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1.

ABSTRACT
The aim of this experiment are to carry out saponification reaction between Sodium

Hydroxide, NaOH and Ethyl Acetate, Et(AC), 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. An experiment using pilot reactor unit called SOLTEQ Plug Flow
Reactor (Model: BP 101), commonly known as PFR, plus some common laboratory apparatus
for titration process. Two solutions Sodium Hydroxide, NaOH and Ethyl Acetate, Et(Ac) were
reacted in the PFR and the product is then analyses by the method of titration to determine how
well did the reaction go. Hence, the experiment was conducted and the result shows that the
amount of conversion of Sodium Hydroxide, NaOH is almost unchanged as residence time
increases. The results is tabulated and calculated.
2.0

INTRODUCTION
Type of chemical reactors remains a highly discussed subject in chemical process

industries worldwide. The reactor is of course, the place where chemical reactions take place.
Hence it is arguably the single most important part of any chemical process design. The design of
a reactor must be finely tuned so that its mechanisms suit the necessities of the process that is to
be carried. Depends on the nature of the materials in both the feed and of course the products, the
reactors may take a wide range of forms. This is why full comprehension of a reactor of a
particular design as well as its working mechanisms is very much vital to actually conduct a
particular chemical process.
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.

3.0

OBJECTIVE

4.0

To study the saponification reaction of ethyl acetate, Et (Ac) and sodium hydroxide,
NaOH.
To determine the reaction rate constant.

THEORY
In a 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 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, namely in both radial and axial directions.
In the ideal tubular reactor, which is called the plug flow reactor, specific assumptions
are made about the extent of mixing:
1
2
3

No mixing in the axial direction, i.e., the direction of flow


Complete mixing in the radial direction
A uniform velocity profile across the radius.
The absence of longitudinal mixing is the special characteristics of this type of reactor. It

is an assumption at the opposite extreme from the complete mixing assumption of the ideal
stirred tank reactor. The validity of the assumptions will depend on the geometry of the reactor
and the flow conditions. Deviations, which are frequent but not always important, are of two
kinds:
1
2

Mixing in longitudinal direction due to vortices and turbulence


Incomplete mixing in radial direction in laminar flow conditions

Mass Balance
For a time element t and a volume element V, the mass balance for species i is given by the
following equation:
QA CA v t- QA CAv+v t - rAVt = 0 (10.1.1)

Where QA : molar feed rate of reactant A to the reactor, mol/sec


CA: concentration of reactant A
rA : rate of disappearance of reactant A, mol/ltsec
The conversion, X, is defined as:
X = (initial concentration - final concentration) / (initial concentration)
Since the system is at steady state, the accumulation term in Equation (10.1.1) is zero.
Equation (10.1.1) can be written as:
-QA CA - rAV = 0 (10.1.2)

Dividing by V and taking limit as V 0


dCA/dV = -rA/QA (10.1.3)
This is the relationship between concentration and size of reactor for the plug flow reactor. Here
rate is a variable, but varies with longitudinal position (volume in the reactor, rather than with
time). Integrating,
-dV/ QA = dCA/rA (10.1.4)
At the entrance: V = 0
CA = CA0
At the exit: V = VR (total reactor volume)

CA = CA (exit conversion)

CA

VR
dCA
=
QA CA 0 rA

5.0

APPARATUS AND MATERIAL

SOLTEQ Plug Flow Reactor (Model: BP101)


Burette
Conical flask
Measuring cylinder
Beakers
0.1M Sodium Hydroxide, NaOH
0.1M Ethyl Acetate, Et(Ac)
0.25M Hydrochloric acid, HCl
Deionised water
pH indicator, Phenolphthalein

6.0

PROCEDURE

General start-up procedures


2

All the valves are ensured closed except V4, V8 and V17.
The following solutions are prepared: 20 litre of NaOH (0.1M) 20 litre of Et(Ac) (0.1M)1

3
4
5
6
7

litre of HCL (0.25M) for quenching


Feed tank B1 was filled with NaOH while feed tank B2 was filled with the Et(Ac).
The water jacket B4 was filled with water and pre-heater B5 was filled with clean water.
The power for the control panel was turned on.
Valves V2, V4, V6, V8, V9 and V11 were opened.
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
8

made sure to be equal.


Both solutions then were allowed to flow through the reactor R1 and overflow into waste

tank B3.
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
about200 rpm to ensure homogeneous water jacket temperature.

Experiment Procedures
1
2
3

The general starts up procedures were performed.


Valves V9 and V11 were opened.
Both the NaOH and Et (Ac) solutions were allowed to enter the plug reactor R1 and

empty into the waste tank B3.


P1 and P2 were adjusted to give a constant flow rate of about 300 ml/min at flow
metersFI-01 and FI-02. Both flow rates were ensured same. The flow rates were

recorded.
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.
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.
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.

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
2
3

The burette was filled up with 0.1 M NaOH solution.


10 mL of 0.25 M HCl was poured in a flask.
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

4
5
6

the saponification reaction.


3 drops of phenolphthalein were dropped into the mixture of sample and HCl.
The mixture then was titrated with NaOH until it turns light pink.
The amount of NaOH titrated was recorded.

7.0 RESULT
Reactor Volume.
Concentration of NaOH in the reactor, CNaOH

: 4L
: 0.1M (2L)

Concentration of NaOH in the feed vessel, CNaOH,f

: 0.1M (2L)

Concentration of HCl quench, CHCl,s

: 0.25 M (0.01L)

Volume of sample, Vs

: 0.05L

Table 1
Flow Rate of

Flow Rate of

NaOH

Et(Ac)

(ml/min)

(ml/min)

301
248
202
148
98
52

300
249
201
149
104
49

Time, (min)

Outlet

Volume of

Conductivity

NaOH

(ml)

6.1
5.9
5.8
5.5
4.8
4.1

14.0
14.4
15.1
16.7
18.9
21.6

5
5
5
5
5
5

Table 2
Residence

Conversion, X,

Reaction Rate

Rate of Reaction, -rA

Time, , (min)

(%)

Constant,k

(mol.L/min)

6.6667
8.0483
9.9255
13.4680
19.8019
39.6039

78.0
78.8
80.2
83.4
87.8
93.2

(L.mol/min)
5.327
4.571
4.081
3.717
3.634
3.461

2.578
2.054
1.599
1.024
5.409
1.600

x
x
x
x
x
x

10-3
10-3
10-3
10-3
10-4
10-4

Conversion Vs Residence Time


95
C
o
n
v
e
r
s
i
o
n

90
85
80
75
70
5

10

15

20

25

30

35

Residence Time ( Min )

Graph of conversion against residence time

SAMPLE OF CALCULATIONS

Residence Time
For flow rates of 300 ml/min :

Residence Time,

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

Total flow rate, Vo

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

( )

= 301 mL/min NaOH + 300 mL/min Et(Ac)


= 601 mL/min

40

45

= 0.601 L/min
Hence,
Residence Time,

4L
0.601 L/min

= 6.6667 min

Other residence times were calculated by the same way, and varying the flow rates.

Conversion
For flow rates of 301 ml/min :
Moles of reacted NaOH, n1,
n1= Concentration NaOH x Volume of NaOH titrated
= 0.1 M x 0.014 L
= 0.0014 mole
Moles of unreacted HCl, n2,
Moles of unreacted HCl = Moles of reacted NaOH
n2 = n1
n2 = 0.0014 mole
Volume of unreacted HCl, V1,

V1

n2
concentration HCl quench

0.0014
0.25

= 0.0056 L

Volume of HCl reacted, V2,


V2

= Total volume HCl V1


= 0.01 0.0056
= 0.0044 L

Moles of reacted HCl, n3,


n3

= Concentration HCl x V2
= 0.25 x 0.0044
= 0.0011 mole

Moles of unreacted NaOH, n4,


n4

= n3
= 0.0011 mole

Concentration of unreacted NaOH,


CNaOH unreacted

n4
volume sample

0.0011
= 0.05

Xunreacted =
=

= 0.0022 M
Concentration of NaOH unreacted
concentration NaOH
0.0022
0.1

= 0.22
= 1 - Xunreacted
= 1 - 0.22
= 0.78
Conversion for flow rate 301 mL/min
Xreacted

0.78 x 100% = 78 %

Reaction Rate Constant,k


k=

v0
X
V TFR C AO 1X

For flow rates of 300 ml/min :


V0

= Total inlet flow rate


= 0.6 L/min

VTFR

= Volume for reactor


= 0.4 L

CAO

= inlet concentration of NaOH


= 0.1 M

= 0.78
k=

0.6
0.78
(0.4)(0.1) 10.78

= 53.182 L.mol/min

Rate of Reaction, -rA


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

= 53.182 (0.1)2 (1-0.78)2


= 0.026 mol.L/min

8.0

DISCUSSION

A saponification reaction between NaOH and Et(Ac) were carried out using pilot Plug Flow
Reactor. The main objectives are to study the effect of residence time on the conversion and to
determine the reaction rate constant.
The reaction between NaOH and Et(Ac) is allowed to occur and mixed in the tank of plug flow
reactor. The flow rates was set at 300 mL/min as an initial value. The solutions were mixed until
it reached a steady state. Samples were taken and titrated to determine the concentration of
NaOH in the reactor and extent of conversion. The step was repeated by using different flow
rates at 250, 200, 150, 100 and 50 mL/min/
The residence time for each flow rates was calculated and tabulated. The residence time were
increasing inversely with decreasing flow rates. The result shown that at flow rate 300 mL/min

the residence time is 6.6667 min. The residence time is 8.0483 min at flow rate of 250 mL/min.
Next, at 200ml/min, 150 mL/min, 100 mL/min and 50 mL/min the residence time were 9.9255,
13.4680, 19.8019 and 39.6039.
From the titration, the conversion for 300 ml/min is 78 %. The conversion were 78.8 % for 250
mL/min, 80.2 % for 200 mL/min, 83.4 % for 150 mL/min, 87.8 % for 100 mL/min and 93.2 %
for 50 mL/min flow rates. The data collected is tabulated. A graph of conversion vs. residence
time was plotted and shows that the conversion is directly proportional to the residence time. The
percentage of conversion increases with increasing residence time. Hence, it can be conclude that
the conversion is more efficient when the residence time is higher in the plug flow reactor. in the
longer the residence time will make the mixture in the reaction mix better. More product will be
formed from the reaction.
Rather than that, in this experiment the rate of reaction between NaOH and Et(Ac) were also
calculated. The result shown that the rate of reaction (Mol/L.Min) for 300 mL/min flow rate is
2.578 x 10-3. The rate of reaction for 250 mL/min flow rate is 2.054 x 10-3. Next, for 200 mL/min
and 150 mL/min are 1.599 x 10-3 and 1.024 x 10-3 respectively. The rate of reaction for 100
mL/min flow rate is 5.409 x 10-4 and 1.600 x 10-4 for 50 mL/min flow rate. The rates of reaction
were decreasing respectively with decreasing flow rates.
9.0

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. Finally, the
conversion of the reaction is higher when the residence time is higher. It can be conclude
that, the conversion of the saponification is directly proportional with residence time.

10.0

RECOMMENDATION

The column needs further rinsing with deionised water to remove excess hydrogen ions

from the column


The titration process must be conducted carefully to obtain the required pink pale of

titration process of acid and base.


Always wear protective clothing, shoes, helmet and goggles throughout the laboratory

session.
Run the experiment after fully understand the unit and procedures.

11.0REFERENCES
1. Boles, M. A. and Y. A. Gengel, Thermodynamics, Engineering Approach , 7th ed.,
McGraw Hill Book Company, St. Louis, MO, 2011, p. 8-12.

2. Harriot, P., W. L. McCabe, and J. C. Smith, Unit Operations of Chemical Engineering, 7th
ed., McGraw-Hill Book Company, St. Louis, MO, 2011, p. 330-340.

3. Occupational Safety and Health Standards for Genreal Industry, 29CFR Part 1910.303,
1994.

4. AdiChemistry [Online] Available from


http://www.adichemistry.com/physical/kinetics/factors/factors-affecting-ratereaction.html

5. Kinetic Supplement [Online] Available from


http://www.usm.edu/polymerkinetics/genkin.pdf . Accessed on 23rd April 2013

6. Reaction law, Reaction Rates and Activation Energy [Online] Available from
http://www.csun.edu/chem/documents/Kinetics.pdf. Accessed on 25th April 2013