CHE 352 TUTORIAL CLASS 05/MARCH/2009

Question 1

The esterification of butanol with acetic acid, using sulfuric acid as a catalyst, was studied in a
batch reactor:
O
H2SO4 C H ─ O ─∥ ─ CH + H O
C4H9OH + CH3COOH 4 9 3 2
C

The reaction was carried out with an excess of butanol. The following data were collected
Acetic acid
Time (hr) concentration
(moles/1)
0 2.327
1 0.7749
2 04514
3 0.3152
4 0.2605

Set up a suitable kinetic model of the homogeneous type.

Solution

Assuming an irreversible bimolecular type second order reaction with C AO = CBO

The reaction then reduces to 2 A → R

The defining second differential equation becomes

dC
− rA = − A = kC A = kC AO (1 − X A )
2 2 2

dt
Upon integration gives
1 1 1  XA 
− =   = kt
C A C AO C AO  1 − X A 
1
Therefore a plot of against t should give a straight line with a slope of k and an intercept of
CA
1 1 1
.⇒ = kt +
C AO CA C AO

1
 Table of values

1
t CA
CA
0 2.327 0.43
1 0.7749 1.29
2 0.4514 2.22
3 0.3152 3.17
4 0.2605 3.84

4.5

4 y = 0.87x + 0.45

3.5

2.5
Series1
1/CA

Linear (Series1)
2

1.5

0.5

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
t

From the graph k = 0.87/hr

The kinetic model of the homogeneous type is given by

− rA = 0.87[C 4 H 9 0 H ][CH 3 COOH ](mols / litre ) / s .

2

2
Question 2

The following data on the conversion of hydroxyvaleric acid into valerolactone were collected.

Time (min) 0 48 76 124 204 238 239

Acid
concentration 19.04 17.6 16.9 15.8 14.41 13.94 13.37
(mol/L)

Determine a suitable kinetic model by means of both the differential and integral method
of kinetic analysis.

Solution

The above reaction can be represented as A → R .

Assuming an irreversible unimolecular –type first order reaction.

Using Differential Method

dC A
The rate equation is given as − rA = − = kC A
dt
Therefore a plot of − rA against C A gives a slope of k

Table of values

t CA − rA log C A log(−rA )
0 19.04 1.279667
48 17.6 0.03 1.245513 -1.52288
76 16.9 0.0281 1.227887 -1.55129
124 15.8 0.0261 1.198657 -1.58336
204 14.41 0.0227 1.158664 -1.64397
238 13.94 0.0214 1.144263 -1.66959
239 13.37 0.0237 1.126131 -1.62525

(a) From graph 1, the equation is y = 0.0018 x − 0.0027 . It implies that the rate constant

k=0.0018/min.

(b) We use graph 2 to test/confirm for the nth –order form of the reaction.

⇒ − rA = kC A ⇒ log( − rA ) = log k + n log C A

n

3
The equation of the plot is y = 1.0848 x − 2.8833 ∴ n ≅ 1 and log k = −2.8833 ⇒ k = 0.0013/min

Graph 1
0.035

y = 0.001x - 0.002
0.03

0.025

0.02
Series1
-rA

Linear (Series1)
0.015

0.01

0.005

0
12 13 14 15 16 17 18 19 20
CA

Graph 2
-1.48
1.1 1.12 1.14 1.16 1.18 1.2 1.22 1.24 1.26 1.28 1.3
-1.5
y = 1.084x - 2.883
-1.52

-1.54

-1.56
log -rA

Series1
-1.58
Linear (Series1)

-1.6

-1.62

-1.64

-1.66

-1.68
log CA

4
Integral Method

Considering the reaction below

A→R
dC A
− rA = − = kC A
dt
Upon integration
C 
− ln A  = kt
 C AO 
C 
Therefore a graph of − ln A  against t should give a straight line with a slope of k.
 C AO 
Table of values

C 
t CA − ln A 
 C AO 
0 19.04 0
48 17.6 0.0786
76 16.9 0.1192
124 15.8 0.186
204 14.41 0.279
238 13.94 0.3118
239 13.37 0.353

From graph 3, the equation of the plot is y = 0.0014 x

⇒ k = 0.0014/min

From the differential and the integral analysis of the problem it has been proved to be a

0.0018 + 0.0013 + 0.0014

Unimolecular first order reaction with k = = 0.0015 /min.
3
Therefore the rate equation of the reaction is − rA = 0.0015C A mol / litre.s

5
Graph 3

0.4

0.35
y = 0.001x

0.3

0.25
-ln(CA/CAO)

Series1
0.2
Linear (Series1)

0.15

0.1

0.05

0
0 50 100 150 200 250 300
t