Table of Contents

ABSTRACT ............................................................................................................................... 3
INTRODUCTION ...................................................................................................................... 4
OBJECTIVES ............................................................................................................................ 4
THEORY .................................................................................................................................... 5
APPARATUS& MATERIALS .................................................................................................. 8
PROCEDURE ............................................................................................................................ 9
RESULTS................................................................................................................................. 10
CALCULATIONS ................................................................................................................... 15
DISCUSSION .......................................................................................................................... 17
CONCLUSION ........................................................................................................................ 18
RECOMMENDATIONS ......................................................................................................... 18
REFERENCES ......................................................................................................................... 19
APPENDIX .............................................................................................................................. 19

ABSTRACT/SUMMARY
The objectives of the experiment were to study the effect of temperature on reaction constant, k
of the saponification reaction between NaOH and ethyl acetate and also to determine the
activation energy of saponification. The reaction rate, rA was measured throughout 5 minutes
interval for 25 minutes at temperature of 30, 40, 50 and 60 C. Then the samples were titrated to
determine the reactions that occur in the reactor. The samples were taken for every 5 minutes for
all temperatures. The reaction constant, k was obtained from slope of graph of 1/Ca vs. time. At
30, 40, 50 and 60 C, the reaction constant, k was 5.9447, 5.4616, 9.7958 and 14.769 Lmol-1min1 respectively. The results can be referring to table 1 to table 4 for each temperature. The results
obtained were according to the theory but for temperature 40C, some error has occurred because
of mishandling the sample. For the second objective, the activation energy was the slope obtained
by comparing the equation of the straight line from the graph to the equation of ln k= -Ea/(RT) +
ln A as we can get from figure 7, graph of ln k vs. 1/T the activation energy was

All

the objectives were achieved. The values of the reaction constant were obtained and the
activation energy was calculated. The experiments were supposed to be conducted carefully so
that the results obtained for calculation are correct.

INTRODUCTION
Reactor is one of the most important parts in industrial sector. Reactor is equipment that changes
the raw material to the product that we want. A good reactor will give a high production and
economical. One of criteria to choose or to design a good reactor is to know the effectiveness of
the reactor itself. There a many types of reactor depending on the nature of the feed materials and
products. One of the most important we need to know in the various chemical reaction was the
rate of the reaction.

By studying the saponification reaction of ethyl acetate and sodium hydroxide to form
sodium acetate in a batch and in a continuous stirred tank reactor, we can evaluate the rate data
needed to design a production scale reactor.

A stirred tank reactor (STR) may be operated either as a batch reactor or as a steady state
flow reactor (CSTR). The key or main feature of this reactor is that mixing is complete so that
properties such as temperature and concentration of the reaction mixture are uniform in all parts
of the vessel. Material balance of a general chemical reaction described below. The conservation
principle requires that the mass of species A in an element of reactor volume dV obeys the
following statement:

(Rate of A into volume element) - (rate of A out of volume element) + (rate of A produced
within volume element) = (rate of A accumulated within vol. element)

OBJECTIVES
The objectives of this experiment are:
1. To determine the effect temperature i=on reaction rate constant, k for batch reaction.
2. To determine the activation energy of saponification.

THEORY
IDEAL STIRRED-TANK REACTOR

A stirred-tank reactor (STR) may be operated either as a batch reactor or as a steady-state

flow reactor (better known as Continuous Stirred-Tank Reactor (CSTR)). The key or main
feature of this reactor is that mixing is complete so that properties such as temperature and
concentration of the reaction mixture are uniform in all parts of the vessel. Material balance of a
general chemical reaction is described below.

The conservation principle required that the mass of species A in an element of reactor volume
V obeys the following statement:

Rate of

Rate of

into

Rate of A

out of

produced

Rate of A
=

Accumulated

within

within

volume

volume

volume

volume

element

element

element

Element

BATCH STIRRED-TANK REACTOR (BSTR)

In batch reactions, there are no feed or exit streams and therefore equation (1) can be simplified
into:
Rate of A
produced

Rate of A
=

accumulated

within

within

volume

volume

element

element

The rate of reaction of component A is defined as:

-rA = 1/V (dNA/dt) by reaction = [moles of A which appear by reaction]

[unit volume] [unit time]

By this definition, if A is a reaction product, the rate is positive; whereas if it is a reactant which
is consumed, the rate is negative.

Rearranging equation,
(-rA) V = NAO dXA
dt

Integrating equation gives,

t = NAO dXA__
(-rA)V
where t is the time required to achieve a conversion XA for either isothermal or non-isothermal

1/-rA

operation.

Area = t

Ca

EFFECT OF TEMPERATURE ON RATE OF REACTION

As we increase the temperature the rate of reaction increases. This is because, if we heat a
substance, the particles move faster and so collide more frequently. That will speed up the rate of
reaction. Collisions between molecules will be more violent at higher temperatures. The higher
temperatures mean higher velocities. This means there will be less time between collisions. The
frequency of collisions will increase. The increased number of collisions and the greater violence
of collisions result in more effective collisions. The rate for the reaction increases. Reaction rates
are roughly doubled when the temperature increases by 10 degrees Kelvin.
In any single homogenous reaction, temperature, composition and reaction rate are
uniquely related. They can be represented graphically in one of three ways as shown in figure 8
below:

r3
r2
r1

APPARATUS AND MATERIALS

Apparatus
1. Continuous stirred tank reactor (Model BP:100)

Figure 1: CSTR

2. Stopwatch
3. Beaker
4. Pipet
5. Volumetric cylinder

Material
1. 0.1M NaOH
2. 0.1M Ethyl acetate
3. 0.25M HCl

PROCEDURE
1. General start-up procedures are perform earlier.
2. Then, overflow tube was adjusted to give a working volume of about 2.5 liters. Pump P1
was switched on and pumping 1.25 liters of 0.1 M of ethyl acetate from the feed pump
into the reactor. Then, stirrer is switched on at a medium speed follow by the heater which
the reaction temperature was set at room temperature of 26oC.
3. Consequently, switched on Pump P2 with the valve was set at maximum flow rate and
pump 0.1 M NaOH into the reactor at same volume of ethyl acetate, 1.25 liters. As soon
as the level of the reactants reached 2.5 liters, switched off Pump P2 and the timer starts
immediately at t0.
4. At the same time, 25 ml of 0.25 M HCl was prepared in a flask to quench with the
sample.
5. After 1 minute of reaction time, 100 ml of sample was collected by opening the sampling
valve and immediately quench the sample with prepared HCL solution.
6. Then, the sample was titrated with 0.1 M NaOH under the hood, to determine the amount
of unreacted HCL in the sample. 3 drops of phenolphthalein was added into the solutions
as prior to the titration.
7. Step 4 to 6 was repeated for reaction times 5, 10, 20, 25 minutes.
8. Step 1 to 7 was repeated for temperatures of 40, 50 and 60oC.
9. All switched are turned off after the experiment done and general shut down procedure
was done immediately.

RESULT
Temperature = 30C
Table 1
Time
(min)

1
5
10
15
20
25

Volume Volume
of
of
titrating unreacted
NaOH quenching
(mL),V1 HCl, V2
(mL)

17
18.7
19.7
21.3
22.1
22.5

6.8
7.48
7.88
8.52
8.84
9

Volume
of HCl
reacted
with
NaOH in
sample,
V3 (mL)

Moles of
HCl
reacted
with
NaOH in
sample,
n1 (mol)

Moles of
unreacted
NaOH in
sample, n2
(mol)

3.2
2.52
2.12
1.48
1.16
1

0.0008
0.00063
0.00053
0.00037
0.00029
0.00025

0.0008
0.00063
0.00053
0.00037
0.00029
0.00025

Concentra- Conversion
tion of
of NaOH
unreacted
in the
NaOH in the reactor, X
reactor, Ca
(%)
(M)

0.016
0.0126
0.0106
0.0074
0.0058
0.005

68
74.8
78.8
85.2
88.4
90

1/Ca

62.5
79.36508
94.33962
135.1351
172.4138
200

1/Ca vs. time(min)

250
y = 5.9447x + 48.659
R = 0.9805

1/Ca

200
150
100
50

time (min)

0
0

10

15

20

25

30

Figure 2: graph of 1/Ca vs. time (min)

Rate constant, k (Lmol-1min-1) = 5.9447

Temperature = 40C
Table 2
Time
(min)

Volume
of
titrating
NaOH
(mL),V1

Volume
of
unreacted
quenching
HCl, V2
(mL)

1
5
10
15
20
25

18
19.5
20.6
21.1
22
22.6

7.2
7.8
8.24
8.44
8.8
9.04

Volume
of HCl
reacted
with
NaOH
in
sample,
V3 (mL)
2.8
2.2
1.76
1.56
1.2
0.96

Moles of
HCl
reacted
with
NaOH in
sample, n1
(mol)

Moles of
unreacted
NaOH in
sample, n2
(mol)

Concentration of
unreacted
NaOH in
the
reactor, Ca
(M)

0.0007
0.00055
0.00044
0.00039
0.0003
0.00024

0.0007
0.00055
0.00044
0.00039
0.0003
0.00024

0.014
0.011
0.0088
0.0078
0.006
0.0048

Conversion 1/Ca
of NaOH
in the
reactor, X
(%)

72
78
82.4
84.4
88
90.4

71.42857
90.90909
113.6364
128.2051
166.6667
208.3333

1/Ca vs time (min)

250
y = 5.4616x + 60.682
R = 0.9701

1/Ca

200
150
100
50

time (min)

0
0

10

15

20

25

30

Figure 3: graph of 1/Ca vs. time (min)

Rate constant, k (Lmol-1min-1) = 5.4616

10

Temperature = 50C

Table 3
Time Volume Volume
(min) of
of
titrating unreacted
NaOH
quenching
(mL)
HCl, V2
(mL)
1
5
10
15
20
25

17.8
20.3
21.6
22.5
22.9
23.4

7.12
8.12
8.64
9
9.16
9.36

Volume
of HCl
reacted
with
NaOH in
sample,
V3 (mL)
2.88
1.88
1.36
1
0.84
0.64

Moles of
HCl
reacted
with
NaOH in
sample, n1
(mol)
0.00072
0.00047
0.00034
0.00025
0.00021
0.00016

Moles of
unreacted
NaOH in
sample, n2
(mol)

Concentration of
unreacted
NaOH in
the reactor,
Ca (M)

0.00072
0.00047
0.00034
0.00025
0.00021
0.00016

0.0144
0.0094
0.0068
0.005
0.0042
0.0032

Conversion 1/Ca
of NaOH
in the
reactor, X
(%)

71.2
81.2
86.4
90
91.6
93.6

69.44444
106.383
147.0588
200
238.0952
312.5

1/Ca vs. time (min)

350
y = 9.7958x + 54.834
R = 0.9903

300

1/Ca

250
200

150
100
50
time (min)

10

15

20

25

30

Figure 4: graph of 1/Ca vs. time (min)

Rate constant, k (Lmol-1min-1) = 9.7958

11

Temperature = 60C

Table 4
Time
(min)

Volume
of
titrating
NaOH
(mL)

Volume
of
unreacted
quenching
HCl, V2
(mL)

1
5
10
15
20
25

19.2
21.1
22.4
22.9
23.5
23.9

7.68
8.44
8.96
9.16
9.4
9.56

Volume
of HCl
reacted
with
NaOH in
sample,
V3 (mL)
2.32
1.56
1.04
0.84
0.6
0.44

Moles of
HCl
reacted
with
NaOH in
sample,
n1 (mol)
0.00058
0.00039
0.00026
0.00021
0.00015
0.00011

Moles of
unreacted
NaOH in
sample, n2
(mol)

Concentration of
unreacted
NaOH in
the reactor,
Ca (M)

0.00058
0.00039
0.00026
0.00021
0.00015
0.00011

0.0116
0.0078
0.0052
0.0042
0.003
0.0022

Conversion 1/Ca
of NaOH
in the
reactor, X
(%)

76.8
84.4
89.6
91.6
94
95.6

86.2069
128.2051
192.3077
238.0952
333.3333
454.5455

1/Ca vs. time (min)

500
450

y = 14.769x + 51.706
R = 0.9678

400

1/Ca

350
300
250
200
150

100
50
0
0

10

15
time (min)

20

25

30

Figure 5: graph of 1/Ca vs. time (min)

Rate constant, k (Lmol-1min-1) = 14.769

12

1/Ca vs. time (min)

500
450

y = 14.769x + 51.706
R = 0.9678
y = 9.7958x + 54.834
R = 0.9903

400
350

y = 5.4616x + 60.682
R = 0.9701

250

T=40 oC
T=50 oC
T=60 oC

200
150

100
y = 5.9447x + 48.659
R = 0.9805

50
0
0

10

15
time (min)

20

25

30

Figure 6: graph of 1/Ca vs. time (min) for 30, 40, 50 and 60 C

ln K vs. 1/T
16
14
12
10
ln K

1/Ca

300

T = 30 oC"

8
6
y = -508.41x + 21.068
R = 0.6802

4
2
0
0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

1/T

Figure 7: graph of ln K vs. 1/T

13

SAMPLE OF CALCULATION

Volume of sample, Vs

= 50 mL

Concentration of NaOH in feed vessel, Ca,f

= 0.1 M

Volume of HCl for quenching, VHCl,s

= 10 mL

Concentration of HCL in standard solution, CHCl,s

= 0.25 M

At temperature = 30 C
Concentration of NaOH entering the reactor, CNaOH,0 = (CNaOH,f) / 2
= 0.1 mol/L / 2
= 0.05 mol/L

Volume of unreacted quenching HCl, V2

= (CNaOH,s / CHCI,s) x V1
= (0.1 / 0.25) x 17
= 6.8 mL

Volume of HCl reacted with NaOH in sample, V3

= VHCl,s V2
= 10 6.8
= 3.2 mL

Moles of reacted HCl with NaOH in sample, n1

= (CHCI,s x V3 ) / 1000
= (0.25 x 3.2) / 1000
= 0.0008 mol

Moles of unreacted NaOH in sample, n2

= n1
= 0.0008 mol

Conc. of unreacted NaOH in the reactor, Ca

= (n2 / Vs) x 1000

= 0.0008 / (50/1000)
= 0.016 mol/L

14

Conversion of NaOH in the reactor, X

= (1 Ca / Ca0 ) x 100%
= ( 1- (0.016 / 0.05) x 100%
= 68 %

To determine the rate constant, k

From the graph of 1/Ca vs. T plotted, the equation of straight line obtained is compared with
equation 1/Ca = kt + 1/Cao
From figure 5,

y = 5.9447x + 48.659

Compared to equation, 1/Ca = kt + 1/Cao

The value of k = 5.9447 Lmol-1min-1.
Rate of reaction, -rA = kCA2
= (5.9447)(0.016)2
= 1.5218 x 10-3

To determine the activation energy, Ea

According to the graph plotted in Figure 6, the equation of straight line obtained was
Y = - 508.41 x + 21.068
Comparing to equation

15

DISCUSSION
The objective of the experiment was to study the effect of temperature on reaction constant, k of
the saponification reaction between NaOH and ethyl acetate. The reaction rate, rA was measured
throughout 5 minutes interval for 25 minutes at temperature of 30, 40, 50 and 60 C.
From Arrheniuss equation, k = Ae-E/RT it show that the temperature has an effect to the
reaction rate constant. It states that when the rate constant doubles, so wills the rate of reaction.
The higher the temperature the faster the molecules move producing much more kinetic energy
than normal. More collision is happen in order for a reaction to occur and thus larger fraction of
molecules to provide the activation energy needed for the reaction. Activation energy, Ea is the
minimum energy needed for the reaction to occur.

In the experiment, the reaction constant, k was obtained from slope of graph of 1/Ca vs.
time. At 30, 40, 50 and 60 C, the reaction constant, k was 5.9447, 5.4616, 9.7958 and 14.769
Lmol-1min-1 respectively. From the graph plotted it can be seen that the reaction constant is
increases with temperature except at temperature 40 C. This was happen because of the
misconduct procedure during the experiment where the sample was not titrated immediately. The
sample collected from the reactor supposed to be titrated immediately under the hood to
determine the amount of unreacted HCL in the sample.

The activation energy was the slope obtained by comparing the equation of the straight
line from the graph to the equation of ln k= -Ea/(RT) + ln A. From figure 7, graph of ln k vs. 1/T
the activation energy was

The reaction was endothermic in which the reaction

absorb energy to form bonds in the reaction. The bonds of the products are higher than the bonds
of the reactants.

16

CONCLUSION
All in all, all the objectives were achieved. The values of the reaction constant were obtained and
the activation energy was calculated. The experiments were supposed to be conducted carefully
so that the results obtained for calculation are correct. As an example for temperature 40 C. We
should know that the sample should be titrated immediately because it may react with the
surroundings. All the mistakes can be corrected for the next experiment for the next time.

RECOMMENDATIONS
1. Make sure all the flask, apparatus that involved in titration process is cleaned from
chemicals because it will affect the titration results.
2. Wait until the system stable before taking the reading, because sometimes, the system is
not well reacted, but students already take the readings.
3. Make sure all valves are in their right positions before starting the experiments to prevent
any damages into the equipment.
4. Before taking the sample, make sure flush the products a little bit, just to ensure there are
no previous product in the outlet stream
5. Do not let the temperature shoot higher or lower than the temperature needed. Make sure
the temperatures are well controlled.

17

REFERENCES

Levenspiel, O, Chemical Reaction Engineering, John Wiley, 1972

Robert H.Perry, Don W.Green, Perrys Chemical Engineers Handbook, McGraw

Hill,1998.

Smith,J.M, Chemical Engineering Kinetics, McGraw Hill, 1981.

Rate Constants and The Arrhenius Equation. Retrieved on OCTOBER 30, 2013 from
http://www.chemguide.co.uk/physical/basicrates/arrhenius.html

APPENDIX
Please refer to the next page.

18