Organophosphorus reagents as extractants-part 3. Synergic effect of triphenyl phosphine oxide and bis(diphenyl phosphinyl) alkanes on extraction of iron(III) from thiocyanate medium with 2,4-pentdione

The extraction of iron(III) from thiocyanate medium was carried out with a synergic combination of 2,4-pentdione (Hacac) and either triphenyl phosphine oxide (Ph(3) PO) or bis (diphenylphosphinyl) alkanes, Ph(2)P(O)(CH(2))(n).P(O)PH(2) [ligand abbreviation, n: dpeO(2), 2; dpbO(2), 4]. Iron(III) was quantitatively separated from its binary mixture with chromium(III), manganese(III), cobalt(II), nickel(II), zinc(II), cadmium(II), mercury(II), lead(II), magnesium(II) and from steel samples. Copper(II) and silver(I) however, interfered. The percentage extraction was 99.0%. The respective extraction constants, K(HA), K(L) or K(syn), for the extracted species, [Fe(NCS)(acac)(2)(H(2)O)] (HA Hacac), Fe(NCS)(3)L(2) [L b Ph(3)PO, dpeO(2) or dpbO(2)], or Fe(NCS)(acac)(2)L were found to be: K(HA), 1.48 x 10(3), K(L), 1.80 x 10(2) (L Ph(3)PO), 2.02 x 10(2) (L dpeO(2) or dpbO(2)) and K(syn), 1.87 x 10(6) (L Ph(3)PO), 2.56 x 10(6) [L dpeO(2) or dpbO(2)].     

Effect of modified fibre glass on the structure and thermophysical properties of pentaplast(pentane)

The results of experimental investigations of the effects of ground fibre glass on the structural parameters and thermophysical characteristics of pentaplast(pentane) were assessed.The degree of crystallinity, thermal conductivity, specific heat and density of pentaplast containing various amounts of modified fibre glass were determined experimentally.The results obtained are discussed in terms of modern theories of the effects of fillers on the properties and structures of polymers.

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Zusammenfassung Es werden die Ergebnisse der experimentellen Untersuchungen des Einfl usses von gemahlenem Fiberglas auf die Strukturparameter und thermophysikalischen Eigenschaften von Pentaplast (Pentan) gewertet.Der Kristallinitätsgrad, das Wärmeleitvermögen, die spezifische Wärme und die Dichte von Pentaplast mit verschiedenem Gehalt an modifiziertem Fiberglas wurde experimentell ermittelt.Die erhaltenen Ergebnisse wurden hinsichtlich moderner Theorien über den Einfluß von Streckmitteln auf die Eigenschaften und die Struktur von Polymeren diskutiert.

     

Chemistry of heteroanalogs of isoflavones. 16. Benzthiazole analogs of isoflavones

The reaction of a-(2-benzthiazolyl)-2, 4-dihydroxy-5-alkylacetophenones with anhydrides and chlorides of carboxylic acids yielded 3-(2-benzthiazolyl)chromones with electron-acceptor and electron-donor substituents, as well as chromones unsubstituted in the 2 -position. Their acylation, alkylation, and aminoacylation reactions and their interaction with electrophilic and nucleophilic reagents were studied.Taras Shevchenko Kiev University, Kiev 252017. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 464–471, April, 1994. Original article submitted March 5, 1994.     

Heteronuclear solid-state correlation spectroscopy

Two-dimensional NMR methods are proposed for correlating the spectra of abundant and dilute spins in solids. The techniques simplify assignment and permit determination of shielding tensors even when extensive overlaps occur. Spin diffusion among abundant spins can be observed indirectly.     

Alpha emitters from uranium mining in the environment

Uranium mining and milling activities usually generate an enhancement of radionuclide concentrations in the environment that may cause increased radiological exposure to mankind. For risk assessment and radiological protection of man and environment in these areas, usually, it is needed to implement radiological surveillance of water, soils, agricultural products, aerosols, and mining waste discharges as well. Radionuclides to be monitored in priority are alpha-emitting nuclides of the uranium natural series. Radioactivity analysis of materials from uranium mining areas of Portugal shows departure from secular radioactive equilibrium amongst uranium series radionuclides, thus rendering invalid the assumption of equilibrium and requiring the actual determination of each radionuclide. Radionuclide measurements performed with high resolution alphaspectrometry, as reported herein, produce accurate results on specific radionuclides that are essential in computing radiation doses to critical groups of the population.     

Modeling and analysis of uranium isotope enrichment by chemical exchange

Starting with an accurate mathematical model a theoretical study for the analysis of the separation of uranium isotopes by chemical exchange has been presented. The experimental data used in this study were obtained by reverse breakthrough technique and the numerical algorithm developed for simulation in previous studies was adapted and found to be suitable for this kind of processes. The model parameters were identified from experimental data and simulations were carried out for different experimental conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of the nature of organic diluents on the extraction of uranium(VI) by bis(2-ethylhexyl) sulfoxide from nitric acid solutions

The extraction of uranium(VI) from nitric acid solutions by bis(2-ethylhexyl) sulfoxide (BESO) has been examined using sixteen inert organic diluents in order to establish the correlation between its distribution coefficient and some physico-chemical properties of the diluents. The extracted solvated species is shown to be UO₂(NO₃)₂·2BESO, irrespective of their nature. The extraction rate is lower in halogen substituted hydrocarbons as compared to the other diluents used. Among benzene derivatives, extraction is found to decrease with number of substituted methyl groups. Extraction efficiency decreases as the organic solvent is varied in the order: benzene>nitromethane>toluene> >nitrobenzene>cyclohexane>p-xylene>monochlorobenzene>dodecane>o-dichlorobenzene> >hexane>decalin>1,2-dichloroethane>1,1,1-trichloroethane>carbon tetrachloride> >tetrachloroethane>chloroform. Among the properties showing good correlations with distribution coefficient are Hansen's three-dimensional solubility parameters and Dimroth's empirical solvent polarity parameters [E _T(30) ]. Polarizability indices are most satisfactorily applicable to a wide variety of solvents.     

Reactor for prechromatographic fusion reactions

An improved design of a reactor for alkaline fusion as a preliminary to chromatographic analysis is described. The reactor allows the use of a significantly reduced sample size, minimizes leakages and facilitates the removal of the reaction products. The use of the reactor is demonstrated by the analysis of several polyester samples exhibiting increased hydrolytic stability.     

Water in carbon nanotubes: adsorption isotherms and thermodynamic properties from molecular simulation

Grand canonical Monte Carlo simulations are performed to study the adsorption of water in single-walled (6:6), (8:8), (10:10), (12:12), and (20:20) carbon nanotubes in the 248-548 K temperature range. At room temperature the resulting adsorption isotherms in (10:10) and wider single-walled carbon nanotubes (SWCNs) are characterized by negligible water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption/desorption hysteresis loops. The width of the hysteresis loops decreases as pore diameter narrows and it becomes negligible for water adsorption in (8:8) and (6:6) SWCNs. Results for the isosteric heat of adsorption, density profiles along the pore axis and across the pore radii, order parameter across the pore radii, and x-ray diffraction patterns are presented. Layered structures are observed when the internal diameter of the nanotubes is commensurate to the establishment of a hydrogen-bonded network. The structure of water in (8:8) and (10:10) SWCNs is ordered when the temperature is 298 and 248 K, respectively. By simulating adsorption isotherms at various temperatures, the hysteresis critical temperature, e.g., the lowest temperature at which no hysteresis can be detected, is determined for water adsorbed in (20:20), (12:12), and (10:10) SWCNs. The hysteresis critical temperature is lower than the vapor-liquid critical temperature for bulk Simple Point Charge-Extended (SPCE) water model.     

The determination of phytoplankton pigments by high-performance liquid chromatography

A simple high-performance liquid Chromatographic method is described for the determination of chlorophylls, chlorophyll degradation products, and carotenoids in phyto-plankton cultures and marine particulate matter. Pigment extraction is carried out with acetone and methanol. After evaporation of the combined extracts under reduced pressure, the pigments are separated on a Partisil-10 stationary phase with a mobile phase consisting of light petroleum (b.p. 60–80°C), acetone, dimethyl sulphoxide and diethylamine(75: 23.25:1.5: 0.25 by volume). When chlorophyll c is present, a further development is performed with a similar, but more polar, solvent mixture. Detection is carried out spectrophotometrically at 440 nm. The method has a sensitivity for the chlorophylls of ca. 80 ng, and for carotene of ca. 5 ng. The coefficient of variation of the Chromatographic stage of the procedure lies in the range 0.6–1.8%.