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Classification
Introduction
NH NH NH NH
A A
Protonated polyaniline (emeraldine)
-2H A
deprotonation
NH NH N N
Materials
Procedures
The aniline hydrochloride, or generally any aniline salt (1), is oxidized at first to
the aniline cation radical (2) (Fig. 2a). Although the detailed reaction mechanism
of aniline polymerization is not fully understood, the formation of the protonated
pernigraniline intermediate (3) (Fig. 2b) is observed during the polymerization and
manifested by the deep blue color of the reaction mixture. At the end of polymeri-
zation, the pernigraniline is reduced with residual aniline to the final product, the
green emeraldine form of PANI (4) (Fig. 2c). During the reaction, the ammonium
peroxodisulfate is reduced to ammonium sulfate (Fig. 2d). Summing all reaction
202 J. Stejskal and I. Sapurina
steps (6), the stoichiometric oxidant/monomer ratio 5/4 = 1.25 is found.[5] This is
why the concentrations of aniline hydrochloride and ammonium peroxodisulfate
were selected in the present protocol as 0.2 M and 0.25 M, respectively.
a
4H 4e
4 NH2.HA 4 NH2.A
1 2
b
8H 8e
NH NH NH NH
A A A A
c
2A +2e
NH NH NH NH
A A
4
d + 10 H + 10 e
5 (NH4)2S2O8 5 (NH4)2SO4 + 5 H2SO4
6
4 NH2.HA + 5 (NH4)2S2O8
NH NH NH NH
A A
+ 5 (NH4)2SO4 + 5 H2SO4 + 2 HA
the acidity because protons (sulfuric acid) are produced during the polymerization
(Fig. 2).
Fig. 3. Temperature profile in the polymerization of aniline (0.2 M aniline hydrochloride oxi-
dized with 0.25 M ammonium peroxodisulfate in 100 ml of aqueous medium).
Comments
(1) The purity of the chemicals is not crucial as far as the yield and properties of
PANI are concerned. The course of the polymerization is, however, acceler-
ated by traces of various compounds.[16]
(2) An equimolar mixture of aniline and hydrochloric acid can be used instead of
aniline hydrochloride. The presence of excess (1 M) hydrochloric acid in the
reaction mixture improves the conductivity of PANI.[13]
(3) Various inorganic and organic acids at various concentrations can be used in-
stead of hydrochloric acid in the polymerization of aniline.[17] The electrical
and material properties of PANI vary correspondingly. Polyaniline is produced
as fused nanogranules. [13] Polyaniline nanotubes are obtained when the oxi-
dation of aniline takes place in the solution of weak acids, such as acetic acid
[18,19] or in water. [20]
(4) When using ammonium peroxodisulfate as an oxidant, sulfuric acid is pro-
duced during the polymerization (Fig. 2). This means that the PANI is partly
protonated also by this acid. Washing of PANI with hydrochloric acid after the
preparation should replace most of the sulfate counter-ions with chloride and
the resulting product is thus PANI hydrochloride. Subsequent rinsing with ace-
204 J. Stejskal and I. Sapurina
Characterization
Elemental composition: The chlorine content reflects the protonation in PANI hy-
drochloride (Table 1), the presence of sulfur corresponds to a partial incorporation
of residual sulfate or hydrogen sulfate anions produced by the reduction of per-
oxodisulfate during polymerization (Fig. 2).
Table 1. Elemental composition of polyaniline [13]
Sample %C %H %N % Cl %S
Polyaniline hydrochloride
Found 59.7 4.9 10.6 11.1 1.0
Calcd.a 66.2 4.6 12.9 16.3 -
Polyaniline base (after deprotonation of polyaniline hydrochloride)
Found 75.0 5.0 13.9 0.6 0.3
Calcd.a 79.5 5.0 15.5 - -
a
Based on the formulae shown in Fig. 1.
chlorine. Some chlorine remains in the PANI base even after deprotonation, indi-
cating partial substitution of the phenyl rings with chlorine.[24] Sulfonation of the
phenyl rings is responsible for the presence of sulfur in the PANI base.[20]
FTIR spectra: The infrared spectrum of PANI hydrochloride shows a broad ab-
sorption at wavenumbers >2000 cm-1, which is characteristic of the conducting
form of PANI [29,30]. Typical peaks in the infrared spectra of PANI hydrochlo-
ride, corresponding to quinone and phenyl ring deformations, are observed at 1569
cm–1 and 1480 cm–1 (Fig. 4). These are blue-shifted to 1590 cm–1 and 1500 cm–1
after deprotonation to PANI base.[31,32] The band at 1374 cm–1, associated with
C–N stretching in the neighborhood of a quinonoid ring, is present in the spectrum
of PANI base but absent from the spectrum of PANI hydrochloride. The absorp-
tion at 1302 cm–1 corresponds to S-electron delocalization induced in the polymers
by protonation [33] and is reduced after the deprotonation. The band characteristic
of the conducting protonated form is found at about 1245 cm–1. The band at 1144
cm–1 can be assigned to a vibration mode of a protonated imine group. It overlaps
the band of in-plane C–H deformation vibrations at 1164 cm–1 observed in PANI
base.[32,34-36] The aromatic-ring and out-of-plane C–H deformation vibrations
manifest themselves in the region of 900–700 cm–1.
Fig. 4. Infra-red spectra of polyaniline hydrochloride and polyaniline base dispersed in potas-
sium bromide pellets.
Molar mass: The mass-averaged molar mass of PANI base determined by gel
permeation chromatography in N-methylpyrrolidone by using the polystyrene
calibration is Mw = 58 100 g mol–1 (Fig. 5). This is the value corresponding to a
degree of polymerization of about 640 aniline units, a value common for the many
polymers met in practice. The molar mass distribution is relatively broad, the
mass-to-number molar-mass ratio being Mw/Mn = 3.3.
Density: The average density of PANI hydrochloride is 1.329 ± 0.027 g cm–3 at
20 °C and that of PANI base 1.245 ± 0.006 g cm–3.[13]
206 J. Stejskal and I. Sapurina
Fig. 5. Molar mass distribution of polyaniline base determined by gel permeation chromatogra-
phy in N-methylpyrrolidone using polystyrene calibration.
References