Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KCl-ZnCl2 mixture

Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KCl-ZnCl₂ mixture of a composition close to the eutectic (50 mol% KCl-50 mol% ZnCl₂). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 °C in an atmosphere consisting of argon and oxygen. For iron different stages are observed in a TG curve. They can be attributed to the different reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is confirmed. For Cr and Ni these stages are not observed. At 8 vol% O₂ only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O₂ the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KCl-ZnCl₂ melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KCl-ZnCl₂ melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O₂)) is present leading to a higher oxidation rate of iron.     

The three-dimensional architecture of the mitotic spindle,analyzed by confocal fluorescence and electron microscopy

Fluorescence microscopy techniques have become important tools in mitosis research. The well-known disadvantages of fluorescence microscopy, rapid bleaching, phototoxicity and out-of-focus contributions blurring the in-focus image are obstacles which still need to be overcome. Confocal fluorescence microscopy has the potential to improve our capabilities of analyzing cells, because of its excellent depth-discrimination and image processing power. We have been using a confocal fluorescence microscope for the study of the mechanism of poleward chromosome movement, and report here (1) a cell preparation technique, which allows labeling of fixation sensitive spindle antigens with acceptable microtubule preservation; (2) the use of image processing methods to represent the spatial distribution of various labeled elements in pseudocolour; (3) a novel immunoelectron microscopic labeling method for microtubules, which allows the visualization of their distribution in semithin sections at low magnification; and (4) a first attempt to study microtubule dynamics with a confocal fluorescence microscope in living cells, microinjected with rhodamine labeled tubulin. Our experience indicates that confocal fluorescence microscopy provides real advantages for the study of spatial colocalization of antigens in the mitotic spindle. It does not, however, overcome the basic limits of resolution of the light microscope. Therefore, it has been necessary to use an electron microscopic method. Our preliminary results with living cells show that it is possible to visualize the entire microtubule network in stereo, but that the sensitivity of the instrument is still too low to perform dynamic time studies. It will be worthwhile to further develop this new type of optical instrumentation and explore its usefulness on both fixed and living cells.     

,,Ehrende Auszeichnung“ oder ,,Aufforderung zur Leistung eines Geldbeitrages“?

In the late 19th and early 20th centuries, many prominent German and Austrian scientists declined the election as a member of the Kaiserliche Leopoldinisch-Carolinische Deutsche Akademie der Naturforscher (in short: Leopoldina) because they were not willing to pay the entrance and membership fees of about one fifth of the monthly salary of a full professor. Many of theses candidates simply did not answer to the president’s notification of being elected. Some of them came up with ,,various reasons not to be discussed”, or referred to their individual financial situation.The physicist Heinrich Hertz, who had become famous by the discovery of electromagnetic waves in the late 1880ies, was the only elected candidate who protested bluntly against what he considered as an unworthy procedure. Although it would not have been a much of a burden for him to afford the requested entrance and membership fees, he refused to adhere to an association whose statues combined the award of an academic distinction with the obligation of financial support. In two letters addressed to Leopoldina President Carl Hermann Knoblauch,Hertz gave his reasons for declining his election to the academy. In the present article, Hertz’s letters to Knoblauch are fully published for the first time.      

On the Mechanism of Palladium(0)-Catalyzed Reactions of Allylic Substrates with Nucleophiles. Origin of the Loss of Stereospecificity

The mechanism of the loss of stereospecificity in palladium-catalyzed nucleophilic substitution of allylic substrates has been investigated. Eight substrates (cis and trans isomers of 1a-d) and two nucleophiles (Et₂NH and NaCH(SO₂Ph)₂) were studied. In the animation reactions two pathways are responsible for the formation of anomalous inversion product, viz., isomerization of the starting material (path B, Scheme 2) and isomerization of the π-allyl intermediate via displacement of palladium by Pd(0) (path C, Scheme 2), the latter of which predominates. In the alkylation the results indicate that loss of stereospecificity is caused only by path C. The use of a more reactive substrate increased the stereospecificity of the reaction and suppressed the isomerization pathway. An analysis of the kinetics is consistent with the hypothesis that path C is the major pathway for the stereochemical loss.     

Electrostatic destabilization of water-in-crude oil emulsions: Application to a real case and evaluation of the Aibel VIEC technology

In the current study, the Aibel Vessel Internal Electrostatic Coalescer (VIEC) technology was tested for a real case scenario encountered in the production train of a UK oil field. Depressurized samples were collected both upstream and downstream of the first stage separator. The separation performance was discussed with respect to water cut and droplet size distribution of the emulsions, and the effect of chemical treatment. Issues with respect to representative sampling and testing have been discussed. The application of an external AC electrical field has been shown to significantly enhance the separation of the aqueous phase from tight emulsions, both when it was used alone and in combination with a commercial demulsifier. By using the VIEC technology, the time for separation could be reduced from 8 min to 2 min and the overall BS&W in the emulsions was improved from 45% or 60% to a residual water content of 5-20%. Destabilization of a 45% water-in-oil emulsion by electrical and chemical treatment (20/40 ppm) produced oil in the 2-7% BS&W range whereas the corresponding tests without applying an electrostatic field led to a BS&W greater than 25%. The achieved results strongly suggest that the VIEC technology can resolve the stable emulsion bands encountered in the Schiehallion train and add flexibility or increased production rate to the process. The results also suggest the importance of further studies on the destabilization performances achieved by electrostatic means.     

Inactivation of FhuA at the cell surface of Escherichia coli K-12 by a phage T5 lipoprotein at the periplasmic face of the outer membrane

Inactivation of phage T5 by lysed cells after phage multiplication is prevented by a phage-encoded lipoprotein (Llp) that inactivates the FhuA outer membrane receptor protein (K. Decker, V. Krauel, A. Meesmann, and K. Heller, Mol. Microbiol. 12:321-332, 1994). Using FhuA derivatives carrying insertions of 4 and 16 amino acid residues and point mutations, we determined whether FhuA inactivation is caused by binding of Llp to FhuA and which regions of FhuA are important for inactivation by Llp. Cells expressing Llp were resistant not only to phage T5 but to all FhuA ligands tested, such as phage phi 80, colicin M, and albomycin, and they were strongly reduced in the uptake of ferrichrome. Most of the FhuA derivatives which were not affected by Llp were, according to a previously published FhuA transmembrane topology model, located in periplasmic turns and in the TonB box close to the periplasm. Since the ligands bind to the cell surface, interaction of FhuA with Llp in the periplasm may induce a FhuA conformation which impairs binding of the ligands. This conclusion was supported by the increase rather than decrease of colicin M sensitivity of two mutants in the presence of Llp. The only Llp-resistant FhuA derivatives with mutations at the cell surface contained insertions of 16 residues in the loop that determines the permeability of the FhuA channel and serves as the principal binding site for all FhuA ligands. This region may be inactivated by steric hindrance in that a portion of Llp penetrates into the channel. Outer membranes prepared with 0.25% Triton X-100 from cells expressing Llp contained inactivated FhuA, suggesting Llp to be an outer membrane protein whose interaction with FhuA was not abolished by Triton X-100. Llp solubilized in 1.1% octylglucoside prevented T5 inactivation by FhuA dissolved in octylglucoside.