V. S. Zavgorodnii, A. A. Petrov
The study examines free radical addition to 1,3-enyne organotin hydrocarbons as part of an effort to assess how tin affects the reactivity of conjugated enyne systems. Triphenylmethyl radicals, generated mainly from hexaphenylethane in benzene, were added to triethyltin vinylacetylene and triethylti…
Yu. N. Sheinker, E. M. Peresleni, A. I. Kol’tsov, N. M. Bazhenov,
This study examines the tautomeric structure of 2-aminothiazoline, a nonaromatic heterocyclic amine for which amino and imino forms had been considered possible. Infrared spectra, including deuteration experiments and dilution studies, were compared with nuclear magnetic resonance spectra in chlorof…
Corresponding Member of the Academy of Sciences of the USSR G. A. RAZUVAEV, A. I. GRAEVSKII,
This paper investigates the oxidation of triethylaluminum and related organoaluminum compounds in heptane solution, a process important both as an impurity-forming reaction in aluminum alkyl synthesis and as a route to alcohol precursors. Using oxygen absorption measurements, conductivity monitoring…
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This study reexamines the acid-catalyzed reactions of delta-3-carene oxide with alcohols, addressing discrepancies in earlier reports on whether isomerization gives aldehydic or ketonic products. Using sulfuric acid in methyl, isopropyl, and tert-butyl alcohols, the authors isolate and characterize …
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This paper examines the stability of emulsions with particular attention to the distinction between reversible droplet coagulation and irreversible coalescence, arguing that emulsion destruction depends on the latter rather than on aggregation alone. The authors measured streaming potentials in high…
N. I. IONOV, M. A. MITTSEV
This paper examines the use of surface ionization as a method for studying catalytic reactions occurring in adsorbed layers on metallic surfaces. Experiments with a heated tungsten filament and magnetic-sector mass spectrometer measured ion emission during joint adsorption of barium atoms with lithi…
I. A. Tutorskii, I. Ya. Slonim, Ya. G. Urman, E. P. Kudryavtseva,
Natural rubber cyclization in phenol media, catalyzed by phosphorus pentoxide, was investigated by nuclear magnetic resonance over 77 to 400 K, with residual unsaturation measured chemically and phase state checked by X-ray diffraction. The NMR line width changes little at early cyclization stages, …
I. A. Smirnov, N. M. Morozov, M. I. Temkin
This paper examines the kinetics of ammonia synthesis on promoted iron catalysts in the presence of water vapor, addressing limitations of earlier poisoning equations that fail to reduce to the standard synthesis rate law when water is absent. A kinetic expression is derived by treating adsorbed nit…
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The study examines the reaction of Delta3-carene oxide with methyl alcohol in the presence of sodium methylate, motivated by earlier evidence that acid catalysis gives mainly the anomalous addition product. The reaction mixture was heated in sealed tubes, fractionated, and analyzed by elemental anal…
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This paper investigates how grafted polyacrylic acid is distributed within synthetic polymer fibers and addresses the low electron-microscopic contrast between grafted and ungrafted polymer regions. Polyethylene, isotactic polypropylene, and capron fibers prepared by radiation gas-phase graft polyme…
R. A. KARAKHANOV
This paper reports a selective route to tetrahydrofuran ketones from furfurylideneacetone and their conversion into gamma diketones. Hydrogenation in the liquid phase over a skeletal palladium aluminum catalyst is shown to reduce first the side chain double bond and then the furan ring while largely…
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The paper analyzes resonant vibrational relaxation in a closed system of interacting harmonic oscillators when first order perturbation theory may fail because transition probabilities can become large. Using the adiabatic approximation and a slow beat condition, it derives transition probabilities …
V. A. Khramchenkov
This paper examines the radiation-initiated bulk polymerization of several fluoroolefins under cobalt-60 gamma irradiation at room temperature, with attention to how fluorine and hydrogen substitution affects chain growth. Polymerization rates, radiation-chemical yields, molecular weights, conversio…
Yu. V. ZEIFMAN, N. P. GAMBARYAN, Academician I. L. KNUNYANTS
This paper reports methods for preparing imines of hexafluoroacetone, compounds previously difficult to obtain by conventional dehydration or ketal routes. The authors describe a catalytic synthesis of the anil from phenyl isocyanate and hexafluoroacetone in the presence of triphenylphosphine oxide,…
L. A. GILYAROVSKAYA
This study examines how a tertiary carbon atom affects the liquid phase oxidation of monomethyl substituted paraffin hydrocarbons in the presence of boric acid. Synthesized 2-methyldodecane and 8-methylpentadecane were oxidized with a dilute oxygen containing gas at 165 to 170°C, and the resulting p…
Yu. A. Zhdanov, G. N. Dorofeenko, S. V. Zelenskaya
This paper examines thin layer chromatography on calcium sulfate as a rapid method for determining and separating carbohydrates and related polyhydroxy compounds. Plates coated with gypsum were tested with chloroform and methanol solvent systems for monosaccharides, disaccharides, and polyhydric alc…
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This paper examines how molecular oxygen affects scission of the main chain in polydimethylsiloxane rubber during high-temperature oxidation. The authors use chemical stress relaxation of preoxidized, structured rubber samples heated in oxygen, nitrogen, or argon to compare rates of network rupture …
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The paper examines the passage of direct current through a symmetric binary 1-1 electrolyte, focusing on the distribution of electric field and ion concentrations near a charged electrode where one ion species is discharged. It proposes a boundary-layer approximation for the diffusion-kinetic equati…
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This note develops an approximate theory for the transition between volumetric thermal ignition and ignition initiated near heated vessel walls in an exothermic reacting substance. Starting from the stationary theory of ignition by a heated surface, it estimates the induction period by solving the t…
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This paper examines thermal rearrangements of allylic and propargylic esters of phosphorous acid as reactions analogous to Claisen rearrangements. The authors compare substituted allyl and propargyl phosphites using product properties and infrared spectra, showing that allylic esters rearrange on he…
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This study examines why titanium electrodeposition from aqueous acidic and alkaline salt solutions is limited and strongly dependent on cathode material. Polarization measurements, gasometric and gravimetric current efficiency determinations, microscopy, chemical and spectral analyses, diffusion exp…
L. Ya. KOBELEV
This paper proposes a quantum-theoretical model for rapid low-temperature polymerization in solid monomers, addressing anomalously high rates, weak or negative activation energies, and rate jumps near phase transitions. The model treats polymerization as collective ordering of quasiparticles, such a…
Corresponding Member of the Academy of Sciences of the USSR M. F. Shostakovskii, G. G. Skvortsova,
This study examines the formation of complexes between tin tetrachloride and vinylaromatic ethers during the initial stages of cationic polymerization, focusing on vinyl ethers of phenol and o-aminophenol, with comparison to aniline. The authors isolated unstable crystalline complexes, characterized…
N. E. Laptieva
This paper examines intramolecular transesterification reactions of substituted esters of gamma-hydroxypropylalkoxysilanes prepared by platinum-catalyzed addition of hydridoalkoxy and hydridoalkylalkoxysilanes to allyloxysilanes. It reports the synthesis and characterization of several new siloxypro…
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This paper examines how hydrogen bonds in quasiaromatic rings of pi-electron molecules behave upon electronic excitation, addressing conflicting interpretations that such rings either persist or rupture. The authors develop an energy argument in which excitation weakens the chromophoric multiple bon…
L. A. DUDINA, Al. Al. BERLIN, L. V. KARMILOVA, N. S. ENIKOLOPYAN
This paper examines changes in the molecular weight of polyformaldehyde during oxidative destruction, motivated by earlier evidence that oxygen initiates depolymerization rather than causing ordinary oxidative degradation. The authors develop a kinetic treatment for random oxygen-initiated chain sci…
V. F. SHUVALOV, R. F. VASIL’EV, L. M. POSTNIKOV, V. Ya. SHLYAPINTOKH
This paper investigates the chemical origin of chemiluminescence observed during the low-temperature gas-phase oxidation of acetaldehyde, a reaction in which emission had been detected well below the usual cold-flame temperature range. The authors recorded the chemiluminescence spectrum at 182 degre…
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The paper proposes a resonance description of chemical reaction rates involving hot atoms, ions, radicals, and molecules at translational energies where the equilibrium complex method and direct knock-out models appear inadequate. Using concepts from scattering theory, including analytic properties …
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This study examines how neutron irradiation and the subsequent radioactive radiation of activated sodium tungstate and sodium sulfate affect their polymorphic transformations and melting behavior. Purified samples were irradiated in a reactor, characterized by beta and gamma spectroscopy and activit…
Academician A. A. BALANDIN, A. A. TOLSTOPYATOVA, V. A. NAUMOV
This paper examines whether organogenic atoms in reacting molecules bind primarily to metal atoms or oxygen atoms on oxide catalyst surfaces, a question important for applying multiplet theory and kinetic methods to catalyst selection. Using previously determined kinetic bond energies for hydrogen, …
S. P. Gabuda, G. M. Mikhailov, K. S. Aleksandrov
This paper investigates the behavior of zeolitic water in harmotome and its relation to the crystal’s symmetry, particularly the apparent tension between an almost centrosymmetric structural model and observed piezoelectricity. Using proton nuclear magnetic resonance on an oriented single crystal ov…
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The paper addresses how to quantify the initiating activity of peroxide initiators in radical polymerization, arguing that commonly used criteria such as decomposition rate, polymerization rate, or initiation rate are not generally universal. It develops a steady-state kinetic treatment distinguishi…
V. T. ALEKSANYAN, E. V. SOBOLEV
This paper examines factors governing the double-bond stretching frequencies in vibrational spectra of conjugated dienes, with attention to the assignment of symmetric and antisymmetric modes in Raman and infrared spectra. Using tabulated spectral data and qualitative force-field analysis, the autho…
V. E. Plyushchev, S. B. Stepina, L. I. Lepeshkova
This paper addresses the separation of trace cesium impurities from rubidium salts, a problem not solved by previously used heteropolyhalide purification methods. The authors examine rubidium and cesium triiodides, determine cocrystallization coefficients for cesium during crystallization of rubidiu…
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This paper examines how the specific surface area of tobermorite, a layered calcium hydrosilicate formed during silicate cement hydration, can be calculated from crystal lattice parameters and water adsorption data. Using a swelling layered-structure model, dilatometric measurements of tobermorite f…
O. V. BRAGIN, A. L. LIBERMAN, G. K. GUR’YANOVA,
This study examines the configurational isomerization and hydrogenolysis of cis- and trans-1,2-dimethylcyclopentanes over carbon-supported rhodium, osmium, iridium, and palladium catalysts under comparable flow conditions in hydrogen. The experiments show that all four catalysts promote mutual inter…
V. D. POKHODENKO, L. N. GANYUK, Corresponding Member of the Academy of Sciences of the USSR
This paper examines the thermal decomposition of bis-(1,3,5-tri-tert-butyl-cyclohexadienone) peroxide, addressing whether its breakdown follows an ionic or homolytic pathway. The authors synthesize and characterize the peroxide by infrared spectroscopy and chemical reduction, then analyze decomposit…
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This study uses electron paramagnetic resonance to examine the primary radical products formed during radiolysis of solid polyvinyl alcohol under vacuum, with sorbed water vapor, and at different irradiation and measurement temperatures. Analysis of spectral shapes, dose dependence, microwave satura…
In a series of communications, diarsenites of various glycols of the general type
The study examines reactions of acid chlorides of dialkylarsenious acids with several diols in pyridine, aiming to prepare mixed diarsenites of arsenious acid. Experiments with diethyl, dipropyl, diisopropyl, and dicyclohexyl derivatives showed that the expected diarsenites generally disproportionat…
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This study examines the ultraviolet absorption, luminescence, and scintillation properties of a series of 2-aryl derivatives of benzoxazole and benzimidazole, including N-substituted benzimidazoles. Spectra were measured in solution, photoluminescence quantum yields were compared with 2,5-diphenylox…
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This study examines how chlorine substituents affect the electronic character and conjugation behavior of the cyclopropane ring in alkyl, alkenyl, and phenyl derivatives of 1,1-dichlorocyclopropane. Raman spectra were measured for several synthesized derivatives and compared through the frequencies …
B. A. FEDOROV, O. B. PTITSYN
This paper proposes a method for determining transverse dimensions of rodlike and anisotropic macromolecules in solution from small-angle X-ray scattering curves plotted as intensity multiplied by the square of the scattering angle. The authors derive the expected position of the maximum for cylindr…
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This paper reports the Friedel-Crafts acylation of ferrocene with the acid chloride of the monomethyl ester of maleic acid to obtain 1-ferrocenoyl-2-carbomethoxyethylene. The product was characterized by elemental analysis, molecular weight determination, infrared spectroscopy, and catalytic hydroge…
Academician A. N. FRUMKIN, D. I. DZHAPARIDZE, G. A. TEODORADZE
This study examines catalytic hydrogen evolution on mercury from hydrochloric acid solutions of diphenylamine at high electrode surface coverages, using electrocapillary, differential capacitance, polarization, and polarographic measurements. The results indicate that diphenylamine molecules and dip…
I. P. BELETSKAYA, G. A. ARTAMKINA, Corresponding Member of the Academy of Sciences of the USSR O. A. REUTOV
This paper investigates the “cosymmetrization” of pairs of para-substituted ethyl alpha-bromomercuriphenylacetates under the action of ammonia, extending earlier work on electrophilic bimolecular substitution at saturated carbon in organomercury salts. Kinetic measurements by nephelometry show that …
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The study examines oxygen quenching of excited states in chemiluminescent solutions during initiated oxidation of ethylbenzene in benzene. By following oxygen consumption in sealed reaction mixtures and applying Stern-Volmer analysis to chemiluminescence intensity, the authors estimate the quenching…
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This paper investigates nucleophilic addition reactions of benzo-alpha-phenoxazinone-9 and 9-dimethylamino-benzo-alpha-phenoxazonium chloride with sulfur-containing nucleophiles, extending reactions previously known for arylamines and p-benzoquinone analogs. The authors show that thiourea, mercapto …
I. Ya. Poddubnyi, V. A. Grechanovskii
This paper examines the concentration dependence of the sedimentation constant of polymers in thermodynamically ideal solvents, a question relevant to molecular weight distribution studies and ultracentrifuge resolution. Sedimentation measurements were made for several polymer solvent systems, inclu…
B. P. SHTARKMAN, S. S. VOYUTSKII, Academician V. A. KARGIN
This paper examines the molecular mechanism of polymer autohesion in materials with ordered supramolecular structures, using polyethylene and plasticized polyvinyl chloride as examples. The authors measure the work of autohesion by delamination after controlled contact times, temperatures, plasticiz…
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This paper investigates the titanium, oxygen system in the range 0 to 35 atomic percent oxygen, addressing earlier indications that suboxide compounds or ordered states may occur within the alpha titanium solid solution region. Alloys prepared by arc melting and heat treated at several temperatures …