Multivariate optimization of mercury determination by flow injection-cold vapor generation-inductively coupled plasma optical emission spectrometry

In this work a procedure for mercury determination by Flow Injection-Cold Vapor Generation-Inductively Coupled Plasma Optical Emission Spectrometry (FI-CVG-ICP OES) has been developed. The system uses a small homemade glass separator constructed to drive the Hg vapor to the plasma. An evolutionary operation factorial design was used to evaluate the optimal experimental conditions for mercury vapor generation, aiming at the low consumption of reagents, the improvement of the analytical signal and consequently greater sensitivity. The procedure allowed the determination of mercury and showed excellent linearity for the concentration range from 0.50 μg L(-1) to 100.0 μg L(-1), with Limits of Detection (LOD) and Quantification (LOQ) of 0.11 μg L(-1) and 0.36 μg L(-1), respectively, and a sampling rate of 36 analyses per hour. The optimized procedure showed good accuracy and precision, and the method was validated by the analysis of two certified reference materials: Buffalo River Sediment (NIST 2704) and human hair (IAEA 085). A good agreement with the certified values was achieved, with recovery values of 99% and 98% and relative standard deviation close to 2%.     

Attenuation of second sound in superfluid 3He-A1

The attenuation of second sound (spin-entropy) wave in the superfluid A1 phase has been measured in magnetic fields up to 11 T and to sufficiently high frequency to observe the bulk attenuation proportional to the square of frequency. The measured attenuation coefficient is compared with the existing theories of hydrodynamics and dissipative coefficients. The resulting "excess" attenuation is discussed in terms of the temperature dependent spin diffusion coefficient in the superfluid.     

Chemometric alternatives for resolution of classical analytical problems Spectrophotometric determination of lanthanide mixtures

The simultaneous determination of lanthanide family elements is one of the greatest problems in analytical chemistry, due to the close similarity of their chemical properties. Spectrophotometric methods are generally of limited use, due to the various mutual spectral interferences involved. By using multivariate calibration methods (partial least-squares regression, PLSR), it was possible to obtain a model that adjusts itself perfectly to the values of the mixture concentrations used in the calibration. The model used absorption spectra in the 290-800 nm range for a set of 20 different mixtures of Ce, Pr, Nd and Sm, and made possible the determination of Ce, Pr and Nd concentrations of a commercial rare-earth product, with significantly greater precision than the conventional univariate calibration method. Determination of the Sm concentrations was not possible, since its concentration was below the concentrations used in the model definition.     

Photoionization of Al IV (neon-type) from its ground 2s 22p 6 1 S e and excited 2s 22p 53p 3,1 P 0 3 S e states using the R-matrix method

The R-matrix method is used to calculate the total photoionization cross-sections from the ground 2s ²2p ^{6 1} S ^e and the first three excited 2s ²2p ⁵3p ^3,1 S ^e states of Al IV, for photon energies ranging from the first ionization threshold to just above the second threshold of the residual ion Al V. The two lowest LS terms of Al V − 2s ²2p ^{5 2} P ⁰, 2s2p ^{6 2} S ^e, 2s2p ^{6 2} S ^e, represented by sophisticated configuration interaction wavefunctions, are included in the R-matrix calculation. The resulting cross-sections are affected by Rydberg series of resonances converging to the 2s2p ^{6 2} S ^e excited threshold.     

Zirconium and hafnium determination by energy dispersive X-ray fluorescence with solid phase preconcentration

Two preconcentration methods has been developed for simultaneous determination of zirconium and hafnium by energy dispersive X-ray fluorescence (EDXRF). The first method is a liquid-solid extraction procedure with the use of an anionic exchange resin modified with xylenol orange. The second is a precipitation procedure carried out in the presence of lanthanum. Both methods permit significant enhancement of sensitivity in comparison with direct measurement in the aqueous phase. The applicability of both procedures for the preconcentration of Zr and Hf prior to their determination by EDXRF was demonstrated by analyzing synthetic mixtures and a sample of zirconium ore. The results obtained with the use of the modified resin show relative standard deviation of about 4% and good agreement with those obtained by spectrographic analysis.