Simultaneous determination of chromium(III) and chromium(VI) in aqueous solutions by ion chromatography and chemiluminescence detection.

A method for the simultaneous determination of chromium(iii) and chromium(vi) in a flow system based on chemiluminescence was developed. A Dionex cation-exchange guard column was used to separate chromium(iii) from chromium(vi), and chromium(vi) was reduced by potassium sulfite, whereupon both species were detected by use of the luminol-hydrogen peroxide chemiluminescence system. Linear calibration for both species was established over the concentration range 1-1000 micrograms l-1. The precision at the 20 micrograms l-1 level was 3.5% for chromium(iii) and 3.3% for chromium(vi), respectively. The detection limit was 0.5 micrograms l-1 for both species. Data were in agreement with Zeeman-effect background corrected atomic absorption spectrometry measurements.     

Quantitative analysis of tricyclic antidepressants in serum from psychiatric patients

A method for the quantitative analysis of tricyclic antidepressants in the serum of psychiatric patients is described. The method can be used for determining amitriptyline, nortriptyline, imipramine, demethyllimipramine, clomipramine, demethylclomipramine, trimipramine and protriptyline. The method consists in a series of extraction steps followed by gas chromatography with flame-ionization detector. The drugs are determined in their native state. The internal standard method is used for the quantitation.     

Studies on the conversions of diols and cyclic ethers—49: Stereochemistry of cyclodehydration of 1,4-diols on the action of brönsted and lewis acids: a comprehensive study

The stereochemistry of the cyclodehydration of (±)- and meso-2,5-hexanediol on the action of various dehydrating agents was investigated. The earlier assumed and confirmed intramolecular S_N2 mechanism for acid-catalysed ring-closure was found to hold in most cases. Various extents of racemisation can be observed on the action of certain Lewis acids, and the solvents concentrated H₂SO₄ and HMPT (hexamethyl phosporic acid triamide) under previously unexamined reaction conditions.     

Microemulsion photopolymerization of methacrylates stabilized with sodium dodecyl sulfate and poly(N-acetylethylenimine) macromonomers

Methyl methacrylate and butyl methacrylate were polymerized in oil-in-water microemulsions that were stabilized by sodium dodecyl sulphate (SDS). A poly(N-acetylethylenimine) (PNAEI) macromer was also included in the recipe, as a cosurfactant and a comonomer. Polymerizations were initiated by UV-irradiation. The average diameters of latex particles, obtained by STM, were in the range of 17-200 nm. The experimental data evidenced that the particle size was mainly dependent on the SDS/PNAEI ratio. Polymerization yields were around 75-85%. The synthesized copolymers have viscosity average molecular weights in the range of 2.1-2.4×10⁶ and glass transition temperatures of 38.0-43.5°C, lower than those obtained without using PNAEI. The investigation by means of FTIR and 1H-NMR techniques revealed that PNAEI was incorporated into the nanoparticles.     

Highly accurate gas chromatographic analysis of reference gases for use in vehicle emission measurements

 A highly accurate gas chromatographic analytical method has been developed for the determination of the composition of gas mixtures. It was tested using a reference gas as an example consisting of 3.5% of CO, 14% of CO₂, 0.2% of propane and residual N₂ intended for the use in vehicle emission measurements. The method is based on comparison measurements with samples of a calibration gas, whose composition is iteratively adapted to that of the sample investigated using a gravimetric gas mixing method. For the gas chromatographic measurement, a molecular sieve column and a polymer column are used in parallel and in isothermal operation. All gas components can be determined by a single gas chromatographic measurement, and the relative uncertainty of measurement achievable is ?0.4%. Received: 6 March 1996/Revised: 30 May 1996/Accepted: 6 June 1996     

Application of Discrete Wavelet Transform in the Analysis of Nonlinear Chemical System

Oscillations of species concentration are phenomena accompanying several types of electrochemical and purely chemical processes. Importance of analyzing of such processes results from both scientific and practical reasons. In the paper the authors deal with investigation of time dependent spectra of various stages of Belousov-Zhabotinsky type chemical oscillations. As the analytical tool the discrete wavelet transform is proposed.     

Experimental observation of light-induced solitary waves of analyte bands in capillary electrophoresis.

The phenomenon of electrophoresis in free solution has been studied theoretically down to the molecular level for decades. In addition, intermolecular photo-induced proton transfer reactions, which occur in a wide class of molecules (phenols and aminoarenes) as well as proteins (green fluorescent protein), were also studied extensively. However, the study of the effect of light-induced electrophoretic mobility changes of the analytes in electrophoresis was begun only recently. In the present work, capillary zone electrophoresis was chosen as the environment to measure the magnitude of these electrophoretic mobility shifts induced by light. Background electrolytes (running electrolytes) with high refractive indices were developed, allowing the capillary to work like an optical fiber. The experimental conditions for obtaining stable coupling and guided laser light along the liquid core are discussed. Experimental evidence of band compression is observed, leading to a solitary wave behavior of the analyte band (2-naphthol). These solitary waves result from competition between thermal diffusion (dispersion mechanism) and a nonlinear (band compression) effect due to the combined electrophoresis phenomenon and absorption of guided light by the molecules of the band (which are subjected to a "reversible intermolecular proton transfer reaction" as one of their decay routes). The possibilities of applying this effect to different methods and techniques are also discussed.     

Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions

The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects. The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore, the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon, and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor, a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene.