Dynamics of caged ions in glassy ionic conductors

At sufficiently high frequency and low temperature, the dielectric responses of glassy, crystalline, and molten ionic conductors all invariably exhibit nearly constant loss. This ubiquitous characteristic occurs in the short-time regime when the ions are still caged, indicating that it could be a determining factor of the mobility of the ions in conduction at longer times. An improved understanding of its origin should benefit the research of ion conducting materials for portable energy source as well as the resolution of the fundamental problem of the dynamics of ions. We perform molecular dynamics simulations of glassy lithium metasilicate (Li2SiO3) and find that the length scales of the caged Li+ ions motions are distributed according to a Levy distribution that has a long tail. These results suggest that the nearly constant loss originates from "dynamic anharmonicity" experienced by the moving but caged Li+ ions and provided by the surrounding matrix atoms executing correlated movements. The results pave the way for rigorous treatments of caged ion dynamics by nonlinear Hamiltonian dynamics.     

Determination of lead by selective chelatometric titration with HEDTA after separation as its sulphate by an improved method of precipitation

A selective titrimetric determination of Pb after separation by a modified method of precipitation as its sulphate is proposed. Pb(II), present as the perchlorate, is precipitated by gentle boiling in 3.6M H(2)SO(4) presaturated with PbSO(4) and free from any extraneous anions. The customary time-consuming evaporation to fumes of sulphuric acid is dispensed with. The precipitate is collected, and dissolved in excess of HEDTA, the surplus of which is back-titrated with Zn(II) at pH 5.0-5.5. Use of Catechol Violet and Xylenol Orange as a mixed indicator gives a sharper end-point. The standard deviation of the proposed method for 60 mg of lead is 0.35 mg. The method has been successfully used to determine Pb in non-ferrous alloys.     

Immobilization of amyloglucosidase onto granular chicken bone

Amyloglucosidase was immobilized onto granular chicken bone (BIOBONE?) by noncovalent interactions. The amount of activity bound relative to an equal amount of free enzyme was 13.6 ?0.4%. The estimated specific activity for amyloglucosidase decreased from 75.3?0.8 to 43.5 ?9.6 U/mg protein upon immobilization. TheKm value of the bone-immobilized enzyme using glycogen as substrate increased from 3.04?0.38 mg/mL (free) to 9.04? 1.51 mg/mL (immobilized), butKm showed no change upon immobilization when starches were used as substrates. A decrease in V_max values occurred upon enzyme immobilization for all substrates, but this largely reflected the percentage of enzyme initially bound to the bone. Immobilization also improved enzyme stability in the presence of various additives (e.g., detergent, KC1, and ethanol) or under low or high pH reaction conditions. Bound amyloglucosidase maintained high activity (>90%) following five cycles of continuous use at moderate (23 ?C) and high (55?C) temperatures. Data derived from Lineweaver-Burk and Arrhenius plots indicated that substrate and product diffusion limitation were minimal.     

Polarographic microdetermination of sulphur in organic compounds after oxygen flask combustion

Summary Three polarographic micro-methods are described for the determination of sulphur in organic compounds after oxygen-flask combustion. The products are converted into sulphuric acid by oxidation with hydrogen peroxide, the excess of which is expelled through boiling. The methods are based upon allowing the sulphuric acid to react with an excess of barium iodate or bromate, then recording polarographically the cathodic reduction wave of the iodate or bromate ion. The bromate methods are superior to the iodate method being simpler and more rapid, and the results are correct to within ca. ±0.5%.

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Zusammenfassung Drei polarographische Mikromethoden zur Bestimmung von Schwefel in organischen Verbindungen nach deren Verbrennung im Sauerstoffkolben wurden beschrieben. Die Verbrennungsprodukte werden durch Oxydation mit Wasserstoffperoxid in Schwefelsäure umgesetzt. Der Überschuß des Oxydationsmittels wird durch Kochen zerstört. Die Schwefelsäure läßt man mit überschüssigem Bariumjodat oder -bromat reagieren und mißt dann polarographisch die kathodische Reduktionswelle des Jodats oder Bromats. Die Bromatmethode ist der Jodatmethode überlegen, da sie einfacher und rascher zu Resultaten führt, die innerhalb ±0,5% korrekt sind.

     

Application of the rotated dropping mercury electrode to the analysis of mixtures of electroactive substances

The use of poylacrylamide is recommended instead of gelatin as an ideal maximum suppressor to be employed with both the rotated dropping mercury electrode (RODE) and conventional dropping electrode (DME). It is retained at the mercury surface over the entire potential range and does not combine with heavy metals. Reproducibility of the measurement of the residual current and that of the limiting current at the RDME were studied, and it was found that accurate determinations of a single constituent (±2%) are possible at concentrations as low as 1 to 2.10^-5M. The variation of the limiting current with potential is much greater at the RDME than at the DME. This effect must be considered in the analysis of a mixture of electroactive species at the RDME. Method have been discussed for making the proper correction for a preceding wave when a limiting current of a mixture of constituents is measured. Because of its high sensitivity and good reproducibility of results, the RDME is recommended for the analysis of solutions containing one or more electroactive species at concentrations less than 10^-4M.     

A simplified sampling technique for use with the Weisz ring oven: application to qualitative analysis of some gold and silver alloys

Up to 100 microg of sample can be collected from gold or silver alloys by rubbing the specimen with the ground hemispherical tip of a 4-mm Pyrex glass rod. Gold alloys are then dissolved in potassium cyanide solution containing hydrogen peroxide; silver alloys are exposed to vapours of nitric acid. Procedures for transfer, ring oven separation and identification of alloy constituents in the sample solutions are described.     

Beiträge zur Chemie des Hydrazins und seiner Derivate. XXXV. Darstellung und Eigenschaften neuer Stickstoff–Wasserstoff-Verbindungen von Barium und Strontium

On the chemistry of hydrazine and its derivatives. XXXV. Preparation and properties of new nitrogen-hydrogen compounds of barium and strontium By thermal decomposition of barium hydrazide, Ba(N₂H₂), and strontium hydrazide, Sr(N₂H₂), under decaline at about 190°C the compounds BaN_0.5H_0.4 resp. SrN_0.5H_0.4 were obtained. In order to characterize them chemical and spectroscopical investigations were carried out.     

Dynamics of charge transfer states on metal surfaces: the competition between reactivity and quenching

The dynamics of excited states of adsorbates on surfaces caused by charge transfer is studied. Both negative and positive charge transfer processes are possible. In particular we are interested in positive charge transfer from a metal surface to molecular or atomic oxygen adsorbed on the surface. Once the negatively charged oxygen on the surface loses an electron it becomes chemically activated. The ability of this species to react depends on the quenching time or back transfer. The analysis of these processes is based on a set of diabatic potential energy surfaces each representing a different charged oxygen species. The dynamics is followed by solving the multichannel time-dependent Schr?dinger equation or Liouville von Neumann equation. Due to the nonadiabatic character of these reactions large isotope effects are predicted.     

First-order mean spherical approximation for inhomogeneous fluids

The first-order mean-spherical approximation (FMSA) [Y. Tang, J. Chem. Phys., 118, 4140 (2003)] is extended to the studies of inhomogeneous fluids by combining with Rosenfeld's perturbative method [Y. Rosenfeld, J. Chem. Phys. 98, 8126 (1993)]. In the extension, the key input-direct correlation function of FMSA-is applied to constructing the free energy density functional. Preserving its high fidelity at the bulk limit, the FMSA shows satisfactory performance for Yukawa fluids near hard and attractive walls. The results are better than or comparable to several other theories reported before for the geometry. The FMSA is found, in particular, more satisfactory than the traditional mean-field theory for predicting density profiles around hard walls. The FMSA is also compared with the full MSA for inhomogeneous fluids, showing no appreciable differences. The inhomogeneous FMSA goes successfully through the self-consistency test for reproducing the radial distribution function of the bulk Yukawa fluid. As far as the computation is concerned, the FMSA can be executed much faster than any nonmean-field theories, and the speed is virtually identical to that of the mean-field theory.     

The RS-.HSR Hydrogen Bond: acidities of alpha,omega-dithiols and electron affinities of their monoradicals

Gas-phase acidities (deltaGo(acid)) have been measured for 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol, using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Adiabatic electron affinities (EAs) of the thiolate monoradicals of these compounds were assigned from electron photodetachment spectra of their corresponding thiolate monoanions, acquired using a cw-ICR. The dithiols exhibit enhanced acidities (up to 8.7 kcal/mol in deltaGo(acid)) and greater EAs (up to 6.7 kcal/mol) than analogous monothiol species. These differences are attributed to an intramolecular RS-.HSR hydrogen bond in the thiolate anion. Considerations of the RO-.HOR hydrogen bond in monoanions of alpha,omega-diols and in the [CH(3)O-.HOCH(3)] complex anion suggest that the RS-.HSR hydrogen bond provides up to 9 kcal/mol extra stabilization.