Dissolution of malachite in aqueous ethylenediaminetetraacetate solution

The kinetics of malachite dissolution in aqueous ethylenediaminetetraacetate (EDTA) solution has been investigated in the temperature range of 298 to 318 K. The dissolution rate of malachite determined under the present set of experimental conditions was found to be independent of agitation speed. The dissolution rate increased with increasing EDTA concentration, but leveled off at higher concentrations. At constant EDTA concentration, an increase in dissolution rate was detected at higher temperatures. A dissolution mechanism involving Langmuir-type EDTA adsorption was proposed, in which the dissolution rate of malachite is controlled by the removal of Cu(II)-EDTA complex from the malachite lattice. The proposed mechanism can explain the dependency of the dissolution rate on EDTA concentration. The activation energies determined at pHs 5, 7.5, and 10 were found to be 51.4, 50.2, and 57.5 kJ mol⁻¹, respectively. The calculated enthalpy changes of EDTA adsorption equilibrium were −43.2, −35.2, and −45.0 kJ mol⁻¹ for pHs 5, 7.5, and 10, respectively. These values are in agreement with the proposed mechanism. Formerly Graduate Student, Department of Metallurgy, Kyoto University, is Formerly Professor, is Professor Emeritus, Department of Metallurgy, Kyoto University.     

Water and solute activities of the solution systems of H2So4-Cuso4-H2O and Hci-Cuci2-H2O

The activities of water, α(H₂O), in the solution system of H₂SO₄-CuSO₄-H₂O were determined by an isopiestic method and those in the solution system of HCl-CuCl₂-H₂O by a transpiration method, both at 298 K. The activities of H₂SO₄ and H⁺ in the solution system of H₂SO₄-CuSO₄-H₂O were also determined at 298 K by the emf method. The water activities in both systems obeyed the Zdanovskii rule relatively well. The α(H₂O) experimentally determined in the sulfate system showed a satisfactory agreement with those calculated from the Robinson-Bower equation, assuming the complete dissociations of H₂SO₄ and CuSO₄, whereas a good agreement between the calculated and experimentally determined α(H₂O) for the chloride system was obtained when the formation of Cu(II) chloro-complexes was taken into consideration. The mean activity coefficients, γ_±, of solutes, including H₂SO₄, HC1, and CuCl₂ in these solution systems, were calculated at 298 K by the McKay-Perring method using the activity data. The γ_±(H₂SO₄) values in the solution system of H₂SO₄-CuSO₄-H₂O were in good agreement with those determined by the emf method. On the other hand, the γ_±(CuSO₄) were calculated at the same temperature based upon the Gibbs-Duhem equation using both measured α(H₂O) and calculated γ_±(H₂SO₄) values, because of solubility limitations.     

Preparation of Monolithic Porous Titania-Silica Ceramics

Monolithic porous ceramics composed of TiO₂ (67 mol%) and SiO₂ (33 mol%) were prepared via casting a melt in the Na₂O-CaO-TiO₂-P₂O₅-SiO₂ system and subsequent acid leaching of the resultant ceramics which are constituted of NaCaPO₄, TiO₂, and amorphous SiO₂. The median pore diameter and specific surface area of the resulting porous ceramics are approximately 1 μm and 40 m², respectively. Amorphous silica surrounds the submicrometer-sized particles of TiO₂ acting as a binder and retaining monolithic forms. No significant shrinkage in the pore size occurred upon heating up to 1000°C.     

Zinc Oxide Varistor Gas Sensors: I, Effect of Bi2O3 Content on the H2-Sensing Properties

Current ( I )-voltage ( V ) characteristics of porous ZnO varistors with different Bi₂O₃ content have been investigated in air as well as in H₂-air mixtures in the temperature range room temperature (RT)-600°C. The I-V characteristics measured at RT remained unchanged in the presence of H₂, but the breakdown voltage clearly shifted to a lower electric field in the temperature range 400–600°C. The breakdown voltage decreased with increasing H₂ concentration in air. The optimum amount of Bi₂O₃ for the largest decrease was found to be 1.0 mol%. Thus, ZnO varistors can be used as a new type of H₂ sensor. The results presented in this study also suggest the important role of excess oxygen ions existing at the ZnO-ZnO grain boundaries in developing the Schottky barrier as well as in the H₂-sensing mechanism of the varistors.     

Sanguineous cerebrospinal fluid in recanalized cerebral infarction

To clarify the causal relationship between spontaneous recanalization of the occluded cerebral artery and development of hemorrhagic infarction, 15 patients with internal carotid or middle cerebral arterial axis occlusion were submitted to consecutive lumbar punctures and follow-up cerebral angiography. Consequently, six of seven recanalized patients had sanguineous cerebrospinal fluid (CSF) on the second or third day after ictus, while only one of eight non-recanalized patients had bloody CSF. It was strongly suggested that recanalization might have an initimate relationship with the development of hemorrhagic infarction.