Metal chelate exchange in the organic phase-II Extraction and exchange constants of dithizonates and diethyldithiocarbamates

Dithizonates and diethyldithiocarbamates of Ag, Tl(I), Cu(II), Zn, Cd, Hg(II), Pb, Fe(II), Co(II), Ni, Pd(II), In(III), As(III), Sb(III), Bi, Se(IV) and Te(IV) have been prepared and their reactions in carbon tetrachloride have been studied spectrophotometrically. From the exchange constants determined, the extraction constants of metal diethyldithiocarbamates have been calculated. Where formation of mixed chelates has been observed, corresponding exchange constants have been determined. Finally, the influence of organic solvents (CCl(4), CHCl(3), C(6)H(6) and C(6)H(5)Cl) on the exchange reaction of zinc diethyldithiocarbamate with dithizone has been investigated.     

Analysis of R. P. Smith's and D. C. Parris-R. B. Mclellan's carbon diffusivity data

A phenomenological model is proposed to account for the variation of carbon diffusivityD(N₁) with composition in austenite. This model is based on Parris-McLellan's statement that the increase ofD(N₁) with carbon concentrationN ₁ is due to the increase in chemical driving force. The gradient of the carbon activity in Wagner's and in Zupp-Stevenson's interpretation is presumed to be the intrinsic driving force. The predictions of the model are compared with carbonD(N₁) values both with [1] and without [5] a chemical concentration gradient. TheD(0) values and the carbon-carbon interaction coefficients ₁ are calculated by the use of the least squares method from the experimental data. The application of Zupp-Stevenson's definition of the activity coefficient ₁ results in a better fit of the theory to the experimental data.     

Interdiffusion in the Co-Ni system-I concentration penetration curves and interdiffusion coefficients

The interdiffusion in the Co-Ni system has been investigated in the temperature range of 950 to 1150 °C, by means of diffusion specimens of pure Co and Ni. The concentration curvesN(x, t) obtained with the aid of an JXA-3 A JEOL electron microprobe were evaluated using the smoothing cubic spline method by means of the Boltzmann-Matano equation. The obtained interdififusion coefficient values ¯D increase with the increasing Ni concentration and satisfy the Arrhenius equation at temperaturesH 990 °C. At lower temperatures the influence of high diffusivity paths may be effective, resulting in higher ¯D values. No expressive influence of atomic (Ni₃Co) or magnetic order on the interdiffusion has been detected. The activation enthalpyH values were found almost concentration independent. A Kirkendall effect study has been carried out with positive results which are presented in Part II of this paper. A new method for the determination of diffusants concentration in the Kirkendall plane was proposed. With the use of this method and of Darken equations the intrinsic diffusion coefficients were calculated. These results are given in Part III.     

Instrumental neutron activation analysis of brewer's yeast

Instrumental neutron activation was used for the determination of 23 trace and minor elements in 4 different samples of brewer's yeast. Detection limits for these elements vary from 2 ppb to 100 ppm. The following average concentrations were found (ppm, dry weight): Al 597, Br 0.36, Cl 1473, Co 0.21, Cu 19, Fe 285, K 16 400, Mg 1355, Mn 8.4, Na 2330, Rb 19, Sb 0.053, Se 1.2, V 2.2 and Zn 80. NBS standard 1569 was also analyzed and the following concentrations (in ppm) were measured: Al 2300, Br 0.65, Ce 0.23, Cl 460, Co 0.26, Cr 2.12, Cu 11, Fe 707, Gd 7.1, Hf 0.13, K 15 500, Mg 1780, Mn 7, Na 510, Rb 16, Sb 0.075, Sc 0.18, Se 0.92, Th 3.7, Ti 38, U 0.49, V 4.1 and Zn 70.     

A method for the palladium-catalyzed allylic oxidation of olefins

Olefins are converted into allylic acetates by treatment in acetic acid with a catalytic amount of palladium bis(trifluoroacetate) and one equivalent of benzoquinone as oxidant. The reaction is selective for oxidation of a terminal methyl group of geranylacetone.     

Heterogeneous reactions of solid nickel(II) complexes. XVIII

The Stoichiometry of thermal decomposition was studied for the following compounds: Ni(NCS)₂(2-Mepy)₂ (I), (Me=methyl, py=pyridine), Ni(NCS)₂(2-Etpy)₂ (II) (Et=ethyl), Ni(NCS)₂(2-Clpy)₂ (III), Ni(NCS)₂(2-Brpy)₂ (IV), Ni(NCS)₂(2-NH₂py)₂ (V), Ni((NCS)₂(2-NH₂py)₂·3/4 (C₂H₅)₂O (VI). The release of volatile ligands 2-Rpy is a one-step process for complexes I, II, III and IV, while for V and VI it is a two-step process, Ni(NCS)₂(2-NH₂py)₁ (VII) being formed as an intermediate complex. It was found that complexes I and II are square-planar; the others exhibited pseudo-octahedral geometry. The differences in stereochemistry of the above complexes are explained by the different electronic properties of 2-Rpy.     

Synthesis, characterization and optical properties of pi-conjugated systems incorporating closo-dodecaborate clusters: new potential candidates for two-photon absorption processes

Non-centrosymmetric pi-conjugated systems incorporating closo-dodecaborate clusters, [NC-C6H4-C(H=N(H)-B12H11]-(2), [NC-C6H4-C(H)=C(H)-C(6)H(4)-C(H)=N(H)-B12H11]-(3), and [NC-C6H4-C(H)=C(H)-C6H4-C(H)=C(H)-C6H4-C(H)=N(H)-B12H11]-(4) have been synthesized by reaction of the monoamino derivative of B12, [B12H11NH3]-(1), with various arylaldehydes, R-C6H4-CHO. These Schiff base-like compounds were fully characterized by multinuclear NMR spectroscopy and mass spectrometry. In order to evaluate these boron rich pi-systems as potential materials for two-photon absorption (TPA) processes, UV linear absorption curves were recorded for 3 and 4, and comparatively studied with those of the boron-free pi-systems NC-C6H4-C(H)=N-CH3(5) and NC-C6H4-C(H)=C(H)-C6H4-C(H)=N-CH3(6). The donor effect of the boron cluster was evidenced by a shift to the lower energy of the absorption band in the spectra of systems incorporating B12. The two photon absorption (TPA) spectrum of compound , obtained by the up-conversion method, shows a resonance at 720 nm with a cross-section sigma(TPA) of 35 x 10(-50) cm(4) s photon(-1) molecule(-1). This value suggests the potential of B12 clusters to be used as new donor groups for the synthesis of non-linear materials.     

Bioaccumulation study of acrylates in algae (<Emphasis Type="Italic">Chlorella kessleri</Emphasis>) by Py-GC and Py-GC/MS

Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the pyrolytical cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2-, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied.     

Die Reaktion der Ferrisalze mit der Isonitroso-thioglykolsäure

Zusammenfassung Die Farbreaktion der Ferrisalze mit der Isonitroso-thioglykolsäure wurde durch die Isolierung dreier basischer innerer Komplexsalze mit 1 bzw. 2 Mol der Säure aufgeklärt (I, II, III). Das Eisen bindet mit der Hauptvalenz das Schwefelatom, mit der Nebenvalenz den Sauerstoff der Carbonylgruppe. Erfassungsgrenze der blauen Färbung 3 Eisen bei der Grenzkonzentration 1:7333000.

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Summary The colour reaction of the ferric salts with the isonitrosothioglycolic acid was enlightened by the insulation of three basic inner complex salts with 1, respectively 2 moles of the acid (I, II, III). The iron is fixed by the principal valency to the sulphur atom, by the secondary valency to the oxygen of the carbonyl group. Limit of identification of the blue colour 3 Fe; concentration limit 1:7333000.

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Résumé (W) Le réaction colorée des sels ferriques avec l'acide isonitrosothioglycolique a été expliquée en isolant trois sels complexes internes basiques, avec respectivement une ou deux molécules d'acide (I. II, III). Le fer avec valence principale, se lie à l'atome de soufre, tandis qu'avec une valence secondaire, il se lie à l'oxygène du groupe carbonyle. Limite de perceptibilité: 3 de fer, avec une limite de dilution: 1:7333000.

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(Experimentell ausgeführt vonB. Mareth.)

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XVI. Mitteilung: Chem. Listy34, 307 (1940)     

Perfluoro anion-exchange polymeric films on glassy carbon electrodes

Solutions of the perfluoro anion-exchange membrane TosHex® in a solvent mixture composed of methanol + isopropanol + water (1:1:1) were prepared and applied in coating glassy carbon electrodes. The evaporated films were used to accumulate the Fe(CN) ₆ redox couple on the electrode surface. The magnitude of the electrochemical response of the loaded films is comparable with that for Nafion® incorporated cationic redox species. The multicharged Fe(CN) ₆ couple accumulated in Tosflex® film causes an ion cross-linking of the polymeric backbone, thus decreasing ion transport in the film substantially.