N. V. Gliki, A. A. Eliseev, and N. M. Marchenko
This paper investigates the crystallization of supercooled water drops into ice granules, emphasizing the use of transmitted polarized light between crossed nicols to characterize their internal crystallographic structure. Experiments with suspended droplets show that, depending on supercooling, dro…
O. Ya. NEILAND and Academician of the Academy of Sciences of the Latvian SSR G. Ya. VANAG
The paper examines the reaction of phenyliodoso acetate and related phenyliodoso compounds with several beta-diketones and beta-keto esters in order to clarify the mechanism of their interaction. On the basis of product isolation, counter synthesis, and ultraviolet and infrared spectral characteriza…
E. N. Paleolog, K. S. Korotkova, and N. D. Tomashov
This study examines the kinetics of hydrogen ion discharge and anodic dissolution on single crystal silicon electrodes in acidic and alkaline electrolytes, using n-type and p-type specimens of different resistivities. Polarization measurements in sulfuric acid, hydrofluoric acid, and potassium hydro…
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This paper examines the structure of products formed by adding alkylsulfenyl chlorides to acrylic acid, substituted acrylic acids, and their esters, a problem complicated by possible isomerization of halo thio propionic derivatives. The authors prepare a series of addition products and use comparati…
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This paper examines the reactivity of newly accessible 1,2-diaryldiboranes toward olefinic and diene hydrocarbons under inert conditions. Experiments with propylene and butene-1 show addition followed by rapid symmetrization to triphenylboron and trialkylboranes, while reactions with butadiene and i…
V. F. BALAKIREV
This study examines the mechanism and kinetics of hydrogen reduction of cobaltous-cobaltic oxide, addressing conflicting interpretations of whether cobalt monoxide is an intermediate phase at low temperatures. Reduction experiments were conducted at 225 to 350 degrees and varied hydrogen pressures, …
R. N. VOLKOV and S. V. ZAVGORODNII
This paper examines the liquid phase autoxidation kinetics of isopropylxylenes and related polyalkylbenzenes with adjacent alkyl substituents. Using catalytic oxidations with manganese and cobalt salts, product analysis, co-oxidation experiments, and isolation or identification of acids, alcohols, k…
N. A. MALAFEEV, V. A. MALYUSOV, N. N. UMNIK, I. V. PODGORNAYA
This paper reports measurements of the saturated vapor pressure of tetrachloroalkanes containing 9 to 17 carbon atoms at low pressures, a range needed for calculations of molecular and high-vacuum distillation processes. The authors used a static tensimetric method in which vapor force deflects a su…
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This communication examines the stereochemistry of intracomplex uranium(VI) compounds formed with several azomethine Schiff bases derived from o-hydroxyaldehydes, ethylenediamine, aromatic amines, and 2-aminopyridine. Elemental analyses and thermal behavior of the complexes are used to infer ligand …
V. F. MIRONOV, N. G. DZHURINSKAYA
The study examines the addition of trichlorogermane to a series of chlorinated ethylenes, reactions that are difficult or low yielding for analogous chlorosilanes. Trichlorogermane was found to add readily without catalysts to vinyl chloride, dichloroethylene, trichloroethylene, and tetrachloroethyl…
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This paper examines whether luminescence quenching can be used to study intramolecular energy transfer along aliphatic methylene chains. A kinetic scheme is developed for gamma-excited solutions containing dioxane solvent, terphenyl activator, and alcohol quenchers, and relative light yields are use…
N. A. BAKH, G. G. BABICHEVA, and V. A. LARIN
This study examines whether leuco bases of triphenylmethane dyes undergo radiation oxidation in oxygen-free organic ketone solutions through products of solvent radiolysis. Nitrogen-saturated solutions, chiefly leuco crystal violet in acetone and methyl ethyl ketone, were irradiated with gamma rays,…
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A thermographic procedure is described for estimating small thermal effects in milligram to centigram samples at temperatures below 0 degrees, including the liquid nitrogen region. The apparatus uses a low-inertia copper, constantan thermocouple, radiant heating in a small evacuated cryostat, and ca…
Academician of the Academy of Sciences of the Latvian SSR G. Ya. Vanag, E. Yu. Gudrinietse,
This paper examines the thiocyanation of 2-arylindandiones-1,3, a previously unexplored class of thiocyanate derivatives related to pharmacologically active indandione anticoagulants. The authors prepare 2-thiocyano-2-arylindandiones by substitution of 2-bromo derivatives with potassium thiocyanate …
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This paper addresses the determination of rate constants and activation energies for elementary reactions of hydrogen atoms with saturated hydrocarbons, reactions important in hydrocarbon oxidation and cracking. The authors propose a modification of inhibition methods based on the increase of the lo…
N. N. SEVRYUGOVA and Corresponding Member of the Academy of Sciences of the USSR N. M. ZHAVORONKOV
The study examines the temperature dependence of the liquid vapor separation coefficient for the isotopic system C13O and C12O over a pressure range extending above atmospheric pressure. Carbon monoxide samples of natural composition and samples enriched to 23 and 32 percent C13 were purified, chara…
O. Ya. NEILAND and Academician of the Academy of Sciences of the Latvian SSR G. Ya. VANAG
This paper examines the formation, reactivity, and structural interpretation of iodonium derivatives obtained from 5-phenylcyclohexane-1,3-dione and phenyliodoso compounds. The authors prepare enolatebetaine phenyl-(5-phenylcyclohexanedione-1,3-yl-2)-iodonium and study its cleavage under acidic, bas…
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This paper investigates the activation energy for thermal dispersal of silver atom groups during the early formation of a latent photographic image in silver bromide emulsions. It develops and extends Meiklyar’s analysis of long-exposure nonreciprocity isopaque curves to cases where the thermally st…
E. G. PEREVALOVA, O. A. NESMEYANOVA, and I. G. LUK’YANOVA
The study reports the synthesis and reactions of ferrocene mono- and disulfinic acids, with emphasis on preparing ferrocenedisulfinic acid by zinc reduction of the corresponding disulfonyl chloride. The authors examine the stability and solubility of the acids and sodium salts, and show that both su…
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Molar volumes of gaseous solutions of water in compressed ethylene were measured by a constant-volume piezometer method at 200 to 300°C and pressures up to about 100 to 150 atm. The experimental pressure, volume, temperature data for several compositions were analyzed with a virial equation of state…
T. I. Sendulskaya and M. Ya. Shpirt
This study examines the coprecipitation of microquantities of germanium, present as germanic acid anions, with ferric hydroxide and evaluates factors affecting its completeness. Experiments varied temperature, contact time, Ge:Fe ratio, germanium concentration, electrolyte addition, and pH, with ger…
The reaction of atomic oxygen with molecular hydrogen, with formation of hydroxyl radicals and hydrogen atoms,
This paper determines the rate constant for the elementary reaction of atomic oxygen with molecular hydrogen to form hydroxyl radicals and hydrogen atoms, a step important in oxidation mechanisms but previously lacking reliable kinetic data. The authors derive a relation between the first ignition l…
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This paper examines whether hydrazine decomposition, initiated as a heterogeneous catalytic reaction, can continue in the gas phase under conditions suggesting a radical chain mechanism. Using differential calorimetry with a thermocouple measuring relative heating between catalyst and gas phase, the…
Corresponding Member of the Academy of Sciences of the USSR K. A. ANDRIANOV and A. I. PETRASHKO
This paper examines the reaction of alkylcyclosiloxanes with titanium tetrachloride as a route to titanium-containing organosilicon compounds. The authors report that octamethylcyclotetrasiloxane and hexaethyltricyclosiloxane react with titanium tetrachloride above 140 degrees Celsius without added …
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This paper examines whether the stretching frequency of the carbonyl group can be used as an indicator of carbonyl bond polarity in compounds with unusual ring structures, especially sydnones and tropone. Using infrared spectra measured on a two-beam spectrometer and integral band intensities determ…
D. N. ANDREEV and E. V. KUKHARSKAYA
This study examines the condensation of trimethylethylsilane and dimethyldiethylsilane under a high-voltage silent discharge at audio frequency in hydrogen, a reaction not previously investigated for tetraalkylsilanes. The authors identify gaseous products and characterize liquid and high-boiling co…
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This paper examines the catalytic role of copper ions in the dissolution of silver in ammoniacal solutions under oxygen depolarization, a process thermodynamically favorable but kinetically hindered by slow electron removal from the metal surface. Using rotating disk experiments in an autoclave, the…
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This study uses Raman combination-scattering spectra to examine the conformational equilibria of cyclohexanone, alpha-chlorocyclohexanone, alpha-methylcyclohexanone, and beta-methylcyclohexanone in liquid form and, for some cases, solution. Splitting of the carbonyl and ring vibrational bands is int…
A. L. LIBERMAN, N. I. TYUN’KINA, and Academician B. A. KAZANSKII
This study examines how side-chain structure affects the relative boiling points of cis and trans stereoisomers in 1,4-dialkylcyclohexanes, a question raised by earlier observations of boiling-point inversion in 1,4-diisopropylcyclohexane. The authors synthesized 1,4-di-n-propylcyclohexane and 1-met…
Corresponding Member of the Academy of Sciences of the USSR V. G. LEVICH and V. A. KIR’YANOV
This paper develops a statistical theory of the electric double layer at a metal, electrolyte interface, addressing limitations of the Gouy and Gouy-Stern treatments arising from neglected interionic correlations and the discrete structure of charge. Using the correlation function method of Bogolyub…
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This paper examines how adsorption of catalysts affects polarographic catalytic hydrogen waves, using quinine in borax solution as the main example. It argues that the observed catalytic current is the sum of a bulk reaction current and a surface reaction current involving adsorbed catalyst, and sho…
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This paper reports photoionization measurements of vapors of aldehydes, ketones, amides, acids, and halogenated ketones containing a carbonyl group, with emphasis on how substituents affect the first ionization potential. The data are interpreted in terms of electron density at the carbonyl oxygen, …
N. S. NIKOLAEV and E. G. IPPOLITOV
This paper reports the preparation of rhenium hexafluoride by fluorinating metallic rhenium with gaseous chlorine trifluoride. Motivated by the difficulty of avoiding oxyfluoride formation in earlier fluorination methods, the authors tested chlorine trifluoride and found that liquid reagent did not …
and CHZHAN CHZHAO-LAN
This study examines the catalytic dehydrogenation of isopentane over chromium oxide, aluminum oxide catalysts at 500 to 600 degrees, with particular attention to kinetic measurements in a fluidized catalyst bed. Experiments in fluidized and fixed beds, combined with chromatographic analysis of produ…
V. I. MIKHEEVA and V. B. BREITSIS
This paper investigates the ternary solubility system sodium borohydride, sodium hydroxide, and water at 0°C, with attention to conditions that stabilize aqueous borohydride solutions and permit isolation of crystalline hydrate forms. Using purified sodium borohydride, sodium hydroxide solution, iso…
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This study examines the liquid-phase oxidation of cyclohexanol by oxygen containing ozone at 50 to 100°C, measuring ozone uptake and the formation of cyclohexanone, peroxides, acids, and esters. Product distributions, inhibitor experiments with hydroquinone, and comparison with thermal oxidation are…
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This paper reports additional measurements of the equilibrium for vapor-phase ethyl alcohol synthesis from ethylene and water at elevated pressures, extending earlier work on the pressure dependence of the equilibrium constant. Using gas mixtures chosen to avoid condensation, the authors compare mea…
Corresponding Member of the Academy of Sciences of the USSR G. B. Bokii and G. A. Kukina
This paper reports an X-ray crystallographic study of cis-ethyleneamminedibromide of platinum, undertaken to clarify the structural trans influence in a compound not complicated by an outer-sphere ion. Using interatomic-function projections and electron-density projections, the authors determine a t…
V. A. Khitrov, V. I. Shatalova, I. S. Smolyaninov, and Yu. I. Sadovskaya
This paper examines how temperature affects the corrosion rates of several metals in acidic media and evaluates the applicability of the Arrhenius relationship to these heterogeneous corrosion processes. Using corrosion measurements for iron, steel, nickel, zinc, aluminum, copper, cadmium, tin, and …
Yu. A. Buslaev and N. S. Nikolaev
The paper investigates the 25°C solubility isotherm of the HF, HfF4, H2O system in order to clarify the interaction of hafnium fluorides with hydrofluoric acid and to compare hafnium and zirconium fluoride solubilities. Using chemical analysis of liquid and solid phases, the study identifies success…
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This paper examines electronic absorption spectra of aromatic hydrocarbons dissolved in anhydrous liquid hydrogen chloride in the presence of aluminum chloride, with attention to the formation of positively charged hydrocarbon species. The authors developed pressure resistant Monel, platinum, and li…
K. I. NARBUTT, R. L. BARINSKII, and I. S. SMIRNOVA
This study investigates fluorescence X-ray spectral analysis using an artificial thulium-170 radioactive source in place of an X-ray tube for excitation of characteristic K radiation from elements between zinc and uranium. Because of the weak fluorescence intensity, the authors used a crystal-free s…
An. N. NESMEYANOV and DE DYK MAN
This study reexamines the vapor pressure of solid chromium, for which earlier measurements from boiling point and open surface evaporation methods gave inconsistent results. The authors used an integral Knudsen effusion method with neutron-activated chromium-51 as a radioactive tracer to quantify co…
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This paper surveys X-ray structural data on complex compounds of divalent Fe, Co, Ni, Cu, Pd, and Pt to identify regularities in coordination geometry, spin state, and ligand effects. Comparing statistical structural data with magnetic and other physicochemical evidence, it argues that Pd and Pt con…
O. M. NEFEDOV, Ya. L. LEVKOV, and Corresponding Member of the USSR Academy of Sciences A. D. PETROV
This paper addresses the preparation of individual aryl chlorides and bromides from aromatic hydroxy compounds, aiming to overcome limitations of direct halogenation and earlier phosphorus pentahalide procedures that produced mixtures and lower yields. The authors propose heating the corresponding p…
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This paper examines the longstanding question of how iodine interacts with starch and amylose in aqueous solution, with attention to conflicting interpretations of iodine starch as a chemical, adsorption, or inclusion complex. The authors use spectrophotometry over 220 to 800 nm, supplemented by col…
Academician Vikt. I. SPITSYN and V. Ya. KABANOV
This study examines the formation and transformation of high-molecular tungsten compounds produced by acidifying aqueous sodium tungstate solutions. Using dilatometric measurements and ultraviolet spectrophotometry, the authors follow sodium paratungstate formation, crystallization, hexatungstate fo…
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The paper addresses the preparation of hexafluoroplatinates, which are difficult to obtain by conventional aqueous or hydrogen fluoride routes because of hydrolysis and poor reactivity of platinum compounds. It reports that metallic platinum dissolves in a bromine and bromine pentafluoride mixture t…
Academician I. L. KNUNYANTS, E. G. BYKHOVSKAYA, V. N. FROSIN, and Ya. M. KISEL
The study examines reactions of nitrosyl fluoride with several fluoroolefins, an area previously little explored beyond inorganic substrates and benzene. Experiments with perfluoroisobutylene, perfluoropropylene, tetrafluoroethylene, trifluoroethylene, and vinylidene fluoride show that nitrosyl fluo…
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This study examines the thermodynamics of the chlorination reaction of uranium dioxide with carbon and chlorine to form uranium oxychloride, using electromotive force measurements with uranium oxide, carbon electrodes in molten alkali chloride electrolytes containing uranium tetrachloride. The autho…