The infrared spectra of solid solutions of some iron and chromium oxides

Oxides Fe_2–x Cr _x O₃ (corundum-type) and Fe_3–y ,Cr _y O₄ (spinel-type) were studied by transmission IR spectroscopy. The wavenumbers corresponding to characteristic absorption maxima depend linearly on the composition of both types of solid solutions, i.e. onx andy. The results show that IR spectroscopy can contribute to the analysis of solid solutions of iron and chromium oxides and of the oxidation products of Fe-Cr alloys.The authors are indebted to Ing. P. Holba for the preparation of synthetic oxide samples. The cooperation of Yu. Borodkin and I. Zuika (Riga) who made the measurements in the far IR region is gratefully acknowledged.     

The Suitability and Usage of 18O and Chloride as Natural Tracers for Bank Filtrate at the Middle River Elbe

Abstract

Flow times and infiltration behaviour are very important for water extraction from riverbank filtration. Both the chloride content and the isotopic composition of oxygen (δ¹⁸O) were found to be suitable indicators for the conditions encountered in the middle course of the River Elbe near Torgau. The ranges for Elbe water were measured to be 20–43 mg Cl/l (1995-97) and -11 to -8.5‰ δ¹⁸O (1993-97). Both methods permitted flow-time spectra at two adjacent sampling profiles incorporating river and production wells to be obtained, indicating the preferred flow paths and the vertical extension of the riverbank filtrate plume in the aquifer. However, since the differences between the mean values for river water and regional groundwater were too small the percentage of river water abstracted from production wells could not be calculated.     

Percolative transport in the vicinity of charge-order ferromagnetic transition in a hole-doped manganite

We report measurements of non-linear charge transport in epitaxial (La_1−x Pr _x )_0.7Ca_0.3MnO₃ thin films fabricated on (100) oriented SrTiO₃ single crystals by pulsed laser deposition. The end members of this series, namely Pr_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3MnO₃ are canonical charge-ordered (CO) and ferromagnetic manganites, respectively. The onset of the CO state in Pr_0.7Ca_0.3MnO₃ is manifested by a pronounced insulating behavior below ∼ 200 K. The CO state remains stable even when a large (∼ 2×10⁵ V/cm) electric field is applied across the thin film samples. However, on substitution of Pr with La, a crossover from the highly resistive CO state to a state of metallic character is observed at relatively low electric fields. The current-voltage characteristics of the samples at low temperatures show hysteretic and history dependent effects. The electric field driven charge transport in the system is modelled on the basis of an inhomogeneous medium consisting of ferromagnetic metallic clusters dispersed in a CO background.     

Polymer chain dynamics in a random environment: heterogeneous mobilities

We present a neutron scattering investigation on a miscible blend of two polymers with greatly different glass-transition temperatures Tg. Under such conditions, the nearly frozen high-Tg component imposes a random environment on the mobile chain. The results demand the consideration of a distribution of heterogeneous mobilities in the material and demonstrate that the larger scale dynamics of the fast component is not determined by the average local environment alone. This distribution of mobilities can be mapped quantitatively on the spectrum of local relaxation rates measured at high momentum transfers.     

Sulphur and oxygen isotopic characters of dissolved sulphate in groundwater from the Pleistocene aquifer in the southern Jordan Valley (Jericho area,Palestine)

Sulphate and chloride concentrations in the shallow Pleistocene aquifer systems in the lower Jordan valley area indicate a general trend of increasing salinity eastward and southward. This study was conducted in one of the important sub-basins feeding the Pleo–Pleistocene aquifer in the Jericho area in the southern part of the valley using S and O isotopes of dissolved sulphate. The results show that sulphate has mainly two contributions to the groundwater. One is the surface seepage, which is present as a salty leachate form with the positive δ³⁴S_sulphate values of primary gypsum in Lisan and Samara formations, and the second is the upwelling saline water which was in contact with a deep secondary gypsum, aragonites and salty rocks and rose up under heavy abstraction with depleted ³⁴S in sulphate and relatively high sulphate and chloride content. The latest was clearly shown in the Arab Project wells to the east that is undergoing a continuous heavy abstraction. The isotopic signatures of S and O in these wells to the east show that this depleted ³⁴S and highly concentrated sulphate might also indicate a dissolved sulphate originating from pyrite oxidation that results from the interaction with a pyrite-rich aquifer, which can well up with salty water under heavy abstraction and is oxidised in the upper aerobic shallow aquifer.     

Formation of “Quasi” Contact or Solvent‐separated Ion Pairs in the Local Environment of Probe Molecules Dissolved in Ionic Liquids

The change from “quasi” contact to “quasi” solvent‐separated ion‐pair configuration in the local environment of a probe molecule in ionic liquids depends on the varying interaction strength of the chosen anions. The ion speciation in these Coulomb fluids could be shown by combining infrared spectroscopy, density functional theory calculations, and natural bond orbital analysis using a low‐self‐clustering probe molecule.