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  • Angiosperms
  • kinetics
  • Springer  (1,407)
  • American Association for the Advancement of Science (AAAS)  (4)
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  • 101
    Electronic Resource
    Electronic Resource
    Absolute Rate Coefficients for the Gas-Phase Reactions of NO3 Radical with a Series of Monoterpenes at T = 298 to 433 K (1999)
    Springer
    Journal of atmospheric chemistry 33 (1999), S. 265-282 
    Details
    ISSN: 1573-0662
    Keywords: atmosphere ; kinetics ; nitrate radical ; monoterpenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The aim of this work is to study the reactivity of some naturally emitted terpenes, 2-carene, sabinene, myrcene, α-phellandrene, d-limonene, terpinolene and γ-terpinene, towards NO3 radical to evaluate the importance of these reactions in the atmosphere and their atmospheric impact. The experiments with these monoterpenes have been carried out under second-order kinetic conditions over the range of temperature 298–433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). This work is the first temperature dependence study for the reactions of the nitrate radical with the above-mentioned monoterpenes. The measured rate constants at 298 K for the reaction of NO3 with such terpenes are as follows: 2-carene, 16.6 ± 1.8, sabinene 10.7 ± 1.6, myrcene 12.8 ± 1.1, α-phellandrene 42 ± 10, d-limonene 9.4 ± 0.9, terpinolene 52 ± 9 and γ-terpinene 24 ± 7, in units of 10-12 cm3 molecule-1 s-1. The proposed Arrhenius expressions, for the reactions of NO3 with 2-carene, sabinene, myrcene and α-phellandrene are, respectively k1 = (1.4 ± 0.7) × 10-12 exp[(741 ± 190/T)] (cm3 molecule-1 s-1), k2=(2.3 ± 1.3) × 10-10 exp[−(940 ± 200/T)] (cm3 molecule-1 s-1), k3 = (2.2 ± 0.2) × 10-12 exp[(523 ± 35/T)] (cm3 molecule1 s-1) and k4 = (1.9 ± 1.3) × 10-9 exp[−(1158 ± 270/T)] (cm3 molecule-1 s-1). A decrease in the rate constants when raising the temperature has also been found for the reaction of d-limonene with NO3 while an increase in the rate constant with temperature has been observed for the reactions of terpinolene and γ-terpinene with NO3. Tropospheric half-lives for these terpenes have been calculated at night and during the day for typical NO3 and OH concentrations showing that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with NO3 radical can be an important, if not dominant, loss process for these naturally emitted organics and for NO3 radicals.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1006178530211
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  • 102
    Electronic Resource
    Electronic Resource
    Laboratory Kinetic Studies of the Reactions of Cl Atoms with Species of Biogenic Origin: δ3-Carene, Isoprene, Methacrolein and Methyl Vinyl Ketone (1999)
    Springer
    Journal of atmospheric chemistry 34 (1999), S. 163-170 
    Details
    ISSN: 1573-0662
    Keywords: δ3-carene ; chlorine atoms ; isoprene ; kinetics ; methacrolein and methyl vinyl ketone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10-10, (2.1 ± 0.5) × 10-10, (3.2 ± 0.5) × 10-10, and (4.9 ± 0.5) × 10-10 cm3 molecule-1 s-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and δ3-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1006214423298
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  • 103
    Electronic Resource
    Electronic Resource
    Growth of Ordered Domains in a Computer Model Alloy with Lattice Misfit (1999)
    Springer
    Journal of statistical physics 95 (1999), S. 23-43 
    Details
    ISSN: 1572-9613
    Keywords: model alloy ; Monte Carlo ; elastic interactions ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We study via Monte Carlo simulations the influence of elastic interactions on the ordering and decomposition of a two-dimensional model binary alloy with antiferromagnetic nearest and ferromagnetic next nearest neighbor type interactions following a quench into the coexistence region. The elastic interaction leads to the development of a platelet morphology for the segregated ordered and disordered regions. A length scale characterizing the coarsening process follows a law of the type R=a+bt 1/3 with the growth b decreasing with the amount of ordered phase; this appears to be due to the presence of anti-phase boundaries between neighboring domains ordered on different sublattices which are difficult to eliminate. The application of uniaxial external stress results in “rafting” of the domains. Many of the simulation results are in agreement with experimentally observed effects in nickel-base superalloys.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004569209618
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  • 104
    Electronic Resource
    Electronic Resource
    Kinetics of Phase Ordering on Curved Surfaces (1999)
    Springer
    Journal of statistical physics 95 (1999), S. 949-979 
    Details
    ISSN: 1572-9613
    Keywords: numerical simulations ; interface description ; kinetics ; phase ordering ; relaxation ; dynamical scaling ; model A ; curved surface ; lipid bilayer ; dominant length scale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract An interface description and numerical simulations of model A kinetics are used for the first time to investigate the intrasurface kinetics of phase ordering on corrugated surfaces. Geometrical dynamical equations are derived for the domain interfaces. The dynamics is shown to depend strongly on the local Gaussian curvature of the surface, and can be fundamentally different from that in flat systems: dynamical scaling breaks down despite the persistence of the dominant interfacial undulation mode; growth laws are slower than t 1/2 and even logarithmic; a new very-late-stage regime appears characterized by extremely slow interface motion; finally, the zero-temperature fixed point no longer exists, leading to metastable states. Criteria for the existence of the latter are derived and discussed in the context of more complex systems.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004502500899
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  • 105
    Electronic Resource
    Electronic Resource
    Sorption Equilibria and Kinetics of Hydrocarbons onto Activated Carbon Samples Having Different Micropore Size Distributions (1999)
    Springer
    Adsorption 5 (1999), S. 25-37 
    Details
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1026481704926
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  • 106
    Electronic Resource
    Electronic Resource
    The detailed kinetics of the desorption of hydrogen from polycrystalline copper catalysts (1999)
    Springer
    Catalysis letters 59 (1999), S. 143-149 
    Details
    ISSN: 1572-879X
    Keywords: hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019080823616
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  • 107
    Electronic Resource
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    Furfural hydrogenation over carbon‐supported copper (1999)
    Springer
    Catalysis letters 60 (1999), S. 51-57 
    Details
    ISSN: 1572-879X
    Keywords: furfural hydrogenation ; Cu/carbon catalysts ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019090520407
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  • 108
    Electronic Resource
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    Study of the ammonia decomposition over iron catalysts (1999)
    Springer
    Catalysis letters 60 (1999), S. 167-171 
    Details
    ISSN: 1572-879X
    Keywords: ammonia decomposition ; iron catalyst ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019007024041
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  • 109
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    Characterization of the heat shock protein response of Atlantic salmon (Salmo salar) (1999)
    Springer
    Fish physiology and biochemistry 20 (1999), S. 279-292 
    Details
    ISSN: 1573-5168
    Keywords: heat shock proteins ; hsp70 ; kinetics ; in vitro ; salmon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The heat shock protein (hsp) response of juvenile Atlantic salmon, Salmo salar was investigated in isolated tissues subjected to various degrees of thermal shock. Distinct but overlapping arrays of proteins from the major hsp families (hsps 100, 90, 70, 60 and small hsps) were induced in branchial lamellae, hepatic tissue and erythrocytes. The two most prominent proteins induced by heat shock (MW ≅ 65 and 66 kDa) were found to be antigenic homologues of mammalian hsps72/73. A 2.6 kb transcript upregulated by the same conditions hybridized with cDNA probes to both human and salmon hsp70. Branchial lamellae exhibited the greatest degree of thermotolerance and mounted the most significant heat shock response. Moderate thermal shock induced more species of proteins in branchial lamellae than in hepatic tissue or erythrocytes, with the rate of hsp65/66 synthesis increased by as much as five fold. Thermal shock induced hsp65/66 eight fold in erythrocytes. In contrast, hepatic tissue which was least tolerant of thermal shock, lacked the inducible hsp65 and exhibited minimal induction of hsp66. Persistence of hsps was tested in erythrocytes, where elevated levels remained in the cells for at least 48 h after heat shock. The temporal pattern and magnitude of the hsp response in the stenothermal Atlantic salmon differed from that previously reported for eurythermal species. Also notable was the limited hsp response mounted by salmon tissues exposed to sodium arsenite, a known inducer of hsps. The characteristics of the hsp response to thermal shock support the significance of these proteins in adaptation of Atlantic salmon to environmental insult.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007743329892
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  • 110
    Electronic Resource
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    Low-temperature heterogeneous oxidation of sulfide ions on a higher Co oxide system in aqueous medium (1999)
    Springer
    Reaction kinetics and catalysis letters 66 (1999), S. 55-62 
    Details
    ISSN: 1588-2837
    Keywords: Oxidation of sulfides ; kinetics ; higher Co oxide IR ; XPS ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Low-temperature heterogenous oxidation of sulfide ions on a higher Co oxide system in aqueous medium has been studied. The effects of pH, temperature and catalyst amount on the kinetic parameters as well as on the selectivity of the oxidation process were investigated. An oxidation mechanism has been proposed based on the results of kinetic investigations and on the data obtained by IR and XPS spectroscopic studies of Co oxide before and after sulfide ion oxidation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02475741
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  • 111
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    Photocatalytic water purification: Destruction of resorcinol by irradiated titania (1999)
    Springer
    Reaction kinetics and catalysis letters 66 (1999), S. 289-295 
    Details
    ISSN: 1588-2837
    Keywords: Resorcinol photooxidation ; kinetics ; intermediates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ethanedial, butanoic acid anhydride and trihydroxybenzenes have been determined as intermediates of resorcinol photocatalytic oxidation. The photoreaction rate shows a 1st order dependence on resorcinol concentration. The calculated reaction rate constant is 2.1×10−8 mol dm−3 s−1, which is similar to the rate constant of phenol photocatalytic oxidation on TiO2 reported beore.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02475803
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  • 112
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    Kinetics of oxidation of diols by ozone in aqueous solution (1999)
    Springer
    Reaction kinetics and catalysis letters 68 (1999), S. 237-242 
    Details
    ISSN: 1588-2837
    Keywords: Diols ; oxidation ; ozone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the oxidation of diols by ozone was investigated by a spectrophotometric method in the temperature interval of 277–304 K. The activation parameters of the reaction were determined.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02475507
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  • 113
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    Kinetics of supramolecular crystallization of concentrated suspensions of monodisperse spherical silica particles (1999)
    Springer
    Reaction kinetics and catalysis letters 68 (1999), S. 387-391 
    Details
    ISSN: 1588-2837
    Keywords: Silica ; monodisperse particles ; supramolecular crystallization ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of supramolecular crystallization of concentrated suspensions is three-dimensional and follows the Avrami-Erofeev equation: A=1-exp[-(kt)m], where m=4. The rate constant k is proportional to the probability of the appearance of a crystallization center in unit volume in unit time and the linear crystal growth rate, which is determined experimentally.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02475528
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  • 114
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    Modeling of oxygen adsorption on silver (1999)
    Springer
    Reaction kinetics and catalysis letters 66 (1999), S. 265-272 
    Details
    ISSN: 1588-2837
    Keywords: Oxygen ; surface ; silver ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different adsorption forms of oxygen on silver are discussed. Four main types of oxygen forming at different temperatures and oxygen pressures have been distinguished. A kinetic model describing the formation and transformations of the oxygen forms and taking into account the surface amorphization has been proposed. Numerical modeling of stationary concentrations using this model gives evidence for a temperature window ΔT=500–800 K, where a quasimolecular oxygen state (E=530.5 eV, Tdes=800–900 K) can exist at high oxygen pressures.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02475800
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  • 115
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    Kinetics of oxidation of aliphatic alcohols by ozone in aqueous solutions (1999)
    Springer
    Reaction kinetics and catalysis letters 68 (1999), S. 257-263 
    Details
    ISSN: 1588-2837
    Keywords: Alphatic alcohols ; oxidation ; ozone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of oxidation of aliphatic alcohols by ozone in aqueous solutions was investigated in the temperature interval of 292–317 K. The activation parameters of the reaction were determined. The dissociation energies of CH-bonds of the studied substrates were calculated with the use of the AM1 semiempirical method.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02475510
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  • 116
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    Thermal Analysis Studies on Isopropylnitrate (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    Details
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010190829563
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  • 117
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    RCTA Techniques Used in Studies of Solid State Reactions in Inorganic Compounds (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 17-26 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; reaction controlled thermal analysis ; stepwise isothermal analysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The Reaction Controlled Thermal Analysis techniques, RCTA, are very useful both in thermogravimetric and dilatometric studies. In the present paper this big family of techniques is divided into three main classes: Quasi-Isothermal techniques (QIA); Controlled Reaction Rate Thermal Analysis (CRTA) and Reaction (Event) Controlled Heating Rate Adaption. After a short presentation of these techniques and the general advantages of RCTA, two examples of kinetic studies on thermal decomposition of Ba- and Ce oxalates by using Stepwise Isothermal Analysis, SIA, introduced by the author is presented and discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010158602719
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  • 118
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    Gegeneration of Deactivated β-Zeolite by Coke Oxidation (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 297-303 
    Details
    ISSN: 1572-8943
    Keywords: β-zeolite ; coke ; cumene ; kinetics ; regeneration ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An accurate description of coke burn off is obtained from a catalyst based on β-zeolite and used for benzene alkylation with propylene giving cumene by using the thermogravimetric technique. A simple empirical kinetic model was successfully applied to interpolate the data of thermogravimetric analysis performed on samples after partial burn off. Different temperatures, partial pressures of oxygen and gas flow rates were the variables studied in order to calculate the apparent rates and the activation energy for the coke oxidation reaction and to outline the best conditions for the industrial regeneration procedure of our proprietary catalyst PBE-1 for cumene synthesis. Combining the unusually long lifetime per reaction cycle with the optimized regeneration procedure leads to an outstanding overall catalyst life.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010178029977
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  • 119
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    DSC Analysis of the Induction Period in the Vulcanisation of Rubber Compounds (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 1107-1113 
    Details
    ISSN: 1572-8943
    Keywords: differential scanning calorimetry ; induction period ; kinetics ; vulcanisation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Vulcanisation of rubber compounds was studied by DSC under isothermal and non-isothermal conditions. The parameters of an Arrhenius-like equation describing the temperature dependence of induction period have been obtained both from isothermal and non-isothermal measurements. A new method for obtaining the kinetic parameters from non-isothermal measurements, based on the dependence of onset temperature of vulcanisation peak on heating rate, is presented. Also, a procedure for the evaluation of temperature difference between the furnace and sample is proposed. It has been shown that the treatment of non-isothermal DSC measurements gives the kinetic parameters free of systematic errors. The new method can also be used for studying other reactions exhibiting the induction period.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010148810569
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  • 120
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    Studies on the Kinetics of the First Order Autocatalytic Decomposition Reaction of Highly Nitrated Nitrocellulose (1999)
    Springer
    Journal of thermal analysis and calorimetry 58 (1999), S. 403-411 
    Details
    ISSN: 1572-8943
    Keywords: first order autocatalytic reaction ; HNNC ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the first order autocatalytic decomposition reaction of highly nitrated nitrocellulose (HNNC, 14.14%N) was studied by using thermogravimetry (TG). The results show that the TG curve for the initial 50% of mass-loss of HNNC can be described by the first order autocatalytic equation $$\frac{{{\text{d}}y}} {{dt}} = - 10^{16.4} \exp \left( { - \frac{{210380}} {{RT}}} \right)y - 10^{16.7} \exp \left( { - \frac{{171205}} {{RT}}} \right)y(1 - y)$$ and that for the latter 50% mass-loss of HNNC described by the reaction equations $$\frac{{dy}} {{dy}} = - 10^{16.3} \exp \left( { - \frac{{169483}} {{RT}}} \right)y\quad (n = 1)$$ and $$\frac{{dy}} {{dt}} = - 10^{16.8} \exp \left( { - \frac{{165597}} {{RT}}} \right)y^{2.61} \quad (n \ne 1)$$
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010163423775
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  • 121
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    CRTA for the Thermoanalytical Screening of Volatile Compounds: 3. Study on thermal destruction process, taking place simultaneously with evaporation process (1999)
    Springer
    Journal of thermal analysis and calorimetry 58 (1999), S. 113-116 
    Details
    ISSN: 1572-8943
    Keywords: coordinationcompounds ; CRTA ; kinetics ; polymerization ; pyrolysis ; quasi-equilibrium ; TG ; thermolysis ; volatility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Quasi-equilibrium thermogravimetry (variant of CRTA) is put to use as an express method of thermoanalytical screening for volatile compounds. During the experiments for P—T relationship calculations (running with several calibrated standard sample holders) the non-volatile (polymerized) residue is formed (and is decomposed with further temperature rising). Thermogravimetric data are used for the calculation of the kinetic parameters for the polymerization reaction, taking place (concurrently with the evaporation) in the melt of the studied volatile compound.
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    URL: http://dx.doi.org/10.1023/A:1010183601559
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  • 122
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    Investigation of the Chemical Action of the Gliding and “Point” Arcs Between the Metallic Electrode and Aqueous Solution (1999)
    Springer
    Plasma chemistry and plasma processing 19 (1999), S. 53-67 
    Details
    ISSN: 1572-8986
    Keywords: Arc ; gliding arc ; gas temperature ; electron temperature ; ion composition ; ion bombardment ; liquid electrode ; dye oxidation ; kinetics
    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 plasma–solution interaction processes for gliding and “point” arcs between the aqueous solution surface and the metal electrode in the gas phase are studied. The plasma, liquid, and surface zones are taken into consideration. The electric field strength is measured, and the gas and electron temperatures and ion composition are estimated for the plasma zone. The cathode fall, water vaporization rate, and active species current yield due to the radiation chemistry mechanism are determined for the surface zone. The efficiency of oxidation of iodine ions and organic dyes by different types of discharge in the liquid zone are investigated. The difference in action of the various discharge types may be connected with various influences of the plasma and surface zone on the oxidation processes.
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    URL: http://dx.doi.org/10.1023/A:1021803932496
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    Modelling the growth of a methanotrophic biofilm: Estimation of parameters and variability (1999)
    Springer
    Biodegradation 10 (1999), S. 177-191 
    Details
    ISSN: 1572-9729
    Keywords: AQUASIM ; biodegradation ; biofilm ; growth ; kinetics ; methane ; modelling ; nitrification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This article discusses the growth of methanotrophic biofilms. Several independent biofilm growths scenarios involving different inocula were examined. Biofilm growth, substrate removal and product formation were monitored throughout the experiments. Based on the oxygen consumption it was concluded that heterotrophs and nitrifiers co-existed with methanotrophs in the biofilm. Heterotrophic biomass grew on soluble polymers formed by the hydrolysis of dead biomass entrapped in the biofilm. Nitrifier populations developed because of the presence of ammonia in the mineral medium. Based on these experimental results, the computer program AQUASIM was used to develop a biological model involving methanotrophs, heterotrophs and nitrifiers. The modelling of six independent growth experiments showed that stoichiometric and kinetic parameters were within the same order of magnitude. Parameter estimation yielded an average maximum growth rate for methanotrophs, μm, of 1.5 ± 0.5 d−1, at 20 °C, a decay rate, bm, of 0.24 ± 0.1 d−1, a half saturation constant, $${\text{K}}_{{\text{S(CH}}_{\text{4}} {\text{)}}} $$ , of 0.06 ± 0.05 mg CH4/L, and a yield coefficient, $$Y_{CH_4 } $$ , of 0.57 ±: 0.04 g X/g CH4. In addition, a sensitivity analysis was performed on this model. It indicated that the most influential parameters were those related to the biofilm (i.e. density; solid-volume fraction; thickness). This suggests that in order to improve the model, further research regarding the biofilm structure and composition is needed.
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    URL: http://dx.doi.org/10.1023/A:1008317906069
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    Kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite (1999)
    Springer
    Journal of applied electrochemistry 29 (1999), S. 191-200 
    Details
    ISSN: 1572-8838
    Keywords: cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003490810114
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    Spectroscopic and Thermal Studies on 2,4,6-trinitro Toluene (TNT) (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 173-185 
    Details
    ISSN: 1572-8943
    Keywords: IRS ; kinetics ; mechanism ; nitro aromatic ; TA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics and mechanism of the initial stage of thermal decomposition of 2,4,6-trinitro toluene (TNT), a widely used high explosive, have been studied, together with its morphology and evolved gaseous products using thermogravimetry (TG), differential thermal analysis (DTA), infrared spectroscopy (IR) and hot-stage microscopy. The kinetics of the thermolysis has been followed by IR after suppressing volatilisation by matrixing and by isothermal TG without suppressing volatilisation to simulate actual user conditions. The best linearity was obtained for Avrami-Erofeev equation for n=1 in isothermal IR and also in isothermal TG. The activation energy was found to be 135 kJ mol−1, with logA (in s−1) 12.5 by IR. The effect of additives on the initial thermolysis of TNT has also been studied. Evolved gas analysis by IR showed that CO2, NO2, NO and H2O are more dominant than N2O, HCN and CO. The decomposition involves the initial rupture of the C-NO2 bond, weakened by hydrogen bonding with the labile hydrogen atom of the adjacent CH3 group, followed by the abstraction of the hydrogen atom of the methyl group by NO2, generated in the initial step.
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    URL: http://dx.doi.org/10.1023/A:1010152626354
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    Kinetics of Thermal Decomposition of Mixed Ligand Trinuclear Compound of Cadmium(II) (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 233-241 
    Details
    ISSN: 1572-8943
    Keywords: cadmium(II) atom ; kinetics ; non-isothermal decomposition ; Schiff-base compound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal C81H78N12O6Cd3 was synthesized and its structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system space group P21/n with cell parameters, a=15.959(4) Å, b=26.222(3) Å, c=25.907(6) Å, β=101.60(2)°. The non-isothermal kinetics of the crystal was studied by use of non-isothermal TG and DTG curves. The kinetic parameters were analyzed by means of integral and differential methods, and mechanism functions of the thermal decomposition reaction for its second step were proposed. The kinetic equation of thermal decomposition is expressed as: dα/dt=Aexp(-E/RT)1.5(1-α)4/3[1/(1-α)1/3-1]−1. The average values of E(kJ mol−1) and lnA/s−1 are 339.25, 43.95, respectively.
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    Re-examination of the Kinetics of the Thermal Dehydroxylation of Goethite (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 301-309 
    Details
    ISSN: 1572-8943
    Keywords: dehydroxylation ; goethite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermal dehydroxylation of aluminuous goethites [1] synthesised from a ferrous salt has been re-examined using the general reaction order kinetic law. The utilised data processing was based on the procedures employed by dissolution kinetics. Recalculation of the activation energies EA of the dehydroxylation yielded the values 130, 132, 128, and 123 kJ mol−1 for pure goethite, goethite with 10, 20, and 30 mol% Al substitution, respectively. The values of EA are in a good agreement with those given for goethite in literature. The EA values are linearly related with the chemically bound excess H2O/OH− in the crystal lattice that is apparently influenced by Al substitution.
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    Thermal Decompositions of (RE)Ba2Cu3O6 (RE=Y, Nd, Er) (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 691-698 
    Details
    ISSN: 1572-8943
    Keywords: activation energy ; kinetics ; solid-state reactions ; superconductors ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetric in situ measurements of oxygen loss from (RE)Ba2Cu3O6 samples (RE=Y, Nd, Er) heated isothermally in a relatively high dynamic vacuum were made with a Cahn RG electrobalance. Single-phase orthorhombic samples of composition (RE)Ba2Cu3O7-x (highest oxygen content) were synthesized from stoichiometric (1:2:3) mixtures of high-purity (RE)2O3, BaCO3 and CuO. The original 1:2:3 mixture was prepared by the two-stage procedure described earlier. The crystal structure of the sample in the original orthorhombic phase was controlled by the X-ray powder method (CuKα radiation) using a Stadi P Stoe diffractometer with a position-sensitive detector. The decomposition curves are described by the sum of exponential terms corresponding to rapid and slow first-order processes in which differently sized grains of the powder samples are involved. The activation energies are estimated from appropriate Arrhenius plots.
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    Thermal Decompositions of the Molybdotellurates of Nickel(II) and Cobalt(II) (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 779-788 
    Details
    ISSN: 1572-8943
    Keywords: cobalt ; dynamic and isothermal methods ; kinetics ; molybdotellurates ; nickel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Molybdotellurates [M(H2O)6]3·[TeMo6O24], with M=Ni(II) and Co(II), were synthesized and characterized by single-crystal X-ray diffraction for compound 1 and X-ray powder diffraction for compound 2, EDAX, IR, electronic spectra in the solid phase and in solution, and magnetic properties. Thermogravimetry and differential scanning calorimetry of both compounds revealed a loss of 11 water molecules through an endothermal process with ΔH=800 kJ mol−1 for the nickel compound and ΔH=833 kJ mol−1 for the cobalt compound. The residual compounds were characterized by chemical analysis, IR and XPS spectroscopy
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    Dehydration Reaction of Manganese(II) Oxalate Dihydrate in the Solid State New Method in the Study of Non-isothermal Kinetics (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 877-884 
    Details
    ISSN: 1572-8943
    Keywords: dehydration ; kinetics ; manganese(II) oxalate dihydrate ; mechanism ; non-isothermal ; TG-DTA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new method was proposed for determining the most probable mechanism function of a solid phase reaction. According to Coats-Redfern's integral equation Eβ→0 was calculated by extrapolating β to zero using a series of TG curves with different heating rates. Similarly, Eα→0 was calculated according to Ozawa's equation. The most probable mechanism function of the solid phase dehydration of manganese(II) oxalate dihydrate was confirmed to be G(α)=(1-α)1/2 by comparing Eα→0 with Eβ→0.
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    Thermoanalytical Study of the Dehydration of Cyclodextrin Inclusion Complexes of Clofibric Acid (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 1329-1334 
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    ISSN: 1572-8943
    Keywords: cyclodextrin complexes ; dehydration ; kinetics ; TG-DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Hydrated inclusion complexes of the hosts β-CD (CD=cyclodextrin), γ-CD and permethylated β-CD with the guest clofibric acid were analysed by TG and DSC methods to characterise their dehydration behaviours. Activation energies for dehydration of the β- and γ-CD clofibric acid complexes, determined by isothermal thermogravimetry, are significantly lower (∼20-25%) than those for the corresponding uncomplexed hydrated CDs. These data can be reconciled with X-ray structural data which show that H2O molecules in the complexes occupy different crystal sites from those occupied in the parent CDs.
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    Non-Isothermal Pyrolysis and Kinetics of Oil Shales (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 953-958 
    Details
    ISSN: 1572-8943
    Keywords: differential scanning calorimeter ; kinetics ; oil shale ; pyrolysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this research, non-isothermal pyrolysis behavior and kinetics of three oil shales were studied by thermal analysis methods. All the thermal effects were endothermic and no exothermic region was observed in DSC curves. When oil shales are heated in nitrogen atmosphere in TG/DTG, two different mechanisms causing loss of mass were observed. The region between ambient temperature and 500 K was distillation. The second mechanism was visbreaking and cracking and it was observed between the region 500 and 800 K. Kinetic parameters of all the samples are determined by Coats and Redfern method and the results are discussed with regard to their accuracy and the ease of interpretation.
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    Kinetics of Solute Flow to Partial Dislocation in Cu–3.4 At.% Sb (1999)
    Springer
    Journal of thermal analysis and calorimetry 57 (1999), S. 607-622 
    Details
    ISSN: 1572-8943
    Keywords: Cu–3.4 At.% Sb alloy ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of solute segregation to partial dislocations in a Cu–3.4 At.% Sb alloy was studied by using a phenomenological approach with differential scanning calorimetry and isothermal calorimetry. The material, severely deformed by repeated bending, presented an excess of dissociated edge dislocations with a dislocation density amounting to about 8.5·1014 m−2, calculated using a prior model of the authors, together with calorimetric recrystallization trace analysis. The kinetics was found to be ruled by two overlapping mechanisms: diffusion of solute atoms mostly through dislocation pipes in the initial and middle stages of the reaction process, acting together with bulk solute diffusion in these stages and later. Bulk solute diffusion increases as the reaction proceeds, as shown by the increasing values of apparent activation energy in the reaction. The exponent of the Mehl-Johnson-Avrami equation used in the phenomenological description was successfully fitted to a time—temperature-dependent function, increasing in agreement with the apparent activation energy behaviour, as may be expected.
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    Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 699-705 
    Details
    ISSN: 1572-8943
    Keywords: interaction in solid phase ; lithium carbonate ; lithium orthosilicate ; kinetics ; solid electrolytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m2g-1 instead of aerosil with one of 175 m2g-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended.
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    Physicochemical Studies and Thermal Decomposition Kinetics of Co(II), Ni(II), Cu(II) and Zn(II) Complexes of Citronellal Anthranilic Acid (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 817-831 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; Schiff-bases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Cobalt(II), nickel(II), copper(II) and zinc(II) complexes of two new Schiff-bases, citronellal anthranilic acid and citronellal-5-bromoanthranilic acid have been synthesized. On the basis of spectral, magnetic and thermal data, octahedral structure was assigned to all complexes [ML2(H2O)2]. Thermal decomposition of these complexes was studied by TG. Kinetic parameters, viz activation energy, E, pre-exponential factor, A, and order of reaction, n, were calculated from the TG curves using mechanistic and non-mechanistic integral equations.
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    Thermogravimetric Analysis of Cobalt(II)-dothiepin Complexes (1999)
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 841-849 
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    ISSN: 1572-8943
    Keywords: cobalt(II)-dothiepin ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The complexes of cobalt(II) with dothiepin (DOT) hydrochloride have been studied for kinetics of thermal degradation by thermogravimetric analysis (TG) and derivative thermogravimetric studies (DTG) in a static nitrogen atmosphere at a heating rate of 10° C min−1. A general mechanism of thermal decomposition is advanced involving dehydration and decomposition process for both organic and inorganic ligands. The thermal degradation reactions were found to proceed in three steps having an activation energy in the range 6.75–170 kJ mol−1. Thermal decomposition kinetics parameters were computed on the basis of thermal decomposition data.
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    Thermal Analysis and Kinetics of Solid-State Reactions Its Application to Education in Chemistry (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 855-861 
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    ISSN: 1572-8943
    Keywords: education ; kinetics ; microscopy ; solid-state reactions ; teaching materials
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In an attempt to show the importance of preparing extensively teaching materials for comprehensive education in thermal analysis at an undergraduate level, the significance of the teaching materials concerning the thermal analysis and kinetics of the solid-state reactions is discussed by reviewing our teaching activities at Hiroshima University. Application of the thermoanalytical techniques to thermal decomposition of basic copper(II) salts is appropriate for an introductory experiment to thermal analysis. Microscopic observations of the textural change during the thermal dehydration of inorganic salt hydrates are suitable for introducing the kinetics of solid-state reactions. A computer practice of drawing the experimental master plot enables students to understand the kinetic theory.
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    Progress in Non-parametric Kinetics (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 843-849 
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    ISSN: 1572-8943
    Keywords: adiabatic calorimetry ; kinetics ; non-parametric kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The non-parametric kinetics (NPK) method has been recently developed for the kinetic treatment of thermoanalytical data. The most significant feature of this method is its ability to provide information about the reaction kinetics without any assumptions either about the functionality of the reaction rate with the degree of conversion or the temperature. This paper presents the results of the application of the method to adiabatic calorimetry. Some data have been obtained by numerical simulation, but also the thermal decomposition of DTBP, a well known first order reaction, has been studied, being the obtained results in good agreement with literature.
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    Pre-Eutectic Densification of Calcium Carbonate Doped with Lithium Carbonate (1999)
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 1461-1473 
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    ISSN: 1572-8943
    Keywords: CaCO3 ; densification ; kinetics ; Li2CO3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pressureless sintering of CaCO3 was carried out, with Li2CO3 (from 0.5 to 8 wt%) as an additive, under different pressures of CO2. Densification occurs between 600 and 700°C. Sintering above the eutectic temperature (T〉662°C) leads to the decomposition of calcium carbonate and the materials become expanded. At 620° under 1 kPa of CO2, a relative density of 96% is reached. Li2CO3 enhances the densification process and grain growth of calcium carbonate. CO2 pressure slows down densification and grain growth kinetics. These results are explained by the influence of carbonate and calcium ion vacancies on the sintering mechanisms.
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    Thermal Behaviour and Decomposition Kinetics for Two Palladium(II) Complexes with 1-aminopyrene and its Derivative (1999)
    Springer
    Journal of thermal analysis and calorimetry 58 (1999), S. 383-391 
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    ISSN: 1572-8943
    Keywords: 1-aminopyrene (apyr) ; N-(2-pyridylmethylene)-1-pyrenylamine (pmpa) ; kinetics ; palladium(II)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition studies for two palladium(II) complexes Pd(apyr)2Cl2 and Pd(pmpa)Cl2 (apyr=1−aminopyrene and pmpa=N−(2−pyridylmethylene)−1−pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, Šesták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.
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    Isothermal and Non-Isothermal Techniques in Kinetic Studies of Reactions in a Photoactive Molecular Material (1999)
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 35 (1999), S. 139-146 
    Details
    ISSN: 1573-1111
    Keywords: dihydropyridine ; photochromism ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermally driven reactions in a crystalline photochromic solid, 1-methyl-2,4,4,6-tetraphenyl-1,4-dihydropyridine (DHP), has been studied. The processes have been monitored by measuring the isothermal bleaching of coloured species produced upon UV irradiation of DHP, and by measuring the heat flow in non-isothermal differential scanning calorimetry experiments. Signatures of two processes were detected; a combination of quantum-chemical calculations and spectroscopic measurements allowed us to attribute them to reactions occurring in the photochromic system.
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    3D Monte Carlo Simulations of Diffusion Limited Cluster Aggregation up to the Sol-Gel Transition: Structure and Kinetics (1999)
    Springer
    Journal of sol gel science and technology 15 (1999), S. 129-136 
    Details
    ISSN: 1573-4846
    Keywords: simulation ; percolation ; aggregation ; structure ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Three-dimensional (3D) Monte Carlo simulations of diffusion limited cluster aggregation at different concentrations (φ) show a crossover from a flocculation regime at short times to a percolation regime close to the gel time (tg). Contrary to suggestions in the literature tg is independent of the system size (L) for large L. The structural and temporal crossovers between flocculation and percolation take place at characteristic values of the cluster mass (mc) and the time (tc) which depend on φ. After normalisation by these characteristic values the crossovers are independent of φ except for very small clusters and at short times. The concentration dependence of mc and tc indicates that the crossover takes place at a given cumulated volume fraction of the clusters independent of φ. At low concentrations the φ-dependence of tg is determined by the cluster growth in the flocculation regime.
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    Similarity between electron donor side reactions in the solubilized Photosystem II–LHC II supercomplex and Photosystem-II-containing membranes (1999)
    Springer
    Photosynthesis research 60 (1999), S. 191-198 
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    ISSN: 1573-5079
    Keywords: fluorescence lifetime ; kinetics ; P680+ ; transient absorption spectroscopy ; water splitting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The PS II–LHC II supercomplex is a novel type of oxygen evolving Photosystem II (PS II) core particle that contains the light harvesting complex proteins Lhcb1/2/4/5 in addition to the PS II reaction centre, oxygen evolving complex (OEC) and inner antennae [Hankamer et al. (1997) Eur J Biochem 243: 422–429]. The 33 and 23 kDa extrinsic proteins in these particles have been localised by image analysis of electron micrographs and averaging techniques [Boekema et al. (1998) Eur J Biochem 252: 268–276]. To assay the functionality of the water splitting complex, we compared the single flash P680+ reduction kinetics in these supercomplexes with those of PS II-rich granal stack membranes (BBYs). We found that the P680+ reduction kinetics in PS II–LHC II supercomplexes were indistinguishable from those in BBYs. We also examined a number of PS II core particles lacking the Lhcb components. All of these had different P680+ reduction kinetics, which we attributed to partial loss of OEC function before and during the measurements.
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    Estimation of rate constants of the partial reactions of carboxylation of ribulose-1,5-bisphosphate in vivo (1999)
    Springer
    Photosynthesis research 60 (1999), S. 247-256 
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    ISSN: 1573-5079
    Keywords: irradiance ; kinetics ; method ; photosynthesis ; regulation ; rubisco
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract An in vivo method for the estimation of kinetic parameters of partial reactions of carboxylation of ribulose 1,5-bisphosphate (RuBP) catalyzed by ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is described. Rubisco in barley, wheat and bean is different in the ability of its active centers to bind RuBP. The rate constant of the formation of the Rubisco-RuBP complex in these plants at 25 °C is 0.414, 0.245 and 0.660 mM-1 s-1, respectively. The rate constant of the reaction of the Rubisco-bound enediol with CO2 does not differ significantly in barley and wheat, and averages 66 mM-1 s-1. Decreased irradiance inhibits Rubisco in two ways: by reducing the concentration of operating catalytic sites and by decreasing the rate constant of binding of RuBP to Rubisco. High concentrations of CO2 inhibit Rubisco by decreasing the concentration of competent carboxylation centers, without any s ignificant influence upon the rate constants of partial reactions.
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    Regulatory mechanisms of poly(ADP-ribose) polymerase (1999)
    Springer
    Molecular and cellular biochemistry 193 (1999), S. 19-22 
    Details
    ISSN: 1573-4919
    Keywords: poly(ADP-ribose)polymerase ; kinetics ; allosterism ; regulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Here, we describe the latest developments on the mechanistic characterization of poly(ADP-ribose) polymerase (PARP) [EC 2.4.2.30], a DNA-dependent enzyme that catalyzes the synthesis of protein-bound ADP-ribose polymers in eucaryotic chromatin. A detailed kinetic analysis of the automodification reaction of PARP in the presence of nicked dsDNA indicates that protein-poly(ADP-ribosyl)ation probably occurs via a sequential mechanism since enzyme-bound ADP-ribose chains are not reaction intermediates. The multiple enzymatic activities catalyzed by PARP (initiation, elongation, branching and self-modification) are the subject of a very complex regulatory mechanism that may involve allosterism. For instance, while the NAD+ concentration determines the average ADP-ribose polymer size (polymerization reaction), the frequency of DNA strand breaks determines the total number of ADP-ribose chains synthesized (initiation reaction). A general discussion of some of the mechanisms that regulate these multiple catalytic activities of PARP is presented below.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1006979220009
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    Effects of phosphatidylinositol 4,5-bisphosphate and neomycin on phospholipase D: Kinetic studies (1999)
    Springer
    Molecular and cellular biochemistry 197 (1999), S. 195-201 
    Details
    ISSN: 1573-4919
    Keywords: phospholipase D ; phosphatidylinositol 4,5-bisphosphate ; neomycin ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract The kinetics of phosphatidylcholine-specific phospholipase D activated by phosphatidylinositol 4,5-bisphosphate (PIP2) and inhibition by neomycin were studied in an enzyme preparation partially purified from human hepatocarcinoma cell line. It was found that phospholipase D was marginally activated by phosphatidyl-4-phosphate (PIP) and phosphatidylethanolamine (PE). In contrast, it was considerably activated by PIP2 in different concentration of phosphatidylcholine (PC). Sphingomyelin (SM), lysophosphatidylcholine (LPC) and phosphatidylserine (PS) were neither substrates nor inhibitors of the phospholipase D. PIP2 induced an allosteric effect on phospholipase D and a negative cooperative effect with respect to phosphatidylcholine as indicated in the Lineweaver-Burk plot. In the absence of PIP2, a straight line was obtained, whereas a downward concave curve was observed in the presence of 25 μM of PIP2. The Hill coefficient and the apparent Km of phosphatidylcholine in the presence of 25 μM PIP2 were calculated to be 0.631 and 10.79 mM, respectively. PIP2 also increased the maximal velocity (Vmax) of the phospholipase D reaction, suggesting that the affinity of substrate to enzyme was decreased, and the turnover number of the enzyme (kcat) was increased by PIP2. The activation of phospholipase D by PIP2 was dose dependent up to 50 μM of PIP2. The Ka of PIP2 was 15.8 mM. Neomycin, a polycationic glycoside, was shown to be an uncompetitive inhibitor of phospholipase D, and revealed the formation of a neomycin-PIP2 complex. The Ki of neomycin was estimated to be 8.7 mM.
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    Kinetics of Inhibition of Green Crab (Scylla serrata) Alkaline Phosphatase by L-Cysteine (1999)
    Springer
    The protein journal 18 (1999), S. 603-607 
    Details
    ISSN: 1573-4943
    Keywords: Alkaline phosphatase ; green crab ; inhibition ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The inhibition of alkaline phosphatase from green crab (Scylla serrata) by L-cysteine has been studied. The results show that L-cysteine gives a mixed-type inhibition. The progress-of-substrate-reaction method previously described by Tsou [(1988), Adv. Enzymol. Related Areas Mol. Biol. 61, 391–436] was used to study the inactivation kinetics of the enzyme by L-cysteine. The microscopic rate constants were determined for reaction of the inhibitor with the free enzyme and the enzyme–substrate complex (ES) The results show that inactivation of the enzyme by L-cysteine is a slow, reversible reaction. Comparison of the inactivation rate constants of free enzyme and ES suggests that the presence of the substrate offers marked protection of this enzyme against inactivation by L-cysteine.
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    URL: http://dx.doi.org/10.1023/A:1020611602818
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    Kinetics of Inhibition of Green Crab (Scylla Serrata) Alkaline Phosphatase by Sodium (2,2′-bipyridine) Oxodiperoxovanadate (1999)
    Springer
    The protein journal 18 (1999), S. 735-740 
    Details
    ISSN: 1573-4943
    Keywords: Alkaline phosphatase ; sodium (2, 2′-bipyridine) oxodiperoxovanadate ; inhibition ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Green crab (Scylla serrata) alkaline phosphatase (EC 3.1.3.1) is a metalloenzyme, which catalyzes the nonspecific hydrolysis of phosphate monoesters. The kinetics of inhibition of the enzyme by sodium (2, 2′-bipyridine) oxodiperoxovanadate, pV(bipy), has been studied. The time course of the hydrolysis of p-nitrophenyl-phosphate catalyzed by the enzyme in the presence of different pV(bipy) concentrations showed that at each pV(bipy) concentration, the rate decreased with increasing time until a straight line was approached, the straight line slopes are the same for all concentrations. The results suggest that the inhibition of the enzyme by pV(bipy) is a slow, reversible reaction with fractional remaining activity. The microscopic rate constants are determined for the reaction of inhibitor with the enzyme.
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    Electrochemical Treatment of Nitrite Using Stainless Steel Electrodes (1999)
    Springer
    Water, air & soil pollution 109 (1999), S. 429-442 
    Details
    ISSN: 1573-2932
    Keywords: electrochemical treatment ; kinetics ; nitrite ; stainless steel electrodes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The efficiency of nitrite removal in an electrochemical cell was investigated in this study using stainless steel electrodes. The experiments were designed to study the effects of current input, volume of the solution, initial pH, and number of electrodes on removal of nitrite at a concentration typical to aquaculture system effluents. Current variation causes opposite trends, while an increase in current would increase the oxidizing efficiency of the system, the voltage induced increase in pH due to hydrogen evolution would decrease the efficiency of the oxidizing agent formed. However, the highest nitrite removal was achieved at a current of 2 A and a complete removal was attained after a duration of ten minutes. A first order reaction model was developed to predict the effect of current on nitrite removal. The energy consumption was directly proportional to the initial pH and the solution volume, while it was inversely proportional to the number of electrodes.
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    Structure‐dependent viscoelastic properties of C9〉‐alkanethiol monolayers (1999)
    Springer
    Tribology letters 7 (1999), S. 67-71 
    Details
    ISSN: 1573-2711
    Keywords: alkanethiol ; self‐assembled monolayers ; quartz crystal microbalance ; viscoelasticity ; kinetics ; ellipsometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Quartz crystal microbalance techniques and in situ spectroscopic ellipsometry are used to probe the structure‐dependent intrinsic viscoelastic properties of self‐assembled CH3(CH2)8SH alkanethiol monolayers adsorbed from the gas phase onto Au(111)‐textured substrates. Physisorbed molecules, mixed chemisorbed‐fluid/solid phases and solid‐phase domain boundaries make sequentially dominant contributions to the measured energy dissipation in the growing monolayer. Deviations from Langmuir adsorption kinetics reveal a precursor‐mediated adsorption channel. These studies reveal the impact of structural heterogeneity in tribological studies of monolayer lubricants.
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    URL: http://dx.doi.org/10.1023/A:1019117319559
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    Rubidium and Cesium Kinetics and Tissue Distributions in Channel Catfish (Ictalurus punctatus) (1999)
    Springer
    Ecotoxicology 8 (1999), S. 287-300 
    Details
    ISSN: 1573-3017
    Keywords: rubidium ; cesium ; kinetics ; clearance-volume model ; fish
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract We used a two-compartment, clearance volume-based model to examine rubidium and cesium pharmacokinetics in channel catfish (Ictalurus punctatus) after intravascular administration. We compared the apparent volumes of distribution in the central and peripheral compartments and the intercompartmental and whole-body clearances of both metals at 20.0 °C and 27.5 °C. Biological half-times of Rb were 15 to 16 d at both temperatures, but Cs biological half-times averaged 101 d and 85 d at 20.0 °C and 27.5 °C, respectively (5 to 7 times longer than those of Rb in the same individual). Both the intercompartmental and total body clearances of Rb were also 6 to 7 times greater than those of Cs. The apparent volumes of distribution for Rb in the central compartments were twice those of Cs and remained constant with temperature. The apparent volumes of distribution of both elements in peripheral compartments were large compared with their corresponding central compartments, and decreased by a similar extent with increased temperature. Cesium tissue to blood ratios were greatest for white muscle, with more than 85% of the Cs present in this tissue. Partitioning of Cs in peripheral tissues apparently decreased with increased temperature conditions. Our results indicate that application of pharmacokinetic modeling techniques can enhance studies of radionuclide kinetics by helping to identify rate-limiting processes within individuals that may control uptake and elimination.
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    URL: http://dx.doi.org/10.1023/A:1008981216690
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    Long-Term Transformation and Redistribution of Potentially Toxic Heavy Metals in Arid-Zone Soils: II. Incubation at the Field Capacity Moisture Content (1999)
    Springer
    Water, air & soil pollution 114 (1999), S. 221-250 
    Details
    ISSN: 1573-2932
    Keywords: arid-zone soils ; field capacity ; fractionation ; heavy metals ; kinetics ; redistribution ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Solid-phase transformation of added Cd, Cu, Cr, Ni, Pb and Zn, in two arid-zone soils incubated in the field capacity moisture regime for one year, were studied. The heavy metals were fractionated into six empirically defined fractions using a selective sequential dissolution (SSD) protocol optimized for arid-zone soils. Each of these fractions was named based on the major soil component targeted for dissolution during the specific SSD step, but it is not assumed that they are mineralogically and chemically totally specific. The transformations of the metals in the two soils incubated at the field capacity regime were compared with those at the moisture saturation regime (Han and Banin, 1997). An initial fast stage of transformation of the soluble metals from the exchangeable (EXC) fraction to the less labile fractions (the carbonate (CARB) fraction for Cd, Pb, Zn, Ni and Cu, and the organic matter (OM) fraction for Cr, and to some extent Cu and Ni) occurred during the fractionation and within one hour after addition. This was followed by a second stage, involving long-term transformation processes of all metals: added Cd was transferred from the EXC into the CARB fraction; added Cr was transferred from the CARB to the OM fraction and Pb was transferred very slowly to the easily reducible oxide (ERO) fraction. Added Cu, Ni and Zn were transferred from the EXC and CARB fractions into the ERO fraction and to some extent OM and RO fractions. In Part I of this series, we reported that during incubation in the saturated moisture regime, Zn and Ni were transferred mainly into the RO and OM fractions. Cadmium, Cr and Pb underwent the same transformation pathways during the slow long-term process, with slightly different rates, in both water regimes. At low levels of addition, the incubated soils moved over one year towards a distribution similar to that of the native soil. At higher levels, the soils still remained removed from the quasi-equilibrium which characterized the native soil, even at the end of one year of incubation.
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    Cascade in muonic and pionic atoms with Z = 1 (1999)
    Springer
    Hyperfine interactions 119 (1999), S. 11-21 
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    ISSN: 1572-9540
    Keywords: exotic atom ; muonic hydrogen ; pionic hydrogen ; cascade ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Recent theoretical and experimental studies of the exotic atoms with Z = 1 are reviewed. An interplay between the atomic internal and external degrees of freedom is essential for a good description of the atomic cascade. The perspective of ab initio cascade calculations is outlined.
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    URL: http://dx.doi.org/10.1023/A:1012642215730
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    Genome characterization and relationships between two species of the genusLobelia (Campanulaceae) determined by repeated DNA sequences (1999)
    Springer
    Plant systematics and evolution 214 (1999), S. 211-218 
    Details
    ISSN: 1615-6110
    Keywords: Campanulaceae ; Lobelia ; Angiosperms ; in situ hybridization ; karyotype evolution ; rDNA ; telomere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Three repeated DNA sequences (rDNA 5S, 18S-5.8S-26S and telomeric repeats) were localised in the genomes ofLobelia brasiliensis andL. imperialis var.kanitzii (subg.Tupa), both with 2n = 28, by fluorescence in situ hybridization (FISH). The results were used to analyse the genomic relationship between the species. With probe pTa71, the karyotypes of these species showed only one NOR site. Probe pTa794, which contains 5S rDNA, demonstrated differences between the species. Telomeric sequences, studied with probe pLT11, were not detected in ectopic sites, but different telomeres showed signals of varying intensity. Based on the results obtained, considerations are made on karyotype evolution inLobelia.
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    Reproductive biology ofCaesalpinia calycina andC. pluviosa (Leguminosae) of the caatinga of north-eastern Brazil (1999)
    Springer
    Plant systematics and evolution 217 (1999), S. 43-53 
    Details
    ISSN: 1615-6110
    Keywords: Leguminosae ; Caesalpinia ; Angiosperms ; bee-pollination ; andromonoecy ; late-acting self-incompatibility ; fruiting success
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The pollination biology, breeding system and fruiting success ofCaesalpinia calycina andC. pluviosa var.sanfranciscana were studied in caatinga vegetation in Bahia, NE Brazil. The principal pollinators for both species were carpenter bees.Caesalpinia calycina is andromonoecious but inC. pluviosa all flowers are hermaphrodite. InC. calycina all selfed flowers were abscised within 72 h despite rapid self-pollen tube growth to the ovary and ovule penetration. Prevention of selfing therefore seems to be controlled by a post-zygotic mechanism. Both species had very low fruit-set and it is suggested that this is at least in part due to geitonogamous pollinations with ovule penetration by self pollen tubes.
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    URL: http://dx.doi.org/10.1007/BF00984921
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    Kinetic measurements of binding of galectin 3 to a laminin substratum (1999)
    Springer
    Glycoconjugate journal 16 (1999), S. 365-373 
    Details
    ISSN: 1573-4986
    Keywords: galectin 3 ; laminin binding ; kinetics ; cooperativity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Galectin 3, a β-galactoside binding protein, contains a C-terminal carbohydrate recognition domain (CRD) and an N-terminal segment including multiple repeats of a proline/tyrosine/glycine-rich motif. Previous work has shown that galectin 3 but not the isolated CRD binds to laminin, a multivalent ligand, with positive cooperativity indicating the formation of multiple interactions although the lectin in solution is monomeric. Using surface plasmon resonance, we find that hamster galectin 3 at sub-µmolar concentrations or its isolated CRD at all concentrations binds to a laminin substratum with similar association (kass; 10 – 30 000 M−1 S−1) and dissociation (kdiss; 0.2 – 0.3 S 1 −1 ) rates and weak affinity (Ka; 1 - 3 X 105 M−1). At higher concentrations of galectin 3 the off rate decreases ten fold leading to increased affinity. Ligation of an N-terminal epitope of galectin 3 with a monoclonal Fab fragment increases association and dissociation rates ten fold. A recombinant protein obtained by deletion of the first 93 N-terminal residues binds to laminin with positive cooperativity and a slowly dissociating fraction (Kdiss; 0.002 S−1) accummulates on the substratum. The data suggest that homophilic interactions between CRD as well as N terminal domains are implicated in galectin 3 aggregation on the substratum leading to positive binding cooperativity.
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    Therps16 intron and the phylogeny of theRubioideae (Rubiaceae) (1999)
    Springer
    Plant systematics and evolution 214 (1999), S. 161-186 
    Details
    ISSN: 1615-6110
    Keywords: Rubiaceae ; Rubioideae ; Angiosperms ; cladistics ; DNA sequences ; phylogeny ; rps16 intron ; taxonomy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The phylogeny of the subfamilyRubioideae (Rubiaceae) was estimated from sequence variation in therps16 intron (cpDNA) in 143 ingroup and 5 outgroup taxa. The analysis largely confirms a recent one based onrbcL sequences, but branch support is often much stronger. Three of the traditional subfamilies are supported,Rubioideae, Cinchonoideae s. str., andIxoroideae s. l. while there is no support forAntirheoideae. TheRubioideae are the sister group of all otherRubiaceae and comprise the tribesAnthospermeae, Coccocypseleae, Cruckshanksieae, Coussareeae, Gaertnereae, Hedyotideae, Knoxieae, Morindeae, Ophiorrhizeae, Paederieae, Pauridiantheae, Perameae, Psychotrieae, Rubieae, Spermacoceae, Theligoneae, andUrophylleae. TheHamelieae andHillieae belong to theCinchonoideae. Rachicallis andSiemensia should be transferred from theHedyotideae to theCinchonoideae. ThePauridiantheae, Urophylleae, Ophiorrhizeae, andRaritebe form the basalmost subclade of theRubioideae. The second basalmost clade consists of the generaLasianthus andPerama. The third basalmost clade consists of the tribesCoussareeae, Coccocypseleae andCruckshanksieae, and the generaDeclieuxia andHindsia. The tribesKnoxieae, Anthospermeae, Argostemmateae, Paederieae, Theligoneae, Rubieae, Hedyotideae, andSpermacoceae are members of one clade. TheKnoxieae are monophyletic ifOtiophora, Otomeria, andPentas are included. The tribeAnthospermeae is supported as monophyletic, but its subtribes are not. ThePaederieae, together withTheligonum, form a paraphyletic grade basal to theRubieae. TheHedyotideae, includingSchismatoclada, form a grade at the base of theSpermacoceae. TheGaertnereae are monophyletic and distinct from thePsychotrieae. TheMorindeae are monophyletic and includeDamnacanthus andMitchella. Schradera is the sister group of theMorindeae. ThePsychotrieae are monophyletic when theGaertnereae, Lasianthus, andDeclieuxia are excluded. The recognition of a subtribeHydnophytineae leaves the rest of thePsychotrieae paraphyletic.Psychotria is paraphyletic with respect to all other genera of the tribe. Approximately 50 genera are here classified for the first time based on molecular data.
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    Magnoliid reproductive organs from the Cenomanian-Turonian of north-western Kazakhstan:Magnoliaceae andIlliciaceae (1999)
    Springer
    Plant systematics and evolution 216 (1999), S. 265-288 
    Details
    ISSN: 1615-6110
    Keywords: Illiciaceae ; Illiciospermum ; Liriodendroidea ; Magnoliaceae ; Angiosperms ; Cretaceous ; fossil seeds ; Kazakhstan
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Cenomanian-Turonian sediments from the Sarbay locality in north-western Kazakhstan have yielded a rich assemblage of plant fossils including well preserved flowers, fruits, and seeds of angiosperms. This work describes fossil seeds assigned to theMagnoliaceae and theIlliciaceae. Three new species of the extinct magnoliaceous genusLiriodendroidea, L. asiatica, L. costata, andL. tenuitesta, are established and new information on the previously described species,L. alata, is provided. TheLiriodendroidea seeds are closely similar to seeds of extantLiriodendron, but are distinguished in being much smaller and winged. A new genus and species,Illiciospermum pusillum, is established based on seeds with close similarity to those of the extant genusIllicium. The seeds are small, anatropous and exotestal with outer epidermis of testa forming a palisade layer. The facets of the palisade cells have deeply undulate anticlinal walls. The micropyle area is seen on the outer integument as a transverse slit placed on a raised strophiole-like structure close to the hilum. TheIlliciospermum seeds represent the first unequivocal record of theIlliciaceae in the Cretaceous. Another seed of possible illiciaceous affinity is described as aff.Illiciospermum sp.
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    Isolation of the male germ unit: organization and function in tobacco (Nicotiana tabacum L.) (1998)
    Springer
    Plant cell reports 18 (1998), S. 143-147 
    Details
    ISSN: 1432-203X
    Keywords: Key wordsNicotiana tabacum ; Male germ unit ; Scanning electron microscopy ; Sperm isolation ; Angiosperms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Sperm cells are released from pollen tubes of tobacco as linked cells, associated with the vegetative nucleus in an assemblage known as the male germ unit (MGU). Using light microscopy, the MGU assemblage appears to be ensheathed by cytoplasmic material of the pollen tube, which may stabilize their association. Following their release, the shape of the sperm cells and vegetative nucleus changes from an ellipsoidal to a more spheroidal morphology. When most of the cytoplasmic material is dispersed, a boundary remains around the two sperm cells. Using scanning electron microscopy, the cytoplasmic material surrounding the MGU appears filamentous, sometimes twisted and rope-like. Based on these observations, the function of the MGU of tobacco is discussed.
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    Molecular structure of trans-[Co(NH3)4(NH2CH3)Cl](ClO4)2 (1998)
    Springer
    Journal of chemical crystallography 28 (1998), S. 69-72 
    Details
    ISSN: 1572-8854
    Keywords: Co(III) complex ; crystal structure ; kinetics ; steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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    Reaction Kinetics for the Anionic Ring-Opening Polymerization of Tetraphenyltetramethylcyclotetrasiloxane Using a Fast Initiator System (1998)
    Springer
    Journal of inorganic and organometallic polymers and materials 8 (1998), S. 111-117 
    Details
    ISSN: 1572-8870
    Keywords: Organosiloxane ; kinetics ; poly(phenylmethylsiloxane) ; catalyst ; anionic ; ring-opening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is well known that the rate of polymerization for an anionic mechanism is dependent on the ability of the bulk material or solvent system to disassociate the ion pair at the propagating chain end. In the anionic ring-opening polymerization of cyclic organosiloxanes in particular, the larger and softer the counter ion, the more rapidly the reaction proceeds. A recently developed phosphazene initiator system provides a large, soft counter ion relative to other traditional initiators used for the polymerization of poly(dimethylsiloxane) (PDMS). This novel initiator system was used in this investigation for the ring-opening polymerization of tetraphenyltetramethylcyclotetrasiloxane (P4) and the reaction kinetics under bulk and solution conditions were investigated. The new initiator system showed a dramatic increase in the rate of polymerization over the conventional potassium hydroxide-catalyzed system. Furthermore, this initiator was sufficiently reactive to be useful for the ring-opening polymerization of P4 at 293 K.
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    Thermal Decomposition Kinetics of Lanthanum Complexes of 1,2-(Diimino-4'-Antipyrinyl)ethane (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 475-480 
    Details
    ISSN: 1572-8943
    Keywords: complexes of lanthanum ; entropy of activation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics and mechanism of the thermal decomposition of perchlorate, nitrate and iodide complexes of lanthanum with the Schiff base 1,2-(diimino-4'-antipyrinyl)ethane (abbreviated as GA) have been studied by TG and DTG techniques. The kinetic parameters like the activation energy, the pre-exponential factor and the entropy of activation were calculated for the major decomposition stages (Stages I and II) using Coats-Redfern equation. The rate controlling process obey ‘Mampel model’ with random nucleation with one nucleus on each particle. The kinetic parameters indicate that the ligands are loosely bound to metal ion and the activated complex formed in the decomposition reaction is more ordered than the reactants.
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    Kinetics and Mechanism of the Oxidation of Molybdenum Sulphide (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 263-267 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; molybdenum sulphide ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    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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    URL: http://dx.doi.org/10.1023/A:1010108813595
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    Mechanism and Kinetics of Thermal Dissociation of Inclusion Complex of Benzaldehyde with β-Cyclodextrin (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 825-833 
    Details
    ISSN: 1572-8943
    Keywords: benzaldehyde ; β-cyclodextrin ; inclusion complex ; kinetics ; mechanism ; thermal dissociation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The inclusion complex of benzaldehyde (BA) with β-cyclodextrin (β-CD) was prepared and was studied by thermal analysis and X-ray diffractometry. The composition of the complex was identified by TG and elemental analysis as β-CD·BA·9H2O. TG and DSC studies showed that the thermal dissociation of β-CD·BA·9H2O took place in three stages: dehydration in the range 70-120°C; dissociation of β-CD·BA in the range 235-270°C; and decomposition of β-CD above 280°C. The kinetics of dissociation of β-CD·BA in flowing dry nitrogen was studied by means of TG both at constant temperature and at linearly increasing temperature. The results showed that the dissociation of β-CD·BA was dominated by a one-dimensional random nucleation and subsequent growth process (A2). The activation energy E was 124. 8 kJ mol-1, and the pre-exponential factor A 5.04·1011 min-1.
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    The Non-Parametric Kinetics A New Method for the Kinetic Study of Thermoanalytical Data (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 933-943 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; non-parametric kinetics method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of the new method non-parametric kinetics for kinetic analysis is discussed. It is shown that this method is able to obtain all the kinetic information needed to reproduce accurately the experimental data. To validate this method a set of numerical simulations of the most commonly used kinetic models has been performed and analysed with the method.
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    Thermal Analysis and Kinetic Study of Decomposition processes of Some Commercial Pesticides I. Triazine derivatives (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 937-956 
    Details
    ISSN: 1572-8943
    Keywords: enthalpy ; GC—MS measurements ; kinetics ; simultaneous TG—DSC ; thermal stability ; 1,3,5 triazine derivatives
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of some commercial pesticides was studied by means of simultaneous TG-DSC measurements. Kinetic parameters relating to liquid—gas-phase transition processes were determined via a dynamic TG technique. Gas chromatography-mass spectrometry were used to make measurements on the gaseous products. The liquid—gas-phase transition processes of these compounds seem to be influenced by the substituent groups rather than by the side-chains. A chlorine substituent destabilizes some compounds, bringing closer together the temperatures of melting and liquid—gas-phase transition processes.
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    URL: http://dx.doi.org/10.1023/A:1010198621609
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    Determination of the Kinetic Parameters of Chemical Reactions on the Basis of Non-Isothermal Measurements A critical review (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 399-406 
    Details
    ISSN: 1572-8943
    Keywords: activation energy ; kinetics ; non-isothermal measurements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A detailed analysis is presented of the applicability of several dependences commonly used for the determination of activation energies from non-isothermal measurements. Reactions proceeding according to different kinetic equations are simulated and the validity of the activation energy values obtained is discussed. The general conclusion is drawn that none of the examined dependences should be used to determine the activation energy. For a rough estimation of activation energy, the Kissinger equation can be applied according to Ockham's razor.
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    Kinetics of the Gas-Phase Reactions of OH and NO3 Radicals and O3 with the Monoterpene Reaction Products Pinonaldehyde, Caronaldehyde, and Sabinaketone (1998)
    Springer
    Journal of atmospheric chemistry 31 (1998), S. 281-297 
    Details
    ISSN: 1573-0662
    Keywords: hydroxyl radical ; nitrate radical ; ozone ; pinonaldehyde ; caronaldehyde ; sabinaketone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Using a relative rate method, rate constants have been measured for the gas-phase reactions of OH and NO3 radicals with pinonaldehyde, caronaldehyde and sabinaketone at 296 ± 2 K. The OH radical reaction rate constants obtained are (in units of 10−12 cm3 molecule−1 s−1): pinonaldehyde, 48 ± 8; caronaldehyde, 48 ± 8; and sabinaketone, 5.1 ± 1.4, and the NO3 radical reaction rate constants are (in units of 10−14 cm3 molecule−1 s−1): pinonaldehyde, 2.0 ± 0.9; caronaldehyde, 2.5 ± 1.1; and sabinaketone, 0.036 ± 0.023, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. Upper limits to the O3 reaction rate constants were also obtained, of 〈2 × 10−20 cm3 molecule−1 s−1 for pinonaldehyde and caronaldehyde, and 〈5 × 10−20 cm3 molecule−1 s−1 for sabinaketone. These reaction rate constants are combined with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals and O3 to calculate tropospheric lifetimes and dominant transformation process(es) of these and other monoterpene reaction products.
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    URL: http://dx.doi.org/10.1023/A:1006010915971
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    Solvent effects in the kinetics of the enantioselective hydrogenation of ethyl pyruvate (1998)
    Springer
    Catalysis letters 55 (1998), S. 73-77 
    Details
    ISSN: 1572-879X
    Keywords: enantioselectivity ; hydrogenation of ethyl pyruvate ; Pt/alumina catalyst ; solvent effects ; kinetics ; solvent polarity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of solvent on the kinetics of enantioselective hydrogenation of ethyl pyruvate by Pt/Al2O3/dihydrocinchonidine is reported. In a non‐polar solvent, toluene, the reaction is approximately zero order in substrate at constant hydrogen pressure, while under the same conditions and at the same substrate concentration, in the polar solvents ethanol and propylene carbonate the reaction shows a first‐order substrate concentration dependence. Fits to a Michaelis–Menten rate expression show that these differences are the expression of the relative magnitudes of the adsorption term in the rate expression, which in turn reflects the influence of the solvent on the adsorption–desorption processes which take place at the catalyst surface.
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    URL: http://dx.doi.org/10.1023/A:1019078727850
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    Study of the Influence of Alkaline Ions (Li, Na and K) on the Structure of the Silicate Entities in Silico Alkaline Sol and on the Formation of the Silico-Calco-Alkaline Gel (1998)
    Springer
    Journal of sol gel science and technology 13 (1998), S. 353-358 
    Details
    ISSN: 1573-4846
    Keywords: silicate ; alkaline ; gelation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The study of silico-calco-alkaline gel is essential to warn against the degradation of concrete due to the alkali-silica reaction. In the laboratory, those gels are simulated by the destabilization of a silico-alkaline sol by calcium ions. Their speed of formation depends on the alkali species. The influence of alkaline ions (Li, Na and K) on the structure of silicate entities in sol and on the gel formation has been studied. The state of polymerization of the silico-alkaline sol was determined by NMR and depends on the alkali species and the molar ratio (Rm = [SiO2]/[A2O] with A = Li, Na or K). It appears that lithium enhances the polymerization. By scattering techniques (SAXS and ELS), the evolution of size and number of scattering particles during gelation can be determined from scattering curves with Guinier approximation. The mechanism of gelation appears as a hierarchic structure composed of several discrete sizes.
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    The Kinetics of Pore Shape Evolution in Alumina (1998)
    Springer
    Journal of materials synthesis and processing 6 (1998), S. 161-167 
    Details
    ISSN: 1573-4870
    Keywords: Alumina ; surface ; kinetics ; diffusion ; SALK
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics of shape evolution of a completely faceted crystal/internal void by surface diffusion was modeled. Arrays of micron-sized cavities were generated in sapphire substrates with known surface orientations using microlithography and ion beam etching and converted to internal intragranular pores of nonequilibrium shape by diffusion bonding of the etched substrate to an identical-orientation unetched sapphire substrate. Pore shape evolution rates during high-temperature anneals were monitored and found to be highly sensitive to the orientation of the substrate surface. The observed evolution rates were compared with the predictions of the kinetic model using diffusivity values for alumina that span the range from the highest to the lowest diffusion constants reported in the literature. The comparison suggests that surface-attachment-limited kinetics (SALK) play a major role in surface mass transport on stable low-index planes of alumina.
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    URL: http://dx.doi.org/10.1023/A:1022665418505
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    Kinetics of Solid State Reactions With Fractal Reagent (1998)
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    Journal of materials synthesis and processing 6 (1998), S. 305-309 
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    ISSN: 1573-4870
    Keywords: Fractals ; solid state reaction ; kinetics ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In the present research we theoretically studied the kinetics of nucleation-limited solid state reactions as influenced by the fractal properties of solid reagent. We consider the model of equal-sized primary particles assembled in fractal cluster. The geometry of such an object is assumed to be described solely by its fractal dimension D and by upper (R max) and lower (R min) cutoffs of fractality further identified with the overall size of the object and the size of the primary particle correspondingly. Depending on the ratio between R max, R min and the radius of the critical nucleus R nucl the following cases are considered: (1) R max ∼ R nucl. In this case the reaction kinetics is described by the equation: α = 1 − B{ln(k′ τ + 1)}D/(D−3), where B, k′ are constants. Numerical solution of this equation gives rise to n-order reaction kinetics with n & 1. (2) R min ≪ R nucl ≪ R max. In this case under certain conditions there can exist non-trivial critical density ρcrit ≠ 0, 1 that favors the formation of the critical nuclei of the new phase. The asymptotic kinetic equation for large times corresponds to n-order reaction with n = (D + 3)/(D + 1). (3) R min ≪ R nucl ∼ R max′. In this case the reaction follows the first-order kinetics with D-dependent rate constant.
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    Evidence for O-dealkylation of 7-pentoxyresorufin by cytochrome P450 2B1/2B2 isoenzymes in brain (1998)
    Springer
    Molecular and cellular biochemistry 189 (1998), S. 201-205 
    Details
    ISSN: 1573-4919
    Keywords: brain ; P450 ; PB ; PROD ; induction ; inhibition ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract O-dealkylation of 7-pentoxyresorufin (PR) was studied in rat brain to characterise the functional activity specific for cytochrome P450 2B1/2B2 isoenzymes in brain microsomes. Brain microsomes catalyzed the O-dealkylation of PR in the presence of NADPH. Pretreatment with phenobarbital (PB; 80 mg/kg body wt, i.p.× 5 days) resulted in 3-4 fold induction of pentoxyresorufin-O-dealkylase (PROD) activity while 3-methylcholanthrene (MC; 30 mg/kg body wt, i.p. × 5 days) did not produce any significant increase in enzyme activity. Kinetic studies revealed that the rate of velocity (Vmax) for the O-dealkylation of PR was significantly increased to 2.9 times higher in brain microsomes isolated from PB pretreated rats. In vitro studies using metyrapone, an inhibitor of P450 2B1/2B2 catalyzed reactions and antibody for hepatic PB inducible P450s (P450 2B1/2B2) significantly inhibited the activity of PROD in cerebral microsomes prepared from PB pretreated animals. These studies suggest that PB inducible isoenzymes of P450, i.e. P450 2B1/2B2 specifically catalyze the O-dealkylation of PR in brain microsomes.
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    Kinetics of the Reconstituted Tricarboxylate Carrier from Eel Liver Mitochondria (1998)
    Springer
    Journal of bioenergetics and biomembranes 30 (1998), S. 555-563 
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    ISSN: 1573-6881
    Keywords: Tricarboxylate carrier ; mitochondria ; transport ; liposomes ; kinetics ; reconstitution ; eel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract The tricarboxylate carrier from eel liver mitochondria was purified by chromatography on hydroxyapatite and Matrix Gel Blue B and reconstituted into liposomes by removal of the detergent with Amberlite. Optimal transport activity was obtained by using a phospholipid concentration of 11.5 mg/ml, a Triton X-114/phospholipid ratio of 0.9, and ten passages through the same Amberlite column. The activity of the carrier was influenced by the phospholipid composition of the liposomes, being increased by cardiolipin and phosphatidylethanolamine and decreased by phosphatidylinositol. The reconstituted tricarboxylate carrier catalyzed a first-order reaction of citrate/citrate or citrate/malate exchange. The maximum transport rate of external [14C]citrate was 9.0 mmol/min per g of tricarboxylate carrier protein at 25°C and this value was virtually independent of the type of substrate present in the external or internal space of the liposomes. The half-saturation constant (K m) was 62 μM for citrate and 541 μM for malate. The activation energy of the citrate/citrate exchange reaction was 74 kJ/mol from 5 to 19°C and 31 kJ/mol from 19 to 35°C. The rate of the exchange had an external pH optimum of 8.
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    On the kinetic coupling and mechanism of aromatic ring hydrogenation (1998)
    Springer
    Reaction kinetics and catalysis letters 63 (1998), S. 47-51 
    Details
    ISSN: 1588-2837
    Keywords: Aromatic ring hydrogenation ; kinetics ; kinetic coupling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Mechanism of catalytic hydrogenation of aromatic rings is discussed. The kinetic coupling concept is considered, which implies that a surface intermediate would be continuously “pumped down” from the equilibrium concentration level by the extremely fast subsequent step. It is demonstrated that due to thermodynamic constrains, the intermediate formation of cyclohexadiene is forbidden.
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    Catalytic reaction accompanied by capillary condensation, 3. Influence on reaction kinetics and dynamics (1998)
    Springer
    Reaction kinetics and catalysis letters 65 (1998), S. 321-329 
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    ISSN: 1588-2837
    Keywords: Catalytic reaction ; capillary condensation ; kinetics ; dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of capillary condensation of reagents on the catalytic reaction kinetics and dynamics was studied. The hydrogenation ofp-xylene over Pt/SiO2 was used as a model reaction. Two types of SiO2 were used (KCK-1 with large pores and KCM-5 with small pores). It was shown that capillary condensation could modify the kinetics and the transition regimes. The proposed mathematical model demonstrates good agreement with experimental results for both steady-state and dynamic regimes, including reaction rate—temperature hysteresis.
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    Evidence for a compensation effect during the temperature-programmed reduction of copper oxide in hydrogen (1998)
    Springer
    Reaction kinetics and catalysis letters 63 (1998), S. 209-217 
    Details
    ISSN: 1588-2837
    Keywords: Copper ; reduction ; kinetics ; compensation effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reduction of copper oxide derived from basic Cu-carbonate in hydrogen has been studied under temperature-programmed conditions (TPR) and the TPR patterns were analyzed by means of Arrhenius plots at constant conversion (Friedman plots). These plots indicate that the reduction process cannot be described on the basis of constant kinetic parameters and reveal the presence of isokinetic temperatures. These suggest the presence of a compensation effect requiring a modification of the rate equation.
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    Quantitative description of the effect of solvent on kinetics of benzophenone oxide decay (1998)
    Springer
    Reaction kinetics and catalysis letters 65 (1998), S. 311-314 
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    ISSN: 1588-2837
    Keywords: Carbonyl oxides ; kinetics ; flash photolysis ; correlation equations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of solvent on rate constants of benzophenone oxide decay was investigated by flash photolysis. A quantitative description of this dependence in the terms of the Koppel-Palm equation suggests that all types of the solvation (non-specific electrostatic and polarizational, specific electrophilic and nucleophilic) strongly affect the reactivity of benzophenone oxide. Besides, strengthening of any effect leads to a decrease of the observed rate constant.
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    Carbon states and kinetics of carbon deposition from ethylene at Pt(110) surface (1998)
    Springer
    Reaction kinetics and catalysis letters 65 (1998), S. 381-388 
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    ISSN: 1588-2837
    Keywords: Carbon ; kinetics ; surface state ; XPS ; photoelectron spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The nature of high temperature carbon states at Pt(110) has been studied by X-Ray Photoelectron Spectroscopy. The formation of diamond-like carbon (DLC) is reported for the first time. The kinetics and temperature-programmed reactions of DLC were numerically simulated.
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    Reaction Between Copper Nitrate Hydrate and Methoxydimethyloctylsilane in Methanol (1998)
    Springer
    Journal of solution chemistry 27 (1998), S. 1123-1138 
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    ISSN: 1572-8927
    Keywords: Sol–gel processing ; hydrolysis ; condensation ; kinetics ; methoxydimethyloctylsilane ; copper nitrate hydrate ; phase diagram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction rate was determined for copper nitrate hydrate with methoxydimethyloctylsilane (MDOS) in methanol. The rate constants of hydrolysis and condensation were established by quantitative measurement of the product and Karl Fischer water determination. The reaction with the hydrated copper salt resulted in the phase separation of an insoluble product from the reaction mixture. The structure of the product was determined, by Fourier Transform Infrared Spectrometry (FTIR) and Nuclear Magnetic Resonance (NMR) to be a dimer of the MDOS. The results showed the alcohol, producing condensation reaction was negligible in the formation of the dimer. contrary to the case for the well-known reaction by trialkoxysilanes and tetraalkoxysilanes.
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    High resolution NMR techniques in catalysis (1998)
    Springer
    Topics in catalysis 5 (1998), S. 133-147 
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    ISSN: 1572-9028
    Keywords: NMR ; catalysis ; high pressure ; dynamic equilibria ; magnetization transfer ; sapphire tube ; gas phase ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract High resolution NMR techniques are applicable to a variety of aspects of catalysis. Methods for studying homogeneously-catalyzed systems under high gas pressure are described along with approaches for obtaining mechanistic and dynamic information. Many of the same techniques may be applied to heterogeneous catalysis by following the reaction chemistry by gas phase NMR.
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    Selectivity from a kinetic point of view: nonlinear behavior of logarithmic product ratios as a function of the reciprocal temperature (1998)
    Springer
    Topics in catalysis 5 (1998), S. 159-176 
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    ISSN: 1572-9028
    Keywords: nonlinear temperature behavior ; Eyring plot ; modified Eyring plot ; selectivity ; selection process ; enantioselectivity ; selection level ; isoinversion principle ; isoinversion temperature ; inversion temperature ; kinetics ; catalysis ; asymmetric hydrogenation ; dihydroxylation ; cocyclization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.
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    Kinetic On-line Evaluation of Chemical Reactions (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 187-194 
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    ISSN: 1572-8943
    Keywords: calorimetry ; kinetics ; on-line ; optimization ; software
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A computer program was developed for kinetic evaluations of calorimetric experiments to predict the further reaction run under adiabatic conditions. Kinetic modeling is based on elementary reaction steps whose rate laws form a set of differential equations. For the continuous parameter optimization time-temperature data and their derivatives are used. A special calorimeter of the ACTRON series with safety equipment was applied to investigate the kinetics of chemical reactions and to test kinetic on-line evaluations. In the paper, examples for the reaction of n-propanol with o-chlornitrobenzene and for the alcoholysis of phenyl isocyanate are given.
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    A Theoretical Approach to the Description of the Thermal Dissociation of N,N,N-Trimethylmethanaminium Halides (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 189-195 
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    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; N,N,N-trimethylmethanaminium halides ; theory ; thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract MNDO/d and PM3 quantum chemistry methods were used to examine reaction pathways and predict thermodynamic and kinetic barriers for the thermal dissociation of isolated conglomerates of N,N,N-trimethylmethanaminium cations (TMA+) and halide anions (X = Cl−, Br− and I−). Theoretically obtained changes in enthalpy and entropy for the above-mentioned process were subsequently supplemented with theoretically determined crystal lattice energies, that enabled prediction of relevant characteristics for the dissociation of crystalline phases. Data thus obtained compare only qualitatively with those available in literature and resulting predominantly from thermoanalytical investigations, although values of theoretical characteristics generally follow the same trends as experimental ones.
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    ASTM Kinetics of Oil Shales (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 567-575 
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    ISSN: 1572-8943
    Keywords: combustion ; differential scanning calorimeter ; kinetics ; oil shale
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis is increasingly being used to obtain kinetic data relating to sample decomposition. In this research differential scanning calorimeter (DSC) was used to determine the combustion kinetics of three (Çan, Himmetoglu and Mengen) oil shale samples by ASTM and Roger & Morris methods. On DSC curves two reaction regions were observed on oil shale sample studied except Çan oil shale. In DSC experiments higher heating rates resulted in higher reaction temperatures and higher heat of reactions. Distinguishing peaks shifted to higher temperatures with an increase in heating rate. Three different kinetic models (ASTM I-II and Rogers & Morris) were used to determine the kinetic parameters of the oil shale samples studied. Activation energies were in the range of 131.8-185.3 kJ mol-1 for ASTM methods and 18.5-48.8 kJ mol-1 for Rogers & Morris method.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010109929197
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    Kinetics and Mechanism of the Natural Mineral Marmatite Oxidation Process (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 35-40 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; marmatite ; oxidation process
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Results obtained by the comparative investigations of the natural mineral marmatite (Zn,Fe)S (Stari Trg, Yugoslavia) oxidation process are presented in this paper. Determination of the oxidation process mechanism was done by thermal analysis methods: DTA-TG-DTG and DSC, while Mössbauer spectroscopy, X-ray and electronic microanalysis were used for phase composition determination of the products formed during the oxidation process. Kinetics of the process was defined for two temperature intervals 862–973 and 1023–1173 K, under isothermal conditions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010196230637
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    Kinetic Studies on the Thermal Dissociation of β-Cyclodextrin·Ethyl Benzoate Inclusion Complexes (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 947-956 
    Details
    ISSN: 1572-8943
    Keywords: β-cyclodextrin ; ethyl benzoate ; inclusion complex ; kinetics ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of β-cyclodextrin·ethyl benzoate·6H2O(β-CD·C6H5COOC2H5·6H2O) was investigated by TG and DSC. The mass loss takes place in three stages: the dehydration occurs at 50-120°C; the dissociation of β-CD·C6H5COOC2H5occurs at 200-260°C; the decomposition of β-CD begins at 280°C. The kinetics of the dissociation of β-CD·C6H5COOC2H5in a dry nitrogen flow was studied by means of thermogravimetry both at constant temperature and linearly increasing temperature. The results show that the dissociation of β-CD·C6H5COOC2H5is dominated by a three-dimensional diffusion process (D3). The activation energy E is 116.19 kJ mol-1and the pre-exponential factor A 6.5358·109min-1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the studies focus on the energy of binding between cyclodextrin and the guest molecule. In this paper, the β-cyclodextrin·ethyl benzoate inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show that the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of van der Waals interaction.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010129028436
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    Tetrachlorosilane Consumption in Radio Frequency Glow Discharge (1998)
    Springer
    Plasma chemistry and plasma processing 18 (1998), S. 509-533 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1021811316740
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  • 189
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    Positronium Conversion Reactions for Testing the Electron Delocalization in 3d Complexes Caused by Ligands (1998)
    Springer
    Structural chemistry 9 (1998), S. 389-394 
    Details
    ISSN: 1572-9001
    Keywords: Positronium chemistry ; kinetics ; spin exchange reactions ; paramagnetic 3d complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate constants of ortho- into para-positronium conversion reactions promoted by paramagnetic 3d complexes were found to be linearly correlated with the delocalization, β of unpaired metal electrons caused by ligands. It is shown here that βs, usually obtained by UV/Vis absorption spectroscopy, may also be deduced from the correlations mentioned above.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1022459813247
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    Energetic Approach to Kinetics of Mechanochemical Process (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 463-473 
    Details
    ISSN: 1572-8943
    Keywords: energetic efficiency ; intensity of treatment ; kinetics ; mechanochemical process
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetics of a mechanochemical process is proposed to describe quantitatively with a problem set-up scaled to energy instead of time. This makes possible the comparability of experimental data obtained in machines with different intensities of treatment.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010130530563
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    Considerations on the Thermal Behaviour and Oxidation Resistance of Cast Iron (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 425-438 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; nodular cast iron ; TG-DTG-DTA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis was used to characterize the thermal behaviour and oxidation resistance of some nodular cast irons. Samples of nodular cast iron in various stages of elaboration, with different chemical compositions, were studied. The samples were heated in air, in the temperature range 291-1273 K, and the thermal (TG, DTG and DTA) curves were recorded. A group of samples with low silicon content exhibit similar behaviour: a continuous increase in mass and an exothermic effect up to 1123 K. The thermal effects correspond to iron oxide (Fe3O4, FeO, Fe2O3) formation. At high temperatures (T〉1123 K), there is a decrease in mass and an endothermic effect. A decrease in the superficial carbon content by combustion (‘decarburization’ effect) occurs in the range of high temperatures. The two effects of oxidation and decarburization depend on the structural changes which occur in cast iron at high temperatures. The decarburization process was modelled and the kinetic parameters were determined (reaction order n=0.76; activation energy E=141 kJ mol-1; pre-exponential factor A=2·102s-1). The oxidation process was studied by non-isothermal methods with regard to two mechanisms: two-dimensional transport for low temperatures, and three-dimensional transport through a sphere for high temperatures. The activation energies were calculated: 68 kJ mol-1 for low temperatures and 122 kJ mol-1 for high temperatures.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010122328746
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  • 192
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    Pyrolysis Analysis and Kinetics of Crude Oils (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 781-788 
    Details
    ISSN: 1572-8943
    Keywords: crude oil ; differential scanning calorimetry ; kinetics ; pyrolysis ; thermal analysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This research presents the results of an experimental study on the determination of pyrolysis behaviour and kinetics of six crude oils by differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). Crude oil pyrolysis indicated two main temperature ranges where loss of mass was observed. The first region between ambient to 400°C was distillation. The second region between 400 and 600°C was visbreaking and thermal cracking. Arrhenius-type kinetic model is used to determine the kinetic parameters of crude oils studied. It was observed that as crude oils gets heavier (°API decreases) cracking activation energy increases. Activation energy of cracking also show a general trend with asphaltene content.
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    URL: http://dx.doi.org/10.1023/A:1010114624345
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  • 193
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    Oxidation of Saturated Fatty Acids Esters DSC investigations (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 211-217 
    Details
    ISSN: 1572-8943
    Keywords: DSC ; fatty acids esters ; kinetics ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    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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    URL: http://dx.doi.org/10.1023/A:1010193624702
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    Obtaining Kinetic Parameters by Modulated Thermogravimetry (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 695-704 
    Details
    ISSN: 1572-8943
    Keywords: activation energy ; decomposition ; kinetics ; modulated temperature ; thermogravimetry ; volatilization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new technique, called modulated thermogravimetry, is introduced as a tool for obtaining continuous kinetic information for decomposition and volatilization reactions. The approach makes use of an oscillatory temperature program to obtain kinetic parameters during a mass loss. MTGA™ may be used under quasi-isothermal conditions to observe a single mass loss or may be combined with linear heating rate or Hi-Res™ controlled rate thermogravimetry to scan from one mass loss region to another. Results obtained are in agreement with those obtained by other kinetic methods.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010171315715
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    The cis-trans Isomerization of Azobenzene in the Molten State: A useful test reaction for the kinetic evaluation of DSC measurements (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 177-185 
    Details
    ISSN: 1572-8943
    Keywords: azobenzene ; DSC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Contrary to the situation in the field of temperature, heat and heat flow rate calibration, so far no generally accepted and easily practicable chemical reaction exists with regard to a kinetic evaluation. A possible reaction would be the well-known first-order cis-trans isomerization of subcooled liquid azobenzene. Surprisingly, the evaluation of measurements performed with a power compensated calorimeter yields activation parameters, which are dependent on the heating rate. The desmearing of the curves does not produce any improvements. However, constant activation parameters are obtained, if a small self-heating of the sample during the exothermic reaction is taken into account.
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    URL: http://dx.doi.org/10.1023/A:1010178610642
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    Thermoxidative Decomposition of Some Polysulfones under Dynamic Conditions of Heating (1998)
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 569-579 
    Details
    ISSN: 1572-8943
    Keywords: bromomethylated polysulfone ; carboxylated polysulfone ; kinetics ; polysulfone ; thermoxidative decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic aspects of the first step of thermoxidative decomposition, under dynamic conditions of heating, of some polysulfones have been studied. The dependence of the kinetic parameters on the heating rate and conversion degree has been established. The compensation effect and conversion function have also been discussed. Polysulfone decomposes by the breaking of the main chain, a process involving very high activation energy. Chemically modified polysulfones show the first step of thermoxidative decomposition at relatively low temperatures. This step corresponds to the elimination of functional side - groups for the bromomethylated polysulfone while in the case of the carboxylated polysolfone, the loss of the carboxyl group is probably accompanied by a crosslinking reaction.
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    URL: http://dx.doi.org/10.1023/A:1010175707790
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    Kinetics and Mechanism of Dehydration of Heteropolyacids (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 235-239 
    Details
    ISSN: 1572-8943
    Keywords: decomposition ; dehydration ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics and mechanism of the dehydration and decomposition of heteropolyacids of molybdenum, tungsten and vanadium (H3+xYx+M12O40·mH2O; Y=Si, P; M=Mo, W) were studied. The data obtained on the dehydration kinetic parameters correlate with the expected structures, of these crystal hydrates, the IR data and X-ray phase analysis.
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    URL: http://dx.doi.org/10.1023/A:1010100611778
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    Thermal Decomposition of BaC2O4·0.5H2O Studied by Stepwise Isothermal Analysis and Non-Isothermal Thermogravimetry (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 397-410 
    Details
    ISSN: 1572-8943
    Keywords: barium oxalate ; kinetics ; non-isothermal thermogravimetry ; stepwise isothermal analysis ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal decomposition of BaC2O4·0.5H2O in air was studied by a combination of stepwise isothermal analysis (SIA) and non-isothermal thermogravimetry. The results from both techniques show that the crystal water is released in one step and that anhydrous barium oxalate is decomposed in one step, while BaCO3 decomposes in three steps to BaO, forming two intermediate compounds with the formulas of BaCO3·(BaO)2 and (BaCO3)0.5·(BaO)2.5. Reaction mechanism analyses using the data from SIA measurements show that the controlling mechanism for all the five decomposition steps in isothermal conditions is a two-dimensional phase-boundary controlled process. Kinetic parameters are obtained for the five decomposition steps from the non-isothermal thermogravimetric data.
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    URL: http://dx.doi.org/10.1023/A:1010124905090
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    Kinetics and Mechanism of the Thermal Decomposition of M(NO3)2·nH2O (M=Cu, Co, Ni) (1998)
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 617-623 
    Details
    ISSN: 1572-8943
    Keywords: kinetics ; nitrates ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper presents the results of simultaneous DTA-TG-DTG and DSC studies on the thermal decomposition of Cu(NO3)2·3H2O, Co(NO3)2·6H2O and Ni(NO3)2·6H2O in an air atmosphere. The mechanism and enthalpies of the investigated processes were determined, as well as the kinetic parameters of the processes run under non-isothermal conditions by means of Kissinger's method. The dependence of the activation energy on the ionic radius of the cations building up the crystal lattices of the investigated compounds was also studied.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010170231923
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    Peroxy Radical Kinetics Resulting from the OH-Initiated Oxidation of 1,3-Butadiene, 2,3-Dimethyl-1,3-Butadiene and Isoprene (1998)
    Springer
    Journal of atmospheric chemistry 29 (1998), S. 267-298 
    Details
    ISSN: 1573-0662
    Keywords: peroxy radicals ; kinetics ; conjugateddienes ; biogenic VOC ; degradation mechanisms ; tropospheric ozone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The laser flash photolysis/UV absorption spectrometry technique has been used to investigate the kinetics of the peroxy radical permutation reactions (i.e. self and cross reactions) arising from the OH-initiated oxidation of isoprene (2-methyl-1,3-butadiene), and of the simpler, but related conjugated dienes, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene. The results of the two simpler systems are analysed to provide values of the rate coefficients for the 6 peroxy radical permutation reactions of the three types of isomeric peroxy radical produced in each system (T = 298 K, P = 760 Torr). The rate coefficients are all significantly larger than values estimated previously by extrapolation of structure-reactivity relationships based on the kinetics of a limited dataset of simpler radicals containing similar structural features. The results are discussed in terms of trends in self and cross reaction reactivity of primary, secondary and tertiary peroxy radicals containing combinations of allyl, β-hydroxy and δ-hydroxy functionalities. Since the peroxy radicals formed in these systems are structurally very similar to those formed in the isoprene system, the kinetic parameters derived from the results of the simpler systems are used to assist the assignment of kinetic parameters to the 21 permutation reactions of the six types of isomeric peroxy radical generated in the isoprene system. Kinetic models describing the OH-initiated degradation of all three conjugated dienes to first generation products in the absence of NOx are recommended, which are also consistent with available end product studies. The model for isoprene is considered to be a further improvement on that suggested previously for its OH-initiated oxidation in the absence of NOx. The mechanism is further extended to include chemistry applicable to ‘NOx-present’ conditions, and calculated product yields are compared with those reported in the literature.
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    URL: http://dx.doi.org/10.1023/A:1005940332441
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