Potassium permanganate is widely used as an oxidizing agent in synthetic

as well as in analytical chemistry and also as a disinfectant. The reactions are

governed by pH of the medium. Among six oxidation states of manganese from +2

to +7, permanganate, Mn(VII) is the most potent oxidation state in acid as well as

in alkaline medium. The oxidation by permanganate ion finds extensive

1-6
application in organic synthesis especially since the advent of phase transfer
3,5
catalysis . Kinetic studies are important sources of mechanistic information on

the reaction as demonstrated by the results referring to unsaturated acids both in

aqueous3-6and non-aqueous media 7.

During oxidation by permanganate, it is evident that permanganate is

reduced to various oxidation states in acidic, alkaline and neutral media.

Furthermore, the mechanism by which the multivalent oxidant oxidizes a substrate

depends not only on the substrate but also on the medium 8 used for the study. In
9,10
strongly alkaline medium, the stable reduction product of permanganate ion is

manganate ion, MnO42-.

Methocarbamol is a central muscle relaxant used to treat skeletal muscle

spasms. It is the carbamate of guaifenesin, but does not produce guaifenesin as a

metabolite, since the carbamate bond is not hydrolyzed metabolically; metabolism

is by Phase I ring hydroxylation and O-demethylation, followed by Phase II

conjugation. All of the major metabolites are unhydrolyzed carbamates11. The

structure of methocarbamol is shown below.

95
 NH2

O O
HO

O
O
H3C

The present study deals with the title reaction to investigate the redox

chemistry of permanganate in basic media and to arrive at a suitable mechanism.

EXPERIMENTAL

Materials

All chemicals used were of analytical reagent grade and double distilled

water was used throughout the work. The solution of methocarbamol (Bayer, AG)

was prepared by dissolving known amount of solid sample in 100 cm3 of double

distilled water. The permanganate solution was prepared and standardised against

oxalic acid12. Potassium manganate solution was prepared as described by

13
Carrington and Symons . NaOH (BDH, Analar) and NaClO4 (BDH, Analar)

were employed to maintain the required alkalinity and ionic strength respectively.

Instruments used

a) For kinetic measurements: CARY 50 Bio UV-vis. spectrophotometer (Varian,

Victoria – 3170, Australia ).

b) For product analysis: GC-MS(Shimadzu 17A gas chromatograph with a

Shimadzu XP -5000A mass spectrometer).

c) Nicolet 5700 - FT-IR spectrometer (Thermo, USA) and 300 MHz 1H NMR

spectrometer (Bruker, Switzerland).

96
Kinetic studies

The oxidation of methocarbamol by permanganate was followed under

pseudo-first order conditions where methocarbamol concentration was excess over

permanganate concentration at 25  0.1C unless otherwise stated. The reaction

was initiated by mixing the required quantities of previously thermostatted

solutions of methocarbamol and permanganate, which also contained definite

quantities of sodium hydroxide and NaClO4 to maintain the required alkalinity and

ionic strength. The application of Beer’s law to permanganate at 526 nm had been

verified between 1.0 x 10-4 - 1.0 x 10-3 under the reaction conditions and observed

extinction coefficient is,  = 2100  50 dm3 mol-1 cm-1 (Fig. IV (i) (p.98)). An

example run is given in Table IV (i) (p.99). The first order rate constants, kobs were

obtained from the plots of log (At - A∞) versus time (Fig.IV (ii) (p.100)). Where At

and A∞ are absorbances of permanganate at time t and ∞ respectively. The plots

were linear upto 80% completion of the reaction and good first order kinetics were

observed.

In the course of measurements, the solution changed from violet to blue and

then to green. The spectrum of the green solution was identical to that of MnO42-.

It is probable that the blue colour originated from the violet of permanganate and

the green from the manganate, excluding the accumulation of hypomanganate. The

formation of Mn(VI) was also evidenced by a decreasing absorbance of Mn(VII)

97
 Fig. IV (i)

Verification of Beer’s law for permanganate concentrations at 526 nm in 0.05 mol

-
dm 3 aqueous alkali at 250C

98
 Table IV (i)

Oxidation of methocarbamol by permanganate in aqueous alkaline medium at

25oC
Example run

[KMnO4] = 1.0 x 10-4; [methocarbamol] = 5.0 x 10-3

[KOH] = 0.15 ; I = 0.17 / mol dm-3

Time Optical density [KMnO4] x 104

(min) (526 nm) (mol dm-3)
0.0 0.209 0.995
0.2 0.201 0.957
0.4 0.193 0.919
0.6 0.186 0.885
0.8 0.181 0.861
1.0 0.171 0.814
1.2 0.162 0.771
1.4 0.156 0.742
1.6 0.148 0.704
1.8 0.142 0.676
2.0 0.133 0.633
2.2 0.128 0.609
2.4 0.124 0.590
2.6 0.122 0.580
2.8 0.118 0.561
3.0 0.114 0.542
3.2 0.110 0.523
3.4 0.105 0.500
3.6 0.100 0.476
3.8 0.094 0.447
4.0 0.088 0.419

99
 Fig. IV (ii)

First order plots of the oxidation of methocarbamol by permanganate in

aqueous alkaline medium at 25oC

[MnO4-] x 10-4 mol dm-3 = 1) 0.50; 2) 1.0; 3) 2.0; 4) 3.0; 5) 4.0; 6) 5.0;

3.5

3.0

2.5
3+ log (A t -A ∞)

6
2.0 5
4
1.5 3
2
1.0
1
0.5

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Time (min)

100
at 526 nm and an increasing absorbance of Mn(VI) at 604 nm during the course of

the reaction(Fig. IV (iii)(p.102)).

The effect of dissolved oxygen on the rate of reaction was verified by

preparing the reaction mixture and following the reaction in an atmosphere of

nitrogen. No significant difference between the results obtained in the presence

and absence of nitrogen.

RESULTS

Stoichiometry and product characterization

Different sets of reaction mixtures containing excess concentration of

permanganate over methocarbamol in the presence of constant amounts of OH-

and NaClO4 were kept for 1 h in closed vessels under nitrogen atmosphere. The

remaining concentration of permanganate was estimated spectrophotometrically at

525 nm. The result indicates , one mole of methocarbamol reacts with four moles

of Mn(VII), as shown in equation 1.

CH3
O O CH3
O O
O O C NH2 + 4[MnO4(OH)]2- O C +
OH
OH

H
(1)
HO C O NH2
C + 4MnO42- + 2H2O
H
O

101
 Fig. IV (iii)

Spectral change during the course of reaction between methocarbamol and

alkaline permanganate

102
 The acidified reaction mixture is extracted by using mixture of solvents i.e

chloroform and ethyl acetate. The main reaction products were eluted in a mixture

of chloroform and ethyl acetate (8 : 2), which were identified as 2-Methoxy

phenoxy acetic acid (I) and Hydroxyl methyl carbamate (II).

The IR spectrum of compound (I) showed the bands at 1682 cm-1 and 3443

cm-1 due to C=O and –OH stretching frequencies of carboxylic acid group

respectively (Fig. IV (iv)(p.104)). Further it was confirmed by its mass spectrum,

which exhibited m/z at 182 (Fig. IV (v)(p.105)). Similarly for compound

(II),Hydroxyl methyl carbamate, IR spectrum bands at 3342 cm-1 and 3251 cm-1

due asymmetric and symmetric frequencies of –NH2 group, a band at 3114 cm-1

due to –OH stretching frequency was observed. The C=O stretching frequency of

CONH2 group was also observed at 1603 cm-1(Fig. IV (vi) (p.106)). Further, the

formation of compound was confirmed by its mass spectrum, which showed m/z

at 91 (Fig. IV (vii)(p.107)).

Reaction orders

The reaction orders were determined from the slopes of log kobs versus log

(concentration) plots by varying the concentration of the drug and alkali in turn

while keeping others constant.

Effect of [permanganate]

The oxidant permanganate concentration was varied in the range of 0.50

x10-4 to 5.0 x 10-4 and the fairly constant kobs values (Table IV(ii)(p.109)) indicate

103
 Fig. IV (iv)

FT-IR spectra of the product, 2-Methoxy phenoxy acetic acid , obtained during the
oxidation of methocarbamol by permanganate in aqueous alkaline medium at
25oC

104
 Fig. IV (v)

GC-MS spectra of the product 2-Methoxy phenoxy acetic acid obtained during the

oxidation of methocarbamol by permanganate in aqueous alkaline medium at

25oC

105
 Fig. IV (vi)

FT-IR spectra of of the product Hydroxyl methyl carbamate obtained during

the oxidation of methocarbamol by permanganate in aqueous alkaline medium at
25oC

106
 Fig. IV (vii)

GC-MS spectra of the product Hydroxyl methyl carbamate obtained during the
oxidation of methocarbamol by permanganate in aqueous alkaline medium at
25oC

107
that order with respect to permanganate concentration was unity. This was also

confirmed by linearity of the plots of log [At - A∞] versus time(Fig. IV (ii)(p.100))

up to 80% completion of the reaction.

Effect of [methocarbamol]

The substrate methocarbamol concentration was varied in the range of 0.6 x

10-3 to 6.0 x 10-3 mol dm-3 at 298K keeping all other reactants concentration and

conditions constant. As the methocarbamol concentration increases the rate of

reaction also increases (Table IV(ii)(p.109)) and from the plot of log kobs versus

log[methocarbamol], an apparent less than unit order dependence on

methocarbamol concentration was observed(Fig. IV (viii)(p.110)).

Effect of [alkali]

The effect of alkali on the reaction rate was studied in the range of 0.2 x 10-1

to 2.0 x 10-1 at constant concentration of methocarbamol and permanganate . The

rate constants increased with the increase in alkali concentration (Table

IV(ii)(p.109))and the order in OH- concentration was less than unity(Fig. IV

(viii)(p.110)).

Effect of ionic strength and dielectric constant of the medium

The effect of ionic strength was studied by varying the sodium per chlorate

concentration from 0.15 to 0.27 mol dm-3 at constant concentrations of

permanganate, methocarbamol and alkali. It was found that the rate constant

108
 Table IV (ii)

Effect of variation of permanganate, methocarbamol and alkali concentrations on

the oxidation of methocarbamol by alkaline permanganate at 25C

I = 0.17 mol dm-3

[MnO4-] x 104 [MET] x 103 [OH-] x 101 kobs x103

(mol dm-3) (mol dm-3) (mol dm-3) (s-1)

0.5 5.0 1.5 3.32

1.0 5.0 1.5 3.34
2.0 5.0 1.5 3.35
3.0 5.0 1.5 3.36
4.0 5.0 1.5 3.36
5.0 5.0 1.5 3.34

1.0 0.6 1.5 0.99

1.0 1.5 1.5 1.75
1.0 2.0 1.5 2.22
1.0 3.0 1.5 2.64
1.0 5.0 1.5 3.69
1.0 6.0 1.5 4.45

1.0 5.0 0.2 0.95

1.0 5.0 0.7 1.92
1.0 5.0 1.0 2.46
1.0 5.0 1.5 3.59
1.0 5.0 1.7 3.91
1.0 5.0 2.0 4.31

109
 Fig. IV (viii)

Order with respect to methocarbamol and hydroxyl ion concentrations on the

oxidation of methocarbamol by permanganate in aqueous alkaline medium at 25oC

3.0

2.5

2.0
5+log kobs

1.5

1.0

0.5

0.0
1.0 1.5 2.0 2.5 3.0
5+log[MET]

2.0

1.6

1.2
4+log kobs

0.8

0.4

0.0
2.0 2.5 3.0 3.5
4+log[OH -]

110
decreased with increasing concentration of NaClO4(Table IV(iii)(p.112)). The plot

of log kobs versus √I was found to be linear with negative slope (Fig.

IV(ix)(p.113)). Dielectric constant of the medium, D was studied by varying the

tert-butyl alcohol at constant concentration of permanganate, methocarbamol and

alkali. It was found that dielectric constant of the medium had no significant effect

on the rate of reaction.

Polymerisation study

The intervention of free radicals in the reaction was examined as follows.

The reaction mixture, to which a known quantity of acrylonitrile monomer was

initially added, was kept for 2 h in an inert atmosphere. On diluting the reaction

mixture with methanol, a white precipitate was formed, indicating the intervention

of free radicals in the reaction. The blank experiments of either permanganate or

methocarbamol alone with acrylonitrile did not induce any polymerisation under

the same condition as those induced for reaction mixture.

Effect of temperature

The kinetics was studied at three different temperatures, 15, 25 and 350C,

under varying concentrations of methocarbamol and alkali , keeping other

conditions constant. The rate constants were found to increase with increase in

temperature. The rate constants (k) of the slow step of Scheme 1 were obtained

from the slopes and intercepts of 1/kobs versus 1/[methocarbamol] and 1/[OH-]

plots at three different temperatures (Table IV (iv)(p.116)and were used to

111
 Table IV (iii)

Effect of variation of ionic strength (I) on the oxidation of methocarbamol by

permanganate in aqueous alkaline medium at 25o C

[permanganate] = 1.0 x 10-4 [MET] = 5.0 x 10-3

[OH-] = 0.15 mol dm-3

I kobs x 10-2
√I
-3
(mol dm ) (s-1)

0.15 0.3872 0.43

0.17 0.4123 0.39

0.20 0.4472 0.36

0.23 0.4795 0.33

0.25 0.5000 0.32

0.27 0.5196 0.31

112
 Fig. IV (ix)

Effect of ionic strength on the oxidation of methocarbamol by permanganate in

aqueous alkaline medium at 25oC

0.65

0.60
3 + logk obs

0.55

0.50

0.45

0.40
0.35 0.40 0.45 0.50 0.55
√I mol dm-3

113
 calculate the activation parameters. The energy of activation was evaluated

from the plot of log k(y*calc) versus 1/T as shown in Fig. IV (x)(p.115), from which

the activation parameters were calculated and are tabulated in Table IV

(iv)(p.116).

DISCUSSION

The permanganate ion is a powerful oxidant in aqueous alkaline

medium. Diode array rapid scan spectrophotometric studies have shown that at

pH[12], Mn(VII) is reduced to Mn(VI), and no further reduction has been

observed. The permanganate in alkaline medium exhibits various oxidation states,

such as Mn(VII), Mn(V) and Mn(VI). The colour of the solution changed from

violet to blue and further to green excluding the accumulation of hypomanganate.

The violet colour originates from pink of permanganate and blue from

hypomanganate during the course of the reaction. The colour change of KMnO4

solution from violet Mn(VII) ion to dark green Mn(VI) ion through blue Mn(V)

ion has been observed.

The reaction between methocarbamol and permanganate in alkaline

medium has a stoichiometry of 1:4 with an order of less than unity for both alkali

and methocarbamol. First order dependence on permanganate concentration has

observed during the reaction. No effect of the products was observed. The following

mechanism has been proposed in the form of Scheme 1.

114
 Fig. IV (x)

Effect of temperature on the oxidation of methocarbamol by permanganate in

aqueous alkaline medium at 25 oC

1/T x 10 3
3.20 3.25 3.30 3.35 3.40 3.45 3.50
-2.20

-2.22

-2.24
logk ( y* cal )

-2.26

-2.28

-2.30

-2.32

-2.34

-2.36

115
 Table IV (iv)

Effect of temperature on the oxidation of methocarbamol by permanganate in

aqueous alkaline medium with respect to slow step of Scheme 1

Temperature 1/T x 103 k x 102 log k log k

(K) (x) (dm3 mol-1 s-1) (y) ( y* cal)

288 3.472 0.45 -2.346 -2.345

298 3.355 0.53 -2.275 -2.277

308 3.246 0.61 -2.214 -2.213

Activation Parameters

Parameters Values

Ea (kJ mol-1) 12.0±0.3

ΔH# (kJ mol-1) 9.0±0.3

ΔS# (JK-1 mol-1) -213±5

ΔG# (kJ mol-1) 73±3

log A 2.0±0.02

116
 K1
MnO4 - + OH - [MnO4 . OH] 2-

CH3
O
O
2- O O C NH2 K2
[MnO4 . OH] + Complex( C)

OH
CH3
O
+
Complex( C) k O + H2C O C NH2 + MnO4 2- + OH -
slow . H O
OH

+ O NH2 fast H
OH - O NH2
H2 C C + HO C C
O H O
(II)

CH3 CH3
O O
2-
+ [MnO4 . OH] 2- fast O + MnO4 + H2 O
O
. H H
OH O

CH3
O CH3
O
fast
O + 2[MnO4(OH)] 2- + 2MnO4 2- + H2O
O
H
OH
O
O
(I)

Scheme 1

The results indicate that the OH- combines first with permanganate to give

an alkaline permanganate species [MnO4.OH]2- in a prior equilibrium step 14, 15

,

117
which is also supported by the observed less than unit order in OH- concentration

and the Michaelis–Menton plot, which is linear with positive intercept. The

permanganate species then reacts with methocarbamol to give a complex (C),

which decomposes in a slow step to give a free radical of 2-methoxy phenoxy

acetic acid (I) and hydroxyl methyl carbamate (II) . Such type of free radicals have
16
been reported in the literature . This free radical of 2-methoxy phenoxy acetic

acid then reacts with three more molecules of permanganate in further fast steps to

yield the product 2-methoxy phenoxy acetic acid as given in Scheme 1.

Spectroscopic evidence for the complex formation between oxidant and

substrate was obtained from UV–vis spectra of [methocarbamol] = 5.0 X 10-3,

[permanganate] =1.0 X 10-4, [OH-] = 0.15 mol dm-3 and mixture of both. A

hypsochromic shift of about 4 nm from 310 nm to 306 nm in the spectra of

potassium permanganate compared with the reaction mixture containing potassium

permanganate and methocarbamol was observed . Such type of complex between a

substrate and an oxidant has been observed in other studies 17.

The rate law for the Scheme 1could be derived as

-d [ MnO4- ]
Rate = = k( C )
dt

= k K1 K2 [MnO4 -][MET] [OH-] ( 2)

- 2-
[MnO4-]T = [MnO4 ]f + [MnO4.OH] + Complex ( C )

- -
= [MnO4-]f + K1 [MnO4 ] [OH ] + K2 [MET] [HMnO4]

118
 - -
= [MnO4-]f 1 + K1 [OH ] + K1K2 [MET] [OH ]

[MnO4 -]T
[MnO4-]f = (3)
1 + K1 [OH -] + K1K2 [MET][OH-]

where T and f stands for total and free concentration of [MnO-4]

Similarly,

[MET]T = [MET]f + [Complex(C)]

= [MET]f + K1K2[MET][OH-][MnO4-] (4)

[MET]T= [MET]f [ 1+ K1K2[OH-][MnO4-]]

[MET]T
[MET]f = (5)
1 + K1K2[OH-][MnO4-]

In view of the low concentration of MnO4- used in the experiment, the term

K1K2[OH-][MnO4-] can be neglected.

Hence,

[MET]f = [MET]T (6)

Similarly,

[OH-]f = [OH -]T (7)

Substituting equations (3), (6) and (7) in equation ( 2 ) and omitting subscripts we

get

119
 k K1 K2 [MnO4-] [OH-] [MET]
Rate =
1+ K1[OH-] + K1K2[MET][OH-] (8)
Rate k K1 K2 [OH-] [MET]
= kobs =
[MnO4-] 1+ K1[OH-] + K1K2[MET][OH-]

The rate law (8) can be rearranged to equation (9) which is suitable for verification

1 1 1 1
= + + (9)
-
k obs k K1K2[MET][OH ] kK2[MET] k
According to equation (9), the plots of 1/kobs versus 1/[OH-] and 1/kobs versus

1/[MET] were linear (Fig. IV(xi)(p.121)); from the intercepts and slopes of such

plots, the reaction constants K1, K2 and k were calculated as(0.67 x 10-1)dm3 mol-1,

(44.2 x 103) dm3 mol-1 and (0.53x10-2) s-1, respectively. The value of K1 is in

neighborhood of literature value (K1 = 5.6 × 10-1) 18.

The thermodynamic quantities for the different equilibrium steps in Scheme 1 can

be evaluated as follows. The methocarbamol and hydroxide ion concentrations

(Table IV(ii)(p.109)) were varied at different temperatures. The plots of 1/kobs

versus 1/[MET] and 1/ kobs versus 1/[OH-] should be linear (Fig. IV(xi)(p.121).

From the slopes and intercepts, the values of K1 are calculated at different

temperatures. A van’t Hoff plot was made for the variation of K1 with temperature

[i.e., log K1 versus 1/T] and the values of the enthalpy of reaction ΔH, entropy of

reaction ΔS and free energy of reaction ΔG, were calculated. These values are also

given in Table IV(v)(p.122). A comparison of the latter values with those obtained

for the slow step of the reaction shows that these values mainly refer to the rate

120
 Fig. IV (xi)

Verification of rate law (8) in the form of (9) for the oxidation of methocarbamol

by permanganate in aqueous alkaline medium at different temperatures

(a) 1/kobs versus 1/[MET] (b)1/kobs versus 1/[OH-]

1.4
1.2
1.0 288 K
1/kobs x 10-3

0.8
0.6 298 K
0.4 308 K
0.2
0.0
0.0 0.5 1.0 1.5 2.0
-3 3 -1
1/[MET] X 10 dm mol

1.8
1.6
1.4 288 K
1/kobs x 10-3 s

1.2
1.0
298 K
0.8
0.6
0.4 308 K
0.2
0.0
0 0.1 0.2 0.3 0.4 0.5 0.6

1/[OH-] x 10-2 dm3 mol-1

121
 Table IV (v)

Effect of temperature on first and second equilibrium step of Scheme 1

Temp. (K) K1 x 102 dm3 mol-1 K2 x10-3 dm3 mol-1

288 4.4 60.4

298 6.7 44.2

308 7.4 32.7

Thermodynamic quantities with respect to K1 and K2

Quantities Using K1values Using K2 values

H (kJ mol-1) 19.56 -22.58

S (J K-1mol-1) 42.41 13.13

G (kJ mol-1) 6.92 -26.63

122
limiting step, supporting the fact that the reaction before the rate determining step
19
is fairly slow and involves a high activation energy . In the same manner, K2

values were calculated at different temperatures and the corresponding values of

thermodynamic quantities are given in Table IV(v)(p.122).The negative value of

ΔS# (-244 ± 11) suggests that the intermediate complex is more ordered than the

reactants 20. The observed modest enthalpy of activation and a higher rate constant

for the slow step indicates that the oxidation presumably occurs via an inner-
21
sphere mechanism.This conclusion is supported by earlier observations . The

moderate value of ΔH# (9.12 kJ/mol) was due to energy of solution changes in the

transition state.

CONCLUSION

It is interesting that the oxidant species MnO4- requires a pH = 12, below

which the system becomes disturbed and the reaction proceeds further to give a

reduced product of the oxidant as Mn(IV). Hence, it becomes apparent that the

role of pH in the reaction medium is crucial. It is also noteworthy that under the

conditions studied, the reaction occurs in successive one electron reduction in a

single step. The description of the mechanism is consistent with all the

experimental evidence. Rate constant of slow step and other equilibrium constants

involved in the mechanism are evaluated and activation parameters with respect to

slow step of reaction were computed. The overall mechanistic sequence described

here is consistent with product, mechanistic and kinetic studies.

123
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