Thermogravimetric analysis of polycarbonates and polythiocarbonates from diphenols with methyl groups

The thermal behaviour of polycarbonates and polythiocarbonates derived from biphenols with methyl groups in the aromatic rings was studied by dynamic thermogravimetry. The thermal degradation temperatures (TDT) were determined, showing that polythiocarbonates are more stable than the corresponding polycarbonates. The kinetic parameters of the thermal decomposition were determined by using the Arrhenius relationship, and showed two steps for the degradation of the polycarbonates, the first being a zero-order process and the second having first-order kinetics; the steps were associated with two different reaction mechanisms. Polythiocarbonates degraded according to first-order kinetics.     

Thermosonimetry of the phase II/III transition of hexachloroethane

A thermosonimetric study has shown that the Phase II/III polymorphic transition of hexachloroethane emits acoustic signals. This solid-solid phase transition is known to occur by a nucleation-growth process during which a nucleus of the new phase, once formed, grows at the expense of the mother phase to form a complete crystal without fracture. Acoustic emissions from a conditioned multi-crystal sample have been used to study the transition. Acoustic activity correlated well with dilatometric measurements. Frequency analysis on waveforms of many hundreds of individual acoustic emissions revealed marked differences between individual signals. Principal-components analysis on 24 signal features revealed a single dispersed cluster with a highly non-uniform distribution of signals. These experiments provided highly reproducible average power spectra. Time-resolved acoustic power spectra were also generated. These additional types of information cannot be obtained by other techniques.     

Negative hyperconjugation in methyl and silyl anions and its effect on the acidities of CH(4-n)Fn CH(4-n)C1n SiH(4-n)Fn and SiH(4-n)Cln

Group separation reactions calculated using an ab intio molecular orbital calculation at the MP4/6-31 + + G(d,p) level of theory, show the negative hyperconjugation between fluorine atoms to be larger in methanes than in silanes. Stabilisation due to negative hyperconjugation is larger in anions than in identically substituted neutral molecules, e.g. 43.1 kcal mol⁻¹ in CF₃⁻ compared with 26.7 kcal mol⁻¹ in CHF₃. By contrast, in chloro-substituted methanes, silanes, methyl anions and silyl anions, group separation energies are approximately zero, indicating no appreciable negative hyperconjugation. An -chloro substituent is more effective than an -fluoro one at delocalising the negative charge of an anion and, as a consequence, the chloromethanes and chlorosilanes are all more acidic than the identically substitued fluoromethanes and fluorosilanes. For chloro-substituted molecules the acidity is linearly dependent on the number of chlorine atoms; for fluoro-substituted molecules stabilisation by negative hyperconjugation results in each additional fluorine atom increasing the acidity by larger increments.     

Effect of the medium on the decomposition rate of di-t-butyl trioxide

Using the chemiluminescence method, the effect of the medium on the overall rate constant of the thermal decomposition of di-tert-butyl trioxide has been studied. In all solvents investigated the decomposition occurs in accordance with a first order rate law. The effect of solvent on the rate constant (0°C) is analyzed.     

Ab initio Calculation of the Electronic Structure and Equilibrium Geometry of Cortisol and Its Derivatives

The molecular geometries of a series of steroid hormones including cortisol, 9-fluorocortisol, 6-fluorocortisol, and 9-chlorocortisol were optimized by 3-21G and 6-31G* ab initio calculations. The results of calculations on both levels are well consistent with each other and with the experiment. The conformational changes and electron density redistribution occurring in going from cortisol to its 6- and 9-halo derivatives were discussed. A conclusion was made that the O and F atoms can participate in hydrogen bonding with the corresponding structural groups of glucocorticoid receptors.     

Structure and Electrochemical Properties of Cation-Exchange Membranes Based on Partially Imidized Polyamidoacid

The transport of water molecules and the distribution of functional groups in polyamidoacid carboxyl-containing cation-exchange membranes based on pyromellitic acid are studied by NMR and ESR techniques. It is shown that the self-diffusion coefficients of water differ in the gel and intergel regions. Structural parameters of conducting channels in the gel regions are determined. In electrodialysis of one-component and binary solutions, polyamidoacid membranes possess higher transport numbers and separation coefficients of counterions that are less hydrated in solution.     

Abstractive chemisorption of O2 on Al(111)

We present experimental evidence that abstraction is a common mechanism (approximately 50%) in the dissociative chemisorption of oxygen on Al(111) at a translational energy of 0.5 eV. As a result of this mechanism, individual isolated O-atoms are observed in scanning tunneling microscopy (STM). At this translational energy ordinary dissociative chemisorption processes also occur, resulting in pairs of adatoms. The ejected O-atoms originating from the abstraction reaction are detected in the gas phase using laser spectrometry. Together, these observations provide compelling evidence for the abstraction mechanism.     

Barrier-discharge plasma treatment of surface water to remove organic compounds

Barrier-discharge plasma treatment of real surface water to remove organic pollutants was studied. Plasma treatment decreases the potential toxicity of snowmelt and rainfall runoff containing ammonium and chloride ions, oil products, phenols, and carboxylic acids (as recalculated for CH₃COOH).     

Free-electron attachment to coronene and corannulene in the gas phase

Electron attachment to the polyaromatic hydrocarbons coronene and corannulene is studied in the electron energy range of about 0-14 eV using a high-resolution crossed electron-neutral beam setup. The major anions observed are the parent anions peaking at about 0 eV with cross sections of 3.8 x 10(-20) and 1 x 10(-19) m(2), respectively. The only fragment anions formed in coronene and corannulene are the dehydrogenated coronene and corannulene anions. Other anions observed in the negative mass spectra at about 0 eV can be ascribed to impurities of the sample. High-level quantum-mechanical studies are carried out for the determination of electron affinities, hydrogen binding energies, and structures of both molecules. The behavior of coronene and corannulene upon electron attachment is compared with that of other polyaromatic hydrocarbons studied previously.     

Selective liquid adsorption and structural properties of montmorillonite and its hexadecylpyridinium derivatives

Summary An X-ray diffraction method was used to study the structures of montmorillonites, the surfaces of which were covered to a systematically increasing extent with hexadecylpyridinium (HDP) cations. It was found that, depending on the degree of cover of the surface, the HDP cations form a mono- or bimolecular layer in the interlayer space. A detailed investigation was made of the selective sorption of binary mixtures on montmorillonite and on HDP-montmorillonites with different surface coverages. The adsorption excess isotherms were determined, as were the adsorption capacities from analysis of the isotherms, and also the equivalent specific surface areas.It was established that from benzene-n-heptane mixtures the benzene is adsorbed only on the external surface of montmorillonite, while in the case of organocomplexes it causes moderate disaggregation.From benzene, alcohols with different numbers of carbon atoms are also preferentially adsorbed on the internal surfaces of montmorillonite; with the rise in the number of carbon atoms, the extent of interlamellar adsorption decreases. In the case of HDP-montmorillonites in methanol-benzene mixtures, the adsorption capacity exhibits a monotonous increase with the degree of organopbility in the range under consideration. In the event of optimum organophility the disaggregation of the organocomplex is complete, and the equivalent specific surface area is 764-778 m² · g^–1. The swelling of the organocomplex, which can be characterized by X-ray diffraction measurement, is in close correlation with the interlamellar liquid adsorption. The results show modification of the surface of montmorillonite with HDP cations fundamentally determines the nature and extent of the selective liquid adsorption.

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Zusammenfassung Die Struktur von mit Hexadecyl-pyridinium(HDP)-Kationen im systematisch gesteigerten Maße bedeckten Montmorilloniten wurde mit der Röntgendiffraktions-Methode untersucht. Es wurde festgestellt, daß die HDP-Kationen, von der Bedeckung der Oberfläche abhängend, im Schichtzwischenraum eine mono- bzw. bimolekulare Schicht bilden. Die selektive Sorption binärer Gemische wurde an Montmorilloniten und an HDP-Montmorilloniten verschiedener Bedeckung eingehend untersucht. Es wurden die Adsorptionsisothermen von Flüssigkeitsgemischen und aus deren Analyse die Adsorptionskapazitäten und die äquivalenten spezifischen Oberflächen bestimmt.Es wurde festgestellt, daß aus Benzol-n-Heptan-Gemischen das Benzol nur an der äußeren Montmorillonite-Oberfläche adsorbiert wird, während es bei Organokomplexen eine mäßige Desaggregation verursacht. Die Adsorption von Alkoholen verschiedener Kohlenstoffzahl aus Benzol erscheint auch an inneren Montmorillonit-Oberflächen bevorzugt; mit zunehmender Kohlenstoffzahl nimmt das Ausmaß der interlamellaren Adsorption ab. Bei HDP-Montmorilloniten zeigt die Adsorptionskapazität aus Methanol-Benzol-Gemischen mit zunehmender Organophilität im untersuchten Gebiet eine monotone Steigerung. Im Falle optimaler Organophilität ist die Desaggregation vollständig, die äquivalente spezifische Oberfläche beträgt 764-778 m²/g. Die durch Röntgenn-diffraktionsmessung charakterisierbare Quellung des Organokomplexes steht mit der interlamellaren Flüssig-keitsadsorption in engern Zusammenhang. Unsere Ergebnisse zeigen, daß Charakter und Ausmaß der selektiven Flüssigkeitsadsorption durch die Modifizierung der Montmorillonit-Oberfläche mit HDP-Kationen grundlegend verändert wird.

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With 14 figures and 4 tables