Biomedical Engineering Reference
In-Depth Information
7.4. Brown and Stock (H.C. Brown and L.M. Stock,
J. Am. Chem. Soc.
, 79, 5175, 1957) reported
some data on the chlorination of toluene in 99.8% acetic acid at 25
C:
Time, s
Toluene, mol/L
Chlorine, mol/L
0
0.1908
0.0313
2790
0.1833
0.0238
7690
0.1745
0.0150
9690
0.1719
0.0123
14,000
0.1682
0.0086
19,100
0.1650
0.0055
Determine a reasonable kinetic sequence (reaction pathways) to explain these data and
the values of the appropriate rate constants.
7.5.
In pulp and paper processing, anthraquinone (AQ) accelerates the delignification of
wood and improves liquor selectivity. The kinetics of the liquid-phase oxidation of
anthracene (AN) to AQ with NO
2
in acetic acid as solvent has been studied by
Rodriguez and Tijero (1989) in a semibatch reactor (batch with respect to the liquid
phase), under conditions such that the kinetics of the overall gas
e
liquid process is
controlled by the rate of the liquid-phase reaction. This reaction proceeds through the
formation of the intermediate compound anthrone (ANT):
NO
2
k
1
NO
2
k
2
C
H
10
ð
AN
Þ !
C
H
O
ð
ANT
Þ !
C
H
O
2
ð
AQ
Þ
14
14
9
14
8
The following results (as read from a graph) were obtained for an experiment at 95
C, in
which
C
AN,0
¼
0.0337 mol L
1
:
C
AN
(mol L
L
1
)
C
ANT
(mol L
L
1
)
C
AQ
(mol L
L
1
)
t
, min
0
0.0337
0
0
10
0.0229
0.0104
0.0008
20
0.0144
0.0157
0.0039
30
0.0092
0.0181
0.0066
40
0.0058
0.0169
0.0114
50
0.0040
0.0155
0.0144
60
0.0030
0.0130
0.0178
70
0.0015
0.0114
0.0209
80
0.0008
0.0088
0.0240
90
0.0006
0.0060
0.0270
Determine the orders of reactions and the values of the rate constants
k
l
and
k
2
.
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