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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 21-36 
    ISSN: 0886-9383
    Keywords: GRAM ; Tucker ; Unfold ; NBRA ; Second-order ; Three-way ; PARAFAC ; Trilinear ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: If an analytical instrument or instrumental method gives a response matrix when analyzing a pure analyte, the instrument or instrumental method is called a second-order method. Second-order methods that generate a response matrix for a pure analyte of rank one are called rank-one second-order methods. If the response matrix of a pure analyte is not rank one, essentially two cases exist: medium rank (between two and five) and high rank (greater than five). Subsequently, medium- and high-rank second-order calibration tries to use medium- and high-rank second-order methods to analyze for analytes of interest in a mixture. A particular advantage of second-order methods is the ability to analyze for analytes of interest in a mixture which contains unknown interferences. Keeping this advantage is the challenge on moving away from rank-one second-order calibration methods. In this paper a medium-rank second-order calibration method is proposed based on least-squares restricted Tucker models. With this method the second-order advantage is retained.
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  • 2
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    Journal of Chemometrics 8 (1994), S. 101-101 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 3
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    Journal of Chemometrics 8 (1994), S. 103-110 
    ISSN: 0886-9383
    Keywords: Taguchi ; Robust design ; Design of experiments ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper is intended to convey the essence of Taguchi's design approach to chemists and others with an interest in chemometrics. Although most Taguchi-style applications worldwide have been in electronics and in elaborately transformed manufactures, examples are increasingly found in chemical processes and in the food industry.Foremost among Taguchi's contributions is the concept of designing processes and products to be robust to the uncontrollable environmental influences which they experience during their operation or lifetime. This concept is explained with a worked example.
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  • 4
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    Journal of Chemometrics 8 (1994), S. 127-145 
    ISSN: 0886-9383
    Keywords: Compression ; Multivariate analysis ; B-splines ; FT-IR spectra ; Second-order ; Two-dimensional ; Hyphenated methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to improve the storage and CPU time in the numerical analysis of large two-dimensional (hyphenated, second-order) infrared spectra, a data-preprocessing technique (compression) is presented which is based on B-splines. B-splines have been chosen as the compression method since they are wellsuited to model smooth curves. There are two primary goals of compression: a reduction of file size and a reduction of computation when analyzing the compressed representation. The compressed representation of the spectra is used as a substitute for the original representation. For the particular example used here, approximately 0.16 bit per data element was required for the compressed representation in contrast with 16 bits per data element in the uncompressed representation. The compressed representation was further analysed using principal component analysis and compared with a similar analysis on the original data set. The results shows that the principal compotent model of the compressed representation is directly comparable with the principal component model of the original data.
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  • 5
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 6
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    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 7
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    Journal of Chemometrics 8 (1994), S. 181-203 
    ISSN: 0886-9383
    Keywords: RAFA ; GRAM ; Eigenvalues ; Bias ; Variance ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rank annihilation factor analysis (RAFA) is a method for multicomponent calibration using two data matrices simultaneously, one for the unknown and one for the calibration sample. In its most general form, the generalized rank annihilation method (GRAM), an eigenvalue problem has to be solved. In this second paper expressions are derived for predicting the bias and variance in the eigenvalues of GRAM. These expressions are built on the analogies between a reformulation of the eigenvalue problem and the prediction equations of univariate and multivariate calibration. The error analysis will also be performed for Lorber's formulation of RAFA. It will be demonstrated that, depending on the size of the eigenvalue, large differences in performance must be expected. A bias correction technique is proposed that effectively eliminates the bias if the error in the bias estimate is not too large. The derived expressions are evaluated by Monte Carlo simulations. It is shown that the predictions are satisfactory up to the limit of detection. The results are not sensitive to an incorrect choice of the dimension of the factor space.
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  • 8
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    Journal of Chemometrics 8 (1994), S. 243-243 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 9
    ISSN: 0886-9383
    Keywords: Fitting ; Non-linear ; Least squares ; Refinement ; Constraints ; MSE ; Confidence ; C ls ; XPS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A non-linear least squares iterative refinement has been implemented which shows high performance on a multiple-peak spectrum including baseline or background. Constraints as well as links within a range are introduced to drive the mathematical optimization: each peak parameter (i.e. height, position, Gaussian/Lorentzian mixing ratio and HWHM on both left and right sides) has assigned to it an allowed range of variation and can be strained to be correlated with other parameters belonging either to the same peak (symmetrical peaks) or to other peaks (doublets, triplets, etc.). Peak shapes typical of XP spectra are used and applications in the field of XPS are discussed. Through emulated curves with Poisson distributed noise, the accuracy and precision of back-calculated (refined) parameters have been estimated. Moreover, a confidence level calculated from X2 and degrees of freedom has been suggested to check the overall fitting of experimental curves where the signal-to-noise ratio is a priori unknown. An application to real C ls XP spectra is described as an example and a list of suggestions is given to match operator requirements. Finally, features of NLLSRC are discussed with respect to other approaches.
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  • 10
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    Journal of Chemometrics 8 (1994), S. 263-272 
    ISSN: 0886-9383
    Keywords: Molecular descriptors ; Principal component analysis ; Chemometrics ; Pattern recognition ; Total surface area ; PCDD PCDF ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New theoretical molecular indices are defined. They contain information about the whole molecular structure in terms of size, shape, symmetry and atom distribution. These indices are calcualted from the (x, y, z) co-ordinates of a molecule within different weighting schemes in a straightforward manner and represent a very general approach to describe molecules, molecular fragments, macromolecules and molecular conformations in a unitary conceptual framework. Their interpretability is quite evident and is defined by the same mathematical properties as the algorithm used for their calculation. Examples on the total surface area, toxicity of PCDD and PCDF and reaction rate of catalysed reactions show a high modelling power of these indices.
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  • 11
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    Journal of Chemometrics 8 (1994), S. 301-302 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 12
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    Journal of Chemometrics 8 (1994), S. 333-347 
    ISSN: 0886-9383
    Keywords: PLS ; ATR ; Paper ; Resolution ; Infrared ; FTIR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attenuated total reflectance Fourier transform infrared spectrometry (ATR-FTIR) has been used to determine the amount of styrene-butadiene latex on the surface of coated papers and to predict the composition of the polymer. Spectrum recording was performed on the sample in its usual form without any modification.For quantitative analysis, partial least squares (PLS) regression, principal component regression (PCR) and multi-linear regression (MLR) were used to calculate models for prediction. The best result is obtained with PLS.We analysed two series of paper samples. The first analysis concerns the measurement of the quantity of latex of a constant quality on the coating surface. For 15 samples the concentration varied between 5 and 25 parts (grams per 100g of mineral pigments). We compared the predictive results at various resolutions. We obtained a relative error of 0.15 parts in latex at 4 cm-1 resolution. The second analysis concerns the measurement of the styrene/butadiene ratio in various types of latex. We obtained a relative error of 0.156 parts for styrene determination and 0.161 parts for butadiene determination.
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  • 13
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    Journal of Chemometrics 8 (1994), S. 375-376 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 14
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    Journal of Chemometrics 8 (1994), S. 391-407 
    ISSN: 0886-9383
    Keywords: Neural networks ; Non-linear multivariate regression ; Pattern classification ; Kalman filter ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Finding methods for the optimization of weights in feedforward neural networks has become an ongoing developmental process in connectionist research. The current focus on finding new methods for the optimization of weights is mostly the result of the slow and unreliable convergence properties of the gradient descent optimization used in the original back-propagation algorithm. More accurate and computationally expensive second-order gradient methods have displaced earlier first-order gradient optimization of the network connection weights. The global, extended Kalman filter is among the most accurate and computationally expensive of these second-order weight optimization methods. The iterative, second-order nature of the filter results in a large number of calculations for each sweep of the training set. This can increase the training time dramatically when training is conducted with data sets that contain large numbers of training patterns. In this paper an adaptive variant of the global, extended Kalman filter that exhibits substantially improved convergence properties is presented and discussed. The adaptive mechanism permits more rapid convergence of network training by identifying data that contain redundant information and avoiding calculations based on this redundant information.
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  • 15
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    Journal of Chemometrics 8 (1994), S. 439-443 
    ISSN: 0886-9383
    Keywords: Pattern recognition ; Principal component analysis ; Inverse mapping ; Optimization ; Material design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inverse mapping method called PCB (principal component backing), in which the point representing an unknown sample from a low-dimensional principal component subspace is back-projected to the high-dimensional original feature space, is proposed. Two sorts of boundary conditions, non-linear inverse mapping and linear inverse mapping, are used to obtain an accurate solution in the PCB method. The method is applied to the material design of high-Tc superconductors, predicting the composition and process conditions for the synthesis of F-doped Bi-based materials. Samples in the ‘optimal’ region with the highest Tc of the Bi-based ceramics have been predicted.
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  • 16
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    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
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    Journal of Chemometrics 8 (1994), S. 37-44 
    ISSN: 0886-9383
    Keywords: Bootstrap ; Confidence interval ; Non-linear regression ; Monte Carlo methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Non-linear regression models describing the toxicity of a mixture of rotenone and pyrethrins as an insecticide, the catalytic dehydration of n-hexyl alcohol and the Michaelis-Menten model for characterizing reaction rates in enzyme systems will be used to illustrate the accuracy of bootstrap methods in non-linear regression. Classical and bootstrap confidence intervals for the parameter estimates will be presented.
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  • 18
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
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    Journal of Chemometrics 8 (1994), S. 102-102 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 20
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    Journal of Chemometrics 8 (1994), S. 111-125 
    ISSN: 0886-9383
    Keywords: PLS regression algorithm ; Kernel ; Many-variable data sets ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fast PLS regression algorithm dealing with large data matrices with many variables (K) and fewer objects (N) is presented For such data matrices the classical algorithm is computer-intensive and memory-demanding. Recently, Lindgren et al. (J. Chemometrics, 7, 45-49 (1993)) developed a quick and efficient kernel algorithm for the case with many objects and few variables. The present paper is focused on the opposite case, i.e. many variables and fewer objects. A kernel algorithm is presented based on eigenvectors to the ‘kernel’ matrix XX TYYT, which is a square, non-symmetric matrix of size N × N, where N is the number of objects. Using the kernel matrix and the association matrices XXT (N × N) and YYT (N × N), it is possible to calculate all score and loading vectors and hence conduct a complete PLS regression including diagnostics such as R2. This is done without returning to the original data matrices X and Y. The algorithm is presented in equation form, with proofs of some new properties and as MATLAB code.
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  • 21
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    Journal of Chemometrics 8 (1994), S. 169-174 
    ISSN: 0886-9383
    Keywords: Kernel algorithm ; PLS ; SVD ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lindgren et al. (J. Chemometrics, 7, 45-49 (1993)) published a so-called kernel algorithm for PLS regression of Y against X when the number of objects is very large. The algorithm is based solely on deflation of the cross-product matrices XTX, YTY and XTY. The algorithm is now described in a shorter and more transparent way and compared with a similar algorithm for the singular value decomposition of XTY.
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  • 22
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    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 23
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    Journal of Chemometrics 8 (1994), S. 241-241 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 24
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    Journal of Chemometrics 8 (1994), S. 273-285 
    ISSN: 0886-9383
    Keywords: GRAM ; Least-squares problem ; Eigenvalue problem ; NIPALS ; Performance index ; Condition number ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we discuss the practical implementation of the generalized rank annihilation method (GRAM). The practical implementation comes down to developing a computer program where two critical steps can be distinguished: the construction of the factor space and the oblique rotation of the factors. The construction of the factor space is a least-squares (LS) problem solved by singular value decomposition (SVD), whereas the rotation of the factors is brought about by solving an eigenvalue problem. In the past several formulations for GRAM have been published. The differences essentially come down to solving either a standard eigenvalue problem or a generalized eigenvalue problem. The first objective of this paper is to discuss the numerical stability of the algorithms resulting from these formulations. It is found that the generalized eigenvalue problem is only to be preferred if the construction of the factor space is not performed with maximum precision. This is demonstrated for the case where the dominant factors are calculated by the non-linear iterative partial least-squares (NIPALS) algorithm. Several performance measures are proposed to investigate the numerical accuracy of the computed solution. The previously derived bias and variance are proposed to estimate the number of physically significant digits in the computed solution. The second objective of this paper is to discuss the relevance of theoretical considerations for application of GRAM in the presence of model errors.
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  • 25
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    Journal of Chemometrics 8 (1994), S. 299-301 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
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    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 27
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    Journal of Chemometrics 8 (1994), S. 349-363 
    ISSN: 0886-9383
    Keywords: Variable selection ; PLS ; Calibration ; Modelling ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modified PLS algorithm is introduced with the goal of achieving improved prediction ability. The method, denoted IVS-PLS, is based on dimension-wise selective reweighting of single elements in the PLS weight vector w. Cross-validation, a criterion for the estimation of predictive quality, is used for guiding the selection procedure in the modelling stage. A threshold that controls the size of the selected values in w is put inside a cross-validation loop. This loop is repeated for each dimension and the results are interpreted graphically. The manipulation of w leads to rotation of the classical PLS solution. The results of IVS-PLS are different from simply selecting X-variables prior to modelling. The theory is explained and the algorithm is demonstrated for a simulated data set with 200 variables and 40 objects, representing a typical spectral calibration situation with four analytes. Improvements of up to 70% in external PRESS over the classical PLS algorithm are shown to be possible.
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  • 28
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    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 29
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    Journal of Chemometrics 8 (1994), S. 409-421 
    ISSN: 0886-9383
    Keywords: Deconvolution ; FT-IR spectroscopy ; Protein conformations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a variety of spectroscopic techniques the fundamental problem exists of determination of the individual spectral components, intrinsically overlapped in the measured spectrum. This is a typical deconvolution problem and several methods and techniques have been proposed for its solution in the technical literature, but suggestions of new approaches are still of interest. A new deconvolution procedure is presented here based on the use of the conjugate gradient minimization algorithm with the addition of sutiable constraints directly obtained by the application to the measured spectrum of the second-derivative operator or more sophisticated resolution enhancement procedures. Since in the examined case deconvolution essentially requires the minimization of a non-convex function, the use of such constraints is extremely important to supply suitable input parameters to the conjugate gradient algorithm to avoid obtaining minimum points which have no physical meaning. In our case each spectral compoent used for deconvolution has been assumed to have a Gaussian analytical definition fully identified by three parameters (amplitude, central frequency, spectral bandwidth), so that the input values required to start the deconvolution process are the number M of Gaussian components and 3M suitable initial approximations of the parameters above. It is shown that all this information can be obtained from the measured data. The deconvolution procedure was implemented by a FORTRAN Microsoft Version 5.1 program and experimental results relative to spectroscopic data obtained by FT-IR analysis of human serum albumin are reported. The results are discussed and compared with data obtained by the use of other techniques.
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  • 30
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 31
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 32
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    Journal of Chemometrics 8 (1994), S. 1-20 
    ISSN: 0886-9383
    Keywords: Discriminant analysis ; Least squares ; Prediction ; Regression ; Relationship ; Structure ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Twenty-two contrasting statistical methods are reviewed for their applicability to QSAR studies and similar prediction-oriented fields. Each method is concisely specified prior to explanatory or critical comment.
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  • 33
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    Journal of Chemometrics 8 (1994), S. 65-79 
    ISSN: 0886-9383
    Keywords: Genetic algorithms ; Full validation ; Feature selection ; Outlier detection ; Multivariate analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Genetic algorithms have been proved to be a very efficient method in the feature selection problem. However, as for every other method, if the validation of the results is performed in an incomplete way, erroneous conclusions can be drawn. In this paper a development of a previous genetic algorithm is presented so that a full validation of the results can be obtained. Furthermore, this algorithm has been shown to perform very well also as an outlier detector, allowing easy identification of the presence of outliers even in cases where the ‘classical’ techniques fail.
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  • 34
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    Journal of Chemometrics 8 (1994), S. 81-93 
    ISSN: 0886-9383
    Keywords: Sensory evaluation ; Cumulative ranks ; Assessor variation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A graphical method of assessing differences between sets of rankings based on cumulative ranks is developed. The method can be used to identify rankings that differ over all or just part of the range of objects ranked. The method is applied to an example of sensory evaluation of green peas in which ten assessors scored six attributes on each of 60 samples.
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  • 35
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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  • 36
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    Journal of Chemometrics 8 (1994), S. 305-331 
    ISSN: 0886-9383
    Keywords: Pyrolysis ; Mass spectroscopy ; Multivariate analysis ; Biological material identification ; Convexity ; Cones ; Subspaces ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work addresses the classification of high-dimensional time-dependent pyrolysis mass spectra of biological samples. The aim was the detection and classification of biological agents, and the developed approach resembles mixture analysis. The data were projected on to a low-dimensional subspace using singular value decomposition. Then a convex cone was formed on this subspace, showing as its corners physically meaningful components of the sample. This technique enabled separation of a biological material signal largely independent of the absolute amount of sample. The detection of the presence of any biological material could be accomplished based on the convex cone alone, without other reference to the mass spectra. Automated clustering of samples was successfully carried out using a minimal spanning tree.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 38
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    Journal of Chemometrics 8 (1994), S. 377-389 
    ISSN: 0886-9383
    Keywords: Kernel PLS regression ; Cross-validation ; Model dimensionality ; Multivariate image regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multivariate images are very large data structures and any type of regression for their analysis is very computer-intensive. Kernel-based partial least squares (PLS) regression, presented in an earlier paper, makes the calculation phase more rapid and less demanding in computer memory. The present paper is a direct continuation of the first paper. In this study the kernel PLS algorithm is extended to include cross-validation for determination of the optimal model dimensionality. To show the applicability of the kernel algorithm, two examples from multivariate image analysis are used. The first example is an image from an airborne scanner of size 9 × 512 × 512. It consists of nine images which are regressed against a constructed dependent image to test the accuracy of the kernel algorithm when used on large data structures. The second example is a satellite image of size 7 × 512 × 512. Several different regression models are presented together with a comparison of their predictive capabilities. The regression models are also used as examples for showing the use of cross-validation.
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  • 39
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    Journal of Chemometrics 8 (1994), S. 99-100 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 41
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    Journal of Chemometrics 8 (1994), S. 147-154 
    ISSN: 0886-9383
    Keywords: RAFA ; GRAM ; Eigenvalue problem ; Complex solution ; Degenerate solution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rank annihilation factor analysis (RAFA) is a method for multicomponent calibration using two data matrices simultaneously, one for the unknown and one for the calibration sample. In its most general form, the generalized rank annihilation method (GRAM), an eigenvalue problem has to be solved. In this first paper different formulations of GRAM are compared and a slightly different eigenvalue problem will be derived. The eigenvectors of this specific eigenvalue problem constitute the transformation matrix that rotates the abstract factors from principal component analysis (PCA) into their physical counterparts. This reformulation of GRAM facilitates a comparison with other PCA-based methods for curve resolution and calibration. Furthermore, we will discuss two characteristics common to all formulations of GRAM, i.e. the distinct possibility of a complex and degenerate solution. It will be shown that a complex solution-contrary to degeneracy-should not arise for components present in both samples for model data.
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  • 42
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 43
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    Journal of Chemometrics 8 (1994), S. 179-180 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 44
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    Journal of Chemometrics 8 (1994), S. 287-292 
    ISSN: 0886-9383
    Keywords: Rank annihilation ; Principal components ; Procrustes rotation ; Multivariate analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the DATa ANalysis (DATAN) algorithm can be expressed in terms of rank annihilation factor analysis (RAFA). Subsequent advances in RAFA are applied to DATAN to eliminate the problems and restrictions associated with DATAN. The extension of DATAN in terms of the trilinear decomposition algorithm is discussed.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 46
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 47
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    Journal of Chemometrics 8 (1994), S. 365-370 
    ISSN: 0886-9383
    Keywords: Censored data ; ECM and EM algorithms ; Incomplete data ; Maximum likehhood ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The purpose of this short communication is to illustrate the use of conditional maximization (CM) in chemometric applications. The CM algorithm is useful in reducing the computational complexity when a high-dimensional and complicated maximization problem arises from fitting chemometric models. It can also be efficiently combined with the expectation-maximization (EM) algorithm for handling incomplete data, a problem that sometimes arises when only a part of the intended data can be collected. Three models from fluorescence spectroscopy are used for illustration.
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 49
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    Journal of Chemometrics 8 (1994), S. 423-437 
    ISSN: 0886-9383
    Keywords: Resolvability ; Evolutionary factor analysis ; Variable selection ; Window factor analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for selecting variables in the non-sequential direction of a two-way data matrix (e.g. wavelength in diode array HPLC) is described. Composition 1 and 2 resolvability indices are calculated according to the size of eigenvalues of uncentred data matrices as a window is moved along the sequential direction. A double-window technique is then performed where resolvability indices are calculated as a window is moved along the non-sequential direction. Some regions have higher resolvability indices and hence are more useful for resolution. Variables are ranked according to resolvability. Two simulations are analysed and it is shown that it is possible to obtain good resolution on a small subset of the original variables.
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 51
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    Journal of Chemometrics 8 (1994), S. 45-63 
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    Keywords: GRAM ; GSVD ; Propagation of errorS ; Correlated noise ; Uncorrelated noise ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of correlated and uncorrelated random errors on the precision of predicted quantitative and qualitative information obtained by analysis with the generalized rank annihilation method (GRAM) are shown. These are discussed in terms of propagation of errors through the algorithm. The effects of colinearity, noise level and noise distribution are compared and discussed.
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    Journal of Chemometrics 8 (1994), S. 97-98 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 54
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    Journal of Chemometrics 8 (1994), S. 155-168 
    ISSN: 0886-9383
    Keywords: Trilinear models ; Tensorial resolution ; PARAFAC ; Swamps ; Two-factor degeneracy ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The alternating least squares PARAFAC algorithm is a useful tool for resolving trilinear three-way data arrays. Occasionally, however, it becomes bogged down for many iterations in the vicinity of a poor quality resolution before moving on to a much superior optimum fit. We investigate this behavior in a simulation study and suggest ways of overcoming the obstacles it presents.
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    Journal of Chemometrics 8 (1994), S. 205-219 
    ISSN: 0886-9383
    Keywords: Fractional factorial design ; Significant effects ; ANOVA ; Probability plotting ; Bayes plot ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents a method for identifying significant effects in fractional factorial designs. The method is based on comparing functions of the estimated effects with a scale invariant reference distribution. The method is illustrated and compared with alternative techniques on a dataset from processed cheese production. The method corresponded well to other methods (probability plotting and Bayes plot) that do not make use of error estimates. These methods were better than F-tests with few (two or four) degrees of freedom for error.
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 57
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    Journal of Chemometrics 8 (1994), S. 245-261 
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    Keywords: Factor analysis ; Spectral resolution ; Two-dimensional luminescence ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A factor analysis algorithm that estimates the spectra of mixture components using the set of most dissimilar rows and/or columns is described and illustrated. This algorithm uses the distance as a measure of spectral similarity and is suitable for application to a variety of the bilinear matrix-formatted data types produced by hyphenated and multidimensional analytical techniqes. The algorithm requires that the data matrix contain at least one row or column that corresponds to the pure spectrum of each component to effect accurate spectral resolution. The performance of the method is illustrated using the resolution of excitation and emission spectra of up to four components from experimental fluorescence excitation-emission matrices (EEMs). In the case of the EEM, characteristic bands in an emission spectrum effect resolution of the excitation spectrum of the corresponding component, while characteristic bands in an excitation spectrum lead to resolution of the corresponding emission spectrum. The use of the set of most dissimilar rows and columns to evaluate the degree of overlap in the component spectra and compare the quality of row and column solutions is also described.
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    Journal of Chemometrics 8 (1994), S. 293-294 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 295-296 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 303-303 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 373-373 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 445-446 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The separation of ethoxylated aliphatic amines from zinc containing effluents with macroporous polymeric adsorbents Wofatit EP 61, EP 62, Y 59, Y 77 and active carbons has been examined. The adsorption behaviour has been investigated as a function of temperature, time and concentration of Na2SO4, ZnSO4 and H2SO4. The macroporous polymers EP 61, Y 77 and Y 59 are capable of separating ethoxylated aliphatic amines from effluents of viscose fibre industry at higher temperatures and under weakly acidic conditions. In contrast to active carbon, inorganic components are not adsorbed on the investigated macroporous resins. Data obtained in a concentration range of 0 to 10 g of adsorbate per litre produced a Langmuir profile for adsorption of ethoxylated aliphatic amines by polymeric adsorbents.
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    Chemical Engineering & Technology - CET 17 (1994) 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
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    Chemical Engineering & Technology - CET 17 (1994), S. 149-160 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Several kinds of diesel soot filters and filter materials of high melting points with eleven different catalytic coatings were prepared. They were calcined at a maximum temperature of 1000°C. The reaction rate and the kinetic parameters of the combustion of diesel soot were determined in a closed loop laboratory reactor. A packed bed of alumina particulates was the most active filter in soot combustion. Catalytic coatings with oxides of vanadium, copper or cerium accelerated the reaction. In each case the effect of the coating was dependent on specific interactions between the catalyst and the filter material. The manner of filtration and the nature of the soot filter are found to be more important for the overall result than the nature of the catalytic coating.
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    Chemical Engineering & Technology - CET 17 (1994), S. 179-186 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The conversion of ethanol over H-ZSM-5 was studied as a function of ethanol partial pressure, reaction temperature, weight hourly space velocity and Si/Al ratio. The results obtained were in qualitative agreement with most of those in the literature. Combination with all published results to give a significant regression model was not possible due to the large scatter of the data from various scientific groups. In mechanistic investigations, temperature programmed reaction measurements of ethanol, diethyl ether and ethene were performed. The formation of ethene from ethanol via direct elimination or from diethyl ether as intermediate could be confirmed. In the conversion of ethanol/water mixtures, the product distribution did not change significantly up to a water content of 60 wt%. Then, a pronounced increase of ethene formation and a considerable decrease of the yields of aromatics was observed. When several reaction mixtures from syngas conversion to ethanol were converted over H-ZSM-5, the coking rate depended on the product distribution in the feed. Product mixtures from processes with higher amounts of compounds having an unfavourable C/H ratio led to rapid deactivation of the zeolite.
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Titanium silicalite-1 samples of different particle size are synthesised and characterised by X-ray diffraction (XRD), photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), Raman and infrared spectroscopy. Size histograms are taken from transmission electron micrographs. Temporal changes of activity and selectivity for the hydroxylation of phenol and anisole are monitored. It is postulated that the p/o product ratios are due to the greater chemisorption of the ortho molecule.
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    Chemical Engineering & Technology - CET 17 (1994), S. 358-363 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cooling breakdown in highly exothermic reaction processes may lead to runaway. The sensitivity and the safety assessment of a batch process on cooling breakdown are studied. The dependence of the minimum cooling time and the maximum allowable time of cooling breakdown for safe operation on the process parameters is investigated.
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Gas diffusion electrodes, made of PTFE-bonded carbon with precious metal catalysts, were investigated as hydrogen consuming anodes in sodium sulphate electrolysis. The catalysts used were platinum and palladium and mixtures of both metals, prepared by two different methods. Various metal meshes were used as current collector. The electrodes performed well in pure sulphuric acid (5-15 wt-%) and in mixtures with sodium sulphate (10 wt-%) at temperatures of 30 to 70°C and current densities up to 5 kA/m2. In long-term experiments, at a current density of 2.6 kA/m2, the electrodes were stable over three months. The electrodes were characterised by stationary current density/potential curves and by galvanostatic current interruption measurements.
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    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Process models are used to formulate knowledge about process behaviour. They are applied, e.g., to predict the process' future behaviour and for state estimation when reliable on-line measuring techniques to monitor the key variables of the process are not available. There are different sources of information available for modelling, which provide process knowledge in different representations. Some elements or aspects may be described by physically based mathematical models and others by heuristically obtained rules of thumb, while some information may still be hidden in the process data recorded during previous runs of the process. Heuristic rules are conveniently processed with fuzzy expert systems, while artificial neural networks present themselves as a powerful tool for uncovering the information within the process data without the need to transform the information into one of the other representations. Artificial neural networks and fuzzy technology are increasingly being employed for modelling biotechnological processes, thus extending the traditional way of process modelling by mathematical equations. However, a sufficiently comprehensive combination of all these techniques has not yet been put forward. Here, we present a simple way of combining all the available knowledge relating to a given process. In a case study, we demonstrate the development of a hybrid model for state estimation and prediction on the example of a yeast production process. The model was validated during a cultivation performed in a standard pilot-scale fermenter.
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    Chemical Engineering & Technology - CET 17 (1994), S. 50-60 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Knowledge of transport processes is of considerable practical importance in the design and performance evaluation of packed bed reactor systems. Acquisition of the required information necessitates a realistic mathematical description of the system. In this study, numerical analysis is performed for forced convective non-Darcian, non-isothermal compressible flow and heat transfer in cylindrical packed beds. Local structural and transport properties are considered. The influence of compressional work as well as viscous dissipation on the thermal field is evaluated and a general criterion provided for assessing the effect of expansion.
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    Chemical Engineering & Technology - CET 17 (1994), S. 73-80 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Due to induced turbulent interactions between particles to be separated and the scrubbing liquid present as droplets, very good collection efficiency down to submicron particle size can be achieved as shown by detailed studies [1]. Assumed are suitable flow conditions, a long residence time and a certain droplet size distribution or a special liquid dispersion system. As the name implies, the cyclone scrubber basically consists of a cyclone. This cyclone serves as a contact space in which the interaction between dust particles and scrubbing liquid droplets takes place, and as a droplet separator. Thus, under normal conditions, a water saturated but dust- and droplet-free gas stream leaves the cyclone. The droplets are generated by a pneumatic atomization nozzle, arranged at the cyclone inlet in the direction of flow. A complete theoretical description of the three-dimensional, three-phase, non-steady turbulent flow in the cyclone scrubber has not been possible up to now. The detailed experimental investigations presented in this work, and covering multiple parameters, led to physically based conclusions about the dominant interactions and separation mechanisms involved. Grade efficiencies which did not fall below 0.75, down to a particle size of 0.5 μm, could be measured by an optical particle counter. Collection efficiency of 99.2% was determined by gravimetric analysis of the dust load, according to VDI-guideline 2066, in the raw and clean gas sections of the dust load, according to VDI-guideline 2066, in the raw and clean gas sections of the cyclone scrubber.
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    Chemical Engineering & Technology - CET 17 (1994), S. 108-111 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: It has been shown that, after a partial deactivation, γ-alumina (γ-Al2O3) is a good catalyst for selective methylation of 1,2-benzenediol in the temperature range of 260-310°C. The main products are the desired 3-methyl-1,2-benzenediol and 2-methoxyphenol, which may be converted in another step into 3-methyl-1,2-benzenediol, giving an overall selectivity for the desired products of 80 to 90%. The catechol forms a strongly chemisorbed surface species on γ-alumina and its steric adsorption model correlates with the kinetic data.
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A batch reactor directly combined with an ultrahigh vacuum apparatus, which is equipped with facilities for catalyst preparation and Auger electron spectroscopy, was used to answer some questions which had arisen in recent studies concerning carbon dioxide hydrogenation on pure metallic and supported Co catalysts. Both oxygen incorporated during oxidation/reduction cycles and carbon deposited when CO2 is hydrogenated penetrate deep into the bulk. This kind of carbon can easily be hydrogenated. CO strongly hinders the reduction of the oxidized Co surface in the H2/CO2 reaction mixture (4 : 1). CO hydrogenation is favoured over CO2 hydrogenation and leads to a higher percentage of C2 to C4 hydrocarbons as compared with CH4 formation.
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    Chemical Engineering & Technology - CET 17 (1994), S. 414-421 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Computer-aided design of a packed column to remove ethanol from aqueous solution with dibutyl butylphosphonate (DBBP) was accomplished with a programme based on the Pratt method and on the slip velocity equation. Reliable data for successful computation were obtained from literature correlations (drop size, hold-up and axial mixing coefficients for different types of packing) and from experimental work (equilibria and kinetics). Equilibrium studies on the H2O-ethanol-dibutyl butylphosphonate system were performed at different temperatures. A decrease in temperature increased the selectivity of the extractant while the distribution coefficient of ethanol, KD ≈ 1.0, remained constant. The behaviour of the system kinetics towards temperature is assessed in order to determine the initial mass transfer flux (892 × 10-3 kg m-2s-1, 30°C) and the activation energy, 22.9 kJ/kmol. The process is governed by the diffusion of the species involved. The influence of the type of packing of the column on its design is analyzed from the inventory volume of the solvent, the total volume of the column and the axial dispersion coefficients under normalised inlet and outlet conditions.
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    Particle and Particle Systems Characterization 11 (1994), S. 6-6 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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    Particle and Particle Systems Characterization 11 (1994), S. 5-5 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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  • 78
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    Particle and Particle Systems Characterization 11 (1994), S. 7-21 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical and practical limits on the applicability of PDA are established, using generalized theoretical formulations of various physical processes governing the operation of a phase Doppler system. Furthermore, several innovative solutions are introduced to prevent the commonly occuring problems of PDA, such as Gaussian profile effect, non-monotonic response and 2π-ambiguity. Generalized formulations have also enabled new applications, such as sizing of submicron particles, particle material recognition, measurements with non-standard geometries. Selected results of measurements in particulate flows, using innovative PDA systems, are also presented.
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  • 79
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    Particle and Particle Systems Characterization 11 (1994), S. 22-34 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Many optical sizing techniques rely on particle/laser interactions. The classical Lorenz-Mie theory describing sphere/plane wave interactions is therefore misleading when designing instruments and processing data when the particle size is not small enough with respect to beam diameters. In such cases the use of the generalized Lorenz-Mie theory is required. After summarizing essential features of the generalized Lorenz-Mie theory for sphere/arbitray wave interactions, this paper describes applications of the theory with some emphasis on the analysis of phase-Doppler anemometers.
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  • 80
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    Particle and Particle Systems Characterization 11 (1994), S. 35-42 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical model has been developed for studying the response of the phase Doppler interferometer when multiple particles are simultaneously present within the measurement probe volume. The developed model incorporates the geometrical optics theory for describing the coherent interaction between the scattered light signals of multiple particles, eachhaving different size, velocity, trajectory, and arrival time. The resulting Doppler signal is processed by a theoretical signal processor which can simulate the performance characteristic of different signal processing schemes that are widely used in phase Doppler interferometry, namely, zero-crossing counter, covariance, autocorrelation and DFT parocessors. The application of the developed model for studying the coherent scattering by two particles has been specifically addressed in this paper. It has been shown that a DFT processor can be used to simultaneously measure the size and velocity of the two particles in most instances. However, for more than two particles, the signal processing scheme becomes more complex because of a quadratic increase in the beat frequency components.
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  • 81
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    Particle and Particle Systems Characterization 11 (1994), S. 55-62 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using a computer model based on Lorenz-Mie and generalized Lorenz-Mie theory, various optical confiugurations of a phase-Doppler system were analysed with regard to their suitability for diameter measurements in the sub-micron range. The major concern in this size range is multi-valuedness of the phase-diameter characteristic, the relatively small signal-to-noise ratio obtained with the very low scattered intensity and the small value of the phase difference to be measured. It is shown numerically and by experiment that for particles in a free stream the multi-valuedness and the shot noise need not prohibit measurements in the sub-micron size range. The major source of phase error results from light scattered form objects or material other than the particle inside the measuring volume. Using an optical set-up with nearly counter-propagating incident beams and a large angle between the detectors, measurements were obtained for particle diameters down to 200 nm, and it is estimated that with some improvements in receiver optics measurement down to 100 nm will be possible.
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  • 82
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    Particle and Particle Systems Characterization 11 (1994), S. 73-83 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This review of the recent developments in the phase Doppler method provides information on the advances made to the method and delineates some potential error sources. Methods used to eliminate these potential error sources are also discussed. It is shown through comparison to the Lorenz-Mie theory and the GLMT that the geometrical optics theory offers a reliable and efficient computational tool for the analysis of the light scattering with the phase Doppler method. The geometrical optics theory was then used to optimize the measurement parameters in the system designs and a significant reduction in the measurement uncertainty was realized. Limitations on the particle concentrations in which the instrument will operate reliably are also addressed. A brief discussion of the instrumentation and, in particular, the signal processing is presented. The advantages in using the Fourier transform approach are discussed. As a demonstration of the capabilities of the instrument, several performance tests were reviewed and examples of the application to spray combustion and turbulent dispersion of particles are given.
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    Particle and Particle Systems Characterization 11 (1994), S. 101-106 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The use of a laser sheet (or elliptical Gaussian beam) in meas-urement techniques is of growing interset. Some of these techniques take advantage of the wavefront curvature of such beams as in a dual-crylindrical wave system (DCW). Nevertheless, up to now, the analysis of the properties of the light scattered by spherical particles form the beam has been carried out largely by using geometrical optics or classical Lorenz-Mie theory. In this paper, the generalized Lorenz-Mie theory (GLMT) is applied to the analysis of an existing DCW measurement system. Differences between the results predicted by classical approaches and by GLMT are emphasized.
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    Particle and Particle Systems Characterization 11 (1994) 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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    Particle and Particle Systems Characterization 11 (1994), S. 121-126 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This study deals with the size measurement of non-spherical particles by the laser diffraction technique. Size analyses of three sets of identical metallic bodies (cubes, tablets and cylinders) were performed by means of a Malvern 2600 instrument. The results prove that under the operating conditions chosen and in the case of anisometric objects, the mean total surface area is not measurable either because the Malvern software, strictly valid for spheres, is not applicable to such particles or because the particles adopt preferential orientations in the measurement cell. Further, a way of processing diffraction data is proposed in order to determine two characteristic dimensions of identical anisometric particles. It is based on the measurement of the minimum and maximum projected surface areas of the particles. The experimental results obtained with our particles show the procedure to be reliable.
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  • 86
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    Particle and Particle Systems Characterization 11 (1994), S. 91-100 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The results of comparative measurements of three different phase-Doppler systems applied to a steady-state water spray are discussed. The three receiving systems, i. e. DANTEC 57X receiving optics with covariance processor, an AEROMETRICS fibre-based receiver with DSA processor and standard INVENT phase-Doppler extension, were used with a 2-D fibre-optics-based transmitting system. A constant scattering angle of 70° was chosen, which is near the Brewster angle for water. Measurements were taken in the spray cone of hollow-cone pressure atomizer at two different axial distances from the nozzle. Local size distributions, size/velocity correlations and the mean diameters D10 and D32 were compared. The results indicate very good agreement between the different systems, especially with respect to the mean diameters. Larger scatter of the results occurs for the measured volume flow rates, but the calculated mean volume flow rates coincide fairly well with the nominal flow rate of the atomizer.
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    Particle and Particle Systems Characterization 11 (1994), S. 145-149 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Laser light scattering (LLS), especially dynamic laser light scattering (DLS), also known as photon correlation spectroscopy (PCS), is a well established method for particle size distribution analysis. It usually involves a Laplace inversion of the field autocorrelation function. However, the resolution is limited because of the ill-conditioned nature of this Laplace inversion. No unique solution exists when noise is present on the data. In contrast with this ill-conditioned nature, the angular dependence of scattered (static) intensities is precisely not ill-conditioned, which allows the resolution of the ill-conditioned inversion of DLS data to be improved. In order to characterize samples with more complicated size distributions, an intensityconstrained multi-angle PCS data analysis program has been developed, which is an alternative way of normalizing the field correlation function to that reported by Cummins and Staples [12]. In this program, the field autocorrelation function is normalized to the scattering intensity by using a predetermined coherent factor at each angle, which provides an additional constraint on the Laplace inversion of multi-angle PCS data analysis. The alternative analysis improves the resolution of PCS and provides a more reliable particle size distribution than single-angle data analysis. Both simulated and measured LLS data are used to illustrate its application, resolution and limitations.
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    Particle and Particle Systems Characterization 11 (1994), S. 339-344 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In phase Doppler anemometry (PDA), phase difference errors are caused by the Gaussian intensity distribution of the laser beam and the curvature of the phase fronts outside of the beam waist. This results in erroneous particle sizes. Based on a physical analysis by geometrical optics [1], this phase difference error is evaluated for reflected mode operation (Part I) and for refracted mode operation (Part II). By varying the particle trajectories statistically, the error in determining the particle size and the mass flow can be simulated. By the method described the error in the measured phase difference can easily be estimated.
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    Chemical Engineering & Technology - CET 17 (1994), S. 112-118 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Kinetic studies as well as morphological and physico-chemical surface studies have been carried out on the deactivation of a palladium carrier catalyst for vinyl acetate synthesis in the ethylene gas phase process. The experiments cover concentration and temperature ranges of technical interest at a total pressure of 900 kPa. The deactivation rate depends on the temperature and the oxygen and acetic acid concentrations. The decline in activity is best described by a rate law of second order relative to the activity number. This behaviour is attributed to the observed aggregation of finely dispersed palladium. It can be concluded that palladium(II) acetate acts as a transport species in a chemically assisted sintering mechanism. At temperatures T ≤ 438 K the more advantageous final texture of the catalyst will only be formed on reaction.
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    Chemical Engineering & Technology - CET 17 (1994), S. 195-200 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Shock tube pyrolysis of propane at temperatures between 1300 K and 2700 K at reflected shock pressures of 500 to 1500 kN/m2 has been investigated. The reaction is of 1st order with a rate constant K = 1.79 × 108 exp (-176.2 kJ/RT) s-1. The major reaction products were acetylene, ethylene and methane, while traces of propylene and ethane were only detected at temperatures below 1500 K. At higher temperatures, propane conversion to acetylene increased at the expense of the other products. Optimum conversions to ethylene and methane, in contrast to that to acetylene, were more sensitive to changes in temperature than to variations in reaction time. However, at reaction pressures above 550 kN/m2, extension of reaction time beyond 0.5 ms did not favour the formation of acetylene. A simple kinetic model which confirmed the experimental optimum product selectivity conditions is put forward.
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    Chemical Engineering & Technology - CET 17 (1994), S. 227-234 
    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: Concentration profiles are measured during the mixing process of carbon dioxide and air, which were injected into the rectangular cross section of a duct. The volume flow rates of both components differ considerably. The non-stationary and three-dimensional concentration fields are measured by optical tomography using holographic interferometry as the measuring principle. Projection data from four different viewing angles are used for tomographic reconstruction by the ART method. Pressure losses due to mixing processes are also measured. Results are presented for different angles of injection and different ratios of momentum flow rate for single and multiple jets of carbon dioxide which were injected into the carrier gas stream of air.
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    Chemical Engineering & Technology - CET 17 (1994), S. 249-254 
    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 automatic apparatus has been developed and set up for the study of drop-interface coalescence. Most other studies have concentrated on events when the drop arrives at the interface with its terminal velocity. In our case, the drop is maintained fixed at the tip of a needle, and the interface is moved towards the drop at a controlled speed. The coalescence times are measured by means of a vectorial video camera focused on the drop. Several times are measured by means of a vectorial video camera focused on the drop. Several parameters have been investigated, such as the drop diameter, the relative drop-interface velocity, the phase system, the presence and the direction of mass transfer.
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    Chemical Engineering & Technology - CET 17 (1994), S. 280-284 
    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 classical two-film model for mass transfer between two fluid phases can only be used to describe the steady state mass transfer mechanism. Both the penetration and the film-penetration model are also valid solely when only one diffusion boundary layer exists at the interface between the phases. With a view to surmounting the limitations of the above models a new model has been developed for the mass transfer between two fluid phases with two diffusion boundary layers at the interface. The new model is based on the two-film concept and the Danckwerts distribution function, and is also able to simulate the unsteady state mass transfer mechanism between two fluid phases with two different boundary layers.
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The results of experimental investigations on distillation columns operating on a lab and on a production scale are presented and compared with the results obtained by simulation. There is good agreement between experiment and simulation. On the basis of these results a dynamic analysis was carried out. It compares the dynamic behaviour of packed and plate distillation columns of the same diameter and same number of theoretical plates. This reflects the influence of the different hold-ups of the two columns.
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  • 95
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    Chemical Engineering & Technology - CET 17 (1994), S. 273-279 
    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 rigorous one-dimensional heterogeneous model is developed for a secondary reformer in an ammonia plant with special emphasis on the catalyst particle models. These are based on the effective diffusivity model and the Stefan-Maxwell model in the catalyst pore and the film around the catalyst particle. The performance of these four models is evaluated for the data collected from a commercial reformer in the complete operating range and recommendations are made regarding the use of appropriate particle models. The models for the catalyst particle show considerable deviations at the particle level but the reformer simulations produce almost identical results at the global level for all the four particle models. The need for a rigorous treatment of interphase resistance to mass transfer has been clearly demonstrated by comparison of the present model with the model of Singh and Saraf.
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    Chemical Engineering & Technology - CET 17 (1994) 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    Particle and Particle Systems Characterization 11 (1994), S. 235-240 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The diffraction patterns of static particles deviate from those of dynamic particles of the same distribution characteristics. Use of diffraction solutions based on independent scattering to analyse such diffraction patterns leads to a narrower size distribution biased towards the smaller sizes. A 2-D coherent diffraction model using an inter-particle relation PDF function is developed. The model clearly demonstrates the terms due to the individual particle diffraction and the terms contributed by the inter-particle correlation, i.e. the coherent effects. The deviation of the static particle diffraction pattern from that of the dynamic particles can be well predicted. The results of this study provide a general solution for utilizing the forward diffraction technique in static particle measurement. One of the important applications of the new model is in the development of a diffraction reference reticle used for diffraction-based particle sizing instruments verification.
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    Particle and Particle Systems Characterization 11 (1994) 
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    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
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    Particle and Particle Systems Characterization 11 (1994), S. 275-283 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This presentation is part of a fundamental investigation into the influence of structural characteristics on particle collection in fibrous filters. The collection on single fibres has been experimentally determined, whereby different fibre configurations were set. For this purpose, particle fluxes upstream and downstream of the fibres were measured simultaneously using an optical particle counter which operates with two purely optically delineated measuring volumes and two detectors. The experimental results are compared with published values.
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    Particle and Particle Systems Characterization 11 (1994), S. 250-257 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Measurements of transmission and enhanced backscattering from powder beds of α-AI 2O3 consisting of particles with different average sizes are reported. The values of the mean free path and the absorption length, as inferred from these measurements, are compared and good agreement between the two measurement is found when the internal reflections are properly taken into account. A particle size measurement method is suggested on the basis of the linear dependence found experimentally between the transport mean free path and the mean particle size.
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