Effect of the nature of the metal oxide on selective transformation of methane under unsteady conditions in the absence of oxidant in the gaseous phase

The catalytic transformation of methane into higher hydrocarbons was studied under unsteady conditions on oxides of various metals (Pb, Fe, Nb, Ti, Cd, Mo, Mg, Zn, Zr, Bi, Mn), and also on Sr-, La-, Y-, and Mn-containing oxides of perovskite structure. It is shown that the effectiveness of the catalysts not only depends on their chemical composition, but also is determined to a considerable degree by the specific surface of the oxides. L. V. Pisarzhevskii Institute of Physical Chemistry, Academy of Sciences of Ukraine, 252039 Kiev, Prosp. Nauki, 31, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 2, pp. 91–95, March–April, 1997.     

Formation of furan derivatives in the course of the Stevens rearrangement of ammonium salts containing 4-allyloxy(phenoxy)-2-butynyl group

Ammonium salts containing phenacyl group in combination with 4-allyloxy(phehoxy)-2-butynyl group, when treated with a suspension of potassium hydroxide in benzene, undergo the 3,2-Stevens rearrangement with the formation of allenic amino ketones which under the reaction conditions give the furan derivatives.     

New materials for sorption of hydrogen

The influence of temperature, duration of thermal treatment, and oxidation modes of the aluminum base on processes in which intermetallic compounds LiLaAl are formed by the method of electrochemical cathodic intercalation was studied. The optimal modes of formation of LiLaAl_ox compounds exhibiting high sorption capacity for hydrogen were determined.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1516–1519.Original Russian Text Copyright © 2004 by Olshanskaya, Sobgaida, Popova.     

New Tricyclic Amides. Synthesis,Structure, and Oxidation with Peroxyphthalic Acid

4-Azatricyclo[5.2.1.0^2,6]dec-8-ene was synthesized and brought into reactions with benzoyl, o-chlorobenzoyl, p-bromobenzoyl, p-, m-, and o-nitrobenzoyl, and bicyclo[2.2.1]hept-2-ene-endo-5,endo-6-dicarboximidoacetyl chlorides in chloroform in the presence of pyridine. The tricyclic amides thus obtained were epoxidated with peroxyphthalic acid prepared in situ by reaction of phthalic anhydride with a 35% aqueous solution of hydrogen peroxide. The structure of newly synthesized compounds was confirmed by IR and ¹H and ¹³C NMR spectroscopy and mass spectrometry. Their NMR spectra were compared with those of previously synthesized N-arylsulfonyl-4-azatricyclo[5.2.1.0^2,6]dec-8-enes on the basis of conformational composition of the corresponding p-nitrophenyl-substituted derivatives, which was determined by PM3 semi-empirical quantum-chemical calculations.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 837–845.Original Russian Text Copyright © 2005 by L. Kas’yan, Okovityi, Tarabara, A. Kas’yan, Bondarenko.     

The determination of the thermodynamic characteristics of Lennard-Jones fluids under isobaric conditions by the method of molecular functions

Integral equation theory for partial distribution functions was used to suggest an effective method for calculating the derivative of radial distribution function with respect to temperature under isobaric conditions. The thermodynamic expansion, compression, and pressure coefficients and isobaric and isochoric heat capacities were calculated for Lennard-Jones fluids. The calculation results were in close agreement with the known thermodynamic relations.     

Phthalocyanines and related compounds: XXXVIII. Synthesis of symmetric taurine- and choline-substituted phthalocyanines

Procedures have been developed for the synthesis of a series of metal complexes derived from water-soluble anionic and cationic octa-4,5-carboxyphthalocyanine-taurine and choline conjugates.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1907–1911.Original Russian Text Copyright © 2004 by Mikhalenko, Soloveva, Lukyanets.For communication XXXVII, see [1].This revised version was published online in April 2005 with a corrected cover date.     

Heterometallic nickel(II) samarium(III) diethylenetriaminepentaacetate, a starting material for the preparation of samarium nickelate films

A reaction of samarium oxide, nickel oxocarbonate, and diethylenetriaminepentaacetic acid (H₅DTPA) taken in stoichiometric proportions in water gave SmNiDTPA · 10H₂O as a glassy solid. The formation of this heterometallic complex was confirmed by data from elemental analysis, IR spectroscopy, thermal analysis, and X-ray fluorescence analysis. An aqueous solution of the complex was used to deposit SmNiO₃ films onto a single-crystal SrTiO₃(001) substrate. The SmNiO₃ phase in films obtained upon 3-h annealing at 500°C was identified by powder X-ray diffraction. Films deposited from a solution of an equimolar mixture of monometallic samarium and nickel diethylenetriaminepentaacetates contained no samarium nickelate.     

Theoretical investigation of 1,4-dioxane complexes with water in the <Emphasis Type="Italic">chair</Emphasis> conformation by semiempiric MNDO/PM3 method

The structure and relative stability of 1,4-dioxane-water, (Diox)_n·(H₂O )_m (n = 1, 2, m = 1–6), molecular complexes have been calculated by semiempirical MNDO/PM3 method. A considerable variety of (Diox)_n·(H₂O )_m isomeric structures was stated. The mean energy of O_Diox…H_W-O_W hydrogen bond in (Diox)_n·(H₂O)_m complexes formed by 1,4-dioxane molecules in the chair conformation amounts to ?2.293 ± 0.210 kcal/mol with the average bond length 2.797 0.015 Å.     

Phthalocyanines and related compounds: XLII. Synthesis of phenyl-substituted tetraazachlorins and tetraazabacteriochlorins

New oxidation-resistant hexaphenyl-substituted tetramethyltetraazachlorin, its nickel complex, and tetraphenyl-substituted octamethyltetraazabacteriochlorin and octamethyltetraazaisobacteriochlorin nickel complexes were synthesized for the first time by mixed condensation of diphenylm aleonitrile with tetramethylsuccinonitrile in the presence of lithium dimethylaminoethoxide or nickel chloride. The products were characterized by electronic absorption, ¹H NMR, and mass spectra. Mixed condensation of diphenylsuccinonitrile with phthalonitrile in the presence of nickel chloride was found to give nickel complexes of phenylsubstituted benzo-fused tetraazaporphyrins rather than their hydrogenated derivatives.     

A thermochemical study of acid-base interactions in aqueous solutions of citric acid

The heat effects of interaction of a solution of citric acid with HNO₃ and KOH were measured calorimetrically at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 (KNO₃). The heat effects of acid dissociation were calculated using the universal HEAT program. The standard thermodynamic characteristics of step dissociation of citric acid were determined.