., 2014.
CHEMICAL KINETICS
AND CATALYSIS
AbstractIn the oxidation of Dsorbitol and Dmannitol by potassium periodate in alkaline mediam, sub
strate inhibition was observed with both the substrates, i.e., a decrease in the rate of the reaction was observed
with an increase in the concentration of substrate. The substrate inhibition was attributed to the formation of
stable complex between the substrate and periodate. The reactions were found to be first order in case of peri
odate and a positive fractional order with hydroxide ions. Arrhenius parameters were calculated for the oxi
dation of sorbitol and mannitol by potassium periodate in alkali media.
Keywords: kinetics, substrate inhibition, Dsorbitol, Dmannitol, potassium periodate, alkaline medium.
DOI: 10.1134/S003602441405015X
1
INTRODUCTION
Studying the oxidation of sugars is very significant
because in most of the living organisms, the major
amount of energy is obtained from carbohydrates [1].
Polyols (viz., inositol, mannitol, sorbitol) are impor
tant osmolytes in various animals, plants and procary
ote organisms [24]. Sorbitol and inositol are signifi
cant osmolytes in the renal medulla of mammals [57].
Dmannitol is abundant in nature, such as in plants,
algae, yeasts, fungi, and bacteria. Mannitol is a major
storage polysaccharide in fungi that also plays an
important role as a metabolite in stress tolerance [8, 9]
from the physiological functions fulfilled by mannitol
in lower and higher eukaryotes [10]. Sorbitol finds
many applications in food, pharmaceutical and cos
metic industries and as additives in many endprod
ucts. It was used as a key intermediate in the synthesis
of ascorbic acid [11].
1
Acid catalysed oxidation of sugars and sugar alco
hols with different oxidants was reported by earlier
researchers [1214]. Most of the studies carried out in
perchloric acid media reported that the reaction was
1 acid catalysed [15, 16]. The kinetics and mechanism
2 of cerium (IV) oxidation of hexitols (Dsorbitol and
Dmannitol) in aqueous sulfuric acid media have been
studied in the presence and absence of surfactants
1 [17]. The ruthenium (III) catalysed oxidation of D
mannitol by cerium (IV) was studied spectrophoto
metrically in aqueous sulfuric acid medium [18]. Ode
3 bunmi and marufu [19] studied oxidation of Dman
nitol and Dsorbitol by KMnO4 in NaHCO3/NaOH
1 The article is published in the original.
780
Sorbitol
Alkali
Temperature
Boric Acid
No Salt
KNO3
KCl
KI
KBr
c, M
DSorbitol
DMannitol
0.00025
0.0005
0.001
0.005
0.025
0.05
0.1
0.05
0.1
0.2
0.5
1.0
35
45
55
0
0.01
0.025
0.05
0.1
0.1
0.1
0.1
3.881
2.854
2.897
3.608
2.854
1.677
1.909
2.246
2.854
3.182
4.182
9.355
2.854
9.197
43.127
2.854
3.012
3.677
4.629
2.854
2.217
2.747
3.192
3.250
18.810
19.000
19.370
46.800
19.000
12.730
12.350
19.000
24.880
33.890
2IO 4 + 2OH
IO 4
19.000
71.460
240.250
19.000
27.03
33.130
49.268
19.000
17.353
21.854
23.374
69.999
+ OH + H 2 O
2
H 3 IO 6 ,
3
[ H 2 IO 6 ]
3 [ OH ]
2 [ IO 4 ] ex
=
1 + 2 [ OH ] + 3 [ OH ]
[OH] M
0.05
0.1
1.0
0.000307612
0.000228251
0.0000393489
= f ( [ OH ] ) [ IO 4 ] cx ,
2 [ OH ]
2
[ H 3 IO 6 ] =
2 [ IO 4 ] ex
1 + 2 [ OH ] + 3 [ OH ]
0.000180027
0.000267163
0.000460572
H 2 I 2 O 10 ,
(3)
IO 4 + 2OH
H 2 IO 6 , log 3 = 8.67.
The composition of different species of periodate in
aqueous alkaline solution can be obtained from the
equilibrium constants K1, K2 and K3. Within the used
alkali concentrations, the amounts of both the species
4
2
[H3I O 6 ]
781
= ( [ OH ] ) [ IO 4 ] cx .
The original overall periodate ion concentration is
No. 5
2014
782
E , kJ/mol
H , kJ/mol
S , J K1 mol1
logPZ
G , kJ/mol
DSorbitol
DMannitol
113.8336
106.5674
111.2728
104.0066
13.31927
6.150066
13.9511
13.57661
115.3752324
105.900888
Vol. 88
No. 5
2014
K4
K5
H3 IO 6 + S
H2 IO 6 + S
Complex C1
Complex C2
= K 2 [ IO 4 ] [ OH ] + K 3 [ IO 4 ] [ OH ]
+ k 1 K 2 K 4 [ S ] [ IO 4 ] [ OH ] + k 2 K 3 K 5 [ S ] [ IO 4 ] [ OH ] ,
[ IO 4 ]
[ IO 4 ] T
=
,
[ OH ] { K 2 + K 3 [ OH ] + k 1 K 2 K 4 [ S ] + k 2 K 3 K 5 [ S ] [ OH ] }
Rate = k 1 [ Complex C 1 ] + k 2 [ Complex C 2 ]
2
= k 1 K 4 [ H 3 IO 6 ] [ S ] + k 2 K 5 [ H 2 IO 6 ] [ S ]
= k 1 K 2 K 4 [ IO 4 ] [ OH ] [ S ] + k 2 K 3 K 5 [ IO 4 ] [ OH ] [ S ]
= [ IO 4 ] [ OH ] [ S ] { k 1 K 2 K 4 + k 2 K 3 K 5 [ OH ] }
[ IO 4 ] T [ S ] { k 1 K 2 K 4 + k 2 K 3 K 5 [ OH ] }
=
.
K 2 + K 3 [ OH ] + k 1 K 2 K 4 [ S ] + k 2 K 3 K 5 [ S ] [ OH ]
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
k1
k2
Products,
Products.
[ IO 4 ] T = [ H 3 IO 6 ] + [ H 2 IO 6 ] + [ Complex C 1 ] + [ Complex C 2 ]
783
Vol. 88
No. 5
2014
784
CONCLUSION
Substrate inhibition was observed in the oxidation
of Dsorbitol/Dmannitol in alkaline medium due to
stable complex formation between the substrate and
periodate.
REFERENCES
Vol. 88
No. 5
2014