Oxygen Sorption and Desorption Properties of Selected Lanthanum Manganites and Lanthanum Ferrite Manganites

Temperature‐programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid‐oxide fuel cell (SOFC) cathode materials (La_0.85Sr_0.15)_0.95MnO_3+δ (LSM) and La_0.60Sr_0.40Fe_0.80Mn_0.20O_3‐δ (LSFM). The powders were characterized by X‐ray diffractometry, atomic force microscopy (AFM), and BET surface adsorption. Sorbed oxygen could be distinguished from oxygen originating from stoichiometry changes. The results indicated that there is one main site for oxygen sorption/desorption. The amount of sorbed oxygen was monitored over time at different temperatures. Furthermore, through data analysis it was shown that the desorption peak associated with oxygen sorption is described well by second‐order desorption kinetics. This indicates that oxygen molecules dissociate upon adsorption and that the rate‐determining step for the desorption reaction is a recombination of monatomic oxygen. Typical problems with re‐adsorption in this kind of TPD setup were revealed to be insignificant by using simulations. Finally, different key parameters of sorption and desorption were determined, such as desorption activation energies, density of sorption sites, and adsorption and desorption reaction order.     

Photooxidation of ethanol on Cu-layer silicate/TiO2 composite thin films

Thin film composites of copper-montmorillonite and TiO₂ were prepared and their optical and catalytic properties for ethanol photooxidation were evaluated. The efficiency of composite Cu-clay/TiO₂ = 20/80 was two-fold higher than the standard TiO₂(P25) photocatalyst.     

Rainforests as concert halls for birds: are reverberations improving sound transmission of long song elements?

In forests reverberations have probably detrimental and beneficial effects on avian communication. They constrain signal discrimination by masking fast repetitive sounds and they improve signal detection by elongating sounds. This ambivalence of reflections for animal signals in forests is similar to the influence of reverberations on speech or music in indoor sound transmission. Since comparisons of sound fields of forests and concert halls have demonstrated that reflections can contribute in both environments a considerable part to the energy of a received sound, it is here assumed that reverberations enforce also birdsong in forests. Song elements have to be long enough to be superimposed by reflections and therefore longer signals should be louder than shorter ones. An analysis of the influence of signal length on pure tones and on song elements of two sympatric rainforest thrush species demonstrates that longer sounds are less attenuated. The results indicate that higher sound pressure level is caused by superimposing reflections. It is suggested that this beneficial effect of reverberations explains interspecific birdsong differences in element length. Transmission paths with stronger reverberations in relation to direct sound should favor the use of longer signals for better propagation.     

A Mathematical Justification for the Herman-Kluk Propagator

A class of Fourier Integral Operators which converge to the unitary group of the Schr?dinger equation in the semiclassical limit ε → 0 in the uniform operator norm is constructed. The convergence allows for an error bound of order O(ε), which can be improved to arbitrary order in ε upon the introduction of corrections in the symbol. On the Ehrenfest-timescale, the result holds with a slightly weaker error bound. In the chemical literature the approximation is known as the Herman-Kluk propagator.     

Controlling the emission profile of a nanowire with a conical taper

The influence of a tapering on nanowire light-emission profiles is studied. We show that, for nanowires with divergent output beams, the introduction of a conical tapering with a small opening angle reduces the beam divergence and increases transmission. This results in a dramatic increase in the collection efficiency of the detection optics. For a realistic tapering and a modest NA, the collection efficiency is enhanced by more than a factor of 2. This improvement is ensured by the adiabatic expansion of the guided mode in the tapering.     

Prediction of Effective Properties of Porous Carbon Electrodes from a Parametric 3D Random Morphological Model

Pore structures have a major impact on the transport and electrical properties of electrochemical devices, such as batteries and electric double-layer capacitors (EDLCs). In this work we are concerned with the prediction of the electrical conductivity, ion diffusivity and volumetric capacitance of EDLC electrodes, manufactured from hierarchically porous carbons. To investigate the dependence of the effective properties on the pore structures, we use a structurally resolved parametric model of a random medium. Our approach starts from 3D FIB-SEM imaging, combined with automatic segmentation. Then, a random set model is fitted to the segmented structures and the effective transport properties are predicted using full field simulations by iterations of FFT on 3D pore space images and calculations based on the geometric properties of the structure model. A parameter study of the model is used to investigate the sensitivity of the effective conductivity and diffusivity to changes in the model parameters. Finally, we investigate the volumetric capacitance of the EDLC electrodes with a geometric model, make a comparison with experimental measurements and do a parameter study to suggest improved microstructures.     

Determination of Arsenic in Drinking Water by Graphite Furnace Atomic Absorption Spectroscopy. An Undergraduate Instrumental Analysis Laboratory

A laboratory exercise, the analysis of arsenic in drinking water by graphite furnace atomic absorption spectroscopy (GFAA), is presented for use in an undergraduate instrumental methods course. The purpose of this GFAA exercise is to expose students to a practical and commonly used application, to provide students with hands-on experience with the instrument, and to reinforce concepts taught in the classroom. Students safely analyze a real-world sample containing an analyte in the parts-per-billion concentration range.     

Mass spectra of porphyrin alkyl esters and their copper complexes. Studies on products from humans and animals with porphyria

Mass spectra of methyl and higher aliphatic esters of biologically important porphyrins—prepared from human and bovine excreta—were recorded. Variation in the number of esterified carboxyl groups (4 to 8) or in the size of the ester groups causes no change in the fragmentation modes; only the abundances of the fragment ions vary. The conversion of a porphyrin ester to its copper-complex (chelate) has been achieved in a simple way. The mass spectra of the copper chelates are compared with those of the free porphyrin esters and minor differences are observed.