TITLE: BATCH REACTOR

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

is the rate of disappearance of reactant A among the reacting species.

Equation (1) can be rearranged to give:

d C A
=kdt (2)
f (C A)
Integrating the equation (2) analytically yields

CA

CA

dCA
=k dt =kt (3)
f (C A )
0

By postulating various forms for

f (C A)

in equation (3) and correlating the

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

Hypothesize a rate equation. For example equation (4),

is the assumed order.

Obtain concentration (
CA

are

CA

r A=k C nA

where n

versus time data from batch experiments. Draw

vs time. Draw tangents at various points. Find the slopes, these slopes
dCA
dt

are the rate of reaction (

r A

at these concentrations.

Taking logs on both sides of the rate equation will give

Plot of

ln (r A )

vs

ln (C A )

ln (r A ) =ln k + n.

will give a straight line with slope 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

Where k is the rate constant,

ko

is the frequency factor, E is the activation energy, R

is the gas constant, T is absolute temperature.

Materials and Equipment:

1. Beaker: 2L 1, 1L 1, 250mL 2
2. Measuring Cylinder: 100mL 2
3. Glass rod
4. Conductivity meter
5. Electric stirrer
6. Water bath
7. Stopwatch
8. 5 L of 0.1 M sodium hydroxide, NaOH
9. 2 L of 0.1 M ethyl acetate, Et(Ac)
10. 500mL of 0.1 M sodium acetate, Na(Ac)
11. 1 L of deionized water, H20
Setup:

Figure 1: Setup of Batch reactor

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

Table 1: Conductivity at different conversion

Graph of Calibration curve of Conductivity, mS/cm vesus Conversion,%

10

f(x) = - 0.1x + 10.04

8 R = 0.97
6

Conductivity, (mS/cm) 4
2
0
0

20

40

60

80

100 120

conversion, (%)

Graph 1: Calibration curve of Conductivity versus Conversion

Experiment 2: Rate of Reaction

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

Table 2.1: Conductivity at different temperature and time

2.1: For integral method

Table 2.2: calculated parameters for rate constant of integral method

Temperatu

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

Table 2.4: Time required reaching 95 % conversion

Graph of 1/CA,M-1 versus Time,min

AT 35C

20.0000
Linear
(AT 35C)
15.0000

1/CA , M-1

AT 45C

Linear (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

Linear (AT 55C)

0.0000
0
2

AT 65C
4

Linear (AT 65C)

10 12 14 16 18 20

Time, min
Graph 2.1: 1/CA, M-1 versus Time, min

2.2: For differential method

Table 2.4: calculated parameters for rate constant of differential method

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

Table 2.6: Time required reaching 95 % conversion

Graph of CA (M) vesusTime(min)

0.1200
0.1000
35C

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)

Graph 2.2: CA (M) vesusTime(min)

Graph of ln(-dCA/dt) vssus ln CA

35C

-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

Graph 2.3: Graph of ln(-dCA/dt) versus ln CA

Calculation:
Concentration of NaOH,

CA

= 0.1 mol/L

Second order reaction:

r A=k C 2(1)
In this reaction, since
C A =C B
Thus,
2

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

Figure2: Graph of Second order reaction for integral method

Differential method,
r A=k C
Where the is the order of reaction
For a second order reaction with equimolar concentration, the fractional conversion is
related to the reaction rate constant by
ln

d C A
=ln (r A )=ln k+ ln C A
dt

dCA
dt

ln

is found from CA vs t by polynomial method

d C A
dt

vs ln CA is plotted for the reaction order

, which is the slope of the

line fit to the data. Thus, rate constant, k can be determined.

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

From the Graph of

versus time plotted,

1
1
The rate constant at 35C, k = 0.2881 M min

Rate of reaction
r A=k C A

0.2881 M 1 min1 (0.1 M )2

0.002881 M min1

Using differential method

From the CA vs t, the polynomial equation is y = 0.0002x2 - 0.0051x + 0.0966
C A =0.0002 t 2 0.0051t +0.0966
dCA
=0.0004 t0.0051
dt

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

449.03 M 1 min1 (0.1 M ) 4.7822

0.0074 M min1

2) Time required to reach 95% conversion

1
1
=
+kt
C A CA 0
1
1
=
+0.2881 t
(10.95)(0.1) 0.1

t=

20010
=659.49 min
0.2881

3) Activation energy determination from Arrehenius plot

k ( T )=Ae

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

Table 3: Calculated parameters for activation energy using Arrhenius plot

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

f(x) = 719.29x - 3.61

-1.3657
-1.4321
-1.4828

1/T

Graph 3: Graph of ln k versus EA/R

By plotting the graph ln k versus EA/R,

E A 1
ln
k
=
+ln A ,
Compare the equation y = 719.29x 3.6098 and
R 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.

The activation energy,

The activation energy is

EA

has been evaluated from the Arrehenius plot ( Graph 3 )

5.98

KJ
mol

, the negative sign indicate the saponification

reaction is an exothermic reaction.

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:

Batch reactor is an economic equipment requirements relatively easy to

use.
When sufficiently vigorous mixing, film diffusion and sometime particle

diffusion can be eliminated.

Constant solution solid ratio is readily maintained in some batch reactor

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:

Desorbed species will be no removed and are allowed to accumulate in the

inherently closed system of the batch reactor. Unless a unidirectional reaction
is being studies, reverse reactions must be taken into account in the data
analysis. The accumulation of desorbed species can sometimes result in

secondary precipitation reactions, which further complicate data analysis.

The mixing method employed may not produce a uniform suspension of no
sufficient to mass transfer of solute. Furthermore, surface area may be increase

by prolonged mixing be some methods.

Sampling and phase separation steps are not always uniform and are operator
dependent.

In the case of rapid surface reaction, sampling and phase

separation are not rapid enough to follow the reaction.

The most appropriate method of continuously monitoring the concentration of
reactants during saponification reaction
According the research of Das, K., Sahoo, P., Magapu, S. B., & Swaminathan,
P (2011), using pulsating conductivity meter is the more appropriate to monitoring the
concentration of the reactant during the saponification. The conductivity meter is
designed in such a way that the conducticity cell forms a part of a specially designed
logic gate oscillator (LGO) circuit. The frequency of LGO changes with the change in
the ionic conductivity of the solution taken in the ceel. The frequency is directly
related to the conductivity of the solution. In the present case, the instrument is
designed in such a way that with a change in conductivity of the solution by 1 S cm -

, there is a change of about 20Hz in pulse frequency. So the data can be monitor the

change of the concentration of the reactant1.

Figure3: the data showing of saponification reaction by pulsating conductivity meter

Precaution
There are some precaution that need to be aware when conduction this experiment.
First, the timer must start once the ethyl acetate solution is completely poured into the
beaker contain 0.1M sodium hydroxide and the initial reading need to be recorded.
Next, prevent the contact of any part of the body into the water bath as it is heated in
high temperature. Other than that, the unit of the conductivity meter must be aware
when the measure of conductivity of the solutions happen because the meter will
show in a smaller unit when the conductivity of the solution is very small.
Furthermore, prevent the contact of the fin of the mechanical overhead stirrer when
the stirrer is in operation as the fin has sharp surface and it is spinning in high
rotational speed which is 250rpm to avoid injuries. Lastly, gloves must be worn all
time to prevent the contact of hands with the chemicals.

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.

Magdi Selim.H and Micheal C. Amacher (1997) Reactivity and transport of

heavy

metal

in

solids.[online]

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c=y#v=onepage&q=advantage%20of%20obtaining%20kinetic%20data%20in
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3. CIEC Promoting Science at the University of York, York, UK. (n.d.).
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27

2016,

from

http://www.essentialchemicalindustry.org/processes/chemical-reactors.html
4. Reactors design and types: Its advantages and disadvantages. (2015).
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