Extraction-spectrophotometric study on the vanadium(V)-2,3-dihydroxynaphthalene — iodonitrotetrazolium chloride — water — chloroform system and its analytical application

The formation of a new ternary ion-associate complex of vanadium(V) with 2,3-dihydroxynaphthalene and iodonitrotetrazolium chloride with a composition ratio of 1:2:1 is reported. The complex is quantitatively extracted from water into chloroform. The molar absorptivity (ɛ) of the extract at λ _max=340 nm is 2.5 × 10⁴ dm³/mol cm, and Beer’s law is obeyed for concentrations ranging from 0.1 to 0.9 μg/cm³ V(V). The following constants are determined: the extraction constant, the association constant, the distribution constant, and the recovery factor. The effects of foreign ions and reagents are studied. A selective and sensitive method is developed for determination of vanadium in steels.     

Ion-exchange method for separation and concentration of platinum and palladium for analysis of environmental samples by inductively coupled plasma atomic emission spectrometry

An ion-exchange procedure is proposed for determination of Pt and Pd in environmental samples, using a Dowex 1-X10 anion-exchange resin. Pt and Pd were separated from the matrix elements in the sample by selective retention on the column as anionic chloro complexes and subsequent elution by circulated thiourea at 60 °C. The eluent, containing Pt and Pd was analyzed by inductively coupled plasma (ICP) atomic emission spectrometry (AES). Average recoveries of 98% and detection limit of 15 ng/g for both metals were achieved. Analysis of Pt and Pd concentrations in road dust, sampled from several sites in Germany was performed. The comparison of the obtained data with the concentrations of Pt and Pd in the same samples, determined by ICP-MS showed a very good agreement.     

Investigation of the extraction equilibria in the system hexachloridorhenate(IV)-neotetrazolium chloride-dichloroethane-water

The neotetrazolium hexachloridorhenate(IV) (NTReCl(6)) has been synthesized and its composition checked. The optimum conditions for the extraction of NTReCl(6) with dichloroethane have been established. The recovery factor for one-fold extraction is R = 74%. The distribution constant, K(D), extraction constant, K(ex), and ion-association constant, beta, have been determined. Neotetrazolium chloride was found to be suitable reagent for extraction-spectrophotometric determination of rhenium(IV) ((NTReCl(6)) = 3.42 +/- 0.20 x 10(4)M(-1) cm(-1)).     

Study of microbuckling of fiber-reinforced composite materials

On the basis of the theory of microbuckling of lamina-reinforced composites and formula predicting the critical composite stress for microbuckling in the shear mode _cs published in the literature, a FORTRAN program for study of the behavior of microbuckling of fiber reinforced composites has been developed. Some types of composite materials (reinforcement of different fibers and epoxy matrix) have been studied. Graphics and curves, accounting for the dependences of the compressive stress at failure _cs from the reinforcement volume k, specimen length L, and shear modulus of resin G_r have been obtained. The comparison of the theoretical diagrams presented here and experimental and theoretical results, published in the literature shows good agreement. The basic conclusion of the work presented here is that the study could be used for other fiber reinforced composites (with different mechanical properties of matrices and fibers).Institute of Mechanics, Bulgarian Academy of Sciences, Sofia, Bulgaria. Published in Mekhanika Kompozitnykh Materialov, Vol. 32, No. 4, pp. 531–538, July–August, 1996.     

Physicochemical fractionation of americium, thorium, and uranium in Chernozem soil after sharp temperature change and soil drought

A sequential extraction procedure was used to study the changes in the physicochemical forms of americium (Am), thorium (Th), and uranium (U) in laboratory-contaminated Chernozem soil as a result of sharp variations of the environmental temperature and soil moisture. The influence of freezing and soil drought on the radio-ecological hazard was evaluated three months after radioactive contamination with aqueous solutions of ²⁴¹Am, ²³⁴Th, and U. The subsequent changes in the physicochemical forms of the actinides, caused by sharp increases in the environmental temperature and soil moisture, were examined for one month. The data showed that continuous freezing increased the potentially mobile forms of Am and Th but had the opposite effect on U. Prolonged soil drought did not influence the fractionation of Am and Th but led to the redistribution of U between the carbonates and organic matter and caused its immobilisation. The sharp increase in the temperature of the frozen soil caused the immobilisation of Am and Th and increased the potential mobility of U. The warming and enhanced humidity of the dry soil led to the immobilisation of Am and redistribution of U between the soil phases.     

Investigation of the solubilization of car-emitted Pt,Pd and Rh in street dust and spiked soil samples

A sequential extraction procedure (three-step), proposed by the Standards, Measurements and Testing Programme (formerly BCR) of the European Union, was applied to street dust and spiked soil samples for the determination of PGEs. Analyses were carried out using inductively coupled plasma-mass spectrometry (ICP-MS). The results indicate that up to 5% from Pt, 70% from Pd and 14% from Rh are in mobile forms in street dust. The results for the soil samples spiked with crushed catalytic converter are significantly lower indicating that PGEs are oxidised more efficiently in natural conditions. Additionally Pt and Pd bound to humic acids were investigated.     

Polymerization of styrene oxide by nitronium tetrafluoroborate

The polymerization of styrene oxide by nitronium tetrafluoroborate in nitromethane and methylene chloride at 5, 20, and 50°C is investigated. GPC analyses of the products combined with isocyanate method show that both cyclic and linear oligomers are formed. In CH₃NO₂ the cyclic dimer and trimer are 2-benzyl-4-phenyl-1,3-dioxolane and 1,3,5-tribenzyl-trioxane, respectively. In CH₂Cl₂ 2,5-diphenyldioxane is isolated. In nitromethane, mainly isomerized structures with acetal linkage are produced, while in methylene chloride isomerization does not proceed. By NMR and IR spectra the presence of C?O and OH end groups in the linear oligomers is shown. There are indications that oligomers are formed both directly from the monomer and by degradation of the polymer.     

Multielement Analytical Spectroscopy in Plant Ionomics Research

Abstract: The study of the ionome (ionomics) is defined as quantitative and simultaneous measurement of the element composition of living organisms and changes in this composition in response to physiological stimuli, development stage, and genetic modifications (Salt et al., Ann. Rev. Plant Biol., Vol. 59, 2008). The necessity of understanding the regulation processes of elements in the organisms demands determination of many elements in the organism, tissue, and cell (Baxter, Plant Biol., Vol. 12, 2009). A prospect for ionomics is environmental pollution where great variety of conditions and pollutants exist resulting in concentration and interelemental changes in the plant ionome. The capabilities of and problems with several multielement analytical techniques, including instrumental neutron activation analysis (INAA), X-ray fluorescence, inductively coupled plasma–atomic emission spectrometry (ICP-AES), inductively coupled plasma–mass spectrometry (ICP-MS), and atomic absorption spectrometry (AAS), which are adequate and most promising in ionomic and environmental studies of plants, are reviewed. References are confined mainly to the last 10–15 years. Information about concentrations, roles, binding forms, and pollution sources of the elements and comparison between methods with respect to limits of detection, determined elements, interferences, and economic considerations are tabulated. Some combinations of instrumental techniques supplementing each other are highly valued, namely, ICP-MS and ICP-AES and INAA and AAS or ICP-AES.     

Defect Formation,T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework—DFT Modeling

We used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favorable by more than 100 kJ/mol. We suggested an approach for experimental identification of the T atom position in Ti-MCM-68 zeolite via simulation of infrared spectra of pyridine and acetonitrile adsorption at Ti. The modeling of adsorption of hydrogen peroxide at Ti center in the framework has shown that the molecular adsorption was preferred over the dissociative adsorption by 20 to 40 kJ/mol in the presence or absence of neighboring T-atom vacancy, respectively.