ABSTRACT

This experiment is conducted to carry out manual conversion determination on

experiment samples to verify the conductivity measurement values, to carry out a

saponification reaction between NaOH and Et(Ac) in CSTR and determine the effect of

residence time onto the reaction extent of conversion also determine the reaction rate constant

.In order to accomplish the objective, the unit being used to perform this experiment is CSTR

40L. The design of the reactor is very important to the success of the production. In this

experiment sodium hydroxide and ethyl acetate react in continuous stirred tank reactor. Both

of reactants feed to the reactor at equimolar flow rate for a certain time. From Graph 1 it

show that conductivity is decrease proportionally with conversion. The result show that,

when residence time is increase, conversion also increase by lowering the flow rate. The

higher conversion is 92.4% at 200 min residence time and 0.2 mL/min total flow rate of

solution. It can be conclude that the higher the flow rate, the smaller the reaction rate constant

and rate of reaction become highest. From the calculation, it was obtained that the value of

conversion is increase when the volumetric flow rate decrease. This prove the theory from

calibration curve. The entire objectives have been achieved and related to the theory of study

.Therefore the experiment is success.

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INTRODUCTION

Reactions are usually the main important part in chemical processes in which
relatively cheap raw materials are converted to more economically favourable products. In
other words, reactions play necessary safety and environmental protection roles. Proper
design and operation of the reactor is needed in order to provide the desired outcome. Such
design is usually depend on chemical kinetics, thermodynamics and transport studies
combined with experience and economic considerations.

Based on all industrial sector, mostly reactor is the main equipment that are used
where it changes from the raw materials into the desire product that are needed. In chemical
engineering area, chemical reactors are vessels that designed to make chemical reaction
occurs. The design of a chemical reactor deals with multiple conditions of chemical
engineering. The criteria for the good reactor is it produced a high production and also
economical. The design and operation of chemical reactors is thus crucial to the whole
success of the industrial operation.

There are many types of reactor depending on the nature of the feed materials and
products. Understanding non-steady behaviour of process equipment is necessary for the
design and operation of automatic control systems. The rate of reaction is most important
thing will be consider in the reactor because it showed the effectiveness of the processing of
the reactor.

A most typical ideal reactor type in chemical engineering field is the continuous
stirred tank reactor. In a continuous-flow stirred-tank reactor (CSTR), reactants and products
are continuously added and withdrawn from the reactor. In practice, mechanical or hydraulic
agitation is required to achieve uniform composition and temperature, a choice strongly
influenced by process considerations. The CSTR is 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

A stirred tank reactor (STR) may be operated either as a batch reactor or as a steady state flow
reactor (CSTR). The key or main feature of this reactor is that mixing is complete so that properties
such as temperature and concentration of the reaction mixture are uniform in all parts of the vessel.

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AIMS/OBJECTIVES

1) To carry out a saponification reaction between sodium hydroxide (NaOH) and ethyl acetate
Et(Ac).

2) To determine the effect of residence time onto the reaction extent of conversion.

3) To determine the reaction rate constant.

THEORY

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
continuos 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 (Fogler, 2011). 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 + 0V rA dv = dNa/dT

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Assumptions:

For steady state dNA / dt = 0.

Well mixed, therefore rA is the same throughout the reactor.
v v

r dv r dv r v
0
a a
0
a

v ( Fao Fa ) / ra
Rearranging the generation,

x ( Fao Fa ) / Fao
In terms of conversion,

v ( Fao x) / ra

Preparation of Calibration Curve for Conversion vs Conductivity

A calibration curve is a 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 a second order reaction, the rate of reaction depends on both
concentration of Et (Ac) and NaOH. However for analysis purposes, the reaction will be
carried out using equimolar feeds of Et(Ac) and NaOH solutions with the same initial
concentration . This ensures that both concentration 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 0.1M ethyl acetate and 0.1M sodium hydroxide.

Residence Time

The reactor`s residence time is defined as the reactor volume divided by the total feed flow
rated

vCSTR

FO
Residence time,

4
 There are some assumption have been made in order to using residence time equation, in
this experiment to reduce the complexity of the system being modeled. These assumption
include, but are not limited to: steady state in flow and out flow, constant volume constant
temperature and uniform distribution of the substance throughtout the volume of the system.
It also assume that chemical degradation does not occur in the system in question and the
particles do not attach to surfaces that would hinder the flow. If there are chemical
degradation occur in a system, the substances that originally entered the system may react
with other existing compounds and causing the residence time to be significantly shorter
since substance would be chemically consumed and effectively be removed from the system
before it was able to naturally flow out of the system.
(http://en.m.wikipedia.org/wiki/residence_time)

Rate of Equation and Rate Law

The rate of reaction for a 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 .........(eq 1)

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

According to the IUPAC`s Gold Book definition the rate of reaction , r in the chemical
reaction is occur in a closed system which is under a constant volume conditions, without
buildup of reaction intermediates, is defined as :

1 d [ A] 1 d [ B ] 1 d [C ] 1 d [ D]
r
a dt b dt c dt d dt

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

The mass balance for a system in general is:

IN OUT + GENERATION- CONSUMPTION = ACCUMULATION

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

APPARATUS

Equipment Apparatus Solutions

Continuous stirred 50 ml burrete 0.1M Sodium
tank reactor (CSTR): hydroxide, NaOH
Model BP 143
200 ml beaker 0.1M Ethyl acetate,
Et(Ac)
Conical flask Deionised water
100 ml measuring Phenolphthalein
cylinder
Conductivity Probe

Figure 2: CSTR Model BP 143

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EXPERIMENTAL 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 ensure initially closed.

3. The feed vessels were charged as follows:

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

b) The NaOH solution was 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

8. The unit was ready for experiment.

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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. Stirrer M1 was switched off.

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

4. The cooling water valve V13 was closed.

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

6. The power for the control panel was turned off.

Preparation of Calibration Curve for Conversion vs. 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 100ml of deionised water.

a) 0% conversion: 100ml NaOH

b) 25% conversion: 75ml NaOH + 25 ml Et (Ac)

c) 50% conversion: 50ml NaOH + 50ml Et (Ac)

d) 75% conversion: 25ml NaOH + 75ml Et (Ac)

e) 100% conversion: 100ml Et (Ac)

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Back Titration Procedures for Manual Conversion Determination

1. A burette was filled up with 0.1 M NaOH solution

2. 10ml of 0.25 M HCl was measured in a flask

3. A 50ml 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 burrete until the mixture was
neutralized. The amount of NaOH titrated was recorded.

Effect of Residence Time of the Reaction in a CSTR

1. The general start up procedures was performed.

2. Both pumps P1 and P2 were switched on simultaneously and valves V5 and V10 were
opened to obtain the highest 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 valves V5 and V10 were readjusted to give a flow rate of about 0.1L/min. Both flow
rate 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 Ql-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 a 50 ml sample was collected. A back titration
procedure was carry out to determine the concentration of NaOH in the reactor and the
extent of conversion.

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9. The experiment (steps 5 to 9) was repeated 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 L/min. Both flow
rates must be same.

RESULTS

Conversion Solution Mixture Concentratio Conductivity

(%) n of NaOH (mS/cm)

(M)
0.1 M NaOH 0.1 M Et(Ac) H2O (mL)

(mL) (mL)
0 100 - 100 0.0500 10.400

25 75 25 100 0.0375 6.440

50 50 50 100 0.0250 2.000

75 25 75 100 0.0125 1.011

100 - 100 100 0.0000 0.312

Table 1: Preparation of calibration curve

CONVERSION VS CONDUCTIVITY
12

10

8 f(x) = - 0.1x + 9.15

R = 0.89

CONDUCTIVITY (mS/cm) 6

0
0 10 20 30 40 50 60 70 80 90 100

CONVERSION (%)

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 Graph 1: Calibration curve (conductivity vs conversion)

SAMPLE VOLUME OF SODIUM HYDROXIDE, NaOH

(mL)
1 23.1
2 21.1
3 19.4
4 19.0
5 18.6
Table 2: Back titration for manual conversion determination

Reactor volume = 40 L

Concentration of NaOH in feed vessel = 0.10 M

Concentration of Et(Ac) in feed vessel = 0.10 M

No Flow rate Flow rate Total Residence Conductivit Exit Conversion

. of NaOH of Et(Ac) flow rate time, y concentration , X (%)
(mL/min) (mL/min) of (min) (mS/cm) of
solution NaOH,CNaOH
F0 (M)
(mL/min)

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1. 0.10 0.10 0.20 200 2.38 0.00038 92.4
2. 0.15 0.15 0.30 133.33 2.58 0.00760 84.8
3. 0.20 0.20 0.40 100 2.80 0.01120 77.6
4. 0.25 0.25 0.50 80 2.99 0.01200 76.0
5. 0.30 0.30 0.60 66.67 3.13 0.01280 74.4
Table 3: Table of calculated data for Experiment 1

Sample Reaction rate constant, k (M-1min-1) Rate of reaction, -r A

(mol/L.min)
1 15.997 0.000231
2 5.507 0.000318
3 3.012 0.000378
4 3.297 0.000475
5 3.4055 0.000558
-1 -1
Table 4: Reaction rate constant, k (M min ) and rate of reaction, -r A (mol/L.min) obtained
from calculation.

Residence time vs Conversion

100
90
80
70
60
Conversion, X (%) 50
40
30
20
10
0
60 80 100 120 140 160 180 200 220

Residence time, (min)

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 Graph 2: Residence time vs conversion

SAMPLE CALCULATIONS

Known quantities:

Volume of sample, Vs= 50 mL

Concentration of NaOH in the feed vessel, CNaOH,f = 0.1 mol/L

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

Concentration of HCl in standard solution, CHCls= 0.25 mol/L

Volume of titrated NaOH, V1= 23.1 mL

Concentration of NaOH used for titration, CNaOHs= 0.1 mol/L

i. Total flowrates of solution F0 (mL/min)

F0= 0.1+0.1 = 0.2 L/min

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ii. Concentration of NaOH that entering the reactor, CNaOHo.

C NaOHo= C NaOHf

= (0.1)

= 0.05 mol/L

iii. Volume of unreacted quenching HCl, V2

V2= (C NaOHs/ CHCls) x V1

= (0.1/0.25) x 23.1

= 9.24 mL

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

V3= VHCls V2

= 10 9.24

= 0.76

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

n1= (CHCls x V3) / 1000

= 0.25 x 0.76/1000

= 0.00019 mol

vi. Moles of unreacted NaOH in sample, n2

n2= n1

= 0.00019 mol

vii. Concentration of unreacted NaOH in the reactor, CNaOH

C NaOH= n2/Vs x 1000

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 = 0.00019/50 x 1000

= 0.0038 mol/L

Viii. Conversion of NaOH in the reactor, X

X = (1- C NaOH/ C NaOHo) x 100%

= (1 0.0038/0.05) x 100%

= 92.4 %

ix. Residence time,

=VCSTR / Fo

= 40 / 0.20

= 200 min

x. Reaction rate constant, k

k = (CAo CA) / CA2

= (0.05 0.0038) / (200 x 0.0062)

= 15.997 M-1min-1

xi. Rate of reaction, -r A

-r A= kCA2

= 15.997 x 0.00382

= 0.000231 mol/L.min

DISCUSSION

Through this experiment, Continuous Stirred Tank Reactors (CSTR) 40 L (model: BP

143) is used in order to study and investigate about saponification reaction. The objective of
this experiment was to carry out saponification reaction between sodium hydroxide solution,
NaOH and Ethyl Aceteta, Et(Ac). Saponification is a process that soap is produced from fats

15
and lye. From this experiment, the effect of residence time onto the reaction of extent of
conversion and the reaction rate constant also were determined. The CSTR model is used to
give visual on the operation system to student, thus students can strengthen their knowledge
about reactor and reaction. The CSTR model is used to predict the behaviour of chemical
reactors, so the key reactor variables such as the dimensions of the reactor, can be estimated.

The experiment is divided into two parts. First is to prepare a calibration curve for
conversion versus conductivity. All the conductivity for each conversion were recorded and
then graph conversion vs conductivity is plotted. The calibration curve is plotted to determine
the conductivity of the reaction between NaOH and Et(Ac) at certain conversion. From graph
1, it can be concluded that the conductivity is decrease proportionally with conversion. When
then conversion increase, the volume of Naoh to be mixed with Et(Ac) is decreased, the
conductivity also decrease. When both reactant with different moles was used, it will give a
significant difference of conductivity.

For the second part of this experiment, is conducted to investigate the effect of
Residence Time of the Reaction in a CSTR. Residence time is normally related to volumetric
flow rate, thus the experiment is conducted in varies flow rate which is 0.10, 0.15, 0.20, 0.25
and 0.30 L/min. All the calculated data that needed in this part were recorded. From the data,
it found that the volumetric flowrate can affect the residence time, . When the flowrate
increase, the conversion will decrease. Residence time, is time that the fluid elements spend
within reactor. When the flow rate is high, the velocity of fluid moving inside the reactor is
high means the reactant spend less time within the reactor. From graph 2, we can conclude
that conversion is linearly increase with residence time. It can be conclude that the longer the
residence time, the more conversion of the reactant. The higher conversion is 92.4% at higher
residence time which is 200 min.

In this experiment, there are some zero error and parallax error occur while taking the

measurement of each data. When taking the reading, the position of eye must be

perpendicular to the reading scale of burette and measuring cylinder. Besides, we have to

rinse all the apparatus before we use it to ensure that all apparatus is clean so that any

chemical put into it does not react with any others chemicals. And the most important is ,

need to immediately added to the HCl in the flask that contain the sample to quench the

16
saponification reaction also to make sure , the sample does not react with others chemical. By

doing all precautions, we can get better results.

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 the conversion of sodium hydroxide.

CSTR is used in order to achieve the objective of this experiment. By done this experiment,

all purposes are met and the result are collected. From the result it show the conversion is

decrease from 92.4% to 74.4% when the flow rate is increase from 0.20 mL/min to 0.60

mL/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

the entire objectives have been achieved and related to the theory of study.

RECOMMENDATIONS

1. Make sure reactor does not have any leaks and valve closed and opened as needed,
controlled the valve carefully and slowly when adjusting the flow rate to obtain 0.10
L/min. It is to make sure flow rate will stabilize and the experiment will run smoothly.
2. Repeat titrations two or three times because a lot of error comes from titration or use
another method other than titration.
3. Divide into two teams which is the first team in charge of the CSTR 40 liters machine
while the second team would carry out the back titration procedures.
4. Take conductivity reading when the conductivity not changes in time because it can
change rapidly in short of time.
5. Make sure the conical flask used is clean before mixing the solution in order to get
accurate reading of conductivity.
6. Before taking the conductivity reading from the conductivity meter, wipe the
conductivity probe with tissue.

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 7. Take conductivity reading when the conductivity not changes in time because it

change rapidly in short time.

8. Hydrochloric acid for quenching should be prepared early and added to the samples as
soon as possible so that the reaction between NaOH and Et(Ac) cannot proceed
because the NaOH that`s not reacted will neutralized by HCl.

REFERENCES

1. Fogler, Scott H.Elements of Chemical Reaction Engineering, 4th ed. Englewood Cliffs,
NJ: Prentice hall, 2011.

2. Schmidt, Lanny D. The Engineering of Chemical Reactions.

3. Residence time access on 03/10/2016 at http://en.m.wikipedia.org/wiki/residence_time

4. Lab manual, Reaction Engineering Labarotory, Exp/CSTR 40L

5. Chemical reactor from https://en.wikipedia.org/wiki/Chemical_reactor

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APPENDICES

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