European J ournal of Scientific Research

ISSN 1450-216X Vol.31 No.2 (2009), pp.237-244

EuroJ ournals Publishing, Inc. 2009
http://www.eurojournals.com/ejsr.htm

Kinetics and Mechanism of the Reaction of Rosaniline
Monochloride with Trioxocarbonate (IV) Ions in
Aqueous Medium


O.A. Babatunde
Corresponding author Department of Chemistry
Nigerian Defence Academy, Kaduna, Nigeria

I.K.Adamu
Federal College of Chemical and Leather, Technology
P.M.B 1034, Samaru, Zaria. Nigeria


Abstract

The stoichiometry, kinetics and mechanism of the reaction of rosaniline
monochloride (Ros) by trioxocarbonate (iv) ion in aqueous medium have been investigated
at 30 1C and I =0.5 mol dm
-3
(NaCl).The kinetic studies indicate first order dependence
on the reaction in both reactants concentration and therefore follow the rate law
] CO [ ] Ros [ k ] Ros [
dt
d
2
3 2
=
Where k
2
=5.62 0.084 x 10
2
dm
3
mol
-1
s
-1

The rate of reaction increased with increase in ionic strength and added cations
catalysed the reaction. Results from spectroscopic investigation and Michaelis-Mentens
plot showed no evidence of the formation of an intermediate complex. The outer-sphere
mechanism is therefore proposed for the reaction.

Introduction
Rosaniline monochloride (triaminotolyldiphenylmethane chloride) is one of the most powerful nuclear
dyes and is widely used as a biological stain. As a dye, it is also very useful in the textile industry. It is
the main component of schiffs reagent often employed for the detection of aldehyde and aldehyde-like
constituents of the cell (1). It is bright red coloured and used in cotton tannin, mordant, printing and
dying. Being a basic fuchsin, it is equally indispensable in bacteriology particularly in Ziech/ Neelseen
method (2, 3).
The kinetics and mechanism of reaction of rosaniline monochloride by chlorite, hydroxide,
sulphite and nitrate ions have been reported (4, 5, 6). In these studies, a stoichiometry of 1:1 and an
order of one was obtained with respect to both [oxidant] and [reactant] for the reaction involving
hydroxide and nitrate ions while for the oxidation by chlorite ions, an order of half with respect to
[reductant ] and one with respect to the [oxidant] was obtained.
Trioxocarbonate (iv) ions are employed in the textile industry as sopping agent and hence play
an important role in textile processing, making study of its kinetics with this dye important.
We hereby report the kinetics and mechanism of the reaction of rosaniline monochloride with
trioxocarbonate (iv) ions. This is with a view to throwing more light on the mechanistic pathway of the
reaction of this dye.
Kinetics and Mechanism of the Reaction of Rosaniline Monochloride with
Trioxocarbonate (IV) Ions in Aqueous Medium 238

Experimental
Material and Reagents
Rosaniline monochloride was obtained from Aldrich Chemical company while all other reagents used
were of BDH (analar grade).
Stock solution of rosaniline monochloride, sodium trioxocarbonate (iv) and sodium chloride
were prepared by dissolving known amounts of reagents in distilled water. Sodium chloride was used
to maintain a constant ionic strength. Corning spectrophotometer model 252 Colorimeter was used to
monitor changes in absorbance of reactions.

Stoichiometry
The stoichiometry of the reaction was determined as reported earlier (7) by spectrophotometric titration
using the mole ratio method by keeping the concentration of rosaniline monochloride constant while
that of the trioxocarbonate(iv) ions was varied from 1 x 10
-5
10 x 10
-5
mol dm
-3
at ionic strength of
0.5 mol dm
-3
(NaCl) at 30 1C.
The absorbance of the reaction mixture was measured at maximum wavelength of 540nm after
the reaction had gone to completion as indicated by the constancy in the absorbance over a period of
two days. A plot of absorbance versus concentrations of trioxocarbonate (iv) ions was made from
which the stoichiometry was evaluated.

Kinetics and order of reactions
All the rate measurements were made using Corning Spectrophotometer model 252 Colorimeter. The
progress of the reactions was monitored by following the decrease in absorbance of the [Ros] at


max

540nm. All kinetic runs were made under pseudo-first order conditions with [CO
3
2
-] in at least 20 fold
excess over [Ros], while the ionic strength was maintained constant for each particular set of reaction
using 0.5 mol dm
-3
(NaCl). The temperature of the reaction remained constant at 30C. The data on the
rate constants are obtained from the measurement of triplicate runs.
Plot of log (A
t
A

) against time (where A and A

t
are the absorbances at the end of the
reaction and at time t respectively) were linear for about 90% of the extent of reaction. Pseudo-first
order rate constants (k
o
) were determined from the slopes of the plots log (A
t
A

) versus time.
Second order rate constants (k
2
) were obtained as ratios of k
o
to [CO
3
2-
]. The rate constants from
replicate runs agreed within 1.1%.

Effect of Ionic Strength
The effect of ionic strength on the rate of the reaction was investigated in the range of 0.2 I 1.0
mol dm
-3
(NaCl) while the concentrations of other reactants were kept constant. The results are
presented in Table1.

Effect of Added Cation
The effect of added cation on the rate of reaction was investigated for [X
nt
] =1 x 10
-2
5.0 x 10
-2
mol
dm
-3
(X
nt
=Li
+
, Ba
+
, Ca
2+
and Mg
2+
) while the concentration of all other reactants and ionic strength
were kept constant. The result is presented in Table 2. The effect of anion on the rate could not be
investigated because most of the anion investigated reacts with Ros.

239 O.A. Babatunde and I.K.Adamu
Test for intermediate Complex Formation
a) The electronic spectra of the reaction mixture after two and five minutes of the commencement of
the reaction were taken over the range 400-600nm and that of Ros was also compared within
same range.
b) The Michaelis-Menten plot of 1/k
o
vs 1/[CO
3
2-
] was made.
Test for free radical
Acrylonitrile was added to the partially oxidized reaction mixture of rosaniline monochloride and
trioxocarbonate (IV) ions in excess methanol and to each of the reactant separately and the
observations were noted.


Results and Discussion
Stoichiometry
Stoichiometric studies indicated that one mole of CO
3
2-
react completely with one mole of Ros. This
gives the overall equation of the reaction to be
Ros +CO
3
2-
Product (1)
This is consistent with what has been reported for similar reactions ( 5, 6 )

Product Analysis
After the completion of the reaction, a colourless solution was obtained and the UV visible spectra of
the product showed no absorption peak at maximum wavelength of 540nm. This indicates the
destruction of the quinoid (chromophore) group.

Kinetics and order of reaction
Plots of log (A
t
A) versus time were linear to about 90% of the reaction. This suggests no
inhibition and that the reaction is first order in [Ros]. Plot of log k
o
versus [CO
3
2-
] gave a slope of 0.98
showing that the reaction is also first order with respect to [CO
3
2-
]. Thus, the rate equation for the
reaction is
] CO [ ] Ros [ k ] Ros [
dt
d
2
3 2
= (2)
Where k
2
=5.62 0.084 x 10
2
dm
3
mol
-1
s
-1

The order of one in the oxidant and reductant concentrations in this reaction conforms with the
already reported order for the redox reactions involving Ros and some other anions (5,6,8).
The result in Table 1 shows that the rate constant of the reaction increased with increase in
ionic strength suggesting a positive Bronsted Debye salt effect. This observation suggests that the
activated complex is formed from two ions of like charges (9). A plot of k
o
vs I gave a linear graph
with a slope of 1.03 showing positive effect as shown in Fig 1.This suggests that the product of the
charges on the reactants in the activated complex is positive(10,11).
Added cation (Li
+
, Ba2
+
, Ca2
+
and Mg
2+
) increased the rate constant for the reaction. This
suggests that substitution of the reaction into inner co-ordination shell most likely did not proceed via
electron transfer (12)
Addition of a solution of acrylonitrite to partially reacted mixture did not give a gel in the
presence of excess methanol, indicating the probable absence of free radicals in the reaction
mechanism. However, there is also the probability of the formation of semiquinone radical which is
difficult to observe experimentally (13)
The plot of 1/ko vs 1/ [CO
3
2
-] gave a straight line which passed through the origin (Fig 2).
Kinetics and Mechanism of the Reaction of Rosaniline Monochloride with
Trioxocarbonate (IV) Ions in Aqueous Medium 240

In addition, a lack of shift in the wavelength of maximum absorption of rosaniline
monochloride in the reaction mixture was observed. This result suggests the absence of intermediate
complex formation.


Reaction Mechanism
The following points are considered in determining the mechanism of the reaction.
The Michaelis- Menten plot of 1/k
o
vs 1/ [CO
3
2-
] was linear without an intercept indicating the
absence of intermediate complex formation. This suggests the outer-sphere mechanism.(14,15,16)
Absence of free radicals in the reaction mixture suggests the contribution of outersphere
mechanism (17).
Absence of spectrophotometric evidence of intermediate complex formation that a precursor
complex is probably not formed prior to electron transfer and that the redox reaction most probably
occurs by the outer-sphere mechanism.
When the reaction mixture was scanned as the reaction progressed, no significant shift from the
absorption maximum wavelength of 540nm.This further suggests absence of intermediate complex
formation during the reaction.
The rate of reaction was enhanced by the presence of added cation. The catalysis is in support
of the outer-sphere mechanism. Similar cation catalysis has been observed for the other Ros systems
(5, 6)
From the points above, one is able to conclude that the reaction of rosaniline monochloride with
trioxocarbonate (iv) ions most probably occurs by the outer-sphere mechanism as proposed below in
Scheme 1.


Acknowledgement
We thank Cadet Officer, M.S. Sule of Chemistry Department, Nigerian Defence Academy, Kaduna for
assisting with some of the experiments.

Table 1: Pseudo-First rate constant and second order rate constant for the reaction of rosaniline and
trioxocarbonate (IV) Ion At 30 1c,
max
=540nm, [Ros] =1 X 10
-4
mol dm
-3


10
4
[CO
3
2
-] moldm
-3
I (NaCl) mol dm
-3
k
o
s
-1
10
-4
k
2
dm
3
mol
-1
s
-1

2.0 0.5 4.02 2.01
3.0 0.5 6.05 2.02
4.0 0.5 8.29 2.07
5.0 0.5 9.87 1.98
6.0 0.5 11.81 1.97
7.0 0.5 14.03 2.00
8.0 0.5 16.01 2.01
9.0 0.5 18.09 1.99
10.0 0.5 20.16 2.02
3.0 0.2 3.84 1.28
3.0 0.4 6.00 2.00
3.0 0.5 6.09 2.03
3.0 0.6 7.74 2.58
3.0 0.8 10.56 3.52
3.0 1.0 13.20 4.40

241 O.A. Babatunde and I.K.Adamu
Table 2: Cation Dependent rate constant for the reaction of ros and trioxocarbonate (IV) ions in aqueous
medium. [Ros] =1.0 x 10
-1
mol dm
-3
,[CO
3
2-
] =3.0 x 10
-4
mol dm
-3
, I =0.5 mol.dm
-3
(NaCl), T =30
1C,
max
=540nm

10
4
[X] mol dm
-3
k
o
s
-1
10
-2
k
2
dm
3
mol
-1
s
-1

10 2.04 2.04
30 6.51 2.17
50 11.34 2.27
Li
+

100 22.80 2.28
10 2.20 2.20
30 7.15 2.38
50 12.60 2.52
B
2+

100 27.48 2.75
10 2.10 2.10
30 6.49 2.16
50 11.88 2.38
Ca
2+

100 25.51 2.55
10 2.17 2.17
30 6.72 2.24
50 11.54 2.31
Mg
2+

100 24.06 2.41

Scheme I

- ' - ' - - '
- - '
' - `
- ' - ' - - '
- - '
' - `
' ~
`
'

- ' - ' - - '

- - '
' - `
' ~ '
~ '
~
~
- ' - ' - - '
- - '
' - `
~
-
'
~
- ' - ' - - '
- - '
' - `
~ -


This mechanism is similar to that reported for rosaniline monochloride and hydroxide ion (5)
Kinetics and Mechanism of the Reaction of Rosaniline Monochloride with
Trioxocarbonate (IV) Ions in Aqueous Medium 242

Figure 1: Plot of log k
2
vs I for the reaction of rosaniline monochloride and trioxocarbonate (IV) ion

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 0.2 0.4 0.6 0.8 1 1.2

I , mol dm
-3

l
o
g

k
2


243 O.A. Babatunde and I.K.Adamu
Figure 2: Michaelis-Mentens plot of 1/k
o
vs 1/ [CO
3
2 -
] for the reaction of Ros and CO
3
2-



0
0.05
0.1
0.15
0.2
0.25
0.3
0 1 2 3 4 5 6
1
/
k
o

m
o
l

d
m
-
3

1/ [CO
3
2-
] mol dm
-3



Kinetics and Mechanism of the Reaction of Rosaniline Monochloride with
Trioxocarbonate (IV) Ions in Aqueous Medium 244

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th
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nd
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