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  • Articles  (124)
  • oxidation  (124)
  • Springer  (124)
  • American Chemical Society
  • 1995-1999  (124)
  • Chemistry and Pharmacology  (124)
  • Technology  (5)
  • 1
    Electronic Resource
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    Springer
    Journal of applied electrochemistry 27 (1997), S. 1275-1282 
    ISSN: 1572-8838
    Keywords: Carbon monoxide ; Pt-Ru/C catalyst ; Tafel slopes ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract CO electrooxidation on a Pt–Ru/C catalyst was investigated in sulphuric acid electrolyte. The physico-chemical properties of the Pt–Ru/C catalyst were studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The influence of temperature, CO partial pressure and proton concentration on the electrochemical oxidation rate was investigated by steady-state galvanostatic polarization measurements. The apparent activation energy decreased from 70 to 30kJmol−1 as the overpotential increased from 0.5 to 0.9V vs NHE. The reaction order with respect to carbon monoxide increased, passing from 0.4 to 1, with the increase of the overpotential from 0.5 to 0.7V vs NHE; a reaction order close to −1 with respect to the protonic concentration was observed, irrespective of the potential. Tafel slopes of about 136mVdec−1 were determined for oxidation of CO and CO/N2 mixtures.
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  • 2
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    Journal of applied electrochemistry 28 (1998), S. 607-612 
    ISSN: 1572-8838
    Keywords: SnO2 anodes ; doping ; high overvoltage anodes ; surface analysis ; oxidation ; water treatment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Doped tin dioxide electrodes have been prepared by a standard spray pyrolysis technique. The electrochemical behaviour of these electrodes has been investigated by cyclic voltammetry in sulphuric acid using the Fe2+/Fe3+ redox couple system as test reaction. Oxygen evolution has been used to study the stability of doped SnO2 electrodes. The SnO2 electrodes doped with antimony and platinum exhibit the highest stability. XPS analysis shows that the oxidation state of Sn, Sb and Pt are +4, +3 and +2, respectively, the probable species being SnO2, Sb2O3 and PtO.
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  • 3
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    Journal of polymers and the environment 3 (1995), S. 199-203 
    ISSN: 1572-8900
    Keywords: Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The thermal oxidative stability of various formulations based on emulsion-grade ABS was studied by the chemiluminescence technique. Emulsion products were found to be essentially less stable than ionic mass polymerization resins. Among the antioxidants studied, Santonox R is clearly more efficient than Irganox 1076 and Irganox 3114, and its superiority is reflected primarily in improved induction period values. The introduction of Tinuvin 770 and Tinuvin 328 UV stabilizers into emulsion resins does not change the durability of the products. In mixtures where both Irganox 1076 and UV stabilizers are present, a certain antagonistic effect was noted at high UV stabilizer concentrations.
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  • 4
    ISSN: 1572-8757
    Keywords: porous carbons ; activation ; oxidation ; surface oxygen groups ; LTPD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A styrene/divinylbenzene copolymer has been used as precursor for making porous carbons with bimodal pore size distributions (i.e., with both microporosity and mesoporosity). Pretreatment of the as-received copolymer by mild oxidation in air, significantly increased the carbon yield after carbonization. Reactivity studies of the polymer-based chars to CO2 clearly show the influences of some important factors such as carbonization temperature, heating rate, soak time on char reactivities. Bimodal porous carbons were prepared by carbonization of the preoxidized styrene/divinylbenzene copolymer in N2, followed by activation in CO2 at different temperatures to different levels of burnoff. The pore structures of the porous carbons produced have been characterized by various techniques such as gas adsorption and mercury porosimetry. The surfaces of the porous carbons produced, and a commercial carbon adsorbent, have been modified with HNO3 and H2O2 treatment at various conditions. Characterization of the surface oxygen functionality, both quantitatively and qualitatively, has been achieved using techniques such as Linear Temperature Programed Desorption (LTPD) and selective neutralization of bases.
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  • 5
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 6
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    Catalysis letters 37 (1996), S. 213-216 
    ISSN: 1572-879X
    Keywords: titanium silicalites ; oxidation ; amines ; hydrogen peroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Titanium silicalite molecular sieves, TS-1 and TS-2 having MFI and MEL structures, respectively, catalyze the oxidation of secondary amines to the corresponding hydroxylamines using hydrogen peroxide as the oxidant. Higher concentrations of H2O2 lead to further oxidation of hydroxylamine to nitrone. Diffuse reflectance spectroscopy shows the formation of a titanium peroxo complex upon addition of hydrogen peroxide to the TS-1 catalyst. The titanium peroxo complex oxidizes the substrate and reforms to a titanyl group.
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  • 7
    ISSN: 1572-879X
    Keywords: oxidation ; cyclohexene ; polyoxometalate-intercalated hydrotalcite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cyclohexene was oxidized with molecular oxygen over transition-metal-substituted polyoxometalate-intercalated hydrotalcites to produce 2-cyclohexene-1-one and 2-cyclohexene-1-ol with high selectivity under mild reaction conditions.
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  • 8
    ISSN: 1572-879X
    Keywords: palladium metal ; oxidation ; toxic organics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In water, metallic palladium was found to catalyze the deep oxidation of a wide variety of functional organics by dioxygen at 80–90°C in the presence of carbon monoxide. Several classes of organic compounds were examined: benzene, phenol and substituted phenols, aliphatic and aromatic halogenated compounds, organophosphorus, and organosulfur compounds. In every case, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 h period. Since the heterogeneous catalyst can be removed by simple filtration, simultaneous water purification and contaminant destruction becomes feasible. For those substrates that are insoluble in pure water, a mixture of water and perfluorobutyric acid was successfully employed as the solvent.
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  • 9
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    Catalysis letters 34 (1995), S. 31-40 
    ISSN: 1572-879X
    Keywords: palladium ; PdO ; alumina ; methane ; oxidation ; carbon ; XPS ; ellipsometry ; structure sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Samples of palladium supported onγ-alumina and a palladium foil were used as catalysts for methane oxidation at 550° C. The samples were quenched quickly in the reaction chamber to room temperature in flowing Ar and then transferred in vacuo for XPS analysis. Structure sensitivity was manifest from an increase in PdO stability and a decrease in carbon deposition relative to Pd with increasing particle size. The results were compared with recent ellipsometric data.
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  • 10
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    Catalysis letters 52 (1998), S. 25-29 
    ISSN: 1572-879X
    Keywords: metallosilicate ; mesoporous ; MCM-41 ; Mo-MCM-41 ; catalysis ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Mo-incorporated MCM-41 has been prepared by direct hydrothermal synthesis. XRD and N2-adsorption measurements showed the characteristics of MCM-41. IR, FT-Raman and UV-VIS DR spectroscopic analyses gave the evidences for the incorporation of Mo in the framework of MCM-41. They are found to be stable and active for cyclohexanol and cyclohexane oxidation reactions with H2O2 as oxidant. Activity of this system has been compared with that of Ti-MCM-41 and molybdena impregnated on pure siliceous MCM-41.
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  • 11
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; calcium-based catalysts ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of propane has been investigated in the presence and absence of tetrachloromethane (TCM) on calcium hydroxyapatite (CaHAp), Ca3(PO4)2, CaSO4 and CaO at 723 K. In the absence of TCM, the conversion of C3H8 on CaHAp was 7.7–9.2% during 6 h on-stream while that on Ca3(PO4)2, CaSO4 and CaO was 0.6, 0 and 0.2–0.4%, respectively. The principal products on all catalysts in the absence of TCM were CO and CO2 with small selectivities to C3H6 and C2H4 (both 5–6%) observed on CaHAp. Upon addition of TCM, the selectivity to C3H6 on all catalysts and the conversion of C3H8 on CaSO4 increased while, with increasing time-on-stream, the changes in the conversion and selectivity were dependent upon the nature of the catalysts. XPS and XRD analyses provide evidence for the presence of chlorine in the surface and/or bulk of three of the catalysts, suggesting that chlorinated species on the solids play a role in the selectivity enhancement, but the absence of chlorine from the sulphate demonstrates the dissimilarities of the catalysts in their abilities to sorb and decompose TCM.
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  • 12
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; strontium hydroxyapatite ; lead hydroxyapatite ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of methane has been investigated on lead hydroxyapatite (PbHAp), strontium hydroxyapatite (SrHAp) and their binary mixtures at 873 K. PbHAp showed no activity for the oxidation of methane, while SrHAp produced carbon monoxide selectively at 2–4% conversion. On binary mixtures of the hydroxyapatites the conversion of methane and the selectivity to C2 compounds reached values higher than those of the separate constituents of the mixture. With tetrachloromethane in the feed stream a similar synergistic effect was observed with conversions of methane and selectivities to CH3Cl higher on the binary mixtures than those on either SrHAp or PbHAp. The strontium-containing hydroxyapatite appears to play a crucial role in the activation of methane, while the presence of the lead-containing analogue is apparently required for the minimization of undesirable processes involving methyl radicals.
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  • 13
    ISSN: 1572-879X
    Keywords: fluorination ; alumina ; platinum catalysts ; oxidation ; oxidation of benzene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Platinum supported on fluorinated alumina is more active for the total oxidation of benzene than is the catalyst with the same Pt loading supported on hydrophilic unfluorinated alumina. The Pt-F/alumina catalyst contains well-dispersed small Pt particles, in contrast to Pt/alumina. The high dispersion is a consequence of a strong metal-support interaction.
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  • 14
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    Catalysis surveys from Japan 3 (1999), S. 55-60 
    ISSN: 1572-8803
    Keywords: acetic acid ; oxidation ; Pd ; heteropoly acid ; ethylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new process for acetic acid production by direct oxidation of ethylene which was established and commercialized is described. The catalyst system consisting of Pd and heteropoly acid exhibits excellent activity and selectivity. The addition of Se or Te to the catalyst system is effective to suppress the formation of carbon dioxide. This new process is applicable to a plant of a wide range of size corresponding to the local demand. Because this new process produces little waste water, it is very friendly to the environment.
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  • 15
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    Catalysis surveys from Japan 2 (1998), S. 121-132 
    ISSN: 1572-8803
    Keywords: zeolite ; metallosilicate ; atom-planting ; modification ; catalysis ; acidity ; shape-selective alkylation ; oxidation ; hydrogen peroxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Atom-planting, a useful method to prepare some metallosilicates having zeolitic structure, was proposed. By treatment of highly siliceous zeolite with metal chloride vapor at selected temperature, metal cation could be introduced into the defect sites (hydroxyl nests) of zeolite framework. By the atom-planting method, some metallosilicates which are difficult to be synthesized by hydrothermal synthesis could be prepared. The vapor phase shape-selective alkylation of ethylbenzene with ethanol, and the liquid phase selective oxidation with hydrogen peroxide on the metallosilicates prepared by atom-planting method were reviewed.
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  • 16
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    Catalysis surveys from Japan 2 (1998), S. 31-44 
    ISSN: 1572-8803
    Keywords: porous heteropoly compounds ; Pt-promoted heteropoly compounds ; shape selectivity ; water-tolerant catalyst ; hydrogenation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper attempts to review recent works on catalysis of porous heteropoly compounds. The salts of heteropolyacids having Keggin structure with large cations like Cs+ are porous materials. For Cs hydrogen salts, the pore width can be controlled by the Cs content. Cs2.5H0.5PW12O40 has the largest amount of protons on the surface among the acidic Cs salts and possesses pores with bimodal distribution in the micro and meso region. Efficient performances were demonstrated for acid-catalyzed reactions such as skeletal isomerization of η-butane in solid-gas system, alkylation and acylation in solid-liquid system, and hydrolysis and hydration in solid-water system. A microporous salt, Cs2.2H0.8PW12O40, exhibited reactant shape selectivity towards direct decomposition of esters. Furthermore, an ultramicroporous bifunctional catalyst, Pt–Cs2.1H0.9PW12O40 of which the pore width is around 5 Å, exhibits reactant shape selectivity for hydrogenation of alkenes and oxidation of hydrocarbons, and product shape selectivity for skeletal isomerization of η-butane.
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  • 17
    ISSN: 1572-879X
    Keywords: TiO2 ; heterogeneous photocatalysis ; oxidation ; substituted toluenes ; zeolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Photocatalytic oxidation of substituted toluenes was investigated on irradiated TiO2 and TiO2 combined with HY15 and HY20 zeolites. In all cases the oxidation occurred in the first step exclusively on either one substituent or the other, but never on both simultaneously. In the presence of a zeolite, photooxidation conversion was higher than that obtained without zeolite.
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  • 18
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; cobalt catalysts ; deactivation ; oxidation ; reduction ; promoters ; rhenium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of water on alumina-supported cobalt catalysts has been studied. The deactivation of supported Co catalysts was studied in a fixed-bed reactor using synthesis gas feeds containing different concentrations of water vapour. Supporting model studies were carried out using H2O/H2 feeds in conjunction with XPS and gravimetry. Rapid deactivation occurs on Re-promoted CO/Al2O3 catalysts when H2/CO/H2O feeds are used, whereas unpromoted CO/Al2O3 shows more stable activity. The results from the gravimetric studies suggest that only a small fraction of the bulk cobalt metal initially present reoxidizes to cobalt oxide during reaction. However, the XPS results indicate significant reoxidation of surface cobalt atoms or highly dispersed cobalt phases, which is likely to be the cause of the observed deactivation. Rhenium is shown to have a marked effect on the extent of reoxidation of alumina-supported cobalt catalysts.
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  • 19
    ISSN: 1572-879X
    Keywords: perovskite ; La1−xSrxFeO3−δ ; dehydrogenation ; oxidation ; ethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Catalysts of the composition La1−xSrxFeO3−δ, 0⩽x ⩽1, have been tested for the oxidative dehydrogenation of ethane in the temperature range 300–800°C. The catalyst is active above 400°C, giving a maximum yield of 37% ethylene at 650°C. Above 650°C, synthesis gas was formed together with methane, suggesting that the reforming reaction and thermal cracking of ethane took place. The catalytic data are compared to conductivity measurements on the same material, and a good correlation between the activity and p-type conductivity has been found. In the phase diagram for the system LaFeO3-SrFeO3−δ, a phase separation to two types of (La, Sr)FeO3−δ perovskites was observed in the La/Sr binary composition in the temperature range below 800°C. The phase separation can elucidate the dependency of the catalytic activity on its p-type conductivity.
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  • 20
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    Catalysis letters 39 (1996), S. 205-208 
    ISSN: 1572-879X
    Keywords: oxidation ; hydroxyapatite ; carbon monoxide ; inhibition ; tetrachloromethane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The introduction of tetrachloromethane (TCM) into the feedstream of CO and O2 inhibits the formation of CO2 on hydroxyapatite. TCM interacts with the surface of hydroxyapatite to form its chlorinated analogue, chlorapatite, which suppresses the oxidation of CO to CO2. Thus, in the oxidative coupling of methane the beneficial effects of the addition of TCM to the feedstream result, at least in part, from the suppression of the further oxidation of CO.
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  • 21
    ISSN: 1572-879X
    Keywords: platinum ; EXAFS ; catalysis ; catalyst deactivation ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract With a new set‐up for in situ EXAFS spectroscopy the state of a carbon‐supported platinum catalyst during aqueous alcohol oxidation has been observed. The catalyst deactivation during platinum‐catalysed cyclohexanol oxidation is caused by platinum surface oxide formation. The detected Pt–O co‐ordination at 2.10 Å during exposure to nitrogen‐saturated cyclohexanol solution is different from what is observed for the pure oxidised platinum surface (2.06 Å).
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  • 22
    ISSN: 1572-879X
    Keywords: catalysis ; combustion ; oxidation ; formic acid ; STM ; molecular beams ; surface diffusion ; surface reactivity ; active sites ; reconstruction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Using a combination of STM and molecular beam reactor data we summarise some important features of a model reaction (formic acid oxidation on Cu(110)) which is of general significance to surface reactivity and to catalysis. Three such features are highlighted here. The first concerns the role of weakly held species (possibly physisorbed) in surface reactions. These species, although of very short lifetime on the surface, can, nevertheless, diffuse over long distances to “find” a sparse distribution of active sites. Thus a very low coverage of oxygen on the surface of Cu(110) increases the sticking probability of all the formic acid molecules which strike the surface to high value (0.82), even though the clean surface is relatively unreactive. The important concept here is the “diffusion circle” or “collection zone” which represents the area of surface visited by the molecule in its short sojourn in the weakly held state. The second theme concerns the concept of the “flexible surface”. We show that the involvement of surface atoms in reactions directs the structure and reactivity for a particular reaction. For formic acid oxidation the liberation of Cu atoms during the removal of oxygen as water leads to gross restructuring of the surface and can lead to “compression” of one reactant (the oxygen in this case) into a lower area, higher local coverage, unreactive state (the c(6×2) oxygen structure). Thirdly, and finally, it is proposed that, for many surface reactions, the surface acts in an analogous way to a solvent, supporting a “dissolved” (highly mobile and fluxional) phase of intermediates at low coverage, which crystallise out above a critical coverage (the 2D “solubility limit”).
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  • 23
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    Catalysis letters 57 (1999), S. 109-113 
    ISSN: 1572-879X
    Keywords: superacid ; zirconia ; molybdenum oxide ; methane ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of zirconia-supported molybdenum oxide catalysts with different molybdenum loadings prepared using conditions reported to generate “superacidity” have been evaluated for their performance as catalysts for methane oxidation. A marked dependence of Mo content on activity has been observed, with the most active material being that with intermediate molybdenum content. 5 wt% MoO3/ZrO2 compares favourably with ZrxCe1-xO2 for methane combustion. The presence of MoO3 is observed to stabilise the tetragonal polymorph of ZrO2 and, as Mo content is increased, dispersed MoO3 crystallites are formed as evidenced by Raman spectroscopy. Temperature-programmed reduction studies evidence differences in the reduction behaviour of the materials as a function of loading. The results indicate that molybdenum oxide supported on monoclinic zirconia gives rise to the most active catalyst. It is tentatively suggested that the formation of a MoO3 monolayer during reaction may be of importance.
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  • 24
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    Catalysis letters 37 (1996), S. 79-87 
    ISSN: 1572-879X
    Keywords: methanol ; oxidation ; copper ; electron spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The role of preadsorbed oxygen present at Cu(111), Cu(110) and polycrystalline surfaces in the oxidation of methanol has been investigated by X-ray and electron energy loss spectroscopies. In addition to the well established formation of methoxy species and its subsequent decomposition and desorption as formaldehyde, a second reaction pathway to surface formate is present. The latter is temperature dependent being undetectable at 260 K at a polycrystalline surface but occurs at a significant rate at 295 K and above. The limitations of experimental data for methanol oxidation by temperature programmed desorption and molecular beam techniques are discussed.
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  • 25
    ISSN: 1572-879X
    Keywords: synergistic effect ; carbon monoxide ; oxidation ; mixed oxides ; iron oxide ; tin oxide ; manganese oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Based on the comparative evaluation of the catalytic activity of Fe2O3, Mn2O3 and SnO2 and their mixed oxides (Fe2O3+SnO2) and (Mn2O3+SnO2), it is shown that the system (Mn2O3+SnO2) shows strong synergistic effects during CO oxidation reaction. Such effects are not observed for the analogous system (Fe2O3+SnO2). Based on the calcination and reduction behaviour of these two mixed oxide systems and the redox potentials of the involved cations, the possible reasons for the observance of synergistic effects for the (Mn2O3+SnO2) system are discussed.
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  • 26
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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  • 27
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    Catalysis letters 40 (1996), S. 47-50 
    ISSN: 1572-879X
    Keywords: Baeyer-Villiger ; titanium silicate molecular sieve ; oxidation ; rearrangement ; titanium peroxo ; triphase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Titanium silicate molecular sieve TS-1 has been found to be an efficient catalyst for Baeyer-Villiger (BV) oxidation of cyclic and aromatic ketones under triphase conditions (solid catalyst along with two immiscible liquid reactants in the absence of any cosolvent), using dilute H2O2. Reactions studied are the oxidation of cyclohexanone and acetophenone. Whereas in the case of cyclohexane,ε-caprolactone, a BV product along with hydroxy and diketones is formed, in the case of acetophenone, phenyl acetate, a BV product along witho- andp-hydroxyacetophenone is formed. The acidic nature of titanium peroxo species, stabilised by water, is proposed to be responsible for such reactions under triphasic reaction conditions.
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  • 28
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    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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  • 29
    ISSN: 1572-879X
    Keywords: oxidation ; metalloporphyrins ; hydroperoxide decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new family of metalloporphyrin complexes having perfluoroalkyl groups in the meso-positions of the ring are active catalysts for the oxidation of isobutane to tert-butyl alcohol, TBA, and for the decomposition of tert-butyl hydroperoxide to TBA. This discovery extends the limited number of meso-substituents that can be used to enhance catalytic activity and fits the postulate that groups that withdraw electrons from the porphyrin periphery give rise to active catalysts for alkane oxidation. The perfluoroalkyl groups also confer oxidative stability, hydrophobicity and lower cost to the catalyst.
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  • 30
    ISSN: 1572-879X
    Keywords: model catalysts ; spin coating ; Pt colloid ; AFM ; XPS ; Si wafer ; particle size ; oxidation ; reduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Platinum particles of 2 nm diameter have been immobilised on oxidised silicon wafers by spin coating with colloidal solutions and characterised by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The coverage and dispersion of the Pt colloids on the Si wafer are controlled by varying the concentration and the spin speed. Under optimal conditions mono-dispersed Pt colloids on silicon wafers are prepared. For the Pt colloids immobilised on the Si wafer, the majority of the stabilising ligands are removed through a reduction (with H2 at 200°C) or an oxidation (in air at 300°C) procedure. AFM showed that particle sizes are retained after the reduction procedure, while significant sintering occurs after oxidation. The mechanism of ligand removal was studied using an in situ XPS reaction cell.
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    Catalysis letters 56 (1998), S. 199-202 
    ISSN: 1572-879X
    Keywords: cerium ; gas carbonic ; propane ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction between CO2 and CeO2 and its role in the surface reactivity of alumina-supported cerium oxide has been studied by programmed thermodesorption (TPD) of CO2 and FTIR spectroscopy. The performance of Ce/Al2O3 systems was then analyzed for the propane oxidation in presence of CO2. The results have shown that the catalytic activity decreased when carbonate species are formed at the surface of CeO2. This behavior was attributed to the presence of CO2 from three different sources: contamination before use, during the handling of the samples, contamination proceeding from the reactants and from CO2 produced by the reaction itself.
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    Catalysis surveys from Japan 3 (1999), S. 27-35 
    ISSN: 1572-8803
    Keywords: oxidation ; oxygen ; alkane ; N‐hydroxyphthalimide ; radical catalyst
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A practical catalytic method to convert alkanes into the corresponding oxygen‐containing compounds with O2 under mild conditions using N‐hydroxyphthalimide (NHPI) in the presence or absence of a transition metal was developed. Thus, cyclohexane was successfully converted into adipic acid in good conversion and selectivity by a combined catalytic system consisting of NHPI and Mn(acac)2. Lower alkane such as isobutane was converted into t‐butyl alcohol (83%) under 10 atm of air by NHPI‐Co(OAc)2 system. Alkylbenzene such as toluene was oxidized to benzoic acid in high yield (81%) under normal temperature and pressure of dioxygen in the presence of a catalytic amount of NHPI and Co(OAc)2. ESR measurements showed that phthalimide‐N‐oxyl generated from NHPI under dioxygen atmosphere is a key species in this oxidation and functions as a radical catalyst.
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    Journal of solid state electrochemistry 3 (1999), S. 179-186 
    ISSN: 1433-0768
    Keywords: Key words Cathodic protection system ; Carbon ; oxidation ; Composite carbon/polymer anode ; Lifetime
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The suitability of a polymeric composite material for use as part of an anode structure in a cathodic protection system has been examined. The composite material was a conductive blend (volume resistivity typically 1.5 Ω cm) of carbon black in a polyethylene binder. A long operational lifetime for the material demands that the rate of carbon loss must be low. In the work reported here, electrochemical and in situ analytical techniques were employed to characterise the performance of the material over a wide range of anodic current densities in a variety of aqueous electrolytes. The predominant anodic electrochemical reaction on the polymeric material is CO2 formation in acid and neutral solutions, which causes loss of carbon from the surface and the development of a non-conducting layer of polyethylene. The characteristics of the reaction suggest that it occurs via the discharge of H2O. In alkaline pH, however, the anodic reactions are more complex. A high OH− concentration (pH 12 or higher) favours the formation of oxygen rather than CO2, particularly at low anodic potentials. The presence of CO3 2− in the electrolyte catalyses the evolution of oxygen at pH values as low as 9. The electrochemical formation of oxygen always occurs in parallel with the generation of some humic acid in the solution.
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  • 34
    ISSN: 1436-5073
    Keywords: oxidation ; titanium aluminide ; SNMS ; niobium effect ; oxygen tracer
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation behaviour of γ-TiAl based alloys with different Nb contents (2–10 At.%) was investigated in air and in argon-20% oxygen at 900 °C using thermogravimetric analysis. The oxide scales were characterized by a combination of optical microscopy, SEM/EDX and X-ray diffraction analyses. Although in all studied cases the presence of niobium improves the oxidation resistance of γ-TiAl, the oxidation kinetics, scale morphology and composition in air differed strongly from that in argon-oxygen. In air the oxidation resistance increases with increasing niobium-content. In Ar/O2 the niobium dependence is far more complex because internal oxidation occurs which is favoured by the presence of niobium. SNMS analysis revealed that the differences in behaviour in the two atmospheres are related to the formation of Ti-rich nitride at the scale/alloy interface during air oxidation. The positive effect of niobium on the oxidation resistance of γ-TiAl is mainly caused by a decrease of the transport processes in the heterogeneous TiO2/Al2O3-surface scale. Nitride formation and/or niobium enrichment at the scale/alloy interface also affect the oxidation behaviour, however these factors are believed to be the result of the decreased transport processes rather than the main reason for the niobium effect.
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    Microchimica acta 125 (1997), S. 401-406 
    ISSN: 1436-5073
    Keywords: fullerenes ; intercalation ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The investigation of structural and electronic properties of the novel family of fullerenes depends on the existence of pure reference materials. Sublimation of the van-der Waals solids is a suitable purification method. Little attention has been paid to the question about the air stability of such sublimed samples in form of crystals or thin films. A combination of thermal desorption spectroscopy, thermal analysis and diffuse reflectance FT-IR spectroscopy is used to show the extent to which oxygen from dry air is intercalated into fullerenes and which detrimental reactivity occurs from attempts to thermally remove („nneal”) air-exposed samples. The conclusion is that any fullerene sample exposed to air will be transformed in part into a polymeric non-fullerene carbon upon thermal treatment to above 400 K irrespective of its initial purity.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 745-753 
    ISSN: 1572-8943
    Keywords: DSC ; kerogen ; oxidation ; pyrolysis ; type determination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate of pyrolysis and oxidation of 8 different samples of oil shale kerogen concentrate (KC) were investigated using DSC analysis. Recently performed thermogravimetric studies (TG and DTG) with the same samples of KC indicated that the activation energy of the pyrolysis of specific KCs increases with increasing paraffinic structure in the KC. An opposite effect, i.e. a decrease of the activation energy with an increase of paraffinic structure was determined in the case of KC oxidation. In this study, using the standard ASTM E-698 method based on the determined temperature at which the maximum heat effect could be observed (exo in the case of oxidation and endo in the case of pyrolysis), an activation energy for the pyrolysis, as well as for the oxidation process was determined and also successfully correlated with the content of paraffinic structure of KC. Thus, the higher content of paraffinic structure in KCs indicates that higher values of the activation energy could be determined either in the case of pyrolysis or oxidation followed by DSC analysis.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1017-1023 
    ISSN: 1572-8943
    Keywords: degradation ; microcalorimetry ; moisture ; oxidation ; permeability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The use of isothermal microcalorimetry (MC) as a sensitive monitor for slow reactions is demonstrated in a number of examples. In Example 1 the spontaneous decomposition of a nitrate ester propellant is studied and the absolute degradation rate estimated. Example 2 illustrates how MC can be used for comparing the rate of oxidative ageing at different O2 concentrations. Synergetic effects between oxygen and moisture in accelerated ageing of nitrile rubber are evaluated from a so-called 4-point test in Example 3. The last example shows a simple MC technique for rapid determination of moisture permeability through a polymeric sealant.
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    Journal of thermal analysis and calorimetry 48 (1997), S. 657-664 
    ISSN: 1572-8943
    Keywords: nickel powders ; oxidation ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Monodispersed fine metal nickel powders of uniform shape and high purity are increasingly required for specific uses in many technological areas, especially in the preparation of electronic materials such as the manufacture of conductive inks and pastes and the formation of catalysts. Metallic nickel powders were prepared in ethylene glycol by the reduction of a nickel solution. Hydrazine was used as a reducing agent. Metal powders were characterized by chemical analysis, scanning electron microscopy (SEM), thermogravimetry (TG), derivative thermogravimetry (DTG) and differential scanning calorimetry (DSC). Particle size distributions were determined using laser light scattering. The reactivity and purity of these fine nickel powders were tested by repeated oxidation and reduction of nickel powders in oxidative and reductive atmospheres.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1501-1507 
    ISSN: 1572-8943
    Keywords: calcium sulphide ; gypsum ; oxidation ; phosphogypsum ; reduction ; stability ; thermogravimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Using a heating rate of 2°C min−1, CaS reacts with oxygen in air from 700°C to form CaSO4, with a complete conversion at 1100°C. Synthesis of CaS from the reaction between CaSO4 containing compounds and carbon compounds in air would not be possible, as the carbon reacts from 600°C with oxygen in the air to give CO2. Heating stoichiometric amounts of carbon and pure CaSO4, synthetic gypsum or phosphogypsum in a nitrogen atmosphere, results in the formation of CaS from 850°C. Using a heating rate of 10°C min−1, the formation of CaS is completed at 1080°C. Addition of 5% Fe2O3 as a catalyst lowers the starting temperature of the reaction to 750°C. Activation energy values at different fraction reaction values (α) differ between 340 and 400 kJ mol−1. The relationship between the activation energy values and conversion (α) indicates that the reaction proceeds via multiple steps.
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    Journal of thermal analysis and calorimetry 54 (1998), S. 25-34 
    ISSN: 1572-8943
    Keywords: activation energy ; kinetic equation ; oxidation ; vanadium oxides ; Zhuravlev equation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract It has been found that the modified Zhuravlev equation, [(1−α)−1/3−1]2=ktn, which describes the kinetics of oxidation of V2O4 and V6O13 in the temperature range 820–900 K and in the oxygen pressure range 1.0–20 kPa, can be derived via the assumption that the changes in the observed activation energy result from the changing contributions of the two diffusion processes controlling the reaction rate. The values of the observed activation energy are in the range 160–175 kJ mol−1 for V2O4 and 188–201 kJ mol−1 for V6O13 in the scope of the experimental oxygen pressures and temperatures and conversion degrees of 0.1–0.9.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1161-1170 
    ISSN: 1572-8943
    Keywords: basicity ; dinitramides ; kinetics ; oxidation ; tanδ ; transition temperatures
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The dinitramide salts of ammonia (ADN), hexamethylenetetramine (HDN), potassium (KDN), and sodium (NaDN) showed a linear relationship between the DSC rate of decomposition at the peak maximum and the DEA tanδ value at the low temperature transition peak. As the cation basicity increased in the series ADN〈HDN〈KDN〈NaDN, there was an increase in the low temperature transition peak, the energy barrier for relaxation, and the decomposition peak temperature, and a decrease in the tanδ value at the low temperature transition peak, specific heat capacity, and the rate and enthalpy of decomposition. The more basic salts were more thermally stable (i.e., higher decomposition temperature) and less energetic (i.e., lower enthalpy of decomposition). The more internal free volume (disorder) present in these salts, the higher the rates of relaxation and decomposition. Five aluminum powders of different surface areas were analyzed by DSC in platinum sample pans, and it was found that the enthalpy and rate of oxidation increased as the particle size of Al decreased while the enthalpy of the Al melt decreased. TG showed a two-step weight gain in the oxidation of Al with plateaus in the 650 and 1130°C regions and the percent weight gain increased as the particle size of Al decreased. Variable DSC and TG heating rate studies showed that the activation energies for the first step in the oxidation process increased as the particle size of Al increased.
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    Journal of thermal analysis and calorimetry 54 (1998), S. 211-217 
    ISSN: 1572-8943
    Keywords: DSC ; fatty acids esters ; kinetics ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidation of saturated fatty acids ethyl esters: laurate, myristate, palmitate and stearate was investigated by means of DSC techniques under isothermal and non-isothermal conditions. The activation energies of isothermal oxidation were similar to each other (112–123 kJ mol−1) and no influence of carbon length on the rate of oxidative decomposition was observed. Results obtained from non-isothermal experiments were similar only for the first stage of oxidation.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 875-881 
    ISSN: 1572-8943
    Keywords: charge transfer ; Kelvin probe ; oxidation ; work function ; zirconia
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The extent of the surface charge, that develops during oxidation of zirconia, is determined using work function measurements for both bulk specimen and thin films. The bulk specimen of yttria-doped zirconia (10 mol%) exhibits maxima of the surface electrical effect at 373 and 973 K (130 and 280 mV, respectively) that can be considered in terms of oxygen chemisorption and oxygen non-stoichiometry. Thin film of undoped zirconia exhibits a maximum at 473 K (260 eV). Addition of yttria (10 mol%) to the thin film results in a substantial reduction of the maximum, to about 140 eV, that is shifted up to 600 K.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1657-1669 
    ISSN: 1572-8943
    Keywords: activation energy ; combustion ; differential scanning calorimetry ; kinetics ; lignite ; oxidation ; thermogravimetric analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis increasingly being used to obtain kinetic data relating to sample decomposition. This work involves a comparative study of several methods used to analyse DSC and TG/DTG data obtained on the oxidation of Beypazari lignite. A general computer program was developed and the methods are compared with regard to their accuracy and the ease of interpretation of the kinetics of thermal decomposition. For this study, the ratio method was regarded as the preferred method, because it permits the estimation of reaction order, activation energy and Arrhenius constant simultaneously from a single experiment.
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    Journal of thermal analysis and calorimetry 52 (1998), S. 327-340 
    ISSN: 1572-8943
    Keywords: aging ; DTA-TG ; oxidation ; polypropylene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Several samples of polypropylene were studied by thermal analysis. The photo-oxidation and the aging of polypropylene films showed a mass loss more than 7% in heating from 20 to 220°C (5°C min-1), cooling to 20°C and reheating to 220°C. The authors observed also a decrease of the melting and crystallization temperatures. The non aged samples or these ones with preservatives are thermo-oxidised and presented an exothermic peak at about 200°C in DTA heating. The DTA-TG simultaneous apparatus is very useful in the study of polypropylene oxidation by making comparative trials according to a well definite procedure.
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    Journal of thermal analysis and calorimetry 53 (1998), S. 263-267 
    ISSN: 1572-8943
    Keywords: kinetics ; molybdenum sulphide ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper reports on the results attained in the determination of the mechanism of oxidation of molybdenum sulphide under non-isothermal conditions in an air atmosphere. The mechanism of the process was determined by simultaneous DTA-TG-DTG, and the kinetic parameters of the reactions involved were obtained according to the methods of Kissinger and Ozawa.
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  • 47
    ISSN: 1572-8943
    Keywords: DSC ; infrared spectrometry ; oxidation ; polyethylenes ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of pure and recycled polyethylene samples was studied by thermal analysis (DTA-TG-DSC): presence of two exothermic peaks and mass loss. The thermo-oxidation products, containing C-O and C=O links, were identified by IR spectrometry and GC-MS spectrometry. The oxidation is easier from low to high density polyethylene.
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    Journal of thermal analysis and calorimetry 57 (1999), S. 473-486 
    ISSN: 1572-8943
    Keywords: cumene ; oxidation ; polymerization ; quinone-amine inhibitors ; solution microcalorimetry ; styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of solution microcalorimetry was demonstrated on two model examples – inhibited oxidation of cumene and radical polymerization of styrene. From the experimental dependences of the rate of heat release on time, the rate constants k 7 of the interaction of an inhibitor with radicals of substrate (RO 2 . or R.) in oxidation or in polymerization were determined for the set of inhibitors of N-aryl N-(2-quinone) amine series. It was shown that these compounds are weak inhibitors of oxidation of cumene and rather efficient inhibitor of polymerization of styrene.
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  • 49
    ISSN: 1572-8986
    Keywords: RF SiCl4 discharge ; mass spectrometry ; kinetics ; decomposition ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Time-resolved mass spectrometry was used for analysis of the plasma reactions in radio frequency (RF) SiCl 4 and SiCl 4 −O 2 discharges as functions of starting partial pressure and electrical power. Molecular concentrations of the reactants and products from SiCl 4 alone and with O 2 were obtained from the mass spectra and used for plotting the kinetic curves. The SiCl 4 and O 2 consumption rates were calculated from the kinetic curves and compared with results of theoretical simulation of the reaction. Direct electron impact decomposition was found to be the main pathway for pure SiCl 4 conversion. On the contrary, the consumption of SiCl 4 in the SiCl 4 +O 2 mixtures was largely chemical. The experimental macrokinetics are in agreement with a model in which oxidation is caused by the atomic oxygen.
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    Plasma chemistry and plasma processing 19 (1999), S. 131-151 
    ISSN: 1572-8986
    Keywords: Styrene ; oxidation ; silent discharge ; plasma ; dielectric barrier
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract A silent discharge plasma reactor has been developed to study the oxidation of styrene vapor in argon/oxygen mixtures. A number of analytical techniques were employed to determine the destruction efficiency and to characterize the intermediate products. The destruction efficiency was measured as a function of initial styrene concentration, temperature, and energy density of the plasma. The formation of solid products was observed in most experiments. At low temperature (100°C), the solid deposit was polymeric in nature, while at high temperature (300°C) the solid appeared to be amorphous carbon. A combination of high temperature and high energy density resulted in high destruction efficiency and minimal production of solid films. The destruction efficiency vs. energy density is shown to be more complex than a simple model predicting exponential behavior. Several reasons for the discrepancy are suggested. The “e-folding” energy density for the destruction of styrene is compared to literature values for other organic compounds, measured using similar types of plasma reactors.
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    Plasma chemistry and plasma processing 19 (1999), S. 383-394 
    ISSN: 1572-8986
    Keywords: Nonthermal plasma ; benzene ; Al2O3 ; BaTiO3 ; oxidation ; absorption ; atmospheric pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The combination of plasma discharge and adsorption was examined for oxidation of dilute benzene in air in a plasma reactor packed with a mixture of BaTiO 3 pellets and porous Al 2 O 3 pellets (i.e., an alumina hybrid reactor). The oxidative decomposition of benzene was enhanced by the benzene concentrating on the Al 2 O 3 pellets. Furthermore, there was a higher selectivity to CO 2 in the products from the hybrid than from a plasma reactor packed with BaTiO 3 pellets alone. The presence of the Al 2 O 3 pellets suppressed the formation of N 2 O.
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    Plasma chemistry and plasma processing 19 (1999), S. 421-443 
    ISSN: 1572-8986
    Keywords: Streamer corona ; NO x removal ; nonthermal plasma ; oxidation ; reduction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract In this paper, the NO-to-NO 2 conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO x removal experiments in N 2 +NO x and N 2 +O 2 +NO x gaseous mixtures, it is supposed that the reverse reaction NO 2 +O→NO+O 2 may not only limit NO 2 production in N 2 +NO x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NO→N 2 +O, induce negligible NO removal provided the O 2 concentration is larger than 3.6%. With adding H 2 O into the reactor, the produced NO 2 per unit removed NO can be significantly reduced due to NO 2 oxidation. NH 3 injection could also significantly decrease the produced NO 2 via NH and NH 2 - related reduction reactions. Almost 100% of NO 2 can be removed in gaseous mixtures of N 2 +O 2 +H 2 O+NO 2 with negligible NO production.
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    Journal of sol gel science and technology 12 (1998), S. 35-48 
    ISSN: 1573-4846
    Keywords: yttrium acetate precursor ; particle coating ; oxidation ; corrosion ; Inconel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract “Sol paint” that yields yttrium-based compounds was prepared by mixing four chemical ingredients, yttrium acetate tetrahydrate precursor, diethanolamine, isopropyl alcohol, and hydrochloric acid, and then applied as oxidation/corrosion resistant coatings for Inconel 625 substrates. Annealing the coatings at 500°C developed a coalescent microstructure of coarse particles consisting of amorphous yttrium carbonate as the major component and crystalline yttrium oxide (Y2O3) as the minor one. At 700°C, the yttrium carbonate was transformed into Y2O3 by decarbonation. Increasing the annealing temperature to 900°C led to the formation of the YCrO3 phase yielded by interaction between Y2O3 and the Cr2O3 which had arisen from the oxidation of the underlying Inconel; the YCrO3 phase created a particle coating with a densified microstructure. There were two key factors in mitigating the degree of oxidation of Inconel at 900°C in air: (1) an uptake of oxygen by Y2O3 in the coatings, and (2) a densified coating layer that suppresses the diffusion and permeation of oxygen through it. Furthermore, inhibiting the rate of NaCl-caused corrosion was not only due to the excellent coverage of particle coatings over the entire surfaces of the substrates, but also may be associated with a good adherence of the coatings to the substrates.
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    Molecular and cellular biochemistry 194 (1999), S. 257-263 
    ISSN: 1573-4919
    Keywords: glycation ; oxidation ; collagen ; diabetes ; free radicals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The present investigation was carried out to understand the effect of metal catalyzed oxidation on glycation and crosslinking of collagen. Tail tendons obtained from rats weighing 200-225 g were incubated with glucose (250 mM) and increasing concentrations of copper ions (5, 25, 50 and 100 μM) under physiological conditions of temperature and pH. Early glycation, crosslinking and late glycation (fluorescence) of collagen samples were analyzed periodically. Early glycation was estimated by phenol sulfuric acid method, and the crosslinking was assessed by pepsin and cyanogen bromide digestion. A concentrationdependent effect of metal ions on the rate of glycation and crosslinking of collagen was observed. Tendon collagen incubated with glucose and 100 μM copper ions showed 80% reduction in pepsin digestion within seven days, indicating extensive crosslinking, whereas collagen incubated with glucose alone for the same period showed only 7% reduction. The presence of metal ions in the incubation medium accelerated the development of Maillard reaction fluorescence on collagen, and the increase was dependent on the concentration of metal ions used. The metal chelator Diethylene triamine penta-acetate significantly prevented the increase in collagen crosslinking by glucose and copper ions. Free radical scavengers benzoate and mannitol effectively prevented the increased crosslinking and browning of collagen by glucose. The results indicate that the metal catalyzed oxidation reactions play a major role in the crosslinking of collagen by glucose. It is also suggested that the prevention of increased oxidative stress in diabetes may prevent the accelerated advanced glycation and crosslinking of collagen.
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    Molecular and cellular biochemistry 177 (1997), S. 245-250 
    ISSN: 1573-4919
    Keywords: cataract ; crystalline ; glycation ; oxidation ; taurine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Modifications in lens protein structure and function due to nonenzymic glycosylation and oxidation have been suggested to play a significant role in the pathogenesis of sugar and senile cataracts. The glycation reaction involves an initial Schiff base formation between the protein NH2 groups and the carbonyl group of a reducing sugar. The Schiff base then undergoes several structural modifications, via some oxidative reactions involving oxygen free radicals. Hence certain endogenous tissue components that may inhibit the formation of protein-sugar adduct formation may have a sparing effect against the cataractogenic effects of sugars and reactive oxygen. The eye lens is endowed with significant concentration of taurine, a sulfonated amino acid, and its precursor hypotaurine. It is hypothesized that taurine and hypotaurine may have this purported function of protecting the lens proteins against glycation and subsequent denaturation, in addition to their other functions. The results presented herein suggest that these compounds are indeed capable of protecting glycation competitively by forming Schiff bases with sugar carbonyls, and thereby preventing the glycation of lens proteins per se. In addition, they appear to prevent oxidative damage by scavenging hydroxyl radicals. This was apparent by their preventive effect against the formation of the thiobarbituric acid reactive material generated from deoxy-ribose, when the later was exposed to hydroxyl radicals generated by the action of xanthine oxidase on hypoxanthine in presence of iron.
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    Molecular and cellular biochemistry 200 (1999), S. 103-109 
    ISSN: 1573-4919
    Keywords: sugar cataract ; dulcitol ; glycation ; oxidation ; pyruvate ; ethyl pyruvate ; attenuation effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Studies describe an attenuation of sugar cataract formation by topical administration of ethyl pyruvate. Cataract formation was induced by feeding young rats a 30% galactose diet. Mature cataracts appeared in about thirty days. Instillation of the eye drops containing 5% ethyl pyruvate decelerated the process significantly. Biochemically, the effect was reflected by lowering in the contents of dulcitol and glycated proteins. The ATP levels were also higher in comparison to the placebo treated group. The effects are hence attributable to the effect of pyruvate in inhibiting dulcitol synthesis and protein glycation, in addition to its antioxidant properties and metabolic support. The use of esterified pyruvate instead of the unesterified pyruvate was preferred because of its greater penetration through the cornea and consequently a higher concentration attained in the aqueous humor.
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  • 57
    ISSN: 1572-9028
    Keywords: ellipsometry ; carbon monoxide ; methane ; palladium ; palladium oxide ; oxidation ; oscillations ; catalyst
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Spectroscopic ellipsometry is used to monitor the surface of a thick Pd‐film catalyst during the oxidation of either carbon monoxide or methane. Dense PdO layers form under sufficiently lean conditions (excess oxygen) for both reactions. A stable metal surface exists in the case of CO, but a very porous PdO layer develops in the case of methane, under rich conditions. There is a large hysteresis in the conditions for PdO formation in the case of CO oxidation. Spontaneous oscillations in catalytic activity and Pd‐surface composition occur for both reactions, the higher activities corresponding to O‐atom‐rich or PdO‐rich surfaces for CO or methane oxidation, respectively.
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  • 58
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    Topics in catalysis 8 (1999), S. 45-55 
    ISSN: 1572-9028
    Keywords: Raman spectroscopy ; surface‐enhanced Raman spectroscopy ; oxidation ; synergy effects ; oxygen exchange ; oxidative coupling of methane ; nitric oxide decomposition ; methanol oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Advantages and limitations of laser Raman spectroscopy (LRS) as an in situ vibrational spectroscopy for the study of catalytic materials and surfaces under working conditions are discussed. Measurements can be carried out at temperatures as high as 1200 K in controlled atmospheres. Modern instrumentation permits time resolutions in the sub‐second regime for materials with high Raman cross sections. Transient studies are thus possible. Several examples are presented of in situ LRS studies including the phase analysis of bismuth molybdate and VPO oxidation catalysts, synergy effects and oxygen exchange in Sb2O3/MoO3 oxide mixtures, intermediates in oxidative coupling of methane, NO decomposition on Ba/MgO catalysts, and transient SERS studies of partial oxidation of methanol on Ag single crystal surfaces and of the reduction of oxide overlayers on electrodeposited Rh layers.
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  • 59
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    Interface science 3 (1995), S. 133-141 
    ISSN: 1573-2746
    Keywords: silicon ; Si/oxide interface ; oxidation ; Monte-Carlo ; thin-films
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Experiments have shown that the early stages of silicon oxidation proceed layer by layer, so that one layer is essentially complete before another develops. Other experiments show that the mechanism does not involve step growth, the most obvious mechanism. We use a new approach to modelling the growth to show that these two observations can be understood when there is a rate-determining step which depends strongly on the local oxide thickness. The rate in question might be the sticking probability, or the rate of incorporation of adsorbed oxygen species into the oxide network. Such mechanisms are possible when transport by an ionic species dominates, contrary to the situation for thicker films. Our modelling suggests the mechanisms are driven by the image interaction, as in earlier suggestions by Stoneham and Tasker, rather than an effect of the electric field central to the Mott-Cabrera mechanism.
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  • 60
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    Journal of sol gel science and technology 8 (1997), S. 443-449 
    ISSN: 1573-4846
    Keywords: coatings ; protection of metals ; oxidation ; corrosion
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Sol-gel derived films can be deposited on metals to improve their resistance to oxidation and corrosion or to modify their surface properties. However, practical applications are limited by problems intrinsic to sol-gel processing or specific of coating/metal systems. Coatings aimed to improve oxidation and wet corrosion resistance have been the most studied. The results published in the literature show that sol-gel coatings may offer good protection against oxidation. More difficult is to achieve a protection against wet corrosion. An important aspect of the application of the sol-gel method for coating metallic objects is also the deposition technique.
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  • 61
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    Journal of sol gel science and technology 8 (1997), S. 443-449 
    ISSN: 1573-4846
    Keywords: coatings ; protection of metals ; oxidation ; corrosion
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Sol-gel derived films can be deposited on metals to improve their resistance to oxidation and corrosion or to modify their surface properties. However, practical applications are limited by problems intrinsic to sol-gel processing or specific of coating/metal systems. Coatings aimed to improve oxidation and wet corrosion resistance have been the most studied. The results published in the literature show that sol-gel coatings may offer good protection against oxidation. More difficult is to achieve a protection against wet corrosion. An important aspect of the application of the sol-gel method for coating metallic objects is also the deposition technique.
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  • 62
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    Journal of sol gel science and technology 14 (1999), S. 75-86 
    ISSN: 1573-4846
    Keywords: silicon oxycarbide ; BlackglasTM ; ceramic matrix composites ; 29Si NMR ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract BlackglasTM polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using 29Si nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.
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  • 63
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    Journal of sol gel science and technology 14 (1999), S. 49-68 
    ISSN: 1573-4846
    Keywords: silicon oxycarbide ; oxidation ; silsesquioxane ; preceramic
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We have undertaken a systematic study of the oxidation chemistry for a range of SiOC ceramics derived from silsesquioxane polymeric precursors. This study examines the oxidation for 500 hours at 600, 800, 1000 and 1200°C for four SiOC powders. The material changes upon oxidation were characterized qualitatively by color change and optical microscopy and quantitatively by weight and composition change. In this study we employ a very easy method that uses the weight change upon oxidation and a carbon analysis after oxidation to arrive at the composition of the oxidized SiOC. Combined these qualitative and quantitative techniques have shown that on oxidation at 800 and 600°C the SiOC composition is more rapidly changed to that of silica than oxidation over the same time frame at 1000 or 1200°C. The data indicates that this difference is due to the relative rates of oxidation of the excess carbon versus the Si—C bonds in the SiOC. At lower temperatures initially the carbon oxidation predominates which leads to higher porosity throughout the material and an increase in the surface area with eventually ‘complete’ oxidation to silica. At higher temperatures the Si—C bond oxidation rate is comparable to the rate of oxidation of carbon. This allows a silica-like surface to build up on the SiOC, which slows all subsequent reactions due to the necessity to diffuse O2 in and COx out of the bulk. Under these oxidation conditions materials that originally contain high amounts of excess carbon are more quickly oxidized to silica than those that contain minimal amounts of excess carbon, as confirmed by elemental analysis and optical microscopy. Regardless of the time or temperature of the oxidation conditions no materials were found to be completely stable to oxidation. SiOC materials with low levels of excess carbon showed the best resistance to change upon oxidation.
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  • 64
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    Physics and chemistry of minerals 26 (1999), S. 506-512 
    ISSN: 1432-2021
    Keywords: Key words Anapaite ; Mössbauer spectroscopy ; oxidation
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    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract Mössbauer spectra (MS) of anapaite (Ca2 Fe2+(PO4)2 · 4H2O) and of a sample after being immersed in a 4% H2O2 solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420 K and 11 to 300 K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe2+ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370 K ± 25 K and 340 K ± 25 K, and the intrinsic isomer shifts as 1.427 ± 0.005 mm/s and 1.418 ± 0.005 mm/s respectively. From the external-field (60 kOe) MS recorded at 4.2 and 189 K for the non-treated sample, the principal component V zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η ≈ 0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE Q(T), cannot be interpreted on the basis of the thermal population of the 5 D electronic levels resulting from the tetragonal compression of the O6 co-ordination. The low-temperature linear behaviour of ΔE Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2 K produces magnetic hyperfine splitting with effective hyperfine fields of −136, −254 and −171 kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H2O2 concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe2+ (∼6.5%) is converted into Fe3+.
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  • 65
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    Russian chemical bulletin 44 (1995), S. 1907-1913 
    ISSN: 1573-9171
    Keywords: photochemical transformations ; 1-arylcyanomethyl-9 ; 10-anthraquinones ; nucleophilic addition ; oxidation ; kinetics ; quantum-chemical calculations
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Photochemical transformations of 1-arylcyanomethyl-9,10-anthraquinones were studied. It was established that under irradiation, the hydrogen atom of the substituted methyl group is transferred to aperi-quinoid oxygen atom to form the corresponding 9-hydroxy1, 10-anthraquinone-1-arylcyanomethides. Dark transformations of photoinduced quinonemethides result from three competing parallel processes: intramolecular transfer of the hydrogen atom, a reaction with a solvent (alcohol), and oxidation by dissolved oxygen. The kinetics of these reactions were studied.
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  • 66
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    Russian chemical bulletin 44 (1995), S. 584-598 
    ISSN: 1573-9171
    Keywords: hydrogen peroxide ; vanadium(v) complexes ; ozone ; catalysis ; oxidation ; alkanes ; arenes ; perfluoroolefins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Reactions of H2O2 in trifluoroacetic acid catalyzed by vanadium(v) compounds were studied. The system under study exhibits unusual behavior: along with oxygen, large quantitaties (10–15 %) of ozone are found in the products of hydrogen peroxide decomposition; difficultly oxidizable compounds (alkanes, arenes, and perfluoroalkenes) are oxidized under mild conditions. The rates of the oxidation of individual substrates are commensurable. However, when two compounds are simultaneously present in the reaction mixture, cyclohexane stops the oxidation of all of the other substrates, arenes suppress the oxidation of perfluoroolefins, and perfluoro-1-octene stops the consumption of internal perfluoroolefins. The effect of the oxidizable substrates on the amount of ozone evolved was studied. Based on the kinetic data obtained, a mechanism that involves the consecutive formation of several active complexes of vanadium(v) responsible for the oxidation of substrates and for the formation of ozone is suggested. In terms of the scheme suggested, the inner-sphere oxidation of the peroxo ligand by the coordinated peroxotrifluoroacetic acid affords a complex incorporating O 3 2− as a ligand. The latter acts as the precursor of the ozone. A mathematical model that adequately describes the experimental data is proposed.
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  • 67
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    Russian chemical bulletin 45 (1996), S. 340-345 
    ISSN: 1573-9171
    Keywords: oxidation ; acid catalysis ; free radicals ; acetonitrile ; p-toluenesulfonic acid ; tert-butyl hydroperoxide ; cyclohexanone
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of formation of free radicals in the cyclohexanone (CH)-tert-butylhydroperoxide (TBHP)-para-toluenesulfonic acid (PTSA) system in acetonitrile was studied. The stoichiometry of the reaction corresponds to the consumption of two TBHP molecules per ketone molecule, whereas the yield of free radicals is -20 % based on the TBHP reacted.
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  • 68
    ISSN: 1573-9171
    Keywords: 1,2,4,5-tetrafluoro-3,6-bis(vinylthio)benzerne ; 1,2,4,5-tetrafluoro-3,6bis(vinylsulfonyl)benzene ; 5,6-difluorobenzo-[a,d]-bis(3,3′-dihydro-1,1′-sulfonylallyl-4,4′-perhydroazine) ; oxidation ; allylamine ; X-ray structural study
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidation of 1,2,4,5-tetrafluoro-3,6-bus (vinylthio)benzene (1) affords 1,2,4,5-tetra fluoro3,6-bis(vinylsulfonyl)benzene (2) in 65 % yield. The reaction of compound 2 with allylamine gives a new heterocyclic compound, 5,6-difluorobenzo-[a,d]-bis(3,3′-dihydro-l,l′-sulfonylallyl-4,4′-perhydroazine) (3). This compound is the product of nucleophilic addition at the vinylsulfonyl group and intramolecular replacement of fluorine atoms of the benzene ring. The structure of compound 3 has been established by X-ray structural study.
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  • 69
    ISSN: 1573-9171
    Keywords: active carbons ; oxidation ; surface chemistry ; n-hexane ; water ; methanol ; adsorption
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of oxidation by nitric acid on the character of oxygen-containing functional surface groups and porous structure of active carbons is considered. Adsorption properties of the initial and oxidized carbons are studied using adsorption isotherms of vapor of n-hexane and polar substances (water and methanol).
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  • 70
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    Russian chemical bulletin 45 (1996), S. 1883-1888 
    ISSN: 1573-9171
    Keywords: decane ; nitric acid ; nitrogen dioxide ; oxidation ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the reaction of decane with nitric acid (25.07–75.53 %) at 57.8 to 119 °C in an acid-decane-gas triphasic system was studied. The main contribution to the rate of heat release is made by the oxidation of decane with nitrogen dioxide in the organic phase proceedingvia the mechanism of a degenerate branched-chain reaction. Nitration plays the role of a chain termination reaction. The acid phase is the source of NO2, whose content increases with oxidation. The equilibrium of the nitrogen dioxide distribution in the triphasic system was analyzed. The kinetic law of the reaction, the dependences of the reaction constants of the initial and catalytic stages on temperature and the acid phase composition were determined. The results allow one to calculate the rate of heat release in the decane-HNO3 system under any conditions of the process.
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  • 71
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    Russian chemical bulletin 45 (1996), S. 1889-1895 
    ISSN: 1573-9171
    Keywords: phenazine di-N-oxide ; radical cation ; hydrocarbons ; oxidation ; mechanism ; O2 effect
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The absorption spectra of phenazine di-N-oxide radical cation (OPO+·) in dichloromethane were recorded by the spectroelectrochemical method in the range from 300 to 700 nm. The reactions of the electrochemically generated OPO+· withpara-substituted toluenes, ethylbenzene, and cumene were studied. Using differential cyclic voltammetry, relative rate constants of reactions of OPO+· with substrates were determined; their correlations with σ+ para constants of substituents gives p = -2.7, which attests to the nonradical character of the reaction of OPO+· with RH. This conclusion is confirmed by the study of the effect of O2 on oxidation of ethylbenzene and cumene.
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  • 72
    ISSN: 1573-9171
    Keywords: α-mercaptoketones ; phosphorylation ; silylation ; stannylation ; oxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Some newS-phosphorylated,S-silylated, andS-stannylated derivatives of α-mercaptoketones were obtained. The reactions of some of these compounds induced by the temperature and by molecular oxygen as well as the phosphorylation of the Si- and Sn-containing derivatives were studied.
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  • 73
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    Russian chemical bulletin 44 (1995), S. 764-765 
    ISSN: 1573-9171
    Keywords: diethyl ether ; ethoxyacetic aldehyde ; triphenylbismuth ; tert-butyl hydroperoxide ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth-tert-butyl hydroperoxide system transform diethyl ether into ethoxyacetic aldehyde. The latter undergoes further conversions under these reaction conditions to give the corresponding hydroxyperoxide, ethoxyacetic acid, and bismuth(III) acylates.
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  • 74
    ISSN: 1573-9171
    Keywords: transition metal complexes ; free radicals ; oxidation ; dimerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of the carbon-centered [(η6-C13H9)Cr(CO)3]− anion (1 −) results in formation of (μ-η6:η6-9,9′-bifluorenyl)bis-chromiumtricarbonyl (3) due to coupling of the intermediate carbon-centered radical (1.). The oxidation of the metal-centered anion [(η5-C13H9)Cr(CO)3]− (2 −), which is isomeric to the 1− anion, gives an equilibrium mixture of the chromium-centered radical {(η5-C13H9)Cr(CO)3}. (2 .) and its dimer [(η5-C13H9)Cr(CO)3]2 (6). Radical2 . readily reacts with MeI and the solvent (THF); the resulting derivatives, (η5-C13H9)Cr(CO)3R (R=Me (10); R=H (7)), undergo fast ricochet inter-ring η5→η6 rearrangements into (η6-9R-C13H9)Cr(CO)3 (R=CH3 (9); R=H (4)).
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  • 75
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    Russian chemical bulletin 45 (1996), S. 2668-2669 
    ISSN: 1573-9171
    Keywords: diphenyl sulfide ; sulfuryl chloride ; oxidation ; chlorination
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction of diphenyl sulfide with sulfuryl chloride was studied. Depending on the reaction conditions, it occurs either as chlorination of the aromatic ring or as oxidation to give sulfoxide.
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  • 76
    ISSN: 1573-9171
    Keywords: alkenes ; catalysis ; oxidation ; iodohydrins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract RuCl3-catalyzed periodate oxidation of alkenes affords isomeric iodohydrins.
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  • 77
    ISSN: 1572-8978
    Keywords: Plasma polymers ; oxidation ; XPS ; photoelectron binding energy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The incorporation of oxygen into nitrogen-containing plasma deposited polymers was studied by X-ray Photoelectron Spectroscopy (XPS). As the oxygen content of the plasma polymer increased, the binding energy of the N 1s photoelectrons increased. Conversely, the binding energy of the O 1s photoelectrons was inversely proportional to the nitrogen content of the plasma polymer. The data from a large number of samples all obeyed the same “universal” correlations of photoelectron binding energy versus chemical composition. The data were described by the same curve regardless of whether the oxygen was incorporated rapidly into the thin film during plasma deposition or whether the oxygen was added slowly during spontaneous oxidation of the film in air. This implies that the same thermodynamic principles of radical reactions governed the addition of oxygen to the plasma polymer. The shift in the O 1s and N 1s photoelectron binding energies as a function of chemical composition was used to monitor the proximity of nitrogen and oxygen. By contrasting the experimental data with a simple binomial model which described the random addition of oxygen to a lattice containing carbon and nitrogen, we were able to show that oxygen was preferentially added near nitrogen-containing groups in plasma polymers.
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  • 78
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    Bioscience reports 17 (1997), S. 521-527 
    ISSN: 1573-4935
    Keywords: Glyceraldehyde-3-phosphate dehydrogenase ; glycolysis ; oxidation ; uncoupling ; thiols ; hydrogen peroxide ; mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Data on alterations of the properties of glyceraldehyde-3-phosphate dehydrogenase upon oxidation of its functional groups are reviewed; a mechanism of uncoupling of oxidation and phosphorylation in glycolysis is considered. Possible ways of regulating uncoupling, and the physiological importance of this process, are discussed.
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  • 79
    ISSN: 1573-904X
    Keywords: sulfur ; protein ; oxidation ; chemometrics ; phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The oxidation of methionine in human Insulin-like Growth Factor I (hIGF-I) in aqueous solution was studied with respect to oxygen, visible light and sodium phosphate. Methods. Aqueous solutions of hIGF-I were prepared with different amounts of phosphate and dissolved oxygen. The solutions were stored either in darkness or exposed to artificial visible light. The oxidized hIGF-I was quantified by RP-HPLC. A two level full factorial experimental design, with two levels of each of the three factors studied, was used. Results. Oxidation was found to be positively correlated with light, oxygen content and, interestingly, phosphate. The increasing effect of phosphate on the oxidation appears not to originate from metal contaminants. The influence of both oxygen and phosphate increased with time. The pH dependence of oxidation indicated the formation of a phosphorylated sulfonium ion as an oxidation intermediate. A significant interaction effect between phosphate and visible light suggested participation of radicals. Conclusions. Factorial experiments provide a valuable tool when studying complex mechanisms with interacting factors. The oxidation of methionine in hIGF-I is significantly affected by light but also by the presence of phosphate buffer.
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  • 80
    ISSN: 1573-904X
    Keywords: iron ; chelator ; oxidation ; methionine/histidine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Site-specific protein oxidation induced by prooxidant/metal/ oxygen has been recognized as one of the major degradation pathways of protein pharmaceuticals. Polyaminocarboxylate (PAC) metal chelators are commonly employed to prevent metal-catalyzed oxidation, for they sequester metals. However, studies have indicated that iron chelates may still be catalytically active due to their specific coordination geometry. The purpose of this study was to investigate how PAC chelators affect prooxidant/metal/oxygen-catalyzed oxidation of peptides containing histidine (His) and methionine (Met). Methods. PACs were applied to a model oxidizing system, dithiothreitol/iron/oxygen, which was shown to promote the oxidation of Met to Met sulfoxide in the two model peptides, GGGMGGG and GHGMGGG. Results. PAC chelators did not suppress the peptide oxidation but significantly changed the product pattern. In particular, the yield of Met sulfoxide dropped significantly, while a number of other products emerged, including oxidation products from the N-terminus and His (if present). Overall, the oxidation became rather non-selective in the presence of PACs. The oxidation kinetics were significantly accelerated by nitrilotriacetate (NTA), ethylenediaminediacetate (HDDA), and ethylenediaminetetraacetate (EDTA), but they were slowed down by ethyl-enebis(oxyethylenenitrilo)tetraacetate (EGTA) and diethylenetriaminepentaacetate (DTPA). Meanwhile the PAC chelators were also observed to undergo degradation. Scavengers of hydrogen peroxide or hydroxyl radicals exerted only partial inhibition on the peptide oxidation. Conclusions. The results of this study are rationalized by the abilities of PAC chelators (i) to extract iron from potential binding sites of the peptides to impair site-specific oxidation, and (ii) to promote the formation of ROS different from the species formed at the peptide metal-binding sites.
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  • 81
    ISSN: 1573-904X
    Keywords: hIGF-I ; oxidation ; methionine ; HPLC ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aim of this work was to study the kinetics of oxidation of methionine in human Insulin-like Growth Factor I (hIGF-I)1 in aqueous solution and in the solid state by the aid of quantification of oxygen. Methods. The oxidized form of hIGF-I was characterized by tryptic peptide analysis, RP-HPLC and FAB-MS and quantified by RP-HPLC. The oxygen content was quantified polarographically by a Clark-type electrode. Results. Second-order kinetics with respect to amount of protein and dissolved oxygen was found to be appropriate for the oxidation of methionine in hIGF-I. The rate constants ranged from 1 to 280 M−1 month−l and had an activation energy of 95 (+/−4) kJ/mole. Light exposure, storage temperature and oxygen content were found to have a considerable impact on the oxidation rates. No significant difference in reaction rates was found for the oxidation of hIGF-I in aqueous solution or in the solid state. A method for decreasing the oxygen content in aqueous solution without purging is described. Conclusions. Polarographic quantification of dissolved oxygen makes it possible to establish the kinetics for oxidation of proteins. The oxidation of methionine in hIGF-I appears to follow second-order kinetics.
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    Pharmaceutical research 13 (1996), S. 457-461 
    ISSN: 1573-904X
    Keywords: nicanartine ; lipoprotein ; oxidation ; plasma binding
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aim of this study is to investigate the plasma protein binding of nicanartine and to measure its antioxidant effect on lipoproteins. Methods. The blood binding was studied with an erythrocyte partitioning method and the lipoprotein oxidation with the conjugated dienes method. Results. Nicanartine was 24.7% LDL (low density lipoprotein)-bound and 29.2% AAG (alphal-acid glycoprotein)-bound. Nicanartine delayed but did not stop the oxidation of the three density classes of lipoprotein HDL (high density lipoprotein), LDL, VLDL (very low density lipoprotein). The addition of AAG to LDL in the conjugated dienes method decreased the nicanartine fraction bound to LDL and decreased its antioxidant effect. The decrease of nicanartine LDL-bound fraction and the decrease in antioxidant effect were not parallel. Conclusions. This suggested that (a) AAG-bound nicanartine dissociated to equilibrate the decrease in LDL-bound nicanartine consummed by oxidation, or (b) the oxidation conditions could involve chemical modifications of nicanartine and therefore modify its affinity for AAG.
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  • 83
    ISSN: 1573-904X
    Keywords: peptide stability ; peptide formulation ; oxidation ; fibrinogen receptor antagonist ; mannitol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To elucidate the structure of a degradation product arising from a lyophilized formulation of a cyclic heptapeptide, and to provide a mechanism to account for its formation. Methods. Preparative HPLC was used to isolate the degradate in quantities sufficient for structural studies. A structure assignment was made on the basis of the compounds spectroscopic properties (UV, MS, NMR) and the results of amino acid analysis. Results. The degradate was identified as a benzaldehyde derivative arising from the oxidative deamination of an aminomethyl phenylalanine moiety. The extent of formation of this product is influenced by the amount of mannitol used as an excipient in the formulation. A mechanism is proposed whereby reducing sugar impurities in mannitol act as an oxidizing agent via the intermediacy of Schiff base adducts which subsequently undergo tautomerization and hydrolysis. Conclusions. Reducing sugar impurities in mannitol are responsible for the oxidative degradation of the peptide via a mechanism that involves Schiff base intermediates. This mechanism may be a potential route of degradation of other arylmethyl amines in mannitol-based formulations.
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    Pharmaceutical research 13 (1996), S. 250-255 
    ISSN: 1573-904X
    Keywords: antiflammin 2 ; oxidation ; stability ; degradation ; HPLC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To study the oxidation of the methionine residue of antiflammin 2 (HDMNKVLDL, AF2) as a function of pH, buffer concentration, ionic strength, and temperature using different concentrations of hydrogen peroxide and to determine the accessibility of methionine residue to oxidation. Methods. Reversed-phase high-performance liquid chromatography (RPHPLC) was used as the main analytical method in determining the oxidation rates of AF2. Calibration curves for AF2 and the oxidation product, methionine sulfoxide of AF2 (Met(O)-3-AF2), were constructed for each measurement using standard materials. Fast Atom Bombardment Mass Spectroscopy (FABMS) was used to characterize the product. Results. Met(O)-3-AF2 was the only oxidation product detected at pH 3.0 to 8.0. The oxidation rates were independent of buffer concentrations, ionic strength, and pH from 3.0 to 7.0. However, there was an acceleration of the rates at basic pHs, and small amounts of degradation products other than Met(O)-3-AF2 were observed in this alkaline region. Conclusions. Oxidation of methionine in AF2 does not cause the biological inactivation reported by other laboratories since this drug is relatively stable under neutral conditions in the absence of oxiding agent.
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  • 85
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    Journal of chemical ecology 25 (1999), S. 611-628 
    ISSN: 1573-1561
    Keywords: Terrestrial isopods ; Oniscidea ; Porcellio scaber ; phenolics ; hydrolysis ; oxidation ; detoxification ; hindgut cuticle ; gut microbiota ; hepatopancreatic bacteria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract When adults of Porcellio scaber fed on litter prior to an artificial diet containing 5% of commercially available tannic acid, 55% of the ingested galloylglucose esters was excreted unchanged, about 25% was hydrolyzed, and 20% was oxidized during the gut passage. After reducing the counts of microorganisms in the gut of P. scaber, the data obtained indicated an important role of ingested platable microorganisms in hydrolyzing gallotannins. Oxidation of phenolics appeared to be mainly due to the endosymbiotic bacteria of the hepatopancreas. Microbial counts in the hindgut were strongly reduced by ingested galloylglucose esters, while gallic acid in the diet (2%) reduced the number of palatable fungi and bacteria less strikingly, and increased the total number of the gut microbiota. Hepatopancreatic bacteria were only slightly affected by ingested tannic acid, since the hepatopancreas contained only few galloylglucose esters. This may be due to the permeability of the hindgut cuticle: the cuticle of the anterior hindgut was freely permeable to gallic acid, while it was nearly impermeable to larger polyphenols. The cuticle of the posterior hindgut was permeable to only about 4% of the gallic acid present in the hindgut lumen. The results are discussed with respect to potentially harmful effects of ingested hydrolyzable tannins and their digestion in Porcellio scaber.
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  • 86
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    Journal of atmospheric chemistry 21 (1995), S. 97-114 
    ISSN: 1573-0662
    Keywords: Sulphur dioxide ; oxidation ; clouds ; riming ; freezing potential
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Experiments have been performed to investigate whether the process of freezing during riming in clouds may induce oxidation of dissolved SO2 to SO 4 2− . The experiments were conducted in a cold room at varying temperatures between −6 and −15 °C. Solutions containing dissolved SO2 and NH4OH in various proportions, in the range of concentrations between 3×10−5 and 10−3 M, were sprayed. Rime was collected on a rotating cylinder and analyzed. Absorption of oxygen from laboratory air was prevented, except in the spray, to avoid spurious oxidation. Blank experiments were made at +3 to +6 °C. The results indicate clearly that, as the dominant cation becomes NH 4 + rather than H+, substantial oxidation of S(IV) occurs during riming. This is consistent with redox reactions taking place as a result of charge separation at the ice-water interface during freezing.
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  • 87
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    Journal of thermal analysis and calorimetry 55 (1999), S. 681-690 
    ISSN: 1572-8943
    Keywords: chromia ; Fe-Cr alloy ; gas-solid reaction kinetics ; H2/H2O gas mixtures ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The high-temperature oxidation behavior of a ferritic alloy (SUS 430) in a SOFC environment, corresponding to the anode (H2/H2O gas mixture) and cathode (air) operating conditions, was determined with regard to application of the alloy as a metallic separator material in SOFC. The oxidation kinetics of Fe-16Cr alloy (SUS 430), was studied by thermogravimetry in H2/H2O gas mixtures with pH/pHO=94/6 and 97/3 and in air, in the temperature range 1023-1223 K, for 3.6 up to 1080 ks. It was found that the protective oxide scale, composed mainly of Cr2O3 with uniform thickness and excellent adhesion to the metal substrate, grows in accordance with the parabolic rate law. The dependence of the parabolic rate constant, kp, of the scale on temperature obeys the Arrhenius equation: kp=6.8×10-4 exp (-202.3 kJ mol-1R-1T-1) for H2/H2O gas mixtures with pH/pHO=94/6. The determined kp was independent of the oxygen partial pressure in the range from 5.2×10-22 to 0.21 atm at 1073 K, which means that the rates of growth of the scale on Fe-16Cr alloy in the above-mentioned atmospheres are comparable. The oxidation test results on Fe-16Cr alloy in H2/H2O gas mixtures and air demonstrate the applicability of SUS 430 alloys as a separator for SOFC.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 981-987 
    ISSN: 1572-8943
    Keywords: nickel phosphates ; nickel phosphides ; Ni-P alloys ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DTA in conjuction with X-ray diffraction analysis with a high-temperature camera and infrared spectroscopy was employed to determine the mechanism of oxidation of Ni-P alloys. Amorphous Ni-P powders were obtained from a nickel(II) sulphate bath as a nickel source and sodium dihydrophosphate(I) as a reducing agent. The crystallization product is composed of two phases: (f.c.c.) Ni and (b.c.t.) Ni3P. The amorphous to crystalline transformation takes place in the temperature range 280–330°C. Ni3P samples were heated from room temperature to 1050°C in air atmosphere at 5°C min−1. It was found that the first stage of oxidation of Ni3P goes through the intermediate phase of Ni12P5 formation to Ni2P. Some exothermic reactions were observed. Heating runs were interrupted after each reaction for crystal structure determination by IR spectrometry. Infrared spectra are reported and it is shown that the structure units present in the amorphous products at about 700°C were the oxoanions PO3 − and P2O7 −. The final products of the oxidation process are NiO and Ni3(PO4)2.
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    Reaction kinetics and catalysis letters 62 (1997), S. 117-120 
    ISSN: 1588-2837
    Keywords: m-xylene ; oxidation ; gas-phase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The gas-phase oxidation ofm-xylene on catalysts for partial hydrocarbon oxidation (Bi−Fe−Co−Ni−Mo−P−O, V−Sb−O and V−Ti−O) has been studied at 325–400°C. 3-Methylbenzaldehyde (for the first two catalysts), or both 3-methylbenzaldehyde and 3-methylbenzoic acid (for the last one) were shown to be the main partial oxidation products.
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    Reaction kinetics and catalysis letters 62 (1997), S. 185-190 
    ISSN: 1588-2837
    Keywords: Methane ; oxidation ; La1−xSrxCoO3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Methane oxidation over perovskite oxide (La1−xSrxCoO3) were investigated under rich oxygen circumstance. The large x in oxide or the higher temperature will promote the lattice oxygen to participate in the reaction. The relative adsorption properties of catalyst and reaction kinetic were also studied.
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    Reaction kinetics and catalysis letters 64 (1998), S. 103-107 
    ISSN: 1588-2837
    Keywords: Ethylene glycol ; glyoxal ; silver ; oxidation ; dehydrogenation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Interaction of ethylene glycol with clean and oxidized surfaces of an Ag catalyst has been studied under pre-catalysis conditions. On a clean surface, ethylene glycol was reversibly adsorbed with the formation of a multilayer coverage. Adsorbed ethylene glycol weakly bonded to the oxidized silver surface leads to the selective formation of glyoxalvia two parallel routes: dehydrogenation and oxidation. Dissociative interaction of ethylene glycol with Ag led to the appearance of formaldehyde and carbon dioxide by-products.
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  • 92
    ISSN: 1588-2837
    Keywords: V2O5−ZrO2 catalyst ; oxidation ; o-xylene ; temperature stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It has been established that at high temperatures (above 450°C) the V2O5−ZrO2 catalyst exhibits a higher selectivity in the oxidation ofo-xylene to phthalic anhydride than does the conventional V2O5−TiO2(a) catalyst. The catalyst selectivity is found to increase with respect to partial oxidation ofo-xylene, the valuable by-product maleic anhydride being obtained. Studies by different physicochemical methods have shown that V2O5−ZrO2 undergoes no significant phase and structural changes under high-temperature conditions.
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    Reaction kinetics and catalysis letters 58 (1996), S. 323-328 
    ISSN: 1588-2837
    Keywords: Formaldehyde ; oxidation ; molybdena ; methanol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A molybdena-silica catalyst showed rapid deactivation in the oxidation of formaldehyde to carbon oxides. The deactivation was greatly retarded by adding water in the feed. Thus, water coproduced in the partial oxidation of methanol to formaldehyde contributes to the relatively stable activity of the molybdena-silica catalyst in the partial oxidation reaction.
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  • 94
    ISSN: 1588-2837
    Keywords: Perovskite ; defect structure ; carbon monoxide ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract For a perovskite system La0.7Sr0.3Co1-xFexO3, the effect of partial substitution of Co by Fe on the particle microstructure and chemical composition of the surface layer has been studied. Iron incorporation was found to cause a structure rearrangement from the hexagonal (at x〈0.05) to the cubic (atx〉0.05) type, which was not accompanied by any appreciable variation of the surface layer composition. A transient sample with x=0.05 was characterized by a high degree of misorientation of microblocks and had the highest activity in the CO catalytic oxidation.
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    Reaction kinetics and catalysis letters 64 (1998), S. 129-137 
    ISSN: 1588-2837
    Keywords: H2S ; oxidation ; oxygen ; oxide catalysts ; catalytic activity ; oscillations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract H2S oxidation with oxygen has been studied on three industrial oxide catalysts (Fe−Cr−Zn, Cu−Cr−Al, V−Ti−Al). Thermodynamically possible changes in the composition of the catalysts have been evaluated. Regularities determining deep or partial oxidation of H2S have been found. Deep oxidation is connected to the presence of active oxygen on the catalyst surface; its removal results in a decrease of activity and increase of the sulfur selectivity. Oscillations caused by periodic adsorption-desorption of sulfur on the catalyst surface have been observed on the most active V−Ti−Al catalysts in oxygen excess.
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    Reaction kinetics and catalysis letters 64 (1998), S. 325-330 
    ISSN: 1588-2837
    Keywords: Diffusion ; oxidation ; solid phase kinetics ; free radicals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Capture of oxygen molecules by deep traps upon their diffusion in methanol/water glasses has been studied at 77 K. Deep traps may exist in matrices in which the oxidation of alkyl radicals is described by a time-dependent rate constant.
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    Reaction kinetics and catalysis letters 64 (1998), S. 343-349 
    ISSN: 1588-2837
    Keywords: Chemical absorption ; oxidation ; sodium sulfite ; cobalt sulfate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A gas-lift bubble column was used to investigate the kinetics of the reaction between oxygen and aqueous solutions of sodium sulfite in the presence of cobalt sulfate catalyst. Reaction orders have been determined for the sulfite, catalyst, and oxygen under high and low oxygen partial-pressure conditions.
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    Reaction kinetics and catalysis letters 66 (1999), S. 97-104 
    ISSN: 1588-2837
    Keywords: Heterogeneous catalysis ; oxidation ; temperature hysteresis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The temperature hysteresis observed in the oxidation of CO on both supported and unsupported catalysts can be explained by the local overheating of active centers rather than by transitions from one steady state to another.
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  • 99
    ISSN: 1588-2837
    Keywords: Catalyst ; ceramic foam ; molten salt ; Nox ; oxidation ; soot
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Diesel soot is combusted simultaneously by two reactions: combustion with NO2 and combustion with O2 with the aid of a molten salt catalyst. Both reaction pathways should always be considered to avoid misinterpretation of experimental data.
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    Reaction kinetics and catalysis letters 57 (1996), S. 3-11 
    ISSN: 1588-2837
    Keywords: Dehydrogenation ; oxidation ; propane ; propylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract At temperatures near 650°C and residence times ofca. 3 s, the homogeneous oxidative dehydrogenation (OXD) of propane to propylene and ethylene approached oxygen limiting conditions, even when the reactor was filled with quartz chips. The addition of catalysts that are known to be effective in the OXD of ethane slightly increased the reaction rate, but the selectivities at a given conversion level were the same as those that were achieved in the homogeneous reaction.
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