1. Synthesis and properties of Polyaniline
by Awad Albalwi
Abstract
Polyaniline which is regarding kind of Inherently Conducting Polymers (ICPs), was prepared by
either chemical and electric­chemical polymerization in acidic medium. Such solvents were used
and compared the affecting on the conductivity between EB solution in DMF and m­cresol
solvents by using UV­ vis spectrum. UV­vis spectra and cyclic voltametry were used to generate
and analyze the spectrum for the polymer films
Introduction
In recent year, polyaniline (PANI) is considered one of the most widely used for the application in
electric devices. That is because PANI has a great electrical conductivity, high chemical stability and
easy synthesis that it can be able to control oxidation state and degree of protonation [1,2]. In addition,
the product of the polymerization (PANI) has been looking forward to develop the application in
different fields including sensors, charge storage systems and protection against corrosion [1]. PANI
can be used to undergo forming dielectric of emeraldine base (EB) with a significant film forming
solvent (N­methyl­2pyrrolidone (NMP) into conductive form of emeraldine salt (ES) by protonic acid
[2]. PANI­ES is due to be solubility with large number of organic solvent depending upon
functionalities of protonic acid such as camphorsulfonic acid (HCSA).

2.
The main properties of polyaniline such as crystallinity, conductivity, molecular weight and
electrochemical behavior rely on the processes and conditions of preparation [3].
​Inherently conducting polymers (ICPs) are conjugation of π­ electrons extending all over the length
of polymer backbone which they are prepared by chemical or electrochemical oxidation with large of
appropriate ​monomeric materials. ​The unique properties of ICPs might be included:
1­ Tuning the conductivity can possibly employed by adjusting the amount of dopant incorporated
within the polymer,
2­ Doping and undoping are reversible process.
3­ Both of the characteristics for the optical and electromagnetic absorption in the UV, visible and near
infrared are involved [4].
There are three of the most studied ICPs are defined below:
The formation of entirely organic conducting polymers depends upon the oxidation state of the
polymer. The process of that formation (oxidation or reduction ) which is called ‘doping”, causes
changing in the electronic structure in order to provide conducting electricity.
In this experiment, the polyaniline was prepared by potentiodynamic polymerization (cyclic

3. voltammetry). Moreover, the change of polyaniline were also examined and compared to their redox
and acid/base chemistry via using a sample of emeraldine base which was provided.
Experiment:
Preparation of stock polyaniline solution
Polyaniline stock solution was prepared by adding 4g of aniline & 20 ml of HCl into 200 mL
water in 1L beaker and then stirred for 10 min.
Potentiodynamic synthesis of polyaniline
The parameters of using cyclic voltammetry for 10 mL of the stock polyaniline solution were :
● Initial potential = final potential= ­0.2 v
● Lower potential limit= ­0.2v
● Upper potential limit= +0.9v
● Number of growth cycles = 10
● Scan rate = 100 m Vs​­1
● Current = 1 mA/ cm​2
Chemical and spectroscopic properties of emeraldine base:
For more details about the procedure refer back to the lab manual.
Result and discussion
Question 1:
From adding different solvent or changing PH of the solvent, the color of the EB solution was
reported as shown in Table 1 below:
Table1.​ the difference color to EB with different solvent.
Samples color
EB solution + DMF Dark blue Prepared
(EB+DMF)+ HCSA Light green Prepared

4. (EB+DMF)+ Hydrazine Blue light (clear) Prepared
(EB+DMF)+Ammonium persulfate Violet Prepared
EB+ m­cresol Blue Provided
(EB+ m­cresol) + HCSA Green Provided
Figure1. ​The UV­Vis spectrum of EB dissolve in DMF, the solution was dark blue and gives
wavelength in between 327­ 626 nm.
Figure2​. The low conductivity was confirmed while EB in DMF which added to HSCA

5. obtaining green light and three bands 354nm (​π­ π*), 410nm (polaron – π*) and 789nm (π­ polaron
band). The pollarons of each tetraneric unit are isolated from each other in order to the twist defect
between aromatic rings. Because of that the conductivity of the polymer has little energy.
Figure3. The spectrum showed that EB in DMF with adding hydrazine were given color exchange
where was from dark blue to light blue (clear) solution. Also, there was only one absorption occurred
by 342nm which due to (π­ π*) transition​.

6.
Figure4​. The spectrum illustrated EB in DMF with ammonium persulfate was converted from
dark blue to give violet color (form pernigraniline state). Moreover, there were two peaks
occurred by 323nm (​π ­ π*) and 592nm (π­ polaron band).
Question2.
Electrochemical polymerization of aniline was used containing a three electrode electrochemical
cell as shown below:
Figure​ .A three­ electrode electrochemical cell [3].

7.
The material and size of the working electrode (WE) which PANI film was grown depended on
using ITO coated glass electrode
Auxiliary electrodes (AE) which made from platinum or stainless steel, has large surface area
therefore they don’t have limit the passage of current.
Reference electrode (RE) used Ag/AgCl electrode in conjunction with NaCl salt bridge as a
reference in aqueous solution.
The procedure of electrochemical polymerization of polyaniline can be concluded by:
1. Radical cation of aniline was formed by oxidation on electrode surface.
2. Coupling of radicals is occurred ultimately between N­ and C­ on the cycle and then
subsequent elimination of two protons.
3. The dimmer will be formed by rearomatization step resulting in propagation of the chain.
4. Oxidation and Doping the polymer were occurred by adding acid (HA).
Question 3
Using m­cresol as a solvent, the polymer backbone has positive charge with negative counterions
that are sitting in the proximity of polymer chains. In case of removing counterions from the
polymer chain, the interaction of positive charges on the polymer backbone will head to extend
the polymer chain from a coillike conformation to an expanded coillike conformation.
Therefore, the existence of m­cresol will change the confirmation because the twists and defects
between aromatic rings are removed. On the other hand, with using DMF as a solvent, the
polymer chains have a coillike confirmation and the polarons of each tetrameric unit are isolated
and polaron ­ π* transition possibly occurred. Moreover, half­ filled ‘polarone band’ that formed by
interaction of separating polaron on the fully protonated for PANI emeradline salt therefore the polaron

8. band has a little dispersion energy.
Based on that, the interaction of m­cresol between the adjacent isolated polaron has increased and
stronger and that led to more scattered in energy. Hence, the observation peak 626 nm for EB in DMF
was corresponded to π­ polaron transitions disappear for EB in m­cresol and then replaced by a broad
free­ carrier tail associated with the intraband transitions among the half filled polaron band.
Conclusion:
In conclusion, it can been seen that the conductivity of polyaniline has mainly influenced by
using and changing the acidity with different electronic structures in different solvents. This kind
of changing can lead to attribute to the differences in geometric structure (conformation) for the
polymer chain of polyaniline. So, the conductivity of m­cresol was greater than DMF solvent
where they were used in this experiment.
Reference
1.Moraes, S. R.; Huerta­Vilca, D.; Motheo, A. J., Characteristics of polyaniline synthesized in
phosphate buffer solution. ​European Polymer Journal ​2004, ​40​ (9), 2033­2041.
2. Xia, Y., et.al., Camphorsulfonic Acid Fully Doped Polyaniline Emeraldine Salt: Conformations in
Different Solvents Studied by an UltravioletNisiblel Near­Infrared Spectroscopic Method, chem.
Mater, 1995, 7, 443­445.
3. pornputtkul, Y., Development of chiral conducting polymers for asymmetric electrosynthesis,
intelligent polymer research institute, 2005, 475
4. ​http://www.conductivepolymers.com/general.htm