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  • oxidation
  • Springer  (26)
  • American Institute of Physics (AIP)
  • American Meteorological Society
  • Wiley
  • 2000-2004
  • 1995-1999
  • 1990-1994  (26)
  • 1965-1969
  • 1993  (26)
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Verlag/Herausgeber
  • Springer  (26)
  • American Institute of Physics (AIP)
  • American Meteorological Society
  • Wiley
  • Wiley-Blackwell  (4)
Erscheinungszeitraum
  • 2000-2004
  • 1995-1999
  • 1990-1994  (26)
  • 1965-1969
Jahr
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Journal of polymers and the environment 1 (1993), S. 275-279 
    ISSN: 1572-8900
    Schlagwort(e): Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene (ABS) ; ABS/polycarbonate blend
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Energietechnik , Maschinenbau
    Notizen: Abstract The thermal oxidative stability of various ABS/PC compounds was studied by means of the chemiluminescence technique. Similarly to pure ABS, Irganox 1076 and Irganox MD 1024 perform as moderate antioxidants in ABS/PC and (ABS/PC + lubricant) blends. Neither Tinuvin 144, Irgaphos 168, nor their mixture affects the durability of the ABS/PC blend. At the same time, (Irgaphos 168 + Tinuvin 144) in combination with Irganoxes was found to provide a noticeable enhancement in durability to the (ABS/PC + lubricant) system. Titanium dioxide pigments by themselves have only a slight influence on the oxidative stability of the ABS/PC blend. Durability of the (ABS/PC + pigment) and (ABS/PC + lubricant) systems was found to be the same and the overall protective effect of Irganox 1076 was similar in both the (ABS/PC + lubricant) and the (ABS/PC + lubricant + pigment) systems. Certain modifiers significantly improve the durability of the ABS/PC compounds, although their function may differ in the systems with and without pigments.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1572-8900
    Schlagwort(e): Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene (ABS)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Energietechnik , Maschinenbau
    Notizen: Abstract The influence of lubricants, UV stabilizers, antioxidants, and metal deactivators on the resistance of ABS to thermal oxidation was studied by means of the chemiluminescence technique. Neither of the additives seems to affect significantly the induction period of oxidation. At the same time, the influence of various additives on the oxidation rate constant is remarkably different: the introduction of lubricants and UV stabilizers increases its value, while antioxidants and metal deactivators have the opposite effect. For the particular systems studied durability is decreased in samples containing the lubricant and UV stabilizers and increased in samples stabilized with the antioxidant and metal deactivator.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1572-879X
    Schlagwort(e): Methane ; formaldehyde ; oxidation ; vanadium oxide ; silica
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Methane oxidation to formaldehyde was studied over a vanadium oxide catalyst supported on silica at 630 °C using the technique known as temporal analysis of products with sequential pulsing of methane and oxygen. This work shows that methane interacts very weakly and oxygen very strongly with the catalyst surface and it is concluded that the initial activation of methane involves an adsorbed oxygen species. Methyl radicals formed in the first step subsequently extract lattice oxygen to yield formaldehyde.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Nutrient cycling in agroecosystems 35 (1993), S. 101-114 
    ISSN: 1573-0867
    Schlagwort(e): Elemental sulfur ; oxidation ; S fertilizers ; thiobacilli ; heterotrophic S-oxidizers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract The use of elemental sulfur (S0) to alleviate widespread S deficiencies in agricultural soils is limited by the unpredictability of its oxidation to plant available sulfate. Here we review the biological, fertilizer and soil-related factors that control S0 oxidation. Sulfur oxidation in soil is mediated primarily by microorganisms, and thus it is the size, composition and activity of the microbial community which dictate oxidation rates. Because S0 oxidation is a biological process, it is strongly influenced by factors directly affecting microbial activity including soil temperature, water potential, and aeration. In many soils these factors represent the primary constraints to S0 oxidation. Oxidation is also influenced by the effective surface area of the S exposed to microbial activity. Thus oxidation is favored by reducing the particle size and abundant populations of heterotrophic bacteria and fungi capable of oxidizing S0, thus the availability of organic substrates from residue additions or root exudates may also affect S oxidation. Previous application of S0 may increase oxidation rates in many soils, presumably by stimulating S0 oxidizing populations. The large number of factors that govern S0 oxidation account for the variability in oxidation rates among soils, climatic regions, and agronomic practices. Many of these factors are subject to agronomic control, however, and it should be possible to devise S fertilizer strategies that exploit the slow release characteristics of S0 to meet crop demands efficiently in a variety of conditions.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Nutrient cycling in agroecosystems 35 (1993), S. 115-126 
    ISSN: 1573-0867
    Schlagwort(e): Elemental sulfur ; shape ; size ; size distribution ; model ; oxidation ; rate ; soils
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Direct and recursive estimation models for the oxidation rate of elemental sulfur (S°) in soil have been proposed, both essentially based on a constant oxidation rate per unit area of exposed surface. Fertilizer S° is taken to consist largely of blocky shaped particles, i.e. having similar dimensions along three axes, which can be treated as equivalent spheres. The most important implication in applying the rate assumption to these shaped particles is that the mass at any time is related to the cube of the time. This has been verified experimentally for oxidation by thiobacilli. Although the assumption is less likely for heterotrophs, experiments involving four soils conformed to the cubic relation. Implications for the particle variables of size and size distribution have been given more limited testing. The data are generally consistent with theory, such as independence of the rate constant with particle size. Assuming an activation energy for the oxidation process implies, in addition to the above, an exponential relation of rate constant with temperature. This is supported by experiment. Values for the activation energy are approximately 85 kJ mol−1, and therefore consistent with the rate limiting step for the oxidation being a chemical or biochemical reaction, rather than a diffusion process. Because absolute rate constants are generated by the models, they are useful for examining the effects of environmental variables not hitherto included. Empirical relationships, once established, can then be included in the model, such as the quadratic relation between rate constant and soil moisture, with the maximum at approximately field capacity. The delay time (the time to reach maximum oxidation rate) was useful, together with the rate constant, for distinguishing species of oxidizing microorganisms. Typically, under optimum conditions at 25°C, thiobacilli have a delay time of several days and a rate constant of 50µg cm−2 day−1 S, while heterotrophs have a negligible delay time but a rate constant of only 5µg cm−2 day−1 S. The cubic model with a single rate constant gave a surprisingly good fit to the oxidation rate over 12 months in New Zealand pastoral soils under field conditions of varying temperature and moisture. This was attributed to the balancing effect of moisture and temperature on the rate constant under the cool temperate climate. A knowledge of the annual average soil temperature is sufficient to provide advice on the optimum particle size for S° fertilizer.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 39 (1993), S. 197-209 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; binary alloys ; two-phase alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The corrosion behavior of binary, two-phase alloys is considered in which the matrix contains mostly the less-noble metal that forms a fast-growing oxide, while the second phase is rich in a component that forms a more stable but slowly-growing oxide. It is assumed that the second phase exists as a dispersion of isolated, rod-like particles. It is further assumed that both phases form external films with no internal oxidation. It is shown that the oxidation behavior of this type of alloy depends on both the oxidation time and the size of the second-phase particles. In particular, for short oxidation times and large second-phase particles the matrix will oxidize faster than the dispersed phase, so that the dispersed particles will be only partly corroded or even incorporated into the matrix-oxide scale as unoxidized islands, forming an irregular alloy-scale interface. On the contrary, for long times and small particle sizes the two phases will tend to oxidize at approximately the same rate, leading to the formation of regular alloy-scale interfaces. The time for the transition between the two corrosion regimes depends not only on the ratio between the rate constants for the growth of the two oxides but also on the size of the dispersed-phase particles, smaller sizes producing shorter transition times. Eventually, under favorable conditions the formation of the fast-growing oxide may even stop, leading to the formation of a protective layer of the most-stable oxide.
    Materialart: Digitale Medien
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  • 7
    ISSN: 1573-4889
    Schlagwort(e): Fe-Cr-Al ; oxidation ; air ; exhaust gas ; aluminum oxide ; oxide adherence ; reactive elements
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract This work evaluated the adherence of oxide grown in air and synthetic exhaust gas on Fe-20Cr-5Al alloys containing strong sulfide-forming elements: Ca, Mg, Y, Ce, La, Ti, and Zr. Results support the theory that reactive elements provide good oxide adherence on alumina-forming materials primarily by tying up sulfur as stable Sulfides; however, other influences on adherence were found. Highly volatile elements, such as Ca and Mg, lose their sulfur-controlling ability by diffusing out of the matrix and into the growing oxide scale. Zirconium results in the growth of an extensive network of oxide pegs into the substrate which improves adherence. Titanium segregates to the alumina scale and acts as a sink for S in the matrix. In synthetic exhaust gas (N2+CO2+H2O), local oxide spalling was observed and was shown to be caused by H2O in the atmosphere. The added benefits of Ti and Zr, i.e., forming oxide pegs and sinks for S, improve adherence in this environment.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 39 (1993), S. 69-91 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium nitride ; ceramic-matrix composites ; rutile ; oxide layers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The mechanism and kinetics of high-temperature (up to 1500°C) oxidation of pressureless-sintered TiN and hot-pressed silicon nitride-TiN, alumina-TiN, aluminum nitride-TiN, and AlON-TiN ceramic composites were studied in air under isothermal and nonisothermal conditions. Analysis of the oxidation products revealed the formation of rutile in the temperature range from 600 to 1000°C. An interaction of TiO2 with the matrix and/or its oxidation products was observed at higher temperatures. The oxidation of TiN-containing composites shows different behavior depending on the temperature. The presence of fine isolated inclusions of TiN (〈30 mass %) in the silicon-nitride matrix does not change the mass gain during oxidation or increases it only slightly, as compared with a TiN-free material. For materials containing a continuous skeleton of TiN (〉30 mass %) a noticeable increase of the oxidation rate was observed.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 39 (1993), S. 155-165 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; sulfidation ; nickel alloys ; stresses
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Two alloys, Ni-20Cr and Ni-15Cr-8Fe, as wire specimens, were exposed to sulfur dioxide between 325 and 800°C, with applied external stresses (mode I). Their mechanical properties have been investigated, and the variation of their radius has been precised by conductivity measurements. For the Ni-20Cr alloy, below 550°C, the failure process combines cracking and corrosion: Cr2S3 crystals formed at the tip of the cracks facilitate their propagation. Above 550°C, no barrier effect is observed, and intergranular corrosion takes place. For the Ni-15Cr-8Fe alloy, mode-I stresses bolster intergranular corrosion.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 39 (1993), S. 211-220 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; sulfidation ; nickel alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Two nickel-base alloys, Ni-20Cr and Ni-15Cr-8Fe, in the form of wire specimens, have been exposed to 100 mbar of sulfur dioxide between 550 and 850°C. For Ni-20Cr, an outer Cr2O3 layer formed only at the beginning of the reaction, but very quickly Ni3S2 grew preferentially at the exterior by outward diffusion of nickel. The reaction rate is regulated by an external interfacial process. A barrier effect was noted near 645°C associated with the formation of NiCr2O4; a new acceleration takes place above 680°C. The external growth of Ni3S2 is attributed to the low radius of curvature of the samples. For Ni-15Cr-8Fe, the reaction mechanism is rather similar, except that no barrier effect occurred. A protective Cr2O3 layer formed above 800°C in both cases.
    Materialart: Digitale Medien
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  • 11
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 39 (1993), S. 231-261 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; single-crystal superalloys ; coating ; reactive-element effect
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Several commercial single-crystal superalloys (CMSX-2, CMSX-3, CMSX-4, CMSX-6, SRR 99) and some laboratory versions of one of them (CMSX-4) with various Y-additions were investigated concerning their oxidation resistance in air at temperatures between 800 and 1200°C. The investigations also included two materials (CMSX-6, SRR 99) with an RT-22 coating. Weight change was recorded for times of up to 1000 hr (in some cases up to 1600 hr). Oxidized coatings and substrates were characterized by metallography, SEM, and microprobe analysis. Most of the alloys showed good oxidation resistance up to 1000°C, while there was complete spalling during cooling after oxidation at 1150°C and 1200°C for the uncoated and Y-free alloys. Coated alloys were superior, however the best behavior was shown by a laboratory version of CMSX-4 containing between 10 and 60 ppm Y. Interdiffusion at 1000°C is tolerable for the coated alloys, but there was extremely rapid degradation of the coating by interdiffusion at 1200°C.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 40 (1993), S. 5-20 
    ISSN: 1573-4889
    Schlagwort(e): sheet resistance ; resistivity ; oxidation ; tantalum nitride ; thin films
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of reactively-sputtered, tantalum—nitride thin films has been studied between 473 and 773 K in air. Films with thicknesses that correspond to sheet resistances of 43, 75, and 150 Ω/□ were evaluated in this study. X-ray diffraction revealed that the films and the oxidation products were amorphous. The oxidation products were characterized with AES and XPS. The oxidation process was monitored by measuring the change in sheet resistance with time. Sheet resistance measurements were performed with a four-point probe. The oxidation kinetics can be represented by the equation ΔR/R n =k′t. ΔR/R is sheet resistance change in %, t is time, and k′ is the rate constant. The oxidation kinetics, for the thickest film, were parabolic above about 598 K, and approximately quartic below this temperature. The 75 Ω/□ films deviated from parabolic kinetics below 603 K, and approached approximate cubic kinetics at 498 K. However, the data were forced to fit parabolic kinetics with good correlation. For the thinnest film, no deviation from parabolic kinetics was observed. The rate constants obeyed the Arrhenius relation. An activation energy of 147 kJ/mole (1.52eV) was calculated, for the thickest film, during parabolic kinetics. This value is approximately equal to the activation energy obtained during quartic kinetics. A model that explains the deviation from parabolic to quartic oxidation kinetics at lower temperatures is presented. In this model, the change in resistance as a function of time was due to simultaneous change in film resistivity, as a result of oxygen dissolution into the film, and oxide-scale growth. The temperature at which this deviation occurs should be a function of film thickness.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 40 (1993), S. 109-118 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; gaseous diffusion ; hafnium carbide ; hafnia ; porosity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract A counter-current gaseous diffusion model is presented to describe the oxidation of hafnium carbide between 1200 and 1530°C. The model separates the porous hafnia scale into two gas diffusion regions separated by a flame front, where O 2 and CO react to form CO 2.In the outer region, O 2 and CO 2 counter-diffuse; in the inner region, CO 2 and CO counter-diffuse. The concentration gradients of each gaseous specie in the pores of the hafnia are determined and the rate of oxidation is calculated. A porosity of 2% and a pore radius of 0.01 μm are representative of the values observed in hafnia during the early stages of HfC oxidation. These values lead to predictions of parabolic rate constants that are close to those measured by thermogravimetric analysis. In addition, the predicted and measured parabolic rate constants are shown to have the same dependence upon temperature and oxygen partial pressure.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 40 (1993), S. 275-294 
    ISSN: 1573-4889
    Schlagwort(e): single crystal ; superalloy ; oxidation ; microstructure ; grain size ; cast and forged alloys
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract Oxidation studies have been carried out on NiCrAl-base alloys in air and air containing 1% sulphur dioxide at 1000°C. The alloys used were in the cast, forged and single-crystalline form. There was considerable difference in the oxidation behavior of the as-cast alloy and that of forged alloy, when the environment contained sulphur dioxide. In the absence of the latter, the behavior of the two alloys was not very different. The oxidation behavior of the single crystals was also very similar to that of the cast and forged alloys, when the atmosphere was oxidizing. A few single-crystalline alloys, however, underwent catastrophic oxidation when about 1% sulphur dioxide gas was present, in a manner similar to that of the cast alloy. Oxidation tests at 1000°C as well as detailed scale analysis indicated that the different microstructure, especially large difference in grain size was probably the main reason for the large difference in their oxidation behavior.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 40 (1993), S. 421-432 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; chromium ; water ; oxygen ; SIMS
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The initial oxidation of pure, polycrystalline-chromium metal with gas mixtures of oxygen-labeled water, H2 18O, and oxygen,16O2, at temperatures 300–730 K has been studied in situ with secondary ion mass spectrometry, SIMS. The fraction of O in secondary ion species: CrO+, Cr2O+, CrOH+, Cr2OH+, CrOH2 +, and Cr2OH2 + originating from water and oxygen was found. The reaction of water and oxygen in the oxygen/water gas mixture with Cr is then revealed. The dissociation of water in its reaction with Cr in such a gas mixture was analyzed. Oxide growth on cleaned Cr surfaces during the reaction with H2O, O2 and H2O/O2 gas was also studied in situ with X-ray photoelectron spectroscopy, XPS. A correlation between a chemical shift in XPS and the OH content in the oxide is discussed.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 39 (1993), S. 221-229 
    ISSN: 1573-4889
    Schlagwort(e): non-isothermal ; oxidation ; 304 stainless steel ; superficial coating ; cerium oxide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The effect of a superficially-applied, cerium-oxide coating on the non-isothermal oxidation behavior of AISI 304 stainless steel in dry air has been investigated. The heating rate employed was 3 K/min up to a final temperature of 1423 K. The reactive oxide coating not only reduced the reaction rate but also facilitated scale adhesion to the alloy substrate. Post-oxidation analyses of the alloy/scale combination using optical microscopy, SEM, EDAX, and XRD provide evidence for a changeover in the mechanism of oxide growth from the scale/gas interface to the alloy/scale interface for the coated steel.
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    Springer
    Russian chemical bulletin 42 (1993), S. 55-59 
    ISSN: 1573-9171
    Schlagwort(e): alkanes ; oxidation ; homogeneous catalysis ; hydrogen peroxide ; vanadium ; hydroxyl radicals
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Alkanes (cyclohexane, hexane, heptane isomers) are effectively oxidized in CH3CN at 20–70°C by hydrogen peroxide when catalyzed by a Bu4NVO3-pyrazine-2-carboxylic acid system. Alkyl hydroperoxide is the main product; an alcohol and a ketone or an aldehyde are also formed. Under these conditions benzene is oxidized to give phenol, while alkyl benzenes yield oxygenation products both of the ring and the side chain. It has been assumed that the interaction of H2O2 with VO3 − gives rise to generation of HO radicals and other radical-like vanadium containing species that abstract a hydrogen atom from an alkane, RH. The radical R. formed reacts with O2 to produce ROO. which is then transformed to alkyl hydroperoxide.
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  • 18
    ISSN: 1573-9171
    Schlagwort(e): bromination ; oxidation ; N-(7-methyl-5-oxo-5H-1,3,4-thiadiazolo[3,2-a]pyrimidin-2-yl)-N-phenylhydrazine ; azo-derivatives
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Synthesis of the title compound is described and its reaction with bromine is studied. This involves oxidation of the hydrazine moiety and sequential bromination of the benzene and thiadiazolopyrimidine nuclei to give, respectively, 2-(4-bromophenylazo)-7-methyl-5-oxo-5H-1, 3,4-thiadiazolo[3,2-a]pyrimidine and 6-bromo-2-(4-bromophenylazo)-7-methyl-5-oxo-5H-1, 3,4-thiadiazolo[3,2-a]pyrimidine.
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  • 19
    ISSN: 1573-9171
    Schlagwort(e): alkylurea nitroxides ; oxidation ; alkylureidooxoammonium salts ; nitrosation ; alkylnitrosoureidooxoammonium salts ; water-soluble alkylnitrosoureas
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract 4-(3-Alkylureido)-2, 2, 6, 6-tetramethylpiperidine-1-oxyls are rapidly oxidized by N2O4 or NOCl to 4-(3-alkylureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium nitrates and chlorides, which are then nitrosated to 4-(3-alkyl-3-nitrosoureido)-2, 2, 6, 6-tetramethyl-1-oxopiperidinium salts. The perchlorates of the latter were prepared by an exchange reaction with HClO4. The nitrosation of alkylureidooxoammonium salts is the first example of chemical modification of oxoammonium derivatives in which the highly reactive 〉N+=O group is inert toward the reagent.
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    Russian chemical bulletin 42 (1993), S. 1027-1031 
    ISSN: 1573-9171
    Schlagwort(e): nitroxyls ; hydrazobenzene ; reduction ; tetranitromethane ; oxidation ; kinetics ; constants ; mechanism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The values of isotropic HFS constantsa N were obtained for nitroxyl radicals (NR) of the piperidine series in hexane and water. The interrelation between rate constants for NR reduction and oxidation reactions, isotropic HFS constantsa N, inductive constants σ″ of the piperidine substituents, and electrochemical characteristics of NR were found. The dependence of the rate constants for the reduction of NR by hydrazobenzene (HB) and its oxidation by tetranitromethane (TNM) upon the Hammett type inductive constantsσ EPR, obtained using HFS constantsa N as the basis, was analyzed. The solvent effect on the reduction and oxidation reaction rate constants, the kinetic isotopic effect of the reduction reaction for a number of NR-HB systems, and alternative reaction mechanisms are considered.
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Russian chemical bulletin 42 (1993), S. 1955-1959 
    ISSN: 1573-9171
    Schlagwort(e): triphenylbismuth diacylates ; oxidation ; phenylation ; alcohols ; diols ; enols ; phenols ; amines ; aminoesters
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Triphenylbismuth diacylates, Ph3Bi(O2CR)2 (R = Me, Et, Ph, CF3, CH=CH2), are novel effective reagents for fine organic synthesis. They oxidize primary and secondary alcohols and di-tert-glycols under mild conditions to form the corresponding carbonyl compounds in high yields;O- andN-phenylate alcohols, enols, and amines; andO- ando-C-phenylate phenols.
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  • 22
    ISSN: 1573-904X
    Schlagwort(e): anti-HIV drugs ; thiocarbamate ; emulsion ; solubilization ; stabilization ; disulfide exchange ; oxidation ; parenteral formulation ; AIDS chemotherapy ; Uniroyal Jr
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The O-alkyl-N-aryl thiocarbamate, I, (2-chloro-5-[[(l-methyl-ethoxy)thioxomethyl]amino]benzoic acid, 1-methylethylester, NSC 629243, also known as Uniroyal Jr.) is an experimental anti-HIV drug with very low water solubility (1.5 µg/mL). Early clinical studies required an injectable solution at ≈15 mg/mL, representing a solubility increase of ≈104-fold. Adequate solubilization of this hydrophobic drug was achieved in 20% lipid emulsions. Extemporaneous emulsions were prepared by adding a concentrated drug solution to a commercially available parenteral emulsion. Various methods of preparation to minimize drug precipitation during its addition and enhance redissolution of precipitated drug were evaluated. The stability and mechanism(s) of decomposition of NSC 629243 in both 20% lipid emulsions and in natural oil vehicles were examined. In lipid emulsions, the shelf life at 25°C varied from 1 to 〉10 weeks, depending on the extent to which air was excluded from the preparation. The shelf life of 50 mg/mL solutions in natural oils at 25°C varied from 〈1 to 〉100 days depending on the oil and its supplier. A qualitative correlation was found between the initial rate of oxidation and the peroxide concentration in the oil. The primary degradation product in both systems was shown to be a disulfide dimer, II, formed via oxidation. Oxidation was inhibited by vacuum-sealing of emulsion formulations or incorporation of an oil-soluble thiol, thioglycolic acid (TGA), into oil formulations. TGA may inhibit oxidation by consuming free radicals or peroxide initiators or by reacting with the disulfide, II, to regenerate the starting drug.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Plant and soil 155-156 (1993), S. 379-382 
    ISSN: 1573-5036
    Schlagwort(e): elemental sulfur ; modelling ; oxidation ; sulfur
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract An elemental S oxidation model has been developed which combines a maximum S release rate with modifiers for temperature and soil moisture conditions. This model has been combined with a pasture growth and CNSP nutrient cycling model to match S oxidation rate to pasture S demand. In two Southern Australian enviroments, 100μm elemental S was superior to 200μm particles whilst in Northern Australia the 200μm particles were superior. These models can be used to match S release to plant demand.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 24
    Digitale Medien
    Digitale Medien
    Springer
    Photosynthesis research 38 (1993), S. 303-308 
    ISSN: 1573-5079
    Schlagwort(e): Mn cluster ; oxidation ; oxygen evolving complex ; potential ; protons
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract The series of complexes [Mn(IV)(X-SALPN)(μ2-O)]2, 1: X=5-OCH3; 2: X=H; 3: X=5-Cl; 4: X=3,5-diCl; 5: X=5-NO2, contain [Mn2O2]4+ cores with Mn-Mn separations of 2.7 Å. These molecules can be protonated to form [Mn(IV)(X-SALPN)(μ2-O,OH)]2 + in which a bridging oxide is protonated. The pKa values for the series of [Mn(IV)(X-SALPN)(μ2-O,OH)]2 + track linearly versus the shift in redox potential with a slope of 84 mV/pKa. This observation suggests that the [Mn2O2]4+ core can be considered as a unit in which the free energy of protonation is directly related to the ability to reduce the Mn(IV) ion. The marked sensitivity of the reduction potential to the presence of protons presents a mechanism in which an enzyme can control the oxidizing capacity of an oxo manganese cluster by the degree and timing of oxo bridge protonation.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 25
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 16 (1993), S. 189-197 
    ISSN: 1573-1111
    Schlagwort(e): calix[4]arene ; oxidation ; hemiketal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The formation of a stable calix[4]arene monohemiketal is described. X-ray crystallographic data provide conclusive evidence for the presence of a stabilizing hydrogen bond.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Interface science 1 (1993), S. 139-146 
    ISSN: 1573-2746
    Schlagwort(e): Silicon ; defects ; hyperfine interactions ; oxidation ; computer simulation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: Abstract We assess several models for the environment of the P b center (Si dangling bond center) at the interface of Si(111) with its oxide. The comparison of hyperfine constants observed with those predicted using large cluster models favors a local structure in which there is an Si-Si bond within the oxide close to the Si dangling bond. Such Si-Si bonds are also suggested by a number of other experiments and are consistent with the “reactive layer” model proposed to rationalize a range of oxidation studies.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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