Influence of normal and radial contributions of local current density on local electrochemical impedance spectroscopy.

A new tri-electrode probe is presented and applied to local electrochemical impedance spectroscopy (LEIS) measurements. As opposed to two-probe systems, the three-probe one allows measurement not only of normal, but also of radial contributions of local current densities to the local impedance values. The results concerning the cases of the blocking electrode and the electrode with faradaic reaction are discussed from the theoretical point of view for a disk electrode. Numerical simulations and experimental results are compared for the case of the ferri/ferrocyanide electrode reaction at the Pt working electrode disk. At the centre of the disk, the impedance taking into account both normal and radial contributions was in good agreement with the local impedance measured in terms of only the normal contribution. At the periphery of the electrode, the impedance taking into account both normal and radial contributions differed significantly from the local impedance measured in terms of only the normal contribution. The radial impedance results at the periphery of the electrode are in good agreement with the usual explanation that the associated larger current density is attributed to the geometry of the electrode, which exhibits a greater accessibility at the electrode edge

Experimental evidence of strong phonon scattering in isotopical disordered systems: The case of LiH_xD_{1-x} crystals

The observation of the local - mode vibration, the two - mode behavior of the LO phonons at large isotope concentration, as well as large line broadening in LIH - D mixed crystals directly evidence strong additional phonon scattering due to the isotope - induced disorder.Comment: 9 pages, 4 figure

Heterocyclic synthesis with nitriles: synthesis of pyrazolopyrimidine and pyrazolopyridine derivatives

The reaction of N1-substituted-5-amino-4-cyanopyrazoles with malononitrile and diethylmalonate occurs with formation of 6-substituted pyrazolo[3,4-d]pyrimidines, and pyrazolo[3,4-b]pyridines respectively. The structures of the products and conceivable mechanisms are discussed.Fundação para a Ciência e Tecnologia - SFRH/BPD/31490/2006Fundo Europeu de Desenvolvimento Regional (FEDER) - POCTI-SFA-3-68

Raman Spectroscopy of Lithium Hydride Corrosion: Selection of an Appropriate Excitation Wavelength to Minimize Fluorescence

The recent interest in a hydrogen-based fuel economy has renewed research into metal hydride chemistry. Many of these compounds react readily with water to release hydrogen gas and form a caustic. Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFT) has been used to study the hydrolysis reaction. The LiOH stretch appears at 3670 cm{sup -1}. Raman spectroscopy is a complementary technique that employs monochromatic excitation (laser) allowing access to the low energy region of the vibrational spectrum (<600 cm{sup -1}). Weak scattering and fluorescence typically prevent Raman from being used for many compounds. The role of Li{sub 2}O in the moisture reaction has not been fully studied for LiH. Li{sub 2}O can be observed by Raman while being hidden in the Infrared spectrum

Characterization Of The Hydrogenation Products Of Bix (phenylethynyl) Benzene (DEB) Getter Using Combined GC/FTIR/MS, FT-Raman, and ATR Spectroscopies (U)

Organic hydrogen getters are utilized to minimize hydrogen accumulation in sealed systems where such build up could produce either a safety problem from pressure build up or corrosion problem due the hydriding of metals contained in the sealed vessel. DEB (1,4 bis (phenyl ethynyl) benzene) is a hydrogen getter that is based on the palladium catalyzed hydrogenation of triple bonds to single bonds in aromatic aryl compound. DEB is a getter mixed with 25% carbon and 1% Pd and pressed into pellets with some porosity. The reaction mechanisms are complex involving solid state reactions with a heterogeneous catalyst leading to the many intermediates

Raman Spectroscopy of UH3 from the Hydrogen Corrosion of Uranium

Hydrogen reacts with a uranium surface to form a fine, pyrophoric metal power (UH{sub 3}). Few spectroscopic studies have been conducted to study this reaction. Advances in Raman spectroscopy permit the application of the Raman method to formally difficult areas of chemistry such as the hydrogen corrosion of uranium: availability of multiple laser excitation wavelengths; fiber optics delivery and collection systems; upgraded instrumentation and detection techniques; and development of special enclosed in situ reactor cells. UH{sub 3} vibrations are expected to occur at low frequencies due to extended U-H-U structure

THE TAMING OF THE SHREW - STUDYING THE INTERACTION OF IONS WITH IONIC CARCERANDS AS MOLECULAR CONTAINERS

Müller A, Diemann E, Krickemeyer E, Che S. THE TAMING OF THE SHREW - STUDYING THE INTERACTION OF IONS WITH IONIC CARCERANDS AS MOLECULAR CONTAINERS. Naturwissenschaften. 1993;80(2):77-78