Zur gruppentheoretischen Bestimmung der Atomzustände in Ligandenfeldern

Zusammenfassung Es wird vorgeschlagen, die Bezeichnungen weak-field-Methode bzw. strong-field-Methode durch (L)-Methode bzw. ()-Methode zu ersetzen.Nach einer kurzen Einführung in die ()-Methode wird mit den Mitteln der Gruppen-und Darstellungstheorie eine Formel abgeleitet, mit deren Hilfe man schnell Rasse und Multiplizität der Terme eines Komplexions in der ()-Methode angeben kann. Einige Spezialfälle dieser Formel und die systematische Bestimmung der ()-Funktionen werden erörtert.

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It is suggested that the misleading designations weak field method and strong field method be replaced by (L) method and () method, respectively.Following a brief introduction to the () method an equation is derived by group theoretical means which leads to rapid classification of the () terms. Several special cases and short cuts are discussed as well as the systematic determination of the () functions.

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Résumé Le remplacement des termes «méthode du champ faible» et «méthode du champ fort» par «méthode (L)» et «méthode ()» est proposé.Après une introduction dans la méthode () une formule est dérivée à l'aide de la théorie des groupes et des représentations, qui donne la représentation irréductible et la multiplicité des termes d'un ion complexe dans le cadre de la méthode (). Quelques cas spéciaux de cette formule et la détermination systématique des fonctions (/gG) sont discutés.

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Ich danke Herrn Professor Dr. H. Hartmann für den Hinweis auf das vorliegende Problem und der Deutsehen Forschungsgemeinschaft für ein Stipendium.     

Adsorption isotherm for a solid electrode: The link between the differential surface tension and capacitance curves

Investigation of thermodynamically equilibrium single-component adsorption from a liquid solution on a solid electrode with allowance made for elastic deformation of its surface is continued. A full electrocapillarity equation is derived from thermodynamics equations for an interphase layer in the absence of irreversible processes. Thermodynamic aspects of the Shuttleworth equation are discussed and the equation is compared with two-dimensional Murnaghan formulas for elastic isotropic media. An adsorption isotherm equation and compatibility equations that had been derived previously are examined in a special case where the derivative of a surface concentration with respect to depends solely on (=()) and a rigorous solution of these is obtained for a deformed electrode ( 0). The effect of and dimensionless electrode potential on the extreme (at an infinitely high adsorbate concentration) value of is studied. The model of two parallel capacitors is considered in detail for a general case. Owing to the use of capacitance curves for an elastically stretched electrode, a formula that expresses the differential surface tension of a nondeformed electrode through such curves is derived for the first time ever.To the memory of my motherTranslated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 20–34.Original Russian Text Copyright © 2005 by Podgaetskii.     

Ethanolysis of penta- and tetramethyldisiloxane catalyzed by aqueous hydrochloric acid

The rates of cleavage of the Si–H bond of penta- and tetramethyldisiloxane have been studied. The reaction is first order in the silane and in the dilute acid. However, at high acid concentrations, the rate of reaction is governed by the acidity function of the system: this may indicate fast reversible proton transfer from the solvent to the organosilane in the rate-determining step.

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Si–H - . . , : , .

     

Dimerization of N-methylanabasine in the presence of metallic sodium

In a study of the dimerization of N-methylanabasine in the presence of metallic sodium under conditions for the dimerization of pyridine, it was found that the reaction does not take place at room temperature while at 50–70° C it leads to the formation of,-di(1-methylpiperid-2-yl)-,-bipyridyl. Oxidation of the latter yielded 4,4-bipyridyl-5, 5-dicarboxylic acid, the decarboxylation of which gave,-bipyridyl.     

Adsorption Isotherm Accounting for the Electrode Elasticity: Special Solutions

The single-phase adsorption on a solid electrode out of a dilute solution is investigated. As a continuation of the previous paper, on the basis of the complete electrocapillarity equation, an adsorption isotherm equation is derived and supplemented by equations of compatibility of the physical quantities. The equations contain a new parameter, , which is a derivative of the dimensionless surface adsorbate concentration by the relative variation of the electrode surface area. Their solution is obtained in relation to the dimensionless charge density of the electrode surface q for the case of = (). As a result of employing a linear model for q by , the problem of determination of the unknown model functions is reduced to common differential equations that use the capacitance or estance curves as the boundary conditions. In the first case, we suggest to calculate the unknown integration parameter by the method of mathematical optimization, employing coulometric data.     

α,β-Butenolides

,-Dibromo--('-carbethoxyacetony)-^,-butenolide (I) reacts with amines in diethyl ether solution to give -bromo-amino--('-carbethoxyacetony)-^,-butenolides. Compounds n are converted to -bromo-amino--('-carbethoxyacetony)-^,-butenolides on reaction with amines. The corresponding arylhydrazones (VI and VII) are obtained by the reaction of I and II with p-nitro- and 2,4-dinitrophenylhydrazines. Compound I reacts with phenylhydrazine to give furopyridazine VIII.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 867–871, July, 1972.     

Intercalation of porphyrin (TMPyP) and copper-porphyrin into γ-zirconium phosphate

Water-soluble ,,,-tetrakis(4-N-methylpyridyl)porphine(TMPyP) was directly intercalated into -zirconium phosphate (-ZrP) with expansion of the interlayer distance from 12.3 to a maximum of 17.2 Å, indicating parallel orientation of porphyrin to the layer of -ZrP. Diffuse reflectance spectra of the intercalate shows that the porphyrin is protonated in the interlayer space. Uptake of Cu²⁺ ions into the porphyrin intercalate takes place with further increase in the interlayer distance. It was observed that TMPyP metalated Cu²⁺ in -ZrP. Copper porphyrin can also be taken up quite easily and an interlayer spacing of 18.6 Å is attained.     

A new improved expression for gamma-ray detection efficiency of Ge(Li) detectors

In the present paper, a new improved expression for -ray detection efficiency of Ge(Li) detectors, ⁰ , is given. It is represented as a continuous function of x (viz. E ^–1) with a maximum and decreases very rapidly to a small positive value as -ray energy, E, drops to 40 keV or lower, but slowly as E rises to 1.7 MeV or higher. Since it can well represent the whole physical process of the -ray detection, this expression may be one of the simplest and most precise representations, for ⁰ at the present time.     

Catalytic phosphorylation of polyfluoroalkanols. 14. Synthesis and diastereomeric conversion of aryl(α-polyfluoroalkylbenzyl) chlorophosphates

Aryl(-polyfluoroalkylbenzyl) chlorophosphates are formed upon catalytic phosphorylation of -polyfluoroalkylbenzyl alcohols with excess aryl dichlorophosphates. Reaction stereochemistry is under thermodynamic control; the product aryl(-polyfluoroalkylbenzyl) chlorophosphates consist of equilibrium mixtures of diastereomers with a statistical (11) ratio of components. Diastereomeric interconversions of aryl(-polyfluoroalkylbenzyl) chlorophosphates occur both in the melt (or in solution) as well as in the crystalline state, but in opposite direction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 433–441, February, 1990.     

Wirkung von γ- und β-Strahlung auf Hefe und deren Nucleinsäurevorstufen

Zusammenfassung Das Überleben der Hefezellen nach - und -Bestrahlung wurde durch das Koloniebildungsvermögen ermittelt; bei gleicher Dosis und Dosisleistung wurden nur schwach unterschiedliche Effekte festgestellt. Das Nucleotidverteilungsmuster zeigte nach -Bestrahlung mit 300 000 rad größere quantitative Änderungen als nach -Bestrahlung. Die Konzentrationen an Nucleosidtriphosphaten war nach -Bestrahlung stärker herabgesetzt.Mit 5 AbbildungenLeiter: Prof. Dr.K. Kaindl.     

Studies in the area of 2,3′-biquinolyl. 1. Arylation and hetarylation of 2,3′-biquinolyl dianion

The 2,3-biquinolyl dianion, when reacting with aryl- and hetaryl halides, forms arylation products at the 4 position, and treatment of these products with alkyl halides or water yields 1-alkyl-4-aryl-1,4-dihydro-2,3-biquinolyls or 4-aryl-1,4-dihydro-2,3-biquinolyls, respectively. Oxidation of the latter yields 4-aryl-2,3-biquinolyls. The cation dependence of the arylation reaction is demonstrated.Stavropol' State University, Stavropol' 355009. Russian Chemical Engineering University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1094–1099, August, 1997.     

Adsorption characteristics of a Hungarian natural mordenite and its acid treated derivatives

A mordenite-containing rock from the Tokaj-mountains was investigated. The effect of the treatment with hydrochloric acid solutions of various molarity was established. From gas adsorption measurements, scanning electron microscopic investigations and measurements with a mercury porosimeter conclusions were drawn on the changes caused by acid treatment. Slight changes in the texture were found, but no damage in the crystal structure could be observed.

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- . . , - , , . - .

     

Synthesis of Cyclic Glycerol Ether Cyclodextrin Derivatives and Investigation of their Binding Properties with Drugs

Epichlorohydrin was reacted with cyclodextrins to form the non-cyclic and cyclic glycerol ethers of - and -cyclodextrin (abbreviated as glyc-CD). Cyclic substitution extends the cyclodextrin cavity in a way that is as rigid and non-polar as the cavity of the parent cyclodextrin. Derivatives with extended cavities should better accommodate large or odd shaped molecules. The binding of drugs to the new cyclodextrin derivatives was investigated, through degradation rate studies and solubilization studies, and compared to that of -cyclodextrin, -cyclodextrin and hydroxypropyl--cyclodextrin. The inclusion binding of small molecules such as acetazolamide, ethoxyzolamide and chlorambucil, in the glyc-CDs was either increased or decreased compared to the other cyclodextrins. However, larger molecules, such as indomethacin and hydrocortisone, always bound better to the glyc-CDs with up to 180% increase in the stability constant. The degradation rate within the cyclodextrin cavity was not affected by the above derivation.     

Effect of traces of water vapor on the rate of ammonia decomposition on polycrystalline platinum

The influence of small (lower than 0.02) molar fractions of water on the rate of ammonia decomposition on platinum wires was studied for ammonia pressures varying between 6.7 and 93.3 kPa and temperatures between 800 and 1700 K. The presence of water strongly inhibited the rate of reaction in all experiments.

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( 0,02) , 6,7 93,3 , 800 1700 K. .

     

Heteropolyacids as catalysts for synthesis of methyl tert-butyl ether

The influence of the composition and structure of heteropolyacids (HPA) on their catalytic activity in the liquid phase synthesis of methyl tert-butyl ether (MTBE) at 42 °C has been studied. The activity of HPA is compared with that of other acid catalysts. The most active are HPA's of the Dawson structure, then come HPA's of the Keggin and Dexter-Silverton structures. HPA salts have low activity in the synthesis of MTBE.

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() () 42°C. . , -. .

     

Phase-fixed double-group 3-Γ symbols. II. General features of double groups and their 3-Γ symbols

Following a general exposition of the theory of 3- symbols [1], we now focus on the particular features encountered when dealing with double groups of (proper as well as improper) point groups.The paper starts with a brief outline of the definition of double groups adopted in the present work. After this, some properties of double group 3- symbols are discussed which are independent of the way the 3- symbols have been constructed. The main part of the paper then deals with the actual generation of 3- symbols for the non-commutative double groups.In the approach described, the 3- symbols become determined in part by adaption of the standard matrix irreps to subgroup hierarchies and then completely, phases included, by the specification of standard basis functions (or, equivalently, standard subduction coefficients).     

Transition metal-chalcogen systems,VII.: The iron-selenium phase diagram

The binary iron-selenium system was investigated by thermoanalytical and isopiestic methods and by X-ray analysis. Combining all results a temperature-concentration diagram was constructed from 20 to 66 at% Se and between 623 and 1,373 K. Two compounds and several NiAs-related structures could be identified. Tetragonal -FeSe with a narrow stability range between 49.0 and 49.4 at% Se at 653 K decomposes by a peritectoid reaction at 730 K. The NiAs-related structures Fe_1-x Se have a wide range of homogeneity from 51.5 to 58.5 at% Se at 823 K. The iron-rich hexagonal -phase extends, from 51.5 to 54.3 at% Se, and transforms to a high temperature modification of unknown structure with a maximum transformation temperature of 1,338 K at 52.8 at% Se. The congruent melting point of the -phase is located at 1,351 K and 52.0 at% Se. At 54 at% Se the -phase undergoes a -transformation to the monoclinic -phase which is stable between 54.3 and 54.6 at% Se. Between 54.6 and 56.4 at% Se two very similar monoclinic phases coexist: the -and the -phase with similara- andb-axes but a simplec- and a doublec-axis, resp. Between 56.4 and 58.5 at% Se the -phase is stable. Orthorhombic -FeSe₂ (marcasite structure) with a very narrow range of homogeneity at 66.6, at% Se decomposes peritectically at 858 K. On the iron-rich side there are three invariant equilibria at high temperatures: a monotectic at 1,234 K and 46.5 at% Se, a eutectic at 1,215 K and 5.5 at% Se, and a eutectoid at 1,149 K. On the selenium-rich side there is a eutectoid at 1,122 K, a monotectic at 1,068 K and 71.5 at% Se, and a peritectic at 1,001 K.

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Übergangsmetall-Chalcogen-Systeme, 7. Mitt.: Das Eisen-Selen-Phasen-Diagramm

Zusammenfassung Das Zweistoffsystem Eisen-Selen wurde thermisch, röntgenographisch und isopiestisch untersucht. Aus den Ergebnissen konnte dasT-x-Zustands-diagramm für den Bereich von 20 bis 66 At%Se und von 623 bis 1 373 K erstellt werden. Zwei Verbindungen und einige, NiAs-ähnliche Strukturen konnten identifiziert werden. Die tetragonale -Phase FeSe besitzt bei 653 K eine schmale Phasenbreite von 49,0 bis 49,4 At%Se und zerfällt peritektoidisch bei 730 K. Die NiAs-ähnlichen Strukturen Fe_1-x Se haben bei 823 K einen breiten Homogenitätsbereich von 51,5 bis 58,5 At%Se. Die eisenreiche hexagonale -Phase reicht von 51,5 bis 54,3 At%Se und wandelt sich bei 1 338 K und 52,8 At%Se in eine Hochtemperaturmodifikation mit unbekannter Struktur, die -Phase, um, deren kongruenter Schmelzpunkt bei 52,0 At%Se und 1 351 K liegt. Bei etwa 54 At%Se geht das hexagonale Gitter infolge einer -Umwandlung in die monokline -Phase über, welche von 54,3 bis 54,6 At%Se reicht. Zwischen 54,6 und 56,4 At%Se liegt ein Zweiphasengebiet von zwei sehr ähnlichen monoklinen Phasen: die -und die -Phase mit ähnlichena- undb-Parametern, aber einfacherc-bzw. doppelterc-Achse. Die monokline -Phase befindet sich zwischen 56,4 und 58,5 At%Se. Die orthorhombische -Phase FeSe₂ mit Markasitstruktur mit einem sehr engen Homogenitätsbereich bei 66,6 At%Se zerfällt peritektisch bei 858 K. An der eisenreichen Seite gibt es bei höheren Temperaturen drei invariante Gleichgewichte: ein Eutektikum bei 5,5 At%Se und 1 215 K, ein Monotektikum bei 46,5 At%Se und 1 234 K und ein Eutektoid bei 1 149 K. An der selenreichen Seite existiert bei 71,5 At%Se und 1 068 K ein Monotektikum, bei 1 122 K ein Eutektoid und bei 1 001 K ein Peritektikum.

     

95Tc and96Tc production by (γ, xn) reactions

The⁹⁹Tc (, 3n)⁹⁶Tc and⁹⁹Tc (, 4n)⁹⁵Tc reactions were studied by irradiation of target⁹⁹Tc with bremsstrahlung from the linear electron accelerator of Tohoku University, up to 50 MeV -energy. The resulting⁹⁶Tc (4.3 d) and⁹⁵Tc (20 h) activities were determined by -spectrometry. The -flux was monitored by the⁹⁹Tc (, )^99mTc reaction. Metallic copper and gold foils were used as additional flux monitors in front of and behind the samples. Their measured radioactivity was utilized for normalizing bremsstrahlung flux calculations, in order to determine reaction cross sections. Cross sections were also determined theoretically, performing calculations in the framework of a neutron cascade evaporation model. Above the (, 3n) and (, 4n) threshold energies the neutron emission channel was supposed to be the only open channel for deexcitation following photoabsorption. The preeguilibrium contribution was considered negligible. The experimental results obtained for the integrated cross section at 30 and 50 MeV fit reasonably well the calculated curves.     

Complete synthesis of serratamolide

Summary 1. A method for the separation and quantitative determination of - and -DNP derivatives of , -DABA, ornithine, and lysine has been proposed.2. A quantitative evaluation of the N N migration in four peptides of , -DABA has been carried out.3. The degree of migration in inactive polymyxin M and the DNP-peptides from a partial hydrolyzate of the inactivated antibiotic has been determined.4. The amino acid composition of the DNP peptide B1 from a partial hydrolyzate of active DNP-polymyxin M has been established.5. The quantitative aspect of the conversion of and diketopiperazines has been studied.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 277–284, 1966     

Dynamics of nickel catalyst carbonization in heating-cooling cycles

Carbonization of a nickel catalyst for methane reforming in methane-carbon dioxide mixture has been studied in heating-cooling cycles at different heating temperatures. Thermogravimetric carbonization curves obtained with different quantities of carbon deposited on the catalyst practically coincide in a very wide range of carbon coverages. Temperature limits for the appearance and disapearance of carbon deposition centers have been determined.

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- . , , . .