Multicomponent analysis with a computerized flow injection system using LED photometric detection

An original computer-controlled solid-state photometer has been developed and its potential for simultaneous multicomponent flow-injection analysis of binary and ternary mixtures is demonstrated. The device is simple in construction. Its principle of operation is based on rapid sequential measurements of the absorbance of the complexes formed by the analytes with chromogenic reagents at the wavelengths corresponding to the emission maxima of three light emitting diodes (563, 580 and 638 nm).     

Note on a theoretical interpretation of the isotopic ratio vOH/vOD versus vOH in isotopically diluted HDO molecules in solid hydrates

A simple intra- and inter-molecular potential for water molecules engaged in hydrogen bonding has been used in a one-dimensional approximation for a theoretical interpretation of the experimental correlation $\text{v}$_OH/$\text{v}$_OD versus $\text{v}$_OH in solid hydrates. The variation in the equilibrium OH(D) distance has also been considered.     

Asymmetric deformation of bubble shape: cause or effect of vortex-shedding?

Two perpendicular projections of rising bubbles were observed in counter-current downstream diverging flow. Evidently, the bubbles did not enter the boundary layer at the channel wall and a plug liquid flow assumption was acceptable in our experimental equipment. This confirmed that the experiment was appropriate for simulation of bubble rises in a quiescent liquid column. Recent data obtained by a high-speed camera permitted recording over a period of 60 s. Image analysis by a tailor-made program provided a time-series of quantities related to the position, size, and shape of bubbles. In addition to determination of the aspect ratio of the equivalent oblate ellipsoid, deviation from this shape was investigated in respect of the difference between the bubble’s centre of mass and the geometrical centre of bubble projection. Autocorrelation of the data indicated that the bubble inclination oscillated harmonically with a frequency of 5–10 Hz; cross correlation showed that the horizontal shift of the centre of mass, as well as the horizontal velocity, increased with increasing bubble inclination, and the vertical shift of the centre of mass increased with an increases in the absolute value of the bubble inclination. There is no significant phase shift in the oscillation of these quantities. The bulky bottom side of the bubbles is in accordance with the model of bubble oscillation induced by instability of the equilibrium of gravity and surface tension forces. The oscillation frequency dependence on surface forces (Eötvös number) is evident, while viscosity does not play a significant role in low-viscosity liquids. Therefore, vortex-shedding is more likely to be an effect of the oscillation and not its cause.     

Syntheses with organoboranes. IX. Vinyl- and 1-alkenyldichloroboranes as ethylene and 1-alkene equivalents for the Diels–Alder reaction

Vinyl- and 1-alkenyldichloroboranes were used as dienophiles for the Diels–Alder reaction with representative aliphatic and cyclic 1,3-dienes. The organoborane adducts were transformed into the corresponding olefins either by protonolysis or by oxidation–mesylation–reduction. Direct protonolysis of the adducts gave in most cases mixtures of olefins whereas the reduction of mesylates with lithium triethylborohydride produced pure olefins in good yields.     

Silicate Xerogels with Dopant-Induced Chirality

A series of silicate xerogels with entrapped chiral amino acids have been obtained via sol-gel technology. The transparent, glassy samples obtained exhibit chirality in the bulk due to the presence of the entrapped asymmetric molecules. Measurements of the optical activity of the doped xerogel samples revealed that the entrapment did not significantly influence the optical activity observed for liquid solutions of the amino acids. Thus, the sol-gel method enables the preparation of amorphous optical materials exhibiting properties of strictly spatially defined molecular systems. Apart from the obvious optical applications, such porous materials with asymmetric centers might find interesting applications in chiral chemical syntheses and separations.     

Simultaneous determination of hydrogen as its iodine equivalent and of nitrogen by a volumetric method

Summary The method developed for simultaneous determination of hydrogen (by means of an equivalent amount of iodine) and of nitrogen by a volumetric method, is based on a flash combustion technique in a stream of CO₂ (100 ml/min) with controlled addition of O₂ (20%). Hydrogen is determined by conversion of water into hydrogen chloride on anhydrous magnesium chloride heated at 600–650° C, and reaction of the hydrogen chloride with Ag₂OI₂ at 220° C to yield iodine, which is collected on silver and weighed. The precision of the determination of hydrogen is excellent, the standard deviation being 0.008–0.017% abs., about a tenth of that obtained by the classical methods. The error in the determination of hydrogen was ±0.006% abs.

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Gleichzeitige Bestimmung von Wasserstoff als dessen Jodäquivalent und von Stickstoff auf volumetrischem Wege

Zusammenfassung Die entwickelte Methode zur gleichzeitigen Bestimmung von Wasserstoff in Form seines Jodäquivalents und von Stickstoff auf gasvolumetrischem Wege beruht auf der Entflammungsmineralisation im CO₂-Strom (100 cm³/min) mit kontrolliertem Zusatz von O₂ (20%). Der Gasstrom wird zusätzlich über P₂O₅ getrocknet. Die dem Wasserstoff äquivalente Jodmenge wird an metallischem Silber gebunden und gravimetrisch bestimmt, wobei Wasser bei 600–650° C mit Magnesiumchlorid in Chlorwasserstoff übergeführt wird, der nachfolgend bei 220° C mit Ag₂Oj₂ zu Jod umgesetzt wird. Für Verbindungen, die neben C, H, N und O auch Br, Cl, P und S enthalten, werden Wasserstoffresultate mit hoher Präzision erzielt:s _H beträgt 0,008 bis 0,017% absolut und ist etwa 10mal kleiner als bei den üblichen, klassischen Methoden. Die Genauigkeit der Wasserstoffbestimmung entspricht einem mittleren Fehler=±0,006% absolut. Die Resultate für den Wasserstoff und Stickstoff verlangen eine Blindwertkorrektur.

     

Matrix elements for internal conversion

The usual separation of internal conversion matrix elements into a momentum integral of the promoting modes and an overlap integral of the accepting mode is shown to introduce large errors. The proper procedure leads to the replacement of Franck-Condon factors by integrals involving the square root of an energy operator.     

The synthesis of 3,6-diamino-2,3,4,6-tetradeoxy-dl-threo-hexopyranose derivatives,substrates for the synthesis of negamycin

Three synthetic routes to derivatives of 3,6 - diamino - 2,3,4,6 - tetradeoxy - DL - threo - hexopyranose were investigated. Addition of sodium azide in acetic acid to 6 - phthalimido - 5,6 - dihydro - 2 - pyrone gave 4-azido compound (7) of the erythro configuration. From methyl 2,4 - dideoxy - β -dl- erythro - hexopyranoside threo 4 - phthalimido - 6 - phthalimidomethyl - tetrahydro - 2 - pyrone (17) was obtained in three steps in low overall yield. Addition of sodium azide in acetic acid to butyl 6 - oxo - 2 - hydroxy - hex - 4 - enoate followed by methylation, amonolysis of the ester group, and reduction gave methyl 3,6 - diacetamido - 2,3,4,6 - tetradeoxy - α - DL - threo - hexopyranoside (26).     

Formation of the radical-cation of monomer in the photoinduced polymerization of isobutylene in the presence of SnCl4

Spectra of isobutylene with SnCl₄ were studied at the temperature of 113°K in the dark and under illumination. Radical-cations of isobutylene are formed by irradiation of the isobutylene–SnCl₄ mixture in n-heptane substantially more slowly than in the isobutylene–TiCl₄ mixture. Polymerization of isobutylene occurs after increasing the temperature up to the melting point of this mixture. The yield of polymer depends on the duration of preirradiation, while the molecular weight of polyisobutylene (M _η) does not depend on the preirradiation of reaction mixture.     

Nitrate ion association with Nd3+

The overall stability constantsK ₁ andK ₂ of NdNO ₃ ²⁺ and Nd(NO₃) ₂ ⁺ complexes were determined (K ₁=1.77;K ₂=1.28) using an extraction method with tri-n-butyl phosphate as the extractant. The ratio ₁/₂ of the stepwise stability constants is discussed. It was established that the Nd(NO₃) ₂ ⁺ complex was an outer-sphere ion pair.

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Die Assoziation von Nitrat-Ion mit Nd³⁺

Zusammenfassung Mittels einer Extraktionsmethode wurden die StabilitätskonstantenK ₁ undK ₂ von NdNO ₃ ²⁺ - und Nd(NO₃)⁺-Komplexen bestimmt (K ₁=1.77;K ₂=1.28; Tri-n-butylphosphat als Extraktionsmittel). Das Verhältnis ₁/₂ der stufenweisen Stabilitätskonstanten wird diskutiert. Es stellte sich heraus, daß der Nd(NO₃)⁺-Komplex als ein Outer-Shere-Ionenpaar vorliegt.