A simple device for continuous and selective detection of water vapour evolved during thermal decomposition reactions

A technique developed for the continuous and selective detection of water vapour formed during thermal decomposition reactions is described. The device can be connected to different types of thermoanalytical instruments without any difficulties. The detector can closely follow changes in the amount of water released during decomposition reactions, with negligible time delay. The signal curves obtained by the detector can be compared to the simultaneously recorded thermoanalytical curves and used to determine the step in which the water was released. The device as a free standing unit can be used to detect water plugs in different gas flows as well.     

Vibrational spectra and infrared dichroism of tetraphenyl-silane,Ph4Si. II.

Vibrational spectra of Ph₄Si have been studied from 600 to 20 cm^?1 in solution, in the melt and in the crystalline state. The assignments proposed for the substituent sensitive benzene ring vibrations, for the skeletal bending modes and ring librations have been supported by polarized IR and Raman measurements. The crystal spectra are interpreted on the basis of the S₄ site symmetry of the molecules in the crystal. Two skeletal bending and four ring librational modes are supposed to appear below 120 cm^?1, in the range of the lattice vibrations.     

The mechanism of thermal decomposition of Co(NO3)2 · 2H2O

The mechanism of thermal decomposition of Co(NO₃)₂ · 2H₂O was found to involve stages in which Co(NO₃)₃ and Co₂O₃ · H₂O are formed both of which decompose to Co₃O₄. During the process, the total cobalt enters the +3 oxidation state, which is consistent with the results reported by Mehandjiev [2].

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Zusammenfassung Es wurde gefunden, daß der Zersetzungsmechanismus von Co(NO₃)₂ · 2H₂O Schritte umfaßt, bei denen Co(NO₃)₃ sowie Co₂O₃ · H₂O gebildet werden, beides weiterzerfallend zu Co₃O₄. Während des Vorganges erreicht das Gesamtkobalt die Oxidationsstufe +3, was mit Ergebnissen von Mehandjiev übereinstimmt [2].

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, , CO₃O₄. , .

     

Selenium speciation by coupling vesicle mediated HPLC with off-line ETAAS and on-line focused microwave digestion HG-AAS detection

A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C(18) reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 microg/L of Se. The detection limit using HPLC-"on line" focused microwave digestion-HG-AAS has been found to be 1 microg/L of Se, with a precision (repeatability) better than +/- 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes.     

Reflectivity and transmitivity of a spatially dispersive crystal

The reflectivity and transmitivity of a spatially dispersive crystal for S-polarized incident light are calculated for a microscopical model in which the interaction among the crystal planes is assumed to fall exponentially with distance. The angle of incidence is arbitrary and the deduced formulae are valid from X-ray to the visible light region. The generalization to the more complicated models is briefly discussed. For solving the problem an algebraic formulation of the Ewald dynamical theory of diffraction is used.     

The Menšov-Paley theorem and related results for double orthogonal series

клАссИЧЕскИЕ тЕОРЕМ ы Ф. РИссА, шлИ И МЕНьшО ВА (сМ., НАпРИМЕР, [3. стР. 102, 121 И 189]) РАспРОстРАНьУтсь, И пРИ ЁтОМ В ОБОБЩЕННОИ пОстАНОВкЕ МАРпИНкЕ ВИЧА И жИгМУНДА [1], с ОДНОМЕРНОгО НА ДВУМ ЕРНыИ слУЧАИ. пУсть {?_i(x)} (i=1, 2,...) И (ψ_k(y) (k=1, 2,...) — ДВЕ сИстЕМы ФУНкцИИ, ОРтО НОРМИРОВАННыЕ НА (НЕ О БьжАтЕльНО кОНЕЧНых) ИНтЕРВАлАх (А, ь) И (с, d), сООтВЕтстВЕННО. пР ЕДпОлАгАЕтсь, ЧтО ∥?_i¦|_v≦M_i И ψ_{k v}≦N_k Дль НЕкОтОРОгОv>2, гДЕМ _iИN _k кОНЕЧНы. ИжУ Ч АУтсь сВОИстВА схОДИ МОстИ ДВОИНых РьДОВ \(\mathop \Sigma \limits_{\iota = 1}^\infty \mathop \Sigma \limits_{\kappa = 1}^\infty c_{ik} \varphi _i (x)\psi _k (y).\) ОсНОВНОИ РЕжУльтАт с ОстОИт В слЕДУУЩЕМ Ут ВЕРжДЕНИИ. тЕОРЕМА 5. пУсть 2u ВыпО лНЕНО УслОВИЕ (3.2).ЕслИ Р ьД (3.3)схОДИтсь, тО РьД (1.16)схОДИтсь пОЧтИ ВсУД У пРИ пРОИжВОльНОИ пЕРЕстАНОВкЕ ЕгО ЧлЕ НОВ. ЕслИ (1.17) —пРОИжВОл ьНАь пЕРЕстАНОВкА РьДА (1.16),mО ВыпОлНЕНА ОцЕНкА (3.4),пР ИЧЕМ ВЕлИЧИНА Ag _q,v ^* жАВИсИт тОлькО От q И v. тЕОРЕМА 5 Дльv=∞ ьВльЕт сь ДВУМЕРНыМ АНАлОгО М тЕОРЕМы МЕНьшОВА—пЁлИ.     

Rapid spectrophotometric determination of chlorate with dimedone bisthiosemicarbazone monohydrochloride

Summary Dimedone bisthiosemicarbazone monohydrochloride has been examined to evaluate its usefulness as a reagent for rapid and sensitive Spectrophotometric determination of chlorate (0.5–5.0 ppm) by oxidation of the reagent in 70% perchloric acid medium and measurement of the yellow product. The molar absorptivity at 417 nm is 1.86×10⁴ l·mole^–1·cm^–1. The relative standard deviation is 1.6% for 2.5 ppm of chlorate.

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Spektropbotometrische Bestimmung von Chlorat mit Dimedonbisthiosemicarbazon-monocblorhydrat (I)

Zusammenfassung Die Verwendbarkeit von I als Reagens für die rasche und empfindliche spektrophotometrische Bestimmung von 0,5–5,0 ppm Chlorat durch Oxydation von I in 70%iger Perchlorsäure und Messung des gelben Reaktionsproduktes wurde untersucht. Die molare Absorptivität bei 417 nm beträgt 1,86×10⁴ l·mol^–1·cm^–1. Die relative Standardabweichung beträgt 1,6% für 2,5 ppm Chlorat.

     

Iron(III)-catalyzed Prins-type cyclization using homopropargylic alcohol: a method for the synthesis of 2-alkyl-4-halo-5,6-dihydro-2H-pyrans

[reaction: see text] A new Prins-type cyclization between homopropargylic alcohol and aldehydes in the presence of FeX(3) to obtain 2-alkyl-4-halo-5,6-dihydro-2H-pyrans in good yield is described. Osmium-catalyzed cis dihydroxylation provided direct access to trans-2-alkyl-3-hydroxy-tetrahydro-pyran-4-ones. Anhydrous ferric halides are also shown to be excellent catalysts for the standard Prins cyclization using homoallylic alcohol. Isolation of an intermediate acetal provides substantiation of a proposed mechanism.     

三芳基膦配体的合成研究

从间溴苯酚出发, 利用新的合成方法经五步反应合成了一系列具有不同烷氧基的芳基膦配体. 改进后的方法可方便地通用于在苯环上具有各种不同基团基的膦配体衍生物的合成, 且有原料易得、操作简单、产率较高的优点.