Amperometric determination of calcium as selenite

Summary An amperometric titration of calcium with selenite is described. Barium, strontium, and other cations forming insoluble selenites interfere, but magnesium does not. The method is rapid and suitable for routine analysis, the error being less than 10 parts per 1000 over the range 50 to 70 mg of calcium.

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Zusammenfassung Ein amperometrisches Titrationsverfahren für Calcium mit Selenit wurde beschrieben. Barium, Strontium und andere Kationen, die unlösliche Selenite bilden, stören, nur Magnesium nicht. Das Verfahren ist rasch und für Routineanalysen geeignet. Im Bereich zwischen 50 und 70 mg Calcium ist der Fehler geringer als 1% relativ.

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Résumé On décrit un titrage ampérométrique du calcium par l'ion sélénite. Le baryum, le strontium et les autres cations formant des sélénites insolubles interfèrent, excepté le magnésium. La méthode est rapide et convient à l'analyse en série, l'erreur étant inférieure à 10 parties pour 1000 dans le domaine de 50–70 mg de calcium.

     

Investigation of nu(N-H) and nu(C-N) stretching modes of propylamine (C3H7NH2) in a binary system C3H7NH2 + CH3OH via concentration dependent Raman study and ab initio calculations

Raman spectra of propylamine (C3H7NH2) and its binary mixtures, C3H7NH2 + CH3OH with varying mole fractions of the reference system, C3H7NH2, C were recorded in two widely apart wavenumber regions, 3100-3600 cm(-1) and 1225-1325 cm(-1). In the former region, the two Raman bands at approximately 3305 and approximately 3326 cm(-1), obtained after the line shape analysis, which were assigned to symmetric nu(N-H) and anti-symmetric nu(N-H) stretching modes, respectively, show a downshift upon dilution. However, whereas the nu(N-H) anti-symmetric mode shows a shift of 18.6 cm(-1), the nu(N-H) symmetric mode shows a much smaller shift (5.7 cm(-1)) between neat liquid and high dilution, C = 0.1. This aspect has been explained using the optimized geometries calculated employing ab initio theory (MP2 level) for the neat C3H7NH2 and its different hydrogen-bonded complexes. The linewidth versus concentration plot for the nu(N-H) anti-symmetric stretching mode, however exhibits a distinct maxima at C = 0.4, which has been explained as a slight departure from the concentration fluctuation model. In the latter region, a symmetric peak is observed, which corresponds to nu(C-N) stretching mode, which shows an upshift upon dilution and an almost linear concentration dependence. This has also been explained in terms of the parameters obtained from the optimized geometries of the different hydrogen-bonded complexes.     

Sensitive and selective methods for determination of antipsychotic drug olanzapine in pharmaceuticals

Two simple and sensitive spectrophotometric methods have been developed for analysis of the antipsychotic drug olanzapine in pharmaceuticals. Method A is based on liberation of iodine by reaction between the drug and potassium iodate, followed by reaction with leuco crystal violet (LCV), the color of oxidized LCV being measured at 598 nm. Method B is based on oxidation of olanzapine with chloramine-T (CAT) in acidic medium, the unconsumed CAT being determined with rhodamine B, measuring the absorbance at 550 nm. Calibration graphs were linear over the ranges of 0.05–2.0 and 0.1–1.6 μg mL^?1 olanzapine for method A and B, respectively. The molar absorptivity, Sandell’s sensitivity, detection limit, and quantitation limit were found to be 1.59 × 10⁵, 0.00132, 0.038, and 0.117, respectively, for method A and 0.953 × 10⁵, 0.00221, 0.064, and 0.192, respectively, for method B. The optimum conditions and other analytical parameters were evaluated. The proposed methods have been applied successfully for analysis of olanzapine in pure form and its dosage forms, and no interference was observed from common excipients present in pharmaceutical formulations.     

Spectrophotometric analysis of trichloroethylene in various environmental and biological samples

A simple sensitive extractive spectrophotometric method for determination of trichloroethylene is proposed. Trichloroethylene is treated with pyridine to form glutaconic aldehyde by heterolytic cleavage of the pyridine ring. Glutaconic aldehyde is further coupled with 4-aminoacetanilide to form an orange–red dye which is extractable in 3-methyl-1-butanol. The extracted dye shows absorption maximum at 520 nm. The system obeys Beer’s law in the range of 0.05–0.8 μg mL^?1. Important analytical parameters such as time, temperature, reagent concentration, acidity etc. have been optimized for complete colour reaction. Sandell’s sensitivity and molar absorptivity for the system were found to be 0.001 μg cm^?2 and 1.2 × 10⁵ L mol^?1 cm^?1, respectively. The proposed method is satisfactorily applied to micro-level determination of trichloroethylene in various environmental and biological samples.     

Precise Vibrational Analysis of B-X System of BiI

The bands of the B-X system of BiI have been photographed in the second order of a 35 ft concave grating spectrograph (with a dispersion of 0.33 Åing;/mm and resolution 2 × 180,000). A precise vibrational analysis of this system has been carried out and the vibrational constants WeYe and WeZe for the upper and lower states have been evaluated for the first time.     

On the directed Full Degree Spanning Tree problem

We study the parameterized complexity of a directed analog of the Full Degree Spanning Tree problem where, given a digraph $D$ and a nonnegative integer $k$, the goal is to construct a spanning out-tree $T$ of $D$ such that at least $k$ vertices in $T$ have the same out-degree as in $D$. We show that this problem is W[1]-hard even on the class of directed acyclic graphs. In the dual version, called Reduced Degree Spanning Tree, one is required to construct a spanning out-tree $T$ such that at most $k$ vertices in $T$ have out-degrees that are different from that in $D$. We show that this problem is fixed-parameter tractable and that it admits a problem kernel with at most $8k$ vertices on strongly connected digraphs and $O\left(k^2\right)$ vertices on general digraphs. We also give an algorithm for this problem on general digraphs with running time $O(5.942^k?n^{O\left(1\right)})$, where $n$ is the number of vertices in the input digraph.     

Assemblies of perylene diimide derivatives with melamine into luminescent hydrogels

We report unique and spontaneous formation of hydrogels of perylene derivatives with melamine. The luminescent gel network is formed by H-type aggregation of the perylene core, supramolecularly cross-linked by melamine units. As a result of controlled aggregation in the extended nanofibers, strong exciton fluorescence emission is observed.     

A variable temperature EPR study of the manganites (La1/3Sm2/3)2/3SrxBa0.33−xMnO3 (x=0.0, 0.1, 0.2, 0.33): Small polaron hopping conductivity and Griffiths phase

Four manganite samples of the series, (La_1/3Sm_2/3)_2/3Sr_xBa_0.33−xMnO₃, with x=0.0, 0.1, 0.2 and 0.33, were investigated by X-band (∼9.5 GHz) electron paramagnetic resonance (EPR) in the temperature range 4-300 K. The temperature dependences of EPR lines and linewidths of the samples with x=0.0, 0.1 and 0.2, containing Ba²⁺ ions, exhibit similar behavior, all characterized by the transition temperatures (T_C) to ferromagnetic states in the 110-150 K range. However, the sample with x=0.33 (containing no Ba²⁺ ions) is characterized by a much higher T_C=205 K. This is due to significant structural changes effected by the substitution of Ba²⁺ ions by Sr²⁺ ions. There is an evidence of exchange narrowing of EPR lines near T_min, where the linewidth exhibits the minimum. Further, a correlation between the temperature dependence of the EPR linewidth and conductivity is observed in all samples, ascribed to the influence of small-polaron hopping conductivity in the paramagnetic state. The peak-to-peak EPR linewidth was fitted to ΔB_pp(T)=ΔB_pp,min+A/Texp(−E_a/k_BT), with E_a=0.09 eV for x=0.0, 0.1 and 0.2 and E_a=0.25 eV for x=0.33. From the published resistivity data, fitted here to σ(T)∝1/T exp(−E_σ/k_BT), the value of E_σ, the activation energy, was found to be E_σ=0.18 eV for samples with x=0.0, 0.1 and 0.2 and E_σ=0.25 eV for the sample with x=0.33. The differences in the values of E_a and E_σ in the samples with x= 0.0, 0.1and 0.2 and x=0.33 has been ascribed to the differences in the flip-flop and spin-hopping rates. The presence of Griffiths phase for the samples with x=0.1 and 0.2 is indicated; it is characterized by coexistence of ferromagnetic nanostructures (ferrons) and paramagnetic phase, attributed to electronic phase separation.