Über die Verdampfungsthermodynamik und die Bildungsenthalpien von CaSe,SrSe und BaSe

On the Thermodynamics of Vaporization and the Enthalpies of Formation of CaSe, SrSe and BaSe The congruent vaporization of the solid compounds CaSe, SrSe and BaSe of stoichiometric composition was studied over the temperature ranges 1832?2138 K, 1862?2122 K and 1860?2158 K, respectively, by the Knudsen effusion weight-loss method. Using enthalpy and entropy data from the literature for gaseous M, MSe, Se₂ and Se (M = Ca, Sr, Ba) and estimated data for the standard entropies and enthalpy functions of solid MSe, it can be shown that within the given temperature ranges CaSe and SrSe vaporize predominatly to the atomic species, while in case of BaSe the mode of vaporization to the atoms and to the molecular species BaSe are of about equal importance. The Se₂-content of the gas phase is very small in all cases. The following second and third law enthalpies and entropies (indices II and III respectively) were derived for the vaporization to the gaseous elements: see “Inhaltsübersicht”. The following standard enthalpies of formation of MSe(s) were derived from the third law enthalpies (in kJ · mol^?1): CaSe: ?445 ± 44; SrSe: ?451 ± 42; BaSe: ?467 ± 44.     

Structure du radical cyano-vinyle CH2=Ċ-CN Etude expérimentale et théorique

Résumé Tout d'abord, on montre par RPE que le radical CH₂=-CN possède à basse température une structure instable pliée et à température plus élevée une structure stable linéaire. Un calcul théorique sur ce radical ainsi que sur le radical butatriényle est en bon accord avec les résultats expérimentaux.

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The structure of the Cyano-Vinyl Radical CH₂=-CN experimental and theoretical study

First, it is shown by ESR that the radical CH₂=-CN at low temperature presents an unstable bent structure and at higher temperature a stable linear structure. A theoretical calculation on this radical and on the butatrienyl one is in good agreement with the experimental results.

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Zusammenfassung Aus ESR Messungen wird gefolgert, daß das Radikal CH₂=-CN bei tiefer Temperatur in einer instabilen gebogenen Struktur und bei höherer Temperatur in einer stabilen linearen Struktur vorliegt. Theoretische Berechnungen stehen sowohl für dieses als auch für das Butatrienyl-Radikal in guter Übereinstimmung mit experimentellen Daten.

     

On the mechanism of the He+ + N2 thermal energy dissociative charge transfer reaction

ICR spectroscopy has been used to reinvestigate the He⁺ + N₂ charge transfer reaction at thermal energies. It is concluded that at least 60% of the N⁺ come from short lived excited (N₂⁺)^*.     

Struktur von S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan und 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan

Structure of S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane and 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 1 ) and 9,10-diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 2 ) have been prepared by the reaction of propionic acid, propionic anhydride and butyric acid, butyric anhydride, respectively, with arsenic(III)-oxide. The crystals of 1 are rhombic, a = 6.902(4), b = 11.121(5), c = 13.988(8), space group P2₁2₁2₁. The crystals of 2 are monoclinic, a = 11.757(10), b = 11.255(10), c = 18.631 (18), β = 91.78(7), space group P2₁/n. The mean bond lengths and angles in 1 are AsO = 1.790 Å, AsC = 1.959 Å, OAsO = 100.60°, CAsO = 99.65°, AsOAs = 128.77°, AsCAs = 118.73°, and in 2 they are AsO = 1.780 Å, AsC = 1.978 Å, OAsO = 101.45°, CAsO = 99.55°, AsOAs = 129.64°, AsCAs = 117.72°.     

Raman and cathodoluminescence spectroscopic investigations on Permian fossil wood from Chemnitz--a contribution to the study of the permineralisation process

Samples of different three-dimensionally preserved fossil plants (Medullosa sp., Dadoxylon sp., Calamodendron striatum, Psaronius sp.) from the Lower Permian petrified forest of Chemnitz were examined with regard to their chemical composition and structural order. Raman spectroscopy and cathodoluminescence microscopy are shown to be powerful tools for such investigations. Silicified wood from Chemnitz-Hilbersdorf generally shows yellow cathodoluminescence (CL) of the cell walls and only weak yellow-brownish CL of the cell lumina. By time-resolved cathodoluminescence spectroscopy, a secondary mineralisation of hydrothermal origin was recognized. The latter is shown by short-lived blue CL at the cell walls extinguishing the yellow signal. Therefore, after the primary silicification step a secondary mineralisation step initiated by hydrothermal processes, seems to have taken place at probably slightly higher temperatures. The resulting silica matrix consists of phanerocrystalline and microcrystalline alpha-quartz as well as microcrystalline moganite, both partially associated with iron oxides. Dadoxylon sp. is a prominent example for parallel permineralisation by alpha-quartz and fluorspar, which is outstanding for the Chemnitz Petrified Forest. CL on this samples shows parallel silicification and fluoritisation, followed by infiltration of iron oxides. Permineralised samples show very low percentage of original organic remains. The seed fern Medullosa, for example, shows dispersed carbon, which is mainly restricted to the centres of the typical star-shaped vascular bundles. Raman spectroscopy revealed that these carbonaceous particles are of an anthracite structure. For experimental confirmation coal samples of different rank, especially anthracite from different geological times and localities, were studied by means of Raman spectroscopy. The remaining pith of the vascular bundles is white-coloured and consists of alpha-quartz and moganite, whereas surrounding tracheides exhibit white and reddish coloured parts. The reddish parts, mainly found in the rays, additionally contain alpha-Fe2O3 and Fe3O4 among the SiO2 polymorphs of alpha-quartz and moganite. Sometimes iron oxides could have dominated permineralisation processes as the peak intensities of distinct parts of the samples suggest.     

Nuclear moments and the change in the mean square charge radius of neutron deficient thallium isotopes

The hyperfine structure, isotope and isomeric shifts in the atomic transition 6p ² P _3/2–7s ² S _1/2, =535 nm have been measured for theI=7 andI=2 states of^{190, 192, 194, 196}Tl; theI=1/2 andI=9/2 states of¹⁹¹Tl and the I=7 isomer of¹⁸⁸Tl. The thallium isotopes were prepared as fast atomic beams at the GSI on-line mass separator following fusion reactions and — in some cases — subsequent-decay. The nuclear dipole moments, electric quadrupole moments and the change in the nuclear mean square charge radius are evaluated. Theuu-isotopes show an isomeric shift which changes sign between¹⁹²Tl and¹⁹⁴Tl.Dedicated to P. Armbruster on the occasion of his 60th birthday     

Formation of the surface charge on silica in mixed solvents

At sufficiently high concentrations of methanol and of alkali salts in aqueous silica dispersions, the negative -potentials of the particles are decreased. This effect is more pronounced with lithium than with other alkali cations, and it is independent on the anion. The NMR spectra indicate lithium adsorption on silica from mixed solvents, but not in the absence of alcohol.Supported by a contract with the XMX Corporation, Burlington, Massachusetts, USA     

Heat-moisture treatment (HMT) on blends from potato starch (PS) and sweet potato starch (SPS)

Journal of Thermal Analysis and Calorimetry - Samples of potato starch (PS), sweet potato starch (SPS) and their binary mixtures, with moisture levels of 10, 15 and 20% (db), were submitted to...     

Generating Excess Protons in Microsolvated Acid Clusters under Ambient Conditions: An Issue of Configurational Entropy versus Internal Energy

Acid dissociation, and thus liberation of excess protons in small water droplets, impacts on diverse fields such as interstellar, atmospheric or environmental chemistry. At cryogenic temperatures below 1 K, it is now well established that as few as four water molecules suffice to dissociate the generic strong acid HCl, yet temperature-driven recombination sets in simply upon heating that cluster. Here, the fundamental question is posed of how many more water molecules are required to stabilize a hydrated excess proton at room temperature. Ab initio path integral simulations disclose that not five, but six water molecules are needed at 300 K to allow for HCl dissociation independently from nuclear quantum effects. In order to provide the molecular underpinnings of these observations, the classical and quantum free energy profiles were decomposed along the dissociation coordinate in terms of the corresponding internal energy and entropy profiles. What decides in the end about acid dissociation, and thus ion pair formation, in a specific microsolvated water cluster at room temperature is found to be a fierce competition between classical configurational entropy and internal energy, where the former stabilizes the undissociated state whereas the latter favors dissociation. It is expected that these are generic findings with broad implications on acid–base chemistry depending on temperature in small water assemblies.     

Thermal, rheological, and structural behaviors of natural and modified cassava starch granules, with sodium hypochlorite solutions

The use of chemically modified starches is widely accepted in various industries, with several applications. In this research, natural cassava starch granules were treated with standard sodium hypochlorite solution at 0.8, 2.0, and 5.0 g Cl/100 g starch. The native and modified starch samples were investigated by means of the following techniques: simultaneous thermogravimetry–differential thermal analysis, which allowed us to verify the thermal decomposition associated with endothermic or exothermic phenomena; and differential scanning calorimetry that was used to determine gelatinization enthalpy as well as the rapid viscoamylographic analysis that provided the pasting temperature and viscosity. By means of non-contact-atomic force microscopy method and X-ray powder patterns diffractometry, it was possible to observe the surface morphology, topography of starch granules, and alterations in the granules’ crystallinity.