Optical pH measurements with water dispersion of polyaniline nanoparticles and their redox sensitivity

A new method for optical pH and redox measurements with a commercially available water dispersion of polyaniline (PANI) nanoparticles (mean particle size, 46 nm) is presented. The pH measurements are based on the acid-base equilibrium of PANI and were carried out either by combining both the automated sequential injection analysis (SIA) and UV-visible spectrophotometric techniques or with a fiber-optic light guide. In the former case, the detection was done in continuous mode at lambda = 800 nm by using the SIA technique for transporting the sample to a flow-through cell, which was placed in the light path of the photometer. With the fiber-optic light guide, the detection was done in batch mode at lambda = 400 and 580 nm. In both methods, fresh pH reagent (PANI) solution was used in each measurement, thus overcoming the problem with hysteresis (memory effect), which is usually observed with PANI films. The PANI nanoparticles were characterized with UV-visible spectroscopy in pH buffer solutions between pH 2-12 and a protonation constant of logK(0.5H,L)(H(0.5)L) = 4.4 was calculated from these data. Fast pH measurements can be done between pH 6 and 10.5 depending on the measuring technique. It is possible to determine pH with an accuracy of 0.1 pH unit between pH 8 and 10.5 (RSD, 0.5-2%). Redox transitions typical for PANI films were also observed for water solutions of PANI nanoparticles in the presence of the hexacyanoferrate(II/III) and the iron(II/III) oxalate redox couples. The absorbance at lambda = 875 nm is linearly dependent on the logarithm of the concentration ratio (0.1-10) of the iron oxalate redox couple.