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  • kinetics  (180)
  • Springer  (180)
  • American Meteorological Society
  • Institute of Physics
  • 1995-1999  (128)
  • 1990-1994  (52)
  • 1940-1944
  • 1997  (58)
  • 1996  (70)
  • 1994  (37)
  • 1990  (15)
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  • Springer  (180)
  • American Meteorological Society
  • Institute of Physics
  • Wiley-Blackwell  (102)
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  • 1995-1999  (128)
  • 1990-1994  (52)
  • 1940-1944
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  • 1
    ISSN: 1572-8927
    Schlagwort(e): Solvolysis ; kinetics ; aqueous solvent mixtures ; Co(III) complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of the solvolysis of [Co(CN)5Cl]3− have been investigated in water +2-methoxyethanol and water + diethylene glycol mixtures. Although the addition of these linear hydrophilic cosolvent molecules to water produces curvature in the variation of log(rate constant) with the reciprocal of the dielectric constant, their effect on the enthalpy and entropy of activation is minimal, unlike the effect of hydrophobic cosolvents. The application of a Gibbs energy cycle to the solvolysis in water and in the mixtures using either solvent-sorting or TATB values for the Gibbs energy of transfer of the chloride ion between water and the mixture shows that the relative stability of the emergent solvated Co(III) ion in the transition state compared to that of Co(CN)5Cl3− in the initial state increases with increasing content of cosolvent in the mixture. By comparing the effects of other cosolvents on the solvolysis, this differential increase in the relative stabilities of the two species increases with the degree of hydrophobicity of the cosolvent.
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 19 (1990), S. 1073-1084 
    ISSN: 1572-8927
    Schlagwort(e): Solvolysis ; kinetics ; mixtures of water+cosolvent
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Rates of solvolysis of the complex cation [Co(4tBupy)4Cl2]+ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy ΔH* and the entropy ΔS* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of ΔH* with ΔS* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (C n+) going to the transition state [M(n+1)+...Cl−] in water and in the mixture using free energies of transfer of the individual ionic species, ΔG t o (i), from water into the mixture. Values for ΔG t o (i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M(n+1)+, more than in the initial state, C n+. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)4Cl2]+ and [Coen2LCl]+ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of ΔG t o (Cl−) from either source.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 23 (1994), S. 483-500 
    ISSN: 1572-8927
    Schlagwort(e): Thermodynamics ; kinetics ; chemical relaxation ; temperature-jump ; amplitudes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Amplitudes of chemical relaxation signals can provide useful information as to the thermodynamics of coupled chemical reactions. The temperature-jump technique has been used to investigate the thermodynamic behavior of the Nickel(II)-3,5-dinitrosalicylate system in buffer solution, where complex formation steps are coupled to proton transfer steps. The analysis of the relaxation curves is based on the transformation of a set of coupled elementary reactions into a set of uncoupled ‘normal reactions.’ By analogy with classical titrations, the experiments have been performed by changing the metal ion concentration at constant ligand concentration and pH. Each measured amplitude is associated in this way to a point of a ‘dynamic titration’ and a procedure is formulated by which the values of the equilibrium constants and enthalpies of the normal reactions are simultaneously obtained by simple linear plots. From the dependence of these parameters on suitable functions of the concentrations of the reactants the values of ΔG° and ΔH° of the individual steps are derived. It is shown that the addition of a buffer (instead of an indicator) influences the stoichiometric coefficients of the normal reaction in such a way that measurable amplitudes are produced in systems that, as the presently investigated, in unbuffered solution would remain insensitive to the external perturbation. The circumstances under which the dynamic method offers advantages over the classical techniques are discussed.
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 2 (1996), S. 265-277 
    ISSN: 1572-8757
    Schlagwort(e): frequency response ; diffusion cell ; kinetics ; diffusion ; heat effects
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract This paper deals with frequency response (FR) analysis of a closed diffusion cell system with two resonators, that is both the LHS and RHS volumes are modulated. The analysis is made for a homogeneous particle described by a single effective diffusivity as well as a biporous pellet described by macropore and micropore diffusions. It is shown that if the perturbation of the volume of the reservoir #2 is lagged behind that of the reservoir #1 by 3π/2, the pressure response in reservoir #1 is significantly enhanced with larger amplitude as well as phase angle. When the perturbations of the two reservoirs are out of phase, the heat effect is reduced and can become insignificant when the two perturbations are completely out of phase (ψ = π). Under such a condition, the pressure difference between the two reservoirs could be doubled. In the case of biporous pellets, it is shown that the FR behaviours obtained for micropore diffusion control and macropore diffusion control are well distinguished. In the former case, the FR system reduces to a traditional batch adsorber one while in the latter case, the FR behaviour is the same as for a two resonator system with homogeneous particles. This difference can be used for the discrimination of micropore and macropore diffusion processes.
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 3 (1997), S. 267-275 
    ISSN: 1572-8757
    Schlagwort(e): characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Adsorption equilibria and dynamics ofn-butane on two activated carbon samples prepared from the physical activation of nutshell are studied in this paper. The micropore size distribution (MPSD) is considered as the main source of solid heterogeneity. Lennard-Jones' potential theory and Dubinin's theory (TVFM) are used in the equilibria data to derive the MPSD, which is well fitted by a Gamma distribution function. The adsorption energy distribution derived from the MPSD is very asymmetric for both the samples studied, and this energy distribution used in the HMSD/HMSMD kinetics models for the study of adsorption dynamics ofn-butane.
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 37 (1996), S. 167-172 
    ISSN: 1572-879X
    Schlagwort(e): dissociation ; kinetics ; Co-Mo sulphide ; H2S
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In this study, a high surface area 4Co∶6Mo∶100γ-Al2O3 sulphide prepared using precipitation from homogeneous solution (PFHS) has been used for the catalytic splitting of hydrogen sulphide into H2 and elemental sulphur. The activity of this new formulation was significantly better than previously reported recipes. Kinetic data collected over a wide range of H2S partial pressures between 883 and 983 K revealed that, although the decomposition followed a first-order law, a mechanism involving H2S adsorption on co-ordinative unsaturation sites of the Co-Mo sulphide catalyst gave a Langmuir-Hinshelwood rate expression that yielded satisfactory model parameters. In particular, the scission of the surface H-S bond appeared to be the rate determining step.
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 1 (1994), S. 26-56 
    ISSN: 1572-882X
    Schlagwort(e): low-temperature degradation ; kinetics ; mechanisms ; electrical insulation ; transformers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract A critical review is given of the degradation of cellulose in the low-temperature region (below about 300°C) of power transformer operation. The large number of kinetic studies, under a variety of environmental conditions from Kraft paper in insulating oil, to cotton and paper in oxygen, are considered in terms of a first-order polymer chain scission model. In many cases, the data are replotted to suit the model. A common activation energy of 111±6 kjmol−1 is calculated and it is shown that the pre-exponential factor, rather than the activation energy, is sensitive to the oxidizing nature of the environment and the susceptibility to degradation of the material. The chemical mechanisms of degradation are reviewed, and conclusions and recommendations are made regarding chemical condition monitoring and life prediction of electrical insulation.
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 37 (1996), S. 173-179 
    ISSN: 1572-879X
    Schlagwort(e): ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Measurements were performed of reaction rate in the process of ammonia synthesis (T=370–470°C) on doubly promoted (DP) (Al2O3, CaO) and triply promoted (TP) (K2O, Al2O3, CaO) iron catalysts. The latter were obtained by impregnation of the reduced and subsequently passivated DP precursors with alcoholic solution of KOH. The studies were carried out under high total pressure (10 MPa) in a wide range of ammonia partial pressure in the gas phase: from 0.25 to about 7 bar. The results are shown to be authoritative for the so-called kinetic regime. The effect of the presence of K+ cations in the catalyst was the stronger, as the temperature of the reaction was the lower and, in particular, the ammonia pressure in the gas phase the higher. The obtained results are in good accordance with the results of Somorjai's studies on activity of iron single crystal surfaces both clean and covered with (K+O) adlayer.
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 27 (1994), S. 79-90 
    ISSN: 1572-879X
    Schlagwort(e): kinetics ; carbon ; oxygen ; recombination ; rhodium ; surface characterisation ; XPS ; AES
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Different mechanisms of atomic carbon and oxygen recombination on a rhodium surface are studied with Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The kinetics of adsorbed carbidic carbon oxidation (carbon coverageθ c ≈ 0.1–0.3 ML) by gas-phase oxygen that proceeds by a Langmuir-Hinshelwood reaction mechanism, provides the value of the activation energy for recombination (E rec ⇂t ≈ 170±20 kJ/mol).E rec ⇂t depends slightly on the carbon coverage. An Eley-Rideal type of reaction was observed for adsorbed oxygen and atomic gas-phase carbon recombination which occurs in a dynamic regime. The low value found for the activation energy (near zero) is consistent with the mechanism that this exothermic reaction is too fast for energy dissipation into the substrate; the energy is mainly transferred into translational, vibrational and rotational energy of CO.
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  • 10
    ISSN: 1572-882X
    Schlagwort(e): accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.
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  • 11
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 4 (1997), S. 1-5 
    ISSN: 1572-882X
    Schlagwort(e): paper ; degradation ; ageing ; kinetics ; modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 3 (1996), S. 243-267 
    ISSN: 1572-882X
    Schlagwort(e): aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Topics in catalysis 1 (1994), S. 305-314 
    ISSN: 1572-9028
    Schlagwort(e): non-Langmuir ; kinetics ; non-linear dynamics ; oscillations ; chaos ; self-organization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of a catalytic reaction is frequently formulated in terms of simple concepts of the Langmuir type. Apart from limitations arising from the non-uniformity of the catalyst's surface and from the coverage dependence of the rate “constants”, several other complications may come into play. These may arise on the “quantum level” where energy flow between the various degrees of freedom may cause failure of simple transition state theory, as well as on the “continuum level” where formulation of rate equations in terms of coupled non-linear differential equations may give rise to a rich scenario of spatio-temporal self-organization, including kinetic oscillations, chaos, and formation of concentration patterns. Several of these phenomena are illustrated by selected examples.
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  • 14
    ISSN: 1572-879X
    Schlagwort(e): propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated γ-alumina or zirconia compared to γ-alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/γ-alumina, Pt/zirconia, Pd/γ-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/γ-alumina, and Pd/zirconia is less active than Pd/γ-alumina.
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 10 (1997), S. 23-26 
    ISSN: 1572-8773
    Schlagwort(e): aromatic donor molecules ; horseradish peroxidase ; kinetics ; lactoperoxidase
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Based on kinetic evidence, it has been shown for the first time that the mode of binding of aromatic donor molecules is similar in horseradish peroxidase and lactoperoxidase; also that the nature of the heme plays an important role in the reaction with hydrogen peroxide, and has no effect on the reaction of the intermediate compound II with aromatic substrates.
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  • 16
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 39 (1996), S. 67-71 
    ISSN: 1572-879X
    Schlagwort(e): non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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  • 17
    ISSN: 1572-879X
    Schlagwort(e): Ultraviolet heterogeneous photocatalysis ; oxidation ; trichloroethylene ; titania ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Kinetics of the gas/solid heterogeneous photocatalytic oxidation of dilute trichloroethylene (TCE) vapors by ultraviolet-illuminated titanium dioxide have been determined using a fixed-bed dynamic photoreactor. Reaction rate dependences on inlet TCE, oxygen and water vapor concentrations were found to consist of both reactant sensitive and insensitive regions. In the reactant sensitive regions, measured limiting apparent reaction rate orders for TCE, oxygen and water vapor are 0.8, 1.7 and — 3, respectively. Water vapor in the reactant stream lowersinitial reaction rates relative to corresponding water free conditions, but is required to sustain photocatalytic activity for extended periods of time.
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  • 18
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Schlagwort(e): ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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  • 19
    ISSN: 1436-5073
    Schlagwort(e): flow injection analysis (FIA) ; mercury ; porphyrin ; kinetics ; spectro-photometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS4) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min−1 for Hg(II) withm-Cl-TPPS4 in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 μl), the method's relative standard deviation was 0.82% (n = 12) at 5.0 μg ml−1 mercury, with a linear range of 0–12.0 μg ml−1 and an analytical frequency of 60h−1. The detection limit (3σ) was 0.025 μg ml−1. Interference studies showed that most metal ions co-existing with Hg2+ could be tolerated at 100-fold excess levels, but Zn2+, Cu2+ and Mn2+ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    Microchimica acta 124 (1996), S. 13-25 
    ISSN: 1436-5073
    Schlagwort(e): kinetics ; rates ; integrating ratemeter ; optimization ; first-order
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The integrating ratemeter is used in concert with the two-rate parameter to form the integrating ratemeter two-rate parameter. Propagation of error theory is applied to the integrating ratemeter two-rate parameter to yield expressions for the precision of rates calculated from the integrating ratemeter two-rate parameter in terms of the precision of the rates measured with the integrating ratemeter. Simulations and experimental results show that in cases where the standard deviation of the rate is relatively constant, the optimum time to make a rate measurement using the integrating ratemeter is also the optimum time to measure either of the rates in the two-rate parameter. If either of the two rates comprising the two-rate parameter is measured at the optimum time, then the precision and accuracy of concentrations measured with this technique are optimized.
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Nutrient cycling in agroecosystems 39 (1994), S. 39-42 
    ISSN: 1573-0867
    Schlagwort(e): Controlled release fertilizers ; kinetics ; mechanism ; nutrient supply ; rate of release ; slow release fertilizers (SRF)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Individual granules within a given granule population of a slow-release fertilizer (SRF) have a different release pattern. The populations studied differed both in relation to the time delay before the start of the release process and to the duration of the release. An association between a short delay period and a rapid release was found. The random reease distribution can be approximated using first-order rate equations. In cases, a term describing a “lag” period should be added. The distribution of release timing among the fertilizer granules may allow a long-lasting nutrient supply to the plant, as long as there are enough granules within the root zone to allow a uniform supply pattern.
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  • 22
    ISSN: 1572-9729
    Schlagwort(e): bioavailability ; builders ; detergents ; kinetics ; mineralization ; sewage sludge ; soil
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Energietechnik , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Tetradecenyl succinic acid (TSA) is the major component of a detergent builder (C12-C14 alkenyl succinic acid), which is inherently biodegradable. 14C-TSA was dosed as a component of sewage sludge into a soil with a history of sludge amendment at final added concentrations of 1.5 and 30 mg (kg soil)-1. In addition, it was dosed to the soil in an aqueous solution to a final added concentration of 30 mg (kg soil)-1. Dose and form were found to have a pronouced effect on the mineralization kinetics. When dosed in a realistic form and concentration (i.e. 1.5 mg (kg soil)-1 as a component of sludge), TSA was mineralized at its highest rate and to its greatest extent, and the mineralization half-life was 2.4 days. When dosed at 30 mg (kg soil)-1 as a component of sludge, mineralization began immediately, and the half-life was 23 days. In contrast, when dosed at this concentration in aqueous solution, the onset of mineralization was preceded by a 13 day lag period and the mineralization half-life was 69 days. Primary biodegradation and mineralization rates of TSA were very similar. Approximately, half the radioactivity was evolved as 14CO2, while the remaining radioactivity became non-extractable, having presumably been incorporated into biomass or natural soil organic matter (humics). This study demonstrated that TSA is effectively removed from sludge-amended soils as a result of biodegradation. Furthermore, it showed the effect that dose form and concentration have on the biodegradation kinetics and the importance of dosing a chemical not only at a relevant concentration but also in the environmental form in which it enters the soil environment.
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Biodegradation 7 (1996), S. 73-81 
    ISSN: 1572-9729
    Schlagwort(e): diesel oil ; biodegradation ; CSTR ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Energietechnik , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract In batch culture diesel oil was degraded rapidly, with a maximum growth rate (for a consortium of microorganisms) of 0.55 h-1. The corresponding yield Y SX was 0.1 Cmol/Cmol. In a continuous stirred tank reactor the maximum dilution rate was about 0.25 h-1, with a yield of 0.3 Cmol/Cmol. With a residence time of 1 day 82% of the influent oil was degraded. In the batch reactor, of the mixture of linear and branched alkanes the linear alkanes were degraded fastest and with the highest yield. Only after most of the linear alkanes had disappeared were the branched alkanes consumed. In a CSTR a large part of the branched alkanes was not degraded.
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  • 24
    Digitale Medien
    Digitale Medien
    Springer
    Pure and applied geophysics 147 (1996), S. 367-375 
    ISSN: 1420-9136
    Schlagwort(e): Induced seismicity ; kinetics ; rock fracture ; rockburst ; earthquake
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geologie und Paläontologie , Physik
    Notizen: Abstract Powerful seismic events, such as earthquakes and rockbursts, are caused by the accumulation of energy in rocks and loss of rock mass stability. Usually methods of their forecasting are based on the registration of anomalous behavior of geophysical fields. However an efficiency of this approach is low. The present paper proposes a kinetic approach to the description of rock fracture process, which can be used for the forecasting of seismic events and an investigation of structure and energy distributions in rock. 3-D and 1-D kinetic equations describing a process of cluster formation in rock were obtained. The equations are invariant to deformation conditions and to the scale level of events. They showed a good agreement with the results of field observations and laboratory experiments. It was also shown that these equations well describe the processes of earthquake, rockburst and rock sample failure preparation. Catalogues of rockbursts in mines were analyzed with the use of the kinetic equations to find out evidence of induced seismic events. The proposed approach makes it possible to reveal trends in rock behavior and thus predict the rock failure at different scale levels.
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  • 25
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 52 (1997), S. 505-506 
    ISSN: 1432-1041
    Schlagwort(e): Key words Ibuprofen; effervescent tablets ; kinetics ; bioavailability
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Materialart: Digitale Medien
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  • 26
    ISSN: 1432-1041
    Schlagwort(e): Key words Diphemanil methylsulphate ; Neonate; antimuscarinic agent ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Materialart: Digitale Medien
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 39 (1990), S. 155-159 
    ISSN: 1432-1041
    Schlagwort(e): Gentamicin ; Dosage ; kinetics ; dose individualization ; dose prediction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary A prospective study was carried out in 40 acutely ill patients to compare the non-kinetic and kinetic approaches to individualization of the dosage regimen of gentamicin. The patients were divided into two equal groups. For the non-kinetic group, the doses were derived from the physician's personal experience, on a mg/kg basis, and by use of nomograms. The total daily dose ranged from 1.43 to 4.5 mg/kg. Based on serum concentration measurements, the dosage regimen for individual patient was calculated by Sawchuk-Zaske's method. The calculated doses were compared to the prescribed doses in each patient. Of the patients on empirically prescribed doses 65% received 36% more drug than the calculated dose and 20% received 36% less than the calculated dose. The calculated dosing intervals were greater than the recommended intervals in 60% of the patients. The gentamicin trough concentration was 〉 2 μg/ml in 70% of the patients. There was a significant tendency to overdosage of the patients. For the kinetic group, following administration of the calculated dose, the steady-state peak and trough concentrations in each patient were measured. The correlation of measured to predicted steady-state serum concentrations was excellent (r=0.9968, p〈0.05). About 85% of the served trough concentrations and 90% of the peak values fell within the therapeutic range. The mean of the prediction error (ME), mean absolute error (MAE), mean squared error (MSE), and root mean squared error (RMSE) of the trough and peak concentrations were calculated. The 95% confidence interval of the ME for the trough and peak concentrations included zero, which shows that the prediction was not significantly biased. A significant relationship between gentamicin clearance and the ratio of the peak and trough concentrations achieved to the administered dose (r=0.873, 0.916 for trough and peak, respectively) was found. The findings suggest that the individualized approach to dosage determination using pharmacokinetic principles, in conjunction with daily monitoring of serum gentamicin concentrations, may provide safe and effective therapy.
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  • 28
    ISSN: 1432-072X
    Schlagwort(e): Key words Auxostat ; Batch culture ; Chemostat ; Continuous culture ; Fermentation control ; Inhibition ; kinetics ; Nutristat ; On-line measurement ; Pentachlorophenol ; Pollutant ; Sphingomonas ; Steady-state conditions ; Toxicity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract A bacterium degrading pentachlorophenol (PCP) as the only source of carbon and energy was grown in a “nutristat”, i.e., a continuous culture with on-line measurement and control of the substrate concentration. We improved the PCP nutristat by incorporation of a personal computer with a proportional integral derivative (PID) algorithm for controlling the medium feed pump. The controlled value deviated from the average (set-point) value by 1% maximally. In the PCP nutristat (30°C), the steady-state dilution rate, and hence, specific growth rate, showed a maximum value of 0.142 ± 0.004 h–1 at set-point PCP concentrations between 37 and 168 μM. At PCP concentrations above 168 μM, the steady-state growth rate decreased because of inhibition. The growth yield coefficient was not seriously affected by the PCP concentration, suggesting that uncoupling was not the inhibitory mechanism. It was concluded that the PCP nutristat is very useful for establishing steady-state conditions that maintain growth-inhibitory PCP concentrations and high cell concentrations, conditions for which the chemostat is not suitable.
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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 35-49 
    ISSN: 1572-8943
    Schlagwort(e): bone cement ; DSC ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Schlagwort(e): compensation effect ; DSC ; kinetics ; TG
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Four computer programs as well as one demo-version for non-linear evaluation of kinetic data in thermal analysis and calorimetry, were presented. The multi-task program TA-kin meets all mathematical requirements for solving the numerical assignments. It is shown that the so-called compensation effect is due to the mathematical structure of the Arrhenius equation. Several applications of TA-kin to a lot of DSC- and TG-measurements and isoperibolic batch experiments as well as adiabatic semi batch experiments realized by precision calorimetry have been discussed.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 569-575 
    ISSN: 1572-8943
    Schlagwort(e): Bi2O3 ; CaCO3 decomposition ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Former studies concerning the formation of the compounds in the pseudobinary systems of Bi2O3-MO type (M =Ca, Sr, Ca+Sr) have shown that the reaction which occurs with the highest rate is that between Bi2O3 and CaO. In the present work CaCO3 was used as CaO source. We carried out an investigation of the thermal decomposition of CaCO3 in the presence of Bi2O3 in comparison with the decomposition of pure CaCO3. The presence of Bi2O3 exerts a complex influence on the CaCO3 decomposition acting on the nucleation as well as on the diffusion of CO2. The decomposition of the samples with low Bi2O3 content follows the mechanism of a contracting sphere. A change from surface nucleation to bulk nucleation is recorded for higher amounts of Bi2O3.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 1437-1450 
    ISSN: 1572-8943
    Schlagwort(e): browning ; crystallization ; glass transition ; kinetics ; milk powder ; water
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract An exotherm, observed in differential scanning calorimetry (DSC) scans of amorphous food materials above their glass transition temperature,T g, may occur due to sugar crystallization, nonenzymatic browning, or both. In the present study, this exothermal phenomenon in initially anhydrous skim milk and lactose-hydrolyzed skim milk was considered to occur due to browning during isothermal holding at various temperatures above the initialT g. The nonenzymatic, Maillard browning reaction produces water that in amorphous foods, may plasticize the material and reduceT g. The assumption was that quantification of formation of water from theT g depression, which should not be observed as a result of crystallization under anhydrous conditions, can be used to determine kinetics of the nonenzymatic browning reaction. The formation of water was found to be substantial, and the amount formed could be quantified from theT g measured after isothermal treatment at various temperatures using DSC. The rate of water formation followed zero-order kinetics, and its temperature dependence well aboveT g was Arrhenius-type. Although water plasticization of the material occurred during the reaction, and there was a dynamic change in the temperature differenceT−T g, the browning reaction was probably diffusioncontrolled in anhydrous skim milk in the vicinity of theT g of lactose. This could be observed from a significant increase in activation energy. The kinetics and temperature dependence of the Maillard reaction in skim milk and lactose-hydrolyzed skim milk were of similar type well above the initialT g. The difference in temperature dependence in theT g region of lactose, but above that of lactose-hydrolyzed skim milk, became significant, as the rate in skim milk, but not in lactose-hydrolyzed skim milk, became diffusion-controlled. The results showed that rates of diffusion-controlled reactions may follow the Williams-Landel-Ferry (WLF) equation, as kinetic restrictions become apparent within amorphous materials in reactions exhibiting high rates at the same temperature under non-diffusion-controlled conditions.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 917-923 
    ISSN: 1572-8943
    Schlagwort(e): copper compound ; coupled technique ; kinetics ; macrocyclic complex ; non-isothermal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The thermal decomposition process of the complex [Cu(NBOCTB)][Cu(NO3)4] H2O has been studied by TG and DTG technique, and possible intermediates of the thermal decomposition have also been conjectured from the TG and DTG curves. The results suggest that the decomposition of the complex involves five steps: The non-isothermal kinetics of steps 1, 2 and 3 have been studied by means of the Achar and Coats-Redfern method based on TG and DTG curves. Step 1 is a ‘Coring and Growth’ mechanism (n= 1), its kinetic equation may be expressed as: dα/dt=Ae−E/RT(1−α). Steps 2 and 3 are both ‘two order chemical reaction’ mechanisms, their kinetic equations can be expressed as: dα/dt=Ae−E/RT(1−α)2.
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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 87-94 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; poly(di-propyl itaconates) ; polymer structure ; thermal degradation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Non-isothermal thermogravimetry was performed in a dynamic nitrogen atmosphere, on a series of poly(di-n-propyl itaconates) (PDnPI) and poly(di-iso-propyl itaconates) (PDiPI) which had been prepared in the presence of various amounts of the chain transfer agentn-dodecyl mercaptan (DDM). Differential thermogravimetry (DTG) showed that both polymers degraded in two stages. The DTG curve of PDnPI had a large first peak followed by a smaller shoulder, whereas the DTG curve of PDiPI was composed of two peaks of almost equal heights. The addition of DDM during the polymerisations in both cases resulted in a similar decrease in the relative area of the first peak.
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  • 35
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 183-191 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; thermooxidative degradation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The results of non-isothermal kinetic analysis of the thermooxidative degradation in air and oxygen of an unsaturated polyester resin are presented. It has been shown that the thermooxidative degradation in oxygen occurs at lower temperatures than the thermooxidative degradation in air. The kinetic parameters of the thermooxidative degradation depend on the heating rate and the oxygen pressure. Two straight lines of InAvs. E (A is the preexponential factor andE is the activation energy), characteristic for the compensation effect, have been obtained for the thermooxidative degradation in air and in oxygen respectively. The difference between the intercepts of these straight lines can be explained by dependence of the pre-exponential factor on the oxygen pressure.
    Materialart: Digitale Medien
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 46 (1996), S. 795-808 
    ISSN: 1572-8943
    Schlagwort(e): DSC ; kinetics ; liquid crystalline polymer ; optical transmittance ; polycarbosilane ; side-chain mesogen ; transition parameters
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
    Materialart: Digitale Medien
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 857-862 
    ISSN: 1572-8943
    Schlagwort(e): analytical methods ; kinetics ; powder milk ; temperature
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract This work present comparative results on powder milk storage quality, obtained from analytical methods. Protein content was determined conventional (Kjeldahl) and colorimetric with biuret reagent at 540 nm and integral quality by thermogravimetric and biological methods. A method was developed for the protein separation of powder milk. Powder milk was submitted to degradation processes at 45, 60 and 80°C for 20 days. The results indicated that protein content values were inconsistent if determinations by Kjeldahl and colorimetric methods and biological tests were compared. There is evidence of thermal decomposition of powder milk as detected by biological and thermogravimetric methods.
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  • 38
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 937-941 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; mebendazole ; quality control ; technology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A study was made of the thermal behavior of the starting materials, their mixtures and the resulting mebendazole tablets. The thermal curves were obtained with a Shimadzu thermobalance, model TGA-50, using an air flow of 50 mL min−1 and a heating rate of 10°C min−1 in the temperature interval 30–900°C. The reaction constant velocities for the mebendazole salt and tablets were determined isothermally, using the Arrhenius expression. The thermal stability of mebendazole tablets is lower than that of the mebendazole salt, due to the presence of starch and lactose in the composition. Analysis of the data reveals that thermogravimetry is a powerful tool in pharmaceutical technology and quality control.
    Materialart: Digitale Medien
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  • 39
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 1081-1091 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; thermal degradation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetic study of thermal degradation takes into account the validity of the Arrhenius equation. From TG data, the activation energy,E a and pre-exponential factor,A, are evaluated. These results are interpreted by using the ‘kinetic compensation effect’ as basis. A linear correlation between In(A) andE a is obtained in all cases studied. However, in a plot of the logarithm of the rate constant as a function of reciprocal temperature for the same series of reactions, the thermal oxidative degradations of Nylon-6 and PVC display a point of concurrence and one isokinetic temperature, whereas those of HIPS and PC do not. Therefore, in the thermal oxidative degradations of Nylon-6 and PVC a ‘true’ compensation effect occurs, which could be related to the bulk properties of metal oxides, such as different valence states, whereas for other polymers it displays only an ‘apparent’ compensation effect. This means that degradation is largely independent of the bulk properties of oxides, but may be related to the distribution of different kinds of active links in the polymer surface having different activation energies.
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  • 40
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 343-348 
    ISSN: 1572-8943
    Schlagwort(e): activation energy ; combustion ; crude oil ; differential scanning calorimetry ; kinetics ; thermogravimetric analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A weighted mean activation energy method was applied to describe the reactivity and combustibility of crude oils via simultaneous TG/DTG. Thermal experiments were conducted with a non-isothermal method at a heating rate of 10
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  • 41
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 385-401 
    ISSN: 1572-8943
    Schlagwort(e): dehydration and decomposition ; kinetics ; Fe(III) chloride
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Fe(III) chloride hydrate (FeCl3·xH2O) undergoes simultaneous dehydration and dehydrochlorination from its molten phase in the temperature range 100–200
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  • 42
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 413-425 
    ISSN: 1572-8943
    Schlagwort(e): alcoholic fermentation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The control of alcoholic fermentation is necessary to obtain a quality wine. The overall dynamic and phenomenological modelling already applied to the simulation of this type of reaction enables us to suggest, in this study, a simple model (of which two variants), are relatively satisfactory. The first variant does not take into account the variation of the ambient temperature; the model translates exactly the first phase of the experimental curve or the moment when highest temperatures are measured. The relaxation phase is less well described because of influence of variation of the ambient temperature is relatively important. The second one considers the system depending on the ambient temperature, the model is correct for the relaxation phase too (the reaction temperature decreases, it nears the ambient temperature). The advantage of this model: It permits one to determine the reaction enthalpy and the kinetic parameters.
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  • 43
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 623-634 
    ISSN: 1572-8943
    Schlagwort(e): bismalleimide/carbon fiber composite ; DMA ; kinetics ; TSC
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The correlation between structure/microstructure and thermomechanical properties has been investigated by the Thermally Stimulated Creep (TSC) technique in a high performance thermostable thermoset matrix composite. The high resolving power of this technique allows us to analyse the α retardation mode. The kinetics of molecular movements liberated at the glass transition has been investigated by the technique of fractional loading: the analysis of each elementary process gives the real compliance and the retardation time as a function of temperature. The values of the activation parameters show the existence of a compensation phenomenon which characterizes the microstructure. It also gives access to the loss compliance of the composite material as a function of temperature and frequency. The predictive calculation of loss compliance has been validated by the results obtained by dynamic mechanical analysis (DMA).
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  • 44
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 769-782 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; non-linear optimization ; reactor time constants ; software ; time constants of sensors
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract All temperature sensors have a finitely time constant. The influence of the sensor time constant gts on the results of kinetic evaluation is demonstrated at four reaction types. The ignorance of the sensor indolence gives incorrect activation parameters. Therefore the determination of Τs is necessary. For the estimation of parameters the nonlinear evaluation program TA-kin was used. With its help it is possible to find the real parameters, also when Τs=32 s, if the real Τs-value was entered.
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  • 45
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1517-1525 
    ISSN: 1572-8943
    Schlagwort(e): β-cyclodextrin ; cinnamyl alcohol ; kinetics ; thermal analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The stability of β-cyclodextrin-cinnamyl alcohol inclusion complex (β-CD·C9H10·8H2O) was investigated using TG and DSC. The mass loss took place in three stages: the dehydration occurred between 50–120°C; the dissociation of β-CD·C9H10O occurred in the range of 210–260°C; and the decomposition of β-CD began at 280°C. The dissociation of β-CD·C9H10O was studied by means of thermogravimetry, and the results showed: the dissociation of β-CD·C9H10O was dominated by a two-dimensional diffusion process (D2). The activation energyE was 161.2 kJ mol−1, the pre-exponential factorA was 4.5×1013 min−1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the interesting of studies focussed on the energy binding cyclodextrin and the guest molecule. In this paper, β-cyclodextrin-cinnamyl alcohol inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show: the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of Van der Waals interaction.
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  • 46
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1553-1564 
    ISSN: 1572-8943
    Schlagwort(e): deconvolution ; differential scanning calorimetry ; feedforward neural networks ; kinetics ; signal filtering ; simulations ; thermal analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Feedforward neural networks have been used for kinetic parameters determination and signal filtering in differential scanning calorimetry. The proper learning function was chosen and the network topology was optimized, using an empiric procedure. The learning process was achieved using simulated thermoanalytical curves. The resilient-propagation algorithm have led to the best minimization of the error computed over all the patterns. Relative errors on the thermodynamic and kinetic parameters were evaluated and compared to those obtained with the usual thermal analysis methods (single scan methods). The errors are much lower, especially in presence of noisy signals. Then, our program was adapted to simulate thermal effects with known thermodynamic and kinetic parameters, generated electrically, using a PC computer and an electronic interface on the serial port. These thermal effects have been generated by using an inconel thread.
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  • 47
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1467-1475 
    ISSN: 1572-8943
    Schlagwort(e): CRTA ; DSC ; kinetics ; synthetic brochantite ; TG-DTA ; thermal decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The reaction pathway of the thermal decomposition of synthetic brochantite, Cu4(OH)6SO4, to copper(II) oxide was investigated through the detailed kinetic characterization of the thermal dehydration and desulferation processes. The dehydration process was characterized by dividing into two overlapped kinetic processes with a possible formation of an intermediate compound, Cu4O(OH)4SO4. The dehydrated sample, Cu4O3SO4, was found first to be amorphous by means of XRD, followed by the crystallization to a mixture of CuO and CuO-CuSO4 at around 776 K. The specific surface area and the crystallization behaviour of the amorphous dehydrated compound depend largely on the dehydration conditions. The thermal desulferation process is influenced by the gross diffusion of the gaseous product SO3, which is governed by the advancement of the overall reaction interface from the top surface of the sample particle assemblage to the bottom.
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  • 48
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 50 (1997), S. 455-462 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; statistical analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A statistical technique based on the Wilcockson criterion is suggested for estimation of the reproducibility of thermoanalytical experiments. Reduction of the whole physicochemical process to a quasi-one-stage process is described.
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  • 49
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 50 (1997), S. 425-430 
    ISSN: 1572-8943
    Schlagwort(e): decomposition ; kinetics ; non-isothermal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The authors present the results concerning the thermal behaviour of three polynuclear coordination compounds of Nd(III) and Co(II) or Fe(III) with triptophan. For the dehydration steps the values of the non-isothermal kinetic parameters have been determined.
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1227-1241 
    ISSN: 1572-8943
    Schlagwort(e): inorganic sulphates ; kinetics ; mechanism ; thermodynamics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Thermal decomposition of different inorganic sulphates are presented. A number of techniques, but mainly TG and DTA, are used to prove the mechanism and kinetics of CaSO4, BaSO4, FeSO4·xH2O, Al2(SO4)3·xH2O under various gas atmospheres. It is shown how the partial pressure of gas components and heating rate may effect the mechanism and kinetic parameters. There are also examples on the effects of some additives and initial treatment on the thermal processes. On the base of the results obtained some recommendations are given concerning the precautions to be taken into account in the thermal decomposition studies and the sulphur recovering.
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  • 51
    Digitale Medien
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1477-1484 
    ISSN: 1572-8943
    Schlagwort(e): CRTA ; kinetics ; particle size distribution ; rate jump method
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetic curves at infinite temperature for the solid-state reactions of the interface shrinkage type were drawn theoretically by taking account the particle size distribution in the sample mixture. The CRTA curves for the reactions with the particle size distribution can be drawn by utilizing the universal kinetic curves at infinite temperature. The proper kinetic treatment for the CRTA curves with the particle size distribution is discussed in connection with the property of the kinetic equation with respect to the particle size distribution. The present kinetic consideration is taken as a simulation for the reactions with a certain distribution in α among the reactant particles, produced preferably by the mass and heat transfer phenomena during the thermoanalytical measurements. The merit of the rate jump method by a single cyclic CRTA curve is also discussed on the basis of the present results.
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  • 52
    Digitale Medien
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1161-1170 
    ISSN: 1572-8943
    Schlagwort(e): basicity ; dinitramides ; kinetics ; oxidation ; tanδ ; transition temperatures
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The dinitramide salts of ammonia (ADN), hexamethylenetetramine (HDN), potassium (KDN), and sodium (NaDN) showed a linear relationship between the DSC rate of decomposition at the peak maximum and the DEA tanδ value at the low temperature transition peak. As the cation basicity increased in the series ADN〈HDN〈KDN〈NaDN, there was an increase in the low temperature transition peak, the energy barrier for relaxation, and the decomposition peak temperature, and a decrease in the tanδ value at the low temperature transition peak, specific heat capacity, and the rate and enthalpy of decomposition. The more basic salts were more thermally stable (i.e., higher decomposition temperature) and less energetic (i.e., lower enthalpy of decomposition). The more internal free volume (disorder) present in these salts, the higher the rates of relaxation and decomposition. Five aluminum powders of different surface areas were analyzed by DSC in platinum sample pans, and it was found that the enthalpy and rate of oxidation increased as the particle size of Al decreased while the enthalpy of the Al melt decreased. TG showed a two-step weight gain in the oxidation of Al with plateaus in the 650 and 1130°C regions and the percent weight gain increased as the particle size of Al decreased. Variable DSC and TG heating rate studies showed that the activation energies for the first step in the oxidation process increased as the particle size of Al increased.
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  • 53
    Digitale Medien
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    Journal of thermal analysis and calorimetry 50 (1997), S. 33-50 
    ISSN: 1572-8943
    Schlagwort(e): Ba[Cu(C2O4)2(H2O)]·5H2O ; decomposition ; dehydration ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The thermal behaviour of Ba[Cu(C2O4)2(H2O)]·5H2O in N2 and in O2 has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (about 80°C), but continues until the onset of the decomposition (about 280°C). The decomposition takes place in two major stages (onsets 280 and 390°C). The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311±30 kJ mol−1 (or 52±5 kJ (mol of H2O)−1). The overall enthalpy change for the decomposition of Ba[Cu(C2O4)2] in N2 was estimated from the combined area of the peaks of the DSC curve as −347 kJ mol−1. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the α-time curves could be described by the three dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125±4 kJ mol−1 and (1.38±0.08)×1015 min−1, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model withn=5. The other process was slow and could also be described by the contracting-geometry model, but withn=2. The values ofE a andA were 206±23 kJ mol−1 and (2.2±0.5)×1019 min−1, respectively, for the fast process, and 259±37 kJ mol−1 and (6.3±1.8)×1023 min−1, respectively, for the slow process.
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  • 54
    Digitale Medien
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    Journal of thermal analysis and calorimetry 46 (1996), S. 49-54 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; solid-phase reactions
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The convexity of localization forms, strictly required by conventional geometric-probabilistic formalism, is not in agreement with many experimental observations concerning solid-phase chemical reactions. In a discussion of the essence of this requirement, it is shown that it may be weakened for non-convex localization forms consistent with the symmetry of a solid reagent and described within the geometric-probabilistic approach in terms of planigons and Wigner-Seitz cells.
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  • 55
    Digitale Medien
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    Journal of thermal analysis and calorimetry 46 (1996), S. 225-236 
    ISSN: 1572-8943
    Schlagwort(e): IR ; kinetics ; TG-DTG-DTA ; l,3,5-triamino-2,4,6-trinitrobenzene
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of the thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) in condensed state has been investigated by high temperature infrared spectroscopy (IR) and thermogravimetry (TG) in conjunction with pyrolysis gas analysis, differential thermal analysis (DTA) and hot stage microscopy. The decomposition proceeds in two main stages under isothermal conditions and the initial stage involving about 24% loss in weight obeys Avrami-Erofe'ev equation (n= 1), and is governed by an activation energy (E) of 150.58 kJ·mol−1 and log(A in s−1) 12.06. The second stage corresponding to 24 to 90% loss in weight gave best fit for Avrami-Erofe'ev equation,n=2, withE=239.56 kJ·mol−1 and log(A in s−1) 19.88 by isothermal TG. The effect of additives, on the initial thermolysis of TATB has also been studied. Evolved gas analysis by IR showed that NH3, CO2, NO2, HCN and H2O are produced in the initial stage of decomposition. The decomposition in KBr matrix in the temperature range 272 to 311.5°C shows relative preferential loss in the -NH2 to -NO2 band intensity which indicates that the rupture of C-NH2 bond, weakened also by the interaction of the NH2 with the neighbouring NO2 group, appears to be the primary step in the thermolysis of TATB.
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  • 56
    Digitale Medien
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    Journal of thermal analysis and calorimetry 46 (1996), S. 285-290 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; system FeSO4·7H2O-MnO2
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Processes which occur during the thermal treatment of system FeSO4·7H2O-MnO2 are of the interest for obtaining MnSO4, which can be easily soluted in water and separated from impurities in manganese slime in zinc metallurgy. Results of the experimental investigations of such processes are given in this paper. Kinetic parameters for the previously defined mechanism were determined using Borchardt and Daniels method.
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  • 57
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    Journal of thermal analysis and calorimetry 46 (1996), S. 377-385 
    ISSN: 1572-8943
    Schlagwort(e): crystallization ; drawing ; kinetics ; Kissinger ; Ozawa ; poly(ethylene terephthalate)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The non-isothermal crystallization kinetics of hot drawn poly(ethylene terephthalate) films were studied using the Kissinger and Ozawa equations. The influence of the initial drawing on the crystallization kinetics was investigated. The values of the apparent activation energy and of the Avrami exponent indicates that the nucleation and growth of crystallites depend greatly on the stress submitted to the samples.
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  • 58
    Digitale Medien
    Digitale Medien
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1223-1238 
    ISSN: 1572-8943
    Schlagwort(e): dehydroxylation ; goethite ; hematite ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of dehydroxylation of synthetic aluminous goethite was studied using isothermal and non-isothermal thermogravimetry. The complete isothermal dehydroxylation can be described by the Johnson-Mehl equation with up to three linear regions in plots of lnln [1/(1−y)]vs. Int Kinetics for the initial stage of dehydroxylation changed from diffusion to first-order through the temperature range 190 to 260°C. The rate of dehydroxylation was reduced by Al-substitution and increased with temperature. Activation energy for dehydroxylation, calculated from the time to achieve a given dehydroxylation extent, varied depending on the extent of dehydroxylation and Al-substitution. Non-stoichiometric OH existed in goethite and some remained in hematite after the complete crystallographic transition.
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  • 59
    Digitale Medien
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1271-1282 
    ISSN: 1572-8943
    Schlagwort(e): CrO3 ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The course of the non-isothermal decomposition of CrO3 in air was explored kinetically, by using a number of widely accepted methods. The credibility of the values obtained from a given kinetic parameter (the reaction order, the activation energy and the frequency factor) was justified on the grounds of (i) a multiple correlation coefficient, and (ii) the merits and demerits of the method adopted. The results obtained may help towards a characterization of the non-isothermal conditions under which the encountered decomposition events and products could be resolved. The study was motivated by the results of previous physicochemical characterization studies [1, 2], in which catalytically important intermediates CrOx(3〈x〈6) were structurally identified.
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  • 60
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1313-1324 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; polyester resin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The isothermal and non-isothermal degradation of a typical styrenated phthalic acid-maleic acid-propylene glycol polyester were measured. Non-isothermal and isothermal kinetic analyses were performed on the various degradation steps observed. The values of the non-isothermal and the isothermal kinetic parameters are in good agreement.
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  • 61
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1671-1679 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; polycarbonate
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Thermal degradation of poly(2,2′,-propane-bis-4-phenyl carbonate) or bisphenol A polycarbonate (PC) alone and in presence of metal oxide as additives have been discussed. Thermal degradation of PC in presence of metal oxide additives may be surface induced catalytic thermo-oxidative degradation. Some metal oxides retard thermo-oxidative degradation of PC.
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  • 62
    Digitale Medien
    Digitale Medien
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1657-1669 
    ISSN: 1572-8943
    Schlagwort(e): activation energy ; combustion ; differential scanning calorimetry ; kinetics ; lignite ; oxidation ; thermogravimetric analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Thermal analysis increasingly being used to obtain kinetic data relating to sample decomposition. This work involves a comparative study of several methods used to analyse DSC and TG/DTG data obtained on the oxidation of Beypazari lignite. A general computer program was developed and the methods are compared with regard to their accuracy and the ease of interpretation of the kinetics of thermal decomposition. For this study, the ratio method was regarded as the preferred method, because it permits the estimation of reaction order, activation energy and Arrhenius constant simultaneously from a single experiment.
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  • 63
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; thermal decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The thermal behaviour of some compounds derived from 5-phenylfuran-2,3-dione was studied. The thermoanalytical data relating to the decomposition steps and intermediates were completed with mass spectrometric analysis and infrared spectroscopy results. For some of the investigated reactions, the kinetic and structural data correlated satisfactorily.
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  • 64
    Digitale Medien
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    Journal of thermal analysis and calorimetry 47 (1996), S. 247-258 
    ISSN: 1572-8943
    Schlagwort(e): ethylene (vinyl acetate) ; kinetics ; polymer
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Ethylene (vinyl acetate), EVA, is a copolymer which is thermally degraded at high temperatures, with acetic acid release at approximately 620 K. This release can be studied by using thermal methods, and in particular thermogravimetric analysis. The present work was focused on establishing the polymer weight loss with temperature in order to calculate the activation energy of the overall deacetylation process. To obtain the final results, a Mettler TC50 instrument coupled with a Mettler TC11 microprocessor was used. The activation energies of four different industrial EVA formulations were calculated. The results obtained by applying different kinetic methods reported in the literature agreed reasonably well; they were compared in order to select the best method of reporting EVA deacetylation results.
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  • 65
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1041-1062 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; polymerization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The method of computer experiments can be successfully applied to radical polymerization with the inclusion of initiation, propagation and termination. The convenient PC-program ‘TAkin’ for non-linear estimation of the parameters of calorimetric and thermoanalytical experiments was applied for determination of the activation parameters of chain propagation and termination. The overall evaluation of three or more data sets was preferred. The determination of the kinetic parameters proceeds satisfactorily of the measured curves are strongly different, e.g. with a changed start temperature of modified application of batch and semi-batch technique, including acceptable experimental errors. Eight recommendations for laboratory experts are given.
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  • 66
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1063-1080 
    ISSN: 1572-8943
    Schlagwort(e): depolymerization ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The method of computer-experiments can be applied successfully on the radical depolymerization under inclusion of initiation, depropagation and termination. The comfortable PC-program ‘TA-kin’ for the non-linear estimation of parameters for TG- or DSC-experiments was applied to the determination of activation parameters of depropagation and termination. Therefore the overall-evaluation of three or more data sets is a prerequisite. The determination of kinetic parameters runs satisfactory if the measured curves are strongly different, e.g. by varying the heating rate, including acceptable experimental errors. Several recommendations for laboratory experts are given. A great support for a very sufficient estimation is the inclusion of simultaneous analysis of the radical concentration.
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  • 67
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1709-1718 
    ISSN: 1572-8943
    Schlagwort(e): kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Results are presented on the thermal behaviour of [Fe(III)2Cu(C2C4)2(OH)4(H2O)2] precursor of copper ferrite. An investigation of the decomposition steps and intermediates was followed by a non-isothermal kinetic analysis of the processable steps.
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  • 68
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    Digitale Medien
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    Journal of thermal analysis and calorimetry 48 (1997), S. 359-366 
    ISSN: 1572-8943
    Schlagwort(e): decomposition ; kinetics ; non-isothermal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Results are presented on the thermal behaviour of two derivatives of malic acid. The decomposition intermediates obtained at about 400
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  • 69
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    Digitale Medien
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    Journal of thermal analysis and calorimetry 49 (1997), S. 45-56 
    ISSN: 1572-8943
    Schlagwort(e): accommodation function ; fractional reaction ; kinetics ; solid-state reaction ; thermal analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The physico-geometric kinetics for the solid-state reactions by thermoanalytical (TA) measurements were reexamined by focusing some fundamental aspects: (1) the fundamental kinetic equation, (2) the kinetic model function, (3) the fractional reaction α, and (4) the apparent kinetic parameters. It was pointed out that some pitfalls in the practical kinetic study are originated by the disagreement between the kinetic information from the TA measurements and the theory of the physico-geometric kinetics. In order to increase the degree of coordination between the theory and practice, several attempts were made from both the theoretical and experimental points of views. The significance of the apparent kinetic parameters was discussed with a possible orientation for obtaining the reliable kinetic parameters.
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  • 70
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    Journal of thermal analysis and calorimetry 49 (1997), S. 255-260 
    ISSN: 1572-8943
    Schlagwort(e): catalytic degradation ; kinetics ; polyethylene
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract HZSM-5 zeolite was screened as catalyst for high density polyethylene degradation at 450
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  • 71
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    Journal of thermal analysis and calorimetry 49 (1997), S. 261-268 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; phenol-formaldehyde resins ; pyrolysis-GC ; thermal degradation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Phenol-formaldehyde resins (I andII), synthesised at a monomer feed ratio of F/P = 1.0 and 1.5, were cured at 130
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  • 72
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1201-1213 
    ISSN: 1572-8943
    Schlagwort(e): calcium aconitate ; DTA ; EGA ; kinetics ; SEM ; TG/DTG ; thermal decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The thermal decomposition of calcium and dicalcium magnesium aconitate hydrates were studied by TG/DTG, DTA, EGA, SEM and other physico-chemical techniques. The decomposition proceeds in four stages: dehydration; oxidation of the carboxylic acid portion of the salt; complete fragmentation of the hydrocarbon portion; and finally, decarboxylation of the metal carbonate to the oxide. The crystal morphologies of the hydrate and anhydrous salts of each compound are very similar. Tricalcium aconitate consists of well-developed twinned crystals and stellate clusters intergrown with flat platy crystals. On the other hand, dicalcium magnesium aconitate crystals are monoclinic with well-developed pinacoidal faces. The activation energy,E d (43±2 kJ mol−1 water), calculated from Borchardt and Daniels' method, for the dehydration process of calcium aconitate trihydrate is of the same order of magnitude as some simple metal salt hydrates. The rate constant, kd increased from 0.04/min at 238°C to greater than 0.86/min at 295°C. It is concluded that the dehydration process is due to cation bound water.
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  • 73
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    Journal of thermal analysis and calorimetry 49 (1997), S. 17-32 
    ISSN: 1572-8943
    Schlagwort(e): Arrhenius equation ; compensation ; distinguishability ; kinetics ; mechanisms ; nonisothermal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract This paper is a review of some of the controversial kinetic aspects of thermal analysis, starting from the ‘šesták questions’ posed in 1979 and looking at developments in some areas since that time. Aspects considered include: temperature programmes and variations, models and mechanisms, kinetic parameters, distinguishability and extent of fit of kinetic models, complementary evidence for kinetic models, the Arrhenius equation and the compensation effect. The value of the ideas of non-isothermal kinetics in chemical education is emphasized.
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  • 74
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    Journal of thermal analysis and calorimetry 47 (1996), S. 445-452 
    ISSN: 1572-8943
    Schlagwort(e): catalysts ; catalyst activity ; catalyst deactivation ; DSC ; gas reactions ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Gas reactions, catalyzed by solid catalysts, can be measured by DSC. In the experimental set-up an open sample pan with catalyst (powder or pellet) is placed on the sample side of the DSC sensor. The reactive gas mixture flows through the cell and reacts on the catalyst surface. The heat effect, caused by this reaction, results into a DSC signal. The calibration procedure is described for quantitative evaluation of the DSC measurements. For illustration four different reaction systems are discussed.
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  • 75
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    Journal of thermal analysis and calorimetry 47 (1996), S. 535-542 
    ISSN: 1572-8943
    Schlagwort(e): cellulose ; kinetics ; thermogravimetry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The complexity of the phenomena which arise during the heating of the various substances seldom can be described by a single reaction kinetic equation. As a consequence, sophisticated models with several unknown parameters have to be developed. The determination of the unknown parameters and the validation of the models requires the simultaneous evaluation of whole series of experiments. We can accept a model and its parameters if, and only if we get a reasonable fit to several experiments carried out at different experimental conditions. In the field of the thermal analysis the method of least squares alone seldom can select abest model or abest set of parameter values. Nevertheless, the careful evaluation of the experiments may help in the discerning between various chemical or physical assumptions by the quality of the corresponding fit between the experimental and the simulated date. The problem is illustrated by the thermal de-composition of cellulose under various experimental conditions.
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  • 76
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1025-1037 
    ISSN: 1572-8943
    Schlagwort(e): crystallographic evaluation ; evaluation with difference procedure ; kinetics ; Rietveld refinement ; X-ray diffraction ; temperature resolved
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Time and temperature resolved X-ray diffraction was used for thermal analysis. Series of diffraction patterns were measured, while the samples are heated/cooled stepwise or isothermally with freely selectable temperature programs. The method was applied for the investigation of the phase transitions of ammonium nitrate and HMX (1,3,5,7-tetranitro-1,3,5,7-tetraaza-cyclooctane), when the identification of phases was required. Its capability in the field of kinetics is demonstrated with the isothermal investigation of the solid state reaction of ammonium nitrate with copper oxide and the non-isothermal investigation of the high temperature corrosion of nickel, which was performed by means of a difference procedure. For obtaining structural details peak fitting and Rietveld refinement were applied for the investigation of ammonium nitrate and HMX.
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  • 77
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    Journal of thermal analysis and calorimetry 49 (1997), S. 617-625 
    ISSN: 1572-8943
    Schlagwort(e): combustion ; kinetics ; lignite ; thermal analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Beypazari lignite was investigated by differential scanning calorimetry (DSC), thermogravimetry (TG), high pressure thermogravimetry (HPTG) and combustion cell experiments. All the experiments were conducted at non-isothermal heating conditions with a heating rate of 10°C min−1, in the temperature range of 20–700°C. DSC-TG data were analysed using an Arrhenius-type reaction model assuming a first-order reaction. For the HPTG data the Coats and Redfern equation was used for kinetic analysis. In the combustion cell experiments the Fassihi and Brigham approach was used in order to calculate kinetic data. Finally a comparison is made between the kinetic results.
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  • 78
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    Journal of thermal analysis and calorimetry 49 (1997), S. 609-615 
    ISSN: 1572-8943
    Schlagwort(e): combustion ; crude oil ; kinetics ; thermogravimetric analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract High pressure thermogravimetric analysis (HPTG) was used in order to study the oxidation of crude oil in a porous medium under pressurised conditions for simulation of in-situ combustion during oil recovery. Three distinct reaction regions were observed from the HPTG curves in an oxidising environment subjected to a constant heating rate. These were low temperature oxidation, fuel deposition and high temperature oxidation. The method of Coats and Redfern was used to obtain kinetic parameters and the results are discussed.
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  • 79
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1527-1533 
    ISSN: 1572-8943
    Schlagwort(e): β-cyclodextrin ; cinnamic aldehyde ; kinetics ; thermal analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The stability of the inclusion complex of β-CD with cinnamic aldehyde was investigated by means of TG and DSC. The mass loss takes place in three stages: dehydration occurs at 50–120°C; dissociation of β-CD·C9H8O proceeds in the range 200–260°C; and decomposition of β-CD begins at 280°C. The kinetics of the dissociation of β-CD·C9H8O was studied by means of thermogravimetry both at constant temperature and with linearly increasing temperature. The results demonstrate that the dissociation of β-CD·C9H8O is dominated by a one-dimensional diffusion process. The activation energyE is 160 kJ mol−1, and the pre-exponential factorA is 5.8×1014 min−1. Scanning electron microscope observations and the results of crystal structure analysis are in good agreement with those of thermogravimetry.
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  • 80
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1485-1492 
    ISSN: 1572-8943
    Schlagwort(e): bias ; constant temperature stability ; isothermal crystallization ; kinetics ; oxidative induction time
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Oxidative induction time (OIT), constant temperature stability (CTS) and isothermal crystallization are examples of isothermal time-to-event (TTE) measurements obtained using differential scanning calorimetry. In TTE experiments, a test specimen is heated/cooled at a constant rate from the setup temperature to an isothermal test temperature. Once the test temperature is achieved, a clock is started and the time to the thermal event (e.g., onset to oxidation, thermal decomposition or crystallization exotherm peak) is measured. Such TTE values may be used to rank stability of the material at the test temperature. Some portion of the reaction of interest, however, takes place during the pre-isothermal period as the test specimen approaches the test temperature. This amount of reaction is unmeasured and represents a bias in the resultant TTE value. An equation has been derived and numerically integrated to estimate this bias. This approach shows that the bias is dependent upon the activation energy of the test reaction, the heating/cooling rate used and the temperature range between the melting temperature and the test temperature. For commonly used heating rates, the bias for OIT and CTS tests is small. Further, the myth that isothermal crystallization kinetics determinations required high cooling rates is dispelled with the bias of less than 0.9 min resulting from heating rates as low as 10°C min−1. Knowledge of magnitude of this bias permits the selection of experimental conditions without the expense of high heating/cooling rate apparatus or extra cost cooling accessories.
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  • 81
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 50 (1997), S. 533-545 
    ISSN: 1572-8943
    Schlagwort(e): Cu-19 at% Al ; dislocations ; kinetics ; segregation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A model is proposed to describe the kinetics of solute segregation to partial dislocations in solid solutions of cold-rolled alloys. The case when half edge and half screw dislocations are present is considered. The model gives account of the kinetic behaviour observed in a deformed Cu-19 at% Al alloy where two unknown processes could be assessed during calorimetric isothermal experiments. The faster process corresponds to segregation to screw dissociated dislocations while the slower one corresponds to segregation to edge dissociated dislocations. Experimental activation energies, larger for edge dislocations, are close to that for pipe diffusion along the partials corrected by pinner binding energy terms. It is also predicted that segregation occurs faster as the dislocation density is increased. A quantitative comparison of experimental results with model predictions is given.
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  • 82
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; Incoloy 909 ; superalloy ; scale ; high temperature ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H20 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified asα-Fe2,O3 (below 1200 K) or FeO (above 1300 K) and CoO · Fe2O3 and FeO · Nb2O5, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H2O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.
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  • 83
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; kinetics ; iron ; iron-nitride
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of α-Fe and ɛ-Fe2N1−z at 573 K and 673 K in O2 at 1 atm was investigated by thermogravimetrical analysis, X-ray diffraction, light-optical microscopy, scanning electron microscopy and electron probe X-ray microanalysis. Upon oxidation at 573 K and 673 K, on α-Fe initially α-Fe2O3 develops, whereas on ɛ-Fe2N1−z initially Fe3O4 develops. In an early stage of oxidation the oxidation rate of ɛ-Fe2N1−z appears to be much larger than of α-Fe. This can be attributed largely to an effective surface area available for oxygen uptake, which is much larger for ɛ-Fe2N1−z than for α-Fe due to the porous structure of ɛ-Fe2N1−z as prepared by gaseous nitriding of iron. The development of a magnetite layer in-between the hematite layer and the α-Fe substrate, at a later stage of oxidation, enhances layer-growth kinetics. After 100 min oxidation at 673 K the (parabolic) oxidation rates for α-Fe and ɛ-Fe2N1−z become about equal, indicating that on both substrates the oxide growth is controlled by the same rate limiting step which is attributed to short-circuit diffusion of iron cations. Oxidizing ɛ-Fe2N1−z increases the nitrogen concentration in the remaining ɛ-iron nitride, because the outward flux of iron cations, necessary for oxide growth, leads to an accumulation of nitrogen atoms left behind.
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  • 84
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 171-184 
    ISSN: 1573-4889
    Schlagwort(e): TiAl, corrosion ; high-temperature ; kinetics ; nitrogen dependence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxide scale formation on γ-TiAl at 800 and 900°C was studied using high temperature X-ray diffraction as anin situ-method. The experiments were performed in air and in He with 20 vol.% O2. The formation of alumina in the form of α-Al2O3 and of TiO2 in the form of rutile was observed in both atmospheres and the formation of TiN was detected in air. Depending on the atmosphere the diffraction peaks of two different additional phases were detected, which do not exist in any data base nor in the Ti-Al-O phase diagram. One of them, the Z-phase, appears in He with 20 vol.% O2 and the other, the X-phase, in air. The Zphase was also found at room temperature after oxidation at 900°C in air. The growth of both phases, X and Z, starts immediately with the oxidation process and follows the parabolic rate law.
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  • 85
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 48 (1997), S. 289-302 
    ISSN: 1573-4889
    Schlagwort(e): oxidation ; titanium ; rutile ; scale ; high temperature ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation behavior of pure titanium has been investigated in the temperature range of 1000 K to 1300 K in CO2 or Ar-10%CO2. Optical microscopy, electron probe microanalyses, and X-ray measurements on the oxide scales formed during oxidation indicate that their structures are nearly independent of temperature and the corrosion atmosphere. The scales consisted of two layers, an external one and an internal one, having a rutile (TiO2) structure. The parabolic rate law was confirmed for growth of the external scale and the permeation depth of oxygen in titanium with apparent activation energies of 266 and 226 kJ/mol, respectively. The rate-determining diffusion species in the oxidation processes are discussed.
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  • 86
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 131 (1994), S. 43-47 
    ISSN: 1573-4919
    Schlagwort(e): angiotensinogen ; kinetics ; recombinant protein ; renin ; species specificity ; transgenic mouse
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The renin-angiotensin system (RAS) is the most important regulator of electrolyte homeostasis and blood pressure. Our recently generated transgenic mice carrying either the human renin (hREN) or human angiotensinogen (hANG) genes did not develop hypertension but dual gene strains obtained by cross-mating separate lines of mice exhibited a chronically sustained increase in blood pressure, suggesting the presence of species-specific reactivity between renin and angiotensinogen. In order to examine this specificity, the present study was designed to perform a strictly comparative study on hydrolysis of hANG by hREN and mouse submandibular renin (mREN)in vitro by using pure proteins. The recombinant hANG (rhANG) and the synthetic human-type tridecapeptide (hTDP), Asp-Arg-Val-Tyr-Ile-His-Pro-Phe-His-Leu-Val-Ile-His, corresponding to the N-terminal sequences of hANG, were used to determine the species specificity of recombinant hREN (rhREN) and mREN. While hTDP was cleaved by both rhREN with similar Km and with the same order of kcat, rhANG was cleaved by mREN with 16.7-fold higher Km and with 28.2-fold lower kcat than by rhREN. These results showed that kcat/Km value of mREN for rhANG was 468-fold lower than that for rhREN acting on rhANG.
    Materialart: Digitale Medien
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  • 87
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 156 (1996), S. 93-100 
    ISSN: 1573-4919
    Schlagwort(e): rat liver nucleus ; oxalate binding protein ; histone III ; purification ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The rat liver nuclear oxalate binding protein was isolated, purified by anion and cation exchange column chromatography using Diethyl Amino Ethyl Sephadex, Carboxy Methyl Cellulose and Carboxy Methyl Sephadex C-50 ion exchangers. The purified oxalate binding protein was found to be H1B of H1 fraction of histories. Kinetic analysis of oxalate binding showed the presence of two affinity sites, one with Kd of 133.5 nM and Bmax of 40 pmoles and another with Kd of 262.5 nM and Bmax of 210 pmoles. The optimal oxalate binding was at pH 4.2 and at 28°C. The oxalate binding was specific and reversible and not due to ionic charge interaction. The IC50 of other dicarboxylates was higher than that of oxalate. EGTA had no effect on oxalate binding but di- and tri-carboxylate carrier inhibitors and thiol modifying agents significantly lowered the binding activity. Oxalate binding to histones was significantly reduced in the presence of DNA or nucleotides, but RNA had no effect. ATP completely inhibited the oxalate binding activity at 1 mM concentration. Different tissues exhibited oxalate binding showing ubiquitous nature. Calf thymus H1 showed maximal binding similar to liver histones.
    Materialart: Digitale Medien
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  • 88
    ISSN: 1573-4846
    Schlagwort(e): zirconium butoxide ; titanium butoxide ; kinetics ; hydrolysis ; condensation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A continuous flowing-rapid mixing technique was combined with FTIR, SAXS and electrical conductivity to study the early stages of polymer formation and growth during the acid-catalyzed hydrolysis and condensation of titanium and zirconium alkoxides. Reaction times as short as 80 milliseconds were investigated. FTIR spectroscopy was used to monitor the water and M–OR concentrations during the reaction. Hydrolysis of ∼25–50% of the alkoxy groups was facile. The FTIR and SAXS data showed that condensation was also very rapid. The activity and mobility of the ions in the solution were monitored by electrical conductivity measurements. The decrease in the normalized solution conductivity during the reaction correlated with the loss of [M–OR]. Furthermore, the radius of gyration of the growing polymers increased rapidly in regimes where the conductivity and [M–OR] decreased fastest. This finding suggests that the mobility of some of the charge carrying species decreases because of the growth in size of the polymers.
    Materialart: Digitale Medien
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  • 89
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 33 (1990), S. 279-299 
    ISSN: 1573-4889
    Schlagwort(e): corrosion SO2 ; chromium ; manganese ; kinetics ; scale analysis ; phase diagram stability
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The corrosion of chromium and manganese by pure SO2 has been investigated in the temperature range 890–1350 K at SO2 pressure from 0.01–0.5 atm. Both metals oxidize according to a parabolic rate law, and the scales consist of an inner region containing a mixture of oxide and sulfide (Cr2O3+ CrS or MnO and MnS) and an outer region of oxide (Cr2O3 or MnO). These two metals have similar thermodynamic behavior, and the main mechanism of reaction is considered to be the direct reaction of the metal with SO2. The results also indicate that in the absence of trace amounts of oxygen, and at sufficiently low temperature (〈950 K), the formation of Mn3O4 does not occur only if a complete description of the atmosphere generated by a SO2-O2-S2 mixture was considered.
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  • 90
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 34 (1990), S. 101-121 
    ISSN: 1573-4889
    Schlagwort(e): nonisothermal oxidation ; kinetics ; iron ; iron-chromium alloys ; reactive-oxide coating
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The nonisothermal oxidation behavior of pure iron and a few iron-chromium alloys in dry air has been studied. The effects of a superficial coating of a reactive oxide, CeO2, on the oxidation behavior were studied. Linear heating rates of 3 K/min and 6 K/min were maintained up to a final temperature ranging from 1273–1473 K. Coatings were applied either from a slurry or an aqueous bath. The CeO2 coating has been found to be effective not only in decreasing the nonisothermal oxidation rate but also in improving the scale adherence. Moreover, the coated samples withstood a number of heating cycles without scale rupture. The mass gain of the samples as a function of temperature was recorded by means of a sensitive balance, and the scales have been characterized by SEM, EPMA, and x-ray diffraction analysis.
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  • 91
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 34 (1990), S. 473-496 
    ISSN: 1573-4889
    Schlagwort(e): Internal nitriding ; 310 stainless steel ; austenitic ; kinetics ; microhardness
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The internal-nitriding behavior in ammonia-hydrogen atmospheres of type-310 stainless steel and 310 to which either 2 wt.% Ti or 3 wt.% Al were added was studied over the range of 550–950°C. An Fe-24Cr binary alloy was included to assess the role of a BCC crystal structure vs the FCC crystal structure of 310 stainless steel. The BCC alloy exhibited the most rapid kinetics as expected. X-ray diffraction showed only the presence of CrN in all the alloys up to 735°C. At 850°C and above, both CrN and Cr2N were detected. The nonformation of TiN and AlN at lower temperatures is attributed to nucleation problems. Precipitates were extremely fine (unresolvable even at 20,000×) at 563°C and became much coarser with increasing temperature. The precipitate density, size, and shape varied across the internal-nitriding zone at the higher temperatures. External scaling was noted at 850°C and above, however, it was not a continuous film. The activation energy of internal nitriding from 563–735°C ranged from 3.8 kcal/mol for 310+2Ti to 18.2 kcal/mol for 310+3Al; from 850–950°C, the activation energy ranged from 44 (310+2Ti) to 56.6 kcal/mol (310+3Al). Microhardness profiles show that an intermediate zone exists between the nitride case and the base metal. The origin of this zone is discussed.
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  • 92
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 41 (1994), S. 235-250 
    ISSN: 1573-4889
    Schlagwort(e): niobium ; oxidation ; morphology ; kinetics ; stresses
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation of niobium at high temperature (900°C) leads to reaction products with “exotic” morphologies. Morphological and kinetics analysis have been undertaken with Nb platelets. A growth mechanism of the oxide at the edges of the platelet is proposed.
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  • 93
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 42 (1994), S. 223-237 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; scale ; oxidation ; zirconium ; purity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of zirconium of different purities were studied over the temperature range of 600–1300°C (α- and β-phases). The structure of the oxidized specimens was examined. TGA, XRD, EPMA, SEM, metallographic analysis, and microhardness measurements were carried out. Impurity elements were found to increase the oxidation rate of technical zirconium. The mechanism of the effect of impurity elements on zirconium oxidation was shown to differ for the α- and β-phases. Activation energies were calculated for the parabolic and linear stages of oxidation.
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  • 94
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 42 (1994), S. 249-263 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; scale ; oxidation ; hafnium ; purity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of hafnium of different purities were studied in the temperature range of 800–1200°C. This paper concerns the structure studies of the oxidized samples. TGA, XRD, SEM methods, and microhardness measurements were used. Hafnium oxidation follows the parabolic rate law, changing with time to the linear one. Oxidation-reaction products are HfO2(moncl) and α-solid solution of oxygen in hafnium. Anomalous oxidation behavior of hafnium having a high impurity content was found in the range 800–950°C. Activation energies for the parabolic and linear oxidation stages were calculated.
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  • 95
    ISSN: 1573-4889
    Schlagwort(e): binary alloys ; oxidation ; transient state ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The initial transient stage in the oxidation of binary alloys forming scales exclusively composed of the most stable oxide is examined by means of a simplified approach which avoids the numerical integration of the diffusion equation for the transport of the metal components in the alloy. At variance with previous solutions to this problem obtained by means of numerical methods, this treatment takes into account also the effect of the gas-scale reaction at the outer surface of the oxide. The concentration of the most-reactive component at the alloy surface changes gradually with time from the initial bulk value towards the corresponding steady-state value without involving any minimum, while the overall rate of the reaction presents a gradual transition from an initial nearly linear towards final parabolic behavior.
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  • 96
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 138 (1994), S. 33-37 
    ISSN: 1573-4919
    Schlagwort(e): poly(ADP-ribose) polymerase ; structure ; chemistry ; kinetics ; automodification ; mechanism(s)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract In this minireview, we summarize recent advances on the enzymology of ADP-ribose polymer synthesis. First, a short discussion of the primary structure and cloning of poly(ADP-ribose) polymerase (PARP) [EC 2.4.2.30], the enzyme that catalyzes, the synthesis of poly(ADP-ribose), is presented. A catalytic distinction between the multiple enzymatic activities of PARP is established. The direction of ADP-ribose chain growth as well as the molecular mechanism of the automodification reaction catalyzed by PARP are described. Current approaches to dissect ADP-ribose polymer synthesis into individual reactions of initiation, elongation and branching, as well as a partial mechanistic characterization of the ADP-ribose elongation reaction at he chemical level are also presented. Finally, recent developments in the catalytic characterization of PARP by site-directed mutagensis are also briefly summarized.
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  • 97
    Digitale Medien
    Digitale Medien
    Springer
    Water, air & soil pollution 95 (1997), S. 399-423 
    ISSN: 1573-2932
    Schlagwort(e): fractionation ; redistribution ; saturation ; kinetics ; heavy metals
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Energietechnik
    Notizen: Abstract Solid-phase transformations of Cd, Cu, Cr, Ni and Zn, added as soluble salts at several levels to two arid-zone soils, were studied over a period of one year. The soils were maintained under a saturated-paste regime and sampled periodically. A selective sequential dissolution procedure was employed to determine the changes in metal distribution among six operationally defined solid-phase fractions. A function, Uts was introduced to measure the fractional attainment of equilibrium of the soils following a perturbation. The direction and rate of redistribution of the added metals in the soils were affected by the nature of the metal, the soil properties and the metal loading level. Cd added to the soils was transferred from the exchangeable (EXC) into the carbonate (CARB) fraction. When soluble Cu, Cr, Ni and Zn were added at low loading levels, metals were transferred from the reducible oxides(RO) bound and easily reducible oxides (ERO) bound fractions and the EXC fraction, into the CARB fraction. However, at the higher loading level, metals were transferred from the EXC and CARB fractions into the organic matter bound (OM), ERO and RO fractions. The Uts function approached lower values as incubation continued but remained removed from 1. The overall flux of metals among fractions was the combined result of the readjustment of the metals in the native soil to changing conditions due to saturation, and the transfer of added soluble metals to the less labile fractions.
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  • 98
    ISSN: 1573-4846
    Schlagwort(e): zirconium butoxide ; titanium butoxide ; kinetics ; hydrolysis ; condensation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A continuous flowing-rapid mixing technique was combined with FTIR, SAXS and electrical conductivity to study the early stages of polymer formation and growth during the acid-catalyzed hydrolysis and condensation of titanium and zirconium alkoxides. Reaction times as short as 80 milliseconds were investigated. FTIR spectroscopy was used to monitor the water and M−OR concentrations during the reaction. Hydrolysis of ∼25–50% of the alkoxy groups was facile. The FTIR and SAXS data showed that condensation was also very rapid. The activity and mobility of the ions in the solution were monitored by electrical conductivity measurements. The decrease in the normalized solution conductivity during the reaction correlated with the loss of [M−OR]. Furthermore, the radius of gyration of the growing polymers increased rapidly in regimes where the conductivity and [M−OR] decreased fastest. This finding suggests that the mobility of some of the charge carrying species decreases because of the growth in size of the polymers.
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  • 99
    Digitale Medien
    Digitale Medien
    Springer
    Oxidation of metals 33 (1990), S. 177-189 
    ISSN: 1573-4889
    Schlagwort(e): kinetics ; oxidation ; titanium hydride ; rutile
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Maschinenbau
    Notizen: Abstract The oxidation kinetics of titanium-hydride powders were studied in the temperature range of 298–1378 K in air at atmospheric pressure. DTA, DSC, X-ray analysis, and scanning electron microscopy were used. Oxidation was found to take place by TiHxOy oxyhydride phases formation. The oxidation reaction rate at temperatures above 870 K was limited by diffusion of oxygen atoms through a rutile scale formed on the surface. The activation energy and preexponential values of the Arrhenius equation for different interaction stages as well as transformation enthalpies were calculated.
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  • 100
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 159 (1996), S. 47-53 
    ISSN: 1573-4919
    Schlagwort(e): acetylcholinesterase ; kinetics ; inhibition ; methotrexate ; anticancer drugs ; human erythrocyte
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract This work addresses the kinetic analysis of the interaction of methotrexate (MTX) with human erythrocyte membrane-bound acetylcholinesterase (AChE, EC 3.1. 1.7). It was found that the MTX effect was independent of time of incubation with AChE before the addition of substrate which proves its reversible action. The IC50 was determined, by three methods, to be 0.73 mM. The Michaelis-Menten constant (Ks) for the hydrolysis of acetylthiocholine iodide (ASCh) by AChE was 0.13 mM in the control system, a value decreased by 30–61% in the MTX treated systems. The Vmax was 1.27μtmole/min/mg protein for the control system while it was decreased by 44–77% in the MTX treated systems. The Linexveaver-Buck plot, Dixon plot, and their secondary replots indicated that the nature of the inhibition was of the linear mixed type, i.e. uncompetitive and noncompetitive. The values of Ki(slope) and KI(tntecept) were estimated as 1.67 and 0.34 mM, respectively.
    Materialart: Digitale Medien
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