Materials and Manufacturing Processes, 21: 263–270, 2006

Copyright © Taylor & Francis Group, LLC

ISSN: 1042-6914 print/1532-2475 online
DOI: 10.1080/10426910500464602

Polyaniline as a Gas-Sensor Material

Partha Pratim Sengupta, Satyananda Barik, and Basudam Adhikari

Materials Science Centre, Indian Institute of Technology, Kharagpur, India

Polyaniline (PANI) was synthesized by oxidative polymerization of aniline using ammonium persulfate in an acid medium. The polyaniline
salt was converted to base form by treatment with ammonium hydroxide. The polyaniline base was dissolved in N-methyl pyrrolidone (NMP) for
film casting. The cast film was doped with HCl for obtaining higher conductivity. Both doped and undoped PANI films were characterized by
UV-visible, FTIR, and XRD analyses. The electrical conductivity of the PANI film was studied by a four-point probe method at room temperature.
Finally, ammonia gas-sensing characteristics of the prepared polyaniline film were studied by measuring the change in electrical conductivity
on exposure to ammonia gas at different concentrations. The influence of concentration of acid during polymerization of aniline and dopant
concentration on the gas sensing characteristics of PANI film are reported in this paper.

Keywords Benzenoid ring; Bipolarons; Chemisorption; Conductivity; Conjugated polymers; Crystallinity; Electrical properties; Film casting;
Four-probe method; Gas-sensor; Measuring cell; Ohmic contact; Polarons; Polyaniline; Probe spacing; Quinone diimine unit; Recovery time;
Response time; Solution casting.

1. Introduction repeat units, where B denotes a benzenoid and Q denotes

Conducting polymers are a new class of materials
with applications in a number of new technologies,
such as energy storage [1], molecular recognition [2],
electromagnetic interference, optoelectronic devices, and
sensors. By virtue of their chemical structure and electrical
conduction characteristics, organic conducting polymers
have gained importance as modern materials. Among
all conducting polymers, polyaniline (PANI) has recently
achieved importance because of its unique conduction
mechanism, easy synthesis, environmental stability, and
easy processability in its non-conductive base form.
Interest in PANI started in the mid 1980s. Polyaniline,
resulting from oxidative polymerization of aniline, consists
of both reduced (B–NH–B–NH) and oxidized (B–N=Q=N–)
The fully reduced form,
The half oxidized polymer,
The fully oxidized form,
Address correspondence to Prof. B. Adhikari, Materials Science Centre,
Indian Institute of Technology, Kharagpur 721302, India; Fax: (91) (3222)
255303; E-mail: ba@matsc.iitkgp.ernet.in
263
a quinoid ring. Polyaniline can be made in any of the
following forms.
Thus, the ratio of amine to imine units yields various
structures: the fully reduced form “leucoemeraldine”
polymer, the half oxidized form “emeraldine,” and the fully
oxidized form “pernigraniline.”
Electroconducting polymers seem very promising for
use in microsensors. The potential of electroconducting
polymers as sensors is based on modulation of their doping
level and by interaction with some gases. This effect results
in an immediately controlled response in conductivity.
Conducting polyaniline has been used as a sensing material
for the detection of various vapors such as methanol,
ethanol, acetone, and benzene [3]. The first practical sensor
for detecting ammonia was developed from conducting
polymer polypyrrole [4]. Low sensitivity and a very long
response time were the drawbacks of this sensor.
The investigation [5] on the effect of ammonia and water
on a polyaniline layer was done by measuring conductance
changes. Sensitivity of PANI to water was an order of
magnitude less than that of ammonia. Polyaniline film
doped with nickel containing anions showed sensitivity
to ammonia gas [6]. Yuan et al. [7] used an HCl-doped
polyaniline film for remote detection of ammonia gases
by simple optical measurement. Cao et al. [8] showed the
ammonia-sensing behavior of a polyaniline blend film with
fast response and good reproducibility.
In the present investigation we came across the effect
of acid on the synthesis of polyaniline. Here we present
some results of investigations on polyaniline synthesis
in the medium of different concentrations of acid and
sensing characteristics of polyaniline to ammonia. These
results prompted us to develop an ammonia sensor. The
principal feature of PANI as ammonia sensor material lies
in its tendency to be protonated by coordination of its
imine nitrogen and easy release of protons in an ammonia
environment.
264
2. Experimental
2.1. Materials
Reagent grade aniline (Merck, India) was distilled prior to
use, and reagent grade ammonium persulphate (NH)4 S2 O8
(Merck, India) was used without further purification.
2.2. Synthesis of Aniline Hydrochloride
Aniline hydrochloride was synthesized by treating 2 mL
of aniline with 3 mL of concentrated HCl in a beaker at
30
C. On cooling the mixture to 2
C using an ice bath, the
solid form of aniline hydrochloride was separated, which
was filtered using a buchner funnel fitted with a water
aspirator. Then the solid polymer was washed with diethyl
ether (approximately 100 mL) to remove aniline.
2.3. Synthesis of Polyaniline
Polyaniline was synthesized by oxidation polymerization
of aniline hydrochloride using ammonium persulfate as
an oxidant. The oxidation of aniline hydrochloride with
ammonium persulfate was performed in an aqueous medium
using an oxidant-to-monomer ratio of 1.25.
Aniline hydrochloride [2.59 g (20 mmol)] was dissolved
in 50 mL distilled water. Ammonium persulfate [5.71 g
(25 mmol)] was dissolved in 50 mL distilled water. Then
both the solutions were mixed. Because the polymerization
of aniline is an exothermic reaction, temperature rises
with the progress of polymerization. After stirring for 1 h,
the solution was left to rest overnight. The precipitate
was filtered and washed with 1 M HCl followed by
further washing with deionized water and diethyl ether.
The obtained polyaniline emeraldine salt was subsequently
treated with 1 M NH4 OH to make it an emeraldine base,
which showed better solubility in an aprotic solvent.
Figure 1.—Gas-sensor set-up.
P. P. SENGUPTA ET AL.
This precipitate was washed with water and acetone and
dried under vacuum at 100
C for 6 h.
2.4. Film Casting
The emeraldine base was dissolved in N-methyl
pyrrolidone (NMP) to make a viscous solution. Using this
solution, the polyaniline undoped films were prepared by
solution casting on a glass plate and by spin casting on a
glass slide.
2.5. Doping
Polyaniline holds a special position among conducting
polymers since it shows high conductivity in doped form.
For protonic doping, the film was dipped in 1 M HCl
solution and kept for different time periods, e.g., from
6 to 48 h. The conductivity was measured for the doped
polyaniline films obtained at different doping levels. During
doping, protonation took place in the quinone di-imine unit
to different extents, depending on the dipping time.
2.6. Electrical Properties
The four-point probe method was used for the
determination of electrical conductivity of the polyaniline
film. This method was also followed for the study of sensor
characteristics of polyaniline.
According to the four-point probe method the resistivity
can be calculated using the relation

= 2SV /I
where S is the probe spacing (mm), which was kept
constant, I is the supplied current in mA, and the
corresponding voltage was measured in mV. Conductivity
can be computed using the relationship  = 1/
.
POLYANILINE AS A GAS-SENSOR 265

2.7. Gas-Sensor Study

The ammonia gas-sensing property of a polyaniline film
was studied using the gas-sensor set-up as shown in Fig. 1.
First, the polyaniline film specimen (1 cm × 1 cm) was
attached to a Bakelite sheet, and then four contacts were
made on the specimen by copper wires and silver paste
with 2 mm distance between the probes. Then, the whole
arrangement was placed inside the measuring cell and
closed airtight. Air was passed through the cell for some
time followed by passing ammonia gas mixed with air
in specific proportions. The constant current was passed
through the polyaniline film by a constant current source,
and a multimeter measured the voltage at an interval of
30 s. Then the gas flow was stopped. After cut-off of the
ammonia gas flow, the resistivity fell and then remained
constant. Again the gas was passed, and the whole process Figure 3.—UV-visible spectrum of undoped polyaniline.
was repeated. The measurements were taken at room
temperature 20 ± 5
C.
3.2. UV-Visible Spectroscopy
3. Results and discussion
The conjugated polymers are often highly colored
3.1. Polyaniline Synthesis because their  −  ∗ energy gap falls within the visible
Although there are reports on the synthesis of polyaniline region. Those wavelengths, which are not absorbed, are
at low temperature, no report is available on the effect transmitted, resulting in the observed color. Typically,
of acid concentration on polyaniline synthesis. We have the emeraldine base of polyaniline exhibits absorbance at
observed that the polymerization of aniline is exothermic. 740 nm. This is attributed to the absorption due to excitation
The extent of exothermicity is dependent on the acidity of of the quinoid structure. Upon doping with HCl, the quinoid
the polymerization medium. The effect of concentration of absorption disappears and a new absorption occurs at
HCl on the polymerization temperature is shown in Fig. 2. It 980 nm due to the polaron structure of the polyaniline
is seen from Fig. 2 that maximum temperature was observed emeraldine salt [9]. The UV-VIS spectra of both doped and
with 3 M HCl. This indicates that the presence of acid at
undoped polyanilines are shown in Figs. 3–4.
some optimum concentration in the polymerization medium
has a definite role. Although we have not come across any
report on the role of acid during polymerization of aniline, 3.3. FTIR Analysis
our observation indicates that there might be a stability From the FTIR spectrum of polyaniline (EB) it is seen
factor for the radical cation [4] formed from aniline oxidant that quinoid and benzenoid ring stretching bands are present
in the presence of acid. A further in-depth investigation is at 1570 and 1484 cm−1 . The relative lower frequency of
underway and will appear in future communications. quinoid and benzenoid ring stretching is due to the salt
formation with HCl [10]. The peak at 1334 cm−1 is assigned
to C–N stretching of secondary aromatic amine, and the

Figure 2.—The effect of polymerization medium at different acid

concentrations 0 M to 7 M with the polymerization temperature. Figure 4.—UV-visible spectrum of doped polyaniline.
266
Figure 5.—FTIR spectrum of polyaniline base.
peak at 1299 cm−1 is assigned to C–N stretching of tertiary
aromatic amine in the quinone di-imine unit
A band at 3500 cm−1 is assigned to N–H stretching of
aromatic amine and another band at 2925 cm−1 is assigned
to aromatic C–H stretching. The peak at 801 cm−1 is due
to an aromatic C–H plane bending. Specific bands from
the FTIR spectrum are shown in Fig. 5. The corresponding
spectrum of polyaniline emeraldine salt is given in Fig. 6.
Figure 6.—FTIR spectrum of polyaniline salt.
P. P. SENGUPTA ET AL.
Figure 7.—XRD pattern of polyaniline base and salt.
3.4. X-Ray Diffraction (XRD) Analysis
The XRD of polyaniline film prepared from saturated
NMP solution was done with a Phillips PW-1710 X-ray
diffractometer using Cu K ( = 1542 A
). X-ray
diffraction patterns of polyaniline base and salt are shown
in Fig. 7. The polyaniline base shows a broad maximum for
the diffraction angle 2 ≈ 193
[11], while the salt exhibits
diffraction peaks at 2 ≈ 207
and 252
[12]. By simple
calculations, the crystallinity of polyaniline base and salt
were found to be about 22% and 48%, respectively. The
peaks indicate that polyaniline is a semicrystalline polymer.
Its intrinsic crystallinity is due to the presence of a polar
nitrogen atom in the main backbone chain, while in the
salt the presence of polarons or charge defects enhances its
crystallinity [12].
3.5. DC Conductivity Measurements
Aqueous HCl solution was used to dope the polyaniline
film. Doping of polyaniline means the incorporation
of polarons by protonation of the nitrogen atom in a
quinone diimine unit [12]. These polarons contribute to the
conductivity of the polymer film.
3.5.1. Influence of extent of doping on conductivity. A
1-M HCl solution was used to dope the polyaniline film.
The polyaniline film was kept immersed in 1 M HCl for
different time periods in order to obtain different doping.
The conductivities of the polyaniline films shown in Table 1
increased with increase of doping level. The result shows
that with the increase of time of doping, the conductivity
increases, and after a certain time it reaches maximum value.
Hence in solution doping, the extent of doping is diffusion
controlled, which indicates that the saturation of polymer
with dopant needs a specific time.
3.5.2. Influence of reaction condition on conductivity.
Polymerizations were done at various conditions, i.e.,
increasing the concentration of acid in the polymerization
medium. The acid concentration referred to here is the
POLYANILINE AS A GAS-SENSOR 267

Table 1.—Conductivity vs. extent of doping of the polyaniline film. Table 3.—Variation of conductivity of polyaniline films after doping for 10 h
by immersing in HCl of different concentrations.
Doping condition Doping Resistivity Conductivity
(concentration of acid, M) time (h) (ohm.cm) (s.cm−1 ) HCl concentration (M) Resistivity (ohm.cm) Conductivity (s.cm−1 )

1.0 10 26886 0.03719 1.0 26886 00372

1.0 13 26040 0.03840 2.0 18144 00551
1.0 18 23657 0.04337 3.0 17790 00562
1.0 24 18603 0.05375 4.0 11086 00902
1.0 36 13613 0.07345 5.0 9621 01039
1.0 48 8468 0.11808 6.0 7798 01282
7.0 4215 02372

progressive change in the concentration of acid (HCl) in the

overall reaction mixture. The salt formed from the reaction
is converted to a base and then the films were prepared
by dissolving them in NMP and casting using a petri dish.
The DC conductivity of these films was measured, and the
results are shown in Table 2. The results in Table 2 show
that the conductivity of the polyaniline films increases to
a maximum value and then decreases beyond 3 M HCl.
The reason for this change in conductivity is increased
crystalline disorder resulting from the bipolaron structure
with high acid concentration (doping composition) [12]. It
may also be due to amine protonation, which will cause
reduced crystallinity and hence conductivity. However,
we consider here similarity of the structural features of
the salt formed directly from reactions at different acid
concentrations and that by post-reaction doping of the same
concentration. The basis of this assumption is a memory
effect, where the base form returns to the salt structure while
doped at the same acid concentration [12].
3.5.3. Influence of concentration of dopant. The
electrical conductivity of polyaniline films was measured
after doping with different concentrations of HCl at a fixed
time (Table 3). The conductivity of the polyaniline films
increases with increasing dopant concentration, indicating
incomplete conversion to salt.
3.5.5. Temperature dependence on conductivity. The
conductivity of the polyaniline film is dependent on
temperature, which can be observed from the temperature-
conductivity graph (Fig. 9). On increasing the temperature,
the conductivity increases. Thus, it shows that the
conduction is purely electronic, where the conductivity is
directly proportional to the temperature. However, due to
loss of protonating acid, some deviation in the linearity of
the curve is found at higher temperature.
3.6. Gas-Sensor Characteristics
In this investigation we have studied ammonia gas sensing
of a polyaniline film. In order to evaluate the ammonia
gas-sensing characteristics of polyaniline we followed the
four-probe technique of resistivity measurement, where
four electrical contacts were made on the polyaniline film
by copper wire and silver paste. The electrically wired
polyaniline film was enclosed in a gas chamber as per the
diagram in Fig. 1. Subsequently, the change in resistivity
of the film was measured by passing ammonia gas through
the glass chamber at a fixed flow rate, and the results
are reported in terms of the change in resistivity of the
polymer film vs. the time of the gas exposed at a fixed
rate. In order to get the recovery time of the polyaniline
gas-sensor, the gas flow was stopped after it reached the

3.5.4. I-V characteristics of polyaniline films. The I-V

characteristic of the polyaniline film was evaluated by
measuring the voltage with varying current at room
temperature. The voltage was measured with varying current
at room temperature in order to see whether the polyaniline
possesses the ohmic contact or rectifying contacts. A linear
relationship of the I-V characteristic is shown in Fig. 8.
From the results it is observed that the polyaniline has an
ohmic behavior.

Table 2.—Influence of acidity of the polymerization medium on the

conductivity of the polyaniline film.

Concentration of acid (HCl) Resistivity of the

in the polymerization post-reaction doped films Conductivity
medium (M) (ohm.cm) (s.cm−1 )

Aqueous solution 13970 00716

1.0 8468 01181
3.0 7936 01260
5.0 15552 00643
7.0 22183 00452 Figure 8.—I-V characteristic of polyaniline film.
268 P. P. SENGUPTA ET AL.

Figure 9.—Change of conductivity of polyaniline with temperature.

saturation level (indicated by constant resistivity), followed Figure 10.—Resistivity vs. time for 5% NH3 in air.
by 5 min purging with air. The sensitivity of the sensor may
be defined as the ratio of the change of resistivity due to
exposure to the test gas to the resistivity of the sample in to set in, increasing the response and recovery times. Here
the air. we have explored the ammonia gas-sensing curves of PANI
at two different concentrations of ammonia solution, 5%

Gas −
Air and 10%. The graphs (Figs. 10–13) show that the resistivity
S=

Air of the polyaniline increases in the presence of ammonia and
after a few minutes becomes saturated. When the ammonia
An ammonia-air mixture was taken from the headspace of gas was cut off, the sensitivity decreased steadily to a
a bottle containing ammonia solution [13]. The ammonia minimum value, but a drift from its original value was
concentration in the mixture was estimated by trapping a observed.
known volume in ice-cold dilute hydrochloric acid solution
that was titrated with standard sodium hydroxide before and Proposed Sensing Mechanism
after ammonia trapping. The estimated ppm of ammonia In the ammonia environment the resistivity of
at different concentrations of ammonia solution along with the polyaniline film increases substantially. When the
their response and recovery times with doped PANI films
are shown in Table 4. The increase of concentration
enhances the rate of diffusion of ammonia molecules
towards and into the polymer thin film. The number of
molecules that achieve contact with the sensing sites on
the film in a given time increases, and therefore the
response time decreases. Increasing concentrations lead to
increased chemisorbed ammonia, which in turn enhances the
desorption rates and sensing site renewal. However, at very
high concentrations, increased competition for the sensing
sites and some amount of irreversibility in desorption appear

Table 4.—Response and recovery times of PANI exposed to different

concentrations of ammonia.

Conc. of Conc. of NH3 Response Recovery

NH3 (%) (ppm) time (s) time (s)

1 100 480 420

3 250 450 390
5 400 360 360
7 550 330 390
10 750 480 420 Figure 11.—Sensitivity vs. time of 5% NH3 in air.
POLYANILINE AS A GAS-SENSOR
Figure 12.—Resistivity vs. time for 10% NH3 in air.
polyaniline sensor is exposed to ammonia gas, the resistivity
of the film increases. The nitrogen atom of the ammonia
molecule is responsible for coordinating with the dopant
proton enabling its sensing characteristics. The nitrogen-free
doublet of ammonia molecules can establish a coordinate
bonding with the free atomic orbital of the dopant proton
[14]. This reaction leads to the deprotonation of polyaniline
nitrogen atoms, favoring the disappearance of charge
carriers and an increase in electrical resistance. When
polyaniline interacts with ammonia, the following reversible
reaction occurs.
PANIH+ + NH3 ↔ PANI + NH4 +
In the presence of ammonia, this reaction goes
predominantly towards the right, as NH3 molecules take
Figure 13.—Sensitivity vs. time of 10% NH3 in air.
269
Scheme 1.—Sensing mechanism of polyaniline film.
up protons from the polyaniline, thus forming energetically
more favorable NH4 + . In reality, in this case we are dealing
with chemical bonding [15]. This follows from the fact
that the process of ammonium ion (NH4 + ) formation is
accompanied by an energy gain because it has a more stable
tetrahedral configuration. On the other hand, the reverse
process (gaining protons by PANI) is also energetically
favorable. Its nitrogen atoms have sp2 hybridized electron
orbitals, so formation of a third -bond with a hydrogen
atom is accompanied by a lowering of the total energy of
the polymer chain. The detailed mechanism is shown in
Scheme 1.
Thus, when ammonia interacts with polyaniline, two
competing processes of proton gain (by ammonia and by
PANI) occur. Since the heat of ammonia adsorption onto
polyaniline is low, the probabilities of the two processes
are more or less the same. The result is that ammonia
gets adsorbed onto polyaniline, which is in essence a
chemisorption process. This ultimately supports functioning
of the proposed device as a sensor.
4. Conclusion
Polyaniline was synthesized, and characterized to produce
freestanding films for ammonia gas-sensing application.
Reaction condition, doping time, and level of doping
were varied, and each was found to affect the overall
conductivity. The emeraldine salt (ES) responded fairly
well to investigation of its ammonia gas-sensing properties.
Results of this investigation have shown the potential of
polyaniline as a gas-sensing material.
Acknowledgment
We gratefully acknowledge the University Grants
Commission, Government of India for providing fellowship
to one of the authors, Partha Pratim Sengupta.
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