Antiferromagnetic Ordering in TmCu2

Intermetallic compound TmCu₂ crystalizes in the orthorhombic structure, orders antiferromagnetically (AF) and exhibits four different AF phases below T _N = 6.5 K. In all these phases the Tm magnetic moment is parallel to the b-axis. The ground-state AF1 (T < 3.4 K) corresponds to the squared-up AF structure with propagation vector ₀₁ = (5/8, 0, 0) and magnetic unit cell 8a × b × c. Narrow phases AF2 and AF3 (3.3 K < T < 3.7 K and 3.6 K < T < 4.6 K) are 'spin-slip'-derivatives from the AF1 structure, yielding propagation vectors ₀₂ = (0.633, 0, 0.02) and ₀₃ = (0.618, 0, 0), respectively. The phase AF4 (4.4 K < T < T _N) is then incommensurate transversal spin-wave with the propagation ₀₄ = (0.64, 0, 0). The co-existence of AF phases indicates the first-order transitions between them.     

Determination of arsenic at a gold-plated carbon paste electrode using constant current stripping analysis

A new stripping method for the determination of arsenic in water samples with a gold film-plated carbon paste electrode has been developed for the use in constant current stripping analysis (CCSA). In the novelized procedure, differentiation between As(III) and chemically pre-reduced As(V), the effect of Cu(II) on the response of arsenic, and the stability of sample solutions were studied in detail. Compared to the voltammetric approach, the method utilizing CCSA offers a more rapid procedure with improved analytical characteristics such as reproducibility, selectivity over the Cu(II) ions, or lower detection limit (3 ppb for As(III) and 0.5 ppb for As(V), respectively). The possibilities of the optimized method are demonstrated by determinations of As(III), As(V), and total arsenic in samples of polluted river water.     

The effect of influential data, model and method on the precision of univariate calibration

Building a calibration model with detection and quantification capabilities is identical to the task of building a regression model. Although commonly used by analysts, an application of the calibration model requires at first careful attention to the three components of the regression triplet (data, model, method), examining (a) the data quality of the proposed model; (b) the model quality; (c) the LS method to be used or a fulfillment of all least-squares assumptions. This paper summarizes these components, describes the effects of deviations from assumptions and considers the correction of such deviations: identifying influential points is the first step in least-squares model building, the calibration task depends on the regression model used, and finally the least squares LS method is based on assumptions of normality of errors, homoscedasticity, independence of errors, overly influential data points and independent variables being subject to error. When some assumptions are violated, the ordinary LS is inconvenient and robust M-estimates with the iterative method of reweighted least-squares must be used. The effects of influential points, heteroscedasticity and non-normality on the calibration precision limits are also elucidated. This paper also considers the proper construction of the statistical uncertainty expressed as confidence limits predicting an unknown concentration (or amount) value, and its dependence on the regression triplet. The authors' objectives were to provide a thorough treatment that includes pertinent references, consistent nomeclature, and related mathematical formulae to show by theory and illustrative examples those approaches best suited to typical problems in analytical chemistry. Two new algorithms, calibration and linear regression written in s-plus and enabling regression triplet analysis, the estimation of calibration precision limits, critical levels, detection limits and quantification limits with the statistical uncertainty of unknown concentrations, form the goal of this paper.     

Luminescence Properties of New Fused Benzothiophene Derivatives and Their Conductive Oligomers Structural and Solvent Effects

The structural and solvent effects on the electronic absorption and fluorescence spectra, and fluorescence quantum yields, of four new fused benzothiophene derivatives, including benzothieno[3,2b]-thiophene (BTT), benzothieno[3,2-b]benzothiophene (BTBT), 6-methoxy[1]benzothieno[3,2b]-thiophene (MeOBTT), and benzothieno[3,2-b]indole (BTI) were investigated at 295 K. The luminescence properties of the corresponding conductive oligomers, poly(BTT) and poly (MeOBTT), electrosynthesized in acetonitrile, were also studied. Satisfactory McRae, Suppan, and Kawski-Chamma-Viallet solvatochromic correlations were established for the four monomers in most solvents. A weak negative solvatochromic behavior was found for these compounds, indicating that their dipole moments are slightly lower in the excited singlet state than in the ground state. Kamlet-Abboud-Taft multiparametric correlations were also obtained for absorption and fluorescence wave numbers and quantum yields, demonstrating the existence of specific solute-solvent interactions. In the case of the oligomers, important red-shifts of the fluorescence emission maxima ( 90–110 nm) relative to the corresponding monomers were observed, which shows the extent of conjugated segments in the oligomer chains.     

On the stereochemistry of photoaddition between α,β-unsaturated ketones and olefins. III.

The α,β-unsaturated ketone $\text{1}$ yields with allene the photocycloadduct $\text{3}$ predicted by our empirical photoaddition rule and the byproduct 7. The formation of this material may be rationalized by the sequence $\text{1}$ → $\text{4}$ → $\text{5}$ → $\text{6}$ → $\text{7}$. The isomeric ketone $\text{2}$ is unreactive under the same conditions, since α addition is prohibited by the rule and β addition is severely blocked.     

Determination of some pharmaceuticals using simple potentiometric sensors of coated-wire type

Summary The preparation of simple potentiometric sensors of the coated-wire type is described and working instructions for their use are given. The sensors prepared from an ordinary aluminium conductor, being simple and cheap, can well serve to monitore the titrations based on ion-pair formation. The application possibilities are discussed and shown as practical examples on analyses of nasal and eye drops containing cationic surfactants or salts of alkaloids.

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Bestimmung einiger Arzneimittel mit Hilfe einfacher potentiometrischer Sensoren

Zusammenfassung Die Herstellung einfacher potentiometrischer Sensoren mit isoliertem Draht und deren Verwendung wurde beschrieben. Aus einfachem Aluminiumdraht sind sie billig und können für Titrationen auf der Grundlage von Ionenpaar-Bildung dienen. Die Möglichkeiten ihrer Anwendung wurden erörtert und praktiziert für die Untersuchung von Nasen- und Augentropfen mit kationischen Schaumbildnern oder von Alkaloidsalzen.

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According to the Poster XII-23 presented at Euroanalysis V, Cracow, August 1984; the comments inserted into the text are a consequence of the discussion.     

Beziehungen zwischen den Verdampfungsw?rmen bin?rer Gemische

Ohne Zusammenfassung     

Influence of deformation on the conductivity and photoconductivity of p-Type CdTe

Samples of p-type CdTe were subjected to deformation. Studies were performed of the influence of 60°-dislocations on the electrical conductivity, on the lifetime of minority carriers and on the relative change of the conductivity due to illumination. Dislocations were produced by bending the sample that was cut at suitable orientation. In this way, one obtained the 60°-dislocations, either of α- or β-type, according to the kind of bending involved. From the measurement of the temperature dependence of the conductivity it was ascertained that an increase in acceptor concentration occurs on the level with activation energy of 0.3 eV (identical to that of V^cd or a complex with V^cd), regardless of the type of dislocations. The concentration of acceptors on the level with activation energy 0.3 eV increases on increasing the dislocation density. The most probable explanation is that the deformation and, especially, annealinginduced migration of the dislocations produced give rise also to V^cd and/or V^Te (both types simultaneously). V^cd acts as an acceptor and V^Te as a donor. It follows that the increase in V^Te can not be established from this measurement. The lifetime of the minority carriers is almost unaffected by introducing the dislocations into the samples. From the temperature dependence of the relative change in conductivity due to illumination one can determine the activation energy of a dislocation level provided that one assumes the dislocations acting as recombination centers. Under this assumption one obtainsE _d =0.21–0.24 eV (for type α) andE _d =0.55–0.59 eV (for type β), measured from the top of the valence band.