Total reflection X-ray fluorescence determination of rare earth elements in mineral water

A method is proposed for determination of lanthanum, cerium, praseodymium, neodymium, and samarium in mineral water by means of total-reflection X-ray fluorescence analysis. In this work, the combined technique of preconcentration of rare earth ions is used. This technique consists of coprecipitation of metal hydroxides on the collector (iron (III) hydroxide) and dispersive liquid–liquid microextraction of their complexes with 1-(2-pyridylazo)-2-naphthol by chloroform in the presence of ethanol. The use of the developed hybrid approach allows simultaneous determination of the mentioned metals in mineral water in the range n(10^–2–10¹) μg/L. The results of analysis of Arkhyz and Rychal-Su mineral waters by the proposed extraction–X-ray fluorescent method are confirmed by the literature data, obtained by inductively coupled plasma mass spectrometry.     

Synthesis,structure, and optical properties of iridium(III) complex with 1-benzyl-2-phenylbenzimidazole and 4,4'-dicarboxy-2,2'-bipyridyne

A new cyclometalated iridium(III) complex [Ir(L)₂(Hdcbpy)] (1) has been synthesized, where L is 1-benzyl-2-phenylbenzimidazole and Hdcbpy is monoprotonated 4,4′-dicarboxy-2,2′-bipyridine. The structure of complex 1 has been determined by X-ray diffraction. The optical properties of complex 1 have been studied, and the quantum yield of luminescence has been measured.     

Speed of flame propagation in CH<Subscript>3</Subscript>Cl + Cl<Subscript>2</Subscript> mixtures during combustion initiated by continuous UV radiation

Flame propagation in a closed tube over mixtures of chloromethane and chlorine of different compositions following ignition by continuous UV radiation is studied. It is found that the rate of combustion in all mixtures except limiting ones grows along with the propagation of the flame front up to its maximum values at nearly 1/3 the tube length and then slows. In limiting mixtures, the speed’s behavior is completely different. It is greatest near the source of UV light and gradually slows with distance from the source. The high speed in the initial section is due to the effect of UV light. The temperature of combustion is lowest in limiting mixtures, and the rate of chlorine molecule photodissociation at this temperature is comparable to and even faster than that of their thermal dissociation. The light in these mixtures thus contributes substantially to the initiation of the chemical reaction. It is concluded that when limiting mixtures are ignited by UV pulses, the speed of flame propagation falls markedly as it proceeds without the influence of radiation, and the character of changes in the speed’s behavior becomes identical to those for other mixtures.     

Formation of tricyclo[6.3.0.02,5]undecane derivatives during attempts to make the rumphellatin A–C oxacarbon skeleton

The results of several approaches to make the 4,4,8-trimethyl-12-oxatricyclo[7.2.1.0^2,5]dodecane motif present in rumphellatins A–C are reported. The strategy adopted involved (9E)-12,12-dimethyl-5-oxatricyclo[8.2.0.0^4,6]dodec-9-en-11-ol as an intermediate, but when attempts were made to connect the third methyl group to the carbon skeleton by reacting the epoxide with MeLi under boron-trifluoride catalysis, an unprecedented transannular reaction occurred. The desired product was not formed; instead, compounds containing a tricyclo[6.3.0.0^2,5]undecane moiety were obtained, in one case in better than 70% yield.     

Structure of a bimolecular crystal of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane and methoxy-<Emphasis Type="Italic">NNO</Emphasis>-azoxymethane

The crystal structure of the bimolecular crystal of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and methoxy-NNO-azoxymethane (МАМ) (1:2) is studied. The CL-20 molecules adopt a ζ-conformation. The crystal structure is formed by layers of CL-20 and МАМ molecules, between which there are shortened NO^δ–?N^δ+O contacts of the neighboring CL-20 and МАМ molecules.     

Forms of solid solution ordering upon decreasing temperature

The work reports different forms of solid solution ordering: from the well-known atom redistribution processes over positions and the decomposition of the solid solution to the formation of superstructures, modulated structures, rotation of atomic groups, splitting of sites. For each ordering form as a crystal chemical phenomenon the position of atoms, molecules, and vacancies in the crystal structure of the solid solution is considered and the place of these processes among the main crystal chemical phenomena is determined. The manifestation of order–disorder processes in phase diagrams of systems is also analyzed: from the classical heterogeneous decomposition of solid solutions to the formation of ordered chemical compounds and other phase transitions. The necessity of a thorough study of the atomic-molecular nature of the solid solution ordering by modern X-ray diffraction crystallographic methods and high-resolution electron microscopy is demonstrated. For each ordering form examples are given, the driving force of the process is distinguished, and a brief literature review is presented.     

Short-time isoprene polymerization under the action of a titanium–magnesium catalyst

The short-time polymerization of isoprene under the action of a TiCl₄/MgCl2?i-Bu₃Al heterogeneous catalyst has been investigated. Pulse mixing of the catalyst and monomer in a cylindrical tubular reactor with a certain length followed by ethanol injection has made it possible to carry out polymerization for 0.1?0.7 s. In the first 0.3 s, when there is a considerable rise in the activity of the catalyst, living polymerization of isoprene takes place. In this period, polyisoprene has up to 95% trans-1,4 units. Extending the polymerization time to 0.7 s diminishes the average molar mass of polyisoprene, broadens its molar mass distribution, and decreases the concentration of trans-1,4 units to 83%. The data of this study have been analyzed on the basis of the kinetic continuity of the polymer chain initiation and growth.     

Y-type zeolites for the catalytic oxidative degradation of organic azo dyes in wastewater

Cobalt- and iron-containing catalysts active in the oxidation of organic dyes with hydrogen peroxide have been prepared from granular synthetic NaY and HY zeolites without a binder by ion exchange followed by heat treatment at 350–500°C. It has been demonstrated by X-ray photoelectron spectroscopy that cobalt and iron in these catalysts are in the form of Co²⁺ and Fe³⁺ ions on the support surface. The FeHY and CoNaY catalysts are most effective and stable in the oxidation of the anionic dye carmoisine in weakly acidic and alkaline media.     

Molecular kinetic aspects of vaporization of volatile coordination compounds with organic ligands

We present results of the experimental study and numerical simulation of radiation-convective heat and mass transfer during the sublimation of spherical particles of metal β-diketonates in a high-temperature inert gas flow (argon or helium). The sublimation process is visualized, and experimental data on the temperature variation dynamics and particle size are obtained. It is shown that at stable transfer of the compound from the particle surface the sublimation proceeds with the formation of large pores in its structure. The effect of inert gas properties on the kinetics of the vaporization process of precursor particles with various initial diameters is analyzed in the temperature range from 200 °C to 330 °C. Due to a higher thermal conductivity and heat capacity of helium as compared with argon, the choice of helium as carrier gas causes an increase in the sublimation intensity.     

Thio acid-mediated conversion of azides to amides – Exploratory studies en route to oroidin alkaloids

The utility of the thio acid-azide coupling reaction to afford amides is explored in imidazole-containing substrates for application in the total synthesis of examples of oroidin alkaloids. Good yields of the expected amides are obtained in both monomeric and dimeric substrates. Bis azides react preferentially at the 2-azido position but hydrosulfenylation and reduction interfere. 2-Thiophenyl and 2-oxo groups were evaluated as 2-amino surrogates, the thioether delivered the expected amide, whereas 2-imidazolone gave a mixture of the expected amide and the hydrosulfenylation product.