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.     

Bonding Properties of a Novel Inorganometallic Complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB = N,N'-Diisopropyl-1,4-diaza-1,3-butadiene), and its Stable Radical-Anion, Studied by UV-Vis, IR, and EPR Spectroscopy, (Spectro-) Electrochemistry, and Density Functional Calculations

Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) ?, b = 13.902(3) ?, c = 19.643(2) ?, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) ?(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion.     

Polyethene with pendant fullerene moieties

Polyethene with fullerene moieties pendant on short-chain branches was prepared by the catalytic copolymerization of ethene and a fullerene-containing vinylic comonomer, yielding polyethene copolymers containing up to 25 wt% of C60.     

Electrical and optical properties of melting Au/Si eutectics on Si(111)

The Au/Si system exhibits an extremely low eutectic temperature of 363°?C. Thin gold films of 200 nm thickness were deposited on Si(111) single-crystals and the electrical and optical properties of the melting mixtures were investigated. The resistivity measurements were performed in situ in a combined LEED/Auger apparatus. A highly resolving spectroscopic ellipsometer was used for the optical analysis in the wavelength range 400–900 nm. The eutectic temperature was found to be lower than for bulk Au/Si samples. The structure analysis showed that small liquid Au/Si islands embedded in the silicon surface are formed by the melting process. Various heating/ cooling cycles show a characteristic hysteresis behaviour.     

Über die katalytische Hydrierung von Chinolen

Zusammenfassung Bei der katalytischen Hydrierung von freien Chinolen werden unter Wasserstoffaufnahme hydroaromatische Verbindungen gebildet, während bei den Chinolen andere Reduktionsmethoden, sowie bei den Chinolacetaten auch die katalytische Hydrierung zur Ausbildung von aromatischen Körpern führen.Unserem verehrten Lehrer, Herrn Prof. Dr.F. Wessely, in Dankbarkeit zum 60. Geburtstag gewidmet.     

Intercalation of Dyes Containing SO3H Groups into Zn–Al Layered Double Hydroxide

The intercalates of Naphthol Yellow S, Tropaeolin 000, and Tropaeolin 00 were prepared by heating [Zn_0.67Al_0.33(OH)₂](CO₃)_0.165 · 0.5H₂O with acidic forms of the dye solutions in an open reaction vessel. The intercalates were characterized by chemical and thermal analysis, X-ray powder diffraction and UV–VIS spectroscopy. A possible arrangement of the dye molecules in the intercalates was suggested on the basis of their chemical compositions and interlayer distances, by taking into account van der Waals dimensions of the guest molecules and by assuming that the structure of the host layers is not changed during the intercalation process.     

Synthesis of silver molybdate clusters driven by laser-annealing

The synthesis of silver rich molybdate clusters is achieved by laser induced chemical reaction of coadsorbed MoO(3) and O(2) molecules on free silver clusters. The reactants MoO(3) and/or O(2) molecules condensed at low temperature (77 K-175 K) on free silver clusters. Then, the silver clusters together with their adsorbed molecules are flashed either ionized with a discharge or ionized and heated by a laser. Then they are cooled down by evaporation. The synthesized chemical compounds are analyzed by a high-resolution time-of-flight mass spectrometer. If only one type of reactant is adsorbed on the cluster, only one oxide molecule is stabilized on the metallic core after the heating and cooling cycle. On the contrary, the coadsorption of the two types of molecules MoO(3) and O(2) on Ag(n) (+), at 77 K, leads to complex aggregates that transform, after laser heating, into a molybdate rich metal clusters. These synthesized species cool down by evaporating silver atoms showing evidence of a binary oxide that is more stable than the metallic core. Moreover we demonstrate that for small size molybdate clusters, a stoichiometric composition may differ from the bulk one.     

HPLC-NMR of fatty alcohol ethoxylates

The application of HPLC-NMR for the analysis of a mixture of fatty alcohol ethoxylates (FAEs) is described. The use of the new generation, cryogenically cooled probes is investigated in respect of the sensitivity advantage that they provide. The FAE mixture is separated using liquid chromatography at the critical point of adsorption. The ability of the method to differentiate between the different end groups and the degree of polymerization of the mixture constituents is investigated. Both on-flow and stop-flow HPLC-NMR techniques were used together with two-dimensional NMR spectroscopy. The results are compared with those obtained by using an evaporative light scattering detector for the HPLC.