WORLD JOURNAL OF PHARMACY AND PHARMACEUTICAL SCIENCES

Sheila et al. World Journal of Pharmacy and Pharmaceutical Sciences

SJIF Impact Factor 5.210

Volume 5, Issue 1, 687-700 Research Article ISSN 2278 4357

KINETIC AND THERMODYNAMIC STUDY FOR THE OXIDATION

OF LEUCINE BY PERCHLORIC ACID SOLUTION OF
CHLORAMINE-T IN PRESENCE OF Ir (III) IN ITS NANO
CONCENTRATION RANGE AS HOMOGENEOUS CATALYST

Abhishek Vermaa, Jyoti Pandeya, Reena Patela, Sheila Srivastava b,*

a
Department of Applied Chemistry, BBAU, Lucknow-226025, U.P., India.
b
Chemical laboratories, Feroze Gandhi College, Raebareli-229001, U.P., India.

Article Received on
ABSTRACT
24 Oct 2015, The kinetics and mechanism of homogeneously Ir(III) chloride
Revised on 15 Nov 2015, catalyzed oxidation of leucine by chloramine-T [CAT] in perchloric
Accepted on 06 Dec 2015
acidic medium in the temperature range 30 to 450C have been
investigated. The reaction is carried out in the presence of mercuric
*Correspondence for
acetate as a scavenger for chloride ion. The experimental results show
Author
Sheila Srivastava first order kinetics with respect to the oxidant [CAT] and catalyst
Chemical laboratories, [Ir(III)] while positive effect with respect to substrate, i.e., leucine was
Feroze Gandhi College, observed. The reaction shows negligible effect of [Hg(OAc) 2], [H+]
Raebareli-229001, U.P.,
and ionic strength of the medium. Chloride ion positively influenced
India.
the rate of reaction. The reaction between chloramine-T and leucine in
acid medium shows 1:1 stoichiometry. To calculate activation parameters, the reactions have
been studied at four different temperatures between 30 to 45C. A mechanism involving the
complex formation between catalyst, substrate and oxidant has been proposed.
Isopentaldehyde has been identified chromatographically and spectroscopically as the final
product of oxidation of leucine. Based on the kinetic data, reaction stoichiometry and product
analysis, a suitable reaction mechanism has been proposed and rate law has been derived.
KEY WORDS: Kinetics, mechanism, Ir(III) catalysis, leucine, chloramine-T.

1. INTRODUCTION
The organic sulphonyl haloamines (N-haloamines), a group of mild oxidizing agents, has
been extensively used for the oxidation of several organic compounds due to its diverse
behavior. The versatile nature of N-haloamines is attributed to the presence of halonium

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cations and nitrogen anions in their structure, which can act as both a base and a
nucleophile[1-5]. As a result, these compounds can react with a wide range of functional
groups to cause numerous kinds of molecular changes. Sodium N-chloro-p-
toluenesulfonamide or Chloramine-T (CAT; p-CH3C6H4SO2NClNa.3H2O) is one of the
prime members of organic halo-amine family and behaves as an oxidizing agent in both
acidic and alkaline media. Depending upon the pH of the medium, it forms various oxidizing
species and thus shows a variety of kinetic results[6-9]. Several researchers have studied the
oxidizing behavior of CAT[10-12] and numerous studies focus on the mechanistic aspects of the
redox reactions in acidic media. In most of the studies one of the species, RNHCl (R =
CH3C6H4SO2), HOCl, or H2OCl+, has been considered as the reactive species[13]. It can
behave as both electrophile and nucleophile depending on the reaction conditions.

Oxidation of amino acid is of great interest due to their biological importance. Besides acting
as the building blocks in protein synthesis, amino acids also play a significant role in
metabolism. They can undergo numerous kinds of reaction depending on whether a particular
amino acid contains non polar groups or polar substituents. Amino acids are used in variety
of applications in biochemical research, microbiology, nutrition, pharmaceuticals and
fortification of foods and feeds. Various researchers have studied the kinetics and mechanism
of oxidation of amino acids[14]. However, the mechanism differs for different reaction
systems. The oxidation of amino acids is also of considerable interest as different oxidants
lead to formation of different oxidation products[15-16]. Oxidative decarboxylation of amino
acids is one of the well reported biochemical processes. The kinetics and oxidation of amino
acids have been documented with various oxidants[17-20]. However, there are only few reports
available in the literature for the oxidation of Leucine[21].

Various transition metal catalysts have been used in the N-haloamine oxidation of organic
substrates[22]. Recently, the use of transition metal ions, such as osmium, ruthenium and
iridium either alone or as binary mixtures, as catalyst in various redox processes has drawn
considerable attention[23]. Iridium(III) chloride is an important platinum group metal ion and
has been extensively used as homogeneous catalyst in a number of redox reactions[24].
Several studies have reported the use of Ir(III) chloride as a non-toxic and homogeneous
catalyst[25-28]. Preliminary experimental results indicate that the reaction of Leucine (leu) with
CAT in the acidic medium without a catalyst were very sluggish but the reaction becomes
facile in the presence of Ir(III) catalyst.

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In the present study, we examine the kinetic and mechanistic aspects of the Ir(III) catalyzed
oxidation of leucine by CAT in acidic medium with the following objectives: (i) to ascertain
the reactive species of catalyst and oxidant, (ii) find the catalytic efficiency of Ir(III), (iii)
identify the oxidation products, (iv) to elucidate the plausible reaction mechanism, (v) to
deduce rate law consistent with kinetic results and (vi) to calculate the activation parameters.

2. EXPERIMENTAL
2.1. Materials
A stock standard solution of chloramine-T (S.D. Fine Chem. Ltd) was prepared by dissolving
its known weight in doubly distilled water and its concentration was estimated
iodometrically. In order to avoid photochemical deterioration, the solution of chloramine-T
was preserved in black coated flask. The standard solution of leucine (E. Merck) was freshly
prepared. Iridium(III) chloride (Johnson Matthey) solution was prepared in HCl of known
strength (0.018 N). Other reagents used were, A.R. grade and their solutions were also
prepared in doubly distilled water. The reaction vessels were also black coated from outside
to avoid photochemical effects.

2.2. Kinetic measurements or Procedure

The kinetic runs were carried out at 350.1 0C. The reaction was initiated by mixing the
already thermostated solution of Leuine to the thermally equilibrated reaction mixture
containing required volume of solution of Chloramine-T, H+, Ir(III) and all other reagents.
Aliquots (5ml) of the reaction mixture were pipetted out at regular intervals of time and
poured into a conical flask containing 5ml of 4% KI solution and 5ml of dilute sulphuric acid.
The librated iodine equivalent to unconsumed oxidant was estimated with standard sodium
thiosulphate solution using starch as an indicator. The initial rates were obtained from the
slope of concentration vs. time graph in the initial stages of the reactions by plane mirror
method.

2.3 Stoichiometry and product analysis

In order to ascertain the stoichiometry of the reaction, different sets of experiments with
0
varying [RNHCl]:[Leucine] ratios were performed at 35 C for 48 h and constant
concentrations of all other reactants under the conditions [RNHCl] >> [Leucine]. Iodometric
estimation of unconsumed [RNHCl] in different sets shows that 1 moles of RNHCl were

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consumed to oxidize 1 mole of Leucine. Accordingly, the following stoichiometric equations

can be formulated:

OH

NH2 + RNHCl + H2O Ir(III)/H+ O + RNH2 + NH3

Leucine Isopentaldehyde + CO2 + HCl

Isopentaldehyde (3-methylbutyraldehyde) , the main product in the oxidation of leucine were

identified by the help of chromatography (TLC) and conventional (spot test) method. The
nature of Isopentaldehyde further confirmed by its IR spectrum (2822 cm-1 due to C-H
stretching , 1722 cm-1 due to C=O stretching and 1390 due to C-H bending) (fig.1).

Fig. 1: IR spectrum of the main product isopentaldehyde

3. RESULT AND DISCUSSION

Kinetics of Ir(III) catalyzed oxidation of Leucine by chloramine-T in acidic medium was
investigated at 35 0C. The kinetic results were collected at several initial concentrations
(Table1). The order of reaction with respect to each reactant was determined by varying the
concentration of oxidant, Leucine, Ir(III) chloride (Table 1), H+ ions, [CI-] and mercuric
acetate one by one in different sets keeping concentration of all other reactants constant at
constant temperature 350C. In each kinetic runs, the initial rate (i.e., dc/dt) of the reaction
was determined from the slope of the tangent drawn at a fixed concentration of chloramine-T
except for the chloramine-T variation in which the slope of the tangent was drawn at fixed

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time. The first order reaction rate constant (k1) for the variation of all the reagents were
calculated:

k1 =
Where [RNHCl]* denotes the [RNHCl] at which (-dc/dt) was determined.

A plot of (-dc/dt) versus [Chloramine-T] was linear with the slope value (0.96) near unity,
which further confirms first order dependence of reaction on chloramine-T (fig. 2). A plot of
(-dc/dt) versus [Ir(III)] gives a slope which is close to the average value of first order rate
constant at 350C. Increase in concentration of Leucine shows positive effect (fig. 3) i.e., (-
dc/dt) values increases with increase in concentration of substrate (Table 1). Variation of
[KCl] concentration shows positive effect on reaction rate (Table 2). Negligible effect of
mercuric acetate eliminate the probability of its involvement either as a catalyst or as an
oxidant. Hence, the function of mercuric acetate is to act as scavenger for any chloride ion
[29]
formed in the reaction . It helps to eliminate the parallel oxidation by Cl2 which would
have been formed as a result of interaction between Cl- and RNHCl ion. Experimental data
indicate negligible effect of ionic strength of the medium on the rate (affected by addition of
NaClO4). In acidic solution of chloramine-T quick formation of RNHCl has been reported[30].
The reaction is unaffected by H+ concentration (Table 2).
Table 1: Effect of variation of oxidant, Leucine, Ir (III) at 350C
[Oxidant] x 103 M (Chloramine-T) [Substrate]x 102 M (Leucine) [Ir(III)] x 105 M (-dc/dt)x107 ML-1s-1
0.80 1.00 6.67 2.15
1.00 1.00 6.67 2.65
1.25 1.00 6.67 3.30
1.67 1.00 6.67 4.42
2.50 1.00 6.67 6.62
5.00 1.00 6.67 13.25
1.00 0.33 6.67 2.36
1.00 0.40 6.67 2.42
1.00 0.50 6.67 2.50
1.00 0.66 6.67 2.60
1.00 1.00 6.67 2.65
1.00 2.00 6.67 2.85
1.00 1.00 2.67 1.07
1.00 1.00 4.01 1.58
1.00 1.00 5.34 2.12
1.00 1.00 6.67 2.65
1.00 1.00 8.02 3.19
1.00 1.00 9.35 3.70
Solution conditions: [Hg(OAc)2] = 1.25 x 10 M, [HClO4] =1.00 x 10 M, [KCl] = 1.00 x 10 -
-3 -3

3
M.

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Table 2: Effect of variation of HClO4, KCl and NaClO4 at 350

[HClO4] x 103 M [KCl] x103M NaClO4 x103M (-dc/dt) x 107ML-1s-1
0.80 1.00 1.00 2.46
1.00 1.00 1.00 2.65
1.25 1.00 1.00 2.56
1.67 1.00 1.00 2.39
2.50 1.00 1.00 2.70
5.00 1.00 1.00 2.50
1.00 0.80 1.00 2.52
1.00 1.00 1.00 2.65
1.00 1.25 1.00 2.75
1.00 1.67 1.00 2.90
1.00 2.50 1.00 3.05
1.00 5.00 1.00 3.20
1.00 1.00 0.80 2.60
1.00 1.00 1.00 2.65
1.00 1.00 1.25 2.56
1.00 1.00 1.67 2.53
1.00 1.00 2.50 2.72
1.00 1.00 5.00 2.68

Solution conditions: [Ir (III)] =6.67 x 10-5 M, [Chloramine-T] = 1.00 x 10-3 M,

[leucine] = 1.00 x 10-2, [Hg(OAc)2] = 1.25 x 10-3 M.

Fig. 2: Plot between (-dc/dt) and [Chloramine-T] for the oxidation of leucine at 35 0C.
[Ir (III)] = 6.67 x 10-5 M, [leucine] = 1.00 x 10-2 , [Hg(OAc)2] = 1.25 x 10-3 M,
[HClO4] =1.00 x 10-3 M, [KCl] = 1.00 x 10-3 M.

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Fig. 3: Plot between (-dc/dt) and [leucine] for the oxidation of Leucine at 35 0C . [Ir (III)]
= 6.67 x 10-5 M, [Chloramine-T] = 1.00 x 10-3, [Hg(OAc)2] = 1.25 x 10-3 M, [HClO4] =1.00
x 10-3 M, [KCl] = 1.00 x 10-3 M.

The kinetic measurements were also taken in the temperature range of 30-450C and the
specific rate constants were obtained at 300, 350, 400 and 450C. These specific rate constants
were used to draw a plot of log k versus 1/T (fig. 4) which was linear. The various activation
parameters were calculated from the slope of curves obtained from the fig. 4. The value of
energy of Activation (E*), Arrhenius factor (A), entropy of activation (S*), free energy of
activation (G*) and enthalpy of activation (H*) were calculated from rate measurement
and these values have been provided in Table-3. Moderate H* and S* values are favorable
for electron transfer reaction. The value of H* was due to energy of solution changes in
transition state. The high positive value of G* represents highly solvated transition state.
The negative value of S* indicates that the intermediate complex is more ordered than the
reactants so the formation of activated complex occurs with reduction in the degree of
freedom. The observed modest enthalpy of activation and higher rate constant for the slow
step shows that oxidation presumably occurs by means of an inner sphere mechanism. This
conclusion is supported by earlier observations. The activation parameters evaluated for the
catalyzed reaction explain the catalytic effect on the reaction. Kinetic observations show that
the reaction under investigation is complex reaction, which usually takes place in more than
one step.

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Table 3: Activation parameters for the oxidation of leucine

Parameters Temperature(0C) Leucine
K1x 104 s-1 30 1.83
4 -1
K1x 10 s 35 2.65
K1x104 s-1 40 3.65
4 -1
K1x 10 s 45 5.32
Log A -- 11.52
E* (k J mol-1) 35 65.49
G* (k J mol ) -1
35 74.16
H * (k J mol ) -1
35 72.09
S* (JK mol )
-1 -1
35 -6.74
Solution conditions: [Ir (III)] = 6.67 x 10 M, [Chloramine-T] = 1.00 x 10-3 M,
-5

[leucine] = 1.00 x 10-2 , [Hg(OAc)2] = 1.25 x 10-3 M, [HClO4] =1.00 x 10-3 M,

[KCl] = 1.00 x 10-3 M

Fig. 4: Arrhenius plot for the oxidation of Leucine. [Ir (III)] = 6.67 x 10-5 M,
[Chloramine-T] = 1.00 x 10-3 M, [leucine] = 1.00 x 10-2 , [Hg(OAc)2] = 1.25 x 10-3 M,
[HClO4] =1.00 x 10-3 M, [KCl] = 1.00 x 10-3 M.

3.1 Mechanism and derivation of rate law

The acidic solution of Iridium chloride exists as [IrCI 6]3-. It has also been reported that
[IrCI6]3- is involved in equilibrium as follows[31]:

[IrCI6]3- + H2O [IrCI5(H2O)]2- + CI-

Thus either [IrCI6]3- or [IrCI5H2O]2- may act as catalytic species [32]

. If [IrCI5H2O]2- is taken
as catalytic species the rate law would require negative effect of chloride ion contrary to the
positive effect of chloride ion on the oxidation rate observed by us. Hence the only choice is

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[IrCI6]3- which when assumed as reactive species of Iridium trichloride in acidic medium,
explains the positive effect of chloride ion. The kinetic results reported in table 1, 2, 3 along
with the above discussion lead us to suggest the following reaction scheme:
k1
2- -
[IrCI5 (H2O)] + CI [IrCI6]3- + H2O
[C1] k-1 [C2]

NH2 k2
CH3CHCOOH + [IrCI6]3- [S-----IrCI6]3-
[S] [C2] k-2 [C3]

k3
3-
[S-----IrCI6] + RNHCl [S-----IrCI6 -----RNHCl]3-
[C3] Slow step (r.d.s)

Fast
3-
[S-----IrCI6 -----RNHCl] + H2O CH3 - CHO + [IrCI6]3- + RNH2 + HCl+ CO2
[P] +NH3

Where,
[S] = Substrate i.e. Leucine
[P] = Product i.e. Isopentaldehyde
Now, Considering the above reaction steps and applying the steady-state treatment with
reasonable approximation, the rate law may be written as

(where K1 = k1/ k-1 )

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In same way,

(where K2 = k2/ k-2 )

Putting the value of [C2] in equation (v), we get :

This gives

Putting the value of C3 in equation (i), we get

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4. CONCLUSION
The following conclusions can be derived in the present study of Ir(III) catalyzed oxidation of
leucine by chloramine-T in acidic medium. (a) Among the various species of Ir(III) in acidic
medium, [IrCl6]3 is considered as the reactive species while (b) RNHCl is the reactive
species of Chloramine-T in acidic medium. (c) In the absence of catalyst oxidation of leucine
by Chloramine-T is very sluggish, but it becomes facile in the presence of Ir(III) catalyst. (d)
The stoichiometry of the reaction was found to be 1:1 and the oxidation products of leucine
were identified (e) Activation parameters were computed from the Arrhenius plot. (f) The
observed results have been explained by a plausible mechanism and the related rate law has
been deduced. It can be concluded that Ir(III) chloride act as an efficient catalyst for the
oxidation of leucine by Chloramine-T in acidic medium.

ACKNOWLEGEMENT
The first author thankfully acknowledges the University Grants Commission, New Delhi,
India for providing financial assistance in the form of Research Fellowship

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