Effect of strontium substitution on the activity of La2-xSrxNiO4 (x=0.0-1.2) in NO decomposition

The aim of this work is to study the effect of Sr substitution on the redox properties and catalytic activity of La2-xSrxNiO4 (x = 0.0-1.2) for NO decomposition. Results suggest that the x = 0.6 sample shows the highest activity. The characterization (TPD, TPR, etc.) of samples indicates that the x = 0.6 sample possesses suitable abilities in both oxidation and reduction, which facilitates the proceeding of oxygen desorption and NO adsorption. At temperature below 700 degrees C, the oxygen desorption is difficult, and is the rate-determining step of NO decomposition. With the increase of reaction temperature (T > 700 degrees C), the oxygen desorption is favorable and, the active adsorption of NO on the active site (NO + V-o + Ni2+ -> NO--Ni3+) turns out to be the rate-determining step. The existence of oxygen vacancy is the prerequisite condition for NO decomposition, but its quantity does not relate much to the activity.

Trends in elasticity and electronic structure of 5d transition metal diborides: first-principles calculations

We investigate the cohesive energy, heat of formation, elastic constant and electronic band structure of transition metal diborides TMB2 (TM = Hf, Ta, W, Re, Os and Ir, Pt) in the Pmmn space group using the ab initio pseudopotential total energy method. Our calculations indicate that there is a relationship between elastic constant and valence electron concentration (VEC): the bulk modulus and shear modulus achieve their maximum when the VEC is in the range of 6.8-7.2. In addition, trends in the elastic constant are well explained in terms of electronic band structure analysis, e.g., occupation of valence electrons in states near the Fermi level, which determines the cohesive energy and elastic properties. The maximum in bulk modulus and shear modulus is attributed to the nearly complete filling of TM d-B p bonding states without filling the antibonding states. On the basis of the observed relationship, we predict that alloying W and Re in the orthorhombic structure OsB2 might be harder than alloying the Ir element. Indeed, the further calculations confirmed this expectation.

Kinetics of extraction and stripping of y(III) by Cyanex 272 as an acidic extractant using a constant interfacial cell with laminar flow

The extraction and stripping kinetics of yttrium(III) with bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, HA) dissolved in heptane as an acid extractant have been investigated by constant interfacial cell with laminar flow. The experimental hydrodynamic conditions have been chosen so that the contribution of diffusion to the measured rate of reaction is minimized. The plot of interfacial area on the rate has shown a linear relationship, which makes the interface the most probable local for the chemical reactions. At the same time, the extraction thermodynamic and kinetic methods are compared to determine the equilibrium extraction constant. A rate equation and the rate-determining step of the extraction and stripping of yttrium(III) have also been obtained, respectively.

Kinetics study on melt grafting copolymerization of LLDPE with acid monomers using reactive extrusion method

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetics studies on reactive extrusion were carried out for the difficulties as expected. In this work, the macromolecular peroxide-induced grafting of acrylic acid and methyl methacrylate onto linear low density polyethylene by reactive extrusion was chosen as the model system for the kinetics study; the samples were taken out from the barrel at five ports along screw axis and analyzed by FTIR, H-1 NMR, and ESR. For the first time, the time-evolution of reaction rate, the reaction order, and the activation energy of graft copolymerization and homopolymerization in the twin screw extruder were directly obtained. On the basis of these results, the general reaction mechanism was tentatively proposed. It was demonstrated that an amount of chain propagation free radicals could keep alive for several minutes even the peroxides completely decomposed and the addition of monomer to polymeric radicals was the rate-controlled step for the graft copolymerization.

Kinetics of cerium(IV) extraction with DEHEHP from HNO3-HF medium using a constant interfacial cell with laminar flow

Studies of the extraction kinetics of cerium(IV) into n-heptane solutions of di(2-ethylhexyl)-2-ethylhexyl phosphonate DEHEHP from HNO3-HF solutions have been carried out using a constant interfacial cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The effects of the stirring rate, specific interfacial area, and temperature on the extraction rate showed that the most probable reaction zone is in the aqueous homogeneous phase. The results were compared with those of the system without HF. It was concluded that the presence of HF decreases the extraction rate of cerium. The addition of HF increases the activation energy for the forward reaction from 21.2 to 55.3 kJ/mol and for the reverse process from 57.9 to 79.0 kJ/mol. According to the experimental data correlated as a function of the concentration of the relevant species involved in the extraction reaction, the corresponding rate equation was deduced as follows:-d[Ce]/dt = k[Ce] center dot B-0.62 center dot HF-0.58 center dot [NO3-](0.57)

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Facilitated ion transfer reactions of 20 amino acids with di.benzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, Ile, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (beta(0)), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization.

Synthesis and characterization of poly(beta-hydroxybutyrate) and poly(epsilon-caprolactone) copolyester by transesterification

To synthesize the copolyester of poly(beta-hydroxybutyrate) (PHB) and poly(epsilon-caprolactone) (PCL), the transesterification of PHB and PCL was carried out in the liquid phase with stannous octoate as the catalyzer. The effects of reaction conditions on the transesterification, including catalyzer concentration, reaction temperature, and reaction time, were investigated. The results showed that both rising reaction temperature and increasing reaction time were advantageous to the transesterification. The sequence distribution, thermal behavior, and thermal stability of the copolyesters were investigated by C-13 NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, wide-angle X-ray diffraction, optical microscopy, and thermogravimetric analysis. The transesterification of PHB and PCL was confirmed to produce the block copolymers. With an increasing PCL content in the copolyesters, the thermal behavior of the copolyesters changed evidently. However, the introduction of PCL segments into PHB chains did not affect its crystalline structure. Moreover, thermal stability of the copolyesters was little improved in air as compared with that of pure PHB.

Effective descriptions of molecular structures and the quantitative structure - Activity relationship studies

In this research. we found CoMFA alone could not obtain sufficiently a strong equation to allow confident prediction for aminobenzenes. When some other parameter. such as heat of molecular formation of the compounds, was introduced into the CoMFA model, the results Were improved greatly. It gives us a hint that a better description for molecular structures will yield a better prediction model, and this hint challenged us to look for another method-the projection areas of molecules in 3D space for 3D-QSAR. It is surprising that much better results than that obtained by using CoMFA Were achieved. Besides the CoMFA analysis. multiregression analysis and neural network methods for building the models were used in this paper.

Study on the transesterification of poly(beta-hydroxybutyrate) and poly(epsilon-caprolactone)

The transesterification of poly(beta-hydroxybutyrate) (PHB) and poly(epsilon-caprolactone) (PCL) was carried out by using stannous octoate as catalyzer in liquid phase. The effects of reaction conditions on the transesterification, including reaction temperature, reaction time and catalyzer content, were investigated. The sequence distribution, crystallization behavior and thermal stability of PHB-co-PCL copolyesters were studied by C-13-NMR, FTIR, DSC, WAXD and TGA. The results showed that the transesterification of PHB with PCL was confirmed to produce a block copolymer, and enhancing reaction temperature and increasing reaction time were advantageous to the transesterification. With the increase in PCL content in the block copolymer, the crystallization behavior of PHB-co-PCL copolyesters changed evidently. On the other hand, the introduction of PCL segment into PHB chains did not change its crystalline structure; moreover, thermal stability of PHB-co-PCL copolyesters was a little improved in air, comparing with that of pure PHB.

Kinetics of cerium(IV) extraction from H2SO4-HF medium with Cyanex 923

Studies of the extraction kinetics of cerium(IV) from H2SO4-HF solutions with Cyanex 923 in n-heptane have been carried out using a constant interfacial area cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The results were compared with those of the system without HF. It was concluded that the addition of HF reduces the activation energy for the forward rate from 46.2 to 36.5 U mol(-1) while it has an opposite effect on the activation energy for the reverse process(the activation energy increased from 23.3 to 90.8 U mol(-1)). Thus, HF can accelerate the rate of cerium(IV) extraction. At the same time, the extraction rate is controlled by a mixed chemical reaction-diffusion rather than by a chemical reaction alone. A rate equation has also been obtained.

Influence of annealing on structure of Nylon 11

Differential scanning calorimeter (DSC), wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), and density techniques have been used to investigate the structural parameters of the solid state of Nylon 11 annealed at different temperatures. The equilibrium heat of fusion Delta H-m(0) and equilibrium melting temperature T-m(0) were estimated to be 189.05 J g(-1) and 202.85 degrees C respectively by using the Hoffman-Weeks approach. The degree of crystallinity (W-c,W-x) ranged approximately 24-42% was calculated by WAXD and compared with those by calorimetry (W-c,W-h) and density (W-c,W-d) measurements. The radius of gyration R-g, crystalline thickness L-c, noncrystalline thickness L-a, long period L, semiaxes of the particles (a, b), electron-density difference between the crystalline and noncrystalline regions eta(c) - eta(a), and the invariant Q increased with increasing annealing temperature. The analysis of the SAXS data was based upon the particle characteristic function and the one-dimensional electron-density correlation function. An interphase region existed between the crystalline and noncrystalline region with a clear dimension of about 2 nm for semicrystalline Nylon 11. Instead of the traditional two-phase model, a three-phase model has been proposed to explain these results by means of SAXS.

Kinetic study of Ce4+ extraction with Cyanex 923

Ce4+ extraction rate from aqueous sulphate solutions by Cyanex923 in heptane was studied using a constant interfacial cell with laminar flow at 30 degreesC. The experimental hydrodynamic conditions were chosen and the contribution of diffusion to the measured rate of reaction was minimized. Cerium extraction rate was measured at different chemical composition by varying the concentrations of hydrogen ion, sulphate and Cyanex923. A cerium-Cyanex923(B) extractive is formed at the interface. The data were analyszed in terms of pseudo-first order constants and a reaction mechanism was developed.

Simultaneous spectrophotometric determination of zinc, cadmium and mercury with hybrid linear analysis

A new method for simultaneous spectrophotometric determination of Zn, Cd and Hg using 2-(5-Br-2-pyridylazo)-5-diethylaminophenol as the color developing reagent was proposed. The absorption spectra of these three complexes have similar features with severe overlap in visible spectral range. For resolving these spectra, hybrid linear analysis was used, and the pure spectrum of each component was obtained from the calibration mixtures by least squares method. The effects of reaction condition, selection of wavelengths, determination of pure spectrum and additivity of absorbances etc. on the determination were discussed. The proposed method offers the advantages of simple, rapid, and accuracy. It has been successfully applied to the simultaneous determination of Zn, Cd and Hg in synthetic sample. A comparison was also made with the partial least squares method.

Catalytic reduction of NO, by CO on hydrotalcites-derived mixed oxides CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu)

Two series of mixed oxides, CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu), were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc). The ratio of Mg: Al: M (or Co: Al: hi) was 3:1:1. The catalytic activity of all samples for the reaction of NO + CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H-2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced. The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al: Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO were investigated respectively for supporting the mechanism.

Calculation formula and synthesis for controlling the composition of hydroxy - Terminated butadiene acrylonitrile cooligomer

In preparing copolymer of the same composition by batch process in two - component copolymerization it is necessary to keep the monomer ratio constant by replenishing the fraction of the more reactive monomer. In this paper a calculation method for monomer feeding is derived, which iscapable of controlling the composition of cooligomer during the course of reaction. Some cooligomers of acrylonitrile and butadiene with relatively the same compositions have been prepared using the replenishing method. The method would be useful for other two - component copolymerization ion process.