Abstract

The conduction of this experiment is based on a few targets, namely to carry out
saponification reaction between Sodium Hydroxide, NaOH and Ethyl Acetate, Et(AC), to
determine the effect of residence time to the reaction's extent of conversion and lastly to evaluate
the reaction rate constant of this particular saponification reaction. To achieve these targets, an
experiment is finely designed so much so that these targets can be finely met. Such experiment
involves using a unit called SOLTEQ Plug Flow Reactor (Model: BP 101), commonly known as
PFR, as well as some common laboratory apparatus for titration process. To put it simply, the
two solutions Sodium Hydroxide, NaOH and Ethyl Acetate, Et(Ac) were reacted in the PFR and
the product is then analysed by the method of titration to determine how well did the reaction go.
Hence, the experiment was conducted and the results shows that the amount of conversion of
Sodium Hydroxide, NaOH is almost unchanged as residence time increases. Further details can
be obtained in the results and discussion sections.

2.0 INTRODUCTION

Reactors are used in the chemical industry for millions of processes. There are many
different types of reactors due to the numerous different factors that can control the formation of
product during the reaction. Plug flow reactors are an idealized scenario where there is no mixing
involved in the reactor. It is the opposite of the continuous-stirred tank reactor (CSTR), where
the reaction mixture is perfectly mixed. The plug flow reactor has an inlet flow composed of the
reactants. The reactant flows into the reactor and is then converted into the product by a certain
chemical reaction. The product flows out of the reactor through the outlet flow. In many
scenarios, a catalyst is involved in the reaction. A catalyst is a substance that is not involved in
the chemical reaction but helps the reaction proceed at a faster rate. In biological reactions, an
enzyme, which is a biological catalyst, coats the wall, and substrate is imported through the inlet
flow.
The Plug Flow Reactor (PFR) is an ideal flow reactor model in which plugs of fluid
are assumed to move from the inlet to the outlet with no mixing or diffusion along the flow path.
In an ideal PFR, a pulse of tracer injected at the inlet would not undergo any dispersion as it
passed through the reactor and would appear as a pulse at the outlet. The degree of dispersion
that occurs in a real reactor can be assessed by following the concentration of tracer versus time
at the exit. This procedure is called the stimulus-response technique. The nature of the tracer
peak gives an indication of the non-ideality that would be characteristic of the reactor under
study.
This equipment is designed to allow the study of the study of reaction rate constant and
the effect of residence time on the conversion in a PFR. Residence time distributions are
measured by introducing a non-reactive tracer into the system at the inlet. The concentration of
the solution is changed according to a known function and the response is found by measuring
the concentration of the solution at the outlet. The residence time distribution(RTD) of a
chemical reactor is a probability distribution function that describes the amount of time a fluid
element could spend inside the reactor.

3.0 OBJECTIVES

3.1 To carry out a saponification reaction between NaOH and Et(Ac) in a plug flow reactor.
3.2 To determine the reaction rate constant.
3.3 To determine the effect of residence time on the conversion in a plug flow reactor.

4.0 THEORY

4.1 Rate of Reaction and Rate Law

Simply put, rate of reaction can be roughly defined as the rate of disappearance of
reactants or the rate of formation of products. When a chemical reaction is said to occur, a
reactant(or several) diminishes and a product(or several) produced. This is what constitutes a
chemical reaction. For example :

aA+bB cC+dD

where A and B represent reactants while C and D represent products. In this reaction, A and B is
being diminished and C and D is being produced. Rate of reaction, concerns itself with how fast
the reactants diminish or how fast the product is formed. Rate of reaction of each species
corresponds respectively to their stoichiometric coefficient. As such :

r A r B r C r D
= = =
a b c d

The negative sign indicates reactants.

A usual equation for rA is :

r A=kC A C B
where
k - rate constant
CA - concentration of A species
CB - concentration of B species
- stoichiometric coefficient of A
- stoichiometric coefficient of B

4.2 Conversion
Taking species A as the basis, the reaction expression can be divided through the
stoichiometric coefficient of species A, hence the reaction expression can be arranged as follows;

b c d
A+ B+ C + D
a a a
Conversion is an improved way of quantifying exactly how far has the reaction moved, or
how many moles of products are formed for every mole of A has consumed. Conversion X A is
the number of moles of A that have reacted per mole of A fed to the system. As seen below;

X A=

molesof Areacted
moles of A fed

4.3

Plug Flow Reactor

This reactor is also known as tubular flow reactor which is usually used in industry
complementary to CSTR. It consists of a cylindrical pipe and is usually operated at steady state.
For analytical purposes, the flow in the system is considered to be highly turbulent and may be
modeled by that of a plug flow. Therefore, there is no radial variation in concentration along the
pipe.
In a plug flow reactor, the feed enters at one end of a cylindrical tube and the product
stream leaves at the other end. The long tube and the lack of provision for stirring prevent
complete mixing of the fluid in the tube. Hence the properties of the flowing stream will vary
from one point to another.
In an ideal tubular flow reactor, which is called plug flow reactor, specific assumptions
are made regarding the extent of mixing;
4.3.1
4.3.2
4.3.3

No mixing in the axial direction

Complete mixing in the radial direction
Uniform velocity profile across the radius.

Tubular reactors are one type of flow reactors. It has continuous inflow and outflow of
materials. In the tubular reactor, the feed enters at one end of a cylindrical tube and the product
stream leaves at the other end. The long tube and the lack stirring prevent complete mixing of the
fluid in the tube.

4.4 Residence Time Distribution Function

Residence Time Distribution is a characteristic of the mixing that occurs in the chemical
reactor. There is no axial mixing in a plug flow reactor, PFR and this omission can be seen in the
Residence Time Distribution, RTD which is exhibited by this class of reactors. The continuous

stirred tank reactor CSTR is thoroughly mixed and its RTD is hugely different as compared to
the RTD of PFR.

5.0 APPARATUS

The unit used in this experiment is SOLTEQ Plug Flow Reactor (Model: BP101)

Fig. 5.1 : SOLTEQ Plug Flow Reactor (Model: BP101)

Plug Flow Reactor (Model: BP101) is used as it has been properly designed for students'
experiment on chemical reactions in liquid phase under isothermal and adiabatic conditions.

Included in the unit is a jacketed plug flow reactor; individual reactant feed tanks and pumps,
temperature sensors and conductivity measuring sensor.
Apart from that, there were also some laboratory apparatus involved such as :
5.1 Burette
5.2 Conical flask
5.3 Measuring cylinder
5.4 ph indicator
5.5 Beakers
Among the chemicals used are :
5.6 0.1 M Sodium Hydroxide, NaOH
5.7 0.1 M Ethyl Acetate, Et(Ac)
5.8 0.1 M Hydrochloric Acid, HCl
5.9 De-ionised water

6.0 PROCEDURES

6.1 General Startup Procedures

6.1.1

All the valves are ensured closed except V4, V8 and V17.

6.1.2

The following solutions are prepared:

i.

20 liter of NaOH (0.1M)

ii.

20 liter of Et(Ac) (0.1M)

iii.

1 liter of HCL (0.25M) for quenching

6.1.3

Feed tank B1 was filled with NaOH while feed tank B2 was filled with
the Et(Ac).

6.1.4

The water jacket B4 was filled with water and pre-heater B5 was filled
with clean water.

6.1.5

The power for the control panel was turned on.

6.1.6

Valves V2, V4, V6, V8, V9 and V11 were opened.

6.1.7

Both pumps P1 and P2 were switched on. P1 and P2 were adjusted to

obtained flow rate approximately 300mL/min at both flow meters Fl01 and Fl-02. Both flow rates were made sure to be equal.

6.1.8

Both solutions then were allowed to flow through the reactor R1 and
overflow into waste tank B3.

6.1.9

Valves V13 and V18 was opened. Pump P3 then was switched on in
order to circulate the water through pre-heater B5. The stirrer motor
M1 was switched on and set up to speed about 200 rpm to ensure
homogeneous water jacket temperature.

6.2 Experiment Procedures

6.2.1

The general starts up procedures were performed.

6.2.2

Valves V9 and V11 were opened.

6.2.3

Both the NaOH and Et(Ac) solutions were allowed to enter the plug
reactor R1 and empty into the waste tank B3.

6.2.4

P1 and P2 were adjusted to give a constant flow rate of about 300

ml/min at flow meters FI-01 and FI-02. Both flow rates were ensured
same. The flow rates were recorded.

6.2.5

The inlet (QI-01) and outlet (QI-02) were started to monitor the
conductivity values until they do not change over time. This is to
ensure that the reactor has reached steady state.

6.2.6

Both inlet and outlet steady state conductivity values were recorded.
The concentration of NaOH exiting the reactor and extent of
conversion from the calibration curve.

6.2.7

Optional. Sampling was opened from valve V15 and 50ml of sample
was collected. A back titration procedure was carried out manually to
determine the concentration of NaOH in the reactor and extent of
conversion.

6.2.8

The experiment was repeated from step 4 to 7 for different residence

times by reducing the feed flow rates of NaOH and Et(Ac) to about
250,200,150,100 and 50 ml/min. Both flow rates were made sure to be
equal.

6.3 Back Titration Procedures

6.3.1

The burette was filled up with 0.1 M NaOH solution.

6.3.2

10 mL of 0.25 M HCl was poured in a flask.

6.3.3

50 mL samples that were collected from the experiment at every

controlled flow rate (300, 250, 200, 150, 100 and 50 mL/min) were
added into the 10mL HCl to quench the saponification reaction.

6.3.4

3 drops of phenolphthalein were dropped into the mixture of sample

and HCl.

6.3.5

The mixture then was titrated with NaOH until it turns light pink.

6.3.6

The amount of NaOH titrated was recorded.

7.0 RESULTS

Conversion

Solution mixtures

Concentration Conductivity
of NaOH (M) (mS/cm)

0.1 m NaOH

0.1 m Na(Ac)

H2O

0%

100 mL

100 mL

0.0500

10.7

25 %

75 mL

25 mL

100 mL

0.0375

9.7

50 %

50 mL

50 mL

100 mL

0.0250

7.5

75 %

25 mL

75 mL

100 mL

0.0125

5.6

100 %

100 mL

100 mL

0.0000

4.0

Table 7.1: Table for Preparation of Calibration Curve

Volume of reactor = 4 L
Concentration of NaOH in feed tank = 0.1 M
Concentration of ethyl acetate, Et(Ac) in feed tank = 0.1 M
Volume of 0.25 M HCL = 10 mL

Flow

Flow

Total

Volu

flow

Outlet

me of

rate of

Conductiv

NaO

solutio

ity

Reaction

Rate

Rate

of

of

o.

NaOH

Et(Ac)

(ml/mi

(ml/mi

n)

n)

306

304

610

9.7

0.3

6.5574

50.6

1.5365

254

259

513

8.4

0.2

7.7973

50.4

1.3032

202

205

407

7.4

0.1

9.8280

50.2

1.0257

152

154

306

6.4

0.1

50.2

0.7711

101

104

205

5.5

0.2

50.4

0.5208

51

53

104

4.7

0.2

50.4

0.2642

ns, Vo
(nL/mi

titrate
Q2

n)

Reside
nce
time, t
(min)

Conversi
on, X
(%)

13.071
9
19.512
2
38.461
5

Table 7.2 : Data and Calculation from the Experiment

8.1 Residence Time

For the data no. 1 in the Table 7.2

constant,
K
(L/mol.
min)

(mL)

8.0 SAMPLE CALCULATIONS

rate

Rate of
reaction,
-rA
(mol/L.
min)

3.7496 X
10-3
3.2061 X
10-3
2.5438 X
10-3
1.9124 X
10-3
1.2813 X
10-3
6.4997 X
10-4

Residence Time,

Reactor volume ( L ) ,V
L
Total flow rate
,v
min 0

( )

Total flow rate, Vo = Flow rate of NaOH + Flow rate of Et(Ac)

= 306 mL/min NaOH + 304 mL/min Et(Ac)
= 610 mL/min
= 0.61 L/min
Hence,

Residence Time,

4L
=
0.61 L/min

= 6.5574 min

8.2 Conversion
For the data no.1 in the Table 7.2:
i.

Moles of reacted NaOH, n1

n1 = Concentration NaOH x Volume of NaOH titrated
= 0.1 M x 0.0003 L
= 0.00003 mol

ii.

Moles of unreacted HCl, n2

Moles of unreacted HCl = Moles of reacted NaOH
n2 = n1
n2 = 0.00003 mol

iii.

Volume of unreacted HCl, V1

V1 =

V1 =

n2
concentration HCl quench

0.00003
0.25

= 0.00012 L
iv.

Volume of HCl reacted, V2

V2 = Total volume HCl V1
V2 = 0.01 0.00012
V2 = 0.00988 L

v.

Moles of reacted HCl, n3

n3= Concentration HCl X V2
n3= 0.25 X 0.00988
n3= 0.00247 mol

vi.

Moles of unreacted NaOH, n4

Moles of unreacted NaOH = Moles of unreacted HCl
n4 = n3
n4 = 0.00247 mol

vii.

Concentration of unreacted NaOH

CNaOH unreacted =

n4
volumeof sample

0.00247
0.05

= 0.0494 M
viii.

Xunreacted

Xunreacted =

Concentration of NaOH unreacted

concentration NaOH

Xunreacted =

0.0494
0.1

Xunreacted = 0.494

ix.

Xreacted
Xreacted = 1- Xunreacted

= 1 - 0.494
= 0.506
x.

Conversion for data No. 1 in Table 7.2

0.506 x 100% = 50.6 %

8.3 Reaction Rate Constant,k

k=

v0
X
V TFR C AO 1X

( )

For data no. 1 in Table 7.2;

V0 = Total inlet flow rate
V0 = 0.61 L/min
VTFR = Volume for reactor = 4 L
CAO = inlet concentration of NaOH = 0.1 M
X = 0.506

0.61 0.506
k=
(4)(0.1) 10.506

= 1.5365 L.mol/min

8.4 Rate of Reaction, -rA

-rA = k (CA0)2 (1-X)2
For data no. 1 in Table 7.2 :
-rA = 1.5365 (0.1)2 (1 - 0.506)2
= 3.7496 x 10-3 mol.L/min

9.0 DISCUSSIONS

This experiment was conducted to determine the reaction rate constant and the effect of
residence time on the conversion in a plug flow reactor. The solutions used are NaOH and
Et(Ac). These two solutions react together in the PFR to complete saponification reaction. In this
experiment, residence times have to be manipulated throughout the experiment and the effects of
each one is studied. Residence time is varied by the means of changing the flow rates of the feed
solutions. This is shown by the formula;

Residence Time,

Reactor volume ( L ) ,V
L
Total flow rate
,v
min 0

( )

From the equation above, it can be seen that residence time is a function of total flow rates of the
feed. Hence, by varying the flow rate of the feed solutions, several residence times can be
obtained and the effects of each one, studied.
After the experiment is conducted, raw data consisting inlet flow rates, conductivity value
and volume of NaOH used in the titration process are tabulated in Table 7.1 of the Result
Section. From the raw data obtained, a series of calculations were made, as seen in the Sample of
Calculation section, and the values of residence times, conversion of the reactions, reaction rate
constants and rate of reactions were determined. These values are tabulated in Table 7.2 of the
Result section.
As the data of residence time and conversion from Table 7.2 is plotted into a graph, the
graph is shown in Graph 7.1. The reason for plotting a graph with these two parameters is so that
the effects of residence time can be studied. Conversion is a property that shows how much of
the reaction has taken place. Hence, by comparing this property with the residence time
parameter, one can analyze the effects of increasing residence time to the reaction itself.

By analyzing Graph 7.1, it can be clearly seen that the conversion of the reaction remains
fairly constant with the increasing residence time. Therefore, one can postulate that residence
time is not a factor for reaction conversion, as far as plug flow reactors are concerned. One can
also postulate that the reason for this phenomenon is that the PFR lacks a good mixing process.
Since the PFR is designed not to stir the solution vigorously to maximize mixing process, the
conversion of the reaction by using PFR is fairly low.
However, since the experiment experienced some major errors in the back titration
procedure, the output of the experiment was affected, and was not acceptable. According to the
laboratory technician, the error was mainly come from instrumental errors. There might be
contaminant in the equipments used and this may be caused by improper handling of the
glassware. They might not be cleaned properly after used previously, and hence affect the
outcomes of the experiments that come afterwards.
Therefore, for the sake of learning and understanding, the data used in this report was
based on the data given by the laboratory technician and from the previous successful
experiment.

10.0

CONCLUSION

Saponification process was completed. However, the outcomes of the experiment were
not accurate and discarded. Then, in order to determine the rate constant and the reaction rate, the
previous data of a successful experiment was used. This was for the sake of learning and
understanding.

11.0

RECOMMENDATIONS

11.1
11.2

Wash the glassware properly after used for convenience of the next users.
Time the sample well. This is to reduce, or if possible, to avoid time-wasting in taking

samples.
Monitor the flow rates constantly in order to make it remains constant throughout the

11.3

reaction, as required.
Before conducting the experiment, locate all valves properly and familiarize with their

11.4

locations.
Stop the titration immediately as soon as the indicator turned pink.

11.5

REFERENCES

Fogler, H.S (2006). Elements of Chemical Reaction Engineering (3rd Edition). Prentice Hall.

Levenspiel, O. (1999). Chemical Reaction Engineering (3rd Edition). John Wiley.

Kinetic

Studies

of

the

Saponification

of

Ethyl

Acetate,

Retrieved

from

http://www.researchgate.net/publication/229360677_Kinetic_Studies_on_Saponification_of_Eth
yl_Acetate_Using_an_Innovative_ConductivityMonitoring_Instrument_with_a_Pulsating_Sensor at 10th OCT 2015
Tracer Studies in a Plug Flow reactor, Retrieved from
http://www.egr.msu.edu/~hashsham/courses/ene806/docs/Plug%20Flow%20Reactor.pdf at 10th
OCT 2015

APPENDICES

Conversion (%) VS Residence Time

50.7
50.6
50.5
50.4
50.3
50.2
Conversion (%)

50.1
50

Residence Time, t (min)

Graph 7.1 : Graph of Conversion VS Residence Time

conversion (%)