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Name of the Experiment: Esterification Of Ethanol In A Batch

Reactor In Presence Of Sulfuric Acid Catalyst
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Date of Performance: 10/07/19
Date of Submission: 17/07/19
Summary
The main objectives of this experiment were to determine the order and overall rate expression
equation of ethanol esterification reaction with acetic acid in presence of sulfuric acid as catalyst. The
temperature was tried to maintain constant and batch reactor was used. Integral method was used to
determine the order from concentration change data. Ethanol and acetic acid was mixed in 7:4 ratio.
The temperature of the reactive system was maintained close to 70°C. A condenser was used to
prevent the escape of any vapor from the reactor and 1 ml liquid samples were taken fiom the
reactor. After the system temperature became stable at 70°C, initial sample was taken and considered
as the initial concentration of all the substances. Samples were collected every 10 minutes and titrated
against 1 N sodium hydroxide (NaOH) to determine the concentration of unreacted acid in the system.
Phenolphthalein was used as the indicator in the titration. The final reading was taken after a day to
determine equilibrium concentrations of the reactants and the product. From the collected data, six
graphs were plotted. The order of the reaction was determined by trying to fit the collected data in the
overall rate expressions for first order irreversible reaction, first order reversible reaction, second order
irreversible reaction (class-I and II) and second order reversible reaction. The regression values (R2)
for all the plots were compared and the reaction was found to follow second order kinetics of class-II
type for irreversible reaction. The use of excess ethanol and concentrated sulfuric acid catalyst
CB
contributed to the irreversibility of the reaction. The final rate expression was found to be: ln =
CA

0.0038×t + 0.6955 and the rate constant was 8.96×10-4 Lmol-1 min-1.

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Experimental Setup:

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Experimental Procedure

1. Acetic acid and ethanol at 7:4 molar ratio was added in a batch reactor with H2SO4 as catalyst.
2. The mixture was heated up-to 70ºC and kept constant.
3. Then the sample was taken and the initial concentration was measured by titrating it with 2N
NaOH at time, t=0s.
4. Initial concentration of ethanol and product was measured using extent of reaction.
5. Similarly, the concentration was measure at 10 minute interval.
6. The final data was taken 1 day later which was assumed as the equilibrium data.
7. The observed data were calculated and calculated data was fitted with the rate equations for
different types of reactions.
8. Most fitted model was taken based on the regression analysis.

Observed Data:

Volume of sample taken = 5mL

Concentration of NaOH = 1N

Purity of acetic acid = 100%

Purity of ethanol = 96%

Density of Acetic Acid = 1.049 g/cm3

Density of Ethanol = 0.789 g/cm3

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Table 1: Data for Cumulative time, Sample volume and Burette reading

No. Cumulative Sample Volume of NaOH (ml)

of Time Volume
Obs. Initial BR Final Difference
(min) (mL)
BR

1 0 1.1 22.2 21.1

2 10 22.2 41.5 19.3

3 20 6.2 25.4 19.2

5
4 40 5.7 20.8 15.1

5 50 20.8 36 15.2

6 60 2.1 15.7 13.6

7 70 15.7 29.1 13.4

8 ∞ 0.9 13.2 12.3

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Calculated Data:

Table 2: Calculation of Concentrations and Extent of Reaction

Concentratio
No. Concentration Concentration
n of Acetic Extent Concentration
of Cumulative of Ethanol of Water
acid of of Ester
Obs Time (min) CB CD
CA reaction CC (mol/L)
. (mol/L) (mol/L)
(mol/L) ε

1 0 4.22 0 8.46 2.07 2.07

2 10 3.86 0.36 8.10 2.43 2.43

3 20 3.84 0.38 8.08 2.45 2.45

4 40 3.02 1.2 7.26 3.27 3.27

5 50 3.04 1.18 7.28 3.25 3.25

6 60 2.72 1.5 6.96 3.57 3.57

7 70 2.68 1.54 6.92 3.61 3.61

8 ∞ 2.46 1.76 6.70 3.83 3.83

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 Table 3: Calculations for First and Second Order Reaction Parameters

No. of Cumulative ln(CA/CA0) ln((KCA – 1/CA ln (CB /CA) ln M

Observations time (min) First Order CC) Second Second Second
Irreversible /(KCA0- Order Order Order
CC0)) Irreversible Irreversible Reversible
First (Type I) (Type II)
Order
Reversible
1 0 0.00 0.00 0.24 0.70 0.00

2 10 -0.09 -0.23 0.26 0.74 0.23

3 20 -0.09 -0.24 0.26 0.74 0.25

4 40 -0.33 -1.15 0.33 0.88 1.15

5 50 -0.33 -1.11 0.33 0.87 1.12

6 60 -0.44 -1.91 0.37 0.94 1.92

7 70 -0.45 -2.08 0.37 0.95 2.09

8 ∞ -0.33 -1.15 0.33 0.70 0.00

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Graphical Representation

Concentration of Acetic Acid vs. Time

7
Concentration of Acetic Acid, CA

4
y = -0.023x + 4.1619
(mol/L)

3 R² = 0.9576

0
0 10 20 30 40 50 60 70 80
Time(min)

Figure 02: Change of Acetic Acid concentration with time

0.00
Trial for First Order Irreversible Reaction

-0.10

-0.20 y = -0.0069x
R² = 0.9631
ln(CA / CAo)

-0.30

-0.40

-0.50

-0.60
0 10 20 30 40 50 60 70 80
Time (min)

Figure 03: Trial with first order irreversible reaction equation

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 Trial for 1st Order Reversible Reaction
0.00

-0.50
ln ( KCA - CC) / ( KCAO - CCO)

-1.00

y = -0.0281x
R² = 0.9389
-1.50

-2.00

-2.50
0 10 20 30
Time40
(min) 50 60 70 80

Figure 04: Trial with first order reversible reaction equation

Trial for 2nd Order Irreversible ( Type I )

0.60

0.50

0.40
1/CA

0.30 y = 0.002x + 0.237

R² = 0.9638

0.20

0.10

0.00
0 10 20 30 Time40(min) 50 60 70 80

Figure 05: Trial with second order irreversible (Type-1) reaction equation

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 Trial for 2nd Order Irreversible ( Type II )
1.80

1.60

1.40

1.20

1.00
ln(CB/CA)

0.80

0.60 y = 0.0038x + 0.6955

R² = 0.9643
0.40

0.20

0.00
0 10 20 30 40 50 60 70 80
Time (min)
Figure 06: Trial with second order irreversible (Type-2) reaction equation

2.50
Trial for 2nd Order Reversible

2.00

1.50
ln ( M )

y = 0.0283x
R² = 0.9394
1.00

0.50

0.00
0 10 20 30 40 50 60 70 80
Time (min)
Figure 07: Trial with second order reversible reaction equation

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Result and Discussion
Table 04: Tabulated result of the esterification of ethanol in a batch reactor in presence of sulfuric acid
catalyst.

Type of reaction R2 values Rate expression Rate constant, k

(Lmol-1min-1)

1st order irreversible 0.9631

1st order reversible 0.9389

CB 8.96 × 10-4
2nd order irreversible (type-I) 0.9638 ln = 0.0038×t + 0.6955
CA

2nd order irreversible (type-II) 0.9643

2nd order reversible 0.9394

From table 4 it is evident that the rate gotten is second order irreversible type-II (see appendix), which
had closest fitting among all (fig.06). As we used a condenser so that no substance can fly away, and
from theoretical background it should have been a second order reversible reaction. We used integral
method for data treatment. It is the simplest way to determine order and rate expression.
The esterification reaction can be expressed as:
CH3COOH + C2H5OH ⇌ CH3COOC2H5 + H2O
Theoretically the reaction should follow second order kinetics for reversible reaction. The rate of
reverse reaction can be reduced by using excess amount of one of the reactants or by removing one of
the products from the system. In this experiment, ethanol was used in excess (molar ratio of ethanol:
acid = 1.65) due to economic reason to facilitate the shift of equilibrium to the right and thus, increasing
the yield of ester.
Sulfuric acid was used as catalyst. It works by providing a H+ environment. So, any acid can be used
as a catalyst. Catalyst was used to increase the rate of reaction.
Any procedure is not beyond errors. There were many potential reasons of error. The temperature was
fluctuating. Final reading was taken at room temperature. Taking 5 cc exactly from reactor was
difficult. As measuring cylinder was used it was not so precise. A pipette should be used to take exactly
5 cc from the measuring cylinder.
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Though the data didn’t give the known expression this experiment gives us the practical knowledge of
reaction kinetics. As a fresher in this field one should have learnt a lot about reaction kinetics.

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Appendix
Sample Calculation
Volume of total solution taken = (320 + 180) mL = 500 mL = 0.5 L
Strength of ethanol = 96% (by mass)
Volume of ethanol solution taken = 320 mL
Molecular weight of ethanol = 46.07 g/mol
[Reference: Perry, R., & Green, D., Perry's Chemical Engineers' Hanbook,(Internation ed.), McGraw-
Hill., p- 2-95, table 2-30]
Density of 95% ethanol solution (@25°C) = 0.7991 g/mL
[Reference: Perry, R., & Green, D., Perry's Chemical Engineers' Hanbook,(Internation ed.), McGraw-
Hill., p- 2-112, table 2-110]
g g
320 mL∗0.7991 ⁄mL∗ 0.96 ⁄g
Concentration of ethanol solution taken, CB1 = g
0.5 L∗46.07 ⁄mol

= 10.54 mol/L
Strength of acetic acid = 100% (by mass)
Volume of acetic acid taken = 180 mL
Molecular weight of acetic acid = 60.05 g/mol
[Reference: Perry, R., & Green, D., Perry's Chemical Engineers' Hanbook,(Internation ed.), McGraw-
Hill., p- 2-96, table 2-30]
Density of acetic acid (@25°C) = 1.044 g/mL
[Reference: Perry, R., & Green, D., Perry's Chemical Engineers' Hanbook,(Internation ed.), McGraw-
Hill., p- 2-110, table 2-107]
g
180 mL∗ 1.044 ⁄mL
Concentration of acetic acid taken, CA1 = g = 6.26 mol/L
0.5 L∗60.05 ⁄mol

10.56 mol⁄L
Molar ratio = Ethanol : Acetic acid = = 1.70
6.26 mol⁄L

Sample calculation for observation no. 2

▪ Concentration of acetic acid (C A)
Volume of NaOH, V1 = 19.3 mL
Normality of NaOH, S1 = 1.0 N
Volume of acetic acid, V2 = 5.0 mL
Here, V1 × S1 = V2 × S2 where, S2 = Normality of acetic acid
V1 × S 1 19.3 ×1.0
⇒ S2 = V2
= 5.0
N = 3.86 N

Since for acetic acid, Normality = Molarity,

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Concentration of acetic acid, C A = 3.86 mol/L

▪ Concentration of ethanol (CB)

Concentration of acetic acid taken, CA1 = 6.26 mol/L
Initial concentration of acetic acid (at time, t = 0), CAO = 4.22 mol/L
CAO − CA1 4.22−6.26
Progression of reaction before data collection began, ε ∗1 = = mol/L
νA (−1)

= 2.04 mol/L
∴ Initial concentration of ethanol (at time, t = 0), CBO = CB1 + ε ∗1 νB
= {10.56 + 2.04 × (-1)} mol/L
= 8.52 mol/L
CA− CA 3.86−4.3
Again, extent of reaction at t>0, ε* = O
= mol/L = 0.44 mol/L
νA (−1)

∴ Concentration of ethanol (at time, t>0), CB = CBO + ε ∗× νB

= {8.60+0.44×(-1)} mol/L
= 8.16 mol/L

▪ Concentration of ester (CR)

Initial concentration of ester at t = 0, CRO = CR1 + ε ∗1 νR
= (0 + 2.04 × 1) mol/L
= 2.04 mol/L
And, concentration of ester (at time, t>0), CR = CRO + ε ∗ νR
= (2.04 + 0.44) mol/L
= 2.48 mol/L

▪ Determination of order of reaction

Trial for 1st order irreversible reaction
The first order irreversible reaction can be expressed as
A B
Rate expression: r = k [CA]
CA
Integrated rate expression: ln [ ] = - kt ……………….. (1)
CA0
C
To compare with equation (1) ln [C A ] vs. t was plotted
A0

Here, CA = Concentration of acetic acid = 3.86 mol/L

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 CAO = Initial concentration of acetic acid = 4.22 mol/L

Where CA0 is the concentration of acetic acid at time, t = 0

C
For observation 4, ln [C A ] = -0.09 at t = 10 min
A0

From figure 04, R2 = 0.9631

Trial for First Order Reversible Reaction

The first order reversible reaction can be expressed as
kf
A P
kr
Where, A denotes Acetic Acid
R denotes product (ester)
The rate expression: r = kf [CA] – kr[CP]
Then the integrated rate expression for the reaction is,
K C -C
- (kf +kr)t = ln[K eqC A -CP ]…………………(2)
eq A0 P0

Right hand side of equation (2) was evaluated and plotted against time to compare the experimentally
obtained data with equation (2)
Keq = Equilibrium constant = kf/kr= CPeq/CAeq= 3.83/2.46 = 1.557
Here, KeqCA- CP = 1.557×3.86 – 2.43 = 3.58
Keq CA0 -CP0 = 1.557×4.22-2.07= 4.5
K C -C
For observation no. 4, ln[K eqC A -CP ] = -0.23 at t = 10 min
eq A0 P0

Trial for Second Order Irreversible reaction

The second order irreversible reaction can be expressed as

k
A+B E (product)

Class-I:
The rate equation for this type of reaction is
1/CA− 1/CA0 = kt

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 So, 1/CA= kt + 1/CA0
So, to compare with it, a graph of 1/CA vs. time was plotted holding intercept at 1/CA0 =0.237.
For observation 5, 1/CA= 1/3.86 = 0.26
So, the coordinate (10, 0.26) was plotted.
Class-II:
The rate equation for this type of reaction is
ln (CB/CA) = (CA0 VB − CB0 VA) kt + ln (CB0/CA0)
So, to compare with it, a graph of ln (CB/CA) vs. time was plotted and trendline was drawn holding
intercept as ln (CB0/CA0)=0.6955.
ln (CB/CA) = ln (8.10/3.86) = 0.74
So, the coordinate (10, 0.74) was plotted

Trial for Second Order Reversible reaction

kf
The reaction can be expressed in the form: A + B R+S
kr
Where,
A = acetic acid
B = ethyl alcohol
R = ethyl acetate
S = water
The rate equation for this type of reaction is
{(K-1)(ε*-ε*eq )-[K(Aeq +Beq )+(Req +Seq )}]ε*eq
ln [ (ε*-ε* ] = [kf (Aeq+Beq) + kr (Aeq+Beq)] t
eq ){(K-1)ε*eq +K(Aeq +Beq )+(Req +Seq )}

So, to compare with it, a graph of ln [M] vs. time was plotted.
K = ɛeq∗2/ (CAeq×CBeq) = 1.762/(2.46×6.70)= 0.188
{(K-1)(ε*-ε*eq )-[K(Aeq +Beq )+(Req +Seq )}]ε*eq
ln [M] = ln [ (ε*-ε* ]
eq ){(K-1)ε*eq +K(Aeq +Beq )+(Req +Seq )}

{(0.188-1)(.36-1.76)-[0.188(2.46+6.70)+(3.83+3.83)}]1.76
=ln [(0.36-1.76){(0.188-1)1.76+0.188(2.46+6.70)+(3.83+3.83)}]

= 0.23
So, the coordinate (10, 0.23) was plotted

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 ▪ Rate constant and Rate expression
From comparison of R2 values, it was seen that the esterification reaction followed the second order
irreversible reaction of class-II.
Therefore, the rate expression for the esterification reaction,
C CBO
ln CB = (CAO νB - CBO νA ) × kt + ln C
A AO
CB
ln = 0.0038×t + 0.6955
From figure 07, the rate expression: CA

Again, slope = (CAO νB - CBO νA ) × k = 0.0038 min-1

0.0038 0.0038 min −1
⇒ k = (C = [4.22×(−1)−8.46×(−1)]mol/L = 8.96 × 10-4 Lmol-1 min-1
AO νB − CBO νA )

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