Determination of interfacial co-ion concentration in ionic micelles by chemical trapping: Halide concentration at the interface of sodium dodecyl sulfate micelles

Products from the spontaneous reaction of a long-chain arenediazonium salt, 2,6-dimethyl-4-hexadecylbenzenediazonium tetrafluoroborate(16-ArN2BF4), in aqueous micellar solutions of sodium dodecyl sulfate (SDS)? are used to estimate the local concentration of chloride and bromide ions at the micellar surface. The arenediazonium ion, 16-ArN2+, which is totally bound to the SDS micelle, reacts by rate-determining loss of N-2 to give an aryl cation that traps available nucleophiles, i,e., H2O, Cl-, and Br-, to give stable phenol, 16-ArOH, and halobenzene products, 16-ArCl and 16-ArBr, respectively. Product yields, determined by HPLC, are related to local concentrations using calibration curves obtained from independent standards. The local concentrations determined by this method are consistent with co-ion concentrations calculated, using a cell model, by numerical integration of the Poisson-Boltzmann equation (PBE) taking into account salt-induced micellar growth. The salt dependence of the intel facial concentrations of Cl- and Br- are identical. indicating no specific interactions in the interfacial co-ion compartment. PBE calculations predict that, in micellar SDS, increasing the concentration of a particular halide salt (NaX) at constant concentration of another halide (NaY) should result in an increase in the local concentrations of both co-ions. Using this chemical-trapping method, this prediction was demonstrated experimentally.

RECENT HEAVY-ION EXPERIMENTS AND STATISTICAL-MODEL OF HADRONS

The combined CERN and Brookhaven heavy ion (H.I.) data supports a scenario of hadron gas which is in chemical and thermal equilibrium at a temperature T of about 140 MeV. Using the Brown-Stachel-Welke model (which gives 150 MeV) we show that in this scenario, the hot nucleons have mass 3 pi T and the pi and rho mesons have masses close to pi T and 2 pi T, respectively. A simple model with pions and quarks supports the co-existence of two phases in these heavy ion experiments, suggesting a second order phase transition. The masses of the pion, rho and the nucleon are intriguingly close to the lattice screening masses.

A new approach for determining stability constants of metal ion complexes in aquatic systems based on flow injection-ion exchange-flame atomic absorption spectrometry coupling

A method based an ion exchange(IE)-atomic absorption spectrometry(AAS) coupled by flow techniques, allowing the determination of formation constants of, at least, the first species of complex systems, in aqueous solution, was developed.The IE-AAS coupling reduces significantly the number of experimental steps in comparison with IE batch methods, resulting in an important increase in analytical rate. The method is simple both from experimental and computational points of view, making possible its utilization by workers without special expertise in the field of complex equilibria in solution. on the other hand, taking into account mainly the amount of hollow cathode lamps available to date, the developed procedure may be applied, within certain limitations, to the study of many systems whose features prevent the use of traditional approaches.

Degradation of the herbicide tebuthiuron using solar photo-Fenton process and ferric citrate complex at circumneutral pH

The influence of pH on the degradation of the herbicide tebuthiuron (TBH) was investigated using in situ generated Fe(III)-citrate complexes (Fe:cit) submitted to the photo-Fenton process under solar irradiation. Using Fe:cit in a wide pH range (2.5-7.5), 100-78% TBH oxidation was achieved respectively from a UV dose of 2.0 J cm(-2) (15 min). Moreover, the oxidation of TBH obtained in the presence of Fe:cit at pH 6.0 was higher than that obtained using Fe(NO3)3 at pH 2.5. A similar behavior is observed for the removal of total organic carbon (TOC) in TBH solutions. In the presence of Fe:cit, 20% and 85% of TOC was removed at pH 7.5 and 2.5, respectively, after 7.5 J cm-2 irradiation, while no mineralization was observed employing Fe(NO3)(3) for the same UV dose. Using Fe(NO3)(3), mineralization was observed only after 11 J cm-2 (8%). A higher mineralization rate was obtained with Fe(NO3)(3) only when a concentration three times higher was employed at pH 2.5. Besides the high efficiency of TBH degradation observed using the ferric citrate complex in the solar photo-Fenton process, it also offers the advantage of application at a pH of up to 7.5. (c) 2007 Elsevier B.V. All rights reserved.

Effects of the high-temperature plasma immersion ion-implantation treatment on corrosion behavior of Ti-6Al1-4V

Nitrogen implantation into Ti alloys at higher temperatures improves their mechanical and corrosion resistance properties by forming a thicker nitride layer. In this paper, two different sets of Ti-6Al-4V samples were plasma immersion ion implantation (PIII)-treated using nitrogen plasma, varying the treatment time from 30 to 150 min (800 degrees C) and the process temperature from 400 degrees C to 800 degrees C (t = 60 min). Nanoindentation measurements of the PIII-treated samples at 800 C during 150 min showed the highest hardness value, 24 GPa, which is about four times bigger than untreated sample hardness. The N penetration at these conditions reached approximately 150 nm as analyzed by Auger spectroscopy. on the other hand, the lowest passive current density (3 x 10(-7) A. cm(-2)) was obtained for a PIII-treated sample during 30 min at higher temperature (800 degrees C). The corrosion resistance of this sample is almost the same as for the untreated specimen. Corrosion behavior evidenced that in strong oxidizing media, all PIII-treated samples are more corrosion resistant than the untreated one. PIII processing at higher temperatures promotes smoothing of the sample surface as observed by scanning electron microscopy (SEM). Grazing incidence X-ray diffraction analyses of the untreated samples identified the two typical Ti phases, Ti alpha and Ti beta. After the implantation, Ti2N and TiO2 phases were also detected.

Development of a potentiometric mefenamate ion sensor for the determination of mefenamic acid in pharmaceuticals and human blood serum

The characteristics, performance, and application of a novel and simple electrode, namely Pt vertical bar Hg vertical bar Hg-2(MF)(2)vertical bar Graphite, where MF stands for mefenamate ion, are described. This electrode responds to MF with sensitivity of (58.9 +/- 0.7) mV decade(-1) over the range 1.0 x 10(-6) to 1.0 x 10(-2) mol L-1 at pH 6.0-9.0 and a detection limit of 6.2 x 10(-7) mol L-1. The electrode is easily constructed at a relatively low cost with fast response time (within 10-25 s) and can be used for a period of 4 months without significant change in its performance characteristics. The proposed sensor displayed good selectivity for mefenamate in the presence of several substances, especially concerning carboxylate and inorganic anions. The potentiometric sensor was successfully applied to the determination of mefenamic acid in pharmaceuticals and human serum samples. (c) 2007 Elsevier B.V. All rights reserved.

Diffusion coefficient of K+ in ion exchanged glasses calculated from the refractive index and the Vickers hardness profiles

The top faces of float glass samples were exposed to vapors resulting from the decomposition of KNO3 at 565 degrees C for up to 32 h. X-ray dispersive spectra (EDS) show that K+ ions migrate into the glass. The K+ concentration profile was obtained and its diffusion coefficient was calculated by the Boltzmann-Matano technique. The mean diffusion coefficient was approximately 10 X 10(-11) cm(2) s(-1). It was observed that the refractive index and the Vickers hardness decrease with the depth (after the removal of successive layers), and their profiles were thus obtained. These profiles enabled the calculation of the diffusion coefficient of K+ through the Boltzmann-Matano technique, with mean results ranging between 6 x 10(-11) and 30 x 10(-11) cm(2) s(-1). (c) 2006 Elsevier B.V. All rights reserved.

Hydrophilization of PVC surfaces by argon plasma immersion ion implantation

Commercial polyvinylchloride (PVC) sheets were treated by plasma immersion ion implantation, PIII. Samples were immersed in argon glow discharges and biased with 25 kV negative pulses. Exposure time to the bombardment plasma changed from 900 to 10,800 s. Through contact angle measurements, the effect of the exposure time on the PVC wettability was investigated. Independent of t, all samples presented contact angles, theta, equal to zero after the treatment. However, in some cases, surface hydrophilization was not stable, as revealed by the temporal evolution of theta. Samples bombarded for shorter periods recovered partially or totally the hydrophobic character while the one exposed for the longest time stayed highly hydrophilic. These modifications are ascribed to the Cl loss and O incorporation as shown by XPS measurements. Furthermore, the mobility of surface polar groups and the variation in the cross-linking degree can also affect the PVC wettability.

Er-doped silica-based waveguides prepared by different techniques: RF-sputtering, sol-gel and ion-exchange

Erbium-activated silica-based planar waveguides were prepared by three different technological routes: RF-sputtering, sol-gel and ion exchange. Various parameters of preparation were varied in order to optimize the waveguides for operation in the NIR region. Particular attention was devoted to the minimization of the losses and the increase of the luminescence efficiency of the metastable I-4(13/2) state of the Er3+ ion. Waveguide properties were determined by m-line spectroscopy and loss measurements. Waveguide Raman and luminescence spectroscopy were used to obtain information about the structure of the prepared films and about the dynamical processes related to the luminescence of the Er3+ ions.

RESONANCE PRODUCTION IN PERIPHERAL HEAVY-ION COLLISIONS

Heavy-ion collisions at ultrarelativistic energies may be used as a powerful source of photons and pomerons. We compute the rates for pseudoscalar meson production through two-photon and two-pomeron scattering, at energies that will be available at RHIC and LHC. Light mesons will mostly be produced by pomeron fusion at large rates, the two processes are comparable for charmed mesons, while electromagnetic production will be dominant for bottom mesons. We discuss the possibility of observing the reaction gammagamma(PP) --> R --> gammagamma, and comment on the particular case where R could be a scalar resonance at 650 MeV.

NONSTANDARD GAMMA-GAMMA-]L+L- PROCESSES IN RELATIVISTIC HEAVY-ION COLLISIONS

We study lepton pair production in heavy-ion collisions with emphasis on nonstandard contributions to the QED subprocess gamma-gamma --> l+l-. The existence of compositeness of fermions and/or bosons can be tested in this reaction up to the TeV mass scale. We show that for some processes the capabilities of relativistic heavy-ion colliders to disclose new physics surpass the possibilities of e+e- or ppBAR machines. In particular, spin-zero composite particles which couple predominantly to two photons, predicted in composite models, can be studied in a broad range of masses.

The effect of EU3+ ion doping concentration in Gd2O3 fine spherical particles

This work reports on the preparation of Gd2O3, cubic system, with spherical particles, narrow size distribution, whether or not doped with 1-5 at.% of Eu3+ and the influence of Eu3+ concentration on optical and morphological properties. Average diameter and size distribution particle analyses were performed for all samples from SEM results. Doped samples were also investigated by luminescence spectroscopy and emission kinetic measurements. All oxide samples present a particle average diameter distribution range from 110 to 150 nm and a decrease of particle average diameter with the presence of Eu3+. The particle size decrease is almost the same for all samples with different doping ion concentration. Therefore, the presence of doping ion may be inhibiting particle growth after the nucleation process. From spectroscopic studies, the doping ion distribution in the surface of oxide samples can be considered homogeneous because concentration quenching is not observed, as well as a significant difference among the calculated lifetime for each sample. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Influence of Zn2+ co-doping ion on Eu3+-O2- associate luminescence in Sr2SiO4

This work reports on the study about the luminescence behavior of Eu3+-O2- associates in Sr2SiO4 doped with Eu3+, or simultaneously doped with Eu3+ and Zn2+ ions, where the Zn2+ doping ion acts as a charge compensating agent. Both Sr2SiO4:Eu3+ and Sr2SiO4:Eu3+,Zn2+ emission spectra show two types D-5(0)-->F-7(0) type transitions, one type related to Eu3+ in the Sr2+ Site, at 577 and 580 nm and the other one related to Eu3+-O2- associates, at 574 nm. Excitation spectra present two CT bands at 275 and 324 nm related to each emission center, respectively. Comparing the relative intensities between the emission spectra, the 0-->0 transition at 574 nm assigned to Eu3+-O2- associates in the Sr2SiO4:Eu3+ emission spectrum is much more intense than the same transition in the Sr2SiO4:Eu3+,Zn2+ emission spectrum. Moreover, in the Sr2SiO4:Eu3+ excitation spectrum, the intensity ratio between the CT band related to the Eu3+-O2- emission center and Eu3+ F-7-->L-5(6) transition is also larger than in the Sr2SiO4:Eu3+,Zn2+ one. Therefore, the presence of Zn2+ species provides an extra charge compensating mechanism, which decreases the formation of Eu3+-O2- associates. (C) 2002 Elsevier B.V. B.V. All rights reserved.