ABSTRACT

TABLE OF CONTENTS

ABSTRACT................................................................................................................... 2
LIST OF FIGURES.......................................................................................................... 3
LIST OF TABLES........................................................................................................... 4
1.0 INTRODUCTION....................................................................................................... 5
2.0 THEORY AND WORKING EQUATION..........................................................................6
3.0 MATERIALS AND METHOD....................................................................................... 9
4.0 RESULT AND DISCUSSION...................................................................................... 10
5.0 CONCLUSIONS AND RECOMMENDATION................................................................15
6.0 NOMENCLATURE................................................................................................... 16
7.0 REFERENCES......................................................................................................... 17
8.0 APPENDICES.......................................................................................................... 18
8.1 RAW DATA......................................................................................................... 18
8.2 SAMPLE CALCULATIONS.................................................................................... 20

LIST OF FIGURES

Figure 1: Schematic diagram of a Plug Flow Reactor.....................................................................5

Figure 2: An RTD curve for a well-mixed reactor...........................................................................6
Figure 3: Graph of Conversion vs. Flow Rate...............................................................................10
Figure 4: Graph of Rate of Reaction vs. Residence Time..............................................................11
Figure 5: Graph of Conversion versus Temperature......................................................................12
Figure 6: Graph of Rate of Reaction versus Residence Time........................................................13

LIST OF TABLE
Table 1: Analyzed Data for Experiment 3.......................................................................................9
Table 2: Analysed Data for Experiment 4...................................................................................12Y
Table A 1: The results for total flow rate of 0.5 L/min..................................................................17
Table A 2:The results for total flow rate of 1.0 L/min...................................................................17
Table A 3: The results for total flow rate of 1.5 L/min..................................................................18
Table A 4: The results for temperature of 40 0C............................................................................18
Table A 5: The results for temperature of 50 0C............................................................................18
Table A 6: The results for temperature of 60 0C............................................................................19

1.0 INTRODUCTION

2.0 THEORY AND WORKING EQUATION

Saponification is a process that produces soap, where esters of fatty acids are mixed with a
strong alkali. Saponification is studiedby using ethyl acetate (ester) and sodium hydroxide (base).
The reaction which occurs is shown by the following equation:
CH3COOC2H5 (aq) + NaOH (aq)

CH3COONa (aq) +C2H5OH(aq)

The effect of a step change input in a plug flow reactor (PFR) is being studied. The residence
time distribution (RTD) is to be constructed for the PFR. Residence time is the average amount
of time that a particle stays in a system. In PFR, all fluid movements have the same residence
time. When a large amount of substance enters a system, residence time will be shorter. In other
words, a large flow rate will result in shorter residence time and thus the conversion will be
lower.

Figure 1: Schematic diagram of a Plug Flow Reactor

In Figure 1, mixed fluid, as shown with an arrow on the left is going through a PFR and PFR
may be modeled as flowing through the reactor as a series of infinitely thin coherent plugs,
each with uniform composition travelling axially with the reactor. The fluid is assumed to be
perfectly mixed radially but not axially. As feed flows down the tubular PFR, the residence time
of the plug is a function of its position in the reactor.
The residence time distribution (RTD) is a type of probability distribution graph to show the
amount of time a mixture could spend in a reactor. This distribution is important in estimating the
yield of a given reaction so that a reactor can be designed according to the desired yield. It can
also be used to troubleshoot existing reactor, if problem occurred.

Figure 2: An RTD curve for a well-mixed reactor

The residence time distribution function can be expressed as :

C A ( t ) dt
0

residencetime , =

(1)

v PFR
F o For a second order equimolar reaction where reactants have same

A
0=C
B 0)
initial concentrations (
, rate law becomes

A= k C A C B=k C2 A =k C 2A (1x )2
r

(2)

For rate constant,

k=

F0
X
[
]
V PFR C A 0 1 X

(3)

Where,
Fo : total inlet flow rate of solution (ml/min)
X

: extent of conversion

CA0 : inlet concentration of reactant NaOH in reactor (M)

CB : inlet concentration of reactant Ethyl Acetate in reactor (M)
CA : exit concentrations of reactant NaOH (M)
V

: volume of reactor

From stoichiometry at constant volumetric flow rate PFR (liquid phase), we obtain

CA CA0(1 X )
(4)
Substitute (3) into (1):
6

 rA

=k

CAO

(1 - X) 2

(5)

Then -rA was written in a differential form.

CAO

FAO
2

(1 - X) 2 =

dX
dV
(6)

1
FAO
2
kCAO 2 (1 X )
dV =
[
] dX

Since FAO = CAO

v
0

dV =

(7)

FAO
kCAO 2

2
0 (1 X )

dX

(8)

Integration

o
V=

Since residence time , = V /

kCAO

X
(1 X )
[

(9)

,
1
k=

CAO

X
(1 X )
[

(10)

3.0 MATERIALS AND METHOD

4.0 RESULT AND DISCUSSION

Experiment 3
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 ,(L)

L
Total Flowrate ,(
)
min

From the equation above, it can be seen that residence time is a function of total flow rates of the
feed. Hence, by varying the flow rate of the feed solutions, several residence times can be
obtained and the effects of each one, studied.
Table 1: Analyzed Data for Experiment 3
Flow rate, F

Residence

Volume of

Conversion,

Rate of

Rate constant,

(L/min)

time, (min)

NaOH used,

reaction, -rA

2.30
2.24
1.71

V(ml)
7.0
4.2
2.8

0.640
0.584
0.556

(mol/L.min)
0.009999
0.010835
0.014466

L/(mol.min)
7.715556
6.261154
7.338198

0.5
1.0
1.5

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 Table A1 in Appendix. 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 1 of the Result
section.
As the data of flow rate and conversion from table 1 is plotted into a graph, the graph is shown in
Figure 1. Figure 2 is plotted based on rate of reaction and residence time. The reason for plotting
a graph consist 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.

Graph of Conversion vs Flowrate

0.66
0.64
0.62
0.6

Conversion, X

0.58
0.56
0.54
0.52
0.5
0.4

0.6

0.8

1.2

1.4

1.6

Flow rate, F(L/min)

Figure 3: Graph of Conversion vs. Flow Rate

By analyzing Figure1, it can be clearly seen that the conversion of the reaction decreases with
the increasing flow rate. Otherwise the conversion increases with increasing residence time. The
10

residence time or space time is the mean time spent by the molecules in the reactor. From Table
1, it is found out that the lower the flow rate, the longer the residence time. When flow rate is
low the molecules of reactants stay longer in the reactor. Thus the time of the molecules spent in
the reactor become longer, and the frequency of collision between molecules increases and this
causes the rate of reaction to increase and leads to higher conversion. Hence, the conversion
increases when the flow rate of reactants decreases. Thus the results prove the theory.

Graph of Rate of Reaction vs Residence Time

0.02
0.01
0.01
0.01

Rate of Reaction, -rA(mol/L.min)

0.01
0.01
0
0
0
0

0.5

1.5

2.5

Residence time, (min)

Figure 4: Graph of Rate of Reaction vs. Residence Time

According to the theory the rate of reaction should decreases with increasing flow rate. However
in this experiment the results deviate from the theory. When the flow rate increases (residence
time decreases) the rate of reaction also increases. This is due to the lack of good mixing process
in the PFR. Otherwise the inaccuracy in rate of reaction could be also due to the formation of the
undesired products at higher rate.

Experiment 4
The main objective of this experiment 4 is to study the effect of temperature on the performance
of this reactor, the PFR. To do that, of course, temperature of the reactor has to be manipulated
throughout the experiment and the effects of each one are studied. Residence time, in this
11

particular experiment, is kept constant by keeping the constant flow rates of the feed solutions.
The raw data for this experiment are tabulated in Table A2 while the calculated values are
tabulated in Table 2. For this the graph of conversion versus temperature and the rate of reaction
versus residence time are plotted to study the effect of temperature on the saponification reaction.

Table 2: Analysed Data for Experiment 4

Temperature

Residence

Volume of

Conversion,

Rate of

Rate

(C)

time

NaOH used

reaction, -rA

constant, k

(min)

(ml)

(mol/L.min)

L/

40

2.94

0.9

0.556

0.008489

(mol.min)
3.6539

50

2.72

1.4

0.528

0.009171

4.1166

60

2.62

2.8

0.518

0.009430

4.7836

Graph of Conversion vs Temperature

0.56
0.55
0.54
0.53

Conversion, X 0.52
0.51
0.5
0.49
35

40

45

50

55

60

65

Temperature, T(C)

Figure 5: Graph of Conversion versus Temperature

From Figure 3, the conversion increases as the temperature increases from 40C to 60C.
Theoretically, conversion should increase when the temperature is raised as explained by using
12

Collision theory. Collision theory explains that successful collisions have enough energy, also
known as activation energy, at the moment of impact to break the preexisting bonds and form all
new bonds. Raising the temperature, thus bringing about more collisions and therefore many
more successful collisions, increases the rate of reaction. In order for a reaction to occur, the
prerequisite is having the collision between the reactant molecules with enough energy. As the
temperature is increased, the reactant molecules are provided with higher kinetic energy hence
the molecules move faster and more likely to collide with each other.

Graph of Rate of Reaction versus Residence Time

0.01
0.01
0.01

Rate of Reaction,-rA(mol/L.min)

0
0
0
0 0.5 1 1.5 2 2.5 3 3.5

Residence time, (min)

Figure 6: Graph of Rate of Reaction versus Residence Time

Figure 4, showed the residence time distribution graph. In this experiment, the peak of the graph
is at 2.62 minutes. This means that most of the reactant molecules spent around 2.62 minutes to
stay in the reactor. The graph shows that rate of reaction increases with the increasing residence
time. Thus the results prove the theory. At higher temperature the reactants gain higher energy.
Thus reaction proceeds at faster rate.
In both experiments, the sample was taken when the conductivity of the reactor contents shown
by the computer had reached the constant value. When the value became constant, the reaction
had reached its equilibrium level or will hardly to have changes in concentration as the reactants
become lesser.

13

5.0 CONCLUSIONS AND RECOMMENDATION

14

6.0 NOMENCLATURE
CA0

Concentration of reactants at inlet of reactor

CA

Concentration of reactants at outlet of reactor

FA0

Initial flow rate of reactants

Fx

Flow rate of reactants

Rate constant of reaction

Molar Concentration

MW

Molecular Weight

n1

Moles of reacted NaOH

n2

Moles of unreacted HCl

n3

Moles of reacted HCl

n4

Moles of unreacted NaOH

Density

-rA

Rate of reaction

Volume of reactants

VTFR

Volume of reactor

Extent of conversion

Residence time

15

7.0 REFERENCES
Ain, N. (2013). Chemical reaction engineering, UMP, Retrived 10 th October 2015 from
http://www.slideshare.net/NurulAin45/chemical-reaction-engineering-28330576
Chemical Reaction Engineering Lab. (n.d). Department of Chemical Engineering, Sathyabama
University, Chennai, India.
H.ScottFogler, Elements of Chemical Reaction Engineering, 4th edition, Prentice Hall
Publishers.
Kyousei, S. (2013). Plug Flow Reactor : Effects of Residence Time, Chemical Engineering
Laboratory III, CHE574, Universiti Teknologi MARA, UiTM. Retrived 10 th October 2015
from http://www.scribd.com/doc/179120412/Plug-Flow-Reactor#scribd
Pearson International Edition. Elements of Chemical Reaction Engineering, 4 th Ed, H. Scott
Fogler
Perry, R.H. and D. Green, eds., Perrys Chemical Engineering Handbook (6th ed.),
McGraw-Hill, New York, 1984.
Schmidt, Lanny D. (1998). The Engineering of Chemical Reactions. New York: Oxford
University Press. ISBN 0-19-510588-5.

16

8.0 APPENDICES
8.1 RAW DATA
Table A 1: The results for total flow rate of 0.5 L/min
Date

Time

F1301(L/min
)

F1302(L/min
)

F1303(L/min
)

T1101(0C)

T1102(0C)

Q1401(mS/cm
)

Q1401(mS/cm
)

Table A 2:The results for total flow rate of 1.0 L/min

Date

Time

F1301(L/min
)

F1302(L/min
)

F1303(L/min
)

17

T1101(0C)

T1102(0C)

Q1401(mS/cm
)

Q1401(mS/cm
)

Table A 3: The results for total flow rate of 1.5 L/min

Date

Time

F1301(L/min
)

F1302(L/min
)

F1303(L/min
)

T1101(0C)

T1102(0C)

Q1401(mS/cm
)

Q1401(mS/cm
)

Table A 4: The results for temperature of 40 0C

Date

Time

F1301(L/min
)

F1302(L/min
)

F1303(L/min
)

T1101(0C)

T1102(0C)

Q1401(mS/cm
)

Q1401(mS/cm
)

Table A 5: The results for temperature of 50 0C

Date

Time

F1301(L/min
)

F1302(L/min
)

F1303(L/min
)

18

T1101(0C)

T1102(0C)

Q1401(mS/cm
)

Q1401(mS/cm
)

Table A 6: The results for temperature of 60 0C

Date

Time

F1301(L/min
)

F1302(L/min
)

F1303(L/min
)

T1101(0C)

8.2 SAMPLE CALCULATIONS

Experiment 3:
Preparation of NaOH;
M 1 V 1=M 2 V 2

M2=0.1M, V2=55L, MW=40 g/mol

M 1=

=2000

g
L

g
g
50 mol
=2000 40
=
MW
L
mol
L

Thus V1 =

(0.1 molL 55 L ) 50 molL =0.11 L

Mass of NaOH =

0.11 L 2000

g
L

= 220 g

Preparation of Ethyl acetate;

M2=0.05M, V2=55L,
M1=

=0.9g/mL, MW=88.1g/mol

1
g
1 mol
mL
mol
=0.9

1000
=10.23
MW
mL 88.1 g
L
L

19

T1102(0C)

Q1401(mS/cm
)

Q1401(mS/cm
)

M 2 V 2 0.05 55
Thus, V1= M 1 = 10.23 =0.540 L
Preparation of Hydrochloric acid for quenching;
=1.017g/mL, MW=35.5g/mol

M2=0.25M, V2=1L,
M1=

1
g
1 mol
mL
mol
=1.017

1000
=29
MW
mL 36.5 g
L
L

Thus, V1=

M 2 V 2 0.25 1
=
=8.6 ml
M1
29

Preparation of NaOH for titration;

=2000

M2=0.1M, V2=1L, MW=40 g/mol

Thus V1 =

g
L

(0.1 molL 1 L ) 50 molL =0.002 L

Mass of NaOH =

0.002 L 2000

g
L

=4g

Residence Time
For flow rates of 0.5 L/min:

Residence Time,

Reactor volume ,(L)

L
Total Flowrate ,(
)
min

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

= 1.78 L/min NaOH + 0.39 L/min Et(Ac)
= 2.17 L/min
20

Reactor volume= 5L
Residence Time,

5L
=2.3 min
2.17 L/mIN

*Other residence times were calculated by the same way, and varying the flow rates and
temperature.
Conversion
Moles of reacted NaOH, n1
n1= Concentration NaOH x Volume of NaOH titrated
= 0.1 M x 0.007 L= 0.0007 mole
Moles of unreacted HCl, n2
Moles of unreacted HCl = Moles of reacted NaOH
n2= n1
n2= 0.0007 mole
Volume of unreacted HCl, V1
n2
V1= concentrationof quench HCl

0.0007
0.25

= 0.0028 L
Volume of HCl reacted, V2
V2= Total volume HCl V1
= 0.01 0.0028
= 0.0072 L
Moles of reacted HCl, n3
n3= Concentration HCl x V2
= 0.25 x 0.0072= 0.0018 mole
21

Moles of unreacted NaOH, n4

n4= n3= 0.0018 mole
Concentration of unreacted NaOH
n4
CNaOH unreacted= volume sample
0.0018
0.05

= 0.036 M
Xunreacted =

Concentration of unreacted NaOH

Concentration of NaOH

0.036
0.1

= 0.36
Xreacted = 1 - Xunreacted
= 1 - 0.36
= 0.64
Conversion for flow rate 0.5L/min
0.64 x 100% = 64%
Hence, at flow rate 0.5L/min of NaOH in the reactor, about 64% of NaOH is reacted with Et
(Ac). Other conversions were calculated by the same way, and varying the flow rates and
temperature.

Reaction Rate Constant, k

22

k=

v0
X
(
)
V TFR C A 0 1X

For flow rates of 0.5 L/min:

V0= Total inlet flow rate= 2.17 L/min
VTFR= Volume for reactor = 5 L
CA0= inlet concentration of NaOH= 0.1 M
X = 0.64
k=

2.17
0.64
5 ( 0.1 ) 10.64

k =7.7156

L
mol . min

Other Reaction Rate Constants were calculated by the same way, and varying the flow rates and
temperature.

Rate of Reaction, -rA;

r A=k ( C A 0 )2 (1X )2
r A=7.7156 ( 0.1 )2 ( 10.64 )2
r A=9.9994 10

mol
L . min

Other Rate of Reactions were calculated by the same way, and varying the flow rates and
flowrates.

23