THE SAPONIFICATION PROCESS OF ETHYL ACETATE AND SODIUM HYDROXIDE BY

USING BATCH REACTOR

MUHAMMAD AMIR BIN MAT ARIS

(55213114396)

SITI HAJAR BINTI MOHAMED

(55213114225)

NABILAH BINTI NORDIN

(55213114016)

NORZAITUL HANIS BINTI KASIM @ MANSOR

(55213114104)

Malaysian Institute of Chemical & Bioengineering Technology

Universiti Kuala Lumpur

DECEMBER 2016

1
 ABSTRACT

The objectives of the experiment were to carry out a saponification reaction besides to
determine the reaction rate constant as well as the effect of temperature on the saponification
reaction in a batch reactor. In this experiment, Ethyl Acetate (Et(Ac)) and Sodium Hydroxide
(NaOH) were used which it were prepared before putting into two different feed tanks and then
pumped into the batch reactor with the initial flow rate of 400 mL/min and 200 mL/min. With the
interval of 5 minutes, the data of flow rate and conductivity is tabulated. As the graph of standard
calibration curve of NaOH of conductivity against concentration NaOH was plotted, it shown
that the higher the concentration of NaOH, the higher the conductivity due to the more ionic
content in the water. Based on Figure 4.2 shows the graph of conversion, X (%) for every
temperature of 40C, 50C and 60C against time, t (min), the highest conversion value at
temperature 40 C is 94.8%, 92.6% at temperature 50 C and 85.4% at temperature 60 C. From
the graph, the slope was the lower the temperature, the higher the conversion. In second order

reaction, the rate law given was calculated to get the value to be use in the graph of 1/ C A

against reaction time for every temperature. The slopes of the entire graph were increasing but

the higher value of 1/ C A for every temperature were decreasing, which are the value of 1/

CA for temperature 40 C are higher than 50 C and 60 C. In theory, the higher value of 1/

CA for every temperature graph supposed increasing. Lastly, the ln k against 1/T graph was

plotted by value that gets from Arrhenius equation. Based on the theory, different temperature
gave different value of k. For instance, the k value at 40C was 0.0075 and at temperature 60 0C,
the k was 0.0067. In addition, the reaction rate constant, k that was calculated showed that at
temperature of 60oC the reaction rate constant was lower than at 40oC. The speed of the reaction
was represented in the reaction rate constant that occurred in a process, this concludes that at
40oC the reaction rate was much faster than 60oC (Reaction Engineering, 2015). Next, the
Activation Energy and Arrhenius constant value were obtained by calculating the slope and
intercept value using the equation. The value activation Energy, Ea calculated was calculated at
60C was 17.7287 KJ/mol whereas at 40oC the activation energy was 16.6644 KJ/mol. This
showed that at 40oC less activation energy was required than at 60 oC. Based on the experiment

2
conducted, there was some problem encountered during the experiment. It was very hard to
stabilize the temperature of the reactor constantly throughout the experiment. The reading of the
temperature was not stable where it was not the same throughout the experiment. The
conductivity meter must be calibrated before use to obtain good result and reproducible data with
the conductivity meter. To minimize the error, it was best to calibrate the cell using a standard
solution with a conductivity within the range.

3
 TABLE OF CONTENT

Page no.

TITLE PAGE i

ABSTRACT ii-iii

TABLE OF CONTENT iv-vi

LIST OF TABLES vii

LIST OF FIGURES viii

CHAPTER 1: INTRODUCTION

1.1 Introduction 1
1.2 Problem Statement 2
1.3 Objective 2
1.4 Significant of Study 3
1.5 Scope of Research 4

CHAPTER 2: LITERATURE REVIEW

2.1 Batch Reactors 5

2.2 Saponification Process 7

2.3 Ethyl Acetate 7

2.4 Sodium Hydroxide

2.4.1 Overview of Sodium Hydroxide 8

2.4.2 Reaction of Sodium Hydroxide

2.4.2.1 Saponification 9

4
 2.4.3 Commercial Production of Sodium Hydroxide 10

CHAPTER 3: METHODOLOGY

3.1 Chemical Preparation 12

3.2 Chemical Preparation

3.2.1 Preparation of Ethyl Aceate, CH3COOCH2CH3 13

(liquid phase)

3.2.2 Preparation of Sodium Hydroxide, NaOH 14

(solid phase)

3.3 Startup Procedure 15

3.4 Experimental Trials 15

3.5 Shutdown Procedure 16

CHAPTER 4: RESULT AND DISCUSSION

4.1 Overview 17

4.2 Analysis of Saponification Process

4.2.1 Standard Calibration Curve of NaOH 17

4.2.2 Effect of Temperature on the Batch Saponification 19

4.2.3 Second Order Reaction 24

4.2.4 Arrhenius Equation 29

CHAPTER 5: CONCLUSION AND RECOMMENDATION

5.1 Conclusion 34

5.2 Recommendation 35

5
REFERENCES 35

APPENDIX

Appendix A: Sample Calculation 36

6
 LIST OF TABLES

TABLES NO. TITLE PAGE

2.1 Physical properties of sodium hydroxide 8

2.2 Chemical properties of sodium hydroxide 9

3.1 List of apparatus and materials 12

4.1 The effect of temperature on the batch saponification at 40 C 19

4.2 The effect of temperature on the batch saponification at 50 C 20

4.3 The effect of temperature on the batch saponification at 60 C 21

4.4 Data of 1/T and ln K 29

7
 LIST OF FIGURES

FIGURE NO. TITLE PAGE

2.1 Batch reactor 6

2.2 Cooling jacket 6

2.3 Flux cooling jacket 6

2.4 Sodium hydroxide in pallets 8

2.5 Equation for hydrolysis of esters 9

2.6 General equation of saponification reaction 10

4.1 Standard calibration curve of NaOH 18

4.2 Graph of Conversion, X(%) for every Temperature 22

of 40oC, 50oC and 60oC against time, t(min)

1
4.3 Graph of C A versus reaction time, t at 40 C

24

1
4.4 Graph of C A versus reaction time, t at 50 C

25

1
4.5 Graph of C A versus reaction time, t at 60 C

26

4.6 Graph of ln K against 1/T 29

8
 CHAPTER 1

INTRODUCTION

1.1 Introduction

Hydrolysis of carboxylic ester under alkaline conditions also known as saponification

reaction since this reaction leads to the formation of soap (Afzal et al., 2013). Saponification is
essentially a soap manufacturing process that takes place by reacting the fatty acid with alkali,
especially triglycerides producing glycerol and carboxylate salts (soap). Saponification between
ethyl acetate (acid) and sodium hydroxide (base) was carried out in a batch reactor.

Batch reactor was a generic term for a type of vessel widely used in the process
industries. The vessel of this type were used for a variety of process operations such as solids
dissolution, product mixing, chemical reactions, batch distillation, crystallization, liquid or liquid
extraction and polymerisation (Springer N., 2014).

Batch reactors are used for most of the reactions carried out in a laboratory because it is
used for small-scale operation, for testing new processes that are difficult to convert to
contionous operations (Fogler H., 2010). The reactants are placed in a test-tube, flask or beaker.
They are mixed together, often heated for the reaction to take place and are then cooled. The
products are poured out and, if necessary, purified. All the reactants in batch reactor are loaded at
once, the concentration then varies with time, but any one time it was uniform throughout.

The main advantage of a batch reactor was high conversion, which can be obtained by
leaving the reactant in the reactor for long periods of time and the unwanted side-reactions also

9
minimized but it also has the disadvantage for high labor costs per batch and the difficulty of
large scale production.

Though sodium hydroxide, basically a salt produced when ethyl acetate undergoes
hidrolysis in alkaline environment which is called as saponification in batch reactor, is not used
specifically for cleansing purposes as soap but has a wide range of industrial applications such as
in pharmaceutical, paint and dying industry, as food additive, in electroplanting industry, as meat
preservative, photography and purification of glucose. Whereas ethanol, a by-product, can be
used as biofuel.

1.2 Problem Statement

In industry, basically the production of soap (sodium acetate) produced low of rate of
reaction and reacted reactant used to produce desired product (Classic Bells, 2016) that will lead
to some loss because of low quality product (low reacted reactant was converted into desired
product that will form).

The experiment this experiment of the effect of temperature towards the saponification
reaction in a batch reactor will be conducted and observed where the temperature was set to
desired temperature to determine the conversion, X (%) against the temperature where according
to the theory, the conversion, X (%) will increase as the temperature increase. The concentration
of NaOH, CNaOH (M) will be obtained from the calibration curve and the conversion will be
obtained from self-calculation from the formula of conversion (see Appendix). The rate constant
is obtained by inserting the value into the formula of Arrhenius equation (see Apendix).The
linear equation of y= mx+c will be plotted and the optimum temperature and activation energy
will be obtained.

This reaction became faster (reaction rate) when the temperature increase where the
temperature will give an affect to the rate of the reaction. Thus, the increase the temperature, the
increase the conversion of which the reactant that has reacted so that the desired product was
formed.

1.3 Objectives

10
The main purpose of these experiment were:

To study the effect of temperature on the saponification reaction in a batch reactor.

To study the relation between the Arrhenius equation, the rate constant and the
activation energy.

1.4 Significant of Study

Hydrolysis of carboxylic ester which is under alkaline conditions also known as
saponification reaction since this reaction leads to the formation of soap (Afzal et al., 2013).
Saponification is essentially a soap industrialized process that takes place by reacting the
fatty acid with alkali, especially triglycerides produce carboxylate salts (soap) and glycerol.
Since the fat or oil starting materials are not soluble in water, the saponification reaction
proceeds very gradually unless some stipulation is made for bringing the fatty ester and base
into the same phase.

Saponification of ethyl acetate and sodium hydroxide solution is a homogeneous

reaction as it only involves liquid phase. Products formed in this reaction are sodium acetate
and ethanol. Sodium acetate possesses both hydrophilic and lipophilic behavior and this
makes it a magnificent surfactant. One can easily find surfactant in a wide range of industrial
applications particularly in hygiene and toiletries products. The main concern of a chemical
reaction is its reaction rate. It shows how quick a number of moles of one chemical species
are being consumed to form another chemical species. Sometimes, it is known as rate law
which is a product of a temperature-dependent term and a composition-dependent term.
Saponification between ethyl acetate (acid) and sodium hydroxide (base) was carried out in a
batch reactor (Afzal et al., 2013).

Batch reactor was a common term for a type of vessel widely used in the industry
process. This kind of vessel was used for a variety of process operations such as product
mixing, solids dissolution, batch distillation, chemical reactions, crystallisation,
polymerisation, and liquid or liquid extraction (Springer N., 2014). Batch reactors are used
for most of the reactions carried out in a laboratory because it is used for small-scale
operation, for testing new process that are complex to convert to contionous operations
(Fogler H., 2010). Then the reactants are put in a test-tube, flask or beaker. They are mixed
together, frequently heated for the reaction to take place and are then cooled. The products

11
 are poured out and, if essential, purified. All of the reactants in batch reactor are loaded at
once, the concentration then varies with time, but any one time it was uniform throughout
(Springer N., 2014).
1.5 Scope of Research

The scope of the research in this project is to identify the effect of temperature on the
batch saponification reaction of ethyl acetate and sodium hydroxide by using batch reactor
and to analyze the conversion, X (%) of the reaction with different and desired water
temperature by self-calculation and using the concentration of sodium hydroxide, C NaOH (M)
initial and final which were obtained from calibration curve. This project had been done at
Laboratory 4 in the University Kuala Lumpur Malaysian Institute of Chemical and
Bioengineering Technology (MICET). Due to the time and budget constrain, an analysis of
the rate constant of the reaction between ethyl acetate and sodium hydroxide under batch
condition was skipped where it can give the information and clear picture about the
comparison between conversion, X (%) against reaction time, t (min) of ethyl acetate and
sodium hydroxide and the rate constant, k (L/mol.min) for the second order reaction under
batch condition. Thus, to save the time, the rate constant of the reaction between ethyl acetate
and sodium hydroxide under batch condition was not analyzed using the titration method in
this project.

CHAPTER 2

LITERATURE REVIEW

12
2.1 Batch Reactor

Batch reactor is a vessel to mix chemicals under very specific conditions. It is known by
the continuous reactor through its cyclic use which is mixing one batch at one time. It consists of
a large, sturdy canister with its own heating and cooling mechanisms. A rotating agitator was put
inside the vessel to mix the chemicals. The input parts of batch reactor was located at the top of
the vessels where we are allowed to add more chemicals that needed to be mixed.

Batch reactors are frequently used in the creation of dyes and some food products, such as
margarine. Batch reactor is widely used in the process industries such as solids
dissolution, product mixing, chemical reactions, batch distillation, crystallization, liquid/liquid
extraction and polymerization. (Chemical, 2011).

A typical batch reactor consists of a tank with an agitator and integral heating/cooling
system. These vessels may vary in size from less than 1 litre to more than 15,000 litres. They are
usually made from steel, stainless steel, glass-lined steel, glass or
exotic alloy. Liquids and solids are usually charged via connections in the top cover of the
reactor. Vapors and gases also discharge through connections in the top. Liquids are usually
discharged out of the bottom.

The advantages of the batch reactor lie with its versatility. A single vessel can carry out a
sequence of different operations without the need to break containment. This is particularly
useful when processing toxic or highly potent compounds.

Agitator is a centrally mounted driveshaft with an overhead drive unit. Impeller blades
was put on the driveshaft but most batch reactors used baffles. The baffles is at stationary which
will disturbed the flow that was caused by the rotating agitator. (Process, 1994).

The products that was produced from batch reactors was either absorb or release heat during
processing. Thus in order to let the reactor to achieve desired temperature, heat has to be added
or remove by the cooling jacket or cooling pipe. There are three types of cooling jackets.

Fig. 2.1 Batch Reactor

13
 The first one is single external jacket. Single jacket was
designed as an outer jacket which surrounds the vessel.
The jacket was used to transfer the fluid flows with the
help of heat around the jackets. They are injected through
the nozzle at high velocity. The temperature in the jacket
will control heating or cooling.

The second cooling jackets is half coiled jackets. It is made

by welding a half pipe surrond the outside layer of vessel which
create a semi circular flow channel. The heat transfer fluid passes
through the channel in a plug flow fashion.
Fig. 1.2 Cooling Jacket

The third cooling jacket is constant flux cooling jacket. It has a

series of 20 or more small jackets elements.

Fig. 2.3 Flux Cooling Jacket

14
2.2 Saponification Process

In general knowledge, saponification process is a process that is used in the production of

soap in industry or as an experiment in university. According to Reid (2016), saponification is an
organic chemical reaction that utilizes an alkali to cleave an ester into a carboxylic acid and
alcohol. Primary usage of this reaction is during the production of soap products. In simple
terms, saponification is the name for a chemical reaction between an acid and a base to form a
salt. When making of soap using the cold process soap making method, oil or fat (which is acid)
is mixed with Lye (which is base) to form soap (which is a salt). The base must always be
composed of one hydroxide ion. For the most part, people use lye (one sodium ion and one
hydroxide ion) as their base. Noticed that the sodium ion does not take part in the reaction at all.
This is because, other bases like potassium hydroxide can be used as well because it is made up
of one hydroxide ion as well. Potassium hydroxide is more prominently used for liquid soap
making. According to Amrita.olabs.edu.in. (2013), soaps are consist of sodium or potassium
salts that consist a long chain fatty acids. When triglycerides in fat/oil react with aqueous NaOH
or KOH, they are converted into soap and glycerol. This is called alkaline hydrolysis of esters.
Since this reaction leads to the formation of soap, it is called the saponification process.

2.3 Ethyl Acetate

Ethyl acetate or also called as ethyl ethanoate with the formula C 4H8O2 is an organic
compound. According to Micheal and Irene (2004), ethyl acetate is a colorless liquid that has a
characteristic sweet smell. Ethyl acetate is used primarily as a solvent and diluent, being favored
because of its agreeable odor low toxicity, and low cost. It is the ester of ethanol and acetic acid
which is manufactured on a huge scale for use as a solvent. Ethyl acetate commonly has a
content of 95% to 98% containing a small amount of water, ethanol and acetic acid. Nicholas
(2016) stated that currently ethyl acetate production routes can be divided into ethanol
dehydrogenation ,esterification, ethylene adduct, and acetaldehyde condensation. In laboratory,
ethyl acetate is not often selected as a reaction solvent because it is prone to hydrolysis and
transesterification. This is because it is quite volatile at room temperature which is 25 C and

15
has a boiling point of 77 C. Due to these properties, it can be removed from a sample by heating
in a hot water bath and providing ventilation with compressed air.

2.4 Sodium Hydroxide

2.4.1 Overview of Sodium Hydroxide

Fig. 2.4 Sodium hydroxide in pallets

Table 2.1: Physical properties of sodium hydroxide

No. Physical Properties Values

Sodium hydroxide (also known as lye or
1. IUPAC name
caustic soda)
2. Chemical formula NaOH
3. Molar mass 39.9971 g/mol
4. Appearance White, waxy and opaque crystals
5. Odor Odorless
6. Density 2.13 g/cm3
7. Melting point 318 C
8. Boiling point 1388 C
(Retrieved from Wikipedia, 2002)

16
 Table 2.2: Chemical properties of sodium hydroxide

No. Chemical Properties Values

1 Specific heat capacity, C 59.66 J/mol.K
2 Standard molar entropy, S298 64 J/mol.K
3 Standard enthalpy of formation, fH298 -427 kJ/mol
4 Gibbs free energy, fG -380.7 kJ/mol
(Retrieved from Wikipedia, 2002)

2.4.2 Reaction of Sodium Hydroxide

2.4.2.1 Saponification

Fig.2.5 Equation for hydrolysis of esters

Sodium hydroxide can be used for the base-driven hydrolysis of esters and to hydrolyze
fats (as in saponification) and form soaps. It is created via electrolysis of sodium chloride. It is a
strong alkaline substance that dissociates completely in water to sodium and hydroxyl ions. This
creates a strong exothermic reaction when it is added to water. Sodium hydroxide is an inorganic
base, which means it is an alkali containing no carbon atoms where it separates into cations
(positively charged sodium) and hydroxide anions (negatively charged) when added to water and
the hydroxide anions decrease the acidity of the water (increasing the pH). This is why sodium
hydroxide is commonly used as a pH adjuster in formulas (Fioravanti, 2011).

The reaction between ethyl acetate and sodium hydroxide are saponification which
produced sodium acetate (soap) and ethyl alcohol (by-product). This reaction is the main reaction
in the manufacturing of soap. The general equation of this reaction is:

17
 CH3COOC2H5 + NaOH CH3COONa + C2H5OH
(Ethyl Acetate) (Sodium Hydroxide) (soap) (by-product)

Fig. 2.6 General equation of saponification reaction

2.4.3 Commercial Production of Sodium Hydroxide

Historically, sodium hydroxide was produced using metathesis reaction by treating

sodium carbonate with calcium hydroxide where sodium hydroxide is soluble while calcium
carbonate is not soluble. Nowadays, sodium hydroxide is produced in solid form and it is
obtained from evaporation of water (commonly seawater). Solid sodium hydroxide is most
commonly sold as prills, flakes and cast blocks (Wikipedia, 2002).

Ca(OH)2 (aq) + Na2CO3 (s) CaCO3 + 2NaOH (aq)

Sodium hydroxide is industrially produced 50 % solution by variations of electrolytic

chloroalkali process where chlorine gas is also produced (Wikipedia, 2002).

In 1998, total world production was around 45 million tones. In 2004, world production
and demand was estimated at 60 million dry metric tonnes and 51 million tones of sodium
hydroxide, respectively. North America and Asia each contributed around 14 million tones while
Europe produced around 10 million tonnes (Wikipedia, 2002).

In petroleum industry, sodium hydroxide is used as an additive in drilling mud to increase

alkalinity in bentonite mud systems and mud viscosity and to neutralize any acid gas such as
carbon dioxide which may be encountered in the geological formation as drilling progresses.
Low quality of crude oil can be improved with sodium hydroxide to remove sulfurous impurities
in a process of caustic washing where sodium hydroxide reacts with weak acids (Wikipedia,
2002).

Sodium hydroxide is a famous base used in industry. It also used in the manufacture of
sodium hydroxide salts and detergents, pH regulation and organic solvents where it is commonly
handled in an aqueous solution since solutions are cheaper and easier to handle (Wikipedia,
2002).

18
 CHAPTER 3

METHODOLOGY

3.1 General Project Design

19
 This research is about to perform the batch saponification reaction of ethyl acetate and
sodium hydroxide of these two solutions using batch reactor and saponification reaction. The
parameters that have been encountered were the conductivity (mS/cm), the concentrations of
NaOH, CNaOH (M) and the conversion, X (%). Next, to analyze the conversion, X (%) of the
reaction with different and desired water temperature by self-calculation and using the
concentration of sodium hydroxide, CNaOH (M) initial and final which were obtained from
calibration curve.

3.2 Chemical Preparations

Table 3.1: List of apparatus and materials

Apparatus Functions Materials Function

6 L of 0.1 M sodium The solutions that
1 L beaker To place the solutions
hydroxide, NaOH need to be prepared
6 L of 0.1 M ethyl The solutions that
Spatula To take the sample
acetate, Et(Ac) need to be prepared
Measuring cylinder To measure the volume To dilute the
Ionized water
of the solutions solutions
Volumetric flask To place and dilute the
solutions
Stopwatch To set the time

3.2.1 Preparation of Ethyl Acetate, CH3COOCH2CH3 (liquid phase)

The volume of ethyl acetate needed, V2 (L) from the original solution was:

20
 mol
M2 V2 ( L)
V1 ( L) L
mol
10.10
L

Where;

M2 = Desired molarity of Ethyl Acetate (mol/L) required in the experiment

V2 = Desired volume of Ethyl Acetate (mol/L) required in the experiment

mol

0 .1 6 ( L)
L
V1 ( L)
mol
10.10
L

V1(L) = 0.0891 L

V1(mL) = 89.11 mL

89.11 mL of ethyl acetate was taken where it was measured by using measuring cylinder
and poured into 1 L volumetric flask to dilute with 910.89 mL (0.9209 L) to get the solutions of
1000 mL (1L) of ethyl acetate. Next, the 1 L of ethyl acetate solutions was mixed and diluted
with 5 L ionized water in the batch reactor feed tank in order to make a 6 L of 0.1 M of ethyl
acetate solutions, Et(Ac).

3.2.2 Preparation of Sodium Hydroxide, NaOH (solid phase)

Weight of NaOH required for experiment, MNaoH

21
 mol g
M NaOH ( g ) M 2 MW NaOH V2 ( L)
L mol

Where;

M2 = Desired molarity of NaOH (mol/L) required in the experiment

V2 = Desired volume of NaOH (mol/L) required in the experiment

Molecular weight of NaOH, MWNaOH = 40.0 g/mol

mol g
m NaOH ( g ) 0.1 40 NaOH 6( L)
L mol

= 36 g

36 g of sodium hydroxide was taken using spatula and put into 1 L beaker. 1 L
of ionized water was mixed and diluted with 1 L ionized water. The 1 L of sodium
hydroxide solutions was mixed and diluted with 5 L ionized water in the batch
reactor feed tank in order to make a 6 L of 0.1 M of sodium hydroxide, NaOH.

3.3 START UP PROCEDURE

Firstly, all of the valves was ensured closed. Next, the power for the control panel was
turned on. Then, the thermostat T1 tank was checked to make sure there was sufficient water.
After that, the cooling water valve V5 was opened and the cooling water was let to flow through

22
the condenser W1. The thermostat T1 was switched on and the water temperature was set to the
desired temperature. Lastly, the unit was ready for experiment.

3.4 EXPERIMENT TRIALS

Before starting the experiment, there are few chemical needed to prepared which is 1L of
sodium hydroxide, NaOH(0.1 M), 250 Ml of ethyl acetate, Et(Ac) (0.1 M), and 250 mL of
hydrochloric acid , HCl (0.1 M). Then, the 200 mL of the 0.1 M ethyl acetate, Et(Ac) solution
were pipetted into a clean dry conical flask. Next, do the same method to the 200 mL of 0.1 M
sodium hydroxide (NaOH) but it was pipetted into a 500 ml empty beaker. After that, 11 clean
and empty conical flask was labelled each of them and a 20 mL of 0.1 M hydrochloric acid, HCl
were pipetted into each of the 11 flask that has been prepared before. A mechanical stirrer was
place onto the sodium hydroxide (NaOH) solution. To mixed the solution, all of the ethyl acetate,
Et (Ac) solution from the conical flask was pour quickly to be stirred equally and at the same
time, a stopwatch is begin to record the time taken roughly during the mid-point of addition of
solution.

After 5 minutes, the reacting mixture was withdraw out by using pipette 20 mL of
mixture and poured into Flask 1 and take note of the time taken by using stopwatch at the mid-
point of delivery. Then, the content of Flask 1 was titrated with 0.1 M sodium hydroxide, NaOH
using two or three drops of phenolphthalein indicator so that the color of the indicator will
change from colorless (acidic) to pink (basic). Once the indicator color was observed, the
titration step was stop. The amount of NaOH needed can be determined. For the leftover 10flask,
do the same step as in this paragraph but proceed with further samples by increasing the time
before titration started. Withdraw the samples at 10 (Flask 2), 15 (Flask 3), 20 (Flask 4), 25
(Flask 5), 30 (Flask 6), 35 (Flask 7), 40 (Flask 8), 50 (Flask 9), 60 (Flask 10) and 70 (Flask 11)
minutes. Finally, after all the samples have been experimented, the result were recorded.

3.5 SHUTDOWN PROCEDURE

The first step of shutdown procedure was to open valve (V5) of the cooling water to
allow it flowing. The thermostat T1 was switched off. Then, the liquid in reaction vessels R1 was

23
let to cool down to room temperature. Switched off the stirrer M1 and valve (V5) of the cooling
water. Next, the valve V1 was opened to drain any liquid from the unit. Lastly, switched off the
power panel at the control panel.

CHAPTER 4

RESULT AND DISCUSSION

4.1 Overview

24
 This experiment is being conducted to carry out a saponification reaction, to determine
the reaction rate constant as well as the effect of residence time on the conversion in a batch
reactor. The chemicals used are Ethyl Acetate (Et(Ac)) and Sodium Hydroxide (NaOH). Both
chemicals are put into two different tanks and pumped into the batch reactor with the initial flow
rate of 400 mL/min. With the interval of 5 minutes, the data for temperature inlet and outlet of
batch reactor, flow rate of NaOH and Et(Ac), and the conductivity were collected. All the
readings, sample calculation and calibration graph are tabulated in appendix.

4.2.1 Standard Calibration Curve of NaOH

The objective of this experiment is to study the effect of temperature on the batch
saponification reaction between sodium hydroxide (NaOH) and ethyl acetate (Et(Ac)) in the
batch reactor. This experiment were run at three different of temperature which are 40 C, 50 C,
and 60 C. Furthermore, the samples were collected every 5 minutes and conductivity test were
conducted by using conductivity meter. The result was tabulated at table 4.1, 4.2, and 4.3.

25
 Graph of standard calibration curve of NaOH,
conductivity (mS/cm) against concentration of NaOH (M)
20
18
16
14
12
10 f(x) = 140x + 4
Conductivity (mS/cm)
8 R = 0.99

6
4
2
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1

Concentration of NaOH (M)

Fig.4.1 Standard calibration curve of NaOH

The concentration of sodium hydroxide increase, the conductivity too was increasing.
This happened due to the concentration of ions in the sodium hydroxide gets higher that it
affected the conductivity to become higher too. As the concentration increase, it will also cause a
decrease in its viscosity and result in increase of the mobility of the ions in solution.

Then, the concentration of NaOH in the reactor was obtained from calibration curve in
figure 4.1. The graph is about the conductivity against calibration curve of concentration of
NaOHby using equation 140X + 4, the concentration of NaOH was calculated. So, when the
value of X (concentration of NaOH) for every temperature was calculated, the conversion, X (%)
was calculated from the formula given at the appendix. In this experiment, there might be some
error when preparing the solution that may affect the others graph.

26
4.2.2 Effect of Temperature on the Batch Saponification

Volume of NaOH = 3L
Volume of Et(Ac) = 3L
Initial concentration of NaOH = 0.1 M
Initial concentration of Et(Ac) = 0.1 M

Temperature = 40 C

Table 4.1: The effect of temperature on the batch saponification at 40 C

1
Concentration of NaOH, Conversion,
Temperature Conductivity CA
Time CNaOH (M) X (%)
(min) (C) (mS/cm)
(From calibration curve) (Self-calculation) ( M
1
)

0 40 5.78 0.0127 87.3 78.74

5 40 5.39 0.0099 90.1 101.01
10 40 5.13 0.0081 91.9 123.37
15 40 4.94 0.0067 93.3 149.25
20 40 4.84 0.0060 94.0 166.67
25 40 4.77 0.0055 94.5 181.82
30 40 4.73 0.0052 94.8 192.31

Volume of NaOH = 3L

27
Volume of Et(Ac) = 3L
Initial concentration of NaOH = 0.1 M
Initial concentration of Et(Ac) = 0.1 M
Temperature = 50 C

Table 4.2: The effect of temperature on the batch saponification at 50 C

1
Concentration of NaOH, Conversion,
Temperature Conductivity CA
Time CNaOH (M) X (%)
(min) (C) (mS/cm)
(From calibration curve) (Self-calculation) ( M
1
)

0 50 5.45 0.0103 89.7 97.09

5 50 5.42 0.0101 89.9 99.01
10 50 5.35 0.0096 90.4 104.17
15 50 5.26 0.0090 91.0 111.11
20 50 5.15 0.0082 91.8 121.95
25 50 5.08 0.0077 92.3 129.87
30 50 5.03 0.0074 92.6 135.14

Volume of NaOH = 3L
Volume of Et(Ac) = 3L
Initial concentration of NaOH = 0.1 M

28
Initial concentration of Et(Ac) = 0.1 M
Temperature = 60 C

Table 4.3: The effect of temperature on the batch saponification reaction at 60 C

1
Concentration of NaOH, Conversion,
Temperature Conductivity CA
Time CNaOH (M) X (%)
(min) (C) (mS/cm)
(From calibration curve) (Self-calculation) ( M
1
)

0 60 6.80 0.0200 80.0 50.00

5 60 6.43 0.0174 82.6 57.47
10 60 6.22 0.0159 84.1 62.89
15 60 6.18 0.0156 84.4 64.10
20 60 6.13 0.0152 84.8 65.79
25 60 6.06 0.0147 85.3 68.03
30 60 6.05 0.0146 85.4 68.49

29
 Graph of conversion, X (%) for every temperature of 40C, 50C and 60C against reaction time, t (min)
100
90
80
70
60
Conversion, X (40c) Conversion, X (50c)2 Conversion, X (60c)
Conversion, X (%) 50
40
30
20
10
0
0 10 20 30 40 50

Reaction time, t (min)

Fig. 4.2 Graph of conversion, X (%) for every temperature of 40C, 50C and 60C against time, t (min)

Based on figure 4.1 and figure 4.2, it can be seen that for temperature of 60C as the time period increased, the conversion got way
more increasing compared to the temperature of 40C slope. This happened during the period between 0-5 minutes where the
temperature of 60C conversion change from 0% up to 81.5% compared to 40C slope which it took more time like the temperature of

30
60C. The reason why it occurred might be related with the figure 4.6 where at higher
temperature, the solution became more concentrated which resulting the conversion becoming
higher.

Besides, by referring the graph conversion, X against time, t, for every temperature, which are 40
C, 50 C, and 60 C, the graph were increasing. The highest conversion value at temperature 40
C is 94.8%, 92.6% at temperature 50 C and 85.4% at temperature 60 C. From the graph, the
slope was the lower the temperature, the higher the conversion. But in theory, the graph should
be the higher the temperature, the higher the conversion. The reason why the result not equal to
the theory because might have some error when reading the conductivity meter. The conductivity
meter that being used to measure the conductivity value was corrupted after the result of
temperature 40 C were taken. So, the next conductivity for temperature 50 C and 60 C were
read by another conductivity meter.

31
4.2.3 Second Order Reaction

Graph of 1/CA (M-1) against reaction time, t (min) at 40c

300

250

200
f(x) = 3.9x + 83.42
R = 0.98
150
1\CA (M-1)
100

50

0
0 10 20 30 40 50

Reaction time, t (min)

1
Fig. 4.3 Graph of C A versus reaction time ,t at 40 c

For figure 4.3, it showed that as the time went by, the concentration of the solution increased and almost reach constant rate at
25 minutes but then there was a slight increases of value at 30 minutes. Then, the value was finally constant at the time between 35-40
minutes which was 69M

32
 Graph of 1/CA (M-1) against reaction time, t (min) at 50c
300

250

200

1/CA (M-1) 150

f(x) = 1.38x + 93.3
100 R = 0.97

50

0
0 10 20 30 40 50

Reaction Time, t (min)

1
Fig. 4.4 Graph of C A versus reaction time ,t at 50 c

33
 Graph of 1/CA (M-1) against reaction time, t (min) at 60c
80

70
f(x) = 2.84x + 51.04
60 R = 0.86

50

1/CA (M-1) 40

30

20

10

0
0 5 10 15 20 25 30

Reaction Time, t (min)

1
Fig. 4.5 Graph of C A versus reaction time, t at 60 c

For figure 4.5, just like the previous graph, the concentration of the solution too was increasing but for the result to achieve
constant rate it only took 15 minutes at 80M. It can be said that when the temperature was lower, the duration of time be taken to reach
constant is slower and the value of the concentration during the constant too was higher compared to the 60C.

34
Next, for second order reaction, the rate law given was calculated to get the value to be use in the graph of 1/ C A against time for

every temperature. The slopes of the entire graph were increasing. But the higher value of 1/ C A for every temperature were

decreasing, which are the value of 1/ C A for temperature 40 C are higher than 50 C and 60 C. In theory, the higher value of 1/

CA for every

35
temperature graph supposed increasing. It might be some error when preparing the solution,
which is the iodized water are not 0 mS/cm. It is because there might have some impurities in the
solution.

OH- ion was the most highly conducive species therefore the conductivities of ethyl acetate,
CH3CO2C2H5 and ethyl alcohol was ignored. Conductivity of the solution was measured by using
the conductivity meter in terms of the specific conductivity, C, which related to NaOH
concentration:

C - C = CA - CA
C0 C CA0 - CA

(Equation 1)

Where:

C = specific conductivity at time t

C0 = specific conductivity at time t = 0
C = specific conductivity at time t =
CA = NaOH concentration at time t
CA0 = NaOH concentration at time t = 0
CA = NaOH concentration at time t =

For the saponification reaction, CA 0 as t , when the reaction was carried out in a
constant volume batch reactor:

CA = NA = C - C = 1 - X
CA0 NAO C0 - C

(Equation 2)

X was the fractional conversion of sodium hydroxide. Equation 2 can also rearranged to

36
 X = C0 C
C0 C

For the second order reaction rate, the fractional conversion was related to the reaction rate
constant k by

X = CAOkt
1-X

(Equation 3)

4.2.4 Arrhenius equation

Table 4.4: Data of 1/T and ln K

Temperature (K) Reaction Rate (min) 1 ln K

T
313.15 19.4870 0.0032 2.97
323.15 6.9161 0.0031 1.93
333.15 2.8389 0.0030 1.04

37
 Graph of ln K against 1/T (K-1)
0

0
f(x) = - 0x + 0
0 R = 1

0
ln K
0

0
2.9699999999999998 1.9300000000000053 1.04

Fig. 4.6 Graph of ln K against 1/T

Next, based on graph 4.5 was being plotted so that to get the Activation Energy and Arrhenius
constant value by calculating the slope and intercept value using the equation. The value
activation Energy, Ea calculated was 3-424.305 kJ/mol.K for the Arrhenius constant.

The saponification reactions activation energy can be calculated from this equation which is:

Ea
K (T) = A e
RT

Ea
ln K = ln A - RT

It can be related with the slope and intercept obtained from the graph where

Y= -0.0001X + 0.0033

To find A,

ln A = 0.0033

38
 1 3 1
A = 1.00331 mol m s

To find Ea , (R = 8.134 J/mol.K)

Ea
- R = - 0.0001

Ea = 8.134 J/mol.K

Lastly, the ln k against 1/T graph was plotted by value that gets from Arrhenius equation.
The slope is decreasing but the final result for activation energy was very smaller. There might
be some error have some error due to the spillage when pouring the solution into the

reactor. Thus, some new NaOH were prepared for 60 C reading. This action somehow will
interrupt the original result. Plus, there may have some error when take the sample at 0 second
for temperature 40 C because the solution in the reactor might not reach the exact amount of
temperature.

The reaction rate constant k was not truly constant, but merely independent of the
concentrations of the species involved in the reaction. The quantity k was referred as specific
reaction rate (constant). It was strongly dependent on the temperature. Based on the theory,
different temperature gave different value of k. For instance, the k value at 40C was 0.0075 and
at temperature 600C, the k was 0.0067. In addition, the reaction rate constant, k that was
calculated showed that at temperature of 60oC the reaction rate constant was lower than at 40oC.
The speed of the reaction was represented in the reaction rate constant that occurred in a process,
this concludes that at 40oC the reaction rate was much faster than 60oC. (Reaction Engineering,
2015) The temperature dependence of the specific reaction rate, k A, could be correlated by an
Arrhenius equation:

k(T) = Ae-E/RT

(Equation 4)

Where;

39
A = pre exponential factor or frequency factor

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

R = gas constant = 8.314 J/mol

T = absolute temperature, K

In this experiment, the temperature independent term was:

k = Ae-E/RT

(Equation 5)

The Arrhenius equation was obtained for the saponification and oxidation reactions.
These results show a good agreement with those found by other investigators (Ortiz et al., 1989;
Cohen and Spencer, 1962). The two reactions show a very different reaction rate and thermal
behaviour.

Based on the theory, if the temperature increase then the reaction rate will also increase
since the collision between the reacting molecules had increased. However, the data obtained
was the opposite with the theory which is Tolmans interpretation of activation. The activation
energy was determined through experiment by carrying out the reaction at 400C and 600C.

Taking natural logarithm of: k (T) = Ae-E/RT

We obtained: ln k (T) = ln A E/R (1/T)

(Equation 6)

Thus, a plot of ln k (T) vs. 1/T was a straight line. The slope was proportional to the activation
energy. Hence, from the theory, the result (table 4.3) was straight line and the slope was
proportional to the activation energy. The equation gaves the basis information to determine Ea.
A graph of ln k vs. 1/T (figure 4.3), the equation was 4.7267x + 4.5611 and reactants have a
negative slope because they were used for the reaction. So, the saponification reaction activation
energy, E and Arrhenius constant, A from the slope and intercept value using the Arrhenius

40
equation. From the equation y = mx + c, showed m was the slope and c as the y-intercept
value. So, Ea/RT was represented by m while A was represented by c that was calculated in
the appendix.

The activation energy that was calculated at 60C was 17.7287 KJ/mol whereas at 40oC
the activation energy was 16.6644 KJ/mol. This showed that at 40oC less activation energy was
required than at 60oC. When the activation energy required was low, the reaction will be easy to
happen. This explained even at higher temperature the reaction rate will still be low. When two
chemicals were added, their molecules will collide with each other sufficiently energy for the
reaction to take place. This was the collision theory. The two molecules will react if they have
enough energy. So, when heating the mixture, the energy level of the molecules will increase.
From kinetic theory, by increasing temperature means the molecules will move faster. The
method that was used in this experiment was called integral method. The reaction order was
determined by first, guessing the reaction order and integrate the differential equation used to
model the batch reactor. If the order we assumed was correct, then the plot of a certain
concentration against time should result to a straight line.

Based on the experiment conducted, there was some problem encountered during the experiment.
It was very hard to stabilize the temperature of the reactor constantly throughout the experiment.
The reading of the temperature was not stable where it was not the same throughout the
experiment. The conductivity meter must be calibrated before use to obtain good result and
reproducible data with the conductivity meter. To minimize the error, it was best to calibrate the
cell using a standard solution with a conductivity within the range.

In conclusion, the graph of this experiment is not follow the theory of this experiment and need
so many recommendations to do to get the correct result based on the theory.

41
 CHAPTER 5

CONCLUSION AND RECOMMENDATION

5.1 Conclusions

Figure shows the graph of conversion, X (%) against time, t (min). By referring to the
graph, it shows that conversion decreases as temperature increases. Theoretically, the graph will
show as temperature increases, the conversion increases. This error may occur because
conductivity meter were change for 50 C and 60 C. The graph also shows that the highest

conversion value occurs at 40 C which is 94.8%. Next, when graph 1/ C A against time for

every temperature were plotted, the slope of the graph is increasing but the higher value of 1/

CA is decreasing. At 40 C, the slopes were higher compared to 50 C and 60 C.

Theoretically, higher value of 1/ C A were supposed to increase as temperature increase. Next,

the ln k against 1/T graph was plotted. From the graph, it shows that the slope is decreasing but
the activation energy was very small. This experiment was conducted to determine the effect of
temperature in the reaction kinetics of the saponification process. Based on the results, it showed
that, at both 40oC and 60oC the conversion of the reactant was increasing. When compared both
of the data obtained from the experiment showed that temperature at 40oC has higher conversion
than 60oC. This proved that the reaction that occurred at 40C was higher than 60 oC. This fact
was supported by the conductivity measurement. The conductivity at 40C was lower than the
conductivity that was measured at temperature 60 oC throughout the experiment. Based on the
theory, the conductivity of a reaction will be higher when there was more reactant available in
the solution. This could only mean one thing that the reactant reacted much faster at 40oC than at
temperature 60oC. This is supported by the conversion data that have calculated. (Reactor, 2013)

42
5.2 Recommendations

As the recommendation, in order to obtain more accurate and desirable result and
data of this experiment in the future, when the reading of conversion is taken using conductivity
meter, parallax error might occur where the reading was obtained from other conductivity meter
for each reading which it may disrupt the readings of tabulated data and the graphs. Next, the
ionized water may not be so pure. Some impurities may not replenish completely which it may
cause an error and affect our solution. Besides, in order to obtain more accurate and precise data,
the experiment should be run at least three times and use the average value for calculation and
the value of calculation of data should be at least in 4 decimal places. This is to ensure the
average value obtained and data that being calculated is more precise and accurate. Other than
that, when filling in the vessel with solution, some solution might spill and the volume input may
not be the volume that we needed. So, a new solution must be prepared and it will also affect the
result and cause some problem. Lastly, during the first experiment, at 40 C, the temperature may
not be accurately 40 C as the reactor has just being turned on, hence an error will occurs.

43
 REFERENCES

amrita.olabs.edu.in. (2013). Saponification-The process of Making Soap. Retrieved from:

http://amrita.olabs.edu.in/?sub=73&brch=3&sim=119&cnt=1

Badger, W.L., and Banchero, J.T. Introduction to Chemical Engineering. McGraw-Hil Book

Company, New York. (1955)

Earle, R.L. Unit Operations in Food Processing. Oxford: Pergamon Press, Inc. (1966)

Grace, H.P. Chemical Engineering Progress, John Wiley & Sons. (1956)

Fioravanti, K. (2011). Personal Care Truth. A closer look at sodium hydroxide. Retrieved from

http://personalcaretruth.com/2011/04/a-closer-look-at-sodium-hydroxide/

Hoegger Supply Company. (2011) Saponification: Explained. Retrieved from:

https://hoeggerfarmyard.com/the-farmyard/soap-making-2/saponification-explained/

Kelly Y. T. L. (2016). The Batch Saponification of Ethyl Acetate. Rate laws and stoichiometric.

Reaction Engineering. UniKL MICET.

Kelly, Y. T. L. (2016). Effect of Temperature on the Batch Saponification Reaction (Experiment

1) manual. Reaction Engineering Lab Manual. UniKL MICET.

NaOH or KOH purity check. (2016). Classic Bells. Retrieved from

http://classicbells.com/soap/purityCheck.html

Perry, R.H and Chilton, C.H. Chemical Engineers Handbook, 5th ed. McGraw-Hill Book

Company, New York. (1973)

Reid, D. (2016). Saponification: Definition, Process & Reaction. Retrieved from:

1
 http://study.com/academy/lesson/saponification-definition-process-reaction.html

Wikipedia. (2002). Sodium hydroxide. Retrieved from

https://en.wikipedia.org/wiki/Sodium_hydroxide

APPENDICES

Appendix A: Sample Calculation

The saponification reactions activation energy can be calculated from this equation which is:

Ea
K (T) = A e
RT

Ea
ln K = ln A - RT

It can be related with the slope and intercept obtained from the graph where

Y= -0.0001X + 0.0033

To find A,

ln A = 0.0033

1 3 1
A = 1.00331 mol m s

To find Ea , (R = 8.134 J/mol.K)

Ea
- R = - 0.0001

Ea = 8.134 J/mol.K

2
3