Zur Kenntnis des Lithiumhydrogensulfids

Jůza, Robert; Laurer, P.

doi:10.1002/zaac.19542750108

Cited by 16 publications

(7 citation statements)

References 13 publications

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“…The hydrogen sulfides [38-401 present a somewhat dilferent picture, owing to the higher degrees of symmetry of these compounds due to the lowering of the dipole moments and increase in the ionic radius in the order OH-, NHz-, SH-. Lithium hydrogen sulfide [41] is isotypic with lithium amide, and the layer character in LiSH is again less highly developed than in LiOH. a-Sodium, cc-potassium, and wrubidium hydrogen sulfides crystallize in a weakly rhombohedrically deformed sodium chloride J sttice, which is the alternative,…”

Section: Lithium Amide [6]mentioning

confidence: 99%

Amides of the Alkali and the Alkaline Earth Metals

Jůza

1964

Angew. Chem. Int. Ed. Engl.

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Following preparative work, the behavior of amides towards excess ammonia (ammoniute jbrmation) and on removal of ammonia (degradation to imides) was studied particularly with regard to the solid state (crystal structure) and the transition to the liquid phase (melting point). Energy relationships are discussed on the basis of enthalpies of formation. Studies on ternary amides and imides are still in the initial stage. -Emphasis is laid here on the establishment ofparallels between amides and hydroxides as well as between the aquo and ammono systems, and also on the differences between the amides with their dipolar NH2anion, and the halides. The results, although still incomplete, permit a survey to be given of experimental data with the aid of information obtained from the pertinent literature. Preparation of the AmidesTwo principal methods are available for the preparation of the amides of alkali metals: reaction of the metal with (a) liquid or (b) gaseous ammonia. The purest products are obtained by the long-established reaction of metals with liquid ammonia [2]. The alkali metals dissolve in ammonia to give the familiar intensely blue solutions. The rate of formation of the metal amide and hydrogen is slow, particularly with the lighter alkali metals. It increases appreciably with rising temperature and with increasing atomic weight of the alkali metal [3,4]. Acceleration of the reaction by catalysts, e.g. iron oxide or platinized platinum, is also possible.Lithium and sodium amides are most readily obtained by sealing the solution of the alkali metal together with the catalyst in a pressure tube, taking care to exclude air and moisture, and allowing the mixture to stand at room temperature until the deep-blue solution is fully decolorized. With potassium, rubidium, and cesium, the reaction is complete after a few hours, even at low temperatures, and it is possible to work at normal pressure, so that the hydrogen formed can escape [S]. The second method depends on the reaction of the molten metal with gaseous ammonia, e.g. at 400 "C for LiNH2 or 300°C for NaNH2. With lithium, higher temperatures must be avoided as the decomposition pressure becomes too high and degradation to the imide occurs. It is advantageous to allow the very mobile molten reaction product to drain away into a cooler zone of the apparatus [6]. In addition, numerous reactions are known in organic chemistry in which alkali amides are formed as byproducts. Mention may be made of the hydrogenation [l] Communication No.

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Section: Lithium Amide [6]mentioning

confidence: 99%

Amides of the Alkali and the Alkaline Earth Metals

Jůza

1964

Angew. Chem. Int. Ed. Engl.

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“…Well-known examples are alkali metal hydroxides, 1-11 hydrogensulfides, [12][13][14][15][16][17][18] and ammonium halides. [19][20][21][22][23] The type of motion and the resulting probability density function 54 strongly depend on the crystalline structure and on the symmetry and magnitude of the potential at the site of the molecular groups.…”

Section: Introductionmentioning

confidence: 99%

Reorientational Dynamics of Amide Ions in Isotypic Phases of Strontium and Calcium Amide. 1. Neutron Diffraction Experiments

Senker¹,

Jacobs²,

Müller³

et al. 1998

J. Phys. Chem. B

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Strontium and calcium amide are ionic compounds crystallizing in a tetragonally distorted anatase structure type. They include asymmetrically charged amide ions (NH 2 -/ND 2 -) which resemble water molecules in their structure and in their charge distribution. By means of temperature-dependent X-ray scattering measurements an anomalous thermal expansion was observed for both compounds (295 K for Sr(ND 2 ) 2 , 370 K for Ca(ND 2 ) 2 ). Fourier analyses based on high-resolution neutron powder diffraction experiments carried out in a large temperature range show especially for the deuterium atoms a remarkably large, anisotropic spatial distribution of the probability density function. It is caused by strongly anisotropic librations of the amide ions. The amplitudes of their normal librations were analyzed using a rigid-body model to parametrize the atomic mean-square displacements of the atoms belonging to the amide ions. They can be described as composed of strong rocking librations with weak temperature dependence and a weak wagging libration with strong temperature dependence.

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“…Lithium hydrogen sulfide has been added to our study as an example of how the H atoms produce the same effect as other monovalent atoms in the structures. It crystallizes in several polymorphs (Jacobs et al, 1989;Juza & Laurer, 1954;Winkler et al, 2003). One of them (P4 2 /mmc; Jacobs et al, 1989) is isotypic to PtS and in the other two, crystallizing in the space group Ama2 and P4 2 /mbc, the LiS-substructures are slight distortions of the PtS-type network, as shown in Figs.…”

Section: The Singular Lihs Sulfidementioning

confidence: 99%

On the charge transfer between conventional cations: the structures of ternary oxides and chalcogenides of alkali metals

Vegas

2012

Acta Crystallogr Sect B

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The structures of ternary oxides and chalcogenides of alkali metals are dissected in light of the extended Zintl-Klemm concept. This model, which has been successfully extended to other compounds different to the Zintl phases, assumes that crystal structures can be better understood if the cation substructures are contemplated as Zintl polyanions. This implies the occurrence of charge transfer between cations, even if they are of the same kind. In this article, the charge transfer between cations is even more illustrative because the two alkali atoms have different electronegativity, so that the less electropositive alkali metal and the O/S atom always form skeletons characteristic of the group 14 elements. Thus, partial structures of the zincblende-, wurtzite-, PbO- and SrAl(2)-type are found in the oxides/sulfides. In this work, such an interpretation of the structures remains at a topological level. The analysis also shows that this interpretation is complementary to the model developed by Andersson and Hyde which contemplates the structures as the intergrowth of structural slabs of more simple compounds.

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Zur Kenntnis des Lithiumhydrogensulfids

Cited by 16 publications

References 13 publications

Amides of the Alkali and the Alkaline Earth Metals

Amides of the Alkali and the Alkaline Earth Metals

Reorientational Dynamics of Amide Ions in Isotypic Phases of Strontium and Calcium Amide. 1. Neutron Diffraction Experiments

On the charge transfer between conventional cations: the structures of ternary oxides and chalcogenides of alkali metals

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