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].

---

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].

---

, , 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.

---

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.     

A density functional theory study on the electrocyclization of 1,2,4,6-heptatetraene analogues: converting a pericyclic to a pseudopericyclic reaction

A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth.     

The group identification of organic compounds by means of thin-layer chromatography

The group identification method was presented based on the constant differences ΔR_f and ΔR_M, calculated from the chromatographic parameters obtained in two different mobile phases. The applicability of this method was proved with higher aliphatic alcohols, acids, and esters.