Reliable evaluation of temperature-independent parameters in correlation of vapour–liquid equilibrium data

A new algorithm/program has been elaborated for simultaneous processing of different sets of vapour–liquid equilibrium data. The program was tested with six binary hexane + isomeric pentanol systems, each of them measured at three different isobaric conditions and one isothermal system of tert-butyl-methyl-ether + 2-methyl-2-propanol measured at three different temperatures. The correlation uses the maximum likelihood method, taking into account real behaviour of vapour phase. The parameters obtained are valid within the whole temperature range of the data, and are consistent in comparison with those obtained from individual correlations of isobars or isotherms. Results are presented for the Wilson and NRTL equations.     

Solvent effects on the redox properties of tris-(1,10-phenanthroline)iron(II/III) complexes

The redox properties of the system Fe(tmphen)₃(II/III) (tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) have been studied in the solvents nitromethane, acetonitrile, propanediol-1,2-carbonate, dimethylformamide, dimethylacetamide, dimethylsulfoxide and of the systems Fe(phen)₃(II/III) (phen=1,10-phenanthroline) and Fe(niphen)₃(II/III) (niphen=5-nitro-1,10-phenanthroline) in the solvents nitromethane, acetonitrile, propanediol-1,2-carbonate and acetone. The redox potentials of Fe(tmphen)₃(II/III) are nearly independent of the solvent suggesting that the system might be used as a reference redox couple similar to the systems ferrocene/ferricinium or bisbiphenylchromium(0/I). In contrast the redox potentials of Fe(niphen)₃(II/III) show a significant decrease with increasing donor number of the solvent which can be explained by nucleophilic attack of solvent molecules at the iron. It is shown that such a mechanism is consistent with the known solvent and salt effects on the kinetics of dissociation of ferroin and ferriin type complexes.     

Einige Gesetzmäßigkeiten der spontanen Umwandlung der Wasserstofform des Montmorillonits in die Aluminium-form

Ohne Zusammenfassung     

Use of SPE—TLC for Quality Control of Rhodiola rosea Extracts

SPE and TLC have been used for qualitative and quantitative analysis of salidroside, rosavin, rosarin, and rosin in commercially available dry extracts from Rhodiola rosea roots. The best separation of all the compounds was achieved on silica gel TLC plates with ethyl acetate—methanol—water, 77 + 13 + 10 (v/v), as mobile phase. UV detection was performed at λ = 215 nm for salidroside and at λ= 245 nm for the rosavins (rosavin, rosarin, and rosin). Detection limits for salidroside and the rosavins were 90 ng and 60 ng per spot, respectively. Results from quantitative analysis confirmed the manufacturer’s declaration of the amounts of salidroside and the rosavins in the extracts.

     

Zur Theorie der Chiralitätsfunktionen

The Algebraic Theory of Chirality Functions is derived by means of exclusively qualitative considerations. Hence, the significance of quantitative results is questionable. Moreover the construction of “Näherungsansätze” (”Approximation-Ansatz”), which may be interpreted as semiempirical methods, is achieved on the basis of plausibility and mathematical simplicity. Since physical arguments are not included, the consistency or inconsistency of “Näherungsansätze” with experimental results do not justify direct physical conclusions.     

Aggregation des menschlichen Serumalbumins unter den Bedingungen der W ärmedenaturierung

Ohne Zusammenfassung     

Phase Analysis of the Binary System of Cryolite (Na3AlF6) and Sodium Metasilicate (Na2SiO3)

The phase analysis of cryolite (Na₃AlF₆) and sodium metasilicate (Na₂SiO₃) was performed by thermal analysis. The eutectic system with a region of two immiscible substances at a concentration of Na₂SiO₃ between 42.8 and 46.3 mol‐% was identified and the eutectic temperature determined to (886±2) °C. Based on the results of mass‐loss measurements, it was assumed that the introduced Na₂SiO₃ reacts with Na₃AlF₆ due to the formation of some nonvolatile stable compounds. The stable reaction products were identified by X‐ray diffraction analysis and IR spectroscopy of the spontaneously cooled samples, which established the formation of NaF and stable amorphous aluminosilicate compounds.     

Ab-initio molecular dynamics based on non-local density functional procedure with Gaussian basis; study of structural and temperature behaviour of metallic clusters

An ab-initio molecular dynamics procedure without precalculation of the Born-Oppenheimer energy surface based on an iterative non-local density functional method employing Gaussian atomic basis has been developed. Analytical gradients are calculated and used for the propagation of nuclei. Sufficiently long trajectories can be calculated at an acceptable computational cost, allowing for analysis of dynamical behaviour of small metallic clusters. This is illustrated on an example of the Li₈ cluster. Temperature behaviour of different type of isomers has been investigated. Calculated power spectra allow to identify the presence of more than one isomeric forms along the given trajectories.     

Sol-Gel Processing of PbZrO3 Thin Films

PbZrO₃ (PZ) thin films have been prepared by 2-methoxyethanol route from lead oxide or lead acetate and zirconium n-butoxide. The use of lead oxide as lead source and the seeding layer of TiO₂ on Pt/TiO₂/SiO₂/Si substrate facilitate the formation of the perovskite phase.