Calorimetric studies of adsorptive properties of metallic carbides and nitrides of transition elements. Adsorption of H2, CO and O2 on titanium nitrides

Adsorption heats of hydrogen, oxygen and carbon monoxide on titanium nitrides have been measured calorimetrically in the temperature range from 473 to 673 K. With increasing Me/N ratio, the adsorption heat of oxygen grows.

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, 473–673 . Me/N.

     

Oligosilanylated Silocanes

A number of mono- and dioligosilanylated silocanes were prepared. Compounds included silocanes with 1-methyl-1-tris(trimethylsilyl)silyl, 1,1-bis[tris(trimethylsilyl)silyl], and 1,1-bis[tris(trimethylsilyl)germyl] substitution pattern as well as two examples where the silocane silicon atom is part of a cyclosilane or oxacyclosilane ring. The mono-tris(trimethylsilyl)silylated compound could be converted to the respective silocanylbis(trimethylsilyl)silanides by reaction with KO^tBu and in similar reactions the cyclosilanes were transformed to oligosilane-1,3-diides. However, the reaction of the 1,1-bis[tris(trimethylsilyl)silylated] silocane with two equivalents of KO^tBu leads to the replacement of one tris(trimethylsilyl)silyl unit with a tert-butoxy substituent followed by silanide formation via KO^tBu attack at one of the SiMe₃ units of remaining tris(trimethylsilyl)silyl group. For none of the silylated silocanes, signs of hypercoordinative interaction between the nitrogen and silicon silocane atoms were detected either in the solid state. by single crystal XRD analysis, nor in solution by ²⁹Si-NMR spectroscopy. This was further confirmed by cyclic voltammetry and a DFT study, which demonstrated that the N-Si distance in silocanes is not only dependent on the energy of a potential N-Si interaction, but also on steric factors and through-space interactions of the neighboring groups at Si and N, imposing the orientation of the p_z(N) orbital relative to the N-Si-X axis.     

Tautomerism of Aza heterocycles: V. Structure of the spontaneous transformation products of 5-methyl-2-phenyl-3,3a,4,5,6,7-hexahydro-2H-pyrazolo-[4,3-c]pyridin-3-one in crystal and solution

5-Methyl-2-phenyl-3,3a,4,5,6,7-hexahydro-2H-pyrazolo[4,3-c]pyridin-3-one exists as zwitterion with a proton localized on the nitrogen atom of the piperidine ring and negative charge delocalized over the pyrazololate fragment. The compound is stable in crystal but ustable in solution. Its chromatographic purification and attempts to recrystallize or synthesize by condensation of phenylhydrazine with alkyl 1-methyl-4-oxopiperidin-3-carboxylate on heating in alcohols or benzene lead to the formation of a complex mixture of products. Among these products, we isolated and identified 3a,3a′-methylenebis(5-methyl-2-phenyl-3,3a,4,5,6,7-hexahydro-2H-pyrazolo[4,3-c]pyridin-3-one), 1-methyl-3-(2-phenylhydrazinylidene)pyrrolidin-2-one, and 5-methyl-2-phenyl-3,5,6,7-tetrahydro-2H-pyrazolo[4,3-c]pyridine. The structure of methyl 3-(2-phenylhydrazinylidene)-4,5-dihydro-3H-pyrrole-2-carboxylate and 3a,5-dimethyl-2-phenyl-3,3a,4,5,6,7-hexahydro-2H-pyrazolo[4,3-c]pyridin-3-one was proved by NMR spectroscopy. 3a,5-Dimethyl-2-phenyl-3,3a,4,5,6,7-hexahydro-2H-pyrazolo[4,3-c]pyridin-3-one was isolated as hydrochloride hydrate whose structure was determined by X-ray analysis.     

Investigation of Ge and C layer deposition on a Si substrate using SIMS profiling

Structures grown using the technique of molecular-beam epitaxy during deposition of carbon and/or germanium atoms on an Si(111) surface were investigated experimentally and theoretically. Experimental profiles of in-depth component distribution were obtained using SIMS-profiling, whereas a complex technique of computer simulation taking into account diffusion and ballistic processes was applied for the calculated profiles.     

Separation of variables in the generalized 4th Appelrot class. II. Real solutions

We continue the analytical solution of the integrable system with two degrees of freedom arising as the generalization of the 4th Appelrot class of motions of the Kowalevski top for the case of two constant force fields [Kharlamov, RCD, vol. 10, no. 4]. The separated variables found in [Kharlamov, RCD, vol. 12, no. 3] are complex in the most part of the integral constants plane. Here we present the real separating variables and obtain the algebraic expressions for the initial Euler-Poisson variables. The finite algorithm of establishing the topology of regular integral manifolds is described. The article straightforwardly refers to some formulas from [Kharlamov, RCD, vol. 12, no. 3].     

Electromagnetic dissociation of relativistic 8B nuclei in nuclear track emulsion

Experimental data on fragmentation channels in peripheral interactions of ⁸B nuclei in nuclear track emulsions are presented. A detailed analysis made it possible to justify selections of events of the electromagnetic-dissociation process ⁸B → ⁷Be + p and to estimate its cross section. Events of ¹⁰C peripheral dissociation that were observed in the same exposure are described.     

A Heterogeneous Process for the Synthesis of Silicon Carbide Fibers

Study of the heterogeneous reaction of SiO₂ with activated carbon fibers has shown that the heterophase reaction (SiO₂ (gas), SiO (gas) + C) gave rise to polycrystalline fibers of - and -SiC, whereas the homophase reaction of SiO with CO on a Si cupel led to the growth of filament crystals of -SiC. In agreement with the proposed mechanism for the origin and growth of SiC crystals, the appearance of Si (l) on the surface of the product is connected to the exo-effect of the formation of silicon carbide.