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  • Articles  (425)
  • maize  (216)
  • 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects
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  • Springer  (425)
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  • Articles  (425)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Entomologia experimentalis et applicata 67 (1993), S. 143-148 
    ISSN: 1570-7458
    Keywords: Nosema marucae ; microsporidium ; production ; biological control ; cereal stem borer ; Chilo partellus ; maize ; sorghum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In a study covering 3 years, experiments were carried out in order to determine the feasibility of producing a microsporidian pathogenNosema marucae in the spotted stalkborerChilo partellus. A maximum yield of 4.9×108 spores/larva (equivalent to 3.1×1010 spores/g fresh larval body weight) was obtained in 3rd instar larvae. It is considered that the production is inexpensive and can be readily adapted for small scale pathogen propagation systems in the tropics.
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  • 2
    ISSN: 1570-7458
    Keywords: Insecta ; Ostrina nubilalis ; pheromone trapping ; maize
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The response of male European corn borer, Ostrinia nubilalis (Hübner) to synthetic pheromone lures containing various isomeric blends of the sex pheromone 11-tetradecenyl acetate was measured in 13 counties in North Carolina. The blends consisted of either 3% Z (‘E strain’), 97% Z (‘Z strain’), or 35% Z (‘hybrid’) 11-tetradecenyl acetate. Response to E strain lures predominated in those counties located in the Coastal Plain (east) of the state, while response to the Z strain pheromone was dominant in the west. A zone of overlap of these broad strain distributions appears to occur in the eastern Piedmont. Within this zone there was substantial response to both E and Z blends. The proportion of these responses changed considerably between generations within years as well as between years. Significantly higher capture rates in hybrid baited traps in parts of the overlap zone may be indicative of increased rates of hybridization between the E and Z strains.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Entomologia experimentalis et applicata 65 (1992), S. 165-170 
    ISSN: 1570-7458
    Keywords: Lepidoptera ; Pyralidae ; stem borer ; suction trap ; behaviour ; maize ; dispersal ; pheromones ; activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The diel flight periodicity of the nocturnal moth Chilo partellus (Swinhoe) (Lepidoptera;Pyralidae) was measured in the laboratory using an actograph and in the field with suction traps. Females showed almost no flight activity on the night of eclosion. Flight activity of mated females peaked before midnight, the period of peak oviposition activity. Male peak activity occurred after midnight coinciding with female eclosion. Presence or absence of females did not affect when or how long males were active. Data on flight activity and reproductive behaviour are discussed in relation to the use of pheromones to protect maize.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Entomologia experimentalis et applicata 64 (1992), S. 11-21 
    ISSN: 1570-7458
    Keywords: European corn borer ; Ostrinia nubilalis ; maize ; water ; drought ; stress ; development ; models ; microenvironment ; irrigation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This study examined the impact of irrigation water on certain aspects of an insect-plant relationship in the field including the assessment of plant-mediated water effects on an herbivore's development, survival, and behavior, and plant damage parameters and host tissue water status. Maize (Zea mays L.) plants were arranged in a randomized complete block design in the field over two years in North Carolina (NC). Four blocks were subjected to three different irrigation treatments initiated ca. one week before anthesis: optimal, intermediate, deficit water supply. Each plant was infested with one (1986) or two (1987) black head stage, E-race European corn borer [Ostrinia nubilalis (Hübn.)] (ECB) egg masses at tasselling. ECB development, tunnelling site, and survival as well as plant tissue water status (tissue % water contents [θ] & leaf water potentials [Ψ]) were recorded through July. The irrigation effect on ECB parameters was slight and variable. Internal stalk temperatures of optimal plants were consistently cooler than their deficit counterparts (1 day-degree/day). With degree-days included as an explanatory variable in the analyses, there were no significant irrigation effects on the ECB parameters, except for total proportion of ECB's bored into maize plant parts. More ECB's bored into drier plants than in optimal plants; however, this trend was not significant in 1987. Plant water indices showed that though Ψ responded to irrigation, there were only minor changes in tissue θ, particularly in view of the larger diurnal tissue changes observed and the relatively high, sustained stalk θ levels seen over all treatments. Examination of ECB pupal θ confirmed that dietary water changes were minor or non-limiting to the insects' developmental physiology, because pupal θ was not sensitive to the irrigation treatments. Though water supply changes have drastic developmental and agronomic consequences for the maize plant, little or no changes were seen in the ECB feeding environment. Furthermore, a plant damage model was developed whereby the total % of ECB's tunnelled into maize was related to the mean larval age. The implications of this model on the understanding of ECB tunnelling behavior, damage potential, and pest management is noted.
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  • 5
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; aqueous solvent mixtures ; Co(III) complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 6 (1977), S. 203-216 
    ISSN: 1572-8927
    Keywords: Glucose ; kinetics ; mixed solvent ; kinetic isotope effect ; enthalpy of activation ; entropy of activation ; tetrahydrofuran ; tert-butanol ; mutarotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The mutarotation rates of glucose in aqueous mixtures of tetrahydrofuran andtert-butanol in the mole fraction (xi) range 0〈xi〈0.2 have been measured at 5° intervals in the range 5–35°C. The kinetic deuterium isotope effects have been determined for the same solvent compositions at 25 and 35°C. A statistical analysis of the Arrhenius plots indicates that the experimental errors, although small, are too large for the establishment of any compensation behavior between ΔH
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  • 7
    Electronic Resource
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    Springer
    Journal of solution chemistry 19 (1990), S. 1073-1084 
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; mixtures of water+cosolvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
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  • 8
    ISSN: 1572-8927
    Keywords: Cu(II) ; kinetics ; reduction ; temperature dependence ; H2O2, NaCl, NaBr, NaClO4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rates of reduction of Cu(II) with H2O2 have been measured in NaCl and NaBr solutions and mixtures with NaClO4 as a function of pH (6 to 9), temperature (5 to 45°C) and ionic composition (0.1 to 6M). The effect of pH on the rates was found to be independent of temperature and ionic composition. The rates increased as a function of [H+] raised to the power of 1.3 to 1.6. Speciation calculations indicate that this pH dependence can be attributed to Cu(OH)2 being the reactive species. The rate constants in NaCl and NaBr and mixtures with NaClO4 were independent of ionic strength, but proportional to the halide concentration raised to the power of 2.0 (0.2 to 2.6M). These results can be attributed to Cu(OH)2Cl 2 2− being the reactive species to reduction with H2O2. The Cu(I) halide complexes formed from the reduction are not easily oxidized with O2 or H2O2. The faster rates in Br− solutions, which form stronger complexes with Cu+, support this contention. Measurements made in NaCl with added NaHCO3, NaB(OH)4 EDTA, NTA and glycine were also made. These measurements indicate that the CuL complexes (L=B(OH) 4 − , CO 3 2− , EDTA, NTA, and glycine) are not very reactive to reduction with H2O2. The addition of Mg2+ or Ca2+ caused the rates to increase due to the formation of MgL or CaL complexes and the resultant release of reactive Cu2+.
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  • 9
    Electronic Resource
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    Journal of solution chemistry 23 (1994), S. 483-500 
    ISSN: 1572-8927
    Keywords: Thermodynamics ; kinetics ; chemical relaxation ; temperature-jump ; amplitudes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 10
    Electronic Resource
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    Journal of solution chemistry 5 (1976), S. 163-169 
    ISSN: 1572-8927
    Keywords: Solvent effects ; tetramethylurea ; hydrolysis ; hydrogen bonding ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Tetramethylurea was hydrolyzed in aqueous hydrochloric acid at temperatures of 80, 90, and 100°C. All reactions were carried out in an excess of both tetramethylurea and water, with first-order dependence on acid concentration being observed. As the concentration of water was increased, the rate of hydrolysis decreased until equimolar amounts of water and tetramethylurea were present. Subsequent addition of water had no effect on the observed rate.
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  • 11
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; reaction activation barrier ; carbon chain growth and termination ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method is established, by which the difference of the reaction activation barriers of carbon chain growth and termination in Fischer-Tropsch (FT) synthesis can be determined from experiments. A FT synthesis is carried out on Fe/Zn catalyst. We apply the method to analyze the experimental result and obtain the difference of reaction activation barriers of carbon chain growth and termination of α-olefins on the catalyst.
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  • 12
    Electronic Resource
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    Cellulose 1 (1994), S. 26-56 
    ISSN: 1572-882X
    Keywords: low-temperature degradation ; kinetics ; mechanisms ; electrical insulation ; transformers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: 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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  • 13
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    Catalysis letters 27 (1994), S. 79-90 
    ISSN: 1572-879X
    Keywords: kinetics ; carbon ; oxygen ; recombination ; rhodium ; surface characterisation ; XPS ; AES
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 14
    ISSN: 1570-7458
    Keywords: insecta ; Ostrinia nubilalis ; egg distribution ; maize
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The relationship between second generation European corn borer (Ostrinia nubilalis Hübner) egg mass numbers and subsequent field corn damage, as measured by stalk cavity numbers, was studied in 79 fields in northeastern North Carolina over three years. A mean of 0.028 egg masses per plant (645 egg masses/23400 plants) was found over the course of the study. Significant differences in oviposition rate were detected between fields and years. Ca. 85% of egg masses were deposited in a five leaf zone surrounding the primary ear; of these, 89% were found on the lower four leaves in this zone. Egg masses appeared to be distributed randomly within fields but at low rates of incidence, and oviposition was relatively uniform between sampling areas within individual fields. Under moderate to high oviposition pressure (mean number of egg masses per plant over the duration of the oviposition period 〉ca. 0.02), eggs laid during the early phases of the oviposition period account for more subsequent stalk damage than eggs laid during the later phases of the oviposition period. Variations in second generation egg mass numbers accounted for ca. 70% of variation in stalk cavity numbers.
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  • 15
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    Topics in catalysis 1 (1994), S. 305-314 
    ISSN: 1572-9028
    Keywords: non-Langmuir ; kinetics ; non-linear dynamics ; oscillations ; chaos ; self-organization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 16
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    Cellular and molecular life sciences 49 (1993), S. 110-117 
    ISSN: 1420-9071
    Keywords: Polymerization ; sickle hemoglobin ; sickle cell disease ; kinetics ; thermodynamics ; polymer domains ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.
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  • 17
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    Entomologia experimentalis et applicata 55 (1990), S. 285-294 
    ISSN: 1570-7458
    Keywords: Graminella nigrifrons ; maize ; oats ; johnsongrass ; development ; fecundity ; host suitability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Description / Table of Contents: Résumé La dynamique des populations (durée de développement de l'œuf à l'adulte, poids et taille des adultes, fécondité) de G. nigrifrons Forbes (Homop. Cicadellidae) a été étudiée au laboratoire à 5 températures sur plantules de maïs (Zea mays L.), avoine (Avena sativa L.) et sorgho vivace (Shorgum halepense (L.) Pers.). Sur les 3 plantes, les mâles se développent en moyenne 1,2 j plus vite que les femelles. Les relations entre vitesse de développement et température ont été déterminées en utilisant à la fois un modèle linéaire et le modèle biophysique à 2 paramètres de Sharpe & DeMichele (1977). Les températures plus basses donnent des adultes des 2 sexes plus gros et plus lourds. Moins de G. nigrifrons se sont développés sur la graminée vivace que sur les 2 graminées annuelles à la température la plus élevée (30°C), tandis qu'à la température la plus basse (18°C) moins de cicadelles se sont développées sur les graminées annuelles. La température semble jouer un rôle significatif en déterminant l'adéquation des plantes comme hôtes convenant au développement de G. nigrifrons. Le potentiel de ponte de cette cicadelle avait été sous-estimé par les étudies précédentes.
    Notes: Abstract Population dynamics of the blackfaced leafhopper, Graminella nigrifrons (Forbes) (Homoptera: Cicadellidae), was studied at five temperatures (18, 21, 24, 27, & 30°C) in the laboratory on seedling maize (Zea mays L.), oats (Avena sativa L.), and the perennial johnsongrass (Sorghum halepense (L.) Pers.). Effects of temperature and host plant on egg to adult mean development time, adult size and weight, and fecundity were determined. Leafhoppers on all three hosts developed fastest at the highest temperature tested (21.3 days), and slowest at the lowest temperature tested (73.2 days). The duration from first to last adult eclosion was shortest at 30°C, (11.5 days) and longest at 18°C (43 days). The sex ratio of males to females did not differ from 1:1, but males developed an average of 1.2 days faster than females on all three hosts. Mean percent development/day ranged from 1.4% at 18°C to 4.7% at 30°C. The relationship of this development rate and temperature was determined using both a linear model and a variable parameter biophysical model. Based on these models, the developmental threshold is estimated at 12–15°C. The lowest temperature yielded larger and heavier adults (312 μg, dry weight) than did the highest temperature (225 μg). Fewer leafhoppers developed on the perennial than the annuals at 30°C and fewer on the annuals than the perennial at 18°C. Our results suggest that early in the season johnsongrass and perhaps other perennials are the superior developmental hosts for this leafhopper, whereas in midsummer when temperatures are highest, annuals are the better hosts.
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  • 18
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 19
    ISSN: 1572-879X
    Keywords: Ultraviolet heterogeneous photocatalysis ; oxidation ; trichloroethylene ; titania ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 20
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    Entomologia experimentalis et applicata 61 (1991), S. 169-177 
    ISSN: 1570-7458
    Keywords: African migratory locust ; crop environment ; oviposition behaviour ; oviposition sites ; maize
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Oviposition by the African migratory locust, Locusta migratoria migratorioides (Orthoptera: Acrididae), was studied in maize and wheat crops on the Orange Free State Highveld. Maize was shown to be the most important oviposition habitat with peak laying taking place in autumn and early winter when highest pod densities were recorded. Laying was mainly concentrated along the middle of the crop interrows in maize and within clearings in the wheat crop. Despite the uniform layout of these crops, the distribution of egg pods was found to be aggregated. Non-reproductive behaviour, such as locust aggregation, basking and feeding, as well as environmental factors appeared to influence the distribution of egg pods in these crops. Secondary selection for optinum soil moisture and compaction on the laying site enhanced the aggregation of pods.
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  • 21
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    Entomologia experimentalis et applicata 65 (1992), S. 57-64 
    ISSN: 1570-7458
    Keywords: Heliothis ; corn ; maize ; insecticide ; Aspergillus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The toxicity and anticholinesterase activity of tremorgenic fungal metabolites, territrems, to the corn earworm, Helioverpa zea (Boddie) (Lepidoptera, Noctuidae) were examined. In oral toxicity studies, territrem A significantly inhibited growth by 40% at 25 ppm and by 89% at 250 ppm. Territrem B and an epoxy-derivative significantly inhibited growth by ca. 45% at 250 ppm. Piperonyl butoxide administered orally synergized the toxicity of the territrems tested. In topical toxicity studies, the epoxy-derivative caused 26% mortality and 25% growth retardation at 10 mg/gm insects. Territrem A and B were not significantly lethal, but did reduce growth by 15–20% at 10 mg/gm insect. Paraoxon tested in the same way caused 100% mortality at 25 ppm orally and 10 mg/gm topically. However, all territrems tested in vitro as inhibitors of H. zea head acetylcholinesterase were at least comparable to or were more active than paraoxon. Topically administered epoxy-territrem B also inhibited H. zea head acetylcholinesterase. The potential for development of new insecticides from a territrem lead structure is discussed.
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  • 22
    ISSN: 1436-5073
    Keywords: flow injection analysis (FIA) ; mercury ; porphyrin ; kinetics ; spectro-photometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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  • 23
    ISSN: 1436-5073
    Keywords: atrazine ; terbuthylazine ; sequential binding ; kinetics ; cross-reactivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Immunoassays for triazine herbicides were tested for their reaction to the variation of the tracer incubation time. By application of a sequential technique the measuring range of atrazine could be expanded to five decades and the total duration of the test could be reduced to about 30 min. In an optimized version a lower detection limit of 9 pmol/l (2 ng/l) was achieved. The detection limit of a sensitive immunoassay for terbuthylazine is also below the concentration limit demanded of the German drinking water regulation (100 ng/l) and reaches 130 pmol/l (30 ng/l). Short tracer incubation times did not lead to increased cross-reactivities in contrast to theoretical models [1, 2]. Different mechanisms, which could cause a shift of the center point of the calibration curve, are discussed, including kinetic considerations.
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    Biodegradation 4 (1993), S. 163-170 
    ISSN: 1572-9729
    Keywords: factorial analysis ; kinetics ; methane ; methanotrophs ; nutrients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of different mineral nutrients on the kinetics of methane biodegradation by a mixed culture of methanotrophic bacteria was studied. The substrate factors examined were ammonia, iron, copper, manganese, phosphate, and sulphide. The presence of iron in the growth medium had a strong effect on the yield coefficient. Yield coefficients up to 0.49 mg protein per mg methane were observed when iron was added at concentrations of 0.10–5.0 mg/l. Iron addition also increased the maximum methane utilization rate. The same effect was observed after addition of ammonium to a medium where nitrate was the only nitrogen source. The observed Monod constant for methane utilization increased with increasing concentration of ammonia. This shows that ammonia is a weak competitive inhibitor as observed by other researchers. Relatively high levels of both ammonia (70 mg/l) and copper (300 µg/l) inhibited the methane degradation, probably due to the toxic effect of copper-amine complexes.
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  • 25
    ISSN: 1573-0832
    Keywords: Fusarium ; maize ; moniliformin ; mycotoxins ; trichothecenes ; zearalenone
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    Topics: Biology , Medicine
    Notes: Abstract Forty Fusarium isolates obtained from maize fields were screened for moniliformin production on maize kernels. Twelve isolates, including seven of F. subglutinans, were found to produce moniliformin at levels ranging from 0.4 to 64 ppm. Twenty six isolates were also screened for production of deoxynivalenol, diacetoxyscirpenol, T-2 toxin and zearalenone. Of these, 22, including all 11 isolates of F. graminearum, produced zearalenone at levels ranging from 0.1 to 96.0 ppm, while 13 produced T-2 toxin at low levels, (〈1.1 ppm). Deoxynivalenol and diacetoxyscirpenol were each produced by six isolates, also at low levels (〈1.0 ppm). Three isolates of F. graminearum and one of F. sambucinum produced four toxins simultaneously.
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  • 26
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    Nutrient cycling in agroecosystems 23 (1990), S. 73-80 
    ISSN: 1573-0867
    Keywords: Nigerian savanna ; maize ; potassium ; zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A three year field study was conducted at five locations in the Nigerian savanna to evaluate the response of early maturing maize variety to varying rates of K and Zn with a view to establishing the K and Zn requirements for maize production in this zone. Treatments consisted of 4 × 3 factorial combinations of 4 levels of K and 3 levels of Zn. Responses to K and Zn fertilization were sporadic and were obtained only in soils of the Southern Guinea savanna and in the soil formed on sedimentary sandstone. There seem to be no problem at present in soils of the Northern Guinea and Sudan savannas where leaching is less intense. It is inferred from this study that K and Zn deficiences are incipient in the high rainfall soils and in the sandstone derived soils. For these soils, 50 kg K/ha and 2–5 kg Zn/ha is suggested as adequate for an early maturing maize crop. Soil data showed that K and Zn responses can be expected when available K and Zn levels fall below 0.1 meq/100 g and 2 ppm respectively.
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  • 27
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    Nutrient cycling in agroecosystems 26 (1990), S. 249-252 
    ISSN: 1573-0867
    Keywords: Long-term manure trial ; residual effect ; model test ; nitrogen availability ; maize ; Italian ryegrass
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Sluijsmans and Kolenbrander developed a simple model to describe the availability of animal manure, assuming a readily available, an easily decomposable and a slowly decomposable N fraction. We tested this model on data from an experiment in which farmyard manure had been applied for eleven successive years to silage maize [Zea mays L.] grown on a light sandy soil. The residual effects of this FYM were then measured by growing Italian ryegrass [Lolium multiflorum Lamk.] in the 12th year. The measured uptake of N by the grass of the FYM residues was then compared with the computed values. The measured amounts of N taken up agreed fairly well with the calculated amounts for applications of 50 and 100 t FYM per ha per year. If the rates of manure application are adjusted to crop requirement, the model shows that the potential, long-term release of N from the residual N fraction of FYM will not exceed 20 kg N per ha. For cattle slurry with a smaller residual fraction, the release will be at most 10% of the total annual N application.
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  • 28
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    Nutrient cycling in agroecosystems 32 (1992), S. 209-222 
    ISSN: 1573-0867
    Keywords: Wheat ; maize ; barley ; rice ; foliar urea ; grain yield ; breadmaking quality
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    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract It has been suggested that there are several potential benefits of providing nitrogen to cereals via the foliage as urea solution. These include: reduced nitrogen losses through denitrification and leaching compared with nitrogen fertilizer applications to the soil; the ability to provide nitrogen when root activity is impaired e.g., in saline or dry conditions, and uptake late in the season to increase grain nitrogen concentration. Factors that influence the degree of foliar absorption in field conditions have not, however, been clearly defined and losses to the atmosphere and soil can occur. Foliar urea applications may also hinder crop productivity although the explanations for this vary, and include desiccation of leaf cells, aqueous ammonia and urea toxicity, biuret contamination and the disruption of carbohydrate metabolism. It has not yet been determined which one, or combinations, of these mechanisms are most important in field situations. When damage has not been severe, foliar urea applications have increased grain yield, particularly when applied before flag leaf emergence and when nitrogen availability is limiting. Increases in grain nitrogen content are often larger when applications of nitrogen fertilizers to the soil are reduced, and when the urea solution is sprayed either at anthesis or during the following two weeks. It is during this period that foliar urea sprays can be of greater benefit than soil applications with regard to nitrogen utilization by the crop. Increases in wheat grain nitrogen concentration following urea application can improve breadmaking quality. Responses in loaf quality may, however, be variable particularly when increases in grain nitrogen content have been large, and/or when the nitrogen: sulphur ratio in the grain is increased. These circumstances have lead to alterations in the proportions of the different protein fractions which influence breadmaking potential. To exploit the full potential benefits of foliar urea application to cereals, more needs to be known about the mechanisms, and thus how to prevent losses of nitrogen from the foliage, and to reduce the phytotoxic influences of sprays. More information is also required to exploit the reported effects that urea may have on limiting the development of cereal diseases.
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    Nutrient cycling in agroecosystems 39 (1994), S. 39-42 
    ISSN: 1573-0867
    Keywords: Controlled release fertilizers ; kinetics ; mechanism ; nutrient supply ; rate of release ; slow release fertilizers (SRF)
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    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: 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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  • 30
    ISSN: 1573-0867
    Keywords: animal manure ; leaching ; maize ; nitrification inhibitor ; nitrogen recovery
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Field experiments with silage maize during eight years on a sandy soil in The Netherlands, showed that dicyandiamide (DCD) addition to autumn-applied cattle slurry retarded nitrification, thus reducing nitrate losses during winter. Spring-applied slurry without DCD, however, was on average associated with even lower losses and higher maize dry matter yields. Economically optimum supplies of mineral N in the upper 0.6 m soil layer in spring (EOSMN), amounted to 130–220 kg ha−1. Year to year variation of EOSMN could not be attributed to crop demand only. According to balance sheet calculations on control plots, apparent N mineralization between years varied from 0.36 to 0.94 kg ha−1 d−1. On average, forty percent of the soil mineral N (SMN) supply in spring, was lost during the growing season. Hence, the amounts of residual soil mineral N (RSMN) were lower than expected. Multiple regression with SMN in spring, N crop uptake and cumulative rainfall as explanatory variables, could account for 79 percent of the variation in RSMN. Postponement of slurry applications to spring and limiting N inputs to economically optimum rates, were insufficient measures to keep the nitrate concentration in groundwater below the EC level for drinking water.
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  • 31
    ISSN: 1572-9680
    Keywords: alley cropping ; maize ; soybean ; soil fertility ; Leucaena leucocephala ; Sesbania sesban ; Albizia falcataria ; Flemingia congesta ; Gliricidia sepium ; Cassia spectabilis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Theee trials to evaluat the potential of alley cropping in maize production on the low fertility, acidic soils in Northern Zambia are described. Leucaena leucocephala, Gliricidia sepium, Sesbania sesban, Albizia falcataria, Fleminga congesta, and Cassia spectabilis, were grown in alley crops with hybrid maize and soybean. All trials received recommended rates of P and K fertiliser; N fertiliser was applied at three rates as a subplot treatment. One trial received lime before establishment. Only in the limed trial was there a significant improvement in maize yields through alley cropping; when no N fertiliser was applied, incorporation of Leucaena leucocephala prunings resulted in an increase of up to 95% in yields, with a smaller improvement being produced by Flemingia congesta. There was a significant correlation between the quantity of prunings biomass applied and the proportional increase in maize yields over the control treatment. It is suggested that the lack of effect of most of the tree species on crop yields was due to low biomass production. An economic analysis showed that alley cropping with limed Leucaena was only profitable when fertiliser costs were high in relation to maize prices. However, lime is both expensive and difficult to obtain and transport for most small scale farmers in the region, and is therefore not a practical recommendation. It is suggested that future alley cropping research should focus on screening a wider range of tree species, including other species of Leucaena, for acid tolerance and higher biomass production.
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  • 32
    ISSN: 1572-9680
    Keywords: Erythrina ; Gliricidia ; alley cropping ; maize ; competition ; nitrogen availability ; Costa Rica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Maize growing next toErythrina hedgerows had 44% lower biomass (p〈0.01) and 35% lower N content (p〈0.1) than maize growing in the middle of the alleys. Maize growing next toGliricidia hedgerows had the same biomass but 56% higher N content (p〈0.1) than maize growing in the middle of the alleys. However these differences did not develop until 2 months after sowing of the maize. Spatial variability in soil nitrogen mineralization and mulch nitrogen release did not explain any of the differences in growth or N uptake of the maize with respect to distance from the trees. It is hypothesized that the slower growth of the maize next to theErythrina trees after 2 months is due to increasing light and/or nutrient competition from the trees as the trees recover from pollarding. The apparent lack of competition fromGlirigidia may be due to different rates of regrowth or different shoot and root architecture. A theoretical model is described demonstrating that if a crop is to take advantage of the higher nutrient availability under alley cropping it must complete the major part of its growth before the trees recover significantly from pollarding, and start competing strongly with the crop.
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  • 33
    ISSN: 1572-9680
    Keywords: alley cropping ; maize ; nitrogen ; organic matter ; soil fertility ; Leucaena leucocephala ; Flemingia congesta
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    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A detailed study of the soil chemical and physical properties in seven-year-old alley cropping trial containingLeucaena leucocephala andFlemingia congesta in Northern Zambia is described. There was a strong correlation between the maize yield and the total amount of nitrogen applied, both from prunings and fertiliser, suggesting that a major reason for the observed benefit from alley cropping, particularly withLeucaena, was due to an improvement in nitrogen supply.Leucaena produced significantly more biomass, and its leaves had higher concentrations of nitrogen, phosphorous and potassium and lower C/N and C/P ratios than did those ofFlemingia. There was also evidence that the trees had a beneficial effect on other soil chemical properties; under the hedgerows, particularly those ofLeucaena, there were higher levels of organic carbon, Mg, K and ECEC, and pH values were also highest. It is suggested that higher levels of organic carbon in the alley crop treatments were responsible for the improvements observed in soil physical properties. Lower bulk density, lower penetration resistance, and a higher infiltration rate and pore volume fraction were measured in the alley crops, although there was no significant change in the soil water release parameters. A deteriorating effect of constant applications of nitrogen fertiliser on soil fertility was observed; as the level of urea application increased, there were significant decreases in Mg, K and pH, increases in Al and soil acidity, and higher penetrometer resistance. These results highlight the urgent need for further research on biological methods of maintaining soil fertility.
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    Antonie van Leeuwenhoek 60 (1991), S. 175-191 
    ISSN: 1572-9699
    Keywords: growing systems ; kinetics ; murein wall ; nucleic acid ; protein ; turnover
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Living organisms do not just grow by synthesizing cellular components. As part of the necessary steps for existence, some components are degraded after synthesis. Even for bacteria in balanced, exponential growth some substances, under some conditions, are turned over. In other phases of growth turnover can be much more extensive, but it is still selective. This review covers studies with animals as a way to put the studies on microorganisms in perspective. The history, the mathematics, and experimental design of turnover experiments are reviewed. The important conclusion is that most of the proteins during balanced growth are very stable in bacteria, although ribosomal proteins are degraded under starvation conditions. Another generalization is that the process of wall enlargement in general is associated with obligatory turnover of the peptidoglycan.
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    Cellular and molecular life sciences 47 (1991), S. 1104-1118 
    ISSN: 1420-9071
    Keywords: Transaminase ; decarboxylase ; serine hydroxymethyltransferase ; pyridoxal 5′-phosphate ; enzyme mechanism ; stereochemistry ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Pyridoxal 5′-phosphate is a coenzyme for a number of enzymes which catalyse reactions at Cα of amino acid substrates including transaminases, decarboxylases and serine hydroxymethyltransferase. Using the X-ray coordinates for a transaminase, aspartate aminotransferase, and the results of stereochemical and mechanistic studies for decarboxylases and serine hydroxymethyltransferase, an active-site structure for the decarboxylase group is constructed. The structure of the active-site is further refined through active-site pyridoxyllysine peptide sequence comparison and a 3-D catalytic mechanism for the L-α-amino acid decarboxylases is proposed. The chemistry of serine hydroxymethyltransferase is re-examined in the light of the proposed decarboxylase mechanism.
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  • 36
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    Aquatic sciences 55 (1993), S. 103-111 
    ISSN: 1420-9055
    Keywords: iron(III) (hydr)oxide ; fulvic acid ; iron redox cycling ; dissolution ; surface reactivity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10−4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the 〉 FeIII-OH/Fe(II) “wheel” coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)3(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.
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  • 37
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    European journal of clinical pharmacology 42 (1992), S. 107-110 
    ISSN: 1432-1041
    Keywords: Phenobarbitone ; Cerebral malaria ; P.falciparum ; kinetics ; drug absorption ; children
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The absorption of intramuscular phenobarbitone 7 mg·kg−1 was studied in 11 Karen children aged between 1.7 and 11 y with severe falciparum malaria. Eight of the children were comatose. Clinical findings were compared with those in 9 further children with severe malaria of similar age range (four of whom were unconscious), who received an identical placebo. One child, who had received placebo, had repeated convulsions and died 1 h after admission to hospital. The remainder made an uncomplicated recovery. There were no convulsions subsequent to treatment, although the study was too small to assess anticonvulsant efficacy. There was no observable toxicity, but phenobarbitone recipients had a significant tendency to deepen in their level of coma or to become sleepy within the 4 h after drug administration. Phenobarbitone was rapidly absorbed, reaching a mean (range) peak concentration of 34.2 [29.3–42.6] μmol·l−1 in a median (range) of 4 (2.5–12) h. These values are comparable to those previously reported in healthy children and in children with febrile convulsions. Intramuscular phenobarbitone is well absorbed in children with severe malaria; the optimum prophylactic anticonvulsant dose remains to be determined.
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  • 38
    ISSN: 1432-1041
    Keywords: Atrial natriuretic peptide ; kinetics ; ageing
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary To study the influence of age on the kinetics of atrial natriuretic peptide (ANP) in man, human (99–126) ANP 2.0 μg·min−1 was infused IV for 60 min in 8 healthy young (18 to 25 y) and 9 healthy elderly (71 to 84 y) subjects. Both baseline ANP values and the levels at the end of infusion were higher in the elderly subjects. The mean residence time of ANP in the two age groups was not significantly different, whereas total body clearance (CL) was markedly diminished in the elderly as compared to the young subjects (mean±SD 3.1±1.0 l·min−1 and 6.2±4.1 l·min−1, respectively). The apparent volume of distribution at steady state was lower in the elderly than in the young, but the difference was not significant (mean±SD 44±19 and 103±111, respectively. The decrease in CL largely explained the higher ANP levels found in the elderly subjects. The MRT and the plasma half-life of the terminal phase did not differ between the two groups. In the elderly but not in the young subjects the calculated endogenous creatinine clearance was closely correlated with the CL (r=0.90, P〈0.001), thereby emphasizing the importance of the kidney in the metabolic clearance of ANP in the elderly.
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  • 39
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    European journal of clinical pharmacology 42 (1992), S. 461-462 
    ISSN: 1432-1041
    Keywords: Talinolol ; Sulfasalazine ; β-adrenoceptor-blocking drugs ; absorption ; drug interaction ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The absorption of talinolol (TA) 50 mg was investigated without and together with the co-administration of sulfasalazine (SASP) 4 g in 11 healthy young volunteers, in order to clarify gastrointestinal transit of TA. Without SASP, the tmax of TA was 2.8 h, Cmax was 112 ng·ml−1 and the half life was 12 h; the AUCo-t was 958 ng·ml−1·h. In the case of concomitant administration of SASP, TA was found only in serum from 3 individuals, with a Cmax of 23 ng·ml−1 and a mean AUCo-t of 84 ng·ml−1·h. TA was not detectable in 5 subjects and it was at the limit of detection (2 ng·ml−1) in 3 subjects. Pharmacokinetic analysis was not possible in any of those individuals. The reason for the interaction appears to be the adsorption of TA by SASP. An interval of 2–3 h should elapse between giving SASP and other drugs.
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  • 40
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    European journal of clinical pharmacology 44 (1993), S. 231-235 
    ISSN: 1432-1041
    Keywords: Carbamazepine ; kinetics ; population pharmacokinetics ; bioavailability ; controlled release ; non-linear model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The absorption properties of a conventional tablet of carbamazepine (T) and a controlled release form of carbamazepine (TCR) have been compared using a nonlinear mixed effect model (NONMEM). Plasma carbamazepine concentration data were obtained from an open, steady-state, crossover bioavailability study in which 494 measurements were obtained from 13 patients, with an equal number of samples per patient for each dosage form. The pharmacokinetic model used was a one-compartment open model with first-order absorption and elimination. The objective function was used as a measure of the goodness of fit of the model to the data. Body weight was an important determinant of carbamazepine clearance (CL) but not volume of distribution (V). Accounting for the interindividual variability in volume of distribution did not significantly influence the objective function. Including different rates of absorption (ka) for the two dosage forms resulted in a significant improvement in the objective function, as well as reducing the interindividual variability in the rate of absorption. Adding a parameter for relative bioavailability (f) of TCR improved the objective function statistically, but an unrealistic value for V was obtained, and the absorption and elimination rates appeared to be transposed in the classical “flip-flop” manner. Fixing V to the value obtained before introducing f did not change the objective function and permitted estimation of f without the confounding influence of excessive parameters. The final population parameter estimates (standard error of estimate) were: CL, 0.0522 (0.0019) l·h−1·kg−1; V, 63.7 (FIXED)l; kaT, 0.312 (0.064) h−1; kaTCR, 0.149 (0.016) h−1; f, 1.01 (0.0326); variance (additive) in CL, 0.291 (0.083) (l·h−1·kg−1)2; residual intrasubject error variance (additive), 0.572 (0.082) (mg·l−1)2. The 95% confidence interval of the extent of absorption (f) of 93.6%–107.4% was well within the generally accepted range of ±20%, while the rate of absorption of Tegretol CR was significantly slower than that of Tegretol, as expected for a controlled release product.
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  • 41
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    European journal of clinical pharmacology 10 (1976), S. 43-48 
    ISSN: 1432-1041
    Keywords: Spironolactone ; acetylsalicylic acid ; fludrocortisone ; kinetics ; pharmacology ; interaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The influence of 600 mg acetylsalicylic acid (ASA) on the renal excretion and clearance of canrenone, the principal unconjugated metabolite of spironolactone, was examined in a double-blind crossover study in six healthy subjects. ASA significantly reduced the urinary excretion, and the fractional excretion, of canrenone between 4 — 6 hours after administration of 50 mg spironolactone. The pharmacological activity of spironolactone, assessed simultaneously by alterations in fludrocortisone-induced urinary electrolyte changes, was slightly but not significantly reduced. The reductions in urinary canrenone excretion correlated with changes in the urinary log 10 Na/K ratio. The results suggest that canrenone may be actively secreted at the proximal renal tubule, and that secretion is blocked by ASA or its conjugates. This is a possible mechanism for the pharmacological interaction between ASA and spironolactone which has been described previously.
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  • 42
    ISSN: 1432-1041
    Keywords: Theophylline ; kinetics ; apnea ; premature newborns ; developmental pharmacology
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Aminophylline (theophylline-ethylenediamine) was administered to 27 premature newborns to prevent apneic spells. Of the 22 patients monitored for theophylline concentration, a therapeutic blood level was reached in 19 in 1–2 days, and 3 stayed below it. ‘Toxic’ blood levels (≥20 µg/ml) were reached in 3 cases, one of whom showed signs of toxicity. Theophylline treatment was not efficient in the prevention of apnea when a serious underlying disease was present. Theophylline blood half-life (mean : 27.0 h) and clearance (mean 12.9 ml/h/kg) confirmed the slow elimination pattern of the drug in the premature infant.
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  • 43
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    European journal of clinical pharmacology 39 (1990), S. 155-159 
    ISSN: 1432-1041
    Keywords: Gentamicin ; Dosage ; kinetics ; dose individualization ; dose prediction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: 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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  • 44
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    European journal of clinical pharmacology 40 (1991), S. 181-185 
    ISSN: 1432-1041
    Keywords: Etizolam ; α-hydroxyetizolam ; healthy subjects ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of etizolam, a new thienodiazepine derivative, has been examined after single and multiple (0.5 mg tablet) (0.5 mg b.d for 1 week) oral therapeutic doses in healthy volunteers. The single-dose kinetic profile of etizolam suggested that absorption after oral dosage was reasonably rapid, the maximum plasma concentration (Cmax) being attained within 0.5–2 h in all subjects. The mean elimination half-life (t1/2) averaged 3.4 h. Consistent with this, steady-state concentration were rapidly achieved and accumulation was extremely limited. Predicted average plasma concentrations (Cp) did not differ significantly from those actually measured at steady-state, suggesting that the kinetics of etizolam was linear, at least at therapeutic doses. The mean wash-out t1/2 was comparable to the elimination t1/2 of the single dose, which means that the drug probably has no effect on hepatic microsomal enzymes and other kinetic variables after repeated dosing. At steady state plasma concentrations of the main metabolite, α-hydroxyetizolam, were higher and disappeared more slowly (mean t1/2 8.2 h) than those of the parent compound. Taken with the fact that in animals the metabolite shows almost the same potency of pharmacological action as etizolam, this suggests that it may contribute significantly to the clinical effects of the parent compound. Based on the kinetic characteristics of the parent drug and its metabolite, etizolam can be regarded as a short-acting benzodiazepine, with elimination kinetics between those of short-intermediate derivatives and ultra-rapidly eliminated benzodiazepines.
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  • 45
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    Journal of thermal analysis and calorimetry 38 (1992), S. 51-70 
    ISSN: 1572-8943
    Keywords: kinetics ; solid-state reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wurde der Einflu\ verschiedener experimenteller Bedingungen (z.B. Probenmasse, Atmosphäre, Aufheizgeschwindigkeit) auf die Zersetzung von NH4VO3, CaCO3 und V2O5 untersucht. Die Ergebnisse zeigen eindeutig, da\ Reaktionsweg und kinetische Parameter in Wirklichkeit nicht die einzelne Verbindung charakterisieren, sondern eher die Kombination von experimentellen Bedingungen und untersuchter Verbindung. Hierdurch ist es meistens unmöglich, “Standardbedingungen≓ zur Berechnung kinetischer Parameter zu wählen, da unter verschiedenen Umständen ganz andere Reaktionswege beschritten werden können.
    Notes: Abstract The influence of various experimental conditions such as sample weight, atmosphere and heating rate on the decomposition of NH4VO3, CaCO3 and V2O5 has been investigated. Results obtained clearly indicate that the course of the reactions and — in turn — the kinetic parameters, are not intrinsic to the particular compound and that they characterize rather the combination of experimental conditions and investigated compound. Such a situation makes it almost impossible to choose ‘standard conditions’ for the calculation of kinetic parameters, because under different circumstances quite different reaction-pathways can occur.
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  • 46
    ISSN: 1572-8943
    Keywords: CRTA ; kinetics ; TA
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird die Anwendbarkeit von herkömmlicher Thermoanalyse (TA) und geschwindigkeitsgesteuerter Thermoanalyse (CRTA) bei kinetischen Untersuchungen diskutiert. Die TA Technik kann eine zuverlässige kinetische Information und sinnvolle kinetische Parameter besonders bei Feststoffumsetzungen liefern. Die CRTA Technik ist andererseits mehr für Zersetzungsprozesse geeignet, bei denen ein oder mehrere Gase freigesetzt werden. Für beide Techniken wird eine einheitliche und geeignete Methode zu kinetischen Analyse vorgeschlagen. Als Beispiel wird diese Methode zur Analyse des Kristallisationsprozesses von Chalkogenidgläsern sowie der Zersetzung von Dolomit angewendet.
    Notes: Abstract The applicability of both conventional Thermal Analysis (TA) and Controlled Rate Thermal Analysis (CRTA) for kinetic analysis is discussed. It is shown that TA method can give a reliable kinetic information and meaningful kinetic parameters especially for solid state transformation. On the other hand the CRTA method is more suitable for decomposition process where one or more gasses are evolved. A consistent and reliable method of kinetic analysis is proposed for both techniques. This method is illustrated to analyze the crystallization process of chalcogenide glass and the decomposition of dolomite.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1999-2003 
    ISSN: 1572-8943
    Keywords: calorimetry ; hydrogen adsorption ; kinetics ; thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels kalorimetrischer und volumetrischer Messungen im Temperaturbereich von 298 bis 363 K wurden die thermodynamischen Eigenschaften der Wasserstoffadsorption an Eisenschichten untersucht. Die kinetischen Eigenschaften wurden mit Hilfe der Dekonvulotion kalorimetrischer Thermogramme ermittelt und mit Literaturangaben zum Haftkoeffizienten verglichen.
    Notes: Abstract Thermodynamic properties of hydrogen adsorption on iron layers evaporated under UHV conditions have been determined from calorimetric and volumetric measurements over the temperature range from 298 K to 363 K. Kinetic properties have been determined with the help of deconvolution of calorimetric curves and compared with the literature data on the sticking coefficient.
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  • 48
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2349-2357 
    ISSN: 1572-8943
    Keywords: dehydrochlorination process ; kinetics ; PVC ; ZnCh catalyzed degradation
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels TG wurden die kinetischen Parameter des Dehydrochlorierungsprozesses (DHCL) von PVC und von mit verschiedenen Mengen von ZnCl2 versetztem PVC bestimmt. Diese Werte wurden mit denjenigen verglichen, die man bei der spektroskopischen Analyse der Zersetzung von ZnCl2-haltigen PVC-Filmen bei verschiedenen Temperaturen im sichtbaren UV-Bereich erhalten hatte. Die Werte der scheinbaren Aktivierungsenergie (E a) sinken mit zunehmendem ZnCl2-Gehalt und die hier erhaltenen Werte sind vergleichbar gut mit denen der vorangehenden Arbeit. Der katalytische Effekt von ZnCl2 auf PVC DHCL-Vorgänge wurde erklärt.
    Notes: Abstract The kinetic parameters of dehydrochlorination (DHCL) process of PVC and PVC mixed with different amount of ZnCl2 have been determined by using thermogravimetric analysis. These values have been compared with those obtained by using UV-visible spectroscopic analysis of PVC film containing ZnCh degraded at different temperatures. The values of apparent activation energy (E a) decreases with the increase of the amount of ZnCl2 and the values obtained in the present work are in reasonable comparison with previous works. The catalytic effect of ZnCl2 on PVC DHCL process is explained here.
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  • 49
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    Journal of thermal analysis and calorimetry 39 (1993), S. 15-20 
    ISSN: 1572-8943
    Keywords: alloys ; high-temperature sulphidation ; kinetics ; new thermobalane
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein neue Apparat zur Untersuchung der Hochtemperatur-Sulfidierung von Metallen in H2/H2S Atmosphare beschrieben. Der Unterschied zwischen diesem Apparat und dem fruher benutzten, besteht im Gasdosierungsystem. Wasserstoff reagiert teilweise mit Schwefel, was eine stabile Zusammensetzung des Gasgemisches beim niedrigen Schwefeldampfdruck sichert. Gewichtsmessungen von Metallen und Legierungen konnen in diesem System bei Temperaturen von 1073 bis 1473 K mit einer Genauigkeit von 10−6 g ausgefuhrt werden.
    Notes: Abstract A new thermogravimetric apparatus for studying the kinetics of metal sulphidation in a H2/H2S gas mixture is described. The main difference between this device and other equipment is the application of hydrogen to obtain a H2/H2S mixture at suitable sulphur partial pressures at a total mixture pressure of 1 atm. The use of the carrier gas allows the measurement of sulphidation kinetics under dynamic conditions and consequently over a much wider pressure range of sulphur vapour, down to 10−12 atm.
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    Journal of thermal analysis and calorimetry 39 (1993), S. 65-74 
    ISSN: 1572-8943
    Keywords: electrical conductivity ; hydrazone complexes ; kinetics
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Bei zwei verschiedenenpH-Werten wurden die Zn-, Cd- und Hg-Komplexe von Isatinisonicotinoylhydrazon hergestellt. Diese wurden thermisch untersucht (TG, DTG, DTA) und die Gleichstromleitfähigkeit von gepreßten Pulverproben als eine Funktion der Temperatur untersucht. Sowohl für die Liganden als auch für die Komplexe wurden die Aktivierungsenergien (ΔE) berechnet, wobei sich für die Liganden niedrigere Werte ergaben. Man fand, daß die Größe von ΔE durch die Art des Metalles und denpH-Wert bei der Herstellung beeinflußt wird.
    Notes: Abstract The complexes of Zn, Cd and Hg of isatin isonicotinoyl hydrazone were prepared at two differentpHs. Their thermal studies (TG, DTG and DTA) have been made and the DC electrical conductivity of compressed powder samples as a function of temperature was investigated. The activation energies (ΔE) were calculated for the ligand and the complexes which showed that the ligand has a lower value of ΔE than the complexes. The magnitude of ΔE was found to be affected by the nature of the metal and thepH of preparation.
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    Journal of thermal analysis and calorimetry 39 (1993), S. 75-86 
    ISSN: 1572-8943
    Keywords: chlorination ; kinetics ; WO3+CCl4 reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels Thermogravimetrie wurde die Chlorierungskinetik von alkaliversetztem (K und Li) Wolframtrioxid untersucht, wobei CCl4 als Chlorierungsreagens fungierte. Die Reaktivität der modifizierten Proben wurden mit der von reinem WO3 verglichen. Für die reinen und für die alkaliversetzten Proben wurden ähnliche scheinbare Aktivierungsenergien gefunden. Der Zusatz von Kalium verursacht jedoch eine starke Abnahme der ursprünglichen Reaktionsgeschwindigkeit, während oberflächiges Lithium keinen Effekt zeigt. Während der Chlorierung wurde eine ständige Senkung der linearen Reaktionsgeschwindigkeit für beide Proben festgestellt, was mit Rückhalteeffekten von oberflächigen Nebenprodukten und Alkalizusätzen erklärt wird. Zur Beschreibung der isothermen TG-Kurven wurde ein entsprechendes kinetisches Modell angenommen, welches auf einer monoton steigenden Inhibition dieser Proben basiert. Die auf der Grundlage dieses Modelles berechnete Kurve stimmt recht gut mit den experimentellen Ergebnissen überein.
    Notes: Abstract The chlorination kinetics of alkali-added (K and Li) tungsten trioxide were studied by thermogravimetry, using gaseous CCl4 as chlorinating agent. The reactivity of the modified samples was compared to the results on the chlorination of pure WO3. Similar apparent activation energies were found for the pure and alkali-added samples. However, potassium additive resulted in a strong decrease of the initial reaction rate, while surface lithium has no influence on it. During the chlorination a continuous decrease of the linear reaction rate was observed for both samples, which was explained by retarding effects of surface by-products and alkali additives. For describing the isothermal TG curves an appropriate kinetic model, based on the monotonously increasing inhibition of these species was assumed. The curve calculated with this model fits well to the experimental results.
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    Journal of thermal analysis and calorimetry 39 (1993), S. 229-238 
    ISSN: 1572-8943
    Keywords: epoxy resins ; kinetics ; thermal stability
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Vernetzungsreaktionen der Epoxidharze Tetraglycidyl-diamino-diphenyl-methan (TGDDM) und Tetraglycidyl-methylen-bis(o-toluidin) (TGMBT) unter Verwendung von Diaminodiphenylsulfon (DDS), Diaminodiphenylmethan (DDM) und Diethylentriamin (DETA) als Vernetzungsmittel wurden kinetisch mittels DSC untersucht. Die dynamischen Scans im Temperaturbereich 20°–300°C wurden analysiert, um unter Anwendung einiger empirischer Gleichungen die Aktivierungsenergie und die Reaktionsordnung des Vernetzungsprozesses zu ermitteln. Die Aktivierungsenergie der einzelnen Epoxy-Systeme liegt im Bereich 71.9–110.2 kJ·mol−1. An der ausgehärteten Harze wurde mittels TG in einer statischen Luftatmosphäre un deiner Aufheizgeschwindigkeit von 10 Grad/min die Kinetik des termischen Abbaues untersucht. Man fand, daß die thermiscehn Abbaureaktionen in einem Schritt ablaufen und ihre Aktivierungsenergie im Intervall 27.6–51.4 kJ·mol−1 liegt.
    Notes: Abstract The curing reactions of the epoxy resins tetraglycidyl diaminodiphenyl methane (TGDDM) and tetraglycidyl methylenebis (o-toluidine) (TGMBT) using diaminodiphenyl sulfone (DDS), diaminodiphenyl methane (DDM) and diethylenetriamine (DETA) as curing agents were studied kinetically by differential scanning calorimetry. The dynamic scans in the temperature range 20°–300°C were analyzed to estimate the activation energy and the order of reaction for the curing process using some empirical relations. The activation energy for the various epoxy systems is observed in the range 71.9–110.2 kJ·mol−1. The cured epoxy resins were studied for kinetics of thermal degradation by thermogravimetry in a static air atmosphere at a heating rate of 10 deg·min−1. The thermal degradation reactions were found to proceed in a single step having an activation energy in the range 27.6–51.4 kJ·mol−1.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 709-713 
    ISSN: 1572-8943
    Keywords: enthalpy of polymerization ; free radical polymerization ; kinetics ; p-alkylphenyl methacrylates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC wurden im Temperaturbereich 348–373 K Reaktionsweg und Kinetik der radikalischen Raumpolymerisation vonp-Alkylphenylmethacrylaten mit AIBN Initiator untersucht. Dabei wurden die Polymerisationsenthalpie, der Monomerrest-gehalt als auch die Geschwindigkeitskonstanten und die Aktivierungsenergien der Gesamt-reaktion bestimmt. Ähnliche Werte für die Gesamtgeschwindigkeitskonstanten weisen darauf hin, daß die relativ kleinen Alkylsubstituenten inp-Stellung des Phenylringes die Polymerisationsgeschwindigkeit nur in sehr kleinem Maße — wenn überhaupt — beeinflussen.
    Notes: Abstract The course and kinetics of free radical polymerization in bulk ofp-alkylphenyl methacrylates with AIBN initiator were studied by DSC, in the temperature range 348–373 K. The enthalpy of polymerization, the residual monomer content, as well as the overall reaction rate constants and the activation energies were determined. The similar values of the overall rate constants indicate that the relatively small alkyl substituents inp-position of the phenyl ring affect the polymerization rate to a very small, if any, extent.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 729-738 
    ISSN: 1572-8943
    Keywords: kinetics ; oil shale pyrolysis ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die im allgemeinen benutzte Kinetikgleichung in der Thermoanalyse von Ölschieferpyrolyse wurde auf der Grundlage einer einfachen kinetischen Gleichung erster Ordnung der Kerogenzersetzung erhalten. Mittels nichtisothermer (NI) oder isothermer (I) TG kann sowohl die Aktivierungsenergie als auch die Reaktionsgeschwindigkeitskonstante der Ölschieferpyrolyse bestimmt werden. Die unter Anwendung von NI oder I ermittelten kinetischen Parameter ermöglichen jedoch keine gute Voraussage des Kerogenumsatzes bei anderen Bedingungen. Es werden hier die Vergleichsergebnisse aus NI- bzw. I-TG von verschiedenen Ölschiefern als auch die Auswirkungen auf die sogenannte kombinierte nichtisotherme und isotherme TG (NI/I) besprochen. Die erhaltenen Ergebnisse zeigen, daß ein Mechanismus angenommen werden muß, der auf einem komplexen Reaktionsschema aus mehr als aus einer einfachen Reaktion basiert.
    Notes: Abstract The kinetic expression commonly used in the thermal analysis of oil shale pyrolysis was derived on the basis of a simple first order kinetic equation of kerogen decomposition. The activation energy, as well as the reaction rate constant of oil shale pyrolysis could be determined by using non-isothermal (NI) or isothermal (I) TG. However, the kinetic parameters determined by using either NI or I did not enable the good prediction of the kerogen conversion at other conditions. The comparative results of the NI and I-TG of different oil shales are discussed in the study, as well as the effects of the so-called combined non-isothermal and isothermal TG (NI/I). The obtained results indicate that a mechanism must be postulated based on a complex reaction scheme which involves more than one simple reaction.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 721-728 
    ISSN: 1572-8943
    Keywords: kinetics
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es werden einige theoretische Überlegungen bezüglich des Einflusses der Form der Konversionsfunktionf(α) auf die Werte der Konversionsrate bei maximalen Reaktionsgeschwindigkeiten (αmax) sowie auf Inflexionspunkte (α∞) der DTG-Kurve angestellt. Die erhaltenen Gleichungen sind unabhängig von der Form vonf(α) durch eine all-gemeine Gültigkeit charakterisiert.
    Notes: Abstract The authors present some theoretical considerations concerning the influence of the form of the conversion functionf(α) on the values of the degree of conversion corresponding to the maximum value of the reaction rate (αmax) as well as on the inflexion points (αinf) of the DTG curve. The obtained equations are characterized by a general validity no matter the form off(α).
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1793-1799 
    ISSN: 1572-8943
    Keywords: hydrated salts ; kinetics ; thermal dehydration ; yttrium formate dihydrate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels isothermer Gravimetrie und bei verschiedenen Wasserdampfdrücken zwischen 5×10−4 und 8 Torr wurde die Kinetik der thermischen Dehydratation von Yttriumformiat-Dihydrat untersucht. Die Dehydratation wird als dreidimensionale Phasengrenzreaktion R3 beschrieben. Dabei wurde ein ungewöhnlicher Einfluß des athmosphärischen Wasserdampfdruckes auf die Dehydratationsgesch windigkeit beobachtet: mit steigendem Wasserdampfdruck wächst die Geschwindigkeit zunächst ebenfalls an, durchquert ein Maximum und sinkt dann nach und nach auf einen konstanten Wert ab. Diese Erscheinung ähnelt dem Smith-Topley-Effekt. Der Mechanismus dieser Erscheinung kann auf der Grundlage der Kristallinität der dehydratierten Produktephase diskutiert werden.
    Notes: Abstract The kinetics of the thermal dehydration of yttrium formate dihydrate was studied by means of isothermal gravimetry under various water vapour pressures from 5×10−4 to 8 torr. On the whole, the dehydration was described as the three dimensional phase boundary reaction, R3. An unusual dependence of the rate of dehydration on the atmospheric water vapour pressure was observed: with increasing water vapour pressure, the rate increased at first, passed through a maximum, and then decreased gradually to a constant value. These phenomena were similar to the Smith-Topley effect. The mechanism of the phenomena can be described on the basis of the crystallinity of the dehydrated product phase.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2053-2065 
    ISSN: 1572-8943
    Keywords: calcination ; high temperature reactions ; kaolinite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Strukturelle Veränderungen bei der Dehydroxylierung von Kaolinit wurden durch die Anwendung einer Blitz-Kalzination untersucht, um kinetisch eingefrorene Kalzinationsprodukte zu erhalten. Der Prozentsatz der Dehydroxylierung wurde durch Veränderung der Verweilzeit im Ofen, durch Ofentemperatur und/oder Heizgeschwindigkeit modifiziert. Diese Kalzinationsbedingungen beeinflußten zwar die Reaktionskinetik, aber die Produkte hingen nur vom Ausmaß der Dehydroxylierung ab. Abweichungen bei Lage und Enthalpie der endothermen Umwandlung zu Metakaolinit und die exotherme Hochtemperaturreaktion von Metakaolinit wurden mittels DSC der Blitz-Kalzinationsprodukte verfolgt und in Beziehung zur Thermogravimetrie gebracht. 27Al Magic-Angle-Spinning NMR Spektren bei hohen magnetischen Feldstärken und Drehgeschwindigkeiten erlauben es, die Reaktion von Kaolinit zu verfolgen und liefern neue Informationen über die Natur der bei der Dehydroxylierung gebildeten Substanzen.
    Notes: Abstract The structural changes occurring during the dehydroxylation of kaolinite have been followed using flash calcination to produce kinetically frozen calcines. The percentage of dehydroxylation was varied by changing the furnace residence time or temperature and/or heating speed. These calcination conditions affected the reaction kinetics, but the products depended only on the extent of dehydroxylation. Changes in the position and enthalpy of the endothermic transformation to metakaolinite and the high temperature exothermic reaction of metakaolinite have been followed using Differential Scanning Calorimetry of the flash calcines and related to Thermogravimetry. 27Al magic-angle-spinning NMR spectra, at high magnetic fields and spin rates, enabled the reaction of kaolinite to be monitored and provides new information on the nature of the species formed in the course of dehydration.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2129-2135 
    ISSN: 1572-8943
    Keywords: kinetics ; thermal dissociation ; ZrO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Im Temperaturintervall von 300 K bis 2670 K wurde im Hochvakuum und bei verschiedenen Aufheizgeschwindigkeiten das thermische Verhalten von Zirkoniumoxid ZrO2 untersucht. Die Experimente wurden mit Hilfe eines schweizer Universal Mettler Thermoanalysators, ausgerüstet mit einem SHT Super-Hochtemperatur-Ofen, ausgeführt. Flüchtige Produkte wurden simultan dazu mit einem Massenspektrometer QMG-101 der Balzers-Company analysiert. Die Auswertung der durch aufgezeichneten TG-, DTG-, DTA- und EGA-Kurven zeigt den komplexen Charakter des untersuchten Prozesses. Die Elementarschritte der Gesamtreaktion wurden definiert und berücksichtigt. Weiterhin wurde der Mechanismus der Thermodissoziation von ZrO2 auch in Abhängigkeit von der Aufheizgeschwindigkeit diskutiert.
    Notes: Abstract The behaviour of zirconium oxide ZrO2 during its heating in the temperature range 300–2670 K under high-vacuum conditions and at different heating rates has been studied. The experiments were performed with a Swiss made Universal Mettler thermoanalyser equipped with a super-high-temperature furnace SHT. Volatile products were analyzed simultaneously by means of a Balzers QMG-101 mass spectrometer. An analysis of the TG, DTG, DTA and EGA curves recorded simultaneously has shown the complex character of the studied process. The elementary steps of the overall process were defined and taken into consideration. The mechanism of the thermal dissociation reaction of ZrO2 as function of the hearing rate was discussed too.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2195-2210 
    ISSN: 1572-8943
    Keywords: kinetics ; lattice energy ; solid-state systems
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird eine allgemeine Methode zur theoretischen Ableitung der Kristallgitterenergie von ionischen Verbindungen, insbesondere von Verbindungen mit einatomigen Ionen beschrieben. Anschließend werden die Möglichkeiten einer theoretischen Voraussage der Gitterenergie komplexer organischer und anorganischer Ionenverbindungen diskutiert. Zuletzt wird die Bedeutung der Gitterenergie bei der Untersuchung der Eigenschaften und des Verhaltens von Feststoffsystemen im Zusammenhang mit der Aussicht auf die Entwicklung eines Modelles zur Beschreibung der Kinetik von Feststoffprozessen gezeigt.
    Notes: Abstract A general approach to the theoretical evaluation of the crystal lattice energy of ionic substances, particularly those composed of monoatomic ions, is outlined in detail. Subsequently, the possibilities of theoretical prediction of the lattice energy of complex organic and inorganic ionic substances are discussed. Lastly, the importance of the lattice energy in examinations of the properties and behaviour of solid-state systems, is treated, together with the prospects of developing a model describing the kinetics of solid-state processes.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1683-1690 
    ISSN: 1572-8943
    Keywords: kinetics
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Auf Grund der bestimmten thermokinetischen Kurven der Zersetzung von Phosphor-Rohstoffen mit Säuren wurde die Abhängigkeit des Umwandlunsgrades der einzelnen Reagenten von solchen Faktoren wie Zeit, Enthalpie u. konstante Zerlegungeschwindigkeit bestimmt.
    Notes: Abstract On the basis of the thermokinetic curves of the phosphor deposits with acids the dependence of the conversion degree upon the time, the enthalpy and the reaction rate constant were determined.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 197-211 
    ISSN: 1572-8943
    Keywords: gas/heat transport ; kinetics ; quasi static-methods
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    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Beim Verlauf von Feststoffreaktionen spielen Wärme- und Gastransport eine wesentliche Rolle. Eine Standardisierung der experimentellen Bedingungen wäre deshalb erforderlich, was jedoch bisher nur bezüglich der Erarbeitung von Simultantechniken gelang. Au\erdem sind diese beiden Transportprozesse dafür verantwortlich, da\ man ausgehend von nichtisothermen Kurven keine kinetischen Parameter berechnen kenn. Quasistatische Methoden scheinen geeignet zu sein, um den störenden Einflu\ dieser Transportprozesse zu eliminieren.
    Notes: Abstract In the course of solid phase reactions heat and gas transport processes play a dominant role. Therefore, it would be necessary to standardize the experimental conditions which succeeded only in part with the elaboration of the simultaneous techniques. Likewise the two transport processes are responsible for the fact that on the basis of non-isothermal curves one cannot calculate kinetic parameters of the reactions. The quasi static-methods seem to be suitable for the elimination of the pernicious effect of these transport processes.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2211-2219 
    ISSN: 1572-8943
    Keywords: kinetics ; polycarbonates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Derivatographische, nichtisotherme Untersuchungen der Zersetzung von Polycarbonaten in Luft liefern nutzbringende Informationen über die charakteristischen Zersetzungstemperaturen und die scheinbaren Aktivierungsenergien der untersuchten Zersetzungsschritte. Dabei wurde folgende Reihenfolge der scheinbaren Aktivierungsenergie der Pyrolyseschritte beobachtet: PC-M PC-C PC-A. Wegen der Abschirmung der Esterketten durch ortho-Methylsubstituenten sind die Werte E für PC-M am höchsten.
    Notes: Abstract Derivatographic non-isothermal investigations of the decomposition of PC in air provide useful information on the characteristic decomposition temperatures and the apparent activation energies of the observed steps of decomposition. The following sequence of apparent activation energies of the pyrolysis step was obtained: PC-M〉PC-C〉PC-A. The values ofE for PC-M are the highest, due to shielding of the ester linkages by the ortho-methyl substituents.
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  • 63
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2377-2383 
    ISSN: 1572-8943
    Keywords: Co(II) succinate complex ; isothermal decomposition ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Unter Anwendung von isothermen und dynamischen thermogravimetrischen Methoden wurde eine kinetische Untersuchung der Dehydratation und der Zersetzung von γ-bestrahltem und unbestrahltem Na2[Co(C4H4O4)2]·7H2O durchgeführt. Die thermische Dehydratation erfolgt in einem Schritt, bestimmt durch ein Random-Keimbildungsmodell (A3), während die Zersetzung der wasserfreien Salze durch ein phasengrenzenkontrolliertes Modell bestimmt wird (R3). Die bei drei Aufheizgeschwindigkeiten erhaltenen kinetischen Parameter stehen in guter Übereinstimmung; jedoch weichen die isotherm geschätzten kinetischen Parameter etwas von den dynamisch ermittelten ab. Bestrahlung mehrt sowohl die Dehydratations- als auch die Zersetzungsreaktionen, beläßt deren Mechanismus jedoch unverändert. Die Aktivierungsenergie sinkt mit zunehmender Strahlungsdosis.
    Notes: Abstract A kinetic study of the dehydration and decomposition of γ-irradiated and unirradiated Na2[Co(C4H4O4)2]·7H2O has been studied using isothermal and dynamic thermogravimetric methods. The thermal dehydration occurs in one step regulated by a random nucleation model (A3), while the decomposition of anhydrous salt is controlled by a phase boundary controlled model (R3). The kinetic parameters obtained at three heating rates are in good agreement; however, the values of the kinetic parameters estimated isothermally are slightly different from those estimated dynamically. Irradiation enhanced both the dehydration and the decomposition reactions but did not modify their mechanisms. The activation energy decreases as the irradiation dose increases.
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  • 64
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2553-2557 
    ISSN: 1572-8943
    Keywords: kinetics ; solid-state reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract For the kinetic description of the solid-state reactions, the dependence of the apparent kinetic parameters on the sample mass and/or particle size is discussed mathematically in relation to some problems on the fractional conversion a. As for the reaction proceeding according to the contracting geometry model, the use of the specific rate constant, independent of the sample mass and particle size, is recommended to obtain the sample mass-independent Arrhenius parameters. It is also pointed out that the distribution of α within the assembly of sample particles disturbs the successful use of α in the kinetic description of the solid-state reactions.
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  • 65
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2639-2647 
    ISSN: 1572-8943
    Keywords: kinetics ; MgO-CaO-Al2O3-SiO2 glasses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Vorliegende Arbeit untersucht mittels thermoanalytischen Untersuchungen die Berechtigung von drei verschiedenen Methoden zur Ermittlung der Aktivierungsenergie der Kristallisation bei Gläsern mit Oberflächen-Kristallisationskeimen im System MgO-CaO-Al2O3-SiO2, wobei Anorthit- und Diopsidkristalle ausgeschieden werden. Die anhand der Kissinger-Gleichung erhaltenen Werte für die Aktivierungsenergie der Kristallisation sind vergleichbar mit denen, die von anderen Autoren für ähnliche Glassysteme erhalten wurden: 90–150 kcal/mol. Die Ergebnisse der kinetischen Analyse mittels der Einfach-Kristallisationspeak Methode sollten korrigiert werden, indem man die Dimensionalität des Kristallwachstums berücksichtigt.
    Notes: Abstract The paper investigated, by means of thermal analysis measurements, the validity of three different methods for the evaluation of the activation energy of crystallization for surface nucleated glasses belonging to the MgO-CaO-Al2O3-SiO2 system, separating anorthite and diopside crystals. The values obtained from Kissinger equation of the activation energy for crystallization are comparable with those obtained by other authors for similar glassy systems, 90 to 150 kcal/mol. The results of the kinetic analysis using single-crystallization-peak method should be corrected taking into account the dimensionality of crystal growth.
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  • 66
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    Journal of thermal analysis and calorimetry 38 (1992), S. 2669-2682 
    ISSN: 1572-8943
    Keywords: kinetics ; pesticides ; thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels simultanen TG-DSC-Messungen und kinetischen Berechnungen bei der DTG-Technik wurde eine thermische Analyse einiger Pestizide durchgeführt. Mit dieser Methode wurde versucht, Verbindungen mit ähnlichen Strukturen anhand der Form und Anzahl von Peaks ihrer thermoanalytischen Kurven zu gruppieren und ihre Eigenschaften mittels thermodynamischen und kinetischen Mengen zu charakterisieren. Geringe Änderungen in der Struktur der Komponenten einer Klasse verursachen größere Veränderungen der thermodynamischen und kinetischen Größen, was in enger Übereinstimmung mit den beobachteten Unterschieden ihrer biologischen Aktivität steht.
    Notes: Abstract The thermal analysis of some pesticides using simultaneous TG-DSC measurements and kinetic calculations by the dynamic TG technique have been carried out. With this technique it was attempted to group compounds with similar structures according to the shape and number of peaks of their thermoanalytical curves and to characterize their features by means of thermodynamic and kinetic quantities. Small variations in the structure of the components of a class make larger variations in the thermodynamic and kinetic values being in close agreement with the observed differences in their biological behaviour.
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  • 67
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    Journal of thermal analysis and calorimetry 38 (1992), S. 267-275 
    ISSN: 1572-8943
    Keywords: kinetics ; poly(chlorethyl methacrylates)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels TG wurde in Gegenwart und in Abwesenheit von Sauerstoff die Kinetik des thermischen Abbaues von Poly(2-mono, 2,2-di- und 2,2,2-trichlorethylmethacrylat) und des nichtchlorierten Poly(ethylmethacrylat) untersucht. Die mit der Flynn-Wall Methode bestimmte Gesamtenergie des thermischen Abbaues steigt mit wachsendem Chlorgehalt des Polymers, wenn der Abbau ohne Sauerstoff erfolgt. In Gegenwart von Sauerstoff wird dieser Trend genau umgekehrt. Mittels DTG konnten die zwei wichtigsten nichtoxidativen Thermolysereaktionen, Depolymerisierung und Vernetzung, als kompetitive Reaktionen nachgewiesen werden. Ganz allgemein wird die thermische Stabilität der untersuchten Polymere durch Sauerstoff herabgesetzt.
    Notes: Abstract The thermal degradation kinetics of poly(2-mono-, 2,2-di- and 2,2,2-trichlorethyl methacrylate) and of the non-chlorinated poly(ethyl methacrylate) were studied by TG in the absence and presence of oxygen. The overall thermal degradation energy, determined by the Flynn-Wall method, increases with increasing chlorine content of the polymer when the degradation is performed in the absence of oxygen, while the trend is reversed in the presence of oxygen. Competition between the two major non-oxidative thermolysis reactions, depolymerization and crosslinking, could be monitored by DTG. Generally, the thermal stability of the investigated polymers is reduced by oxygen.
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  • 68
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    Journal of thermal analysis and calorimetry 38 (1992), S. 391-396 
    ISSN: 1572-8943
    Keywords: intensive heating and cooling method and technique ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird eine neue Methode und ein neues Verfahren von thermoanalytischen Versuchen zur Untersuchung thermischer Zersetzungsprozesse sowie auch zur Bestimmung kinetischer und thermophysikalischer Eigenschaften von Feststoffen und Flüssigkeiten bei intensivem Erhitzen oder Abkühlen beschrieben.
    Notes: Abstract A new method and technique of TA-experiment are suggested for investigating thermal decomposition processes, as well as for determining kinetic and thermophysical characteristics of solid and liquid substances under conditions of intensive heating or cooling.
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  • 69
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    Journal of thermal analysis and calorimetry 38 (1992), S. 421-428 
    ISSN: 1572-8943
    Keywords: kinetics ; meso lithium potassium tartrate dihydrate ; molten hydrated salt
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Meso-Lithiumkaliumtartrat-Dihydrat schmilzt noch vor der Dehydratation, eine kinetische Untersuchung dieser Reaktion wurde vollzogen. Dieses System ist interessant für die Abschätzung kinetischer Parameter von Prozessen mit gleichbleibender Geschwindigkeit ohne Gegenwart zugesetzter Lösungsmittel. Die Ergebnisse sind von Interesse bei überlegungen zu Mechanismen von Feststoffreaktionen oder Reaktionen im kondensierten Zustand, bei denen Schmelzen als Möglichkeit auftritt. Die Freisetzung der ersten 1.2 H2O aus den Einkristall-Dihydratreaktanden ist eine Reaktion nullter Ordnung, anschlie\end wird die Geschwindigkeit verlangsamt und unterliegt bis 1.6 H2O einem Ausdruck erster Ordnung. Der Vorgang weist eine hohe Aktivierungsenergie auf: 23010 kJ/mol (bei 350–380 K). Die Freisetzung des restlichen Wassers erfolgt in einer langsameren Reaktion erster Ordnung, man erhält das wasserfreie Salz. Die Dehydratation von zerkleinerten pulverisierten Reaktanden verlief anfangs relativ schneller, verlangsamt dann jedoch ganz und gar und unterliegt einer ersten Reaktionsordnung. Es wird geschlu\folgert, da\ die Dehydratation des Salzes durch die Freisetzungsgeschwindigkeit des Wassers an der Oberfläche kontrolliert wird, wobei das Wasser innerhalb der Reaktionsschmelze relativ beweglich ist.
    Notes: Abstract Meso lithium potassium tartrate dihydrate melted before dehydration and a kinetic study of this reaction has been completed. This system is of interest in establishing the kinetic characteristics of a homogeneous rate process in the absence of added solvent. Results are of interest in considering the mechanisms of solid or condensed state reactions where melting is a possibility. The evolution of the initial 1.2H2O from the single crystal dihydrate reactants was zero order, the rate then became deceleratory and the first order expression was obeyed to 1.6H2O. The activation energy of the process was high, 230±10 kJ mol−1 (350–380 K). Evolution of the remaining water occurred by a slower first-order process to give the anhydrous salt. The dehydration of crushed powder reactant was initially relatively more rapid but was deceleratory throughout, obeying the first order equation. It is concluded that salt dehydration is controlled by the rate of surface release of water that is comparatively mobile within the reactant melt.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 429-435 
    ISSN: 1572-8943
    Keywords: compensation effect ; experimental conditions ; kinetics ; NaHCO3 ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels TG wurden sowohl bei konstanter als auch bei linear ansteigender Temperatur die Arrheniusschen Konstanten und das Kinetikgesetz der thermischen Zersetzung von Natriumhydrogencarbonat bestimmt. Dabei wurde der Einflu\ der Probengrö\e (0.5–10mg) und der Partikelgrö\e auf das Geschwindigkeitsverhalten untersucht. Mit Proben kleiner als etwa 5 mg ist der Einflu\ der Aufheizgeschwindigkeit nicht so gro\, wie bei grö\eren Proben. Die ermittelten Arrheniusschen Parameter und das ermittelte Kinetikgesetz, bestimmt mittels der Methode von Ozawa, stehen in ausgezeichneter übereinstimmung mit den isotherm ermittelten Resultaten. Die Aktivierungsenergie E bei einer Probe mit einer Masse von etwa 1 mg war nahezu konstant, unabhängig vom Reaktionsgrad. Jede änderung des Arrheniusschen Parameters infolge von veränderten Versuchsbedingungen wurde in Verbindung mit dem kinetischen Kompensationseffekt diskutiert.
    Notes: Abstract The Arrhenius parameters and kinetic obedience were determined by TG at constant temperatures as well as at linearly increasing temperatures for the thermal decomposition of sodium hydrogencarbonate. Effects of the sample size (0.5–10 mg) and the particle size on the rate behavior were examined. With such a sample size smaller than ca. 5 mg, an effect of the heating rate was not so critical as is the case with the larger sample size. The Arrhenius parameters and kinetic obedience determined by use of the Ozawa method were in excellent agreement with those determined isothermally. The activation energyE determined with ca. 1 mg of sample was nearly constant independently of the fractional reactiona. Any change in the Arrhenius parameters with different experimental conditions was dicussed in connection with the kinetic compensation effect.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 575-582 
    ISSN: 1572-8943
    Keywords: kinetics ; shapes of TG curves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Unter theoretischen Aspekten bezüglich derjenigen Faktoren, die die experimentelle Auflösung thermogravimetrischer Kurven beeinflussen, wird ein möglicher Weg zur Steigerung der Genauigkeit thermogravimetrischer Untersuchungen diskutiert.
    Notes: Abstract From a theoretical consideration concerning the factors affecting the experimentally resolved shapes of thermogravimetric curves, the possible way to increase the accuracy of the thermogravimetric measurements were discussed.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 935-941 
    ISSN: 1572-8943
    Keywords: kinetics ; solid-solid reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein Modell zur Beschreibung des einleitenden Schrittes von diffusionskontrollierten Feststoffreaktionen beschrieben. Die erhaltene kinetische Gleichung wurde zur Bestimmung der Aktivierungsenergie der Reaktion LiCl(s) + NaF(s)=LiF(s) + NaCl(s) aus DTA-Daten angewendet.
    Notes: Abstract A model describing the initial step of diffusion-controlled solid-solid reactions is presented. The kinetic equation obtained was used to evaluate the activation energy of the reaction LiCl(s)+NaF(s)=LiF(s)+NaCl(s) from DTA data.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 929-933 
    ISSN: 1572-8943
    Keywords: integral methods ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Integrationsmethoden zur Berechnung kinetischer Parameter von heterogenen Reaktionen unter nicht isothermen Bedingungen werden im allgemeinen nach der Methode der kleinsten Quadrate erarbeitet und der ermittelte Korrelationskoeffizient dient als ein Kriterium für die Auswahl der besten Integrationsmethode. Mittels drei verschiedenen Integrationsmethoden wurde eine Analyse verschiedener experimenteller Daten durchgeführt. Die Ergebnisse zeigen, daß dieses Kriterium allein nicht ausreicht, um ausreichende Informationen über die kinetischen Parameter zu liefern. Es scheint deshalb, daß die Verwendung der einen oder anderen Integrationsmethode einfach eine Wahl des Anwenders darstellt.
    Notes: Abstract The integral methods proposed to compute the kinetic parameters of heterogeneous reactions under non-isothermal conditions are usually worked by the help of the least squares method and the obtained correlation coefficient is taken as a criterion to choose the best integral method. An analysis of several experimental data by mean of three different integral methods was performed by us and the results pointed out that this criterion, by itself, is not enough to provide reliable information on the kinetic parameters. It appears, thus, that the use of an integral method or another is a simple matter of researcher's choice.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 953-959 
    ISSN: 1572-8943
    Keywords: kinetics ; poly(di-n-alkyl itaconates) ; thermal stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels nichtisothermer und auch isothermer TG wurde die nichtoxidative thermische Zersetzungskinetik von Poly(di-n-alkylitakonaten) untersucht, dabei bewegt sich die Länge der Alkylkette von Methyl bisn-Oktyl. Die Aktivierungsenergie der thermischen Zersetzung und die charakteristischen Masseverlusttemperaturen nehmen mit steigender Substituentlänge ab. Aussehen der DTG-Kurven hängt von der Größe der Alkylkette ab. Die verschiedenen DTG-Maxima wurden verschiedenen Initiierungs schritten der Depolymerisierung zugeschrieben. Man fand, daß im Intervall Mw zwischen 104 und 107 g·mol die thermische Stabilität der Poly(di-n-hexylitakonate) unabhängig von der anfänglichen molaren Masse der Probe ist.
    Notes: Abstract The non-oxidative thermal degradation kinetics of poly(di-n-alkyl itaconates), ranging from the methyl to then-octyl derivatives, were studied by non-isothermal and isothermal TG. The thermal degradation activation energy and characteristic mass loss temperatures were found to decrease with increasing substituent size. The shapes of the DTG curves were dependent on the size of the alkyl substituent. The different DTG maxima were ascribed to various modes of initiation of depolymerisation. The thermal stability of poly(di-n-hexyl itaconate) was found to be independent of the initial molar mass of the sample in the range ofM w from 104 to 107 g/mol.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 981-988 
    ISSN: 1572-8943
    Keywords: kinetics ; mineral salts ; rapid TA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Für thermische Zersetzung und Synthese von Mineralsalzen wurden die kinetischen Kurven unter den Bedingungen schnellen Aufheizens in Annäherung der Aufheizbedingungen in einem Niedertemperatur-Plasmastrom ermittelt. Die kinetischen Eigenschaften wurden zur Berechnung der Umwandlungen bei einem chemischen Plasmareaktor verwendet.
    Notes: Abstract Kinetic curves of thermal decomposition and synthesis of mineral salts are obtained in the conditions of rapid heating approaching the heating conditions in a low-temperature plasma flow. The kinetic characteristics are used in calculations of transformations in the path of a chemical plasma reactor.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1509-1524 
    ISSN: 1572-8943
    Keywords: kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Cu(II)-komplexe von Acenaphthoquinonmono-(4-methyl-quinolinyl)-hydrazon (AMH) der allgemeinen Zusammensetzung [CuLX2] (mitL=AMH;X=Cl, Br, I, OAc oder NO3) -ausgenommen die Sulfato-komplexe, die über die allgemeine Zusammensetzung [CuLSO4]2 verfügen — wurden hergestellt und mittels Elementaranalyse, Messungen des magnetischen Momentes, Leitfähigkeitsmessungen, IR, elektronen- und EPR-spektroskopischen Techniken und durch Thermoanalyse untersucht. Für alle Komplexe wurde eine planare Geometrie gefunden. Die TG-Kurven zeigen, daß die Komplexe in einem Schritt zersetzt werden, wobei am Ende dieses Schrittes CU2O gebildet wird.
    Notes: Abstract A software is described enabling kinetic analysis under non-isothermal or isothermal conditions from DSC, or from TG data. The program offers thirteen methods of kinetic analysis for DSC, three for isothermal analysis and two for TG, with eight different functions for the choice of the proper mechanism for each of them.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1949-1957 
    ISSN: 1572-8943
    Keywords: alloys ; heat-flux differential scanning calorimetry ; kinetics ; metals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird ein allgemeine mathematische Behandlung von Wärmefluß-DSC gegeben. Es verbindet Gleichungen für den Wärmetransport in der Kalorimeterzelle mit einer Annäherung der Verfestigung von Metall oder Legierung, die in diesem Gerätetyp durchgeführt werden. Es werden die Unterschiede zwischen: Temperaturevolution, Kinetik latenter Wärme und Unterkühlungsevolution innerhalb der Probe und zwischen: Temperaturevolution, aufgezeichnetes Signal und gemessene Unterkühlung an der Monitorstation diskutiert.
    Notes: Abstract A general mathematical treatment for heat-flux differential scanning calorimetry is given. It combines equations derived for heat transfer in the calorimeter cell with an approach to the solidification of metal or alloy carried out in this type of instrument. The differences are discussed between temperature evolution, kinetics of latent heat and undercooling evolution within the sample, and temperature evolution, recorded signal and measured undercooling at the monitoring station.
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    Journal of thermal analysis and calorimetry 38 (1992), S. 1979-1988 
    ISSN: 1572-8943
    Keywords: cellulase complex ; enzymatic activities ; flow-microcalorimetryl ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird eine Methode zur Bestimmung der enzymatischen Aktivität des Trichoderma viridae Zellulase Komplexes beschrieben. Dazu wurde ein LKB 2277 Thermoaktivitätsmonitor und ein kontinuierlicher Flüsigkeitsmischer verwendet. Bei der Bestimmung der enzymatischen Aktivität von Proben des rohen Zellulasekomplexes wurden drei Substanzen verwendet: Zellobiose, Karboxymethylzellulose (CMC) und Hemizellulose. Anhand der Ergebnisse wurden einige kinetische Parameter für die Zellobiaseaktivität ermittelt. Außerdem wurde eine Endprodukt-Inhibition von Zellobiase sowie Karboxymethylzellulaseaktivität durch Glukose beobachtet. Das beschriebene Verfahren erlaubt eine direkte Bestimmung der verschiedenen Enzymaktivitäten des Zellulasekomplexes. Wegen ihrer hohen Empfindlichkeit und Einfachheit handelt es sich hier um ein sehr nützliches Werkzeug zur Untersuchung des Zellulasekomplexes, indem die optimalen Bedingungen für die enzymatische Spaltung zelluloser Substanzen bestimmt und verschiedene Mechanismen von Feedback-Kontrolle durch die Produkte der Enzymtätigkeit beobachtet werden. Das Verfahren trägt vollkommen allgemeinen Charakter und kann auch bei anderen Ezymsystemen Anwendung finden.
    Notes: Abstract A method for measuring enzymatic activities of the Trichoderma viridae cellulase complex is described. The LKB 2277 Thermal activity monitor and a flow-mix mode were used. Enzymatic activities of samples of a crude cellulose complex have been determined using three substrates: cellobiose, carboxymethyl cellulose (CMC) and xylan. Some kinetic constants for cellobiase activity have been evaluated from the obtained results. A process of the end-product inhibition of cellobiase resp. carboxymethyl cellulase activity by glucose has been observed too. The described method allows a direct determination of various enzymatic activities of the cellulase complex. Because of the high sensitivity and the simplicity, the method is a very suitable tool for studying the cellulase complex, determining the optimal conditions of enzymatic break-down of the cellulosic materials and observing various mechanisms of the feed-back control by products of enzymatic action. The procedure is completely general in nature and is applicable to other enzymatic systems.
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    Journal of thermal analysis and calorimetry 39 (1993), S. 87-95 
    ISSN: 1572-8943
    Keywords: gamma radiation effects ; graphite-hematite system ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels isothermer und dynamischer TG wurde im Graphit-Eisen(III)oxidsystem in Luft der Einfluß von60Co-Gammastrahlung und von verschiedenen Probenzusammensetzungen auf die Reduktion von Hämatit zu Eisen untersucht. Entsprechend verschiedener theoretischer Modelle heterogener Reaktionen wurde eine kinetische Analyse der isothermen Daten durchgeführt und die Ergebnisse zeigten, daß das dreidimensionale Phasengrenzenmodell die beste Übereinstimmung liefert. Die Analyse der dynamischen TG-Daten wurde mittels der Integralmethode von Ozawa, der Coats-Redfem-Methode und einer zusammengesetzten Methode auf der Grundlage der modifizierten Coats und Redfern Gleichung durchgeführt. Die Aktivierungsparameter wurden berechnet und die Ergebnisse der verschiedenen Methoden miteinander verglichen und diskutiert. Strahlung scheint keine Änderung des Reaktionsmodelles oder des Mechanismus hervorzurufen. Durch Bestrahlung gibt es aber ein Absinken der Aktivierungsenergie und des Frequenzfaktors sowie ein Absinken der Halbwertszeit der Reaktion, was bei höheren Temperaturen und höherer Dosis bemerkenswert groß ist.
    Notes: Abstract The effects of60Co-gamma radiation and of various sample composition on the reduction of hematite to iron in the graphite-iron(III) oxide system in air were studied using isothermal and dynamic TG techniques. Kinetic analysis of isothermal data were performed according to various theoretical models of heterogeneous reactions and the results showed that the three-dimensional phase boundary model gives the best fit of data. Analysis of dynamic TG data were made using Ozawa integral method, Coats-Redfern method and a composite method based on the modified Coats and redfern equation. The activation parameters were calculated and the results of the different methods were compared and discussed. Radiation apparently did not introduce a change in the reaction model or mechanism. However, there is a decrease in activation energy and frequency factor upon irradiation and a decrease in the half-life time of the reaction which is remarkable at the higher temperatures and higher doses.
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    Journal of thermal analysis and calorimetry 39 (1993), S. 217-220 
    ISSN: 1572-8943
    Keywords: DSC ; edible oils ; isothermal method ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Unter Einsatz der isothermen Methode wurden kinetische Untersuchungen der thermooxidativen Zersetzung einiger Speiseöle durchgeführt. Zur Bestimmung des Umwandlungsgrades wurde ein DS-Kalorimeter von DuPont eingesetzt. Grundlage der Untersuchung bildeten Leinöl, Rizinusöl und Olivenöl.
    Notes: Abstract The thermooxidative decompositions of some edible oils were investigated. Isothermal measurements of convention were made with a Du Pont differential scanning calorimeter. Linseed oil, castor oil, olive oil and cod-liver oil were investigated.
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    Journal of thermal analysis and calorimetry 39 (1993), S. 351-358 
    ISSN: 1572-8943
    Keywords: epoxy resin ; kinetics ; polyamide hardener
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Mittels DSC wurde die Optimierung des Einsatzverhältnisses von Epoxidnovolackharz Dobeckot E4 und Polyamidhärtungsmittel EH411 durchgeführt. Die Daten ergaben, daß ein Harz-Polyamid-Verhältnis von 100∶40 bzw. 100∶50 das Optimum zu sein scheint, bei dem die Aushärtung am größten ist. Mittels isothermer und dynamischer DSC-Methoden wurden die kinetischen Parameter für diese Ansätze ermittelt. Unter Anwendung der isothermen DSC-Methode im Temperaturbereich 70°–90°C wurde die Geschwindigkeitskonstante für den Aushärtungsprozeß dieser Ansätze ermittelt. Diese wurden mittels Extrapolation der erhaltenen Angaben für höhere Temperaturen auch für die Temperatur 201°C (Raumtemperatur) vorhergesagt. Vorhergesagte und experimentell ermittelte Werte stehen in guter Übereinstimmung zueinander.
    Notes: Abstract The optimization of proportions of novolac epoxy resin, Dobeckot E4 and polyamide hardener, EH411 has been established by DSC and the data indicates that resin-polyamide, 100∶40 and 100∶50, appear to be optimum where ‘extent of cure’ is maximum. The kinetic parameters for these formulations have been evaluated using isothermal and dynamic modes by employing DSC. The rate constants have been evaluated for curing process of these formulations using isothermal DSC mode in the temperature range of 70°–90°C. These have also been predicted at 20°±1°C (room temperature) by extrapolating the data obtained at elevated temperatures. A comparison of the predicted values with the experimental values shows that there is a good agreement between them.
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  • 82
    ISSN: 1573-4889
    Keywords: tantalum alloy ; oxygen ; dissolution ; kinetics ; oxides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Oxygen was added to T-111 (Ta-8W-2Hf, wt.%) at 820 and 990°C at an oxygen pressure of about 3×10−4 Torr (4×10−2N/m2). The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at% oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990°C. The vaporization of WO3 has no apparent affect on the doping reaction.
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  • 83
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    Oxidation of metals 11 (1977), S. 127-132 
    ISSN: 1573-4889
    Keywords: Duplex oxides ; copper oxidation ; kinetics ; oxygen partitioning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The theory for the growth of a double oxide layer proposed by Yurek, Hirth, and Rapp, has been applied to copper using experimental rate-constant data obtained by Valensi. Calculated thicknesses of the layers agree very well with experimentally measured values.
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  • 84
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    Oxidation of metals 9 (1975), S. 459-472 
    ISSN: 1573-4889
    Keywords: Cr ; oxidation ; kinetics ; Cr2O3 grain size ; short-circuit diffusion ; surface ; preparation ; Fe-Cr
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Cr was oxidized in 1 aim O2 at 980, 1090, and 1200°C. ElectropolishedCr and some orientations of etched Cr oxidize rapidly and develop compressive stress in the growing Cr2O3; other orientations oxidize slowly, apparently free of stress. SEM examination of fracture sections shows that the thick oxide is polycrystalline whereas the thin oxide on etched Cr is monocrystalline. It is deduced that the monocrystalline oxide grows by lattice diffusion of cations outward, and the polycrystalline layer by the two-way transport of cation diffusion outward and anion diffusion inward along oxide grain boundaries. The consequent formation of oxide within the body of the polycrystalline layer generates compressive stress and leads to wrinkling by plastic deformation. The activation energy for oxidation of Cr by cation lattice transport is 58 kcal/mole. Polycrystalline Cr2O3 forms on Fe-26Cr alloy, whether electropolished or etched; oxidation is accordingly rapid and accompanied by compressive stress.
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  • 85
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    Molecular and cellular biochemistry 131 (1994), S. 43-47 
    ISSN: 1573-4919
    Keywords: angiotensinogen ; kinetics ; recombinant protein ; renin ; species specificity ; transgenic mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: 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.
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  • 86
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    Biochemical genetics 15 (1977), S. 1113-1124 
    ISSN: 1573-4927
    Keywords: cytoplasmic male sterility ; maize ; mitochondria ; cytochrome oxidase ; succinate dehydrogenase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The mechanism of cytoplasmic male sterility was investigated in maize by isolating mitochondria from seedlings and various anther stages and analyzing cytochrome oxidase and succinic dehydrogenase biochemically and electrophoretically. Sterile anthers exhibited a lack of biochemical activity and fewer isozymatic bands for cytochrome oxidase. No apparent differences were detected biochemically or electrophoretically between fertile and sterile anthers for succinate dehydrogenase.
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    Biochemical genetics 15 (1977), S. 509-519 
    ISSN: 1573-4927
    Keywords: anthocyanin biosynthesis ; flavonoid ; maize ; pigment genes ; UDPG ; flavonol glucosyltransferase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The enzyme UDPglucose:flavonol 3-O-glucosyltransferase is shown to be under the coordinate control of three genes involved in anthocyanin biosynthesis in the aleurone of maize: C, R, and Bz. Of the three, Bz appears to be the structural gene. Data presented here (dosage comparisons, induction in the mutant c-p, and effect of paramutation at R) indicate that the enzyme is inducible by substances resulting from the action of the C and R genes and that active forms of C and R are required for this induction. Mechanisms of regulation of the Bz gene by C and R are discussed.
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    Biochemical genetics 17 (1979), S. 1173-1180 
    ISSN: 1573-4927
    Keywords: gene duplication ; alcohol dehydrogenase ; electrophoretic mobility mutants ; maize
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The alcohol dehydrogenase-1 FC m (Adh-FC m ) duplication in maize was subjected to ethyl methanesulfonate (EMS) mutagenesis. Of the mutants recovered, eight produced ADH polypeptides with altered electrophoretic mobility. Four produced new mobilities of the progenitor F with no change of the Cm molecule; the remainder altered only the Cm enzyme. No cases were found in which the electrophoretic mobilities of the two types of subunits were simultaneously altered, and no complete nulls lacking both F and Cm were recovered. These observations confirm the duplicate nature of the FCm complex.
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  • 89
    ISSN: 1573-4927
    Keywords: mutator ; transposable element ; alcohol dehydrogenase ; maize ; gene expression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A secondary mutant, derived from an allele of maize alcohol dehydrogenase 1 (Adh1) carrying a Mutator transposable element (Mu1) in its first intron, was reported to exhibit a threefold decrease in ADH enzymatic activity and steady-state RNA levels compared to the original mutant. The original mutant,Adh1-S3034 (abbreviatedS3034), was previously characterized at the molecular level. The derivative, abbreviatedS3034b, has now been cloned; at the DNA sequence level the insertion and surroundingAdh1 sequences are indistinguishable fromS3034. Furthermore, in our lines there is no difference in relative ADH activities between products of the two putative alleles. A comparison of gene expression in heterozygotes obtained by crossing to different tester lines reveals a correlation between the measured decrease in levels of ADH polypeptide produced by the mutant allele and the background in which it is measured; this effect is distinct from any background-related variation in the expression of the progenitor allele. It does not appear to be attributable to alternative patterns of DNA modification. It appears to reflect a background-associated difference in the level of normalAdh1-RNA produced. Thus the previously reported distinction betweenS3034 andS3034b may be due to differences in the extent to which the mutant allele and a given genetic background interact to produce functionalAdh1-RNA.
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    Oxidation of metals 10 (1976), S. 85-95 
    ISSN: 1573-4889
    Keywords: boron carbide ; oxidation ; kinetics ; chromatography method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thermogravimetry and gas-adsorption chromatography were used to study the kinetics of formation of solid and gaseous products during the hightemperature oxidation of compact boron carbide in oxygen at 740 Torr. Oxidation resistance was observed at temperatures up to 1200°C. The main oxidation products were B2O3 and CO2. Oxidation was paralinear; the carbon consumption exceeded the consumption of boron as compared to the ratio of these elements in the compound B4C. This difference resulted in carbon depletion of the carbide layer in the substrate near the scale〉.
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  • 91
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    Oxidation of metals 10 (1976), S. 361-376 
    ISSN: 1573-4889
    Keywords: metals ; scale structure ; epitaxy ; kinetics ; diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An explanation of the deviation from the parabolic law is the treatment which considers both shortcircuit and lattice diffusion in the oxide scale. In this study we examine how the oxidation kinetics are influenced by changing the structure of the scale of copper oxide in order to confirm the role of short-circuit diffusion in determining the oxidation rate. In addition we explain the oxidation kinetics of copper and nickel by using a model of the scale structure which includes recrystallization and grain growth. Results are as follows: (1) The nucleation and growth behavior of oxide have a direct effect on the structure and in turn the oxidation kinetics due to short-circuit diffusion. (2) A modified treatment is valid in the region where volume diffusion and short-circuit diffusion play an important role in which it is necessary to consider the scale structure such as the grain size distribution and the boundary width. (3) When recrystallization takes place it is necessary to consider the model of a two-layered scale structure which is different in properties and morphology. (4) In this region the rate curves are S-shaped when oxide recrystallization takes place and exhibit a transition from a parabolic to an nth-power relationship (n〉2) when grain growth takes place.
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  • 92
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    Oxidation of metals 11 (1977), S. 225-239 
    ISSN: 1573-4889
    Keywords: tantalum ; oxidation ; high temperature ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of tantalum in oxygen-nitrogen and oxygen-inert gas mixtures at925°C has been studied. The oxygen pressure was close to 0.5 atm in all experiments, and partial pressures of the second component of from 0 to 180 Torr were employed. Spherical specimens were used to provide quantitatively significant kinetic data. A model has been proposed which suggests that the oxygen pressure at the reaction interface close to the metal surface is lower than the external pressure because of the finite permeability of the porous outer oxide layer, and that the inert gas effectively reduces the permeability. The model gives good quantitative agreement with the experimental results.
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    Oxidation of metals 11 (1977), S. 365-381 
    ISSN: 1573-4889
    Keywords: cobalt oxidation ; kinetics ; parabolic rate constant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Precise values of parabolic rate constants of cobalt oxidation have been determined over a wide range of temperature (950–1300°C) and oxygen pressure (6.58× 10−4−0.658 atm). The dependence of the calculated values of parabolic rate constants k″p on oxygen pressure and temperature can be described by the following empirical equation: $$k''_p = const. \cdot {\text{p}}_{O_2 }^{{\text{1/n}}} \cdot exp ( - {\text{E}}_{\text{k}} /RT)$$ The exponent 1/n decreases with an increase in temperature from 1/3.40 at 950°C to 1/3.96 at 1300°C, whereas the activation energy Ek decreases with an increase in the oxygen pressure from 41.7 to 38.1 kcal/mole.
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    Oxidation of metals 13 (1979), S. 77-88 
    ISSN: 1573-4889
    Keywords: BaTiO3 ; kinetics ; solid state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The solid-state reaction between barium carbonate and rutile powders to form barium metatitanate BaTiO3 was studied by thermogravimetric analysis, X rays, and microscopy. Phase-stability domains were drawn in a temperature— $${\text{p}}_{CO_2 } $$ , diagram. The dependence of the reaction kinetics on $${\text{p}}_{CO_2 } $$ , $${\text{p}}_{O_2 } $$ or $${\text{p}}_{N_2 } $$ is discussed. In particular, the rate continuously decreases when $${\text{p}}_{CO_2 } $$ , or $${\text{p}}_{N_2 } $$ increases, but it reaches a maximum as a function of $${\text{p}}_{O_2 } $$ .
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  • 95
    ISSN: 1573-4889
    Keywords: Cu-Si alloys ; oxidation ; kinetics ; silica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of Cu-Si alloys (containing up to 4.75 wt. % Si) in $${\text{p}}_{O_2 } $$ =0.01 atm from 800 to 1000°C has been investigated using thermogravimetry and other techniques. A 0.04% Si alloy followed a parabolic oxidation law with a rate similar to that of pure Cu. As the Si concentration increased the rate decreased and became irregular owing to SiO2 particles or flakes at the alloy-scale interface. It is considered that sintering of SiO2 particles and rupture of the sinter because of contraction during sintering are responsible for the irregular kinetics. A SiO2 layer forms directly on the 4.75% Si alloy which oxidizes uniformly. The SiO2 was always amorphous. In pure CO2 a similar pattern of amorphous SiO2 particles, flakes, and layers occurs.
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  • 96
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    Oxidation of metals 13 (1979), S. 283-298 
    ISSN: 1573-4889
    Keywords: oxidation ; surface alloys ; Fe-Cr alloys ; iron ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of several surface and bulk Fe-Cr alloys and iron at 300°C and 4×10−6 Torr oxygen was studied. The surface alloys were fabricated by implantation of 25 keV Cr ions into the outermost 300Å of polycrystalline iron samples. The oxide thickness as a function of oxygen exposure was obtained using proton-excited X-ray analysis, and composition profiles of oxide films were obtained using Auger electron spectroscopy and ion sputtering. The addition of Cr to Fe by surface and bulk alloying caused the oxidation rate to decrease and changed the oxidation kinetics from parabolic (for Fe) to logarithmic (for Cr concentrations ≥4.7at.%). Interpretation of the data in terms of simple oxidation theories indicates that the Cr additions may reduce the oxidation rate by altering the electronic properties of the metal-oxide interface.
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    Oxidation of metals 13 (1979), S. 255-272 
    ISSN: 1573-4889
    Keywords: oxidation ; Fe-C ; graphite deposition ; nonadherent oxide ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of Fe-C alloys containing 0.5 and 1.0% C was studied in 1 atm O2 at 700° C. The oxidation rate is considerably slower than for pure Fe. The oxide scale formed is detached, multilayered, and overoxidized, containing little or no FeO. A thin film of graphite was identified at the metal-oxide interface by electron diffraction. It is proposed that the slow oxidation and abnormal scale are caused by a residue of graphite left at the metal surface from the oxidation of Fe3C. This inhibition of the oxidation of Fe by carbon at 700°C is in contrast to the stimulation observed at 500°C.
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    Oxidation of metals 13 (1979), S. 301-309 
    ISSN: 1573-4889
    Keywords: NiO ; Electrical conductivity ; gas-solid equilibria ; kinetics ; equivalent circuit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In a previous work it has been stated that the NiO electrical conductivity changes connected to the oxygen pressure changes may be considered as a transitory phenomenon. A mixed kinetics case controlled by the formation of surface cation vacancies and their diffusion in the bulk is proposed to explain the reaction process. By means of an equivalent electrical circuit in good agreement with the kinetics model it was possible to reproduce the experimental phenomenon.
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    Oxidation of metals 13 (1979), S. 481-504 
    ISSN: 1573-4889
    Keywords: kinetics ; sulfidation ; Fe-Cr-Al alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of aluminium on the kinetics and mechanism of high-temperature sulfidation of Fe-Cr alloys containing 20 at.% chromium has been investigated. It has been found that the addition of aluminum greatly improves the scaling resistance of Fe-Cr alloys against attack by sulfur vapors at high temperatures.
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  • 100
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    Oxidation of metals 37 (1992), S. 65-80 
    ISSN: 1573-4889
    Keywords: internal oxidation ; kinetics ; alloys ; silver ; oxide particles ; coalescence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Gravimetric measurements at low temperatures (〈600°C) and for dilute Ag-Mg alloys have given further information about the mechanism of oxide formation. This investigation shows that the fixation rate of oxygen is very high, which assumes the existence of species in an oxidized form, including one or two magnesium atoms called “elementary species” and denoted as MgO* and Mg2O*. When there are no free magnesium atoms, there is a coalescence process with the fixation of oxygen atoms or MgO* and Mg2O*: this process leads to the formation of the first “clusters” including an oxygen excess. At low temperatures, the thermal fluctuations do not permit significant changes. There is no significant increase in cluster size, but a rearrangement of these clusters toward a compact structure with the release of excess oxygen. Their size is less than 1 nm.
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