Mathematical modelling of the oxidation of nickel titanium alloys

A one-dimensional bulk reaction model for the oxidation of nickeltitanium is formulated, with preferential oxidation of titaniumbeing included. The modelling is directed at the better understandingof the dominant mechanisms involved in the oxidation processand their significance for the biocompatibility of the alloy.Two different regimes for the relative diffusivities of oxygenand the metals are investigated. By assuming fast bulk reactions,different asymptotic structures emerge in different parameterregimes and the resulting models take the form of moving boundaryproblems. Different profiles of nickel concentration are obtained:in particular a nickel-rich layer (observed in practice) ispresent below the oxide/metal interface for the case when oxygenand the metals diffuse at comparable rates.     

Liquid-phase noncatalytic butene oxidation with nitrous oxide

The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation energies and have the first orders with respect to the alkene and N₂O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation of terminal and internal alkenes C₂—C₈ with nitrous oxide were analyzed using the previously published data. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–933, April, 2005.     

PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine （Co2Pc2） and binuclear ferric phthalocyanine （Fe2Pc2）, were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives （Mt2Pc2） were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.     

The synthesis of azo compounds from nitro compounds using lead and triethylammonium formate

Aromatic nitro compounds were reduced to the corresponding symmetrically substituted azo compounds using lead as catalyst and triethylammonium formate as hydrogen donor. Various azo compounds containing additional reducible substituents including halogens, nitrile, acid, phenol, ester, methoxy functions, etc, have been synthesized in a single step by the use of this reagent. The conversion is reasonably fast, clean, high yielding and occurs at room temperature in methanol.     

1H and 13C NMR spectroscopic study of oxidation of D,L‐cystine and 3,3′‐dithiobis(propionic acid) with hydrogen peroxide in aqueous solution

The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D₂O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu²⁺ cations, but not Fe³⁺ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.     

纳米KMn8O16粉体的室温固相合成与表征

室温或近室温固相反应要求绿色化、清洁化[1,2]。我们以KMnO4和MnCl2·4H2O为原料,用室温固相氧化还原反应制备氧化锰粉体时,得到了一种对H2O2分解具有较高催化活性的纳米KMn8O16粉体,用XRD、SEM、IR等技术对其进行了表征,发现研磨时间对粉体性能有显著影响。1　实验部分1 1　粉体的制备按摩尔比(2∶3)准确称取一定量的分析纯KMnO4和MnCl2·4H2O,分别置于玛瑙研钵中充分研细,再混合研磨,固相反应立即发生,体系颜色逐渐加深,并有刺激性气体产生,充分研磨后70℃恒温12h,固相产物依次经水洗至中性、醇洗、抽滤,真空干燥得黑色粉…     

New efficient catalysts for the aerobic oxidation of ethers

Some nickel, copper, and silver salts or complexes are efficient catalysts for the oxidation of benzylic ethers with oxygen in 1,2-dimethoxyethane. Salts of the weakly coordinating anion trifluoroacetate are particularly efficient, approaching (and, in some cases, improving) the yields obtained with cobalt(II) chloride, the best catalyst so far reported.     

The 2D Rancieite-type manganic acid and its alkali-exchanged derivatives: Part I — Chemical characterization and thermal behavior

The 2D Rancieite type manganic acid was prepared by reduction of KMnO₄ in acidic medium. Its ion exchange behavior allows to prepare alkali derivatives. All compounds were characterized with use of a combination of X-ray diffraction, chemical analyses, TGA, magnetic measurements and spectroscopic techniques. The evolution of their chemical composition versus temperature was studied between 180 and 400 °C. It shows that the dehydration process is partly reversible in these compounds whereas the weak reduction is irreversible. The 2D Rancieite-type manganic acid is readily different from a Birnessite-type phyllomanganate, as shown by several features: the interlayer distance, the ion exchange capacity, the thermal behavior, the interlayer cation content, the manganese average oxidation state, the magnetic behavior and the IR spectrum.     

Kinetic Studies of Electrochemical Oxidation of 1,3-Benzenedithiol

The electrochemical oxidation of 1, 3-benzenedithiol was investigated in a 0. 100 mol/L tetrabutylammonium perchlorate/acetonitrile electrolyte. The electrochemical techniques used were potential sweep, bulk electrolysis, rotating disc and the potential step method. The combination of the techniques yielded the number of electrons transferred per molecule, the reaction order, the transfer coefficient, the diffusion coefficient and concentration of dithiol anions, the standard heterogeneous rate constant as well as the formal potential and equilibrium constant of the preceeding dissociation reaction. This paper also illustrates the methods for studying the electrode kinetics of reactions which (a) involve a chemical reaction preceeding the electron-transfer process, (b) have insoluble polymer products, and (c) are totally irreversible.