A novel germanate, Cu2Fe2Ge4O13, with a four tetrahedra oligomer

The structure of Cu₂Fe₂Ge₄O₁₃, previously thought to be CuFeGe₂O₆, has been determined from single-crystal X-ray diffraction data to be monoclinic, P2₁/m, a=12.1050(6), b=8.5073(4), c=4.8736(2) Å, β=96.145(1)°, Z=2, with R1=0.0231 and wR2=0.0605. The unique structure has an oligomer of four germanate tetrahedra, cross-linked laterally by square-planar copper ions, joined end-to-end by a zigzag chain of edge-sharing iron oxide octahedra. Running along the a-direction the metal oxide chain consists of alternating Cu-Cu and Fe-Fe dimers. A hypothetical series of homologous structures (Cu_n−2Fe₂Ge_nO_3n+1 with n=3,4,…,∞) with different length germanate oligomers is proposed, where as n increases, the infinite chain of the CuGeO₃ is approached. In this context, Cu₂Fe₂Ge₄O₁₃ is viewed as being built from blocks of CuGeO₃ and the Fe oxide chains. This material has significance to the study of low-dimensional mixed-spin systems.     

Chemiluminometric determination of carvedilol in a multi-pumping flow system

In this work a simple, fast, sensitive and selective flow-based procedure for the chemiluminometric determination of carvedilol, a recent non-cardioselective β-blocker with noteworthy antioxidant activity, is proposed. The developed methodology takes advantage of the antioxidant capacity of carvedilol to inhibit the chemiluminescence response resulting from the oxidation of luminol by hypochlorite, by acting as a hypochlorite scavenger. The analytical process was implemented in a multi-pumping flow system that employs multiple solenoid actuated micro-pumps as the only active components. These acted as solution insertion, propelling and commuting units assuring an easily controlled, low cost, compact and reliable analytical system.A linear working range for carvedilol concentrations ranging from 1.2 × 10⁻⁷ to 3.0 × 10⁻⁶ mol l⁻¹ (r > 0.999, n = 6), was obtained, with a detection limit of 8.7 × 10⁻⁹ mol l⁻¹. The system handles about 65 samples per hour yielding precise results (R.S.D. < 1.3%, n = 10). Recoveries within 95 and 104% were obtained.     

Optical and Electrical Properties of Polymerizing Plasmas and Their Correlation with DLC Film Properties

Diamond-like carbon (DLC) films were grown from radiofrequency plasmas of acetylene-argon mixtures, at different excitation powers, P. The effects of this parameter on the plasma potential, electron density, electron temperature, and plasma activity were investigated using a Langmuir probe. The mean electron temperature increased from about 0.5 to about 7.0 eV while the mean electron density decreased from about 1.2 × 10⁹ to about 0.2 × 10⁹ cm^–3 as P was increased from 25 to 150 W. Both the plasma potential and the plasma activity were found to increase with increasing P. Through actinometric optical emission spectrometry, the relative concentrations of CH, [CH], and H, [H], in the discharge were mapped as a function of the applied power. A rise in [H] and a fall in [CH] with increasing P were observed and are discussed in relation to the plasma characteristics and the subimplantation model. The optical properties of the films were calculated from ultraviolet-visible spectroscopic data; the surface resistivity was measured by the two-point probe method. The optical gap, E _G, and the surface resistivity, _s, fall with increasing P. E _G and _s are in the ranges of about 2.0–1.3 eV and 10¹⁴–10¹⁶ /, respectively. The plasma power also influences the film self-bias, V _b, via a linear dependence, and the effect of V _b on ion bombardment during growth is addressed together with variation in the relative densities of sp² and sp³ bonds in the films as determined by Raman spectroscopy.     

Vinyl polymerization of acrylonitrile by the Ce(IV)-glucose redox system

Aqueous polymerization of acrylonitrile (M) initiated by the Ce(IV)-glucose (R) redox system has been studied under nitrogen in the temperature range of 30–40 °C. The rate of polymerization (Rp) is proportional to [M]², [R] and inversely proportional to [Ce(IV)]. The rate of ceric ion disappearance is proportional to [R] and [Ce(IV)]. The end group in the polymer is characterised by IR spectra. A suitable kinetic scheme has been proposed and explained in the light of these experimental findings.     

Anomalies of the partition coefficient and properties of crystals in the region of low concentrations of an isomorphous admixture. 1. Unusual decomposition of solid solutions of the NaCl—CdCl2 system

Solid solutions NaCl—CdCl₂ were studied in an interval of CdCl₂ concentrations of 0.05—3 mol.% by Raman spectroscopy. The molecular form Na₂CdCl₄ decomposes: Na₂CdCl₄ 2Na⁺ + Cd²⁺ + 2Cl₂ ^– + 2e^–; 2Na + 2e^– 2Na⁰. Free sodium atoms form color centers of crystal (F centers) in the region of jumpwise changing the partition coefficient of CdCl₂ in NaCl (K jump).     

Thermodynamique des melanges binaires LiPO3-Pb(PO3)2: Diagramme de phases et étude thermodynamique du liquide

Study of solid-liquid phase diagram of LiPO₃-Pb(PO₃)₂ binary system, in certain calcination conditions, shows the existence of several metastable phasis. When heated at a temperature of 723 K the binary mixtures lead uncompletely to a defined compound Pb₂Li(PO₃). On heating these ternary solid mixtures, three eutectic reactions have been observed: LiPO₃+Pb(PO₃)₂→Liquid at a temperature of 793 K(1) LiPO₃+Pb₂Li(PO₃)₅→Liquid at a temperature of 843 K (2) Pb₂Li(PO₃)₅+Pb(PO₃)₂→Liquid at a temperature of 891 K (3) The metastable liquid phase appears in the system at temperature of 793 K. DTA experiments performed on the binary LiPO₃-Pb(PO₃)₂ mixtures, show a superposition of two diagrams. The first one is metastable and the second represents the stable equilibrium phase diagram. Measurements of liquid enthalpy of binary LiPO₃-Pb(PO₃)₂ system at temperature of 979.65 K were reported. The corresponding values were very small and so the binary system can be considered as athermal. Assuming an ideal behaviour, the liquidus curves in the metastable diagram were calculated and the eutectic reaction (LiPO₃-Pb(PO₃)₂→Liquid) was confirmed at 793 K. This revised version was published online in August 2006 with corrections to the Cover Date.     

对位叠式循环方波伏安法：Ⅱ.平行催化体系

本文提出平行催化体系的对位叠式循环方波伏安法，并对共作了系统的研究，推导了这一方法的催化电流理论方程，并用验验证这理论的正确性，得到其各脉冲电流皆为同方向，对位叠式循环催化电流相当于将电流叠加４次，而波形不受方波幅度大小的影响，因而灵敏度和分辨率有较大提高，优于其它方波伏安法。     

Flow-injection determination of inorganic forms of nitrogen by gas diffusion and conductimetry

A flow-injection—conductimetric method was applied to the determination of ammonia, nitrate and nitrite at concentrations down to 5, 20 and 20 ng ml^?1, respectively. Ammonia was determined by merging the injected sample with an alkaline solution (NaOHEDTA) and passing the mixture through a diffusion cell. The ammonia released was collected by a flowing stream of deionized water that passed through a conductance flow cell. Nitrate and nitrite concentrations were determined after reduction to ammonia in alkaline medium using a column filled with metallic zinc. The ammonia produced was then measured as described above. About 60 samples per hour can be processed with a relative standard deviation of about 1%. Satisfactory agreement was observed between results for ammonia in samples of natural water and nitrate in tap and mineral water determined by the proposed method and by standard spectrophotometric procedures. Speciation can be achieved by adding sulphanilic acid to remove nitrite from the sample and determining the ammonia without the use of the column.     

A nonequilibrium entropy for dynamical systems

It is proposed to define entropy for nonequilibrium ensembles using a method of coarse graining which partitions phase space into sets which typically have zero measure. These are chosen by considering the totality of future possibilities for observation on the system. It is shown that this entropy is necessarily a nondecreasing function of the timet. There is no contradiction with the reversibility of the laws of motion because this method of coarse graining is asymmetric under time reversal. Under suitable conditions (which are stated explicitly) this entropy approaches the equilibrium entropy ast+ and the fine-grained entropy ast–. In particular, the conditions can always be satisfied if the system is aK-system, as in the Sinai billiard models. Some theorems are given which give information about whether it is possible to generate the partition used here for coarse graining from time translates of a finite partition, and at the same time elucidate the connection between our concept of entropy and the entropy invariant of Kolmogorov and Sinai.Research supported in part by NSF grants PHY78-03816 and PHY78-15920.     

InIII-Phthalocyanine: Darstellung,Eigenschaften und Kristallstruktur von Tetra(n-butyl)ammonium-cis-di(nitrito-O,O′)phthalocyaninato(2–)indat(III)

In^III-Phthalocyanines: Synthesis, Properties, and Crystal Structure of Tetra(n-butyl)ammonium-cis-di(nitrito-O,O')phthalocyaninato(2–)indate(III) [In(Cl)Pc^2?] reacts with (ⁿBu₄N)NO₂ in acetone yielding green-blue (ⁿBu₄N)^cis[In(NO₂)₂Pc^2?], which crystallizes in the monoclinic space group P2₁/n (No. 14). Both nitrite anions are coordinated as chelating nitrito-O,O'(NO₂) ligands to In^III in cis-geometry. Consequently In^III is octa-coordinated within a distorted “quadratic” antiprism and directed towards the Pc^2?-ligand. One of the NO₂ ligands has equivalent N? O bonds similar to free nitrite, while the other has asymmetric N? O bonds. Both (In,O,N,O) rings are approximately planar with a dihedral angle of 80°. The Pc^2? ligand is distorted in an asymmetrically convex manner. Partially overlapping pairs of Pc^2? ligands related by an inversion center form double layers, which are separated by layers containing the (ⁿBu₄N)⁺ cations. The cyclic voltammogram shows three electrode processes, which are assigned to the redox pairs: Pc^3?/Pc^2? (?0.94 V) < In^I/In^III (-0.78 V) < Pc^2?/Pc^? (0.64 V). The UV-VIS-NIR spectra and vibrational spectra are discussed.