Preconcentration methods for the determination of trace elements in water by x-ray fluorescence spectrometry: Part 2. Interference studies

Seven methods for the preconcentration of fifteen elements for their subsequent measurement by x-ray fluorescence spectrometry have been evaluated for their susceptibility to interferences. A two-level factorial experimental design has been used, enabling an economical and meaningful comparison of the seven methods to be made. A scheme for rating the methods on the basis of the effect of several interfering species is proposed. Use of such a scheme has enabled an objective comparison of the methods considered to yield their relative ranks. It is also shown that spectral and chemical interferences can be discerned to some extent. Combination of the response rating proposed earlier and the interference rating schemes reported here gives rise to an overall comparison and rank for the methods, allowing an objective choice of the optimal method(s) to be made.     

Angle-resolved elastic peak electron spectroscopy: Role of surface excitations

We analyze the possibility of determining the surface excitation parameter (SEP) from the dependence of the elastic backscattering signal intensity on the emission angle. It has been found that the shape of this dependence is reasonably well described by the theoretical model implemented in a typical Monte Carlo simulation strategy. As shown recently, the mean percentage deviation between the experimental angular dependence and the theoretical dependence is equal to 8.82% at 200 eV, 6.28% at 500 eV and 4.69% at 1000 eV. In the theoretical model used, the surface energy losses were ignored. Close inspection of the deviations between theory and experiments indicates systematic trends that can be ascribed to the surface energy losses. We found here that taking into the account the surface energy losses further improves the agreement between theory and experiment. The total mean percentage deviation, equal to 6.65%, decreases to 5.59% if the mathematical form of the Chen formula for SEP is used, or to 5.16% if the Oswald expression is used. The material dependent coefficients in the expression of SEP derived from the emission angle dependence of the elastic peak intensity differ from these coefficients resulting from other methods. We conclude that the determination of SEP from shape of the angular dependence requires the experimental data of high quality, and the reliable theoretical model describing elastic electron backscattering.     

New Ternary Hafniumhalides: Cs[Hf2Br9] and Rb[Hf2Br9]

The syntheses and crystal structures of two new ternary hafnium compounds, Cs[Hf₂Br₉] ( 1 ) and Rb[Hf₂Br₉] ( 2 ), are described. Both compounds are obtained in high yield from the chemical reaction of HfBr₄ and CsBr or RbBr, respectively, in the presence of a small amount of elemental Al at 450 °C in sealed silica tubes. They crystallize isostructurally in the monoclinic space group P2/n. The lattice parameters are a = 9.946(1) ( 1 ) and 9.9388(4) Å ( 2 ), b = 6.6580(9) ( 1 ) and 6.6695(3) Å ( 2 ), c = 12.930(2) ( 1 ) and 12.8435(6) Å ( 2 ), and β = 112.479(6)° ( 1 ) and 112.726(2)° ( 2 ). The crystals of the two compounds contain dinuclear tri‐μ‐bromido‐hexabromido‐dihafnate(–) complex anions, [Hf₂Br₉]^–, besides the alkali metal cations. The complex anions can be described as face‐sharing bioctahedral units.     

Solubility and Thermodynamic Properties of Dipotassium or Disodium Hydrogenphosphates in Aqueous Solutions at Various Temperatures

Journal of Solution Chemistry - In this investigation, calculated and experimental solubilities of the binary aqueous solutions of dipotassium hydrogenphosphate and disodium hydrogenphosphate have...     

Photoelectron emission from thin overlayers

Photoelectron signal intensities calculated for a thin overlayer from theoretical models taking elastic photoelectron collisions into account are shown to be very weakly dependent on the substrate material. This result has been obtained for photoelectrons analyzed in XPS spectrometers equipped with typical X-ray sources, i.e. sources of Mg Kα and Al Kα radiation. Low sensitivity to the substrate material is due to the fact that trajectories of photoelectrons emitted in the overlayer and entering the substrate have a low probability to reach the analyzer without energy loss. On the other hand, the signal intensity of photoelectrons emitted in the overlayer is found to be distinctly affected by elastic photoelectron scattering. Consequently, a theoretical model that can accurately describe the photoelectron intensity from an overlayer deposited on any material (e.g. on a substrate of the same material as the overlayer) can be a useful basis for a universal and convenient method for determination of the overlayer thickness. It is shown that the formalism derived from the kinetic Boltzmann equation within the so-called transport approximation satisfies these requirements. This formalism is postulated for use in overlayer-thickness measurements to avoid time-consuming Monte Carlo simulations of photoelectron transport, and also to circumvent problems with determining the effective attenuation lengths for overlayer/substrate systems.     

Investigation of phase composition of ilmenites and influence of this parameter on thermokinetics of reaction with sulphuric acid

Ilmenite is a valuable source of titanium and is applied as the main raw material in the technology of titanium white pigment production. Ilmenite is found in many places in the earth, and its elemental as well as phase compositions very strongly depend on the place of origin. Deposits located in Australia, China, India, and Norway in Europe are well known places where ilmenites are exploited industrially. Main phases that were identified in these ilmenites are ilmenite FeTiO₃, hematite Fe₂O₃, geikielite MgTiO₃ and pseudorutile Fe₂Ti₃O₉. Enstatite MgSiO₃, MnTiO₃, and kleberite (determined also as hydroxylian pseudorutile with approximate formula FeTi₃O₆(OH)₃) are minor phases present in ilmenites. Calorimetric investigations of reactions of these ilmenites with sulphuric acid in standard conditions demonstrated significant differences in the shape of temperature and thermal power curves. On the basis of these investigations, it can be concluded that the shape of the thermal power curve is different for each of ilmenite and can be treated as a fingerprint of their phase composite.     

Soret and Dufour effects on heat and mass transfer by mixed convection over a vertical surface saturated porous medium with temperature dependent viscosity

The diffusion‐thermo and thermal‐diffusion effects on heat and mass transfer by mixed convection boundary layer flow over a vertical isothermal permeable surface embedded in a porous medium were studied numerically in the presence of chemical reaction with temperature‐dependent viscosity. The governing nonlinear partial differential equations are transformed into a set of coupled ordinary differential equations, which are solved numerically by using Runge–Kutta method with shooting technique. Numerical results are obtained for the velocity, temperature and concentration distributions, and the local skin friction coefficient, local Nusselt number and local Sherwood number for several values of the parameters, namely, the variable viscosity parameter, suction/injection parameter, Darcy number, chemical reaction parameter, and Dufour and Soret numbers. The obtained results are presented graphically and in tabulated form, and the physical aspects of the problem are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Projections of Veronese surface and morphisms from projective plane to Grassmannian

In this note, we describe the image of ?² in Gr(2, ?⁴) under a morphism given by a rank two vector bundle on ?² with Chern classes (2, 2).     

周期性负载变化提高乙醇燃料电池效率(英文)

We present a simple method to increase the efficiency of a direct ethanol fuel cell by a periodic modulation of the load(pulsed mode). The fuel cell was periodically short circuited with a resistor(1 Ω) for a few seconds(high load period) followed by a low load period of up to 100 s when the resistor was disconnected. The open circuit voltage(OCV) values before and after the short circuit of the cell showed an increase of up to 70 mV. The higher OCV was due to the oxidation and removal of strongly adsorbed CO during the electric short circuit when the electric potential of the anode was increased to be close to the cathode potential. The depoisoned anode surface was much more active directly after the short circuit. The slow decrease of the OCV observed after the short circuit was caused by the subsequent poisoning of the anode surface, which can be neutralized by another short circuit. In general, a stable increase in cell performance was obtained by repetition of the electric short circuit. The data showed that the pulse mode gave an increase in the power generated by the direct ethanol fuel cell by up to 51% and was 6% on average. It is anticipated that this mode of operation can be used also in different types of polymer electrolyte membrane fuel cells where CO poisoning is a problem, and after optimization of the parameters, a much higher gain in efficien-cy can be obtained.