Compounds with symmetrical tricobalt chains wrapped by dipyridylamide ligands and cyanide or isothiocyanate ions as terminal ligands

Three new linear compounds of the type Co(3)(dpa)(4)X(2), where dpa is the anion of di(2-pyridyl)amine and X is NCS(-) (5), CN(-) (6), and N(CN)(2)(-) (7), have been prepared, and their structures and magnetic behavior have been studied. In all of them, including three different solvates of 5, the Co(3) chains are symmetrical with Co-Co distances of ca. 2.31-2.32 A. The appearance of four lines in the (1)H NMR spectra of the three compounds is also consistent with a symmetrical structure in solution. For all compounds, the magnetic behavior is quite similar with mu(eff) of ca. 1.9-2.0 micro(B) at temperatures between 1.8 and 200 K. As the temperature increases, the effective moments increase gradually, but since saturation is not reached, even at 400 K, the high-spin state cannot be assigned.     

Determination of dispersity of crushed granite

Summary Experimental crushed granite column breakthrough curves, using ⁹⁹Tc as spike tracer and ³H as invariant tracer, were analyzed by different linear regression techniques. Dispersity of crushed granite and the retardation factor of ⁹⁹TcO₄^- on the crushed granite were determined simultaneously by one linear regression. Dispersity of crushed granite was also obtained with ³H as invariant tracer by the other linear regression. The dispersities found by spike source and invariant source methods are compared. Experimental results show that the dispersity found by the spike source method is close to that found by the invariant source method. This indicates that dispersity is only a characteristic of the dispersion medium.     

Ion flotation of rhodium(III) and palladium(II) with anionic surfactants

The ion flotation of rhodium(III) and palladium(II) with some anionic surfactants has been investigated. Two flotation procedures are proposed for the separation of some platinum metals, based on differences in the kinetic properties of the chloro-complexes of rhodium(III), palladium(II) and platinum(IV). The first involves the selective flotation of Rh(H(2)O)(3+)(6) from PdCl(2-)(4) and PtCl(2-)(6) in dilute hydrochloric acid with sodium dodecylbenzenesulfonate (SDBS). After precipitation of the hydroxide and redissolution in dilute acid, the Rh(III) is converted into Rh(H(2)O)(3+)(6), Pd(II) and Pt(IV) remaining as PdCl(2-)(4) and PtCl(2-)(6) respectively, and separation is achieved by floating the Rh(H(2)O)(3+)(6) with SDBS. The second is for separation of Pd(II). Prior to flotation, the solution of PdCl(2-)(4) and PtCl(2-)(6) is heated with ammonium acetate to convert PdCl(2-)(4) into Pd(NH(3))(2+)(4). The chloro-complex of Pt(IV) is unaffected. The complex cation, Pd(NH(3))(2+)(4), is then selectively floated with SDBS. The procedures are fast, simple and do not require expensive reagents and apparatus.     

PA.FPNS: its synthesis and use in spectrophotometric determination of magnesium

A new polymeric chromogenic reagent PA.FPNS has been synthesized by condensing polyallylamine (PA) with 3-(4-formylphenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (FPNS) and its properties studied. In alkaline media, PA.FPNS reacts with magnesium to form a water-soluble blue complex, whose absorption maximum is at 604 nm. The molar absorptivity (varepsilon) of the complex is 5.2 x 10(4)l mol(-1) cm(-1), which is four times that of the FPNS-Mg complex, and Beer's law is obeyed over the range 0-0.35 mug ml(-1) magnesium. Compared to the corresponding low-molecular-weight FPNS and other chromogenic reagents, PA.FPNS offers considerably improved sensitivity and selectivity for magnesium, which may be attributed to incorporating FPNS into a water-soluble polymer and the effect of the polymeric chain on the reaction microenvironment. Also, a simple and sensitive spectrophotometric method for the determination of magnesium has been developed and applied to water and human fluid samples with satisfactory results.     

Crystalline titanium dichloride—an active catalyst in ethylene polymerization. II. Polymer structure,polymerization variables,and scope

Polymerization of ethylene with ball-milled titanium dichloride leads to a completely linear polymer with terminal unsaturation corresponding to approximately one carbon–carbon double bond per molecule. Polymerization rate is first-order in both monomer and catalyst concentration at 140°C. Due to a thermal deactivation of the catalyst, the polymerization rate falls sharply with temperature above 180°C. Propylene and butene-1 will copolymerization with ethylene in this system, propylene more efficiently than butene-1. Evidence for copolymerization of trans-2-butene, but not of the cis-isomer or of isobutene, in trace concentrations is presented. Propylene is homopolymerized to a product low in isotactic content. The significance of the structural and (limited) kinetic data in terms of the mechanism of polymerization are discussed.     

Instrumental neutron activation analysis of large samples: A pilot experiment

A large sample INAA (LS-INAA) was conducted based on available experimental conditions. Four different materials, e.g., a quartz-sand and three wastes from an incineration plant were analyzed on sample size of 1 kg. The neutron flux spatial distribution was determined by irradiation of flux monitors in the sample. The gamma-ray apparent counting efficiency was evaluated based on the effective-solid angle concept, using linear attenuation coefficients calculated from an iteration process. The k ₀- and the modified monostandard methods were modified for the LS-INAA. To check the LS-INAA performance, a conventional small sample INAA was carried out for the quartz sand and a waste. All detected elements in the LS-INAA are presented and the discussion is conducted to explore the sources of errors in the LS-INAA. As a pilot experiment, the information from this work will be used in constructing irradiation and counting devices for the new FRM-II neutron source in Garching, Germany.     

Direct injection of plasma to determine pseudoephedrine by high performance liquid chromatography with column switching

An HPLC method has been developed for the determination of pseudoephedrine in plasma using column switching. Preparation of the sample was simple in that only 1000 microL of water was added to 200 microL of plasma before injection. A 900 microL aliquot was injected onto the precolumn. Double distilled water was used to elute and remove proteins and polar components in the sample. The components retained on the precolumn were flushed forward onto the analytical column by the mobile phase (acetonitrile-0.2 mol/L ammonium sulphate, 10:90 v/v) with automated column switching. The limit of determination of pseudoephedrine in plasma was 12 ng/mL. The relative standard deviations of intra- and inter-assay for the determination of pseudoephedrine in plasma were 1.2-9.8% over the concentration range 1020-21.8 ng/mL. The mean recovery by on-line solid phase extraction was 94.76% (RSD = 1.1%).     

Differential determination of arsenic (III) and total arsenic with L-cysteine as prereductant using a flow injection non-dispersive atomic absorption device

Speciation of arsenic in environmental samples gains increasingly importance, as the toxic effects of arsenic are related to its oxidation state. A method was developed for the determination of trace amounts of arsenic (III) and total arsenic by flow injection hydride generation coupled with an in-house made non-dispersive AAS device. The total arsenic is determined after prereduction of arsenic (V) to arsenic (III) with L-cysteine in a low concentration of hydrochloric, acetic or nitric acid. The conditions for the prereduction, hydride generation and atomization were systematically investigated. A quartz tube temperature of 800 degrees C was found to be optimum in view of peak shape and baseline stability. Pb(II), Ni(II), Fe(III), Cu(II), Ag(I), Al(III), Ga(II), Se(IV), Bi(III) were checked for interfering with the 2 microg/L As(V) signal. A serious signal depression was only observed for Se(IV) and Bi(III) at a 150-fold excess. With the above system, arsenic was determined at a sampling frequency of about 1/min with a detection limit (3sigma) of 0.01 microg/L using a 0.5 mL sample. The reagent blank was 0.001+/-0.0003 absorbance units and the standard deviation of 10 measurements of the 2 microg/l As signal was found to be 1.2%. Results obtained for standard reference materials and water samples are in good agreement with the certified values and those obtained by ICP-MS     

An immune algorithm for resolution of multicomponent overlapping chromatograms

A novel immune algorithm for resolution and quantitative determination of the components in overlapping chromatograms was proposed by imitating biological immune systems. The algorithm takes an overlapping chromatogram as its input and subtracts the chromatograms of standard samples from the input by iteration of a network. When the residual does not change, the network will converge and chromatographic information of the components in overlapping chromatogram will be obtained. Both simulated and experimental data sets were investigated by the method. Results showed that both resolved results and recoveries of quantitative determination are satisfactory. Comparing with conventional least-square method, the immune algorithm is fast in calculation.