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1) ABSTRACT

In chemical engineering, a chemical reactor is used as a container-like to contain chemical


reactions in it. A chemical reactor design deals with multiple aspects of chemical
engineering and chemical reactions. A plug flow reactor (PFR) being one of them,
designed in the area of chemical engineering. The objective of this experiment is to carry
out saponification reaction between sodium hydroxide (NaOH) and ethyl acetate (Et(Ac)),
to determine the reaction rate constant, and to determine the effect of residence time on the
conversion. The experiment is done my first, starting up the general start-up procedure of
the equipment. After the general start-up, both NaOH and Et(Ac) entered the reactor and
sample was taken at different feed flow rates of 300, 250, 200, 150, 100, and 50. The
sample was then immediately taken for titration, following back titration procedure. After
all samples have been taken, general shut-down procedure was done on the equipment.
After the result was obtained, calculations were made and graph of conversion versus
residence time was plotted. The reading of the graph shows that the conversion of NaOH
dropped from residence time of 6.6667 minute to 8.0000 minute. After 8.0000, the
conversion of NaOH all increases from 67.48%, to 69.48%, 80.80%, 84.00%, and 92.40%
for 8.0000 minute, 10.0000 minute, 13.3333 minute, 20.0000 minute, and 40.0000 minute,
respectively. The objectives initially set for this experiment was all obtained successfully.

2) INTRODUCTION

In chemical engineering, a chemical reactor is used as a container-like to contain chemical


reactions in it. A chemical reactor design deals with multiple aspects of chemical
engineering and chemical reactions. The designers will always ensure that the reaction
held in the reactor proceeds with the highest efficiency towards the desired output product,
producing the highest yield of product that required the least amount of money to purchase
and operate (Schmidt and Lanny, 1998).
A plug flow reactor (PFR), 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, namely in both radial and axial directions.

Figure 2.1 Plug flow reactor

Plug flow conditions means that all the material processed through the reactor must have
the same residence time so that the chemicals exiting the reactor have witnessed the same
reaction conditions of reactive species contact-time aging-temperature history.

3) OBJECTIVE
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To carry out saponification reaction between NaOH and Et(Ac).


To determine the reaction rate constant.
To determine the effect of residence time on the conversion.

4) 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

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 it
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=k C A C B
Where:
k

rate constant

CA

concentration of A species

CB

concentration of B species
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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 XA is the number of moles of A that have reacted per mole of A fed to the
system. As seen below:
X A=

moles of A reacted
moles of A fed

4.3 Plug Flow Reactors


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 modelled 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:
1. No mixing in the axial direction
2. Complete mixing in the radial direction
3. A 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) APPARATUS AND MATERIAL

5.1

APPARATUS
1.
2.
3.
4.
5.
6.

SOLTEQ Plug Flow Reactor (Model: BP101)


Burette
Conical flask
Measuring cylinder
pH indicator
Beakers

5.2

MATERIALS
1.
2.
3.
4.

0.1M sodium hydroxide, NaOH


0.1M ethyl acetate, Et(Ac)
0.1M hydrochloric acid, HCl
De-ionised water

6) PROCEDURE

6.1

General Start-Up Procedure


1. All valves are closed except valves V4, V8, and V17.
2. The following solutions are prepared:
20 litre of sodium hydroxide, NaOH (0.1M)
20 litre of ethyl acetate, Et(Ac) (0.1M)
1 litre of hydrochloric acid, HCl (0.25M), for quenching
3. Feed tank B1 is filled with NaOH solution while feed tank B2 is filled with Et(Ac)
4.
5.
6.
7.

solution.
Water jacket B4 and pre-heater B5 was filled with clean water.
The power for the control panel was turned on.
Valves V2, V4, V6, V8, V9, and V11 were opened.
Both pumps P1 and P2 were switched on. P1 an P2 were adjusted to obtained flow
of approximately 200 mL/min at both flow meters F1-01 and F1-02. Both flow

rates are set the same


8. Both solutions were allowed to flow through reactor R1 and overflowed into the
waste tank B3.
9. Valves V13 and V18 were opened. Pump P3 was switched on for water to circulate
through pre-heater B5. Stirrer motor M1 was switched on and the speed is set to
200 rpm to ensure homogenous water jacket temperature.
10. Unit is ready for experiment.

6.2

Experimental procedure
1. General start-up procedure is performed as in Section 6.1.
2. Valves V9 and V11 were opened.
3. Both NaOH and Et(Ac) solution is allowed to enter the plug reactor R1 and was
emptied into the waste tank B3.
4. P1 and P2 were adjusted to give a constant flow of 300 mL/min at flow meters FI01 and FI-02. Both flow rates are made sure to be the same and the flow rates are
recorded.
5. The inlet (QI-01) and outlet (QI-02) conductivity values were monitored until they
do not change over time. This ensures that the reactor has reached steady state.
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 was found.
7. Sampling valve V15 was opened and a 50 mL sample was collected for back
titration procedure.
8. Experiment was repeated from step 4 to step 7 with different residence time by
reducing the feed flow rates of NaOH and Et(Ac) to 250, 200, 150, 100, and 50
mL/min. Both flow rates are made sure the same.

6.3

Preparation of calibration curve for conversion vs. conductivity


1. The following solutions were prepared:
1 litre of sodium hydroxide, NaOH (0.1M)
1 litre of sodium acetate, Na(Ac) (0.1M)
1 litre of deionised water, H2O
2. The conductivity and NaOH concentration was determined for each conversion
values by mixing the following solutions into 100 mL of deionised water.
0% conversion : 100 mL NaOH
25% conversion : 75 mL NaOH + 25 mL Na(Ac)
50% conversion : 50 mL NaOH + 50 mL Na(Ac)
75% conversion : 25 mL NaOH + 75 mL Na(Ac)
100% conversion : 100 mL Na(Ac)

6.4

Back titration procedure


1. A burette is filled with 0.1M NaOH solution.
2. 10 mL of 0.25M HCl was measured in a flask.
3. 50 mL of sample was obtained from step 7 of experiment and was immediately
added to the HCl in the flask to quench saponification reaction.
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4. A few drops of pH indicator were added into the mixture.


5. The mixture was titrated with NaOH solution from the burette until the mixture is
neutralized. The amount of NaOH used was recorded.

6.5

General shut-down procedure


1. Pumps P1, P2, and P3 were switched off. Valves V2 and V6 were closed.
2. The heaters are switched off.
3. The cooling water circulating the reactor is kept while the stirrer motor is running
to allow the water jacket to cool down to room temperature.
4. Power for the control panel is turned off.

7) RESULT AND CALCULATION

7.2

Result of preparation of calibration curve

Conversion

0.1M NaOH
(mL)

0%
25%
50%
75%
100%

Solution Mixtures
0.1M
H2O (mL)
Na(Ac)

Concentratio

Conductivity

n of

(mS/cm)

NaOH(M)

(mL)
100
100
0.0500
75
25
100
0.0375
50
50
100
0.0250
25
75
100
0.0125
100
100
0.0000
Table 7.1 Table of preparation of calibration curve

6.39
4.24
1.397
0.615
0.00191

Conductivity vs Conversion
7
6
f(x) = - 1.64x + 7.45
R = 0.92

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Conductivity vs Conversion
Conductivity (mS/cm) 3

Linear (Conductivity vs Conversion)

2
1
0
0

25

50

100

100

Conversion (%)

Figure 7.1 Graph of conductivity vs conversion


7.2

Result of experiment

Flowrate of

Flowrate of

Total inlet

NaOH

Et(Ac)

flowrate

(mL/min)

(mL/min)

(mL/min)

300
250
200
150
100
50

300
250
200
150
100
50

Vo
600
500
400
300
200
100

Outlet Conductivity
Q1
Q2

Volume of
NaOH titrated
(mL)

7.6
8.0
8.1
7.2
6.5
6.2

6.7
7.0
6.8
5.7
5.0
4.2

23.50
16.87
17.37
20.23
21.03
23.07

Residence time,

Conversion, X,

Reaction rate constant, k

Rate of reaction, -rA

, (min)
6.6667
8.0000
10.0000
13.3333
20.0000
40.0000

(%)
94.00
67.48
69.48
80.80
84.00
92.40

(L.mol/min)
23.5000
2.5938
2.2765
3.1563
2.6250
3.0395

(mol.L/min)
8.460 x 10-4
2.743 x 10-3
2.121 x 10-3
1.164 x 10-3
6.720 x 10-4
1.756 x 10-4

Table 7.2 Effect of residence time on reaction

Conversion vs Residence Time


100
95
90
85
Conversion
vs Residence
f(x) = 1.51x
+ 76.07Time
80 R = 0.06

Linear (Conversion vs Residence Time)

75
70
65
60
6.6666999999999996

10

13.333299999999999

Figure 7.2 Graph of conversion vs residence time

10

20

40

7.3

Sample of calculation
Vol of sample, Vs

: 50 mL

Conc. NaoH in feed vessel, CNaOH,r

: 0.1 mol/L

Vol. HCl quenching, VHCl,s

: 10 mL

Conc. HCl standard soln, CHCl,s

: 0.25 mol/L

Conc. NaOH for titration, CNaOH,s

: 0.1 mol/L

(A) Sample: flowrate

= 300 mL/min of NaOH


300 mL/min of Et(Ac)

(B) Volume of titrating NaOH

= 23.50 mL = 0.02350 L

C NaOH ,std
C HCl ,std

0.1mol / L
0.25mol / L

(C) Volume of quenching HCl unreacted


with NaOH in sample

x (B)

x 0.02350L

= 9.4 x 10-3 L
(D) Volume of HCl reacted with NaOH in = VHCl (C)
sample

= 10 mL 9.4 mL
= 0.6 mL
= 0.6 x 10-4 L

(E) Mole of HCl reacted with NaOH in = CHCl,std x (D)


sample

= 0.25 mol/L x (0.6 x 10-4) L


= 1.5 x 10-5 mol

(F) Mole of NaOH unreacted in sample

= (E)
= 1.5 x 10-5 mol

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s
V

(E)

1.5 10 mol
0.05 L

(G) Concentration of NaOH unreacted with


Ethyl Acetate, CA

= 3 x 10-3 mol/L
(H) Steady state fraction conversion of
NaOH (XA)

CA
1
=
C AO
3 103 mol/ L
= 1 0.05 mol/ L
= 0.94

(I) Concentration of NaOH reacted with = CNaOH,O (G)


= 0.05 mol/L (3 x 10-3) mol/L

Ethyl Acetate

= 0.047 mol/L
(J) Mole of NaOH reacted with Ethyl = (I) x Vs
Acetate in sample

= 0.047 mol/L x 0.05 L


= 2.35 x 10-3 mol

(K) Concentration of Ethyl Acetate reacted


with NaOH

(J )
Vs

2.35 10 mol
0.05 L

= 0.047 mol/L
(L)

Concentration

unreacted, CB

of

Ethyl

Acetate = CEA,O (K)


= 0.1 mol/L 0.047 mol/L
= 0.053 mol/L

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(M) Residence time,

V CSTR
F0

4.0 L
0.6 L /min

= 6.6667 min
For reaction rate constant number 1,
V0 = Total inlet flow rate = 600 mL/min = 0.6 L/min
VTFR = Volume for reactor = 4 L
CAO = Inlet concentration of NaOH = 0.1 M

V0
X
(
)
V TFR C A 0 1X

0.6 L/min
0.94
(
)
(4 L)(0.1 M ) 10.94

(N) Reaction rate constant, k

(O) Rate of reaction, -rA

= 23.5 M.L/min
= k(CA0)2 (1 X)2
= 23.5 (0.1)2 (1 0.94)2
= 0.0141 M.L/min

The calculation steps above were repeated for all data and the graph was plotted.

8) DISCUSSION

In this experiment, two substances have been used in the plug flow reactor which is
sodium hydroxide, NaOH, and ethyl acetate, Et(Ac). The residence time and conversion of
NaOH are calculated and tabulated in table 7.2. For the residence time,

, of 6.6667

min, the conversion of NaOH is 94%. At the 8 th minute of residence time, the conversion
of NaOH dropped to 67.48%. As for the 10.0000 minute of residence time, the conversion
of NaOH increased for 2% from 67.48% at 8.0000 minute to 69.48% at 10 th minute. As the
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residence time increases to 13.3333 min, conversion of NaOH has a sudden increase to
80.80%. The conversion of NaOH was further increased to 84% at the residence time of
20.0000 minute. Lastly, at 40.0000 min of residence time, the final conversion of NaOH
obtained was at 92.40%. All these data was the plotted into graph in figure 7.2 of
conversion versus residence time.
While in titration procedure, when both flowrates are at 300 mL/min, the volume of
NaOH titrated is 23.50 mL. When the flowrates are at 250 mL/min, the volume of NaOH
titrated dropped to 16.87 and later at 200, 150, 100, and 50 mL/min, the volume of NaOH
titrated increases to 17.37, 20.23, 21.03, and 23.07 mL respectively. This follows
accordingly to the theory that whereas concentration is higher at lower flow rate, more
volume of NaOH is used in titration to neutralize the sample.
From the graph 7.2 plotted, initially, it shows a drop of NaOH conversion from
6.6667 minute of residence time to 8.000 minute of residence time. This is being due to
error while performing the experiment. The sample might be exposed to long before
titration is performed on them. As for the rest of the graph chart, the conversion of NaOH
gradually increases with residence time. The data mainly shows that the longer the
residence time, the percentage of conversion increases which abides the expected result
where the longer time left in the reactor, more reaction occurs between NaOH and Et(Ac).

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Figure 8.1 Rate of reaction vs time


The rate of reaction for this reactor shows that it decreases over time. There was a
stable supply of heat, making temperature a constant variable, and no unnecessary heat is
applied onto the system. This makes the particle speed slower as time increases, losing
energy. In the end, the reaction becomes slower until it reaches equilibrium where there are
no more changes in the rate of reaction as shown in figure 8.1 above.

9) CONCLUSION

The objective of this experiment is successfully achieved. Saponification reaction between


NaOH and Et(Ac) was obtained in the reactor. Through the data obtained and certain
calculation, both reaction rate constant and effect of residence time on the conversion was
also known. Furthermore, a graph was also plotted in light of more understanding of the
relation between these two data.

10) RECOMMENDATION

All valves should be properly placed before starting the experiment.


Titration should be done as soon as the sample is taken, to avoid any

contaminations into the sample.


Temperature should also be constantly monitored so that it remains the same

throughout the experiment.


Perform general start-up and shut-down procedure so that the equipment is in the
best shape.

11) REFERENCE
Schmidt, Lanny D., The Engineering of Chemical Reactions. New York: Oxford
University Press, 1998.
Plug

Flow

Reactor

Static

Mixer.

(n.d.).

Retrieved

http://www.stamixco-usa.com/plug-flow-reactors
15

April

19,

2015,

from

12) APPENDIX

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