1

Contents
ABSTRACT ............................................................................................................................... 2
INTRODUCTION ..................................................................................................................... 3
AIMS.......................................................................................................................................... 4
THEORY ................................................................................................................................... 5
PROCEDURE ............................................................................................................................ 7
APPARATUS AND MATERIAL ............................................................................................. 9
RESULT .................................................................................................................................. 10
SAMPLE OF CALCULATION .............................................................................................. 12
DISCUSSION .......................................................................................................................... 15
CONCLUSION ........................................................................................................................ 16
RECOMMENDATIONS ......................................................................................................... 17
REFERENCES / APPENDICES ............................................................................................. 17












2

ABSTRACT

The experiment was divided into two parts which were Experiment 1 and Experiment
2. The objectives were to carry out saponification reaction between Sodium Hydroxide,
NaOH and Ethyl Acetate, Et (Ac) in a plug flow reactor, to determine the rate of reaction,
rate law and reaction rate constant, to determine the conversion of NaOH in the reactor and to
determine the effect of residence time on the conversion in a plug flow reactor. Plug flow
reactor (Model: BP 101) was used in this experiment. Feed flow rate of the NaOH and the
Et(Ac) was set to be the manipulated variable. The flow rates were varied to 300 ml/min, 250
ml/min, 200 ml/min, 150 ml/min, 100 ml/min and 50 ml/min. General start up procedure was
performed before conducting the experiments. Initially, P1 and P2 were adjusted to give a
constant flow rate of 300 ml/min. Then, the flow rates were recorded. Both inlet and outlet
conductivity were monitored until they did not change with time. This is to ensure that the
plug reactor has reached steady state. 50 ml sample was collected. The sample was mixed
with 10 ml Hydrochloric acid, HCl and a drop of phenolphthalein. Volume of titrated NaOH
was recorded. Based on the result, as the feed flow rates decreased, the volume of titrated
NaOH and the percentage of conversion were increased. In the other hand, as the feed flow
rates decreased, the rate of reaction decreased. Figure 2 shows that the percentage of
conversion increases with the increases in residence time.






3

INTRODUCTION

The plug flow reactor (PFR) is a model used to describe chemical reactions in
continuous, flowing systems of cylindrical geometry. The PFR model is used to predict the
behavior of chemical reactors of such design, so that key reactor variables, such as the
dimensions of the reactor, can be estimated. Fluid going through a PFR may be modeled as
flowing through the reactor as a series of infinitely thin coherent "plugs", each with a uniform
composition, traveling in the axial direction of the reactor, with each plug having a different
composition from the ones before and after it. The key assumption is that as a plug flows
through a PFR, the fluid is perfectly mixed in the radial direction but not in the axial direction
(forwards or backwards). Each plug of differential volume is considered as a separate entity,
effectively an infinitesimally small continuous stirred tank reactor, limiting to zero volume.
As it flows down the tubular PFR, the residence time ( ) of the plug is a function of its
position in the reactor. In the ideal PFR, the residence time distribution is therefore a Dirac
delta function with a value equal to .
The PFR model works well for many fluids which are liquids, gases, and slurries.
Although turbulent flow and axial diffusion cause a degree of mixing in the axial direction in
real reactors, the PFR model is appropriate when these effects are sufficiently small that they
can be ignored. In the simplest case of a PFR model, several key assumptions must be made
in order to simplify the problem, some of which are outlined below. Note that not all of these
assumptions are necessary, 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.

4

The assumptions are:
Steady state
Plug flow
Constant density
Single reaction
PFRs are used to model the chemical transformation of compounds as they are
transported in systems resembling pipes. A typical plug flow reactor could be a
tube packed with some solid material which is catalyst. Typically these types of reactors are
called packed bed reactors or PBR's.


Figure 1: Schematic diagram of Plug flow reactor


AIMS

1. To carry out a saponification reaction between NaOH and Et(Ac) in a plug flow
reactor (PFR).
2. To determine the rate of reaction, rate law, and raction rate constant.
3. To determine the conversion of NaOH in the reactor.
4. To determine the effect of residence time on the conversion in a plug flow reactor
(PFR).

5

THEORY

Rate of Reaction

Consider the reaction below


A + 2 B 3 C
The stoichiometric coefficient for species B is twice that of species A. Thus the concentration
of B will decline twice as fast as that of species A. Similarly, the concentration of species C
increases three times as fast as the concentration of A decreases. Conceptually there should
be a single, unambiguous rate for a reaction.
The rate of reaction, r, is defined to be the slope of the concentration-time plot for a species
divided by the stoichiometric coefficient of that species. Additionally, if the species is a
reactant, the negative value of the slope is used, because the slope is negative and a positive
rate is desired. For the example shown above

Rate Law


The rate law is a mathematical expression that predicts the rate of a reaction from the
concentrations of reactants. This rate law is the product of the rate constant (k) and each
reactant concentration taken to some power. The values for the rate constant and the
concentration powers have to be measured experimentally. An example of a rate law and its
rate constant is shown below. Consider the hypothetical reaction:
X + 2 Y > Z
6

Rate is the change of a reactant or product concentration per unit time during reaction (in
units of M/sec). Mathematically:
Rate = -D[X]/Dt = -D[Y]/2Dt = D[Z]/Dt
Example: Suppose the rate law was the following
Rate = k [X][Y]2
The rate is first order reaction with respect to [X] which means that it is proportional to [X]
taken to the first power ([X]
1
).
When [X] is doubled, the rate is doubled.
[2]
1
= 2
When [X] is tripled, the rate is tripled.
[3]
1
= 3

Conversion
The conversion, X
A
is the number of moles of reactant that have reacted per mole of reactant
fed to the system.
X
A
=




Residence time,
The residence time distribution (RTD) of a reactor is a characteristic of the mixing that
occurs in the chemical reactor.
Residence time, =

where:

= reactor volume

= total feed flow rates

7

PROCEDURE

GENERAL START-UP PROCEDURES.


1. All valves are closed except valve V4, V8 and V17.
2. Tank B1 is filled with deionized water and tank B2 is filled with 0.05M NaCl
solution.
3. The power for the control panel is turned on.
4. Clean water is filled in the water jacket B4 and the pre heater B5.
5. Stirrer motor M1 is switched on and the speed is set to about 200 rpm.
6. Valve V2, V4 AND V 10 are opened and pump P1 is switched on. Flow rate P1 is
adjust to 150 ml/min at FT-01. Valve V10 is closed, pump P1 is switched off.
7. Valve V6, V8 and V12 are opened. Pump P2 is switched on. Flow rate P2 is adjust to
150 ml/min at FT-02. Valve V12 is closed, pump P2 is switched off.
8. The unit is ready for experiments

GENERAL SHUT DOWN PROCEDURES.

1. Pump P1, P2 and P3 are switched off. Valve V2 and V6 are closed.
2. The cooling water is kept circulating through the reactor while the stirrer motor is
running to allow the water jacket to cool down to room temperature.
3. All liquid are drain by opening V1 to V19. The feed tank is rinsed with the clean
water.
4. The power for the control panel is turned off.





8

EXPERIMENT 1

1. The general start-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. Make sure that both flow rates are the same. The flow rates
were recorded.
5. The inlet (QI-01) and outlet (QI-02) conductivity values were started monitored 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 were found.
7. Sampling valve V15 was opened and a 50ml sample was collected. A back titration
procedure was carried out to manually determine the concentration of NaOH in the
reactor and extent of conversion.
8. Step 4 to 7 were repeated 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. make sure that both
flow rates are the same.






9

EXPERIMENT 2

1. A burette is filled up with 0.1M NaOH solution.
2. 10 ml of 0.25M HCl is measured in a flask.
3. 50 ml sample is obtained from the experiment and the sample is added to the HCl
immediately in the flask to quench the saponification reaction.
4. A few drops of pH indicator are 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.



APPARATUS AND MATERIAL

Beaker
Conical flask
Burette
Dropper
Measuring cylinder
Plug flow reactor (Model: BP 101)


0.1 M of Sodium Hydroxide solution
0.1 M of Ethyl Acetate
Deionised water
0.25 M Hydrochloric acid






10

RESULT

EXPERIMENT 1



Reactor volume = 4 L
Concentration of NaOH in the feed
tank
= 0.1 M
Concentration of Et(Ac) in the feed
tank
= 0.1 M





No
Flowrate
of
NaOH
(ml/min)
Flowrate
of
Et(Ac)
(ml/min)
Total flow
rate of
solution,V
o

(ml/min)
Residence
time
Outlet
conductivity
Conversion,
% , X
Rate
Constant, k
(L/mol.min)
Rate of
reaction
(mol/L.min)
First
inlet
Second
outlet
1 300 300 600 0.6667 10.3 8.6 19.6% 3.6567
0.0236
2 250 250 500 0.8000 9.6 7.6 22.0% 3.5256
0.0214
3 200 200 400 1.0000 8.0 6.5 24.4% 3.2275
0.0184
4 150 150 300 1.3333 7.0 5.5 41.6% 5.3425
0.0182
5 100 100 200 2.0000 5.5 4.1 53.2% 5.6838
0.0124
6 50 50 100 4.0000 4.6 3.7 66.4% 4.9405
0.0056







11


Figure 2: Graph of Conversion against Time






EXPERIMENT 2



Titration sample (ml) Volume of NaOH (ml)
50 4.9
50 5.5
50 6.1
50 10.4
50 13.3
50 16.6










y = 14.186x + 14.696
0
10
20
30
40
50
60
70
80
0 1 2 3 4 5
C
o
n
v
e
r
s
i
o
n
,

X

(
%
)

Residence Time (min)
Conversion against Residence Time
12

SAMPLE OF CALCULATION

NaOH + HCl NaCl + H
2
O

Unknown quantity
Concentration of NaOH in the reactor, C
NaOH
= 0.1 M

Known quantities
Volume of sample, V
s
= 50 mL
Concentration of NaOH in the feed vessel, C
NaOH,f
= 0.1 M
Volume of HCI for quenching, V
HCI,s
= 10 mL
Concentration of HCI in standard solution, C
HCI,s
= 0.25 M
Volume of titrated NaOH, V
1
= 25.45 mL
Concentration of NaOH used for titration, C
NaOH,s
= 0.1 M

Sample Calculation (for sample flow rate of 50 ml/min)
Concentration of NaOH entering the reactor, C
NaOH,o

= (C
NaOH,f
)/ 2
=

= 0.05 mol/L

Volume of unreacted quenching HCI, V
2

=

x V
1

=

x 16.6
= 6.64 mL

Volume of HCI reacted with NaOH in sample, V
3

= V
HCI,s
- V
2

= 10 6.64
= 3.36 mL


Moles of HCI reacted with NaOH in sample, n
1
13


= C
HCI,s
x V
3

= 0.25 x

= 8.40 x 10
-4
mol


Moles of unreacted NaOH in sample, n
2
= n
1
= 8.4 x 10
-4
mol



Concentration of unreacted NaOH in the reactor, C
NaOH

= n
2
/ ( V
s
/

1000 )
=

= 0.0168 mol/L




Conversion of NaOH in the reactor, X
= (1 -

) x 100%
= (1

) x 100 %
= 66.4 %


Residence time,
=

=


x



= 4.000 min

Rate constant, k
=

)

where X is taking from the calculation in experiment 2
14

=

)
= 4.9405 L/mol.min


Rate of reaction, -r
= k

(1-X)
2
= (4.9405)(0.1)
2
(1-0.664)
2

= 0.0056

moL/L.min



























15

DISCUSSION

This experiment was divided into two parts which were Experiment 1 and Experiment
2. Experiment 1 was conducted to carry out saponification reaction between Sodium
Hydroxide, NaOH and Ethyl Acetate, Et (Ac) in a plug flow reactor, to determine the rate of
reaction, rate law and reaction rate constant, to determine the conversion of NaOH in the
reactor. Experiment 2 was conducted to determine the effect of residence time on the
conversion in a plug flow reactor. The feed flow rates of both experiments were varied to 300
ml/min, 250 ml/min, 200 ml/min, 150 ml/min, 100 ml/min and 50 ml/min. The speed of the
stirrer motor was set to 200 rpm.
Based on the result of the experiment, when the feed flow rates were set at 300
ml/min, 250 ml/min, 200 ml/min, 150 ml/min, 100 ml/min and 50 ml/min, the rate of reaction
were 0.0236 mol/L.min, 0.0214 mol/L.min, 0.0184 mol/L.min, 0.0124 mol/L.min and
0.0056 mol/L.min respectively. The result showed that the rate of the reaction decreases
when the feed flow rate decreases. This happened because of the high flow rate of the PFR,
the concentration of the reagents decrease and the concentration of the product increases thus
the rate of reaction will slow. According to the collision theory, the rate of reaction should
increase with increase of the concentration since the rate is directly proportional to the
collision frequency.
Next, the reaction rate constant ,k , when the feed flow rates were set at 300 ml/min,
250 ml/min, 200 ml/min, 150 ml/min, 100 ml/min and 50 ml/min, the k values were 3. 6567
L/mol.min, 3.5256 L/mol.min, 3.2275 L/mol.min, 5.3425 L/mol.min, 5.6938 L/mol.min and
4.9405 L/mol.min respectively. The results shows that the reaction rate constant decreases at
the initial flow rate to 200 ml/min and it increased at flow rate of 150 ml/min. Finally, the
reaction rate constant decreased to 4.9405 L/mol.min at flow rates of 50 ml/min. The
percentage of conversion increases with the decreases of the feed flow rate.
16

Figure 3 presents the graph of conversion against residence time. As the reagents
flows down the tubular PFR, the residence time ( ) of the plug is a function of its position in
the reactor. The graph shows that as the residence time increases, the conversion will
increases. The residence time can be made to be longer by decreasing the flow rate of the
solutions provided the volume of the reactor remain constant. This will follows the residence
times formula in Theory section.
In Experiment 2, a back titration was conducted to measure the amount of NaOH
needed to neutralize 50 ml of sample at different feed flow rates. The result showed that as
the flow rate decreases, the volume of NaOH titrated increases. This phenomenon is
according to the theory where the concentration is higher at lower flow rate, thus, more
volume of NaOH titrated is needed to naturalize the samples solution.




CONCLUSION

As a conclusion, the experiments are successful as all the objectives are achieved. It
can be concluded that the feed flow rates affects the rate of reaction, reaction rate constant
and the percentage of conversion. As the flow rates are decrease, the rate of reaction will
decrease and the percentage of the conversion increase. The longer residence times in the
reactor, the greater the conversion of NaOH. Finally, as the feed flow rate decreases, the
volume of NaOH titrated to neutralize the sample will increase.





17

RECOMMENDATIONS

Repeat the back titration method and get the average volume of NaOH to get more
accurate results.
Rinsed the conical flasks and beaker to remove any impurities.
During conducting the back titration method, put a white paper above the conical
flask to determine the colour changes of the solution more accurately.
During taking the volume of NaOH titrated, the eyes must perpendicular to the scale o
the burette to avoid parallax error.
Ensure that there is no leakage at the valve of the equipment.

REFERENCES / APPENDICES

AdiChemistry [Online] Available from
http://www.adichemistry.com/physical/kinetics/factors/factors-affecting-rate-
reaction.html Accessed on 26th April 2013
Enzyme Techology [Online] Available from
http://www.lsbu.ac.uk/water/enztech/cstr.html Accessed on 26th April 2013
Kinetic Supplement [Online] Available from
http://www.usm.edu/polymerkinetics/genkin.pdf . Accessed on 23rd April 2013.
Reaction law, Reaction Rates and Activation Energy [Online] Available from
http://www.csun.edu/chem/documents/Kinetics.pdf. Accessed on 25th April 2013