A Report on

“Experiment-2: ESTERIFICATION OF ETHANOL IN A BATCH

REACTOR IN PRESENCE OF SULFURIC ACID CATALYST”

Submitted to:
Mr. Ahaduzzaman Nahid
Assistant Professor
Department of Chemical Engineering
Bangladesh University of Engineering and Technology

Submitted by:
Tasnim Ahmed
ID: 1802023
Level-4, Term-1

Date of Performance: 16,08.23

Date of Submission: 23.08.2023

Group: 05 (A1)
(1802021, 1802022, 1802023, 1802024, 1802025)
Abstract
The main objective of this experiment was to observe the esterification reaction of Ethanol and
Acetic acid and determine the order of the reaction by plotting the observed data and comparing
with theoretical model for first and second order reactions. This experiment helps us understand
the kinetics of reaction and gives us insight about the mechanism it follows. In this experiment,
esterification reaction of Ethanol and Acetic acid was studied in a batch reactor at constant
temperature and volume. 320 mL of Ethanol and 180 mL of Acetic acid (7:4 mixture) were taken
in a conical flask as reactants along with 98% Sulfuric acid as catalyst and the mixture was then
heated. The temperature was maintained around 80C. After fixed time intervals (10 mins),
10mL of reactor outlet samples were taken and titrated with Sodium hydroxide of known
concentration (2N) using a Phenolphthalein indicator. The titration result indicated to the
decrement of reactant concentration, and it reached equilibrium after infinite time and that data
was taken the next day. From all the observed data the concentration profile was generated with
respect to time and plotted and compared with first and second order reversible and irreversible
reaction graph. R2 value was used as the measurement for determining the reaction order of the
system. It was found from plots that the reaction was a first order irreversible reaction, and the
rate equation was found to be of the form -ln (CA/ CA0) = 0.0033t with a R2 value of 0.9922.
MATERIALS AND METHODS

Apparatus Used:

 Magnetic stirrer
 Water-cooled condenser
 Conical flask
 Conical reaction vessel
 Measuring cylinders (50 ml and 10 ml)
 Burette
 Thermometer
 Digital balance or weighing scale

Chemicals Utilized:

 Distilled water
 Ethanol solution (96%)
 Acetic acid solution (96%)
 Phenolphthalein as an indicator
 Sulfuric acid (H₂SO₄) solution
 Solid sodium hydroxide (NaOH)
Experimental Setup

Fig 1: Schematic diagram of the experimental setup.

EXPERIMENTAL PROCEDURE

In the experiment, 320 ml of ethanol was measured and placed in a conical jar with a controlled
outlet valve, while 180 ml of acetic acid was supplied in the same manner. A drop of H 2SO4
catalyst was added, and the jar was placed on a magnetic stirrer with a magnetic bar. To avoid
concentration-dependent effects, a water-cooled condenser was placed atop the conical jar,
allowing volatile components to be reintroduced into the reaction mixture. In addition, the
condenser prevented potentially explosive vapor pressure buildup. A thermometer was used to
measure the reaction temperature, which progressively climbed and steadied at around 80 °C. A
2N concentrated NaOH solution was made for titration purposes by dissolving 40 g of NaOH in
a small jar and diluting it in a volumetric flask. A burette containing this solution was clamped
for later titration. At 80 °C, a 10 mL sample was removed from the reactor vessel, immediately
diluted with 40 ml of distilled water to stop the reaction and transferred to a conical flask. The
diluted sample was titrated with NaOH solution from the burette after the phenolphthalein
indicator was introduced. The conclusion of the titration was indicated by the sample solution
turning light pinkish purple, indicating the complete reaction of unreacted acetic acid with
NaOH. The volume of NaOH solution used was recorded, allowing for the calculation. The
volume of NaOH solution used was recorded, allowing the concentration of unreacted acetic acid
to be calculated.
Observed Data
Reaction temperature = 60°C

Volume of ethanol= 320 mL

Volume of acetic acid = 180 mL

Concentration of NaOH = 2N

Purity of acetic acid = 99%

Purity of ethanol= 97%

Density of ethanol = 0.797 gm/mL

Density of acetic acid = 1.05 gm/mL

Table 1: Table showing cumulative time, sample volume taken for titration and volume of NaOH.

Observation Cumulative Sample Volume of NaOH (mL)

No. Time Volume
Initial Final Burette Difference
(min) (mL)
Burette Reading (mL)
Reading (mL)
(mL)

1 0 10 0.1 35.7 35.6

2 30 0 33.5 33.5
3 40 0 32.5 32.5
4 50 0 30.6 30.6
5 60 0 28.7 28.7
6 70 0 28.4 28.4
7 80 0 27 27
8 90 0 26.1 26.1
9 100 0 25.9 25.9
10 110 0 24.5 24.5
11 ∞ 0 20.1 20.1
Calculated Data
Table 2: Table showing calculated data of concentration of reactants and products and extent of reaction
at different times.

Obs. Concentration Extent of Concentration Concentration Concentration

No. of acetic acid, reaction, of ethanol, CB of ethyl of water, CD
CA (mol/L) ζ* (mol/L) (mol/L) acetate, CC (mol/L)
(mol/L)
1 7.12 0 10.66 0 0
2 6.7 0.42 10.24 0.42 0.42
3 6.5 0.62 10.04 0.62 0.62
4 6.12 1 9.66 1 1
5 5.74 1.38 9.28 1.38 1.38
6 5.68 1.44 9.22 1.44 1.44
7 5.4 1.72 8.94 1.72 1.72
8 5.22 1.9 8.76 1.9 1.9
9 5.18 1.94 8.72 1.94 1.94
10 4.9 2.22 8.44 2.22 2.22
11 4.02 3.1 7.56 3.1 3.1
 Table 3: Table showing calculated data for the parameters of first order kinetics.

Obs. Cumulative time First order kinetics

No. (min) Irreversible Reversible
CA K C A−C C
−ln ( ) −ln ( )
C A0 K C A 0−C C 0
1 0 0.000 0.0000
2 30 0.061 0.1456
3 40 0.091 0.2231
4 50 0.151 0.3895
5 60 0.215 0.5891
6 70 0.226 0.6246
7 80 0.277 0.8093
8 90 0.310 0.9491
9 100 0.318 0.9830
10 110 0.374 1.2592
11 ∞ 0.572
 Table 4: Table showing calculated data for parameters of second order kinetics.
Obs. Cumulative time Second order kinetics
No. (min) Irreversible Irreversible Reversible
(Type I) (Type II)
1 1 CB ln(M)
−
CA C A0 CA
ln ⁡( )
CB0
C A0
1 0 0.0000 0.000 0.000
2 30 0.0088 0.021 0.182
3 40 0.0134 0.031 0.276
4 50 0.0229 0.053 0.474
5 60 0.0338 0.077 0.704
6 70 0.0356 0.081 0.744
7 80 0.0447 0.101 0.951
8 90 0.0511 0.114 1.104
9 100 0.0526 0.117 1.141
10 110 0.0636 0.140 1.438
11 ∞ 0.1083 0.228
Graphical Representation

Concentration Profile of Acetic Acid

8
Concentration of Acetic Acid (mol/L)

7
f(x) = 8.514027048172E-06 x² − 0.022249534294549 x
6
+ 7.21506538504526
R² = 0.977354587659743
5

0
0 20 40 60 80 100 120

Cumulative Time t (min)

Figure 2: The concentration profile of acetic acid during the experimental time

1st Order Irreversible

0.400

0.350
f(x) = 0.00328844809911319 x
0.300 R² = 0.992247415752894
-ln(CA /CAo)

0.250

0.200

0.150

0.100

0.050

0.000
0 20 40 60 80 100 120

Cumulative time T (min)

Figure 3: A plot of concentration vs time for 1st order irreversible reaction.

 1st order Reversible
1.4000

1.2000

-ln(kCA -Cc )/(kCAo-Cco) 1.0000 f(x) = 0.00995626701505246 x

R² = 0.98003097487722
0.8000

0.6000

0.4000

0.2000

0.0000
0 20 40 60 80 100 120

Cumulative Time t (min)

Figure 4: A plot of concentration vs time for 1st order reversible reaction.

2nd order Irreversible (Type-I)

0.0700

0.0600
f(x) = 0.000537032834804654 x
0.0500 R² = 0.988153647580724
(1/CA - 1/CAo)

0.0400

0.0300

0.0200

0.0100

0.0000
0 20 40 60 80 100 120

Cumulative Time t (min)

Figure 5: A plot of concentration vs time for 2nd order (type I) irreversible reaction.
 2nd order Irreversible (Type-II)
0.160

0.140
ln((CB /CA)/(CB0/CA0))
0.120 f(x) = 0.00120214497580325 x
R² = 0.989933659577082
0.100

0.080

0.060

0.040

0.020

0.000
0 20 40 60 80 100 120

Cumulative Time T (min)

Figure 6: A plot of concentration vs time for 2nd order (type II) irreversible reaction.

2nd Order Reversible

1.600

1.400

1.200 f(x) = 0.0116234283054237 x

R² = 0.984095329505331
1.000

0.800
lnM

0.600

0.400

0.200

0.000
0 20 40 60 80 100 120

Cumulative Time t (min)

Figure 7: A plot of concentration vs time for 2nd order reversible reaction.

Results and Discussion

Table 5: The R2 values obtained from linearized graphs of different reaction types.

Order of reaction Reaction type Rate expression R2 value

equation
Irreversible reaction CA 0.9922
- ln = 0.0033t
First order CA O

Reversible reaction K CA - CC 0.98

- ln = 0.01t
K CA - CC
O O

Irreversible reaction 1 1 0.9882

−
C A C A = 0.0005t
Type – I 0

Second order Irreversible reaction CB 0.9899

/C
Type – II C A B = 0.0012t 0

ln( ¿
CA 0

Reversible reaction ln M = 0.0116t 0.9841

From the above plots, it can be seen that the experiment follows the first order irreversible
reaction model, and the overall rate expression equation is -ln (CA/ CA0) = 0.0033t.

A total of 5 graphs were plotted to get the reaction order. The equation of the graph with the
highest R2 value was taken as the result. The graph for the 1 st order irreversible reaction has the
highest value of R2 which is 0.9922.

The following reaction occurred in our experiment:

CH3COOH + C2H5OH = CH3COOC2H5 + H2O (In presence of conc. H2SO4 catalyst)

Here H2SO4 is used because the yield of esterification reaction increases with removal of water. So here
sulfuric acid acts as a desiccant as well as a catalyst. The optimum temperature needs to be maintained for
higher yield for esterification reaction. Which was supposed to be maintained around 60C in our
reaction. But for our experiment the temperature was not very strictly maintained. The
concentration varies rapidly with temperature, which might have led to some erroneous result.
The reaction was done in a 7:4 ratio because for 1:1 stoichiometric ratio the theoretical model
cannot work for second order reversible reaction.

For our experiment, there was fluctuation in some data points and this could have resulted due to
the following reasons:

1. The fluctuation of temperature might have changed the composition.

2. The initial strength or purity of the reactants are unknown.
3. During the experiment there was some human error while making the 2N solution and
hence might have caused error in titration.
4. The volume of the system was supposed to be constant and hence there was a use of
reflux condenser. But the removal of sample should cause volume change in the reactor
and hence some error.

Even though there were some errors in the experiment, but the experiment was successful to
establish that esterification is a first order irreversible reaction as it follows this kinetic
model.
Appendix

Sample Calculation

The molar ratio of ethanol to acetic acid = 7:4

Density of acetic acid, ρA = 1.05 gm/mL

Density of ethanol, ρB = 0.789 g/mL

Let the volume of ethanol = b mL

Volume of acetic acid = (500 - b) mL

No of moles of ethanol = [b×0.789] 46.07

= 0.0171 b mol

No of moles of acetic acid = [(500 - b)×1.05] 60.05

= 0.0175 (500 - b) mol

therefore,

0.0171 b 7
= Solving, b=320 mL
0.0175 × ( 500−b ) 4

So, the volume of ethanol = 320 mL

Volume of acetic acid = 180 mL

Purity of ethanol = 97%

Purity of acetic acid = 99%

320 ×0.79 ×1
Taken concentration of ethanol, C Bi= × 0.97=10.66 mol /L
0.5× 1× 46

180 ×1.05 × 1
Taken concentration of acetic acid , C Ai = ×0.99=6.237 mol / L
0.5 × 1× 60
At time, t = 0 min,

We know, V1 S1 = V2 S2

Where,V1 = Volume of NaOH = 35.6 ml

S1 = Normality of NaOH = 2 N

V2 = Volume of Sample = 10 ml

S2 = Normality of acetic acid

S1 ×V 1 2 ×35.6
Now, concentration of acetic acid, S2= = =7.12 N
V2 10

Since the molecular weight of the sample is equal to its equivalent weight i.e. 60.05, so we can
say the numerical value of the normality of the solution is equal to the molarity of the sample
solution.

So, Intial concentration when t=0, CAo = S2 = 7.12 mol/ L

Initial extent of reaction, ξ*o = (CAi-CAo) = (6.237-7.12)=-0.883

As it is negative, so the extent of reaction is considered to be 0.

Concentration of ethanol, CBo= (CBi- ξ*o) = (10.66-0) = 10.66 mol/L

Concentration of ester Cco = ξ*o = 0 mol/L

For the 3rd observation:

We know, V1 S1 = V2 S2

Where,V1 = Volume of NaOH = 32.5 mL

S1 = Normality of NaOH = 2 N

V2 = Volume of Sample = 10 mL

S2 = Normality of acetic acid

S1 ×V 1 2 ×32.5
Now, concentration of acetic acid, S2= = =6.50 N =6.50 mol / L
V2 10
Concentration of acetic acid, CAc= 6.50 mol/L

Extent of reaction, ξ* = (CAo-CA) = (7.12 – 6.50) = 0.62 mol/L

Concentration of ethanol, CB= (CBo- ξ*) = (10.66 – 0.62) = 10.04 mol/L

Concentration of ester Cc = (Cco+ ξ*) = 0 + 0.62 = 0.62 mol/L

1. First Order Irreversible Reaction:

Rate expression: r = -kCA

Integrated rate expression: = -kt

For 3rd observation, −ln ( Cao

Ca
)=−ln ( 7.12
6.5
)=0.091
2. First Order Reversible Reaction

The rate expression: r = (kf CA – krCC)

Then the integrated rate expression for the reaction is,

= - (kf +kr)t

3.1
K = Equilibrium constant = kf/kr= CC∞/CA∞= =0.77
4.02

0.77 ×5.68−0.62
−ln =0.223
Here, - = 0.77 ×7.12−0.62

3. Second Order Irreversible Reaction

For type I:

The rate equation for this type of reaction is:

1 1
− = kt
CA Co
 1 1 1 1
Now, − = − =0.013
C A C o 6.50 7.12

For type-II:

The rate equation for this type of reaction is:

CB C Bo
ln = (CAo υB − CBo υA) kt + ln
CA C Ao

C B ×C Ao 10.04 × 7.12
Here, ln =ln =0.031
C A × C Bo 6.50 ×10.66

4. Second Order Reversible Reaction

The rate equation for this type of reaction is

lnM = [kf (CA∞+CB∞) + kr (CC∞+CD∞)] t

Where,

3.1 ×3.1
K = (CC∞×CD∞)/(CA∞×CB∞) = =0.3162
4.02 ×7.56

ln M =

= 0.276

All the equations are plotted and from the R2 values, the best fitted curve is selected.

The first order irreversible reaction gives the highest R2 value i.e., 0.9922.

Where, slope of the curve = 0.0033.

Therefore, the rate constant, K = 0.0033 min-1 and the rate equation is -ln (CA/ CA0) = 0.0033t.
 MARKING SCHEME
ChE-402
A Normal Report on
ESTERIFICATION OF ETHANOL IN A BATCH REACTOR IN PRESENCE OF
SULFURIC ACID CATALYST

Name: Tasnim Ahmed

Student No. 1802023
Sections Marks Allocated Marks Obtained

Abstract 10%

Materials and Method 10%

Results & Discussion 25%

Quality of Figures 10%

Quality of Tables 10%

Observed Data + Data Sheet 7%

Calculated Data 10%

Sample calculation 8%
 Overall Presentation 10%

Incorrect font/Spacing/ -10%

Alignment/Formatting