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Che 352
Che 352
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
Solution
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
2
Question 2
The following data on the conversion of hydroxyvaleric acid into valerolactone were collected.
Determine a suitable kinetic model by means of both the differential and integral method
of kinetic analysis.
Solution
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.
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
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 the differential and the integral analysis of the problem it has been proved to be a
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