Abstract

This experiment was conducted to determine the relationship of the temperature of the
reactor with the conversion and also determining the activation energy of the reaction by reacting
Sodium Hydroxide, NaOH with Ethyl Acetate inside a jacketed 40 L Continuous Stirred Tank
Reactor (Model BP 143). We varied the temperature at three different temperatures, which were
at 40, 50 and 60 degree C. We kept the flow rate of both reactants at 0.2 L/min. The results show
that the relationship between the temperature with the conversion is the higher temperature the
higher the percentage of conversion. The value of activation energy obtained was 541.956 J.

Introduction

A reactor is common need in any industry as the function of a reactor is specified space
that is designated for chemical reactions to occur. A reactor is rated based on their high product
output, efficient, and also economical. In addition to that, in designing a reactor for a specific
process, the knowledge of the type of chemicals used in the feed stream and also the chemicals
that are produced at the product stream is crucial. This can have a significant effect on its
production, efficiency and also its feasibility. The widely used reactor in the chemical
engineering industry is the Continuous Stirred Tank Reactor (CSTR).

In the CSTR, the feed stream is stirred continuously as the reactants are being fed
constantly into the reactor. The CSTR has a low driving force which made it possible for a better
control of exothermic and endothermic reactions. If a higher conversion of product is required,
then more CSTR is used and they are aligned in series. The continuous stirred tank reactor
(model BP 143) unit is suitable for student experiments on continuous chemical reactions. The
unit consists of jacketed reaction fitted in the agitator and condenser. The unit comes complete
with vessels for raw materials and product, feed pumps, and thermostat.

Theory

The Rate Equation and Rate Law.

The rate of reaction basically represents the amount of time taken in for a reaction to
occur. An example for the previous statement is oxidation, a reaction that could take days or even
years to complete whilst combustion is a reaction that occur almost instantaneously.

Consider a typical chemical reaction:

a A + bB pP + qQ

(eq 1.1)

The letters a,b,p and q represents the stoichiometric coefficients while the capital letters A
and B represents the reactants and P and Q are products. According to IUPAC's Gold
Book definition the reaction rate r for a chemical reaction occurring in a closed system under
constant-volume conditions, without a build-up of reaction intermediates, is defined as:

General Mole Balance Equation

IN - OUT + GENERATION -CONSUMPTION= ACCUMULATION

Mass is a conservative entity, hence given a control volume V the sum of mass flows entering the
system will be equal to the sum exiting minus (plus) the consumed (generated) or accumulated
fractions.

Assumptions
Steady state, therefore dNA/dt = 0

Well-mixed therefore is the same throughout the reactor.

Rearranging the generation, V = (FAo FA)/ -rA
In terms of conversion,

X = (FAo FA) / FAo

V = (FAoX) / -rA

Residence Time

The reactors residence time is defined as the reactor volume divided by the total feed flow rates.

Residence time, =

V CSTR
F0

In terms of concentration;
=

CAoCA
r A

Where CAo = Concentration of A at initial

CA = Concentration of A at final
-rA = reaction rate

Conversion
As species A has become the basis of calculation, the progress of the reaction can be quantified
by observing how many moles of products are formed for every mole of A consumed. This
parameter is called Conversion. In short, conversion is number of moles of A that has reacted
divided by Number of moles of A originally exists at the beginning of the experiment. As such :

Effects of Temperature.

Figure 2: Activation energy diagram

When conducting this experiment, we vary the temperature of the reactor as we want to
see what would happen if we had done so. In theory as the temperature increase, the conversion
would increase as we kept the runtime of the reactor as a constant. The conversion increases
because when the reactor has a high temperature the heat energy would transfer to the particles
with less energy. When the particles have achieved the amount of energy needed and collide with
other particles with the right orientation would result in a reaction. With the added heat energy
would speed this process. This energy that is needed to be overcome is called activation energy.
This can be seen from the figure above.

Objectives

To verify the conductivity values by manual determination on experimental samples.

To carry out saponification reaction between NaOH and Et(Ac) in CSTR.

To determine the effect of temperature difference of the reactor onto the conversion.

To determine the reaction rate constant.

To determine the reactions activation energy.

Aparattus and Materials

1. Continuous stirred tank reactor. Model: BP 143

2. 50 mL burette
3. 200 mL beaker
4. Conical flask
5. Solution :
I-

Sodium hydroxide, NaOH (0.1M)

II-

Ethyl acetate, Et (Ac) (0.1M)

III-

Deionised water

IV-

Phenolphthalein

6. 100 mL measuring cylinder.

7. Dropper.

Figure 3: CSTR (BP 143)

Procedure

General start-up Procedures:

1

The following solution were prepared:

i

40L of sodium hydroxide, NaOH (0.1 M)

ii

40 L of ethyl acetate, Et (Ac) (0.1M)

iii

1 L of hydrochloric acid, HCl (0.25M) , for quenching.

All valves were initially closed.

The feed vessels were charged as follows:

i

The charge port caps for vessels B1 and B2 were opened.

ii

The NaOH solution was carefully poured into vessel B1 and Et (Ac) solution was
poured into vessel B2.

iii

The charge port caps for both vessels were closed.

The power for control panel was turned on.

Sufficient water in thermostat T1 was checked. Refill as necessary.

The overflow tube was adjusted to give a working volume of 10L in the reactor R1.

Valves V2, V3, V3, V7, V8 and V11 were opened.

The unit was ready for experiment.

General shut-down Procedures:

1

The cooling water valve V13 was kept open to allow the cooling water to continue
flowing.

Pumps P1 and pumps P2 were switched off. Stirrer M1 was switched off.

The thermostat T1 was switched off. The liquid in the reaction vessel R1 was let to cool
down to room temperature.

Cooling water V13 was closed.

Valves V2, V3, V7, and V8 were closed. Valves V4, V9 and V12 were opened to drain
any liquid from the unit.

The power for control panel was turned off.

Preparation of Calibration Curve for Conversion vs Conductivity:

The following solution were prepared:

i

1 L of sodium hydroxide, NaOH (0.1M)

ii

1 L of sodium acetate , Et (Ac) (0.1M)

iii

1 L of deionised water, H2O.

The conductivity and NaoH concentration for each valu were determined by mixing the
following solution into 100 mL of deionised water.
i

0% conversion

: 100 mL NaOH

ii

25% cinversion

: 75 mL NaOH + 25 mL Et (Ac)

iii

50% conversion

: 50 mL NaOH + 50 mL Et (Ac)

iv

75% conversion

: 23 mL NaOH + 75 mL Et (Ac)

100% conversion

: 100 mL Et (Ac)

Back Titration Procedures for Manual Conversion Determination:

1

A burette was filled up with 0.1 M NaOH solution.

10 mL of 0.25 M HCl was measured in a flask.

A 50 mL sample was obtained from the experiment and immediate the sample was added
to the HCl in the flask to quench the saponification reaction.

A few drops of pH indicator were added into the mixture.

The mixture was titrated with NaOH solution from the burette until the mixture was
neutralized. The amount of NaOH titrated was recorded.

Effect of Temperature on the reaction in the CSTR.

1. The general start-up procedure was performed.

2. Pump 1 and Pump 2 were switched on and both valves 10 and 5 were open fully as to fill
the reactor to the desired volume of 10 L.
3. As the volume of in the reactor reached 10 L, both valves 10 and 5 were adjusted to
achieve a flow rate of 0.2 L/min.
4. Set the temperature at 40 degree C at the heater at the top of the reactor. Reminder!
Please turn on the heater when the reactor is already filled, this is to avoid cracking due to
shock experienced by the reactor caused by sudden contraction of molecules from the
difference in temperature.,
5. The M1 stirrer was switched on.
6. The conductivity reading was monitored closely at Q1, it will stabilize around 5 10
minutes.
7. When stable reading is observed, the conductivity value shown at Q1 was recorded.
8. After recording the conductivity value, a sample was collected at V12 and immediately
the process for titration began.
9. The sample was titrated and the volume used was recorded.
10. Repeat step 4 9 by varying the temperature to 50 and 60 degree C.

Results

Reactor volume = 40 L
Concentration of NaOH in feed vessel = 0.1 M
Concentration of Et (Ac) in feed vessel = 0.1 M

Conversion
(%)

Solution mixtures
0.1M NaOH 0.1M Et(Ac)

H2O

Concentratio

Conductivity

n of NaOH

(mS/cm)

(M)
0
25
50
75
100

100mL
75mL
50mL
25mL
-

25mL
50mL
75mL
100mL

100mL
100mL
100mL
100mL
100mL

0.0500
0.0375
0.0250
0.0125
0.0000

7.66
5.40
2.90
1.300
0.157

conductivity

Conduvtivity (mS/cm)

9
8
7
6
5
4
3
2
1
0

f(x) = - 0.08x + 7.3

R = 0.98
conductivity
Linear (conductivity)

0 20 40 60 80 100120

Conversion (%)

Graph 1: Conductivity versus conversion

Back titration to determine the conversion of NaOH;

Temperature
(oC)
40
50
60
70

First titration

Amount of NaOH react (mL)

Second titration
Third titration

Average

25
22.5
23
24

24
23.2
23.5
24

24
23
23.3
24.03

23
23.2
23.5
24.1

No

Temperature

Flow

Flow

Total flow

Residence

Condictivity

(oC)

rate of

rate of

rate of

time,

(mS/cm)

NaOH

Et (Ac)

solutions,Fo

T(min)

(L/min)
0.2
0.2
0.2
0.2

(L/min)
0.2
0.2
0.2
0.2

(L/min)
0.4
0.4
0.4
0.4

100
100
100
100

1
2
3
4

40
50
60
70

No Exit concentration of
1
2
3
4

NaOH, CNaOH (M)

0.003
0.004
0.008
0.00194

2.71
2.54
2.47
2.32

Conversion, X (%)

k (L/mol-1min-1)

94
92
93.2
96.12

52.22
28.75
40.31
127.697

Conversion vs reactor temperature

97
96
95
94

Conversion, X

93

Conversion

92
91
90
89
35

40

45

50

55

60

65

70

75

Reactor temperature, T

Graph 2: Conversion, X against reactor temperature, T

ln k vs 1/T
6
5
4

ln k

f(x) = - 65.19x + 5.2

ln k

Linear (ln k)

2
1
0
0.01

0.01

0.02

0.02

1/T

0.02

0.02

0.02

0.03

Graph 3: ln k against 1/T

Discussion

This experiment was conducted to determine the effect of temperature on the conversion.
To minimize any deviation of the results, the flow rate of feed entering the reactor was set at a
constant rate of 0.2 L/min for both reactants. Then the experiment was run at three different
temperatures starting at 40, 50 and 60 degree C. With the results that had been obtained three
graphs were plotted.

From the graph of conductivity vs conversion shows that as the conversion increases the
conductivity decreases steadily. This is may be due to the products of the reaction increases in
the reactor decreases the capability of the solution to flow electricity. Another reason is that as
the reaction precedes the concentration of NaOH decreases, this is because the presence of
NaOH helps with the electrical flow.

The next graph is the graph of conversion vs temperature should show the conversion of
the reactant steadily increases, but on the other hand, at section of 40 to 50 degree C shows a
drop in the conversion from 94 to 92 %. This could be a result of contaminants during the
sampling or titration process where the sample was exposed towards the environment. Another
possibility is that the conical flask was not cleaned properly that the contaminant had reacted
with the NaOH that gave a drop in the result. This was not seen from the conversion at 50 to 60
degree C and from 60 to 70 degree C.

The last graph depicts the result ln K vs 1/T in order to determine the activation energy
based on Arrheniuss Law. The Slope that was from the graph is -65.186 and the y-intercept is at

5.2032. As it was expressed from the theory that the slope can be used to obtain activation energy
and the value is 541.956 J.

Conclusion

We can conclude that as the temperature is increased it would increase the conversion. In
addition to that, with the higher temperature will also give a higher rate of reaction as this was
explained in theory where with the higher temperature means that even more energy to be
absorbed by the lesser energized particles which in the end increases the collision in the right
orientation of the particles. This is also supported by the graph that was obtained from results.
This experiment also shows that the K constant is dependent on the temperature. This is because
it can be satisfied by the Arrheniuss Law. From this law we can also determine the activation
energy based on the graph that had been obtained and also by doing a simple calculation, even
so, we used the graph to obtain the activation energy.

Recommendation

1. Make sure reactor does not have any leaks and valve closed and opened as needed,
controlled the valve carefully and slowly when adjusting the flow rate to obtain 0.10
L/min. It is to make sure flow rate will stabilize and the experiment will run smoothly.
2. Repeat titrations two or three times because a lot of error comes from titration or use
another method other than titration.
3. It is better to prepare the Hydrochloric acid first, so that when the sample is collected, it
can be quickly quenched. This will avoid further reaction of the sample after it is
collected.

Reference

1. Mohd. Danish, Al Mesfer, Rashid M. M., 2015, Effect of Operating Conditions on CSTR
performance : an Experimental Study, Department of Chemical Engineering, College of
Engineering, King Khalid University, Vol. 5, Issue 2.
2. Abdala, A., 2010, Elements of Chemical Reaction Engineering, The Petroleum Institute,
Abu Dhabi.
3. McCabe. (2005). Unit Operations of Chemical Engineering.
4. McGuire, J.T. (1990). Pumps for Chemical Processing.
5. Fogler. H.S (2005). Elements of Chemical Reaction Engineering.