Ion exchange equilibria between (Mn,Co)O solid solution and (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions at 1100oC

The compositions of the (Mn,Co)O solid solution with rock salt structure in equilibrium with (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions have been determined by X-ray diffraction measurements at 1100° C and an oxygen partial pressure of 10–10 atm. The ion exchange equilibria are quantitatively analysed, using values for activities in the (Mn,Co)O solid solution available in the literature, in order to obtain activities in the spinel solid solutions. The MnAl2O4-CoAl2O4 solid solution exhibits negative deviations from Raoult's law, consistent with the estimated cation disorder in the solid solution, while the MnCr2O4-CoCr2O4 solid solution shows slightly positive deviations. The difference in the Gibbs free energy of formation of the two pure chromites and aluminates derived from the results of this study are in good agreement with recent results obtained from solid oxide galvanic cells and gas-equilibrium techniques.

Inter and intra crystalline ion exchange equilibria in the system Fe Cr Al O

The tie lines delineating ion-exchange equilibria between FeCr2O4FeAl2O4 spinel solid solution and Cr2O3Al2O3 solid solution with corundum structure have been determined at 1373 K by electron microprobe and EDAX point count analysis of oxide phases equilibrated with metallic iron. Activities in the spinel solid solution are derived from the tie lines and the thermodynamic data on Cr2O3Al2O3 solid solution available in the literature. The oxygen potentials corresponding to the tie-line composition of oxide phases in equilibrium with metallic iron were measured using solid oxide galvanic cells with CaOZrO2 and Y2O3ThO2 electrolytes. These electrochemical measurements also yield activities in the spinel solid solution, in good agreement with those obtained from tie lines. The activity-composition relationship in the spinel solid solution is analysed in terms of the intra-crystalline ion exchange between the tetrahedral and octahedral sites of the spinel structures. The ion exchange is governed by site-preference energies of the cations and the entropy of cations mixing on each site.

Low temperature synthesis of layered NaxCoO2 and KxCoO2 from NaOH/KOH fluxes and their ion exchange properties

We report a low temperature synthesis of layered Na0×20CoO2 and K0×44CoO2 phases from NaOH and KOH fluxes at 400°C. These layered oxides are employed to prepare hexagonal HCoO2, LixCoO2 and Delafossite AgCoO2 phases by ion exchange method. The resulting oxides were characterised by powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM and EDX analysis. Final compositions of all these oxides are obtained from chemical analysis of elements present. Na0×20CoO2 oxide exhibits insulating to metal like behaviour, whereas AgCoO2 is semiconducting.

Seeded-growth, nanocrystal-fusion, ion-exchange and inorganic-ligand mediated formation of semiconductor-based colloidal heterostructured nanocrystals

This article highlights different synthetic strategies for the preparation of colloidal heterostructured nanocrystals, where at least one component of the constituent nanostructure is a semiconductor. Growth of shell material on a core nanocrystal acting as a seed for heterogeneous nucleation of the shell has been discussed. This seeded-growth technique, being one of the most heavily explored mechanisms, has already been discussed in many other excellent review articles. However, here our discussion has been focused differently based on composition (semiconductor@semiconductor, magnet@semiconductor, metal@semiconductor and vice versa), shape anisotropy of the shell growth, and synthetic methodology such as one-step vs. multi-step. The relatively less explored strategy of preparing heterostructures via colloidal sintering of different nanostructures, known as nanocrystal-fusion, has been reviewed here. The ion-exchange strategy, which has recently attracted huge research interest, where compositional tuning of nanocrystals can be achieved by exchanging either the cation or anion of a nanocrystal, has also been discussed. Specifically, controlled partial ion exchange has been critically reviewed as a viable synthetic strategy for the fabrication of heterostructures. Notably, we have also included the very recent methodology of utilizing inorganic ligands for the fabrication of heterostructured colloidal nanocrystals. This unique strategy of inorganic ligands has appeared as a new frontier for the synthesis of heterostructures and is reviewed in detail here for the first time. In all these cases, recent developments have been discussed with greater detail to add upon the existing reviews on this broad topic of semiconductor-based colloidal heterostructured nanocrystals.

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

Hydrodynamics in an expanded bed of large size ion-exchange resin, and natural product adsorption

Successful applications of expanded bed adsorption (EBA) technology have been widely reported in the literature for protein purification. Little has been reported on the recovery of natural products and active components of Chinese herbal preparations using EBA technology. In this study, the hydrodynamic behavior in an expanded bed of cation resin, 001 x 7 Styrene-DVB, was investigated. Ephedrine hydrochloride (EH) was used as a model natural product to test the dynamic binding capacity (DBC) in the expanded bed. EBA of EH directly from a feedstock containing powdered herbs has also been investigated. These particles are different from commercially available expanded bed adsorbents by virtue of their large size (20S to 1030 gm). When the adsorbent bed is expanded to approximately 1.3 to 1.5 times its settled bed height, the axial liquid-phase dispersion coefficient was found to be of the order 10(-5) m(2) s(-1), which falls into the range 1.0 x 10(-6) to 1.0 X 10(-5) m(2) s(-1) observed previously in protein purification. Because of the favorable column efficiency (low axial dispersion coefficient), the recovery yield and purification factor values of EH directly from a feedstock reached 86.5% and 18, respectively. The results suggest that EBA technology holds promise for the recovery of natural products and active components of Chinese herbal preparations.