TABLE OF CONTENTS

Title No. of page

Abstract 2

Introduction 2-3

Aims / Objectives 3

Theory 4-6

Apparatus 7

Procedures 8-10

Results 11-13

Sample calculations 13-15

Discussion 16-17

Conclusion 17

Recommendations 17

References 18

Appendices 19

1
ABSTRACT

Experiment is conducted to carry out manual conversion determination on experiment samples

to verify the conductivity measurement values. A part from that, the objectives to study
saponification reaction between sodium hydroxide solution, NaOH and ethyl acetate in CSTR
and determine the effect of residence time onto the reaction extent of conversion. Finally, to
calculate the reaction rate constant of the experiment. In order to accomplish the objectives, the
unit used to perform this experiment is CSTR 40L. In this experiment, sodium hydroxide solution
and ethyl acetate react in continuous stirred tank reactor. Both of reactants feed to the reactor at
equal molar flow rate for certain time. From first graph which is calibration curve, it show that
conductivity is decrease with increase of conversion. While the second graph is conversion
versus residence time shows that when residence time increase, conversion also increase by
lowering the flow rate. The highest conversions which 87.2% at 200 min residence time and 0.2
L/min total flow rate of solution. The lowest conversion is 85.2% at 66.67 min and 0.6 L/min flow
rate. Based on the data that was obtained, it can be concluded that the higher the flow rate, the
smaller the rate constant and the highest rate of reaction. It can be prove by using calculation of
rate law. From the calculation, the value of conversion increases with decreases of volumetric
flow rate. So, the theory from the calibration was proved. The highest rate of reaction, rA is
5.1799x10-4 mol/Lmin and the rate constant, k is 5.322 minL/mol.

INTRODUCTION

In the industrial chemical processes, mostly a reactor is the key item of equipment in which raw
materials undergo a chemical change to form desired products. The design and operation of
chemical reactors are very crucial to whole success of the industrial operation. There are many
types of reactors depending on the nature of the feed materials and products. Understanding
non-steady behavior of process equipment is necessary for the design and operation of
automatic control system. The rate of reaction is the most important thing will be consider in the
reactor because it showed effectiveness of the processing in the reactor. One particular type of
process equipment is continuous stirred tank reactor (CSTR).

Continuous stirred tank reactor, also known as vat-or backmix , is a common ideal reactor type
in chemical engineering. A CSTR often refers to model used to estimate the key unit operation
variables when using a continuous agitated-tank reactor to reach a specified output. Reactant
and products are continuously added and withdrawn from the reactor. In practice, mechanical or
hydraulic agitation is required to achieve uniform composition and temperature. The CSTR is

2
idealized opposite of the weel-stirred batch and tubular plug flow reactor. Analysis of selected
combination of these reactor types can be useful in quantitatively evaluating more complex gas,
liquid and solid flow behavior.

In this experiment, the CSTR (model: BP143) unit used for study on chemical reaction in liquid
phase which is under adiabatic and isothermal condition. The units consist of jacketed reaction
fitted in the agitator and condenser. The unit comes complete with vessels for raw material and
product, feed pumps and thermostat. The reactor is modeled in order to perform the
saponification reaction where the reaction is occurs between the sodium hydroxide, NaOH and
ethyl acetate, Et (Ac). The saponification process between this compounds produced sodium
acetate in a batch and the continuous stirred tank reactor evaluate the rate data needed to
design a production scale reactor.

AIMS

There are 4 main objectives of the experiments:

1. To carry out manual conversion determination on experiment samples to verify the

conductivity measurement values.
2. To study saponification reaction between NaOH and Et (Ac) in CSTR.
3. To determine the effect of residence time onto the reaction extent of conversion.
4. To calculate the reaction rate constant of the experiment.

3
THEORY

Saponification is an organic chemical reaction that utilizes an alkali to cleave an ester into
carboxylic acid and alcohol. The equation below shows the saponification process between
sodium hydroxide, NaOH and ethyl acetate(irreversible reaction) to produce sodium acetate and
by product ethanol.

C2H5O2CCH3 + NaOH CH3CO2Na + H3CCH2OH

ethyl acetate + sodium hydroxide sodium acetate + ethanol

Continuous Stirred tank Reactor (CSTR)

Figure 1: Stirred tank

CSTR is used primarily for liquid phase reaction. It is normally operated at steady state with
continuous flow and is assumed to be perfectly mixed; consequently, there is no time
dependence or position dependence of the temperature, the concentration or the reaction rate
inside the CSTR. The feed assumes a uniform composition throughout the reactor exit stream
has the same composition as in the tank.

General Mole Balance Equation

FAo FA + 0 A dv = dNA/dt

Assumptions:

For steady state, dNA/dt = 0

Well mixed, therefore r, is the same throughout the reactor.

4

0 A dv = rAv

v = (FAo FA) / rA

Rearrange the generation.

x = (FAo FA) / FAo

In terms of conversion.

v = (FA0 x) / -rA

Preparation of Calibration Curve for Conversion against Conductivity

A calibration curve is method used in analytical chemistry to determine the concentrations an

unknown sample solution. It is a graph generated by experimental means, with the
concentration of solution plotted on the x-axis and the observable variable.

The reaction to be studied is the saponification reaction of ethyl acetate Et (Ac) and sodium
hydroxide (NaOH). Since this is second order reaction, the rate of reaction depends on both
concentration of Et (Ac) and NaOH solution. However for analysis purpose, the reaction will be
carried out using equal molar feeds of Et (Ac) and NaOH solution with the same initial
concentration. This ensures that both concentrations are similar throughout the reaction.

NaOH + Et (Ac) Na(Ac) + EtOH

In this experiment, it is required to calibrate the conductivity measurement of conversion values

for the reaction between 0.1 M ethyl acetate and 0.1 M sodium hydroxide:

Residence Time

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

Residence time, = vCSTR / Fo

There are some assumptions have been made in order to using residence time equation, in this
experiment to reduce the complexity of the system being modeled. These assumptions include
constant volume and temperature and uniform distribution of substance throughout the volume
of the system but are not limited to steady state. Other than that, it also assume that chemical

5
degradation does not occurs in a system and the particles do not attach to surface that would
hinder the flow.

Rate of Equation and Rate Law

The rate of reaction for reactant and products in a particular reaction can be defined as how fast
or slow the reaction takes place.

Consider the chemical reaction as below:

aA + bB cC + dD

The lowercase later a, b, c and d refer to the stoichiometric coefficient while the capital letter
which A, B, C and D refer to the reactants and products.

Rate of reaction by IUPACs Gold Book where the symbol is r or R in the chemical reaction
occurs in a closed system which is under constant-volume conditions, without build up of
reaction intermediates is defined as:

1 [] 1 [] 1 [] 1 []
r= = = =

Where [A], [B], [C] and [D] are referred to the concentration of the substances. Based on IUPAC
the times must be in second and the rate of reaction must be positive sign.

6
APPARATUS

1. Continuous stirred tank reactor: Model BP143

2. 50 ml burette
3. 200 ml beaker
4. Conical flask
5. 100 ml measuring cylinder
6. Conductivity probe
7. Solution:
a) Sodium hydroxide, NaOH (0.1 M)
b) Ethyl acetate, Et(Ac) (0.1 M)
c) Deionised water
d) Phenolphtalein

FIGURE 2: CSTR (model: BP143)

7
OPERATING PROCEDURES

General Start-Up Procedures

1. The following solution were prepared:

a) 40 L of sodium hydroxide, NaOH (0.1M)
b) 40 L of ethyl acetate, Et (Ac) (0.1M)
c) 1 L of hydrochloric acid, HCL (0.25M), for quenching
2. All valves were ensured initially closed.
3. All feed vessels were charged as follows:
a) The charge port caps for vessels B1 and B2 were opened
b) The NaOH solutions were carefully poured into vessel B1 and Et (Ac) solution
was poured into vessel B2
c) The charge port caps for both vessels were closed
4. The power for the control panel was turned on.
5. Sufficient water in thermostat T1 tank was checked. Refill as necessary.
6. The overflow tube was adjusted to give a working volume of 10 L in the reactor R1.
7. Valves V2, V3, V7, V8 and V11.

General Shut-Down Procedures

1. The cooling water valve V13 was kept open to allow the cooling water to continue
flowing.
2. Both pumps P1 and P2 were switched off.
3. The thermostat T1 was switched off. The liquid in the reaction vessel R1 was left to cool
down to room temperature.
4. The cooling water valve V13 was closed.
5. Valves V2, V3, V7and V8 were closed. Valve V4, V9 and V12 were opened to drain any
liquid from the unit.
6. The power for the control panel was turned off.

8
Preparation of Calibration Curve for Conversion against Conductivity

1. The following solution were prepared:

a) 1 L of sodium hydroxide, NaOH (0.1M)
b) 1 L of sodium acetate, Et (Ac) (0.1M)
c) 1 L of deionised water, H2O
2. The conductivity and NaOH concentration for each conversion value were determined by
mixing the following solution into 100 ml of deionised water.
a) 0% conversion: 100 ml NaOH
b) 25% conversion: 75 ml NaOH + 25 ml Et (Ac)
c) 50% conversion: 50 ml NaOH + 50 ml Et (Ac)
d) 75% conversion: 25 ml NaOH + 75 ml Et (Ac)
e) 100% conversion: 100 ml Et (Ac)

Titration Procedures for Manual Conversion Determination

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 immediate the sample was
added to the HCl in the flask to quench the saponification reaction.
4. A few drops of pH indicator were added into a mixture.
5. The mixture was titrated with NaOH solution from the burette until the mixture was
neutralized. The amount of NaOH titrated was recorded.

9
Effect of Residence Time of the Reaction in a CSTR

1. The general start-up procedure was performed.

2. Both pumps P1 and P2 were switched on simultaneously and valves V5 and V10 were
opened to obtain the lightest possible flow rate into the reactor.
3. The reactor was filled up with both of the solution until it is just about to overflow.
4. The valve V5 and V10 were readjusted to give a flow rate of about 0.1 L/min. Both flow
rates must be same. The flow rate was recorded.
5. The stirrer M1 was switched on and the speed was set about 200rpm.
6. The conductivity value at Q1-401 was started monitoring until it does not change over
time. This is to ensure that the reactor has reached steady state.
7. The steady state conductivity value was recorded and the concentration of NaOH extent
of conversion in the reactor was found out from the calibration curve.
8. Sampling valve V12 was opened and 50 ml sample was collected. A back titration
procedure was carried out to determine the concentration of NaOH in the reactor and the
extent of conversion.
9. The experiment was repeated (steps 5-9) for different residence times by adjusting the
feed flow rates of NaOH and Et (Ac) to about 0.15, 0.20, 0.25 and 0.30. Both flow rates
must be the same.

10
RESULTS

Table 1: Preparation of Calibration Curve

Conversion Solution Mixtures Concentration Conductivity

0.1 M NaOH 0.1 M Et (Ac) H2O of NaOH (M) (mS/cm)
0% 100 ml - 100 ml 0.0500 14.490

25% 75 ml 25 ml 100 ml 0.0375 8.990

50% 50 ml 50 ml 100 ml 0.0250 4.750

75% 25 ml 75 ml 100 ml 0.0125 3.150

100% - 100 ml 100 ml 0.0000 0.127

Graph 1: Calibration curve

16 Graph of Conductivity (mS/cm) against Conversion

(%)
14

12

10
Conductivity (mS/cm)

8 y = -0.1383x + 13.215
R = 0.9578
6

0
0 20 40 60 80 100 120
-2
Conversion (%)

11
Table 2: Result effect Residence Time of Reaction in CSTR

Reactor volume: 40L

Concentration of NaOH in feed vessel: 0.1 M

Concentration of Et (Ac) in feed vessel: 0.1 M

No. Temperature Flow Flow Total flow Residence Conductivity

(oC) rate of rate of rate of time, (mS/cm)
NaOH Et(Ac) solutions, (min)
(L/min) (L/min) Fo (L/min)
1. 29.8 0.10 0.10 0.20 200.00 2.64

2. 30 0.15 0.15 0.30 133.33 2.63

3. 30.2 0.20 0.20 0.40 100.00 2.64

4. 30.4 0.25 0.25 0.50 80.00 2.67

5. 30.5 0.30 0.30 0.60 66.67 2.71

No Total flow Volume of Exit Conversion,

rate of NaOH titrated concentration X (%)
solutions, Fo (ml) of NaOH, CNaOH
(L/min) (M)
1. 0.20 21.8 0.0064 87.5

2. 0.30 21.3 0.0074 85.2

3. 0.40 21.7 0.0066 86.8

4. 0.50 21.5 0.0070 86.0

5. 0.60 21.3 0.0074 85.2

12
Graph 2: Conversion against Residence time

87.5

87
Conversion, X (%)

86.5
y = 0.01x + 84.918
R = 0.3419

86

85.5

85
0 50 100 150 200 250
Residence timt, (min)

CALCULATIONS

Sample calculation

Known quantities:

Volume of sample, Vs = 50 ml

Concentration of NaOH in the feed vessel, CNaOH,f = 0.1 M

Volume of HCL for quenching, VHCl,s = 10 ml

Concentration of HCl in standard solution, CHCl,s = 0.25 M

Concentration of NaOH used in titration, CNaOH,s = 0.1 M

Volume of titrated NaOH, V1 = 21.8 ml

Total flow rate of solution, Fo = 0.2 L/min

13
 i. Concentration of NaOH entering the reactor, CNaOH,o
1
CNaOH,o = 2 CNaOH,f
1
= 2 (0.1 M)
= 0.05 M

ii. Volume of unreacted quenching HCL, V2

V2 = CNaOH,s / CHCl,s (V1)

0.1
= (21.8 )
0.25

= 8.72 ml

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

V3 = VHCl,s V2
= 10.00 ml 8.72 ml
= 1.28 ml

iv. Moles of HCl reacted with NaOH in sample, n1

n1 = (CHCl,s x V3) / 1000 = (0.25 x 1.28) / 1000 = 0.00032 mol

v. Moles of unreacted NaOH in sample, n2

n2 = n1 = 0.00032 mol

vi. Concentration of unreacted NaOH in the reactor, CNaOH

= (n2 / Vs) x 1000
=0.00032/50 x 1000
=0.0064 M

vii. Conversion of NaOH in the reactor, X

X = (1-CNaOH/CNaOH,o) x 100%
= (1-0.0064/0.05) x 100%
= 87.2%

14
viii. Residence time, (min)
= VCSTR/ Fo
= 40L / 0.2 L/min
= 200 min

ix. Reaction rate constant, k

k = (CAo CA)/CA2
= (0.05 0.0064) / 200 x 0.00642
= 5.322 min L/mol

x. Rate of reaction, -rA

-rA = kCA2
=5.322 min L/mol x 0.00642
=2.1799x10-4 mol / L min

15
DISCUSSIONS

In this experiment we are investigate about saponification reaction by using Continuous Stirred
Tank Reactor (CSTR) 40L (model: BP143). This experiment has been conducted to carryout
saponification between NaOH and Et(Ac) to determine the effect of residence time onto the
reaction extent of conversion and the reaction rate constant, beside to compare with manually
conversion. The CSTR model is used to predict the behavior of chemical reactors, so the key
reactor variables such as the dimensions of the reactor can be estimated. In this experiment,
the reaction of saponification is quenching with hydrochloric acid to stop the reaction. The
reaction rapidly reacts and back titration is done to investigate the volume reacted.

From the raw data that was collected after the experiment, two graphs have been plotted which
are conductivity versus conversion for manually conversion experiment and conversion X
versus residence time for the reaction in CSTR. The calibration curve is plotted to determine the
conductivity of the reaction between NaOH and Et(Ac) at certain percentage of conversion.
From the first graph, we can conclude that conductivity is decrease proportionally with
conversion. It shows that conductivity is decrease when the volume of NaOH is decrease. When
both reactants with different mole were used, it will give significant difference of conductivity.
Because of ethyl acetate as reactant and ethanol as product are not electric conductor, the
conductivity of the mixture measurement can be used to measure the concentration of
unreacted NaOH that remains solution that relate to conversion.

Volumetric flow rate is related to residence time therefore an experiment is conducted in varies
flow rate which is 0.1, 0.15, 0.20, 0.25 and 0.30 L/min. From the data that have been collected,
we can conclude that conversion increase as the volumetric flow rate is decrease. Fluid entering
the reactor at time t and will exit at time t + . Residence time, is time that the fluid elements
spend within reactor. At high flow rate, the velocity of fluid moving inside the reactor is high
means the reactants spend less time within residence time. It can be concluded that the longer
the residence time, more conversion of the reactants. The highest conversion is 87% at higher
residence time which is 200min.

From the calculated result, the reaction rate constant increase as volumetric flow rate is
decrease. When the reaction rate constant decrease, the rate of reaction will increase. The rate
of reaction is highest which is rA = 5.1799x10-4 mol/Lmin and the rate constant k = 5.322
minL/mol. There is more moles of NaOH converted for less volume of NaOH solution require.
This is important key design to have high conversion for large scale production. Besides that,

16
from all calculation that was obtained, we can conclude that the value of conversion increases
when the volumetric flow rate decreases. This proved theory of calibration curve from this
experiment. Therefore, the objective of the experiment is achieved.

CONCLUSION

As for the conclusion, the purpose of this experiment to determine the reaction rate constant
and as well as the effect of residence time on conversion of sodium hydroxide solution, NaOH.
CSTR is used in order to acjieve the objective of this experiment. By completing this
experiment, all purpose are met and the result are collected.

From the result it shown conversion decrease from 87.2% to 85.2% when the flow rate increase
from 0.2L/min to 0.6L/min. From the graph conversion versus residence time, it can be conclude
that conversion is increase proportionally with residence time. This proved the theory from the
calibration curve from the first experiment. When increasing the flow rate, the reaction rate
constant become smaller and the rate of reaction become higher. The experiment is successful
because all the objectives have been achieved.

RECOMMANDATIONS

There are a number of recommendations on this study:

1. Before experiment begin, make sure all the valves closed and open as needed and no
leaks from the reactor in order to make sure CSTR 40L machine is running appropriately
to prevent harm to the machine.
2. Control the valve carefully when trying to adjust the flow rate to make sure the flow rate
is stabilized.
3. During titration, the eyes should be parallel to the meniscus to get accurate readings in
order to avoid parallax error.
4. The titration process should be done slowly in order to get the first point in which the
light pink color.
5. The sample must be added quickly into HCl to avoid any experiment error due to lightest
addition and volatility of HCl.
6. Glove and goggle should be put on when dealing with chemicals such as HCl and
sodium hydroxide.
7. Clean the apparatus such as burette and beaker before using it in order to remove
certain chemical that stick to the wall to avoid inaccurate result.

17
REFERENCES

1. https://en.wikipedia.org/wiki/Continuous_stirred-tank_reactor (11/4/2016)
2. "Saponification: Definition, Process & Reaction | Study.Com". Study.com. N.p., 2016. Web. 11
Apr. 2016.
3. Golubitsky, Martin, David G Schaeffer, and Ian Stewart. Singularities And Groups In Bifurcation
Theory. New York: Springer-Verlag, 1985. Print.
4. "IUPAC Gold Book - Rate Of Reaction, V". Goldbook.iupac.org. N.p., 2016. Web. 11 Apr. 2016.
5. "Chemical Reactors". Essentialchemicalindustry.org. N.p., 2016. Web. 16 Apr. 2016.

18
APPENDICES

CSTR reactor in industrial used to

50ml water sample make poly(ethane)

Titration of NaOH

19