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  • 1995-1999  (1,685)
  • 1995  (1,685)
  • Analytical Chemistry and Spectroscopy  (1,554)
  • Industrial Chemistry and Chemical Engineering
  • Nuclear reactions
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  • 1995-1999  (1,685)
Year
  • 1
    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
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  • 2
    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
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 229-229 
    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
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 230-231 
    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
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 232-236 
    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
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 343-362 
    ISSN: 0886-9383
    Keywords: straight line calibration ; errors in both axes ; uncertainties ; linear regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calibration is a fundamental step in the calculation of the unknown concentration of analyte in most analytical methods. It is known that for certain methodologies, if only the errors in the independent variable are taken into account, there may be considerable errors in the estimation of the value of the regression coefficients, the derived statistical parameters and in some cases the sought for response and concentration values. This paper reviews the calibration methods including some references to procedures for the detection of outliers and robust regression when there are errors in both axes. The advantages and limitations of the different approaches are discussed and a comparative study is made of the approaches of several techniques for which computer programmes have been developed based on the algorithms put forward by the different authors. Finally, some trends of future development in this field are envisaged.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 363-372 
    ISSN: 0886-9383
    Keywords: PLS regression ; orthogonal expansion ; optimization ; Lagrange multipliers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple iteration algorithm that is faster and less memory-intensive than the NIPALS iteration algorithm for PLS regression is presented. The iteration algorithm is obtained by treating the orthogonal expansion or decomposition of a matrix X as an extremum problem subject to normalization and orthogonality constraint conditions and then solving the problem by use of the method of Lagrange multipliers. The main idea in this method is to find the transformation vector r. The latent variable t is expressed exactly as the linear combination of X-variables with the vector r so that the final regression coefficients can be conveniently provided. In the algorithm the recursion of the orthogonal projection is needed, which is derived by use of a matrix inverse formula. Algorithms are established from the equation for calculating the vector r that are suitable for dealing with three cases of large data sets. The first case is when the number of objects is very large, the number of variables is relatively small and the number of Y-variables is equal to or greater than the number of X-variables. The second case is when the number of objects is very large, the number of variables is relatively small and the number of X-variables is greater than the number of Y-variables. The last case is when the number of variables, either X- or Y-variables, or both, is very large and the number of objects is small.
    Additional Material: 4 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 431-432 
    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
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 451-457 
    ISSN: 0886-9383
    Keywords: non-linear regression ; optimization ; robust methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several robust regression methods, including a new proposal, are described and their properties discussed. Resistance to various types of outliers and non-normality is demonstrated. The techniques are applied to non-linear regression models from chemical kinetics and calibration. Optimization of the types of objective functions encountered when applying robust regression is considered.
    Additional Material: 5 Ill.
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  • 10
    ISSN: 0886-9383
    Keywords: PLS ; kernel algorithm ; multivariate calibration ; EM algorithm ; cross-validation ; missing data ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This is Part II of a series concerning the PLS kernel algorithm for data sets with many variables and few objects. Here the issues of cross-validation and missing data are investigated. Both partial and full crossvalidation are evaluated in terms of predictive residuals and speed and are illustrated on real examples. Two related approaches to the solution of the missing data problem are presented. One is a full EM algorithm and the second a reduced EM algorithm which applies when the number of missing values is small. The two examples are multivariate calibration data sets. The first set consists of UV-visible data measured on mixtures of four metal ions. The second example consists of FT-IR measurements on mixtures consisting of four different organic substances.
    Additional Material: 5 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 439-439 
    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
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995) 
    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
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  • 13
    ISSN: 0886-9383
    Keywords: sequential response surface modelling ; Williamson ether synthesis ; SN2 ; optimization ; reaction kinetics ; reaction mechanism ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this work the utility of a new method for determining kinetic parameters by sequential response surface modelling, previously described (Part 1), is shown by applying it to an experimental study of a reaction with known kinetics. The nucleophilic substitution reaction between ethoxide and benzyl chloride, the Williamson ether synthesis, was selected as a model reaction. This reaction is known to proceed with second-order kinetics. The method gives access to estimates of initial reaction rate which can be further used to obtain estimates of activation energy and reaction order of reactants. The results obtained are in good agreement with the estimated values of these parameters obtained with conventional kinetic experiments.
    Additional Material: 2 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 483-487 
    ISSN: 0886-9383
    Keywords: fractional factorial design ; multiresponse ; PLS ; PCA ; reduced-rank regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents an interpretation of PLS applied to orthogonal explanatory variables. In particular, it is shown that in fractional factorial multiresponse experiments PLS2 gives identical results to ordinary least squares applied to principal components of the response variables. The general relationship is that the reduced-rank regression algorithm which first projects Y onto the X-space and then truncates this matrix by principal component analysis before performing ordinary least squares estimation gives the same predictor as PLS2 and SIMPLS if all the non-zero eigenvalues of XTX are identical.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 471-481 
    ISSN: 0886-9383
    Keywords: batch prediction ; continuum regression ; multivariate calibration ; sequential prediction ; simultaneous prediction ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In analytical chemistry a single fitted calibration model is used repeatedly to predict the level of the analyte of interest for the specimens comprising the prediction set. Unlike the calibration (or training) set, which is often limited in size, the prediction set can be very large.In the case of multivariate calibration a number of methods such as PLS and PCR are commonly used to construct the calibration model. The set of instrumental measurements and the reference analyte level are available for each specimen in the calibration set. For specimens in the prediction set, only the instrumental measurements are available, since the problem is to predict the analyte level for these specimens. It is not widely recognized that predictions of the analyte levels for individual specimens can be improved by utilizing seemingly unrelated information from the instrumental measurements associated with the other members of the prediction set. In the case of PCR there exists a very straightforward procedure for doing this. A description of the various sources of prediction errors is provided to explain the ability of PCR to utilize this additional information. The use of PCR in this context is illustrated with both a synthetic and a real example.
    Additional Material: 1 Ill.
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  • 16
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 531-531 
    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
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 509-520 
    ISSN: 0886-9383
    Keywords: canonical variates ; discriminant analysis ; partial least squares ; principal components ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new set of derived variables is proposed for exhibiting group separation in multivariate data on for preprocessing such data prior to discriminant analysis. The technique combines optimal features of canonical variate analysis and principal component analysis: the derived variables are linear combinations of the original variables that optimize the canonical variate criterion (ratio of between-group to within-group variance) but subject to the orthogonality constraints of principal components. In this formulation the canonical variates can be derived even when the within-group matrix is singular (i.e. when there are more variables than objects in the data matrix). A simple computational algorithm for extraction of these variables is proposed. The methods are illustrated on several data sets and compared with alternative techniques such as principal component analysis and partial least squares.
    Additional Material: 7 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 489-507 
    ISSN: 0886-9383
    Keywords: QSAR ; partial least squares ; robust regression ; CoMFA ; weighted regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A robust implementation of partial least squares (PLS) is developed in which the method of iteratively reweighted least squares is adapted for use with PLS. The result is a PLS algorithm which is robust to outliers and is easy to implement. Examples and case studies are presented, followed by two Monte Carlo studies designed to explore the behavior of the method.The paper begins with the motivation and intended applications for the procedure. A discussion is given of the method of interatively reweighted least squares (IRLS) for outlier detection. The procedure, given the name IRPLS, is then presented. Three case studies illustrate how the procedure works on various types of data and how it should be used. The first Monte Carlo study is designed to determine whether the IRPLS procedure correctly identifies multiple outliers in a wide variety of configurations. The second Monte Carlo study is designed to estimate the breakdown bound of the procedure.
    Additional Material: 6 Ill.
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  • 20
    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
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  • 21
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 309-322 
    ISSN: 0886-9383
    Keywords: simulated annealing ; messy genetic algorithms ; optimization of multimodal objective functions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of simulated annealing is modified so that the concept of messy chromosomes is applied. Constituent genes of messy chromosomes are specified by their respective names (indices) and values (alleles) simultaneously. Unlike simple chromosomes (binary vectors), messy chromosomes may be either under- or overspecified with respect to the problem being solved. The messy simulated annealing algorithm is a very robust and efficient stochastic optimization method which is able to find correct minima of deceptive or highly multimodal objective functions. This is shown by way of a number of simulations.
    Additional Material: 7 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 323-326 
    ISSN: 0886-9383
    Keywords: partial least squares ; biased regression ; ordinary least squares ; minimum length least squares ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An algebraic proof is given that in partial least squares (PLS) regression the Euclidean length of the estimator is shrunk in comparison with the ordinary least squares estimator or with PLS estimators based on a larger number of dimensions.
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  • 23
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 329-330 
    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
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  • 24
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995) 
    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
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  • 25
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 389-409 
    ISSN: 0886-9383
    Keywords: multivariate image analysis ; principal component analysis ; exploratory data analysis ; projection in multivariate space ; graphical visualization ; noise ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multivariate image analysis (MIA) is a powerful tool for many image segmentation and classification problems, but the interpretation and understanding of the original and resulting multidimensional (multivariate) data are not always easy. A strategy for MIA has been proposed which describes its usage on multivariate images for segmentation tasks. MIA starts with principal component analysis (PCA) and then continues with interactive analysis of the output from PCA. In this paper a number of extensions to MIA are proposed. The extensions are the suggestion to incorporate preprocessing of the multivariate image in MIA, the suggestion to use synthetic multivariate image models which create a clear-cut situation, and new visualization tools which improve the interactivity and understanding of the results. Extended MIA is applied on synthetic multivariate image data simulating a possible application with large noise, positron emission tomography (PET). As a result of the interactive analysis, suggestions for preprocessing emerge. The developed methodology for handling the noise is then applied on real PET image data with good results.
    Additional Material: 20 Ill.
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  • 26
    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
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  • 27
    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
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  • 28
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 330-336 
    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: Industrial product quality control is a typical mathematical programming and optimization problem. Unfortunately, complete and precise models are not always available for many industrial processes. A fuzzy relation modelling approach is proposed to describe approximate relationships among system variables and reconcile empirical equations. Symmetric fuzzy decision-making is transformed into a non-linear function maximization problem. The approach is applied to optimization of a wood chip refining process. It is used either to improve pulp quality within the refiner operation range, or to reduce operation costs while maintaining an acceptable pulp quality.
    Additional Material: 5 Ill.
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  • 29
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 343-348 
    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 high temperature coal pyrolysis reactor was developed and its operation demonstrated on a scale of 8 t/h. Pyrolysis is performed in a circulating fluidized bed reactor at 850-950°C. The developed process was integrated into smokeless fuel production technology and tested. Experimental data and reactor performance are presented.
    Additional Material: 12 Ill.
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  • 30
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995) 
    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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  • 31
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 359-363 
    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: The thermal decomposition of hydromagnesite has been studied using thermogravimetric analysis. The experiments were conducted in a nitrogen atmosphere with pellets of hydromagnesite in the temperature range 300 to 550°C, and also with powder samples under non-isothermal conditions at a heating rate of 10°C/min. It is found that the reaction proceeds in two stages: dehydration followed by decomposition. The dehydration reaction is controlled by external mass transfer whilst the decomposition reaction is controlled by both external and internal mass transfer. The activation energy for the dehydration reaction was found to be 2.67 × 107 J/kmol. From the non-isothermal analysis the activation energy for the decomposition of magnesium carbonate was found to be 1.62 × 108 J/kmol.
    Additional Material: 6 Ill.
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  • 32
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 349-358 
    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 methane pyrolysis were studied in a tubular flow reactor in the temperature range 1200 to 1500°C at atmospheric pressure. To avoid excessive carbon formation the reaction time was short and the methane feed was diluted with hydrogen. Ethene, ethyne, benzene and hydrogen were the main gaseous products. Ethane was observed as a product at very low conversions of methane. More than 90% selectivity was obtained for C2 products. The ratio of ethyne to ethene increased with increasing temperature. The yield of C2 products is limited by gas-phase equilibrium at lower temperatures. Formation of carbon was strongly depressed by hydrogen at higher temperatures. The maximum yield of ethyne was found to increase from about 10% to about 50% when the temperature was increased from 1200 to 1500°C, with hydrogen dilution H2: CH4 = 2: 1. A mechanistic reaction model was used to simulate the pyrolysis of methane at the actual conditions. A sensitivity analysis was performed to evaluate the elementary reactions which influence the formation and consumption of the species in the model system.
    Additional Material: 7 Ill.
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  • 33
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 364-369 
    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: Fluid catalytic cracking, a common secondary process employed in the petroleum industry, is used to convert heavier feedstocks into products such as liquefied Petroleum Gas (LPG), motor gasoline, diesel etc. The present study focuses on developing a three lump fraction kinetic model to estimate the yield of C5 up to 370°C cut (motor gasoline and middle distillates). A Micro Activity Test (MAT) apparatus was used to estimate the parameters in the kinetic model. The study is useful in evolving a procedure to simulate plant performance using experimental data obtained in the MAT apparatus for a particular catalyst and feedstock in terms of the product yield pattern.
    Additional Material: 5 Ill.
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  • 34
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 380-385 
    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: Packings with vertical walls, especially structured packings, are distinguished by their high efficiency and low pressure drop per mass transfer unit. Yet for these types of packings there is still no universal relationship for calculating gas-film-controlled mass transfer coefficients. The present work proposes such an equation. For arranged and structured packings the new equation fits the experimental data, both new results and those taken from the literature, with a mean error of 9%.
    Additional Material: 3 Ill.
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  • 35
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    Chemical Engineering & Technology - CET 18 (1995), S. 440-444 
    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: Acidic zeolite LZ-M-8 was used to catalyse the hydrolysis reaction of inulin into fructose. Fructose contents of 96% and 75% were obtained when commercial inulin and Jerusalem artichoke extract were used respectively as substrates. Zeolite LZ-M-8 was found to be extremely selective towards inulin hydrolysis as compared to fructose decomposition. Formation of hydroxymethyl furfural (HmF) was not detected and it was confirmed that zeolite LZ-M-8 does not adsorb HMF. The catalytic activity of the zeolite remained intact upon repeated use of the catalyst. The superiority of the zeolite over other catalysts used in inulin hydrolysis was demonstrated experimentally.
    Additional Material: 6 Ill.
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  • 36
    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: Ethyl tert-butyl ether (ETBE) is an alternative fuel oxygenate that can be produced in the liquid phase by addition of ethanol to isobutene catalyzed by sulfonic acid ion exchange resins. A generalized Langmuir-Hinshelwood rate expression is formulated in terms of the liquid phase activities of the reactants that is quasi-autocatalytic due to ethanol. This microkinetic model is combined with the generalized Maxwell-Stefan equations for a detailed investigation of the influence of multicomponent mass transfer limitations inside the macropores of the heterogeneous catalyst. The model is used for revision of experimental rate data for ETBE synthesis in the literature. The analysis reveals that reverse diffusion of isobutene can occur by strong interaction with ethanol and the catalyst effectiveness factor can exceed unity.
    Additional Material: 8 Ill.
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  • 37
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 284-291 
    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: An experimental investigation in a tube wall reactor with catalyst-coated inner wall is presented. Yields of formaldehyde of more than 70% can be obtained in the selective methanol dehydrogenation over alkalialuminate. Models for the reactor and the system of most important homogeneous reactions are derived. Different models describing the catalytic action are proposed. The results can only be explained by a new type of catalytic reaction, not described so far in the literature. Reducing gases like hydrogen and methanol lead to a volatilization of material from alkalialuminate which apparently catalyzes the dehydrogenation in the gas phase. Calculations and experimental evidence lead to the conclusion that this material should be sodium atoms. These are engaged in the homogeneous radical chain reaction by regulating the concentration of hydrogen atoms.
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  • 38
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 292-294 
    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 determination of the composition of multi-component mixtures is the basis by which a number of technical and physical problems in the field of power and process engineering are modelled. In order to calculate chemical states of equilibrium in the gas phase, a calculation method will be presented which is founded on a minimization of the Gibbs enthalpy. This method is characterized by a high reliability in convergency, considerable independence of starting vectors and by a moderate requirement for programming. These characteristics are achieved by a transformation of variables which results in numerically more favourable solutions to the non-linear equation system. Calculated equilibrium compositions (including dissociation and ionisation) for a stochiometric mixture of hydrogen and oxygen in a temperature range of 300-12000 K and a pressure of 105 Pa as well as the application of the method will be demonstrated.
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  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995) 
    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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  • 40
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 302-309 
    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 phenomenological approach to evaluating the agglomeration rate of growing crystals is presented. Crystals larger than the Kolmogoroff microscale collide because of the fluctuating velocity field. Bridges between the crystals form as a result of competition between crystalline growth and the turbulent velocity fluctuations on the opposite sides of the agglomerate.Crystals smaller than the Kolmogoroff microscale collide because of viscous laminar microshear stresses within the same turbulent eddy, are kept close together by Van der Waals forces and are joined together by crystalline bridges that grow between them. The strength of these bridges depends on the supersaturation level during the moments following the collision.These two sets of phenomena lead to two different preferential generation mechanisms for agglomerates. One example involving important agglomeration effects is developed for each case: the crystallization of adipic acid belongs to the first group (large crystals), whereas the precipitation of calcium oxalate monohydrate is typical of the second case (small crystals).
    Additional Material: 7 Ill.
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  • 41
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 295-301 
    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 batch crystallization of potassium chloride from aqueous solution is investigated without impurities, with zinc chloride I (30, 100, 1000 ppm), with sodium hexametaphosphate II (100 ppm) and potassium hexacyanoferrate (II) III (100, 500, 1000, 16 × 25 ppm). The dominant particle size of the pure system LN, D = 427 μm increases by 40% by addition of I and by 250% by addition of II. While I does not affect the habit II changes it from cubes to octahedrons. In cases of low concentration, III leads to dendrites.It is shown that addition of III decelerates growth and increases the metastable zone width. Hence a high supersaturation is formed, the solution impoverishes fast while III gets incorporated and therefore a strong nucleation starts in a relatively pure solution. By quasi-continuously adding 16 × 25 ppm of III the dominant particle size increases by 160% with little fines. In this case the content of III in the product is relatively low.
    Additional Material: 9 Ill.
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  • 42
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 315-323 
    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 safe operation of a batch polymerisation reactor assumes sufficient knowledge about all the possible reactions. An investigation has been made in order to predict, with the aid of a mathematical model based on a detailed reaction mechanism, the runaway ability of a styrene batch suspension polymerisation reactor. The results of the simulation were compared with the experimental data obtained from a bench-scale test cell.
    Additional Material: 6 Ill.
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  • 43
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 166-170 
    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: Venturi jet scrubbers are widely used in chemical industries as an efficient gas-liquid contacting equipment. They are simple in design, have no moving parts, operate with circulating liquid and are reliable in service. Moreover, due to high relative velocity of liquid and gas, considerable overall mass transfer can be produced. In spite of their wide application, readily usable design data are not available in literature, particularly for units producing a gas flow by their own pumping action. The purpose of this paper is to introduce the equipment and its application for H2S removal. The effects of various parameters such as gas and liquid flow rates as well as pressure on hydrodynamics and mass transfer performance of the equipment are investigated. Results of experiments have been shown graphically.
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  • 44
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 171-177 
    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 condensers with high condensation rates or in falling film evaporators the falling film at the vertical tube wall shows a turbulent flow pattern. For optimal dimensioning of these apparatuses the knowledge and the description of the heat transfer in this turbulent falling film is necessary. Especially in fluids with a low thermal conductivity in liquid phase (i.e. hydrocarbons) the main heat transfer resistance is in the falling film, also if there are several components in gas phase. For calculating the heat transfer usually dimensionless Nusselt equations were used. These equations mainly base on experimental results which were found with water vapour as test fluid. It is shown that these equations fail for fluids with low thermal conductivity resp. high Prandtl numbers. Based on a Nusselt equation for turbulent tube flow a new equation for turbulent film flow is derived. A comparison between calculated and measured data for Prandtl numbers up to 50 shows good agreement.
    Additional Material: 8 Ill.
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  • 45
    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: An approach to feedforward distillation control based on inverse computation of nonlinear stage models is presented. The feedforward model calculates dynamic trajectories of manipulated variables from measured disturbances and product purity set points independently of the control configuration. Because the model includes the dominant dynamics and nonlinearities of the column, dynamic decoupling of the control loops is achieved. A superimposed linear controller only has to compensate model uncertainties and disturbances that cannot be measured. The proposed approach improves the control performance. Simulation studies show the applicability of the method to multicomponent distillation as well as to distillation trains. Experiments on a pilot plant scale binary distillation column verify the simulation results.
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  • 46
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 183-192 
    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 mass spectrometer is capable of making rapid, repetitive multicomponent analyses with measurement times as short as a second or less. Mass spectrometers used to be too expensive to be used for process analyses, but simpler and cheaper versions have been developed during the last decade. Mass spectrometers are commonly used within the petrochemical industry, but their use for fuel gas streams is not so widespread. This paper describes tests on a quadrupole mass spectrometer in three different gasification projects. Calibration methods and analysis accuracies obtained are accounted for. On the basis of the tests, it can be concluded that the quadrupole mass spectrometer is very suitable for continuous analysis of complex process streams. An important result is that the separation of CO and N2, an analysis problem that is traditionally regarded as difficult, worked very well. The analysis frequency was approximately once per minute, which should be enough for most control loops.
    Additional Material: 9 Ill.
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  • 47
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 193-202 
    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 vapour-liquid equilibria of the binary systems perfluoromethylcyclohexane-pentafluorobenzene, benzene-pentafluorobenzene, benzene-methylperfluorobutanoate and perfluoromethylcyclohexane-methylperfluorobutanoate have been measured at 333.07 K and 343.12 K using a dynamic circulation still of the Sieg-Röck type. The thermodynamic consistency of the measurements was tested by two different methods. New UNIFAC interaction parameters [1] were calculated for the following groups: ACH-ACF, ACF-CF2, CF2-COO, ACCH2-ACF, ACH-CF2. The abbreviations stand for the following increments: ACH = aromatic CH group, ACF = aromatic CF group, CF2 = aliphatic CF2 group, COO = ester group and ACCH2 = side chain CH group.
    Additional Material: 8 Ill.
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  • 48
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 203-209 
    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: An experimental set-up is presented for the measurement of reaction rates in the liquid phase synthesis of tertiary amyl methyl ether (TAME) from methanol and a mixture of 2-methyl-1-butene and 2-methyl-2-butene using an acidic ion exchange resin (Lewatit SPC 118) as catalyst. The reaction was performed in a continuous-flow recycle reactor at a temperature of 333.15 K and a pressure of 1.6 MPa. Determination of the age distribution (Fcurve) of the reactor showed that mixed flow is approached at a recycle ratio of R = 10. Experiments were performed to reveal the limits of operating conditions where the various resistances do not affect the rate. In agreement with estimation of Reynolds numbers, hindrance by external mass transfer can be excluded at a volumetric flow rate of 10 ml/min and a recycle ratio of R = 10. The maximum temperature increase of the whole particle resulting from limitation of external heat transfer was estimated to be about 3 K. Variation of the size of resin particles revealed the existence of a critical methanol concentration, above which reaction rates can be determined without influence of internal mass transport phenomena. The maximum temperature increase in the particle was estimated to be 0.3 K.
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  • 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: A solid state electrochemical reactor is described in which reactants can be oxidised at high temperatures over an anode/catalyst using co-fed oxygen gas as well as electrochemically supplied oxygen. The setup permits injection of isotopic pulses in the reactant streams. The composition and isotopic distribution in the products are recorded with a quadrupole mass spectrometer. The use of the system is exemplified by oxidation of methane over a Au + SrFeO3-δ//YSZ anode at 800-850°C. Pulses of 18O2 in the stream of co-fed O2 were used to study the reactivity and products of gaseous oxygen as distinguished from the electrochemically supplied oxygen. The results indicate that the anode used supports oxygen pumping, but is only moderately active for methane oxidation. The products are mainly CO and CO2. The content of 18O in the products is low, indicating that methane oxidation takes place by 16O-rich lattice oxygen. In comparison, a reference Au//YSZ electrode was found to be a slower anode for oxygen pumping, but a better catalyst for the reaction between CH4 and gaseous O2, seemingly involving adsorbed oxygen.
    Additional Material: 7 Ill.
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  • 50
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 156-165 
    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 flow of two immiscible liquids and the influence of an additional inserted gas phase in horizontal pipes is investigated. The experiments are carried out in a transparent horizontal pipe with an inner diameter of 59 mm and a total length of 48 m. Experimental results are presented for the flow regimes of the two phase and three phase flow of oil, water and gas mixtures. The effect of phase inversion on the pressure drop is measured. The experimental results obtained for the three phase flow of oil, water and air indicate that drag reduction is possible by injecting gas in laminar flowing mixtures of oil and water. In the aerated slug flow regime of oil, water and air a water dominated and an oil dominated flow system can be distinguished. The pressure drop of the three phase flow system is of the magnitude as the pressure drop of the two phase flow of gas and the dominating liquid phase.
    Additional Material: 13 Ill.
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  • 51
    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: During recent years the air stripping process has been increasingly applied to the cleaning of water contaminated by volatile organic compounds (VOC). The present contribution compares various methods of treating VOC-contaminated water, with a special focus on removal efficiency and economic aspects. In particular, air stripping, a universally used cleaning method, is described in greater detail. Design and operational aspects are worked out for packed stripping towers for the special case of water contaminated with chlorinated hydrocarbons. Experimental results substantiate predictions of various operating conditions, packing types and scale-up effects.
    Additional Material: 9 Ill.
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  • 52
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    Chemical Engineering & Technology - CET 18 (1995), S. 337-342 
    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: Neural networks can be an attractive alternative to mathematical modelling of complex and poorly understood processes if input/output data can easily be obtained. Woodchip refining falls into this category. The mechanism of the refining process is still being studied and no thorough models have yet been developed. A feed-forward neural network is proposed for modelling of woodchip refiners. The outputs predicted by the neural network are compared with industrial refiner data. It is also shown that a modified neural network structure can be used to optimize refiner operation and product quality. The advantages and disadvantages of neural network model application in simulation and optimization of industrial processes are discussed.
    Additional Material: 9 Ill.
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  • 53
    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: Results are reported for the oxidative coupling of methane on silica-supported alkaline earths prepared from either their acetates or chlorides with and without alkali metals as dopants and in the absence or presence of carbon tetrachloride (TCM). The addition of small quantities of TCM to the methane feedstream produces increases in the conversion of methane and the selectivities to C2 hydrocarbons which correlate with the increase in cation size and thus are inversely related to the polarizing abilities of the cations.
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  • 54
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995), S. 324-329 
    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 performance of packed bed adiabatic gas absorbers has been analyzed using the enthalpy and material balance equations incorporating a new parameter, fr, defined as the fraction of the heat of absorption that is accounted for in the gas stream. An experimental programme to evaluate fr was carried out and the data correlated. It was found that fr was dependent on the thermo-physical properties and the hydrodynamic conditions. It is postulated that the mechanism by which this heat transfer occurs is by turbulence at the interface and by entrainment.
    Additional Material: 4 Ill.
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  • 55
    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 basic sites of various oxide catalysts for the oxidative dimerisation of methane were studied by FTIR spectroscopy of adsorbed molecular probes (chloroform and CO2). The methods used are compared and the advantage of CO2 as probe for specifying the basic sites is demonstrated. The strengths of the basic sites were seen to correlate with the spectral parameters of the surface carbonates. Differences in spectral responses of carbonates are attributed to the different states of oxygen participating in their formation. The concentration of the strongest sites was estimated. A study of the catalytic activity of this system indicates that the system's activity in oxidative methane coupling depends on the presence and concentration of strong basic sites on the catalyst surface.
    Additional Material: 4 Ill.
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  • 56
    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 simple design of an adiabatic reactor for the production of hydrogen from methanol without external heating has been explored. Heat and steam are generated by oxidising part of the methanol and are removed in the process of reforming methanol to hydrogen. The reactor design emphasises the degree of control that can be achieved in a two-bed system by controlling the air to methanol and water to methanol ratios in the feed. Predictions of the model are compared with experimental testing to allow optimisation of the process. Up to 75% of methanol can be converted to hydrogen.
    Additional Material: 9 Ill.
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  • 57
    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 feasibility of methane coupling as an add-on unit to a naphtha cracker was studied. The existing cold box was used for separation of ethylene and unconverted methane, but arrangements were made for separation of the coupling by-products. The cracker's methane was used as a feedstock. The concept is technically and economically feasible at spring 1992 prices, provided the catalyst meets the assumed 30% conversion and 80% C2 selectivity.
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  • 58
    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: Two vanadia/titania catalysts, containing 1 and 8 wt% vanadia on anatase, have been investigated for the selective oxidation of o-xylene to phthalic anhydride. In a comparative study, activity and selectivity in o-xylene oxidation were measured using an integral reactor and a reactor with external product recirculation, with the objective of studying the influence of backmixing in the latter on the reaction behaviour. Adsorbed surface species were investigated by means of in-situ diffuse reflectance FT-IR spectroscopy, using an environmental chamber which corresponds to an integral reactor. No difference in activity and selectivity in o-xylene oxidation was observed between the two catalysts. FT-IR studies showed adsorbed o-xylene, benzoate and a high concentration of phthalic anhydride on the surface of both catalysts. o-Xylene oxidation follows a sequential reaction path, with o-tolualdehyde as the first intermediate and phthalide, phthalic anhydride and maleic anhydride as sequential products. No evidence was found for a direct oxidation-path of o-xylene to phthalic anhydride. Total oxidation products CO and CO2 are formed by direct oxidation of the o-xylene and by oxidation of the reaction products. Due to greatly reduced concentration and temperature gradients, the recycle reactor proved to be highly suitable for studying the extremely exothermic oxidation of o-xylene.
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  • 59
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    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 18 (1995) 
    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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  • 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: A kinetic model of the oxidative coupling of methane (OCM) over lanthanum oxide is developed on the basis of mechanistic conclusions obtained elsewhere. A reaction scheme is proposed, and the kinetic parameters corresponding to the different kinetic equation are optimized. Experimental and calculated reaction rates are compared with the aim of testing the proposed scheme and validating the basic mechanistic assumptions.
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  • 61
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    Chemical Engineering & Technology - CET 18 (1995), S. 225-228 
    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 simple and inexpensive Pbs-FET with high sensitivity and short response time was developed which consists of a PbS layer on a pH-sensitive gate of a field effect transistor. The PbS-layer was prepared with simple wet precipitations technique. The PbS-FET has about the same selectivities for Pb2+ -and for Cu2+ -ions, but only slight sensitivity for Cd2+ -and Zn2+ -ions. The sensor was integrated in a FIA system. By variing the injection time the measuring range varied between 10-1-10-6 and 10-2-10-8 mol Pb2+/1. The PbS-FET-FIA system is suitable for monitoring of Pb2+ concentrations in drinking water.
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  • 62
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    Chemical Engineering & Technology - CET 18 (1995), S. 229-242 
    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: For the design, simulation and optimization of sulphur retention in atmospheric fluidized bed coal combustors, a mathematical model is needed that would be able to predict the behaviour of the combustor in a wide range of operating conditions. In this work, a sensitivity analysis of the sulphur retention predictions of the different hypotheses, equations and parameters, which define the different submodels and phenomena occurring in the combustor, has been carried out. It has been found that the hypotheses related to the gas flow, devolatilization type and sulphur distribution in the pyrolysis products imply an important division among models. The greatest effect on sulphur retention predictions is exercised by the parameters defining the fines elutriation and sorbent sulphation capacity. However, those corresponding to the bed hydrodynamics (minimum fluidization velocity and bed expansion) do not have a significant effect on the sulphur retention predictions.The sulphur retentions obtained in the combustion of high sulphur lignites with eight different limestones were used for model validation. A good fit of the experimental sulphur retentions was found, without using any adjustable parameter. Finally, a simulation of the process was made. The great effect of the bed height, air velocity and the particle size distribution of the limestone must be pointed out, as well as the effect of its reactivity through the maximum conversion attainable by each particle size.
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  • 63
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    Chemical Engineering & Technology - CET 18 (1995), S. 434-439 
    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 theoretical analysis is presented for the time-dependent vertical motion of spherical particles in a gas stream. Laminar, transitional and turbulent flows are considered, and equations are developed to predict particle velocity and distance travelled as functions of time in both stagnant and slowly-moving gases. In both cases the equations are shown not to be universally applicable, and algorithms for estimating the limits within which they remain valid are briefly presented.
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  • 64
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    Chemical Engineering & Technology - CET 18 (1995), S. 425-433 
    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: Turbidimetry has proved to be an efficient method for the quantitative study of powder agglomeration for particle sizes in the region of 1 μm. This work presents a new application of the technique for the agglomeration of α-alumina in water and in n-heptane. The method of determining the kinetic parameters of agglomeration from the initial time-evolution of turbidity is explained.Turbulent flow in the reactor has also been characterised by laser anemometry. From the turbulence intensity, the number of collisions per unit time is calculated and the agglomeration rate can therefore be determined.Good agreement is found between the values obtained respectively from turbidimetric and hydrodynamic measurements. Addition of KOH modifies the zeta potential of alumina in water and influences the agglomeration kinetics. This can also be quantitatively characterised by turbidimetry. The experimental results obtained for alumina particles of diameter 0.3 μm and 1 μm are interpreted according to the DLVO model of interaction between particles.
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  • 65
    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 influence of altervalent cation doping of TiO2 carriers on the chemisorptive and catalytic properties of supported Pt and Rh crystallites has been investigated. It was observed that doping of the carrier with higher valence cations leads to suppression of the H2 and CO chemisorption capacity of Pt catalysts, while their activity in hydrogenation and oxidation reactions is significantly reduced. The opposite effects were observed in the case of Rh catalysts supported on higher valence doped TiO2. These catalysts were found to possess higher activity in CO and CO2 hydrogenation, in aromatics hydrogenation and in CO and C2H4 oxidation. Their stability characteristics were also found to be superior to those of the undoped Rh/TiO2 catalyst. These effects are believed to originate from an electronic type interaction at the metal-support interface, induced by doping, which results in electron transfer from the support to the metal crystallites.
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  • 66
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    Chemical Engineering & Technology - CET 18 (1995), S. 33-40 
    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: Single liquid drop velocities in structured packings have been measured to aid calculation of throughput of liquid extraction columns using characteristic (single drop) velocities. Solvent drops were passed through two types of glass and two types of steel structured packing and further work was done using sloping glass tubes. Existing wall-effect equations for drop velocity reduction in vertical tubes were considered and that given by Clift et al. [1] was used as a basis for correlation of structured packing data. Drop breakage was studied in order to improve understanding of drop size distribution development in packed columns. Drops broke only rarely within the structured packing; most of the breakage occurred as a drop hit the exposed edges on entry to a piece of packing. An energy balance equation was used to correlate critical conditions for breakage of drops hitting glass blades at various angles. Under the conditions used all those drops moving at terminal velocity had enough energy to break but a condition exists when drops may be small enough to have insufficient energy to break.
    Additional Material: 12 Ill.
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  • 67
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    Chemical Engineering & Technology - CET 18 (1995), S. 41-48 
    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: Studies have been made on the extent and mechanism of breakage of single liquid drops of organic liquids immiscible in water rising through short sections of Kühni liquid-liquid extraction columns. Information on drop breakage probabilities is required for calculation of drop size distributions developed under counter-current column operating conditions. The breakage probability data from two small diameter Kühni columns containing one, three or five stages have been correlated as a function of a modified Weber number based on the shearing forces on drops. The critical condition for breakage, giving a maximum stable drop size, is based on an impeller Weber number. Characteristic velocities of drops were measured relative to terminal velocity and the ratio was tentatively correlated with a function of an impeller Reynolds number together with the fractional free area of the perforated plates used to separate compartments. The drops were found to break predominantly at the holes in the plates, not at the turbine, in the region of transitional Reynolds number used in this work. The results apply only to non-turbulent conditions so further work on larger diameter equipment is called for.
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  • 68
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    Chemical Engineering & Technology - CET 18 (1995), S. 49-58 
    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 paper describes the design principles of multistage molecular evaporators with a wiped film which are used for gentle distillation of low-volatility blends of thermolabile materials. The conditions of distillation in an evaporator with a convex evaporation surface are discussed, along with problems relating to the function of the segmented wiper in the formation of the retarded liquid film and the functional principles of closing elements in a multistage evaporator with a single evaporating cylinder and of the built-in entrainment separator in the distillation space, which is designed to retain splashing spray. A TMO 65 three-stage molecular evaporator is described, with an evaporating cylinder having a diameter of 65 mm and a total evaporating area of 0.19 m2. This pilot-plant evaporator can be used in the small-capacity production of specialty chemicals or in technological research as a verification unit for establishing data necessary for the operation of large evaporators. These possible applications are documented by the results obtained on fractionation of various important materials. Fractional distillation of crude monoacylglycerols (M) containing 35 to 55% M afforded concentrates containing over 90% M, at yields of 78 - 95% M in the product fraction. Fractionation of oligomers of higher α-olefins gave distillate cuts with high contents of the respective n-mer, suitable for use as synthetic lubricating oils. Fractionation of polyalkylaromatic residue from the production of monoalkylbenzenes produced a distillate fraction with excellent electrical insulation properties. Finally, purification of technical diane-bis-glycidyl ether yielded over 75% of a product fraction which was found suitable for production of insulating material for electrical equipment operating at voltages of 6 to 15 kV.
    Additional Material: 3 Ill.
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  • 69
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    Chemical Engineering & Technology - CET 18 (1995), S. 371-379 
    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: Up to now, the only equations that were known for calculating mass transfer during two-phase countercurrent flow in packed columns were those that apply to the range extending up to the loading point. The gas and liquid streams flow separately through the column below but not above this point. Above it, the shear stress in the gas stream supports an increasing quantity of liquid in the column, with the result that the liquid holdup greatly increases. Finally, at the flood point, the liquid accumulates to such an extent that column instability occurs. Mass transfer in this upper loading range can be described if these fluid dynamic relationships are taken into consideration. The algorithm that is presented here for its prediction is based on theoretical and experimental studies.
    Additional Material: 7 Ill.
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  • 70
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    Chemical Engineering & Technology - CET 18 (1995), S. 386-396 
    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 article we present results for the viscosity and the mass transfer rates of hydrogen/air, hydrogen/oxygen, methane/air and methane/oxygen mixtures in the temperature range from 1000 to 7000 K and a pressure range from 103 to 106 Pa. In addition, the combustion ratio is varied from 0 to ∞. The transport properties are calculated from the first order solution of the Chapman Enskog approach to the Boltzmann equation, assuming chemical equilibrium composition. An extensive literature study was performed to derive experimental and/or theoretically based data for the respective binary interaction potentials. The values of the collision integrals, as derived from a complex numerical integration procedure, are correlated to an approximation formula. In addition, the exact solutions of the kinetic theory are compared to frequently used empirical mixture rules. For the mixture viscosity an easy approximation formula is deduced from the gas-kinetic theory.
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  • 71
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    Chemical Engineering & Technology - CET 18 (1995), S. 397-402 
    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 computer program has been developed for the simulation of gas-liquid absorption columns. The calculations are based on known assumptions and methods - the two-film theory. Mass and energy balances together with chemical reactions are carried out for each tray of the column. The results obtained from the simulation procedure are compared with those measured at industrial plants. For the items “rich solution temperature” and “calculated number of trays” the agreement of calculated and measured results are satisfactory. However, for the CO2 and H2S content of the streams only few comparisons could be made due to the fact that no measured values are available.
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  • 72
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    Chemical Engineering & Technology - CET 18 (1995), 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: This paper describes an original system for automated solid-phase peptide synthesis (SPPS) that was developed in our laboratories. The synthesizer is equipped with separate activator and batch reactors, and was designed to operate under either manual or computer control. Two metering pumps, which constitute the core of the entire apparatus, provide for the delivery and transfer of reagents and solvents in the appropriate quantities and in the correct sequence, and permit simultaneous condensation and activation operations that result in considerable time saving. Various applications to the synthesis of biologically important peptides, utilizing the most widely used strategies in SPPS, are presented as examples of this improved technology.
    Additional Material: 8 Ill.
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  • 73
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    Chemical Engineering & Technology - CET 18 (1995), S. 260-268 
    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: Large quantities of sludge containing considerable amounts of zinc are obtained on treatment of waste water from the production of viscose fibres for textiles and industrial applications. A process has been proposed [7, 10] for the recovery of zinc from one such sludge, in the first step of which zinc is transferred to the liquid phase with liberation of hydrogen sulphide. In connection with this work a model was developed which provides a kinetic description of zinc liberation from various sludges and the parameters of this model fitted to the measured data by means of linear regression.
    Additional Material: 7 Ill.
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  • 74
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    Chemical Engineering & Technology - CET 18 (1995), S. 256-259 
    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 efficiency of 6-aminopenicillanic acid (6-APA) production by enzyme-catalyzed hydrolysis of penicillin G using penicillin G amidase (E. C. 3.5.1.11) immobilized in polyacrylamide gel can be improved by using a lower substrate concentration and an optimized low buffer concentration. In a continuous process the combination of a stirred-tank reactor and a plug-flow reactor gives optimum productivity. Since precipitation of 6-APA is the crucial step in downstream processing, the product concentration has to be as high as possible. This can be achieved by concentrating the product solution by reverse osmosis.
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  • 75
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    Chemical Engineering & Technology - CET 18 (1995), S. 248-255 
    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 work a Sulzer structured packing, Mellapak 250Y, was studied for applications in the field of absorption. A new model was proposed which makes it possible to estimate the packing surface that actually takes part in the process. In the course of these studies, new experimental data were obtained relating to the absorption of 1,1,1-trichloroethane using Genosorb 300, a mixture of polyethylene glycol dimethyl ethers produced by Hoechst S.p.A., as absorption liquid. The results obtained with the proposed model are in agreement both with the experimental measurements made in the course of the work and with experimental absorption measurements reported by other authors on water systems.
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  • 76
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    Chemical Engineering & Technology - CET 18 (1995), S. 278-283 
    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: Deactivation kinetics and coke removal kinetics were derived from experimental studies on the disproportionation of ethylbenzene with a protonated Y-faujasite (Z-14) in a loop reactor under supercritical conditions. Derivation of the steady state kinetics of ethylbenzene disproportionation permitted determination of the catalyst activity. At small educt mole fractions of ethylbenzene, owing to the modest removal of coke the deactivation kinetics can be described by a power relationship. The rate of coke removal can be correlated with the activity and the deactivation rate of the catalyst.
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  • 77
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    Chemical Engineering & Technology - CET 18 (1995), S. 68-74 
    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: Although vortex formation is usually an undesirable phenomenon in the process industry, satisfactory process conditions and results can also be obtained in unbaffled agitated vessels in the presence of a vortex. This fact and especially the low power requirements in these systems, with their immediate relevance to the energy problem in the process industry, show the true importance of vortex formation in agitated vessels. This article reviews the literature results and the correlations proposed for the prediction of vortex depth in unbaffled agitated vessels with various types of single and multiple impeller systems and presents a critical discussion on the basis of a theoretical analysis.
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  • 78
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    Chemical Engineering & Technology - CET 18 (1995) 
    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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  • 79
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    Chemical Engineering & Technology - CET 18 (1995), S. 75-89 
    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: Starting with a brief review of the development of the circulating fluid bed (CFB) reactor principle, its main features as an important tool for efficient and thus environmentally acceptable processing of fine particulate solids, typically less than 150 μm diameter, are discussed. Various new industrial processes and high temperature process options starting with alumina calcination are described. Developing applications in the cement, metallurgical and chemical industries are approaching large-scale industrial importance. Efficient combustion or pressure gasification of fossil fuels and carbon-containing residues, fulfilling increasingly strict environmental legislation, is by far the most rapidly expanding field of application. In support of these developments our fundamental understanding of the fluid dynamics of CFB riser and of cyclone precipitation at high solid loadings has to be steadily improved. The reaction behaviour of aggregating fine particulate solids of varying size distributions also remains an open question.
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  • 80
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    Chemical Engineering & Technology - CET 18 (1995), S. 90-95 
    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 fluid flow in a filter chamber, consisting of a rotating disk and a stationary plate, has been numerically investigated. A proposed model provided acceptable predictions for shear rate and frictional torque in laminar and turbulent flow regimes. Owing to the pronounced effect of the shear stress on the filtration rate, the data obtained were used in analysis of the influence of hydrodynamics on the shear stress field in the filter chamber.
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  • 81
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    Chemical Engineering & Technology - CET 18 (1995), S. 96-109 
    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 modelling of pressures in silos has been attempted by numerous researchers using a variety of different methods. Starting with the work of Janssen, the slice element method, the method of characteristics, the finite element method and the method of granular dynamics are reviewed. Every model needs constitutive parameters which have to be found from experiments. A method to calibrate the more recent - and highly complex - constitutive models from general tests is presented. Besides the models for silo pressures, several models of flow in silos are considered.
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  • 82
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    Chemical Engineering & Technology - CET 18 (1995), S. 110-117 
    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 octane enhancer tertiary amyl methyl ether (TAME) is produced by liquid phase synthesis from methanol and a mixture of isoamylenes, namely 2-methyl-1-butene and 2-methyl-2-butene, using a sulfonic acid ion exchange resin as catalyst. Three reactions take place simultaneously in TAME synthesis: etherification of the two methylbutenes and their isomerisation. In order to study the equilibrium of the multiple reactions in TAME synthesis, the thermodynamic properties of the compounds in the liquid phase and equilibrium constants were calculated using a modified UNIFAC method to describe the nonideality of the system. Four parameters influencing the equilibrium conversion were derived and discussed in detail. Supplemental experiments were performed at three temperatures in the range from 303 to 343 K and at different initial molar ratios of educts. Equilibrium conversions of methanol were determined from these experiments and compared with calculated values. At 298 K the predicted activity based equilibrium constant was 22.9 for TAME synthesis from 2-methyl-1-butene and 1.6 for TAME synthesis from 2-methyl-2-butene; for isomerisation of 2-methyl-1-butene to 2-methyl-2-butene a value of 14.3 was obtained.
    Additional Material: 6 Ill.
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  • 83
    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 effect of Cl- ion addition to a Li+-ZnO catalyst has been studied with respect to the oxidative coupling of CH4 and the oxidative dehydrogenation (OXD) of C2H6. Increasing the Cl/Li ratio from 0.65 to 0.90 had relatively little effect on the CH4 conversion, whereas the C2H4/C2H6 ratio was enhanced significantly as a result of an increase in the OXD reaction rate. Conversely, loss of Cl- from the catalyst during the reaction had a much more deleterious effect on ethane OXD activity than on methane coupling activity. Addition of Cl- ions at a Cl/Li ratio of 0.9 caused a decrease both in the number of basic sites and in the basic strength of these sites, as determined by temperature-programmed desorption of CO2. The similarities between the results obtained over Li+-ZnO-Cl- catalysts and those previously reported for Li+-MgO-Cl- catalysts confirm that basicity of the host oxide plays only a minor role in determining the properties of these chlorided catalysts.
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  • 84
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    Chemical Engineering & Technology - CET 18 (1995), S. 310-314 
    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: Ways, benefits and limitations of extracting the form and size of single latex particles or particle size distributions out of the surface topography of non-coalesced latex films obtained by atomic force microscopy (AFM) are discussed. The general ways to generate the desired information out of topographical information in terms of height, surface curvature and lateral extensions are shown for idealized particles and measurement conditions. The different sources of information are evaluated for practical use and the analysis of particle size distributions is demonstrated by practical examples. The information content in lateral particle dimensions is shown to be the most advantageous for practical use.Determination of latex particle size distributions by AFM is shown to be an interesting alternative to the arsenal of available methods with respect to exactness of results, time consummation and instrumentation costs.
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  • 85
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    Journal of Chemometrics 9 (1995), S. 3-20 
    ISSN: 0886-9383
    Keywords: Deconvolution algorithms ; Instrumental analysis ; Spectrometry ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Deconvolution algorithms for measurand reconstruction are considered. Their metrological and numerical properties are briefly characterized. Six algorithms most frequently used for instrumental applications are selected for closer analysis. Their comparative study is based on the use of spectrometric-type synthetic data, calorimetric-type synthetic data and spectrometric real-world data. Conclusions concerning computational complexity and accuracy of the compared algorithms as well as their metrological applicability are drawn.
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  • 86
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    Journal of Chemometrics 9 (1995), S. 67-68 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    Journal of Chemometrics 9 (1995), 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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  • 88
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    Journal of Chemometrics 9 (1995) 
    ISSN: 0886-9383
    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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    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 9 (1995) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Journal of Chemometrics 9 (1995), S. 125-135 
    ISSN: 0886-9383
    Keywords: Procrustean analysis ; FT-IR spectroscopy ; NIR spectroscopy ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Procrustean methods allow the fitting of a given matrix to another given matrix observed on the same objects. In the traditional approach orthogonal constraints are imposed upon the transformation matrix, whereas in the alternative approach Procrustean analysis may be performed without such constraints. The two methods (with and without constraints) were compared on data dealing with mid- and near-infrared spectra of oil. The aim was to reconstruct the mid-infrared spectral information using data from the near-infrared spectra. Unconstrained Procrustean analysis proved to be the more efficient for both the calibration and verification sets. Furthermore, the analysis of the transformation matrix between the two infrared ranges made it possible to indicate wavelengths and wave numbers corresponding to the same chemical groups.
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  • 92
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    Journal of Chemometrics 9 (1995), S. 139-141 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
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    Journal of Chemometrics 9 (1995) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 94
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    Journal of Chemometrics 9 (1995), S. 1-2 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 95
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    Journal of Chemometrics 9 (1995), S. 137-138 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 96
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    Journal of Chemometrics 9 (1995), S. 91-123 
    ISSN: 0886-9383
    Keywords: H-principle ; PCA ; PLS regression ; latent variable models ; quadratic models ; sensitivity analysis ; outlier tests ; prediction variances ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present here an algorithmic approach to modelling data that includes principal component analysis (PCA) and partial least squares (PLS). In fact, the numerical algorithm presented can carry out PCA or PLS. The algorithm for linear analysis and extensions to non-linear analysis applies to both PCA and PLS. The algorithm allows for combination of PCA and PLS types of models and therefore extends modelling to new types of models that involve combination of regression models and ‘selection of variation’ models, which is the idea of PCA-type models. The fact that the algorithm carries out both PCA and PLS shows that PCA and PLS are based on the same theory. This theory is based on the H-principle of mathematical modelling. The algorithm allows tests for outliers, sensitivity analysis and tests of submodels. These aspects of the algorithm are treated in detail. We compute various measures of sizes, e.g. of components, of the covariance matrix, of its inverse, etc. that show how much the algorithm has selected at each step. The analysis is illustrated by data from practice.
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  • 97
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    Journal of Chemometrics 9 (1995), S. 69-89 
    ISSN: 0886-9383
    Keywords: chemometrics ; pattern recognition ; class modeling ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different estimators of the Mahalanobis distance (such as that based on the Defrise - Gussenhoven correction) are studied and compared with respect to the bias on the distance and the characteristics (sensitivity and specificity) of the class model.Results obtained using estimators with critical values from χ2-statistics are compared with those obtained using estimators with critical values from β-statistics (training set) and Hotelling statistics (evaluation set).Tables are reported for D-statistics (useful for simulating populations of two categories with selectable theoretical sensitivity and specificity) and for critical values of the Mahalanobis distance obtained from β-statistics.For objects of the training set the estimator of the Mahalanobis distance based on the estimate of the covariance matrix produces models with the optimum sensitivity. The same model has too low a sensitivity for objects of the model category in the evaluation set, but good specificity for objects of outer categories.The estimator with the Defrise-Gussenhoven correction produces enlarged models with too high a sensitivity for objects in the training set, good sensitivity for objects of the model category in the evaluation set and low specificity for objects of outer categories.
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  • 98
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    Journal of Chemometrics 9 (1995) 
    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
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  • 99
    ISSN: 0886-9383
    Keywords: pattern recognition ; infrared spectra ; factor analysis ; maximum likelihood method ; entropy of information ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectral region from 700 to 3600 cm-1 is subdivided into several wave number intervals. The peaks in each interval are summarized by means of three encoding algorithms. Using a factor model of kcommon factors, the total extractable variacnce (com) of a given set of intervals is calculated and correlated with the redundancy of information in all these intervals. The value of com is verified by analysis of the factor loadings aik (factor pattern). Finally, the information content of some chosen sets of intervals coded by the three selected feature algorithms will be correlated to the probability of information flow through a serial-parallel network. The encoding using only wave numbers was found to be the most effective.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 59-66 
    ISSN: 0886-9383
    Keywords: Mathematical approximation ; Sigmoid curve ; Sensitometric curve ; Photographic material ; Non-linear regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper studies the application possibilities of various mathematical analytical functions to models of approximation of sigmoid sensitometric curves of photographic materials. The newly developed functions have been tested along with approximation functions taken from the literature: the former fulfil the statistical criteria of fitting the regression and experimental curve in the best way. The model functions can be used not only for objective determination of sensitometric quantities but also for determination of the general sensitivity (speed) of photographic materials.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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