ISSN 1990-7931, Russian Journal of Physical Chemistry B, 2018, Vol. 12, No. 3, pp. 412–421. © Pleiades Publishing, Ltd.

, 2018.

KINETICS AND MECHANISM

OF CHEMICAL REACTIONS. CATALYSIS

Spectral and Mechanistic Investigation of Oxidation of Rizatriptan

by Silver Third Periodate Complex in Aqueous Alkaline Medium1
Aftab Aslam Parwaz Khana, b, *, Anish Khana, b, Abdullah M Asiria, b, **, and Heba A Kashmerya
a
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589 Saudi Arabia
b
Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, 21589 Saudi Arabia
*e-mail: aapkhan@kau.edu.sa
**e-mail: aasiri2@kau.edu.sa
Received August 3, 2017

Abstract⎯The oxidation of Rizatriptan by diperiodatoargentate(III) has been studied by spectrophotometry at neu-

tral pH. The kinetics of the reaction of Rizatriptan has been shown to principle of non-complementary oxidation
steps. The initial step involves the deprotonated of the diperiodatoargentate(III) with the alkali; this rearranges during
the displacement of a ligand to give free periodate and takes up another ligand monoperiodateargentate(III), com-
bines with a substrate to endow with an intermediate complex which decomposes within a slow step to provide the
final product in the following step with a first-order rate constant. The main product was identified by spot test, Fou-
rier-transform infrared spectroscopy, Nuclear magnetic resonance and Liquid chromatography-mass spectrometry
spectrum. A conceivable mechanism including pre equilibrium of adducts development between the complex and
reductant was planned from the kinetics study. The rate conditions got from system can clarify all exploratory phe-
nomena, and the activation parameters alongside rate constants of the rate determining step were ascertained.

Keywords: dihydroxy diperiodatoargentate third, rizatriptan, mechanistic reaction

DOI: 10.1134/S199079311803003X

INTRODUCTION AND STATEMENT metric [11–14], electrochemical sensor [15], Fluori-

OF THE PROBLEM
Rizatriptan was first synthesized by the pharma-
ceutical company Merck Sharp and Dohme Ltd., in the
year 1994. Rizatriptan chemical name is N,N-dimethyl-
amino-2-[5-(1H-1,2,4-triazol-1-yl-methyl)-1H-indol-
3-yl] ethanamine and shown balls and sticks 3D view
in Fig. 1. The molecular formula of Rizatritan (RTB)
is C15H19N5 · C6H5COOH and its molecular weight is
391.47 g mol–1. Physically pure RTB is a white amor-
phous and odorless powder [1]. RTB is soluble in
water, chloroform, dimethyl form amide, methanol,
acetonitrile and acetic acid. It is used for the acute
treatment of migraine in adults and the activation of
5-HT1B/1D receptor leading to selective vasocon-
striction of certain cranial extra cerebral blood vessel
segments [2–6]. The metabolism, disposition and in
vitro pharmacokinetics of RTB has been reported. It
has been done that metabolic pathway of rizatriptan
for the oxidative deamination, aromatic hydroxylation
by N-oxidation in presence of air [7]. Several methods
have been explored for RTB including liquid chroma-
tography [8], Liquid chromatography-mass spectrom-
etry spectrum (LC-MS/MS) [9], High-performance
liquid chromatography (HPLC) [10], spectrophoto-
1 The article is published in the original.
metric and colorimetric [16] techniques. Diperioda-
toargentate third is an effective oxidizing agent in ant-
acid medium with a reduction potential of 1.74 V [17].
Many researchers have utilized diperiodatoargentate
third as an oxidizing agent for the oxidation of different
organic and inorganic substrates [18–20]. It was
accounted for that they didn’t touch base at the conceiv-
able active species of diperiodatoargentate(III) (DPA) in
soluble base medium. However a few researchers to give
confirm for the reactive type of DPA in alkaline medium
rely on pH values [21]. However, here is scarcely a few
references in the direction of the vitro kinetics of oxida-
tion of RTB in the literature. Therefore understanding
the mechanism of oxidative degradation of RTB is of
importance in medicinal and redox chemistry. In this
manner RTB has been chosen as a substrate with a spe-
cific end goal to investigate its oxidation by diperioda-
toargentate(III) in basic medium and expected to explore
the kinetics of redox nature of the Ag(III) in such media
and to land at a conceivable mechanism.
EXPERIMENTAL
Materials and Methods
The reagents utilized as a part of this examination
were all of scientific quality and arranged in double

412
 SPECTRAL AND MECHANISTIC INVESTIGATION
Fig. 1. 3D balls and sticks view of RTB.
distilled water was utilized all throughout the experi-
mental. A stock solution of RTB was set up by dissolv-
ing appropriate amount of sample in double distilled
water. The required concentration of RTB was utilized
from its stock solution. KNO3 and KOH were utilized
to keep up the ionic strength and alkalinity of the reac-
tion, individually. AgNO3 solution was utilized to
study the product effect of Ag(I). A stock solution of
IO4- was prepared by dissolving a known weight of
KIO4 in hot water and used after keeping overnight to
attain equilibrium. Its concentration was determined
iodometrically, [22] at neutral pH maintained, using
phosphate buffer. Diperiodatoargentate was synthe-
sized by Ag(I) in being there of KIO4 while as
described somewhere else [23–25]. The complex of
DPA was characterized as of its UV spectra, its exhib-
ited 3 peaks at 216, 225 and 362 nm. These spectral
features were the same to those revealed for diperioda-
toargentate [23]. The magnetic moment review
revealed to the composite is diamagnetic. The com-
pound prepared was examined [26] for silver and KIO4
by acidifying of the material with HCl, recovering and
measuring the AgCl used for Ag, and titrating the iodine
liberated when excess of KI was placed into the filtrate
for periodate. The stock solution of diperiodatoargen-
tate was used for the required concentration of diperio-
datoargentate in the reaction system. During the stud-
ied constant concentration (1.0 × 10–4 dm–3 mol) of
KIO4 was utilized all through the experiment unless or
else avowed. In this way, the possibility of oxidation of
RTB by IO4− was tried and found to there was no tre-
mendous interference due to periodate under expei-
mental form. The total [IO4− ] and [OH–] was calcu-
lated by considering the quantity present in the diperi-
odatoargentate solution and that furthermore
included. Study runs were also done in nitrogen air to
grasp the effect of dissolved oxygen on the rate of the
reaction. No significant difference in the results was
gotten under a nitrogen environment. In context of the
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 12
413
in escapable contamination of carbonate in the basic
medium, the effect of carbonate was also done the study.
Included carbonate had no effect the response rate.
Kinetic Measurements
The kinetic study were performed on a Lamda-
950, Perkin Elmer, Germany UV-Visible Spectropho-
tometer under pseudo first request condition where
[RTB] > [DPA] at 25°C, unless appeared. The reac-
tion was started by mixing the DPA to RTB solution,
which correspondingly contained all required concen-
tration of KNO3, KOH, and KIO4; and the progress of
reaction was taken by spectrophotometrically at 360 nm
by checking decrease in absorbance as a result of DPA
(Fig. 2). It was experimental that there is an immate-
rial interference from other species show up in the
reaction mixture at this wavelength. The pseudo-first
order rate constants, kobs, were determined from the
log abs versus time graphs. The graphs were prompt up
to 75% completion of reaction. The rate constants
were replicate to within ±5%.
DESCRIPTION OF THE RESULTS
AND DISCUSSION
Examination of Oxidation of Products
Different set of reaction mixtures with varying con-
centrations of reactants diperiodatoargentate to RTB
in presence of [OH–] and KNO3 were kept for 6 hours
in shut vessel under nitrogen environment. The rest of
the concentration of DPA was assessed by spectropho-
tometrically at 360 nm (Fig. 2). The outcomes demon-
strate that 1 : 2 Stoichiometry as given in condition (1).
N
N
N
N + 2Ag(III) + 2OH−
N
H
(1)
N
O
N
HN
N + Ag(I) + 2H+.
N
O H H
The RTB–DPA reaction was allowed to progress
for 24 h under stirred conditions in alkali condition. After
completion of the reaction, water insoluble and water sol-
uble products were observed. The water insoluble prod-
uct was filtered, dried and the purity was checked using
thin-layer chromatography (TLC) technique with 1 : 1
benzene and ethanol as eluting solvent. The main reac-
tion product was identified as 1-({3-[2-(dimethyl-
amino)ethyl]-1H-indol-35-yl}methyl)-1,2,4-triazoli-
No. 3 2018
414 AFTAB ASLAM PARWAZ KHAN et al.
Absorbance
1.200
0.902
0.605
0.307
0.010
300 350
Fig. 2. UV-Vis spectra of product, 1-({3-[2-(dimethylamino)ethyl]-1H-indol-5-yl} methyl)-1,2,4-triazolidine-3,5-dione
obtained during the oxidation of RTB by DPA in aqueous solutions recorded at room temperature.
dine-3,5-dione. The nature of product was confirmed
by its IR spectrum. IR spectrum of product showed a
sharp absorption peak at 3287 cm–1 (due to N–H
stretch), 3125 cm–1 (due aromatic secondary N–H
stretch), 1262 (due to aliphatic amine), 1755 (due to
imide in phase) and 1655 (due to imide out of phase)
(Fig. 3). Further these products were also confirmed
by 1HNMR (Nuclear magnetic resonance (NMR)).
1HNMR for product, δ/ppm (500 MHz, DMSO):
2.00–2.25 [m, 4H, –CH2], 4.70 [s, 6H, –N(CH3)2,
6.98–7.27 [m, 4H, Aromatic H], 7.80–8.41 [s, 2H,
Heterocyclic H] and 8.39 [s, 1H, N–H]. Additional
these product was characterizedby HR-MS that gives
m/z at 300 amu. The molecular weight of RTB being
269 amu clearly indicates the oxidized product. The
development of Ag(I) in reaction was distinguished by
adding KCl for the reaction mixture, which created
white turbidity because of the formation of AgCl.
Evaluation of Reaction Order
Reaction orders were determined from the slope of
logkobs vs. logConc graphs by varying the concentra-
tions of RTB, alkali, and periodate, in turn, while
keeping all other concentrations and conditions con-
sistent.
Effect of [DPA(III)]
The oxidant of DPA concentration was varied in
the range of 1.0 × 10–5–1.0 × 10–4 dm–3 mol and the
genuinely constant kobs values show that order with
respect to [DPA] was one (Table 1). It was confirmed
by linearity of the plots of log [absorbance] versus time
(r = 0.9934, S = 0.03) up to 75% completion of the
reaction.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
400 450 500
Wavelength, nm
Effect of [Rizatriptan]
The Effect of RTB on the rate of reaction was deter-
mined at constant concentrations of OH–, DPA, and
periodate at a constant ionic strength of 0.25 dm–3 mol.
The substrate, RTB was varied in the range of 0.2 ×
10–3–2 × 10–3 dm–3 mol. The kobs values increased
with increasing concentration of RTB. The order with
respect to [RTB] was found to be less than unity (r =
0.9878, S = 0.239) (Table 1).
Effect of [Alkali]
The effect of salt on the reaction has been exam-
ined in the range of 6.0 × 10–4 to 1.0 × 10–3 dm–3 mol
at constant concentrations of RTB, DPA, and a con-
stant ionic strength of 0.25 dm–3 mol at 25°C. The rate
constants increase with increase in [alkali] and order
was found to be less then unity (Table 1).
Effect of [Periodate]
Periodate was varied from 1.0 × 10–4 to 1.0 ×
10 dm–3 mol keeping all other reactant concentra-
–3
tions fixed. It was experimental that the rate constants
diminished with increase in [IO4] (Table 1).
Effect of Ionic Strength and Dielectric
Consistent of the Medium
Both had no effect on the rate of reaction.
Effect of Temperature
The effect of temperature on the kobs values were
calculated at 25, 30, 35 and 40°C. The rate constants,
Vol. 12 No. 3 2018
 SPECTRAL AND MECHANISTIC INVESTIGATION 415

Transmittance, %

58.0
54.0
50.0
46.0
42.0
38.0
34.0
30.0
26.3
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000
Wavelength, nm
Fig. 3. FTIR (Fourier-transform infrared spectroscopy) spectrum of product, 1-({3-[2-(dimethylamino)ethyl]-1H-indol-5-yl}
methyl)-1,2,4-triazolidine-3,5-dione obtained during the oxidation of RTB by DPA.

1/[OH–] × 10–2 dm6 mol–2

0 0.1 0.2 0.3 0.4 0.5 0.6
0.30 0.5

0.25
0.4
1/kobs × 103, s

0.20

1/kobs × 103
0.3
0.15
0.2
0.10

0.05 0.1

0
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
1/[RTB] × 103 dm3 mol–1
Fig. 4. Plots of 1/kobs versus 1/ [OH–] and 1/ [RTB] for verification of rate law 7 at 25°C.

k, of the slow step of Scheme were obtained from the
graph of 1/kobs versus 1/[RTB] (Fig. 4). The values are
given in (Table 2). The activation parameters for the
rate determining step were acquired by the least square
method for plot of logk versus 1/T and are displayed in
(Table 2).
Effect of Initially Added Products
The initially added products, Ag(I) did not have
any noteworthy effect on the rate of the reaction.
Free Radical Trapping Experiment
In the reaction conditions utilized for kinetic esti-
mations, the redox coordination be full of 8% acrylo-
nitrile did not initiate polymerization of acrylonitrile,
involving that free radicals are most likely not included
in the reaction medium, which is the situation in prior
work [27–29]. Under the there examination, we have
gotten the confirmation for the reactive species of
diperiodatoargentate in basic condition. In perspec-
tive of the solid adaptable environment of silver third
species, considers on the kinetics of oxidation of a
variety of organic and inorganic substrates have pulled
in consideration. Among the different types of
Ag(III), Ag(OH)4–, diperiodatoargentate, and eth-
ylenebis(biguanide), silver(III) occupied the greatest
consideration of scientists on account of their relative
stability [30]. The stability of Ag(OH)4– is extremely
touchy on the way to traces of dissolved oxygen and
different impurities in the reaction medium, and this
had not pulled in much consideration. Be that as it

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 12 No. 3 2018

416 AFTAB ASLAM PARWAZ KHAN et al.

Table 1. Effect of variation of [DPA], [RTB], and [OH–] on the rate of oxidation of RTB at 298 K
[DPA] × 105, [RTB] × 10 4, [OH] × 103, [IO4− ] × 10 4,
kobs × 103, s–1 Kcal × 103, s–1
dm–3 mol dm–3 mol dm–3 mol dm–3 mol
Variation of DPA
1.0 1.0 3.0 0.4 3.98 4.12
3.0 1.0 3.0 0.4 3.97 4.12
5.0 1.0 3.0 0.4 3.99 4.12
6.0 1.0 3.0 0.4 3.98 4.12
8.0 1.0 3.0 0.4 3.97 4.12
10.0 1.0 3.0 0.4 3.98 4.12
Variation of RTB
5.0 0.4 3.0 0.4 2.92 2.90
5.0 0.5 3.0 0.4 3.75 3.72
5.0 1.0 3.0 0.4 3.98 4.12
5.0 2.0 3.0 0.4 4.42 4.45
5.0 3.0 3.0 0.4 4.85 4.72
5.0 4.0 3.0 0.4 5.15 5.10
Variation of OH
5.0 1.0 0.6 0.4 2.86 2.88
5.0 1.0 0.8 0.4 3.54 3.56
5.0 1.0 3.0 0.4 3.96 4.12
5.0 1.0 4.0 0.4 4.35 4.36
5.0 1.0 5.0 0.4 4.86 4.85
5.0 1.0 6.0 0.4 5.14 5.10
Variation of IO4−
5.0 1.0 3.0 0.1 5.25 5.24
5.0 1.0 3.0 0.2 4.84 4.85
5.0 1.0 3.0 0.4 4.15 4.12
5.0 1.0 3.0 0.6 3.98 3.96
5.0 1.0 3.0 0.8 3.25 3.22
5.0 1.0 3.0 1.0 2.72 2.71

may, the two types of Ag(III), DPA and EBS, are sig-
nificantly stable [20, 21, 31, 32]. DPA is utilized as a
part of exceptionally basic medium, and EBS is utilized
as a part of especially acidic medium. A writing study
uncovers that the H2O soluble diperiodatoargentate has
a chemical formula [Ag(IO6)2]7– with dsp2 arrangement
of square planar structure, like DPA complex with two
bidentate ligands, periodate to shape a planar atom. At
the point when a similar atom is utilized as a part of
basic medium, it is probably not going to exist as
[Ag(IO6)2]7– as periodate is known to be in different
protonated frames dependent upon pH of the solution
as H5IO6 and H4IO6− in pH ≤ 7; H3IO62 − and H2IO36−
4−
in pH > 7 and dimeric form, H2I2O10 in alkaline
medium with concentrated solution. Though, H5IO6,
H4IO6− and H2I2O104−
may be ignored as the reaction
medium is basic and little [IO4] used in the studies.
Therefore, in the present basic medium, the primary
species are relied upon designate H3IO62 − and H2IO36− .
Diperiodatoargentate may be showed as [Ag(H3IO6)2]–/
[Ag(H2IO6)]3– depending on pH of the reaction
medium. The similar speciation of periodate in alkali
was reported in lieratures [33]. Given that, the reaction
was upgraded through concentration of OH–, included
[IO4−] hindered the rate and first order reaction in con-
centration of diperiodatoargentate and partial order in
[RTB], the accompanying mechanistic reaction has
been proposed which additionally clarifies all explor-
atory perceptions in Scheme 1.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 12 No. 3 2018

 SPECTRAL AND MECHANISTIC INVESTIGATION 417

Table 2. Activation and thermodynamics parameters for the oxidation of RTB

Temperature, K k × 103, s–1 logk 1/T × 103
(a) Effect of temperature with respect to slow step of the Scheme 1
293 3.71 0.5694 3.413
298 4.12 0.6148 3.356
303 5.26 0.7209 3.300
308 6.35 0.8027 3.246
Parameters Values
(b) Activation parameters
Ea, kJ mol–1 48.20
ΔH±, kJ mol–1 42.50
ΔS±, J K–1 mol–1 –120.00
ΔG±, kJ mol–1 85.40
(c) Temperature, K K1, dm6 mol–2 K2 ×10–4, dm3 mol–1 K3 × 10–4, dm3 mol–1
293 3.98 3.67 3.87
298 4.12 4.12 4.12
303 5.57 5.35 5.68
308 6.16 6.54 6.74
(d) Thermodynamic
Using K1 values Using K2 values Using K3 values
parameters
ΔH±, kJ mol–1 47.0 14.2 -21.5
ΔS±, J K–1 mol–1 174 14.8 26.22
ΔG±, kJ mol –25.2 11.5 -16.52

K1
[Ag(H3IO6)2]− + OH− [Ag(H2IO6)(H3IO6)]2− + H2O

K2
[Ag(H2IO6)(H3IO6)]2− + 2H2O [Ag(H2IO6)(H2O)2] + [H3IO6]2−

N N K3
N + [Ag(H2IO6)(H2O)2] Complex (C)
N
H N
O
k N
Complex (C) HN
slow
N + [Ag(I) + H2IO6(H3IO6)]2−
N
O H H

fast
H+ + OH− H2 O
N N
O
N N fast N
N + [Ag(H2IO6)(H2O)2] HN
N + [Ag(I) + H2IO6(H3IO6)]2− .
N N
H O H H
Scheme 1. Detailed Scheme for the oxidation of RTB by diperiodatoargentate in basic medium.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 12 No. 3 2018

418 AFTAB ASLAM PARWAZ KHAN et al.

In the prior equilibrium step 1, the concentration of

OH- deprotonated the DPA to give a deprotonated
DPA; in the second step displacement of a ligand,
periodate happens to give free [IO4− ] which is confirm
by decrease in the rate with increase in [periodate]
(Table 1). It might be normal that lower silver perio-
date species, for ex ample, monoperiodateargentate is
more important in the reaction than the diperioda-
toargentate. The inverse fractional order in [H3IO6]2–
may likewise be because of this reason. Within the pre
rate determining step, this monoperiodateargen-
tate(III) (MPA), combines with a molecule of RTB to
give an intermediate complex which decomposes in a
slow step to give the final product as shown in Fig. 5 Fig. 5. 3D balls and sticks view of the product of RTB.
balls and sticks 3D structure. Thus, all these results
toward a mechanism of the type as in Scheme 1. On
the basis of square planar configuration of DPA, the
configuration of MPA and complex might be sug- [DPA]T = [DPA] f + K1[DPA] f [OH− ]
gested as shown in Fig. 6. K 2[Ag(H2IO6 )(H3IO6 )]2 −
Spectroscopic confirmation in favor of the com- + 2−
[H3IO6 ]
plex formation between oxidant and substrate was −
obtained through UV vis study. A bathochromic shift K1K 2 K 3[RTB][DPA] f [OH ]
of around 4 nm from 336 to 340 nm into the spectrum + ,
[H3IO62 − ]
of diperiodatoargentate was observed (Fig. 2).
The rate law utilized for the Scheme potentially [DPA]T = [DPA] f + K1[DPA] f [OH− ]
could be determined as:
K1K 2[DPA] f [OH− ]
−d[DPA] +
Rate = = kK 3[RTB][Ag(H2IO6 )(H2O)2 ] [H3IO6 ]
2−
dt −
kK 2K 3[RTB][Ag(H2IO6 )(H3IO6 )]
2− K1K 2 K 3[RTB][DPA] f [OH ]
= (2) + ,
2−
[H3IO6 ] [H3IO62 − ]
kK1K 2 K 3[RTB][DPA][OH− ]  K K [OH− ]
= . −
[DPA]T = [DPA] f 1 + K1[OH ] + 1 2 2 −
[H3IO62 − ]  [H3IO6 ]
The total [DPA]T, is given as K K K [RTB][OH ] −
+ 1 2 3 .
[DPA]T = [DPA] f + [Ag(H2IO6 )(H3IO6 )]2 − [H3IO62 − ] 
+ [Ag(H2IO6 )(H2O)2 ] + [Complex (C)], Therefore,

[DPA]T [H3IO62 − ]
[DPA] f = . (3)
[H3IO62 − ] + K1[OH− ][H3IO62 − ] + K1K 2[OH− ] + K1K 2 K 3[RTB][OH− ]

Similarly, Similarly
− −
[OH ]T = [OH ] f [RTB]T = [RTB] f + [Complex (C)],
K1K 2[DPA] f [OH− ] K1K 2 K 2[RTB][DPA][OH− ]
+ K1K 2[DPA][OH ] + −
. [RTB]T = [RTB] f + 2−
.
[H3IO62 − ] [H3IO6 ]
In perspective of the low concentrations of diperioda- In perspective of the low concentrations of diperioda-
toargentate and H3IO62 − used in the experiment second toargentate, OH–, and H3IO62 − used,
and third terms may be neglected.
[RTB]T = [RTB] f . (5)
Therefore
Substituting equations (3)–(5) in equation (2) and
[OH− ]T = [OH− ] f . (4) omitting the subscripts T and f, we get,

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 12 No. 3 2018

 SPECTRAL AND MECHANISTIC INVESTIGATION 419

MPA
DPA

Complex

Fig. 6. Square planar configuration of DPA, MPA and complex.

−d[DPA] kK1K 2 K 3[RTB][DPA][OH− ]

Rate = = 2− − 2− − −
,
dt [H3IO6 ] + K1[OH ][H3IO6 ] + K1K 2[OH ] + K1K 2 K 3[RTB][OH ]
−
(6)
kK1K 2 K 3[RTB][OH ]
kobs = .
[H3IO6 ] + K1[OH ][H3IO62 − ] + K1K 2[OH− ] + K1K 2 K3[RTB][OH− ]
2− −

The rate law (6) can be rearranged into the following According to equation (7), other conditions being
form (7), which is suitable for verification constant, the graphs of 1/kobs vs. l/[OH–], 1/[RTB]
and [H3I06]2– be linear as showed up in Figs. 4 and 7.
[H3IO62 − ] [H3IO62 − ] From the intercepts and slope of such plots, the reac-
1/kobs = + tion constants K1, K2, K3 and k were calculated in
K1K 2 K 3[RTB][OH− ] kK 2K 3[RTB] (7) Tables 1 and 2 respectively. On the other hand, Com-
+ 1 + 1. plex formation was demonstrated kinetically through
kK 3[RTB] k the non-zero intercept of the graph 1/kobs versus
1/[RTB] (Fig. 4) for conceivable arrangement of an
intermediate complex between the oxidant and sub-
strate, alike to the renowned Michaelis–Menten [34]
1/kobs × 103, s mechanism designed for enzyme substrate reactions.
4.0
The equilibrium constant K1 is more prominent than K2.
3.5 This might be ascribed to the more noteworthy pro-
pensity of diperiodatoargentate to experience depro-
3.0 tonation contrasted with the hydrolyzed species in
basic medium. The insignificant effect of ionic
2.5
strength(I) and dielectric constant of medium (D), on
2.0 the rate of reaction clarifies subjectively the inclusion
of neutral molecule, as found in Scheme 1.
1.5
The thermodynamic amounts for dissimilar equi-
1.0 librium steps, in Scheme 1 can be assessed as takes
0 1 2 3 4 5 after. The RTB periodate and hydrox ide ion concen-
[H3IO–2
6 ] × 10 –4
, mol dm–3
trations were changed at a variety of temperatures as
given in Table 2. A van’t Hoff plot was made for the vari-
Fig. 7. Verification of rate law 7 for ortho periodate in favor ety of K1 with temperature (logK1 versus 1/T (r > 0.9824,
of the oxidation of RTB. S < 0.1211) and the estimations of the enthalpy of reac-

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 12 No. 3 2018

420 AFTAB ASLAM PARWAZ KHAN et al.
tion ΔH, entropy of reaction ΔS and free energy of
reaction ΔG, were calculated in Table 2.
A comparison of the final values with those
obtained for the slow step of the reaction confirms that
these values mainly refer to the rate limiting step, sup-
porting the way that the reaction before the rate deter-
mining step is somewhat slow and includes high acti-
vation energy [35–38]. Once more, it has been
accounted for [39–41] that the entropy of activation
ΔS± has a tendency to be more negative for reactions of
an inner sphere, whereas the reactions of positive ΔS±
values continue by means of an outer-sphere mecha-
nism. The obtained large negative values of ΔS± (Table 2)
proposes that the inner-sphere mechanism where the
exchange of an electron happening from RTB to DPA
through a silver particle as a connecting ligand.
Besides, large negative values of ΔS± show that there is
a decreasing in the irregularity surrounded by the oxi-
dation procedure. This prompts to the arrangement of
compacted intermediate complex and such activated
complex is additional requested than the reactants
because of loss of degree of freedom [42, 43]. Then
again, the positive value of ΔH± shows that the com-
plex formation is endothermic. Additionally, the posi-
tive value of ΔG± suggests enhanced formation of the
intermediate with increasing temperature and in addi-
tion to the non-spontaneity of the complex formation.
CONCLUSION
The most interesting feature of this study is the
decomposition of the silver(III) periodate complex.
The outcome presented at this point clearly show that
the oxidizing agent, DPA was utilized as a part of a via-
ble and economical process. The main product was
identified with the spot test, Fourier-transform infra-
red spectroscopy, NMR and LC-MS spectrum. The
dynamic types of DPA was observed chosen
[Ag(H2IO6)(H3IO6)]2–. The stoichiometry of the reac-
tion was found to be 1 : 2. The results demonstrate to
the part of pH in the reaction system is critical. An
overall mechanism sequence is proposed and the rate
law is derived.
ACKNOWLEDGMENTS
Center of Excellence for Advanced Materials and
Chemistry Department, King Abdulaziz University,
Jeddah, Saudi Arabia is highly acknowledged.
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