Determination of arsenic in diesel, gasoline and naphtha by graphite furnace atomic absorption spectrometry using microemulsion medium for sample stabilization

A procedure for the determination of As in diesel, gasoline and naphtha at μg L⁻¹ levels by GFAAS is proposed. Sample stabilization was achieved by the formation of three component solutions prepared by mixing appropriate volumes of the samples propan-1-ol and nitric acid aqueous solution. This mixture resulted in a one-phase medium, which was indefinitely stable. No changes in the analyte signals were observed over several days in spiked samples, proving long-term stabilization ability. The use of conventional (Pd) and permanent (Ir) modification was investigated and the former was preferred. Central composite design multivariate optimization defined the optimum microemulsion composition as well as the temperature program. In this way, calibration using aqueous analytical solutions was possible, since the same sensitivity was observed in the investigated microemulsion media and in 0.2% v/v HNO₃. Coefficients of correlation larger than 0.999 and an As characteristic mass of 22 pg were observed. Recoveries (n=4) obtained from spiked samples were 98±4, 99±3 and 103±5%, and the limits of detection in the original samples were 1.8, 1.2 and 1.5 μg L⁻¹ for diesel, gasoline and naphtha, respectively. Validation was performed by the analysis of a set of commercial samples by independent comparative procedures. No significant difference (Student’s t-test, p<0.05) was observed between comparative and proposed procedure results. The total determination cycle lasted 4 min for diesel and 3 min for gasoline and naphtha, equivalent to a sample throughput of 7 h⁻¹ for diesel and 10 h⁻¹ for gasoline and naphtha.     

Simultaneous imbibition-heat convection process in a non-Darcian porous medium

In the present work, the nonisothermal imbibition process in a porous medium was numerically analyzed using a non-Darcian model for the momentum equation and energy equations for the wetting and dry zones. In order to show the thermal character of the problem, we assume initially that the porous medium is found at a uniform temperature T0 and suddenly begins the imbibition process into the porous medium with a penetrating fluid at temperature T1. The physical influence of nondimensional parameters such as Peclet number, Pe, effective heat capacity number, beta(w), porous Reynolds number, Re(p), and the inertial coefficient of the porous medium, F, serve us to evaluate the position and velocity of the imbibition front as well as temperature profiles in both zones. In particular, for values of Re(p)F/beta(w)>1, we recover a type of nonisothermal Washburn law. The numerical predictions show that the imbibition front and the temperature fields strongly depend on the above nondimensional parameters, revealing a clear deviation of the simple Washburn law.     

Weighted oscillator strengths and lifetimes for the S XIV spectrum

The weighted oscillator strengths gf and the lifetimes for S XIV presented in this work have been calculated in a multiconfigurational Hartree–Fock relativistic approach. In this calculation, the electrostatic parameters were optimized by a least-squares procedure in order to improve the adjustment to experimental energy levels. This method produces gf values that are in better agreement with observed line intensities and lifetime values closer to the experimentally determined ones. In this work we presented all the experimentally known electric dipole S XIV spectral lines. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 473–476, 2009.     

Mathematical Model for Surface‐Initiated Photopolymerization of Poly(ethylene glycol) Diacrylate

Summary: A general mathematical model has been developed to describe the surface initiated photopolymerization of PEG‐DA forming crosslinked hydrogel membranes upon the surface of a substrate. Such membranes are formed by photopolymerizing a PEG‐DA prepolymer solution by initiation with eosin‐Y‐functionalized surfaces and TEA using VP as accelerator. Experimental measurements of the thickness of hydrogel membranes compare well with the model. The model is developed by using the pseudo‐kinetic approach and the method of moments, and is capable of predicting the crosslink density and thickness of the hydrogel membrane. Parametric sensitivity of the effects of PEG‐DA, VP and coinitiator TEA concentration towards the crosslink density and the thickness of the hydrogel is also investigated. The results obtained for different PEG‐DA and VP concentrations suggest that the concentration ratio of these two monomers is a key parameter in controlling the gel thickness and permeability. This model can also be applied to systems where drugs, proteins or cells are encapsulated through surface initiated photopolymerization to predict the growth and crosslink density profiles of the encapsulating membrane. In a previous study we have experimentally demonstrated that these membranes could be made to attach covalently to the surface of the underlying substrate.

Comparison of experimental measurements and model simulation of PEG‐DA hydrogel membrane thickness versus laser duration at high PEG‐DA concentrations.     

GaAsN/AlAs/AlGaAs double barrier quantum wells grown by molecular beam epitaxy as an alternative to infrared absorption below 4 μm

In this work, we report on the design, growth and characterization of GaAsN/AlAs/AlGaAs double barrier quantum well infrared detectors to achieve intraband absorption below 4 μm. Due to the high effective mass of N-dilute alloys, it is common for these N-containing double barrier quantum well structures to have more than one bound state within the quantum well, enabling the possibility of achieving multispectral absorption from these confined levels to the quasi-bound. Based on a transfer matrix calculation we will study the influence of the potential parameters, in particular the well width and the introduction of a GaAs spacer layer in between the N-well and the AlAs barriers. We will compare the case in which there are two confined levels with the case in which only one level is bound, like in the conventional AlGaAs/AlAs/GaAs structures. On the basis of the simulation, we have grown and characterized some N-containing double barrier detectors. Moreover, an optimization of the post-growth annealing treatments of the GaAsN quantum well structures has also been performed. Finally, room temperature absorption measurements of both as-grown and annealed samples are presented and analyzed.     

Oxydehydrogenation of ethylbenzene to styrene on a P?Ni?Mn based catalyst

The oxydehydrogenation of ethylbenzene to styrene over a P−Ni−Mn catalyst, has been studied in the range of 650–770 K. The kinetic behavior of the main reaction can be described by a redox type model and the oxidation of styrene with a power law. The model predictions are in good agreement with the experimental observations.