4 | P a g e

OBSERVED DATA

Volume of sample taken = 5 ml
Concentration of NaOH = 2N
Density of Acetic Acid = 1.05 g/cc
Density of Ethanol = 0.79 g/cc

Table 01: Observed Data for Esterification of Ethanol and Acetic Acid in Batch Reactor with
H
2
SO
4
Catalyst
No. of
Obs.
Cumulative
Time,
t
(min)
Sample
Volume
(ml)
Volume of NaOH (ml)
Initial BR
Final
BR
Difference
1 0
5
0.7 16 15.3
2 10 16 30.9 14.9
3 20 30.9 45.5 14.6
4 30 1 15.3 14.3
5 40 15.3 29.6 14.3
6 50 29.6 43.7 14.1
7 60 0.4 14.1 13.7
8 70 14.1 27.9 13.8
9 2.7 15.5 12.8








5 | P a g e

CALCULATED DATA

Table 02: Calculated Data of Reactant and Product Concentrations and Extent of Reaction










Cumulativ
e Time, t
(min)
Strength of
CH
3
COOH
C
A
(mol/L)
Extent of
Reaction

*
= C
A0
- C
A
(mol/L)
Strength of
C
2
H
5
OH
C
B
( mol/L )
Strength of
CH
3
COOC
2
H
5
C
E
( mol/L
)
Strength of
H
2
O
C
W
( mol/L )
0 6.12 0.18 10.7946 0.18 0.18
10 5.96 0.34 10.6346 0.34 0.34
20 5.84 0.46 10.5146 0.46 0.46
30 5.72 0.58 10.3946 0.58 0.58
40 5.72 0.58 10.3946 0.58 0.58
50 5.64 0.66 10.3146 0.66 0.66
60 5.48 0.82 10.1546 0.82 0.82
70 5.52 0.78 10.1946 0.78 0.78
2.16 4.14 6.8346 4.14 4.14
6 | P a g e

Table 03: Calculated Data for Determining Rate Expression for 1
st
Order Irreversible
Reaction
Cumulative Time, t (min) ln(C
A
)
0 1.812
10 1.785
20 1.765
30 1.744
40 1.744
50 1.730
60 1.701
70 1.708


Table 04: Calculated Data for Determining Rate Expression for 1
st
Order Reversible Reaction
Cumulative Time, t (min) ln(KC
A
- C
E
)
0 0.207
10 0.033
20 -0.121
30 -0.303
40 -0.303
50 -0.447
60 -0.814
70 -0.709

7 | P a g e

Table 05: Calculated Data for Determining Rate Expression for 2
nd
Order Irreversible
Reaction (Type-I)
Cumulative Time, t (min) 1/C
A
(L/mol)
0 0.163
10 0.168
20 0.171
30 0.175
40 0.175
50 0.177
60 0.182
70 0.181


Table 06: Calculated Data for Determining Rate Expression for 2
nd
Order Irreversible
Reaction (Type-II)
Cumulative Time, t (min) ln(C
B
/C
A
)
0 0.567
10 0.579
20 0.588
30 0.597
40 0.597
50 0.604
60 0.617
70 0.613
8 | P a g e

Table 07: Calculated Data for Determining Rate Expression for 2
nd
Order Reversible
Reaction
Cumulative Time, t (min) ln(M)
0 -1.109
10 -0.985
20 -0.895
30 -0.807
40 -0.807
50 -0.750
60 -0.636
70 -0.665















9 | P a g e

SAMPLE CALCULATION
Calculation of the Volume of Ethanol (B) and Acetic Acid (A) Required

Let the volume of ethanol, E = x ml
Total volume = 500 ml
So, the volume of acetic acid, A = (500 x) ml
No. of moles of ethanol, n
E
=
m
M

=
V
M

=
x ml 0.79 g ml
46 g mol

= 0.0172x mol

No. of moles of acetic acid, n
A
=
( ) 500 - x ml 1.05 g ml
60 g mol
= 0.0175(500 - x) mol
Now, from the molar ration we know,
0.0172x
0.0175(500 - x)
=
4
7

or, x = 320ml

Thus, Volume of Ethanol = 320 ml
Volume of acetic acid = 180 ml
No. of moles of ethanol = 0.0172 320 = 5.5 mol
No: of moles of acetic acid = 0.0175 180 = 3.15 mol

Initial concentration of Ethanol, C
B0
=
5.5mol 1000ml
500ml 1L



= 11 mol/L

Initial concentration of Acetic Acid, C
A0
=
3.15mol 1000ml
500ml 1L



= 6.3 mol/L
10 | P a g e

Calculation for Observation No. 2

In this observation concentration of sample was calculated after 10 min.

We know,
V
1
S
1
= V
2
S
2

1 1
2
2
V S 9.9 2
or, S = =
V 5

or, S
2
= 5.96 mol/L
so, C
A
S
2
= 5.96 N

Where, V
1
= volume of NaOH solution = 9.9 ml
S
1
= strength of NaOH solution = 2 N = 2 mol/L
V
2
= volume of acetic acid = 5 ml
S
2
= strength of acetic acid

-

= (C
A0
- C
A
) = (6.3 5.96) mol/L = 0.34 mol/L
C
B
= (C
E0
-
-
) = (11 0.34) mol/l = 10.66 mol/L
C
E
=
-
= 0.34 mol/L

Equilibrium Data, at t =
V
1
S
1
= V
2
S
2

S
2
=
2
1 1
V
S V
=
5
2 8 . 12
= 5.12 N
S
2
= C
A
= 5.12 mol/L

*

= (C
A0
- C
A
) = (6.3 5.12) = 1.18 mol/L
C
B
= (C
B0
-
-
) = (11 1.18) = 9.82 mol/L
C
E
=
*

= 1.18 mol/L
Equilibrium constant (for 1st order reaction), K =
E
A
C
C

= 0.2305

11 | P a g e



For first order irreversible reaction, ln(C
A
)
= ln(5.96)
= 1.785

For first order reversible reaction, ln(KC
A
C
E
)
= ln[(0.2305

5.96) - 0.34)]
= 0.03322 mol/L

Now,
f
r
k
k
= 0.2305 and from Fig 05, k
f
+ k
r
= 0.0138 min
-1

So, k
f
= 0.0026 min
-1
and k
r
= 0.0112 min
-1


For second order irreversible reaction (Type-I), 1/ C
A
= 1/5.96 = 0.168 L/mol

For second order irreversible reaction type II, ln(C
B
/C
A
) = ln(10.66/5.96) = 0.579

From Fig 07, (C
A0

B
- C
B0

A
) k = 0.0007 min
-1

So, k

=
)] 1 ( 11 [ )] 1 ( 3 . 6 [
0007 . 0

= 1.4910
-04
L mole
-1
min
-1


Equilibrium constant (for 2nd order reaction), K =
B A

-
C C
2
) (

=
82 . 9 12 . 5
) 18 . 1 (
2

= 0.028






12 | P a g e

For second order reversible reaction,
lnM = ln
( )
( )
* * *
* * *
{(K - 1) ( - ) - [K(A + B ) + E + W ]}
( - ){(K - 1) + K(A + B ) + E + W }



= -0.985

Where,
A + B

= 5.12 + 9.795 = 14.915
E + W

= 1.18 + 1.18 = 2.36
Now,
f
r
k
k
= 0.028 and from Fig 08, ( )
f r
[k (A + B ) + k E + W ]

= 0.0063 min
-1

So, k
f
= 6.3510
-05
L mole
-1
min
-1
and k
r
= 2.2710
-03
L mole
-1
min
-1























13 | P a g e

GRAPHICAL REPRESENTATION


Figure 03: Plot of Strength of Acetic Acid vs Cumulative Time


Figure 04: Plot of ln(C
A
) vs Cumulative Time
0
1
2
3
4
5
6
7
0 200 400 600 800 1000 1200
S
t
r
e
n
g
t
h

o
f

C
H
3
C
O
O
H
,

C
A

(
m
o
l
/
L
)


Cumulative Time, t (min)
Plot of Strength of Acetic Acid vs Cumulative Time
y = -0.0015x + 1.8005
R = 0.9419
1.68
1.7
1.72
1.74
1.76
1.78
1.8
1.82
0 10 20 30 40 50 60 70 80
l
n
(
C
A
)


Cumulative Time, t (min)
Plot of ln(C
A
) vs Cumulative Time
14 | P a g e


Figure 05: Plot of ln(KC
A
- C
E
) vs Cumulative Time


Figure 06: Plot of 1/C
A
vs Cumulative Time
y = -0.0138x + 0.1773
R = 0.9432
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0 10 20 30 40 50 60 70 80
l
n
(
K
C
A

-

C
E
)


Cumulative Time, t (min)
Plot of ln(KC
A
- C
E
) vs Cumulative Time
y = 0.0003x + 0.1651
R = 0.9447
0.16
0.165
0.17
0.175
0.18
0.185
0 10 20 30 40 50 60 70 80
1
/
C
A

(
L
/
m
o
l
)

Cumulative Time, t (min)
Plot of 1/C
A
vs Cumulative Time
15 | P a g e


Figure 07: Plot of ln(C
B
/C
A
) vs Cumulative Time


Figure 08: Plot of ln(M) vs Cumulative Time
y = 0.0007x + 0.5722
R = 0.9436
0.56
0.57
0.58
0.59
0.6
0.61
0.62
0.63
0 10 20 30 40 50 60 70 80
l
n
(
C
B
/
C
A
)


Cumulative Time, t (min)
Plot of ln(C
B
/C
A
) vs Cumulative Time
y = 0.0063x - 1.0521
R = 0.9338
-1.2
-1.1
-1
-0.9
-0.8
-0.7
-0.6
0 10 20 30 40 50 60 70 80
l
n
(
M
)


Cumulative Time, t (min)
Plot of ln(M) vs Cumulative Time
16 | P a g e

RESULTS

From the plotted graphs, following results were obtained.

Table 08: Results of the Experiment
Order of
Reaction
Type of
Reaction
Equilibrium
Constant, K
Rate Expression
Equation
R
2
Value Rate Constant
1
st

Irreversible
0.2305
y = -0.0015x + 1.8005 0.9419 k = 0.0015 min
-1

Reversible y = -0.0138x + 0.1773 0.9432
k
f
= 0.0026 min
-1

k
r
= 0.0112 min
-1

2
nd

Irreversible
(Type-I)
0.028
y = 0.0003x + 0.1651 0.9447
k = 0.0003
L mole
-1
min
-1

Irreversible
(Type-II)
y = 0.0007x + 0.5722 0.9436
k = 1.4910
-04

L mole
-1
min
-1

Reversible y = 0.0063x - 1.0521 0.9338
k
f
= 6.3510
-05

L mole
-1
min
-1

k
r
= 2.2710
-03

L mole
-1
min
-1










17 | P a g e

DISCUSSIONS

It is seen from the result table that the R-square value for each type of reaction is almost tends
to 1. But among them the type of second order irreversible reaction Type I the R-square value
is the greatest. So Esterification of ethanol is chosen as a Second Order Irreversible Reaction
of Type I for which rate constant, k = 0.0003 L mole
-1
min
-1
and the rate expression is, ln (C
B
/
C
A
) = 0.0003 t + 0.1651


While performing the experiment the reactant temperature was maintained at 80
o
C because it
is the optimum reaction temperature for maximum yield with desirable reaction rate.

Since the position of equilibrium controls the amount of the ester formed, the use and excess
of either the carboxylic acid or the alcohol increases the yield. Ethanol was chosen as the
excess reactant for economic reasons, since ethanol is less expensive of the two.

Yield of an esterification reaction can also be increased by removing water from the reaction
mixture as it is formed. So, sulfuric acid was chosen as catalyst, as it has the provision for
remove water.


Despite of all necessary caution while conducting the experiment, no rate expression was
perfectly fitted with experimental data. Deviation from accuracy of the graph may be
explained with the following reasons:


- The rate expressions used are valid for the constant volume system. But our system
was not of constant volume because during each observation we took 5 ml of sample
from the reactor.
- Sufficient time was not provided for attaining equilibrium condition.
- The temperature was fluctuating from the inception of the experiment. So it was hard
to keep the temperature at 80

C.
- The concentrations of the solutions used were tested at an earlier time, not at the time
of the experiment. Since the concentrations of the reactants and the titrating solution
greatly influences the results, any deviation from the assumed concentration can cause
a substantial error.
18 | P a g e

- The determination of order strongly depends on the perfect measurement of
concentration. The burette used for the purpose was not in a very good operating
condition and some error might be induced by the inconsistent titration data provided
by the burette.
- Again, when the experiment was been conducted the first data had been collected
after 25 minutes. So, sufficient data have not been collected, which induced problem
in plotting the graphs.