EPR spectroscopy and polarography of nitroazoles. 3. Nitropyrazoles

The results of an EPR investigation are presented with polarographs of electrochemical excitation of nitropyrazoles in acetonitrile. It is shown that 3- and 4-nitropyrazoles are excited in two single-electron stages with formation of dianion radicals. Upon excitation, N-alkylnitropyrazoles form stable anion radicals. 1-Nitro- and 1,4-dinitropyrazoles are excited upon splitting off of the NO₂ anion. Excitation potentials of the nitropyrazoles and hyperfine interaction constants for the corresponding ion radicals are given.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 523–527, April, 1982.     

Kinetics of Gold Electrodeposition from Cyanide Electrolytes at a Monitored Surface Coverage by Thallium Atoms

A procedure for measuring kinetic parameters of gold electrodeposition in the presence of catalytically active thallium(I) ions while monitoring the coverage of the gold surface by thallium adatoms, , is described. The procedure accounts for the duration of contact between a freshly renewed surface of gold and a thallium-containing solution and assumes that the incorporation rate of thallium adatoms is proportional to and the current density of gold electrodeposition. At = const, kinetic dependences correspond to the Tafel equation. Values of and i ₀ increase with . At = 0.3, 0.6 and i ₀ 3 × 10^–4 A cm^–2, which conforms to values calculated from anodic curves obtained in similar conditions.     

Adsorption of Carbon Tetrachloride on Pyridinium Montmorillonite

Effect of substitution of Na⁺ by pyridinium on the surface and pore structures of montmorillonite is studied by CCl₄ vapor adsorption.     

Migration of 99Tc in a Weak Loess Aquifer: A Field Column Experiment

The migration of ⁹⁹Tc in a weak loess aquifer was investigated in-situ with undisturbed aquifer medium columns. The columns were obtained horizontally at a depth of 3236 m in an Underground Research Facility (URF). Quartz containing ³H (HTO) and ⁹⁹Tc (in the form of ⁹⁹TcO₄ ^-) was introduced into one end of the columns and the columns were covered tightly. Aquifer water was introduced into the columns directly from an experimental shaft in the UFR. Effluents from the columns were collected and the activity of ³H and ⁹⁹Tc were determined with a liquid scintillation analyzer. The breakthrough curves of ³H and ⁹⁹Tc indicate that ⁹⁹Tc migrates a little faster than that ³H does in the aquifer.     

Diverse redox-active molecules bearing O-, S-, or Se-terminated tethers for attachment to silicon in studies of molecular information storage

A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols.     

L X-ray production cross sections, average L shell fluorescence yield and intensity ratios in heavy elements

L X-ray fluorescence cross sections, and intensity ratios were measured for elements in the 70￡Z￡92 atomic range at the excitation energy 59.5 keV using a Si(Li) detector. Furthermore, L X-ray fluorescence cross sections and intensity ratios were calculated for elements in the same range. The average L shell fluorescence yields were derived using experimental L X-ray fluorescence cross sections and theoretical photoionization cross sections. The obtained results were compared with other experimental and theoretical values. This revised version was published online in August 2006 with corrections to the Cover Date.     

Adsorption of chlorobenzene on V2O5/Al2O3 catalyst under dynamic conditions

Frontal chromatography was used to study the adsorption dynamics and adsorption equilibrium of chlorobenzene on a 5% V₂O₅/Al₂O₃ catalyst at temperatures of 50 and 100°C. The mixed-diffusion model was employed to describe the elution curve and evaluate the effective coefficients of external mass exchange and diffusion within transport pores.     

Rapid Determination of Explosives and Narcotics Using a Multicapillary-Column Gas Chromatograph and an Ion-Mobility Spectrometer

A gas chromatograph for the rapid determination of explosives (2,4-dinitrotoluene, 2,4,6-trinitrotoluene, and pentaerythritol tetranitrate) and narcotics (heroin, cocaine hydrochloride, and crack) is described, and its analytical characteristics are presented. The instrument was equipped with a multicapillary column and an ion-mobility spectrometer as a detector.     

Potential and Current Distributions in Chlorine Diaphragm Electrolyzers with Gas Removal from the Back Side of External Electrodes and Possibility of Electrolysis Intensification

The cell voltage balance components of monopolar and bipolar electrolyzers were analyzed on the basis of calculations in terms of a mathematical model of the potential and current distributions along the cell height and tests of a laboratory electrolyzer of industrial height. Ways to diminish energy expenditure and to intensify diaphragm electrolysis of aqueous sodium chloride solutions were substantiated theoretically and experimentally.     

Determination of rare earth elements by neutron activation analysis in altered ultramafic rocks from the Akwatia District of the Birim diamondiferous field,Ghana

Summary Rare earth element (REE) analysis using instrumental neutron activation (INAA) was carried out on ultramafic rocks from the Akwatia District of the Birim diamondiferous field, Ghana, with the primary objective of investigating their kimberlitic characteristics. The total REE concentrations range from 113 to 1610 ppm and fall within the interval of those reported in the literature for kimberlites. Despite the marked difference in the REE contents, all the analyzed samples show similar REE patterns that resemble those of kimberlites. However, compared to most of the kimberlites, the ultramafic rocks have small negative Eu anomalies and low light-REE/heavy-REE ratios, suggesting that the rocks have been significantly assimilated by crustal rocks.