Catal Lett (2009) 132:285291

DOI 10.1007/s10562-009-0107-8

Kinetics and Mechanism of Ru(III)-Catalyzed Oxidation

of Paracetamol by Chloramine-T in Aqueous Acidic Medium
Ajaya Kumar Singh Reena Negi Bhawana Jain
Yokraj Katre Surya P. Singh Virender K. Sharma

Received: 3 June 2009 / Accepted: 19 July 2009 / Published online: 31 July 2009
Springer Science+Business Media, LLC 2009

Abstract The present paper deals with the kinetics and

mechanism of Ru(III)-catalyzed oxidation of paracetamol
by chloramine-T (CAT) in aqueous perchloric acid medium
at 303 K. The experimental result shows a first order
dependence on paracetamol at its low concentrations, but
tending towards zeroth order at its higher concentrations.
The reactions follow a first order rate dependence with
respect to oxidant [CAT] and [Ru(III)]. The reaction showed
negative fractional-order dependence on the rate for [H?]
and p-toluenesulphonamide. Variation in [Cl-] and ionic
strength of the medium did not bring about any significant
change on the rate of reaction. The decrease in the reaction
rate with decrease in the dielectric constant of the medium
was observed in the oxidation of paracetamol. Kinetic
and equivalence studies together with product analysis,
observed effect of dielectric constant of the medium on the

Electronic supplementary material The online version of this

article (doi:10.1007/s10562-009-0107-8) contains supplementary
material, which is available to authorized users.
A. K. Singh (&)
R. Negi
B. Jain
Department of Chemistry, Govt. V. Y. T. PG. Autonomous
College, Durg, Chhattisgarh 491001, India
e-mail: ajayaksinghau@gmail.com;
ajayaksingh_au@yahoo.com; ajayaksingh_au@yahoo.co.in
Y. Katre
Department of Chemistry, Kalyan Mahavidyalya,
Sector-7, Bhilai, Durg, Chhattisgarh, India
S. P. Singh
Department of Applied Chemistry, Graduate School
of Engineering, Osaka University, Suita, Osaka, Japan
V. K. Sharma
Chemistry Department, Florida Institute of Technology,
Melbourne, FL 32901, USA

rate of reaction and activation parameters furnished a basis

for the formation of a common reaction mechanism for the
Ru(III)-catalyzed oxidation of paracetamol by CAT in the
acidic medium.
Keywords Kinetics
Oxidation
Chloramine-T

Paracetamol
Ru(III) catalysis

1 Introduction
Chloramine-T (CAT) is the most important member of
organic halo-amine family and behaves as an oxidizing
agent in both acidic and alkaline media. It is versatile
oxidizing agent and has shown a variety of kinetic results
due to formation of its various oxidizing species depending
upon pH of the medium [14]. Generally CAT undergoes a
two-electron change in its reactions resulting in the formation of the reaction product, p-toluenesulphonamide or
PTS (p-CH3C6H4SO2NH2) and sodium chloride. A detailed
review of the chemistry of CAT and related N-haloarylsulfonamides has been reported [5]. It can behave as both
electrophiles and nucleophiles depending on the reaction
conditions [6].
Paracetamol (4-hydroxyacetanilide or acetaminophen or
4-acetamidophenol) is a well-known drug that finds extensive applications in pharmaceutical industries. It is also
used as an intermediate for pharmaceutical (as a precursor
in penicillin) and azo dye, stabilizer for hydrogen peroxide,
photographic chemicals [79].
In 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 been
attracted considerable interest [10]. The utility of Ru(III)
chloride as a nontoxic and homogenous catalyst has been

123

286

A. K. Singh et al.

known [11, 12] but scant attention has been paid to explore
the catalytic role of Ru(III) with N-halo compounds as
oxidant. The mechanism of catalysis depends on the nature
of substrates, the oxidants, and experimental conditions
[13]. A perusal of literature revealed that still there is scant
information on the mechanistic aspects of Ru(III) catalyzed
oxidation of paracetamol by CAT. In the present study, we
report the results of the detailed investigation on the kinetic
and mechanistic aspects of Ru(III) catalyzed oxidation of
paracetamol by CAT in acidic medium at 303 K. The
objectives of the present study are: (1) to ascertain real
reactive species of catalyst and oxidant, (2) to elucidate the
plausible reaction mechanism, and (3) to deduce rate law
consistent with kinetic results and to calculate activation
parameters.

amount of the CAT, HClO4, Ru(III) chloride and water,

were mixed in black coated conical flask and thermo stated
at 303 K for thermal equilibrium. After allowing sufficient
time to attain the temperature of the experiment, requisite
volume of paracetamol solution, also thermo-stated at the
same temperature was rapidly pipette out and poured into
the reaction vessel. The total volume of reaction mixture
was 100 mL in each case. 5 mL aliquots of the reaction
mixture was pipette out at different intervals of time and
quenched with 4% acidified potassium iodide solution. The
progress of the reaction was monitored by iodometric
estimation of unconsumed CAT. Each kinetic run was
studied for 75% reaction. The rate of reaction (-dc/dt) was
determined by the slope of the tangent drawn at a fixed
[CAT] in each kinetic run. The order of reaction in each
reactant was calculated with the help of loglog plot of
(-dc/dt) versus concentration of the reactants.

2 Experimental
2.3 Stochiometry and Product Analysis
2.1 Materials and Methods
Paracetamol solution (S.D. fine chem.) was prepared by
dissolving appropriate amount in double distilled water.
The stock solution of CAT (Loba, AR) was prepared in
doubled distilled water and standardized idometrically.
A solution of Ruthenium (III) chloride (E. Merck) was

Different set of the reaction mixture containing paracetamol, Ru(III), HClO4 with excess of CAT were equilibrated
for 72 h at 303 K. Estimation of unconsumed CAT in each
set, revealed that for the oxidation of each mole of paracetamol 2 moles of CAT were consumed. Accordingly, the
following stoichiometry equation may be formulated:

O
HO

N
H

CH3 + 2TsNHCl + 2H2O

Ru (III)/H+

2TsNH 2+ CH3COOH + 2HCl +

HO

Quinone oxime

prepared by dissolving a known weight of RuCl3 (S.D. fine

chem.) in HCl of known strength. The Ruthenium(III)
concentration was then assayed by EDTA titration [13].
Sodium perchlorate, perchloric acid (E. Merck) was used
without further purification by preparing their solution in
double distilled water. The permittivity of the reaction
mixture was attired by the addition of acidic acid in
varying proportions (v/v), and the values of the dielectric
constant of wateracetic acid mixtures.
2.2 Kinetic Measurements
A thermostatic water bath was used to maintain the desired
temperature within 0.1 C. The appropriate volume of

123

The main reaction product was identified as quinone

oxime. The nature of quinone oxime was confirmed by
its IR spectrum (1,652 cm-1 due to C=O stretching,
1,615 cm-1 due to C=N stretching of oxime, 3,332 cm-1
due to OH stretching). It was further confirmed by its
melting point 131 C (literature m.p. 132 C). Further,
Quinone oxime was subjected to GCMS analysis. For
GCMS analysis, reaction mixture was extracted with
diethyl ether and ether layer was concentrated by low
evaporation. Product was analyzed by GCMS, JEOLJMS (Mate-MS system, Japan). The mass spectrum
showed a molecular peak at 123 amu confirming Quinone
oxime product. Acetic acid was identified by spot
test [14].

Kinetics and Mechanism of Ru(III)-Catalyzed Oxidation

287

3 Kinetic Results and Discussion

The kinetics of Ru(III) catalyzed oxidation of paracetamol
by CAT was investigated at several initial concentrations
of the reactants in acidic medium at 303 K. The initial rate
(dc/dt) of the reaction in each kinetic run was determined
by the slope of the tangent drawn at fixed concentration of
oxidant (CAT). In the variation of oxidant, tangent has
been drawn at a fixed time. The first order rate constant (k1)
was calculated as
k1

dc=dt
CAT

Under the pseudo-first-order condition of [PA] 

[CAT] with other reaction conditions remaining constant,

the order with respect to [CAT] was found to be unity, as

indicated by the linearity of the plots of (-dc/dt) versus
[CAT] (Table 1). At lower concentration of [PA], the rate
of reaction followed first order kinetics which shifted to
zero order at its higher concentrations (Table 1). The plot
of rate constant k1 versus [Ru(III)] was linear passing
through the origin, suggesting first order dependence of the
rate of reaction on the [Ru(III)] (Table 1). With increasing
the concentration of H?, the value of reaction rate
decreased (Table 1). This showed negative effect of [H?]
on the rate of reaction of paracetamol. Variations of ionic
strength of the medium and [Cl-] did not bring about any
significant change in k1 values under the constant
experimental conditions. The rate of reaction increased
with increasing in dielectric constant of the medium (by

Table 1 Effect of variation of [CAT], [PA], [Ru(III)], [H?] and [PTS] on the rate of oxidation of paracetamol at 303 K
[CAT] 9 103
mol dm-3

[PA] 9 102
mol dm-3

[Ru(III)] 9 105
mol dm-3

[H?] 9 101
mol dm-3

[PTS] 9 103
mol dm-3

-dc/dt 9 107
mol dm-3 s-1

k1 9 104 s-1

k 9 104 s-1

0.10

1.00

5.90

1.00

1.00

0.40 0.12

4.20

3.92

0.25

1.00

5.90

1.00

1.00

1.00 0.14

4.00

3.83

0.50

1.00

5.90

1.00

1.00

2.02 0.16

4.21

3.83

0.60

1.00

5.90

1.00

1.00

2.80 0.20

4.63

3.85

0.80

1.00

5.90

1.00

1.00

3.51 0.31

4.30

3.90

1.00

1.00

5.90

1.00

1.00

4.00 0.25

4.25

3.90

1.00

0.50

5.90

1.00

1.00

2.02 0.15

2.12

2.22

1.00

1.00

5.90

1.00

1.00

4.00 0.23

4.20

3.94

1.00

1.20

5.90

1.00

1.00

5.11 0.25

5.37

4.55

1.00

1.60

5.90

1.00

1.00

6.50 0.13

6.80

5.68

1.00

2.40

5.90

1.00

1.00

7.62 0.32

8.02

7.22

1.00

3.00

5.90

1.00

1.00

9.41 0.10

9.90

9.44

1.00

1.00

1.46

1.00

1.00

1.00 0.36

1.05

1.08

1.00

1.00

2.00

1.00

1.00

1.61 0.28

1.69

1.30

1.00
1.00

1.00
1.00

3.00
4.30

1.00
1.00

1.00
1.00

2.20 0.31
3.12 0.15

2.30
3.28

2.06
2.90

1.00

1.00

5.90

1.00

1.00

4.00 0.14

4.20

3.93

1.00

1.00

7.10

1.00

1.00

5.05 0.30

5.20

1.00

1.00

5.90

0.20

1.00

7.61 0.12

8.01

4.71
10.7

1.00

1.00

5.90

0.40

1.00

6.53 0.13

6.87

7.50

1.00

1.00

5.90

0.60

1.00

5.61 0.35

5.90

5.82

1.00

1.00

5.90

0.80

1.00

4.82 0.14

5.07

4.71

1.00

1.00

5.90

1.00

1.00

4.00 0.26

4.20

3.90

1.00

1.00

5.90

1.20

1.00

3.83 0.25

4.03

3.42

1.00

1.00

5.90

1.80

1.00

2.31 0.18

2.43

2.44

1.00

1.00

5.90

2.00

1.00

1.91 0.30

2.01

2.20

1.00

1.00

5.90

1.00

1.00

4.00 0.31

4.20

3.90

1.00

1.00

5.90

1.00

2.00

2.73 0.41

2.87

2.34

1.00

1.00

5.90

1.00

3.00

1.98 0.12

2.08

1.63

1.00
1.00

1.00
1.00

5.90
5.90

1.00
1.00

4.00
5.00

1.11 0.12
0.90 0.21

1.16
0.94

1.23
0.99

1.00

1.00

5.90

1.00

8.00

0.70 0.33

0.73

0.63

123

288

A. K. Singh et al.

increasing the percentage of acetic acid by volume).

Addition of PTS in the reaction mixture showed that the
rate of reaction decreased with increasing [PTS] (Table 1).
A plot of log k1 versus log [PTS] was linear with fractional
slope (-0.858) indicating that PTS is involved in a fast
pre-equilibrium to the rate determining step. The reaction
was performed at different temperatures (303318 K).
From the linear Arrhenius plot of log k1 versus 1/T, the
activation energy (Ea = 61.5 kJ mol-1) was calculated.
With the help of the energy of activation, values of the
other activation parameters such as enthalpy of activation
(DH# = 58.98 kJ mol-1), entropy of activation (DS# =
-111.05 JK-1 mol-1), Gibbs free energy of activation
(DG# = 92.62 kJ K-1 mol-1) and Arrhenius factor (A =
7.2) were also calculated.
3.1 Test of Free Radicals
The intervention of free radicals was examined as follows,
the reaction mixture, to which a known quantity of acrylonitrile scavenger had been added initially, was kept in an
inert atmosphere for 24 h. When the reaction mixture was
diluted with methanol, no precipitate resulted, suggesting
that there is no participation of free radicals in the reaction.
3.2 Reactive Species of CAT
Chloramine-T is a strong electrolyte and in aqueous solution it behaves as oxidant. The possible oxidizing species
in acidic solution of CAT are TsNH2Cl, TsNHCl, TsNCl2,
and HOCl [1416]. It was found that the rate of reaction
decreased on addition of PTS. Considering the above facts,
the species HOCl can safely be taken as the most reactive
oxidizing species in the reaction, which gives a rate law
capable of explaining all the kinetic observations and other
effects [17].

RuCl2 H2 O3 OH Cl

RuCl3 H2 O2 OH H2 O
With increase in the concentration of chloride ion in our
experiments, there was no change in the oxidation rate.
Therefore, [RuCl2(H2O)3OH] was the most likely reactive species in the reaction of paracetamol with CAT.
Considering the reactive species of Ru(III) and CAT and
with the help of above experimental findings, the plausible
reaction mechanism is proposed (Scheme 1).
3.4 Spectral Evidence for the Reactions Shown
in the Proposed Reaction Scheme
Spectroscopic evidence for the complex formation between
oxidant and substrate was obtained from UVVIS spectra
of paracetamol, CAT and a mixture of both. Absorption
maxima appear at 240 nm for paracetamol, 220 nm for
CAT and 225 nm for PA-CAT. A hypsochromic shift of
15 nm from 240 to 225 nm of paracetamol suggested that
complexation occurs between CAT and paracetamol. In
view of these findings, it is likely that Scheme 1, reaction
(II) is more probable for explaining the oxidation of paracetamol by CAT. The formation of complex between
Ru(III) and CAT-PA mixture was also evidenced spectra of
both CAT-paracetamol and CAT-PA-Ru(III) in which a
shift of CAT-PA from 225 to 230 nm.
3.5 Reaction Scheme
Based on the reactive species of Ru(III), CAT, and observations of above experimental results in addition to fact that
1 mol of paracetamol was oxidized by 2 moles of CAT, the
probable reaction mechanism is proposed (Scheme 1).
Taking all steps in Scheme 1 for the oxidation of paracetamol by CAT, the following rate law Eq. 1 may be written
in terms of decrease in concentration of CAT.

3.3 Reactive Species of Ru(III) Chloride

Rate 
A study for the chloro complexes of Ru(III) in 0.1 M KCl at
pH 0.4, 1.0 and 2.0 at 25 C suggested four major species, i.e.
[RuCl4(H2O)2]-, [RuCl3(H2O)3], [RuCl2(H2O)4]?, and [Ru
Cl(H2O)5]2? [18]. Expect for [RuCl2(H2O)4]?, the stability
of the species decreased with increase in pH and a high
instability at pH 2.0. The [RuCl2(H2O)4]? species was,
however, quite stable at pH 2.0, which is in equilibrium with
its hydrolyzed from, [RuCl2(H2O)3OH] [19, 20].

RuCl2 H2 O4  H2 O
RuCl2 H2 O3 OH] H3 O

With increase in the concentration of chloride ion, the

hydrolyzed form may also form [RuCl3(H2O)2OH]- (C2)
through equilibrium with Cl- ion

123

dCAT
dt

2kK1 K2 K3 RuIIIPACATT
H TsNH2  K1 H  K1 K2 PA](1 K3 Ru(III)])
1

Since [Ru(III)] is in the order of 10-5, the inequality

K3[Ru(III)]  1, can be taken as valid one. Now with this
inequality Eq. 1 will reduce to Eq. 2.
Rate

2kK1 K2 K3 RuIIIPACATT
H TsNH2  K1 H  K1 K2 PA]

Equation 2 confirms all the observed orders with respect

to different species, which can be verified by reversing
Eq. 2 into Eq. 3.

Kinetics and Mechanism of Ru(III)-Catalyzed Oxidation

K1

TsNHCl + H 2O

PA

(I)

HOCl + TsNH2
H O

K2

HOCl

289

N C CH3 + H+

H O

:O

(II)

Cl

(C1)

H
C1

+ [RuCl 2(H2O)3OH]

K3
H

(C2)

H
H

RuCl 2(H2O)3OH

O
C

CH3

:O

Cl

RuCL 2(H2O) 3OH

O
C

CH3

:O

Cl

(III)

(C 3)

+ H 2O

H
k

. .
H O
. .

. .
O
. . H + Cl

(IV)

+ CH3COOH + RuCl 2(H2O)3OH

(C3)

H
H

. .
O
. .

. .
. .
TsNHCl
.O. H Ru(III)/H+ H .O.

. .
.O.

O + H 2O

. .
O
. .

(V)

Quinone oxime
Scheme 1 Reaction path for the oxidation of paracetamol by CAT in the presence of Ru(III) chloride

CATT
H TsNH2 
H 

2kK1 K2 K3 Ru(III)PA 2kK2 K3 Ru(III)PA

Rate
1
3

2kK3 Ru(III)
Equation 3, indicates that if a plot is made between
[[CAT]T/rate] and [TsNH2] or [H?] or 1/[PA] or 1/[Ru(III)]
straight lines with positive intercepts on y-axis will be
obtained. Straight lines with positive intercepts on y-axis
obtained by the plots of [[CAT]T/rate] vs. [TsNH2],
1/[Ru(III)] (Fig. 1), [H?] and 1/[PA] (Fig. 2) on one
hand proves the validity of the rate law (2) and on the other
hand proves the proposed reaction scheme on the basis of
which the rate law (2) has been derived. From the values of
the intercept and slope of the plots, the values of K1, K2
and kK3 have been calculated and found to be

4.54 9 10-5 mol dm-3, 65.75 and 14.84 mol-1 dm3 s-1,
respectively.
3.6 Effect of Dielectric Constant and Calculation
of the Size of the Activated Complex
In order to find out the effect of dielectric constant of the
medium on the rate of reaction, the reaction has been
studied with different dielectric constant (D) of the medium
at constant concentration of all other reactants at constant
temperature. The dependence of the rate constant on the
dielectric constant of the medium is given by the following
equation:
log k1 log k0 

ZA ZB e2 N
1

2:3034p
dAB RT D

123

290

A. K. Singh et al.

ion-dipole interaction. The former concept agrees with the

present observations. The value of dAB has been evaluated
with the help of slope of straight line and found to be
3.58 A.

-3

[PTS] x 10 3(mol dm )
8

0
0

8
10

12

14

-4

[CAT]/rate x 10 (s)

10

-4

[CAT]/rate x 10 (s)

10
12

16

0
0

6
5

-1

1/[Ru(III)] x 10 (mol dm )

Fig. 1 Plot between [CAT]/rate versus [PTS] and 1/[Ru(III)] of

Ru(III)-catalysed oxidation of paracetamol by chloramine-T at 303 K.
[CAT] = 1.00 9 10-3 mol dm-3, [PA] = 1.00 9 10-2 mol dm-3,
[H?] = 1.00 9 10-1 mol dm-3

1.5

0.5

0
0
0.1
0.15
0.2
0.25
0.3
0.35

(s)

0.05
-4

2.5
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0

[CAT]/rate x 10

-4

[CAT]/rate x 10 (s)

1/[PA] x 10-2(mol-1dm3)

0.4
0.5

1
1

1.5

0.45

-3

[H+] x 10 (mol dm )

Fig. 2 Plot between [CAT]/rate versus [H?] and 1/[PA] of Ru(III)catalysed oxidation of paracetamol by chloramine-T at 303 K. [CAT] =
1.00 9 10-3 mol dm-3, [Ru(III)] = 5.90 9 10-5 mol dm-3

where k0 is the rate constant in a medium of infinite

dielectric constant, ZA and ZB are the charges of reacting
ions, dAB refers to the size of activated complex, T is
absolute temperature and D is dielectric constant of the
medium. This equation shows that if a plot is made
between log k1 versus 1/D, a straight line having slope
equal to -ZAZB e2N/2.303(4peo)dABRT will be obtained.
The effect of changing the solvent composition on the rate
of reaction has been discussed in detail in the well known
publications by Frost and Pearson [21]. For the limiting
case of zero angle approach between two dipoles or an iondipole system, Amis [22] has shown that a plot of log k1
versus 1/D gives a straight line, with a negative slope for a
reaction between a negative ion and a dipole or between
two dipoles, while a positive slope result for a positive

123

4 Conclusion
The Ru(III) catalysed oxidation of paracetamol by CAT
was studied in acidic medium at 303 K. The following
conclusion can be easily drawn: (a) In the absence of catalyst oxidation of paracetamol by CAT is very sluggish, but
it becomes facile in the presence of Ru(III) catalyst, (b) the
reactive species of CAT is TsNHCl not CAT itself. (c)
Oxidation products were identified and activation parameters were evaluated. (d) The observed results have been
explained by a plausible mechanism and the related rate
law. It can be concluded that Ru(III) act as an efficient
catalyst for the oxidation of paracetamol by CAT in acidic
medium.
Acknowledgments One of us (A. K. Singh) is thankful to UGC,
Regional Office, Bhopal, MP, India for Research Project Grants. We
are thankful to DST-FIST for providing us instrumental facilities for
research work in our Chemistry Department. Authors wish to thank
reviewers for greatly improving the paper.

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