Über einige Komplexboride von Übergangsmetallen

Zusammenfassung Dreistofflegierungen in dem Kombinationen {Mo, W}-{Fe, Co, Ni}-B; {V, Nb, Ta, Mo, W}-B-Al werden vornehmlich auf die Existenz von Komplexboriden hin untersucht. Die isotypen Phasen Mo₂CoB₂, Mo₂NiB₂, W₂FeB₂, W₂CoB₂ und W₂NiB₂ sind strukturell mit Mo₂FeB₂ verwandt, aber doch von dieser Phase verschieden. Gefunden werden außerdem die isotypen Phasen MoCoB und WCoB. Das Problem der -Phase wird diskutiert. In manchen Fällen tritt ein Zwischenzustand auf, der vermutlich durch Stapelfehler einer Unterzelle (c/3 in hexagonaler Aufstellung) hervorgerufen wird. Neben dem Auftreten ternärer Phasen bei Nb-B-Al und Ta-B-Al wird eine ausgeprägte Mischphasenbildung: (Nb, Al)B₂ und (Ta, Al)B₂ beobachtet. Der Dreistoff: Mo-B-Al ist durch die ternäre Phase MoBAl gekennzeichmet, ferner tritt der durch Al stabilisierte CrB-Typ auf (Mo_0,45B_0,50Al_0,05). Die Gleichgewichtsverhältnisse in denT-B-Al-Dreistoffen werden abgeschätzt.

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Alloys of the combinations {Mo, W}-{Fe, Co, Ni}-B, {V, Nb, Ta, Mo, W}-B-Al have been examined with respect to the existence of complex borides. The phases of the approximate formula Mo₂CoB₂, Mo₂NiB₂, W₂FeB₂, W₂CoB₂ and W₂NiB₂ have been found to be isotypic. They do however not correspond to Mo₂FeB₂ having U₃Si₂ structure. Two other complex borides of formula MoCoB and WCoB have been detected having the same crystal structure. The problem of the -phases which partially contain boron will be discussed considering the supposedly occurring stacking faults of a subcell unit (c=c/3 for hexagonal symmetry). Besides formation of ternary compounds for: Nb-B-Al and Ta-B-Al an extended solid solution (Nb, Al)B₂ and (Ta, Al)B₂ has been observed. The Mo-B-Al-system is characterized by the ternary phase of formula MoBAl. Mo-monoboride having CrB-type has been found to be stabilized by a small amount of Al, thus Mo_0,45B_0,50Al_0,05 being formed. The phase equilibria within the ternary systems have been established for the major part.

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Mit 4 Abbildungen     

Oxidation stability of crosslinked polyethylene. Isothermal DTA method

Isothermal differential thermal analysis has been used to study the thermooxidative stability of two grades of crosslinked polyethylene in the temperature range from 120°C to 230°C. Induction times of thermooxidative degradation were measured from 2 minutes up to 3590 hours. Oxidation Induction time and mechanical failure in oven ageing experiments coincided over the measured temperature range. The degree of crosslinking was not strongly affected by the oxidative reaction. The Arrhenius-plots of DTA results showed curvature at 150°C, so straight line extrapolations from short-term experiments at elevated temperatures to low temperatures and long times are not possible. Thermoanalytically measured residual thermooxidative stability decreased linearly with ageing time and showed great scattering of the results.

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Zusammenfassung Die isotherme Differentialthermoanalyse ist als Methode zur Abschätzung der thermooxidativen Beständigkeit von Polyolefinen seit längerem bekannt. In der vorliegenden Arbeit wird über isotherme DTA-Messungen an Proben aus vernetztem Polyäthylen im Temperaturbereich von 230°C bis 120°C berichtet, wobei Oxidationsinduktionszeiten bis zu 3590 Stunden gemessen wurden. Die Auftragung der Oxidationsinduktionszeiten in Arrhenius-Diagrammen zeigte für vernetztes Polyäthylen keine für Extrapolationszwecke geeignete Linearität des Logarithmus der Oxidationsinduktionszeiten über der reziproken absoluten Temperatur über weitere Bereiche der Meßzeiten bzw. Prüftemperaturen. Die thermoanalytisch bestimmten Oxidationsinduktionszeiten stimmten mit dem Steilabfall der Reißdehnung in Ofenalterungsversuchen überein während der über den Gelgehalt ermittelte Vernetzungsgrad vom thermooxidativen Abbau nicht signifikant beeinflußt wurde. Somit können aufwendige Ofenalterungsversuche durch experimentell einfache isotherme DTA-Versuche ersetzt werden. Die Messung der thermooxidativen Restbeständigkeit im isothermen DTA-Versuch bei erhöhter Prüftemperatur ermöglicht einen wesentlich deutlicheren Einblick in den thermooxidativen Schädigungszustand eines Polyolefins während der Induktionsperiode des thermooxidativen Abbaus als die Messungen des Vernetzungsgrades oder der Reißdehnung. Die Abnahme der thermooxidativen Restbeständigkeit erfolgt im Fall des vernetzten Polyäthylen in allen Fällen linear über der Alterungszeit.

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120–230°. 2 3590 . . . 150°, . .

     

Catalyzed Determination of Phenylalanine with a Mimic Enzyme Constructed of β-Cyclodextrain Derivant

Phenylalanine was catalyzed and determined with mimic phenylalanine oxidase constructed by the reaction of -cyclodextrin (or -CD) and m-carboxyl benzenesulfonyl chloride with iron trichloride in hydrogen peroxide. The method is simple and convenient. The linear range of this method is 0–0.8233 mmol/L, the detection limit is 8.354 mol/L, the RSD is 0.96% (n = 8), and the recovery rate is 95.8–103.5% when used to test an edulcorator (aspartame) sample.     

Isotopic hydrogen exchange in 1- and 2-aryl-5-methyltetrazoles

The rate constants for basic deuterium exchange of the methyl group (k_D) in 2-phenyl-5-methyl-tetrazole (I) and 1-aryl-5-methyltetrazole (II) and its derivatives with a polar substituent (R) in the phenyl ring were measured. The increased CH acidity of II as compared with I [k_D(II)/k_D(I)20] is in agreement with the calculated and experimental values regarding the character of the electron-density distribution in the molecules. The effect of R on the rate of deuterium exchange of the methyl group correlates with the ° constants (=3.0, r = 0.997). The results of measurement of the kinetic isotope effect during deuterium (tritium) exchange in II (k_D/k_T1.8) are discussed in connection with the peculiarities of the stepwise reaction mechanism.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No.1, pp. 127–130, January, 1978.     

Das Solvosystem Phosphoroxychlorid, 23. Mitt.: Photometrische Titrationen von Chloriden mit Eisen(III)-chlorid

Zusammenfassung Zahlreiche kovalente Chloride bilden mit FeCl₃ in POCl₃ Chloroniumtetrachloroferrate. HgCl₂, BCl₃, TiCl₄, SnCl₄ und PCl₅ geben ein Chloridion, ZnCl₂ und AlCl₃ zwei Chloridionen, letzteres zum Teil auch das dritte Chloridion an FeCl₃ ab. Die Donorstärke nimmt in der Reihe Et₄NClKCl1/2 ZnCl₂ 1/2 AlCl₃>TiCl₄>PCl₅1/3 AlCl₃[SbCl₆]^–HgCl₂ >BCl₃SnCl₄ ab. SbCl₅ ist in POCl₃ ein stärkerer Akzeptor als FeCl₃. Die Unterschiede gegenüber dem Lösungsmittel Phenylphosphoroxychlorid werden diskutiert.Mit 1 Abbildung22. Mitt.:M. Baaz, V. Gutmann undL. Hübner, Mh. Chem.91, 694 (1960).     

Oxidation of Formic and Oxalic Acids in an Electrodeless Electrochemical Reaction

Decomposition of formic and oxalic acid and of sodium formate and sodium oxalate (0.1 M solutions) in an electrodeless electrochemical reaction was studied. The oxidation kinetics was analyzed in terms of the previously developed model. The decomposition yields of formic acid and sodium formate are 0.5 and 1 molecule/(100 eV), respectively, which is comparable with the radiation-chemical decomposition yield, taking into account the installation efficiency.     

Simple screening method for the fast determination of clenbuterol in animal feeds

Summary A simple method for the determination of clenbuterol is described. It is extracted from the sample at pH 3 and then at pH 11, followed by partitioning the analyte into water at pH 3 and reextraction into ethyl acetate at pH 9. Clenbuterol is oxidized with KMnO₄ to clenbuteron for GC-determination. Recoveries for 0.01– 1.0 mg/kg were between 70% and 110% (standard deviation ±14%, n = 18).

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Eine einfache Screening-Methode zur schnellen Bestimmung von Clenbuterol in tierischen Futtermitteln

     

New palladium nanoclusters. Synthesis,structure, and catalytic properties

The reduction of palladium(ii) carboxylates Pd₃(OCOR)₆ (R = Me, Et, CHMe₂, CMe₃) with hydrogen in alcohol solutions containing 1,10-phenanthroline (phen) and subsequent oxidation with oxygen gave new palladium nanoclusters, mainly particles with a nearly spherical metal core and an average size of 18 . Based on elemental analysis, NMR, X-ray photoelectron spectroscopy, and EXAFS, nanoclusters were described by the idealized formula Pd₁₄₇phen₃₂O₆₀(OCOR)₃₀. The specimens contained up to 25% smaller 55-atomic Pd clusters with a 10 metal core. New nanoclusters catalyze hydrogenation of alkynes and alkenes, reduction of nitriles with formic acid, oxidation of aliphatic and benzylic alcohols, oxidative esterification of ethylene and propylene, and disproportionation of benzyl alcohol into toluene and benzaldehyde.     

Study of free volume parameters of polystyrenes of different molecular architecture by positron annihilation lifetime measurement

Differences of size, content and size distribution of free volumes in linear branched and three-armed polystyrenes, synthesized by radical and anionic processes, were observed by positron annihilation lifetime measurements. The temperature dependence of an average free volume radius was quite similar among polystyrenes of different architectures and molecular weight distributions. The free volume radius increased with temperature, from 0.27 nm (T:60 K) to 0.29 nm (T:260 K) and 0.30 nm (T _g:363 K), then to 0.35 nm (423 K), showing turning at and transition temperature. The free volume content decreased from 60 K to 220 K to 300 K showing peculiar minimum at 220 K to 300 K depending on the molecular shape, increased above 320 K, upto 340 to 360 K. The free volume contents decreased with an increase of molecular weight and by an addition of oligomer or plasticiser, suggesting differences in relaxation time or molecular motion between the edge and middle portions of molecular chain and filling effect of smaller molecules in free volumes, respectively. The apparent free volume fraction showed clear variations atT andT _g. Size distribution of free volumes suggested more complicated behavior of free volume upon the molecular relaxations and filling effect.     

On the use of a dead-time meter for pile-up corrections

Correction for pile-up losses in the amplifier is possible by the dead-time fraction indicator of the ADC in case of long-lived radionuclides. If the dead-time meter has been calibrated, an accuracy of 1.5% is feasible up to a dead-time fraction of 25%. The precision decreases from 1.5% at 10% dead-time fraction to 3% at a deadtime fraction of 30%.     

The composition of volatile and particulate hydrocarbons in urban air

Summary The hydrocarbon composition of the particle and gas phases in the urban atmosphere has been studied by filtration and parallel adsorption on active charcoal and polyurethane foam (PUF). Gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS) have been used for the analysis of the organic matter extracts obtained with each system. In the case of the particle and PUF samples these extracts were fractionated into aliphatic and aromatic compounds. This approach has allowed to identify up to 247 hydrocarbon molecules showing that C0–C5 alkylbenzenes are the major compounds in the charcoal extracts whereas C14–C23 n-alkanes, C0–C4 alkylnaphthalenes, C0–C4 alkylbiphenyls and C3–C5 alkylbenzenes are those predominantly found in the PUF materials. The particles essentially contain C17–C38 n-alkanes and parent polycyclic aromatic hydrocarbons (PAH). These qualitative differences are paralleled by a progressive concentration decrease from the more to the less volatile hydrocarbons. Thus, the total charcoal extracts average 80 g/m³, the PUF compounds represent 4 /m³ and the particle hydrocarbons 0.7 g/m³. These latter airborne materials are essentially composed of petrogenic residues 0.6 g/m³ (aliphatic fraction) whereas the pyrolytic PAH only involve 0.08 g/m³.     

Purification of 3-ethoxycarbonylquinuclidine and its conversion to 3-quinuclidinecarboxylic acid and 3-quinuclidinylmethanol

3-Ethoxycarbonylquinuclidine obtained by the Grob method is a mixture of 3-ethoxycarbonyl-1-azabicylo-[2.2.2]- and, according to ¹³C NMR data, 5-ethoxycarbonyl-5-azatricyclo[3.2.1.0^2,7]octanes (1621). 3-Ethoxy-carbonylquinuclidine was purified by recrystallization of the hydrochloride, hydrolyzed by water to 3-quinuclidinecarboxylic acid, and reduced by LiAlH₄ to 3-quinuclidinylmethanol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, 1509–1512, November, 1992.     

Enthalpy of Solution of Squalane in Alcohols

Enthalpy of solution at 25°C of squalane in butyl alcohols and 1-octanol is determined calorimetrically. The endothermic effect of dissolution increases in the order 1-OctOH < BuOH < i-BuOH < t-BuOH. A linear correlation is found between the enthalpies of solution of squalane and hexadecane, from which the enthalpy of solution of squalane in methanol is determined. The contributions of the cavity formation and solute-solvent interaction to the enthalpy of solution are estimated by multiple regression analysis. The enthalpy of cavity formation is only slightly dependent on the length of the main chain of an alcohol and also on the branching type, varying in the order 1-OctOH BuOH i-BuOH < MeOH s-BuOH < t-BuOH. Interaction of squalane with alcocols increases in the order MeOH < t-BuOH < BuOH < i-BuOH s-BuOH < 1-OctOH.     

Modification of Non-Hydrolytic Sol-Gel Derived Alumina by Solvent Treatments

The effect of wetting non-hydrolytic derived alumina xerogels with water and organic solvents in the 20–70°C range on the alumina's properties was investigated. Wetting with organic solvents does not affect the alumina. However, contact with water was found to change the sharp crystallization at 800°C to a continuous crystallization starting at 450°C. Water treatment for a day at room temperature (RT) followed by second calcination decreased the surface area by 10%. This decrease in surface area is less pronounced with increasing wetting periods. On the other hand water treatment at 50–70°C followed by a second calcination resulted in a surface area increase of up to 15%. Upon water treatment the total pore volume has decreased from 0.65 (cm³/gr) to 0.48 (cm³/gr) and the average pore size decreased from 6.8 nm to 4.1 nm. The Cl content was found to be uneffected by the water treatment, remaining at 2.5% wt. Wetting with water at elevated temperature (70°C) accelerated the morphological changes, eliminating the crystallization peak at 800°C in one hour. A dissolution-reprecipitation mechanism is suggested to explain the results. In addition, Mass-Spectroscopy of the effluent gas during heat treatment revealed the emission of CO₂ and water upon phase transition into -Al₂O₃, at 1150–1300°C.     

First experiments on transmutation studies of129I and237Np using relativistic protons of 3.7 GeV

First experiments on the transmutation of long-lived¹²⁹I and²³⁷Np using relativistic protons of 3.7 GeV are described. Relativistic protons generate in extended Pb-targets substancial neutron fluences. These neutrons get moderated in paraffin and are used for transmutation as follows:¹²⁹I(n,)¹³⁰I and²³⁷Np(n,)²³⁸Np. The isotopes¹³⁰I (T _1/2-12.36 h) and²³⁸Np (T _1/2=2.117 d) were identified radiochemically. One can estimate the transmutation cross-section (n,) in the given neutron field as (¹²⁹I(n,))=(10±2)b and (²³⁷Np(n,))=(140±30)b The experiments were carried out in November 1996 at the Synchrophasotron, LHE, Dubna, Russia. The investigation has been performed at the Laboratory of High Energies, JINR, Dubna.     

Non-Aqueous Capillary Electrophoresis with Indirect Photometric Detection for Direct Analysis of Pb2+, Zn2+ and Cd2+ Ions

A new approach, based on non-aqueous capillary electrophoresis separation and indirect photometric detection, was established for the determination of the transition metal ions Pb²⁺, Zn²⁺ and Cd²⁺. Under optimized conditions, the method produced baseline separation of these three metal ions. The linear range and detection limits were 1050µM, 1.9µM for Cd²⁺; 1050µM, 2.1µM for Zn²⁺; and 20100µM, 3.8µM for Pb²⁺, respectively.     

Radiolysis of nitrous oxide adsorbed on alumina ionic mechanism of radiolysis of nitrous oxide on alumina with small surface areas

A mechanism is proposed for the radiolysis of adsorbed N₂O describing the experimental dependences of the radiation-chemical yields of O _st ^– and N₂ on N₂O coverages.

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N₂O, - O _st ^– N₂ N₂O.

     

Effect of H/D-isotope substitution on the solubility and solvation thermodynamics of krypton in methanol solutions of carbamide

The solubility of gaseous krypton in CO(NH₂)₂—CH₃OH (CD₃OH) and CO(ND₂)₂—CH₃OD solutions with carbamide concentrations of up to 1.5 solvomolality units (0.026 mole fractions) was measured at 278, 288, 298, 308, and 318 K and at a partial gas pressure of 101325 Pa. The thermodynamic functions of dissolution (solvation) of krypton and the standard Setchenov coefficients were calculated. The solvation of Kr molecules increases upon deuterium substitution and with an increase in the temperature and carbamide concentration. In these solutions, specific contacts between the carbamide and methanol molecules play the predominant role.     

Insertion of 3d- and 4f-Elements into Silver Iodide

The interaction of manganese and some 4f-metals (M) with silver iodide is studied. The samples are obtained by sputtering M onto the surface of polycrystalline AgI films (0.2 m, 300 K) in a vacuum. Optical absorption in the samples is interpreted as the insertion of M ions into AgI with the formation of dopants AgI:M. A new phase with an optical bandgap of 3.7 eV emerges in the samples with elevated concentrations of La, Ce, Pr, Nd, Sm, or Dy (n _M/n _Ag 0.1). X-ray diffraction patterns for such samples with Sm correspond to structures with large interfacial distances, for example, 0.99, 0.87, 0.76, and 0.67 nm. In air, AgI forms in the samples with a new phase; this process is hindered by the sputtered protective coatings. According to optical absorption data, X-ray diffraction, and local microanalysis the Mn insertion into AgI is followed by the formation of a new phase (2Ag:Mn:4I), which may belong with solid electrolytes Ag₂MI₄, where nonmagnetic M are known (Zn, Cd, Sn, Hg, Pb).     

Reactions between ammonium sulphate and metal oxides (metal=Cr,Mn and Fe) and thermal decomposition of the products

The reactions between ammonium sulphate and three metal oxides (Cr₂O₃, MnO₂ and Fe₂O₃) were studied. It was confirmed by X-ray diffraction and chemical analysis that stable reaction intermediates were formed consecutively in the course of the reactions.These were (NH₄)₃M(SO₄)₃ and NH₄M(SO₄)₂ for Cr₂O₃ and Fe₂O₃ and (NH₄)₂Mn₂(SO₄)₃ for MnO₂. The thermal decompositions of these intermediates and of the metal sulphates were carried out. The contracting-volume equation was valid for the decomposition of all the intermediates. The Arrhenius parameters were determined.

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Zusammenfassung Es wurden die Reaktionen zwischen Ammoniumsulfat und drei Metalloxiden (Cr₂O₃, MnO₂ und Fe₂O₃) untersucht. Durch Röntgendiffraktion und chemische Analyse wurde bestätigt, dass im Verlaufe der Reaktion stabile Zwischenprodukte gebildet werden. Es handelt sich dabei um (NH₄)₃M(SO₄)₃ und NH₄M(SO₄)₂ im Falle von Cr₂O₃ und Fe₂O₃ und um (NH₄)₂Mn₂(SO₄)₃ im Falle von MnO₂. Diese Zwischenprodukte und die Metallsulfate wurden thermisch zersetzt. Die Volumenkontraktionsgleichung war für die Zersetzung all dieser Zwischenprodukte gültig. Die Arrheniusparameter wurden bestimmt.

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Cr₂O₃, MnO₂ Fe₂O₃. , . , (NH₄)₃M(SO₄)₃ NH₄M(SO₄)₂, (NH₄)₂Mn₂(SO₄)₃. . . .