Recent Papers

Determination of the Structure of Some Isomeric Disubstituted Ferrocenes from Infrared Absorption Spectra

Cathodic deposition of carbon from molten carbonates

Electrolysis of an equimolar lithium and potassium carbonate melt was investigated at 580 to 600 °C using platinum and gold electrodes to clarify cathodic and anodic processes in molten carbonates. The experiments showed that the only cathodic product was a dense powdery carbon deposit with a curren…

Synthesis of 1,3-Disubstituted 5,6,7,8-Tetrahydroisochromylium Salts

This paper reports the synthesis of 1,3-disubstituted 5,6,7,8-tetrahydroisochromylium salts from beta,gamma-unsaturated ketones obtained by crotonic condensation of cyclohexanone with acetone, acetophenone, 2-acetothienone, and 2-methyl-5-acetylfuran. Acylation with acid anhydrides in the presence o…

Monomeric Trihalophosphoranes of the Cyclic Series and Some of Their Transformations. Syntheses Based on Phosphorus Tribromide

This paper reports the addition of phosphorus trihalides, especially phosphorus tribromide, to conjugated dienes as a route to cyclic trihalophosphoranes, a class of organophosphorus compounds previously difficult to isolate. The authors describe moisture-excluding procedures, including gradual solv…

On Open Cycles in the Cellulose Molecule

This paper examines whether part of the anhydroglucose residues in cellulose can exist with pyranose rings opened at the 1,5 bond, a possibility suggested by the presence of oxidized groups and by prior observations on carbohydrate reactions in acidic media. Hydrate cellulose samples were acid treat…

Polycondensation in Emulsions

This paper examines emulsion polycondensation as a distinct mode of polymer synthesis in which the polymer-forming reaction occurs within the bulk of one emulsion phase rather than at the phase boundary. Using the synthesis of poly-metaphenylene isophthalamide from metaphenylenediamine and isophthal…

Separation Diagrams and Series in Extraction

The paper examines regularities of component separation in liquid extraction systems by analyzing extraction rays and proposing separation diagrams based on the separation coefficient rather than only distribution coefficients. Using data from nine studied systems, chiefly nitrate systems with tribu…

Vibrational Spectra and Aromaticity of Six-Membered Azacycles

This paper examines whether vibrational influence coefficients, derived from semiempirical force constants, can be correlated with electronic structure and aromaticity in benzene, cyclohexane, pyridine, and related six-membered azacycles. By inverting published force-constant matrices, the study com…

Dielectric Permittivity of Organic Solvents and Thermodynamic Properties of Sodium Iodide Solutions in Water, Methanol, Acetone, and a Dioxane–Water Mixed Solvent

This paper examines how dielectric permittivity and the chemical nature of solvents influence the thermodynamic properties of sodium iodide solutions. Integral heats of solution at 25 degrees C are compared for water, methanol, acetone, and dioxane, water mixtures adjusted to match the dielectric pe…

On the Nature of Active Centers in the Hydrogen Isotope Exchange Reaction on $\gamma$-Irradiated Silica Gel

This study examines the active centers responsible for hydrogen adsorption and isotopic hydrogen exchange on gamma irradiated silica gel. Silica gels with varying impurity contents were irradiated and analyzed by catalytic measurements, hydrogen adsorption, optical absorption, and EPR spectroscopy. …

Adsorption of perfluorinated fatty acids at solution–air and solution–mercury interfaces

This study compares the adsorption of trifluoroacetic, perfluoropropionic, and perfluorobutyric acids at solution, air and solution, mercury interfaces. Electrocapillary curves, surface tension measurements, and potential difference measurements were used to evaluate interfacial activity, shifts of …

Formation of Excited Ethyl Radicals in the Interaction of Hot Hydrogen Atoms with Ethylene

This communication investigates whether excited ethyl radicals are formed when hot hydrogen atoms add to ethylene and how their reactivity differs from that of thermal ethyl radicals. Hydrogen iodide, ethylene mixtures were photolyzed under ultraviolet irradiation to generate nonequilibrium hydrogen…

On Two Modifications of Gelatin

This paper examines the long-standing distinction between two gelatin modifications, alpha and beta, interpreted in terms of molecular conformation. Using films prepared from photographic gelatin under different drying temperatures, the author compares swelling kinetics, density, dimensional changes…

Polarization curves for electrodes partially immersed in an electrolyte solution

This paper develops a theoretical description of polarization curves for smooth electrodes partially immersed in an electrolyte, motivated by their relevance to gas porous electrode processes. Considering hydrogen diffusion through an electrolyte film followed by electrochemical discharge, the autho…

Radiolysis of Aqueous Ferrous Sulfate Solutions Induced by Decimicrosecond Electron Pulses

The study examines the radiolysis of aerated and oxygenated aqueous ferrous sulfate solutions in sulfuric acid under decimicrosecond electron pulses, with attention to how high absorbed dose rates affect ferric ion formation and oxygen consumption. Electron pulses of about 6 · 10^-7 s were generated…

Radiation Synthesis of Polymers Based on Trimeric Cyclic Dimethylphosphinoborine

This study examines the radiation-induced polymerization of trimeric cyclic dimethylphosphinoborine, motivated by the expected stability of polycyclic phosphinoborine structures and analogies with borazole polymerization. The monomer was irradiated with 800 kV electrons in sealed evacuated ampoules …

Hydrazinolysis – a New Method for Studying the Structure of Nitrogen-Containing Polymers with Conjugated Bonds

This paper examines hydrazinolysis as a chemical method for investigating insoluble and infusible nitrogen-containing polymers with conjugated bonds, particularly systems in which infrared spectroscopy cannot distinguish the relative roles of C=C and C=N bonds. The authors treat polyazines, poly-Sch…

Dependence of Hydrogen Chemisorption at the Metal–Solution Interface on the pH of the Solution

This paper examines how solution pH affects hydrogen chemisorption at the rhodium solution interface, using charge curves for compact rhodium and previously obtained data for rhodium black in sulfuric acid solutions at constant sulfate concentration. By superposing charge curves and analyzing potent…

On the acid-base properties of complex compounds of platinum(II) containing $\alpha$-methylhydroxylamine

This study examines whether proton dissociation in divalent platinum complexes containing coordinated hydroxylamine occurs from the amido group or the hydroxo group. Cis and trans isomers of diamminobis(alpha-methylhydroxylamine)platinum(II) chloride were synthesized and characterized by elemental a…

THE ROLE OF THE H-BOND IN THE PROCESSES OF DEACTIVATION OF EXCITED ELECTRONIC STATES OF MOLECULES LEADING TO THE FORMATION OF RADICALS

This study examines how hydrogen-bonded complexes influence the deactivation of excited electronic states and radical formation in molecules containing carbonyl or nitrogen chromophoric groups. Luminescence, infrared, and EPR spectra were measured for anthraquinone, acridone, aromatic amine derivati…

New lead-containing perovskite compounds of complex composition

This paper reports the targeted synthesis and X-ray characterization of new lead-containing perovskites of complex composition, selected using crystal-chemical constraints, electroneutrality, and a tolerance factor near unity. Ceramic samples containing two or three different B-site ions were fired …

Synthesis and Characterization of Molybdenum Sesquisulfide $(\mathrm{Mo}_2\mathrm{S}_3)$

Molybdenum sesquisulfide, Mo2S3, was synthesized from high purity molybdenum powder and sulfur in evacuated quartz ampoules by staged heating to 500, 900, and 1400°C, and its physical and crystallographic properties were examined. The product was a lead-gray metallic crystalline aggregate with elong…

Synthesis of Polyesters Containing Triple Bonds in the Chain

This study examines the synthesis of polyesters containing conjugated triple bonds by joint oxidative dehydropolycondensation of propargyl and dipropargyl esters with p-diethynylbenzene. The authors selected aromatic, bisphenol, fluorinated bisphenol, benzoate, phenoxy, and quinizarin derivatives to…

On the Mechanism of Reactions of Esters of Trivalent Phosphorus Acids with Silicon and Tin Alkyl Halides

This paper examines the mechanism of reactions between esters of trivalent phosphorus acids and alkyl halides of silicon and tin, reactions known to yield products containing P-O-Si or P-O-Sn bonds rather than the usual Arbuzov products. Using ethyl diethylphosphinite with trialkylchlorosilanes and …

On the mechanism of diene polymerization under the influence of complex catalysts based on cobalt compounds

This paper examines the mechanism of diene polymerization initiated by complex cobalt catalysts, addressing conflicting interpretations obtained from deactivation of growing chains with isotopically labeled alcohols. The authors compare cobalt systems with reference anionic, cationic, and coordinati…

Synthesis of Semisymmetric Tris-Amides of Boric Acid

This paper examines the preparation of semisymmetric tris-amides of boric acid by transamination of tris(dimethylamino)boron and tris(diethylamino)boron with aliphatic and aromatic amines. The authors argue that the greater reactivity of the dimethylamino derivative limits its use with lower aliphat…

Coupling of Halogenation and Arylation Reactions of Hydrochlorosilanes

This paper examines whether the exothermic radical halogenation of hydrochlorosilanes can be coupled with the otherwise difficult arylation of silicon hydrides by aromatic compounds. Experiments using light-initiated chlorination of mixtures of trichlorosilane or related silicon hydrides with benzen…

Bimetallic Derivatives of Chromium, Molybdenum, and Tungsten Carbonyls

This paper reports the synthesis and characterization of mixed bimetallic derivatives of chromium, molybdenum, and tungsten carbonyls containing tin or lead substituents. Sodium salts of tricarbonyl pi-cyclopentadienyl metal carbonyls were reacted with triphenyltin, triphenyllead, or diphenyltin chl…

Mechanism of Methane Steam Reforming Reactions

This paper examines the reaction mechanism of methane conversion with steam to produce synthesis gas, focusing on limitations in earlier schemes that combined methane thermal decomposition with subsequent reactions of its products. Using literature thermochemical data, bond dissociation energies, an…

Studies of the Thermodynamic Properties of Gallium Tellurides by the Electromotive Force Method

The study examines the thermodynamic properties and phase behavior of gallium tellurides in the gallium tellurium system, with particular attention to Ga2Te3, GaTe, and the proposed tellurium-rich GaTe3 phase. Concentration electrochemical cells with liquid gallium and solid gallium tellurium alloys…

The promotion of a skeleton nickel catalyst by molybdenum

This study examines the promotion of skeleton nickel catalysts by molybdenum introduced into Ni-Al alloys for liquid-phase hydrogenation of o-nitrophenol, potassium maleate, and allyl alcohol. Reaction rates and catalyst potentials were measured simultaneously after alkaline leaching of alloys with …

On the Nature of Coordination Compounds of Boron Halides and Diborane in Ether Solutions

This study examines the nature of coordination compounds formed by boron halides, organoboron chlorides, chloroborane, and diborane in ether or tetrahydrofuran solutions. Molecular weight determinations and electrical conductivity measurements over broad concentration ranges are used to infer equili…

On the Influence of Semiconductor-Type Additives on the Radiation Polymerization of Acrylonitrile and Methyl Methacrylate

This study examines how solid oxide additives of semiconductor character affect the low-temperature gamma-radiation polymerization of acrylonitrile and methyl methacrylate. Experiments with several oxides show that n-type additives such as zinc oxide, titanium oxide, and chromium oxide do not accele…

Study of Catalysts Obtained by the Reaction of Sodium Borohydride with Heavy Metal Salts

This study examines the chemical nature and properties of platinum, palladium, and rhodium catalysts prepared by reducing aqueous metal chloride solutions with sodium borohydride. The authors analyze the resulting black precipitates for metal, boron, and hydrogen content, measure hydrogen evolution …

Kinetics of Cumene Cracking on Zeolite $10\mathrm{X}$

This study examines cumene cracking over calcium-form zeolite 10X as a model reaction for comparing crystalline zeolite catalysts with amorphous aluminosilicate cracking catalysts. Using integral and differential kinetic methods over approximately 475-550 °C, the authors measured conversion, product…

NMR Spectra and Ebullioscopy of Lithium Alkoxides

This study examines the association and bonding of lithium alkoxides, principally tert-butoxylithium and n-butoxylithium, using ebullioscopy and proton and lithium-7 NMR spectroscopy. Ebullioscopic measurements indicate that tert-butoxylithium is strongly associated in cyclohexane and benzene, consi…

Dipole Moments of a Radical and a Molecule: Diphenyl Nitroxide and Diphenylhydroxylamine

This study compares the dipole moment of the diphenyl nitroxide radical with that of the corresponding molecule, diphenylhydroxylamine, as a way to probe charge distribution associated with an unpaired electron. The compounds were synthesized by a literature method, and their dipole moments were mea…

On the possibility of chromatographic separation on gas-liquid columns without the use of an inert carrier gas

This paper examines a preparative gas-liquid chromatographic method that separates mixtures without an inert carrier gas, using an undiluted, readily soluble compound as a pseudodisplacer. Experiments with hydrocarbon mixtures on polar and nonpolar stationary liquids show that components can leave t…

On the Radical Mechanism of Curing Resole Resins

This paper examines the role of free-radical processes in the curing mechanism of resol phenol-formaldehyde resins. The authors test whether radicals formed during curing can initiate polymerization of triethylene glycol dimethacrylate, using infrared spectroscopy to compare double-bond consumption …

THE COMPENSATION EFFECT AND THE TRUE ACTIVATION ENERGIES OF CERTAIN CHEMICAL PROCESSES

The paper examines the compensation effect in chemical kinetics as a consequence of measured activation parameters arising from the superposition of independent reaction pathways, such as spontaneous and catalyzed processes. It derives relations showing how effective Arrhenius activation energy and …

EPR spectrum and rearrangement of the radical formed upon oxidation of ionol–$\mathrm{CD}_3$

This study examines the radical formed during oxidation of deuterium labeled 2,6-di-tert-butyl-4-methylphenol, using ionol labeled in the para methyl group to test a proposed phenoxyl to benzyl radical rearrangement. Ionol-CD3 was prepared by isotopic exchange with potassium amide in liquid deuterat…

On the difference in reactivity of geometrically isomeric compounds of composition $[\mathrm{PtA}_2\mathrm{X}_4]$

This paper examines the differing reactivity of geometrical isomers of tetravalent platinum complexes of the composition [Pt(NH3)2Cl4], with the aim of providing a rapid means of distinguishing cis and trans forms. The authors test the action of excess potassium iodide on aqueous suspensions or solu…

Effect of the Reaction Mixture on the Catalyst under Catalytic Conditions

This paper examines how reaction mixtures can change the state and activity of catalysts under operating catalytic conditions, rather than merely under equilibrium exposure to reactants. It proposes a general kinetic classification of catalyst, reaction mixture systems according to whether catalyst …

Formation of ion radicals under the action of $\gamma$-radiation on the tetrahydrofuran–styrene system at – $196^\circ$

This study examines ion radical formation during gamma irradiation of frozen tetrahydrofuran and styrene solutions in tetrahydrofuran at minus 196 degrees C using electron paramagnetic resonance spectroscopy. Irradiated tetrahydrofuran produced a five component hyperfine spectrum attributed to a tet…

Dipole Moments and Structure of Intracomplex Copper Compounds with Aromatic Schiff Bases

This paper examines the stereochemistry in solution of intracomplex copper(II) compounds formed with aromatic Schiff bases from ortho-hydroxyaldehydes, a question left ambiguous by magnetic and polarization data. The authors synthesize a series of substituted Cu(Lig)2 complexes and measure magnetic …

On the Additivity of Activation Free Energies of Gas-Phase Free-Radical Reactions

This paper examines whether free energies of activation in gas-phase free-radical substitution reactions can be represented as additive sums of independent molecular and radical increments. Using published kinetic data, especially for reactions of methyl and trifluoromethyl radicals with hydrocarbon…

On the Role of the Primary Protective Film in the Oxidation of Metals in Aqueous Solutions

This paper examines how native oxide protective films affect the early and later oxidation of iron and steel in water and potassium chloride solutions in the presence of air. Using colorimetric, volumetric, and later gravimetric measurements over temperatures from 0 to 90 degrees Celsius, the author…

On the Synthesis of High-Molecular-Weight Amides and Hydrazides of Penicillins

This communication describes the covalent attachment of benzylpenicillin and phenoxymethylpenicillin to water-soluble polymer chains as part of a broader effort to modify medicinal compounds by incorporation into polymers. Copolymers of vinylamine with vinyl alcohol and of acrylic acid hydrazide wit…

On Pentaethanodiferrocene

This paper reexamines a ferrocene reaction product previously assigned the structure pentaethanodiferrocene, formed under the action of aluminum chloride. Using elemental analysis, molecular weight determination, infrared spectroscopy, proton magnetic resonance spectra, acetylation behavior, and com…

Gas Chromatographic Determination of Nitrogen and Oxygen in Organic Compounds

A gas chromatographic method is proposed for the simultaneous determination of nitrogen and oxygen in organic compounds from a single micro sample. The procedure decomposes 5 to 10 mg of substance by pyrolysis at 900°C in a rarefied stationary helium atmosphere over nickelized carbon black, converti…