X-ray fluorescent and EXAFS studies of the electronic and spatial structure of dialkyl sulfides and their PdCl2 complexes in extraction systems

SK_α, SK_β, ClK_β, ClK_β, and PdL_β2 X-ray fluorescent and PdK EXAFS spectra were obtained for some organic solutions of dialkyl sulfide complexes with palladium chloride. Solvent effects on the electronic and spatial structure of complexes in solution are discussed. In the benzene solution of [PdCl₂2(C₆H₁₃)₂S], complex molecules interact with solvent molecules along a coordinate that is perpendicular to the plane of the complex molecule. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurmal Strukturnoi Khimii, Vol. 35, No. 4, pp. 105c111, July–August, 1994. Translated by L. Smolina     

Effect of pH and gaseous ammonia flow rate on the composition and structure of ammonium uranate

Ammonium uranate was precipitated from uranyl nitrate solution using gaseous ammonia, then filtered, washed with demineralized water and dried. The influence of pH and ammonia flow rate on their composition and structure were examined by X-ray diffraction analysis, making use of additional information obtained from infrared analysis.     

The speciation of arsenic in seawater and marine species

Dissolved inorganic arsenic species were determined in natural waters and selected marine species. Prior to irradiation by NAA samples were preconcentrated and the As(III) and As(V) species separated by APCDT-chloroform extraction. Marine samples were digested by microwave heating. Interpretation of data was achieved by comparing the ratio of As(III)/As(V) in the samples and correlating it with the prevailing environmental conditions.     

A transportable gamma spectroscopy system applied to the measurement of fission products

Normally, gamma-ray spectroscopy is performed by equipment positioned in the SLOWPOKE-2 Facility at the Royal Military College; however, there have occasionally been requirements for analyses externally. A transportable gamma spectroscopy system was thus assembled by acquiring a commercially available multichannel analyzer, analysis program and detector, and by designing and constructing a transportable shielding castle. It was then used to take measurements of fission product concentrations at several research reactors.     

Problems of adhesion

Many discrepancies in the theory of adhesion are connected with the confusion of processes of bond-forming and bond-breaking which have very different character. The former consumes several decimal orders of magnitude more work than would correspond to a reversible process.

The most important cause of this is the work needed to separate the parts of the electric double layer formed at the contact of two bodies. The corresponding electrostatic attraction plays the most important part in adhesion of solid bodies and especially of powder particles. It explains especially the photo controlled adhesion of powders. In contrast to this the separation of particles imbedded in a liquid may be realized nearly reversibly when the rate of process is not very high. The theory of adhesion (coagulation) of lyophobic colloid particles (the Derjaguin-Landau-Verwey-Overbeek theory) takes into consideration the Van der Waals forces and ionic-electrostatic interactions. Recently this theory has included in its scope the phenomena of repeptization.     

Solubility of carbon dioxide in aqueous solutions of sodium chloride: Experimental results and correlation

The solubility of carbon dioxide in aqueous solutions of sodium chloride was measured in the temperature range from 40 to 160°C, up to 6 mol-kg salt solutions and total pressures up to 10 MPa. Pitzer's⁽¹⁾ equations as well as the Chen and Evans⁽²⁾ model were used to correlate the new data. Results are reported and compared to literature data and correlations.     

Synthesis of unsaturated polyester resins for large sized composites

A series of unsaturated polyesters based on phthalic anhydride (PHA), maleic anhydride (MA), ethylene glycol (EG), diethylene glycol (DG), triethylene glycol (TG), propylene glycol (PG), styrene (Sty) and acrylonitrile (AN) were prepared. The molecular weights of the prepared polyesters were determined by end-group analysis. The effect of the structure of the resin on its curing behavior has been investigated. On the basis of the experimental study, the following were concluded: (1) The maximum curing temperature (T_max) is related to the molecular weight of the glycol incorporated in these castings. In this context the T_max was found to decrease with increasing the molecular weight. Meanwhile the time to peak temperature t_max was increasing. (2) The higher the percentage of AN in the crosslinking monomer system, the slower a resin cures. (3) The values of T_max were found to be influenced to a large extent by the percentage of AN.     

O− and OH− chemical ionization of some fatty acid methyl esters and triacylglycerols

O^? and OH^? react with fatty acid methyl esters (FAMES) under chemical ionization conditions both as Bronsted bases to form [M - H]^? and as nucleophiles to form the carboxylate ion RCOO^?. O^? shows a much greater tendency to react as a nucleophile than does OH^?. The [M - H]^? ions fragment by elimination of CH³OH, with unsaturation in certain positions in the fatty acid hydrocarbon chain promoting this elimination for unknown reasons. The reaction of O^? and OH^? with triacylglycerols leads to [M - H]^?, characteristic of the molecular mass, and to carboxylate ions characteristic of the fatty acid(s) present in the lipid. The presence of the three ester functions in the lipids greatly enhances the formation of carboxylate ions compared to the FAMES.     

Cubane derivatives 1. Synthesis and molecular structures of the esters of 1,4-cubanedicarboxylic acid

An effective method of esterification of 1,4-cubanedicarboxylic acid with alkylsulfuric acids is proposed. The derivatives of alkanols with substantially different pK_a Valus are obtained in high yields. Molecular structures of the esters obtained are confirmed by various methods. The X-ray study showed a remarkable effect of the nature of an alkyl radical on the geometry of the cubane core.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp.668–672, April, 1994.The authors thank Dr. G. V. Lagodzinskaya for analyzing the NMR spectra and for useful discussions.     

Production of carbon soot with a high content of C60 and C70 fullerenes by electric arc

The effect of the parameters of the electric arc (helium pressure, current and voltage, clearance between electrodes) and of the peculiarities of the setup design (arrangement of electrodes, distance between the arc and the cooling surface, temperature of the soot condensation surface) on the yield of fullerenes has been studied. Conditions for producing soot with a C₆₀ and C₇₀ content up to 43% (toluene extract) have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 805–809, May, 1994.The authors are grateful to N. G. Spitsyna and A. V. Dubovitskii for the determination of the content of C₆₀ and C₇₀ fullerenes in the extract.The work was financially supported by the Russian Foundation for Basic Research (Project 93-03-18705).