Polyaniline (PANI) has been prepared by the oxidation of aniline with ammonium peroxydisulfate in the 0-4 M phosphoric acid. The maximum conductivity of PANI, 15.5 S cm(-1), was found with PANI prepared in the presence of I M phosphoric acid. The mass loss after deprotonation with ammonium hydroxide revealed that relatively large amounts of phosphoric acid were associated with PANI if the polymerization had been carried out at higher acid concentration. This suggests the protonation of both the imine and amine nitrogens in PANI, the increased adsorption of phosphoric acid by PANI, or the presence of polyphosphate counter-ions. The increasing content of phosphoric acid is also reflected in the increase of sample density. FTIR spectra of ammonium salts collected after deprotonation proved that the counter-ions of the sulfate type, resulting from the decomposition of peroxydisulfate, always participated in the protonation of PANI. The proportion of sulfate to phosphate counter-ions was reduced as the concentration of phosphoric acid in the medium increased. Thin PANI films were produced in situ on glass surfaces immersed in the reaction mixture during the polymerization of aniline. Optical absorption has been used to assess their thickness, 70-140 nm, which was found to be virtually independent of the acid concentration. The film conductivity was comparable with the conductivity of the PANI powders produced at the same time. Colloidal dispersions were obtained when the reaction mixture contained poly (N-vinylpyrrolidone). The particle size, 200-260 nm, and polydispersity, determined by dynamic light scattering, were virtually independent of the concentration of phosphoric acid. The films produced on glass during the dispersion polymerization of aniline were thinner, 20-90 nm, compared with those grown in the precipitation polymerization. (c) 2005 Elsevier Ltd. All rights reserved.