13C NMR coupling constants in delocalized organo-alkali metal compounds. Models of polymerization systems

2,5-Diphenyl-2,5-dipotassiohexane, 2-lithio-4,4-dimethyl-2-phenylpentane, and 1-lithio-2,5,5-trimethylhexene-2 have been prepared, all labelled with¹³C in the position adjacent to the alkali metal atom. The¹³C NMR spectra of these compounds have been measured and the¹³CC coupling constants found for the charged atom. The first two compounds have coupling constants consistent with an sp² hybridized C_α, with relatively little effect of the charge on the coupling constant. The third compound, when dissolved in either THF or benzene, gave much smaller coupling constants, which are more difficult to interpret.     

Comparison of figures of merit for fluorimetric analysis of rhodamine complexes of gallium and indium by excitation with pulsed laser and by xenon arc sources

Optimum conditions have been established for formation and extraction of indium-Rhodamine complexes, and limits of detection found for fluorimetric determination of gallium and indium by means of Rhodamine dyes, using the excitation with pulsed laser and xenon arc sources.     

The determination of pd,pt, au,ag and ir in copper by neutron activation analysis

The determination of palladium, platinum and gold in copper metal by neutron activation analysis is described. The matrix activity was separated from the noble metals by cation-exchange adsorption. Gold was extracted; palladium and platinum were precipitated. The precipitates were counted with a low-energy photon detector. The gold results were checked by instrumental neutron activation analysis. Silver, iridium, selenium, antimony and arsenic were also determined simultaneously.     

EPR studies of isotopic exchange involving adsorbed oxygen species on MgO

In the EPR spectra of ¹⁷O₂^? adsorbed on MgO, the hyperfine lines due to ¹⁷O(I = $\text{5}\text{2}$) have been used to monitor the isotopic exchange with gas phase oxygen. The predicted behaviour of the different possible mechanisms (place exchange and/or isotopic exchange) is compared with the experimental results which show that, on MgO at room temperature, isotopic exchange occurs via an intermediate species which is tentatively identified as O₄^?.     

Etude de la Fragmentation de Derives Substitues Polycycliques du Benzodioxinne-1,4

The mass spectra of five polycyclic 1,4 benzodioxin derivatives have been studied. The breakdown patterns of the more important ions have been suggested by comparison with three compounds in a deuterated specific position. Some rearrangements are produced by specific hydrogen migration and a few others after scrambling.     

Mechanism of vinyl chloride polymerization

An overall mechanistic scheme for the suspension polymerization of vinyl chloride is presented. The process can be resolved into five discrete stages, each of which presents a unique environment for the interaction of the systems parameters. It is shown that the surface area of the polymer formed during the reaction is not a major factor in autoacceleration and that the increase of kinetic chain length with conversion is due to a radical dilution effect. The latter is a direct result of the difference in rates between polymerization and radical formation, the former being greater. The increase of the initial polymerization rate and the reduction of autoacceleration brought about by chain transfer agents can be explained by the lower diffusion rate and greater bulkiness of the chain transfer agent radical relative to that of the monomer radical. The chaintransfer agent CBr₄ is preferentially absorbed by PVC from solution in vinyl chloride. With lauryl peroxide as initiator it is shown that the “hot spot” is the result of a build-up of initiator in the monomer caused by its exclusion from the polymer phase. Vinyl chloride was found to dissolve 0.03% PVC at ambient temperature and to have no effect on the decomposition rate of lauryl peroxide.     

Conformations of luteoskyrin and rugulosin in solution

The pigments Luteoskyrin (Ls) and Rugulosin (Rg) might adopt a priori two extreme conformations, a planar and an angular one. To determine the predominant conformation in solution, the nature of the lowest energy transition of the chromophores and the presence of intramolecular H-bonding have been investigated. The solvent effects on electronic absorption and CD spectra indicated the π-π* nature of the lowest energy transition. Treatments of the electronic absorption results according to McRae and Kosower relations, IR absorption and PMR spectra suggested the presence of strong intra-molecular H-bonds. From these results it was concluded that Ls and Rg adopted in a variety of solvents the most planar conformation.     

Studies on the exchange characteristics of [Co(NH3)6]3+ in amberlite IRC-50

Summary The exchange of Co(NH₃)₆]³⁺-ions on amberlite IRC-50 resin has been studied at room temperature. For this exchange process the cations are effective in the order: Cs⁺<Rb⁺<K⁺<Na⁺<Li⁺<NH₄ ⁺<Mg²⁺ <Ca²⁺<H⁺ and (C₂H₅)₄N<(CH₃)₄N⁺ ≪Cetyltrimethylammonium-ion <Cetylpyridinium-ion. The logarithm of the selectivity coefficient gives linear graphs when plotted against the radius of the hydrated ions or the reciprocals of theDebye-Hückel parameter?.     

A high resolution mass spectrometric measurement system for a vacuum fusion apparatus

A high resolution mass spectrometric read-out system for a vacuum fusion apparatus is described. Rapid analyses are possible and the rate at which various gases are evolved can be monitored. Gas mixture assays are accomplished by scanning the nominal mass 28 peak. Serial measurements of CO⁺, N₂⁺ and C₂H₄⁺ are made. Thus detection and measurement of evolved hydrocarbons are possible. The results for silver and tin from a conventional vacuum fusion apparatus and the mass spectrometer apparatus are compared.     

Zur Hemmung der katalytischen Jodwirkung auf das system Cer(IV)-sulfat—arsenige Säure

Zusammenfassung Die Hemmung der katalytischen Jodwirkung auf die Redoxreaktion Cer(IV)-sulfat—arsenige Säure wird hinsichtlich ihrer Vorund Nachteile bei analytischer Anwendung untersucht. Brucinacetat gibt mit Ceriion in schwefelsaurer Lösung nachFischl eine quantitativ auswertbare Farbreaktion. Kritische Untersuchungen hierzu ergeben, daß die Lösungen zur vollen Entwicklung und Stabilität der orangeroten Farbe (Absorptionsmaximum 470 nm) mindestens 10 bis höchstens 12 Min. auf 105° zu erhitzen sind. Die Anwendung auf die Jodbestimmung im Blutserum nachSpitzy, Reese undSkrube bietet infolge methodischer Komplizierung keinen besonderen Vorteil.

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Summary The inhibition of the catalytic action of iodine on the redox-reaction ceric sulphate—arsenious acid was investigated with regard to the advantages and disadvantages in its analytical application. Brucine acetate gives, according toFischl, a quantitative colour reaction with ceric ions in sulphuric acid. Critical investigations carried out show that the solution only develops a stable, orange-red colour (absorption maximum 470 nm) between 10 and 12 minutes heating. Application of this procedure to the determination of iodine in blood serum by the method ofSpitzy, Reese, andSkrube introduces complications and has, therefore, no special advantage.

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Résumé Etude des avantages et des inconvénients de l'emploi en chimie analytique de l'inhibition de l'effet catalytique de l'iode sur la réaction d'oxydo-réduction cerium(IV)-sulfate—acide arsenieux. Avec les ions cériques l'acétate de brucine donne, en solution sulfurique, d'aprèsFischl, une réaction colorée susceptible d'être employée pour une détermination quantitative. Des recherches critiques ont montré que les solutions devaient être chauffées pendant au moins 10 min. et au plus 12 min. à 105° pour développer complètement la couleur rouge orangé et obtenir sa stabilité (maximum d'absorption à 470 nm). L'application à la détermination de l'iode dans le sérum sanguin d'aprèsSpitzy, Reese etSkrube n'offre aucun avantage particulier du fait de la complication de la méthode.