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Objective:
1. To determine the reaction rate of saponification reaction at given temperature
by measuring the conversion against reaction time.
2. To evaluate the reaction rate constant at constant temperature using differential
and integral methods of analysis.
3. To evaluate the rate constant at different temperatures and activation energy
determination from Arrehenius Plot.
Introduction:
A batch reactor is a vessel in which the chemicals are placed to react. Batch reactors
are normally used in small- scale laboratory set-ups to study the kinetics of chemical
reactions. The variation of a property of the reaction mixture is observed as the
reaction progresses in order to determine the order and rate constant of a chemical
reaction. Data collected consist of concentration of the component, volume of the
system and physical property like electrical conductivity.
Theory :
For any given reaction in a constant volume system, the rate of the reaction can be
represented by:
r A=kf ( C A )=
Where
rA
d C A
(1)
dt
CA
CA
dCA
=k dt =kt (3)
f (C A )
0
f (C A)
resulting equation with the experimental data, the rate constant k, and order of the
reaction can be determined assuming that the rate of reaction can be expressed by an
equation of form:
r A=k C nA ( 4)
The values of n and k can determined experimentally.
Differential method of analysis
Obtain concentration (
CA
are
CA
r A=k C nA
where n
vs time. Draw tangents at various points. Find the slopes, these slopes
dCA
dt
r A
at these concentrations.
Plot of
ln (r A )
vs
ln (C A )
ln (r A ) =ln k + n.
(order) if the assumed form of rate equation is correct. k may be obtained from
the intercept.
The reaction rate, r is generally depend on the reactant concentration and rate constant
(k). The rate constant can be determined by using a known empirical reaction rate that
is adjusted for temperature using the Arrhenius temperature dependence. Generally, as
the temperature increase so does the rate at which the reaction occurs. The
temperature dependency of rate is given by Arrhenius equation:
k ko e
E
RT
ko
RESULT:
Experiment 1: Calibration Curve
Conversion
NaOH
Et
water(
Conductivity
(%)
0
25
50
75
100
(mL)
100
75
50
25
0
Ac( mL)
0
25
50
75
0
mL)
100
100
100
100
100
(ms)
9.23
8.50
5.51
2.42
0.0081
Conductivity, (mS/cm) 4
2
0
0
20
40
60
80
100 120
conversion, (%)
Time(min)
0
3
6
9
12
15
18
conductivity (mS/cm)
35C
45C
55C
19.2
13.24
12.31
7.92
7.18
7.16
7.15
7.02
6.79
6.77
6.71
6.69
6.6
6.57
6.63
6.52
6.49
6.61
6.45
6.45
6.59
65C
11.89
6.51
6.34
6.30
6.28
6.28
6.27
Rate
constant, Rate
re
35C
45C
55C
65C
k
0.2881
0.2552
0.2270
0.2388
of
reaction
(M/min)
0.0029
0.0026
0.0023
0.0024
Table 2.3: Calculated rate constant and rate of reaction using integral method
Temperatu
Time
re
35C
45C
55C
65C
(min)
659.5
744.5
837.0
795.6
taken
20.0000
Linear
(AT 35C)
15.0000
1/CA , M-1
AT 45C
f(x)
f(x) =
= 0.24x
0.29x
+ 13.06
11.5
0.26x
12.07
0.23x +
12.3
10.0000
5.0000
AT 55C
AT 65C
4
Time, min
Graph 2.1: 1/CA, M-1 versus Time, min
Temperatu Oder
re
35C
45C
55C
65C
of rate
reaction
4.7822
4.0714
3.2498
1.928
constant, k
449.0346
79.5511
11.1039
1.9005
rate
of
reaction
(M/min)
0.0074
0.0067
0.0062
0.0224
Table 2.5: Calculated rate constant and rate of reaction using differential method
Temperatu Time
re
35C
45C
55C
65C
taken
(min)
0.4
2.4
17.1
100.0
Polynomial (35C)
f(x)
=
f(x)
0x^2
0.01x
+
0.09
f(x) =
= 0x^2
0x^2 --- 0.01x
0.01x +
+ 0.1
0.09
0.0800
CA (M)
45C
Polynomial (45C)
65C
Polynomial (65C)
0.0600
0.0400
0.0200
55C
Polynomial (55C)
0.0000
0
10
12
14
16
18
20
Time(min)
-3.0000
-2.8000
-2.6000
-2.4000
Linear (35C)
45C
Linear
(45C)
f(x) =
= 4.07x
4.78x
+ 4.38
6.11
f(x)
+
= 3.25x
+ 2.41
f(x) f(x)
= 1.93x
- 0.64
-5.5000
-6.0000
ln(-dCA/dt)
65C
-4.5000
-2.2000 -5.0000
-2.0000
55C
Linear (55C)
-6.5000
-7.0000
Linear (65C)
-7.5000
-8.0000
ln CA
Calculation:
Concentration of NaOH,
CA
= 0.1 mol/L
r A=k C A (2)
The OH ion is the most highly conductive species, thus ethyl acetate may be ignored.
C A =(1X )C A 0(3)
Where X is the fractional conversion of NaOH,
Integral method,
For a second order reaction with equimolar concentration, the fractional conversion is
related to the reaction rate constant by
1
1
=
+ kt(4 )
C A CA 0
d C A
=ln (r A )=ln k+ ln C A
dt
dCA
dt
ln
d C A
dt
Sample calculation:
1) For temperature = 35 C
At t= 3 min, the conductivity is 7.92 mS
Using integral method,
Using the line equation of calibration curve,
y=0.0981 x+10.038
X=
10.038 y
0.0981
= 0.2159
C A =(1X )C A 0
( 10.2159 ) 0.1 M
= 0.0784 M
1
=12.7535 M 1
CA
1
CA
1
1
The rate constant at 35C, k = 0.2881 M min
Rate of reaction
r A=k C A
From
dCA
dt
, the graph of ln
( ddtC )
A
y=4.7822 x +6.1071
Compare with
ln
( ddtC )=lnk + ln C
A
vs ln CA is plotted,
ln k =6.1071
1
k =449.03 M min
Rate of reaction
r A=k C A
t=
20010
=659.49 min
0.2881
ln k =
E a
RT
E A 1
+ln A
R T
( )
y=mx +c
(M-1
min-1)
ln k
T (C)
35.000
T ( K)
308.15
1/T
0.2881
-1.2444
0
45.000
00
318.15
0.0032
0.2552
-1.3657
0
55.000
00
328.15
0.0031
0.2270
-1.4828
0
65.000
00
338.15
0.0030
0.2388
-1.4321
00
0.0030
Graph of ln k vs 1/T
ln k
-1.1000
-1.1500
0.0029
-1.2000
-1.2500
-1.3000
-1.3500
-1.4000
-1.4500
-1.5000
-1.5500
0.0030
0.0031
0.0032
0.0033
-1.2444
1/T
( )
We know that
m=
E A
=719.29
R
E A =5980.18
E A =5.98
And
J
mol
KJ
mol
ln A=3.699
A=0.0247 M 1 min1
DISCUSSION:
From the experiment 2, the rate of reaction of ethyl acetate, Et(Ac) and sodium
hydroxide, NaOH has been studied. The saponification of ethyl acetate and sodium
hydroxide will produce sodium acetate and ethanol. The reading from the
conductivity meter is due to the OH- ions. As the reaction proceed with time, the
conductivity of the mixture of Et(Ac) and NaOH will decrease with time as shown in
Table 2.1 for 35 C ,45 C , 55 C and 65 C respectively. The reason cause the
decrease of conductivity is because with the progress of the reaction, highly
conducting OH ions in the solution were replaced by an identical number of less
conducting acetate ions resulting in a continuous decrease in conductivity of solution.
(Das, Sahoo, Magapu, & Swaminathan, 2011)
Besides, the conversion, X increase as the time proceed as more reactants are being
converted to the products. Theoretically, the rate constant, k and the rate of reaction
should increase when the temperature of saponification reaction is increased by
interval of 10 C from 35 C to 65 C. However, the result we obtained is not same
with the expected result as the rate constant and rate of reaction show in table 2.3 is a
decreasing trend with the increased of temperature. At high temperature, more kinetic
energy is provided to the reactants to increase the probability of collision between
reactant molecules and overcome the activation energy to form the products. The error
in our result may due to the insensitivity of conductivity meter to detect the
conductivity changes in the solution as the reaction at high temperature (55 C & 65
C) is considerably fast. Therefore, error in the conductivity will lead to false rate
constant and rate of reaction. By compare the integral method and differential method,
the order of the saponification reaction calculated by using integral method is 2 while
the order calculated by using differential method is not equal to 2. This indicate
differential method is less accurate and the error can be avoid if large amount and
accurate data is provided when differential method is being used.
EA
5.98
KJ
mol
The rate constants for forward and reverse reaction treating the saponification
reaction as reversible reaction
In this experiment, the saponification of ethyl acetate and sodium hydroxide is a
reversible reaction. The forward reaction is very fast once the ethyl acetate mixed
with sodium hydroxide. The forward reaction happened faster than the reverse
reaction until it reaches equilibrium. The reaction of saponification is given as shown:
C 4 H 8 O2 + NaOH C 2 H 4 O2 Na+C 2 H 6 O
At equilibrium state, the forward and reverse reaction is balance and there is no net
change in concentration of reactant and product.
r forward =r reverse
By substituting the rate law for the forward and reverse reaction:
k forward [ C 4 H 8 O2 ] [ NaOH ] =k reverse [ C 2 H 4 O2 Na ][ C2 H 6 O ]
The forward and reverse rate constant are both constants, so the ratio of forward rate
constant to reverse rate constant can be known as equilibrium constant.
K c=
k forward [ C 2 H 4 O2 Na ][ C2 H 6 O ]
=
k reverse
[ C 4 H 8 O2 ] [ NaOH ]
At any rate for forward and reverse reaction, the ratio will remain the same all the
time.
The advantage of the batch reactor for obtaining kinetic data:
use.
When sufficiently vigorous mixing, film diffusion and sometime particle
system
Reaction condition such as pH, ionic strength and removal of CO 2 and O2
are easily to controlled.
The disadvantage or limitation of the batch reactor for obtaining kinetic data:
, there is a change of about 20Hz in pulse frequency. So the data can be monitor the
Application
Batch reactor needs a certain time to complete a reaction of chemicals, so it need
higher amount of time to produce numbers of product. Thats mean, batch reactor can
only produce small amount of product compare to other reactor. Because of low cost
and easy to operate, batch reactors are usually used in small scale industries. Next,
batch reactor is also uses some small pieces of equipment to produce various kind of
product. For some expensive products, batch reactor can also be used in those
productions. Products such as pharmaceuticals, dyes and dye intermediates are
produced by using batch reactor. Other than that, batch reactors are also used in
manufacture of colorants and margarine which is widely used in our life.
Conclusion:
The results that obtained had successfully calculated reaction rate, reaction rate
constant and activation energy of saponification reaction. Although there are some
errors need to improve, the results that obtained are can be accepted.
REFERENCES:
1. Das, K., Sahoo, P., Magapu, S. B., & Swaminathan, P. (2011, August 25).
Kinetic Studies on Saponification of Ethyl Acetate using an Innovative
Conductivity-Monitoring Instrument with a Pulsating Sensor. Retrieved from
https://www.researchgate.net/publication/229360677_Kinetic_Studies_on_Sap
onification_of_Ethyl_Acetate_Using_an_Innovative_ConductivityMonitoring_Instrument_with_a_Pulsating_Sensor
2.
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2016,
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