Beruflich Dokumente
Kultur Dokumente
., 2015.
CHEMICAL KINETICS
AND CATALYSIS
b School
AbstractEffect of added chloride ions on kinetics and pathway of reaction between cyclic ketones (five to
eight membered rings) and dichloroisocyanuric acid (DCICA) was studied in aqueous acetic acidperchlo
ric acid medium. Formation of aliphatic dicarboxylic acids as the end products demonstrates the ring cleav
age oxidation. Positive effect of acid and negative effect of dielectric constant on the reaction rate reveals a
interaction between positive ion (oxidant in the form of H2OCl+) and dipolar substrate molecule. Zero and
first orders by oxidant in absence and presence of added chloride ions illustrates the participation of substrate
as enolic form of ketone and protonated ketone, respectively, in the rate determining steps. The observed
order of reactivity of cyclic ketones (cyclohexanone > cyclooctanone > cyclopentanone > cycloheptanone)
was explained on the bases of ring strain, change of hybridization and conformational considerations. The
envisaged plausible mechanism based on order of reactants in presence and absence of added chloride ions
was substantiated by the order of Arrhenius parameters.
Keywords: dichloroisocyanuric acid, cyclic ketones, kinetics, chloride ion, enolisation, reaction pathway.
DOI: 10.1134/S0036024415030176
1
INTRODUCTION
C 3 O 3 N 3 H ( Cl ) 2 + 4I + 2H
(1)
C 3 O 3 N 3 ( H ) 3 + 2I 2 + 2Cl .
Under the employed reaction conditions, rates of
selfdecomposition of DCICA were negligible com
pared to the rates of studied reactions. Both in air and
in a deaerated atmosphere, the rate constants
remained practically unaltered. In this study, average
376
cyclo
cyclo
cyclo
cyclo
hexanone pentanone heptanone octanone
9.8
18.2
45.7
119.0
211.4
2.5
6.7
10.2
20.8
76.8
1.3
3.1
6.1
17.8
32.1
8.1
16.6
41.3
113.5
202.6
4.8
8.9
18.2
26.7
50.1
2.2
5.3
6.7
12.3
21.1
0.8
2.3
3.1
4.6
9.1
4.8
7.7
16.6
22.6
46.5
18.2
22.7
23.4
29.5
39.2
41.5
6.7
5.9
6.6
7.3
8.0
9.2
3.1
3.2
3.4
3.5
4.0
5.3
16.6
16.7
17.9
20.3
21.2
26.9
18.2
18.2
18.6
18.7
6.7
6.7
7.0
6.8
3.1
3.1
3.1
3.1
16.6
16.6
16.9
16.8
18.2
34.2
57.1
87.2
6.7
8.2
11.3
14.2
3.1
3.5
4.5
6.0
16.6
19.6
27.4
34.4
377
No. 3
2015
378
cyclo
cyclo
cyclo
cyclo
hexanone pentanone heptanone octanone
[Ketone]
0.0025
50.9
0.005
76.2
0.0125
285.5
0.025
601.8
0.0375
1103.0
[Acid]
0.0250
15.0
0.0500
41.1
0.1000
76.2
0.1500
98.5
0.3000
189.0
Solvent
composition
15%
76.2
35%
85.7
55%
110.7
70%
132.6
[Oxidant]
0.00025
76.8
0.0005
76.2
0.001
77.2
0.002
77.00
]
[Added Cl
0.00125
76.2
0.00250
84.7
0.00500
99.6
0.01000
117.9
Temperature,
C
35
76.2
40
116.8
45
210.9
50
318.0
7.1
19.1
53.8
189.0
194.7
5.6
11.7
28.6
61.3
146.4
33.2
65.8
188.5
409.9
807.1
5.1
13.1
19.1
37.3
55.7
3.3
6.9
11.7
14.4
28.7
12.5
27.8
65.8
87.0
128.1
19.1
25.0
34.9
42.4
11.7
11.9
12.8
23.7
65.8
81.8
96.9
119.9
20.7
19.1
20.2
19.7
12.1
11.7
12.4
11.6
66.8
65.8
65.3
66.3
19.1
26.0
33.8
35.5
11.7
12.0
12.5
18.3
65.8
79.7
96.9
105.4
19.1
39.9
79.3
111.0
11.7
24.7
47.8
61.6
65.8
94.1
154.4
263.6
Vol. 89
No. 3
2015
379
Addition
of chloride ions
Cyclohexanone
86
84
102
115
Cyclopentanone
43
40
252
118
Cycloheptanone
37
34
278
110
Cyclooctanone
42
39
248
116
Cyclohexanone
81
78
52
94
Cyclopentanone
99
96
Cycloheptanone
93
91
25
98
Cyclooctanone
73
70
79
94
E, kJ/mol
H, kJ/mol
S, J/(mol K)
3.4
G, kJ/mol
97
H2OCl + Cl
Cl2 + H2O.
(5)
Order of Activity of Cyclic Ketones
In the present study, the order of oxidation of cyclic
ketones by DCICA is: cyclohexanone > cyclooc
tanone > cyclopentanone> cycloheptanone. A similar
order of reactivity was observed in the oxidation of
cyclic ketones by other oxidatants like quinolinium
dichromate [31], benzyltriethylammonium chloro
chromate [15], pyridinium chlorochromate [17], lead
tetraacetate [32], whereas, in some cases cyclopenta
one has shown a slightly higher rate of reaction com
pared to octanone when the oxidants were vanadium
(V) [14], DCDMH [21].
In the present study, the observed jagged nature of
cyclic ketones with respect to the number of carbon
atoms in the ring might be probably due to Istrain
value, the value of which depends on change in coor
dination number. The reactions are favoured when the
charge of covalency is from 4 to 3 (or) 4 to 5 and are
opposed when the change is from 3 to 4. Hence, five or
seven membered rings experience a significant strain
and at the same time, a strain free condition can be
observed in sixmembered rings [33]. It means that the
observed reactivity order can be explained from the
comparative ease in change of hybridization from sp2
to sp3 in the order [34]: C6 > C8 > C5 > C7. In fact, the
NMR spectroscopic studies show that in aqueous
medium, the content of enol form of cyclooctanone is
highest (9.3%) compared to cyclohexanone (1.18%)
and cycloheptanone (0.56%) [35]. But in the present
Vol. 89
No. 3
2015
380
Vol. 89
No. 3
2015
(H2C)n
H2
C
O +H
C
H2C
K1
H2
C
CH
C
H2C
OH + 2H2OCl
C
H
O O
C
+
+ H2O + 2HCl + 2H
O
C O
H2C
C
H2 n
C
H
OH + H
Enol
H2
C
k
slow
OH
H
Oxonium ion
Cyclo ketone
H2C
H2
C
(H2C)n
C
H2C
C
H2
(H2C)n
H2
C
(H2C)n
+
381
Enol
OH
H2
C
H2C
C
H2 n
C
O O
+
+ 2H2OCl
O
C O
H2
C
H2C
C
H2 n
O O
C
+
+ HCl + H
O
C O
OH
HOCl + H+
S + H+
SH+
k0
EN + H2OCl+
+
K1
(7)
H2OCl+,
(8)
SH+,
(9)
EN + H+,
(10)
K2
fast1
Products,
(11)
v = k 0 [ SH ] = k 0 K 2 [ S ] [ H ] .
This rate expression is consistent with observed
kinetics in the absence of chloride ion, viz., zero order
with respect to [DCICA] and first order by [ketone]
and [H+].
Vol. 89
No. 3
2015
382
REFERENCES
H2OCl+ + Cl
SH+ + Cl2
Complex
k1
fast
Cl2 + H2O,
Complex,
Products,
+
k 1 K 2 K 3 [ HOCl ] T [ H ] [ Cl ] [ S ]
Rate = k1[SH+][Cl2] =
.
( 1 + K 3 [ Cl ] )
The given above rate law explains the observed
reaction orders i.e., unit order in oxidant, substrate
and acid, fractional order with respect to [Cl].
CONCLUSIONS
In the oxidation of ketones by DCICA in acidic
medium, hypohalous acidium ion (H2OCl+) and
molecular chlorine (Cl2) were the active oxidizing spe
cies in the presence and absence of added chloride
ions, respectively. Without added chloride ions, the
mechanism involved was acid catalyzed enolisation of
ketones in a slow and rate determining step, followed
by its subsequent fast interaction with H2OCl+ giving
dicarboxylic acids as final products. However, in pres
ence of chloride ions, the protonated ketone and
molecular chlorine form an intermediate in a rate
determining step and the intermediate breaks down to
dicarboxylic acids.
Vol. 89
No. 3
2015
383
Vol. 89
No. 3
2015