ABSTRACT

The experiment was conducted to achieve the objectives which are

to carry out a saponification reaction between NaOH and Et(Ac), to
determine the reaction rate constant, and to determine the effect of
residence time on the conversion. The experiment was performed by
mixing NaOH and Et(Ac) together in the SOLTEQ Tubular Flow
Reactor (Model: BP 101) to produce Na(Ac) and EtOH and let to react
until inlet and outlet conductivities were stable. The flow rate was
changed from 0.30 to 0.05 L/min with 0.05 L/min interval. The conversion
value was calculated first from the initial and final concentrations of NaOH
for each flow rate. The final concentration of NaOH was determined by
obtaining the volume of titrated NaOH from back titration of the sample.
The conversion obtained shows a rise from 83.6% to 99.2%. The reaction
rate constants show fluctuations from 15.293, 16.439, 14.667, 32.591,
and 9.417 to 62.000 L/mol.min for each flow rate in descending order. The
effect of residence time on the conversion in PFR is determined by
calculating the residence time for each flow rate at a constant volume.
The residence time increases as the flow rate decreases. The plot of graph
of conversion against residence time shows that the conversion increases
as the residence time increases from 83.6% to 99.2% for 6.667 min to
40.000 min respectively.

1.0

INTRODUCTION

The chemical reactor is an essential in chemical process. It is designed to

contain chemical reactions that causes the reactants contained to change
form physically or/and chemically. The determination of type of reactor
depends on the highest efficiency towards the desired output product
while economical. Another type of reactor usually used in industry aside
from continuous-stirred tank reactors (CSTR) and batch reactors is the
tubular reactor or also known as plug flow reactor (PFR).
It consists of a cylindrical pipe and is commonly operated at steady
state. In the reactor, the fluid is completely unmixed and flows down the
tube as a plug. It is assumed that the concentration and reaction rate vary
continuously in axial direction while there is no variation in radial direction
through the reactor. Thus, it can be assumed that radial mixing is infinitely
rapid. Each plug of fluid is assumed to be uniform in temperature,
composition and pressure.

Figure1.1: Plug flow reactor

The reactor is used often for large scale and slow continuous gasphase reactions where the flow is generally turbulent. It is relatively easy
to maintain with no moving parts and it usually produces the highest
conversion per reactor volume of any of the flow reactors.

The conversion in PFR is a function of the residence time, which

depends on the flow rate and the reactor volume. As the residence time is
inversely proportional to flow rate, an increase in flow rate results in a
small value of residence time. Conversion is expected to increase as the
residence time increases.

2.0

AIMS/OBJECTIVES

The experiment was performed to achieve the objectives which are to

carry out a saponification reaction between NaOH and Et(Ac), to
determine the reaction rate constant, and to determine the effect of
residence time on the conversion.

3.0

THEORY

The general chemical reaction is described as following:

aA + bB

cC + dD

For a continuous flow reactor operating in a steady state, the

compositions do not vary with time but only with position in the reactor.
The residence time, is the time of reaction mixture spent in the reactor
and emerging with the conversion, X (Backhurst et al., 1994). It is
obtained by dividing reactor volume by the volumetric flow rate entering
the reactor:
=

V TFR
0

(3.1)
In this experiment, the volumetric flow rate varies in a constant volume.
The flow rate is set by adjusting the pump until the desired flow rate is
achieved and become constant for every experiment.
3

Conversion refers to the proportion of a reagent which reacts in the

system, or the number of A that have reacted per mole of A fed to the
system (Fogler, 2014). For irreversible reactions, as is the experiment, the
maximum conversion is 1.0 or 100% that is complete conversion. It can
also be written as the following in a constant-density situation (V or
constant):
X=

N AoN A F AoF A C Ao C A
=
=
N Ao
F Ao
C Ao

(3.2)
Reaction rates are basically empirical expressions that describe the
dependence of the rate of transformation on the parameters in the system
(Schmidt, 2005). It is often found in the form
r A=k C A C B
(3.3)
Where rA is the reaction rate (mol/dm 3.s), k is the reaction rate constant
and CA and CB is the concentration of reactants (mol/dm3) raise to the
powers and respectively. In the experiment, both and values are 1
as it is assumed as elementary reaction. The overall order of reaction is
the sum of and , making the experiment as second order reaction.
r A=k C A C B
Since CAo = CBo,
r A=k ( C Ao (1X ) )2

r A=k C A

r A=k C Ao (1X )

(3.4)
In an ideal TFR or PFR, specific assumptions are made about the
extent of mixing. They are no mixing in the axial direction, complete
4

mixing in the radial direction, and a uniform velocity profile across the
radius, thus producing the following equation from the general mole
balance (Harriott, 2003).
F Ao

V =
FA

dF A
r A

(3.5)
By using the design calculation of PFR, the reaction rate constant, k
can be calculated by the following equation.
k=

o
X
V TFR C Ao 1 X

(3.6)
Where, k is the reaction rate constant, o is the total inlet flow rate of
solutions, VTFR is the reactor volume, CAo is the inlet concentration of
reactant NaOH in the reactor, and X is the percentage of conversion.

4.0

MATERIAL AND APPARATUS

4.1

Material
0.1 M of ethyl acetate, Et(Ac), 0.1 M of sodium acetate, Na(Ac), 0.1
M of sodium hydroxide, NaOH, 0.25 M of hydrochloric acid, HCl, pH
indicator and water.

4.2

Apparatus

4.2.1 Conductivity calibration

Conductivity meter, measuring cylinder, and beaker.

Figure 4.1: Conductivity calibration diagram

4.2.2 Experiment
Table 4.1: Table of equipment and instruments in SOLTEQ
BP101
Tag
R1
B1,

Equipment
Tubular reactor
Feed tanks

Tag
FI 01
FI 02

Instruments
NaOH flow meter (L/min)
Et(Ac) flow meter (L/min)

B2
B3

Waste tank

QI 01

Inlet conductivity

B4

Water jacket

QI 02

(mS/cm)
Outlet conductivity

Pre-heater

TIC

(mS/cm)
Temperature controller

Feed pumps

01
TI 02

(C)
Pre-heater temperature

B5
P1,
P2

(C)

Table 4.1: Table of valves in SOLTEQ BP101

Tag
V1
V2
V3
V4
V5

Location
Drain valve for feed tank B1
Inlet valve for pump P1
De-ionized water supply to feed tank
B1
Drain valve for feed tank B2
Inlet valve for pump P2

Initial position
Close
Close
Close
Close
Close
6

V6

Valve for feed inlet to reactor from FI

Close

V7
V8

01
Drain valve for FI 01
Valve for feed inlet to rector from FI

Close
Close

02
Drain valve for FI 02
Drain valve for water jacket B4
Drain valve
By-pass valve for pump P3
Inlet flow for pre-heater B5
Sampling valve
Sampling valve
Drain valve
Cooling water outlet

Close
Close
Close
Close
Close
Close
Close
Close
Close

V9
V10
V11
V12
V13
V14
V15
V16
V17

Figure 4.2: PID of SOLTEQ BP101

4.2.3 Back titration

Burette, measuring cylinder, conical flask, and retort stand.

Burette containing NaOH

Conical flask containing mixture of sample, HCl and pH indicator

Figure 4.3: Back titration diagram

8

5.0

METHODOLOGY/EXPERIMENTAL PROCEDURE

5.1

General start-up
1. All valves were ensured initially closed except valves V4, V8 and
V17.
2. The following solutions were prepared:
a. 20 liter of sodium hydroxide, NaOH (0.1 M).
b. 20 Liter of ethy acetate, Et(Ac) (0.1 M).
c. 1 liter of hydrochloric acid, HCl (0.25 M), for quenching
3. The feed tank B1 was filled with the NaOH solution and feed tank
B2 with the Et(Ac) solution.
4. The water jacket B4 and pre-heater B5 were filled with clean
water.
5. The power for the control panel was turned on.
6. Valves V2, V4, V6, V8. V9 and V11 were opened.
7. Both pumps P1 and P2 were switched on. P1 and P2 were
adjusted to obtain flow of approximately 300 mL/min at both flow
meters FI-01 and FI-02. Both flow rates were made sure the
same.
8. Both solutions were allowed to flow through the reactor R1 and
overflow into the waste tank B3.
9. Valves V13 and V18 were opened. Pump P3 was switched on to
circulate the water through pre-heater B5. Stirrer motor M1 was
switched on and the speed was set to about 200 rpm to ensure
homogeneous water jacket temperature.
10. The unit was ready for experiment.

5.2

Calibration curve
1. The following solutions were prepared:
a. 1 liter of sodium hydroxide, NaOH (0.1 M).
b. 1 liter of sodium acetate, Na(Ac) (0.1 M).
c. 1 liter of deionised water, H2O.
2. The conductivity and NaOH concentration for each conversion
values were determined by mixing the following solutions into
100 mL of deionised water:
a. 0% conversion: 100 mL NaOH
b. 25% conversion: 75 mL NaOH + 25 mL Na(Ac)
c. 50% conversion: 50 mL NaOH + 50 mL Na(Ac)
d. 75% conversion: 25 mL NaOH + 75 mL Na(Ac)
e. 100% conversion: 100 mL Na(Ac)

5.3

Experiment
1. The general start-up procedures were performed as in Section 5.1
2. Valves V9 and V11 were opened.
3. Both the NaOH and Et(Ac) solutions were allowed to enter the
plug reactor R1 and emptied into the waste tank B3.
4. P1 and P2 were adjusted to give constant flow rate of about 300
mL/min at flow meters FI-01 and FI-02.both flow rates were made
sure the same. The flow rates were recorded.
5. The inlet (QI-01) and (QI-02) conductivity values were started
monitoring until they did not change over time. This was to
ensure that the reactor had reached steady state.
6. Both inlet and outlet steady state conductivity values were
recorded. The concentration of NaOH exiting the reactor and
extent of conversion from the calibration curve were found.
7. Sampling valve V15 was opened and a 50 mL sample was
collected. A back titration procedure was carried out to manually
determine the concentration of NaOH in the reactor and extent of
conversion.
8. Steps 4 to 7 were repeated for different residence times by
reducing the feed flow rates of NaOH and Et(Ac) to about 250,
200, 150, 100 and 50 mL/min. Both flow rates were made sure
the same.

5.4

Back titration
1. A burette was filled up with 0.1 M NaOH solution.
2. 10 mL of 0.25 M HCl was measured in a flask.
3. A 50 mL sample was obtained from the experiment and the
sample was immediately added to the HCl in the flask to quench
the saponification reaction.
4. A few drops of pH indicator were added into the mixture.
5. The mixture was titrated with NaOH solution from the burette
until the mixture was neutralized. The amount of NaOH titrated
was recorded.

5.5

General shut-down
1. Both pumps P1, P2 and P3 were switched off. Valves V2 and V6
were closed.
2. The heaters were switched off.

10

3. The cooling water was kept circulating through the reactor while
the stirrer motor was running to allow the water jacket to cool
down to room temperature.
4. All liquid from the unit was drained by opening valves V1 to V19
as the equipment was not going to be used for long period of
time.
5. The power for the control panel was turned off.

6.0

RESULTS
Table 6.1: Calibration curve data

Conversi
on (%)
0
25
50
75
100

Solution mixture (mL)

0.1 M
0.1 M
Water
NaOH

Na(Ac)

100
75
50
25
-

25
50
75
100

100
100
100
100
100

Concetratio

Conductivit

n of NaOH

y (mS/cm)

(M)
0.0500
0.0375
0.0250
0.0125
0.0000

9.500
6.460
3.350
0.924
0.236

11

Graph of conductivity (mS/cm) against conversion (%)

10
f(x) = - 0.1x + 8.91
R = 0.96

8
6
Conductivity (mS/cm)

4
2
0
0

20

40

60

80

100

120

Conversion (%)

Figure 6.1: Calibration curve of conductivity against conversion

Table 6.2: Experimental data for back titration

No

1
2
3
4
5
6

Volume,

Flow rate

Flow rate

Total flow

Residence

VPFR (L)

of NaOH,

of Et(Ac),

rate, 0

time,

NaOH,0

Et(Ac),0

(L/min)

(min)

(L/min)
0.30
0.25
0.20
0.15
0.10
0.05

(L/min)
0.30
0.25
0.20
0.15
0.10
0.05

0.60
0.50
0.40
0.30
0.20
0.10

6.667
8.000
10.000
13.333
20.000
40.000

4
4
4
4
4
4

Table 6.3: Experimental data for back titration (continued)

12

No

1
2
3
4
5
6

Inlet

Outlet

Conversio

Reaction

Rate of

conductivi

conductivit

n, X (%)

rate

reaction,

ty, Q1

y, Q2

constant,

-rNaOH

(mS/cm)

(mS/cm)

(mol/L.min

(L/mol.min

)
15.293
16.439
14.667
32.591
9.417
62.000

0.00103
0.00072
0.00053
0.00016
0.00022
9.9210-6

8.9
8.4
8.2
7.9
7.6
7.2

8.3
7.7
7.5
7.0
6.6
6.2

83.6
86.8
88.0
95.6
90.4
99.2

Graph of conductivity (mS/cm) against conversion (%)

10
Conductivity (mS/cm)

5
0
82

f(x)
f(x) =
= -- 0.09x
0.12x +
+ 16.41
17.85
R
R =
= 0.8
0.79

84

86

88

90

92

94

96

98 100 102

Conversion (%)
Inlet conductivity, Q1 (mS/cm)
Linear (Inlet conductivity, Q1 (mS/cm))
Outlet conductivity, Q2 (mS/cm)
Linear (Outlet conductivity, Q2 (mS/cm))

Figure 6.2: Experimental conductivity against conversion

13

Graph of conversion, X (%) against residence time, (min)

104
100

R = 0.69

96
92
Conversion, X (%)

88
84
80
76
72
5

10

15

20

25

30

35

40

45

Residence time, (min)

Figure 6.3: Conversion against residence time from back titration

7.0

CALCULATIONS
Table 7.1: Known quantities

Volume of sample, Vs
0.05 L
Concentration of NaOH in feed 0.1 mol/L
sample, CNaOH,f
Volume of HCl

for

quenching, 0.01 L

VHCl,s
Concentration of HCl in standard 0.25 mol/L
solution, CHCl,s
Volume of titrated NaOH, V1
0.0209 L
Concentration of NaOH used for 0.1 mol/L
titration, CNaOH,s

1. Residence time,
14

V CSTR
0

4L
0.6 L /min

=
6.667 min
2. Concentration of NaOH at the inlet, CNaOH,0
1
C
CNaOH,0 =
2 NaOH ,f
=

1
( 0.1 mol/ L )
2

=
0.05 mol/L
3. Volume of unreacted quenching HCl, V2

V2

C NaOH ,s
V
C HCl ,s 1

0.1 mol/ L
( 0.25
mol/ L )

(0.0209 L)

0.00836 L

4. Volume of HCl reacted with NaOH in sample, V3

V3
=
VHCl,s V2
=
0.01 0.00836
=
0.00164 L
5. Number of moles of HCl reacted with NaOH in sample, n1
n1
=
CHCl,s V3
=
0.25 mol/L 0.00164 L
=
0.00041 mol
6. Concentration of unreacted NaOH in sample, CNaOH as n2 = n1
n2
CNaOH =
Vs
=
=

0.00041
0.05
0.0082 mol/L

7. Conversion of NaOH in the reactor, X

C NaOH
(1
)100
X
=
C NaOH ,0

15

0.0082
) 100
0.05

(1

83.6%

8. Reaction rate constant, k

o
X
k
=
V TFR C NaOH ,o 1X

=
=

0.6 L/min
0.836
mol 10.836
(4 L)(0.05
)
L

15.293 L/mol.min

9. Rate of reaction, -rNaOH

-rA
=
kCNaOH2
=
(15.293 L/mol.min)(0.0082 mol/L)2
=
0.00103 mol/L.min

8.0

DISCUSSION

Plug flow reactor (PFR) is a reactor for continuous chemical reactions

system in a cylindrical shape. The fluid going through the reactor refers to
as a plug, each with a constant volume, temperature, total pressure or
composition and inlet reactant ratio (Butt, 2000). The residence time of
the plug is the position of the fluid in the reactor. In this experiment, the
saponification of NaOH and Et(Ac) were performed by mixing the
substances together in the reactor. The general equation for the
saponification reaction is
NaOH + Et(Ac)

Na(Ac) + EtOH

Based on the results, it is found that the conductivity is decreasing

along with the decreasing concentration. The conductivity or specific
conductance is a measure of ability of an electrolyte or a solution to
conduct electricity. The conductivity is decreasing due to the less ionic
content in the water. The calibration data in Table 6.1 show that as the
16

concentration of NaOH decreases from 0.0500 M to 0.0000 M, the

conductivity also decreases from 9.50 mS/cm to 0.236 mS/cm. The
pattern is also similar to the change in flow rate. It can be seen that as
flow rate decreases from 0.3 L/min results in inlet and outlet conductivities
8.9 mS/cm and 8.3 mS/cm to 0.05 L/min results in that of 7.2 mS/cm and
6.2 mS/cm respectively.
It is also found that the conductivity is inversely proportional to the
conversion due to the conductivity decreases as the conversion increases.
This is shown by both Figures 6.1 and 6.2 for calibration and experimental
respectively. The experimental data also show the same pattern for inlet
and outlet conductivity. Hence, it can be concluded that the experimental
value followed the theoretical value.
In order to determine the experimental conversion of NaOH, the
sample was taken for back titration to determine the volume of titrated
NaOH for each flow rate reading. From the conversion data obtained for
every flow rate, the reaction rate constant and the reaction rate can be
calculated to achieve the second objective. It is assumed that the reaction
is elementary; making the reaction in the experiment is a second order
reaction. The reaction rate constant is calculated with equation (3.6)
obtained from the design of reactor. The equation shows that the higher
the flow rate, the higher is the reaction rate constant. However, the
results show some fluctuations.
Both conductivities at inlet and outlet were also taken to show that
the system in the reactor had been stable for at certain flow rate. Since
the plot of conductivity against conversion of experimental followed that
of theoretical, the experimental data for the plot of conversion against
residence time to show the effect of residence time on the conversion of
NaOH for the final objective is considered valid.
Residence time is the time distribution required for elements at
various radial positions to traverse the given length (Butt, 2000). The
residence time can be calculated by using equation (3.1). The equation
17

also shows that the residence time is inversely proportional to the flow
rate. Thus, the decrease in the flow rate from 0.3 L/min to 0.05 L/min
causes the residence time to increase from 6.667 min to 40 min.
Figure 6.3 shows that the conversion is increases as the residence
time increases. Conversion refers to how many moles pf products are
formed for every mole of NaOH consumed. It is found that at 6.667 min,
NaOH had experienced 83.6% conversion and at 40 min, the conversion is
99.2%. The results obtained are reasonable as more NaOH is consumed
together with Et(Ac) to produce sodium acetate, Na(Ac) and ethanol, EtOH
until there is no more NaOH in the reactor. The conversion would be
completed at 100% ideally.

9.0

CONCLUSION

The objectives of the experiment are to achieve the objectives which are
to carry out a saponification reaction between NaOH and Et(Ac), to
determine the reaction rate constant, and to determine the effect of
residence time on the conversion.
The first objective is achieved by mixing NaOH and Et(Ac) together
in the plug flow reactor (PFR) to produce Na(Ac) and EtOH and let to react
for a certain period of time at a desired flow rate. The flow rate was
changed from 0.30 to 0.05 L/min with 0.05 L/min interval.
To achieve the second objective, the conversion value is calculated
first from the initial and final concentrations of NaOH for each flow rate.
The final concentration of NaOH was determined by obtaining the volume
of titrated NaOH from back titration of the sample. The conversion
obtained shows a rise from 83.6% to 99.2%. The reaction rate constants
show fluctuations from 15.293, 16.439, 14.667, 32.591, and 9.417 to
62.000 L/mol.min for each flow rate in descending order.
Finally, the effect of residence time on the conversion in PFR is
determined by calculating the residence time for each flow rate at a
18

constant volume. The residence time increases as the flow rate decreases.
The plot of graph of conversion against residence time shows that the
conversion increases as the residence time increases from 83.6% to
99.2% for 6.667 min to 40.000 min respectively.
In a nutshell, the experiment was completed successfully as the
objectives of the experiment are able to be achieved.

10.0 RECOMMENDATIONS
In order to make sure that the data collected is accurate, several
recommendations are suggested. One of them is the experiment needs to
be conducted repeatedly for at least three times per flow rate change.
This is to ensure that the data taken does not deviate far from the
theoretical data. The average value is then used for the calculation
involved in the experiment. All of the values involve in the experiment are
also should be taken in approximately 4 decimal places to gain a more
precise and accurate data.
There are some fluctuations in the results obtained. The reason of
the errors could be because the time interface for the value of
conductivity at inlet and outlet to be stable is too short. Since there are
quite few times where the value seems to already stabilize but actually
are not and the data might have been taken during that particular time
which then lead to the deviation from the theoretical value of the
conductivity. Therefore, the conductivities should be taken when the
readings are constant for a minimum of 3 seconds.
Other than mentioned above, the minor errors such as zero error
and parallax error should also be avoided by ensuring the bottom of NaOH
solution curve is in line with zero in the burette and the reading of the
burette is taken with the eye level is parallel to the scale. The bubbles at
the mouth of burette should also be removed to gain an accurate data.

19

11.0 REFERENCE
Backhurst, J. R., Coulson, J. M., Harker, J. H. & Richardson, J. F. (3rd ed.).
(1994). Chemical and biochemical reactors and process control. In
Chemical engineering (Vol. 3, pp. 43). Burlington: ButterworthHeinemann
Butt, J. B. (2nd ed.). (2000). Reaction kinetics and reactor design (pp. 234235). New York, NY: Marcel Dekker, Inc.
Fogler, H. S. (4th ed.). (2014). Elements of chemical reaction engineering
(pp. 14-17). Essex: Pearson Education Limited
Harriott, P. (2003). Chemical reactor design (pp. 106-107). New York, NY:
Marcel Dekker, Inc.
Schmidt, L. D. (2nd ed.). (2005). The engineering of chemical reactions (pp.
155-156). New York, NY: Oxford University Press, Inc.

12.0 APPENDIX

20