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81.
    
AAS as a highly sensitive and specific single element technique is ideally suited as a detector for speciation analysis. The combinations of chromatographic separation with element specific detectors (flame AAS, electrothermal AAS (ETAAS), hydride generation AAS (HGAAS)) provide powerful approaches to the determination of all species. Sample stabilisation is the area that requires most attention as it still represents the main source of problems encountered in speciation work. The correct speciation depends on how the sample is handled prior to analysis. Unfortunately, no universal procedure has been found. Anything that changes redox conditions, pH or complexation equilibrium is clearly unacceptable.  相似文献   
82.
This work is devoted to the numerical solution of the Navier–Stokes equations for compressible viscous fluids. Finite element approximations and stabilization techniques are addressed. We present methods to implement discontinuous approximations for the pressure and the density. An upwinding methodology is being investigated which combines the ideas behind the stream line Petrov–Galerkin method and the flux limiter methods aiming to introduce numerical diffusion only where it is necessary.  相似文献   
83.
The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H2O and D2O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H2O and D2O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007  相似文献   
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Analysis of stochastic processes governed by the Langevin equation is discussed. The analysis is based on a general method for non-parametric estimation of deterministic and random terms of the Langevin equation directly from given data. Separate estimation of the terms corresponds to the decomposition of process dynamics into deterministic and random components. Part I of the paper presented several possibilities for qualitative and quantitative analysis of process dynamics based on such decomposition. In Part II, some of these analysis possibilities are applied to experimental datasets from metal cutting and laser-beam welding.  相似文献   
87.
Aeroacoustic resonant oscillations (aeolian tones) are studied for flow past two plates forming a cross in a square cross section channel. Possible oscillation modes are classified on the basis of admissible symmetry groups and the existence of the modes is proved. The infinite linear system of equations for these modes obtained by the sewing method was simplified and studied numerically. Curves of eigenfrequency versus plate length are constructed. The form of the eigenfunctions is studied.  相似文献   
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The contribution of electrons moving at large angles to the barrier junction plane to the tunnel current is calculated. This contribution turns out to be small only if the Fermi energy of the electrons equals several electron volts. Otherwise, specifically, when the Fermi energy is no higher than 1–2 eV, this contribution dominates in high and thin potential barriers. It is found that the tunnel magnetic resistance in ferromagnet-insulator-ferromagnet contacts correlates with this contribution. It is this correlation that is responsible for a decrease in this contribution as the potential barriers get lower and thicker.  相似文献   
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