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1.
A platinum-lined flowing autocláve facility was used to investigate the solubility behavior of magnetite (Fe3O4) in alkaline sodium phosphate and ammonium hydroxide solutions between 21 and 288°C. Measured iron solubilities were interpreted via a Fe(II)/Fe(III) ion hydroxo-, phosphato-, and ammino-complexing model and thermodynamic functions for these equilibria were obtained from a least-squares analysis of the data. A total of 14 iron ion species were fitted. Complexing equilibria are reported for 8 new species: Fe(OH)(HPO4)–, Fe(OH)2(HPO4)2–, Fe(OH)3(HPO4)2–, Fe(OH)(NH3)+, Fe(OH)2(PO4)3–, Fe(OH)4(HPO4)3–, Fe(OH)2(H2PO4)–, and Fe(OH)3(H2PO4)3–. At elevated temperatures, hydrolysis and phosphato complexing tended to stabilize Fe(III) relative to Fe(II), as evidenced by free energy changes fitted to the oxidation reactions.
相似文献
2.
Dhanpat Rai Dean A. Moore Andrew R. Felmy Kevin M. Rosso Harvey BoltonJr. 《Journal of solution chemistry》2010,39(6):778-807
To determine the solubility product of PuPO4(cr, hyd.) and the complexation constants of Pu(III) with phosphate and EDTA, the solubility of PuPO4(cr, hyd.) was investigated as a function of: (1) time and pH (varied from 1.0 to 12.0), and at a fixed 0.00032 mol⋅L−1 phosphate concentration; (2) NaH2PO4 concentrations varying from 0.0001 mol⋅L−1 to 1.0 mol⋅L−1 and at a fixed pH of 2.5; (3) time and pH (varied from 1.3 to 13.0) at fixed concentrations of 0.00032 mol⋅L−1 phosphate and 0.0004 mol⋅L−1 or 0.002 mol⋅L−1 Na2H2EDTA; and (4) Na2H2EDTA concentrations varying from 0.00005 mol⋅L−1 to 0.0256 mol⋅L−1 at a fixed 0.00032 mol⋅L−1 phosphate concentration and at pH values of approximately 3.5, 10.6, and 12.6. A combination of solvent extraction and spectrophotometric
techniques confirmed that the use of hydroquinone and Na2S2O4 helped maintain the Pu as Pu(III). The solubility data were interpreted using the Pitzer and SIT models, and both provided
similar values for the solubility product of PuPO4(cr, hyd.) and for the formation constant of PuEDTA−. The log 10 of the solubility product of PuPO4(cr, hyd.) [PuPO4(cr, hyd.)
\rightleftarrows\rightleftarrows
Pu3++PO43-\mathrm{Pu}^{3+}+\mathrm{PO}_{4}^{3-}] was determined to be −(24.42±0.38). Pitzer modeling showed that phosphate interactions with Pu3+ were extremely weak and did not require any phosphate complexes [e.g., PuPO4(aq), PuH2PO42+\mathrm{PuH}_{2}\mathrm{PO}_{4}^{2+}, Pu(H2PO4)2+\mathrm{Pu(H}_{2}\mathrm{PO}_{4})_{2}^{+}, Pu(H2PO4)3(aq), and Pu(H2PO4)4-\mathrm{Pu(H}_{2}\mathrm{PO}_{4})_{4}^{-}] as proposed in existing literature, to explain the experimental solubility data. SIT modeling, however, required the inclusion
of PuH2PO42+\mathrm{PuH}_{2}\mathrm{PO}_{4}^{2+} to explain the data in high NaH2PO4 concentrations; this illustrates the differences one can expect when using these two different chemical models to interpret
the data. Of the Pu(III)-EDTA species, only PuEDTA− was needed to interpret the experimental data over a large range of pH values (1.3–12.9) and EDTA concentrations (0.00005–0.256 mol⋅L−1). Calculations based on density functional theory support the existence of PuEDTA− (with prospective stoichiometry as Pu(OH2)3EDTA−) as the chemically and structurally stable species. The log 10 value of the complexation constant for the formation of PuEDTA− [
Pu3++EDTA4-\rightleftarrows PuEDTA-\mathrm{Pu}^{3+}+\mathrm{EDTA}^{4-}\rightleftarrows \mathrm{PuEDTA}^{-}] determined in this study is −20.15±0.59. The data also showed that PuHEDTA(aq), Pu(EDTA)45-\mathrm{Pu(EDTA)}_{4}^{5-}, Pu(EDTA)(HEDTA)4−, Pu(EDTA)(H2EDTA)3−, and Pu(EDTA)(H3EDTA)2−, although reported in the literature, have no region of dominance in the experimental range of variables investigated in
this study. 相似文献
3.
Dirk Zahn 《无机化学与普通化学杂志》2004,630(10):1507-1511
The initial steps of nucleation of calciumphosphates in aqueous solution are elucidated by means of quantum / classical molecular mechanics simulations. A special focus is dedicated to the role of the protonation state of the phosphate ion. The crystallization of calciumphosphates including entirely deprotonated phosphate ions is found at much lower pH values than required for finding the (PO4)3? species in water. In such cases the depronation of the hydrogenphosphate ion has to occur during crystal growth. According to our findings, the [Ca2+··(PO4)3?··Ca2+] ion triple is the smallest stable aggregate, which may be expected to contain an entirely deprotonated phosphate ion. 相似文献
4.
《Arabian Journal of Chemistry》2020,13(6):5750-5764
Herein, we describe the growth and morphology of well-defined dyed crystals of KH2PO4 (potassium dihydrogen orthophosphate; KDP) containing organic azo (sunset yellow; SSY) dye in the {1 0 1} & {0 0 1} pyramidal growth sectors. An understanding on selective dye inclusion in various growth sector of host crystal is proposed, which will help in designing novel tailor-made dyed photonic crystals. The structural analysis and the identification of various functional groups present in as grown KDP crystals were carried out using powder XRD, FTIR and Raman studies. Solid state transmittance spectra for dyed KDP crystals displayed three absorption peaks at 230 nm, 311 nm and 477 nm, which were blue shifted for SSY dye in KDP crystal relative to neutral aqueous solution of SSY dye. These blue shifts in the absorption maxima confirm the successful incorporation of sunset yellow dye into the pyramidal growth sectors of dyed KDP crystals. The band around 409 nm in the photoluminescence emission spectrum indicates a violet emission. SSY dye doped KDP crystals showed enhanced dielectric properties and thermal stability as compared to pure KDP crystal. The mechanical strength of the KDP crystals estimated using Vickers microhardness test was found to decrease with the increase in SSY dye doping. 相似文献
5.
Dr. Xiaochuan Duan Dr. Di Li Dr. Huili Zhang Dr. Jianmin Ma Prof. Dr. Wenjun Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7231-7242
In the work presented here, well‐dispersed ferric giniite microcrystals with controlled sizes and shapes are solvothermally synthesized from ionic‐liquid precursors by using 1‐n‐butyl‐3‐methylimidazolium dihydrogenphosphate ([Bmim][H2PO4]) as phosphate source. The success of this synthesis relies on the concentration and composition of the ionic‐liquid precursors. By adjusting the molar ratios of Fe(NO3)3 ? 9H2O to [Bmim][H2PO4] as well as the composition of ionic‐liquid precursors, we obtained uniform microstructures such as bipyramids exposing {111} facets, plates exposing {001} facets, hollow spheres, tetragonal hexadecahedron exposing {441} and {111} facets, and truncated bipyamids with carved {001} facets. The crystalline structure of the ferric giniite microcrystals is disclosed by various characterization techniques. It was revealed that [Bmim][H2PO4] played an important role in stabilizing the {111} facets of ferric giniite crystals, leading to the different morphologies in the presence of ionic‐liquid precursors with different compositions. Furthermore, since these ferric giniite crystals were characterized by different facets, they could serve as model Fenton‐like catalysts to uncover the correlation between the surface and the catalytic performance for the photodegradation of organic dyes under visible‐light irradiation. Our measurements indicate that the photocatalytic activity of as‐prepared Fenton‐like catalysts is highly dependent on the exposed facets, and the surface area has essentially no obvious effect on the photocatalytic degradation of organic dyes in the present study. It is highly expected that these findings are useful in understanding the photocatalytic activity of Fenton‐like catalysts with different morphologies, and suggest a promising new strategy for crystal‐facet engineering of photocatalysts for wastewater treatment based on heterogeneous Fenton‐like process. 相似文献
6.
Yu. V. Pleskov Yu. E. Evstefeeva M. D. Krotova V. Ya. Mishuk V. A. Laptev Yu. N. Pal'yanov Yu. M. Borzdov 《Russian Journal of Electrochemistry》2002,38(6):620-625
Effects of crystal structure on the electrochemistry of boron-doped high-temperature-high-pressure diamond single crystals grown from an Ni–Fe–C–B melt are studied. On the {111}, {100}, and {311} faces, the linear and nonlinear electrochemical impedance spectra and the electrochemical kinetics in the Fe(CN)6
3_/4_ redox system are measured. The acceptor concentration in the diamond interior adjacent to these faces was determined from the Mott–Schottky plots and the amplitude-demodulation measurements. It varies in the 1018 to 1021 cm–3 range. The difference in the electrochemical behavior of individual crystal faces is primarily attributed to different boron acceptor concentrations in the growth sectors associated with the faces. 相似文献
7.
A platinum-lined, flowing autoclave facility is used to investigate the solubility/phase behavior of zinc(II) oxide in aqueous sodium phosphate solutions at temperatures between 17 and 287°C. ZnO solubilities are observed to increase continuously with temperature and phosphate concentration. At higher phosphate concentrations, a solid phase transformation to NaZnPO4 is observed. NaZnPO4 solubilities are retrograde with temperature. The measured solubility behavior is examined via a Zn(II) ion hydrolysis/complexing model and thermodynamic functions for the hydrolysis/complexing reaction equilibria are obtained from a least-squares analysis of the data. The existence of two new zinc(II) ion complexes, Zn(OH)2(HPO4)2– and Zn(OH)3(H2PO4)2–, is reported for the first time. A summary of thermochemical properties for species in the systems ZnO–H2O and ZnO–Na2O–P2O5–H2O is also provided. 相似文献
8.
Solid-solute phase equilibria in aqueous solutions,VIII: The standard gibbs energy of La2(CO3)3·8H2O
Anh Mai Nguyen Erich Königsberger Harald Marhold Heinz Gamsjäger 《Monatshefte für Chemie / Chemical Monthly》1993,124(10):1011-1018
The solubilities of lanthanum carbonate La2(CO3)3·8H2O in solutionsS
0([H+]=H mol kg–1, [Na+]=(I–H) mol kg–1, [ClO
4
–
]=I mol kg–1) at various fixed partial pressures of CO2 have been investigated at 25.0 °C. The hydrogen ion molality and the total molality of La(III) ion in equilibrium with the solid phase were determined by e.m.f. and analytical methods, respectively. The stoichiometric solubility constants
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