Kinetic studies for the esterification of acetic acid with epichlorohydrin over an anion exchange resin catalyst

The kinetics of the esterification reaction between acetic acid and epichlorohydrin catalysed by Purolite A-520E strong basic anion exchange resin was studied. The effects of certain parameters such as stirring speed, particle diameter, temperature, catalyst amount and molar ratio between reactants were experimentally determined. It was found that the overall reaction rate is intrinsically kinetically controlled. The partial orders of reaction with respect to catalyst, acetic acid and epichlorohydrin were determined. A reaction mechanism is proposed. Based on chromatographic data and taking into account the partial orders of reaction, a more detailed kinetic model is suggested.      

Two-dimensional infrared correlation spectroscopic studies of polymer blends--specific interactions in polyethylene adipate/cholesteryl palmitate blends

Generalized two-dimensional infrared (2D IR) correlation spectroscopy has been applied to the study of the conformational changes and specific interactions in blends of polyethylene adipate (PEA) and cholesteryl palmitate (CP). IR spectra of CP, PEA, and their blends of different compositions: 10/90, 16/84, 32/68, 64/36, and 80/20 have been recorded. In order to apply 2D IR correlation analysis, the samples are divided into two sets: set A with high PEA content 0/100, 10/90, 16/84, 32/68 CP/PEA and set B with high CP content 64/36, 80/20 and 100/0 CP/PEA. The 2D IR synchronous correlation analysis separates the bands of PEA from those of CP. The cross-peaks in 2D IR asynchronous correlation analysis are indicative of the specific interaction or the conformational change in the blends. The bands of CO, OH and C-O vibrations of PEA, and CH(3) and C-O vibrations of CP that are very sensitive to the intermolecular hydrogen bonding effect and consequently the partial miscibility of components, have been assigned by 2D correlation analysis.     

DSC investigation of nanocrystalline TiO<Subscript>2</Subscript> powder

The aim of the article is to investigate the influence of particle size on titanium dioxide phase transformations. Nanocrystalline titanium dioxide powder was obtained through a hydrothermal procedure in an aqueous media at high pressure (in the range 25–100 atm) and low temperature (≤200 °C). The as-prepared samples were characterized with respect to their composition by ICP (inductive coupled plasma), structure and morphology by XRD (X-ray diffraction), and TEM (transmission electron microscopy), thermal behavior by TG (thermogravimetry) coupled with DSC (differential scanning calorimetry). Thermal behavior of nanostructured TiO₂ was compared with three commercial TiO₂ samples. The sequence of brookite–anatase–rutile phase transformation in TiO₂ samples was investigated. The heat capacity of anatase and rutile in a large temperature range are reported.     

Polyazomethine with m-tolylazo side groups: thermal,dielectric and conductive behaviour

Using solution polycondensation, a new polyazomethine with m-tolylazo side groups (PAz) exhibiting thermotropic liquid crystalline phase was synthesised and its chemical structure was characterised with generally accepted methods. Its phase transition temperatures were detected with both polarising optical microscopy and differential scanning calorimetry. Using dielectric spectroscopy method, both real and imaginary parts of the permittivity were investigated in wide regions of temperature (from ?100°C to 170°C) and frequency (from 1 Hz to 1 MHz). Analysis of frequency dependent permittivity allowed finding three relaxations (α, β₁ and β₂) in PAz. β-relaxations were described with the Arrhenius equation, whereas α-relaxation was described with the Vogel–Fulcher–Tammann equation. The alternating current conductivity (ACC) of PAz was studied in the same regions of temperature and frequency. The frequency dependent ACC was described with an exponent power equation. Presentation of ACC as a function of inverse temperature allowed us to describe ACC with the Arrhenius equation.     

Solution polymerization of vinyl monomers in the presence of poly(N-acetyliminoethylene) macroazoinitiators

New block copolymers with poly(N-acetyliminoethylene) and vinyl sequences were obtained by a two-step synthetic approach. In the first stage macroinitiators of poly(N-acetyliminoethylene) type, with azo groups inserted in the main chain, were prepared. They were latter used in the radical polymerization of some vinyl monomers [styrene, methacrylic acid, methyl methacrylate, butyl methacrylate, β-(N-carbazolyl)ethyl acrylate, β-(methacryloyfoxy)ethyl 3,5-dinitrobenzoate]. The resulting block copolymers were characterized by spectral methods, elemental analysis, gel permeation chromatography, and electron microscopy. The kinetic study of the thermal and photochemical decomposition of the synthesized macroazoinitiators, as well as the polymerization data, suggest a dependence of their initiating efficiency on the length of the poly(N-acetyliminoethylene) segments. © 1994 John Wiley & Sons, Inc.     

Anion Recognition by Uranyl–Salophen Derivatives as Probed by Infrared Multiple Photon Dissociation Spectroscopy and Ab Initio Modeling

The vibrational features and molecular structures of complexes formed by a series of uranyl–salophen receptors with simple anions, such as Cl^?, H^?, and HCOO^?, have been investigated in the gas phase. Spectra of the anionic complexes were studied in the $\tilde \nu $ =800–1800 cm^?1 range by mass‐selective infrared multiple photon dissociation (IRMPD) spectroscopy with a continuously tunable free‐electron laser. The gas‐phase decarboxylation of the formate adducts produces uranyl–salophen monohydride anions, which have been characterized for the first time and reveal a strong U?H bond, the nature of which has been elucidated theoretically. The spectra are in excellent agreement with the results obtained from high‐quality ab initio calculations, which provided the structure and binding features of the anion–receptor complexes.     

Temperature effect over structure and photochemical properties of nanostructured SnO<Subscript>2</Subscript> powders

We successfully synthesized tin dioxide nanoparticles with polyhedral morphology via an ethylene glycol assisted sol-gel approach. The structural characteristics of three tin dioxide samples were investigated after being thermally treated at 400°C, 600°C and 800°C. X-ray diffraction (XRD) patterns clearly show the formation of single phase tin dioxide nanoparticles, with crystallite size of 6–20 nm, in good correlation with Fourier transform infrared (FTIR) spectra. Transmission electron microscopy (TEM) analysis confirms the formation of 6nm polyhedral nanoparticles for the 400°C sample. Ultraviolet-visible (UV-Vis) and photoluminescence (PL) spectra suggest a high concentration of oxygen vacancies. The oxygen vacancy concentration increases with temperature, due to the combined action of the formation of V_O and the energetic O compensation. X-ray photoelectron spectroscopy (XPS) analysis also confirms the formation of single phase tin dioxide and the presence of oxygen vacancies in good agreement with UV-VIS and PL data.

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Synthesis and characterization of ZnO nanostructures obtained in mixtures of ionic liquids with organic solvents

ZnO nanoparticles were synthesized in mixtures of ionic liquids based on imidazolium cation with organic solvents (dimethyl sulfoxide and ethylene glycol) by a simple, one-step solution route at low temperature. The effect of these mixtures on the morphology, size and properties of as obtained ZnO nanopowders was investigated. The obtained nanopowders have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), UV-Vis absorption spectroscopy (UV-Vis) and photoluminescence (PL). The effect of the ionic liquid mixture on the photocatalytic degradation of methylene blue has been analysed. The XRD studies confirmed the hexagonal wurtzite structure of the obtained ZnO powder. The UV-Vis absorption spectra present the typical shape for ZnO, with a broad band situated in the UV region, with the maximum around 360 nm. The calculated band-gap energy is in interval 3.25–3.28 eV. The synthesized ZnO nanopowders have high photocatalytic activity against methylene blue, the best results being obtained when 1-ethyl-3-methylimidazolium tetrafluoroborate was used as the solvent.

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