Untersuchung der thermischen Eigenschaften von Alkalibenzolsulfonaten

Zusammenfassung Der Einfluß von Atmosphäre, Aufheizungsgeschwindigkeit und Spülgasgeschwindigkeit auf die thermische Zersetzung von Alkalibenzolsulfonaten wurde untersucht. Kristallwassergehalt, Dehydratations-temperatur und -wärme, gegebenenfalls die Zusammensetzung, Art, Temperatur und Wärme der Modifikationsänderungen, Schmelzpunkte und Schmelzwärmen der Verbindungen wurden bestimmt. Die Zersetzung verläuft in zwei Abschnitten. In dem ersten Hauptteil entstehen in Inertgasatmosphäre Diphenyloxid, Diphenyl, Diphenylsulfon, Benzol, Phenol, Thiophenol, Diphenylsulfid, Thiantren, Diphenylenoxid und wahrscheinlich Diphenylensulfid, weiterhin Koks, Schwefeldioxid, Natriumsulfit und wenig Natriumsulfat, Natriumsulfid, Acetylen und Wasser. Im zweiten Hauptzersetzungsvorgang entstehen Natriumsulfid und Kohlenoxid. Die Produkte wurden isoliert und analysiert. Dazu wurden Derivatographie, Differentialthermoanalyse, Gaschromatographie, Infrarotspektroskopie, kontinuierliche thermische Titration und chemische Methoden gemeinsam angewandt.

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Summary An investigation was made of the influence of the atmosphere, rate of temperature rise, and velocity of the purging gas on the thermal decomposition of alkali benzene sulfonates. The crystal water content, the dehydration temperature and heat, and if need be the composition, the kind, temperature, and heat of the modification changes, melting points and heats of fusion of the compounds, were determined. The decomposition proceeds in two stages. In the first main stage (in an inert atmosphere) the resulting compounds include diphenyl oxide, diphenyl, diphenylsulfone, benzene, phenol, thiophenol, diphenyl sulfide, thianthrene, diphenylene oxide and probably diphenylene sulfide; also coke, sulfur dioxide, sodium sulfite and a little sodium sulfate, sodium sulfide, acetylene, water. Sodium sulfide and carbon monoxide are formed in the second main decomposition. The products were isolated and analyzed. Furthermore, use was made of derivatography, differential thermal analysis, gas chromatography, infra red spectroscopy, continuous thermal titration, and chemical methods.

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Résumé On a étudié l'influence de l'atmosphère, de la vitesse d'échauffement et de balayage du gaz, sur la décomposition thermique des benzène-sulfonates alcalins. On a déterminé la teneur en eau de cristallisation, la température et la chaleur de déshydratation, éventuellement la composition, la nature, la température et la chaleur des changements d'état, les points de fusion et les chaleurs de fusion des composés. La décomposition s'effectue en deux temps. Tout d'abord, en atmosphère inerte, il se forme de l'oxyde de diphényle, du diphényle, de la diphénylsulfone, du benzène, du phénol, du thiophénol, du sulfure de diphényle, du thianthrène, de l'oxyde de diphénylène et probablement du sulfure de diphénylène, et aussi du coke, de l'anhydride sulfureux, du sulfite de sodium et, en moins grande quantité, du sulfate de sodium, du sulfure de sodium, de l'acétylène et de l'eau. Dans une deuxième étape de la décomposition principale, du sulfure de sodium et de l'oxyde de carbone prennent naissance. On a isolé et analysé ces produits. Pour cela, on a utilisé simultanément la dérivatographie, l'analyse thermique différentielle, la chromatographie en phase gazeuse, la spectroscopie infrarouge, le titrage thermique en continu et les méthodes chimiques.

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Vorgetragen beim Symposium für analytische Chemie in Graz, 29. September bis 1. Oktober 1965.     

Discussion on the method for the measurement of the flexural modulus of coupled materials and reasons of the shifts of theQ −1 maxima caused by coupling

Summary When measuringQ ^–1 and the flexural resonance frequency of bars clamped at one end, constituted by a viscoelastic polymeric material glued to a rigid support of modulusE ₁, it is possible to calculate the componentsE ₂ andE ₂ of the complex elastic modulus of the polymeric material examined. In this work the minimum (critical) value of the ratioa=E ₂ /E ₁=a _c and the values of the ratioQ ₂ ^–1/Q ^–1=F ₁ are evaluated beyond which no exact calculation ofE ₂ and ofQ ₂ ^–1 is possible.Within the confidence limits of the linear viscoelasticity theory, these values depend on the accuracy of measurement of both frequency and resonance curve, as well as on the instrument employed, on the operating temperature and on the ratio between the thicknesses of the two coupled materials.In order to keep outside the critical conditions, the most convenient method involves the use of measurements of coupled test-pieces having different ratiosz between their thicknesses and of supports having different modulusE ₁, depending on the field of temperature of the analysis ofE ₂ and tg ₂ concerning and E.P.R. elastomer and a vulcanized cis-1,4 polyisoprene in very wide ranges of temperature comprising the glass transition. Moreover, it is demonstrated by analysis the shift on the temperature axis of the tg maximum of the composite test-piece with respect to the position of the tg maximum of the polymeric material alone.With 11 figures and 1 table     

Thermodynamic excess quantities in the adsorption of sodium alkylsulfonates at the air-solution interface

Colloid and Polymer Science - Data on the surface tension of sodium alkylsulfonate solutions at different temperatures and surfactant concentrations are presented. By applying the thermodynamic...     

A Study of Amorphous Precursors for PbZrO3-PbTiO3 Based Ceramic Materials

Amorphous precursors for PbZrO₃ and PbTiO₃ ceramics were prepared from lead acetate and the transition metaln-propoxide inn-propanol orn-butoxide inn-butanol and hydrolysed with an excess of water. According to GLC and TGA/EGA analyses, the type of alkoxide group influences distinctly the structure of heterometallic precursors, i.e., oxo or acetate bridging, and the amounts of hydroxyl and organic groups bound to the metal network. The local environments of metal atoms in the amorphous precursors were also studied by EXAFS. The analysis reveals that in Pb−Zr precursors alkoxide groups modify the coordination spheres of the zirconium atoms. Conversely, local environments of both lead and titanium atoms within the analysed range of 3.4 A depend weakly on the type of alkoxide used.     

Two-photon absorption and energy band structure of orthorhombic Hg2Cl2 crystals

Dependence of two-photon absorption (TPA) rate on the state of polarization of a laser beam is investigated in the low-temperature orthorhombic modification of Hg₂Cl₂ crystals. Theoretical calculations of the dependence of TPA rate on the direction of polarization vector of the beam are performed for centrosymmetric points, Y, Z, T, R andS of the Brillouin zone. The domain structure of real crystals is taken into consideration and it is shown that periodicity of the polarization dependence may indicate whether TPA is due to transitions either at, Y, Z, T orR, S points. The polarization dependence of TPA cannot, however, distinguish between points inside these two groups. Comparison of theory with a low-temperature (T 8·5 K) experimental curve of polarization dependence is discussed. It is shown that the experiment can be explained in main features by a model of noninteracting oriented linear dipoles. Further, on the basis of TPA measurements, a simple energy band structure of Hg₂Cl₂ is proposed regarding Hg₂Cl₂ crystal as a linear chain of molecules.The authors express thanks to Dr. . Barta for supplying the Hg₂Cl₂ crystals, Dr. Z. Bryknar for critical comments and Dr. B. Velický for stimulating discussion. We thank also Dr. V. Kohlová for assistance during measurement.     

A model of processes determining the intensity of DAPS and AEAPS signals

A simple model including different processes important for the creation of APS signals formed by electrons is proposed. Mean probabilities of elastic and inelastic interactions of electrons with individual atom layers in the solid are introduced. The contribution of different layers to the DAPS and AEPS signals and the dependence of these signals on the interaction parameters are calculated.I am indebted to dr. J. Pavluch for valuable discussions.     

Some features of solar wind protons, α particles and heavy ions behaviour: The Prognoz 7 and Prognoz 8 experimental results

The paper describes the results of investigations of the solar wind ions, carried out on board the high apogee Prognoz 7 and Prognoz 8 Earth's satellites with the aid of an SKS instrument (USSR) and a Monitor instrument (USSR-SSR). Behaviour of proton and that of components on the front of Earth's bow and interplanetary shock waves were compared by means of the energoanalysis and energy-mass analysis techniques. In several long-term periods of observation the solar wind heavy ions — oxygen, silicon and iron were determined. It enabled us to estimate the solar corona chemical composition and electron temperature.Presented at the 5th General Assembly IAGA/IAMAP August 5–17, 1985, Prague, Czechoslovakia.     

How large can a hereditarily separable or hereditarily Lindelöf space be?

The main result of this paper is that ifV satisfies GCH andω ₁<λ<μ are arbitrary regular cardinals, then in some cardinal preserving forcing extensionW ofV we have λ^<λ=λ=2 ^N 0,μ=2 ^λ and there are a hereditarily separableX ?2 ^λ with |X|= \(2^{\aleph _0 } \) =μ and a hereditarily LindelöfY ?2 ^μ withw(Y)= \(2^{2^\aleph 0} \) =μ. So far similar results have only been obtained under the assumption of CH.     

Separation and determination of volatile compounds in synthetic wine samples by gas chromatography using UV-visible molecular absorption spectrometry as detector

This paper shows the separation and determination of eight compounds containing the OH group (ethanol, pentanol, 3-methyl-1-butanol, hexanol, phenol, benzyl-alcohol, phenylethanol and geraniol) in synthetic wine by gas chromatography using UV-Vis molecular absorption spectrometry as detection system. All the parameters affecting the separation and determination were optimised using some methods of experiment design. The analytical characteristics of each compound were calculated and detection limits ranging from 2.3 to 74 mg l(-1) have been obtained.