On Aging of Acid-Catalyzed Silica Sols—A Dynamic Light Scattering Study

Dynamic light scattering experiments in acid-catalyzed silica sols are discussed. It is shown that in spite of limited parameter accuracy and limited absolute knowledge of the particle sizes, the scattering data from various experiments are comparable with one another and give information about structural differences. Measurements at various angles indicate changes between non-spherical and nearly spherical particles and allow the estimation of gelling times before gelation.     

The s-p bonded representatives of the prominent BaAl4 structure type: a case study on structural stability of polar intermetallic network structures

This work presents a detailed, combined experimental and theoretical study on the structural stability of s-p bonded compounds with the BaAl4 structure type (space group I4/mmm, Z = 2) as part of a broad program to investigate the complex questions of structure formation and atomic arrangements in polar intermetallics. From ab initio calculations employing pseudopotentials and a plane wave basis set, we extracted optimized structural parameters, binding energies, and the electronic structure of the systems AeX(III)4, AeX(II)2X(IV)2, AeX(II)2X(III)2 (Ae = Ca, Sr, Ba; X(II) = Mg, Zn; X(III) = Al, Ga; X(IV) = Si, Ge). For all systems we found a pronounced pseudo-gap in the density of states separating network X42- bonding from antibonding electronic states that coincides with the Fermi level for an electron count of 14 electrons per formula unit, the optimum value for stable BaAl4-type polar intermetallics. However, the synthesis and structural characterization (from X-ray single crystal and powder diffraction data) of the new compounds AeZn2-Al2+, AeZn2-deltaGa2+delta (Ae = Ca, Sr, Ba; delta = 0-0.2) and AeMg0.9Al3.1, AeMg1.7Ga2.3 (Ae = Sr, Ba) manifested that electron deficiency is rather frequent for BaAl4-type polar intermetallics. The site preference for different "X" elements in the ternary systems was quantified by calculating "coloring energies", which, for some systems, was strongly dependent on the size of the electropositive Ae component. The Ae2+ cations decisively influence the nearest neighbor distances in the encapsulating polyanionic networks X4(2-) and the structures of these networks are surprisingly flexible to the size of the Ae component without changing the overall bonding picture. A monoclinically distorted variant of the BaAl4 structure occurs when the cations become too small for matching the size of encapsulating X4(2-) cages. An even larger size mismatch leads to the formation of the EuIn4 structure type.     

Photoreaktionen kleiner organischer Moleküle. 4. Mitt. Absorptions-spektren,Photoionen- und Resonanzphotoelektronenspektren von Vinylbromid.

Ohne Zusammenfassung     

Determination of lithium and halogens and the significance of lithium to the understanding of cosmochemical processes

With a newly developed method fluorine and the other halogens have been measured in terrestrial, meteoritic and lunar samples. As a valuable byproduct lithium was determined also via teh reactions⁶Li (n,α)t→¹⁶O (t, n)¹⁸F. From our measurements the following new values for the “cosmic” abundance are derived (in atoms per 10⁶ Si atoms) F 750, Cl 4350, Br 8.83, and I 1.14. We could show that the Li/Be or Li/Zr ratios can be used to estimate the ratio of the Mg-silicates to the group of refractory elements and in course to calculate the bulk composition of the Moon and other planetary objects.     

Peak recognition technique by a computer program copying the human judgement

Summary It is still difficult to determine peaks and peak boundaries properly, though peak recognition is very important for the precision of quantitative data. A new computer program overcomes these problems using a method which is adapted from human judgements. The algorithm was developed for HPLC but can also be used in other fields of analytical chemistry.     

Automatische Analyse und Simulation von NMR-Spektren

Analytical and Bioanalytical Chemistry -     

An extremal problem related to probability

Summary We consider a walk from a stateA ₁ to a stateA _n+1 in which the probability of remaining atA _i isp _i , and the probability of progressing fromA _i toA _i+1 is 1 –p _i . The probabilityW _nk of reachingA _n+1 fromA ₁ in exactlyn + k steps can then be expressed as a polynomial of degreen + k in then variablesp ₁,,p _n . We determine the maximum value ofW _nk and the (unique) choice (p ₁,,p _n ) for which this extremum occurs.Dedicated to Professor Otto Haupt with best wishes on his 100th birthday