Compehensive two-dimensional gas chromatography (GC×GC) and its applicability to the characterization of complex (petrochemical) mixtures

In general, petrochemical products contain only a limited number of chemical classes of compounds (sample dimensionality). The enormous number of individual components within these classes, however, soon puts limitations upon a single chromatographic technique when it comes to adequate characterization of these products. Comprehensive two-dimensional gas chromatography (GC×GC) clearly opens the possibility of estimating the composition of hydrocarbon mixtures in a far more detailed fashion than hitherto possible. Although the emphasis of papers of GCxGC thus far almost exclusively applies to the unsurpassed peak-capacity, in the oil industry there is a need for characterization, rather than for analyzing all the individual compounds. In principle a GCxGC system can provide an almost perfect match between its intrinsic properties and the dimensionality of oil samples. To establish the applicability of GCxGC towards petrochemical analytical challenges, a commercially aavailable prototype instrument was subjected to an exhaustive characterization of a typical hydrocarbon precess stream and a fast characterization of a light gas oil. Although there are no fundamental limitations towards the quantitative aspects of a GCxGC system, this paper confines itself to qualitative results only. Quantitative aspects of GCxGC will be published in a forthcoming paper.     

Analysis of anthracycline antitumour drugs in tissues and body fluids using liquid chromatography

Anthracyclines, with doxorubicin as the major representative, are amongst the most important chemotherapeutic agents used in cancer therapy. In order to reduce the severe side effects associated with their use, and to increase therapeutic efficacy, analogue development still continues, and analytical requirements change concomitantly. The available methods for bioanalysis of anthracyclines are summarized, with emphasis on high-performance liquid chromatography. Attention is paid to sample pretreatment, the possibilities of liquid—liquid and solid-phase extraction, and the chromatographic behaviour of the anthracyclines.     

Amperometry with two polarizable electrodes. XVI

Summary Conditions for the magnesium determination in alkaline solution by EDTA titration with biamperometric indication were examined. The most preferable pH range was found to be above 9.6. A reliable determination can be carried out in the presence of Ca, Ni, Cu and Co up to the ratio of 11. In the case of higher concentrations of Cu and Ni masking with potassium cyanide can be used. In this case, however, a change of the titration curves occurs.A new method for the determination of water-hardness by biamperometric indication is proposed. It is rapid and accurate and meets the requirements of routine and research work (error: ±1%).

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Zusammenfassung Die Bedingungen für die Magnesiumbestimmung in alkalischer Lösung durch Titration mit ÄDTA bei biamperometrischer Endpunktsanzeige wurden untersucht. Der günstigste pH-Bereich liegt über 9,6. Zuverlässige Bestimmungen können in Gegenwart von Ca, Ni, Cu und Co bis zum Verhältnis 11 ausgeführt werden. Höhere Konzentrationen an Cu oder Ni können mit KCN maskiert werden, wobei allerdings eine Umkehrung der Kurven auftritt.Ein Verfahren zur Wasserhärtebestimmung mit biamperometrischer Indikation wird vorgeschlagen, das schnell durchzuführen ist und genaue Werte liefert (Fehler ±1%).

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Part XV: Vorlíek, J., and P. Peták: Microchem. J. 12, 466–471 (1967).     

The synthesis of 4‐amino‐3‐(2‐pyridyl)pyrazolo[5,1‐c][1,2,4]triazine and some of its derivatives

A mixture of both geometrical isomers of hydrazones 3a‐3e was obtained by the coupling reactions of pyrazole‐3‐diazonium salts 2a‐2d and benzenediazonium chloride 2e with 2‐pyridylacetonitrile 1 . Hydrazones 3a‐3d were cyclized to the corresponding 4‐amino‐3‐(2‐pyridyl)pyrazolo[5,1‐c][1,2,4]triazines 4a‐4d.     

Kinetic parameters of the In(III)/In(I) electrode reaction in bromide medium

The electrode kinetic parameters of the In(III)/In(I) couple in acidic 4M bromide solution have been determined by means of the rotating disc electrode technique.

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Die elektrochemisch-kinetischen Parameter des In(III)/In(I)-Redoxsystems in Bromidlösung (Kurze Mitteilung)

Zusammenfassung Die elektrochemisch-kinetischen Parameter am In(III)/In(I)-Redoxsystem wurden in saurer 4-M-Bromidlösung mittels der rotierenden Scheibenelektrode bestimmt.

     

The reaction of N-Acylpyridinium salts with indole

Depending on the solvent used and the ratio of the reactants, N-acylpyridinium salts condense with indole to give 3-(N-acyl-1,4-dihydro-4-pyridyl)indole ( 1 ) or 4-(N-acyl-3-indolyl)pyridinium chloride ( 3 ). Compound 1 is an intermediate in the formation of compound 3 . The reaction mechanism has been studied, and a hydrogen transfer reaction is suggested as a key step. Alkaline hydrolysis, e.g., of 4-(N-acetyl-3-indolyl)pyridinium chloride ( 3a ), gave 3-(4-pyridyl)indole ( 2a ). The reaction of α-chlorosubstituted acyl halides with indole, in the presence of pyridine constitutes a convenient synthesis of 3-chloroacylindoles.     

C.I. Calculations on the lower transitions in the terphenyl and quaterphenyl di-valent ions

Energies and transition dipole moments for the lower electronic transitions in the terphenyl and quaterphenyl di-valent ions have been calculated starting from the Pople SCF MO's for the ground state ions. The configuration interaction included about one-hundred singly and doubly excited configurations. The results of the calculations for the lower allowed electronic transitions are in very satisfactory agreement with the experimental spectra.     

The clas program for classification and evaluation

Multivariate classification methods are needed to assist in extracting information from analytical data. The most appropriate method for each problem must be chosen. The applicability of a method mainly depends on the distributional characteristics of the data population (normality, correlations between variables, separation of classes, nature of variables) and on the characteristics of the data sample available (numbers of objects, variables and classes, missing values, measurement errors). The CLAS program is designed to combine classification methods with evaluation of their performance, for batch data processing. It incorporates two-group linear discriminant analysis (SLDA), independent class modelling with principal components (SIMCA), kernel density estimation (ALLOC), and principal component class modelling with kernel density estimation (CLASSY). Most of these methods are implemented so as to give probabilistic classifications. Multiple linear regression is provided for, and other methods are scheduled. CLAS evaluates the classification method using the training set data (resubstitution), independent test data, and pseudo test data (leave-one-out method). This last method is optimized for faster computation. Criteria for classification performance and reliability of the given probabilities, etc. are determined. The package contains flexible possibilities for data manipulation, variable transformation and missing data handling.     

Stroboskopisehe Untersuchungen über den zeitlichen Aufbau,die optische Absorption und das Nachleuchten gesteuerter Funkenentladungen

Zusammenfassung In elektrischen Funkenentladungen lassen sich Zündphase, Bogenphase und Abklingphase unterscheiden, die besondere charakteristische Eigenschaften aufweisen. Ihre Untersuchung wird durch ein neu entwickeltes Stroboskop ermöglicht, dessen Phasenlage beliebig gegenüber der periodischen Funkenfolge verstellt werden kann. Durch optische Absorption kann im abklingenden Funken nicht nur der atomare Metalldampf durch seine Grundlinien nachgewiesen werden, sondern auch seine molekularen Reaktionsprodukte mit der umgebenden Atmosphäre lassen sich durch Bandenabsorption feststellen. Das Nachleuchten abklingender Funkenentladungen wird im wesentlichen durch das Nachleuchten des aktiven Stickstoffs getragen, wenn der Metalldampfgehalt der Funkenstrecke gering gehalten wird. Gegen Ende der Nachleuchtphase lassen sich Sprüherscheinungen an den Elektroden feststellen, bei denen kleine Partikelchen mit unterschiedlichen, zum Teil spiralig verlaufenden Bahnkurven ausgeschleudert werden. Die Flugbahnen der Teilchen weisen auf starke Gasströmungen in der Funkenstrecke hin.

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Summary In electrical spark discharges it is possible to distinguish ignition phase, arc phase, and decay phase. These display special characteristic properties. It is possible to study them by means of a newly developed stroboscope, whose phase position can be adjusted at will against the periodic succession of sparks. Through optical absorption, not only the atomic metal vapor can be detected, through its ground lines, in the decaying sparks but also its molecular reaction products with the surrounding atmosphere can be established through the band spectrum. The phosphorescence of decaying spark discharges is essentially due to the afterglow of the active nitrogen, if the metal vapor of the spark gap is kept low. Toward the end of the phosphorescence phase, spray phenomena may be observed at the electrodes, in which tiny particles with distinctive, in part spiral, orbital curves are ejected. The flight paths of these particles indicate strong gas currents in the spark gap.

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Résumé On peut distinguer dans la décharge par étincelles, la phase d'ignition, la phase d'arc et la phase de décroissance. On explique ainsi certaines propriétés caractéristiques. On peut étudier ces diverses phases à l'aide d'un dispositif stroboscopique nouveau réglable à volonté pour observer la même phase d'étincelles qui se succèdent périodiquement. Grâce a l'absorption optique on peut détecter soit une vapeur atomique métallique par ses raies caractéristiques pendant la période de décroissance des étincelles, soit les réactions moléculaires qui se produisent dans les gaz environnants grâce aux spectres de bandes. La phosphorescence pendant la décroissance de l'étincelle est due essentiellement à la postluminescence de l'azote actif, si la tension de vapeur du métal entre les électrodes est suffisamment basse. Pendant la fin de la période de phosphorescence on observe sur les électrodes des phénomènes de pulvérisation avec formation de très petites particules qui sont éjectées en décrivant des trajectoires en spirales. Les trajectoires aériennes de ces particules révèlent l'existence de forts courants gazeux entre les électrodes.