Bangladesh University of Engineering and Technology

Course No. ChE 402

Course Title: Chemical Engineering Laboratory V

A Report
on
ESTERIFICATION OF ETHANOL IN A BATCH REACTOR IN PRESENCE OF
SULFURIC ACID CATALYST.

Submitted by,
S. M. Nafiz Ahmed
201602036
Md. Abid Afridi
201602037
Shah Sayed Zalal Uddin Ahmed
201602038
Zaki Alam Pushan
201602039
Mehedi Hasan
201602040

Level: 04
Term: 01
Group: A2

Submitted to,
Swarit Ahmed Shadman
Department of Chemical Engineering,
Bangladesh University of Engineering and Technology

Date of Performance: 11 March, 2021

Date of Submission: 21 March, 2021
Experimental Setup

Figure – 1: Experimental setup for esterification of ethanol in a batch reactor in presence of

sulfuric acid catalyst.
Observed Data

Experimental Data

Volume of ethanol, VB = 320 ml

Strength of ethanol (g/g) = 96 %

Volume of acetic acid, VA = 180 ml

Strength of acetic acid (g/g) = 100%

Total volume, V = 500 ml

Strength of NaOH, Sb = 2 N

Molecular weight of ethanol, MB = 46.07 g/mol

Molecular weight of acetic acid, MA = 60.05 g/mol

Reaction Temperature = 80 °C

Collected Data

Density of ethanol at 30 0C, ρB = 0.797 g/cm3

[Reference: Richard M. Felder, Ronald W. Rousseau; “Elementary principles of Chemical

Processes”, 3rd edition, New York – 2005, pg 630]

Density of acetic acid, ρA = 1.05 g/cm3

[Reference: Richard M. Felder, Ronald W. Rousseau; “Elementary principles of Chemical

Processes”, 3rd edition, New York – 2005, pg 628]
 Table – 01: Observed data for titration of sample of acetic acid by 2N NaOH solution

Obs. Cumulative time Volume of Volume of NaOH (mL)

No. (min) Sample Taken Initial Initial Initial
(mL) burette burette burette
reading reading reading
1 0 0 15.7 15.7
2 20 15.8 30.9 15.1
3 35 3.7 18.5 14.8
4 50 19.2 33.7 14.5
5 65 5 1.4 15.6 14.2
6 80 16.4 30.5 14.1
7 95 1.7 15.7 14
8 110 15.7 29.6 13.9
9 Infinity 0.5 14.3 13.8

Table – 02: Calculated data for plotting the graphs to fit the first order rate expressions

Obs Time Concentrati ln Extent Concentration Keq = ln(KeqCA - CP)

. no (min) on of acetic (CA/CAo) of of ester, CP kf/kr
acid, CA reaction (mol/L)
(mol/L) , ε*
1 0 6.28 1.837 0.02 0.02 -0.14
2 20 6.04 1.798 0.24 0.26 -0.52
3 35 5.92 1.778 0.36 0.38 -0.78
4 50 5.8 1.758 0.48 0.50 -1.14
5 0.141
65 5.68 1.737 0.60 0.62 -1.70
3
6 80 5.64 1.730 0.64 0.66 -1.99
7 95 5.6 1.723 0.68 0.70 -2.39
8 110 5.56 1.716 0.72 0.74 -3.09
9 Infinity 5.52 1.708 0.76 0.78

Table – 03: Calculated data to plot the graphs to fit the second order rate expressions

Obs. Time 1/CA Concentratio ln Keq M ln M

no (min) n of ethanol, (CB/CA)
CB
(mol/L)
1 0 6.28 11.11 0.570 1.00 0
2 20 6.04 10.87 0.588 1.49 0.40
3 35 5.92 10.75 0.597 1.96 0.68
4 50 5.8 10.63 0.606 2.84 1.04
5 65 5.68 10.51 0.615 0.76 5.02 1.62
6 80 5.64 10.47 0.619 6.73 1.91
7 95 5.60 10.43 0.621 10.13 2.32
8 110 5.56 10.39 0.625 20.34 3.01
9 Infinity 5.52 10.35 0.629
Graphical Representations

6.4
f(x) = 7.06 x^-0.05
R² = 0.99
Concentration of acetic acid, CA [mole/L]

f(x) = 0 x² − 0.01 x + 6.28

6.2 R² = 1

5.8

5.6

5.4

5.2
0 20 40 60 80 100 120

Cumulative time (min)

Figure -2: Plot between concentration of acetic acid and time

1.85

f(x) = − 0 x + 1.82
R² = 0.94
1.8
ln CA

1.75

1.7

1.65
0 20 40 60 80 100 120

Cumulative time (min)

 Figure -3: Plot between lnCA and time

0.5

0
f(x) = − 0.03 x + 0.02
R² = 0.98
-0.5
ln (KeqCA - CP)

-1

-1.5

-2

-2.5

-3

-3.5
0 20 40 60 80 100 120

Cumulative time (min)

Figure – 4: ln(KeqCA - CP) vs time plot for 1st order reversible reaction

0.19

0.18 f(x) = 0 x + 0.16

R² = 0.94

0.18

0.17
1/CA [L/mol]

0.17

0.16

0.16

0.15

0.15
0 20 40 60 80 100 120

Cummulative time (min)

Figure – 5: 1/CA vs cumulative time plot for 2nd order irreversible reaction of Class I
 0.63
f(x) = 0 x + 0.58
R² = 0.94
0.62

0.61

0.6
ln (CB/CA)

0.59

0.58

0.57

0.56

0.55

0.54
0 20 40 60 80 100 120

Cumulative time (min)

Figure – 6: ln [CB/CA] vs cumulative time for 2nd order irreversible reaction of Class II

3.5

f(x) = 0.03 x − 0.16

2.5 R² = 0.98

2
ln M

1.5

0.5

0
0 20 40 60 80 100 120

Cumulative time (min)

Figure – 7: ln (M) vs cumulative time for 2nd order reversible reaction

Appendix

Calculation for 2nd observed data:

CH3COOH + C2H5OH H 2→SO 4 CH3COOC2H5 + H2O

A B C D

Initial volume of ethanol solution taken = 320 mL

Initial volume of acetic acid solution taken = 180 mL

Total volume of mixture = (320+180) mL = 500 mL = 0.5 L

Density of 96 wt% ethanol solution = 0.7974 g/mL

Initial concentration of ethanol, CBi

0.7974 g solutio 0.96 g ethanol 1mol ethanol 1

= 320 mL solution × × × ×
mL solution g solution 46 g ethanol 0.5 L mixture

= 10.65 M

Initial concentration of acetic acid measured, C Ai

1.05 g solution 1 g acetic acid 1mol acetic acid 1

= 180 mL solution × × × ×
mL solution g solution 60 g acetic acid 0.5 L mixture

= 6.3 M

From 1st observation,

Strength of NaOH solution, S1 = 2 N = 2 M

Volume of sample taken, V2 = 5 mL

Volume of NaOH used in titration, V1 = 15.7 mL

We know, S1V1 = S2V2

S 1 ×V 1 2× 15.7
» S2 = = = 6.28 M
s2 5

Initial concentration of acetic acid, CAo = S2 = 6.28 M

Initial extent of reaction, ε o* = (CAi - CAo) = (6.3 – 6.28) mol/L = 0.02 mol/L
CBo = (CBi - ε o*) = (10.65–6.28) mol/L = 4.37 mol/L

CCo = CDo = ε o* = 0.02 mol/L

For observation no. 2,

In this observation, concentration of sample was calculated after 30 min

Strength of NaOH solution, S1 = 2 N = 2 M

Volume of sample taken, V2 = 5 mL

Volume of NaOH used in titration, V1 = 15.1 mL

We know, S1V1 = S2V2

We know;

V1 S1 = V 2 S2 Where, V1 = volume of NaOH solution = 15.1 ml

15.1× 2
S2 = S1 = strength of NaOH solution = 2 N =2 mol/L
5

S2 = 6.04 mol/L V2 = volume of acetic acid = 5 ml

⇒ CA≡ S2 = 6.04 mol/L S2 = strength of acetic acid

Extent of reaction at t = 20 min

=(CAi - CA) = (6.3 – 6.04) mol/L = 0.26 mol/L

CB = (CBi -) = (10.65 – 0.26) mol/L= 10.39 mol/L

CC = CD = CCo + ε = (0.02+0.26) mol/L = 0.28 mol/L

Equilibrium Data, at t = ∞

CA∞ = 5.52 mol/L

CB∞ = 10.35 mol/L

CC∞= CD∞ = 1.92mol/L

ε ∞* = 0.76 mol/L

Here,

ln (CA/ CA0)
= ln (6.04/6.28) = 1.798

K C A −C C 0.141× 6.04−0.28
ln ( KCAo−CCO )
= ln (
0.141 ×6.28−0.02
) = -0.415

1 1
= =0.165
C A 6.04

C B 10.35
ln = =0.587
C A 6.04

The rate expression is:

ln [M] = ln [{( K−1)¿ ¿]

= {(0.141−1)×( 0.26−0.76)−¿ ¿ =0.402