ABSTRACT

Plug flow reactor is a pipe-shaped tank where a reaction occur within the walls coated
with a catalyst and an inlet flow of pure reactant. This experiment was conducted by using
SOLTEQ Plug Flow Reactor (model: 101). The aims of this experiment are to carry out the
saponification reaction between NaOH and Et(Ac) in plug flow reactor, to determine the
reaction rate constant and the rate of reaction of the saponification process. Besides that 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. The feed of the
tanks are filled with sodium hydroxide, NaOH solution and ethyl acetate, Et(Ac) solutio n.
Switched on the power for the control panel and also both pumps P1 and P2. The pumps are
adjusted to obtained flow rate of 300 mL/min. Always make sure the speed of the stirrer M1 is
about 200 rpm to ensure homogeneous water jacket temperature. The conductivity values are
recorded once they are at steady state. A sample is collected to be used for back titration. The
sample is added with HCL and titrated with NaOH until it turns light pink. The amount of
NaOH titrated is recorded. The procedures are repeated for different flow rates which are 250,
200, 150, 100 and 50 mL/min. After done the experiment, the value of residence time,
conversion, reaction rate constant and rate of reaction is calculated. Then, a graph of conversion
factor against residence time is plotted. From the graph, it can be concluded that the conversion
factor is directly proportional to the residence time. As the residence time increases, the
conversion factor also increases. Further details can be obtained in the results and discussio n
sections.

INTRODUCTION
Reactions are usually the heart of the chemical processes in which relatively cheap raw
materials are converted to more economically favourable products. In other cases, reactions
play essential safety and environmental protection roles. In chemical engineering, chemica l
reactors are defined as vessels that are designed to use for chemical reactions. Also referred to
as a reaction vessel, the reactants contained are substances that change form after a chemica l
reaction. One example is a pressure reactor. The design of a chemical reactor deals with
multiple aspects of chemical engineering. Chemical engineers design reactors to maximize net
present value for the given reaction.
Reactors are used in the chemical industry for millions of processes, from the
production of high-fructose corn syrup (HFCS) to the formation of polyester and everywhere
in between. There are many type of reactor that can be used in a chemical reaction which are
batch reactor, continuous stirred reactor tank (CSTR), plug flow reactor (PFR), semi batch
reactor and catalytic reactor. In this experiment, the focused reactor is plug flow reactor. Plug
flow reactor is a pipe-shaped tank where a reaction occur within the walls coated with a catalyst
and an inlet flow of pure reactant.

Inlet Flow

Outlet Flow

The plug flow reactor model (PFR, sometimes called continuous tubular reactor, CTR,
or piston flow reactors) is a model used to describe chemical reactions in continuous, flowing
systems of cylindrical geometry. 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. It is impossible to have no mixing at
all during a reaction, but the amount of mixing in the reactor can be minimized.
Plug flow reactors are frequently used in the chemical industry due to the non-mixing
property of the reactors. Plug flow reactors are also frequently used in biological reactions
when the substrate are flows into the reactor and converted into a product which an enzyme is
used in the reaction. Since plug flow reactors have an inlet and outlet stream, it is very useful
for continuous production.

PFRs are used to model the chemical transformation of compounds as they are
transported in systems resembling "pipes". The "pipe" can represent a variety of engineered or
natural conduits through which liquids or gases flow. (e.g. rivers, pipelines, regions between
two mountains, etc.)
An ideal plug flow reactor has a fixed residence time: Any fluid (plug) that enters the
reactor at time t, will exit the reactor at time t + , where is the residence time of the reactor.
The residence time distribution function is therefore a dirac delta function at . A real plug flow
reactor has a residence time distribution that is a narrow pulse around the mean residence time
distribution.
A typical plug flow reactor could be a tube packed with some solid material (frequently
a catalyst). Typically these types of reactors are called packed bed reactors or PBR's.
Sometimes the tube will be a tube in a shell and tube heat exchanger.
Plug flow reactors have a high volumetric unit conversion, run for long periods of time
without maintenance, and the heat transfer rate can be optimized by using more, thinner tubes
or fewer, thicker tubes in parallel. Disadvantages of plug flow reactors are that temperatures
are hard to control and can result in undesirable temperature gradients. PFR maintenance is
also more expensive than CSTR maintenance. The applications of plug flow reactor are for
large scale and continuous production, homogeneous or heterogeneous reactions, fast and high
temperature reactions.
. In this experiment, the 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. By using this particular unit, students will be capable to conduct the typical
saponification reaction between ethyl acetate and sodium hydroxide among the others reaction.
AIM
The aims of this experiment are:
1. To carry out the saponification reaction between sodium hydroxide, NaOH and ethyl acetate,
Et(Ac) in tubular flow reactor.
2. To determine the reaction rate constant.
3. To determine the effect of residence time on the conversion in the tubular flow reactor.

THEORY
4.1 Plug Flow Reactors
This reactor 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 var y
from one point to another.
In an ideal tubular flow reactor, which is called plug flow reactor, specific assumptio ns
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.
General Mole Balance Equation
IN - OUT + GENERATION = ACCUMULATION

At steady state-

Differentiating, that gives-

For single reactions in terms of conversion-

The differential form of the PFR mole balance is-

The integral form is-

4.2 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:
+

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:

= = =

The negative sign indicates reactants.

A usual equation for rA is:

=
Where:
k

Rate constant

CA

concentration of species A

CB

concentration of species B

stoichiometric coefficient of A

stoichiometric coefficient of B

4.3 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:

+ +

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:
=

4.4 Residence Time Distribution Function

Residence Time Distribution is a characteristic of the mixing that occurs in the chemica l
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.

APPARATUS/MATERIALS
Equipment

SOLTEQ
Reactor

Apparatus
Plug
(Model:

Flow

Burette

Materials

BP

0.1 M sodium hydroxide,

NaOH solution

101)

Conical flask

0.1 M ethyl Acetate, Et(Ac)

solution

Measuring

cylinder

0.25 M hydrochloric acid,

HCl

Beaker

Phenolphthalein

pH indicator

Deionised water

SOLTEQ Plug Flow Reactor (Model: BP101)

PROCEDURE
General Startup Procedures
1. All the valves are ensured closed except V4, V8 and V17.
2. The following solutions are prepared:
20 liter of sodium hydroxide, NaOH solution (0.1M)
20 liter of ethyl acetate, Et(Ac) solution (0.1M)
1 liter of hydrochloric acid 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 about
200 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 sodium hydroxide, NaOH and ethyl acetate, 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 FI01 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 sodium hydroxide, NaOH and ethyl acetate, 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 sodium hydroxide, NaOH solution.
2. 10 mL of 0.25 M hydrochloric, 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 saponifica tio n
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.
RESULT
Conversion

Solution Mixture

(%)

H2 O (mL)

Concentration

Conductivity

of NaOH (M)

(mS/cm)

0.1 M

0.1 M

NaOH

Et(Ac)

(mL)

(mL)

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

CONDUCTIVITY (mS/cm)

CONVERSION VS CONDUCTIVITY
12
10
8
6

y = -0.1024x + 9.1536
R = 0.8927

4
2
0
-2 0

20

40

60

80

100

CONVERSION (%)

No

Flow Rate of NaOH

Flow Rate of

(ml/min)

Et(Ac)

Conductivity
Inlet Q1

Volume of
NaOH

Outlet Q2

(ml/min)

titrated (ml)

300

300

7.8

8.1

17.3

250

250

7.5

7.9

18.9

200

200

7.1

7.6

20.5

150

150

6.9

7.5

21.6

100

100

6.5

7.4

22.8

50

50

5.9

6.6

23.5

Table 2a
No

Residence

Conversion,

Reaction Rate

Rate of Reaction, -rA

Time, (min)

X, (%)

Constant, k

(mol.L/min)

(L.mol/min)
1

6.667

84.6

8.24

1.95 x 10-3

8.000

87.8

8.995

1.339 x 10-3

10.000

91.0

10.11

8.19 x 10-4

13.333

93.2

10.27

4.753 x 10-4

20.000

95.6

10.86

2.103 x 10-4

40.000

97.0

8.083

7.275 x 10-5

Table 2b

Conversion vs residence time

98

Conversion (%)

96
94
92
90
88

86
84
82
0

10

15

20

25

30

35

40

45

Residence time, (min)

Graph 2: Conversion (%) vs residence time, (min)

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SAMPLE CALCULATION
Residence time
For flow rates of 300 mL/min:
( ) ,

Residence time,

Total flow rate, Vo

= Flow rate of NaOH + flow rate of Et(Ac)

),

= 300 mL/min NaOH + 300 mL/min Et(Ac)

= 600 mL/min
= 0.6 L/min
Hence,
Residence time,

4
0.6 /

= 6.667 min
Conversion
For flow rates of 300 mL/min:
Moles of reacted NaOH, n1
n1 = concentration of NaOH x volume of NaOH titrated
= 0.1 M x 0.0173 L
= 0.00173 mole
Moles of unreacted HCl, n2
Moles of unreacted HCl = moles of reacted NaOH
n2 = n1
n2 = 0.00173 mole
Volume of unreacted HCl, V1
V1 =
=

2

0.00173
0.25

= 0.00692 L
Volume of HCl reacted, V2
V2 = total volume HCl V1
= 0.01 0.00692
= 0.00308 L

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Moles of reacted HCl, n3

n3 = concentration HCl x V2
= 0.25 x 0.00308
= 0.00077 mole
Moles of unreacted NaOH, n4
n4 = n3
= 0.00077 mole
Concentration of unreacted NaOH,
4

CNaOH unreacted =
=

0.00077
0.05

= 0.0154 M
Xunreacted =
=

0.0154
0.1

= 0.154
Xreacted = 1 - Xunreacted
= 1 0.154
= 0.846
Conversion for flow rate 300 L/min
0.846 x 100% = 84.6 %
Hence, at flow rate 300 L/min of NaOH in the reactor, about 84.6 % of NaOH is reacted with
Et(Ac).
Reaction rate constant, k

k=

(1 )

For flow rate 0f 300 mL/min:

Vo

= total inlet flow rate

= 0.6 L/min

VT PFR = Total volume for reactor

=4L
CAO = inlet concentration of NaOH
= 0.1 M

12

X = 0.846
0.6

0.846

k = (4)(0.1) (10.846 )
k = 8.24 L.mol/min
Rate of reaction, -rA
-rA = k(CAo )2 (1 X)2
For flow rate of 300 mL/min
-rA = (8.24)(0.1)2 (1 0.846)2
= 1.95 x 10-3 mol.L/min

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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 cylindr ic a l
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 flow ing
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.
In this particular experiment, the solutions used are NaOH and Et(Ac). These two
solutions reacts 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. 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, =

( ) ,

),0

From table 1, it is shown the data that needed to do the calibration curve. The calibratio n
curved is based on the conductivity and conversion. The graph 1 is plotted for the calibratio n
curve. From the graph plotted, it can be concluded that the conductivity is decrease
proportionally with conversion. When the conversion increase, the volume of Naoh to be mixed
with Et(Ac) is decreased, the conductivity also decrease. When both reactant with differe nt
moles was used, it will give a significant difference of conductivity.
After, the experiment is conducted, raw data consisting inlet flow rates, conductivity
value (Q1 and Q2) and volume of NaOH used in the titration process are tabulated in Table 2a
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 2b of the Result section.
From the calculated residence time and conversion, the graph of residence time,
against conversion (%) is plotted. The graph is shown in graph 2. From the graph plotted, it
show that the conversion is increased as the residence time is increase. The longer the residence
time of the reactant in the reactor, the more of the reactant that are converted and more products
are produced.
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

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
Graph 2.
RECOMMENDATION
There are several recommendations that can be done in this experiment for improving the data
such as:
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. Make sure the speed of the stirrer of M1 is about 200 rpm to ensure homogeneous water
jacket temperature.
5. Back titration should be done immediately after the sample were collected to avoid
contaminant.
6. Titration should be immediately stopped when the indicator turned pink.
7. Pumps should never be run dry.

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REFERENCES
1) Plug flow reactor. Retrieve from https://www.scribd.com/doc/29195386/Plug-FlowReactor on 21 October 2016.
2) Chemical reactors. Retrieve from
http://www.essentialchemicalindustry.org/processes/chemical-reactors.html on 21 October
2016.
3) Plug flow reactors. Retrieve from
http://www.umich.edu/~elements/5e/asyLearn/bits/pfrfinal/index.htm on 21 October 2016.
4) Reactor theory and practices. Retrieve from
https://www.cs.montana.edu/webworks/projects/stevesbook/contents/chapters/chapter008/sec
tion002/blue/page004.html on 21 October 2016.
5) Fogler, Scott H. Elements of Chemical Reaction Engineering, 4 th ed. Englewood Cliffs,
NJ: Prentice hall, 2011.
6) Schmidt, Lanny D. The Engineering of Chemical Reactions.

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