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ABSTRACT

This is the experiment of plug flow reactor (PFR). The reaction to be studied is the
saponification reaction of ethyl acetate Et(Ac) and sodium hydroxide NaOH. The calibration
curve of conversion vs conductivity is also perform in this experiment. The objectives of this
experiment are to perform saponification reaction between NaOH and Et(Ac), to determine the
reaction rate constant and to study the effect of residence time on the conversion. This
experiment is done by varying the residence time by manipulating the flow rate of the system.
The flow rate of both feeds, Et(Ac) and NaOH is the same and varied from 300mL/min to 50
mL/min. From the result, the percentage of conversion of NaOH is increasing with the increase
of residence time. When the total flowrate of the residence is 6.6667 mins, the conversion is
89.4%. Then as the total flow rate provided for the system is decreased, the residence time is
increasing and that makes the conversion of NaOH to increase as well. When the total flowrate is
40 mins, the conversion is increasing to 96.8%. The lower flow rate gives a higher residence
time and helps increasing the conversion of the reaction.

INTRODUCTION

Plug Flow Reactor (PFR) is the the third general type of reactor. 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. The system may be either contained or open. An ideal plug flow reactor has a fixed
residence time. 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. Sometimes the tube will be a tube in a shell and tube heat exchanger.
Plug flow reactors are used for the applications of large scale reactions, fast reactions,
homogeneous or heterogeneous reactions, continuous production and high temperature reactions.
The advantages of Plug Flow Reactors are they 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 Pug Flow Reactor (Model : BP 101) has been designed for student demonstration on
reactor ad reaction behavior. This mobile bench type of unit consists of mainly a reactor (PFR)
made of flexible tubing, hot water jacket with a variable speed stirrer, a heating system, reactant
feeding systems and instruments for the measurement and control of reaction temperature and
reactants flow rates. Students will conduct continuous saponification reaction of ethyl acetate
and sodium hydroxide. A conductivity measurement is provided and students will relate the
conductivity value to extent of reaction. Students will study the effects of residence time and
reaction temperature on the reaction rate constant. Students will also conduct RTD studies on the
reactor.

OBJECTIVES

To perform saponification reaction between NaOH and Et(Ac)


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

THEORY

In the simplest case of a PFR model, several key assumptions must be made in order to
simplify the problem. Note that not all of these assumptions are needed. However the removal of
these assumptions does increase the complexity of the problem. The PFR model can be used to
model multiple reactions as well as reactions involving changing temperatures, pressures and
densities of the flow. Although these complications are ignored in what follows, they are often
relevant to industrial processes.
Assumptions:
a) plug flow
b) steady state
c) constant density (reasonable for some liquids but a 20% error for polymerizations valid
for gases only if there is no pressure drop, no net change in the number of moles, nor any
large temperature change)
d) single reaction occurring in the bulk of the fluid (homogeneously).
A material balance on the differential volume of a fluid element, or plug, on species i of axial
length dx between x and x + dx gives:
[accumulation] = [in] [out] + [generation] [consumption]

Accumulation is 0 under steady state therefore, the above mass balance can be rewritten as
follows:
Fi(x) Fi(x+dx) + Atdxvir = 0
where:
x is the reactor tube axial position, m
dx the differential thickness of fluid plug
the index i refers to the species i
Fi(x) is the molar flow rate of species i at the position x, mol/s
D is the tube diameter, m
At is the tube transverse cross sectional area, m2
is the stoichiometric coefficient, dimensionless
r is the volumetric source/sink term (the reaction rate), mol/m3s.
The flow linear velocity, u (m/s) and the concentration of species i, Ci (mol/m3) can be
introduced as:

On application of the above to Equation 1, the mass balance on i becomes:

When like terms are cancelled and the limit dx 0 is applied to Equation 2 the mass balance on
species i becomes:

The temperature dependence of the reaction rate, r, can be estimated using the Arrhenius
equation. Generally, as the temperature increases so does the rate at which the reaction occurs.
Residence time, is the average amount of time a discrete quantity of reagent spends inside the
tank.
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Assume:
a) Isothermal conditions, or constant temperature (k is constant)
b) Single irreversible reaction (A = 1)
c) First order reaction (r = k CA)
After integration of Equation 3 using the above assumptions, solving for CA(x) we get an explicit
equation for the concentration of species A as a function of position:

where CA0 is the concentration of species A at the inlet to the reactor, appearing from the
integration boundary condition.
Conversion
One of the reactants is choosed as the basis of calculation and the other species involved is
related in the reaction to this basis. Consider the general equation
aA + bB cC + dD
We will choose A as our basis of calculation.
A+

b
a

c
d
C+ D
a
a

The basis of calculation is most always the limiting reactant. The conversion of species A in a
reaction is equal to the number of moles of A reacted per mole of A fed.
Design equation for Plug Flow Reactor:
dF A
dV

= rA

In terms of conversion FAo

dX
dV

= -rA

V = FAo

dX
rA
0

The volume of PFR can be represented as shaded area under the curve.
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

Apparatus :

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

0.25 M Hydrochloric Acid, HCl

De-ionised water

METHODOLOGY/PROCEDURES

A. Preparation of Calibration Curve for Conversion vs. Conductivity


The reaction to be studied is the saponification reaction of ethyl acetate Et(Ac) and sodium
hydroxide NaOH. Since this is a second order reaction, the rate of reaction depends on both
concentrations of Et(Ac) and NaOH. However, for analysis purposes, the reaction will be carried
out using equimolar feeds of Et(Ac) and NaOH solutions with the same initial concentrations.
This ensures that both concentrations are similar throughout the reaction.
NaOH + Et(Ac) Na(Ac) + EtOH
The following procedures will calibrate the conductivity measurements of conversion values for
the reaction between 0.1 M ethyl acetate and 0.1 M sodium hydroxide:
Procedures:
1. The following solutions is prepared:
a) 1 liter of sodium hydroxide, NaOH (0.1 M)
b) 1 liter of sodium acetate, Na(Ac) (0.1 M)
c) 1 liter of deionised water, H2O
2. The conductivity and NaOH concentration for each conversion values are determined by
mixing the following solutions into 100 ml of deionised water:
a) 0% conversion : 100 ml NaOH
b) 25% conversion : 75 ml NaOH + 25 ml Na(Ac)
c) 50% conversion : 50 ml NaOH + 50 ml Na(Ac)
d) 75% conversion : 25 ml NaOH + 75 ml Na(Ac)
e) 100% conversion : 100 ml Na(Ac)
B. Back Titration Procedures for Manual Conversion Determination
It is advisable to carry out manual conversion determination on experiment samples to verify the
conductivity measurement values. The following procedures will explain the method to carry out
back titration on the samples. It is based on the principle of quenching the sample with excess

acid to stop any further reactions, then back titrating with a base to determine the amount of
unreacted acid.
Procedures:
1. A burette is filled up with 0.1 M NaOH solution.
2. 10 ml of 0.25 M HCl is measured in a flask.
3. A 50 ml sample from the experiment is obtained and immediately added to the HCl in the flask
to quench the saponification reaction.
4. A few drops of pH indicator is added into the mixture.
5. The mixture is titrated with NaOH solution from the burette until the mixture is neutralized.
The amount of NaOH titrated is recorded.
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 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 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.

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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.

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RESULT

Reactor Volume

: 4L

Concentration of NaOH in feed tank : 0.1M (20L)


Concentration of Et(Ac) in feed tank : 0.1M (20L)

Flow

Flow

Total

Residen

Outlet

rate of

rate of

flow

ce

conductivi

on,

NaOH

Et(Ac)

rate of

time, t

ty

X (%)

(mL/mi

(mL/mi

solution

(min)

(mS/min)

n)

n)

FT 01
300
250
200
150
100
50

Conversi Reaction

s, V0

FT 02
300
250
200
150
100
50

(mL /

Q10 Q2

min)
600

02

11.2

9.8

500
400
300
200
100

6.6667
8
10
13.3333
20
40

9.6
8.3
7.5
6.8
5.8

8.3
7.2
6.3
5.6
5.8

89.4
89.8
92.8
93.6
93.6
96.8

Rate

Vol of

Rate

of

NaOH

Constan

Reacti

Titrate

on

(L/mol.

(mol/L

(mL)

min)

.min)

2.1085

2.3691

19.7

2.2010

x 10-4
2.567 x

19.9

3.2222

10-4
1.6704

21.4

3.6563

x 10-4
1.4976

21.8

3.6563

x 10-4
1.4976

21.8

7.5625

x 10-4
7.744 x

23.4

10-5

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Conversio
n

Solution Mixtures
0.1M
0.1M
H2O
NaOH

0%
25%
50%
75%
100%

100mL
75mL
50mL
25mL
-

Na(Ac)
25mL
50mL
75mL
100mL

100mL
100mL
100mL
100mL
100mL

Concentratio

Conductivit

n of NaOH

(M)
0.0500
0.0375
0.0250
0.0125
0.0000

(mS/ cm)
10.7
9.7
7.5
5.6
4.0

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SAMPLE CALCULATIONS
Residence Time:
Calculation for flow rates of 300 ml/min:
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
=

Residence Time,

Reactor volume ( L ) ,V
4L
=
0.6
L/min
L
Total flow rate
, v0
min

( )

= 6.6667 mins

Conversion:
Calculation for flow rates of 300 ml/min :
Moles of reacted NaOH, n1
n1
= Concentration NaOH x Volume of NaOH titrated
= 0.1 M x 0.0197 L
= 0.00197 mole
Moles of unreacted HCl, n2 = Moles of reacted NaOH, n1
n2 = 0.00197 mole
Volume of unreacted HCl, V1
V1

n2
concentration HCl quench

0.00197
0.25

= 0.00788 L
Volume of HCl reacted, V2
V2 = Total volume HCl V1

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= 0.01 0.00788
= 0.00212 L
Moles of reacted HCl, n3
n3
= Concentration HCl x V2
= 0.25 x 0.00212
= 0.00053 mole
Moles of unreacted NaOH, n4
n4
= n3
= 0.00053 mole
Concentration of unreacted NaOH
CNaOH unreacted

n4
volume sample

0.00053
0.05

= 0.0106 M
Xunreacted
Xunreacted =
=

Concentration of NaOH unreacted


concentration NaOH
0.0106
0.1

= 0.106
Xreacted
Xreacted = 1 - Xunreacted
= 1 - 0.106
= 0.894
Conversion for flow rate 300 mL/min,
0.894 x 100% = 89.4 %

Reaction Rate Constant, k


k=

v0
X
V TFR C AO 1X

)
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For flow rates of 300 ml/min :


V0

= Total inlet flow rate


= 0.6 L/min

VTFR

= Volume for reactor


=4L

CAO

= inlet concentration of NaOH


= 0.1 M

= 0.894
k=

0.1
0.894
(4)(0.1) 10.894

= 2.1085 L.mol/min

Rate of Reaction, -rA


-rA = k (CA0)2 (1-X)2
For flow rates of 300 ml/min :
-rA

= 2.1085 (0.1)2 (1-0.894)2


= 2.3691 x 10-4 mol.L/min

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DISCUSSION

Conversion vs Conductivity
12
10
8
Conductivity (mS/cm)

f(x) = - 0.07x + 11
R = 0.99

6
4
2
0
0 10 20 30 40 50 60 70 80 90 100
Conversion

For the preparation of calibration curve for conversion vs conductivity, the NaOH
solution and Na(Ac) is mixed to give a value of conversion from 0% which means a pure NaOH
solution and also 100% conversion which means a pure Na(Ac) solution produced. The curve
obtained is shown in the figure above. From the graph, for 0% conversion, the conductivity value
is 10.7 mS/cm. The 100% conversion gives the conductivity value of 4.0 mS/cm. The higher the
conversion of NaOH, the lower the conductivity value obtained based on the result. The best fit
lined constructed from the result gives the line of y = -0.07x + 11. Thus, the slope obtained is
-0.07 while the y-intercept is 11 mS/cm.
The decrease in the conductivity value of the solution is because of the decrease in the
ionic activity of a solution in term of its capacity to transmit current. As the electrical current is
transported by the ions in solution, the conductivity increases as the concentration of ions
increases. Thus, the higher conversion of the NaOH gives a lower ionic activity for the
preparation of the calibration curve result. From the experiment, the conductivity of the reactant
also decreases as the conversion increases. The 89.4% conversion gives a conductivity value of
11.2mS/cm for the NaOH and 9.8mS/cm for the Et(Ac). When the conversion increases the

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conductivity value is decreasing. The highest conversion which is 96.8% from the flowrate of 50
mL/min for each feeds gives the lowest conductivity value of 5.8 mS/cm.

For the experiment of investigating the effect of conversion on residence time, the
reaction to be studied is the saponification reaction of ethyl acetate Et(Ac) and sodium hydroxide
NaOH. The reaction is carried out using equimolar feeds of Et(Ac) and NaOH solutions with the
same initial concentrations. This ensures that both concentrations are similar throughout the
reaction. The flowrate of both feeds are also the same throughout the experiment. The flowrates
is then varied from 300mL/min to 50 mL/min in order to gives variation in the residence time.
The residence time is determined from the equation:
=
Residence Time,

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

( )

The results obtained from the experiment is shown in the graph above. From the graph,
we can see that the percentage of conversion of NaOH is increasing with the increase of
residence time. When the total flowrate of the residence is 6.6667 mins, the conversion is 89.4%.
Then as the total flow rate provided for the system is decreased, the residence time is increasing
and that makes the conversion of NaOH to increase as well. When the total flowrate is 40 mins,
the conversion is increasing to 96.8%.

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The design of a plug flow reactor is usually cylindrical and long. Feed enters the reactor
at the inlet and continuously flow and exit at the outlet without the help of agitation or stirrer.
Thus, the composition in the reactor will be different from one point to another also. The
conductivity in unit helps in order to know the reaction in the reactor stability of the system.
From the result, when flowrate is high, the reactants only have a little time to make contact with
each other before exiting the outlet. Thus, the lower flowrate helps the conversion to increase as
the contact between the reactants is longer before exiting the outlet. As the plug flow reactor has
a very low mixing process, thus lowering the flowrate of the or might as well said as increasing
the residence time, helps the reaction process to takes place better to gives higher conversion
value. As for the reaction rate of the reaction, -rA from the result it is decreasing as the residence
time is higher while the rate constant, k is increasing.

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CONCLUSION

As a conclusion, the objectives for this experiment is achieved. This is because we get to
perform saponification reaction between NaOH and Et(Ac) by using the plug flow reactor unit
and then determine the reaction rate constant for each reaction which is different from each
flowrate introduced to the system. Besides that we also get to study the effect of residence time
on the conversion which is the lower flowrate gives a higher residence time and increasing the
conversion in the reaction. This is because the design of the plug flow reactor itself which having
a poor mixing process. Thus higher residence time helps increasing conversion in the reaction
process. From this experiment, it is also discovered that when the conversion value is high, the
conductivity value is decreasing.

RECOMMENDATION

1. It is recommended that the same experiment is conducted by using other type of reactor
in order to know which reactor will give a better process for the reaction and their
characteristics can be compared.
2. It is recommended that the flowrate of the feed to be varied and not constant to know
how will it affects the reaction process in the plug flow reactor.
3. It is also recommended to varied the concentration of the feed for example like how
would the reaction process go if the feed introduced into the system is not equimolar.

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REFERENCES

1. Fogler, H.S (2006). Elements of Chemical Reaction Engineering (3rd Edition). Prentice
Hall.
2. Levenspiel, O. (1999). Chemical Reaction Engineering (3rd Edition). John Wiley.
3. Laboratory Manual Tubular Flow Reactor.
4. Reactor Theory and Practice. Plug Flow Reactor (PFR). Retrieved on 27th March from
http://www.cs.montana.edu/webworks/projects/stevesbook/contents/chapters/chapter008/
section002/blue/page004.html
5. Wikipedia. Plug Flow Reactor Model. Retrieved on 27th March from
http://en.wikipedia.org/wiki/Plug_flow_reactor_model

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APPENDIX

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