Kinetics of Electropolymeri-

zation of 1-Amino-9,10-
anthraquinone
WAHEED A. BADAWY, KHALED M. ISMAIL, SHYMAA S. MEDANY
Chemistry Department, Faculty of Science, Cairo University, 12613 Giza, Egypt
Received 3 August 2010; revised 26 October 2010; accepted 26 October 2010
DOI 10.1002/kin.20541
Published online 11 January 2011 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: 1-Amino-9,10-anthraquinone was electropolymerized on platinum substrates ei-
ther fromaqueous or nonaqueous electrolytes. The aqueous electrolyte was 6.0 mol L
1
H
2
SO
4
,
and the nonaqueous solvent was acetonitrile containing lithium perchlorate, LiClO
4
, as a sup-
porting electrolyte. The formed polyaminoanthraquinone was stable, and the polymerization
process was reproducible. The kinetics of the electropolymerization process was investigated
by determining the charge consumed during the electropolymerization as a function of time
at different concentrations of the electrolyte components. The results of chronoamperometry
have been used to determine the orders of reaction. In either aqueous or nonaqueous solution,
the electropolymerization process follows rst-order kinetics with respect to the monomer
concentration. In nonaqueous solution, the very small concentrations of water did not affect
the order of reaction. The order of reaction with respect to the traces of water and the sup-
porting electrolyte concentration was found to be zero. In aqueous solution, the order of the
electropolymerization reaction with respect to the concentration of H
2
SO
4
was found to be neg-
ative (0.66), which means that the aqueous electrolyte inhibits the polymerization reaction.
C
2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 141146, 2011
INTRODUCTION
In recent years, the development of modied elec-
trodes has been an active area of research, triggered by
their potential technological applications [13]. The
modied electrodes are prepared by coating metallic
or semiconductor electrodes with a thin lm of elec-
troactive polymer. Electrochemical polymerization is
a promising method for lm coatings owing to its
prospects for ne control over the parameters of lm
thickness and homogeneity [4]. This control is im-
portant when the kinetics and mechanism of charge
transport through the lm is to be studied.
Correspondence to: Waheed A. Badawy; e-mail: wbadawy@
cu.edu.eg and wbadawy50@hotmail.com.
c
2011 Wiley Periodicals, Inc.
An extensive work is devoted to a new class of
organic polymers produced by electropolymerization
of various kinds of aromatic compounds (e.g., NH
2
and/or OHgroups containingheterocyclic, polynuclear,
and vinyl group) owing to the large eld of potential
applications of the resulting polymers themselves as
well as the composite electrode materials [5]. Among
the polynuclear aromatic compounds, the polynuclear
amines containing one NH
2
group such as 1-amino-
9,10-anthraquinone [6,7], 5-amino-2-mercapto-1,3,4-
thiadzole [8], N-acetylaniline [911] and two NH
2
groups such as 1,8-diaminocarbazole [12] and N-(1-
naphthyl)ethylene-diamine dihydrochloride) [13] have
been used for the preparation of polymeric lm-coated
electrodes. The electrogenerated conducting polymer
lms were deposited on different substrates. Substrates
other than noble metals have been used, for example,
142 BADAWY, ISMAIL, AND MEDANY
the preparation of poly(N-ethylaniline) on a copper
electrode [14]. The electropolymerization process is
complicated and represents a sequence of oxidation,
coupling, and deprotonation reactions. It is an exten-
sion of the ECE mechanism(where E =electron trans-
fer and C = chemical step). Also, the E(CE)
n
notation
was suggested.
Many studies have been carried out to clarify the ki-
netics of the electropolymerization processes [1520].
The investigation of the reaction order with respect to
the monomer and the electrolyte in the electropolymer-
ization process is an important issue where it provides
information about the nature of reactions, the chemi-
cal structure, and the way to improve some physical
properties of the polymer, for example, its electrical
conductivity. The kinetics of the electropolymerization
process and the determination of the order of the reac-
tion with respect to each component of the electrolyte
in either aqueous or nonaqueous medium represent the
main task of this paper.
EXPERIMENTAL
1-Amino-9, 10-anthraquinone (AAQ) (Merck) was
used as a monomer without further purication. HPLC-
grade acetonitrile (ACN) (Fischer) was used as re-
ceived. Sulfuric acid, lithium perchlorate, and other
chemicals were analytical-grade reagents and used as
received. The solutions were prepared using triply dis-
tilled water.
A standard three-electrode all-glass cell was used
as the electrochemical cell. The working electrode is a
platinum-rotating disk of a constant geometrical area
of 0.071 cm
2
. A silver/silver chloride (Ag/AgCl/3 mol
L
1
KCl) was used as a reference electrode and a plat-
inum wire as the counterelectrode. Before each exper-
iment, the working electrode was polished mechani-
cally with alumina powder down to 1.0-m diameter,
washed with triply distilled water, and then rubbed
against a smooth cloth. All electrochemical measure-
ments were carried out using the electrochemical work
station, IM6 (Zhaner Elektrik, Kronach, Germany).
The experiments were carried out at room temperature
(25 1C), and the potentials were measured against
and referred to the silver/silver chloride reference elec-
trode (E
o
= 0.2225 V vs. normal hydrogen electrode
(NHE)).
The formation of poly(1-amino-9,10-anthraqui-
none), (PAAQ) was carried out potentiodynamically
in nonaqueous media using 5.0 10
3
mol L
1
AAQ in ACN, containing 0.2% H
2
O and 0.1 mol L
1
LiClO
4
at a scan rate of 100 mV s
1
in the poten-
tial range from 0.5 to 1.8 V [6] and potentiostati-
cally using 5.0 10
3
mol L
1
AAQ/0.1 mol L
1
LiClO
4
/ACN solutions at +1.4 V for 25 min. The
lm preparation in an aqueous medium was carried
out potentiodynamically using 5.0 10
3
mol L
1
AAQ/6.0 mol L
1
H
2
SO
4
solution at a scan rate of
100 mV s
1
and potential range from 0.0 to 1.3 V
on the platinum substrate. The potentiostatic forma-
tion was carried out in 5.0 10
3
mol L
1
AAQ and
6.0 mol L
1
H
2
SO
4
solutions at +1.1 V for 780 s [7].
RESULTS AND DISCUSSION
Preparation of PAAQ in Aqueous
and Nonaqueous Media
Figures 1a and 1b show typical It curves moni-
tored during the potentiostatic formation of AAQ on
a platinum electrode. In aqueous solutions, three dis-
tinct regimes were recorded, whereas in nonaqueous
solutions only two regimes were recorded. The rst
regime, I, is present in both the curves and attributed
to an initial instantaneous drop in the current, which
is characteristic for the diffusion and electroadsorption
of a monomer on the electrode surface. The second
regime, II, that is present only in an aqueous medium,
is attributed to the nucleation and growth of a new
phase on the electrode surface. The third regime, III,
is recorded in both the media and represents a steady
state, where unidirectional growth of the lm is taking
place [7,21,22].
Kinetic Behavior of PAAQ
Assuming that the polymerization obeys the following
equation:
M+E P
where M is the monomer, E is the electrolyte, and P is
the polymer, then the kinetic equation can be formu-
lated as
r
p
= d[W]/dt = k[E]
a
[M]
b
(1)
where r
p
is the polymerization rate, that is, the mass of
electrogenerated polymer, W, per unit time per square
centimeter of the electrode surface, a and b are the reac-
tion orders with respect to the electrolyte and monomer,
respectively, and k is the specic rate constant of the
polymerization process.
Electropolymerization data provide kinetic param-
eters on the assumption that only a charge transfer
reaction is taking place at the electrode surface. From
the synthesis of the It transients, the polymerization
International Journal of Chemical Kinetics DOI 10.1002/kin
KINETICS OF ELECTROPOLYMERIZATION OF 1-AMINO-9, 10-ANTHRAQUINONE 143
Figure 1 (a) It transient monitored during the formation of PAAQ in aqueous medium on Pt electrode at +1.1 V for 13 min;
(b) It transient monitored during the formation of PAAQ in a nonaqueous medium on a Pt electrode at +1.4 V for 25 min.
charge density (Q, mC cm
2
) can be evaluated by
integration of the corresponding chronoamperograms
[18,19,23] when the electrolyte or the monomer con-
centration was varied. If the electrogenerated polymer
is the only species produced, the charge consumed dur-
ing the electropolymerization process, Q, should be
proportional to the mass of the electrogenerated poly-
mer, W, that is,
Q = kW (2)
The charge consumed, the electrolyte concentration,
and the monomer concentration can be correlated by
means of Eq. (3):
dQ/dt = kd[W]/dt = kr
p
= k[E]
a
[M]
b
(3)
or expressed in a logarithmic form as
log dQ/dt = log k +a log[E] +b log[M] (4)
Kinetics of PAAQ Formation in a Nonaqueous
Medium. Figure 2a shows the polymerization charge,
Q, versus time, t , corresponding to the PAAQ elec-
trogeneration from a constant 5.0 10
3
mol L
1
AAQ concentration as a function of the electrolyte
concentration in the range 0.51.5 mol L
1
LiClO
4
,
and Fig. 2b presents Q versus t plots associated with
the PAAQ electrogeneration from a constant 0.1 M
LiClO
4
concentration as a function of the monomer
concentration in the range (3.55.0) 10
3
mol L
1
.
Figure 2c presents Q versus t plots associated with
the PAAQ electrogeneration from 5.0 10
3
mol L
1
AAQ and 0.1 mol L
1
LiClO
4
as a function of wa-
ter content ranging between 0.004% and 2.4%. The
applied potential was +1.4 V, and the polymerization
time changes from 2 to 1500 s. The kinetic informa-
tion was taken very carefully at the initial stages of
the electropolymerization up to 1000 s, and no signi-
cant deviations were recorded. After longer time, some
deviations from linearity could occur.
The graphs show good linearity between the poly-
merization charge and the electrogeneration time. The
slopes of the lines resulting from the logarithmic plots,
that is, log dQ/dt versus log [LiClO
4
] and log dQ/dt
versus log [AAQ], yield reaction order values with
respect to the LiClO
4
electrolyte and AAQ monomer,
respectively. The logarithmic plot in each case was con-
structed and presented as an insert in the corresponding
graph. The values of the reaction order corresponding
to the AAQ monomer, b, LiClO
4
, a, and water, c, were
calculated. The reaction order with respect to AAQwas
found to be 0.999, which means that the polymeriza-
tion reaction is rst order with respect to the monomer
concentration. The calculated values for LiClO
4
and
water were 0.056 and 0.04, respectively. This means
that the reaction is zero order with respect to both
the supporting electrolyte, LiClO
4
, and the traces of
water. It means that neither the supporting electrolyte
nor water plays an active role in the kinetics of the
International Journal of Chemical Kinetics DOI 10.1002/kin
144 BADAWY, ISMAIL, AND MEDANY
Figure 2 (a) Polymerization charge versus time as a function of the AAQ monomer concentration at 1.4 V. The insert presents
log dQ/dt versus log [AAQ] linear relation. (b) Polymerization charge versus time as a function of the LiClO
4
concentration at
1.4 V. The insert presents log dQ/dt versus log [LiClO
4
] linear relation. (c) Polymerization charge versus time as a function of
water content in ACN at 1.4 V. The insert presents log dQ/dt versus log [H
2
O] linear relation.
International Journal of Chemical Kinetics DOI 10.1002/kin
KINETICS OF ELECTROPOLYMERIZATION OF 1-AMINO-9, 10-ANTHRAQUINONE 145
polymerization process. The kinetic equation control-
ling the AAQ polymerization in a nonaqueous solution
is then given by
r
p
= k[LiClO
4
]
0.056
[AAQ]
0.999
[H
2
O]
0.04
This means that the rate of the polymerization is
directly proportional to the monomer concentration,
that is,
r
p
= k[AAQ]
Kinetics of PAAQ Prepared in an Aqueous Medium.
The kinetics of polymerization of AAQ in aqueous
solutions was also investigated following the same
scheme. In this case, the kinetic equation can be
Figure 3 (a) Polymerization charge versus time as a function of the AAQ monomer concentration at 1.1 V. The insert presents
log dQ/dt versus log [AAQ] linear relation. (b) Polymerization charge versus time as a function of sulfuric acid concentration
at 1.1 V. The insert presents log dQ/dt versus log [H
2
SO
4
] linear relation.
International Journal of Chemical Kinetics DOI 10.1002/kin
146 BADAWY, ISMAIL, AND MEDANY
represented by
r
p
= k[AAQ]
a
[H
2
SO
4
aq]
b
AAQ and sulfuric acid concentrations were varied, al-
ternatively, keeping one of them constant to evaluate
their respective reaction orders. In the rst series of
experiments, the AAQ concentration was varied from
(3.5 to 5.0) 10
3
mol L
1
at a constant 6.0 mol L
1
H
2
SO
4
concentration and the rate was calculated. The
rate of polymerization was then calculated at a con-
stant monomer concentration of 5.0 10
3
mol L
1
,
and the concentration of H
2
SO
4
was varied between
5.5 and 6.5 mol L
1
. The results of these experiments
are presented in Figs. 3a and 3b, respectively. The log-
arithmic plots, that is, log dQ/dt versus log [AAQ] and
log dQ/dt versus log [H
2
SO
4
], showgood linearity and
are represented as inserts in Figs. 3a and 3b, respec-
tively. The slope of the line resulting from log dQ/dt
versus log [AAQ] is 1.01, which implies that the order
of polymerization reaction follows rst-order kinetics
with respect to the monomer concentration.
The slope of the line presented in Fig. 3b is negative
and equal to 0.66, which implies that sulfuric acid has
high solubility and inhibits the polymerization reaction
[2426]. The kinetic equation of the polymerization
process is therefore
r
p
= k[AAQ]
1.01
[H
2
SO
4
aq]
0.66
CONCLUSION
1. PAAQ thin lms are prepared conveniently and
reproducibly by the electropolymerization of
AAQ on Pt substrates from either aqueous or
nonaqueous media. The process is fast and not
expensive.
2. Chronoamperometry was used to determine the
order of the electropolymerization reaction and
the corresponding kinetic equations.
3. The electropolymerization process follows rst-
order kinetics with respect to AAQ in both the
aqueous and nonaqueous solutions.
4. The supporting electrolyte, LiClO
4
, and traces
of water (in nonaqueous medium) follow zero-
order kinetics, whereas H
2
SO
4
(in the aqueous
medium) had a negative order of 0.66.
The authors are grateful to the Alexander von Humboldt
(AvH) Foundation and Cairo University for providing the
electrochemical workstation.
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International Journal of Chemical Kinetics DOI 10.1002/kin