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  • kinetics  (727)
  • phosphorus  (682)
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  • 1
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    European journal of nutrition 26 (1987), S. 125-137 
    ISSN: 1436-6215
    Keywords: vitamin C ; functions ; kinetics ; pool ; saturation ; requirements ; RDA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Zusammenfassung Die Bedeutung von Vitamin C für den menschlichen Organismus wird aus den wichtigen Funktionen ersichtlich, an denen das Vitamin beteiligt ist, wie zum Beispiel Kollagen- und Karnitinsynthesen. In neuerer Zeit entdeckt wurde seine Rolle bei der Noradrenalinsynthese, der Inaktivierung von freien Radikalen sowie der Verhinderung der Nitrosaminbildung. Die Vielfalt dieser Vitamin-C-abhängigen Funktionen läßt erkennen, daß die Bedarfsfestsetzung für Vitamin C nicht nur die Verhütung der Mangelkrankheit Skorbut anvisieren, sondern auch berücksichtigen sollte, daß alle diese Funktionen jederzeit genügend Vitamin C zur Verfügung haben müßten, um optimal reagieren zu können. Das Konzept der Gewebesättigung kommt diesem Ziel am nächsten. Studien mit einem kinetischen Modell haben ergeben, daß eine Sättigung mit täglicher Einnahme von 100 mg Vitamin C bei Nichtrauchern und von 140 mg bei Rauchern eintritt, Mengen, die als optimale Werte gelten können. Bei verschiedenen Krankheiten dürfte der Bedarf höher sein; die genauen Mengen müssen jedoch erst noch ermittelt werden.
    Notes: Summary The importance of vitamin C is reflected in its multifunctional roles which include participation in collagen and carnitine syntheses, promotion of iron absorption and the more recently discovered participation in noradrenaline synthesis, inactivation of free radical chain reactions, prevention of N-nitroso compound formation and more. Given the many extra-antiscorbutic functions of the vitamin, the Recommended Dietary Allowances (RDA) should not just prevent deficiency disease but should aim at providing sufficient amounts for all vitamin C-dependent functions to operate at full capacity. The concept of vitamin C tissue saturation is best able to meet this demand. The use of kinetic models has shown that the body pool is saturated with a daily intake of 100 mg vitamin C in non-smokers and 140 mg in smokers, amounts that may be regarded as optimal RDA values. Certain disease states may be accompanied by still higher vitamin C requirements but the exact amounts are not yet known.
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  • 2
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    Colloid & polymer science 261 (1983), S. 188-189 
    ISSN: 1435-1536
    Keywords: Polymerization ; kinetics ; redox polymerization ; acrylamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 3
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    Colloid & polymer science 266 (1988), S. 958-964 
    ISSN: 1435-1536
    Keywords: a-Se colloids ; photoadsorption ; kinetics ; activation energy ; compensation effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this study, a model is developed to explain in microscopic terms the results obtained from thermally activated photoadsorption experiments in a-Se colloids. The observed compensation effect can be described for two different cases. At low efficiency adsorption, the process is controlled by the potential at the boundary layer. In the high efficiency adsorption case, the process is controlled by diffusion transport.
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  • 4
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    Colloid & polymer science 262 (1984), S. 366-373 
    ISSN: 1435-1536
    Keywords: kinetics ; isothermal crystallization ; polymer ; spherulite ; differential scanning calorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In the DSC technique, isothermal crystallization experiments are usually performed on thin flat specimens, but their interpretation generally uses theories developed for an unbounded volume. In this paper, isothermal crystallization of spherical entities in the volume limited by two parallel infinite planes is considered. Our model, derived from Avrami's theory, gives an analytical expression for the transformed volume fraction as a function of time. It is shown that the influence of thickness becomes important when thickness becomes of the order of or smaller than the average spherulite radius. The main effects of a decreasing thickness are a slower crystallization kinetics and a decrease in the Avrami exponent. These results can be used to interpret experimental data obtained in isothermal polymer crystallization.
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  • 5
    ISSN: 1435-1536
    Keywords: Phospholipid bilayer ; kinetics ; laser temperature jump ; phase transition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The iodine-laser temperature-jump technique has been used to investigate the main phase transition in single shell vesicles of dimyristoylphosphatidylcholine. The probe molecules DPH and TMA-DPH were incorporated into the lipid bilayer and laserT-jump experiments with turbidity and flourescence polarization detection were performed. We found three well separated relaxation processes between 5 μs and 10 ms. The relaxation signals showed strong cooperativity in the relaxation times as well as in their corresponding amplituedes. We attributed the relaxation to the formation and dissolution of clusters of different order inside the bilayer.
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  • 6
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    Colloid & polymer science 265 (1987), S. 58-64 
    ISSN: 1435-1536
    Keywords: Polymerisation ; emulsion ; styrene ; methylmethacrylate ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The dependence of emulsion polymerisation rates on a number of important parameters is considered. Attention is paid to the use of seeded emulsion systems for the evaluation of radical desorption coefficients (k o). Experimental conditions are shown to be important. When the average number of radicals per particle is low, large changes in the rate coefficient for chain termination do not have a large effect on the kinetics. With styrene and methylmethacrylate, radical re-absorption by the polymer particles is shown to be important and radical capture efficiences can be high. Consistency is established between the results of a number of workers and values fork o are shown to be lower than those calculated from chain transfer rates.
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  • 7
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    Colloid & polymer science 261 (1983), S. 621-625 
    ISSN: 1435-1536
    Keywords: Polyamide 6 ; crystallisation ; kinetics ; titania
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics of isothermal and nonisothermal crystallization of polyamide-6 (PA6) containing titania was studied by means of DSC. It was found thatTiO 2 causes an acceleration in the crystallization of polyamide-6 and lowers the value of the Avrami exponent,n. The presence of TiO2 does not affect equilibrium melting pointT m 0 , glass temperatureT g, or surface free energiesσ e andσ of the basal and lateral surfaces.
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  • 8
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    Fire technology 20 (1984), S. 47-63 
    ISSN: 1572-8099
    Keywords: Extinguishment ; fire modeling ; mass loss ; heat release ; char ; reflash ; sprinklers ; radiant flux ; kinetics ; reaction rate ; heat loss ; ash ; latent heat ; spray density ; extinguishing agents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying
    Notes: Abstract The Ad Hoc Mathematical Fire Modeling Working Group was organized about seven years ago to facilitate voluntary cooperation and coordination in developing mathematical fire modeling capability. The group has a steering committee of representatives of agencies that support fire modeling and related research. These include the National Bureau of Standards' Center for Fire Research, Factory Mutual Research Corp., the Naval Research Laboratory, NASA, and the Federal Aviation Agency. The Group holds plenary meetings when it seems desirable to do so (about once each 1 1/2 years), and workshops on topical subjects. Three workshops were held in 1983. Normally, Group meetings are held before or after other meetings at which a number of interested personnel would likely be present. Minutes are mailed to those who attended and to others (including European and Japanese personnel) who have indicated interest. This workshop was arranged by Ron Alpert of Factory Mutual Research Corp. and held at their facilities at Norwood, MA, in November 1983.
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  • 9
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    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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  • 10
    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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  • 11
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    Journal of solution chemistry 11 (1982), S. 339-346 
    ISSN: 1572-8927
    Keywords: Carbon dioxide ; hydrolysis ; aqueous solution ; kinetics ; activation volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pressure dependence of the dehydration reaction of H2CO3 was measured in acidic aqueous solution for pressures up to 1 kbar using a high-pressure stopped-flow instrument. The corresponding volume of activation was found to be 6.4±0.4 cm3-mol−1 at 25°C and 0.5 ionic strength. Volume equation calculations result in a value of −9.9±1.9cm3-mol−1 for the volume of activation for the hydrolysis of CO2 under the same conditions. For the first time, the reaction mechanism can be interpreted in terms of dissociative and associative modes, respectively. These data are used to construct an overall reaction volume profile.
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  • 12
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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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  • 13
    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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  • 14
    ISSN: 1572-8927
    Keywords: Temperature jump ; kinetics ; thermodynamics ; TRIS ; iminodiacetic acid ; magnesium ion ; phenol red
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Equations describing the temperature jump amplitudes associated with a system of two coupled reactions (TRIS-phenol red) as well as the ternary system (Mg2+-iminodiacetic acid-phenol red) are presented. The termodynamic parameters calculated from experimentally measured temperature perturbation amplitudes using a multiparametric curve fitting procedure are found to be in good agreement with those determined from pH- and costant rate thermometric titrations. For phenol red, pK I =7.55, ΔH I =3.45 kcal, and for Mg2+ iminodiacetic acid, log K M =2.84, ΔH M =3.25 kcal, were obtained. It is shown that this method can be used to determine accurate thermodynamic enthalpy changes over a narrow temperature interval of less than 1.0°C from a single experiment requiring about 50 μl of sample solution.
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  • 15
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    Journal of solution chemistry 12 (1983), S. 771-781 
    ISSN: 1572-8927
    Keywords: Ultrasonics ; kinetics ; aqueous solution ; iso-butyl cellosolve
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ultrasonic absorption and velocity measurements in aqueous solution of iso-butyl cellosolve (ethylene glycol iso-butyl ether) as a function of the concentration are reported. The two relaxational absorptions have been attributed to the perturbation of the equilibria expressed by AB⇌A+B and Aα(1/n)An where A is the solute, B is the solvent, AB is the complex and A n is the solute aggregate. The rate constants for each step have been determined. From the concentration dependence of the maximum excess absorption per wave length, the enthalpy change and the volume change for the reaction between the solute and the solvent have been determined for aqueous solutions of butyl cellosolve (ethylene glycol n-butyl ether), iso-butyl cellosolve and propyl cellosolve (ethylene glycol n-propyl ether). The results are consistent with a hydrogen bonding reaction. The effect of the ethers on water structure are considered and it is clear that the fraction of water molecules which can hydrogen bond to the solute decreases with the increasing hydrophobicity of the solute.
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  • 16
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; aqueous solvent mixtures ; Co(III) complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the solvolysis of [Co(CN)5Cl]3− have been investigated in water +2-methoxyethanol and water + diethylene glycol mixtures. Although the addition of these linear hydrophilic cosolvent molecules to water produces curvature in the variation of log(rate constant) with the reciprocal of the dielectric constant, their effect on the enthalpy and entropy of activation is minimal, unlike the effect of hydrophobic cosolvents. The application of a Gibbs energy cycle to the solvolysis in water and in the mixtures using either solvent-sorting or TATB values for the Gibbs energy of transfer of the chloride ion between water and the mixture shows that the relative stability of the emergent solvated Co(III) ion in the transition state compared to that of Co(CN)5Cl3− in the initial state increases with increasing content of cosolvent in the mixture. By comparing the effects of other cosolvents on the solvolysis, this differential increase in the relative stabilities of the two species increases with the degree of hydrophobicity of the cosolvent.
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  • 17
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    Journal of solution chemistry 6 (1977), S. 203-216 
    ISSN: 1572-8927
    Keywords: Glucose ; kinetics ; mixed solvent ; kinetic isotope effect ; enthalpy of activation ; entropy of activation ; tetrahydrofuran ; tert-butanol ; mutarotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The mutarotation rates of glucose in aqueous mixtures of tetrahydrofuran andtert-butanol in the mole fraction (xi) range 0〈xi〈0.2 have been measured at 5° intervals in the range 5–35°C. The kinetic deuterium isotope effects have been determined for the same solvent compositions at 25 and 35°C. A statistical analysis of the Arrhenius plots indicates that the experimental errors, although small, are too large for the establishment of any compensation behavior between ΔH
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  • 18
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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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  • 19
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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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  • 20
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    Journal of solution chemistry 19 (1990), S. 1073-1084 
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; mixtures of water+cosolvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Rates of solvolysis of the complex cation [Co(4tBupy)4Cl2]+ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy ΔH* and the entropy ΔS* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of ΔH* with ΔS* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (C n+) going to the transition state [M(n+1)+...Cl−] in water and in the mixture using free energies of transfer of the individual ionic species, ΔG t o (i), from water into the mixture. Values for ΔG t o (i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M(n+1)+, more than in the initial state, C n+. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)4Cl2]+ and [Coen2LCl]+ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of ΔG t o (Cl−) from either source.
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  • 21
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    Journal of solution chemistry 2 (1973), S. 217-238 
    ISSN: 1572-8927
    Keywords: Cation ; energies ; H. S. Frank ; M. Eigen ; R. G. Wilkins ; kinetics ; ligand substitution ; mechanism ; mixed solvents ; nonaqueous ; solvation ; solvent ; solvent structure ; solvent exchange ; transition metal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The role of the solvent in reactions involving ions is considered in relation to the structure of liquids. The rate constants and activation parameters for ligand substitutions at divalent transition metal cations in various solvents are compared with those for solvent exchanges. The differences are related to structural properties of the solvents, represented by their heats of evaporation and fluidities, and interpreted with the aid of a model developed from that of Frank and Wen. Water is not a typical solvent.
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  • 22
    ISSN: 1572-8927
    Keywords: Cu(II) ; kinetics ; reduction ; temperature dependence ; H2O2, NaCl, NaBr, NaClO4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rates of reduction of Cu(II) with H2O2 have been measured in NaCl and NaBr solutions and mixtures with NaClO4 as a function of pH (6 to 9), temperature (5 to 45°C) and ionic composition (0.1 to 6M). The effect of pH on the rates was found to be independent of temperature and ionic composition. The rates increased as a function of [H+] raised to the power of 1.3 to 1.6. Speciation calculations indicate that this pH dependence can be attributed to Cu(OH)2 being the reactive species. The rate constants in NaCl and NaBr and mixtures with NaClO4 were independent of ionic strength, but proportional to the halide concentration raised to the power of 2.0 (0.2 to 2.6M). These results can be attributed to Cu(OH)2Cl 2 2− being the reactive species to reduction with H2O2. The Cu(I) halide complexes formed from the reduction are not easily oxidized with O2 or H2O2. The faster rates in Br− solutions, which form stronger complexes with Cu+, support this contention. Measurements made in NaCl with added NaHCO3, NaB(OH)4 EDTA, NTA and glycine were also made. These measurements indicate that the CuL complexes (L=B(OH) 4 − , CO 3 2− , EDTA, NTA, and glycine) are not very reactive to reduction with H2O2. The addition of Mg2+ or Ca2+ caused the rates to increase due to the formation of MgL or CaL complexes and the resultant release of reactive Cu2+.
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  • 23
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    Journal of solution chemistry 23 (1994), S. 483-500 
    ISSN: 1572-8927
    Keywords: Thermodynamics ; kinetics ; chemical relaxation ; temperature-jump ; amplitudes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Amplitudes of chemical relaxation signals can provide useful information as to the thermodynamics of coupled chemical reactions. The temperature-jump technique has been used to investigate the thermodynamic behavior of the Nickel(II)-3,5-dinitrosalicylate system in buffer solution, where complex formation steps are coupled to proton transfer steps. The analysis of the relaxation curves is based on the transformation of a set of coupled elementary reactions into a set of uncoupled ‘normal reactions.’ By analogy with classical titrations, the experiments have been performed by changing the metal ion concentration at constant ligand concentration and pH. Each measured amplitude is associated in this way to a point of a ‘dynamic titration’ and a procedure is formulated by which the values of the equilibrium constants and enthalpies of the normal reactions are simultaneously obtained by simple linear plots. From the dependence of these parameters on suitable functions of the concentrations of the reactants the values of ΔG° and ΔH° of the individual steps are derived. It is shown that the addition of a buffer (instead of an indicator) influences the stoichiometric coefficients of the normal reaction in such a way that measurable amplitudes are produced in systems that, as the presently investigated, in unbuffered solution would remain insensitive to the external perturbation. The circumstances under which the dynamic method offers advantages over the classical techniques are discussed.
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  • 24
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    Journal of solution chemistry 5 (1976), S. 163-169 
    ISSN: 1572-8927
    Keywords: Solvent effects ; tetramethylurea ; hydrolysis ; hydrogen bonding ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Tetramethylurea was hydrolyzed in aqueous hydrochloric acid at temperatures of 80, 90, and 100°C. All reactions were carried out in an excess of both tetramethylurea and water, with first-order dependence on acid concentration being observed. As the concentration of water was increased, the rate of hydrolysis decreased until equimolar amounts of water and tetramethylurea were present. Subsequent addition of water had no effect on the observed rate.
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  • 25
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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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    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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  • 27
    ISSN: 1572-8757
    Keywords: characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
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    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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  • 28
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
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    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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  • 29
    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; reaction activation barrier ; carbon chain growth and termination ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A method is established, by which the difference of the reaction activation barriers of carbon chain growth and termination in Fischer-Tropsch (FT) synthesis can be determined from experiments. A FT synthesis is carried out on Fe/Zn catalyst. We apply the method to analyze the experimental result and obtain the difference of reaction activation barriers of carbon chain growth and termination of α-olefins on the catalyst.
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  • 30
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    Catalysis letters 37 (1996), S. 167-172 
    ISSN: 1572-879X
    Keywords: dissociation ; kinetics ; Co-Mo sulphide ; H2S
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    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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  • 31
    ISSN: 1572-879X
    Keywords: selective catalytic reduction ; nitric oxide reduction ; phosphorus ; acid property
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    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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  • 32
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    Cellulose 1 (1994), S. 26-56 
    ISSN: 1572-882X
    Keywords: low-temperature degradation ; kinetics ; mechanisms ; electrical insulation ; transformers
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    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A critical review is given of the degradation of cellulose in the low-temperature region (below about 300°C) of power transformer operation. The large number of kinetic studies, under a variety of environmental conditions from Kraft paper in insulating oil, to cotton and paper in oxygen, are considered in terms of a first-order polymer chain scission model. In many cases, the data are replotted to suit the model. A common activation energy of 111±6 kjmol−1 is calculated and it is shown that the pre-exponential factor, rather than the activation energy, is sensitive to the oxidizing nature of the environment and the susceptibility to degradation of the material. The chemical mechanisms of degradation are reviewed, and conclusions and recommendations are made regarding chemical condition monitoring and life prediction of electrical insulation.
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  • 33
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    Adsorption 6 (2000), S. 137-147 
    ISSN: 1572-8757
    Keywords: adsorption ; kinetics ; linear driving force model ; process design
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    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Linear Driving Force (LDF) model for gas adsorption kinetics is frequently and successfully used for analysis of adsorption column dynamic data and for adsorptive process designs because it is simple, analytic, and physically consistent. Yet, there is a substantial difference in the characteristics of isothermal batch uptake curves on adsorbent particles by the LDF and the more rigorous Fickian Diffusion (FD) model. It is demonstrated by using simple model systems that the characteristics of the adsorption kinetics at the single pore or the adsorbent particle level are lost in (a) evaluating overall uptake on a heterogeneous porous solid, (b) calculating breakthrough curves from a packed adsorbent column, and (c) establishing the efficiency of separation by an adsorptive process due to repeated averaging of the base kinetic property. That is why the LDF model works in practice.
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  • 34
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    Catalysis letters 37 (1996), S. 173-179 
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
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    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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  • 35
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    Catalysis letters 27 (1994), S. 79-90 
    ISSN: 1572-879X
    Keywords: kinetics ; carbon ; oxygen ; recombination ; rhodium ; surface characterisation ; XPS ; AES
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Different mechanisms of atomic carbon and oxygen recombination on a rhodium surface are studied with Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The kinetics of adsorbed carbidic carbon oxidation (carbon coverageθ c ≈ 0.1–0.3 ML) by gas-phase oxygen that proceeds by a Langmuir-Hinshelwood reaction mechanism, provides the value of the activation energy for recombination (E rec ⇂t ≈ 170±20 kJ/mol).E rec ⇂t depends slightly on the carbon coverage. An Eley-Rideal type of reaction was observed for adsorbed oxygen and atomic gas-phase carbon recombination which occurs in a dynamic regime. The low value found for the activation energy (near zero) is consistent with the mechanism that this exothermic reaction is too fast for energy dissipation into the substrate; the energy is mainly transferred into translational, vibrational and rotational energy of CO.
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  • 36
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; kinetics ; ruthenium catalysts ; promotional effect
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of NH3 synthesis over carbon-based ruthenium catalysts promoted with barium or alkali was studied. Both the ammonia partial pressure dependencies of the reaction rates (T = 400°C, p = 63 bar, H2 : N2 = 3 : 1) and the pressure variations of the activity (T = 370°C, p= 4–63 bar, H2 : NN2 = 3 : 1) were found to be different for Ba and for the alkali (K, Cs). Ba–Ru/C proved to be more sensitive to the NH3 content and to the total pressure. The rate of synthesis over the alkali-promoted catalysts is, in turn, much stronger influenced by the ruthenium dispersion. TOFs of NH3 synthesis for the promoted samples at 370°C and 4 bar (Ba 0.085 1/s, Cs 0.05 1/s, K 0.035 1/s) are significantly higher than that for the Ru(0001) basal plane (0.0085 1/s results from the literature data at 370°C, 2 bar). The most active Ru/C samples (Ba or Cs) exceed significantly the fused iron catalyst, especially at high conversions.
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  • 37
    ISSN: 1572-882X
    Keywords: accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
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    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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  • 38
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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
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    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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  • 39
    ISSN: 1572-8927
    Keywords: Enthalpies of reaction ; heats of reaction ; kinetics ; ester hydrolysis ; microcalorimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The conditions under which the Picker flow microcalorimeter can be used to measure enthalpies and rates of reactions were investigated. For this purpose, systematic studies were made of the enthalpies of neutralization of HCl, HBr, HNO 3 , acetic, proprionic, and butyric acids with NaOH, enthalpies of hydrolysis of methyl and ethyl acetate with NaOH, and the reaction rates of the ester hydrolysis with NaOH. The general procedure and various sources of error are discussed and it is concluded that enthalpies of slow reactions can be measured to about 1% when the calorimeter is operated in the quasi-isothermal mode and the reaction rates to about 3% when operated in the quasi-adiabatic mode.
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  • 40
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    Cellulose 4 (1997), S. 1-5 
    ISSN: 1572-882X
    Keywords: paper ; degradation ; ageing ; kinetics ; modelling
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    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
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  • 41
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    Cellulose 3 (1996), S. 243-267 
    ISSN: 1572-882X
    Keywords: aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
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    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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  • 42
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    Journal of solution chemistry 3 (1974), S. 881-887 
    ISSN: 1572-8927
    Keywords: Binary aqueous mixtures ; solubilities ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A treatment which predicts the solubilities of gases in solvent mixtures is examined in the context of the analysis of kinetic data for reactions in aqueous mixtures. The treatment is qualitatively successful to some extent in resolving the effects of changes in the initial state of the reacting substrate in the activation parameters.
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  • 43
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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
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    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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  • 44
    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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  • 45
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    Journal of solution chemistry 15 (1986), S. 221-229 
    ISSN: 1572-8927
    Keywords: Ultrasonics ; kinetics ; aqueous solution ; triethylene glycol monobutyl ether
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The ultrasonic absorption from 6.5 to 220 MHz and velocities at 2.5 MHz have been measured in aqueous solution of triethylene glycol monobutyl ether as a function of concentration at 25°C. A single relaxational excess absorption, observed from 0.60 to 2.5 mol-dm−3, is attributed to a perturbation of an equilibrium associated with solute-solvent interaction. Rate constants for the forward and reverse processes have been determined from the concentration dependence of the relaxation frequency, and the influence on the water structure by an addition of the solute has been considered. Solution densities were also measured in order to obtain the expansivity of the solution. The standard volume and enthalpy changes of the reaction have been estimated from the concentration dependence of the maximum excess absorption per wave length. A linear relationship between the number of oxyethylene groups and the free energy change between bonded water and nonbonded water is established.
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  • 46
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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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  • 47
    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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  • 48
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    Topics in catalysis 1 (1994), S. 305-314 
    ISSN: 1572-9028
    Keywords: non-Langmuir ; kinetics ; non-linear dynamics ; oscillations ; chaos ; self-organization
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of a catalytic reaction is frequently formulated in terms of simple concepts of the Langmuir type. Apart from limitations arising from the non-uniformity of the catalyst's surface and from the coverage dependence of the rate “constants”, several other complications may come into play. These may arise on the “quantum level” where energy flow between the various degrees of freedom may cause failure of simple transition state theory, as well as on the “continuum level” where formulation of rate equations in terms of coupled non-linear differential equations may give rise to a rich scenario of spatio-temporal self-organization, including kinetic oscillations, chaos, and formation of concentration patterns. Several of these phenomena are illustrated by selected examples.
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  • 49
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    Topics in catalysis 11-12 (2000), S. 327-333 
    ISSN: 1572-9028
    Keywords: hydrodenitrogenation ; toluidine ; methylcyclohexylamine ; kinetics ; nickel-promoted molybdenum sulphide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The hydrodenitrogenation (HDN) of o-toluidine and its reaction intermediates was studied over a NiMo/γ-Al2O3 catalyst. The kinetics of the HDN of methylcyclohexylamine and of the hydrogenation of cyclohexene were also studied. Hydrogenation of o-toluidine alone produces methylcyclohexene and methylcyclohexane. When a sufficient quantity of cyclohexene is added during the HDN of toluidine, methylcyclohexylamine, the first intermediate in the hydrogenation of toluidine, becomes detectable. Because of its strong adsorption constant and high rate constant for reacting further to methylcyclohexene and methylcyclohexane, methylcyclohexylamine is not observed in the HDN of toluidine. Adding cyclohexene decreases the adsorption of methylcyclohexylamine, thus enabling its detection. The rate and adsorption constants of methylcyclohexylamine and cyclohexene in the HDN of methylcyclohexylamine were calculated by fitting the kinetic data to a Langmuir–Hinshelwood equation. A two-site model was used to describe the surface reactions, with one site for the methylcyclohexylamine reactions and the other for the cyclohexene reaction.
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    Aquatic sciences 53 (1991), S. 263-272 
    ISSN: 1420-9055
    Keywords: Lake ecosystem ; chl-a ; phosphorus ; nitrogen ; river flow ; thermocline ; simulation model ; multiple regression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The management variables which primarily affect phytoplankton biomass (as chl-a) in Lake Mjøsa, Norway, are total phosphorus loading (TP) and the timing and volume of water through flow (by active storage reservoirs). The response of the lake to changes in these factors is studied using a simulation model of the lake ecosystem. Chl-a responses from both observed data and the simulated results are extracted by multiple regression. Results show that decreasing TP load decreases chl-a, but less at low TP levels (〈 10 mg TP · m−3). There is also a certain time period for peak river flow which gives the least yield of chl-a per unit TP. This time period occurs in early summer (i.e., around June 10) if the total phosphorus load is low, and later if the load is high. Both observations and simulation results show that a high water flow increases chl-a at low epilimnion depths (〈 15 m), but that the same high water flow decreases chl-a when epilmnion is deep.
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  • 51
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    Aquatic sciences 52 (1990), S. 199-220 
    ISSN: 1420-9055
    Keywords: Eutrophication ; lake management ; phosphorus ; ecosystem ; chlorophyll-a ; mathematical modelling
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    Topics: Biology
    Notes: Abstract We compare results of a new model for predicting the short term inter annual changes in chlorophyll-a (chl-a) in lakes after reductions in total phosphorus (TP) to predictions made by least squares regression models. In the new method, slopes of chl-a/TP graphs (both axes in mg · m−3) are depicted in frequency diagrams and used to extract information on the expected, short term chl-a/TP response. The short term response for nine shallow (〈 10 m deep) and nutrient rich lakes to changes in TP was found to be: Chl-a = 0.49 · TP + 17.3, and for nine deep, P-limited lakes: Chl-a = 0.08 · TP + 3.5. If the TP-reduction is known to be greater than 10 mg · m−3, the expected slope increases to 0.58 for shallow lakes and to 0.26 for deep lakes. The slope, 0.58, is 8% lower than the slope for the long term response calculated by regression for the shallow lakes. For deep lakes the slope, 0.26, is 2 to 3 times higher than that calculated by regression, indicating that reductions in TP for deep lakes give greater effects than least squares regression equations suggest. We have also calculated the reduction in TP which will give about 80% probability that a reduction in chl-a will be observed next year. For shallow, P-limited lakes this reduction is about 30 mg · m−3 (5% of average initial in-lake TP concentration), and for deep lakes about 14 mg · m−3 (35% of average initial in-lake TP concentration).
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  • 52
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    Aquatic sciences 52 (1990), S. 256-268 
    ISSN: 1420-9055
    Keywords: Vertical mixing ; stratification ; phosphorus ; Lake Constance
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    Topics: Biology
    Notes: Abstract Depth variable vertical eddy diffusion coefficients for heat (K z) were calculated from continuously measured temperature profiles in Überlinger See (western part of Lake Constance). The temperatures were averaged over vertical intervals of 10 m yielding 14 discrete values (maximum depth of Überlinger See: 147 m). A linear fit from 10 June to 29 September 1987 was used to smooth the significant temperature fluctuations caused by internal seiches of Lake Constance. Assuming horizontal homogeneity for the smoothed data the Gradient-Flux-Method was applied to compute vertical diffusion coefficientsK z at different depths using the depth variable volumes and surfaces of the 14 layers. The resulting mean diffusion coefficients for the period from June to September are 0.04 cm2/s near the thermocline and up to 0.8 cm2/s in deeper strata (accuracy: ± 50%). It is shown that horizontal mixing between Überlinger See and Obersee (main lake) alters the computation ofK z by less than 50%. A relationship betweenK z and stability (Brunt-Väisälä) frequencyN is found which corresponds well to the theory of internal wave induced turbulence. Combining the diffusion coefficients with measured phosphorus profiles, a phosphorus flux from the hypolimnion to the epilimnion of (0.7 ± 0.4) mg P m−2 d−1 was calculated, corresponding to about 20% of the average external loading per area of Lake Constance in 1986.
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  • 53
    ISSN: 1420-9055
    Keywords: Sediment ; interstitial water ; phosphorus ; iron ; persulfate digestion
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    Topics: Biology
    Notes: Abstract It is shown that sorption of orthophosphate to iron compounds, formed during persulfate digestion, can cause a significant underestimation of total dissolved phosphorus in interstitial waters rich in iron and poor in phosphorus. Labelling the samples with carrier free32PO4 before digestion allows to correct for these losses.
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    Cellular and molecular life sciences 49 (1993), S. 110-117 
    ISSN: 1420-9071
    Keywords: Polymerization ; sickle hemoglobin ; sickle cell disease ; kinetics ; thermodynamics ; polymer domains ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.
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  • 55
    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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  • 56
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    Adsorption 6 (2000), S. 349-357 
    ISSN: 1572-8757
    Keywords: sulfadiazene ; adsorption ; kinetics
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    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10−3 mol cm−3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl−, SO2− 4 and PO3− 4 (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.
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  • 57
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated γ-alumina or zirconia compared to γ-alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/γ-alumina, Pt/zirconia, Pd/γ-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/γ-alumina, and Pd/zirconia is less active than Pd/γ-alumina.
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  • 58
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    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Keywords: furfural hydrogenation ; Cu/carbon catalysts ; kinetics
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    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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  • 59
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    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Keywords: ammonia decomposition ; iron catalyst ; kinetics
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    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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  • 60
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    Catalysis letters 64 (2000), S. 65-75 
    ISSN: 1572-879X
    Keywords: NO reduction ; CH3OH ; La2O3 ; methyl nitrite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Nitric oxide (NO) reduction by methanol was studied over La2O3 in the presence and absence of oxygen. In the absence of O2, CH3OH reduced NO to both N2O and N2, with selectivity to dinitrogen formation decreasing from around 85% at 623 K to 50–70% at 723 K. With 1% O2 in the feed, rates were 4–8 times higher, but the selectivity to N2 dropped from 50% at 623 K to 10% at 723 K. The specific activities with La2O3 for this reaction were higher than those for other reductants; for example, at 773 K with hydrogen a specific activity of 35 μmol NO/s m2 was obtained whereas that for methanol was 600 μmol NO/s m2. The Arrhenius plots were linear under differential reaction conditions, and the apparent activation energy was consistently near 14 kcal/mol with CH3OH. Linear partial pressure dependencies based on a power rate law were obtained and showed a near‐zero order in CH3OH and a near‐first order in H2. In the absence of O2, a Langmuir–Hinshelwood type model assuming a surface reaction between adsorbed CH3OH and adsorbed NO as the slow step satisfactorily fitted the data, and the model invoking two types of sites provided the best fit and gave thermodynamically consistent rate constants. In the presence of O2 a homogeneous gas‐phase reaction between O2, NO, and CH3OH occurred to yield methyl nitrite. This reaction converted more than 30% of the methanol at 300 K and continued to occur up to temperatures where methanol was fully oxidized. Quantitative kinetic studies of the heterogeneous reaction with O2 present were significantly complicated by this homogeneous reaction.
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  • 61
    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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  • 62
    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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  • 63
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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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  • 64
    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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  • 65
    ISSN: 1572-879X
    Keywords: Ultraviolet heterogeneous photocatalysis ; oxidation ; trichloroethylene ; titania ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetics of the gas/solid heterogeneous photocatalytic oxidation of dilute trichloroethylene (TCE) vapors by ultraviolet-illuminated titanium dioxide have been determined using a fixed-bed dynamic photoreactor. Reaction rate dependences on inlet TCE, oxygen and water vapor concentrations were found to consist of both reactant sensitive and insensitive regions. In the reactant sensitive regions, measured limiting apparent reaction rate orders for TCE, oxygen and water vapor are 0.8, 1.7 and — 3, respectively. Water vapor in the reactant stream lowersinitial reaction rates relative to corresponding water free conditions, but is required to sustain photocatalytic activity for extended periods of time.
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  • 66
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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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  • 67
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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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  • 68
    ISSN: 1572-879X
    Keywords: hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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  • 69
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    Catalysis letters 69 (2000), S. 103-107 
    ISSN: 1572-879X
    Keywords: dicyclopentadiene ; Wacker oxidation ; Pd(AcO)2 ; benzoquinone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of dicyclopentadiene catalyzed by palladium(II) acetate and benzoquinone in the presence of perchloric acid was studied. Tricyclodecenone in high selectivity (85–98%) at a conversion of dicyclopentadiene up to 76% was obtained. The kinetic model assumed the significant inhibition complexation between dicyclopentadiene and tricyclodecenone with the catalytic species.
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  • 70
    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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  • 71
    ISSN: 1436-5073
    Keywords: aluminium oxide ; phosphorus ; XRF ; RBS ; FTIR
    Source: Springer Online Journal Archives 1860-2000
    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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  • 72
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    Microchimica acta 94 (1988), S. 277-278 
    ISSN: 1436-5073
    Keywords: kinetics ; FT-IR ; temporal resolution
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A system for performing gas-phase rapid scanning Fourier transform infrared time-resolved Spectrometry (FT-IR/TRS) has been evaluated. This technique can be applied to the study of the lifetimes and reactivity of transient species and can provide detailed information regarding reaction rate constants. Temperature-jump experiments have been initiated and preliminary results are presented.
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  • 73
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    Microchimica acta 101 (1990), S. 273-279 
    ISSN: 1436-5073
    Keywords: aluminium analysis ; phosphorus ; sulfur ; chlorine
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Multi-step procedures for the determination of phosphorus, sulfur and chlorine are described and tested against established methods and on reference materials. Phosphorus is separated as hydrogen phosphide, extracted as phosphomolybdic acid, reduced to molydenum blue and measured photometrically (detection limit 0.05 μg/g). Sulfur is separated after reduction as hydrogen sulfide or by means of pyrohydrolysis and measured by ICP-OES (detection limit 0.1 μg/g). Chloride can be measured by ion chromatography after pyrohydrolytic separation (detection limit 0.1 μg/g). The determination of sulfur was also successfully tested on copper and steel samples.
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  • 74
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    Microchimica acta 94 (1988), S. 323-328 
    ISSN: 1436-5073
    Keywords: FTIR spectroscopy ; kinetics ; polymers ; rheo-optics ; variable-temperature measurements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rapid-scanning capability of FTIR instrumentation has revitalized the field of vibrational spectroscopy in polymer research and will be discussed with reference to the study of polyurethane kinetics, the temperature dependence of hydrogen bonding in polyamide 6 and strain-induced crystallization in a polydimethylsiloxane elastomer.
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  • 75
    ISSN: 1436-5073
    Keywords: phosphorus ; tungsten ; preconcentration ; ICP-OES
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method for the separation and preconcentration of traces of phosphorus from tungsten was developed. Solid phase extraction of the phosphovanadomolybdate complex performed on a micro-column was applied. Phosphorus was determined by optical emission spectroscopy (OES) with inductively coupled plasma (ICP) excitation. A limit of detection of 0.4 μg/g P with respect to the solid phase is obtained. By directly coupling the extraction/elution step to the ICP instrument a detection limit of 0.06 μg/g P in W was achieved. Besides, the complexity of spectral evaluation in ICP-OES determinations of traces in spectralline-rich matrices is discussed.
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  • 76
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    Microchimica acta 88 (1986), S. 245-247 
    ISSN: 1436-5073
    Keywords: Schöniger-flask method ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract By use of a fused-silica hook for holding the sample packet in a Schöniger combustion flask, even difficultly combustible phosphorus compounds can be completely decomposed.
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  • 77
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    Microchimica acta 109 (1992), S. 201-209 
    ISSN: 1436-5073
    Keywords: phosphonate base scale inhibitor ; brine ; direct current plasma ; inductively coupled plasma atomic emission spectrometry ; phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The determination of phosphonate base scale inhibitors in brines by direct current plasma (DCP) and inductively coupled plasma atomic emission spectrometry (ICP-AES) is described. The first method is based on a direct nebulization of the brine samples and plasma using the phosphorus line at 213.618 nm. The second method involves extraction of phosphorus as phospho-antimonyl molybdate complex into methylisobutyl ketone (MIBK) phase and analysis of the extract for molybdenum using the Mo 313.260 nm line. Comparison between the proposed methods and an established recommended method [1] shows excellent agreement between the results in addition to the sensitivity and ease of automation provided by AES.
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  • 78
    ISSN: 1436-5073
    Keywords: flow injection analysis (FIA) ; mercury ; porphyrin ; kinetics ; spectro-photometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS4) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min−1 for Hg(II) withm-Cl-TPPS4 in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 μl), the method's relative standard deviation was 0.82% (n = 12) at 5.0 μg ml−1 mercury, with a linear range of 0–12.0 μg ml−1 and an analytical frequency of 60h−1. The detection limit (3σ) was 0.025 μg ml−1. Interference studies showed that most metal ions co-existing with Hg2+ could be tolerated at 100-fold excess levels, but Zn2+, Cu2+ and Mn2+ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.
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  • 79
    ISSN: 1436-5073
    Keywords: atrazine ; terbuthylazine ; sequential binding ; kinetics ; cross-reactivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Immunoassays for triazine herbicides were tested for their reaction to the variation of the tracer incubation time. By application of a sequential technique the measuring range of atrazine could be expanded to five decades and the total duration of the test could be reduced to about 30 min. In an optimized version a lower detection limit of 9 pmol/l (2 ng/l) was achieved. The detection limit of a sensitive immunoassay for terbuthylazine is also below the concentration limit demanded of the German drinking water regulation (100 ng/l) and reaches 130 pmol/l (30 ng/l). Short tracer incubation times did not lead to increased cross-reactivities in contrast to theoretical models [1, 2]. Different mechanisms, which could cause a shift of the center point of the calibration curve, are discussed, including kinetic considerations.
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  • 80
    ISSN: 1436-5073
    Keywords: kinetics ; rates ; integrating ratemeter ; optimization ; first-order
    Source: Springer Online Journal Archives 1860-2000
    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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  • 81
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    Biodegradation 4 (1993), S. 163-170 
    ISSN: 1572-9729
    Keywords: factorial analysis ; kinetics ; methane ; methanotrophs ; nutrients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of different mineral nutrients on the kinetics of methane biodegradation by a mixed culture of methanotrophic bacteria was studied. The substrate factors examined were ammonia, iron, copper, manganese, phosphate, and sulphide. The presence of iron in the growth medium had a strong effect on the yield coefficient. Yield coefficients up to 0.49 mg protein per mg methane were observed when iron was added at concentrations of 0.10–5.0 mg/l. Iron addition also increased the maximum methane utilization rate. The same effect was observed after addition of ammonium to a medium where nitrate was the only nitrogen source. The observed Monod constant for methane utilization increased with increasing concentration of ammonia. This shows that ammonia is a weak competitive inhibitor as observed by other researchers. Relatively high levels of both ammonia (70 mg/l) and copper (300 µg/l) inhibited the methane degradation, probably due to the toxic effect of copper-amine complexes.
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  • 82
    ISSN: 1573-0417
    Keywords: Great Basin ; climatic variations ; productivity ; organic matter ; nitrogen ; phosphorus ; hardwater lake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Sediment cores from the shallow and deep basins of Pyramid Lake, Nevada, revealed variations in composition with depth reflecting changes in lake level, river inflow, and lake productivity. Recent sediments from the period of historical record indicate: (1) CaCO3 and organic content of sediment in the shallow basin decrease at lower lake level, (2) CaCO3 content of deep basin sediments increases when lake level decreases rapidly, and (3) the inorganic P content of sediments increases with decreasing lake volume. Variations in sediment composition also indicate several periods for which productivity in Pyramid Lake may have been elevated over the past 1000 years. Our data provide strong evidence for increased productivity during the first half of the 20th Century, although the typical pattern for cultural eutrophication was not observed. The organic content of sediments also suggests periods of increased productivity in the lake prior to the discovery and development of the region by white settlers. Indeed, a broad peak in organic fractions during the 1800's originates as an increase starting around 1600. However, periods of changing organic content of sediments also correspond to periods when inflow to the lake was probably at extremes (e.g. drought or flood) indicating that fluctuations in river inflow may be an important factor affecting sediment composition in Pyramid Lake.
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  • 83
    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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  • 84
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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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  • 85
    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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  • 86
    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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  • 87
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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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  • 88
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    Nutrient cycling in agroecosystems 1 (1980), S. 95-101 
    ISSN: 1573-0867
    Keywords: soil fertility ; phosphorus ; potassium ; green manure ; crop rotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Changes in the soil phosphorus and potassium status on three farming systems in the Northeast Polder during 25 years are related to the fertilizer regime over this period. The changes in the nutrient status of the soil are reflected in fertilizer policy. High rates of phosphate dressings markedly increased the phosphate status of the soil and built up a reserve of phosphate. In contrast, the potassium status decreased by about half, because only potatoes in the rotation were dressed with potassium. Methods of fertilization are discussed and suggestions are made with regard to possible improvements.
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  • 89
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    Nutrient cycling in agroecosystems 13 (1987), S. 155-159 
    ISSN: 1573-0867
    Keywords: triticale ; contents of nitrogen ; phosphorus ; potassium ; calcium ; magnesium ; trace elements ; heavy metals ; stage of growth
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Description / Table of Contents: Zusammenfassung Es wurden die Schwankungen in den Konzentration von N, P, K, Ca, Mg, Fe, Mn, Zn, Cu, B, Ba, Be, Bi, Sn, Sr, Sb, Ti, Te, V, Se, As und Hg in Triticale unter Feldbedingungen untersucht. Von der Bestockung bis zur Vollreife wurden alle 10 Tage von je 0.5 m2 pro Parzelle Pflanzenproben genommen. In allgemeinen haben die Konzentrationen von Frühjar bis zur Ernte abgenommen. Der elementengehalt in Triticale war demjenigen der übrigen Getreidearten verschieden, aber der Trend der Änderungen war ähnlich.
    Notes: Abstract The variation of N, P, K, Ca, Mg, Fe, Mn, Zn, Cu, B, Ba, Be, Bi, Sn, Sr, Sb, Ti, Te, V, Se, As and Hg concentrations was studied under field conditions in triticale. The samples were collected every 10 days from tillering to full ripening stage using plant material from 0.5 m2 per plot. The concentrations generally decreased from early growth to harvest. The elemental concentrations in triticale differed from the other cereals, but the variation's trend was similar.
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  • 90
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    Nutrient cycling in agroecosystems 14 (1987), S. 135-142 
    ISSN: 1573-0867
    Keywords: nitrogen ; phosphorus ; soil and crop residues management practices ; maize yield ; Plinthudult ; Cameroon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The shortening of fallow period in several areas in tropical Africa has reduced soil fertility and exposed soils to erosion and run-off. Fertilizer application and crop conservation practices are needeed to sustain high crop yield and to conserve the natural resource base for upland crop production in the continent. Field trials were carried out to evaluate the effect of fertilizer application and soil and crop residues management practices on yield of maize (Zea mays L.) planted on a Plinthudult soil at Bertoua, Eastern Cameroon. Maize yields increased significantly with nitrogen and phosphorus fertilizer application. Under the rainfall pattern prevailing in the area, the amount of nitrogen required for maximum yield was higher in the second season. On the other hand, the amount of phosphorus required for maximum yield appeared to decrease with time. The burning of crop residues and weeds prior to planting together with no-till practive gave higher yield of maize than other soil and crop residues management practices.
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  • 91
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    Nutrient cycling in agroecosystems 17 (1988), S. 101-118 
    ISSN: 1573-0867
    Keywords: Nitrogen ; phosphorus ; potassium ; organic matter ; fallow ; forecasting ; fertilizer requirement ; Sierra Leone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The quantities of nitrogen, phosphorus and potassium supplied by an ‘average’ African soil cleared from bush fallow, assuming no losses, were approximated. Values ranged from 23 to 120 Kg N ha−1, 1.8 to 12 Kg P ha−1, 47 to 187 Kg K ha−1, depending on type of fallow, length of fallow, drainage and extent of depletion of native supplies. Additional amounts of 4 to 5 Kg N ha−1, 4 to 6 Kg P ha−1 and 14 to 20 Kg K ha−1 are obtained from the ash. Using crop nutrient removal data and approximate efficiencies of native and fertilizer N, P and K, fertilizer requirements at the reconnaissance level were estimated for selected target yields. For newly cleared uplands at cropping/fallow ratio of 2:7, N fertilizer requirements for cassava (30 t ha−1), maize (4 t ha−1), and sweet potato (16 t ha−1), were 138, 98, 42 kg ha−1 respectively. Wetland rice (4 t ha−1) required 55 kg N ha−1. Corresponding P fertilizer requirements for cassava, maize, sweet potato, upland rice (1.5 t ha−1) and ground-nut (1 t ha−1) were 190, 80, 30, 30 and 16 kg P ha−1 respectively. Wetland rice required 83 kg P ha−1. Substantial residual values of applied P are to be expected. Cassava required 60 kg ha−1 of K on newly cleared land. In soils of lowered nutrient status higher N, P, and K fertilizer requirements were indicated for all crops. Land use data from Sierra Leone were used to illustrate how the total quantities of N, P and K fertilizers in a country in the forest zone of Africa can be approximated. Fertilizer needs in Sierra Leone were in decreasing order P 〉 N ≫ K. N, P and K requirements were estimated to be 10,000 t, 20,000 t and 4,000 t respectively. The nutrient balance sheet method described in this paper is a useful tool to estimate the order of magnitude of fertilizer requirement at selected target yields for countries in Africa.
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  • 92
    ISSN: 1573-0867
    Keywords: farmyard manure ; maize ; nitrogen ; phosphorus ; rice ; wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Field experiments with rice-wheat rotation were conducted during five consecutive years on a coarse-textured low organic matter soil. By amending the soil with 12t FYM ha−1, the yield of wetland rice in the absence of fertilizers was increased by 32 per cent. Application of 80 kg N ha−1 as urea could increase the grain yield of rice equivalent to 120 kg N ha−1 on the unamended soil. Although the soil under test was low in Olsen's P, rice did not respond to the application of phosphorus on both amended and unamended soils. For producing equivalent grain yield, fertilizer requirement of maize grown on soils amended with 6 and 12 t FYM ha−1 could be reduced, respectively to 50 and 25 per cent of the dose recommended for unamended soil (120 kg N + 26.2 kg P + 25 kg K ha−1). Grain yield of wheat grown after rice on soils amended with FYM was significantly higher than that obtained on unamended soil. In contrast, grain yield of wheat which followed maize did not differ significantly on amended or unamended soils.
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  • 93
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    Nutrient cycling in agroecosystems 20 (1989), S. 27-32 
    ISSN: 1573-0867
    Keywords: Cropping system ; phosphorus ; rice ; wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A long term field experiment was conducted on a sandy loam soil from 1983 to 1987 to determine how to best apply phosphorus fertilizer in a rice-wheat cropping system. The treatments included 9 combinations of phosphorus application either to both rice and wheat or to rice or wheat alone. Direct application of phosphorus at 13 kg/ha to both the crops resulted in significantly higher total productivity of the rice-wheat cropping system as compared with 26 kg P/ha applied either to rice or wheat alone. Phosphorus at 13 kg/ha for rice and 26 kg/ha for wheat was as efficient as 13 kg P/ha for rice and 13 kg P/ha for wheat. The higher rate of P (26 kg/ha) applied to both rice and wheat resulted a decline in the total productivity. The residual effects of phosphorus applied to either rice or wheat were significant to the succeeding crop but was inferior to its direct application. Phosphorus increased the leaf area index, chlorophyll content of leaves, and interception of more photosynthetically active radiation (PAR) which resulted in increased grain yield of rice and wheat. Phosphorus status of the surface soil declined markedly, in the absence of P application from 15.4 to 6.4 kg P/ha. Phosphorus applied at 26 kg P/ha to both the crops resulted a build up of the available P status of soil. Phosphorus application at 13 kg/ha to both rice and wheat maintained the phosphorus status of the soil at original level.
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  • 94
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    Nutrient cycling in agroecosystems 36 (1993), S. 127-133 
    ISSN: 1573-0867
    Keywords: hydrology ; water balance ; phosphorus ; Streamflow ; Peel-Harvey
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This paper discusses the land types, hydrologic characteristics and processes, and the major modification of these, in relation to mechanisms and magnitude of phosphorus losses to drains and riverine systems which discharge to the Peel-Harvey estuary. About 75% of the coastal plain part of the catchment is cleared of native vegetation and used for dryland, dairy and beef grazing. There are small areas devoted to irrigated pasture and commercial horticulture. Seventy-five percent of the soils of the catchment are sandy surfaced with a poor capacity to retain phosphorus. Though the area is flat, catchment water yields are high because of a large winter rainfall excess and low soil storage capacity. Drainage schemes have been constructed in much of the catchment to remove excess water quickly. This was required initially to allow agricultural expansion and is now important for protecting a growing infrastructure which serves the most populous region of Western Australia.
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  • 95
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    Nutrient cycling in agroecosystems 21 (1989), S. 19-22 
    ISSN: 1573-0867
    Keywords: VAM fungi ; phosphorus ; molybdenum ; interaction ; maize
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Vesicular arbuscular mycorrhizal fungi (VAM) when applied to soils can result in marked increases in plant growth and P uptake. Application of molybdenum can also result in a synergistic interaction with phosphorus, with reslutant increases in plant dry matter production. The current investigation was designed to evaluate P X Mo X VAM interactions on yield and P uptake of sweet corn (Zea mays L.) The experiment was conducted in the greenhouse using soils from Missouri and Jamaica (West Indies) which were very low in available soil P. Corn was grown in pots amended with P and VAM, with and without Mo. Colonizing Jamaican soil amended with P withGlomus etunicatum increased shoot dry matter weights significantly. Greatest P uptake occured in treatments receiving the highest application of P and mycorrhizal inoculation. There was a significant difference between the two soils with respect to treatment effects on micronutrient accumulation of the test crop. The decreases in Cu, Zn, Mn, and Mo concentration of corn leaves between control and the treated pots, is attributed to dry matter dilution effect. The results indicated that mycorrhizal inoculation increased the dry matter significantly in Jamaican soil amended with P, however not in Missouri soil.
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  • 96
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    Nutrient cycling in agroecosystems 37 (1994), S. 1-22 
    ISSN: 1573-0867
    Keywords: animal slurries and manures ; applications to soils ; carbon- ; nitrogen- ; phosphorus ; contamination ; crop production ; dissemination ; hazardous organics ; heavy metals ; inputs ; macro- and micronutrients ; pathogens ; sewage sludges ; survival- ; transfer- ; transport and adsorption rates in soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The European Community is producing annually about 300 × 106 tons of sewage sludges as well as about 150, 950,160 and 200 tons of domestic, agricultural, industrial and other wastes (street litter, dead leaves etc.). About 20–25% of the German sewage sludges, which contain in average about 3.8,1.6, 0.4, 0.6, 5.3% DM−1 N, P, K, Mg and Ca, 202, 5, 131, 349, 53, 3 and 1446 mg kg−1 DM Pb, Cd, Cr, Cu, Ni, Hg, Zn as well as ca. 37 and 5 mg kg−1 Dm polychlorinated hydrocarbons and biphenyls, are recycled annually as fertilizer. In addition environmental impacts on the arable land of Germany may derive from 76,19.2, 64.7, 33.6, 7.8 and 0.1 kg ha−1 a−1 of N, P, K, Ca, Mg and Cu added as animal manures. Besides heavy metals and hazardous organics pathogens are disseminated with organic wastes. Crop production and soil fertility generally profit from the considerable amounts of plant nutrients and carbon in sewage sludges, animal slurries and manures, but the physicochemical soil properties, the composition of microbial, faunal and plant communities as well as the metabolic processes in the soil-, rhizo- and phyllosphere are changed by organic manuring. Consequences for the soil carbon-, nitrogen-and phosphorus-cycle are discussed. Impacts of heavy metals and hazardous organics on the soil biomass and its habitat as well as on transport mechanisms and surival times of disseminated pathogens in soils are reviewed with emphasis on the German situation. A proposal for future strategies (landscape recycling) is made.
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  • 97
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    Nutrient cycling in agroecosystems 27 (1991), S. 107-111 
    ISSN: 1573-0867
    Keywords: Liming ; phosphorus ; heathland ; copper ; fertilization ; forest
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Forest fertilization in the Netherlands has played an important role in the phase of afforestation of former heathlands. Research started in the early fifties, but results were not applied in practical forestry. A review is presented on forest fertilization in practice, and on the main results of the activities of De Dorschkamp on NPK fertilization, liming and micronutrients application. Attention is paid to problems which have developed during the past ten years.
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    Nutrient cycling in agroecosystems 26 (1990), S. 253-269 
    ISSN: 1573-0867
    Keywords: Nitrogen ; phosphorus ; sulphur ; nutrient balances ; surface waters ; North Sea ; Baltic Sea ; eutrophication ; hypertrophication ; primary production
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Dissolved inorganic nitrogen and phosphorus, their relationship to each other (DIN/DIP) as predisposing (nutrient) factors, as well as prevailing weather as a triggering factor all work together to induce the primary production and hence the eutrophication (hypertrophication) process in surface waters. Sulfate likewise is a decisive predisposing factor influencing the eutrophication process by reducing N availability but increasing P availability and thus acting towards an N limitation of the primary production. This is one of the reasons why marine (coastal) waters and estuaries often exhibit N limitation with respect to primary production, while freshwater ecosystems often tend to exhibit P limitation. Within the N and P balance of agriculture of some countries of Western Europe (Netherlands, Denmark, Switzerland, FRG, UK and Sweden for N, resp. Netherlands, FRG and GDR for P) more the level than the efficiency of the N and P applications indicates the extent of the nutrient surplus. Despite 59–73% N utilization in plant production, the rate of 13–23% for agriculture as a whole equals to the 12–21% efficiency of N use in animal production. The varying N surplus in agriculture in the separate countries of 124 to 465 kg N ha−1 a−1 is determined almost exclusively by the level of the N application and not by its efficiency. The situation is similar for P: In spite of P utilization in plant production of 59–76%, P utilization in total agriculture is only 11–38%, or comparable to the P efficiency within animal production of 10–34%. The differing P excess balance of 55 to 88 kg P2O5 ha−1 a−1 is influenced by the level of the P application. The N and P efficacy of total agriculture hence is determined almost completely by that of animal production, since 83–95% (N basis) and 76–94% (P basis) of the total plant production (on top of the nationally varying levels of N and P use via imported feeds) are fed to animals — with the low N and P utilization cited above. Agriculture's share of the N and P emissions into surface water of several countries/regions in Western Europe (FRG, Netherlands, Italy, Denmark, Switzerland, Norway) ranges from 37 to 82% resp. 27 to 38%. Its share in the flus into the North Sea catchment basin will be about 60% for N and 25% for P related only to the anthropogenic material carried by the rivers. Agriculture's share in the atmospheric N emissions into the North and Baltic Seas can be estimated at about 65% or 55%, resp. while the remaining approx. 35% or 45%, resp. are traceable primarily to anthropogenic burning processes. For agriculture the priority lies in limiting N emissions into surface water caused by leaching, erosion and NH3 emissions, and reducing P emissions mainly through soil conservation (protection against erosion) and water protection. As regards N this means a demand for comprehensive protection of groundwater and atmosphere differentiated according to the potential for losses or the risk of losses on a site, also outside the protection zones. As regards P only those areas can be included in the demand for reduction of emissions that are actually threatened by erosion or surface runoff. Plenty of short-term and long-term measures are available to agriculture to reduce N and P emissions. Especially the long-range measures (such as creating nutrient balances on farms and fields, the integration of animal and plant production, maintaining maximum livestock densities according to the ability of areas to absorb nutrients, altered feeding programs in animal nutrition, changes in livestock keeping (slurry→deep litter), increasing the internal and external recycling of N and P) are capable of bringing about a satisfactory degree of success within the next 20 to 30 years.
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    Nutrient cycling in agroecosystems 40 (1994), S. 165-173 
    ISSN: 1573-0867
    Keywords: Animal manure ; eutrophication ; ground water ; nitrogen ; phosphorus ; surface runoff
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract With the rapid growth of the poultry industry in Oklahoma, U.S.A., more litter is applied to farm land. Thus, information is required on the impact of applications on regional soil and water resources. The effect of soil and poultry litter management on nitrogen (N) and phosphorus (P) loss in runoff and subsurface flow from four 16 m2 plots (Ruston fine sandy loam, 6 to 8% slope) was investigated under natural rainfall. Plots under Bermudagrass (Cynodon dactylon) received 11 Mg litter ha−1, which amounts to contributions of approximately 410 kg N and 140 kg P ha−1 yr−1. In spring, litter was broadcast on 3 of the plots; the upper half of one and total area of the other two. One of the total-area broadcast plots was tilled to 6 cm, the other remained as no till. The fourth plot served as a control. Relative to the control, litter application increased mean concentrations of total N and total P in runoff during the 16-week study for no-till (15.4 and 5.8 mg L−1) and tilled treatments (16.7 and 6.1 mg L−1). However, values for the half-area application (5.6 and 2.0 mg L−1) were similar to the control (5.7 and 1.3 mg L−1). Interflow (subsurface lateral flow at 70 cm depth) P was not affected by litter application; however, nitrate-N concentrations increased from 0.6 (control) to 2.9 mg L−1 (no till). In all cases, 〈 2 % litter N and P was lost in runoff and interflow, maintaining acceptable water quality concentrations. Although litter increased grass yield (8518 kg ha−1) compared to the control (3501 kg ha−1), yields were not affected by litter management. An 8-fold increase in the plant available P content of surface soil indicates long-term litter management and application rates will be critical to the environmentally sound use of this nutrient resource.
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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.
    Type of Medium: Electronic Resource
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