Rearrangements in cobaltic fluoride fluorinations of cycloalkanes with seven or more ring carbons

Cyclo-heptane, -octane, -decane, -dodecane and -octadecane have been fluorinated in the vapour phase with cobaltic fluoride. The perfluorocarbons obtained revealed varying degrees of skeletal rearrangements. Thus, cycloheptane gave perfluoro-cycloheptane and -methylcyclohexane; cyclooctane gave at least eight fluorocarbons including-bicyclo(3,3,0)octane and -cyclooctane; cyclodecane gave a complex mixture from which were isolated perfluoro cis- and trans-bicyclo(4,4,0)decanes but no perfluorocyclodecane; cyclododecane and cyclooctadecane gave complex fluorocarbon mixtures in which none of the fluorocarbons with the original cycloalkene skeleton could be detected.Tetradecafluorobicyclo(3,3,0)octane gave dodecafluorobicyclo (3,3,0)oct-1(5)-ene and decafluorobicyclo(3,3,0)octa-di-1(5), 2-ene when pyrolysed over iron gauze.The fluorination of cyclooctane also afforded 1$\text{H}$-pentadecafluorocyclooctane which was dehydrofluorinated to tetradecafluorocyclooctene. This was converted to a range of derivatives including dodecafluorosuberic acid, 1,2-dichlorotetradecafluorocyclooctane, 1-methoxy tridecafluorocyclooctene and tetradecafluorocyclooctanone.     

Neue Wege der Analytik durch Kombination der direkten quantitativen Dünnschicht-Chromatographie mit elektronischer Datenverarbeitung

A computer program for direct evaluation of thin-layer chromatograms, which already was described earlier [3] has been tested with a laboratory and some technical formulations of a pesticide. Results have been compared with those obtained by two conventional methods. Mean relative standard deviation calculated from results compiled by electronic data processing (method A) is about 6%, compared to 10% received by graphic method (method C) which is employed by most investigators. In addition, overall time of analysis is 34% higher if graphic method is used. Method A saves time and expense especially in routine analysis because working of the process is easier and may be performed even by assistent personal. The proposed method is suitable for the determination of different active ingredients and impurities even in difficult technical products.     

Zur Kenntnis von Natrium-hexafluoromanganat(III)

Sodium hexafluoromanganate(III) has been synthesized by heating equimolecular quantities of Na₂MnF₅ and NaF in argon atmosphere. The compound is monoclinic witha=5.56 (1) Å,b=5.84 (1) Å,c=8.10 (2) Å, =90.7 (2) andZ=2. It is a high spin complex with _eff and the deformation of the octahedra is evident from its IR-spectra. Two enantiotropic transitions (at 562 and 653°C) and the melting point at 800°C have been observed.

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8. Mitt.: Mh. Chem.106, 483 (1975).     

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     

The continuation of the periodic table up to Z = 172. The chemistry of superheavy elements

The chemical elements up toZ = 172 are calculated with a relativistic Hartree-Fock-Slater program taking into account the effect of the extended nucleus. Predictions of the binding energies, the X-ray spectra and the number of electrons inside the nuclei are given for the inner electron shells. The predicted chemical behaviour will be discussed for all elements betweenZ = 104-120 and compared with previous known extrapolations. For the elementsZ = 121–172 predictions of their chemistry and a proposal for the continuation of the Periodic Table are given. The eighth chemical period ends withZ = 164 located below Mercury. The ninth period starts with an alkaline and alkaline earth metal and ends immediately similarly to the second and third period with a noble gas atZ = 172.

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Zusammenfassung Mit einem relativistischen Hartree-Fock-Slater Rechenprogramm werden die chemischen Elemente bis zur Ordnungszahl 172 berechnet, wobei der Einfluß des ausgedehnten Kernes berücksichtigt wurde. Für die innersten Elektronenschalen werden Voraussagen über deren Bindungsenergie, das Röntgenspektrum und die Zahl der Elektronen im Kern gemacht. Die voraussichtliche Chemie der Elemente zwischenZ = 104 und 120 wird diskutiert und mit bereits vorhandenen Extrapolationen verglichen. Für die ElementeZ =121–172 wird eine Voraussage über das chemische Verhalten gegeben, sowie ein Vorschlag für die Fortsetzung des Periodensystems gemacht. Die achte chemische Periode endet mit dem Element 164 im Periodensystem unter Quecksilber gelegen. Die neunte Periode beginnt mit einem Alkali- und Erdalkalimetall und endet sofort wieder wie in der zweiten und dritten Periode mit einem Edelgas beiZ = 172.

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Resumé Les éléments chimiques jusqu'áZ = 172 sont calculés à l'aide d'un programme Hartree-Fock-Slater relativiste en tenant compte de l'extension du noyau. On fournit des prédictions quant aux énergies de liaison, aux spectres X et au nombre d'électrons dans les noyaux pour les couches électroniques internes. Le comportement chimique prévu est discuté pour tous les éléments entreZ = 104–120 et comparé aux extrapolations connues auparavant. Pour les éléments Z =121–172 on effectue des prévisions de propriétés chimiques et l'on propose un prolongement du Tableau Périodique. La huitième période chimique se termine àZ = 164 sous le mercure. La neuviéme période débute avec un métal alcalin et alcalino-terreux et se termine comme la seconde et la troisième période avec un gaz rare àZ = 172.

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This work has been supported by the Bundesministerium für Wissenschaft und Bildung and by the Deutsche Forschungsgemeinschaft.     

Wirkungsgrade in der Welt des Lebens und der Technik

Zusammenfassung Um der oft gehörten Meinung entgegenzutreten, die energetischen Wirkungsgrade lebender Organismen seien wesentlich höher als die technischer Verfahren, werden entsprechende Werte miteinander verglichen. Der sehr niedrige Wirkungsgrad der Photosynthese zusammen mit der kleinen Energiedichte der Sonnenstrahlung erzwang ab einer kritischen Größe die Aufspaltung in Energiesammler, die Pflanzen, und Verbraucher chemischer Energie, den Tieren. Dank den 10 mal höheren Wirkungsgraden in der Technik, lassen sich Solarmobile bauen, die von der auf sie fallenden Sonnenstrahlung angetrieben werden. Wegen des Multiplikationsgesetzes der Teilwirkungsgrade ergeben sich sowohl für die Speicherung der Sonnenenergie in den fossilen Brennstoffen wie in der Nahrungskette extrem niedrige Wirkungsgrade.

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Efficiencies in the world of life and in engineering

One often hears the opinion, that the efficiencies in the world of life are higher than in engineering. To disprove this, many values of efficiency of corresponding processes are compared. The very low efficiency of photosynthesis in living plants together with the low density of solar radiation has led the world of life to split into collectors of energy, the plants, and consumers of chemical energy, the animals. Thanks to the ten times higher efficiencies of solar cells, it is possible, to produce solar mobiles, vehicles that move driven by solar radiation.

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Herrn Prof. Dr.-Ing. U. Grigull zum 75. Geburtstag gewidmet     

On the diffusion field in the neighborhood of two identical spheres

Summary Under steady state conditions the reduction in the diffusive flux into a sphere due the presence of a neighboring, identical sphere is calculated. Taking the flux into a sphere as 1 when the particles are at infinite separation, the flux decreases to a minimum value of 0.693 when the spheres are touching.

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Zusammenfassung Unter stationären Bedingungen wird die Abnahme des Diffusionsflusses in eine Kugel, bedingt durch eine benachbarte identische Kugel, berechnet.Wird der Diffusionsfluß in eine Kugel gleich 1 gesetzt, wenn die Partikel unendlich weit voneinander entfernt sind, so nimmt der Diffusionsfluß auf einen Minimalwert von 0,693 ab, wenn sich die Kugeln berühren.

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With 2 figures     

Umsetzung von hydrobromiertem 1,4-Polybutadien mit lithiumorganischen Verbindungen

Ohne ZusammenfassungMit 1 Abbildung und 1 Tabelle