Modern Analysis

The important advances being made in modern analytical methods are indicative of the fundamental changes that are occuring in the theory and practice of “analytical chemistry”. “Information optimization” demands a new approach in teaching and research, and calls for the intergration of chemistry with other scientific and technical disciplines.     

Darstellung verschiedener 2,6-disubstituierter 4-Sulfanilamidopyrimidine 7. Mitt. über neue N1-substituierte Sulfanilamide

Zusammenfassung Im 2,6-Dichlor-4-aminopyrimidin wurden die beiden Chloratome wahlweise gemeinsam oder zweistufig gegen Alkoxyoder Alkylmercaptoreste ausgetauscht. Partiell reagiert bevorzugt das 2-ständige Halogenatom, während das 6-ständige derberer Bedingungen zum Umsatz bedarf. Die so erhaltenen gleichartig oder verschieden in 2,6-Stellung durch Alkoxy- bzw. Alkylmercaptoreste substituierten 4-Aminopyrimidine wurden mit N-Carbäthoxysulfanilsäurechlorid acyliert und durch alkal. Verseifung die entsprechenden 2,6-disubstituierten 4-Sulfanilamidopyrimidine gewonnen.     

Investigation of HfO(+) interference in the determination of platinum in a catalytic converter (cordierite) by inductively coupled plasma mass spectrometry

The determination of Pt in cordierite is subject to strong interference by spectral overlap from HfO(+) ions with all Pt isotopes. Two mathematical correction methods based on the HfO(+)Hf(+) ratio and a method for the chemical separation of Hf based on adsorption chromatography and isotope dilution were investigated to correct for this interference. Flow infection was used to prevent clogging of the cone orifice. To enhance the sensitivity and thus lower the detection limit, thermospray nebulization was used for sample introduction and the method was compared with pneumatic nebulization. In addition, the memory effects were evaulated for both systems. Analysis of artificial solutions (1 ng Pt ml(-1)) yielded results within 3% of the true value. Th Pt content (ca. 50 ng g(-1)) of a cordierite sample, previously exposed to exhaust gases, could be determined with precisions of about 10-25% and the results agreed with earlier determinations by other workers.     

Analysis and classification of individual outdoor aerosol particles with SIMS time-of-flight mass spectrometry

Individual aerosol particles sampled in the north of the city Karlsruhe were analysed with a TOF-SIMS instrument. The results confirmed the integral analysis of many particles [1]. In order to employ a signal pattern analysis of the negative secondary ions for the classification of organic compounds an earlier classification scheme for 5 keV Ar⁺ bombardment was found to be generally also applicable for the TOF-SIMS conditions. Two main classes of particles were distinguished, which consist of submicron mainly organic particles of vehicle traffic provenance on one side and coarse particles of geogenic sources on the other side. Additionally, the geogenic class could be devided into a fraction consisting of lime soil and a fraction with alumo-silicate soil. A quantification of the class population was performed by counting the particles of different type.     

Styrene emulsion polymerization: Particle-size distributions

Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments.     

Caracterisation physico-chimique de couches minces de polymere obtenues par decharge electrique dans des vapeurs de styrene

Thin polymer layers, obtained by polymerization of styrene vapour in an electrical discharge, are insoluble in solvents for usual polystyrene. However, characterization of the gas discharge polymer, by i.r. spectroscopy, by visible and near u.v. spectroscopy and by chemical microanalyses, show that this material is very near to ordinary polystyrene; this conclusion is further indicated by similarity of the glass transition temperatures of the polymers. However, there are some spectral differences, and an evident reactivity to oxygen and to atmospheric moisture.     

Benzothiazolium derivatives. III. Nucleophilic substitution reactions of benzothiazolium salts

The reactions of 2,3-dihydrothiazolo[2,3-b]benzothiazolium bromide 1 (A^? ?Br^?) with certain nucleophilic reagents have been performed for the purpose of ascertaining the reaction pathways and identifying the group that is displaced from the central carbon atom of the dithiocarbamate system. The nature of complex salt-like intermediates formed initially from 1 (A^? ?Br^?) has been studied and confirmed. For comparison, a number of nucleophilic substitution reactions of 2-methylthio-3-methylbenzothiazolium iodide 17 and 2-dimethylamino-3-methylbenzothiazolium perchlorate 18 have been examined.     

Untersuchung der M?glichkeiten zur indirekten inversvoltammetrischen Bestimmung von Edelmetallspuren

Zusammenfassung Mit Hilfe der indirekten inversvoltammetrischen Methode wurden analytische Bestimmungsmöglichkeiten für die Edelmetalle Hg, Pt, Au und Ag in Verbindung mit Thioharnstoff, Thionalid, 2-Mercaptobenzthiazol und Rubeanwasserstoff untersucht. Während sich für Hg und Ag in jedem Fall gute Bestimmungsmöglichkeiten ergaben, traten für Pt und Au immer dann Schwierigkeiten auf, wenn in alkalischer Lösung gearbeitet werden mußte. Weiterhin werden Möglichkeiten zur einfachen Siliconisierung und luftblasenfreien Füllung der Kemulaelektrode vorgeschlagen.

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Summary Investigations were made in order to find out the analytical possibilities for the determination of the noble metals Hg, Pt, Au and Ag by means of inverse voltammetry of thiourea, thionalide, 2-mercaptobenzothiazole and dithio-oxamide. In each case Hg and Ag can be determined exactly, whereas the determination of Pt and Au in alkaline solutions is difficult. Simple devices for siliconising and air-free filling of the Kemula electrode are proposed.

     

Zur Verwendung von Quecksilber(I)-nitrat als reduktometrisches Reagens

Ohne ZusammenfassungVgl. diese Z. 137, 129 (1952/53); 138, 118 (1953)