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) solution.
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 discussion 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, chemical 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 chemical 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.

Outlet Flow

Inlet 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 continuousstirred 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.
2

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

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 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.
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:
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=k C A C B
Where:
k

Rate constant

CA

concentration of species A

CB

concentration of species B

stoichiometric coefficient of A
5

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:
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

4.4 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.

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
0.25 M hydrochloric acid,

Measuring

cylinder
Beaker

HCl
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
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.
8

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
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.
RESULT
Conversion
(%)

Solution Mixture
H2O (mL)

Concentratio

Conductivit

n of NaOH

y (mS/cm)

0.1 M

0.1 M

NaOH

Et(Ac)

(mL)
100

(mL)
-

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

(M)

CONVERSION VS CONDUCTIVITY
15
10

CONDUCTIVITY (mS/cm)

f(x) = - 0.1x + 9.15

R = 0.89

5
0

20

40

60

80

100

CONVERSION (%)

Table 1: Preparation
of calibration curve

No

Flow Rate of NaOH

Flow Rate of

(ml/min)

Et(Ac)

1
2
3
4
5
6

(ml/min)
300
250
200
150
100
50
Table 2a

300
250
200
150
100
50
No

1
2
3
4
5
6

Conductivity
Inlet Q1
Outlet Q2
7.8
7.5
7.1
6.9
6.5
5.9

8.1
7.9
7.6
7.5
7.4
6.6

Volume of
NaOH
titrated (ml)
17.3
18.9
20.5
21.6
22.8
23.5

Residence

Conversion,

Reaction

Rate of

Time, (min)

X, (%)

Rate

Reaction, -rA

Constant, k

(mol.L/min)

6.667
8.000
10.000
13.333
20.000
40.000

84.6
87.8
91.0
93.2
95.6
97.0

(L.mol/min)
8.24
1.95 x 10-3
8.995
1.339 x 10-3
10.11
8.19 x 10-4
10.27
4.753 x 10-4
10.86
2.103 x 10-4
8.083
7.275 x 10-5
10

Table 2b

Conversion vs residence time

100
95
90

Conversion (%)

85
80
75

10

15

20

25

30

35

40

45

Residence time, (min)

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

SAMPLE CALCULATION
Residence time
For flow rates of 300 mL/min:
Reactor volume ( L ) , V
L
Total flow rate(
), V
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
11

Hence,
Residence time,

4L
0.6 L /min

= 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 =
=

n2
concentration HCi quench
0.00173
0.25

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

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
12

Concentration of unreacted NaOH,

n4
volume sample

CNaOH unreacted =

0.00077
0.05

= 0.0154 M
concentrationof NaOH unreacted
concentration NaOH

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
Vo

k = V TFR C AO 1X

For flow rate 0f 300 mL/min:

Vo

= total inlet flow rate

= 0.6 L/min

VTPFR = Total volume for reactor

=4L
CAO = inlet concentration of NaOH
= 0.1 M
X = 0.846
k=

0.6
0.846
( 4 )(0.1) 10.846

)
13

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

DISCUSSION

14

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.
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,

Reactor volume ( L ) ,V
L
Total flow rate
, v0
min

( )

From table 1, it is shown the data that needed to do the calibration curve. The
calibration curved is based on the conductivity and conversion. The graph 1 is plotted for the
calibration 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 different 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.

15

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.

16

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, 4th ed. Englewood Cliffs,
NJ: Prentice hall, 2011.
6) Schmidt, Lanny D. The Engineering of Chemical Reactions.

17