Photodissociation of molecular bromine in solid H2 and D2: spectroscopy of the atomic bromine spin-orbit transition

We report 355 nm photodissociation studies of molecular bromine (Br2) trapped in solid parahydrogen (pH2) and orthodeuterium (oD2). The product Br atoms are observed via the spin-orbit transition ((2)P(1/2)<-- (2)P(3/2)) of atomic bromine. The quantum yield (Phi) for Br atom photoproduction is measured to be 0.29(3) in pH2 and 0.24(2) in oD2, demonstrating that both quantum solids have minimal cage effects for Br2 photodissociation. The effective Br spin-orbit splitting increases when the Br atom is solvated in solid pH2 (+1.1%) and oD2 (+1.5%); these increases are interpreted as evidence that the solvation energy of the Br ground fine structure state ((2)P(3/2)) is significantly greater than the excited state ((2)P(1/2)). Molecular bromine induced H2 infrared absorptions are detected in the Q1(0) and S1(0) regions near 4150 and 4486 cm(-1), respectively, which allow the relative Br2 concentration to be monitored as a function of 355 nm photolysis.     

煤中溴的淋滤行为研究

在不同pH值条件下对来自重庆磨心坡矿煤样进行柱淋滤实验,用电感耦合等离子体质谱法( ICP-MS )测定煤中溴的含量及四种淋滤介质在不同时间段获取的淋出液中溴的浓度。结果表明,淋滤液的pH值、淋滤时间、煤中溴的赋存形态及在煤中赋存部位对溴的淋出有重要影响。淋滤液的酸性越强,煤中溴的最大淋出浓度越大,一定时间内溴的总淋出率也越高。 pH值为2的淋滤液,在淋滤前40h内淋出溴的量占总淋出量的80.65%;pH值为4的淋滤液,在淋滤前50h内淋出溴的量占总淋出量的89.42%。在酸性淋滤液作用下,首先被淋出的是存在煤颗粒表面的碳酸盐态和铁锰结合态溴,然后煤基质内部的水溶态和离子交换态溴才被淋出。柱淋滤实验表明,煤中溴在风化过程中,会被酸性雨水淋溶出来进入周围土壤或地表水体,造成周围环境溴的富集。     

Occurrence of bromine in plants and soil

The usefulness of X-ray fluorescence analysis for the determination of bromine in soil and plants is demonstrated by comparing the results with those obtained by activation analysis. An abnormal accumulation of bromine in some soils, plants and cigarettes has been found. Volcanic ash soil accumulates bromine in its humic acid. The large ratio of chlorine to bromine in river water may be explained by the accumulation of bromine in humus of soil. The possibility of bromine contamination of food and cigarettes, due to the application of agricultural chemicals, is pointed out.     

Investigation of the reaction of quinoline with bromine in nitrobenzene

The reaction of quinoline with bromine in nitrobenzene solvent is investigated using the properties of isomolar series. These properties, viscosity, conductivity, density, depression of the freezing point, are determined using a constant molar concentration of C₉H₇N +Br₂, 0.05 per mole of C₆H₅NO₂. It is shown that the nitrobenzene solution of quinoline forms with bromine a complex with the composition C₉H₇N · Br₂. The molecular conductivity of this complex in nitrobenzene solvent increases with dilution.     

Nucleophilic substitution of bromine in vicinal bromotrifluoroalkylamines

SecondaryN-(2-bromo-3,3,3-trifluoropropyl)-N-alkylamines cyclize under the action of bases to yield aziridines. TertiaryN-(2-bromo-3,3,3-trifluoropropyl)amines react with S-nucleophiles to give products of bromine substitution.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 955–957, May, 1994.     

On the unusual fluorescence X-ray intensity variations in iron-silicon and aluminium-silicon-copper alloys

Summary The unusual fluorescence X-ray intensity variations in iron-silicon and aluminium-silicon-copper alloys have been investigated. In these alloys, the unusual behaviour was found not only in the fluorescence X-ray intensity of the Si K line but also in that of Fe K. It was confirmed that the phenomenon occurred not only when the primary crystals having large differences of the mass-absorption coefficients for the X-ray of the elements to be analyzed precipitated on both sides of the eutectic point and/or the intermetallic compound but also when there was a large difference in the effective volume ratio between the primary phase and the secondary phase. Therefore, the phenomenon should be considered in the fluorescence X-ray analysis of actual samples such as alloys of light metals, ores, oxides, and other compounds.

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Über ungewöhnliche Intensitätsveränderungen bei der Röntgenfluorescenz von Fe-Si- und Al-Si-Cu-Legierungen

Zusammenfassung Das ungewöhnliche Verhalten wurde bei der Si K- und auch bei der Fe K-Linie festgestellt. Die Erscheinung tritt nicht nur auf, wenn Primärkristalle mit stark unterschiedlichen Massenabsorptionskoeffizienten für die Röntgenlinien der zu untersuchenden Elemente sich auf beiden Seiten des eutektischen Punktes und/oder der intermetallischen Verbindung abscheiden, sondern auch, wenn ein großer Unterschied im effektiven Volumenverhältnis zwischen der primären und sekundären Phase vorhanden ist. Diese Veränderungen müssen bei der Röntgenfluorescenzanalyse von Leichtmetallegierungen, Erzen, Oxiden u. ä. berücksichtigt werden.

     

Activation analysis of bromine in rock samples

A simple method for the radiochemical neutron activation analysis of bromine in rock samples is described. The irradiated samples are ignited in an induction furnace in a flow of air for four minutes. The bromine expelled is collected onto activated charcoal which is measured using a Ge(Li) detector. The yield of the chemical separation is 85–100% and the detection limit is 7 ppb. The method is discussed and results for the analysis of 14 USGS standard rock samples are presented.     

Rapid neutron activation of bromine using 6.1-minute bromine-82M: Application to the determination of bromine in blood plasma

Résumé Une méthode rapide de dosage du brome dans le plasma sanguin par analyse par activation neutronique est décrite. En mesurant le brome 82m par spectrométrie X, l'analyse dans des échantillons plasmatiques de 10 μl peut être faite en 10 minutes. En présence de grandes concentrations de sodium et de chlore, telles que celles du plasma normal, la plus petite quantité de brome décelable est d'environ 5 ng. Les erreurs statistiques mises à part, l'erreur expérimentale introduit une marge d'incertitude d'environ ±2%. On compare les avantages de différents détecteurs utilisés.      

Pulse radiolysis studies of the reactions of bromine atoms and dimethyl sulfoxide–bromine atom complexes with alcohols

Dimethylsulfoxide (DMSO)–Br complexes were generated by pulse radiolysis of DMSO/bromomethane mixtures and the formation mechanism and spectral characteristics of the formed complexes were investigated in detail. The rate constant for the reaction of bromine atoms with DMSO and the extinction coefficient of the complex were obtained to be 4.6×10⁹ M⁻¹ s⁻¹ and 6300 M⁻¹ cm⁻¹ at the absorption maximum of 430 nm. Rate constants for the reaction of bromine atoms with a series of alcohols were determined in CBrCl₃ solutions applying a competitive kinetic method using the DMSO–Br complex as the reference system. The obtained rate constants were ∼10⁸ M⁻¹ s⁻¹, one or two orders larger than those reported for highly polar solvents. Rate constants of DMSO–Br complexes with alcohols were determined to be ∼ 10⁷ M⁻¹ s⁻¹. A comparison of the reactivities of Br atoms and DMSO–Br complexes with those of chlorine atoms and chlorine atom complexes which are ascribed to hydrogen abstracting reactants strongly indicates that hydrogen abstraction from alcohols is not the rate determining step in the case of Br atoms and DMSO–Br complexes.     

Improvements in the microdetermination of chlorine and bromine in organic compounds

Summary Schöniger's method for the microdetermination of halogen has been improved by using ammonium hydroxide solution as an absorbing solution instead of sodium hydroxide solution in order to simplify the after treatment. On boiling the absorbing solution, interfering ions can be removed together with excess ammonia. Ammonium halide which formes in the solution is titrated with AgNO₃ solution in the presence of an adsorption indicator. Satisfactory results are obtained more rapidly.

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Zusammenfassung Um die Weiterbehandlung der Absorptionslösung bei der Mikrobestimmung der Halogene nachSchöniger zu vereinfachen, wurde an Stelle von Natronlauge Ammoniaklösung verwendet. Durch Kochen der Absorptionslösung können störende Ionen zugleich mit dem Ammoniaküberschuß entfernt werden. Das in der Lösung entstandene Ammoniumhalogenid wird mit Silbernitrat in Gegenwart eines Adsorptionsindikators titriert. Bei verkürzter Analysendauer werden zufriedenstellende Ergebnisse erzielt.

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Résumé On a amélioré la méthode deSchöniger pour le microdosage des halogénes en utilisant une solution d'ammoniaque comme absorbant à la place de la solution d'hydroxyde de sodium afin de simplifier le traitement ultérieur. En faisant bouillir la solution d'absorption on peut éliminer les ions gênants avec de l'ammoniaque en excés. On titre l'halogénure d'ammonium qui se forme en solution, par une solution d'AgNO₃ en présence d'un indicateur d'adsorption. On a obtenu des résultats satisfaisants plus rapidement.

     

Coulo-bipotentiometric titrations in the analysis of bromine in bromine-doped cadmium chalcogenides

The detection of bromine in the 60–1300 p.p.m. range in Cd-chalcogenideshas been proved feasible by a d.e.p. version of argentometric titration, where the titrant (silver ions) is coulo-generated. The analytical method described seems to meet the requirements of the simplicity necessary when routine work is needed and when small samples (about 20–100 mg) are available.     

Mechanism of the azide–bromine reaction in aqueous medium

Results on the oxidation of N by Br₂ in neutral and acid media are presented. The rate of the reaction is found to be proportional to [N] and [Br₂]. The gaseous product of oxidation is found to be pure nitrogen. The stoichiometry of the reaction is The reaction shows a positive salt effect. It is found that the addition of Br^? stabilizes the complex BrN₃, which decomposes into Br^? and N₂: The spectroscopic measurements also support the kinetic observation. The equilibrium constant K, the rate constants and the thermodynamic parameters were calculated. It is observed that H⁺ ion inhibits the reaction. The mechanism is discussed in terms of the kinetic results.     

中国煤中溴的含量及分布

在测试分析中国27个省、直辖市和自治区的305个煤样中溴含量的基础上,从煤的不同成煤年代、不同变质程度以及不同聚煤区等方面分析和考查中国煤中溴的分布状况。结果表明,中国煤中溴的含量为0.12~69.66μg/g,因其对数值呈正态分布,故可用其几何平均值(7.04μg/g)表征中国煤中溴的含量,该值低于大多数其他国家煤中溴的平均含量,和日本煤中溴的平均值(7.10μg/g)较为接近。按煤中溴的平均值,中国13个省市小于5μg/g;9个省为5~15μg/g;5个省市高于15μg/g。根据煤的变质程度,中国煤中溴含量按照烟煤、无烟煤、褐煤、次烟煤顺序依次下降;根据成煤地质年代,按早石炭纪、新近纪、晚石炭纪、早二叠纪、中侏罗纪、晚三叠纪、早侏罗纪、晚侏罗纪、古近纪、中石炭纪依次下降;根据聚煤区,按西北、华北、华南、滇藏和东北聚煤区依次下降。中国煤中溴的分布受多种因素的影响,任何单一因素和其没有密切的相关性。     

Factors determining the reactivity of the bromine atom toward haloalkanes

Experimental data concerning reactions of the bromine atoms with haloalkanes and carbonyl compounds (25 reactions) have been analyzed within the intersecting parabolas model. The following factors have an effect on the activation energy of these reactions: enthalpy of reaction, triplet repulsion, electronegativity of reaction center atoms, dipole–dipole and multidipole interactions of the reaction center with polar groups, and the interaction of π electrons with electrons of the reaction center. The increments characterizing the contribution from each factor to the activation energy of the reaction have been calculated. The increment ΔEμ, which characterizes the dipole–dipole interaction in the transition state, and the dipole moment of the polar group (μ) are correlated by the following empirical equation: ln(ΔE _μ/Σμ) = ?0.14 + 0.47(ΔE _μ/Σμ) ? 0.024(ΔE _μ/Σμ)².