TITLE: Continuous Stirred Tank Reactor (CSTR)

OBJECTIVE:

To observe and control the operation of a continuous-stirred tank reactor.

To determine the effect of the flow rate on conversion rate in a continuous-
stirred tank reactor.

INTRODUCTION:

The Continuous Stirred Tank Reactor (CSTR) configuration is widely used in

industrial applications and in wastewater treatment units. The CSTR are simple and
easier to design for isothermal operation. CSTR are useful in quantitatively evaluating
gas, liquid and slow flow behaviors.

The general working principle of CSTR : CSTR are open systems, which mean the
material free to enter or exit the system. CSTR are operated on a steady-state basis,
where the conditions in the reactor don't change with time. Reactants are
continuously introduced into the reactor, while products are continuously removed.
CSTR are the reactor was well mixed, so the contents have relatively uniform
properties such as temperature, density and concentration of the reaction mixture.
Other than that, conditions in the reactor's exit stream are the same as those inside the
tank.

MATERIAL AND EQUIPMENT:

1 Continuous Stirred Tank Reactor

2 Distilled water
3 Stopwatch
4 Beaker (2 L)
5 Volumetric flask (1 L)
6 Measuring cylinder 100 mL
7 2.3% sodium hydroxide
8 5% ethyl acetate
9 0.1 M sodium acetate
10 0.1 M sodium hydroxide

SETUP:
Figure 1: The labelling diagram of the Continuous Stirred Tank Reactor

Figure 2: The flow diagram of the Continuous Stirred Tank Reactor

RESULT:

Experiment 1: Calibration Curve Conductivity versus Conversion

Conversion 2.3% Sodium 5 % Ethyl Deionised Conductivity

(%) Hydroxide Acetate water, (mL) (mS/cm)
(NaOH) (Et(Ac))
solution (mL) solution (mL)
0 100 0 100 58.0
25 75 25 100 41.0
50 50 50 100 26.1
75 25 75 100 11.09
100 0 100 100 0.0266
Table 1: Results for experiment 1

Graph of conductivity versus conversion

70
60
50 f(x) = - 0.58x + 56.41

40
Conductivity (mS/cm) 30

20
10
0
0 20 40 60 80 100 120

Conversion (%)

Graph 1: Graph of Conductivity versus Conversion

Experiment 2: Determine the Effect of Flow Rate on Conversion Rate

Dosing rate at 20% and reaction temperature at 45

 Time (min) Conductivity (mS/cm)) Conversion (%)
1 2 1 2
0 22.1 4.0 83.41 97.64
3 45.5 4.0 65.02 97.64
6 43.6 3.8 66.51 97.80
9 35.7 3.7 72.72 97.88
12 34.2 4.7 73.90 97.09
15 32.1 4.8 75.55 97.01
Table 2: Result for experiment 2 of dosing rate: 20%

Dosing rate at 30% and reaction temperature at 45

Time (min) Conductivity (mS/cm) Conversion (%)

1 2 1 2
0 15.1 4.2 88.92 97.48
3 34.2 4.3 73.90 97.41
6 27.2 4.1 79.40 97.56
9 29.2 4.5 77.83 97.25
12 27.6 4.0 79.09 97.64
15 25.4 4.0 80.82 97.64
Table 3: Result for experiment 2 of dosing rate: 30%

Dosing rate at 40% and reaction temperature at 45

Time (min) Conductivity (mS/cm) Conversion (%)

1 2 1 2
0 6.6 3.7 95.60 97.88
3 28.1 3.8 78.69 97.80
6 28.7 4.2 78.22 97.48
9 28.6 3.7 78.30 97.88
12 31.5 5.8 76.02 96.23
15 31.4 4.7 76.10 97.09
Table 4: Result for experiment 2 of dosing rate: 40%

Dosing rate at 50% and reaction temperature at 45

Time (min) Conductivity (mS/cm) Conversion (%)
1 2 1 2
0 8.4 3.7 94.18 97.88
3 44.1 17.6 66.12 86.95
6 42.6 18.0 67.30 86.64
9 41.8 8.2 67.92 94.34
12 41.8 10.3 67.92 92.69
15 41.2 8.8 68.40 93.87
Table 5: Result for experiment 2 of dosing rate: 50%

Graph of Conductivity 1 versus time

50
45
40
35
Dosing Rate: 20%
30
Dosing Rate: 30%
Conductivity 1 25
Dosing Rate: 40%
20
Dosing Rate: 50%
15
10
5
0
0 2 4 6 8 10 12 14 16

time

Graph 2: Graph of Conductivity 1 versus Time

 Graph of Conductivity 2 versus Time
20

15
Dosing Rate: 20%
Dosing Rate: 30%
Conductivity 2 10
Dosing Rate: 40%
Dosing Rate: 50%
5

0
0 2 4 6 8 10 12 14 16

Time

Graph 3: Graph of Conductivity 2 versus Time

Graph of Conversion 1 versus time

120

100

80 Dosing Rate: 30%

Dosing Rat: 20%
Conversion 1 60
Dosing Rate: 40%
40 Dosing Rate: 50%

20

0
0 2 4 6 8 10 12 14 16

time

Graph 4: Graph of Conversion 1 versus Time

 graph 2 of conversion 2 versus time
100

95
Dosing Rate: 20%
Dosing Rate: 30%
conversion 2 90
Dosing Rate: 40%
Dosing Rate: 50%
85

80
0 2 4 6 8 10 12 14 16

time

Graph 5: Graph of Conversion 2 versus Time

At 15 min and reaction temperature at 45 :

Dosing Rate Conductivity (mS/cm) Conversion (%)

(%) 1 2 1 2
20 32.1 4.8 75.55 97.01
30 25.4 4.0 80.82 97.64
40 31.4 4.7 76.10 97.09
50 41.2 8.8 68.40 93.87
Table 6: Result for experiment 2 of different dosing rate at 45
 Graph of conductivity versus dosing rate
45
40
35
30
25 Conductivity 1
Conductivity (mS/cm) 20
Conductivity 2
15
10
5
0
15 20 25 30 35 40 45 50 55

Dosing rate (%)

Graph 6: Graph of Conductivity versus Dosing Rate at15 min

Graph of conversion versus dosing rate

120

100

80

60 Conversion 1
Conversion (%)
Conversion 2
40

20

0
15 20 25 30 35 40 45 50 55

Dosing rate (%)

Graph 6: Graph of Conversion versus Dosing Rate at 15 min

Experiment 3:

Dosing rate at 30% and reaction temperature at 35

Time (min) Conductivity (mS/cm) Conversion (%)

1 2 1 2
0 22.6 4.2 83.02 97.48
3 36.4 4.2 72.17 97.48
6 35.0 4.6 73.27 97.17
9 34.4 4.9 73.74 96.93
12 32.1 5.3 75.55 96.62
15 31.8 5.5 75.79 96.46
Table 7: Result for experiment 3 of dosing rate 30% at 35

Dosing rate at 30% and reaction temperature at 40

Time (min) Conductivity (mS/cm) Conversion (%)

1 2 1 2
0 20.0 2.9 85.06 98.51
3 35.5 3.7 72.88 97.88
6 33.3 3.1 74.61 98.35
9 32.3 3.3 75.39 98.19
12 31.7 3.7 75.86 97.88
15 31.2 4.1 76.26 97.56
Table 8: Result for experiment 3 of dosing rate 30% at 40
 Rate of reaction, -rA
Time 30 40 45
(min) 1 2 1 2 1 2
0 0.5634 0.6615 0.5772 0.6685 0.6034 0.6615
3 0.4897 0.6615 0.4946 0.6642 0.5015 0.6610
6 0.4972 0.6594 0.5063 0.6674 0.5388 0.6620
9 0.5004 0.6578 0.5116 0.6663 0.5282 0.6599
12 0.5127 0.6557 0.5148 0.6642 0.5367 0.6626
15 0.5143 0.6546 0.5175 0.6620 0.5484 0.6626
Rate constant, k
Time 30 40 45
(min)
1 2 1 2 1 2
0 0.1886 10.0535 0.2496 29.0609 0.4744 10.0535
3 0.0610 10.0535 0.0649 14.2634 0.0711 9.5105
6 0.0672 7.9462 0.0758 23.6596 0.1225 10.7323
9 0.0700 6.7357 0.0815 19.6296 0.1037 8.4222
12 0.0828 5.5390 0.0853 14.2634 0.1185 11.4817
15 0.0847 5.0413 0.0886 10.7323 0.1439 11.4817
ln k
Time 30 40 45
(min) 1 2 1 2 1 2
0 -1.6682 2.3079 -1.3879 3.3694 -0.7458 2.3079
3 -2.7964 2.3079 -2.7349 2.6577 -2.6444 2.2524
6 -2.7006 2.0727 -2.5796 3.1638 -2.0993 2.3733
9 -2.6588 1.9074 -2.5068 2.9770 -2.2662 2.1309
12 -2.4917 1.7118 -2.4621 2.6577 -2.1331 2.4408
15 -2.4688 1.6177 -2.4234 2.3733 -1.9387 2.4408
Table 9: Result for experiment 3 of rate of reaction, rate constant and ln k data

Dosing rate for 30% at 15 minutes with temperature of 35 , 40 and 45

:

Temperature, K 1/T, K-1 ln k1 ln k2

308.15 0.0032 -2.4688 1.6177
313.15 0.0032 -2.4234 2.3733
318.15 0.0031 -1.9387 2.4408
Table 10: Result for experiment 3 of dosing rate 30% at 35 , 40 and 45

 A graph of ln k against 1/T
3.0000

f(x) = - 8104.61x + 28.03

2.0000
R = 0.82

1.0000 lnk1
Linear (lnk1)
ln k 0.0000
0.0031 0.0032 0.0032 0.0033 0.0033 lnk2
Linear (lnk2)
-1.0000

-2.0000
f(x) = - 5173.17x + 14.25
R = 0.81
-3.0000

1/T

Graph 7: Graph of ln k versus 1/T at 15 min

CALCULATION:

Part 1: Conversion, X

[
X = 1
]
( K K e )
( K o K e )
100

Where K = measured value for conductivity (mS/cm)

K o = initial conductivity for 2.3% sodium hydroxide solution (128.2 mS/cm)

 K e = conductivity of end product (1 mS/cm for a 5 % sodium acetate solution)

Taking dosing rate: 30% and temperature reaction at 45 after 15 min as

example:

For conversion 1 ( K = 32.1 mS/cm)

[
X = 1
(25.41 )
( 128.21 )] 100

80.82

For conversion 2 ( K = 4.8 mS/cm)

[
X = 1
( 128.21 )]
( 4.01 )
100

97.64

Part 2: Rate of Reaction, -rA

The rate of reaction is determined with the formula:

F AO X A
r A=
V

where FA0 = Initial feed rate of A

XA= Experimental Conversion

V= Volume of reactor

From data,

Density of Et(Ac) = 897 kg/ m3, MW= 88.11 g/mol

 L
Given that the volumetric flowrate , v=19
h

L L L
30 dose=0.3 x 19 =5.7 =0.095
h h min

Since the time of reaction is 15 min,

L
V =0.095 15 min
min

1.425 L

L g 1 mol mol
Molar flowrate , F AO =0.095 897 0.967
min L 88.11 g min

From part 1, the rate of reaction of conversion 1 is calculated by:

(0.967)(0.8082)
r A=
1.425

mol
0.5484
L min

From part 1, the rate of reaction of conversion 2 is calculated by:

(0.967)(0.9764)
r A=
1.425

mol
0.6626
L min
Part 3: Rate Constant, k

The reaction proceeds with second order in respect to A and B, thus:

r A=k C A C B

C A =C Ao (1X )

Assume C Ao =C Bo , the rate of reaction simplifies the equation to become:

r A=k C Ao2 (1X )2

r A
k= 2 2
C Ao (1X )

The intial concentration of A , C Ao is calculated by :

mol
0.967
F min mol
C Ao = A 0 = =10.179
v L L
0.095
min

From part 1, the rate constant of conversion 1 is calculated by:

0.5484
k=
( 10.179 )2 (10.8082)2

L
0.1439
mol min

From part 1, the rate constant of conversion 2 is calculated by:

0.6626
k=
( 10.179 )2 (10.9764)2

L
11.4817
mol min

Part 4: The Activation Energy, E and Pre- Exponential Factor, A

The reaction rate constant dependence on temperature is given as

E
( )
RT
k =A e

where A = pre-exponential factor of frequency factor

E = activation energy, kJ/mol or cal/mol

R= universal gas constant

E 1
k =
R T ()
+ ln A

ln

[Y = m X + C]

From Graph 7,

The line equation for ln k1 is given by:

y=5173.2 x +14.246

E 1
k =
R T() + ln A

Compare : ln

E
Slope : =5173.2
R

J J kJ
E=5173.2 K x 8.314 E=43009.98 =43
K mol mol mol

The line equation for ln k2 is given by:

y=8104.6 x+ 28.029

E 1
k =
R T() + ln A

Compare : ln
 E
Slope : =8104.6
R

J J kJ
E=8104.6 K x 8.314 E=67381.64 =67.38
K mol mol mol
DISCUSSION:

Findings

In this experiment, the relationship between the flow rate and the conversion of ethyl
acetate and sodium hydroxide has been determined and observed. It is known that the
saponification for ethyl acetate and sodium hydroxide will form sodium acetate and
ethanol.

C H 3 COOC H 2 C H 3 + NaOH C H 3 COONa+C H 3 C H 2 OH

According to the calibration curve, when the volume of sodium hydroxide is reduced
and volume of ethyl acetate is increased, the conductivity of the solution will decrease
linearly. This is because sodium hydroxide is a high conductivity compound due to
OH ion. When the volume of NaOH decrease, there will be less OH ions and it will
react to form sodium acetate which is lower in conductivity. At high volume of NaOH
solution, NaOH will be in excess and unreacted which lead to high conductivity of
solution.

From the result for dosing rate of 20%, 30%, 40% and 50% at 45C, the conductivity
of the solution mixture fluctuate every 3 minutes in a total of 15 minutes. In other
word, the conversion of ethyl acetate and sodium hydroxide will not affect by time.
According to theoretical result, the conductivity of product solution will decrease and
it means that the conversion will increase. This is because there will be more reaction
occur when the reactants stay longer in the CSTR and it leads to formation of more
products. By changing the dosing rate of ethyl acetate and sodium hydroxide, the
conductivity and conversion of the product changed as well. The conversion of the
product increase when the dosing rate increase from 20% to 30% and it decrease
again when dosing rate increase from 30% to 50%. But in theoretical result, the
conversion of the reaction will decrease when we increase the flow rate of the
reactants into the reactor. This is because when the flow rate into the reactor
increased, the outlet flow rate of the reactor will increase as well. The solution will
have a lesser residence time in the reactor and hence it lead to lesser conversion into
products.
In this experiment, there is lack of information to find the reaction rate constant, k due
to not conducting the experiment in different temperature. In the theoretical result, the
conversion of saponification between ethyl acetate and sodium hydroxide will
increase when the temperature of the reactor and reactant increases. The reaction rate
constant will also increase eventually.

The result that we obtain is less accurate when it is compared to the theoretical result.
This is cause by some error of obtaining the result and the operation of the CSTR.
First, it is observed that the flow rate of ethyl acetate into the CSTR is different with
the flow rate of sodium hydroxide although the dosing rate that is adjusted are the
same. Next, the outlet flow rate of the CSTR is not steady and it leads to fluctuation
of the conductivity for the outlet flow.

Residence time

Residence time is the mean amount of times that a particle stays in a particular system
which used in non-ideality of industrial and natural processes. This measurement
varies directly with the amount of substance that is present in the system as follow:

systemcapacity
residence t ime= hold a substance
flow rate of the substance through the system

and the generic variable form of this equation is as follow:

V
=
q

Where is used as the variable of residence time, V is the capacity of the system,

and q is the flow rate of the system.

However, the non-ideality of industrial and natural processes leads engineers to

develop corrections to the ideal models, in order to use them with less restriction. For
this reason, residence time distribution (RTD) is introduced, which is a function that
describes the evolution of the average instantaneous concentration versus the elapsed
time. For chemical rector, residence time distribution is a probability distribution
function that describes the amount of time that a fluid element could spend inside the
reactor. The feed of CSTR spends different times inside the reactor and therefore there
is a distribution of residence times of materials within the reactor. There are few
assumptions to be made which are the reactor is at steady-state which indicate
constant volume, the fluid is incompressible and the transport at the inlet and outlet
take places only by advection when using the RTD theory. External residence time
distribution, E(t) is used to present the distribution of residence time. It has the units

-1
of time and defined as E ( t ) dt=1 .
0

Figure 3: The CSTR RTD curve

where E(t) dt is the fraction of the feed spent a period of time, t in the reactor.

For an ideal CSTR is based on the assumption that the flow at the inlet is completely
and instantly mixed into the bulk of the reactor. The reactor and the outlet fluid have
identical, homogeneous compositions at all times. An ideal CSTR has an exponential
residence time distribution which is

1
1
E (t)= e

Volume of CSTR affects the conversion of reactants into products

From the design equation of CSTR that we have studied,

F AO X
V=
(r A )exit
Where V is the volume of the reactor, F AO is the inlet of A, X is the

conversion of reactant A, and (r A )exit is the rate of reaction.

From the design equation, we know that as volume of CSTR increase, the conversion

of reactant A will increase as well. For more precision, the residence time, of the

reactant in the reactor increase with the higher volume of reactant in the reactor, V

with a fixed volumetric flow rate, Q . Therefore, the reactant has more time to react

in the reactor hence the conversion will be higher.

From experimental study of the research article of the effect of operating condition on
CSTR performance, the result of Figure 4 has showed that the volume of the reactor is
increase linearly with the conversion of the reaction.

Figure 4: Variation of rate constant and conversion with reactor volume

Le Chateliers principle

Le Chateliers principle states that when the dynamic equilibrium of a chemical

reaction is disturbed, the position of equilibrium will move to the direction which to
offset the changes in the system. By utilize the Le Chatelier s principle, the product of
chemical reactions can be increase by manipulate certain variable such as system
pressure, system temperature, and change of concentration.

The saponification reaction of ethyl acetate Et(Ac) and sodium hydroxide is

exothermic reaction. The chemical equation is given by:
NaOH + Et(Ac) Na(Ac) + EtOH

There are some ways to increase the conversion in this system:

1) Since the reaction is exothermic (heat is released), as the system temperature

is reduce , the equilibrium will move such a way that the temperature increase.
Thus , the equilibrium position will move to the right (formation of Na(Ac)
and EtOH) to release more heat to increase the system temperature.

2) Change of system pressure has no effect on the conversion of saponification

reaction. Pressure is the consequence of the collision between gas molecules
and the container wall. Since both of the reactant and product of saponification
is in liquid phase, thus the increase or decrease the system pressure makes no
difference to the position of equilibrium.

3) The concentration either the NaOH or Et(Ac) can be increase to increase the
conversion. When the concentration of reactant is increase, the position of
equilibrium will move such a way to decrease the concentration again. This
can be accomplish by formation of Na(Ac) and EtOH and the conversion rate
of saponification process will increase.

In a nut shell, the rate of conversion of saponification process can be increase by

reduce the system temperature and increase the concentration of reactant.

Next, the production of ammonia from nitrogen gas and hydrogen gas (Haber
process) is exothermic. The equation of this reaction is given as below:

N2(g) + 3H2(g) 2NH3 H = -92kJ/mol

There are some variable which can be manipulate to increase the conversion of this
system to produce ammonia such as:

1) Since this reaction is exothermic(heat is released), as the system temperature is

reduce , the equilibrium will move such a way that the temperature increase.
Thus , the equilibrium position will move to the right (formation of
ammonia)to release more heat to increase the system temperature.
 2) Since the product and reactant of this reaction is in gas phase, Thus, change of
system pressure will change the conversion. . Pressure is the consequence of
the collision between gas molecules and the container wall. The more gas
molecules present in the container, the higher the pressure. The equation above
show the left hand side has 4 moles of gas while the right hand side has 2 mole
of gas. If the system pressure is increase, the position of equilibrium will move
to the right to produce fewer molecules. As a result, the pressure will be
reduced.

3) The concentration either the N2 or H2 can be increase to increase the

conversion. When the concentration of reactant is increase, the position of
equilibrium will move such a way to decrease the concentration again. This
can be accomplish by formation of NH3and the conversion rate of Haber
process will increase.

In a nut shell, the rate of conversion of saponification process can be increase by

reduce the system temperature, increase the concentration of reactant and increase the
system pressure.

Advantages and disadvantage of CSTR

The advantages of continuous stirred tank reactor (CSTR) is the construction of CSTR
is simple and the cost of construction is low. If the volume of CSTR is large, it will
have long residence time. Thus, reactant will spend more time inside the reactor and
the conversion will increase. Next, it is quite easy to control the temperature with this
type of reactor.

There are some disadvantages of CSTR. The usage of CSTR is not suitable for high
pressure reaction because of cost consideration. To run a high pressure reaction, a
complex sealing arrangement is required for the agitator. Therefore, the overall cost of
the CSTR will increase. Besides, due to poor agitation, there is possibilities where
prefect mixing cannot be achieved. Therefore, the assumption of well mixed for the
CSTR is not suitable when interpret the results. Other techniques such as residence
time distribution can be applied in order to get a meaningful result.
Application

The application of CSTR is these reactors are normally employed on commercial

scale mainly for liquid phase reaction at low or medium pressure. Beside, It is
commonly used in industrial processing of homogeneous reactions (only liquid phase)
and usually used in series

Precautionary Steps

Several precautions have to be taken this experiment as it can affect the data results
significantly. First of all, do not add any water to the how water tank in order to
decrease the temperature in the process of the experiment as the apparatus will
immediately shut down when it running. Besides that, ensure that the valves are fixed
and tighten to ensure the there is no chemical split out during the experiment.

Recommendations
Some recommendations can be applied to improve the reliability of result. First, make
sure there is sufficient NaOh and Et(Ac) in the NaOH feed tank and Et(Ac) feed tank
respectively. This can prevent the interruption of the reactant supply when the reaction
is run at high flow rate. Second, a more reliable dosing pump should be used in this
experiment as the existing dosing pump in the CSTR is not reliable where the setting
flow rate of the pump will experience fluctuation. Lastly, when the experiment is
repeated with different dosing rate, the previous solution that has been left inside the
CSTR reactor should drain out completely. This will make the obtained result more
precise.

CONCLUSION:

According to the result, the conductivity and conversion of saponification between

ethyl acetate and sodium hydroxide is not affected by time. When dosing rate or flow
rate of the reactant into the reactor increase, the conversion of the reaction decreases.
The reaction rate constant is depends on the temperature by referring the theoretical
result. The conversion is not really accurate due to the uneven flow rate of the reactant
into the reactor and cause inaccurate of the result.

REFERENCES:

1. Mohd Danish et al. Int. Journal of Engineering Research and Applications

(2015), Effect of Operating Conditions on CSTR performance: an
Experimental Study. Retrieved 8 July 2016, from
http://www.ijera.com/papers/Vol5_issue2/Part%20-%202/K502027478.pdf
2. Das, K., Sahoo, P., Magapu, S. B., & Swaminathan, P. (2011). Kinetic Studies
on Saponification of Ethyl Acetate using an Innovative Conductivity-
Monitoring Instrument with a Pulsating Sensor. Retrieved 8 July 2016, from
https://www.researchgate.net/publication/229360677_Kinetic_Studies_on_Sap
onification_of_Ethyl_Acetate_Using_an_Innovative_Conductivity-
Monitoring_Instrument_with_a_Pulsating_Sensor