1.

INTRODUCTION

A tubular reactor is a vessel through which flow is continuous, usually at steady state, and
configured so that conversion of the chemicals and other dependent variables are functions of
position within the reactor rather than of time. Flow in tubular reactors can be laminar, as with
viscous fluids in small-diameter tubes, and greatly deviate from ideal plug-flow behavior, or
turbulent, as with gases. There are tubular flow reactors applications which are:
Large-scale reactions
Fast reactions
Homogeneous or heterogeneous reactions
Continuous production
High-temperature reactions
In an ideal plug flow reactor, 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.
High temperature reactions Residence Time Distribution (RTD) analysis is a very efficient
diagnosis tool that can be used to inspect the malfunction of chemical reactors. Residence time
distributions are measured by introducing a non-reactive tracer into the system at the inlet. The
concentration of the tracer is changed according to a known function and the response is found
by measuring the concentration of the tracer at the outlet. The selected tracer should not modify
the physical characteristics of the fluid and the introduction of the tracer should not modify the
hydrodynamic conditions. In general, the change in tracer concentration will either be a pulse or
a step.
The residence time distribution of a real reactor deviated from that of an ideal reactor,
depending on the hydrodynamics within the vessel. A non-zero variance indicates that there is
some dispersion along the path of the fluid, which may be attributed to turbulence, a nonuniform velocity profile, or diffusion. If the mean of the E (t) curve arrives earlier than the

expected time
it indicates that there is stagnant fluid within the vessel. If the residence time
distribution curve shows more than one main peak it may indicate channeling, parallel paths to
the exit, or strong internal circulation.
2.0

OBJECTIVES
1. To study the effects of residence time on a reaction by using a Plug Flow Reactor.
2. To determine the reaction rate constant by saponification reaction between Sodium
Hydroxide, NaOH and Ethyl Acetate, Et(Ac).
1

3.0

THEORY

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 diminishes and a product produced. This is what constitutes a chemical reaction. For
example:
aA + bBcC+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=k C A C B
Where
k - Reaction rate constant
CA - concentration of A species
CB - concentration of B species
- stoichiometric coefficient of A
- stoichiometric coefficient of B
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:
2

X A=

moles of A reacted
moles of A fed

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
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:
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.
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.

4.0

MATERIAL AND APPARATUS

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 :
burette
conical flask
measuring cylinder
ph indicator
Beakers
Among the chemicals used are :
0.1 M Sodium Hydroxide, NaOH
0.1 M Ethyl Acetate, Et(Ac)
0.1 M Hydrochloric Acid, HCl
De-ionised water

5.0

PROCEDURES

General Startup Procedures

1. All the valves are ensured closed except V4, V8 and V17.
2. The following solutions are prepared: 20 liter of NaOH (0.1M)20 liter of Et(Ac) (0.1M)1
liter of HCL (0.25M) for quenching.
3. Feed tank B1 was filled with NaOH while feed tank B2 was filled with the Et(Ac).
4. The water jacket B4 was filled with water and pre-heater B5 was filled with clean water.
5. The power for the control panel was turned on.
6. Valves V2, V4, V6, V8, V9 and V11 were opened.
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 Fl-01 and Fl-02. Both flow rates were
made sure to be equal.
8. Both solutions then were allowed to flow through the reactor R1 and overflow into waste
tank B3.
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
about200 rpm to ensure homogeneous water jacket temperature.
Experiment Procedures
1. The general starts up procedures were performed.
2. Valves V9 and V11 were opened.
3. Both the NaOH and Et (Ac) solutions were allowed to enter the plug reactor R1 and
empty into the waste tank B3.
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.
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. 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.
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.
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.

Back Titration Procedures

1. The burette was filled up with 0.1 M NaOH solution.
2. 10 mL of 0.25 M HCl was poured in a flask.
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.
4. 3 drops of phenolphthalein were dropped into the mixture of sample and HCl.
5. The mixture then was titrated with NaOH until it turns light pink.
6. The amount of NaOH titrated was recorded.

6.0

RESULTS

Calibration Curve
Conversion

0%
25 %
50 %
75 %
100 %

Solution Mixture
0.1 M NaOH
100 mL
75 mL
50 mL
25 mL
-

Flowrate of NaOH
and Et(Ac) (mL/min)
300
250
200
250
100
50

Residence Time,

0.1 M Et(Ac)
25 mL
50 mL
75 mL
100 mL

Conductivity
(ms/cm)

0.0500
0.0375
0.0250
0.0125
0.0000

7.660
5.400
2.900
1.300
0.157

Water
100 mL
100 mL
100 mL
100 mL
100 mL

Conductivity
Q1
8.2
8.5
8.7
7.7
7.3
6.2

Q2
6.9
7.0
7.1
6.0
5.4
4.7

Conversion, X (%)

Reaction rate
constant, k
(L.mol/min)
3.567
2.945
2.333
1.750
1.178
0.589

(min)
6.67
8.00
10.00
13.33
20.00
40.00

Concentration
of NaOH (M)

70.4
70.2
70.0
70.0
70.2
70.2

Volume of NaOH
(mL)
10.2
8.5
8.7
9.5
12.0
11.5
Rate of Reaction, -rA
(mol.L/min)
3.125 x 10-3
2.615 x 10-3
2.0997 x 10-3
1.575 x 10-3
1.046 x 10-3
5.230 x 10-4

70.5
70.4
70.3
70.2

Conversion, X (%)

70.1
70
69.9
69.8
69.7
5

10

15

20

25

30

35

40

45

Residence Time, (min)

7.0

SAMPLE CALCULATION

Residence time
=

reactor volume ,liter (V )

total flow rate , L/min(V 0 )

Total flow rate, V0 = flow rate of NaOH + flow rate of Et(Ac)

= 300 ml/min NaOH + 300 ml/min of Et(Ac)
= 600 ml/min
= 0.6 L/min
4L
=
=6.6667 min
0.6 L/min
Conversion
Moles of NaOH reacted, n1
n1 = concentration of NaOH x volume of NaOH titrated
= 0.1M x 0.0102 L
= 0.00102 mol
Moles of unreacted HCl, n2
Moles of unreacted of HCl = moles of reacted NaOH
n1 = n2 = 0.00102 mol
Volume of unreacted HCl, V1
n2
0.00102mol
V 1=
V 1=
0.25 mol / L
concentration HCl quenc h
V 1=0.00408 L
Volume of HCl reacted, V2
V2 = total volume of HCl V1
= 0.01 L 0.00408 L
= 0.00592 L
Moles of reacted HCl, n3
n3 = concentration HCl x V2
= 0.25 mol/L x 0.00592 L
= 0.00148 mol
Moles of unreacted NaOH, n4
n4 = n3 = 0.00148 mol
Concentration of unreacted NaOH

10

C NaOH unreacted =

n4
volume sample

C NaOH unreacted =

0.00148 mol
0.05 L

C NaOH unreacted =0.0296 M

Xunreacted
X unreacted =

X unreacted =

concentration of NaOH unreacted

concentrationof NaOH

0.0296 mol/ L
0.1 mol/ L

X unreacted =0.296

Xreacted
Xreacted
= 1 - Xunreacted
= 1 - 0.296
= 0.704
Conversion for flow rate 300 ml/min,
0.704 x 100% = 70.4%

Reaction Rate Constant, k

k=

k=

0.6 L/min
0.1 mol
4L
L

k =3.567

V0
X
V TFR C A 0 1X

Flow rate
V0
VTFR
CA0
X
0.704
10.704

= 300 ml/min
= total inlet flow rate = 0.6 L/min
= volume for reactor = 4 L
= inlet concentration of NaOH = 0.1M
= 0.704

L
. mol
min

Rate of Reaction, -rA

11

r A=k (C A 0)2 (1X )2

r A=0.003125

r A=

3.567 L
. mol( 0.1mol / L)2 (10.704)2
min

mol
.L
min

12

8.0

DISCUSSION

Plug Flow Reactor (PFR) is a type of reactor that consists of a cylindrical pipe and is usually
operated at steady state. 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. The fluid in PFR is considered to be thin, unmixed
layer of volume segments or 'plugs', hence the name.
As seen in figure 2, the solution in the tube is treated as a series of layers of volume segments
that are unmixed with the segment before and after it. Like a series of plugs, stacked together in a
pipe. In this particular experiment, the solutions used are NaOH and Et(Ac). These two solutions
react together in the PFR to complete saponification reaction. The main objective of
this particular experiment is to study the effect of residence time on the performance of this
reactor, the PFR. To do that, of course, residence times have to be manipulated throughout the
experiment and the effects of each one is studied. Residence time, in this particular experiment,
is varied by the means of changing the flow rates of the feed solutions. This is shown by the
formula:
Residence time
reactor volume ,liter (V )
= total flow rate , L/ min(V 0 )

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 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 the Result section.
As the data of residence time and conversion is plotted into a graph. The reason for plotting a
graph consisting 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 the graph and tabulated data, it can
be clearly seen that the conversion of the reaction remains fairly constant with the increasing
residence time.

13

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.
The experiment also aims to evaluate the reaction rate constants and rate of reaction values
of the reaction. Both of these properties have been determined in the result section.

14

9.0

CONCLUSION

The experiment was conducted with several objectives in mind. The first one is to carry out a
saponification process between Sodium Hydroxide, NaOH and Ethyl Acetate, Et (Ac). By using
a Plug Flow Reactor, PFR, these two substances were flowed into the reactor, mixed and let to
react for a certain period of time. By doing that, saponification process was completed. The
experiment also targets to determine the reaction rate of this particular reaction. This was also
done by calculating the reaction rate as seen in the Sample Calculation section. Lastly, the main
objective of this experiment is to study the relationship between the residence time and the
conversion of the reactants. This relationship was successfully studied and graphed in the Result
section.
10.0

RECOMMENDATIONS

1. It is better to time the sample well so that time-wasting in taking samples can be reduced
or, if possible, avoided.
2. All valves should be properly placed before the experiment started.
3. Flow rates should be constantly monitored so that it remains constant throughout the
reaction, as needed.
4. Titration should be immediately stopped when the indicator turned pink.
5. Pumps should never be run dry.
11.0

REFERENCES

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

PrenticeHall.
2. Levenspiel, O. (1999). Chemical Reaction Engineering (3rd Edition). John Wiley.
3. The Plug Flow (Retrieved from http://www.konferenslund.se/p/L16.pdf on 18th
October 2013)
4. Reaction Kinetics (Retrieved from http://smk3ae.files.wordpress.com/2007/10/reaksikinetik.pdf on the 18th October 2013)
12.0

APPENDICES

15