Kinetic analysis of derivative curves in thermal analysis

Two methods of obtaining kinetic parameters from derivative thermoanalytical curves are proposed. The methods are based on the general form of kinetic formulae and are applicable to general types of reactions governed by a single activation energy. One method utilizes the linear relation between peak temperature and heating rate in order to estimate the activation energy, and only the information of the rate of conversion versus the temperature is necessary. The other method needs the information of both the conversion and the rate of conversion versus the temperature, and the Arrhenius plot is made for an assumed kinetic mechanism.

     

Approaches to bioresponse-linked instrumental analysis in water analysis

A new concept based on hyphenation of biotests, for biological selection, and chemical analysis is introduced for water analysis. Biomolecular recognition components such as receptors, enzymes, and nucleic acids integrated in biological reaction chains are used for binding and selective enrichment of known and unknown biologically active substances in water samples; this is followed by identification and quantitation. The coupling of biomolecular recognition and binding to chemical analysis can be achieved either in discrete analytical steps, e.g. binding and elution of bioactive ligands from affinity columns followed by chemical analysis, or by methods capable of monitoring the binding of the ligand and simultaneous verification of its identity. This analytical strategy, denoted bioresponse-linked instrumental analysis (BLIA), enables detection of potential biological effects and identification of the analyte causing these effects. Several examples are presented.     

Multivariate correlation analysis and its application in environmental analysis

A new method for handling correlation problems is described. The multivariate auto- and cross-correlation method allows the calculation of relationships between two functions including one or several variables with respect to changes in time or distance. Two applications from environmental analytical chemistry demonstrate the advantages of the method. Transport rates of heavy metals in river water can easily be measured and sampling procedures for suspended dusts can be rationalized.     

Thorium ore analysis by X-rays in neutron activation analysis

The possibility of using characteristic X-rays from radioactive elements in activatio analysis was investigated during this work with particular emphasis on (n, ) products. The detection sensitivities for some elements are determined by X-rays employing a²³⁵Pu-Be neutron source. The technique has been applied to the analysis of thorium ores from the Anatolia Region, with great accuracy.     

Processing and error analysis of signals in flow-injection analysis

The processing and error analysis of signals in flow-injection systems were systematically studied by simulation and experimental measurements. The content includes an error analysis for peak-height and peak-area signal, a least-squares filtering procedure applied to the flow-injection curve and a peak recognition to remove interferences from air bubbles. Simulation results were obtained by statistical processing of peak-height and peak-area values from Gaussian curves to which noise had been added. The experimental measurements were done by an automatic flow-injection device to obtain detailed information for each individual point of a peak. 2-(2-Arsenophenylazo)-7-(2,6-dichlorophenylazo-4-sulphonic acid)-1,8-dihydroxynaphthalene-3,6-disulphonic acid (DCSA) was used for measuring physical dispersion alone, and Fe(II)-o-phenanthroline for the measurement of both physical dispersion and chemical reaction. The results from computer simulation and experiments agreed well.     

The application of thiosalts in analysis a new scheme of qualitative analysis: Insoluble substances in qualitative analysis

A scheme has been proposed for the systematic detection of compound's in the insoluble residue obtained in qualitative analysis of the common elements.     

Surface analysis in microelectronics

The contribution given by surface analysis to solve some problems encountered in the production of electronic power devices have been discussed. Mainly two types of problems have been faced. One of these deal with interfacial chemistry. Three examples have been investigated. The first applies to the improvement of the quality and the reliability of plastic packages through the optimization of the resin/metal and resin/die adhesion. The second relies to the adhesion between polyimide and silicon nitride used in the multilevel technology. The third example refers to the so called die-attach process and related problems. Another area of interest in microelectronics is that of the erosion of various types of surfaces and the possibility of wrong etching. A few examples of the application of surface analytical techniques for these problems will be presented. XPS and SIMS working in imaging and multipoint analysis mode, scanning acoustic microscopy, contact angle measurements as well as peeling and tensile strength measurements are the main tools used to obtain useful data.     

SPME in environmental analysis

Recent advances in the use of solid-phase microextraction (SPME) in environmental analysis, including fiber coatings, derivatization techniques, and in-tube SPME, are reviewed in this article. Several calibration methods for SPME, including traditional calibration methods, the equilibrium extraction method, the exhaustive extraction method, and several diffusion-based calibration methods, are presented. Recent developed SPME devices for on-site sampling and several applications of SPME in environmental analysis are also introduced.      

Substoichiometry in trace analysis

Substoichiometric methods of analysis are simple in principle and involve the addition of a smaller amount of reagent than is required for complete reaction with the element to be determined. They can be used with great effect in trace analysis.     

Selectivity in multicomponent analysis

Figures of merit for judging the selectivity of procedures for multicomponent analysis are compared with respect to their performance under different experimental conditions. The condition number of the calibration matrix is evaluated as being the most general selectivity measure. Practical selectivities based on the condition number are given for atomic and molecular spectroscopy and for electroanalytical methods. The most promising data reduction schemes, such as factor analysis or partial least squares in latent variables are discussed for systems with unselective sensors.     

Surface analysis in microelectronics

The contribution given by surface analysis to solve some problems encountered in the production of electronic power devices have been discussed. Mainly two types of problems have been faced. One of these deal with interfacial chemistry. Three examples have been investigated. The first applies to the improvement of the quality and the reliability of plastic packages through the optimization of the resin/metal and resin/die adhesion. The second relies to the adhesion between polyimide and silicon nitride used in the multilevel technology. The third example refers to the so called die-attach process and related problems. Another area of interest in microelectronics is that of the erosion of various types of surfaces and the possibility of wrong etching. A few examples of the application of surface analytical techniques for these problems will be presented. XPS and SIMS working in imaging and multipoint analysis mode, scanning acoustic microscopy, contact angle measurements as well as peeling and tensile strength measurements are the main tools used to obtain useful data.     

Advances in fingerprint analysis

Fingerprints have been used in forensic investigations for the identification of individuals since the late 19th century. However, it is now clear that fingerprints can provide significantly more information about an individual. Here, we highlight the considerable advances in fingerprinting technology that can simultaneously provide chemical information regarding the drugs ingested and the explosives and drugs handled by a person as well as the identity of that individual.     

Fluoroberyllates in chemical analysis

Barium can be precipitated as barium fluoroberyllate, Ba[BeF₄], with ammonium fluoroberyllate in the presence of ethylenediaminetetraacetic acid at pH 6–7. Lead does not precipitate under these conditions and a good separation can be effected. The precipitate is dried at 110° C and weighed.     

Chemometrics in pharmaceutical analysis

Chemometrics is now a well established discipline prompting independent research and development in its own right but, for their continuing success, chemometric developments must be relevant to the real needs of analysis. Pharmaceutical analysis, i.e., physical and chemical assessment of drugs and their dosage forms, needs more formal application of mathematical and statistical methods. The organisation of the laboratory, the development, optimization, assessment and interpretation of methods, and the evaluation of the data produced can all benefit from the application of chemometrics. Here, a selection of the more challenging problems facing the pharmaceutical analyst is presented, the potential for chemometrics is considered and some consequent implications for utilisation, against a background of control and regulation are discussed.     

Pervaporation in chemical analysis

Unlike thermal processes such as distillation, pervaporation relies on the relative rates of solute permeation through a membrane and is a combination of evaporation and gas diffusion. The analytical pervaporation systems consist of a membrane module suitable for liquid sample introduction and a vacuum (or a sweeping gas) on the permeate side. It has been used in a wide range of applications including the analysis of various organic and inorganic compounds, and sample concentration. It has been directly interfaced with gas chromatography, spectrophotometry, capillary electrophoresis, electrochemical detectors, liquid chromatography, and mass spectrometry. A wide range of liquids, slurries, and solids samples has been analyzed using these techniques. This review highlights the basic principles of the pervaporation and the state of its current development as applied to analytical chemistry.     

GeneMCL in microarray analysis

Accurately and reliably identifying the actual number of clusters present with a dataset of gene expression profiles, when no additional information on cluster structure is available, is a problem addressed by few algorithms. GeneMCL transforms microarray analysis data into a graph consisting of nodes connected by edges, where the nodes represent genes, and the edges represent the similarity in expression of those genes, as given by a proximity measurement. This measurement is taken to be the Pearson correlation coefficient combined with a local non-linear rescaling step. The resulting graph is input to the Markov Cluster (MCL) algorithm, which is an elegant, deterministic, non-specific and scalable method, which models stochastic flow through the graph. The algorithm is inherently affected by any cluster structure present, and rapidly decomposes a graph into cohesive clusters. The potential of the GeneMCL algorithm is demonstrated with a 5,730 gene subset (IGS) of the Van't Veer breast cancer database, for which the clusterings are shown to reflect underlying biological mechanisms.     

Standardization in thermal analysis

The present state of the certification of the reference materials for thermal analysis is considered. Six sets of reference materials for temperature calibration, resulting from the research work of the ICTA Standardization Committee, are discussed.

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Zusammenfassung Die gegenwÄrtige Lage der Attestierung von Referenzmaterialien für die thermische Analyse wird erörtert. Sechs Sets von Referenzmaterialien, die vom ICTA-Standardisierungskomitee zur Temperaturkalibrierung in Vorschlag gebracht wurden, werden diskutiert.

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The author is most grateful to Professor P. D. Garn, Akron University, USA, and to Dr. Robert C. Mackenzie, The Macaulay Institute for Soil Research, Aberdeen, Scotland, for published material and unpublished data concerning the problems of ICTA standards and the nomenclature of thermal analysis.