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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' journal of analytical chemistry 357 (1997), S. 69-73 
    ISSN: 1432-1130
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract  To characterize the real stoichiometry of ceramic high-temperature superconductors of the Y-Ba-Cu-O type and the Bi(Pb)-Ca-Sr-Cu-O type complex, chemical methods including digestion, separation and subsequent titrimetric determination of the elemental components were investigated. Using optimized automatic titration procedures with photometric, potentiometric or voltametric equivalence point detection, a high accuracy of the analytical results could be achieved. The random as well as the systematic errors are less than 0.5%. The exact stoichiometric coefficients of the components and thereby the phase compositions or the single phase character of the materials were determined and compared with the results of X-ray diffraction measurements.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Analytica Chimica Acta 219 (1989), S. 273-279 
    ISSN: 0003-2670
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemometrics and Intelligent Laboratory Systems 8 (1990), S. 79-86 
    ISSN: 0169-7439
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemometrics and Intelligent Laboratory Systems 24 (1994), S. 197-203 
    ISSN: 0169-7439
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1432-1130
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract For successful application of simultaneous ICP atomic emission spectrometry for major component determinations in multi-component materials the accuracy of the method has to be improved. As a contribution to solve this problem a combined procedure for multi-component standard sample preparation, optimum calibration and different variations of internal standard corrections is described. Variance-weighted multi-line calibrations give most accurate results. Internal standard corrections are effective, if the time-dependent spectral line intensity fluctuations of the standard and the analyte elements are well correlated. Their sensitivities against some responsible device parameter variations are investigated. On the basis of multi-line measurements of the analyte and internal standard elements a “group-selected internal standard correction” (GS-ISC) method is applied and results in relative errors of less than 1% even for extreme fluctuations of the raw intensities. For rapid routine determination methods of materials with variable element compositions the added line intensities of the internal standard element can be used to correct the added analyte line raw intensities (“intensity addition internal standard correction” (IA-ISC) method). These accuracy optimization procedures are applied for the analysis of the soft magnetic material permalloy using the internal standard element In.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' journal of analytical chemistry 366 (2000), S. 146-151 
    ISSN: 1432-1130
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract For quality tests of ceramic Bi-Pb-Sr-Ca-Cu-O superconductor materials (precursors and final products) accurate stoichiometric determinations of the metallic major components are necessary. Three methods were developed during the last decade in our group. Their properties and the results obtained are compared. The first classical analytical procedure requires to much manpower. The second combined chemical-spectrometric procedure is a routine method today, but also unsuitable for rapid tests. A new fully spectrometric procedure was recently developed using a simultaneously working Echelle spectrometer with CID detector, autosampler and a special self-made data evaluation software. The basis of this method are multi-line measurements of each analyte element, a new method of spectral line selection for main component precision determinations, multi-component calibrations, and frequent external standardizations. For this method the sum of the confidence intervals of all element determinations was less than 1%, and no systematic error was detected.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' Zeitschrift für analytische Chemie 238 (1968), S. 241-251 
    ISSN: 1618-2650
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Kinetik und der Mechanismus der von Kobaltionen katalysierten Tiron-Wasserstoffperoxid-Reaktion werden untersucht. Bei der Oxydation des Tirons bildet sich ein farbloses Produkt unbekannter Struktur, dessen Konzentrationszunahme zur photometrischen Messung der Reaktionsgeschwindigkeit dient. Unter den gewählten Bedingungen (3,56 · 10−4 M Tiron, 0,1 M Wasserstoffperoxid, pH 10,3) verläuft die Reaktion bezüglich der Tiron- und Katalysatorkonzentration nach der 1. Ordnung. Die katalytische Reaktion, deren Geschwindigkeitskonstante zu 4,7 · 104 l Mol−1 · s−1 ermittelt wurde, kann zur Kobaltbestimmung im Bereich von 0,6–10 ng/ml verwendet werden. Die Ergebnisse der Untersuchungen über die Oxydationsgeschwindigkeit des Tirons und über die Zersetzungsgeschwindigkeit des Wasserstoffperoxids in Abhängigkeit vom pH-Wert deuten darauf hin, daß die Zersetzung des Wasserstoffperoxids Voraussetzung für die Oxydation des Tirons ist. Während Tiron selbst eine stabilisierende Wirkung auf das Oxydationsmittel ausübt, katalysiert ein in Gegenwart von Kobaltionen entstehender Komplex dessen Zersetzung.
    Notes: Summary The kinetics and the mechanism of the tiron-hydrogen peroxide reaction catalysed by cobalt ions are investigated. The oxidation of tiron results in a product of unknown structure, whose increase of concentration is utilized for photometric reaction rate measurements. On the conditions used (3.56 · 10−4 M tiron, 0.1 M hydrogen peroxide, pH 10.3) the reaction is of the first order with respect to tiron and catalyst concentration. The catalytic reaction, the rate constant of which was evaluated to be 4.7 · 104 l · Mol−1 · s−1, can be used for the determination of cobalt in the range from 0.6 to 10 ng/ml. The results of the investigations on the oxidation rate of tiron and on the decomposition rate of hydrogen peroxide in dependence on pH indicate that the decomposition of hydrogen peroxide is a prerequisite for the oxidation of tiron. Whereas tiron itself shows a stabilizing effect on the oxidant, the complex formed in presence of cobalt ions catalyses the decomposition of hydrogen peroxide.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' Zeitschrift für analytische Chemie 314 (1983), S. 555-559 
    ISSN: 1618-2650
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Analysenbedingungen für die Zinkbestimmung in Zinkoxidkristallen durch komplexometrische Rücktitration eines etwa 10 %-igen DCTE-überschusses mit aus Reinstzink hergestellter Ma\lösung werden aus den Ergebnissen der Computersimulationen der Titrationskurven (Teil I dieser Publikation) und den gegebenen apparativen Voraussetzungen abgeleitet. Die Titrationen erfolgen bei pH 5,3 mit Xylenolorange als Indicator und photometrischer Indication eines vorgewÄhlten Endpunktes. Die absolute Standardabweichung des Bestimmungsverfahrens betrÄgt 0,03 %. Das Verfahren ist geeignet, die HomogenitÄt von Zinkoxid-Halbleiterkristallen bezüglich Verunreinigungen, z.B. eingeschlossener Fremdphasen, zu charakterisieren. Die Analysen von undotiertem einphasigen Zinkoxid der oberen und der unteren Phasengrenze ergeben jedoch keinen signifikant unterschiedlichen Zinkgehalt.
    Notes: Summary The conditions for the procedure of zinc determination in zinc oxide crystals by complexometric back titration of a 10% DCTA excess with a standard solution prepared from high-purity zinc are derived from the results of computer simulation of titration curves (part I of this paper) and from the apparative suppositions. The titrations are carried out at pH 5,3 with xylenol orange as indicator and with photometric indication of a pre-set end-point. The absolute standard deviation is 0.03%. The method is suitable for characterizing the homogeneity of zinc oxide semiconductor crystals regarding contaminants, for example enclosed foreign phases. However, no significantly different zinc concentrations are obtained from the analyses of undoped single-phase zinc oxide of the upper and the lower phase boundary.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' Zeitschrift für analytische Chemie 249 (1970), S. 22-25 
    ISSN: 1618-2650
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Oxydation von Tiron mit Wasserstoffperoxid wird zur Bestimmung von Kobaltspuren nach einer integralen kinetischen Methode verwendet. Eichkurven in den Bereichen 12-1, 1,2-0,1 und kleiner als 0,12 ng Kobalt/ml werden durch Messung der Extinktion des Tiron-Oxydationsproduktes bei 336 nm nach festgelegten Reaktionsdauern von 4 min, 1 und 24 h in Abhängigkeit von der Kobaltkonzentration erhalten. Die Standardabweichungen für die drei Meßbereiche betragen 0,5, 0,04 und 0,016 ng Kobalt/ml, und die Erfassungsgrenze des Verfahrens liegt bei 0,03 ng Kobalt/ml. Zur Bestimmung von Kobaltspuren in Molybdän werden die Matrix und die störenden Spurenelemente Eisen und Nickel mit Hilfe eines stark basischen Anionenaustauschers abgetrennt. Auf diese Weise können 4,8·10−6% Kobalt in Molybdän bestimmt werden.
    Notes: Abstract The oxidation of tiron by hydrogen peroxide is applied to the determination of trace concentrations of cobalt by means of an integral kinetic method. Calibration curves in the intervals of 12-1, 1.2-0.1 and less than 0.12 ng cobalt/ml are obtained by measuring the extinction of the oxidation product of tiron at 336 nm after fixed reaction times of 4 min, 1 and 24 h, respectively, as a function of the cobalt concentration. The corresponding standard deviations amount to 0.5, 0.04 and 0.016 ng cobalt/ml and the limit of identification („Erfassungsgrenze“) of the method amounts to 0.03 ng cobalt/ml. For the determination of cobalt traces in molybdenum the matrix and the interfering trace elements iron and nickel are separated by means of a strong basic ion exchanger. In this way 4.8×10−6% cobalt in molybdenum can be estimated.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Fresenius' Zeitschrift für analytische Chemie 314 (1983), S. 451-458 
    ISSN: 1618-2650
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es werden die Titrationskurven für die komplexometrische Zinkbestimmung in Form der Rücktitration eines DCTE-Überschusses in Gegenwart eines metallochromen Indicators abgeleitet und die Kurven für verschiedene Parameter (pH-Wert, Stabilitätskonstante des Zink-Indicator-Komplexes, Zink-Ausgangskonzentration, DCTE-Überschußkonzentration) mit einem Rechner simuliert. Aus dem Verlauf der Titrationskurven werden optimale Bedingungen für eine Präzisions-Zinkbestimmung und die systematischen Auswertefehler ermittelt, wenn der Schnittpunkt der extrapolierten geraden Kurventeile, der Wendepunkt oder ein vorgewählter Endpunkt als Kriteria für den Äquivalenzpunkt verwendet werden. Für Titrationen von 10−3 N Zinklösungen bei pH 5,5, mit Xylenolorange als Indicator und einem 10%igen DCTE-Überschuß beträgt der theoretische systematische Fehler in allen drei Fällen 〈0,1%. Sollen Lösungen mit sehr unterschiedlichem Zinkgehalt analysiert werden, kann der Fehler durch eine additive Konstante oder exakter durch Anwendung einer Eichkurve eliminiert werden.
    Notes: Summary The titration functions for the complexometric determination of zinc in form of back titration of an excess of DCTA in the presence of a metallochromic indicator are derived and the curves for different parameters (pH-value, stability constant of the zinc indicator complex, initial zinc concentration, DCTA excess concentration) were simulated by means of a computer. Optimum conditions for the high-precision determination of zinc and the systematic error of evaluating the results are deduced from the shape of the titration curves for the cases of utilizing the intersection point of the extrapolated linear branches of the titration curves, the inflection point or a pre-set end-point as criteria for the equivalent point. The theoretical systematic error for titrations of 10−3N zinc solutions at pH 5.5, with xylenol orange as indicator and a 10% excess of DCTA is in all three cases 〈0.1%. In case of analyzing solutions with very different zinc amounts the error can be eliminated by an additive constant or more exactly by a calibration curve.
    Type of Medium: Electronic Resource
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