Determination of oxygen in titanium by the micro bromination method

Summary A new micro bromination method is proposed for the determination of oxygen in titanium. The sample is mixed with carbon and treated with bromine at 825° C in a quartz boat, using argon as a carrier gas. The oxygen in the sample combines with the carbon to form carbon monoxide, which is then oxidized to carbon dioxide with hot copper oxide. The carbon dioxide is absorbed by a weighed absorption tube containing soda-asbestos. The bromine and titanium tetrabromide are removed by a cold trap cooled by dry ice and alcohol. To remove the last traces of bromine or bromine compounds, a soda tube and silvergauze heated to 650° are used. The method has been satisfactorily applied to the determination of oxygen in commercial titanium.

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Zusammenfassung Eine neue Mikromet-hode zur Bestimmung von Sauerstoff in Titan durch Bromierung wird vorgeschlagen. Die Probe wird mit Kohlenstoff gemischt und bei 825° C in einem Quarzschiffchen mit Brom behandelt, wobei Argon als Trägergas dient. Der in der Probe enthaltene Sauerstoff reagiert mit dem Kohlenstoff zu Kohlenmonoxyd, das dann über erhitztem Kupferoxyd zu Kohlendioxyd oxydiert wird. Dieses wird in einem gewogenen Absorptionsröhrchen an Natronasbest gebunden. Brom und Titantetrabromid werden in einer Falle mit Trockeneis und Alkohol ausgefroren. Zur Entfernung der letzten Spuren Brom oder Bromverbindungen dient ein auf 650° erhitztes Röhrchen mit Natron und Silberdrahtnetz. Das Verfahren hat sich zur Bestimmung von Sauerstoff in handelsüblichem Titan zufriedenstellend bewährt.

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Résumé Les auteurs proposent une nouvelle microméthode de bromuration pour le dosage de l'oxygène dans le titane. L'échantillon mélangé avec du carbone est traité par le brome à 825° C dans une nacelle de quartz sous courant d'argon utilisé comme gaz de transport. L'oxygène de l'échantillon se combine au carbone sous forme d'oxyde de carbone qui est oxydé en anhydride carbonique sur oxyde de cuivre à chaud. L'anhydride carbonique est absorbé et pesé dans un tube absorbeur rempli d'amiante sodé. Le brome et le tétrabromure de titane sont retenus dans un piège refroidi par le système glace carbonique-alcool. Les dernières traces de brome et de composés bromés sont éliminées à l'aide d'un tube à soude et d'une toile d'argent chauffée à 650°. La méthode a été appliquée avec succès au dosage de l'oxygène dans le titane commercial.

     

Allylic-type diindium reagents. Reactivity toward electrophiles and cascade coupling reactions with imines

The allylic-type diindium reagents A and B were prepared from 3-bromo-1-iodopropene (1a) and 4-bromo-2-iodobut-2-ene (1b), respectively, and their reactions with electrophiles were investigated. The diindium reagents A and B were initially reacted with imines and the resulting vinylindium compounds were then treated with organic halides in the presence of Pd(PPh(3))(4) to give linear N-aryl and N-tosyl homoallylic amines. Diindium A is stable in a small amount of water in solvent, whereas B is easily protonated to give a crotylindium reagent. The reaction of B with benzaldehyde gives mainly the 1,3- and 1,5-diols via a spontaneous coupling with two molecules of the aldehyde, in contrast to A, which reacts with one molecule of carbonyl compounds to give the vinylindium compounds.     

Effect of alcohols on the gamma-radiation-induced polymerization of ethylene

Gamma-radiation-induced polymerization of ethylene in alcohols such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl alcohols was carried out under a pressure of 400 kg./cm.²at 30°C. at a dose rate of 1.4 × 10⁵ rad/hr. in a batch reactor of 100 ml. capacity. The yield and molecular weight of polymer formed in the alcohols (except tert-butyl alcohol) were much lower than those of the bulk polymerization under the same conditions, whereas the addition of tert-butyl alcohol increased the yield and reduced the molecular weight. From the infrared spectra of the polymers and those of the bromination products it was concluded that only primary OH exists in the polymer formed in methyl alcohol and that both primary and secondary OH are in the polymer formed in other primary alcohols. Both secondary and tertiary OH were observed in the polymer when the secondary alcohols were used, and only tertiary OH in the case of tert-butyl alcohol. These polymers were found to contain small amounts of vinylidene unsaturation and methyl group. On the basis of these results the roles of the alcohols in the polymerization are discussed.     

Photoelectron spectroscopy of cluster anions of naphthalene and related aromatic hydrocarbons

The electronic structures and structural morphologies of naphthalene cluster anions, (naphthalene)(n)(-) (n=3-150), and its related aromatic cluster anions, (acenaphthene)(n)(-) (n=4-100) and (azulene)(n)(-) (n=1-100), are studied using anion photoelectron spectroscopy. For (naphthalene)(n) (-) clusters, two isomers coexist over a wide size range: isomers I and II-1 (28 < or = n < or =60) or isomers I and II-2 (n > or = ~60). Their contributions to the photoelectron spectra can be separated using an anion beam hole-burning technique. In contrast, such an isomer coexistence is not observed for (acenaphthene)(n) (-) and (azulene)(n) (-) clusters, where isomer I is exclusively formed throughout the whole size range. The vertical detachment energies (VDEs) of isomer I (7 < or = n < or = 100) in all the anionic clusters depend linearly on n(-13) and their size-dependent energetics are quite similar to one another. On the other hand, the VDEs of isomers II-1 and II-2 produced in (naphthalene)(n)(-) clusters with n > or = approximately 30 remain constant at 0.84 and 0.99 eV, respectively, 0.4-0.6 eV lower than those of isomer I. Based upon the ion source condition dependence and the hole-burning photoelectron spectra experiments for each isomer, the energetics and characteristics of isomers I, II-1, and II-2 are discussed: isomer I is an internalized anion state accompanied by a large change in its cluster geometry after electron attachment, while isomers II-1 and II-2 are crystal-like states with little structural relaxation. The nonappearance of isomers II-1 and II-2 for (acenaphthene)(n)(-) and (azulene)(n)(-) and a comparison with other aromatic cluster anions indicate that a highly anisotropic and symmetric pi-conjugated molecular framework, such as found in the linear oligoacenes, is an essential factor for the formation of the crystal-like ordered forms (isomers II-1 and II-2). On the other hand, lowering the molecular symmetry makes their production unfavorable.     

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions: the effect of molecular shape on molecular assembly and ion core character

Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions, (o-TP)n(-) (n = 2-100), (m-TP)n(-) (n = 2-100), and (p-TP)n(-) (n = 1-100), respectively, are conducted to investigate the effect of molecular shape on the molecular aggregation form and the resultant ion core character of the clusters. For (o-TP)n(-) and (m-TP)n(-), neither magic numbers nor discernible isomers are observed throughout the size range. Furthermore, their vertical detachment energies (VDEs) increase up to large n and depend linearly on n(-1/3), implying that they possess a three-dimensional (3D), highly reorganized structure encompassing a monomeric anion core. For (p-TP)n(-), in contrast, prominent magic numbers of n = 5, 7, 10, 12, and 14 are observed, and the VDEs show pronounced irregular shifts below n = 10, while they remain constant above n = 14 (isomer A). These results can be rationalized with two-dimensional (2D) orderings of p-TP molecules and different types of 2D shell closure at n = 7 and 14, the monomeric and multimeric anion core, respectively. Above n = 16, the new feature (isomer B) starts to appear at the higher binding side of isomer A, and it becomes dominant with n, while isomer A gradually disappears for larger sizes. In contrast to isomer A, the VDEs of isomer B continuously increase with the cluster size. This characteristic size evolution suggests that the transition to modified 2D aggregation forms from 2D ones occurs at around n = 20.     

Diffusion and pair interactions of CO molecules on Pd(111)

The diffusion and interactions of CO molecules on Pd(111) were studied by scanning tunneling microscopy. By following the random walk motion of individual molecules as a function of temperature, an activation energy barrier for diffusion of 118 +/- 5 meV was determined. The interaction between CO molecules was found to be repulsive for pairs separated by one or two Pd(111) lattice distances, and weakly attractive at a separation of sqrt[3].     

Silver granules as an absorbent of halogens and oxides of sulphur

Summary A preparation of silver granules has been used as an absorbent for halogens and sulphur. Its absorptive capacities for halogens and for sulphur were determined at various temperatures. The capacities are favorably compared with that of electrolytic silver wool. Having a granular form, the material is more conveniently used than electrolytic silver wool, and is applicable to the determination of carbon-hydrogen, halogens, sulphur or oxygen.

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Zusammenfassung Gekörntes Silber wurde zur Absorption von Halogenen und Schwefel verwendet. Seine Absorptionskapazität für die genannten Elemente wurde bei verschiedenen Temperaturen bestimmt. Sie ist gleich gut wie die elektrolytisch gewonnener Silberwolle. Die körnige Form ist aber besser zu handhaben als Silberwolle und eignet sich für die Bestimmung von Kohlenstoff und Wasserstoff, der Halogene, des Schwefels und des Sauerstoffs.

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Résumé On a utilisé une préparation de grains d'argent comme absorbant des halogènes et du soufre. On a déterminé ses capacités d'absorption pour les halogènes et pour le soufre à températures variées. Le pouvoir absorbant subit une comparaison favorable avec celui de la laine d'argent électrolytique. En raison de la forme granulaire, l'utilisation est plus facile que celle de la laine d'argent électrolytique. On peut l'appliquer au dosage du carbone, d'hydrogène, des halogènes, du soufre ou de l'oxygène.