Electrochimica Acta 52 (2007) 5294–5303

Synthesis of fully and partially sulfonated polyanilines

derived from ortanilic acid: An electrochemical and
electromicrogravimetric study
Abraham Guadalupe Cano Márquez, Luz Marı́a Torres Rodrı́guez ∗ , Antonio Montes Rojas
Laboratorio de Electroquı́mica, CIEP-Facultad de Ciencias Quı́micas, Universidad Autónoma de San Luis Potosı́,
Avenida Dr. Manuel Nava No. 6, Zona Universitaria, C.P 78210, San Luis Potosı́, S.L.P, Mexico
Received 28 November 2006; received in revised form 14 February 2007; accepted 14 February 2007
Available online 20 February 2007

Abstract
The electrochemical polymerization of 2-aminobenzene sulfonic acid, also called ortanilic acid (o-ASA), on a gold electrode precoated with
polyaniline (PANI), has been carried out. We proved that the electropolymerization of o-ASA is enhanced on PANI electrodes, resulting in thicker
films obtained in aqueous media at room temperature. The electrosynthesized film (P(o-ASA)) was characterized by cyclic voltammetry, FTIR and
nuclear magnetic resonance. The compensation of P(o-ASA) charge was evaluated using electrochemical quartz crystal microbalance combined
with cyclic voltammetry, which showed that the electroneutralization process mainly involves cations. Additionally, copolymers of aniline and
o-ASA were electrosynthesized, using a metallic electrode modified with PANI also as a working electrode. The degree of sulfanation of copolymers
has been modulated with the proportions of monomers in the electrosynthesis solution. The studies reveal a more important participation of cations
in fully sulfonated polyaniline than in partially sulfonated polyaniline.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Polyaniline; Sulfonated; EQCM study; Charge compensation process; 2-Aminobenzene sulfonic acid

1. Introduction [12]. In addition, some SPANIs are n-dopable [13,14]. Such

Self-doped polyanilines represent one of the most interesting
types of polyaniline (PANI) derivatives. These polymers bear
aniongenic functional groups, such as –COOH [1–4], –OH [5],
–SO3 H [1,6–16] directly or spacer bound to the aromatic ring.
Among self-doped PANIs, special interest has been devoted to
sulfonated polyaniline (SPANI) because the sulfonic acid group
is a strong acid, and because there is a wide variety of sul-
fonated aromatic amines commercially available. Introducing
these groups in the PANI chain determines many distinctive
properties of SPANI, different from those of the parent polymer
[6,7], such as: high solubility in aqueous media [8,9], elec-
trochemical activity in alkaline and neutral media [1,10], the
property of self-doping [11], and the fact that its conductivity
does not change when treated with aqueous solutions at pH ≥ 4
∗ Corresponding author. Tel.: +52 48 26 24 40x561; fax: +52 48 26 23 71.
E-mail address: luzmaria@uaslp.mx (L.M. Torres Rodrı́guez).
properties make them a suitable choice, better than PANI, for
applications, such as biosensors [15] due to physiological pH
values; or rechargeable batteries, since SPANIs are capable of
storing more specific energy than PANI [16] as a function of
self-doping.
SPANIs have been synthesized by both chemical and elec-
trochemical methods. In the second case, the synthesis has been
performed mainly by copolymerization of aniline and sulfonated
aniline monomers, such as: orthanilic acid [17,18], metanilic
acid [1,19–22], sulfanilic acid [18], aniline-2, 5-disulfonic acid
[23], and more recently, disulfonated aminonaphtyl derivatives
[24].
Homopolymerization of sulfonated aromatic amines has
also been reported, either by casting the electrosynthesized
homopolymer from solution [25,26] or by electrodeposition
[13,14,18,27,28]. Nevertheless, in the latter case difficulties,
such as formation of thin films and low polymerization rates
were noted. Thiemann and Brett [18] observed that a particularly
important parameter at the initial stages of electrodeposition of

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.02.048
 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303
poly(4-aminobenzene sulfonic acid) is the electrode material. It
was found that, whereas the monomer polymerizes on glassy car-
bon, its electrodeposition on ITO electrodes is extremely slow. In
this respect, it has been reported that the electropolymerization
of substituted anilines is more effective on polyaniline modified
electrodes [29,30] than on bare surfaces. Thus, the electrosyn-
thesis of fully sulfonated polyanilines can be improved by using
a precoated polyaniline electrode.
As a consequence of the difficulties of the electrodeposi-
tion of fully sulfonated PANIs, the properties of these films
have not been studied enough, e.g. to our knowledge there are
no studies on the charge compensation process. Contrarily, for
partially sulfonated PANIs, this process has been evaluated in
different works [11,31–33]. These studies have revealed that
the electroneutralization of copolymers is mainly achieved by
cation participation, which suggests that in the case of fully
sulfonated PANIs cation participation can be increased, due
to the presence of more sulfonic groups for electroneutraliza-
tion.
Hence, the aim of this study is: (1) to establish a more advan-
tageous method of electrodeposition of fully sulfonated PANI
than those previously reported, based on electrochemical oxi-
dation of 2-aminobenzene sulfonic acid, also called ortanilic
acid (o-ASA), onto a gold substrate previously modified with
PANI, as well as on the electrochemical and spectroscopic char-
acterization of the obtained film. (2) To determine the influence
of the film sulfonation degree on the charge compensation dur-
ing the redox process by studying electrochemical quartz crystal
microbalance (EQCM) measurements, the charge compensation
process of the obtained homopolymer and partially sulfonated
polyaniline (copolymers of aniline and o-ASA).
2. Experimental
2.1. Chemicals
Aniline was distilled and kept in dark, all the other chemi-
cals were reagent grade and used without further purification.
The aqueous solutions were prepared using deionized water
(1.1 ␮−1 cm−1 ), and the solutions were deoxygenated by purg-
ing with nitrogen gas. After this, a nitrogen atmosphere was kept
over the solution during each run.
2.2. EQCM measurement
Electrochemical measurements were conducted using a PAR
273A (Princeton Applied Research) potentiostat–galvanostat
coupled to an electrochemical quartz crystal microbalance Seiko
model QCA922, both controlled by WinEchem V. 1.5 installed
on a personal computer.
A typical three electrode cell was used consisting of a 9 MHz
AT-cut quartz crystal coated with gold (0.1963 cm2 ) as working
electrode, platinum wire as counter electrode, and Ag/AgCl in
3 M NaCl as reference electrode. On the other hand, the quartz
crystal was mounted in a home-made cell, in which one side
of the crystal was kept out of the solution to prevent capacitive
shunting.
5295
The sensitivity constant of the quartz crystal electrode was
determined by potentiostatic deposition of silver, and was found
to be 1.714 × 108 Hz g−1 cm2 . This data is comparable to the
theoretical value of 1.81 × 108 Hz g−1 cm2 established by the
Sauerbrey equation [34]. In order to verify that the film behaves
as a rigid layer, the polymer oxidative charge and total mass
change (m) were evaluated from the polymer growth curves.
The m–Q graph was linear showing that the equation of Sauer-
brey could be applied.
2.3. Spectroscopy
For IR measurements, the polymer samples were mixed and
pressed with KBr. The FTIR spectra were obtained by means
of a Termo Nicolet 470 FTIR. 1 H RMN and 13 C RMN spectra
were recorded using a Brüker DMX-500 Hz spectrometer having
deuterated solvents as internal references.
3. Results and discussions
3.1. Electrosynthesis of a homopolymer
We tried to grow a homopolymer film, hereinafter referred to
as P(o-ASA), onto three different substrates: bare Au, aniline-
aminobenzene sulfonic acid copolymer/Au, as well as PANI/Au.
The electroxidation of o-ASA onto gold was performed either
by controlled potential electrolysis or potential sweeping. In
agreement with references [25,26], no characteristic growth was
observed. As a matter of fact, no film deposition was obtained.
In the case of copolymer/Au substrate, the copolymer was
electrosynthesized as reported by Barbero and Kötz [17] by
cycling the electrode potential between 200 and 900 mV at
50 mV s−1 in a 0.05 M o-ASA and 1 × 10−3 M aniline aqueous
solution. These conditions were chosen because they proved to
produce a film with a high sulfonation degree, resulting in a
substrate similar to the homopolymer. Deposition of P(o-ASA)
on a copolymer precoated electrode was achieved by repeated
linear potential scanning, though repeated scans over the range
−180 to 1020 mV at 50 mV s−1 in a 0.05 M o-ASA plus 0.5 M
H2 SO4 aqueous solution did not result in homogeneous film for-
mation. Finally, at the PANI/Au substrate a successful growth
of P(o-ASA) was achieved by repeated scans over the range
−200 mV to 1200 mV at 50 mV s−1 , as can be seen in Fig. 1. Two
important facts can be emphasized. First, the current intensity
increases steadily at each scan, which is characteristic of poly-
mer growth during deposition. Second, during the first cycles
(Fig. 1A(a)), the voltammogram resembles that of PANI. Nev-
ertheless, at subsequent cycles (Fig. 1A(b)) the redox peaks get
closer, until they reach a steady value (Fig. 1A(c)). It should
be noticed that the small separation between peaks is a dis-
tinctive feature for self-doped PANIs [6,7]. The obtained film
was adherent enough to resist mechanical stress without peeling
off when washed with water, and was visible to the naked eye.
In order to have an idea of the amount of deposited film, the
peak current density of potentiodynamic curves in monomer-
free solution of P(o-ASA) was compared to that obtained by
Zhang et al. [13]. The values for the same film grown in dif-
5296 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303
Fig. 1. (A) Cyclic voltammograms of poly(o-ASA) electrodeposition on a PANI modified Au electrode (0.1963 cm2 ): (a) 3 cycles, (b) 8 cycles, (c) 17 cycles. Working
solution: o-ASA (0.07 M) and H2 SO4 (0.5 M). Scan rate: 50 mV s−1 . (B) Change of mass during electrodeposition of P(o-ASA) recorded simultaneously with the
cyclic voltammograms shown in (A).
ferent synthesis conditions at the same scan rate, were around
6.1 mA cm−2 and 0.9 mA cm−2 , respectively. It should be men-
tioned that, for the latter case, the film was obtained by applying
a constant current for 6.5 h. It means that the electrodeposition
method reported here has a much higher polymerization rate
of P(o-ASA) (19.5 mC cm−2 h−1 ). This value is also greater
than that reported for aniline-o-aminobenzene sulfonic acid
copolymer (0.1 mC cm−2 h−1 ) [17]. However, during P(o-ASA)
polymerization, colored soluble oligomeric products were seen
near the electrode, which indicates an efficiency yield below
100%.
Furthermore, the mass change was simultaneously recorded
during electropolymerization. As shown in Fig. 1B, a uniform
mass increment occurs at each cycle reaching a value of ca.
6000 ng. EQCM measurements also show that the deposition
rate is lower for the first cycles. This is probably due to par-
tial covering of the electrode’s surface with P(o-ASA), which
results in a cyclic voltammogram similar to the voltammogram
of PANI growth at this stage of polymerization. Afterwards, the
mass increase is higher, and the cyclic voltammetry response no
longer resembles to the response of PANI, being characteristic
of SPANIs. We think that this is due to the full coverage of the
electrode with the sulfonated polymer. At this point, deposition
of P(o-ASA) on P(o-ASA) takes place.
The enhanced electrodeposition of substituted PANI on a
precoated polyaniline electrode has been associated with the
formation of electrocatalytic sites at the PANI surface [29].
We propose that this could be related to the charge compen-
sation process of PANI. In fact, during electroxidation of PANI
positive charges are generated at the polymer chain, which are
compensated by the incorporation of anions from the solution.
Consequently, the –SO3 group of o-ASA is incorporated into
the PANI film as a dopant anion, anchoring o-ASA monomers
on the PANI surface. Then, when the oxidation potential of
o-ASA is attained, the o-ASA monomer is polymerized on
PANI. During reduction, the anion cannot be ejected from PANI
because P(o-ASA) is trapped within the PANI chains. This
explanation is consistent with the fact that no noticeable film
formation was obtained on an aniline-aminobenzene sulfonic
acid copolymer/Au electrode, because the electroneutralization
in the oxidation process for this film is mainly caused by proton
ejection. As a result, the group –SO3 H cannot be anchored to
the copolymer film.
3.1.1. Effect of substrate thickness on P(o-ASA)
polymerization
In the course of this study, we observed the effect of thickness
of the predeposited PANI substrate on the electropolymerization
of P(o-ASA). Therefore, several potential sweeps ranging from
1 to 10 cycles were performed for the electrodeposition on a
PANI substrate.
Electrodeposition of P(o-ASA) on a PANI substrate, syn-
thesized by application of ten repetitive scans, resulted in a
thick film (Fig. 1). On the other hand, during potentiodynamic
electroxidation of o-ASA over a thin PANI film produced by
performing only one scan of potential, the voltammograms
resembled those obtained for sulfonated anilines on a bare metal-
lic electrode [25], characterized by an oxidation peak placed
at about 1 V attributed to monomer oxidation, and a redox
process around 0.6 V due to the product formed during the elec-
troxidation. The peak current of this process hardly increased
with successive potential cycling, although no polymer film was
found on the electrode’s surface. These results show that the
thickness of PANI substrate is decisive in the electrochemical
deposition of P(o-ASA).
In order to find the optimum quantity of PANI substrate, we
calculated the anodic charge of P(o-ASA) from the voltammetric
responses obtained both during deposition (last cycle) and in
monomer-free 0.5 M H2 SO4 media. The obtained results are
shown in Fig. 2 as a function of the number of cycles applied
for the electropolymerization of PANI.
It was observed that the charge obtained for the last cycle
of polymerization is higher than the obtained for the film in
0.5 M H2 SO4 . This result confirms that the polymerization yield
 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303
Fig. 2. Integrated anodic charge of P(o-ASA): (䊉) during polymerization (last
cycle); (×) in H2 SO4 solution (0.5 M) as a function of cycle number applied
during electrosynthesis of PANI substrate.
was less than 100%. The obtained curves also show that, when
electroxidation takes place on thinner PANI films (one to four
cycles) no noticeable film deposition is obtained, whereas PANI
precoated electrodes synthesized from a minimum of five cycles
generate a uniform P(o-ASA) film. The deposited charge of P(o-
ASA) increases gradually with the amount of PANI substrate,
and attains a steady value. Therefore, in order to obtain P(o-
ASA) films a minimum of five cycles must be performed during
PANI synthesis.
3.2. Electrochemical characterization of films
After electrosynthesis, the film was analyzed by cyclic
voltammetry in 0.5 M H2 SO4 P(o-ASA). The resulting voltam-
mogram was stable and the film could be cycled repeatedly
without considerable change in the electrochemical response.
As can be seen in Fig. 3a, the cyclic voltammogram has two
overlapping oxidation peaks (I, II) as well as their cathodic
counterparts at around 425 and 595 mV. This response is simi-
lar to the parent PANI, except that the two sets of redox peaks
Fig. 3. Cyclic voltammetry of (a) electrochemically deposited P(o-ASA) on
PANI/Au (0.1963 cm2 ) and (b) PANI/Au (0.1963 cm2 ). Working solution:
H2 SO4 (0.5 M). Scan rate: 50 mV s−1 .
5297
are closer. The reduced separation of the two peaks for SPANI
has been associated with steric effects caused by the bulky sul-
fonic acid substituent [6,7]. This behavior contrasts with that
reported by Thiemann and Brett [18] for electropolymeriza-
tion of o-ASA on glassy carbon electrodes, which reports three
anodic current maxima at 0.3, 0.49 and 0.66 V versus SCE at the
cyclic voltammogram of P(o-ASA); furthermore, the shape of
the curves is different. This discrepancy could be attributed to
the different conditions of electrosynthesis, as well as to the elec-
trode material, different upper limit of oxidation, and monomer
concentration.
Finally, the response of P(o-ASA) was compared with the
cyclic voltammogram of PANI used for precoating the electrode.
As shown in Fig. 3, the curves are different. The current is higher
for P(o-ASA) and the second oxidation couple is shifted nega-
tively even more than the peak of PANI, whereas the first couple
is shifted positively. These differences show that the film at the
electrode’s surface is mainly P(o-ASA).
Additionally, cyclic voltammetry was performed at different
scan rates. The peak heights scale linearly with the sweep rate
in the range 5–250 mV s−1 , but only in the case of the anodic
current of process I, the linear dependence between these vari-
ables remains no more than 25 mV s−1 . For this process, a plot
of the peak current versus the square root of the scan rate was
linear with zero different intercept, indicating that the current is
controlled by diffusion. This deviation from the expected behav-
ior of a surface-confined electroactive species can be originated
by mass transport limitations within the film or charge transfer
limitations at the substrate film interface [35].
Moreover, the solubility of P(o-ASA) was evaluated and the
results show that the film is highly soluble both in neutral and
alkaline media, barely soluble in acidic media and completely
insoluble in organic media, such as acetonitrile and acetone. This
behavior is in agreement with a high molecular weight polymer
linked to sulfonic acid groups.
3.2.1. Redox processes at P(o-ASA) modified electrodes
The electrochemical behavior of the hydroquinone–
benzoquinone (HQ/BQ) redox couple was tested using a P(o-
ASA) film modified electrode as working electrode. Cyclic
voltammetric response obtained from scans between −100
and 950 mV at 50 mV s−1 , shows two redox processes, one
attributed to the process of P(o-ASA), and the other asso-
ciated with the quasireversible redox transition between HQ
and BQ. For the HQ/BQ redox process, both the observed
E as well as the current for the P(o-ASA) modified elec-
trode were higher than those obtained on bare gold. These
evidences show that the quinone–hydroquinone couple acts
more irreversibly for the P(o-ASA) modified electrode, which
indicates that P(o-ASA) inhibits the electrochemical reaction.
This behavior is contrary to that reported for PANI [36], and
copolymer aniline/m-aminobenzene sulfonic acid (metanilic
acid) [22] coated electrodes, which show an electrocatalytic
ability toward this redox couple. The opposite behavior of the
quinone/hydroquinone couple on P(o-ASA) and PANI indicates
that the redox reaction proceeds mainly onto the surface of
P(o-ASA). Otherwise, the redox reaction would be carried out
5298 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303
principally on the PANI’s surface and electrocatalytic behavior
would be obtained.
3.2.2. Effect of pH value on the cyclic voltammograms of
P(o-ASA)
To investigate the influence of the pH on the redox behavior
of the P(o-ASA), cyclic voltammograms of electrochemically
synthesized films prepared under the same conditions as above,
were recorded in solutions of different pH values. However, the
P(o-ASA) is soluble in solutions of neutral and alkaline pH; in
consequence, it was impossible to obtain the potentiodynamic
curves of the electrodeposited P(o-ASA). Therefore, in order to
determinate the electrochemical behavior of P(o-ASA), it was
necessary to measure the voltammograms for the polymer in
solution and not as a film. The obtained results are shown in
Fig. 4, the cyclic voltammograms are almost equal for both
pH and display a reversible wave at E◦ = 291 mV correspond-
ing to electrochemical activity of P(o-ASA). The resemblance
between the curves obtained at pH 4 and 7 demonstrates that
the electroactivity of P(o-ASA) is independent from pH in the
studied interval. For the case of pH 7, the upper scan limit
was extended as a result of an irreversible anodic peak situ-
ated in 625 mV associated with film degradation. Additionally,
it should be mentioned that the obtained cyclic voltammograms
Fig. 4. Cyclic voltammograms of P(o-ASA) (100 mg L−1 ) on Au electrode
(0.1963 cm2 ) in (NH4 )2 SO4 (0.5 M) aqueous solution at: (a) 400, (b) 300, (c)
200, (d) 150, (e) 100, (f) 75, (g) 50, (h) 25, (i) 15, (j) 10, (k) 5 mV s−1 . Solution
pH: (A) pH 4, (B) pH 7.
Fig. 5. P(o-ASA) FTIR spectra.
are similar to those reported by Li et al. [10] for other sulfonated
polyaniline.
3.3. Spectroscopic analysis of P(o-ASA)
3.3.1. Fourier transformed infrared spectroscopy
The FTIR spectra of the film measured using KBr pellets
can be seen in Fig. 5. The obtained spectrum is similar to that
reported by Zhang et al. [13] for the P(o-ASA) synthesized in a
mixed solvent of acetonitrile and water. The FTIR spectra give
similar bands to those of a PANI films as well as the broad band
centered at 3437 cm−1 attributed to unresolved NH stretching
modes, the peaks at 1632 and 1483 cm−1 due to the stretching
of aromatic carbons and the C–N stretching band that appears at
1200 cm−1 . In addition to the characteristic bands of the parent
PANI, the spectrum showed distinctive peaks of the sulfonic
group as well as very intense bands at 1060 and 1022 cm−1
assigned to the asymmetric and symmetric O S O stretching
vibrations, whereas another band, seen at 664 cm−1 , is attributed
to the C–S stretching. In summary, the spectra is consistent with
the presence of SO3 − groups attached to the aromatic rings.
3.3.2. Nuclear magnetic resonance spectroscopy
Once the presence of the characteristic peaks due to the sul-
fonic acid group was confirmed, the NMR H+ and C13 spectra
were obtained with the aim of determining the type of coupling
during polymerization.
In the NMR H+ case (Table 1), there is a signal at 2.5 ppm
that belongs to DMSO-d6 , whereas at 6.2 ppm the signal is due
to H2 O and/or to –NH group; the three bands found between 7.3
and 8 ppm belong to aromatic hydrogen atoms. Their coupling
constants (J) are shown in Table 1.
The J values show that H(6) is ortho-coupled with H(5),
which generates a doublet centered at 7.362 ppm. H(5) is also
ortho-coupled with H(6) which produces a doublet. Then, it
couples at meta with H(3). As a result, the signal, centered at
7.73 ppm, doubles again. Finally, H(3) is meta-coupled only with
H(5), which causes a doublet centered at 7.955. According to the
observed signals, the only available carbon atom for polymer-
ization is C(4), which implies that it takes place as a head-to-tail
mechanism. On the other hand, on comparing these spectra with
 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303 5299

Table 1
Aromatic hydrogens of P(o-ASA)
Atom J (Hz) Coupling Signal Location (ppm)

H(3) 2.0 meta Doublet 7.95

H(5) 8.25; 2.5, 2.0 ortho; meta, meta Double doublet 7.73
H(6) 8.0 ortho Doublet 7.95

Coupling constants.

those of the parent PANI [19], peaks belonging to H(3), H(5) and
H(6) are seen to shift toward lower wavelengths. This fact is in
agreement with the presence of the –SO3 H group. Furthermore,
it should be pointed out that this group is found as –SO3 − , due
to the fact that there is no signal corresponding to the –SO3 H
group (around 12 ppm).
In addition, the C13 spectra showed signals (Table 2) located
between 123 and 130 ppm, which correspond to quaternary car-
bon atoms, while those found between 136 and 140 ppm belong
to methynic or aromatic atom carbons. It should be mentioned
that each signal was assigned with the aid of tables.
3.4. Charge compensation dynamics in monomer-free
solutions
It is a well-known fact that charge compensation is attained
mainly by proton participation in sulfonated polyanilines [11,17,
31–33]. In order to confirm this behavior, the ion exchange prop-
erties P(o-ASA) were investigated by EQCM. Fig. 6A shows the
cyclic voltammogram and the corresponding mass change of a
P(o-ASA) film in 0.5 M H2 SO4 .
It can be seen that at the beginning of the scanning no redox
processes occur, and both the current and the mass remain almost
constant. When the potential becomes more oxidative, the first
oxidation process takes place accompanied by a mass decrease;
this behavior is maintained to attain the second oxidation peak
(held at 585 mV). These evidences clearly show that electroneu-
tralization in this potential range is mainly caused by proton
expulsion, in good agreement with the cationic transport model
and in opposition to the behavior of conducting polymers con-
taining mobile counter-anions. On the other hand, at the end
of the second oxidation process, a mass increment occurs as a
consequence of anion uptake. It should be mentioned that the
mass change for full oxidation is different from that reported
for the parent PANI [37], where an important mass reduction is
observed.
In order to evaluate the extent of anion participation, the mass
change upon oxidation of P(o-ASA) in 0.5 M acidic solutions
Table 2
Carbon atom location obtained for P(o-ASA)
Atom Type Location (ppm)
C(l) Methynic 139.52
C(2) Methynic 136.36
C(3) Quaternary 123.69
C(4) Methynic 129.98
C(5) Quaternary 128.22
C(6) Quaternary 125.16
was measured for acids with anions of different molar mass
(Table 3). The cyclic voltammetry response was very similar for
all the acids, while the mass decrease obtained for the first peak
oxidation was independent of the molar mass of the anion. This
result shows that charge compensation is achieved mainly by
proton ejection. At the same time, the increase in mass associated
with the second oxidation process is different for each anion size,
but no lineal relation between the size of anion and the change
of mass is observed. This indicates that for the oxidation in this
region of potential, the mass increase is not only originated by
the incorporation of anion, which would be reflected in a linear
relationship between the anion size and the mass increase, but
also results from the cation departure.
To obtain more quantitative information for the first process,
mass–charge curves were plotted and molar mass equivalents
of the exchanged species were calculated from their slopes.
As shown in Fig. 6B, two well-delineated regions are present,
the first one corresponding to the first oxidation process of the
film and characterized by a negative slope indicating that the
charge compensation is mainly effected by ejection of species;
the second region, however, presents a positive slope, which
means that electroneutralization is made principally by anion
insertion.
Taking into account that the charge compensation during
the first oxidation process of P(o-ASA) is held exclusively by
ejection of cations, the molar mass equivalent (MME) of the
exchanged species would be −19 g mol−1 , corresponding to
a hydronium ion (H3 O+ ). However, as shown in Table 3, the
calculated MMEs differ from this value, thus suggesting the
participation of anion and/or dissolvent; as the MMEs are very
similar (taking into account the experimental error) for all acids,
the charge compensation is thereby independent of the anion
size. Consequently, significant participation of anions in the
electroneutralization is discarded. These observations suggest
that the electroneutralization of P(o-ASA) is achieved mainly
by proton expulsion and probably solvent incorporation. It is
important to mention that the MME for the first process was
estimated also for eight different sweep rates ranging from 5 to
200 mV s−1 in H2 SO4 (0.5 M) and 0.5 M camphorsulfonic acid
Table 3
MME calculated for the first redox process of P(o-ASA)
Molar mass of anion (g mol−1 ) MME (g eq−1 )
HCl 35.5 −2.9
HNO3 62.0 −2.8
H2 SO4 97.1 −6.3
HClO4 99.4 −5.4
HCS 231.3 −4.0
5300 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303

Fig. 6. (A) (a) Potentiodynamic and (b) electromicrogravimetric responses for a P(o-ASA) film deposited on PANI/Au (0.1963 cm2 ) electrode. Working solution:
H2 SO4 (0.5 M). Scan rate: 50 mV s−1 . (B) Mass change–charge plots for P(o-ASA). Data calculated from (A).

(HCS). The obtained values were practically independent of the
sweep rate and anion size of the acid used.
In order to analyze the influence of cation size on the
charge compensation mechanism, we have studied current and
mass responses of P(o-ASA) simultaneously measured during
redox reactions in 0.5 M lithium tetrafluoroborate (TFBLi) and
0.5 M tetraethylammonium tetrafluoroborate (TFBTEA) in ace-
tonitrile. These electrolytes were chosen because of the huge
differences in cation size. Since P(o-ASA) is soluble in neutral
aqueous solution, it was necessary to work in organic media, i.e.
in acetonitrile, in which it is insoluble. The obtained results are
shown in Fig. 7; in both cases, the potentiodynamic response is
characterized by a considerable decrement in the film electroac-
tivity in comparison with that obtained in the aqueous media. In
fact, during the first scans the cyclic voltammograms of P(o-
ASA) are characterized by a broad anodic peak centered at

Fig. 7. (A) Cyclic voltammetry and EQCM profiles on cycling at 50 mV s−1 of a P(o-ASA) films in: (a) 0.5 M TFBLi and (b) 0.5 M TFBTEA in acetonitrile. (B)
Plots of m/Q for P(o-ASA) films in acetonitrile solutions of (C) TFBLi (0.1 M) and (D) TFBTEA (0.1 M). Data calculated from (A and B).
 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303
0.670 V and a cathodic wave at −0.060 V. However, at succes-
sive scans, when the mass response is stabilized, the anodic peak
vanishes as is shown in Fig. 7. It should be mentioned that after
the scans were performed in acetonitrile, the films were analyzed
using cyclic voltammetry (CV) in 0.5 M H2 S04 aqueous solu-
tion. The polymer electroactivity was very similar to that shown
in Fig. 6A. Therefore, a different cyclic voltammetry behav-
ior shown in acetonitrile is not a consequence of destruction or
solubilization of the film.
On the other hand, the mass change profile is different for the
two cations (Fig. 7). In the case of TFBLi, the obtained curve
is complex, showing an augmentation of mass at the beginning
of the scan where negative current (reduction) is present; in the
region where maximum current is attained a decrease in mass is
observed even at the end of the scan. This behavior suggests that
the electroneutralization throughout the entire region of film oxi-
dation is mainly achieved by cation expulsion. When the scan is
reversed, the current is still positive (oxidation), and the decrease
of mass continues, but when the current turns negative (reduc-
tion), a mass increase is observed. As there is an increase in
mass during reduction and a decrease in mass during oxida-
tion, the electroneutralization during film oxidation is achieved
principally through the cation ejection.
In the TFBEA case, the curve mass/potential has shown a
significant mass decrease in almost the entire region of potential
during film oxidation, whereas a small mass increase is observed
only at the end of the scan. This indicates that charge compen-
sation is accomplished principally by expulsion of cation during
the oxidation process. It is important to note that the mass change
in the potential region of the second redox process in acetonitrile,
of both TFBEA and TFBLi, is different from those occurring in
aqueous media, where an important augmentation of mass is
observed.
To clarify the nature of the exchanged species during the
oxidation, mass-charge curves were plotted and they are shown
in Fig. 7C and D. Based on these curves, the equivalent mass
exchanges from the beginning of the first oxidation process were
calculated; the values obtained were −2.3 and −111 g mol−1
for TFBLi and TFBTEA, respectively. In the case of TFBLi,
the value is bigger that the molar mass of cation (−7 g mol−1 ).
This result shows that there is a contribution of anions and/or
solvent to the electroneutralization process. Meanwhile in the
TFBTEA case, the value obtained is rather close to the mass
of tetraethylammonium cation (116 gmol−1 ), which indicates
that the charge compensation for the first oxidation process is
achieved exclusively through the cation ejection. These results
are in accord with Mello et al. [32], who demonstrated that anion
participation is strongly dependent on cation size.
3.5. Comparisons of charge compensation process in
aqueous media of partially and fully sulfonated polyanilines
It is established that the dopant level (the term commonly
used to denote the number of charge balancing counter ions per
unity of monomer) for substituted PANI ranges from 0.29 to
0.33 for the first oxidation process, and from 0.33 to 0.34 for the
second process, respectively [38]. Therefore, PANI film with a
5301
minimum of 30% sulfonation degree has enough dopant ions
bound for electroneutralization in the first oxidation process.
This means that the level of cation participation in the charge
compensation mechanism would be equal for both a copoly-
mer (30% degree of sulfonation or more) and a homopolymer,
for the first process. In order to determine whether the cation
participation in the charge compensation process is limited by
the quantity of sulfonic acid groups linked to PANI chain or
not, the current and mass responses to a potential scan were
simultaneously measured in 0.5 M H2 SO4 for different copoly-
mers. The electrosynthesis of copolymers was performed using
different ratios of aniline and o-ASA while keeping the con-
centration constant (0.07 M). The growth of different polymers
was obtained by repeated cyclic voltammogram scans between
−180 and 1050 mV on PANI/Au electrode.
To determine whether the sulfonation degree of copolymers
depends on the composition of electrosynthesis solution, FTIR
spectroscopy was carried out for the films obtained with the
following proportions of o-ASA:aniline, 50:50 and 30:70. The
spectra show that the relation between the intensity of absorption
peak at 1061 and 1200 cm−1 bands, characteristic of sulfonic
group, and the bands centered at 1638 and 1480 cm−1 due to
the stretching of the benzenoid and quinoid structures of PANI,
is greater for the film obtained with the solution containing the
highest quantity of o-ASA. This result shows that the number
of sulfonic groups in the film can be modulated by varying the
composition of working solution. It should be mentioned that
the intensity of bands at copolymer FTIR spectra indicates the
considerable sulfonation degree. This result is relevant in the
sense that the copolymers reported, obtained on a bare metallic
electrode, require a 1:10 proportion of aniline and sulfonated
monomer to obtain a sulfonation degree of the order of 25% [32].
After the electrochemical synthesis, the films were removed
from the preparation medium, washed with H2 SO4 (0.5 M) and
studied by EQCM with both an aqueous solution containing
0.5 M H2 SO4 and HCS (0.5 M) solution as supporting elec-
trolyte. Cyclic voltammograms and mass change profiles versus
potential obtained in H2 SO4 are similar to those obtained in
HCS. The results obtained for H2 SO4 are shown in Fig. 8. The
potentiodynamic response shows that an increase in proportion
of o-ASA in the synthesis solution results in a reduction of the
separation between the peaks of the film. This suggests that the
percentage of sulfonated aniline in the polymer increases with
the quantity of sulfonated monomer in the synthesis solution. In
fact, the small separation between the observed peaks when sul-
fonic group is incorporated into the film, means that the greater
is the amount of –SO3 − groups in the polymer, the smaller is
the the gap between the peaks.
Concerning the curves of mass change versus potential, two
aspects are of interest: the mass variation observed during the
forward sweep in the potential region between 600 and 900 mV
and the mass change of the first process. In the first case, the mass
is seen to change with the composition of the solution employed
in the electrosynthesis. In the case of PANI film and the film
obtained with the 10:90 electrosynthesis solution, a consider-
able mass decrease occurs in this potential region, associated
with the deprotonization of the film [37]. On the other hand, in
5302 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303

Fig. 8. (a) Cyclic voltammetric response and (b) mass change vs. potential curves recorded in H2 SO4 (0.5 M) during potential cycles at 50 mV s−1 , for polymers
obtained from H2 SO4 (0.5 M) solutions and different o-ASA:aniline proportions while keeping the concentration constant (0.07 M), (A) 0:100, (B)10:90, (C) 30:70,
(D) 50:50; (E) 70:30 and (F) 100:00. Mass data were filtered by Microal Origin 6.0 using the 5-point adjacent average method.

the case of films obtained with working solutions at higher ratios
of o-ASA, the mass remains practically constant in this region of
potential. Finally, in the case of P(o-ASA), a slight mass increase
is seen. This result shows that the charge compensation process
in this potential region is sensitive to the presence of sulfonic
groups in the films. The greater is the percentage of these groups,
the greater is the extent of neutralization due to the incorporation
of species in the polymer matrix. The second aspect of interest
is associated with the variation of mass during the first oxida-
tion process: for the majority of copolymers an mass increase
is observed, which means anion participation in the electroneu-
tralization of the film. Only copolymers with a greater degree of
sulfonation present a small decrease in mass during the partial
oxidation of the film, thus evidencing a greater cation partici-
pation in charge compensation. However, this decrease is minor
in comparison with that obtained for the homopolymer. In con-
clusion, the qualitative analysis of the curves suggests that the
degree of film sulfonation influences cation participation in elec-
 A.G. Cano Márquez et al. / Electrochimica Acta 52 (2007) 5294–5303
troneutralization during the first oxidation process, because the
mass decrease increases with the sulfonation degree. It should
be mentioned that the electrosynthesis and EQCM test in H2 SO4
(0.5 M) and HCS (0.5 M) were repeated obtaining similar results.
4. Conclusion
This study has demonstrated that the electro-oxidation of o-
ASA on PANI modified electrodes gives rise to the formation
of sulfonated homopolymers; these films, unlike those obtained
on bare metallic electrodes, are thick and adherent. The quantity
of electrodeposited P(o-ASA) is dependent on PANI thickness.
The result of EQCM shows that electroneutralization during the
first oxidation process of P(o-ASA) is carried out mainly through
the ejection of cations. Additionally, o-ASA and aniline copoly-
mers were electrosynthetized, the sulfonation degree of the films
obtained was modulated with the proportion of monomers in the
electrosynthesis solution. The proportion of charge compensa-
tion derived from cation transport increases with the percentage
of sulfonic groups in the film.
Acknowledgements
The support for this work by the Universidad Autónoma de
San Luis Potosı́ via FAI is gratefully acknowledged. A.G. Cano
Márquez thanks CONACYT scholarship (180914).
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