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IJSRD - International Journal for Scientific Research & Development| Vol.

3, Issue 11, 2016 | ISSN (online): 2321-0613

Induced Electron Transfer Reaction of Cobalt (III) Complexes of


Hydroxy Acids by 2, 2-Bipyridinium Bromo Chromate (BPBC) in the
Presence of Surfactant Medium
C.Vijayakumar1 K. Subramani2
1,2
Department of Chemistry
1,2
Islamiah College, Vaniyambadi 635752 (T.N.) India
Abstract The kinetics mechanistic studied of BPBC with
Cobalt (III) bound and unbound complexes of -hydroxy
acid in micellar medium at 323 K in 50% acetic acid 50 %
water. In this reaction the rate of oxidation shows pseudo
first order kinetics each in Cobalt (III)] and BPBC. It rules
out the synchronous C-C bond fission and electron transfer
to Cobalt (III) centre. With increasing micelles
concentration an increase in the rate is observed. Oxidation
of Cobalt (III) complexes increases with increase in
temperature. The kinetic and stoichiometric results have
been accounted by a suitable mechanism.
Key words: Hydroxy Acids, 2,2Bipyridinium
Bromochromate, Sodium Lauryl Sulphate, Cetyl Trimethyl
Ammonium Bromide, TRITON-X100

cleavage accompanied by an induced electron transfer to the Co


(III) in the complex and one electron transfer to the oxidant. The
contest between the two mechanisms became interesting and
produced definite results when mild oxidizing agents like BPBC
were kinetically followed. The structure of BPBC is given below
O
-

NH

Cr Br

Fig. 1: Structure of BPBC


II. EXPERIMENTAL

2,2-Bipyridine (A.R. Qualigens, India), HBr, chromium trioxide


from (SD Fine chemicals. India 95%) Preparation of BPBC to
16.75 ml of 6 M hydrobromic acid (0.11mole) is added 10.0g.
I. INTRODUCTION
(0.11mole) of chromium trioxide rapidly while stirring. After
Chromium (VI) reagents have been widely used in organic dissolution of the chromium trioxide is complete, 15.6 g.
chemistry for the oxidation of primary and secondary alcohols to (0.1mole) of 2, 2-bipyridine is added in portions while stirring
carbonyl compounds. Pyridine chromium trioxide complexes vigorously. A yellow slurry results which is stirred for 1 hour at
and pyridinium bromo chromate have been especially useful room temperature. The slurry is then collected on a sintered
reagents for the mild oxidation of primary alcohols to aldehydes. glass funnel and washed with two 15 ml portions of cold
There are, however, some significant difficulties associated with distilled water. The resulting solid yellow filter cake is dried for
the reagents. For instance, chromium containing by-products 3 hours in vacuum at room temperature.The resulting product is
often contaminate the desired products, requiring time 2,2-bipyridinium bromochromate, its purity was checked by an
consuming purifications. A novel compound 2, 2-bipyridinium iodometric method and is obtained in a typical yield of 26.8 g.
chlorochromate, 2, 2-bipyridinium bromo chromate has been which is 92% of the theoretical yield. Mandelic, lactic and
discovered which is useful as an oxidizing agent. The compound glycolic acids from (SD Fine chemicals. India 95%)
is especially useful as an oxidizing agent in reactions which
HClO4 (Merck, India 95%) was standardized using
require relatively mild oxidizing conditions, such as the standard sodium carbonate (BDH.AR) solution with methyl
conversion of primary or secondary alcohols to carbonyl orange as an indicator. Acetic acid was purified by standard
compounds. Evolution 60 thermo spectrophotometer has been method and the fraction distilling at 1180C was collected. The
utilize to study the oxidation of -hydroxyacids1 such as cobalt (III) complexes of alpha-hydroxy acids were prepared as
mandelic acid, lactic acid, glycolic acid and their Cobalt (III) their perchlorates using the method of Fau and Gould 4. The
Complexes using Pyridinium dichromate as an oxidant in the surfactants used in the present work are sodium lauryl sulphate
presence of surfactant. Surfactants are often used in the (NaLS) and cetyl trimethylammonium bromide5 (CTAB).The
formulations of pesticides and herbicides2. They have also found surfactants are purified by adopting earlier procedure 6 Kinetic
a wide range of applications because of their unique solution measurements of the oxidation of cobalt (III) complexes of properties such as detergency, solubilisation, and surface hydroxy acids and unbound ligands were carried out under
wetting capabilities in diverse areas such as chemical as well as pseudo first order conditions in 50% acetic acid 50% water at 55
biochemical research3. Surface active materials are major 2oC by following the concentration of BPCC at 365 nm with
building blocks of many physical, chemical, anti-biological the help of an UV visible spectrophotometer. The total volume
systems. They have been introduced into several commercial of reaction mixture in the spectrophotometric cell was kept as
products such as antiseptic agents in cosmetics and as 2.5 ml in each kinetic run all the solutions for the experiments
germicides7, and have also found a wide range of applications in were maintained at the specified temperature in an electrically
diverse areas such as mining, petroleum, and pharmaceutical operated thermo stated bath. Perchloric acid was used as the
industries. A mechanism involving the C-C bond cleavage source of H+ ions and ionic strength was maintained by
leading to the formation of aldehydes as the product was NaClO .Stoichiometric studies for the oxidation of Penta
4
proposed. The formation of keto acids by the C-H cleavage of ammine cobalt (III) complexes of alpha-hydroxy acids and
the alpha-hydroxy acids was reported with many chromium (VI) unbound ligands by BPBC were carried out with the oxidant in
oxidant3. In the case of complexes, the hydroxyl group of the excess. The [H+] and ionic strength were maintained as such in
bound ligand is free for oxidation with C-H cleavage leading to the corresponding rate measurements. After ten half-lives when
the formation of keto complexes. Formation of aldehydes as a the reaction was nearing 80% completion the concentration of
product is possible with decarboxylation and synchronous C-C

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169

Induced Electron Transfer Reaction of Cobalt (III) Complexes of Hydroxy Acids by 2, 2-Bipyridinium Bromo Chromate (BPBC) in the Presence of
Surfactant Medium
(IJSRD/Vol. 3/Issue 11/2016/037)

unreacted BPBC was determined spectrophotometrically.The B. Rate Dependence of Bound Co (III) of Hydroxy Acids
difference in the concentration of the oxidant [BPBC] was in Micellar Medium
measured and then the stoichiometry was calculated from the The reaction proposes that BPBC oxidizes OH centre of the
ratio between reacted [oxidant] and [substrate]. The amount of cobalt (III) bound - hydroxy acids at a rate comparable to
cobalt (III) reduced was also calculated from the decrease in the that of the unbound ligand and there is 99 % reduction at the
absorbance measured for the Co (III) complex (Table 1).All cobalt(III) centre The kinetic data for the oxidation of the
kinetic measurements were carried out by the spectro pentaamminecobalt (III) complexes by BPBC in presence of
photometer. The spectrophotometer was kept at 365 nm the Perchloric acid catalyst and maintained temperature 55
monitoring changes the absorbance of the progress reaction.502 0.20C is given in the Table 2.The behaviour of the
nm was set for remaining Cr (VI) by monitoring changes of the complexes were similar to the free ligands and the reaction
cobalt (III) complexes. The required -hydroxy acid, HClO4 and showed a total pseudo first order dependence on them and
BPBC were premixed in a reaction vessel, thermostated in an oil the reagent. The rates of oxidation of complexes were found
bath, and BPBC solution (thermally equilibrated) was then to be higher than the corresponding free ligands showing
added prior to the absorbance measurements.
that the oxidation was facilitated by complexation. Further
the absence of keto complexes in the product and formation
A. Product Analysis
of aldehydes as the only organic product confirm the C-C
Co (II) was estimated after the completion of reaction, by
cleavage. The reduction of Co (III) to Co (II) to an extent of
diluting the reaction mixture 10-fold with concentrated HCl,
99% showed an induced electron transfer from the ligand to
allowing evolution of chlorine to cease, and then measuring the
the metal due to decarboxylation and synchronous cleavage
absorbance at 692 nm. The amount of Co (II) estimated to
of the C-C bond in the complexes. BPBC undergoes a one
nearly 40% of [Co (II)] initial. After 48h, the product was
electron change and the overall reaction between BPBC and
extracted with ether and analysed iodoimetrically for the
the complexes could be written as:
amount of aldehyde formed in the case of the [Mandelato] and
[C6H5CH (OH) COO CoIII] +O2CrBrO-bPyH+
[Lactato] Cobalt (III) complexes, the dimeric Co (III) complex,
C6H5CHO + CrV+ CoII + CO2
and unbound mandaleic acid. The yield of aldehyde in all these
The rate equation for this reaction could be deduced as
cases is nearly 60% [Co (III)] initial. After neutralization of the
Rate = K [CoIII Complex] [BPBC]
reaction mixture with sodium bicarbonate, the pH of the
Table-1 shows the Stoichiometric Data of 2,2aqueous layer was adjusted to about 6.5 and the aqueous layer
biPyridinium bromo Chromate oxidation of pentaammine
was separated by filtration in the case of both free ligands and
cobalt (III) complexes of bound and unbound alpha
corresponding complexes. On evaporation of water under
hydroxy acids in presence NaLS at maintained temperature
reduced pressure, the product separated and the percentage
550.2OC and alternatively changed micelles such as Cetyl
yield was calculated. Though the yield of mandelic acid was
Trimethyl ammonium Bromide (CTAB) and TRITON-X100
nearly quantitative, the estimation of mandaleic acid complex
respectively.
was less nearly quantitative. In both the cases the IR spectra of
102
the product agreed with that of authentic samples of mandalic
102
102 BPBC
BPBC
102 [Compound]
acid or the [mandelato] cobalt (III) complex.
[Compound]
Final
Initial
BPBC : [ BPBC]
mol dm-3
III. RESULT AND DISCUSSION
Mandelic acid
A. Rate Dependence of Free Ligand of Hydroxy Acids in
1.0
1.0
9.30
0.70
1.00:0.70
Micellar Medium
2.0
10.0
8.50
1.50
1.00:0.75
3.0
20.0
17.5
2.25
1.00:0.75
The rate of BPBC oxidation of alpha-hydroxy acids had been
followed under pseudo first order condition by keeping excess of
Lactic acid
the alpha-hydroxy acid concentration than the reagent
1.0
1.0
9.28
0.72
1.00 : 0.72
summarized kinetic data for the oxidation of -hydroxy acids
2.0
10.0
8.52
1.48
1.00 : 0.74
and their CoIII complexes by BPBC in presence of perchloric
3.0
20.0
17.78
2.22
1.00 : 0.74
acid of anionic and cationic micells at 550.2C.BPBC induced
Glycolic acid
electron transfer in pentaammine cobalt(III) complexes of alpha1.0
1.0
9.24
0.76
1.00 : 0.76
hydroxy acids seems to involve nearly synchronous C-C fission
2.0
10.0
8.52
1.48
1.00 : 0.74
and reduction at cobalt(III)centre. An explanation for the higher
3.0
20.0
17.72
2.28
1.00 : 0.70
reactivity of lactic acid involving C-H cleavage was given based
CoIII Mandelato
on the higher acidity of C-H proton. In the present investigation,
1.0
1.0
9.64
0.36
1.00 : 0.36
the absence of such an observation leads to C-C cleavage.
2.0
10.0
9.30
0.70
1.00 : 0.35
Finally product analysis confirmed the formation of aldehydes
3.0
20.0
18.98
1.02
1.00 : 0.34
due to C-C cleavage and not formed keto acids.
CoIII Lactato
Stoichiometric analysis showed that the following
1.0
1.0
9.65
0.35
1.00 : 0.35
overall reaction
2.0
10.0
9.26
0.74
1.00 : 0.37
C6H5CH (OH) COOH + O2CrBrO-bPyH+ + H+
3.0
20.0
18.89
1.11
1.00 : 0.37
C6H5CHO + H2O + OCrCO-bPyH+
CoIII Glycolato
The rate equation for this reaction could be
1.0
1.0
9.62
0.38
1.00 : 0.38
deduced as
2.0
10.0
9.26
0.74
1.00 : 0.37
Rate = K [alpha-hydroxy acid] [BPBC]

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170

Induced Electron Transfer Reaction of Cobalt (III) Complexes of Hydroxy Acids by 2, 2-Bipyridinium Bromo Chromate (BPBC) in the Presence of
Surfactant Medium
(IJSRD/Vol. 3/Issue 11/2016/037)

3.0
20.0
18.92
1.08
1.00 : 0.36
Table 1: Stoichiometric Data for BPBC oxidation of Co (III)
bound and unbound hydroxy acids in presence of Sodium
Lauryl Sulphate (NaLS) at 55 0.2 C
[HClO4]
= 1.00x10-1 mol dm-3
[NaLS]
= 1.00x10-2 mol dm-3
Temperature
= 55 0.2C

0.5
1.0
1.5
2.0
2.5

1.210 1.441 1.587


2.423 2.885 3.173
3.637 4.330 4.762
4.852 5.772 6.352
6.067 7.222 7.942
Lactic acid
0.5
1.556 1.731 1.905
1.0
3.114 3.465 3.814
C. Effect varying of Temperature
1.5
4.677 5.200 5.724
The reaction has been carried out at four different temperatures
2.0
6.238 6.932 7.634
-3
-3
-2
keeping [BPBC] =10 mol dm Mandellic Acid =1.00 x10 mol
2.5
7.792 8.660 9.545
-3
dm (Table 2).Absorbance decrease the while reaction time of
Table
3:
Kinetic
data
for
the
oxidation of alpha-hydroxy
BPBC with alpha hydroxy acid. The rate constants were
acids free ligands by BPBC
calculated by the integrated rate equation. The graph of
= 10-3mol dm-3
logarithm of absorbance versus time was linear and the rate [BPBC]
= 0.1 mol dm-3
constants calculated from the slope of the graph. Temperature [HClO4]
Temperature
= 55 0.2C
increases rate also increased.
[Micelles]
= 1.00x10-2 mol dm-3
4
-1
Time(s)
log(Absorbance)
10 k s
1

Fig 1: First order dependence plot


104k1s-1
102[-hydroxyacids]
-3
mol dm
NaLS Triton CTAB
Glycolic acid
0.5
0.916 1.111 1.306
1.0
1.831 2.224 2.617
1.5
2.751 3.339 3.922
2.0
3.674 4.456 5.232
2.5
4.595 5.572 6.547
Mandelic acid

Glycolic acid
Mandelic acid
Lactic acid

5.0

9
.99
= 0 000
e
.
p
= 1 000
slo
pe
1.
slo e =
p
slo

4.9
4.8
4.7

4+logk1

0
-0.18111
0.00
306
-0.21396
2.513
604
-0.24642
2.308
902
-0.27819
2.242
1203
-0.30980
2.146
1505
-0.33363
2.284
1807
-0.36856
2.396
2106
-0.40012
2.468
2409
-0.43063
2.577
2708
-0.45967
2.644
3004
-0.49214
2.675
Table 2: Kinetic data on the effect of Temperature
[BPBC]
=
10-3mol dm-3
[HClO4]
=
0.1 mol dm-3
Temperature
=
55 0.2C
Mandellic Acid =
1.00 x10-2 mol dm-3
[NaLS]
=
1.00x10-2 mol dm-3

4.6
4.5
4.4
4.3
4.2
4.1
1.6

1.7

1.8

1.9

2.0

2.1

2.2

2.3

2.4

2.5

2+log[alpha-Hydroxy acids]

Fig 2: Dependence of rate on -hydroxy acid with CTAB


104k1s-1
102[(NH3)5Co(III)-L]
-3
mol dm
NaLS Triton CTAB
Glycolic acid
0.5
1.216 1.357
1.588
1.0
2.430 2.713
3.173
1.5
3.647 4.073
4.764
2.0
4.864 5.434
6.344
2.5
6.085 6.790
7.935
Mandelic acid
0.5
1.306 1.615
1.905
1.0
2.615 3.234
3.811
1.5
3.912 4.853
5.721
2.0
5.230 6.474
7.630
2.5
6.548 8.095
9.540
Lactic acid
0.5
1.806 2.006
2.207
1.0
3.614 4.014
4.412
1.5
5.423 6.026
6.621
2.0
7.232 8.030
8.832
2.5
9.048 10.043 11.045
Table 4: Kinetic data for the oxidation of CoIII complexes of
alpha-hydroxy acids and bound ligands by BPBC
[BPBC]
= 2.00x10-1mol dm-3
[HClO4]
= 0.1mol dm-3
Temperature
= 55 0.2C
[Micelles]
= 1.00 x10-2 mol dm-3

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171

Induced Electron Transfer Reaction of Cobalt (III) Complexes of Hydroxy Acids by 2, 2-Bipyridinium Bromo Chromate (BPBC) in the Presence of
Surfactant Medium
(IJSRD/Vol. 3/Issue 11/2016/037)

IV. CONCLUSION

Glycolato & CTAB


Mandelato & CTAB
Lactato & CTAB

5.1
5.0

9
.99
0
= 0 1.00 9
pe
9
=
slo ope = 0.9
l
s
pe
slo

4.9
4.8

The kinetics and oxidation cobalt (III) of -Hydroxy acids


viz, glycolic acid, mandelic acid, lactic acid by 2,2bipyridinium bromo chromate in surfactant medium have
been using a novel chromium (VI) oxidant. In this reaction
C-C cleavage occurs leading reduction at CoIII centre. In this
reaction C-C cleavage occurs leading reduction at Co III
centre. The rate of the increase the observed presence
surfactant NaLS, CTAB and TRITON. Among the
surfactant which CTAB enhances the rate much more than
the TRITON, NaLS. Temperature increases the rate of the
reaction increases with micelles CTAB higher than the
TRITON, NaLS.

4+logk1

4.7
4.6
4.5
4.4
4.3
4.2
4.1
1.6

1.7

1.8

1.9

2.0

2.1

2.2

2.3

2.4

2.5

III

2+log[Co ]

Fig 3: Dependence of rate on [Co (III)] with CTAB

D. Mechanism
The reaction was show that pseudo first order dependence on the
ACKNOWLEDGEMENT
BPCC with CoIII -Hydroxy acids and alpha-Hydroxy acids. It
involve two steps. Mechanism proposes that BPBC oxidizes OH We express sincere thanks to Department of Chemistry,
centre of the cobalt (III) bound alpha - hydroxy acids at a rate Islamiah College Vaniyambadi and VME society for
comparable to that of the unbound ligand and there is
100 % providing the necessary facilities for the successful
reduction at the cobalt (III) centre, forms a chromate ester with completion of this research work.
cobalt (III) Mandelato complex which can decompose in a slow
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Induced Electron Transfer Reaction of Cobalt (III) Complexes of Hydroxy Acids by 2, 2-Bipyridinium Bromo Chromate (BPBC) in the Presence of
Surfactant Medium
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