SKTK 3731

POLLUTION CONTROL AND REACTION

LABORATORY
SECTION 01

EXPERIMENT 2: SAPONIFICAATION OF ETHYL

ACETATE AND SODIUM HYDROXIDE IN CSTR

Lecturer: DR. NORZITA BINTI NGADI

Group 3
NAME MATRIC NO.
SHASHIADARINI A/P N. MURALI A18KT0276
TESHINI A/P HARI RAM A18KT0303
MUHAMMAD IZZAIM REDZA BIN MOHD ISRAN A17KT5215
MUHAMMAD ASRAF BIN SUHAIMI A17KT3001
HARIFT KARUNIAWAN RAHMAT
1.0 ABSTRACT

This experiment was conducted to study the saponification reaction of sodium hydroxide and
ethyl acetate in a Continuous-Stirred Tank Reactor (CSTR). This experiment as also
conducted to understand a CSTR system, study it and the effect of flow changes. Apart from
that, this experiment is to study the rate constant and reaction order of saponification reaction
between sodium hydroxide and ethyl acetate using graphical technique.

First, the apparatus are set-up and the conductivity calibration curve with different molar
concentrations were prepared to determine reaction kinetics and the rate law of the process.
After that, the experiment was carried out according to the procedure and the data obtained
from the experiment were recorded in the table. The process was repeated a few times by
using different flow rates of feed each time. The calculations for concentration of input and
output chemicals, rate of reaction and the space time of CSTR are used for theoretical values.
The discussion section shows graph plotted using results obtained.

From the result obtained, it shows that on the graph concentration versus time, we get
the value of rate constant. Other than that, the reaction order is proven to be a second order of
reaction based on linear graph of concentration versus time. The errors and recommendations
were also discussed in the discussion section. The conclusion section concludes all the
objectives and calculations on this experiment.
2.0 INTRODUCTION

This experiment was conducted to study saponification reaction between sodium hydroxide
and ethyl acetate in a continuous-stirred tank reactor (CSTR). The process was conducted to
eventually produce soap, usually from fat and lye. The saponification process involves base
hydrolysis of triglycerides, which are esters of fatty acids to form sodium salt of carboxylate.

Apart from saponification, the other purposes of this experiment are to investigate the
operational behaviour of a reaction in CSTR and to calculate the reactant conversion based on
conductivity calibration curve. Also, the significance of doing this
experiment was to verify the reaction order obtained from the hypothesis of the experiment
and
to determine the rate constant of saponification reaction between sodium hydroxide and ethyl
acetate using graphical and analytical technique. Then, the results from both techniques were
compared. In fact, the experiment was conducted to compare the reaction kinetics, rate law
and conversion in a batch reactor to the one in a CSTR system for the same reaction.

The reaction kinetics and rate law of saponification reaction in a CSTR can be
determined using conductivity calibration curve. Conductivity is defined as a measure of how
well a solution conducts electricity. A solution should contain charged particles, or ions to
carry a current. Most conductivity measurements are made in aqueous solutions, and the ions
responsible for the conductivity come from electrolytes dissolved in the water.

There are two ways to calibrate conductivity sensors. The sensor can be
calibrated against a solution of known conductivity or it can also be calibrated against a
previously calibrated sensor and analyser. Normally, the sensor should be calibrated at a
point near the midpoint of the operating range calibration changes the cell constant. For this
experiment, the calibration curve is prepared using different molar concentrations of sodium
hydroxide and sodium acetate.
3.0 LITERATURE REVIEW

A continuous tank reactor (CSTR) is a batch reactor equipped with an impeller or other
mixing device to provide efficient mixing. It is the most basic of the continuous reactors used
in chemical processes. CSTRs are open systems, because materials can enter and exit the
system which operate at steady state condition and the conditions do not change with the
time. CSTRs are very well mixed, so the contents have relatively uniform properties such as
temperature, density etc. The conditions in the reactor’s exit stream are same are the same as
those inside the tank. Systems connecting several CSTRs are used when the reaction is too
slow.

3.1 THEORY

The stoichiometry of the saponification reaction between sodium hydroxide (NaOH) and
ethyl acetate (EA, CH3OOOC2H5) is:

NaOH + CH3OOOC2H5 CH3COONa + C2H5OH (1)

Sodium Ethyl Sodium Ethyl
Hydroxide Acetate Acetate Alcohol

Saponification between sodium hydroxide (NaOH, denotes as A) and ethyl acetate (EA,
denotes as B) is basically second order elementary reaction. For a steady-state constant
volume isothermal CSTR, the design equation is,

V= voCAOX/(-rA)

where V is the reactor volume, X is the reactant and υo is the total volumetric flow rate feeds
into the reactor. For an elementary-bimolecular second order reaction, the rate equation is:

-r A = kCACB
Basically, reactant conversion, X, can be calculated using the following equation:

X=1-CA/CA0

X=1- CB/CB0

The design equation of a CSTR also can be written in terms of initial concentrations, reactant
conversion, reactor volume and feed flow rate. Thus, we need to use the relations:

CA=CA0(1-X)

CB=CB0(1-X)=CA0(1-X), when CB0=CA0

Therefore,

-rA=KcA02(1-X)2

If we combine the above equations, we see that

V=v0X/(KcA0(1-X)2

And further simplified to

V=v0X/KCA0(1-X)2

4.0 METHODOLOGY

4.1 Calibration graph plot

 Conductivity calibration curve is prepared using three points:

i. X = 0.0, use 10 mL 0.1M NaOH
ii. X = 0.5, use a mixture of 5 mL NaOH and 5 mL sodium acetate
iii. X = 1.0, use 10 mL 0.1M sodium acetate
4.2 Operating procedure

1. 9L solution of 0.1M NaOH (8g per 2L H2O) and 9L solution of 0.1M EA (19.6mL
per 2L H2O) are prepared and these solutions were poured into tanks T1 and T2
respectively.
2. Next, pumps P1 and P2, and stirrer S1 are switched on. The feed flow rates into the
CSTR are adjusted to be at 40 cm /min using valves F1 and F2. The stopwatch was
3

started immediately as the pumps and stirrer were switched on. The conductivity and
temperature of the reaction medium in the CSTR were measured for every 2 minutes
for over 30 minutes.
3. When liquid level inside the CSTR reached 2000 cm (2L), the space time,
3

conductivity and temperature of the reaction medium were recorded.

4. Then, the reaction is flowed into the buffer tank by opening valve V3. Measurements
were continued taken for 10 minutes.
5. After 30 minutes, valves F1 and F2 were closed, and pumps P1 and P2 were stopped.
All liquids were discharged through valve V4.
6. The experiment was repeated for different feed flow rates at 60 cm , 100 cm and 120
3 3

cm .3

7. All residual NaOH and Ethyl Acetate were discharged once the experiments were
done.
8.   The pilot plant was cleaned up.
5.0 RESULTS

Conductivity vs Conversion
12000

10000

8000
Conductivity

6000

4000

2000

0
0 0.2 0.4 0.6 0.8 1 1.2
Conversion

Graph 1: Graph of conductivity against conversion of three different concentrations

1/Ca vs time
140

120

100

80
1/Ca

60 f(x) = − 2.16 x + 70.08

40

20

0
0 5 10 15 20 25 30 35
Time

Graph 2: 1/Ca vs time for v0=40cm^3/min

 1/Ca vs time
40
35
30
25
f(x) = − 0.39 x + 24.18
1/Ca

20
15
10
5
0
0 5 10 15 20 25 30
time

Graph 3: Graph of 1/Ca vs time for v0=60cm^3/min

1/Ca vs time
40
35
30
25
1/Ca

20 f(x) = − 0.54 x + 22.59

15
10
5
0
0 5 10 15 20 25 30
time

Graph 4: Graph of 1/Ca vs time for v0=100cm^3/min

 1/Ca vs time
25

20

15
f(x) = 0.06 x + 13.1
1/Ca

10

0
0 5 10 15 20 25 30
time

Graph 5: Graph of 1/Ca vs time for v0=120cm^3/min

6.0 DISCUSSION

After calculations, the reaction conversion and rate constant were determined. Based on the
graph 1, the linear equation that were obtained is y= -9040x + 9153.3. The conductivity
reaction curve represents the conversion-conductivity relationship of the reaction mixture and
provide the mean to get concentration versus time data. Hence, the value of conversion at
every minute were calculated followed by the concentration of Ca, Cb, Cc and Cd.

1/Ca = Cao + kt
 By using graphical method, the slope of the graph indicates the rate constant of the
saponification reaction. The average value of rate constant is -0.7578 L/mol.min whereas
while using the analytical method, the value of the rate constant is 1.7094 L/mol.min. There
were some differences between the two rate constant due to several factor. First, the must be
some mistake when taking the measurement of the sodium hydroxide and ethyl acetate.
Second, the are also fault inside the CSTR machine. Lastly, the calculations in this
experiment were slightly wrong and undetectable causing the value to split.

Batch reactor CSTR

Reaction Kinetics Same speed Same speed

Rate Law Second order Second order

Conversion Conversion increases with Time usually increases with

the time spent inside the the increasing reactor
reactor. The more the time volumes. The bigger the
spent, the more reactant is reactor, the more time it will
converted until reach take the reactants to flow
equilibrium. completely through the
reactant and more time to
react.

Some recommendations to improve the results is to study the experiment before doing any
type of calculations. Other than that, try to be careful when doing the calculations.

7.0 CONCLUSION
From this experiment, it can be said that the conversion of sodium hydroxide reacts with
ethyl acetate influence by the flowrate of the feed. From the data, at slowest flowrate, the
conversion is the highest, whereby, at the fastest flowrate, the conversion is the lowest.
Looking at the calibration curve graph, it is shown that the lower the conductivity, the easier
for the conversion to occur. From this experiment, the data can be concluded that it is in line
with the calibration curve graph. From the technique to obtain rate constant, the value is
different as graphical analysis value is lower than analytical method. This is because, there
must be some error in data measurement during the experiment. The reaction order for this
experiment is the second order reaction.

8.0 REFERENCES

1. Fogler,H.S., “Elements of Chemical Reaction Engineering”, 4th Edition,Prentice Hall,

New Jersey, 2006.
2. Davis, M.E and Davis, R.J, “Fundamentals of Chemical Reaction Engineering”, Mc-Graw-
Hill, New York, 2003

9.0 APPENDICES

Table 1. Calibration Data

0.05M NaOH
Calibration Data 0.1M NaOH + 0.1M Sodium Acetate
0.05M Sodium Acetate

Conversion 0.0 0.5 1.0

10,200 2,540 1,160

Conductivity (μS)

Table 2. Experimental Data: Flow Rate = 40cm3/min

Time, t Conductivity Temp. Conversion CA CB CB CD

 (min) (μS) (oC) (mol) (mol/L) (mol/L) (mol/L) (mol/L)

300 25.3 X0.912926 8.704 8.704 0.09129 0.9129

0 x10^-3 x10-3

350 26.1 X0.908161 9.1839 x 9.1839 x 0.09082 0.09082

2 10^-3 10^-3

1172 26.8 X0.829832 0.01702 0.01702 0.08298 0.08298

4

2330 27.0 X0.719486 0.02805 0.02805 0.07195 0.07195

6

4180 27.0 X0.543198 0.04568 0.04568 0.05432 0.05432

8

4060 27.1 X0.554633 0.04454 0.04454 0.05546 0.05547

10

3940 27.1 X0.566068 0.04339 0.04339 0.05661 0.05661

12

3820 27.1 X0.577503 0.04225 0.04225 0.05775 0.05775

14

3740 27.1 X0.585126 0.04149 0.04149 0.05851 0.05851

16

3740 27.1 X0.585126 0.04149 0.04149 0.05851 0.05851

18

3460 27.1 X0.611808 0.03882 0.03882 0.06118 0.06118

20

3540 27.1 X0.604184 0.03958 0.03958 0.06042 0.06042

22

3670 27.1 X0.591797 0.04082 0.04082 0.05918 0.05918

24

3820 27.1 X0.577503 0.04225 0.04225 0.05775 0.05775

26

3960 27.1 0.564162 0.04358 0.04358 0.05642 0.05642

28

3980 27.1 0.562257 0.04377 0.04377 0.05623 0.05623

30

CA: concentration of NaOH

CB: concentration of EA

CC: concentration of sodium acetate

CD: concentration of ethyl alcohol

Table 3. Experimental Data: Flow Rate = 60cm3/min

Time, t Conductivity Temp. Conversion CA CB CB CD

(min) (μS) (oC) (mol) (mol/L) (mol/L) (mol/L) (mol/L)

2510 27.0 0.02977 0.02977 0.07023 0.07023

0 0.702334

3190 27.2 0.637536 0.03625 0.03625 0.06375 0.06375

2

3600 27.3 0.598467 0.04015 0.04015 0.05985 0.05985

4

6740 27.4 X0.299255 0.07007 0.07007 0.02993 0.02993

6

6250 27.5 X0.345947 0.06541 0.06541 0.03459 0.03459

8

5970 27.5 X0.372628 0.06274 0.06274 0.03726 0.03726

10

5930 27.5 X0.37644 0.06236 0.06236 0.03764 0.03764

12

5770 27.5 X0.391686 0.06083 0.06083 0.03917 0.03917

14

5630 27.5 X0.405027 0.05960 0.05960 0.04050 0.04050

16

5520 27.6 X0.415509 0.05845 0.05845 0.04155 0.04155

18

5450 27.6 X0.422179 0.05778 0.05778 0.04222 0.04222

20

5410 27.6 X0.425991 0.05740 0.05740 0.04260 0.04260

22

5410 27.6 X0.425991 0.05740 0.05740 0.04260 0.04260

24

5370 27.6 X0.429803 0.05702 0.05702 0.04298 0.04298

26

28

30

CA: concentration of NaOH

CB: concentration of EA

CC: concentration of sodium acetate

CD: concentration of ethyl alcohol

Table 4. Experimental Data: Flow Rate = 100cm3/min

Time, t Conductivity Temp. Conversion CA CB CB CD

(min) (μS) (oC) (mol) (mol/L) (mol/L) (mol/L) (mol/L)

2920 27.3 X0.663265 0.03367 0.03367 0.06633 0.06633

0

2490 27.2 X0.704239 0.02958 0.02958 0.07042 0.07042

2

8000 27.5 X0.179188 0.08208 0.08208 0.01792 0.01792

4

7590 27.6 X0.218258 0.07817 0.07817 0.02183 0.02183

6

6960 27.6 X0.278291 0.07217 0.07217 0.02783 0.02783

8

7260 27.7 X0.249703 0.07503 0.07503 0.02497 0.02497

10

7220 27.7 X0.253515 0.07465 0.07465 0.02535 0.02535

12

7150 27.7 X0.260185 0.07398 0.07398 0.02602 0.02602

14

7140 27.7 X0.261138 0.07389 0.07389 0.02611 0.02611

16

7220 27.7 X0.253515 0.07465 0.07465 0.02535 0.02535

18

7280 27.8 X0.247798 0.07522 0.07522 0.02478 0.02478

20

7270 27.8 X0.248751 0.07512 0.07512 0.02488 0.02488

22

7520 27.8 X0.224928 0.07751 0.07751 0.02249 0.02249

24

26

28

30
CA: concentration of NaOH

CB: concentration of EA

CC: concentration of sodium acetate

CD: concentration of ethyl alcohol

Table 5. Experimental Data: Flow Rate = 120cm3/min

Time, t Conductivity Temp. Conversion CA CB CB CD

(min) (μS) (oC) (mol) (mol/L) (mol/L) (mol/L) (mol/L)

4170 27.4 X0.544151 0.04558 0.04558 0.05442 0.05442

0

8750 27.5 X0.107721 0.08923 0.08923 0.01077 0.01077

2

8920 27.6 X0.091521 0.09085 0.09085 0.00915 0.00915

4

8670 27.7 X0.115344 0.08847 0.08847 0.01153 0.01153

6

7830 27.7 X0.195388 0.08046 0.08046 0.01954 0.01954

8

7600 27.7 X0.217305 0.07827 0.07827 0.02173 0.02173

10

8150 27.7 X0.164895 0.08351 0.08351 0.01649 0.01649

12

8070 27.8 X0.172518 0.08275 0.08275 0.01725 0.01725

14

7950 27.8 X0.183953 0.08160 0.08160 0.01840 0.01840

16

7030 27.8 X0.27162 0.07284 0.07284 0.02716 0.02716

18

6210 27.8 X0.349759 0.06502 0.06502 0.03496 0.03496

20

5480 27.8 X0.419321 0.05807 0.05807 0.04193 0.04193

22

5630 27.8 X0.405027 0.05950 0.05950 0.04050 0.04050

24

26
 28

30

CA: concentration of NaOH

CB: concentration of EA

CC: concentration of sodium acetate

CD: concentration of ethyl alcohol

Table 6. Experimental Data: Space Time

Flow Rate Space Time Conductivity Temp. Conversion

υo τ T X
(cm3/min) (min) (μS) (oC)

28 3960 27.1 0.5642

40

17 5450 27.6 0.4222

60

13 7170 27.7 0.2583

100

12 8130 27.8 0.1668

120

Calculations

Based on Graph 1, the linear equation of the curve is y= -9040x + 9153.3 where y is
Conductivity and x is Conversion

When flow rate is at 40cm^3/min, the conductivity at time=10 is 4060 µS, the conversion
value is

y = -9040x + 9153.3

4060 = -9040x + 9153.3

x = 0.554633

For the concentration of NaOH after the reaction after the reaction, Ca

Ca = Cao(1-X)

= 0.1(1-0.55463)
 =0.04454 mol/L

For concentration of ethyl acetate, Cb

Ca =Cb

Cb = 0.04454 mol/L

For concentration of Sodium Acetate, Cc

Cc = CaoX

= 0.1(0.55463)

=0.055463 mol/L

For concentration of ethyl alcohol, Cd

Cc =Cd

Cd = 0.055463 mol/L

Four linear graphs of 1/Ca vs time were plotted, which indicates the second order reaction of
the saponification reaction process

1/Ca = 1/Cao + kt

By using graphical method, the value of k is

kavg = (-2.1621 - 0.3897 - 0.5425 + 0.0632)/4

= -0.7578 L/mol.min

By using analytical method, the equation simplified

V =v0X/KCA0(1-X)2

k = 40(0.5642)/2000(0.1)(1-0.5642)^2
k = 0.5941 L/mol.min

The calculation were repeated using the X values from 60,100 and 120 cm^3/min

So, the k average is

Kavg = (0.5941 + 0.7106 + 1.9357 + 3.5971)/4

Kavg = 1.7094 L/mol.min