1926

Kinetics and mechanistic study of the

ruthenium(III) catalyzed oxidative deamination and
decarboxylation of L-valine by alkaline
permanganate
Dinesh C. Bilehal, Raviraj M. Kulkarni, and Sharanappa T. Nandibewoor

Abstract: The kinetics of ruthenium(III) catalyzed oxidation of L-valine by permanganate in alkaline medium at a con-
stant ionic strength has been studied spectrophotometrically. The reaction between permanganate and L-valine in alka-
line medium exhibits 2:1 stoichiometry (KMnO4:L-valine). The reaction shows first-order dependence on the
concentration of permanganate and ruthenium(III) and less than unit-order dependence on the concentrations of L-valine
and alkali. The reaction rate increases both with an increase in ionic strength and a decrease in solvent polarity of the
medium. Initial addition of reaction products did not significantly affect the rate. A mechanism involving the formation
of a complex between catalyst and substrate has been proposed. The activation parameters were computed with respect
to the slowest step of the mechanism.

Key words: oxidation, L-valine, catalysis, ruthenium(III), kinetics.

Résumé : Faisant appel à des méthodes spectrophotométriques, on a étudié la cinétique de l’oxydation de la L-valine
par le permanganate, catalysée par le ruthénium(III), en milieu alcalin et à force ionique constante. En milieu alcalin,
la réaction entre le permanganate et la L-valine présente une stoechiométrie de 2:1 (KMnO4:L-valine). La réaction pré-
sente une dépendance du premier ordre avec les concentrations de permanganate et de ruthénium(III) et cette dépen-
dance est inférieure à l’unité pour les concentrations de L-valine et de base. La vitesse de réaction augmente avec une
augmentation de la force ionique et avec une diminution dans la polarité du solvant. L’addition initiale de produits
réactionnels n’affecte pas la vitesse de façon significative. On propose un mécanisme impliquant la formation initiale
d’un complexe entre le catalyseur et le substrat. On a calculé les paramètres d’activation par rapport à l’étape la plus
lente du mécanisme.

Mots clés : oxydation, L-valine, catalyse, ruthénium(III), cinétique.

[Traduit par la Rédaction] Bilehal et al. 1933

Introduction The oxidation by permanganate ion finds extensive appli-

Potassium permanganate is widely used as an oxidizing
agent in synthetic as well as in analytical chemistry and also
as a disinfectant. The reactions with permanganate are gov-
erned by pH of the medium. Among the six oxidation states
of manganese from 2+ to 7+, permanganate Mn(VII) is the
most potent oxidation state in both acid and alkaline medium.
The manganese chemistry involved in these multistep redox
reactions is an important source of information as the manga-
nese intermediates are relatively easy to identify when they
have sufficiently long life times and the oxidation states of the
intermediates permit useful conclusions as to the possible
reaction mechanism including the nature of intermediates.
Received February 2001. Published on the NRC Research Press
Web site at http://canjchem.nrc.ca on December 14, 2001.
D.C. Bilehal, R.M. Kulkarni, and S.T. Nandibewoor.1 P.G.
Department of Studies in Chemistry, Karnatak University,
Dharwad 580 003, India.
1
Corresponding author (fax: 0836-747-884; e-mail:
karuni@bgl.vsnl.net.in).
cations in organic syntheses (1–7), especially since the ad-
vent of phase transfer catalysis (3, 4, 6), which permits the
use of solvents such as methylene chloride and benzene. Ki-
netic studies are important sources of mechanistic informa-
tion on the reactions, as demonstrated by the results
referring to unsaturated acids in both aqueous (1, 3, 7) and
nonaqueous media (8).
During the oxidation by permanganate, it is evident that
permanganate is reduced to various oxidation states in
acidic, alkaline, and neutral media. Furthermore, the mecha-
nism by which the multivalent oxidant oxidizes a substrate
depends not only on the substrate but also on the medium
(9) used for the study. In strongly alkaline medium, the sta-
ble reduction product (10, 11) of permanganate ion is
manganate ion, MnO24 - . No mechanistic information is
available to distinguish between a direct one-electron reduc-
tion to Mn(VI) (Scheme 1) and a mechanism in which a
hypomanganate is formed in a two-electron reduction fol-
lowed by a rapid oxidation of the hypomanganate ion (12)
(Scheme 2).
L-valine is one of the essential basic amino acids, which is
essential in the nutrition of mammals. Its role is crucial in

Can. J. Chem. 79: 1926–1933 (2001) DOI: 10.1139/cjc-79-12-1926 © 2001 NRC Canada
Bilehal et al. 1927

Scheme 1. Fig. 1. Spectral changes during the ruthenium (III) catalyzed oxi-
dation of L-valine by alkaline permanganate (scanning time inter-
k 1¢ val = 1 min). [MnO-4 ] = 2.0 × 10–4, [L-valine] = 2.0 × 10–3,
Mn(VII) + S ® Mn(VI) + S× [Ru(III)] = 7.5 × 10–8, [OH–] = 0.30, I = 0.50 mol dm–3.

k 2¢
Mn(VII) + S×® Mn(VI) + Products
Where, S = substrate; k2¢ >> k1¢

Scheme 2.
k 3¢
Mn(VII) + S ® Mn(V) + Products
k 4¢
Mn(VII) + Mn(V) ® 2 Mn(VI)
Where, S = substrate; k4¢ >> k3¢

the development of organs, especially in children. It also

finds applications in medicine and pharmaceuticals. Amino
acids have been oxidized by a variety of oxidizing agents
(13). Although several types of organic (14) and inorganic
(10, 11) substrates are oxidized by permanganate in aqueous
alkaline medium, there are only a few reports on the oxida-
tion of amino acids by aqueous alkaline permanganate. The
kinetic investigation of the oxidation of amino acids has
been carried out under different experimental conditions
(15). In many cases it was reported that amino acids undergo
oxidative decarboxylation. Jayaprakash Rao et al. (16) sug-
gested that the oxidation of amino acids by two-electron oxi-
dants such as diperiodatoargentate(III) in alkaline medium
involves a two-electron transfer, which produces an imino
acid intermediate in the rate determining step. This interme-
diate subsequently undergoes hydrolysis to yield the keto ac-
ids. One electron oxidants such as ceric sulphate (17),
peroxomonosulphate (18), and hexacyanoferrate(III) (19)
also oxidize amino acids to keto acids. But other studies
with amino acids report the oxidation products as the corre-
sponding aldehydes (20). Thus, the study of amino acids be-
comes important because of their biological significance and lyst. The present study deals with the title reaction to inves-
their selectivity towards the oxidants. tigate the redox chemistry of permanganate and L-valine in
Ruthenium(III) is known to be an efficient catalyst in sev- presence of a catalysis.
eral redox reactions particularly in alkaline medium (21).
The mechanism of catalysis can be quite complicated due to Experimental
the formation of different intermediate complexes, free radi-
cals, and different oxidation states of ruthenium. The kinet- Materials and methods
ics of fast reactions between ruthenate(VII), RuO-4 , and Stock solution of L-valine (Sisco Research Labs, India) was
manganate(VI), i.e., MnO24 - , have been studied (22) and the prepared by dissolving the appropriate amount of sample in
reaction is presumed to proceed via an outer-sphere mecha- doubly distilled water. The solution of potassium permanga-
nism. The rapid exchange between MnO24 - and MnO-4 has nate (BDH) was prepared and standardized against oxalic acid
been studied in detail by a variety of techniques (23). The (25). Potassium manganate solution was prepared as de-
uncatalyzed reaction between L-valine and permanganate in scribed by Carrington and Symons (26).The solution was
alkaline medium has been studied previously (24). A micro standardized by measuring the absorbance on a Hitachi 150-
amount of ruthenium(III) is sufficient to catalyze the reac- 20 spectrophotometer with a 1 cm quartz cell at 608 nm (e =
tion in alkaline medium and a variety of mechanisms are 1530 ± 20 dm3 mol–1 cm–1). The ruthenium(III) solution was
possible. Thus, to explore the mechanism of oxidation by prepared by dissolving a known weight of RuCl3 (S.D. Fine
permanganate ion in strongly aqueous alkaline medium and Chemicals) in 0.20 mol dm–3 HCl. Mercury was added to the
to check the selectivity of L-valine towards permanganate in ruthenium(III) solution to reduce any Ru(IV) formed during
catalyzed system, we have selected ruthenium(III) as a cata- the preparation of ruthenium(III) stock solution and kept for a

© 2001 NRC Canada

1928
H H
Ru(III)
[1] CH3 C CH-COOH + 2MnO 4– + 2OH–
H 3C NH2
day. The ruthenium(III) concentration was assayed (27) by
EDTA titration.
All other reagents were of analytical grade and their solu-
tions were prepared by dissolving the requisite amounts of
the samples in doubly distilled water. NaOH and NaClO4
were used to provide the required alkalinity and to maintain
the ionic strength, respectively.
Kinetic procedure
All kinetic measurements were performed under pseudo-
first-order conditions with [L-valine]:[MnO-4 ] ³ 10:1 at a con-
stant ionic strength of 0.50 mol dm–3. The reaction was initi-
ated by mixing previously thermostated solutions of MnO-4 ,
and L-valine, which also contained the necessary quantities
of Ru(III), NaOH, and NaClO4 to maintain the required al-
kalinity and ionic strength, respectively. The temperature
was uniformly maintained at 26 ± 0.1°C. The course of reac-
tion was followed by monitoring the decrease in the
absorbance of MnO-4 in a 1 cm quartz cell of a Hitachi
model 150-20 spectrophotometer at its absorption maximum
of 526 nm as a function of time. The application of Beer’s
law to permanganate at 526 nm had been verified, giving e =
2083 ± 50 dm3 mol–1 cm–1 (lit. (10) e = 2200 dm3 mol–1 cm–1).
The first-order rate constants (kobs) were evaluated by plots
of log [MnO-4 ] vs. time. The first-order plots in almost all
cases were linear to 80% completion of the reaction and kobs
were reproducible within ±5%.
During 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 MnO24 - . It is probable
that the blue colour originated from the violet of permanga-
nate and the green from the manganate, excluding the accu-
mulation of hypomanganate. It is also evident from the Fig. 1
that the absorbance of permanganate decreases at 526 nm,
whereas the absorbance of manganate increases at 608 nm.
The effect of dissolved oxygen on the rate of reaction was
checked by preparing the reaction mixture and following the
reaction in an atmosphere of nitrogen. No significant differ-
ence between the results obtained under the nitrogen and in
the presence of air was observed. In view of the ubiquitous
contamination of basic solutions by carbonate, the effect of
carbonate on the reaction was also studied. Added carbonate
had no effect on the reaction rate. However, fresh solutions
were used when conducting the experiments.
Results
Stoichiometry and product analysis
The reaction mixtures containing an excess permanganate
concentration over L-valine and constant concentration of
Ru(III) (0.30 mol dm–3), NaOH, and an adjusted ionic
strength of 0.50 mol dm–3 was allowed to react for 2 h at
Can. J. Chem. Vol. 79, 2001
CH3 C
2–
CHO + 2MnO 4 +
H3C
NH3 + CO2 + H2O
26 ± 0.1°C. After completion of the reaction, solid KI was
added followed by acidification by 10% H2SO4. The remain-
ing MnO-4 was then titrated against standard sodium
thiosulphate (28). The results indicated that two mol of
MnO-4 are consumed by one mol of L-valine as given by
eq. [1]. The main reaction products were identified as alde-
hyde by spot test (29), ammonia by Nessler’s reagent (30),
and manganate by its visible spectrum. CO2 was qualita-
tively detected by bubbling N2 gas through the acidified re-
action mixture and passing the liberated gas through a tube
containing lime water (31). The quantitative estimation of
aldehyde by 2,4-DNP derivative (32), yielded nearly 74%.
The nature of the aldehyde, was confirmed by its IR spec-
trum (33), which showed a carbonyl stretching at 1729 cm–1
and a band at 2928 cm–1 due to aldehydic C—H stretching,
thus confirming the presence of isobutylaldehyde. It was fur-
ther observed that the aldehyde does not undergo further ox-
idation under the present kinetic conditions. The test for
corresponding acid was negative.
Reaction orders
The reaction orders were determined from the slopes of
log kobs vs. log (concentration) plots by varying the concen-
tration of reductant, catalyst, and alkali in each, while keep-
ing others constant. The oxidant, potassium permanagate,
concentration was varied in the range of 5.0 × 10–5 to 5.0 ×
10–4 mol dm–3, and the fairly constant kobs values indicate
that the order with respect to [MnO-4 ] was one. This was also
confirmed by varying the concentration of MnO-4 , which did
not show any change in pseudo-first-order constants (kobs)
values as shown in Table 1. The substrate L-valine was var-
ied in the range of 5.0 × 10–4 to 5.0 × 10–3 mol dm–3 at
26°C; the order with respect to [L-valine] was found to be
less than unity. The catalyst Ru(III) was varied in the range
of 1.0 × 10–8 to 1.0 × 10–7 mol dm–3 at 26°C; the order with
respect to [Ru(III)] was found to be unity. The effect of al-
kali on the reaction was studied at constant concentrations of
L-valine, Ru(III), and potassium permanganate and at a con-
stant ionic strength of 0.50 mol dm–3 at 26°C. The rate con-
stant increased with the increase in the concentration of
alkali, indicating an apparent less than unit order depend-
ence on [alkali] as given in Table 1.
Effect of initially added products
The externally added products such as manganate, ammo-
nium hydroxide, and aldehyde did not show any significant
effect on the rate of the reaction.
Effect of ionic strength and dielectric constant
The effect of ionic strength was studied by varying the
sodium perchlorate concentration from 0.3 to 2.0 mol dm–3
at constant concentrations of permanganate, L-valine, and
© 2001 NRC Canada
Bilehal et al. 1929

Table 1. Effects of [L-valine], [MnO-4 ], [Ru(III)], and [OH–] on ruthenium(III) catalyzed oxidation of
–3
L-valine by KMnO4 at 26°C; I = 0.50 mol dm and error ±4%.
3
kobs × 10 (s–1)
[MnO-4 ] × 104 [L-valine] × 103 [OH–] [Ru(III)] × 108
(mol dm–3) (mol dm–3) (mol dm–3) (mol dm–3) Expt. Calcd.
0.5 2.0 0.3 7.5 3.60 3.67
1.0 2.0 0.3 7.5 3.70 3.67
2.0 2.0 0.3 7.5 3.75 3.67
3.0 2.0 0.3 7.5 3.70 3.67
5.0 2.0 0.3 7.5 3.60 3.67
2.0 0.5 0.3 7.5 2.45 2.38
2.0 1.0 0.3 7.5 3.03 3.11
2.0 2.0 0.3 7.5 3.75 3.67
2.0 3.0 0.3 7.5 4.07 3.91
2.0 5.0 0.3 7.5 4.16 4.12
2.0 2.0 0.05 7.5 1.05 1.03
2.0 2.0 0.1 7.5 1.76 1.81
2.0 2.0 0.2 7.5 2.80 2.92
2.0 2.0 0.3 7.5 3.75 3.47
2.0 2.0 0.5 7.5 4.68 4.61
2.0 2.0 0.3 1.0 0.51 0.49
2.0 2.0 0.3 2.5 1.31 1.22
2.0 2.0 0.3 5.0 2.60 2.45
2.0 2.0 0.3 7.5 3.75 3.67
2.0 2.0 0.3 10.0 5.06 4.90

Fig. 2. Plot of log kobs vs. I1/2 and log kobs vs. 1/D. Table 2. Thermodynamic activation parame-
1/2 ters for the ruthenium(III) catalyzed oxidation
I
of L-valine by aqueous alkaline permanganate
1.50 1.25 1.00 0.75 0.50 0.25 0 with respect to slow step of Scheme 3.
0.95 0.3
Activation parameters Values
–1
Ea (kJ mol ) 72 (±4)
0.93 DH‡ (kJ mol–1) 69 (±4)
0.5
DS‡ (J K–1 mol–1) 75 (±4)
DG‡ (kJ mol–1) 46 (±3)
0.91
3 +log kobs
3+ log kobs

0.7
0.89 decrease in the dielectric constant of the medium. The plot
of log kobs vs. 1/D was linear with positive slope as shown in
0.9 Fig. 2.
0.87
Test for free radicals
The reaction mixture was mixed with acrylonitrile mono-
0.85 1.1 mer and kept for 2 h in an inert atmosphere. On diluting
1.30 1.35 1.40 1.45 1.50 1.55 1.60 with methanol a white precipitate was formed, indicating the
1 / D x 10-2 intervention of free radicals in the reaction.

alkali. It was found that the rate constant increased with in-
crease in concentration of NaClO4 and the plot of log kobs
vs. I1/2 was linear (Fig. 2).
The effect of dielectric constant (D) was studied by vary-
ing the tert-butanol–water content in the reaction mixture
with all other conditions being constant. Attempts to mea-
sure the relative permittivities were not successful. However,
they were computed from the values of pure liquids (34).
The solvent did not react with the oxidant under the experi-
mental conditions. The rate constants (kobs) increased with a
Effect of temperature
The rate of the reaction was measured at four different
temperatures with varying the concentration of OH–, keeping
other conditions constant. The rate was found to increase
with increase in temperature. The rate constant (k) of the
slow step of Scheme 3 were obtained from the intercept of
the plots of [Ru(III)]/kobs vs. 1/[OH–] for different tempera-
tures. The energy of activation corresponding to these con-
stants were evaluated from the plot of log k vs. 1/T and other
activation parameters for reaction were calculated and are
given in Table 2.

© 2001 NRC Canada

1930 Can. J. Chem. Vol. 79, 2001

Scheme 3.
O 2–
OH
K1
MnO4– + OH – O Mn

O O

K2
R CH-COO- + [Ru(H2O)5OH]2+ Complex ( C ) + H2O

NH2

O 2–
OH
k
(C)+ O Mn R- CH. + MnO42- + [Ru(H2O)4OH]2+ + HCO3–
Slow
O O NH2

O 2–
OH

R- CH. + fast
O Mn R- CHO + MnO42- + NH3

O O
NH2

H
where
R = C--CH 3

CH3

The probable structure of complex ( C ) is

OH +
H2O
H2O Ru OC(O)CH(NH2)R
H2O
OH2

Discussion
Permanganate ion (MnO-4 ) is a powerful oxidant in an
aqueous alkaline medium, and because it exhibits many oxi-
dation states, the stoichiometric results and pH of the reac-
tion media play an important role. Under the prevailing
experimental conditions at pH > 12, the reduction product of
Mn(VII) is stable and further reduction of Mn(VI) might be
stopped (10, 11). Diode Array Rapid Scan Spectrophotomet-
ric (DARSS) studies have shown that at pH > 12, the prod-
uct of Mn(VII) is Mn(VI) and no further reduction was
observed as reported by Simandi et al. (10). However, on
prolonged standing, the green Mn(VI) is reduced to Mn(IV)
under our experimental conditions.
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 fur-
ther to green excluding the accumulation of hypomanganate.
The violet colour originates from pink of permanganate and
blue from hypomanganate is observed during the course of
the reaction. The colour change of KMnO4 solution from the
violet Mn(VII) ion to the dark green Mn(VI) ion through the
blue Mn(IV) ion has been observed.
It is interesting to identify the probable species of ruthe-
nium(III) chloride in alkaline medium. Electronic spectral
studies (21) have confirmed that ruthenium(III) chloride ex-
ists in hydrated form as [Ru(H2O)6]3+. In the present study it
is quite probable that the species [Ru(H2O)5OH]2+ might as-
sume the general form [Ru(III)(OH)x]3–x. The value of x
would always be less than six because there are no definite
reports of any hexahydroxy species of ruthenium. The re-
mainder of the coordination sphere will be filled by water mol-
© 2001 NRC Canada
Bilehal et al.
Fig. 3. Plot of [Ru(III)]/ kobs vs. 1/[L-valine] and [Ru(III)]/kobs
vs. 1/[OH–] (conditions as in Table 1).
ecules. Hence under the experimental conditions [OH–] >>
[RuIII], RuIII is mostly present as the hydroxylated species
[Ru(H2O)5OH]2+.
The reaction between permanganate and L-valine in alka-
line medium has a stoichiometry of 1:2 with a first-order de-
pendence on the concentration of MnO-4 and Ru(III) and less
than unit order dependence on both theconcentration of al-
kali and L-valine. No effect of added products such as alde-
hyde and ammonia was observed. It is known that L-valine
exists as deprotonated form in basic medium (24). The re-
sults suggest that first alkali combines with permanganate to
form an alkali–permanganate species [MnO4·OH]2– in a pre-
equilibrium step (35). L-valine in the deprotonated form re-
acts with ruthenium(III) species to form a complex (C).
Complex C reacts with the alkali–permanganate species in a
slow step to form a free radical derived from L-valine, which
further reacts with another permanganate species in a fast
step to yield the products. The experimental results can be
accommodated as seen in Scheme 3.
Spectroscopic evidence for complex formation was not
successful, since there is no change in the lmax (except some
hyperchromicity is observed) for the mixture of L-valine and
ruthenium(III) compared with that of L-valine or ruthe-
nium(III) itself. This might be due to the involvement of
weak interactions. However, the evidence for complex for-
mation is obtained by kinetic studies (i.e., from the Michae-
lis–Menten plot). The plot of [Ru(III)]/kobs vs. 1/[L-valine] is
linear with an intercept supporting the Ru(III)–L-valine com-
plex. Such type of substrate–catalyst complex formation has
been reported previously (36). The observed modest
enthalpy of activation, relatively low value of the entropy of
activation and higher rate constant for the slow step of the
mechanism, indicates that oxidation presumably occurs by
an inner-sphere mechanism. This conclusion is supported by
earlier work (37). Since Scheme 3 is in accordance with
generally well-accepted principle of non-complementary ox-
idations taking place in a sequence of one-electron steps, the
reaction would involve a radical intermediate. Since per-
1931
manganate is a one-electron oxidant in alkaline medium, the
reaction between substrate and oxidant would give rise to a
radical intermediate. A free radical scavenging experiment
revealed such a possibility. This type of radical intervention
in the oxidation of amino acids has also been observed ear-
lier (20).
The thermodynamic quantities for the first equilibrium
step in Scheme 3 and activation parameters for the limiting
step in Scheme 3 can be evaluated as follows: the hydroxyl
ion concentration as in Table 1 was varied at four different
temperatures and the K1 value was determined at each tem-
perature. The values of K1 (dm3 mol–1) were obtained as 3.2,
5.0, 6.8, and 8.1 at 26, 30, 35, and 40°C, respectively. A
Vant Hoff’s plot was made for the variation of K1 with tem-
perature (i.e., log K1 vs. 1/T) and the values of the enthalpy
of the reaction (DH), entropy of the reaction (DS), and free
energy of reaction (DG), were calculated as 47.9 kJ mol–1,
–74.3 J K–1 mol–1, and 70.6 kJ mol–1, respectively. Similarly
the L-valine concentration as in Table 1 was varied at four
different temperatures and the K2 value was determined at
each temperature. The values of K2 (dm3 mol–1) were ob-
tained as 2.2 × 103, 3.5 × 103, 4.7 × 103, and 6.4 × 103 at 26,
30, 35, and 40°C, respectively. A plot was made for the vari-
ation of K2 with temperature (i.e., log K2 vs. 1/T) and the
values of DH, DS, and DG, were calculated as 51.9 kJ mol–1,
–6.1 J K–1 mol–1, and 53.8 kJ mol–1, respectively. A compar-
ison of the latter values with those obtained for the slow step
of the reaction shows that these values mainly refer to the
rate limiting step, supporting the fact that the reaction before
the rate determining step are fairly rapid and involves only
little activation energy.
Scheme 3 leads to the following rate law, and can be de-
rived as follows:
Rate
[2] = k obs =
[MnO-4 ]
k K1K2 [L -val][ Ru(III)][OH- ]
1 + K1[OH- ] + K2 [L -val] + K1K2 [OH- ][L -val]
The terms (1 + K1K2[OH –][Ru(III)][MnO-4 ]), (1 + K1[MnO-4 ]),
and (1 + K2[Ru(III)]) also should be in the denominator of
eq. [2], but in view of low concentration of MnO-4 and ruthe-
nium(III) used, they approximate to unity. Thus the above
eq. [2] can be rearranged to the following form, which is
used for the verification of the rate law.
[Ru(III)] 1
[3] =
kobs k K1K2 [L -val][OH- ]
1 1 1
+ + -
+
k K2 [L -val] k K1[OH ] k
According to eq. [3], the plots of [Ru(III)]/kobs vs. 1/[L-val]
and [Ru(III)]/kobs vs. 1/[OH–] should be linear, which is veri-
fied in Fig. 3. The slopes and intercepts of such plots lead to
the values of k, K1, and K2 at 26°C of 12.2 (±0.6) × 104 dm3
mol–1 s–1, 3.2 (±0.1) dm3 mol–1, and 2.2 (±0.1) × 103 dm3
mol–1, respectively. Using these values, the rate constants
under different experimental conditions were calculated by
eq. [2] and compared with experimental data. There is a
good agreement between them, which supports the
© 2001 NRC Canada
1932
Scheme 3. The value of K1 is in good agreement with earlier
work (38).
The effect of ionic strength on the rate can be understood
essentially on the basis of ionic species as in Scheme 3. The
effect of solvent on the reaction kinetics has been described
detail in the literature (39). In the present study the rate de-
termining step involves the reaction between two ions and so
eq. [4] is applicable:
[4] ln k = ln k¥ – ZAZB e2/kBTrABD
where k¥ is the rate constant in a medium of infinite dielec-
tric constant, rAB is the sum of the ionic radii, ZA and ZB are
the charges on the two ions, and D is the dielectric constant
of the medium. The observed linear plot of log kobs vs. 1/D
with positive slope (Fig. 2) is in accordance with eq. [4] as
ZA and ZB have opposite charges (Scheme 3). The values of
DH‡ and DS‡ were both favourable for electron transfer pro-
cess. The value of DS‡, within the range for radical reaction,
has been ascribed to the nature of electron pairing and
unpairing processes and to the loss of degree of freedom for-
merly available to the reactants upon the formation of a rigid
transition state (40).
Conclusions
It is interesting that the oxidant species [MnO-4 ] requires a
pH > 12, below which the system becomes disturbed and the
reaction will proceed further to give a reduced product of the
oxidant as Mn(IV), which slowly develops yellow turbidity.
Hence, it becomes apparent that in carrying out this reaction
the role of pH in a reaction medium is crucial. It is also
noteworthy that under the conditions studied the reaction oc-
curs in two successive one-electron reductions (Scheme 3)
rather than two-electron in a single step (Scheme 2). A mi-
cro amount of Ru(III) is sufficient to catalyze the title reac-
tion. It is interesting to note that uncatalyzed reaction
follows a two path mechanism, while catalyzed reaction fol-
lows a single path. The description of the mechanism is con-
sistent with all the experimental evidence including both
kinetic and product studies.
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