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.     

Synthesis,characterization and a thermogravimetric study of copper,cobalt and tin mono- and bis-adducts with ethyleneurea,ethylenethiourea and propyleneurea

This paper describes the synthesis, characterization and a thermogravimetric (t.g.) study of 11 adducts of general formula MCl₂·nL (M = Cu, Co and Sn; n = 1 and 2 for Sn, and 2 for Cu and Co; L = ethyleneurea eu, ethylenethiourea etu, and propyleneurea pu). The i.r. results shows that the eu and pu adducts are coordinated through oxygen, whereas for etu nitrogen is the coordination site. The (C=O) or (C=S) trend is: Cu > Co > Sn. The t.g. curves show that the adducts release ligand molecules in a single mass loss step. As regards considering adducts with the same stoichiometry, the observed thermal stability trend is: etu > pu > eu.     

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.     

Iron(III)-catalyzed Prins-type cyclization using homopropargylic alcohol: a method for the synthesis of 2-alkyl-4-halo-5,6-dihydro-2H-pyrans

[reaction: see text] A new Prins-type cyclization between homopropargylic alcohol and aldehydes in the presence of FeX(3) to obtain 2-alkyl-4-halo-5,6-dihydro-2H-pyrans in good yield is described. Osmium-catalyzed cis dihydroxylation provided direct access to trans-2-alkyl-3-hydroxy-tetrahydro-pyran-4-ones. Anhydrous ferric halides are also shown to be excellent catalysts for the standard Prins cyclization using homoallylic alcohol. Isolation of an intermediate acetal provides substantiation of a proposed mechanism.     

Simultaneous determination of neodymium, erbium and holmium in rare earth mixtures with 2-phenyltrifluoroacetone and octylphenol poly(ethyleneglycol) ether by third-derivative spectrophotometry

The complexes of the rare earth metals with 2-phenyltrifluoroacetone in the presence of TX-100 are reported. The characteristic absorbances of neodymium, holmium and erbium complexes can be increased by factors of 8.5, 31 and 15 respectively, compared to those of the cholrides. The third-derivative spectra have been used to eliminate the interference of cerium, and the sensitivities are increased again by factors of 7.4, 5.5 and 6.5. A method for the direct determination of neodymium, erbium and holmium in rare earth mixtures is proposed.     

Combining thermal analysis with other techniques to monitor the decomposition of poly(m-phenylene isophthalamide)

The pyrolysis behaviour of Nomex, poly(m-phenylene isophthalamide) fibres under argon has been investigated up to a temperature of 1173 K with different methods to get direct information on the progressive changes taking place in the solid material and its carbon fibre residues. The main stages of the pyrolytic degradation of the fibres were determined by thermal analysis (TG and DTA) and their chemical and morphological evolution through the different steps was subsequently followed by Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) measurements, respectively, on samples treated to various temperatures. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ab initio analytical potential energy surface and quasiclassical trajectory study of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+))-->OH(+)(X (3)Sigma(-))+H((2)S) reaction and isotopic variants

An analytical potential energy surface (PES) representation of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+)) system was developed by fitting around 600 CCSD(T)/cc-pVQZ ab initio points. Rate constant calculations for this reaction and its isotopic variants (D(2) and HD) were performed using the quasiclassical trajectory (QCT) method, obtaining a good agreement with experimental data. Calculations conducted to determine the cross section of the title reaction, considering collision energies (E(T)) below 0.3 eV, also led to good accord with experiments. This PES appears to be suitable for kinetics and dynamics studies. Moreover, the QCT results show that, although the hypotheses of a widely used capture model are not satisfied, the resulting expression for the cross section can be applied within a suitable E(T) interval, due to errors cancellation. This could be a general situation regarding the application of this simple model to ion-molecule processes.