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  • Articles  (536)
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  • kinetics  (286)
  • phosphorus  (250)
  • Springer  (536)
  • American Physical Society
  • 1995-1999  (536)
  • 1
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    Springer
    Journal of applied electrochemistry 29 (1999), S. 1171-1176 
    ISSN: 1572-8838
    Keywords: alloys ; cyclic voltammetry ; electrodeposition ; electroless deposition ; nickel ; phosphorus ; zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Electroless Ni–Zn–P alloy deposition from a sulphate bath, containing sodium hypophosphite as reducer, was investigated. To increase the plating rate, the deposition parameters were optimized. The effect of process parameters (T, pH and [Zn2+]) on the plating rate and deposit composition was examined and it was found that the presence of zinc in the bath has an inhibitory effect on the alloy deposition. As a consequence, the percentage of zinc in the electroless Ni–Zn–P alloys never reaches high values. Using cyclic voltammetry the electrodeposition mechanism of Ni–Zn–P alloys was investigated. It was observed that the zinc deposition inhibits the nickel discharge and, as a consequence, its catalytic activity on hypophosphite oxidation. It was also found that increase in temperature or pH leads to the deposition of nickel rich alloys.
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  • 2
    ISSN: 1572-8854
    Keywords: Octahedral ; phosphorus ; chloride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound [P(tpp)Cl2]+Cl− crystallizes in the space group P21/n witha=10.701(2),b=24.860(2),c=14.799(2), β=94.24(2)°,Z=4. The phosphorus atom has an octahedral coordination geometry formed by the four nitrogen atoms (Np) of the porphyrinato group and the two chloride ions. The average phosphorus-chloride distance is 2.150(1) Å, with phosphorus situated 0.006 Å below the porphyrin ring.
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  • 3
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    Journal of applied electrochemistry 27 (1997), S. 1198-1206 
    ISSN: 1572-8838
    Keywords: alloy ; amorphous ; anomalous ; hydrogen ; iron ; nickel ; phosphorus ; plating
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract In this study we have investigated the electrodeposition of amorphous iron–nickel–phosphorus alloys from a sulfate electrolyte. Fe-Ni alloys are known to exhibit an ’anomalous‘ type of plating behaviour in which deposition of the less noble metal is favoured. We have found that the codeposition of phosphorus from hypophosphite in the electrolyte led to a reversal to a ’normal‘ behaviour. This reversal was due both to the suppression of iron and enhancement of nickel partial currents. The overall deposition process is dominated by the hydrogen evolution reaction. This is exacerbated by the low pH needed to codeposit sufficient phosphorus to achieve an amorphous structure.
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  • 4
    ISSN: 1572-8838
    Keywords: alloys ; electroless ; microstructure ; morphology ; nickel ; phosphorus ; zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Electroless Ni–Zn–P alloy coatings were obtained on an iron substrate from a sulfate bath at various pH values. The effects of changes in bath pH on alloy composition, morphology, microstructure and corrosion resistance were studied. Scanning electron microscopy was performed to observe the morphological change of the deposits with bath pH. Coating crystallinity was investigated by grazing incidence asymmetric Bragg X-ray diffraction and transmission electron microscopy. A transition from an amorphous to polycrystalline structure was observed on increasing the bath alkalinity, and thus decreasing the phosphorus content of the alloys. A single crystalline phase corresponding to face-centred-cubic nickel was identified in the alloys obtained from a strong alkaline solution. An increase in zinc percentage up to 23% in the deposits does not change the f.c.c. nickel crystalline structure. Corrosion potential and polarization resistance measurements indicated that the corrosion resistance of electroless Ni–Zn–P alloys depends strongly on the microstructure and chemical composition. The deposits obtained at pH 9.0–9.5 and with 11.4–12.5% zinc and 11.8–11.2% phosphorous exhibited the best corrosion resistance.
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  • 5
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    Journal of applied electrochemistry 29 (1999), S. 191-200 
    ISSN: 1572-8838
    Keywords: cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
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  • 6
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    Journal of chemical crystallography 28 (1998), S. 69-72 
    ISSN: 1572-8854
    Keywords: Co(III) complex ; crystal structure ; kinetics ; steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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  • 7
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    Adsorption 1 (1995), S. 133-151 
    ISSN: 1572-8757
    Keywords: PSA process ; sensitivity ; equilibria ; kinetics ; heats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.
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  • 8
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    Adsorption 2 (1996), S. 265-277 
    ISSN: 1572-8757
    Keywords: frequency response ; diffusion cell ; kinetics ; diffusion ; heat effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with frequency response (FR) analysis of a closed diffusion cell system with two resonators, that is both the LHS and RHS volumes are modulated. The analysis is made for a homogeneous particle described by a single effective diffusivity as well as a biporous pellet described by macropore and micropore diffusions. It is shown that if the perturbation of the volume of the reservoir #2 is lagged behind that of the reservoir #1 by 3π/2, the pressure response in reservoir #1 is significantly enhanced with larger amplitude as well as phase angle. When the perturbations of the two reservoirs are out of phase, the heat effect is reduced and can become insignificant when the two perturbations are completely out of phase (ψ = π). Under such a condition, the pressure difference between the two reservoirs could be doubled. In the case of biporous pellets, it is shown that the FR behaviours obtained for micropore diffusion control and macropore diffusion control are well distinguished. In the former case, the FR system reduces to a traditional batch adsorber one while in the latter case, the FR behaviour is the same as for a two resonator system with homogeneous particles. This difference can be used for the discrimination of micropore and macropore diffusion processes.
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  • 9
    ISSN: 1572-8757
    Keywords: characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption equilibria and dynamics ofn-butane on two activated carbon samples prepared from the physical activation of nutshell are studied in this paper. The micropore size distribution (MPSD) is considered as the main source of solid heterogeneity. Lennard-Jones' potential theory and Dubinin's theory (TVFM) are used in the equilibria data to derive the MPSD, which is well fitted by a Gamma distribution function. The adsorption energy distribution derived from the MPSD is very asymmetric for both the samples studied, and this energy distribution used in the HMSD/HMSMD kinetics models for the study of adsorption dynamics ofn-butane.
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  • 10
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 11
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    Catalysis letters 37 (1996), S. 167-172 
    ISSN: 1572-879X
    Keywords: dissociation ; kinetics ; Co-Mo sulphide ; H2S
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, a high surface area 4Co∶6Mo∶100γ-Al2O3 sulphide prepared using precipitation from homogeneous solution (PFHS) has been used for the catalytic splitting of hydrogen sulphide into H2 and elemental sulphur. The activity of this new formulation was significantly better than previously reported recipes. Kinetic data collected over a wide range of H2S partial pressures between 883 and 983 K revealed that, although the decomposition followed a first-order law, a mechanism involving H2S adsorption on co-ordinative unsaturation sites of the Co-Mo sulphide catalyst gave a Langmuir-Hinshelwood rate expression that yielded satisfactory model parameters. In particular, the scission of the surface H-S bond appeared to be the rate determining step.
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  • 12
    ISSN: 1572-879X
    Keywords: selective catalytic reduction ; nitric oxide reduction ; phosphorus ; acid property
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract To examine the influence of phosphorus on the commercial V2O5(WO3)/TiO2 SCR catalyst, measurements were carried out by means of infrared and Raman spectroscopy, XPS, and NO reduction measurement as a function of phosphorus loading. Phosphorus added to the catalyst was found to disperse well over the catalyst without a significant agglomeration up to 5 wt% P2O5 addition. The number of the hydroxyl groups bonded to the vanadium and titanium species decreased readily with increasing amount of phosphorus. Correspondingly, the hydroxyl groups bonded to the phosphorus species were formed. NH3 adsorbed on both hydroxyl groups bonded to vanadium and phosphorus as ammonium ions, implying that the P–OH groups formed are also responsible for the Brønsted acidity. The NO reduction activity was found to be decreased with increasing amount of phosphorus; however, the influence of phosphorus was relatively small irrespective of the large amount of phosphorus addition. The deactivation might be caused by the change in the nature of the surface hydroxyl groups as Brønsted acid sites. Phosphorus species might partially wrap the surface V=O and W=O groups, which might also contribute to the deactivation.
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  • 13
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    Catalysis letters 37 (1996), S. 173-179 
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Measurements were performed of reaction rate in the process of ammonia synthesis (T=370–470°C) on doubly promoted (DP) (Al2O3, CaO) and triply promoted (TP) (K2O, Al2O3, CaO) iron catalysts. The latter were obtained by impregnation of the reduced and subsequently passivated DP precursors with alcoholic solution of KOH. The studies were carried out under high total pressure (10 MPa) in a wide range of ammonia partial pressure in the gas phase: from 0.25 to about 7 bar. The results are shown to be authoritative for the so-called kinetic regime. The effect of the presence of K+ cations in the catalyst was the stronger, as the temperature of the reaction was the lower and, in particular, the ammonia pressure in the gas phase the higher. The obtained results are in good accordance with the results of Somorjai's studies on activity of iron single crystal surfaces both clean and covered with (K+O) adlayer.
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  • 14
    ISSN: 1572-882X
    Keywords: accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.
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  • 15
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    Journal of solution chemistry 27 (1998), S. 1123-1138 
    ISSN: 1572-8927
    Keywords: Sol–gel processing ; hydrolysis ; condensation ; kinetics ; methoxydimethyloctylsilane ; copper nitrate hydrate ; phase diagram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction rate was determined for copper nitrate hydrate with methoxydimethyloctylsilane (MDOS) in methanol. The rate constants of hydrolysis and condensation were established by quantitative measurement of the product and Karl Fischer water determination. The reaction with the hydrated copper salt resulted in the phase separation of an insoluble product from the reaction mixture. The structure of the product was determined, by Fourier Transform Infrared Spectrometry (FTIR) and Nuclear Magnetic Resonance (NMR) to be a dimer of the MDOS. The results showed the alcohol, producing condensation reaction was negligible in the formation of the dimer. contrary to the case for the well-known reaction by trialkoxysilanes and tetraalkoxysilanes.
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  • 16
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    Cellulose 4 (1997), S. 1-5 
    ISSN: 1572-882X
    Keywords: paper ; degradation ; ageing ; kinetics ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
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  • 17
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    Cellulose 3 (1996), S. 243-267 
    ISSN: 1572-882X
    Keywords: aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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  • 18
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    Journal of inorganic and organometallic polymers and materials 8 (1998), S. 111-117 
    ISSN: 1572-8870
    Keywords: Organosiloxane ; kinetics ; poly(phenylmethylsiloxane) ; catalyst ; anionic ; ring-opening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is well known that the rate of polymerization for an anionic mechanism is dependent on the ability of the bulk material or solvent system to disassociate the ion pair at the propagating chain end. In the anionic ring-opening polymerization of cyclic organosiloxanes in particular, the larger and softer the counter ion, the more rapidly the reaction proceeds. A recently developed phosphazene initiator system provides a large, soft counter ion relative to other traditional initiators used for the polymerization of poly(dimethylsiloxane) (PDMS). This novel initiator system was used in this investigation for the ring-opening polymerization of tetraphenyltetramethylcyclotetrasiloxane (P4) and the reaction kinetics under bulk and solution conditions were investigated. The new initiator system showed a dramatic increase in the rate of polymerization over the conventional potassium hydroxide-catalyzed system. Furthermore, this initiator was sufficiently reactive to be useful for the ring-opening polymerization of P4 at 293 K.
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  • 19
    ISSN: 1572-8900
    Keywords: Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 20
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    Topics in catalysis 5 (1998), S. 133-147 
    ISSN: 1572-9028
    Keywords: NMR ; catalysis ; high pressure ; dynamic equilibria ; magnetization transfer ; sapphire tube ; gas phase ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract High resolution NMR techniques are applicable to a variety of aspects of catalysis. Methods for studying homogeneously-catalyzed systems under high gas pressure are described along with approaches for obtaining mechanistic and dynamic information. Many of the same techniques may be applied to heterogeneous catalysis by following the reaction chemistry by gas phase NMR.
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  • 21
    ISSN: 1572-9028
    Keywords: nonlinear temperature behavior ; Eyring plot ; modified Eyring plot ; selectivity ; selection process ; enantioselectivity ; selection level ; isoinversion principle ; isoinversion temperature ; inversion temperature ; kinetics ; catalysis ; asymmetric hydrogenation ; dihydroxylation ; cocyclization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.
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  • 22
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 23
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    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Keywords: furfural hydrogenation ; Cu/carbon catalysts ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
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  • 24
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    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Keywords: ammonia decomposition ; iron catalyst ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
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  • 25
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 26
    ISSN: 1572-8773
    Keywords: aromatic donor molecules ; horseradish peroxidase ; kinetics ; lactoperoxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Based on kinetic evidence, it has been shown for the first time that the mode of binding of aromatic donor molecules is similar in horseradish peroxidase and lactoperoxidase; also that the nature of the heme plays an important role in the reaction with hydrogen peroxide, and has no effect on the reaction of the intermediate compound II with aromatic substrates.
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  • 27
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    Catalysis letters 31 (1995), S. 431-438 
    ISSN: 1572-879X
    Keywords: partial hydrogenation of benzene ; production of cyclohexene ; kinetics ; reaction mechanism ; ruthenium catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method has been developed for direct measurement of reaction rates in a continuously operated slurry (CST-) reactor. In contrast to the usual procedure in a two-liquid-phase system the reactor contains only one liquid phase, an aqueous zinc chloride solution in which a ruthenium lanthanoxide catalyst is suspended. The selectivity of benzene hydrogenation with respect to cyclohexene is higher when the new one-liquid-phase procedure is applied. With decreasing degree of benzene conversion the selectivity with respect to cyclohexene approaches 100%. The conclusion is that cyclohexane is formed only by consecutive hydrogenation of cyclohexene.
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  • 28
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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  • 29
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    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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  • 30
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    Catalysis letters 55 (1998), S. 73-77 
    ISSN: 1572-879X
    Keywords: enantioselectivity ; hydrogenation of ethyl pyruvate ; Pt/alumina catalyst ; solvent effects ; kinetics ; solvent polarity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of solvent on the kinetics of enantioselective hydrogenation of ethyl pyruvate by Pt/Al2O3/dihydrocinchonidine is reported. In a non‐polar solvent, toluene, the reaction is approximately zero order in substrate at constant hydrogen pressure, while under the same conditions and at the same substrate concentration, in the polar solvents ethanol and propylene carbonate the reaction shows a first‐order substrate concentration dependence. Fits to a Michaelis–Menten rate expression show that these differences are the expression of the relative magnitudes of the adsorption term in the rate expression, which in turn reflects the influence of the solvent on the adsorption–desorption processes which take place at the catalyst surface.
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  • 31
    ISSN: 1572-879X
    Keywords: hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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  • 32
    ISSN: 1432-0789
    Keywords: Key words Phosphorus dynamics ; Olsen ; phosphorus ; Soil phosphorus fractions ; Manure ; Soybean-wheat rotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  Soil P availability and efficiency of applied P may be improved through an understanding of soil P dynamics in relation to management practices in a cropping system. Our objectives in this study were to evaluate changes in plant-available (Olsen) P and in different inorganic P (Pi) and organic P (P0) fractions in soil as related to repeated additions of manure and fertilizer P under a soybean-wheat rotation. A field experiment on a Typic Haplustert was conducted from 1992 to 1995 wherein the annual treatments included four rates of fertilizer P (0, 11, 22 and 44 kg ha–1 applied to both soybean and wheat) in the absence and presence of 16 t ha–1 of manure (applied to soybean only). With regular application of fertilizer P to each crop the level of Olsen P increased significantly and linearly through the years in both manured and unmanured plots. The mean P balance required to raise Olsen P by 1 mg kg–1 was 17.9 kg ha–1 of fertilizer P in unmanured plots and 5.6 kg ha–1 of manure plus fertilizer P in manured plots. The relative sizes of labile [NaHCO3-extractable Pi (NaHCO3-Pi) and NaHCO3-extractable P0 (NaHCO3-P0)], moderately labile [NaOH-extractable Pi (NaOH-Pi) and NaOH-extractable P0 (NaOH-P0)] and stable [HCl-extractable P (HCl-P) and H2SO4/H2O2-extractable P (resisual-P)] P pools were in a 1 : 2.9 : 7.6 ratio. Application of fertilizer P and manure significantly increased NaHCO3-Pi and -P0 and NaOH-Pi, and -P0 fractions and also total P. However, HCl-P and residual-P were not affected. The changes in NaHCO3-Pi, NaOH-Pi and NaOH-P0 fractions were significantly correlated with the apparent P balance and were thought to represent biologically dynamic soil P and act as major sources and sinks of plant-available P.
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  • 33
    ISSN: 1436-5073
    Keywords: aluminium oxide ; phosphorus ; XRF ; RBS ; FTIR
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Phosphorus-doped aluminium oxide thin films were deposited in a flow-type ALE reactor from AlCl3, H2O and from either P2O5 or trimethyl-phosphate. Structural information of the films was obtained from Fourier transform infrared (FTIR) spectra. Rutherford backscattering spectroscopy (RBS) was used to quantitatively determine the composition of the films. The P/Al intensity ratios calculated from X-ray fluorescence (XRF) results were in a linear relation with the P/Al concentration ratios calculated from RBS results. For comparison, the intensity ratios of the phosphorus peak (P=O) at about 1250 cm−1 and the aluminium peak (Al-O) at about 950 cm−1 were determined from the IR absorption spectra. The calibration of FTIR peak intensities was done by plotting the intensity ratios of phosphorus and aluminium peaks against the P/Al concentration ratios measured by RBS. FTIR gave also a linear calibration curve with RBS but the method is less suitable for routine analysis of P/Al ratio than XRF.
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  • 34
    ISSN: 1436-5073
    Keywords: kinetics ; rates ; integrating ratemeter ; optimization ; first-order
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The integrating ratemeter is used in concert with the two-rate parameter to form the integrating ratemeter two-rate parameter. Propagation of error theory is applied to the integrating ratemeter two-rate parameter to yield expressions for the precision of rates calculated from the integrating ratemeter two-rate parameter in terms of the precision of the rates measured with the integrating ratemeter. Simulations and experimental results show that in cases where the standard deviation of the rate is relatively constant, the optimum time to make a rate measurement using the integrating ratemeter is also the optimum time to measure either of the rates in the two-rate parameter. If either of the two rates comprising the two-rate parameter is measured at the optimum time, then the precision and accuracy of concentrations measured with this technique are optimized.
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  • 35
    ISSN: 1573-0417
    Keywords: diatoms ; eutrophication ; lake management ; paleolimnology ; British Columbia ; lakes ; phosphorus ; training sets
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Eighteen lakes were added to a published training set of 46 British Columbia (BC) lakes in order to expand the original range of total phosphorus (TP) concentrations. Canonical correspondence analysis (CCA) was used to analyze the relationship between diatom assemblages and environmental variables. Specific conductivity and [TP] each explained significant (P≤0.05) directions of variance in the distribution of the diatoms. The relationship between diatom assemblages and [TP] was sufficiently strong to warrant the development of a weighted-averaging (WA) regression and calibration model that can be used to infer past trophic status from fossil diatom assemblages. The relationship between observed and inferred [TP] was not improved by the addition of more eutrophic lakes, however the [TP] range and the number of taxa used in the transfer function are now superior to the original model. Diatom species assemblages changed very little in lakes with TP concentrations greater than 85 µg 1−1, so we document the development of a model containing lakes with TP≤85 µg 1−1. The updated model uses 59 training lakes and covers a range of species optima from 6 to 41.9 µg 1−1 TP, and a total of 150 diatom taxa. The updated inference model provided a more realistic reconstruction of the anthropogenic history of a highly eutrophic BC lake. The model can now be used to infer past nutrient conditions in other BC lakes in order to assess changes in trophic status.
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  • 36
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    Journal of paleolimnology 20 (1998), S. 47-55 
    ISSN: 1573-0417
    Keywords: diatoms ; spatial variability ; canonical correspondence analysis ; lake eutrophication ; transfer functions ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Diatom analyses were undertaken of sediment cores covering a range of water depths in a small eutrophic lake (Lough Augher, Co. Tyrone, N. Ireland). The significance of between-core variability in diatom relative frequency stratigraphy was assessed by Canonical Correspondence Analysis (CCA) where the ordination axes were constrained to external environmental variables (sediment depth, core location coordinates, water depth, effective fetch, distance-from-shore and distance-from-inflow). After the removal of the effect of sediment age by partialling it out, the resultant first two axes from the partial-CCA were significantly correlated with water depth and distance-from-shore, indicating non-uniform diatom stratigraphies across the lake. Despite this variability, all cores show the same succession of species and, therefore, record the eutrophication of the lake. Diatom-inferred total phosphorus (DI-TP) was inferred for six cores using weighted averaging regression and calibration. Apart from considerable differences of DI-TP in surficial sediment samples, there was good between-core repeatability of DI-TP profiles. These data support the use of DI-TP for establishing background nutrient concentrations for lakes, and associated implications for lake restoration schemes using single cores. Comparisons of DI-TP profiles and total diatom accumulation rate data for the individual cores indicate that diatom production peaked prior to the maximum TP concentrations in the lake.
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  • 37
    ISSN: 1573-0417
    Keywords: carbon isotopes ; diatoms ; lake management ; nitrogen isotopes ; phosphorus ; radium-226 ; sediments ; trophic state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract We explored the use of carbon and nitrogen isotopes (δ13C and δ15N) in sedimented organic matter (OM) as proxy indicators of trophic state change in Florida lakes. Stable isotope data from four 210Pb-dated sediment cores were compared stratigraphically with established proxies for historical trophic state (diatom-inferred limnetic total phosphorus, sediment C/N ratio) and indicators of cultural disturbance (sediment total P and 226Ra activity). Diatom-based limnetic total P inferences indicate a transition from oligo-mesotrophy to meso-eutrophy in Clear Lake, and from eutrophy to hypereutrophy in Lakes Parker, Hollingsworth and Griffin. In cores from all four lakes, the carbon isotopic signature of accumulated OM generally tracks trophic state inferences and cultural impact assessments based on other variables. Oldest sediments in the records yield lower diatom-inferred total limnetic P concentrations and display relatively low δ13C values. In the Clear, Hollingsworth and Parker records, diatom-inferred nutrient concentrations increase after ca. AD 1900, and are associated stratigraphically with higher δ13C values in sediment OM. In the Lake Griffin core, both proxies display slight increases before ~1900, but highest values occur over the last ~100 years. As Lakes Clear, Hollingsworth and Parker became increasingly nutrient-enriched over the past century, the δ15N of sedimented organic matter decreased. This reflects, in part, the increasing relative contribution of nitrogen-fixing cyanobacteria to sedimented organic matter as primary productivity increased in these waterbodies. The Lake Griffin core displays a narrow range of both δ13C and δ15N values. Despite the complexity of carbon and nitrogen cycles in lakes, stratigraphic agreement between diatom-inferred changes in limnetic total P and the stable isotope signatures of sedimented OM suggests that δ13C and δ15N reflect shifts in historic lake trophic state.
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  • 38
    ISSN: 1573-0417
    Keywords: diatoms ; Everglades ; phosphorus ; wetland ; calibration ; multivariate ; Florida
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract The relationship between diatom taxa preserved in surface soils and environmental variables at 31 sites in Water Conservation Area 2A (WCA-2A) of the Florida Everglades was explored using multivariate analyses. Surface soils were collected along a phosphorus (P) gradient and analyzed for diatoms, total P, % nitrogen (N), %carbon (C), calcium (Ca), and biogenic silica (BSi). Phosphorus varied from 315-1781 μg g-1, and was not found to be correlated with the other geochemical variables. Canonical correspondence analysis (CCA) was used to examine which environmental variables correlated most closely with the distributions in diatom taxa. Canonical correspondence analysis with forward selection, constrained and partial CCA, and Monte Carlo permutation tests of significance show the most significant changes in diatom assemblages along the P gradient (p 〈 0.01), with additional species differences correlated with soil C, N, Ca, and BSi. Weighted-averaging (WA) regression and calibration models of diatom assemblages to P and BSi were developed. The diatom-based inference model for soil [P] had a high apparent r2 (0.86) with RMSEboot = 218 μg g-1. Indicator diatom species identified by assessing species WA optima and WA tolerance to [P], such as Nitzschia amphibia and N. palea for high [P] (~1300-1400 μ g-1) and Achnanthes minutissima var. scotica and Mastogloia smithii for low [P] (~400-600 μg g-1), may be useful as monitoring tools for eutrophication in WCA-2A as well as other areas of the Everglades. Diatom assemblages analyzed by cluster analysis were related to location within WCA-2A, and dominant taxa within clusters are discussed in relation to the geochemical variables measured as well as hydrology and pH. Diversity of diatom assemblages and a ‘Disturbance Index’ based on diatom data are discussed in relation to the historically P-limited Everglades ecosystem. Diatom assemblages should be very useful for reconstructions of [P] through time in the Florida Everglades, provided diatoms are well preserved in soil cores.
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  • 39
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    Journal of paleolimnology 20 (1998), S. 31-46 
    ISSN: 1573-0417
    Keywords: phosphorus ; Lake Okeechobee ; lead-210 dating ; eutrophication ; phosphorus loading
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Phosphorus accumulation rates in depositional zone sediments of Lake Okeechobee were determined in 11 mud-zone cores and two peat-zone cores dated by 210Pb. Although difficulties were encountered in interpreting 210Pb data from some sites, reliable dating of sediments from the mud zone of this shallow lake is possible. Sediment accumulation rates in this zone have increased during the present century by an average of about twofold, and accumulation of organic sediments in the lake during pre-settlement times apparently was much slower than during the past century. Concentrations of all forms of sedimentary P but especially nonapatite inorganic-P and organic-P also have increased since pre-settlement times and especially since about 1940. Annual P accumulation rates in the lake's sediments have increased about fourfold during the 1900s, with most of the increase occurring in the past 40–50 years. The recent accumulation rate of sedimentary P (past ~ 10 years) agrees within a factor of 1.5 with the net retention of P in the lake calculated from published input-output mass balances.
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  • 40
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    Nutrient cycling in agroecosystems 41 (1995), S. 167-178 
    ISSN: 1573-0867
    Keywords: phosphorus ; workshop ; environment ; review
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A workshop was held in 1990 in Muscle Shoals, Alabama to discuss current and future research on phosphorus in agriculture. Twenty four presentations were given in areas ranging from basic to applied research. For five of the research areas presented at the workshop, this paper presents a literature review, a review of presentations at the workshop, and a discussion of future research ideas.
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  • 41
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    Nutrient cycling in agroecosystems 43 (1995), S. 109-115 
    ISSN: 1573-0867
    Keywords: phosphorus ; European network ; maintenance fertilization ; fixation capacity ; comparison of methods
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract After three years of a research network project on mineral phosphorus fertilization including five experimental fields located in Europe the first results are discussed. Crop response was very significant to TSP application in the alluvial calcareous polder soil of Netherlands, and in the brown silty acid soil of Scotland, both having a low level of P availability and a high fixation capacity. In the alluvial sandy loam on chalk in England, a response was observed to the first fertilization level equal to the previous crop export of phosphorus. In the brown sandy-silty soil on sand in Germany the highest rate of TSP led to a response in the third year. No effect on the final yields was observed in the brown silt loam of Belgium characterised by a textural B horizon with a high P fixation capacity. The critical values for phosphorus fertilization are discussed as the amount of P needed to maintain a target value of soil phosphorus. Concerning the supply of the different soils, no balance was reached in the Dutch and Scottish soils, a steady state was reached in the English soil with the return of the previous crop removal and the critical value for P was lower than the return of the previous crop export in the German and Belgian soils. According to the eight methods of P determination compared in the network, the P contents in the plow layer were raised in the soils of Netherlands, England and Scotland. They remained at the same level or fluctuated depending on the soil testing methods in Germany and in Belgium. High correlations exist between the different methods used in routine analysis, except for the calcium cloride and calcium acetate lactate method. Annual fluctuations in the soil P were detected at different depths depending on analytical methods and need further research.
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  • 42
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    Nutrient cycling in agroecosystems 43 (1995), S. 131-136 
    ISSN: 1573-0867
    Keywords: phosphorus ; titanium ; fertilizer efficiency ; plant nutrition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract To study the titanium effect on P nutrition, a greenhouse experiment withCapsicum annuum L., cv. Bunejo plants growing under differential P fertilization was conducted. All the plants were grown under identical conditions and they only differred in the P fertilization and in Ti supply. Plant biomass production of the Ti-untreated plants was affected by the diminution of the P-feed, but the plants growing under the lowest P supply did not showed any deficiency symptom during the crop cycle. All the Ti-treated plots showed a significative increase of the plant biomass against their corresponding untreated references. The biomass enhancement was mainly caused by the increase of the fruit yield with an absolute enhancement of 62% in the plants growing under the lowest P feed, and of 45% in the plants with a complete P support.
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  • 43
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    Nutrient cycling in agroecosystems 43 (1995), S. 209-215 
    ISSN: 1573-0867
    Keywords: phosphorus ; saturation ; inventory ; leaching ; eutrophication
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The last three decades, pig breeding has evolved towards a specialised, large scaled, land independent bio-industry in the province of West-Flanders. Subsequently, in certain regions, very high amounts of liquid pig manure are produced each year. This pig slurry is used as a fertilizer at a rate which very often exceeds normal agricultural practices. Because of the nonequilibrium between the phosphorus crop requirements and the P-inputs, phosphates accumulate in the soil. However, the phosphate sorption capacity of a soil is limited. Once the sorption capacity is exceeded, phosphates will start leaching through the soil profile. Since, during winter, in these areas, the groundwater table is situated at a depth of less than 1.0 m, phosphate breakthrough might take place. In the sandy loam soil region (± 1000 km2) of the province, an inventory of the P status of the soil was made. The region was sampled according to a regular grid with 2 km intervals. At random, some sample points were only 500 m apart. This resulted in a total of 296 samplings. In view of fertilizer recommendations, lactate extractable P of the plough layer (0-30 cm) was determined. A maximum value of 101 mg P 100 g−1 of air dry soil, a minimum value of 6 mg P 100 g−1 and a median value of 31 mg P 100 g−1 were found, indicating that for half of the spots monitored, the P status of the soil is high to very high. An oxalate extraction was done to investigate the phosphate saturation of the soil profile (0-90 cm). Based on a critical phosphate saturation degree of 30%, more than half of the soil profiles are phosphate saturated. Phosphate leaching at a rate higher than 0.1 mg ortho-P 1−1 at a depth of 90 cm can be expected. Therefore, a restriction of the P fertilization should be highly recommended. The geostatistical processing of the data using block kriging resulted in a spatial continuous estimate of the phosphate saturation degree. A good agreement was found between the pig density and the phosphate saturation degree of the soil profile.
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  • 44
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    Nutrient cycling in agroecosystems 45 (1995), S. 221-233 
    ISSN: 1573-0867
    Keywords: fertilizer recovery ; modelling ; nitrogen ; nutrient efficiency ; nutrient surplus ; phosphorus ; Poland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Research on nutrient losses from agricultural systems should try to relate these losses to farm characteristics. This was done for private farms in two districts in Poland. Using data from a farm survey, nutrient surpluses and Nutrient Use Efficiency (NUE, defined as the ratio of outgoing and incoming nutrients) were calculated for nitrogen and phosphorus. Both nutrient surplus and NUE are relatively high. A model was developed to estimate surpluses and NUE from farm characteristics like location, farm size, fertilizer application level, animal density, grass production and sugar beet or potato area. The results of the model are satisfying for nutrient surplus (R2=0.9) and nitrogen NUE (R2=0.4). Estimation of phosphorus NUE was not satisfactory. High surpluses are associated with high fertilizer applications, high animal density and high grass production while an increasing share of sugar beets leads to lower surpluses. A high nitrogen NUE is associated with low fertilizer applications, low animal density and little grass production, and with a high sugar beet area share. Results suggest that, with exception of sugar beet, fertilizer recovery in Poland is very low. Sugar beet, however, combines high fertilizer applications with low surpluses and high NUE. The outcome of the model can be used in the design of environmental policies. The paper ends with some remarks on the type of measures that can be taken, and the effects these will have on private farms in Poland.
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  • 45
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    Nutrient cycling in agroecosystems 46 (1996), S. 81-90 
    ISSN: 1573-0867
    Keywords: elemental sulfur ; granule size ; nitrogen ; phosphorus ; potassium ; S oxidation ; sulfur fertilizers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Experiments were undertaken to determine the effect of granule size and nutrients in granulated compound fertilizers fortified with finely divided elemental sulfur (So) on the rate of So oxidation. In one experiment, So was banded together with or apart from triple superphosphate (TSP) while in two others, So was granulated with nutrient and inert carriers. A fourth experiment examined response to S in an So-fortified TSP from a range of granule sizes. Response and, in some cases, So recovery (using 35S labels) by test crops (maize, wheat, upland rice) was measured. In all experiments, P mixed with So increased plant growth and S recovery above treatments in which P and So were physically separated. There was however, no effect of distance of separation on S recovery. In one experiment, N as urea and N and P as diammonium phosphate (DAP) were also found to enhance response to So although to a lesser degree than P alone. These observations were attributed to a nutritional requirement of So-oxidizing microorganisms for P and N. Granulation of So with carriers also influenced oxidation rate, as inferred from the fertilizer S recovery. For a given So concentration, the effect was inversely proportional to the mean diameter of granules. It is shown that this relationship can be explained if one assumes that So particles in granules collapse into a fixed number of aggregates per granule irrespective of granule size when the soluble nutrient carrier dissolves and diffuses away from the point of application.
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  • 46
    ISSN: 1573-0867
    Keywords: long-term experiments ; phosphorus ; rice ; nutrient balance ; phosphorus uptake ; fertilizer P response ; soil testing ; ion-exchange resin ; phosphorus supplying capacity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Data from long-term experiments at 11 sites in Asia with a wide range of nutrient input treatments and yield levels were used to quantify crop P requirements of rice (Oryza sativa L.) and the P balance in intensive, irrigated rice systems. Uptake of 1.8–4.2 kg P was required to produce one ton of grain yield. Physiological P use efficiency varied between 220 to 900 kg grain kg P-1. Without added P, there was a net loss of 7 to 8 kg P ha-1 per crop; with added P there was a net gain of 4 to 5 kg P ha-1 per crop. Phosphorus adsorption kinetics on mixed-bed ion-exchange resin capsules provided an integrative measure of soil P status, P diffusion, and acid-induced P solubilization. The resin capsule was a sensitive tool to characterize buildup or depletion of soil P as a result of different P balances. Both Olsen-P and the resin capsule were suitable methods to predict P uptake of tropical lowland rice. It is hypothesized that both methods measure a similar soil P pool which is soluble under alkaline, aerobic conditions but transformed into acid-soluble P froms as a result of submergence and reduction. Present recommendations for P fertilizer use on rice of 20–25 kg P ha-1 are adequate to maintain yields of 5–6 t ha-1, but sustaining higher yields of 7–8 t ha-1 will require farm-specific management strategies based on knowledge of the long-term P balance and soil P-supplying capacity.
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  • 47
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    Nutrient cycling in agroecosystems 46 (1996), S. 71-79 
    ISSN: 1573-0867
    Keywords: ammonium poly-phosphate ; diammonium orthophosphate ; fertilizer reaction ; gram ; Indian soils ; phosphorus ; P uptake ; single superphosphate ; triple superphosphate ; yield
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Laboratory studies on the characterization of soil-fertilizer P reaction products were carried out by reacting three-soils occurring in a toposequence in the plateau region of Bihar (India) with saturated solutions of diammonium orthophosphate (DAP), triple superphosphate (TSP) and ammonium polyphosphate (APP) for 1 hour and 24 hours. The reaction products (precipitates) formed in the solutions after 120 days of incubation were isolated and identified through X-ray diffraction technique. Results indicate the formation of Brushite [CaHPO4 · 2H2O, Strengite (FePO4 · 2H2O), Variscite (AIPO4 · 2H2O) and Fe4(P2O7)3 as major soil-fertilizer P reaction products in these soils with ortho-and polyphosphates as source of phosphorus. Pot cultures were used to evaluate the relative efficiency of reaction products (Struvite, Brushite, Variscite and Strengite), orthophosphates (DAP and SSP) and polyphosphate (APP) as sources of P for gram (Cicer arietinum L.) in a typical acid soil. Results indicate significant response of gram to different sources and level of added P. The dry weight and P uptake at 0, 6 and 12 mg P kg-1 soil were 0.406, 0.519 and 0.609 (g pot-1); and 0.289, 0.428 and 0.575 (mg P pot-1), respectively. Among the sources , struvite proved to be superior or equally effective as APP, DAP or SSP as sources of P for gram. Uptake of P also varied significantly with different P sources and levels of P application. Strengite was least effective in enhancing yield and P uptake by the crop.
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  • 48
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    Nutrient cycling in agroecosystems 44 (1995), S. 1-8 
    ISSN: 1573-0867
    Keywords: aerobic incubation ; cation-anion-exchange resin ; phosphorus ; resin beads ; resin membranes ; suspension incubation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Six Portuguese soils of varying P sorption capacity were incubated aerobically at 30° C without and with added P in order to give 0.1.mg P L−1 in the soil solution. Two methods of measuring extractable P were compared: (i) mixed-bed cation-anion-resin beads in bags and (ii) a simpler method with anion-resin membrane only. The bag method extracted about twice and 1.5 times as much as the strip method, respectively, without and with added P. The relationships were much closer after one extraction for 2 hours (r = 0.982, p 〈 0.01) instead of the cumulative extraction of 24 hours (r = 0.635,p 〉 0.05.). P recovery after incubation was inversely related to some soil properties as organic matter, buffer capacity, selective dissolution Al forms (Alox and Ald) and P sorption. It is suggested that the simpler resin membrane method is more adequate to assess P for many studies of P reaction with soil. A simpler incubation method was tried, consisting of incubation as a soil suspension in water at a high temperature (50° C). The results suggested that this method gave similar results to aerobic incubation, with the advantage that there was no need to measure the required and final water contents of incubated soil.
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  • 49
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    Nutrient cycling in agroecosystems 46 (1996), S. 179-187 
    ISSN: 1573-0867
    Keywords: electrical conductivity ; leaching ; nitrogen ; pH ; phosphorus ; potassium ; release pattern ; slow-release fertilizers ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract We studied the effect of temperature on the release of N, P, and K from slow-release fertilizers (SRF). The study was conducted in micro-lysimeters filled with moist peat medium. Increasing the temperature from 4 to 12°C slightly increased N release from three different slow-release N (SRN) carriers with different particle sizes and coating thicknesses. At 21°C the rate of release was significantly different than the other two temperatures. Urea formaldehyde (UF), sulphur coated urea (SCU) and coated calcium nitrate (CCN), incubated in sphagnum moss peat, released between 3 and 20% of the applied N in six weeks. For eight synthetic and organic NPK carriers, the release pattern was similar to UF and SCU. However, the leaching losses of N from the NPK fertilizers were up to twenty times more than for the SRN products. Except for Osmocote® and Duna, which released 30–40% of the applied N as mineral-N within six weeks, all other slow-release and slowly mineralized NPK carriers acted like readily water-soluble compound NPK. Temperature did not affect the nutrient release from NPK fertilizers.
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  • 50
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    Nutrient cycling in agroecosystems 50 (1998), S. 321-324 
    ISSN: 1573-0867
    Keywords: nutrient modelling ; leaching ; nitrogen ; phosphorus ; schematization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In context of preparing the Fourth National Policy Document on Water Management in the Netherlands effects of different scenarios of fertilizer management on nitrogen (N) and phosphorus (P) leaching from rural areas into Dutch surface waters were analyzed. The manuscript offers insight into the model instrument that is used to simulate the different scenarios. Main parts of the modelinstrument are: a procedure to schematize the Netherlands in horizontal areal units, field scale mechanistic models for water and nutrient behaviour in the soil and an empirical model for fertilizer additions.
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  • 51
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    Nutrient cycling in agroecosystems 51 (1998), S. 209-215 
    ISSN: 1573-0867
    Keywords: Desorption ; kinetics ; microbial transformation ; phosphate ; soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The improvement of P management in agriculture and environment requires a good understanding of residual effect of applied P in soils. The specific adsorption of P on variable charge minerals has been considered as the major mechanism that leads to a very low utilization of P fertilizer by crops within a growing season in Chinese red soils. Soil incubation and isotope tracing analysis were carried out to examine the transformation kinetics and potential availability of added specifically sorbed 32P in two pH contrasting light textured soils. The 32P recovered by 0.5 M NaHCO3 extraction and microbial biomass-P measurement from the added specifically sorbed 32P in the soils was well described by a first-order reaction and a Langmuir-type kinetic model, with correlation coefficients (R) being, on average, 0.938 and 0.959, respectively. The half-life (t1/2, from the first-order model) of the four tested mineral-P complexes ranged from 29 to 47 d in the acid sandy soil and 33 to 105 d in the neutral silty soil. Goethite-P was the most stable among the four tested mineral-P complexes. The potential availability of the mineral complex P (q m , in percent of total 32P added) obtained from the Langmuir equation ranged from 43.7 to 90.9% for the four mineral-P complexes, and decreased in the order: Al oxide-P (90.9%) 〉 montmorillonite-P (86.2%) 〉 kaolinite-P (77.5%) 〉 goethite-P (60.2%) in the acid sandy soil, whereas the order was Al oxide-P (89.3%) 〉 kaolinite-P (86.2%) 〉 montmorillonite-P (82.6%) 〉 goethite-P (43.7%) in the neutral silty soil. Based on the release rate and potential availability, kaolinite-P and Al oxide-P could be important sources for residual effect of applied P in variable-charge soils. The goethite-P has the lowest release rate and potential availability among the mineral-P complexes, implying that iron oxides may be the most important variable-charge mineral responsible for P fixation in the Chinese red soils.
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  • 52
    ISSN: 1573-0867
    Keywords: agriculture ; catchment ; fertilizer ; historical ; manure ; nitrate ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A suggested increase in the growth of macrophytic algae within the Ythan estuary (N.E. Scotland) over recent years has been linked to the increased amounts of nitrogen in the form of NO3–N entering the estuary from the river. The increased NO3 concentration in the river has been associated with recent changes in farming practices in this predominantly agricultural catchment. Terrestrially derived phosphorus is also considered to contribute increasingly to eutrophication of fresh waters. Historical agricultural census data together with appropriate surveys of fertilizer practice were used to calculate the total quantities of fertilizer and manure derived N and P applied annually over the wholeYthan catchment during the period 1960 – 1990. While the total agricultural land area has remained similar, significant changes in cropping practice have occurred. In particular, a greater proportion of land is given to autumn sown crops while the area of grassland has declined. These changes in farming practice are associated with differences in both the total amounts and timing of fertilizer applied. The use of inorganic N in the catchment has trebled since 1960 and is currently approximately 6400 tonnes (104 kg N/ha). The use of P has decreased by more than a quarter to 1274 tonnes (21 kg P/ha) over a similar time period. There has been no obvious change in total quantity of N and P derived from animal manures, estimated to be 44 and 11 kg per ha, respectively, when averaged over the area of agricultural land. Cattle and sheep numbers have remained relatively constant and together account for approximately 80% of the manure N and 70% of the manure P produced annually. However, poultry have declined by 70% since 1960 while pig numbers have increased six-fold. The average annual application rate of manure derived N over the whole catchment (44 kg/ha) is considerably below that proposed at the farm scale in the EC Nitrate Directive (210–170 kg/ha). However, on a local scale difficulties may arise for large manure producing concerns such as dairy or pig units.
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  • 53
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    Nutrient cycling in agroecosystems 55 (1999), S. 7-14 
    ISSN: 1573-0867
    Keywords: fertiliser formulation ; nutrients ; phosphorus ; relative humidity ; soil moisture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Phosphorus lost in runoff from agricultural land leads to the enrichment of surface waters and contributes to algal blooms. Fertilisers are one source of this P. To compare the water available P of different fertiliser formulations in the laboratory it is necessary to control environmental conditions, temperature, relative humidity and soil water content, prior to simulating rainfall. Two chambers were designed in which relative humidity and soil water content were controlled using salt solutions. An initial design comprising a sealed chamber with three layers of soil samples over a salt bath was found to be inferior to a single layer design. The changes in water content of soil samples were used to test the single layer chamber in a constant temperature environment (15 °C) using a saturated KCl solution (90% relative humidity). Based on the final soil water content of the samples, the spatial variation within the chamber was within tolerable limits. The single layer chamber was used for a simulation experiment comparing the water available P of two commercial fertilisers. Using a saturated resorcinol solution (95% relative humidity) soil samples were equilibrated at 15 °C for 21 days, fertiliser added, and the water available P measured up to 600 h after fertiliser application. The results indicate that the amount of water available P was related to the fertiliser compound and exponentially related to the time since fertiliser application. It was concluded that the single layer chamber is suitable for controlling relative humidity and soil water content in trials such as these where the water available P of fertilisers are being compared.
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  • 54
    ISSN: 1573-0867
    Keywords: dairy systems ; feeds ; fertilizers ; phosphorus ; P surplus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Inputs of phosphorus (P) above requirements for production on dairy farms lead to surplus P with increased risk of P transfer in land run-off to surface waters causing eutrophication. The impact of reducing surplus P inputs in purchased feeds and fertilizers on milk and forage production was investigated in a comparison of three dairy farm systems on chalkland soils in southern England over a 3-year period. In accordance with current commercial practice, no attempt was made to regulate P inputs in system 1, which accumulated an average annual surplus of 23 kg P ha-1. Progressive reductions in purchased feed and/or fertilizer inputs into systems 2 and 3 decreased surplus P to 17 and 3 kg ha-1, respectively, without apparently limiting either milk or herbage dry matter production. The estimated reduction in faecal P output from system 3 cows fed a low P diet compared to system 1 cows fed a high P diet was 26%. Milk P concentrations significantly (P 〈0.001) increased in systems 2 and 3 which included maize in the diet. Output of P in milk and meat products, as a proportion of the total dietary P inputs, increased from 28% in system 1 to 36% in system 3. Surplus P was greatest in continuous maize fields receiving both dairy manure and starter P fertilizer. Withholding P fertilizer in system 3 did not reduce P offtake in cut herbage on soils of moderate P fertility. Total annual losses of P in storm run-off and leaching were no greater than annual inputs of P from the atmosphere (0.5 kg ha-1). The results indicate there is scope to reduce surplus P on commercial dairy farms without sacrificing production targets at least in the short term. Purchased feeds are the largest of the P inputs on intensive dairy farms, yet these are rarely quantified on commercial holdings.
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  • 55
    ISSN: 1573-0867
    Keywords: leaching ; phosphorus ; poultry litter ; soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract To determine P loadings, added through poultry litter, sufficient to cause downward movement of P from the cultivated layer of a sandy soil, six rates of poultry litter were applied annually for four years to a site in central England. (total loading 0 – 1119 kg P ha-1). A single extra plot also received an extra 1000 kg ha-1 as triple superphosphate (TSP; total loading 2119 kg P ha-1) and three other treatments received 200 – 800 kg ha-1 P as TSP only. Annual soil sampling in 30-cm increments to 1.5-m depth provided information on P build-up in the topsoil and P movement to depth. There were strong linear trends between P balance (P applied – P removed in crops) and total P, Olsen bicarbonate extractable P and water-soluble P in the topsoil. Phosphorus from TSP and poultry litter fell on the same regression lines, suggesting that both would be equally effective as fertilizer sources. We calculated that 100 kg ha-1 surplus total P would increase the Olsen extractable P content by c. 6 mg kg-1 and the water-soluble P by c. 5 mg kg-1. Thus, relatively large amounts of P would need to be applied to raise soil P status. We found some evidence of P movement into the soil layers immediately below cultivation depth. However, neither soil sampling nor soil solution extracted through Teflon water samplers showed evidence of movement into the deep subsoil (1 m) despite large P loadings.
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  • 56
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    Nutrient cycling in agroecosystems 54 (1999), S. 259-266 
    ISSN: 1573-0867
    Keywords: bahiagrass ; manure ; pasture fertilization ; phosphorus ; phosphorus cycling ; Spodosol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Bahiagrass (Paspalum notatum Flugge) pasture fertilization recommendations have traditionally been based upon clipping studies. Inclusion of P from manure, not originally considered when P recommendations were developed for pastures, may minimize the need for P fertilization without reducing bahiagrass production or P uptake. The objective of this research was to determine if manure contributes greatly to the P crop nutrient requirement. A 2-year field study utilized a factorial arrangement of 0 and 6.9 Mg air-dried manure ha-1 with 0, 17, 34, 51, and 68 kg inorganic P ha-1 from triple superphosphate to evaluate bahiagrass yield, root distribution, and P uptake response on a Myakka fine sand (sandy, siliceous, hyperthermic Aeric Alaquod). Because air-dried manure was used in the field study, a greenhouse study was employed to confirm that there were no differences in bahiagrass yield or P uptake from either air-dried or fresh cattle (Bos spp.) manure sources. There were no manure or manure by P interaction effects on yield or P uptake of bahiagrass indicating that manure source did not effect grass production in the greenhouse. In the field study, bahiagrass roots were distributed into the Bh horizon, and the Bh horizon had at least four times more Mehlich-1 extractable P than that of the Ap horizon. This horizon was most likely acting as a main source for P-uptake by the grass. This observation was further confirmed by no yield response to levels of inorganic P application in 1989. A linear-response-and-plateau (R2=0.196) relationship with a critical point of 15.4 kg P ha-1 was found in 1990. Bahiagrass yield and P uptake were not dependent on P fertilization, either from manure or inorganic P, due to the availability of P from the Bh horizon.
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  • 57
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    Nutrient cycling in agroecosystems 47 (1996), S. 243-250 
    ISSN: 1573-0867
    Keywords: fertilizer value ; nitrogen ; phosphorus ; poultry manure ; urea ; wetland rice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Poultry manure applied alone or in combination with urea at different N levels was evaluated as a N source for wetland rice grown in a Fatehpur loamy sand soil. Residual effects were studied on wheat which followed rice every year during the three cropping cycles. In the first year, poultry manure did not perform better than urea but by the third year, when applied in quantities sufficient to supply 120 and 180 kg N ha−1, it produced significantly more rice grain yield than the same rates of N as urea. Poultry manure sustained the grain yield of rice during the three years while the yield decreased with urea. Apparent N recovery by rice decreased from 45 to 28% during 1987 to 1989 in the case of urea, but it remained almost the same (35, 33 and 37%) for poultry manure. Thus, urea N values of poultry manure calculated from yield or N uptake data following two different approaches averaged 80, 112 and 127% in 1987, 1988 and 1989, respectively. Poultry manure and urea applied in 1:1 ratio on N basis produced yields in between the yields from the two sources applied alone. After three cycles of rice-wheat rotation, the organic matter in the soil increased with the amount of manure applied to a plot. Olsen available P increased in soils amended with poultry manure. A residual effect of poultry manure applied to rice to supply 120 or 180 kg N ha−1 was observed in the wheat which followed rice and it was equivalent to 40 kg N ha−1 plus some P applied directly to wheat.
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  • 58
    ISSN: 1573-0867
    Keywords: pasture fertilization ; phosphorus ; potassium ; nutrient budget ; nutrient efficiency
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Dairy farming is the main agricultural activity of the Basque Country. A dairy farm is characterized as a system with soils and crops, forage, cattle and manure as main components, and in such a system, nutrient cycling is very important to maintain soil fertility and optimize forage production. To quantify nutrient transfers in the cycle, a simple system was developed and has been applied to seventeen farms to examine its ability to achieve a balanced P and K fertilization. These farms have provided data on inputs (fertilizer, feeds, concentrates), pasture and manure management, and outputs (milk production), and soil samples have been taken from farm pastures. Phosphorus and K in excreta and uneaten pasture is used with a relatively high efficiency as suggested by the relatively high efficiency of P and K utilization by the pasture that usually ranges from 70 to 90%. Concentrate feeding (3000 kg cow−1 yr−1) represents one of the main P and K inputs in Basque Country dairy farms, averaging 26 and 66 kg ha−1, respectively. Besides, release of K in the soil through slow liberation from non-exchangeable sites was estimated as 30 kg ha−1. Thus, a high efficiency in excreta recycling would diminish substantially P and K mineral fertilizer needs. Farm nutrient budgets appear to be a convenient tool for determining nutrient shortages and surpluses at farm level, and thus they are considered as a first step to support a better management of maintenance fertilization of permanent pastures.
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    Nutrient cycling in agroecosystems 45 (1995), S. 193-197 
    ISSN: 1573-0867
    Keywords: cation activity ; phosphorus ; potassium chloride ; soil solution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The electrolyte concentration of the soil solution affects the availability of some nutrients in the soil, especially of P, but it is not know at what salt concentration the reactions start to be significantly affected and their magnitude. This study was carried out to evaluate the effect of rates of potassium chloride (KCl) on some soil parameters that determine supplying of P, K, Ca, Mg, and Al in an unlimed acid soil. Increasing rates of KCl (from zero up to 2000 mg K kg−1) were applied to soil samples fertilized with 360 mg P kg−1. Solution (Cli) and exchangeable (Csi) forms of P, Ca, Mg, K, and Al were determined in the treated soil samples after 30-days of incubation; cation activity in solution and their selectivity coefficients were then calculated. Addition of KCl at rates equal to or above 500 mg K kg−1 caused a large relative increase on P in the soil solution (Pli) but a small and insignificant increase on the absolute value of Pli. All forms of soil K increased with increases on K applied, and buffer power for K varied according to the range of soil K. At all KCl rates, K displaced Ca, Mg, and Al from the solid phase to the soil solution, but had no effect on the extractable values. The relative preference of cations for the adsorption sites increased with increase on cation valency, and only those selectivity coefficients involving K were affected by K applied.
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  • 60
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    Journal of statistical physics 95 (1999), S. 23-43 
    ISSN: 1572-9613
    Keywords: model alloy ; Monte Carlo ; elastic interactions ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We study via Monte Carlo simulations the influence of elastic interactions on the ordering and decomposition of a two-dimensional model binary alloy with antiferromagnetic nearest and ferromagnetic next nearest neighbor type interactions following a quench into the coexistence region. The elastic interaction leads to the development of a platelet morphology for the segregated ordered and disordered regions. A length scale characterizing the coarsening process follows a law of the type R=a+bt 1/3 with the growth b decreasing with the amount of ordered phase; this appears to be due to the presence of anti-phase boundaries between neighboring domains ordered on different sublattices which are difficult to eliminate. The application of uniaxial external stress results in “rafting” of the domains. Many of the simulation results are in agreement with experimentally observed effects in nickel-base superalloys.
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  • 61
    ISSN: 1572-9729
    Keywords: bioavailability ; builders ; detergents ; kinetics ; mineralization ; sewage sludge ; soil
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Tetradecenyl succinic acid (TSA) is the major component of a detergent builder (C12-C14 alkenyl succinic acid), which is inherently biodegradable. 14C-TSA was dosed as a component of sewage sludge into a soil with a history of sludge amendment at final added concentrations of 1.5 and 30 mg (kg soil)-1. In addition, it was dosed to the soil in an aqueous solution to a final added concentration of 30 mg (kg soil)-1. Dose and form were found to have a pronouced effect on the mineralization kinetics. When dosed in a realistic form and concentration (i.e. 1.5 mg (kg soil)-1 as a component of sludge), TSA was mineralized at its highest rate and to its greatest extent, and the mineralization half-life was 2.4 days. When dosed at 30 mg (kg soil)-1 as a component of sludge, mineralization began immediately, and the half-life was 23 days. In contrast, when dosed at this concentration in aqueous solution, the onset of mineralization was preceded by a 13 day lag period and the mineralization half-life was 69 days. Primary biodegradation and mineralization rates of TSA were very similar. Approximately, half the radioactivity was evolved as 14CO2, while the remaining radioactivity became non-extractable, having presumably been incorporated into biomass or natural soil organic matter (humics). This study demonstrated that TSA is effectively removed from sludge-amended soils as a result of biodegradation. Furthermore, it showed the effect that dose form and concentration have on the biodegradation kinetics and the importance of dosing a chemical not only at a relevant concentration but also in the environmental form in which it enters the soil environment.
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    Mangroves and salt marshes 2 (1998), S. 37-42 
    ISSN: 1572-977X
    Keywords: mangrove ; phosphorus ; distribution ; dynamics ; exportation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The distribution and dynamics of phosphorus have been studied in the mangroves of Sepetiba Bay, Brazil. Leaf fall contributes 3.0 kg P ha=1yr=1to the sediment. The total above ground biomass of the R. mangle stand was about 65.3 t ha=1, the P accumulation was 3.9 kg P ha=1where 63% of the total P-biomass was accumulated in the leaves. The biomass of below ground roots was about 8.2 tha=1 and accumulated 16% of total P-biomass. Sediment contained 452 kg P ha=1 where P combined with calcium (P-Ca) was the main fraction (260 kg ha=1). The annual flux of P as litter fall was small (〈 1%) compared to total P in the sediment reservoir. The annual export of P by macrodetritus corresponds to 0.05% of the total sediment reservoir.
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  • 63
    ISSN: 1572-9729
    Keywords: bacteria ; degradation ; denitrification ; kinetics ; stoichiometry ; toluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Batch experiments were carried out to investigate the stoichiometry and kinetics of microbial degradation of toluene under denitrifying conditions. The inoculum originated from a mixture of sludges from sewage treatment plants with alternating nitrification and denitrification. The culture was able to degrade toluene under anaerobic conditions in the presence of nitrate, nitrite, nitric oxide, or nitrous oxide. No degradation occurred in the absence of Noxides. The culture was also able to use oxygen, but ferric iron could not be used as an electron acceptor. In experiments with14C-labeled toluene, 34%±8% of the carbon was incorporated into the biomass, while 53%±10% was recovered as14CO2, and 6%±2% remained in the medium as nonvolatile water soluble products. The average consumption of nitrate in experiments, where all the reduced nitrate was recovered as nitrite, was 1.3±0.2 mg of nitrate-N per mg of toluene. This nitrate reduction accounted for 70% of the electrons donated during the oxidation of toluene. When nitrate was reduced to nitrogen gas, the consumption was 0.7±0.2 mg per mg of toluene, accounting for 97% of the donated electrons. Since the ammonia concentration decreased during degradation, dissimilatory reduction of nitrate to ammonia was not the reductive process. The degradation of toluene was modelled by classical Monod kinetics. The maximum specific rate of degradation, k, was estimated to be 0.71 mg toluene per mg of protein per hour, and the Monod saturation constant, K s , to be 0.2 mg toluene/l. The maximum specific growth rate, μ max , was estimated to be 0.1 per hour, and the yield coefficient, Y, was 0.14 mg protein per mg toluene.
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    Biodegradation 7 (1996), S. 73-81 
    ISSN: 1572-9729
    Keywords: diesel oil ; biodegradation ; CSTR ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In batch culture diesel oil was degraded rapidly, with a maximum growth rate (for a consortium of microorganisms) of 0.55 h-1. The corresponding yield Y SX was 0.1 Cmol/Cmol. In a continuous stirred tank reactor the maximum dilution rate was about 0.25 h-1, with a yield of 0.3 Cmol/Cmol. With a residence time of 1 day 82% of the influent oil was degraded. In the batch reactor, of the mixture of linear and branched alkanes the linear alkanes were degraded fastest and with the highest yield. Only after most of the linear alkanes had disappeared were the branched alkanes consumed. In a CSTR a large part of the branched alkanes was not degraded.
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    Environmental geology 30 (1997), S. 224-230 
    ISSN: 1432-0495
    Keywords: Key words Sediment ; Washington ; DC ; Pollution ; phosphorus ; nutrients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  Sediments in the rivers and basins around Washington, DC, have high concentrations of phosphorus, which, based on geographic distributions, is largely derived from urban runoff and municipal sewage. Dissolved-particulate phosphate exchange reactions and biological uptake of dissolved phosphorus from the water column may be an added source of phosphorus to the sediments. Concentrations of total sedimentary phosphorus ranged from 24 to 56 μm P/g-dw, and were highest in areas near combined sewer outfalls. As a part of this study, sedimentary phosphorus was fractionated into Fe-P, Ca-P, Al-P, and organic phases using a selective-sequential leaching procedure. The distribution of the phases in all sediments analyzed follow the order , Fe-P〉Ca-P〉Al-P. Spatial variations in the amounts of phosphorus in the different phases is related to the sources of phosphorus to the area. The proportions of occluded Al-P and organic P are 10–20% of the total P, respectively. This suggests that phosphorus from natural sources is small compared to anthropogenic inputs in this area. The high leachable Fe-P and Ca-P in these sediments might contribute a substantial amount of P to the water column under conditions of remobilization.
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    Pure and applied geophysics 147 (1996), S. 367-375 
    ISSN: 1420-9136
    Keywords: Induced seismicity ; kinetics ; rock fracture ; rockburst ; earthquake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Powerful seismic events, such as earthquakes and rockbursts, are caused by the accumulation of energy in rocks and loss of rock mass stability. Usually methods of their forecasting are based on the registration of anomalous behavior of geophysical fields. However an efficiency of this approach is low. The present paper proposes a kinetic approach to the description of rock fracture process, which can be used for the forecasting of seismic events and an investigation of structure and energy distributions in rock. 3-D and 1-D kinetic equations describing a process of cluster formation in rock were obtained. The equations are invariant to deformation conditions and to the scale level of events. They showed a good agreement with the results of field observations and laboratory experiments. It was also shown that these equations well describe the processes of earthquake, rockburst and rock sample failure preparation. Catalogues of rockbursts in mines were analyzed with the use of the kinetic equations to find out evidence of induced seismic events. The proposed approach makes it possible to reveal trends in rock behavior and thus predict the rock failure at different scale levels.
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    European journal of clinical pharmacology 52 (1997), S. 505-506 
    ISSN: 1432-1041
    Keywords: Key words Ibuprofen; effervescent tablets ; kinetics ; bioavailability
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    Topics: Chemistry and Pharmacology , Medicine
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  • 68
    ISSN: 1432-1041
    Keywords: Key words Diphemanil methylsulphate ; Neonate; antimuscarinic agent ; kinetics
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    Topics: Chemistry and Pharmacology , Medicine
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  • 69
    ISSN: 1432-072X
    Keywords: Key words Auxostat ; Batch culture ; Chemostat ; Continuous culture ; Fermentation control ; Inhibition ; kinetics ; Nutristat ; On-line measurement ; Pentachlorophenol ; Pollutant ; Sphingomonas ; Steady-state conditions ; Toxicity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A bacterium degrading pentachlorophenol (PCP) as the only source of carbon and energy was grown in a “nutristat”, i.e., a continuous culture with on-line measurement and control of the substrate concentration. We improved the PCP nutristat by incorporation of a personal computer with a proportional integral derivative (PID) algorithm for controlling the medium feed pump. The controlled value deviated from the average (set-point) value by 1% maximally. In the PCP nutristat (30°C), the steady-state dilution rate, and hence, specific growth rate, showed a maximum value of 0.142 ± 0.004 h–1 at set-point PCP concentrations between 37 and 168 μM. At PCP concentrations above 168 μM, the steady-state growth rate decreased because of inhibition. The growth yield coefficient was not seriously affected by the PCP concentration, suggesting that uncoupling was not the inhibitory mechanism. It was concluded that the PCP nutristat is very useful for establishing steady-state conditions that maintain growth-inhibitory PCP concentrations and high cell concentrations, conditions for which the chemostat is not suitable.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 35-49 
    ISSN: 1572-8943
    Keywords: bone cement ; DSC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Keywords: compensation effect ; DSC ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Four computer programs as well as one demo-version for non-linear evaluation of kinetic data in thermal analysis and calorimetry, were presented. The multi-task program TA-kin meets all mathematical requirements for solving the numerical assignments. It is shown that the so-called compensation effect is due to the mathematical structure of the Arrhenius equation. Several applications of TA-kin to a lot of DSC- and TG-measurements and isoperibolic batch experiments as well as adiabatic semi batch experiments realized by precision calorimetry have been discussed.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 569-575 
    ISSN: 1572-8943
    Keywords: Bi2O3 ; CaCO3 decomposition ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Former studies concerning the formation of the compounds in the pseudobinary systems of Bi2O3-MO type (M =Ca, Sr, Ca+Sr) have shown that the reaction which occurs with the highest rate is that between Bi2O3 and CaO. In the present work CaCO3 was used as CaO source. We carried out an investigation of the thermal decomposition of CaCO3 in the presence of Bi2O3 in comparison with the decomposition of pure CaCO3. The presence of Bi2O3 exerts a complex influence on the CaCO3 decomposition acting on the nucleation as well as on the diffusion of CO2. The decomposition of the samples with low Bi2O3 content follows the mechanism of a contracting sphere. A change from surface nucleation to bulk nucleation is recorded for higher amounts of Bi2O3.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1437-1450 
    ISSN: 1572-8943
    Keywords: browning ; crystallization ; glass transition ; kinetics ; milk powder ; water
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An exotherm, observed in differential scanning calorimetry (DSC) scans of amorphous food materials above their glass transition temperature,T g, may occur due to sugar crystallization, nonenzymatic browning, or both. In the present study, this exothermal phenomenon in initially anhydrous skim milk and lactose-hydrolyzed skim milk was considered to occur due to browning during isothermal holding at various temperatures above the initialT g. The nonenzymatic, Maillard browning reaction produces water that in amorphous foods, may plasticize the material and reduceT g. The assumption was that quantification of formation of water from theT g depression, which should not be observed as a result of crystallization under anhydrous conditions, can be used to determine kinetics of the nonenzymatic browning reaction. The formation of water was found to be substantial, and the amount formed could be quantified from theT g measured after isothermal treatment at various temperatures using DSC. The rate of water formation followed zero-order kinetics, and its temperature dependence well aboveT g was Arrhenius-type. Although water plasticization of the material occurred during the reaction, and there was a dynamic change in the temperature differenceT−T g, the browning reaction was probably diffusioncontrolled in anhydrous skim milk in the vicinity of theT g of lactose. This could be observed from a significant increase in activation energy. The kinetics and temperature dependence of the Maillard reaction in skim milk and lactose-hydrolyzed skim milk were of similar type well above the initialT g. The difference in temperature dependence in theT g region of lactose, but above that of lactose-hydrolyzed skim milk, became significant, as the rate in skim milk, but not in lactose-hydrolyzed skim milk, became diffusion-controlled. The results showed that rates of diffusion-controlled reactions may follow the Williams-Landel-Ferry (WLF) equation, as kinetic restrictions become apparent within amorphous materials in reactions exhibiting high rates at the same temperature under non-diffusion-controlled conditions.
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  • 74
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    Journal of thermal analysis and calorimetry 48 (1997), S. 917-923 
    ISSN: 1572-8943
    Keywords: copper compound ; coupled technique ; kinetics ; macrocyclic complex ; non-isothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition process of the complex [Cu(NBOCTB)][Cu(NO3)4] H2O has been studied by TG and DTG technique, and possible intermediates of the thermal decomposition have also been conjectured from the TG and DTG curves. The results suggest that the decomposition of the complex involves five steps: The non-isothermal kinetics of steps 1, 2 and 3 have been studied by means of the Achar and Coats-Redfern method based on TG and DTG curves. Step 1 is a ‘Coring and Growth’ mechanism (n= 1), its kinetic equation may be expressed as: dα/dt=Ae−E/RT(1−α). Steps 2 and 3 are both ‘two order chemical reaction’ mechanisms, their kinetic equations can be expressed as: dα/dt=Ae−E/RT(1−α)2.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 87-94 
    ISSN: 1572-8943
    Keywords: kinetics ; poly(di-propyl itaconates) ; polymer structure ; thermal degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Non-isothermal thermogravimetry was performed in a dynamic nitrogen atmosphere, on a series of poly(di-n-propyl itaconates) (PDnPI) and poly(di-iso-propyl itaconates) (PDiPI) which had been prepared in the presence of various amounts of the chain transfer agentn-dodecyl mercaptan (DDM). Differential thermogravimetry (DTG) showed that both polymers degraded in two stages. The DTG curve of PDnPI had a large first peak followed by a smaller shoulder, whereas the DTG curve of PDiPI was composed of two peaks of almost equal heights. The addition of DDM during the polymerisations in both cases resulted in a similar decrease in the relative area of the first peak.
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  • 76
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    Journal of thermal analysis and calorimetry 49 (1997), S. 183-191 
    ISSN: 1572-8943
    Keywords: kinetics ; thermooxidative degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The results of non-isothermal kinetic analysis of the thermooxidative degradation in air and oxygen of an unsaturated polyester resin are presented. It has been shown that the thermooxidative degradation in oxygen occurs at lower temperatures than the thermooxidative degradation in air. The kinetic parameters of the thermooxidative degradation depend on the heating rate and the oxygen pressure. Two straight lines of InAvs. E (A is the preexponential factor andE is the activation energy), characteristic for the compensation effect, have been obtained for the thermooxidative degradation in air and in oxygen respectively. The difference between the intercepts of these straight lines can be explained by dependence of the pre-exponential factor on the oxygen pressure.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 795-808 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; liquid crystalline polymer ; optical transmittance ; polycarbosilane ; side-chain mesogen ; transition parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 857-862 
    ISSN: 1572-8943
    Keywords: analytical methods ; kinetics ; powder milk ; temperature
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This work present comparative results on powder milk storage quality, obtained from analytical methods. Protein content was determined conventional (Kjeldahl) and colorimetric with biuret reagent at 540 nm and integral quality by thermogravimetric and biological methods. A method was developed for the protein separation of powder milk. Powder milk was submitted to degradation processes at 45, 60 and 80°C for 20 days. The results indicated that protein content values were inconsistent if determinations by Kjeldahl and colorimetric methods and biological tests were compared. There is evidence of thermal decomposition of powder milk as detected by biological and thermogravimetric methods.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 937-941 
    ISSN: 1572-8943
    Keywords: kinetics ; mebendazole ; quality control ; technology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A study was made of the thermal behavior of the starting materials, their mixtures and the resulting mebendazole tablets. The thermal curves were obtained with a Shimadzu thermobalance, model TGA-50, using an air flow of 50 mL min−1 and a heating rate of 10°C min−1 in the temperature interval 30–900°C. The reaction constant velocities for the mebendazole salt and tablets were determined isothermally, using the Arrhenius expression. The thermal stability of mebendazole tablets is lower than that of the mebendazole salt, due to the presence of starch and lactose in the composition. Analysis of the data reveals that thermogravimetry is a powerful tool in pharmaceutical technology and quality control.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1081-1091 
    ISSN: 1572-8943
    Keywords: kinetics ; thermal degradation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic study of thermal degradation takes into account the validity of the Arrhenius equation. From TG data, the activation energy,E a and pre-exponential factor,A, are evaluated. These results are interpreted by using the ‘kinetic compensation effect’ as basis. A linear correlation between In(A) andE a is obtained in all cases studied. However, in a plot of the logarithm of the rate constant as a function of reciprocal temperature for the same series of reactions, the thermal oxidative degradations of Nylon-6 and PVC display a point of concurrence and one isokinetic temperature, whereas those of HIPS and PC do not. Therefore, in the thermal oxidative degradations of Nylon-6 and PVC a ‘true’ compensation effect occurs, which could be related to the bulk properties of metal oxides, such as different valence states, whereas for other polymers it displays only an ‘apparent’ compensation effect. This means that degradation is largely independent of the bulk properties of oxides, but may be related to the distribution of different kinds of active links in the polymer surface having different activation energies.
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    Journal of thermal analysis and calorimetry 48 (1997), S. 343-348 
    ISSN: 1572-8943
    Keywords: activation energy ; combustion ; crude oil ; differential scanning calorimetry ; kinetics ; thermogravimetric analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A weighted mean activation energy method was applied to describe the reactivity and combustibility of crude oils via simultaneous TG/DTG. Thermal experiments were conducted with a non-isothermal method at a heating rate of 10
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    Journal of thermal analysis and calorimetry 48 (1997), S. 385-401 
    ISSN: 1572-8943
    Keywords: dehydration and decomposition ; kinetics ; Fe(III) chloride
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Fe(III) chloride hydrate (FeCl3·xH2O) undergoes simultaneous dehydration and dehydrochlorination from its molten phase in the temperature range 100–200
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    Journal of thermal analysis and calorimetry 48 (1997), S. 413-425 
    ISSN: 1572-8943
    Keywords: alcoholic fermentation ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The control of alcoholic fermentation is necessary to obtain a quality wine. The overall dynamic and phenomenological modelling already applied to the simulation of this type of reaction enables us to suggest, in this study, a simple model (of which two variants), are relatively satisfactory. The first variant does not take into account the variation of the ambient temperature; the model translates exactly the first phase of the experimental curve or the moment when highest temperatures are measured. The relaxation phase is less well described because of influence of variation of the ambient temperature is relatively important. The second one considers the system depending on the ambient temperature, the model is correct for the relaxation phase too (the reaction temperature decreases, it nears the ambient temperature). The advantage of this model: It permits one to determine the reaction enthalpy and the kinetic parameters.
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    Journal of thermal analysis and calorimetry 48 (1997), S. 623-634 
    ISSN: 1572-8943
    Keywords: bismalleimide/carbon fiber composite ; DMA ; kinetics ; TSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The correlation between structure/microstructure and thermomechanical properties has been investigated by the Thermally Stimulated Creep (TSC) technique in a high performance thermostable thermoset matrix composite. The high resolving power of this technique allows us to analyse the α retardation mode. The kinetics of molecular movements liberated at the glass transition has been investigated by the technique of fractional loading: the analysis of each elementary process gives the real compliance and the retardation time as a function of temperature. The values of the activation parameters show the existence of a compensation phenomenon which characterizes the microstructure. It also gives access to the loss compliance of the composite material as a function of temperature and frequency. The predictive calculation of loss compliance has been validated by the results obtained by dynamic mechanical analysis (DMA).
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    Journal of thermal analysis and calorimetry 48 (1997), S. 769-782 
    ISSN: 1572-8943
    Keywords: kinetics ; non-linear optimization ; reactor time constants ; software ; time constants of sensors
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    Topics: Chemistry and Pharmacology
    Notes: Abstract All temperature sensors have a finitely time constant. The influence of the sensor time constant gts on the results of kinetic evaluation is demonstrated at four reaction types. The ignorance of the sensor indolence gives incorrect activation parameters. Therefore the determination of Τs is necessary. For the estimation of parameters the nonlinear evaluation program TA-kin was used. With its help it is possible to find the real parameters, also when Τs=32 s, if the real Τs-value was entered.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1517-1525 
    ISSN: 1572-8943
    Keywords: β-cyclodextrin ; cinnamyl alcohol ; kinetics ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of β-cyclodextrin-cinnamyl alcohol inclusion complex (β-CD·C9H10·8H2O) was investigated using TG and DSC. The mass loss took place in three stages: the dehydration occurred between 50–120°C; the dissociation of β-CD·C9H10O occurred in the range of 210–260°C; and the decomposition of β-CD began at 280°C. The dissociation of β-CD·C9H10O was studied by means of thermogravimetry, and the results showed: the dissociation of β-CD·C9H10O was dominated by a two-dimensional diffusion process (D2). The activation energyE was 161.2 kJ mol−1, the pre-exponential factorA was 4.5×1013 min−1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the interesting of studies focussed on the energy binding cyclodextrin and the guest molecule. In this paper, β-cyclodextrin-cinnamyl alcohol inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show: the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of Van der Waals interaction.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1553-1564 
    ISSN: 1572-8943
    Keywords: deconvolution ; differential scanning calorimetry ; feedforward neural networks ; kinetics ; signal filtering ; simulations ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Feedforward neural networks have been used for kinetic parameters determination and signal filtering in differential scanning calorimetry. The proper learning function was chosen and the network topology was optimized, using an empiric procedure. The learning process was achieved using simulated thermoanalytical curves. The resilient-propagation algorithm have led to the best minimization of the error computed over all the patterns. Relative errors on the thermodynamic and kinetic parameters were evaluated and compared to those obtained with the usual thermal analysis methods (single scan methods). The errors are much lower, especially in presence of noisy signals. Then, our program was adapted to simulate thermal effects with known thermodynamic and kinetic parameters, generated electrically, using a PC computer and an electronic interface on the serial port. These thermal effects have been generated by using an inconel thread.
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    Journal of thermal analysis and calorimetry 49 (1997), S. 1467-1475 
    ISSN: 1572-8943
    Keywords: CRTA ; DSC ; kinetics ; synthetic brochantite ; TG-DTA ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction pathway of the thermal decomposition of synthetic brochantite, Cu4(OH)6SO4, to copper(II) oxide was investigated through the detailed kinetic characterization of the thermal dehydration and desulferation processes. The dehydration process was characterized by dividing into two overlapped kinetic processes with a possible formation of an intermediate compound, Cu4O(OH)4SO4. The dehydrated sample, Cu4O3SO4, was found first to be amorphous by means of XRD, followed by the crystallization to a mixture of CuO and CuO-CuSO4 at around 776 K. The specific surface area and the crystallization behaviour of the amorphous dehydrated compound depend largely on the dehydration conditions. The thermal desulferation process is influenced by the gross diffusion of the gaseous product SO3, which is governed by the advancement of the overall reaction interface from the top surface of the sample particle assemblage to the bottom.
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    Journal of thermal analysis and calorimetry 50 (1997), S. 455-462 
    ISSN: 1572-8943
    Keywords: kinetics ; statistical analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A statistical technique based on the Wilcockson criterion is suggested for estimation of the reproducibility of thermoanalytical experiments. Reduction of the whole physicochemical process to a quasi-one-stage process is described.
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    Journal of thermal analysis and calorimetry 50 (1997), S. 425-430 
    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; non-isothermal
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors present the results concerning the thermal behaviour of three polynuclear coordination compounds of Nd(III) and Co(II) or Fe(III) with triptophan. For the dehydration steps the values of the non-isothermal kinetic parameters have been determined.
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    Journal of thermal analysis and calorimetry 52 (1998), S. 569-579 
    ISSN: 1572-8943
    Keywords: bromomethylated polysulfone ; carboxylated polysulfone ; kinetics ; polysulfone ; thermoxidative decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic aspects of the first step of thermoxidative decomposition, under dynamic conditions of heating, of some polysulfones have been studied. The dependence of the kinetic parameters on the heating rate and conversion degree has been established. The compensation effect and conversion function have also been discussed. Polysulfone decomposes by the breaking of the main chain, a process involving very high activation energy. Chemically modified polysulfones show the first step of thermoxidative decomposition at relatively low temperatures. This step corresponds to the elimination of functional side - groups for the bromomethylated polysulfone while in the case of the carboxylated polysolfone, the loss of the carboxyl group is probably accompanied by a crosslinking reaction.
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    Journal of thermal analysis and calorimetry 53 (1998), S. 397-410 
    ISSN: 1572-8943
    Keywords: barium oxalate ; kinetics ; non-isothermal thermogravimetry ; stepwise isothermal analysis ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal decomposition of BaC2O4·0.5H2O in air was studied by a combination of stepwise isothermal analysis (SIA) and non-isothermal thermogravimetry. The results from both techniques show that the crystal water is released in one step and that anhydrous barium oxalate is decomposed in one step, while BaCO3 decomposes in three steps to BaO, forming two intermediate compounds with the formulas of BaCO3·(BaO)2 and (BaCO3)0.5·(BaO)2.5. Reaction mechanism analyses using the data from SIA measurements show that the controlling mechanism for all the five decomposition steps in isothermal conditions is a two-dimensional phase-boundary controlled process. Kinetic parameters are obtained for the five decomposition steps from the non-isothermal thermogravimetric data.
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    Journal of thermal analysis and calorimetry 54 (1998), S. 695-704 
    ISSN: 1572-8943
    Keywords: activation energy ; decomposition ; kinetics ; modulated temperature ; thermogravimetry ; volatilization
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new technique, called modulated thermogravimetry, is introduced as a tool for obtaining continuous kinetic information for decomposition and volatilization reactions. The approach makes use of an oscillatory temperature program to obtain kinetic parameters during a mass loss. MTGA™ may be used under quasi-isothermal conditions to observe a single mass loss or may be combined with linear heating rate or Hi-Res™ controlled rate thermogravimetry to scan from one mass loss region to another. Results obtained are in agreement with those obtained by other kinetic methods.
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  • 94
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    Keywords: β-cyclodextrin ; ethyl benzoate ; inclusion complex ; kinetics ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of β-cyclodextrin·ethyl benzoate·6H2O(β-CD·C6H5COOC2H5·6H2O) was investigated by TG and DSC. The mass loss takes place in three stages: the dehydration occurs at 50-120°C; the dissociation of β-CD·C6H5COOC2H5occurs at 200-260°C; the decomposition of β-CD begins at 280°C. The kinetics of the dissociation of β-CD·C6H5COOC2H5in a dry nitrogen flow was studied by means of thermogravimetry both at constant temperature and linearly increasing temperature. The results show that the dissociation of β-CD·C6H5COOC2H5is dominated by a three-dimensional diffusion process (D3). The activation energy E is 116.19 kJ mol-1and the pre-exponential factor A 6.5358·109min-1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the studies focus on the energy of binding between cyclodextrin and the guest molecule. In this paper, the β-cyclodextrin·ethyl benzoate inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show that the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of van der Waals interaction.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 233-241 
    ISSN: 1572-8943
    Keywords: cadmium(II) atom ; kinetics ; non-isothermal decomposition ; Schiff-base compound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal C81H78N12O6Cd3 was synthesized and its structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system space group P21/n with cell parameters, a=15.959(4) Å, b=26.222(3) Å, c=25.907(6) Å, β=101.60(2)°. The non-isothermal kinetics of the crystal was studied by use of non-isothermal TG and DTG curves. The kinetic parameters were analyzed by means of integral and differential methods, and mechanism functions of the thermal decomposition reaction for its second step were proposed. The kinetic equation of thermal decomposition is expressed as: dα/dt=Aexp(-E/RT)1.5(1-α)4/3[1/(1-α)1/3-1]−1. The average values of E(kJ mol−1) and lnA/s−1 are 339.25, 43.95, respectively.
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    Journal of thermal analysis and calorimetry 55 (1999), S. 301-309 
    ISSN: 1572-8943
    Keywords: dehydroxylation ; goethite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of thermal dehydroxylation of aluminuous goethites [1] synthesised from a ferrous salt has been re-examined using the general reaction order kinetic law. The utilised data processing was based on the procedures employed by dissolution kinetics. Recalculation of the activation energies EA of the dehydroxylation yielded the values 130, 132, 128, and 123 kJ mol−1 for pure goethite, goethite with 10, 20, and 30 mol% Al substitution, respectively. The values of EA are in a good agreement with those given for goethite in literature. The EA values are linearly related with the chemically bound excess H2O/OH− in the crystal lattice that is apparently influenced by Al substitution.
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  • 98
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 841-849 
    ISSN: 1572-8943
    Keywords: cobalt(II)-dothiepin ; kinetics ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The complexes of cobalt(II) with dothiepin (DOT) hydrochloride have been studied for kinetics of thermal degradation by thermogravimetric analysis (TG) and derivative thermogravimetric studies (DTG) in a static nitrogen atmosphere at a heating rate of 10° C min−1. A general mechanism of thermal decomposition is advanced involving dehydration and decomposition process for both organic and inorganic ligands. The thermal degradation reactions were found to proceed in three steps having an activation energy in the range 6.75–170 kJ mol−1. Thermal decomposition kinetics parameters were computed on the basis of thermal decomposition data.
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  • 99
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    Electronic Resource
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    Journal of thermal analysis and calorimetry 56 (1999), S. 297-303 
    ISSN: 1572-8943
    Keywords: β-zeolite ; coke ; cumene ; kinetics ; regeneration ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An accurate description of coke burn off is obtained from a catalyst based on β-zeolite and used for benzene alkylation with propylene giving cumene by using the thermogravimetric technique. A simple empirical kinetic model was successfully applied to interpolate the data of thermogravimetric analysis performed on samples after partial burn off. Different temperatures, partial pressures of oxygen and gas flow rates were the variables studied in order to calculate the apparent rates and the activation energy for the coke oxidation reaction and to outline the best conditions for the industrial regeneration procedure of our proprietary catalyst PBE-1 for cumene synthesis. Combining the unusually long lifetime per reaction cycle with the optimized regeneration procedure leads to an outstanding overall catalyst life.
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  • 100
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 953-958 
    ISSN: 1572-8943
    Keywords: differential scanning calorimeter ; kinetics ; oil shale ; pyrolysis ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this research, non-isothermal pyrolysis behavior and kinetics of three oil shales were studied by thermal analysis methods. All the thermal effects were endothermic and no exothermic region was observed in DSC curves. When oil shales are heated in nitrogen atmosphere in TG/DTG, two different mechanisms causing loss of mass were observed. The region between ambient temperature and 500 K was distillation. The second mechanism was visbreaking and cracking and it was observed between the region 500 and 800 K. Kinetic parameters of all the samples are determined by Coats and Redfern method and the results are discussed with regard to their accuracy and the ease of interpretation.
    Type of Medium: Electronic Resource
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