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  • 1990-1994  (8,092)
  • 1890-1899
  • Analytical Chemistry and Spectroscopy  (7,463)
  • Industrial Chemistry and Chemical Engineering  (629)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 263-272 
    ISSN: 0886-9383
    Keywords: Molecular descriptors ; Principal component analysis ; Chemometrics ; Pattern recognition ; Total surface area ; PCDD PCDF ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New theoretical molecular indices are defined. They contain information about the whole molecular structure in terms of size, shape, symmetry and atom distribution. These indices are calcualted from the (x, y, z) co-ordinates of a molecule within different weighting schemes in a straightforward manner and represent a very general approach to describe molecules, molecular fragments, macromolecules and molecular conformations in a unitary conceptual framework. Their interpretability is quite evident and is defined by the same mathematical properties as the algorithm used for their calculation. Examples on the total surface area, toxicity of PCDD and PCDF and reaction rate of catalysed reactions show a high modelling power of these indices.
    Additional Material: 4 Tab.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 273-285 
    ISSN: 0886-9383
    Keywords: GRAM ; Least-squares problem ; Eigenvalue problem ; NIPALS ; Performance index ; Condition number ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we discuss the practical implementation of the generalized rank annihilation method (GRAM). The practical implementation comes down to developing a computer program where two critical steps can be distinguished: the construction of the factor space and the oblique rotation of the factors. The construction of the factor space is a least-squares (LS) problem solved by singular value decomposition (SVD), whereas the rotation of the factors is brought about by solving an eigenvalue problem. In the past several formulations for GRAM have been published. The differences essentially come down to solving either a standard eigenvalue problem or a generalized eigenvalue problem. The first objective of this paper is to discuss the numerical stability of the algorithms resulting from these formulations. It is found that the generalized eigenvalue problem is only to be preferred if the construction of the factor space is not performed with maximum precision. This is demonstrated for the case where the dominant factors are calculated by the non-linear iterative partial least-squares (NIPALS) algorithm. Several performance measures are proposed to investigate the numerical accuracy of the computed solution. The previously derived bias and variance are proposed to estimate the number of physically significant digits in the computed solution. The second objective of this paper is to discuss the relevance of theoretical considerations for application of GRAM in the presence of model errors.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 287-292 
    ISSN: 0886-9383
    Keywords: Rank annihilation ; Principal components ; Procrustes rotation ; Multivariate analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the DATa ANalysis (DATAN) algorithm can be expressed in terms of rank annihilation factor analysis (RAFA). Subsequent advances in RAFA are applied to DATAN to eliminate the problems and restrictions associated with DATAN. The extension of DATAN in terms of the trilinear decomposition algorithm is discussed.
    Additional Material: 1 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 127-130 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A novel reactor arrangement for the anionic polymerization of styrene described in this paper comprises alternating adiabatically operated plug-flow reactors and heat exchangers. A novel tube-bundle recycle reactor is presented for the bulk polymerization of styrene and acrylonitrile.
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 138-140 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The reaction in aqueous solutions between carbon disulphide and morpholine has been studied experimentally at 303 K using a conductimetric stopped-flow technique. The observed pseudo-first order rate constant does not vary linearly with amine concentration but follows the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{obs} = k_{Am} [R_2 NH]^2 + k_w [R_2 NH][H_2 O] $$\end{document} .This equation is compatible both with (i) zwitterion intermediate and (ii) single-step termolecular reaction mechanisms which were previously proposed for the corresponding reactions of CO2 and COS. Values of rate constants kAm and kw at 303 K are also reported.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 365-373 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The productivity of fermentations is often limited by end product inhibition. This can be avoided by continuous removal of the inhibiting product from the broth. Such in-situ separation can be conveniently accomplished by liquid-liquid extraction. As an example, the continuous fermentation of ethanol by the thermophilic, anaerobic bacterium Clostridium thermohydrosulfuricum is investigated in a 20-1 fermenter with simultaneous in-situ extraction by oleyl alcohol as organic solvent. Continuous fermentations with and without in-situextraction were carried out with systematic variation of the independent operating conditions, viz. feed glucose concentration, broth flow rate and solvent flow rate. The experimental results of 18 steady states are reported. They show that in-situ extractions doubles the yield, selectivity and space-time yield of ethanol in comparison to fermentations without in-situ extraction. A biomodel elucidates the influence of feed glucose concentration, broth flow rate and solvent flow rate on the productivity of the fermentation process. Finally, a cost model was developed for the investigated fermentation which allows economic evaluation of the results of experiments and simulation. A sensitivity study elucidates the economic limits and advantages of fermentation with in-situ extraction compared to a common fermentation without product separation.
    Additional Material: 10 Ill.
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  • 7
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gas diffusion electrodes, made of PTFE-bonded carbon with precious metal catalysts, were investigated as hydrogen consuming anodes in sodium sulphate electrolysis. The catalysts used were platinum and palladium and mixtures of both metals, prepared by two different methods. Various metal meshes were used as current collector. The electrodes performed well in pure sulphuric acid (5-15 wt-%) and in mixtures with sodium sulphate (10 wt-%) at temperatures of 30 to 70°C and current densities up to 5 kA/m2. In long-term experiments, at a current density of 2.6 kA/m2, the electrodes were stable over three months. The electrodes were characterised by stationary current density/potential curves and by galvanostatic current interruption measurements.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 242-248 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The purpose of this paper is to investigate the swelling of emulsion liquid membranes using dithio-DEHPA as carrier. The application of interest was the removal of zinc from a synthetic aqueous solution which simulates a zinc plant effluent. The effect of several variables such as the concentration of carrier in the membrane, stirring speed and permeation time on the swelling of the emulsion is reported. Experimental results show that occlusion depends mainly on the amount of carrier in the membrane and can be significant when the concentration of carrier is lower than 6.0%. The interfacial tension analysis confirms that the size of globules is influenced by the concentration of carrier in the membrane. Stirring speed and permeation time are related to the water transport and must be kept at low values.
    Additional Material: 5 Ill.
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  • 9
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Process models are used to formulate knowledge about process behaviour. They are applied, e.g., to predict the process' future behaviour and for state estimation when reliable on-line measuring techniques to monitor the key variables of the process are not available. There are different sources of information available for modelling, which provide process knowledge in different representations. Some elements or aspects may be described by physically based mathematical models and others by heuristically obtained rules of thumb, while some information may still be hidden in the process data recorded during previous runs of the process. Heuristic rules are conveniently processed with fuzzy expert systems, while artificial neural networks present themselves as a powerful tool for uncovering the information within the process data without the need to transform the information into one of the other representations. Artificial neural networks and fuzzy technology are increasingly being employed for modelling biotechnological processes, thus extending the traditional way of process modelling by mathematical equations. However, a sufficiently comprehensive combination of all these techniques has not yet been put forward. Here, we present a simple way of combining all the available knowledge relating to a given process. In a case study, we demonstrate the development of a hybrid model for state estimation and prediction on the example of a yeast production process. The model was validated during a cultivation performed in a standard pilot-scale fermenter.
    Additional Material: 9 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 67-72 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The pyrolysis of polyvinyl chloride (PVC) has been described in terms of a relatively simple kinetic model, based on a large number of laboratory tests. The model predictions are in a good agreement with experimental data, regarding hydrochloric acid and non-condensable combustible gases. Therefore, the proposed model can be used to predict with good approximation the distributions of the above classes of compounds, in the whole range of applied experimental conditions.
    Additional Material: 11 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 414-421 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Computer-aided design of a packed column to remove ethanol from aqueous solution with dibutyl butylphosphonate (DBBP) was accomplished with a programme based on the Pratt method and on the slip velocity equation. Reliable data for successful computation were obtained from literature correlations (drop size, hold-up and axial mixing coefficients for different types of packing) and from experimental work (equilibria and kinetics). Equilibrium studies on the H2O-ethanol-dibutyl butylphosphonate system were performed at different temperatures. A decrease in temperature increased the selectivity of the extractant while the distribution coefficient of ethanol, KD ≈ 1.0, remained constant. The behaviour of the system kinetics towards temperature is assessed in order to determine the initial mass transfer flux (892 × 10-3 kg m-2s-1, 30°C) and the activation energy, 22.9 kJ/kmol. The process is governed by the diffusion of the species involved. The influence of the type of packing of the column on its design is analyzed from the inventory volume of the solvent, the total volume of the column and the axial dispersion coefficients under normalised inlet and outlet conditions.
    Additional Material: 6 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 285-289 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this study, a simple and effective technique for determining overall mass transfer coefficients in fixed bed sorption columns with recycle is presented. This new technique is free of the assumption of negligible time rate of solute concentration change in the fluid, i.e. (∂c/∂t) = 0, which has been widely used in former fixed bed sorption column analyses.
    Additional Material: 5 Ill.
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  • 15
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The results of experimental investigations on distillation columns operating on a lab and on a production scale are presented and compared with the results obtained by simulation. There is good agreement between experiment and simulation. On the basis of these results a dynamic analysis was carried out. It compares the dynamic behaviour of packed and plate distillation columns of the same diameter and same number of theoretical plates. This reflects the influence of the different hold-ups of the two columns.
    Additional Material: 7 Ill.
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  • 16
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using methods of statistical thermodynamics, adsorption isotherms for the description of multicomponent chemisorption of different-sized molecular species are derived by assuming the adsorbing surface to be energetically homogeneous and by neglecting lateral interactions between the adsorbed particles. In the first part of this contribution, the adsorption equilibria for a mixture of different-sized chain molecules adsorbed on a lattice of coordination number z are discussed supposing each unit of a given chain to bind to one adsorption site only. In the second part, the coadsorption of molecular species consisting of a different number of segments on a continuous surface is treated. A comparison of the predicted to the measured isotherms for the coadsorption of two freon species on activated carbon shows that the proposed equations describe the results of the coadsorption measurements sufficiently well, provided the adsorption data for the pure components have been determined experimentally.
    Additional Material: 6 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 325-337 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Single, binary, ternary and quaternary adsorption equilibria of CO2, CO, CH4 and N2 on molecular sieve 5A and activated carbon were experimentally determined over a pressure range from 10-4 to 101 MPa, a temperature range from 303 to 363 K and at various compositions. The adsorption equilibria of steam reformer gases as needed for the hydrogen purification in pressure swing adsorption units were measured by using a circulating volumetric method. For the temperature-dependent correlation of pure gas isotherm fields the Toth equation, which is a favorable model for heterogeneous adsorbents, was extended by two parameters accounting for the temperature-dependencies of the saturation loading and the heterogeneity parameter. Multicomponent equilibria were successfully predicted from single component isotherms by the Ideal Adsorbed Solution Theory based on the accurate representation of the pure component data by this temperature dependent Toth equation. Other thermodynamic models like the HIAS, the MIAS, the SPD or the VS theory and the Statistical Thermodynamics Model were also applied to the prediction of the adsorption equilibrium and the temperature and pressure dependence of the selectivity, with comparable success, which is due to the quasi-ideal adsorption behavior even at a high pressure.
    Additional Material: 24 Ill.
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  • 18
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Manganese mixed oxide composite layers of about 1 μm thickness on titanium sheet as substrate were fabricated by firing of the corresponding nitrates at a typical temperature of 400°C in air. The activity of these anodes was evaluated by cyclic voltammetry (10 mV/s) and the stability was determined by chronopotentiometry (2.5 mA/cm2) in 1M H2SO4. The oxidation of 2-propanol was examined as a simple electroorganic model reaction. The quality of a first category of mixed oxides with general composition MnMe2O4 decresed in the order Me = Co, Ni, Fe. In a second group with the general formula MeMn2O4 a decrease in the order Me = Co, Cu, Fe, Ni, Ti, Zn, Cd, Ca, Mg, (Zn, Ge), Li was observed. The corresponding candidates of the second group were superior to those of the first. The anode service life τ of the optimum spinel anode CoMn2O4/Ti is dependent on the current density, according to jλ τ = const. (λ = 1.7). Thus high current densities are precluded. The mechanism has been discussed in terms of a heterogeneous redox catalysis: surface Mn(VII) states are formed in a slow electrochemical step. In a subsequent fast chemical oxidation of the organic molecule the original reduced state is regenerated. This also explains the comparatively good service life of these anodes.
    Additional Material: 9 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 354-357 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A process for the manufacture of pure 4-methyl-1-pentene by catalytic dimerization of propylene has been developed in three stages. The first stage involves preparation of a new process catalyst, which contains metallic sodium and potassium deposited on a Bulgarian natural zeolite, the support having been passivated previously by potassium carbonate. The experimental results demonstrate the advantages of the resulting catalyst over exisisting technology, namely 36% conversion and 92% selectivity relevant to liquid isomers. The second development stage concerns the technological regime of chemical reaction for production of 4-methyl-1-pentene. In the third stage, the regime conditions and equipment ensuring desired quality of the product and utilization of the unreacted propylene returned to the reactor are determined. Based on the studies of all stages, a flowsheet is proposed for synthesis and separation of the reaction mixture of isomeric hexenes to give pure 4-methyl-1-pentene.
    Additional Material: 4 Ill.
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  • 20
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Titanium silicalite-1 samples of different particle size are synthesised and characterised by X-ray diffraction (XRD), photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), Raman and infrared spectroscopy. Size histograms are taken from transmission electron micrographs. Temporal changes of activity and selectivity for the hydroxylation of phenol and anisole are monitored. It is postulated that the p/o product ratios are due to the greater chemisorption of the ortho molecule.
    Additional Material: 4 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 149-160 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Several kinds of diesel soot filters and filter materials of high melting points with eleven different catalytic coatings were prepared. They were calcined at a maximum temperature of 1000°C. The reaction rate and the kinetic parameters of the combustion of diesel soot were determined in a closed loop laboratory reactor. A packed bed of alumina particulates was the most active filter in soot combustion. Catalytic coatings with oxides of vanadium, copper or cerium accelerated the reaction. In each case the effect of the coating was dependent on specific interactions between the catalyst and the filter material. The manner of filtration and the nature of the soot filter are found to be more important for the overall result than the nature of the catalytic coating.
    Additional Material: 18 Ill.
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  • 22
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Combined XPS and SIMS measurements, partly supplemented by XRD investigations, were utilized to detect precious metal/support interactions on catalysts containing various precious metals. The Klemm-Bronger reaction between Pt and α-Al2O3 on methane/ammonia catalysts was used as a standard reference. Evidence was found for different stages of Pt/Al interactions and changing electronic properties of Pt on the surfaces of these Pt/α-Al2O3 catalysts by means of XPS and SIMS, and in the bulk material by XRD. The SIMS investigations on Pt and Rh on γ-Al2O3 showed that, even at temperatures around 500 °C, Rh/Al interactions can appear to a small extent in the topmost atomic layers, whereas the Pt/γ-Al2O3 specimens did not show any measurable effects. After on-road operation, enhanced SIMS cluster-ion signals as well as anomalous XPS signal contributions were measured on the surfaces of used three-way automotive emission control catalysts. These signals did not appear for the fresh catalysts. By analogy with the related results reported on the methane/ammonia catalysts, the ion signals were used as qualitative surface probes indicating the presence of precious metal/support interactions, especially between Rh and Al.
    Additional Material: 6 Ill.
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  • 23
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The catalytic oxidation of fluorene to 9-fluorenone in a fluidized-bed reactor was investigated by modeling of the reactor and simulation of its performance. The “Bubble Assemblage Model” of Kato and Wen, the “Bubbling Bed Model” of Kunii and Levenspiel and the “Countercurrent Backmixing Model” of Potter were applied. From a comparison of simulation results obtained by the various fluidized-bed models and a fixed-bed model conclusions were drawn about the influence of interphase mass transfer and gas backmixing on the conversion of fluorene and slectivity of 9-fluorenone formation. Furthermore, the dependence of conversion and selectivity on temperature and hydrodynamic conditions was investigated. In particular, the implications of a change of hydrodynamic conditions for scale-up were analysed. The highest yield of 9-fluorenone predicted for a bench-scale fluidized bed amounted to 88% (XF = 97%, SNON = 91%). This yield was lower than in a fixed-bed reactor (YNON = 92%, XF = 99%, SNON = 93%). A further drop of the yield was predicted when scaling-up from a bench-scale reactor to a commercial size unit (YNON = 54%, XF = 86%, SNON = 63%).
    Additional Material: 11 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 179-186 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The conversion of ethanol over H-ZSM-5 was studied as a function of ethanol partial pressure, reaction temperature, weight hourly space velocity and Si/Al ratio. The results obtained were in qualitative agreement with most of those in the literature. Combination with all published results to give a significant regression model was not possible due to the large scatter of the data from various scientific groups. In mechanistic investigations, temperature programmed reaction measurements of ethanol, diethyl ether and ethene were performed. The formation of ethene from ethanol via direct elimination or from diethyl ether as intermediate could be confirmed. In the conversion of ethanol/water mixtures, the product distribution did not change significantly up to a water content of 60 wt%. Then, a pronounced increase of ethene formation and a considerable decrease of the yields of aromatics was observed. When several reaction mixtures from syngas conversion to ethanol were converted over H-ZSM-5, the coking rate depended on the product distribution in the feed. Product mixtures from processes with higher amounts of compounds having an unfavourable C/H ratio led to rapid deactivation of the zeolite.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 187-194 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The formation of verbenol, verbenone and acids during liquid phase ozone-initiated oxidation of α-pinene has been investigated; temperature, ozone partial pressure and ozone initiation time were the variables studied. While increasing temperature promotes the formation of secondary products, the other two variables affect mainly the selectivity. Thus, an ozone partial pressure and ozone initiation time of 1014 Pa and 10 min, respectively, lead to the highest selectivities. Kinetic expressions for the formation of verbenol and verbenone, which are consistent with experimental data, have also been developed from a free radical mechanism.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 1-9 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In a process of precipitation, two or more reactants form a product. In many cases, the solubility of this product is very low and high supersaturation is generated which leads to nucleation and crystal growth. The number of the formed nuclei and their growth govern the particle size distribution of the precipitate. As a rule, the precipitate is separated from the mother liquor in a centrifuge or on a filter. This separation and the subsequent drying process of very fine particles can be very expensive with respect to investment and energy costs. Therefore, it is desirable to produce as coarse a precipitate as possible with a narrow crystal size distribution.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 21-29 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The desulphurization of synthesis gas with zinc ferrite was studied in a laboratory-scale fixed-bed reactor. Desulphurization efficiency of 97-99% was obtained. The inlet hydrogen sulphide concentration was about 2600 ppm. A flat breakthrough curve showed that diffusion through the sulphide layer controlled the rate of sulphidization. The degrees of utilization varied between 5 and 11%. Experimental data formed the basis of a kinetic evaluation with the fixed bed model and the unreacted core model. Rate constants, reaction orders, and effective diffusion constants were calculated. When chemical reaction controlled the rate, the order of reaction was between zero and unity. The rate of reaction increased with temperature. Effective diffusivities were of the order of 10-5 m2 s-1, increasing slightly in the temperature range between 500 and 600°C. The activation energy was determined as 54 kJ mol-1, which corresponds to an unexpectedly strong temperature dependence of the diffusion-controlled reaction. The low degrees of utilization, and also the strong temperature dependence, are explained by sintering of the sulphidized zinc ferrite.
    Additional Material: 9 Ill.
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  • 28
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 41-46 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The hydroxycarbonate of nickel and aluminium (Ni/ Al = 3) with a hydrotalcite-like structure is an outstanding precursor of the active component of supported nickel catalysts. Good mechanical strength and suitable nickel content of these catalysts, which are necessary for practical applications, can be achieved by mechanical mixing of this compound with an additional support. The catalyst prepared from a mixture of 56.5 wt-% of nickel-aluminium hydroxycarbonate and 43.5 wt-% of γ-alumina was proven to have a stable catalytic activity in the methanation reaction at 2 MPa and 800 K.
    Additional Material: 5 Ill.
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  • 29
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 34-40 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Catalytic dehydrogenation of methanol is a promising process of producing water-free formaldehyde. The present paper reviews research in this field. As effective catalysts mainly transition metal compounds as well as oxides and salts containing sodium have been reported. Several catalysts exhibit high activity and high selectivity, for formaldehyde at low conversions while further efforts have to be made to improve catalyst stability and selectivity at high conversions. Catalytic dehydrogenation of methanol to formaldehyde is compared with methanol oxidation.
    Additional Material: 3 Ill.
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  • 30
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The separation of ethoxylated aliphatic amines from zinc containing effluents with macroporous polymeric adsorbents Wofatit EP 61, EP 62, Y 59, Y 77 and active carbons has been examined. The adsorption behaviour has been investigated as a function of temperature, time and concentration of Na2SO4, ZnSO4 and H2SO4. The macroporous polymers EP 61, Y 77 and Y 59 are capable of separating ethoxylated aliphatic amines from effluents of viscose fibre industry at higher temperatures and under weakly acidic conditions. In contrast to active carbon, inorganic components are not adsorbed on the investigated macroporous resins. Data obtained in a concentration range of 0 to 10 g of adsorbate per litre produced a Langmuir profile for adsorption of ethoxylated aliphatic amines by polymeric adsorbents.
    Additional Material: 5 Ill.
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  • 31
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 50-60 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Knowledge of transport processes is of considerable practical importance in the design and performance evaluation of packed bed reactor systems. Acquisition of the required information necessitates a realistic mathematical description of the system. In this study, numerical analysis is performed for forced convective non-Darcian, non-isothermal compressible flow and heat transfer in cylindrical packed beds. Local structural and transport properties are considered. The influence of compressional work as well as viscous dissipation on the thermal field is evaluated and a general criterion provided for assessing the effect of expansion.
    Additional Material: 12 Ill.
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  • 32
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 47-49 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The phrase “further remarks” in the title of this short paper is meant to imply that reactions and dimensionless groups are not only purely algebraic concepts, but definite numerical values can also be associated with them; in stoichiometry this evaluation may relate, for example, to the heat of reaction and, in dimensional analysis, to what is called a dimensionless number. On the basis of the evaluation concept, it will be shown that a counterpart of Hess' law in thermochemistry is valid in dimensional analysis.
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  • 33
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 88-94 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Inertial deposition of aerosol droplets (diameter: 1-14 μm) on steel spheres (diameter: 3-9 mm) was investigated. Air velocity was varied between 7 and 28 m/s (corresponding sphere Reynolds numbers: 1400-17000). The impaction on single spheres as well as that on linear arrays of eight spheres was measured. Theoretical results, based on potential flow investigations were verified by single sphere experiments. Of special interest was the range of lower Stokes numbers, where the theoretically predicted limit of deposition cannot be verified. The experiments on sphere arrays were for the first time performed in the low Stokes number range. Deposition on the leading sphere, relative to that on the shielded spheres, exhibits a maximum in the high Stokes number range, but this changes drastically in the low Stokes number range. Here, maximum deposition can be found on the shielded spheres while the leading sphere shows a markedly lower deposition.
    Additional Material: 12 Ill.
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  • 34
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 73-80 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Due to induced turbulent interactions between particles to be separated and the scrubbing liquid present as droplets, very good collection efficiency down to submicron particle size can be achieved as shown by detailed studies [1]. Assumed are suitable flow conditions, a long residence time and a certain droplet size distribution or a special liquid dispersion system. As the name implies, the cyclone scrubber basically consists of a cyclone. This cyclone serves as a contact space in which the interaction between dust particles and scrubbing liquid droplets takes place, and as a droplet separator. Thus, under normal conditions, a water saturated but dust- and droplet-free gas stream leaves the cyclone. The droplets are generated by a pneumatic atomization nozzle, arranged at the cyclone inlet in the direction of flow. A complete theoretical description of the three-dimensional, three-phase, non-steady turbulent flow in the cyclone scrubber has not been possible up to now. The detailed experimental investigations presented in this work, and covering multiple parameters, led to physically based conclusions about the dominant interactions and separation mechanisms involved. Grade efficiencies which did not fall below 0.75, down to a particle size of 0.5 μm, could be measured by an optical particle counter. Collection efficiency of 99.2% was determined by gravimetric analysis of the dust load, according to VDI-guideline 2066, in the raw and clean gas sections of the dust load, according to VDI-guideline 2066, in the raw and clean gas sections of the cyclone scrubber.
    Additional Material: 12 Ill.
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  • 35
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 81-87 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Plasma arc welding processes are used in the off-shore industry for construction and maintenance of underwater structures and pipelines in a wet environment. At greater water depths the density of the plasma gas increases because of the greater hydrostatic pressure. This causes conductive heat losses to the wet environment to increase. To maintain the energy flux to the workpiece to be welded, the plasma arc has to burn in a local dry area with an inside pressure of 1 bar. This requirement can be fulfilled by a rotating cylinder with a liquid film flowing down the inner wall. The flow around the rotating cylinder is experimentally investigated. The rotating cylinder is placed above the work surface which is simulated by a flat plate. Because of the centrifugal forces of the rotating flow inside the gap between the lower end of the cylinder and the flat plate the water is forced out of the cylinder. The velocity distribution in the flow is measured by laser Doppler anemometry. The phase distribution in the two-phase flow in the gap is measured by local electrical probes. The static pressure inside the gaseous atmosphere is reduced in comparison to the hydrostatic pressure of the surrounding water. The pressure reduction is given by the void fraction, the phase distribution and the volume flow rates of both phases in the gap as well as by the speed of revolution and the design of the cylinder and the work surface. The influence of these parameters on heat transfer from the workpiece to the two-phase flow regime is also investigated.
    Additional Material: 12 Ill.
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  • 36
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    Chemical Engineering & Technology - CET 17 (1994), S. 95-101 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The process of homogenization of liquids in a tall vessel equipped with a multiple impeller was studied. Up to four standard Rushton turbines and/or six pitched-blade turbines were used. The mixing time in the system was measured by the conductivity method. A continuous time history of the tracer concentration at several points in the system was recorded. The data were interpreted by means of an adapted cell model of the flow within the stirred vessel with several impellers based on the assumption of well mixed cells and intercellular flow of liquid. The liquid transfer flow rate between the cells, as a parameter of the model, was calculated from experimental data. A good agreement between the time dependence of concentration obtained experimentally and that calculated from theory was obtained. A direct relationship between the flow numbers between cells and those of impellers was established.
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  • 37
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    Chemical Engineering & Technology - CET 17 (1994), S. 108-111 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It has been shown that, after a partial deactivation, γ-alumina (γ-Al2O3) is a good catalyst for selective methylation of 1,2-benzenediol in the temperature range of 260-310°C. The main products are the desired 3-methyl-1,2-benzenediol and 2-methoxyphenol, which may be converted in another step into 3-methyl-1,2-benzenediol, giving an overall selectivity for the desired products of 80 to 90%. The catechol forms a strongly chemisorbed surface species on γ-alumina and its steric adsorption model correlates with the kinetic data.
    Additional Material: 7 Ill.
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  • 38
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    Chemical Engineering & Technology - CET 17 (1994), S. 112-118 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Kinetic studies as well as morphological and physico-chemical surface studies have been carried out on the deactivation of a palladium carrier catalyst for vinyl acetate synthesis in the ethylene gas phase process. The experiments cover concentration and temperature ranges of technical interest at a total pressure of 900 kPa. The deactivation rate depends on the temperature and the oxygen and acetic acid concentrations. The decline in activity is best described by a rate law of second order relative to the activity number. This behaviour is attributed to the observed aggregation of finely dispersed palladium. It can be concluded that palladium(II) acetate acts as a transport species in a chemically assisted sintering mechanism. At temperatures T ≤ 438 K the more advantageous final texture of the catalyst will only be formed on reaction.
    Additional Material: 9 Ill.
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  • 39
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A continuous production process has been developed up to pilot scale (300 l) for FDH production with the methylotrophic yeast Candida boidinii. A high cell mass specific FDH activity (50 U/g) is achieved by process computer controlled supply of pure methanol to operate the reactor at an optimum methanol concentration of 10 g/l. The maximum FDH spacetime yield achievable with this process control involves a residence time of 7 h. The FDH space-time yield (STY) and FDH concentration are a function of the oxygen transfer rate (OTR) of the fermenter (maximum STY = 255 U/(l h) at kLa = 870 l/h). For a reasonable compromise between high FDH space-time yield and high FDH concentration, an optimum residence time is adjustable by regulating the supply of nutrient salt solution in relation to the OTR of the fermenter. On a pilot scale (200 l continuously stirred tank reactor) roughly 4 million U of FDH were produced within 10 days at a residence time of 14.3 h. Isolation of intracellular FDH enzyme was performed using extraction with an aqueous two-phase system (PEG/K2HPO4). A technical product quality of 1.2 U/mg FDH was achieved without any chromatographic purification step.
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  • 40
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 41
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    Chemical Engineering & Technology - CET 17 (1994), S. 141-143 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A prototype “autocirculation”-type reactor has been designed and constructed at the N.I.O.C. Research Institute, Tehran and a mathematical model describing the concentration versus time profile subsequently developed. The model encompasses mass transfer considerations and kinetic studies of the regeneration reaction. For this purpose, the rate equation for iron complex oxidation, proposed by Japanese researchers, was modified and a new rate equation presented. This rate equation has been widely used in the above mentioned mathematical model. With this model, the vessel volume for a time-dependent H2S feed has been calculated for a “ZDDP” production unit.
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  • 42
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    Chemical Engineering & Technology - CET 17 (1994), S. 145-148 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In order to illustrate the use of CFD in providing an understanding of mixing processes, three examples, mixing in a pipe, homogenization with a static mixer and flow in a mixing vessel with a Rushton turbine, are discussed and compared with experimental results. Special attention is focussed on the resultant concentration distribution, which is closely linked to turbulent properties. A semi-empirical model is presented for a quantitative prediction of the initial turbulent conditions. Using special numerical techniques a mixing vessel with wall-separated baffles, which represents a problem generally regarded as beyond the capabilities of numerical analysis, can be simulated.
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  • 43
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    Chemical Engineering & Technology - CET 17 (1994), S. 358-363 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cooling breakdown in highly exothermic reaction processes may lead to runaway. The sensitivity and the safety assessment of a batch process on cooling breakdown are studied. The dependence of the minimum cooling time and the maximum allowable time of cooling breakdown for safe operation on the process parameters is investigated.
    Additional Material: 8 Ill.
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  • 44
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 45
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    Chemical Engineering & Technology - CET 17 (1994), S. 374-381 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the proposed combined sterilisation and concentration method, the original milk is first sterilised under conditions of continuous flow and after reaching the desired sterilisation temperature the product is concentrated by means of flash evaporation during subsequent cooling. Addition of stabilisers to maintain the thermal stability of the concentrate during sterilisation is not necessary in this process. The method presupposes that cooling with concentration is carried out under sterile conditions. This is technically quite feasible on use of multistage flash evaporation.
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  • 46
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    Chemical Engineering & Technology - CET 17 (1994), S. 195-200 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Shock tube pyrolysis of propane at temperatures between 1300 K and 2700 K at reflected shock pressures of 500 to 1500 kN/m2 has been investigated. The reaction is of 1st order with a rate constant K = 1.79 × 108 exp (-176.2 kJ/RT) s-1. The major reaction products were acetylene, ethylene and methane, while traces of propylene and ethane were only detected at temperatures below 1500 K. At higher temperatures, propane conversion to acetylene increased at the expense of the other products. Optimum conversions to ethylene and methane, in contrast to that to acetylene, were more sensitive to changes in temperature than to variations in reaction time. However, at reaction pressures above 550 kN/m2, extension of reaction time beyond 0.5 ms did not favour the formation of acetylene. A simple kinetic model which confirmed the experimental optimum product selectivity conditions is put forward.
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  • 47
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This contribution presents a chemical reactor model of a circulating fluidized bed (CFB) which takes into account adsorption effects and provides a description of the vertical profiles of gas concentration in the riser. The oxidation of NO is used as an example of a heterogeneous catalytic reaction. Mass transfer between the gas phase and solid particles in the CFB was investigated at various temperatures and solids mass flow rates. The measurements show that the mass transfer coefficient decreases with increasing solids mass flux and that the CFB resembles a bubbling fluidized bed as regards gas-solid contacting.
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  • 48
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    Chemical Engineering & Technology - CET 17 (1994) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 49
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    Chemical Engineering & Technology - CET 17 (1994), S. 210-215 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of the pseudohomogeneous liquid phase synthesis of a high molecular weight ester in a stirred tank reactor using cobalt chloride as catalyst has been studied at various temperatures, catalyst concentrations, and acid/alcohol molar ratios. A kinetic model has been determined that predicts the experimental results quite well.
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  • 50
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 293-294 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 51
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 52
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    Journal of Chemometrics 8 (1994), S. 301-302 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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  • 53
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    Journal of Chemometrics 8 (1994), S. 303-303 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 54
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    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 55
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    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 56
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    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 57
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    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 58
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    Journal of Chemometrics 8 (1994), S. 111-125 
    ISSN: 0886-9383
    Keywords: PLS regression algorithm ; Kernel ; Many-variable data sets ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fast PLS regression algorithm dealing with large data matrices with many variables (K) and fewer objects (N) is presented For such data matrices the classical algorithm is computer-intensive and memory-demanding. Recently, Lindgren et al. (J. Chemometrics, 7, 45-49 (1993)) developed a quick and efficient kernel algorithm for the case with many objects and few variables. The present paper is focused on the opposite case, i.e. many variables and fewer objects. A kernel algorithm is presented based on eigenvectors to the ‘kernel’ matrix XX TYYT, which is a square, non-symmetric matrix of size N × N, where N is the number of objects. Using the kernel matrix and the association matrices XXT (N × N) and YYT (N × N), it is possible to calculate all score and loading vectors and hence conduct a complete PLS regression including diagnostics such as R2. This is done without returning to the original data matrices X and Y. The algorithm is presented in equation form, with proofs of some new properties and as MATLAB code.
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  • 59
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    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 60
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    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Journal of Chemometrics 8 (1994), S. 375-376 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 62
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    Journal of Chemometrics 8 (1994), S. 377-389 
    ISSN: 0886-9383
    Keywords: Kernel PLS regression ; Cross-validation ; Model dimensionality ; Multivariate image regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multivariate images are very large data structures and any type of regression for their analysis is very computer-intensive. Kernel-based partial least squares (PLS) regression, presented in an earlier paper, makes the calculation phase more rapid and less demanding in computer memory. The present paper is a direct continuation of the first paper. In this study the kernel PLS algorithm is extended to include cross-validation for determination of the optimal model dimensionality. To show the applicability of the kernel algorithm, two examples from multivariate image analysis are used. The first example is an image from an airborne scanner of size 9 × 512 × 512. It consists of nine images which are regressed against a constructed dependent image to test the accuracy of the kernel algorithm when used on large data structures. The second example is a satellite image of size 7 × 512 × 512. Several different regression models are presented together with a comparison of their predictive capabilities. The regression models are also used as examples for showing the use of cross-validation.
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  • 63
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    Journal of Chemometrics 8 (1994), S. 102-102 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 65
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    Journal of Chemometrics 8 (1994), S. 179-180 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 66
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 67
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 68
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 69
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 70
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    Journal of Chemometrics 8 (1994), S. 181-203 
    ISSN: 0886-9383
    Keywords: RAFA ; GRAM ; Eigenvalues ; Bias ; Variance ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rank annihilation factor analysis (RAFA) is a method for multicomponent calibration using two data matrices simultaneously, one for the unknown and one for the calibration sample. In its most general form, the generalized rank annihilation method (GRAM), an eigenvalue problem has to be solved. In this second paper expressions are derived for predicting the bias and variance in the eigenvalues of GRAM. These expressions are built on the analogies between a reformulation of the eigenvalue problem and the prediction equations of univariate and multivariate calibration. The error analysis will also be performed for Lorber's formulation of RAFA. It will be demonstrated that, depending on the size of the eigenvalue, large differences in performance must be expected. A bias correction technique is proposed that effectively eliminates the bias if the error in the bias estimate is not too large. The derived expressions are evaluated by Monte Carlo simulations. It is shown that the predictions are satisfactory up to the limit of detection. The results are not sensitive to an incorrect choice of the dimension of the factor space.
    Additional Material: 3 Ill.
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  • 71
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    Keywords: Fitting ; Non-linear ; Least squares ; Refinement ; Constraints ; MSE ; Confidence ; C ls ; XPS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A non-linear least squares iterative refinement has been implemented which shows high performance on a multiple-peak spectrum including baseline or background. Constraints as well as links within a range are introduced to drive the mathematical optimization: each peak parameter (i.e. height, position, Gaussian/Lorentzian mixing ratio and HWHM on both left and right sides) has assigned to it an allowed range of variation and can be strained to be correlated with other parameters belonging either to the same peak (symmetrical peaks) or to other peaks (doublets, triplets, etc.). Peak shapes typical of XP spectra are used and applications in the field of XPS are discussed. Through emulated curves with Poisson distributed noise, the accuracy and precision of back-calculated (refined) parameters have been estimated. Moreover, a confidence level calculated from X2 and degrees of freedom has been suggested to check the overall fitting of experimental curves where the signal-to-noise ratio is a priori unknown. An application to real C ls XP spectra is described as an example and a list of suggestions is given to match operator requirements. Finally, features of NLLSRC are discussed with respect to other approaches.
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  • 72
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 74
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    Journal of Chemometrics 8 (1994), S. 243-243 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 75
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    Journal of Chemometrics 8 (1994), S. 245-261 
    ISSN: 0886-9383
    Keywords: Factor analysis ; Spectral resolution ; Two-dimensional luminescence ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A factor analysis algorithm that estimates the spectra of mixture components using the set of most dissimilar rows and/or columns is described and illustrated. This algorithm uses the distance as a measure of spectral similarity and is suitable for application to a variety of the bilinear matrix-formatted data types produced by hyphenated and multidimensional analytical techniqes. The algorithm requires that the data matrix contain at least one row or column that corresponds to the pure spectrum of each component to effect accurate spectral resolution. The performance of the method is illustrated using the resolution of excitation and emission spectra of up to four components from experimental fluorescence excitation-emission matrices (EEMs). In the case of the EEM, characteristic bands in an emission spectrum effect resolution of the excitation spectrum of the corresponding component, while characteristic bands in an excitation spectrum lead to resolution of the corresponding emission spectrum. The use of the set of most dissimilar rows and columns to evaluate the degree of overlap in the component spectra and compare the quality of row and column solutions is also described.
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  • 76
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    Journal of Chemometrics 8 (1994), S. 295-296 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 77
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    Journal of Chemometrics 8 (1994), S. 299-301 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 78
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 79
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    Journal of Chemometrics 8 (1994), S. 1-20 
    ISSN: 0886-9383
    Keywords: Discriminant analysis ; Least squares ; Prediction ; Regression ; Relationship ; Structure ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Twenty-two contrasting statistical methods are reviewed for their applicability to QSAR studies and similar prediction-oriented fields. Each method is concisely specified prior to explanatory or critical comment.
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  • 80
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    Journal of Chemometrics 8 (1994), S. 37-44 
    ISSN: 0886-9383
    Keywords: Bootstrap ; Confidence interval ; Non-linear regression ; Monte Carlo methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Non-linear regression models describing the toxicity of a mixture of rotenone and pyrethrins as an insecticide, the catalytic dehydration of n-hexyl alcohol and the Michaelis-Menten model for characterizing reaction rates in enzyme systems will be used to illustrate the accuracy of bootstrap methods in non-linear regression. Classical and bootstrap confidence intervals for the parameter estimates will be presented.
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  • 81
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    Journal of Chemometrics 8 (1994), S. 349-363 
    ISSN: 0886-9383
    Keywords: Variable selection ; PLS ; Calibration ; Modelling ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modified PLS algorithm is introduced with the goal of achieving improved prediction ability. The method, denoted IVS-PLS, is based on dimension-wise selective reweighting of single elements in the PLS weight vector w. Cross-validation, a criterion for the estimation of predictive quality, is used for guiding the selection procedure in the modelling stage. A threshold that controls the size of the selected values in w is put inside a cross-validation loop. This loop is repeated for each dimension and the results are interpreted graphically. The manipulation of w leads to rotation of the classical PLS solution. The results of IVS-PLS are different from simply selecting X-variables prior to modelling. The theory is explained and the algorithm is demonstrated for a simulated data set with 200 variables and 40 objects, representing a typical spectral calibration situation with four analytes. Improvements of up to 70% in external PRESS over the classical PLS algorithm are shown to be possible.
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  • 82
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    Journal of Chemometrics 8 (1994), S. 365-370 
    ISSN: 0886-9383
    Keywords: Censored data ; ECM and EM algorithms ; Incomplete data ; Maximum likehhood ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The purpose of this short communication is to illustrate the use of conditional maximization (CM) in chemometric applications. The CM algorithm is useful in reducing the computational complexity when a high-dimensional and complicated maximization problem arises from fitting chemometric models. It can also be efficiently combined with the expectation-maximization (EM) algorithm for handling incomplete data, a problem that sometimes arises when only a part of the intended data can be collected. Three models from fluorescence spectroscopy are used for illustration.
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  • 83
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    Journal of Chemometrics 8 (1994), S. 373-373 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
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    Journal of Chemometrics 8 (1994), S. 147-154 
    ISSN: 0886-9383
    Keywords: RAFA ; GRAM ; Eigenvalue problem ; Complex solution ; Degenerate solution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rank annihilation factor analysis (RAFA) is a method for multicomponent calibration using two data matrices simultaneously, one for the unknown and one for the calibration sample. In its most general form, the generalized rank annihilation method (GRAM), an eigenvalue problem has to be solved. In this first paper different formulations of GRAM are compared and a slightly different eigenvalue problem will be derived. The eigenvectors of this specific eigenvalue problem constitute the transformation matrix that rotates the abstract factors from principal component analysis (PCA) into their physical counterparts. This reformulation of GRAM facilitates a comparison with other PCA-based methods for curve resolution and calibration. Furthermore, we will discuss two characteristics common to all formulations of GRAM, i.e. the distinct possibility of a complex and degenerate solution. It will be shown that a complex solution-contrary to degeneracy-should not arise for components present in both samples for model data.
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  • 86
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    Journal of Chemometrics 8 (1994), S. 127-145 
    ISSN: 0886-9383
    Keywords: Compression ; Multivariate analysis ; B-splines ; FT-IR spectra ; Second-order ; Two-dimensional ; Hyphenated methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to improve the storage and CPU time in the numerical analysis of large two-dimensional (hyphenated, second-order) infrared spectra, a data-preprocessing technique (compression) is presented which is based on B-splines. B-splines have been chosen as the compression method since they are wellsuited to model smooth curves. There are two primary goals of compression: a reduction of file size and a reduction of computation when analyzing the compressed representation. The compressed representation of the spectra is used as a substitute for the original representation. For the particular example used here, approximately 0.16 bit per data element was required for the compressed representation in contrast with 16 bits per data element in the uncompressed representation. The compressed representation was further analysed using principal component analysis and compared with a similar analysis on the original data set. The results shows that the principal compotent model of the compressed representation is directly comparable with the principal component model of the original data.
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  • 87
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    Journal of Chemometrics 8 (1994), S. 101-101 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 88
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 89
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    Journal of Chemometrics 8 (1994), S. 445-446 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 90
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    Journal of Chemometrics 8 (1994), S. 305-331 
    ISSN: 0886-9383
    Keywords: Pyrolysis ; Mass spectroscopy ; Multivariate analysis ; Biological material identification ; Convexity ; Cones ; Subspaces ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work addresses the classification of high-dimensional time-dependent pyrolysis mass spectra of biological samples. The aim was the detection and classification of biological agents, and the developed approach resembles mixture analysis. The data were projected on to a low-dimensional subspace using singular value decomposition. Then a convex cone was formed on this subspace, showing as its corners physically meaningful components of the sample. This technique enabled separation of a biological material signal largely independent of the absolute amount of sample. The detection of the presence of any biological material could be accomplished based on the convex cone alone, without other reference to the mass spectra. Automated clustering of samples was successfully carried out using a minimal spanning tree.
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  • 91
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    Journal of Chemometrics 8 (1994), S. 333-347 
    ISSN: 0886-9383
    Keywords: PLS ; ATR ; Paper ; Resolution ; Infrared ; FTIR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attenuated total reflectance Fourier transform infrared spectrometry (ATR-FTIR) has been used to determine the amount of styrene-butadiene latex on the surface of coated papers and to predict the composition of the polymer. Spectrum recording was performed on the sample in its usual form without any modification.For quantitative analysis, partial least squares (PLS) regression, principal component regression (PCR) and multi-linear regression (MLR) were used to calculate models for prediction. The best result is obtained with PLS.We analysed two series of paper samples. The first analysis concerns the measurement of the quantity of latex of a constant quality on the coating surface. For 15 samples the concentration varied between 5 and 25 parts (grams per 100g of mineral pigments). We compared the predictive results at various resolutions. We obtained a relative error of 0.15 parts in latex at 4 cm-1 resolution. The second analysis concerns the measurement of the styrene/butadiene ratio in various types of latex. We obtained a relative error of 0.156 parts for styrene determination and 0.161 parts for butadiene determination.
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  • 92
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    Journal of Chemometrics 8 (1994), S. 21-36 
    ISSN: 0886-9383
    Keywords: GRAM ; Tucker ; Unfold ; NBRA ; Second-order ; Three-way ; PARAFAC ; Trilinear ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: If an analytical instrument or instrumental method gives a response matrix when analyzing a pure analyte, the instrument or instrumental method is called a second-order method. Second-order methods that generate a response matrix for a pure analyte of rank one are called rank-one second-order methods. If the response matrix of a pure analyte is not rank one, essentially two cases exist: medium rank (between two and five) and high rank (greater than five). Subsequently, medium- and high-rank second-order calibration tries to use medium- and high-rank second-order methods to analyze for analytes of interest in a mixture. A particular advantage of second-order methods is the ability to analyze for analytes of interest in a mixture which contains unknown interferences. Keeping this advantage is the challenge on moving away from rank-one second-order calibration methods. In this paper a medium-rank second-order calibration method is proposed based on least-squares restricted Tucker models. With this method the second-order advantage is retained.
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  • 93
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    Journal of Chemometrics 8 (1994), S. 45-63 
    ISSN: 0886-9383
    Keywords: GRAM ; GSVD ; Propagation of errorS ; Correlated noise ; Uncorrelated noise ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of correlated and uncorrelated random errors on the precision of predicted quantitative and qualitative information obtained by analysis with the generalized rank annihilation method (GRAM) are shown. These are discussed in terms of propagation of errors through the algorithm. The effects of colinearity, noise level and noise distribution are compared and discussed.
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  • 94
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    Journal of Chemometrics 8 (1994), S. 81-93 
    ISSN: 0886-9383
    Keywords: Sensory evaluation ; Cumulative ranks ; Assessor variation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A graphical method of assessing differences between sets of rankings based on cumulative ranks is developed. The method can be used to identify rankings that differ over all or just part of the range of objects ranked. The method is applied to an example of sensory evaluation of green peas in which ten assessors scored six attributes on each of 60 samples.
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  • 95
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    Journal of Chemometrics 8 (1994), S. 65-79 
    ISSN: 0886-9383
    Keywords: Genetic algorithms ; Full validation ; Feature selection ; Outlier detection ; Multivariate analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Genetic algorithms have been proved to be a very efficient method in the feature selection problem. However, as for every other method, if the validation of the results is performed in an incomplete way, erroneous conclusions can be drawn. In this paper a development of a previous genetic algorithm is presented so that a full validation of the results can be obtained. Furthermore, this algorithm has been shown to perform very well also as an outlier detector, allowing easy identification of the presence of outliers even in cases where the ‘classical’ techniques fail.
    Additional Material: 6 Ill.
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  • 96
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    Journal of Chemometrics 8 (1994), S. 391-407 
    ISSN: 0886-9383
    Keywords: Neural networks ; Non-linear multivariate regression ; Pattern classification ; Kalman filter ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Finding methods for the optimization of weights in feedforward neural networks has become an ongoing developmental process in connectionist research. The current focus on finding new methods for the optimization of weights is mostly the result of the slow and unreliable convergence properties of the gradient descent optimization used in the original back-propagation algorithm. More accurate and computationally expensive second-order gradient methods have displaced earlier first-order gradient optimization of the network connection weights. The global, extended Kalman filter is among the most accurate and computationally expensive of these second-order weight optimization methods. The iterative, second-order nature of the filter results in a large number of calculations for each sweep of the training set. This can increase the training time dramatically when training is conducted with data sets that contain large numbers of training patterns. In this paper an adaptive variant of the global, extended Kalman filter that exhibits substantially improved convergence properties is presented and discussed. The adaptive mechanism permits more rapid convergence of network training by identifying data that contain redundant information and avoiding calculations based on this redundant information.
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  • 97
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    Journal of Chemometrics 8 (1994), S. 409-421 
    ISSN: 0886-9383
    Keywords: Deconvolution ; FT-IR spectroscopy ; Protein conformations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a variety of spectroscopic techniques the fundamental problem exists of determination of the individual spectral components, intrinsically overlapped in the measured spectrum. This is a typical deconvolution problem and several methods and techniques have been proposed for its solution in the technical literature, but suggestions of new approaches are still of interest. A new deconvolution procedure is presented here based on the use of the conjugate gradient minimization algorithm with the addition of sutiable constraints directly obtained by the application to the measured spectrum of the second-derivative operator or more sophisticated resolution enhancement procedures. Since in the examined case deconvolution essentially requires the minimization of a non-convex function, the use of such constraints is extremely important to supply suitable input parameters to the conjugate gradient algorithm to avoid obtaining minimum points which have no physical meaning. In our case each spectral compoent used for deconvolution has been assumed to have a Gaussian analytical definition fully identified by three parameters (amplitude, central frequency, spectral bandwidth), so that the input values required to start the deconvolution process are the number M of Gaussian components and 3M suitable initial approximations of the parameters above. It is shown that all this information can be obtained from the measured data. The deconvolution procedure was implemented by a FORTRAN Microsoft Version 5.1 program and experimental results relative to spectroscopic data obtained by FT-IR analysis of human serum albumin are reported. The results are discussed and compared with data obtained by the use of other techniques.
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  • 98
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    Journal of Chemometrics 8 (1994), S. 423-437 
    ISSN: 0886-9383
    Keywords: Resolvability ; Evolutionary factor analysis ; Variable selection ; Window factor analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for selecting variables in the non-sequential direction of a two-way data matrix (e.g. wavelength in diode array HPLC) is described. Composition 1 and 2 resolvability indices are calculated according to the size of eigenvalues of uncentred data matrices as a window is moved along the sequential direction. A double-window technique is then performed where resolvability indices are calculated as a window is moved along the non-sequential direction. Some regions have higher resolvability indices and hence are more useful for resolution. Variables are ranked according to resolvability. Two simulations are analysed and it is shown that it is possible to obtain good resolution on a small subset of the original variables.
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  • 99
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 439-443 
    ISSN: 0886-9383
    Keywords: Pattern recognition ; Principal component analysis ; Inverse mapping ; Optimization ; Material design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inverse mapping method called PCB (principal component backing), in which the point representing an unknown sample from a low-dimensional principal component subspace is back-projected to the high-dimensional original feature space, is proposed. Two sorts of boundary conditions, non-linear inverse mapping and linear inverse mapping, are used to obtain an accurate solution in the PCB method. The method is applied to the material design of high-Tc superconductors, predicting the composition and process conditions for the synthesis of F-doped Bi-based materials. Samples in the ‘optimal’ region with the highest Tc of the Bi-based ceramics have been predicted.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
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