Kinetic parameters of interphase exchange of oxygen in high-temperature proton conductors BaCe0.95Nd0.05O3- and SrCe0.95Y0.05O3- are determined using an isotope exchange method in the temperature range 630-820°C at oxygen pressures of 2.7-13.3 gPa and diffusion coefficients for oxygen are calculated. Effective energies of activation of oxygen exchange and diffusion coefficients for oxygen are calculated. Dependence of exchange characteristics and the diffusion coefficients on the oxygen pressure in the gas phase is investigated. The oxygen exchange on the surface of studied oxides is shown to proceed only with the participation of oxygen of the oxides, which causes high rates of interphase exchange of oxygen of studied cerates of barium and strontium. It is shown that the obtained data satisfactorily agree with those found in the relevant literature. 相似文献
Measurements of the major cations Ca and Mg by the technique of diffusive gradients in thin films (DGTs) were systematically evaluated. The concentration in solution was calculated using Fick’s first law of diffusion from the directly measured flux to the DGT device. A selective cation exchange resin (Bio-Rad Chelex®100), which has been used extensively with DGT for trace metals, such as Cd2+, Cu2+ and Ni2+, was used for this work.
Elution of Ca and Mg from the resin with 1 M HNO3 was very reproducible. Measurements of Ca and Mg concentrations in synthetic solutions agreed well with the theoretical predictions. The negative response on uptake caused by lowered pH was investigated. Uptake was found to decline below pH 5. The capacity of the DGT device for Ca and Mg was also investigated to establish maximum deployment times for given concentrations.
Experiments with filtered and modified lake water show that DGT can be used to measure Ca and Mg when trace metals are present in the solution. An in situ deployment of DGT combined with an ultrafiltration study suggest that the Mg concentration measured by DGT is similar to the concentration found in the fraction <1 kDa. 相似文献
A variety of biomolecules and their variants, which have previously been problematic to separate, have been analysed using a novel anion-exchange resin based on a non-porous polystyrene polymeric support with a hydrophilic coating and grafted tentacular quaternary ammonium functional groups. The hydrophilic coating results in minimal interaction between the support and the biomolecule, while the highly flexible tentacular-like anion-exchange groups increase the ionic interaction potential and act as an umbrella to hold the proteins away from the surface. Because of the removal of silanophilic interactions, minimisation of hydrophobic interactions, and the highly flexible nature of the tentacle-like ion exchangers, ionic interactions can therefore dominate the separation. As such this phase is highly suited to the separation of highly charged biomolecules and their variants. This polymeric strong anion-exchange (SAX) support was packed into a fused-silica capillary column and, using a salt concentration gradient, various recombinant proteins were analysed by -HPLC resulting in baseline resolution.Awarded a poster prize on the occasion of the Euranalysis XIII conference, Salamanca, Spain, 5–10 September 2004 相似文献
The structure of NH4-substituted chabazite, (NH4)3.30Ca0.30Na0.07K0.01[Al3.98Si8.02O24]·8.4H2O, (trigonal, space group \(R\bar 3m\), rhombohedral unit cell: a = 9.423(1) Å, α = 94.66(2)°, V = 827.9(2) Å 3, Z = 1) has been determined by single crystal X-ray diffraction. The structure is compared to that of the natural chabazite. NH4+ cations occupy two of four cationic positions of original chabazite, one position being shared with H2O. Hydrogen atoms were localized and the orientation of NH4 tetrahedra was revealed. Their low coordination on H2O determined a substantial decrease of H2O content in the modified structure. 相似文献
Magnesium alkylidene carbenoids were generated from 1-chlorovinyl p-tolyl sulfoxides with i-PrMgCl at −78 °C in THF or toluene via the sulfoxide-magnesium exchange reaction. Reaction of the generated magnesium alkylidene carbenoids with lithium acetylides or lithium thiolates gave conjugated enynes or vinyl sulfides, respectively, in moderate to good yields. The intermediate of this reaction was found to be the alkenyl anion and it could be trapped with some electrophiles to give tetra-substituted conjugated enynes and vinyl sulfides. 相似文献
An ion-exchange method was used to determine complexation constants for the Ni-oxalate and Ni-carbonate systems in a NaClO4 background electrolyte. The Ni-oxalate data were interpreted in terms of a single Niox(aq) complex having log K1 values for Ni2+ + ox2– Niox(aq) of 3.9 ± 0.1 (I.S. = 0.5 mol-L–1 p[H] = 7.1) and 4.4 ± 0.1 (I.S. = 0.1 mol-L–1 p[H] = 8.6) at 22 ± 1C. Specific ion-interaction theory (SIT) was used to obtain log K1 = 5.17 ± 0.05 (95% confidence level and = –0.23 ± 0.15) at I.S. = 0. The Ni-carbonate studies were carried out at p[H] values of 7.5, 8.5, and 9.6 in 0.5 mol-L–1 NaClO4/NaHCO3 solutions. The NiCO3(aq) species was the dominant complex in the [CO32–] concentration ranges studied at all three p[H] values. A log K1 value for Ni2+ + CO32– NiCO3(aq) of 2.9 ± 0.3 was deduced at I.S. = 0.5 mol-L–1. Extrapolating this value to zero ionic strength using the SIT approach yielded log K1 = 4.2 ± 0.3 (95% confidence level and = –0.26 ± 0.04). The data allowed upper bound values for the complexation constants for NiHCO3+ and Ni(CO3)22– to be estimated, i.e., log K < 1.4 for Ni2+ + HCO3– NiHCO3+, and log K2 < 2 for NiCO3(aq) + CO32– Ni(CO3)22–, respectively. 相似文献
Thermodynamic and mechanistic features of the chalcogen exchange reaction between [RGa(
3-Te)]4 and elemental sulfur or selenium have been studied employing density functional theory (DFT) calculations using the BL3YP basis set and Stuttgart pseudopotentials. For [MeGa(
3-E)]4 (E=S, Se, Te) the correlation between the calculated parameters and diffraction data for their isolable analogs is greater than 98%. Each step of the conversion of [MeGa(
3-Te)]4 to [MeGa(
3-E)]4 via [Me4Ga4(
3-Te)4–x(
3-E)x] (E=S, Se) is predicted to occur as a series of isolated reactions. The entropy change for each chalcogen exchange is small in magnitude and corresponds to the degree of cage distortion within the cubane molecules. Calculations performed on [MeGa(
3-Te)]4...S8 and [MeGa(
3-Te)]4-S suggest that an increase in electrophilicity of the gallium next to a surface bound tellurium may result in nucleophilic cage opening for which intermediate structures are calculated. 相似文献
Diffusion coefficients of tetradecyltrimethylammonium bromide in aqueous solutions have been determined at 25, 95 and 135 °C using the Taylor dispersion technique. The diffusion coefficient exhibits a minimum at a surfactant concentration above the critical micelle concentration (CMC). The results are interpreted in terms of electrostatic coupling and rapid exchange between micelle, surfactant monomer and counterions. 相似文献