L. A. KIPRIANOVA, A. F. REKASHEVA
This study examines the kinetics and mechanism of hydrolysis of vinyl acetate and substituted vinyl benzoates catalyzed by mercury acetate in the presence of sulfuric acid. Rates were measured in aqueous alcoholic solution, varying ester, catalyst, acid, and water concentrations, and substituent eff…
Ya. E. Geguzin, V. I. Solunskii
This study examines whether an externally applied electric field affects diffusion porosity during interdiffusion in alkali halide single crystals, where charged vacancies are expected to contribute to pore development. Experiments were performed on three layer KBr, KCl, KBr specimens annealed at 65…
B. M. Mitsiuk, Z. Z. Vysotsky, M. V. Polyakov
This study examines how the polarity of the intermicellar liquid and its interaction with silicic acid hydrogel particles affect the porous texture of silica xerogels. Hydrogels were converted to alcogels by replacing water with a homologous series of aliphatic alcohols, either in the liquid phase o…
B. Ya. SUKHAREVSKII, S. V. LYSAK
This paper examines how dislocations affect the temperature characteristics of the martensitic polymorphic transformation of cristobalite. A thermodynamic model is developed in which dislocation energy influences both nucleation of the new phase and the temperature of the true allotropic transformat…
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This paper examines the reaction of di-(diethyl)-amidoalkyl esters of phosphorous acid with esters of monochloroacetic acid as an extension of known rearrangements of phosphites and amidoalkyl phosphites with alpha-halocarbonyl compounds. The authors show that these reactions proceed with heat evolu…
A. A. TRAPEZNIKOV
This study examines mechanical degradation of polymer molecules in concentrated solutions during the prestationary stage of deformation, using polyisobutylene in vaseline oil and polymethyl methacrylate in acetone as model systems. Measurements with an elastorelaxometer relate shear stress and rever…
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This study examines whether excitation of electrons from the valence band to the conduction band controls the thermal decomposition rate of ionic azides. Silver azide and barium azide were decomposed while exposed to X-rays, and in the silver azide case also ultraviolet light, with simultaneous meas…
Corresponding Member of the Academy of Sciences of the USSR K. A. Andrianov
The paper examines reactions of phenyl isocyanate with alkylsilazanes and related trialkylsilyl-substituted ureas, a reaction class that had only recently been reported. Through preparative reactions, elemental and molecular-weight analyses, hydrolysis products, and infrared spectra, the authors arg…
E. B. Lyudvig, A. R. Gantmakher, Academician S. S. Medvedev
This study examines the mechanism of cationic polymerization of styrene and alpha-methylstyrene in ethyl chloride using tin tetrachloride with water as cocatalyst, focusing on kinetic anomalies such as induction periods, S-shaped rate curves, and changes in molecular weight. Dilatometric kinetic mea…
B. M. MIKHAILOV, A. Ya. BEZMENOV, L. S. VASIL’EV, V. G. KISELEV
The study reexamines products formed by hydroboration of 1,3-butadiene with diborane, questioning the earlier assignment of the main product as a single di-1,4-(1-boracyclopentyl)butane compound. Fractionation, alkaline hydrogen peroxide oxidation, and gas liquid chromatographic analysis of oxidatio…
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Radiometric titration was applied to study nonequilibrium coprecipitation in the system zinc, cobalt, and tetrarhodanomercurate during gradual addition of lithium tetrarhodanomercurate, using zinc-65 and cobalt-60 indicators. Mixtures with trace zinc, trace cobalt, and equal zinc and cobalt contents…
K. A. SHARIFOV, A. S. ABBASOV
This paper examines how the band gap of nonmetallic solids is related to thermodynamic measures of bond strength, assessing limitations of correlations based on heats of formation, electronegativity differences, atomization energy, and lattice energy. The authors argue that a more general linear rel…
A. B. TERENT’EV
The study examines telomerization of ethylene with glacial acetic acid initiated by tert-butyl peroxide at 140 degrees and 15 to 40 atm as a route to even-numbered saturated carboxylic acids. Reaction products were fractionated and analyzed by gas liquid chromatography, with selected acids isolated …
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The study examines the electrochemical reduction of benzhydrazide and p-nitrobenzhydrazide at a dropping mercury electrode in acidic to near-neutral solutions. Classical polarography and oscillopolarography, supplemented by measurements using a Kalousek switch, are used to identify reduction waves a…
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The paper addresses the problem of selecting an appropriate adsorption isotherm for organic substances at electrode surfaces, comparing criteria based on the behavior of differential adsorption functions. It derives a more general criterion from equations of state of the form involving a coverage fu…
Corresponding Member of the USSR Academy of Sciences N. I. Shuikin, B. L. Lebedev,
This paper investigates the previously unexplored vinylation of saturated cyclic compounds by acetylene with formation of carbon, carbon bonds. Using di-tert-butyl peroxide as a radical initiator, cyclohexane, decalin, tetrahydrofuran, dioxane, and tetrahydropyran were reacted with acetylene in a ro…
N. S. Kozlov, A. D. Nikolaev
This study examines the acid-catalyzed addition of antipyrine to the azomethine bond of Schiff bases, motivated by the mobile hydrogen at the fourth carbon atom of antipyrine and the potential physiological interest of its derivatives. Using hydrochloride salts of the amines present in the Schiff ba…
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This study reports the synthesis and characterization of tetrahydrates of perrhenates of the rare-earth elements, excluding promethium, and yttrium, with the general composition Me(ReO4)3 · 4H2O. The compounds were obtained by crystallization from perrhenate solutions and analyzed chemically, by den…
A. I. Titov, M. V. Sizova, P. O. Gitel’
This paper reports a method for preparing beta-chloroalkyldichlorophosphines by addition of phosphorus trichloride to olefins in the presence of aprotic Lewis acids such as aluminum chloride. The authors propose an ionic mechanism involving donor-acceptor complexes, ionization to electrophilic phosp…
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This paper reports a simplified synthesis of xenon difluoride from xenon and fluorine under ordinary temperature and elevated pressure, in contrast to earlier methods requiring heating, irradiation, electric discharge, or specialized apparatus. The authors argue that severe conditions are unnecessar…
I. G. ARZAMANOVA, E. N. GURYANOVA, I. P. GOLDSHTEIN
A dielectrometric titration method is developed for determining thermodynamic constants of molecular compound formation in nonpolar solutions. The approach measures changes in dielectric constant and density during stepwise addition of one component, uses deviations of titration curves from extrapol…
V. A. PUCHKOV, V. M. STEPANOV, N. S. VULFSON, A. M. ZYAKUN,
This study addresses the difficulty of identifying amino acid derivatives released during peptide sequencing by Edman-type procedures, where phenylthiohydantoins may give weak or non-diagnostic molecular and fragment peaks. The authors examine methylthiohydantoins of amino acids as alternative deriv…
S. S. BATSANOV, L. M. DORONINA, N. V. PODBEREZSKAYA
This study investigates mixed-anion chromium compounds formed from divalent chromium sulfide, motivated by the covalent character of Cr-S bonding and the expected oxidation behavior of chromium in such systems. Chromium sulfide was synthesized from the elements, then reacted with selenium or telluri…
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This paper reports the hydrothermal synthesis and characterization of new garnet-type compounds in which octahedral positions are occupied by vanadium, indium, or scandium ions. Using chloride solutions as solvents at about 550°C and 1300 atm, the author prepared several calcium, cadmium, and mangan…
Corresponding Member of the USSR Academy of Sciences K. A. KOCHESHKOV
This paper describes the preparation of organozinc compounds of the type R2Zn in aromatic, heterocyclic, araliphatic, and aliphatic series using Grignard reagents and zinc chloride. The authors isolate several products as dioxanates by precipitating magnesium salts with dioxane, obtaining diphenylzi…
A. D. PETROV
The study investigates the reaction of chlorocarbene, generated from methylene chloride and methyllithium, with benzene and several alkylbenzenes as a route to substituted methyltropylidenes. Experiments varying temperature, reagent ratios, and addition rate showed optimal formation near 30 to 40 °C…
N. A. ADROVA, L. K. PROKHOROVA, Corresponding Member of the Academy of Sciences of the USSR M. M. KOTON
This paper reports the synthesis of polymers containing dibenzborimidazoline units in the main chain as part of a study of heat-resistant polymers with rigid heterocyclic structures. Polycondensation of 3,3-diaminobenzidine with either the tetrabutyl ester of p-phenylenediboronic acid or tetraacetyl…
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This study examines the infrared absorption spectrum of crystalline potassium ferricyanide under high pressure, focusing on the 4197 cm−1 band assigned to an overtone vibration of the ferricyanide complex. Spectra recorded during compression show a pressure induced shift of this band toward higher f…
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This study examines the structure of the electrical double layer on high-purity gallium, testing whether regularities established for mercury electrodes also apply to another liquid metal. Differential capacitance was measured on a dropping gallium electrode in 1 N solutions containing various catio…
Yu. N. Surovoi, V. I. Alekseev, L. A. Shvartsman
This paper investigates the thermodynamics of complex iron, molybdenum carbides of the type (Fe x Mo y)2C, a class for which data were limited compared with simple transition metal carbides. Carbides with several iron contents were synthesized, structurally identified as having the Mo2C structure, a…
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This paper applies the thermodynamics of irreversible processes to heterogeneous catalysis, focusing on the recombination of gas atoms on solid surfaces. The authors model an open two-phase system consisting of a gaseous atomic-molecular mixture and a solid catalyst, derive entropy production and li…
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This paper examines stationary one-dimensional linear pyrolysis of condensed substances, focusing on polymethyl methacrylate, and addresses whether the decomposition rate can be related directly to surface or heater temperature. The authors combine experimental measurements of decomposition rate, pl…
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This paper examines relationships among viscosity, low-frequency Raman spectra, and thermodynamic parameters in the homologous series of normal paraffins from C5 to C18. Activation energies derived from the temperature dependence of viscosity are compared with Raman frequencies below 500 cm-1 in liq…
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This paper examines the structure of electronic absorption bands of hexaaquocobalt(II) and cobalt(II) complexes with oxygen-containing organic ligands in solution, focusing on the 25,000 to 13,000 cm⁻¹ region used to infer coordination symmetry. Using recording spectrophotometry and graphical differ…
Ya. A. Ugai, E. P. Domashevskaya
This paper examines the nature of chemical bonding in group III to group V semiconductor compounds, challenging the model of Mooser and Pearson that assumes electron transfer from the group V atom to the group III atom before tetrahedral covalent bonding. Using x-ray spectral analysis of the antimon…
A. A. TRAPEZNIKOV, R. A. AVETISYAN
This study examines how wave motion and aging affect the ability of cetyl alcohol monolayers to reduce water evaporation. Using a controlled water bath, a mechanical wave generator, vapor absorption measurements, and surface pressure measurements, the authors compared clean and monolayer-covered sur…
Academician A. A. GRINBERG, YUAN KAN
The paper reports the synthesis and characterization of tetravalent platinum triglycocollate derivatives, especially the previously unobtained compound [Ptgl3]Cl. Oxidation of sodium diglycocollatoplatinate(II) with hydrogen peroxide gave a dihydroxo platinum(IV) intermediate, which was converted by…
R. G. MIRSKOV
A method is described for synthesizing oxygen-containing organotin acetylene compounds in which the triple bond is in the alpha position relative to tin. The approach involves reacting acetylene derivatives containing an acetylenic hydrogen atom with hexaethylstannoxane, and is illustrated by the pr…
Academician I. L. KNUNYANTS, G. A. SOKOLSKII, M. A. BELAVENTSEV
This paper examines the structure and reactivity of fluorine-containing beta-sultones formed from fluorinated olefins and sulfur trioxide, with emphasis on tetrafluoroethane-beta-sultone and related isomers. Using reactions of trifluorovinyl chlorosulfate, halogen exchange, thermal isomerization, an…
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This paper examines the thermochemistry of extracting cerium(IV) nitrate from aqueous solution with tributyl phosphate, a system complicated by hydrolysis and possible transfer of basic salts into the organic phase. Using direct calorimetric measurements at 25 degrees, the authors determined heats o…
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This paper examines conditions for preparing concentrated nitric acid solutions of pentavalent plutonium and using them to synthesize Pu(V) compounds. Stability experiments over pH 2 to 6 and plutonium concentrations from 0.5 to 5 g/l indicate that Pu(V) is most stable at pH 3.5 to 4.5 and at concen…
Corresponding Member of the Academy of Sciences of the USSR V. V. VOEVODSKII
This study examines whether benzene derivatives photosensitize the low-temperature decomposition of saturated hydrocarbons under ultraviolet irradiation. Dilute frozen solutions of substituted aromatic compounds in 3-methylpentane and partially deuterated 3-methylpentane at 77 K were irradiated, wit…
I. I. Astakhov, E. S. Vaisberg, B. N. Kabanov
This study examines the mechanism of anodic film growth during corrosion of lead in sulfuric acid, focusing on how acid concentration, temperature, polarization time, and cobalt sulfate affect film composition and structure. Smooth lead electrodes were anodically polarized in sulfuric acid solutions…
A. Ya. Khorlin, A. G. Venyaminova, N. K. Kochetkov
The paper determines the structure of kalopanax-saponin A, a hederagenin bioside isolated from the roots of Kalopanax septemlobum and containing arabinose and rhamnose. The authors use methylation, acid hydrolysis, chromatographic identification of methylated sugars, mass spectrometry, infrared and …
The alkaloid cocaine
This study examines the stereochemistry and conformation of four isomeric methyl esters of ecgonine, compounds related to the cocaine series, using infrared spectroscopy. Analysis of hydroxyl stretching bands, dilution effects, and solvent-dependent shifts in C-O stretching vibrations is used to dis…
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A thermodynamic method is developed for deriving extraction equations for ternary aqueous salt solutions contacted with an extractant insoluble in the aqueous phase. Using the McKay and Perring differential equation together with isopiestic data, the authors relate salt activities in the organic pha…
Corresponding Member of the Academy of Sciences of the USSR B. K. Vainshtein, G. V. Gurskaya
The paper reports an X-ray crystallographic determination of the structure of L-phenylalanine hydrochloride, adding phenylalanine to the set of amino acids with known atomic structures. Crystals grown from hydrochloric acid solution were analyzed from 933 Cu K-alpha reflections in space group P21212…
A. A. TRAPEZNIKOV, T. A. LOMONOSOVA
This study examines the phase behavior of mono-oxyethylated hexadecanol and octadecanol, surface-active alcohol derivatives relevant to water evaporation suppression, with particular attention to hydration, polymorphism, and equilibrium with condensed monolayers. Equilibrium two-dimensional pressure…
GIL'M KAMAI, Z. L. KHISAMOVA
This paper reports the first preparation of N-substituted organoarsenic derivatives of ethylenimine through reactions of ethylenimine with monoalkyl, dialkyl, and aryl haloarsines in the presence of triethylamine. The authors obtained mono- and diethylenimides of alkyl and aryl arsonous acids, chara…
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The study uses proton nuclear magnetic resonance to examine the state of water and hydrogen in phosphomolybdic acid hydrates with different water contents. Measurements of absorption line shapes, second moments, and temperature dependences from 77 to 293 K show that dehydration changes the proton st…