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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-


cations in organic syntheses (1–7), especially since the ad-
Potassium permanganate is widely used as an oxidizing vent of phase transfer catalysis (3, 4, 6), which permits the
agent in synthetic as well as in analytical chemistry and also use of solvents such as methylene chloride and benzene. Ki-
as a disinfectant. The reactions with permanganate are gov- netic studies are important sources of mechanistic informa-
erned by pH of the medium. Among the six oxidation states tion on the reactions, as demonstrated by the results
of manganese from 2+ to 7+, permanganate Mn(VII) is the referring to unsaturated acids in both aqueous (1, 3, 7) and
most potent oxidation state in both acid and alkaline medium. nonaqueous media (8).
The manganese chemistry involved in these multistep redox
reactions is an important source of information as the manga- During the oxidation by permanganate, it is evident that
nese intermediates are relatively easy to identify when they permanganate is reduced to various oxidation states in
have sufficiently long life times and the oxidation states of the acidic, alkaline, and neutral media. Furthermore, the mecha-
intermediates permit useful conclusions as to the possible nism by which the multivalent oxidant oxidizes a substrate
reaction mechanism including the nature of intermediates. 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
Received February 2001. Published on the NRC Research Press available to distinguish between a direct one-electron reduc-
Web site at http://canjchem.nrc.ca on December 14, 2001.
tion to Mn(VI) (Scheme 1) and a mechanism in which a
D.C. Bilehal, R.M. Kulkarni, and S.T. Nandibewoor.1 P.G. hypomanganate is formed in a two-electron reduction fol-
Department of Studies in Chemistry, Karnatak University, lowed by a rapid oxidation of the hypomanganate ion (12)
Dharwad 580 003, India. (Scheme 2).
1
Corresponding author (fax: 0836-747-884; e-mail: L-valine is one of the essential basic amino acids, which is
karuni@bgl.vsnl.net.in). 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 Can. J. Chem. Vol. 79, 2001

H H
Ru(III)
[1] CH3 C CH-COOH + 2MnO 4– + 2OH– CH3 C
2–
CHO + 2MnO 4 +

H 3C NH2 H3C

NH3 + CO2 + H2O

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

Effect of temperature
alkali. It was found that the rate constant increased with in- The rate of the reaction was measured at four different
crease in concentration of NaClO4 and the plot of log kobs temperatures with varying the concentration of OH–, keeping
vs. I1/2 was linear (Fig. 2). other conditions constant. The rate was found to increase
The effect of dielectric constant (D) was studied by vary- with increase in temperature. The rate constant (k) of the
ing the tert-butanol–water content in the reaction mixture slow step of Scheme 3 were obtained from the intercept of
with all other conditions being constant. Attempts to mea- the plots of [Ru(III)]/kobs vs. 1/[OH–] for different tempera-
sure the relative permittivities were not successful. However, tures. The energy of activation corresponding to these con-
they were computed from the values of pure liquids (34). stants were evaluated from the plot of log k vs. 1/T and other
The solvent did not react with the oxidant under the experi- activation parameters for reaction were calculated and are
mental conditions. The rate constants (kobs) increased with a 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 colour of the solution changed from violet to blue and fur-
ther to green excluding the accumulation of hypomanganate.
Permanganate ion (MnO-4 ) is a powerful oxidant in an The violet colour originates from pink of permanganate and
aqueous alkaline medium, and because it exhibits many oxi- blue from hypomanganate is observed during the course of
dation states, the stoichiometric results and pH of the reac- the reaction. The colour change of KMnO4 solution from the
tion media play an important role. Under the prevailing violet Mn(VII) ion to the dark green Mn(VI) ion through the
experimental conditions at pH > 12, the reduction product of blue Mn(IV) ion has been observed.
Mn(VII) is stable and further reduction of Mn(VI) might be It is interesting to identify the probable species of ruthe-
stopped (10, 11). Diode Array Rapid Scan Spectrophotomet- nium(III) chloride in alkaline medium. Electronic spectral
ric (DARSS) studies have shown that at pH > 12, the prod- studies (21) have confirmed that ruthenium(III) chloride ex-
uct of Mn(VII) is Mn(VI) and no further reduction was ists in hydrated form as [Ru(H2O)6]3+. In the present study it
observed as reported by Simandi et al. (10). However, on is quite probable that the species [Ru(H2O)5OH]2+ might as-
prolonged standing, the green Mn(VI) is reduced to Mn(IV) sume the general form [Ru(III)(OH)x]3–x. The value of x
under our experimental conditions. would always be less than six because there are no definite
The permanganate in alkaline medium exhibits various reports of any hexahydroxy species of ruthenium. The re-
oxidation states, such as Mn(VII), Mn(V), and Mn(VI). The mainder of the coordination sphere will be filled by water mol-
© 2001 NRC Canada
Bilehal et al. 1931

Fig. 3. Plot of [Ru(III)]/ kobs vs. 1/[L-valine] and [Ru(III)]/kobs manganate is a one-electron oxidant in alkaline medium, the
vs. 1/[OH–] (conditions as in Table 1). 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
ecules. Hence under the experimental conditions [OH–] >> values of DH, DS, and DG, were calculated as 51.9 kJ mol–1,
[RuIII], RuIII is mostly present as the hydroxylated species –6.1 J K–1 mol–1, and 53.8 kJ mol–1, respectively. A compar-
[Ru(H2O)5OH]2+. ison of the latter values with those obtained for the slow step
The reaction between permanganate and L-valine in alka- of the reaction shows that these values mainly refer to the
line medium has a stoichiometry of 1:2 with a first-order de- rate limiting step, supporting the fact that the reaction before
pendence on the concentration of MnO-4 and Ru(III) and less the rate determining step are fairly rapid and involves only
than unit order dependence on both theconcentration of al- little activation energy.
kali and L-valine. No effect of added products such as alde- Scheme 3 leads to the following rate law, and can be de-
hyde and ammonia was observed. It is known that L-valine rived as follows:
exists as deprotonated form in basic medium (24). The re-
sults suggest that first alkali combines with permanganate to Rate
form an alkali–permanganate species [MnO4·OH]2– in a pre- [2] = k obs =
[MnO-4 ]
equilibrium step (35). L-valine in the deprotonated form re-
acts with ruthenium(III) species to form a complex (C). k K1K2 [L -val][ Ru(III)][OH- ]
Complex C reacts with the alkali–permanganate species in a 1 + K1[OH- ] + K2 [L -val] + K1K2 [OH- ][L -val]
slow step to form a free radical derived from L-valine, which
further reacts with another permanganate species in a fast The terms (1 + K1K2[OH –][Ru(III)][MnO-4 ]), (1 + K1[MnO-4 ]),
step to yield the products. The experimental results can be and (1 + K2[Ru(III)]) also should be in the denominator of
accommodated as seen in Scheme 3. eq. [2], but in view of low concentration of MnO-4 and ruthe-
Spectroscopic evidence for complex formation was not nium(III) used, they approximate to unity. Thus the above
successful, since there is no change in the lmax (except some eq. [2] can be rearranged to the following form, which is
hyperchromicity is observed) for the mixture of L-valine and used for the verification of the rate law.
ruthenium(III) compared with that of L-valine or ruthe-
nium(III) itself. This might be due to the involvement of [Ru(III)] 1
[3] =
weak interactions. However, the evidence for complex for- kobs k K1K2 [L -val][OH- ]
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 1 1 1
+ + -
+
linear with an intercept supporting the Ru(III)–L-valine com- k K2 [L -val] k K1[OH ] k
plex. Such type of substrate–catalyst complex formation has
been reported previously (36). The observed modest According to eq. [3], the plots of [Ru(III)]/kobs vs. 1/[L-val]
enthalpy of activation, relatively low value of the entropy of and [Ru(III)]/kobs vs. 1/[OH–] should be linear, which is veri-
activation and higher rate constant for the slow step of the fied in Fig. 3. The slopes and intercepts of such plots lead to
mechanism, indicates that oxidation presumably occurs by the values of k, K1, and K2 at 26°C of 12.2 (±0.6) × 104 dm3
an inner-sphere mechanism. This conclusion is supported by mol–1 s–1, 3.2 (±0.1) dm3 mol–1, and 2.2 (±0.1) × 103 dm3
earlier work (37). Since Scheme 3 is in accordance with mol–1, respectively. Using these values, the rate constants
generally well-accepted principle of non-complementary ox- under different experimental conditions were calculated by
idations taking place in a sequence of one-electron steps, the eq. [2] and compared with experimental data. There is a
reaction would involve a radical intermediate. Since per- good agreement between them, which supports the
© 2001 NRC Canada
1932 Can. J. Chem. Vol. 79, 2001

Scheme 3. The value of K1 is in good agreement with earlier 10. L.I. Simandi, M. Jaky, C.R. Savage, and Z.A. Schelly. J. Am.
work (38). Chem. Soc. 107, 4220 (1985).
The effect of ionic strength on the rate can be understood 11. P.L. Timmanagoudar, G.A. Hiremath, and S.T. Nandibewoor.
essentially on the basis of ionic species as in Scheme 3. The Transition Met. Chem. 22, 193 (1997); P.L. Timmanagoudar,
effect of solvent on the reaction kinetics has been described G.A. Hiremath, and S.T. Nandibewoor. Polish J. Chem. 70,
detail in the literature (39). In the present study the rate de- 1459 (1996); S. Nadimpalli, R. Rallabandi, and L.S.A.
termining step involves the reaction between two ions and so Dikshitulu. Transition Met. Chem. 18, 510 (1993).
eq. [4] is applicable: 12. R.G. Panari, R.B. Chougale, and S.T. Nandibewoor. Polish J.
Chem. 72, 99 (1998).
[4] ln k = ln k¥ – ZAZB e2/kBTrABD 13. D.S. Mahadevappa, K.S. Rangappa, N.N.M. Gowda, and B.
Thimmegouda. Int. J. Chem. Kinet. 60, 589 (1986); K. Bal
where k¥ is the rate constant in a medium of infinite dielec- Reddy, B. Sethuram, and T. Navaneeth Rao. Indian J. Chem.
tric constant, rAB is the sum of the ionic radii, ZA and ZB are 20A, 395 (1981).
the charges on the two ions, and D is the dielectric constant 14. J. Szammer, M. Jaky, and O.V. Germasimov. Int. J. Chem.
of the medium. The observed linear plot of log kobs vs. 1/D Kinet. 20A, 395 (1981).
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