Corresponding Member of the Academy of Sciences of the USSR B. P. NIKOLSKII, E. A. MATEROVA,
This study examines how the composition of zirconyl phosphate precipitates affects their ion exchange, conductivity, selectivity, and membrane electrode behavior. Samples with different zirconium to phosphorus oxide ratios were prepared by precipitating zirconium salts with phosphoric acid under var…
Academician of the Academy of Sciences of the Ukrainian SSR I. N. FRANTSEVICH, V. A. LAVRENKO
This paper investigates heterogeneous recombination of hydrogen atoms on platinum, addressing conflicting reports that had treated platinum as a possible absolute recombination standard. Hydrogen atoms generated in a high voltage discharge were directed onto a platinum wire resistance thermometer, a…
B. D. BEREZIN
Rhodium(III) phthalocyanine is synthesized from anhydrous rhodium chloride and phthalonitrile and characterized as the hydrogensulfate complex, with the oxidation state of rhodium confirmed by dichromate oxidation in sulfuric acid. Its dissociation kinetics in concentrated sulfuric acid are compared…
L. N. KUTSEVA, R. M. ASEEVA, L. G. CHERKASHINA, A. I. SHERLE,
This study examines whether organic polymers with conjugated bond systems can act as semiconductor catalysts for mild oxidation reactions, focusing on the formation of hydroperoxides from alkylaromatic hydrocarbons and cyclohexane. Polymeric copper phthalocyanines, polymeric copper tetraazaannulene …
V. G. GLUKHOVTSEV, S. V. ZAKHAROVA, Corresponding Member of the Academy of Sciences of the USSR A. D. PETROV
This study examines Michael-type additions of furan alcohols and related derivatives to alpha,beta-unsaturated aldehydes and ketones under acidic conditions, with attention to how functional groups in the furan side chain affect ring hydrogen mobility. The authors compare reactive and unreactive sub…
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This study examines the thermal stability of scandium fluoride and its interaction with magnesium fluoride, motivated by the potential use of ScF3 in producing scandium and magnesium alloys. ScF3 and MgF2 were prepared chemically, then investigated by continuous weighing, thermal analysis, and X-ray…
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High-resolution NMR is applied to the solvation of paramagnetic ions in alcohol, water mixtures, using selective broadening and narrowing of the ethyl alcohol CH3 and CH2 lines as water displaces alcohol from ion solvation shells. Solutions of copper, manganese, and chromium salts in deuterated etha…
Corresponding Member of the Academy of Sciences of the USSR I. M. Gelfand, I. I. Pyatetskii-Shapiro,
The paper formulates the determination of crystal structures from X-ray diffraction intensities as a problem of finding the global minimum of a function comparing calculated and experimental moduli of structure amplitudes. It argues that for many crystals, especially molecular crystals with rigid or…
V. E. PLYUSHCHEV, V. M. AMOSOV, M. B. VARFOLOMEEV
This paper reports the synthesis and characterization of lower crystalline hydrates of yttrium, lanthanum, and lanthanide perrhenates, a class of compounds previously little studied. Rare-earth oxides were dissolved in purified perrhenic acid, using excess oxide to ensure neutralization, followed by…
Yu. N. KONDRAT’EV
This paper examines the role of titanium dioxide in the crystallization and structure formation of glass crystalline materials in the Li2O, Al2O3, SiO2, TiO2 system. A series of glass compositions was melted and studied by the polythermal method, with crystallization behavior related to calculated r…
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This paper examines discrepancies between isotope vapor pressure ratios measured directly by the differential method and indirectly by Rayleigh distillation, focusing on boron trifluoride and methane. The authors argue that nonequilibrium evaporation during Rayleigh experiments can introduce a kinet…
L. S. BRESLER, Corresponding Member of the Academy of Sciences of the USSR, B. A. DOLGOPLOSK;
This study examines the copolymerization of butadiene-1,3 with 2,3-dimethylbutadiene-1,3 in the presence of anionic, cationic, and complex organometallic catalysts. Using carbon-14 labeled butadiene, glass-transition measurements, copolymer composition analysis, and infrared spectroscopy, the author…
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This paper examines a possible origin of the asymmetric doublet intensities observed in Mössbauer absorption spectra of powdered organotin and related tin compounds. It develops a theoretical treatment of quadrupole splitting in crystalline electric fields, averaging the angular dependence of transi…
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This paper proposes a general stepwise mechanism for the radiolysis of dilute aqueous solutions of aromatic and heteroaromatic compounds, including thiophene, pyridine, furan, benzene, and pyrrole. Using gamma irradiation experiments with product analysis by nephelometry and ultraviolet and infrared…
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The paper examines why compounds of the type MXk-2Y2 sometimes exhibit multiple geometrical isomers and sometimes appear as only one stable form. Using the maximum overlap method, the authors estimate relative stabilities by comparing overlap matrices for square, octahedral, distorted tetrahedral, t…
Academician A. N. Frumkin, B. I. Podlovchenko
This paper investigates the origin of negative potential shifts that arise when ethanol is introduced into electrolyte solutions contacting a platinized platinum electrode. Using potential relaxation measurements, electrode washing, charging curves, pH variation, and oxidation-rate observations, the…
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This paper examines why cyclopentadiene reacts differently with vinyl and isopropenyl-type dienophiles in diene synthesis, particularly the contrasting endo and exo adduct preferences of methyl acrylate and methyl methacrylate. Using a linear free energy comparison of rate constants for reactions wi…
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Infrared spectroscopy was used to examine elementary processes occurring during acidification of sodium tungstate solutions and to clarify the mechanism of sodium paratungstate formation. Spectra of solid tungsten compounds and acidified solutions were compared in regions corresponding to tungstate …
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This paper develops a model for porous gas electrodes in which electrochemical reaction occurs on broad pores emptied of electrolyte, while ionic current is carried through narrow electrolyte-filled pores. Using a one-dimensional treatment for hydrogen ionization at small polarization, the analysis …
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This paper investigates why reported yields of echinopsine from seeds of Echinops species vary sharply with extraction and alkalization conditions. By comparing ammonia, sodium carbonate, and sodium hydroxide treatments, followed by chromatographic separation and UV and IR spectral analysis, the aut…
P. G. ALI-ZADE, G. A. MARTYNOV, V. G. MELAMED
This paper examines how image forces and asymmetric Debye atmospheres modify charge distribution in the electric double layer, extending the Gouy-Chapman approach to cases with a nonzero interfacial potential. The authors introduce an additional ion energy term into the Poisson-Boltzmann equation, u…
Corresponding Member of the Academy of Sciences of the USSR K. A. Andrianov, Ionel Haiduc,
This study reports the preparation and structural examination of previously undescribed unsaturated derivatives of the cyclotrisilazane ring. Vinyl-substituted cyclosilazanes were synthesized by ammonolysis of methylvinyldichlorosilane and by co-ammonolysis with dimethyldichlorosilane, yielding seve…
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This paper examines how adding proton donors changes the polarographic reduction mechanism of quinones, nitro compounds, and related substances in the nonprotogenic solvent dimethylformamide. It argues that the strong positive shift of the second reduction wave, with little change in the first, is b…
V. I. Vladimirova, G. M. Zhabrova, B. M. Kadenatsi,
This study examines the low-temperature dehydrogenation of cyclohexane under the combined action of ionizing radiation and oxide catalysts with different electronic properties. Cyclohexane adsorbed on oxides including silica gel, alumina, aluminosilicate, zirconia, magnesia, zinc oxide, and nickel o…
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This study investigates the initiation mechanism of ethylene polymerization catalyzed by a soluble Ziegler-type complex formed from bis(cyclopentadienyl)titanium dichloride and dimethylaluminum chloride. Using visible absorption spectroscopy, electron paramagnetic resonance, and kinetic measurements…
Corresponding Member of the Academy of Sciences of the USSR K. A. KOCHESHKOV
This study examines the association and structure of aliphatic organolithium complexes, focusing on how the CH2,Li group participates in bonding and aggregation. Infrared spectra were measured for isotopically substituted ethyllithium and several higher n-alkyllithium compounds in vapor, solution, a…
Academician S. S. MEDVEDEV
Electronic absorption spectroscopy is evaluated as a method for probing the nature and polarity of carbon, alkali metal bonds in living polymer carbanions and related organometallic compounds. Spectra were measured for alkali metal derivatives formed from dienes, styrene, 1,1-diphenylethylene, anthr…
Corresponding Member of the Academy of Sciences of the USSR R. Kh. FREIDLINA, E. Ts. CHUKOVSKAYA
This study examines dicyclohexyl peroxydicarbonate as an initiator for reactions of silicon hydrides with unsaturated compounds, aiming to avoid the high temperatures or catalyst limitations associated with earlier methods. Methyldichlorosilane was reacted with allyl acetate, allyl chloride, and dec…
I. P. Gragerov, A. F. Levit, Yu. A. Zonov, M. Ya. Turkina
This study examines the mechanism of benzene oxidation using isotopic labeling and low-voltage mass spectrometry to detect whether phenyl radicals participate in reactions of mixed deuterated and protonated benzene. Benzene was oxidized with Fenton’s reagent, pernitrous acid, acidic permanganate, an…
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This study examines how the radioactivity of molybdenum anhydride containing molybdenum-99 affects its specific surface area. Nine samples prepared under identical conditions with different specific activities were measured by rarefied-air filtration using Deryagin’s method and by krypton adsorption…
N. S. GARIFYANOV, N. S. KUCHEVYAVENKO, V. N. FEDOTOV
Electron paramagnetic resonance was used to study liquid and supercooled acidic solutions of pentavalent molybdenum compounds, including molybdenyl chloride and pentamolybdenyl sulfate, as well as solutions in nonpolar solvents. Measurements at 9320 and 300 MHz over 77 to 380 K characterized g facto…
V. A. SHARPATYI, Academician S. S. MEDVEDEV
The paper examines whether free-radical polymerization can occur in substituted triazine rings whose polymerization enthalpy estimated from bond energies is near zero, if precipitation and strong intermolecular interactions lower the free energy of the polymer. Substituted triazines and trifluoroace…
Anhydrous perchloric acid exists under ordinary conditions only in the form of the equilibrium
The study examines the melting diagram of the ternary system Cl2O7, SO3, and H2O in the high-acid region near the composition of perchloric acid, with the aim of assessing whether anhydrous perchloric acid can appear as an individual crystallizing phase in the presence of dehydrating sulfur trioxide…
A. A. VERTMAN, Corresponding Member of the Academy of Sciences of the USSR A. M. SAMARIN, E. S. FILIPPOV
This paper reexamines the nickel-rich region of the Ni-C phase diagram after viscosity and electrical-conductivity measurements of liquid alloys suggested inconsistencies with the accepted diagram. Alloys prepared from electrolytic nickel and high-purity graphite were studied by contactless electric…
A. R. GANTMAKHER, Academician S. S. MEDVEDEV
This study examines how alkali metals, organoalkali compounds, solvent polarity, additives, and temperature affect the microstructure of polybutadiene formed by butadiene polymerization. Using vacuum polymerization and infrared analysis of 1,2, 1,4-cis, and 1,4-trans units, the authors compare lithi…
I. G. Bolesov, M. N. Kolosov, Academician M. M. Shemyakin
This paper reports the synthesis of a hydronaphthacene oxytriketone structurally related to the antibiotic demethyltetracycline, as part of studies on tetracycline synthesis and structure activity relationships. The route proceeds from trans-benzoylacrylic acid and butadiene through cyclohexane and …
L. G. BERG, V. P. KOVYRZINA
This study examines why static and thermographic methods give markedly different dissociation pressures and temperatures for cadmium carbonate. Using thermographic measurements at varied pressures, the authors tested the effects of crystallochemically related additives, including sodium chloride, si…
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The study examines how the symmetry and ligand composition of Ti3+ aquo and fluoro complexes in aqueous solution affect proton nuclear relaxation rates. Using spin echo nuclear magnetic resonance measurements and room temperature electron paramagnetic resonance, the authors measured longitudinal and…
E. I. Tinyakova, Corresponding Member of the USSR Academy of Sciences B. A. Dolgoplosk,
This study examines the cationic activity of components of the cobalt catalytic system used for stereospecific butadiene polymerization and investigates the end groups of the resulting polybutadiene chains. Using vinyl butyl ether polymerization, the authors show that cobalt chloride, including its …
Corresponding Member of the Academy of Sciences of the USSR V. G. LEVICH, Z. Ch. GRABOVSKY, V. Yu. FILINOVSKY
This paper develops a theoretical treatment of kinetic and catalytic currents at a stationary hanging drop electrode, emphasizing how spherical electrode curvature modifies results known for plane electrodes. The authors formulate diffusion and bulk reaction equations for reversible chemical transfo…
B. N. KABANOV, V. D. KASHCHEEV
This paper examines the mechanism of anodic activation and dissolution of passive iron in acidic perchlorate media, with comparison to sulfuric and hydrochloric acid solutions. Using potentiostatic and chronoamperometric observations together with colorimetric determination of dissolved iron valence…
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This paper examines the coagulating action of electrolytes on aqueous montmorillonite dispersions using structural and mechanical criteria rather than primarily electrokinetic measures. Fifteen percent suspensions of Gorb bentonite, identified mainly as montmorillonite with a kaolinite-like admixtur…
Yu. M. KORENEV, Corresponding Member of the Academy of Sciences of the USSR, A. V. NOVOSELOVA
The paper investigates the previously undescribed binary BeF2, ZrF4 system as part of a broader study of fluoride phase relations. Alloys prepared from ammonium double fluorides were examined by thermal analysis and X-ray phase analysis, with precautions against zirconium fluoride sublimation and wi…
Nik. A. NESMEYANOV, S. T. ZHUZHLIKOVA, Corresponding Member of the Academy of Sciences of the USSR
This paper reports electrophilic sulfonation of phosphorus ylides with sulfur trioxide, preferably as the dioxane sulfur trioxide complex in dichloroethane, to form crystalline phosphonium sulfobetaines. Several ylides, including diphenylmethylene, carbomethoxymethylene, benzoylmethylene, and acetyl…
V. M. EMEL’YANOVA, Yu. I. PECHERSKAYA, V. B. KAZANSKII
This study examines the relationship between catalytic activity and electron paramagnetic resonance spectra in molybdenum oxide catalysts for ethylene polymerization. Molybdenum oxide was deposited on or coprecipitated with several supports, reduced in hydrogen, tested for polymerization activity un…
V. P. MELESHKO, O. N. MYAGKAYA
This study examines how swelling of ion-exchange membranes governs their permeability to vapors of light and heavy water. Using a sulfonated polystyrene cation-exchange membrane in different salt forms, the authors measured permeability manometrically for water mixtures with varying deuterium oxide …
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This paper reports the synthesis of o-fluoro-omega-nitrostyrene and an investigation of its polymerization as a nitroolefin monomer for high-molecular compounds. The monomer was prepared by condensation of o-fluorobenzaldehyde with nitromethane in the presence of sodium hydroxide, and polymerization…
V. V. LOSEV, A. I. MOLODOV
This paper examines how fluoride ions affect the anodic dissolution and cathodic deposition processes of indium amalgam under conditions of complex formation. Using polarization measurements combined with radiochemical determination of reaction rates, the authors compare fluoride-containing solution…
N. N. ZEMLYANSKII, E. M. PANOV, N. A. SLOVOKHOTOVA,
This paper describes a stepwise method for preparing linear organotin compounds containing stannoxane bonds and reactive acetate terminal groups. Controlled hydrolysis of dibutyltin diacetate and subsequent higher homologs in the presence of diazomethane is used to form discrete members of the serie…
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The study examines the addition of trialkyl phosphites to acetylenecarboxylic acids containing the conjugated system C≡C, C=O, focusing on propiolic and tetrolic acids. Reactions with several phosphites produced colorless, water-soluble liquids that gave tests for unsaturation, and infrared and anal…