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Showing papers in "Russian Chemical Bulletin in 1977"


Journal ArticleDOI
TL;DR: In this paper, it was shown that there is a direct proportionality between the change in free energy of the vacancy solution and the relative alteration of the dimensions of the X type calcium and lanthanum ion exchange zeolite under krypton adsorption.
Abstract: Dilatometer and adsorption measurements have established that there is a direct proportionality between the change in free energy of the vacancy solution and the relative alteration of the dimensions of the X type calcium and lanthanum ion exchange zeolite under krypton adsorption. Adsorption increases the value of the isotropic coefficient of compression of each of these zeolites by one order of magnitude.

16 citations


Journal ArticleDOI
TL;DR: The stoichiometry of the reactions of oxopiperidinium salts with alcohols is determined by the rate of interaction of the interaction with ROH, RO− and N − with varying with the pH and the initial, concentrations in the system as mentioned in this paper.
Abstract: 1 Oxidation of primary and secondary alcohols by oxopiperidinium salts clearly results from the transfer of an alcoholate anion and a hydride ion from the alcohol to the oxopiperidinium cation (\(\begin{array}{*{20}c} \backslash \\ / \\ \end{array} \mathop N\limits^ + = O\)) The primary product from the\(\begin{array}{*{20}c} \backslash \\ / \\ \end{array} \mathop N\limits^ + = O\) reduction is the hydroxypiperidine (\(\begin{array}{*{20}c} \backslash \\ / \\ \end{array} N---OH\)), which then reacts with the\(\begin{array}{*{20}c} \backslash \\ / \\ \end{array} \mathop N\limits^ + = O\) to form the nitroxyl radical 2 The stoichiometry of the reactions of the oxopiperidinium salts with alcohols is determined by the rate of interaction of the\(\begin{array}{*{20}c} \backslash \\ / \\ \end{array} \mathop N\limits^ + = O\) with ROH, RO− and\(\begin{array}{*{20}c} \backslash \\ / \\ \end{array} N---OH\) varying with the pH and the initial, concentrations in the system 3 Alcohol oxidation by nitroxyl radicals in acid solution proceeds through radical disproportionation, followed by interaction of the\(\begin{array}{*{20}c} \backslash \\ / \\ \end{array} \mathop N\limits^ + = O\) and the alcohol

12 citations


Journal ArticleDOI
TL;DR: In this paper, the concentrations of the H5O2+ and H3O+ ions, and also of the h3O−·HSO4− ion pairs, in aqueous H2SO4 solutions were calculated based on literature data.
Abstract: 1. Based on the literature data, we calculated the concentrations of the H5O2+ and H3O+ ions, and also of the H3O+·HSO4− ion pairs (or H2SO4·H2O hydrates), in aqueous H2SO4 solutions (ranging from 2.04 to 100% H2SO4). 2. It is postulated that the H3O+ ions can exist only in solutions that contain more than 76% H2SO4, where less than two water molecules correspond to each proton.

12 citations


Journal ArticleDOI
TL;DR: In this article, the authors measured the adsorption isotherm and dilatometric curve for zeolite CaNaX at 180°K and established that a proportionality exists between the change in free energy of the vacant solution and the relative change in the size of zeolites during xenon adaption.
Abstract: 1. We measured the adsorption isotherm and dilatometric curve for zeolite CaNaX during the adsorption of xenon at 180°K. 2. It was established that a proportionality exists between the change in the free energy of the vacant solution and the relative change in the size of zeolite CaNaX granules during xenon adsorption. 3. The hydrostatic stress coefficient for zeolite CaNaX during xenon adsorption was determined. 4. The hydrostatic stress coefficient of the studied zeolite granule is practically independent of the nature of the adsorbate.

12 citations


Journal ArticleDOI
TL;DR: In this article, a study of the effects of krypton adsorption on type X zeolites at −50, −93, and −120°C was conducted.
Abstract: 1. Study has been made of the isotherms for krypton adsorption on type X zeolites at −50, −93, and −120°C and the accompanying changes in the dimensions of the zeolite granule resulting from this adsorption. 2. For the adsorption of krypton on zeolite NaX at −93°C, the alteration of the zeolite granule dimensions and the differential heat of adsorption are similarly affected by changes in the degree of filling. 3. At low degree of filling, the contraction of NaX zeolites increases with rising temperature.

7 citations


Journal ArticleDOI
TL;DR: In this paper, optical microscopy and x-ray spectral analysis jointly give a qualitative picture of the changes which have occurred in natural weathered ilmenite, which can only partly be used to get detailed quantitative determinations.
Abstract: 1. In an investigation of natural weathered ilmenite, optical microscopy and x-ray spectral analysis jointly give a qualitative picture of the changes which have occurred. A microprobe can only partly be used to get detailed quantitative determinations, because it cannot be used to determine the finely intermingled weathered products. 2. Reduction of natural ilmenite by carbon monoxide is a topochemical process. During reduction below 1000°C, manganese or magnesium diffuses ahead of the approaching reaction front and forms a narrow enriched zone in which the Fe2+ in the ilmenite lattice is replaced by Mn2+ or Mg2+, while Ti4+ is replaced by Ti3+ to a lesser extent. In some particles the dissolved concentrations in the enriched zone reach levels high enough to prevent reduction of Fe2+, and thus isolate large regions of the particle from reduction. This “boundary effect” is less marked below 1000°C. 3. Oxidation converts monocrystalline particles of ilmenite to polycrystalline ones of pseudobrookite with disseminated particles of rutile. During gas reduction of preoxidized material at 1000°C, the fragments of the particles are reduced topochemically, each in its own zone of liquid enrichment, and metallic iron is concentrated at the boundaries of the fragments. The total amount of ilmenite isolated under the influence of the liquid enrichment zone is reduced, and the sintering tendency of the particles is minimized. 4. Gas reduction of preoxidized ilmenite at 1200°C leads to the formation of metallic iron and a solid solution of anosovite (Fe3−xTixO5 containing dissolved Mn2+). 5. Reduction of preoxidized ilmenite by carbon at 1200°C creates more favorable conditions for reduction than those in a gaseous mixture of CO and CO2.

7 citations


Journal ArticleDOI
TL;DR: In this paper, a study has been made of the isotopic structures of the IR absorption bands of dichlorocarbene and dichlorosilylene, each stabilized in an Ar matrix at 15-20°K.
Abstract: A study has been made of the isotopic structures of theν 1 andν 3 IR absorption bands of dichlorocarbene and dichlorosilylene, each stabilized in an Ar matrix at 15–20°K. A determination has been made of the valence angles, force constants, and vibration frequencies,ν 1,ν 2, andν 3 for various isotopic CCl2 and SiCl2 molecules.

6 citations



Journal ArticleDOI
TL;DR: The hydrogen transfer rate is proportional to the concentration of tris(triphenylphosphine) complexes of ruthenium(II) or rhodium(I) chloride, alkanol, and ketone as discussed by the authors.
Abstract: 1. The hydrogen transfer rate is proportional to the concentration of tris(triphenyl-phosphine) complexes of ruthenium(II) or rhodium(I) chloride, alkanol, and ketone. High ketone concentrations retard the process. 2. The UV spectrum of the product of the reaction of RhCl(PPh3)3 with cyclohexanone exhibits a new absorption band and two isobestic points; this is due to formation of mono -and diketone forms of the rhodium complex. 3. A mechanism is proposed for the catalytic effect of the complexes, including ligand dissociation, oxidative attachment of the alcohol, and coordination of the ketone molecule with formation of an intermediate six-membered compound.

6 citations


Journal ArticleDOI
TL;DR: In this paper, basic crystalline hafnium ditungstate Hf(OH)2W2O7·2H2O was obtained, which crystallizes as a tetragonal lattice.
Abstract: 1. Basic crystalline hafnium ditungstate Hf(OH)2W2O7·2H2O was obtained, which crystallizes as a tetragonal lattice. Ignition of the compound gave anhydrous hafnium tungstate with a cubic lattice, which is stable in the air up to 700–750°. 2. The anhydrous zirconium and hafnium ditungstates were obtained from the basic zirconium and hafnium tungstates, which are found in the metastable state at room temperature, and which decompose when heated to 700–750°.

6 citations


Journal ArticleDOI
TL;DR: It has been shown experimentally that the expression for the temperature dependence of the nonstationary BCP rate contains a term in the exponential Boltzmann factor as mentioned in this paper, which indicates that changes in the temperature markedly affect the ratio of relative rates of energy conversion along the various channels.
Abstract: 1. It has been shown experimentally that the expression for the temperature dependence of the nonstationary BCP rate contains a term in the exponential Boltzmann factor. 2. The temperature has a marked effect on the rate and evolution of energy in branching-chain processes, i.e., changes in the temperature markedly affect the ratio of relative rates of energy conversion along the various channels.

Journal ArticleDOI
TL;DR: The reaction of chloromethyl(triphenylphosphine) gold with KI and NaCN gave, respectively, triphenylPHosphinegold iodide and methyltriphenyl-phosphonium dicyanoaurate.
Abstract: 1. We discovered the reaction of inserting the methylene group at the gold-chlorine bond to give chloromethyl (triphenylphosphine) gold. 2. The triphenylphosphine complexes of acetylacetonate-ferrocenyl-, and acetonylgold react with diazomethane to give vinyl(triphenylphosphine) gold. 3. The reaction of chloromethyl(triphenylphosphine)gold with KI and NaCN gave, respectively, triphenylphosphinegold iodide and methyltriphenylphosphonium dicyanoaurate.

Journal ArticleDOI
TL;DR: The position of the charge transfer band in these spectra is determined by the inductive and steric characteristics of the substituents at the silicon atom in the tetracyanoethylene-1, 1, 1-dialkylsilacyclobutane system.
Abstract: 1. A study has been made of the absorption spectra in the tetracyanoethylene-1,1-dialkylsilacyclobutane system. The position of the charge-transfer band in these spectra is determined by the inductive and steric characteristics of the substituents at the silicon atom. 2. First ionization potentials for the 1,1-dialkylsilacyclobutanes have been determined. 3. The ethylene-like character of the highest occupied molecular orbitals determines both the structure dependence of the ionization potentials of the silacyclobutanes and the ability of the latter to interact with the tetracyanoethylene π orbitals.

Journal ArticleDOI
TL;DR: The molecular structure of dimethylsulfonium cyclopentadienylide was established by the x-ray structure analysis method, and it was shown that the S atom is coplanar with the cyclopenedienyl ring as discussed by the authors.
Abstract: The molecular structure of dimethylsulfonium cyclopentadienylide was established by the x-ray structure analysis method, and it was shown that the S atom is coplanar with the cyclopentadienyl ring, and that the S-C distance (cyclopentadienyl) is shorter than the S-C distances (methyl).

Journal ArticleDOI
TL;DR: The corresponding corresponding heteroorganic derivatives of bis-m-carboranyls were synthesized by the reaction of dilithium bis-nocboranyl with (CH3)3SiCl, (CH 3)3SnCl, and CH3HgI as discussed by the authors.
Abstract: 1. The reaction of the dilithium derivatives of the bis-o- and bis-m-carboranyls and of bis-(o-carbo-ranyl)ethane with CO2 and formaldehyde gave the dicarboxylic acids and the dihydroxymethyl derivatives of the indicated biscarboranyls. 2. The corresponding heteroorganic derivatives of bis-m-carboranyl were synthesized by the reaction of dilithium bis-m-carboranyl with (CH3)3SiCl, (CH3)3SnCl, and CH3HgI.

Journal ArticleDOI
TL;DR: The condensation products imply function as catalysts for styrene formation, their activity in this reaction being higher than that of the aluminum oxide itself as mentioned in this paper, and carbon dioxide is formed through combustion of the condensation product, rather than from ethylbenzene and styrene.
Abstract: 1. Styrene formation in the oxidational dehydrogenation of ethylbenzene on an aluminum oxide catalyst is directly from the ethylbenzene through an earlier proposed mechanism, rather than from intermediate condensation products through a consecutive mechanism. 2. The condensation products imply function as catalysts for styrene formation, their activity in this reaction being higher than that of the aluminum oxide itself. 3. Carbon dioxide is formed through combustion of the condensation products, rather than from ethylbenzene and styrene.

Journal ArticleDOI
TL;DR: The yield of products from the condensation of aliphatic ketones with diethyl phosphite and ammonia depends on the order of introduction of the reactants into the reaction as mentioned in this paper.
Abstract: 1. We have synthesized a series of optically active substitutedα-aminoethylphosphonic acids and their ethyl esters. 2. The yield of products from the condensation of aliphatic ketones with diethyl phosphite and ammonia depends on the order of introduction of the reactants into the reaction.

Journal ArticleDOI
TL;DR: In this paper, the formation of paramagnetic intermediates with a chelate structure is demonstrated by ESR, where E = Al, Ga, In, and Tl, with 3,5-di-t-butyl-1,2-benzoquinone and 3,6-dim-t -butyl 1,2 -benzoquinone proceed by a one-electron transfer mechanism.
Abstract: 1. The reactions of E(C2H5)3, where E = Al, Ga, In, and Tl, with 3,5-di-t-butyl-1,2-benzoquinone and 3,6-di-t-butyl-1,2-benzoquinone proceed by a one-electron transfer mechanism. 2. The formation of paramagnetic intermediates with a chelate structure is demonstrated by ESR.


Journal ArticleDOI
TL;DR: In this article, a study of UV spectra and comparison of calculated values of the energies of the protonated complexes of alkyl and arlhydrazones was conducted.
Abstract: 1. Protonation centers for alkyl-and arlhydrazones have been established from a study of UV spectra and comparison of calculated values of the energies of the protonated complexes. 2. Inversion of the protonation center occurs in the alkylhydrazones, but all of the phenylhydrazones protonate at the imine-nitrogen atom.


Journal ArticleDOI
TL;DR: The reaction of 2-formylcyclohexanone with α-aminoacetoacetic acid ester in acetic acid leads to the formation of 2 carbethoxy-4,5-tetramethylenepyrrole as mentioned in this paper.
Abstract: 1. The reaction of 2-formylcyclohexanone withα-aminoacetoacetic acid ester in acetic acid leads to the formation of 2-carbethoxy-4,5-tetramethylenepyrrole with an admixture of the isomeric 2-carbethoxy-3,4-tetramethylenepyrrole, which is also isolated during the reaction of 2-formylcyclohexanone with aminomalonic acid ester. 2. The condensation of 2-formylcyclohexanone with glycine ethyl ester, followed by the cyclization of the intermediate enamine with acetic anhydride, leads to the formation of 1-acetyl-3,4-tetramethylenepyrrole. 3. The reaction of 2-ethoxyoxalylcyclohexanone withα-aminoacetoacetic acid ester yields 2-carbethoxy-3-carboxy-4,5-tetramethylenepyrrole.


Journal ArticleDOI
TL;DR: In this paper, a study of the kinetics of the reaction of p-nitrophenylbis(chloromethyl)-phosphinate with primary and secondary amines was made.
Abstract: Study has been made of the kinetics of the reaction of p-nitrophenylbis(chloromethyl)-phosphinate with primary and secondary amines. Reaction proceeds through rupture of the ester bond at the P atom and is catalyzed by a second amine molecule. The reaction rate is determined by induction and steric effects in the amine substituents. The activation energy for the reaction with n-butylamine is negative.

Journal ArticleDOI
TL;DR: In this paper, a study of the binary alloys of Pd with Ni, Ti, Cu, and Rh as regards the transformations of 1, 2-cyclohexanediol was conducted.
Abstract: A study of the binary alloys of Pd with Ni, Ti, Cu, and Rh as regards the transformations of 1, 2-cyclohexanediol disclosed that the character of the products is strongly dependent on the nature of the second component of the alloy. Cyclohexanone and phenol predominate in the products obtained on the binary Pd alloys that contain Ni, Ti, or Cu, while the Pd-Rh alloys are selective catalysts for the dehydrogenation of 1,2-cyclohexanediol to pyrocatechol without forming phenol.

Journal ArticleDOI
TL;DR: In this article, the cyanoaminocobaltate complex ions [Co(CN)3am]−, prepared by partial substitution of CN ligands in the [Co (CN)5]− complex by an amine (α,α′-dipyridyl, diethylenetriamine, ethylene- and propylenediamine), under mild conditions selectively catalyze the conversion of cis-1,3-pentadiene into the trans isomer.
Abstract: 1. The cyanoaminocobaltate complex ions [Co(CN)3am]−, prepared by partial substitution of CN ligands in the [Co(CN)5]− complex by an amine (α,α′-dipyridyl, diethylenetriamine, ethylene- and propylenediamine), under mild conditions selectively catalyze the conversion of cis-1,3-pentadiene into the trans isomer. 2. The high stereoselectivity of the process is due to the coordination of the cis-diene with the complex in the more stable transoid conformation, and of the trans isomer in the less stable, cisoid conformation. 3. The cyanoaminocobaltate complex ions studied catalyze the selective hydrogenation of trans-1,3-pentadiene with a complete retention of the configuration, while [Co(CN)3en]− in an aqueous acetone directs the reaction exclusively in the direction of formation of 1-pentene.

Journal ArticleDOI
TL;DR: The reaction of β-hydroxyalkyl Sulfides with α olefin oxides proceed through the formation of sulfonium ions as mentioned in this paper, and true rate constants, valid over a wide range of concentrations, have been determined for the various steps in the reaction of n-octylβ-hydroxethyl sulfide with propylene oxide.
Abstract: 1. The reactions ofβ-hydroxyalkyl Sulfides withα olefin oxides proceed through the formation of sulfonium ions. 2. True rate constants, valid over a wide range of concentrations, have been determined for the various steps in the reaction of n-octylβ-hydroxyethyl sulfide with propylene oxide.

Journal ArticleDOI
TL;DR: In this paper, the authors investigated the reaction of BCl3 with R4N[C(NO2)3] (R is CH3 or C2H5), which decomposes at 20°C with evolution of tetraalkylammonium tetrachloroborates and nitrogen tetroxide.
Abstract: 1. The authors have investigated the reaction of BCl3 with R4N[C(NO2)3] (R is CH3 or C2H5). In CHCl3 or liquid BCl3, one obtains unstable complexes R4N[Cl3B ←:C(NO2)3], which decompose at 20°C with evolution of tetraalkylammonium tetrachloroborates and nitrogen tetroxide. 2. They have obtained indirect proof of the possibility of disproportionation of R4N[Cl3BC(NO2)3] to R4NBCl4 and R4N{B[C(NO2)3]4}. Attempts to synthesize R4N{B[C(NO2)3]4} and R4N{Al[C(NO2)3]4} by replacing Cl by C(NO2)3 in R4NBCl4 and R4NAlCl4 led to formation of unstable products, decomposing spontaneously at −30 and −10°C, respectively.