Characterization of the products of aniline peroxydisulfate oligo/polymerization in media with different pH by resonance Raman spectroscopy at 413.1 and 1064 nm excitation wavelengths

The pH-structure correlation of the products of aniline peroxydisulfate reaction was mainly investigated by resonance Raman spectroscopy. The reactions of aniline and ammonium peroxydisulfate were carried out in aqueous solutions of initial pH ranging from 4.9 to 13.2 and monomer/oxidant molar ratio of 4/1. For an initial pH of 4.9, the spectroscopic techniques showed that the emeraldine salt form of polyaniline (PANI-ES) is the main product, corroborating that the usual head-to-tail coupling mechanism is taking place. The resonance Raman spectra at 1064 nm exciting wavelength were useful to detect the emeraldine salt as a minor product for reactions at an initial pH of 5.3-11.5. The Raman spectra of the main product of the reaction at initial pH of 13.2 excited at 1064 and 413.1 nm showed new spectral features consistent with 1,4-Michael-type adducts of aniline monomers and 1,4-benzoquinone-monoimine unit. These compounds and their products of hydrolysis/oxidation are the predominant species for the reaction media of initial pH from 5.3 to 13.2. In order to get PANI with different nanoscale morphologies, a pH value of more than 0 or 1 was used in the aniline polymerization. The spectroscopic data obtained in this work reveal that head-to-tail coupling does not occur when aniline reacts at media pH higher than about 5. It is suggested that chemical structures of the products of aniline oxidation by an unusual mechanism are the driving force for the development of assorted morphologies. Copyright (C) 2011 John Wiley & Sons, Ltd.

Development of a spectrophotometric Sequential Injection Analysis (SIA) procedure for determination of ammonium: A Response Surface Methodology (RSM) approach

This paper describes the optimization and use of a Sequential Injection Analysis (SIA) procedure for ammonium determination in waters. Response Surface Methodology (RSM) was used as a tool for optimization of a procedure based on the modified Berthelot reaction. The SIA system was designed to (i) prepare the reaction media by injecting an air-segmented zone containing the reagents in a mixing chamber, (ii) to aspirate the mixture back to the holding coil after homogenization, (iii) drive it to a thermostated reaction coil, where the flow is stopped for a previously established time, and (iv) to pump the mixture toward the detector flow cell for the spectrophotometric measurements. Using a 100 mu mol L(-1) ammonium solution, the following factors were considered for optimization: reaction temperature (25 - 45 degrees C), reaction time (30 - 90 s), hypochlorite concentration (20 - 40 mmol L(-1)) nitroprusside concentration (10 - 40 mmol L(-1)) and salicylate concentration (0.1 - 0.3 mol L(-1)). The proposed system fed the statistical program with absorbance data for fast construction of response surface plots. After optimization of the method, figures of merit were evaluated, as well as the ammonium concentration in some water samples. No evidence of statistical difference was observed in the results obtained by the proposed method in comparison to those obtained by a reference method based on the phenol reaction. (C) 2010 Elsevier B.V. All rights reserved.