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991.
Zusammenfassung In der vorliegenden Arbeit wird das Sedimentations-gleichgewicht des Systems Na6[H2W12O40]-NaClO4-H2O bei 25 °C untersucht. Die scheinbare Ladungszahl des Natriummetawolframats wird als Funktion der NaClO4-MolalitätmNaClO4 ermittelt. Aus dieser Abhängigkeit kann für die summarische Dissoziation des NatriummetawolframatsNa2[H2W12O4o] 6Na+ + [H2W12O40]6– die DissoziationskonstanteK in Gegenwart von NaClO4 als Fremdelektrolyt zuK=0,08 mol6·kg–6 bestimmt werden.Der Kreuzdifferentialquotient ( PXz , ist der Trace-Aktivitätskoeffizient des Natriummetawolframats) wird ebenfalls als Funktion der NaClO4-Molalität ermittelt.Die Konzentrationsabhängigkeit des Trace-Aktivitätskoeffizienten zeigt einen Verlauf, wie er unseres Wissens nach noch nicht von anderen Autoren beobachtet wurde.
Summary An ultracentrifugal study of the sedimentation equilibrium of the system Na2[H2W12O40]-NaClO4-H2Oat 25 °C is presented. The dependency of the apparent charge of the sodium metatungstate on NaClO4-molality is investigated. From these data the dissociation constant for the dissociation of the sodium metatungstate in the presence of NaClO4 according to the equationNa[H2W12O40] 6Na+ + [H2W12O40]6– is calculated toK=0.08 mol6·kg–6. The cross differential quotient ( PXz is the trace activity coefficient of the sodium metatungstate) shows a behavior in its dependence on NaClO4-molality which to our knowledge has not yet been reported by other authors.


Mit 5 Abbildungen und 1 Tabelle  相似文献   
992.
With the help of a commercial heat-flux calorimeter the enthalpy change was measured as a function of the interlamellar spacing for lamellar precipitated Cu-In samples. This is related to the replacement of the two-phase structure (α + δ) by the homogeneous solid solution (α0. From this, the specific interfacial enthalpy of the α-δ interface was determined to be ΔHδ = 1100 ± 550 mJ m?2. A value of ΔHc = 1320 ± 60 J mol?1 results for the chemical part of the total measured transformation enthalpy. A value of ΔSδ = 0.66 mJ m?2 K?1 was estimated for the specific interfacial entropy and using the Gibbs-Helmholtz equation the specific interfacial free energy was calculated as ΔGδ = 700 ± 400 mJ m?2 at 600 K.  相似文献   
993.
Oligoethers with hydroxyl end-groups were prepared in boiling toluene from bis(chloromethyl)methylphosphine oxide and glycols used as monosodium glycolates. From these oligoethers and diisocyanates (hexamethylenediisocyanate and 2,4-toluene-diisocyanate), phosphorus-containing polyurethanes were synthesized.  相似文献   
994.
Intramolecular coordination in dimethylaluminium phenoxides (with an ortho-substituted ring) was investigated. Only strongly donating groups in the phenoxy ring (COOMe) displayed strong intramolecular coordination. All compounds investigated formed donor-acceptor complexes with hexamethylphosphoramide (HMPA). Dimethylaluminium methylsalicilate coordinated HMPA without splitting the intramolecular carbonyl oxygen—aluminium bond, which suggests formation of the pentacoordinated aluminium atom.  相似文献   
995.
We present a new experimental determination of the Compton profiles of CH4 and C2H4 molecules using high energy electron impact. The observable q range has been extended up to 10 au (6 au for C2H4). Good agreement is found with an earlier X-ray scattering experiment and with new theoretical calculations.  相似文献   
996.
The stoichiometry of the various stages involved in the thermal decomposition of ammonium metavanadate has been shown to correspond to a stepwise decrease in the ratio of ammonia and water to V2O5, with V2O5 being the final product in vacuum, in air and in argon. In ammonia, VO2 is formed. The actual stages and intermediates are dependent upon the prevailing atmosphere. Chemical analyses, together with infrared absorption spectra and X-ray powder data, have enabled the intermediates and products to be characterized and the structural changes involved in the decomposition to be discussed.
Zusammenfassung Es wurde gezeigt, daß die verschiedenen Stufen in der thermischen Zersetzung von Ammoniummetavanadat dem stufenweisen stöchiometrischen Verlust von Ammonia und Wasser entsprechen. In Vakuum, Sauerstoff und Argon ist V2O5, in Ammoniak VO2 das Endprodukt. Die Zwischenprodukte der einzelnen Stufen sind von der umgebenden Gasatmosphäre abhängig. Durch chemische, infrarot- und röntgenspektroskopische Analyse gelang es, diese zu charakterisieren und so die durch die Zersetzung hervorgerufenen strukturellen Umlagerungen zu deuten.

Résumé On montre que les différentes étapes de la décomposition thermique du métavanadate d'ammonium correspondent à la diminution progressive de l'eau et de l'ammoniac par rapport à V2O5; cet oxyde constitue le produit final dans le vide, dans l'air et dans l'argon. Dans l'ammoniac, c'est VO2 qui se forme. Les étapes respectives et les intermédiaires dépendent de l'atmosphère qui prévaut. A l'aide de l'analyse chimique, des spectres d'absorption infrarouge et des données de rayons X sur poudre, on a pu caractériser les intermédiaires et les produits formés, ainsi que les changements structuraux provoqués par la décomposition.

, V2O5. , V2O5. . , , .


We wish to acknowledge helpful comments from Prof. L. Glasser and Dr. N. H. Agnew and financial support from the National Institute for Metallurgy, Johannesburg, South Africa.  相似文献   
997.
Extraction of arsenic(V) from sulfuric acid solutions with various extractants in multistage counter-current extraction-stripping systems was compared. The extraction ability of the extractants studied showed the following order: ENIM 100>TBP=CYANEX 923>2-methylhexanol. The extraction depends significantly on the number of extraction stages and the phase ratios in extraction. The effects of the number of stripping stages and the phase ratio in stripping are less important.  相似文献   
998.
The structure of an extracellular mannan formed by the yeastBullera tsugae has been studied. It has been shown that the repeating unit of this polysaccharide contains -(13)- and -(14)-bound D-mannopyranose residues in equimolar ratio. A comparison has been made of the polymer under investigation with the extracellular mannan from a yeast of the genusRhodotorula. Leningrad Institute of Pharmaceutical Chemistry. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 746–750, November–December, 1985.  相似文献   
999.
It has been shown that the “internal” isotope distribution within a given molecular species at the natural abundance level is accessible by a new method, SNIF-NMR, which is based on deuterium NMR. Relative internal factors, Ri/j,have been defined which enable the isotope content of a given site, i, to be compared to that of another molecular site, j, taken as the reference. Several referencing methods intended to provide direct access to relative externals, Ti , and absolute, (D/H)i , site-specific parameters, are now discussed from both the theoretical and the experimental points of view. In the intramolecular referencing method, which involves a time-consuming chemical transformation of the sample, the risk exists of more or leas systematic errors resulting from discriminating fractionation effects. However this technique offers, conversely, an interesting way of investigating kinetic isotope effects without the need for specific labelling. In spite of its lower spectral precision the external referencing method has the advantage of being fast and less sensitive to systematic errois and may be used for direct rough routine determinations of the site-specific isotope contents. More precise results can be obtained, at the price of contaminating the sample, when an intermolecular reference is added and signal heights are used, remembering however that the intensity parameters then have no strict physical meaning in terms of absolute isotope contents. The site-specific parameters, Ti and (D/H)i thus accessible, provide new information on the mechanisms of the fractionation effects occurring in natural conditions and examples are considered.  相似文献   
1000.
Use of a novel coupling reagent, N,N-bis[2-oxo-3-oxazolidinyl]phosphorodiamidic chloride (BOPDC) in the synthesis of oligodeoxyribonucleotides is described. This reagent allows the synthesis of phosphotriesters in high yields (70–80%) without detectable side reactions. Synthesis of a hexanucleotide, d(A-A-C-C-C-G) is presented as an example.  相似文献   
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