state and is usually
operated so as to be quite well mixed. CSTR is
generally modeled as having no spatial variations
in concentration, temperature, or reaction rate
throughout the vessel. It is normally used in the
large production scale.
2.0 OBJECTIVE
The objective of this experiment is to determine
the order of reaction and kinetic parameter in a
homogeneous reaction (Saponification). The
kinetics parameters such as rate constant k,
frequency factor, A and activation energy, E are
determined at two different temperatures in batch
reactor and Continuous-Stirred Tank Reactors
(CSTR).

3.1 General Mole Balance Equation

Input - Output + Generation = Accumulation
V
dN i
Fi0 Fi ri dV
dt
E3.1
3.2 Design Equation In Batch Reactor

1 dN A
V dt
dC
dC
rA A B kC A C B
dt
dt
rA

The amounts of A and B which have disappeared

at any time t are CA0XA = CB0XB for both A and B,
thus the equation above may be write in terms of
XA

rA C A0

dX A
k(C A0 C A0 X A )(C B0 C A0 X A )
dt

Since CA0 = CB0, then

C A0

dX A
2
kC A0 (1 X A ) 2
dt
dC A
2

kC A
dt

By integrated of above differential equation

1
1

kt
C A C A0
E3.2.1
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
A + B
(a x) (a x)

C + D
(x) (x)

From E3.2.1, CA0 = a , and CA = a-x, hence

x
kt
a (a x)

E3.2.2
2

x
By plot
versus t, there is a straight line
a (a x)

with slope = k

second part wills the homogeneous reaction in

continuous reactor (CSTR). The reactant use in
the homogeneous reaction is ethyl acetate and
NaOH.
4.2 Experimental Procedure

x
a(a x)

4.2.1 Homogeneous Reaction In Batch Reactor

slope = k

t
3.3 Design Equation In Continuous Reactor
Accumulation is zero in CSTR because of steady
state in continuous reactor with well mixed and
constant volume (A0 = A). The equation E3.1
becomes
FA0 FA + rAV = 0
A0CA0 ACA + (-kCA2)V = 0
hence,

v(CA0 C A )
2
VC A

4.2.2 Homogeneous Reaction In CSTR Reactor

E3.3
3.4 Arrhenius Equation
k = A exp(-E/RT)

Firstly, the reactor is filled with water and stirrer

rotation is set at 80% from maximum scale. The
reactor temperature is set at 25oC. Then solution
is both filled into the tanks respectively. Water
from the reactor is flow out when required
temperature is achieved. Next, both reactants are
feed into the reactor at 100ml/min and the mixture
is left for a while until temperature is stabilized.
*20ml of the mixture are taken out from the
reactor as t=0. Then 0.1M HCl in excess of 25ml
is added to the mixture instantly to neutralize
unreacted NaOH. 2-3 drop of phenolftalein is
filled into the solution and the solution is titrating
with NaOH instantly to determine the excess of
HCl. This step* is repeated after 30 seconds and
every 3 minutes interval for seven times. Then the
experiment is repeated at 30oC

E3.4

This is known as Arrhenius equation which has

been verified empirically to give the temperature
behaviour of most reaction rate constant within
experimental accuracy over fairly large
temperature range. From the kinetic theory of
gases, the factor e-E/RT gives the fraction of the
collisions between molecules that together have
this minimum energy E.
4.0 EXPERIMENTAL METHODOLOGY
4.1. Description of the experimental set up
A liquid phase chemical reactor is used in this
experiment. It can operate as a batch reactor or
continuous reactor (Refer Figure 4.1 and Figure
4.2 in Appendix).The experiment procedure is
divided into two parts. The first part will be a
homogeneous reaction in batch reactor while the

The reactor is emptied and the stirrer speed is set

at 80% of maximum scale. The tank is filled with
5 liter reactant respectively. The flow rate of each
reactant is set at 40 ml/min and the reactor is set at
required temperature like in Section 4.2.1 (25 oC
and 30oC). When the reactor is filled with 1 liter
reactant, step* in Section 4.2.1 is repeated for
every 5 minutes interval for nine time.
5.0 RESULT AND DISCUSSION
5.1 Assumption
The rate constant, k depends only to the parameter
temperature only. Whereas for activation energy, E
and frequency factor, A, it is assumed to be a
constant.
5.1.1 For Batch Reactor
A batch reactor is usually well mixed. So we may
neglect spatial variation in the temperature and
3

species concentration. Beside we also assumed

that all the reactant enter the reactor at the same
time. There is isothermal reaction and no side
reaction.

5.1.2 For Continuous Reactor (CSTR)

CSTR is also a well mixed reactor and there is no
side reaction. The temperature and concentration
are identical everywhere within reaction vessel.
The flow rate of both reactants into the reactor is
same and it is constant throughout the vessel.
5.2 Results
5.2.1 For Batch Reactor

40.5

9.4

9.8

5.3 Analysis Data

In this experiment the concentration of NaOH in
reactor at time t is determined by instantly
neutralize the 20ml sample taken out from reactor
with 25 ml of 0.1M HCl (excess). After that, the
solution is titrate by 0.1M NaOH. Then, the
concentration of NaOH in reactor at time t is
derived from calculation. (Refer to Appendix)
5.3.1 For Batch Reactor
Graph x/[a(a-x)] vs t is plotted for reaction at
batch reactor at T=25C and 30C

Table 5.2.1: NaOH used in titration at different

temperature in batch reactor.

Time, t
(min)
0
0.5
3.5
6.5
9.5
12.5
15.5
18.5
21.5

NaOH used in titration, VNaOH (ml)

T=25C
T=30C
0
0
1.3
1.8
3.6
3.8
4.5
4.6
5.1
5.9
5.8
6.4
6.5
6.6
6.5
6.8
6.7
7.2

Figure 5.3.1: Graph x/[a(a-x)] vs Time at Different

Temperature

5.3.2 For Continuous Reactor (CSTR)

A graph of concentration of NaOH vs t is plotted
at continuous reactor at T=25C and 30C

5.2.2 For Continuous-Flow Reactor (CSTR)

Table 5.2.2: NaOH used in titration at different
temperature in CSTR reactor.

Time, t
(min)
0
0.5
5.5
10.5
15.5
20.5
25.5
30.5
35.5

NaOH used in titration, VNaOH (ml)

T=25C
T=30C
7.8
8.2
7.7
8.1
8.1
8.4
8.3
8.5
8.2
8.7
8.5
8.6
8.3
8.6
8.6
8.9
9.1
9.6

Figure 5.3.2: Graph Concentration of NaOH vs

Time at Different Temperature

5.4 Analysis Result

5.4.1 For Batch Reactor
4

From equation E3.2.2, we know that the slope of

the Figure 5.3.1 is equal to the specific reaction
rate constant, k of the reaction at the temperature
respectively. Therefore
T1 = 25C, k1 = 0.1668 L/(mol-min)
T2 = 30C, k2 = 0.1815 L/(mol-min)
Besides from E3.4 we know that
T1 =298.15K (25C), k1 = A exp(-E/RT1)
T2 =303.15K (30C), k2 = A exp(-E/RT2)
By solving these two equation simultaneously,

ln

k1 E 1 1
( )
k 2 R T2 T1

E5.4.1

Thus we found that

E = 12.694 kJ/mol and
A = 27.94 L/(mol-min)
5.4.2 Continuous Reactor (CSTR)
Reactor volume, V = 1 liter
Total flow rate of the reactant, v = 0.08 L/min
CA0 = 0.1 mol/L.
The concentration, CA is equal to the
concentration of NaOH when the reactor is
achieved steady state. Average is taken.
From Figure 5.3.2,
T = 25C, CA = 0.083 mol/L,
T = 30C, CA = 0.0813 mol/L.
By applied equation E3.2.2,
We found that
T1 = 25C, k1 = 0.1974 L/(mol-min)
T2 = 30C, k2 = 0.2263 L/(mol-min)
By using E5.4.1
E = 20.534 kJ/mol and
A = 781.5 L/(mol-min)
5.4 Discussion
5.4.1 For Batch Reactor
From Figure 5.3.1, there is a straight line pass
through the origin. This shows that the reaction
between ethyl acetate and NaOH follows an
elementary rate laws which in this case is second
order reaction. Besides, it is found that the slope
of the graph for 30oC is deeper than the 25 oC. The
slope of the graph in this case is equal to the
specific reaction rate constant, k. This mean that
the specific reaction rate constant, k at 30 oC is
greater than the k at 25oC. This result obeys the
theory. As we know, specific reaction rate is

strongly dependent to temperature. When the

temperature increase, molecules of the reactant
obtain more energy that cause the kinetics energy
of the molecules become higher and collision
between molecules of reactant are also increase.
Therefore the reaction rate will increase and
therefore the specific reaction rate constant will
increase. By using the Arrhenius equation, the
value of activation energy, E and frequency factor,
A can be calculated from the E5.4.1 and E3.4.
Since the temperature change in our experiment is
very small, it is assumed to be same at 25 oC and
30oC. In our experiment, the values for E = 12.694
kJ/mol and for A = 27.94 L/(mol-min). However
as we see from the graph, we can said that not all
the points are in the straight line. This maybe due
the some error occur during our experiment which
we will discuss it in Section 5.5
5.4.2 For Continuous Reactor (CSTR)
From Figure 5.3.2 we can see that there is a nearly
horizontal line. This means that concentration of
NaOH is nearly constant with time. This result
obey the theory which state that the there is no
spatial variations in concentration, temperature, or
reaction rate throughout the vessel. There is a
steady state inside continuous reactor. The
concentration, CA is equal to the concentration of
NaOH when the reactor reaches the steady state.
However average is taken is our calculation.
From Figure 5.3.2 the concentration of NaOH is
approximately 0.083 mol/L at 25oC and 0.0813
mol/L at 30oC. By using E3.2.2 specific reaction
rate constant, k is calculated. It is observed that k
at 30oC is higher than k at 25oC. This is because
the rate constant is higher at higher temperature
and vise versa. Then by apply Arrhenius equation,
the values for E = 20.534 kJ/mol and A = 781.5 L/
(mol-min). However the horizontal line that we
obtained is not constant. This maybe due to the
some error occur during experiment which we
may discuss it in Section 5.5.
5.4.3 Comparison Between Batch Reactor And
Continuous Reactor.
From experiment, we found that the rate constant,
k, activation energy, E and frequency factor for
both batch and continuous reactor at the same
temperature vary slightly. The difference of rate
constant between both types of reactor is about
20%. These disobey the theory because as we
5

know rate constant depends to the temperature

only. So the it should be the same for the same
temperature. On the other hand, the difference for
activation energy and frequency factor is much
greater for both types of reactor. All these may be
due to the error occur which we will discuss in
Section 5.5.
5.5 Error Occur
In this experiment, there are some error occur
which may cause the result that we obtain deviate
from the theory.
5.5.1 Insufficient Of Apparatus
From what we have observed during the
experiment, firstly, we found that the pumping
system is not function well. The pumps are
supposed to control the flow rate of the reactant
into the reactor which in this case NaOH and ethyl
acetate should have same molar flow rate.
Unfortunately, we found that one of the reactant
finished faster than the others although the level
and volumetric flow rate of both reactants is set to
be the same. Secondly, we also found that the
position of stirrer in reactor is too high and the
rotational speed is not fast enough. This make the
reactant cannot mix well before react and
therefore some reactant maybe flowing out before
react at all.
5.5.2 Error Occur In Titration
In titration, there is a lot of approximation. Firstly
for batch reactor, since the reaction rate is varying
with time, a little bit slow in the titration will
cause the reactant to react more. Besides, in our
titration, we use phenolftalein as indicator. We
stop our titration when the colour of the solution
start turns to pink colour. However error maybe
occurs here because we cant get the accurate
point where the solution turns to pink colour. We
are supposed to take 20ml sample out from the
reactor but in our case, because of the time
limited, we just made a approximation only. All
these errors therefore make what we get in the
experiment is not more accurate.
5.5.3 Error Occur In Assumption
To simplify our calculation, we assumed that rate
constant is only depend to temperature only but

actually in liquid system, the rate constant also

depend to the other parameter such as ionic
strength and choice of solvents. Although these
other variable may exhibit much less effect than
temperature but it still contributes to the
inaccuracy in our calculation. On the other hand,
theoretically A and E should not be constant and
instead it is a temperature dependent. However,
the application of the macroscopic Arrhenius law
in this experiment assumed that A and E are both
constant and has been found to fit well for a wide
range of temperature. Besides we are supposed to
carry out our experiment in isothermal condition.
However we found out it is very difficult for us to
maintain the temperature at a desired temperature.
The temperature is increasing during the reaction.
This may be due to the energy released from the
reaction. Besides there may also have other side
reaction others than saponification between ethyl
acetate and NaOH.
6.0 CONCLUSION
The reaction between ethyl acetate and NaOH is a
second order reaction. For batch reactor, the rate
constant at 25oC is 0.1668 L/(mol-min)and at 30oC
is 0.1815 L/(mol-min). The value of activation
energy, E = 12.694 kJ/mol and frequency factor, A
= 27.94 L.mol-1.min-1. For CSTR reactor, the rate
constant at 25oC is 0.1974 L/(mol-min) and at
30oC is 0.2263 L/(mol-min). The value of
activation energy, E = 20.534 kJ/mol and
frequency factor, A =781.5 L.mol-1.min-1.
7.0 RECOMMODATION
It is recommend to buy a new apparatus since the
one that we have now already very old. However,
if it cant afford to buy a new one some
modification should be done on the apparatus.
Firstly, the pumping system should be improved to
increase its efficiency. Besides the stirrer should
be in the middle of the reactor and increase the
rotational speed so that the reactant can mixed
well. The lab assistant should make sure that the
concentration of reactant that prepared by them is
standardizing. During titration, try to avoid
making approximation, be careful, and
concentrate when titrate. Stop immediately when
the colour turns to pink colour. Titration must be
do in fast because the concentration of the reactant
is varying with time and vaporized. Try to
maintain the temperature of the reactor by
6

adjusting the temperature.

8.0 NOMENCLATURE
A = frequency factor
C = Concentration (mole/L)
C0 = Initial concentration (mole/L)
E = activation energy (J/mole)
F = molar flow rate (mole/min)
k = rate constant L/(mol-min)
N = amount of component (mole)
R = Universal gas constant (8.314 J/mole.K)
r = rate of reaction (mole/min.L))
T = Absolute temperature (K)
t = time(min)
V = reactor volume (L)
= volumetric flow rate (L/min)
X = Conversion
Subscript A = reactant A
Subscript B = reactant B
9.0 REFERENCES
Charles G. Hill, Jr. An Introduction to
Chemical Engineering Kinetics and Reactor
Design, John Wiley & Sons.
Fogler, H. Scott, Elements of Chemical
Reaction Engineering, 3rd edition, Prentice-Hall
International