Der Einfluß von Grenzflächenerscheinungen auf den Stoffübergang und die Prozeßführung in Gegenstromkolonnen mit überkritischem CO2

Zusammenfassung Mittels des Einsatzes einer Hochdrucksichtzelle wurden Eigenschaften der Kontaktbereiche in Trennverfahren mit unterschiedlichen wäßrigen Lösungen und CO₂ unter hohen Drücken untersucht. Die Methode des hängenden Tropfens wurde zur Messung der Grenzflächenspannung bis zu Drücken von 280 bar angewandt. Der mit dem Druck abnehmende Verlauf weist nach der Gibbs'schen Theorie auf die Anreicherung von CO₂ in der Phasengrenze. Weiterhin wurde die für Packungskolonnen bedeutsame Feststoffbenetzung in Abhängigkeit von Druck und Oberflächenbeschaffenheit des Feststoffes untersucht. Der die Feststoffbenetzung charakterisierende Kontaktwinkel wurde mittels der Methode der gekippten Platte vermessen und ergab eine schlechtere Benetzung bei höheren Drücken und glatten Stahloberflächen.

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The effect of interfacial phenomena on mass transport and performance of separations in countercurrent columns with supercritical CO₂

Interfacial phenomena affecting countercurrent separation processes have been studied in systems containing aqueous solutions and CO₂ at elevated pressures by means of a high pressure optical cell. The pendant drop method was applied in order to measure the interfacial tension up to 280 bar. The decreasing course as a function of the pressure is due to the adsorption of CO₂ at the interface according to Gibbs' law. Further, wetting characteristics have been investigated as they are of considerable importance to packed columns. Therefore, the contact angle was determined by the method of the tilting plate and came out to increase with pressure and smoothness of the solid surface, indicating the loss of wettability.

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Implicitly representing arrangements of lines or segments

Anarrangement ofn lines (or line segments) in the plane is the partition of the plane defined by these objects. Such an arrangement consists ofO(n ²) regions, calledfaces. In this paper we study the problem of calculating and storing arrangementsimplicitly, using subquadratic space and preprocessing, so that, given any query pointp, we can calculate efficiently the face containingp. First, we consider the case of lines and show that with (n) space¹ and (n ^3/2) preprocessing time, we can answer face queries in (n)+O(K) time, whereK is the output size. (The query time is achieved with high probability.) In the process, we solve three interesting subproblems: (1) given a set ofn points, find a straight-edge spanning tree of these points such that any line intersects only a few edges of the tree, (2) given a simple polygonal path , form a data structure from which we can find the convex hull of any subpath of quickly, and (3) given a set of points, organize them so that the convex hull of their subset lying above a query line can be found quickly. Second, using random sampling, we give a tradeoff between increasing space and decreasing query time. Third, we extend our structure to report faces in an arrangement of line segments in (n ^1/3)+O(K) time, given(n ^4/3) space and (n ^5/3) preprocessing time. Lastly, we note that our techniques allow us to computem faces in an arrangement ofn lines in time (m ^2/3 n ^2/3+n), which is nearly optimal.The first author is pleased to acknowledge the support of Amoco Fnd. Fac. Dev. Comput. Sci. 1-6-44862 and National Science Foundation Grant CCR-8714565. Work on this paper by the fifth author has been supported by Office of Naval Research Grant N00014-87-K-0129, by National Science Foundation Grant NSF-DCR-83-20085, by grants from the Digital Equipment Corporation, and the IBM Corporation, and by a research grant from the NCRD—the Israeli National Council for Research and Development. The sixth author was supported in part by a National Science Foundation Graduate Fellowship. This work was begun while the non-DEC authors were visiting at the DEC Systems Research Center.     

Synthesis of some 4-substituted-2-(o-halogenophenyl)-1,2,3-triazoles

Mesoaldehyde 1,3-dioxime was treated with either 2,4,6-trichlorophenyl- (a), o-fluorophenyl- (b), or o-bromophenyl- (c) hydrazine to give the corresponding mesoaldehyde 1,3-dioxime-2-halogenophenylhydrazones (1a,b,c). The latter were O-acetylated with acetic anhydride, and cyclized to triazole 4-oximes (3b, c) or triazole 4-O-acetyloximes ( 6a,b,c ) with cesium carbonate, then converted to nitriles ( 7a,b,c ) by refluxing with acetic anhydride followed by pyrolysis, or to aldehydes ( 4a,b,c ) by hydrolysis. The nitriles ( 7a,b,c ) were also converted to acids ( 9a,b,c ), esters ( 10a,b,c ), amides ( 8a,c ), an alcohol (11a), and an amine ( 12a ). In addition, tetrazoles of two types were prepared. The first ( 13d,e ) were obtained from the acid chlorides by the action of 5-aminotetrazole, whereas the second ( 14f ) was produced from the respective nitrile by the action of ammonium azide.     

The effect of crown ethers on the alkylation of a cyclic β-keto ester

The effects of crown ethers (6 and 7) on the reactions of sodium (2a) and potassium enolates (2b) of 2-ethoxycarbonylcyclohexanone (1) with isopropyl iodide in dimethylsulfoxide and dimethoxyethane have been investigated. When the addition of crown ether promoted dissociation of ion pair 2 in either of the two solvents, the total rate of reaction (k_t) increased and the ratio of carbon- (3) to oxygen-alkylation (4 and 5) products decreased. The results are consistent with the involvement of both the ion pair and more dissociated species in alkylation and with greater reactivity for the latter.     

Enantioselective enzymes for organic synthesis created by directed evolution

A new concept for the creation of enzymes displaying improved enantioselectivity in a given reaction is described; it is based on "evolution in the test tube". Accordingly, proper molecular biological methods for random mutagenesis, gene expression, and high-throughput screening systems for the rapid assay of enantioselectivity are combined. Several rounds of mutagenesis and screening are generally necessary in order to create mutant enzymes that show high degrees of enantioselectivity, as in the case of the lipase-catalyzed hydrolytic kinetic resolution of a chiral ester in which the original enantioselectivity of 2 % ee (E = 1) increases to > 90% ee (E = 25).     

R?ntgenspektrometrische Bestimmung von Eisen-55 in Luftstaub- und Niederschlagsproben

Zusammenfassung Eisen-55 wurde in Neuherberg bei München seit März 1970 in monatlich gesammelten Luftstaubproben und seit Januar 1971 in Monatsniederschlagsproben bestimmt. Nach dem Veraschen der Proben wurde Eisen durch Extraktion' mit Di-iso-propyläther abgetrennt. Zur weiteren Entfernung störender Radionuklide des Fallouts wurde eine Ionenaustauschertrennung angeschlossen. Nach der elektrolytischen Abscheidung des Eisens auf Kupferplättchen wurden die Röntgenspektren mit einem Proportionalzähler sowie einem Si(Li)-Detektor aufgenommen.Die mittlere spezifische Luftaktivität betrug in Neuherberg 1,0 fCi/m³ im Jahr 1970 (ab März), 1,2 fCi/m³ im Jahr 1971 und 0,36 fCi/m³ im Jahr 1972. Die dem Boden durch den Niederschlag zugeführte Aktivität wurde zu 697 pCi/m² · Jahr für 1971 und 178 pCi/m² · Jahr für 1972 bestimmt.Vortrag anläßlich der Tagung Spurenanalyse, 2. bis 5. April 1973 in Erlangen.     

Chloride-catalyzed oxidation of phenol in pulsed-laser irradiation titanium dioxide sols

The kinetics of photolysis of phenol in presence of two kinds of TiO₂ colloid in acid aqueous solution medium was studied by transient absorption spectroscopy. The absorbance and quantum yield of the phenoxyl radicals is strongly influenced by the chloride ions. The process of laser flash photolysis of phenol in the presence of chloride has been discussed.