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1983[X]
21Author    M. Blander, Z. NagyRequires cookie*
 Title    Coulomb Complexing and the Solubilization of Oxides in Halide Melts  
 Abstract    Coulomb attractions between polyvalent cations and anions in alkali halide melts lead to the formation of complex ions and to the solubilization of oxides of some cations by their halides. We have observed such solubilizations of A1 2 0 3 in LiCl-KCl eutectic melts. In addition, we predict and observe the dissolution of a number of other oxides by A1C1 3 in LiCl-KCl melts. We also predict that solubilization will be better in other halide solvents. Our results suggest possible new media for pyrometallurgy and chemical and electrochemical processes. 
  Reference    Z. Naturforsch. 38a, 116—119 (1983); received September 27. 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0116.pdf 
 Identifier    ZNA-1983-38a-0116 
 Volume    38 
22Author    Brian Cleaver, Pietro ZaniRequires cookie*
 Title    The Effect of Pressure on the Electrical Conductivity of the Molten Halides of Mercury and the Molten Iodides of Cadmium, Gallium and Indium  
 Abstract    The electrical conductivities of molten HgCl 2 , HgBr 2 , Hgl 2 , Cdl 2 , Gal 3 and Inl 3 were measured to pressures of 1 GPa (10 kbar), using a heated pressure vessel pressurised with argon. Additionally, the conductivities of Cdl 2 and HgCl 2 were measured from 2 to 6 GPa, using a tetrahedral anvil apparatus. In every case the conductivity rose with pressure initially, and this is thought to be due to an increase in the degree of self-ionisation of the liquid. For Cdl 2 and Hgl 2 a maximum was observed in the conductivity isotherm below 1 GPa, and for HgCl 2 the conductivity fell with pressure from 2 to 6 GPa, implying that a maximum exists between 1 and 2 GPa. At the maximum the degree of ionisation approaches unity, and there is a balance between the competing effects of pressure in increasing the degree of ionisation and in reducing the ionic mobilities. 
  Reference    Z. Naturforsch. 38a, 120—127 (1983); received October 11 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0120.pdf 
 Identifier    ZNA-1983-38a-0120 
 Volume    38 
23Author    R. Conradt, J. Richter, H. WettichRequires cookie*
 Title    Fused Salt Concentration Cells with Transference Transport Numbers of Molten Alkali Chloride and Silver Chloride Mixtures  
 Abstract    By emf measurements on concentration cells with silver electrodes the transport numbers of molten NaCl + AgCl, KCl + AgCl, RbCl + AgCl, and CsCl + AgCl have been determined over the whole concentration range at temperatures between 800 and 1075 K. All systems show an "inversion point" (equal cation mobilities), which shifts to higher silver chloride concentrations with higher temperatures. At high dilutions the diluted cation is always the less mobile one. 
  Reference    Z. Naturforsch. 38a, 128—134 (1983); received October 22 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0128.pdf 
 Identifier    ZNA-1983-38a-0128 
 Volume    38 
24Author    Chao-Cheng Yang, Ryuzo Takagi, Isao OkadaRequires cookie*
 Title    Internal Mobilities in Molten Systems (Na-K)N0 3 and (K-Cs)N0 3  
 Abstract    Internal mobility ratios in melts of the binary systems (Na-K)N0 3 and (K-Cs)N0 3 have been measured with the KJemm method in a wide range of concentration and temperature. From these and the available data on densities and conductivities, the internal mobilities have been calculated. In both systems the Chemla effect has been observed at relatively high temperature. The internal mobilities of Na + and K + seem to be well expressed by b — [A/{V— V 0)] exp(-E/RT) (V: molar volume; V 0 , A and E are parameters) in the respective systems (Na-M)N0 3 (M = K, Rb and Cs) and (K-M)N0 3 (M = Rb and Cs). The internal mobilities in the binary alkali nitrate melts can be qualitatively rationalised in terms of the attraction effect, the free space effect and the agitation effect. 
  Reference    Z. Naturforsch. 38a, 135—141 (1983); received October 11 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0135.pdf 
 Identifier    ZNA-1983-38a-0135 
 Volume    38 
25Author    E. Nassif, P. Lamparter, W. Sperl, S. SteebRequires cookie*
 Title    Structural Investigation of the Metallic Glasses Mg85.5Cui4.5 and Mg 7 oZn 3 o  
 Abstract    The total structure factors as well as the total pair correlation functions for amorphous Mg85.5Cu l45 (by neutron and X-ray diffraction) and for amorphous Mg 7 oZn 3 o (by X-ray diffraction) were determined. Both alloys show similar chemical short range order effects. From the total pair correlation function of the Mg 8 5. 5 Cu 14 .5 glass, partial coordination numbers and atomic distances could be extracted. Comparison with the structure of crystalline Mg 2 Cu suggests that the short range order around the copper atoms is similar in the amorphous and the crystalline phase. The densities of both amorphous alloys were measured yielding negative excess volumina. 
  Reference    Z. Naturforsch. 38a, 142—148 (1983); received September 30 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0142.pdf 
 Identifier    ZNA-1983-38a-0142 
 Volume    38 
26Author    M. Heming, G. LehmannRequires cookie*
 Title    Correlation of Zero Field Splittings and Site Distortions V. Mn 2+ in Cs2Zn 3 S 4  
 Abstract    In platelets of Cs 2 Zn 3 S 4 with about 4% of the Zn substituted by Mn two nonequivalent centers of isolated Mn 2+ were observed in addition to a broad EPR signal near g = 2 which is assigned to clusters of interconnected MnS 4 units. The fine structure and hyperfine structure parameters for the single-ion centers (all in units of 1CT 4 cm -1) are: b° 2 = -318.3 ±3; ^ = -210.3 ±2; A y = -62.7; A. = -63.6 ± 0.8; b 2 = — 890 + 18; ^ = -743 + 36; ^ = -60.6; A z = — 61.4 ± 0.8; for centers I and II, resp. Center II arises from Zn sites of C 2 site symmetry while for center I assignment to either one of two sites with D 2 site symmetry is possible. The larger hyperfine splitting constants as well as the superposition analysis favor the larger sites which are not occu-pied by Zn, but are partly occupied in the analogous Mn (and Co) compounds. Superposition analysis yields the same value of + 0.12 ± 0.02 cm"' for the intrinsic zero field splitting parameter b 2 of the bridging MnS 4 units in both sites. g : is significantly higher than the free ion value in-dicating a higher degree of covalency than in Cds and CdGa 2 S 4 . 
  Reference    Z. Naturforsch. 38a, 149—153 (1983); received November 15 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0149.pdf 
 Identifier    ZNA-1983-38a-0149 
 Volume    38 
27Author    R. Schieder, G. WinnewisserRequires cookie*
 Title    Observation of the Zeeman Effect of Ozone by Doppler Free Laser Spectroscopy  
 Abstract    The Zeeman effect of rotational-vibrational transitions of ozone has been studied with a C0 2 laser at 9.6 (am by means of saturation spectroscopy. The observed Zeeman pattern of the v 3 transitions 16 89 — 16 88 and 11 92 — 1 2 9i3 are analyzed and compared with calculations. The previously proposed assignments are confirmed. 
  Reference    Z. Naturforsch. 38a, 154—156 (1983); received December 21 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0154.pdf 
 Identifier    ZNA-1983-38a-0154 
 Volume    38 
28Author    W. Kjebsch, Koichi Yamada, G. WinnewisserRequires cookie*
 Title    Diode Laser Spectrum of OCS: The vi Band at 2062 cm  
 Abstract    The V| band of OCS has been measured in the wavenumber range 2026 to 2081 cm -1 to an accuracy better than 0.0008 cm" 1 using a diode laser spectrometer. The width of the observed lines is essentially Doppler-limited. The observed lines could be assigned to the following hot bands: ll'O-Ol'O, 12°0-02°0, 12 2 0 -02 2 0, 10°1-00°1, ll'l-Ol'l of OCS and to 10°0-00°0 and 1 l'O-Ol'O of the isotopic species OC 34 S and OC 33 S in natural abundances. These data provide a secondary standard in this wavelength region. 
  Reference    Z. Naturforsch. 38a, 157—162 (1983); received December 16 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0157.pdf 
 Identifier    ZNA-1983-38a-0157 
 Volume    38 
29Author    M. Somer, W. Bues, W. BrücknerRequires cookie*
 Title    Schwingungsspektren von Tetraphosphordekasulfid P4S10  
 Abstract    Vibrational Spectra of Tetraphosphorus decasulfide P4S10 The solid state i.r. and the solid an molten state Raman spectra of the cage compound P4S10 have been recorded. An assignment of the vibrational frequencies, mainly based on polarization data, is proposed. For P 4 S i0 an improved preparation method is reported. During melting the P4S10 units remain unchanged but partly lose terminal sulfur. Thermic decomposition reactions are given. They are reversible. 
  Reference    Z. Naturforsch. 38a, 163—166 (1983); eingegangen 23. Oktober 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0163.pdf 
 Identifier    ZNA-1983-38a-0163 
 Volume    38 
30Author    J. Bohmann, W. WitschelRequires cookie*
 Title    On the Operator Formulation of the Polyatomic Molecule Partition Function  
 Abstract    The Nielsen Hamiltonian of the general polyatomic molecule including anharmonicity and its resonances, Coriolis-coupling and its resonances, and rotation-vibration interaction are treated by statistical perturbation theory in its operator form. By generating function methods and operator theorems, which are treated in an appendix, cumbersome calculations with non-commuting operators are avoided. The results for H 2 0 and S0 2 agree very well with accurate numerical calculations from the literature. Qualitative conclusions on the convergence of the perturbation series are drawn from the numerical calculations for model systems. 
  Reference    Z. Naturforsch. 38a, 167—183 (1983); received October 29 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0167.pdf 
 Identifier    ZNA-1983-38a-0167 
 Volume    38 
31Author    G. Jancsó, Gy Jákli, Cs FetzerRequires cookie*
 Title    Vapour Pressure Isotope Effects of Chloroform  
 Abstract    The vapour pressure difference between CHC1 3 and CDC1 3 is measured by differential capacitance manometry between -60 and +60 °C. The results can be expressed by the equation ln(p H //? D) = 5.507 x 10~ 3 -6.269/7". The vapour pressure of CHC1 3 between -98 and +62°C has also been determined. The experimental H/D vapour pressure isotope effect data together with the available literature values on the l2 C/ l3 C and 35 C1/ 37 C1 isotope effects are interpreted within the framework of the statistical mechanical theory of isotope effects in condensed systems. The results show that the anharmonicity constant of the CH stretching vibration decreases by about 4% on the vapour-liquid transition. 
  Reference    Z. Naturforsch. 38a, 184—190 (1983); received July 28 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0184.pdf 
 Identifier    ZNA-1983-38a-0184 
 Volume    38 
32Author    Bärbel Maessen, Max WolfsbergRequires cookie*
 Title    Estimates of Dielectric Shifts in Infrared Spectra of Pure Liquids for Use in the Theoretical Evaluation of Vapor Pressure Isotope Effects  
 Abstract    Observed fundamentals in infrared spectra of pure liquids are red-shifted by the so-called "dielectric effect". This dielectric shift is an excited state effect, and the observed fundamentals must be corrected before one deduces the isotope effects on the zero-point vibrational energy which are needed in the theoretical evaluation of vapor pressure isotope effects. A simple formula is applied to calculate the dielectric shift, which requires only the molar concentration and the integrated absorption coefficient for the fundamental. 
  Reference    Z. Naturforsch. 38a, 191—195 (1983); received December 20 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0191.pdf 
 Identifier    ZNA-1983-38a-0191 
 Volume    38 
33Author    O. E. Polansky, M. Zander, I. MotocRequires cookie*
 Title    Topological Effect on MO Energies, II. * On the MO Energies of Structurally Related Aza-arenes  
 Abstract    The recently introduced approach of S, T isomers [1] has been applied to aza-benzenes and aza-perylenes. Ab initio and HMO calculations as well as experimental results clearly show that the S.T approach is a suitable means to derive definite predictions concerning the MO patterns and HOMO energies of structurally related aza-arenes. 
  Reference    Z. Naturforsch. 38a, 196—199 (1983); received December 8. 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0196.pdf 
 Identifier    ZNA-1983-38a-0196 
 Volume    38 
34Author    Peter Nikolov, Filip FratevRequires cookie*
 Title    A New Class of Organic Luminophores With a Stilbene Chromophore: 3-Phenylmethylene-l(3 H)-Isobenzofuranones  
 Abstract    A new class of luminophores with a stilbene chromophore, 3-phenylmethylene-l(3H)-iso-benzofuranones (BPH's), has been investigated. The fluorescence occurs in the region 26000-16000 cm -1 , the maximal quantum yield being about 0.6. As a result of substitution or higher polarity of the solvent the nn* state of the BPH's separates from the fluorescently inactive n n* state. The S 0 -S 2 absorption transition of the BPH's results from an excitation which is practically localized in the stilbene fragment. The good linear correlation of the fluorescence and absorption maxima and 0-0 transitions in ethanol with the <7 p -Hammett constants has been used for an interpretation of the changes in the potential hyperfaces of S 0 and S, states. 
  Reference    Z. Naturforsch. 38a, 200—205 (1983); received April 17 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0200.pdf 
 Identifier    ZNA-1983-38a-0200 
 Volume    38 
35Author    G. Jancsó, P. BoppRequires cookie*
 Title    The Dependence of the Internal Vibrational Frequencies of Liquid Water on Central Force Potentials  
 Abstract    The differences in the liquid phase internal vibrational frequencies of water, obtained from molecular dynamics (MD) simulations, between the two versions of the central force model of Rahman and Stillinger (CF1 and CF2) are investigated by employing the theory of Buckingham on solvent effects. It is found that the differences can be essentially accounted for by the different O —H stretching cubic anharmonic force constants of CF1 and CF2. A significantly improved agreement between the results of MD simulations and spectroscopically observed liuqid phase frequencies could be achieved by using a harmonic force field, supplemented by a cubic stretching force constant, for the intramolecular interactions of water, and the CF2 potential for the intermolecular interactions. 
  Reference    Z. Naturforsch. 38a, 206—213 (1983); received November 23. 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0206.pdf 
 Identifier    ZNA-1983-38a-0206 
 Volume    38 
36Author    GyI. Szász, K. HeinzingerRequires cookie*
 Title    A Molecular Dynamics Study of the Structure of an Aqueous CsF Solution  
 Abstract    A molecular dynamics simulation of a 2.2 molal aqueous CsF solution has been performed employing the ST2 water model. The basic periodic cube with a sidelength of 18.50 A contained 200 water molecules, and 8 ions of each kind, corresponding to an experimental density of 1.26 g/cm 3 . The simulation extended over 6.5 ps with an average temperature of 307 K. The structure of the solution is discussed by means of radial distribution functions and the orientation of the water molecules. The computed hydration numbers in the first shell of Cs + and F" are 7.9 and 6.8, respectively; the corresponding first hydration shell radii are 3.22 A and 2.64 A, respectively. Values for the hydration shell energies and the heat of solution have been calculated. 
  Reference    Z. Naturforsch. 38a, 214—224 (1983); received December 16 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0214.pdf 
 Identifier    ZNA-1983-38a-0214 
 Volume    38 
37Author    E. Kálmán, I. Serke, G. Pálinkás, G. Johansson, G. Kabisch, M. Maeda, H. OhtakiRequires cookie*
 Title    Complex Formation in an Aqueous ZnBr 2 Solution Based on Electron Diffraction, X-ray Scattering and Raman Spectra  
 Abstract    Electron and X-ray scattering as well as Raman spectra of as aqueous solution of ZnBr 2 with a Br -/Zn ++ ratio of 3 : 1 have been studied. The existence of hexaaquo, di-, tri-and tetra-bromo complexes in solution has been established by all three methods. Octahedral hexaaquo and tetrahedral Zn(H 2 0) 4 _ n Br n complexes with n = 2, 3,4 are consistent with electron and X-ray structure functions. The inner sphere type complexes have interatomic distances of 2.2 A for Zn ++ —H 2 0, 2.4 A for Zn ++ -Br, 3.93 A for Br-Br and 2.91 A for W-W interactions with average numbers of contacts 2.4, 2.22, 1.33 and 1.1 respectively. 
  Reference    Z. Naturforsch. 38a, 225—230 (1983); received September 30 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0225.pdf 
 Identifier    ZNA-1983-38a-0225 
 Volume    38 
38Author    E. Kálmán, I. Serke, G. Pálinkás, M. D. Zeidler, F. J. Wiesmann, H. Bertagnolli, P. ChieuxRequires cookie*
 Title    The Molecular Structure and Hydrogen Bond Geometry in Liquid Formamide: Electron, Neutron, and X-Ray Diffraction Studies  
 Abstract    Dedicated to Professor Alfred Klemm on the occasion of his 70th birthday Electron, neutron and X-ray diffraction patterns of liquid formamide have been measured at a temperature of 25 °C. Analysis of the diffraction data yields the molecular structure and the average geometry of the hydrogen bond. The molecular parameters obtained from liquid diffraction experiments are in good agreement with those from gas electron diffraction for the free molecule. The mean O...N and O...H hydrogen bond distances are 2.9 A and 1.9 A, respectively. Four H-bonds per molecule are found on the average. The deviation of the H-bonds from the linearity is estimated. 
  Reference    Z. Naturforsch. 38a, 231—236 (1983); received October 4 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0231.pdf 
 Identifier    ZNA-1983-38a-0231 
 Volume    38 
39Author    M. Molitor, W. Müller-Warmuth, H. W. Spieß, R. SchöllhornRequires cookie*
 Title    NMR Studies on Intercalation Compounds of Layered Chalcogenides with Methylamines and Ammonia  
 Abstract    NMR wideline and pulse techniques have been used to study orientation and molecular motions of the intercalation compounds of niobium disulfide with monolayers of mono-, di-, and trimethylamine, tetramethylammonium and ammonia. Specific information has been obtained from the 'H and 2 D spectra and from spin-lattice relaxation measurements of the selectively deuterated monomethylamines. Models for the arrangement of the various molecules within the layers and for the motions have been derived. One-dimensional rotation of CH 3 and NH 3 groups, rapid intermolecular exchange of NH, NH 2 and NH 3 protons, as well as translational and reorientational motions of whole molecules are of importance. Interpretation of spin-lattice relaxation rates at various temperatures and frequencies yields details of some of these mo-tion and numerical values for the activation energies. 
  Reference    Z. Naturforsch. 38a, 237—246 (1983); received December 6 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0237.pdf 
 Identifier    ZNA-1983-38a-0237 
 Volume    38 
40Author    Y. MarcusRequires cookie*
 Title    The Volume Change on Ion-Pairing of Symmetrical Electrolytes  
 Abstract    The increase in the standard partial molar volume of a symmetrical electrolyte on ion-pairing, A V x , calculated from the experimental association constant at ambient pressure, the isothermal compressibility, the dielectric constant of the solvent and its pressure coefficient, is as good a measure of this quantity as values calculated from more elaborate experimental procedures, such as the pressure coefficient of the association constant or high precision density determinations in dilute solutions. 
  Reference    Z. Naturforsch. 38a, 247—251 (1983); received October 26 1982 
  Published    1983 
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 TEI-XML for    default:Reihe_A/38/ZNA-1983-38a-0247.pdf 
 Identifier    ZNA-1983-38a-0247 
 Volume    38 
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