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1.
IntroductionOver the past few years, dimethyl carbonate(DMC) has been proven to be an efficientmethylating,methoxylating, and methoxycarbonylating agent inorganic syntheses, in which DMC is used to replace thetoxic methyl halides, dimethyl sulfate or carb 相似文献
2.
Inhibition of the reduction of Cr(VI) at the magnetite–water interface by calcium carbonate coatings
The effect of calcium carbonate coatings on the reduction of aqueous chromate on the magnetite(1 1 1) surface has been investigated using a combination of synchrotron based X-ray photoemission spectroscopy (PES) and X-ray absorption near edge structure (XANES) spectroscopy, along with laboratory-based powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). CaCO3 coatings (dominantly calcite with minor quantities of aragonite and vaterite) of thicknesses ranging from 10 Å to 20 m were grown on magnetite(1 1 1) surfaces by exposure to supersaturated aqueous solutions followed by evaporation of the solution—a process that mimics pore-water evaporation in vadose zones leading to the formation of caliche and calcium carbonate coatings on mineral grains. Coating thicknesses were determined from attenuation of the Fe 2p photoemission signal by the carbonate coating. For coatings less than 15 Å thick, Cr 2p photoemission and Cr LII, LIII-edge XANES spectra show that chromate is reduced by the underlying magnetite surface; however, as the minimum coating thickness increases beyond 15 Å, the magnetite surface becomes passivated and further chromate reduction ceases. Our findings suggest that carbonate coatings on natural magnetite grains can significantly reduce or eliminate their ability to reduce Cr(VI), which is a toxic and highly mobile environmental contaminant. 相似文献
3.
Summary. This review reveals that, in contrast to the general opinion, the aqueous speciation of nickel is poorly known. Besides the
fairly well established first hydrolysis constant, data are scarce and only poor estimates can be derived for higher Ni hydrolysis
constants from a few solubility studies. The situation is even worse in the case of aqueous carbonate complexes. No reliable
experimental study has been published so far and almost all numbers reported in thermodynamic databases are unacceptable estimates.
In this review we scrutinise all these published estimates and propose expectation ranges of nickel carbonate complex stability
through correlation with other known thermodynamic constants. Solubility constants for a few simple nickel solids are known
or have been estimated from thermochemical data. However, none of these simple solids is of geochemical relevance at ambient
conditions. Based on field evidence, classes of solids are identified which potentially govern nickel concentrations in ground
and surface waters. Recent spectroscopic data indicate that magnesium clay minerals and layered double hydroxides are the
most prominent candidates for nickel-bearing solids at ambient conditions.
Corresponding author. E-mail: wolfgang.hummel@psi.ch
Dedicated to the memory of Prof. Rolf Grauer
Received January 14, 2003; accepted January 24, 2003
Published online May 15, 2003 相似文献
4.
Dhanpat Rai Dean A. Moore Nancy J. Hess Kevin M. Rosso Linfeng Rao Steve M. Heald 《Journal of solution chemistry》2007,36(10):1261-1285
Chromium(III)-carbonate reactions are expected to be important in managing high-level radioactive wastes. Extensive studies
on the solubility of amorphous Cr(III) hydroxide solid in a wide range of pH (3–13) at two different fixed partial pressures
of CO2(g) (0.003 or 0.03 atm.), and as functions of K2CO3 concentrations (0.01 to 5.8 mol⋅kg−1) in the presence of 0.01 mol⋅dm−3 KOH and KHCO3 concentrations (0.001 to 0.826 mol⋅kg−1) at room temperature (22±2 °C) were carried out to obtain reliable thermodynamic data for important Cr(III)-carbonate reactions.
A combination of techniques (XRD, XANES, EXAFS, UV-Vis-NIR spectroscopy, thermodynamic analyses of solubility data, and quantum
mechanical calculations) was used to characterize the solid and aqueous species. The Pitzer ion-interaction approach was used
to interpret the solubility data. Only two aqueous species [Cr(OH)(CO3)22− and Cr(OH)4CO33−] are required to explain Cr(III)-carbonate reactions in a wide range of pH, CO2(g) partial pressures, and bicarbonate and carbonate concentrations. Calculations based on density functional theory support
the existence of these species. The log 10
K° values of reactions involving these species [{Cr(OH)3(am) + 2CO2(g)⇌Cr(OH)(CO3)22−+2H+} and {Cr(OH)3(am) + OH−+CO32−
⇌Cr(OH)4CO33−}] were found to be −(19.07±0.41) and −(4.19±0.19), respectively. No other data on any Cr(III)-carbonato complexes are available
for comparisons. 相似文献
5.
A novel gas diffusion-flow injection method has been developed for the rapid and sensitive determination of total inorganic carbon (TIC) in water. The method is based on the diffusion of CO2 across gas permeable membrane from a donor stream containing 0.1 M HCl to an acceptor stream of sodium acetate (10−5 mol l−1 and pH 10). The CO2 trapped in the acceptor stream passes through an electrochemical flow cell contains a tungsten oxide wire and a silver/silver chloride electrode, where it was sensitively detected. The parameters affecting the sensitivity of the electrode such as buffer concentration, pH, flow rate and injected volume were studied in detail. The electrode response was linear in the concentration range from 5 to 100 μg ml−1 CO32− with a correlation coefficient (R2) of 0.998. Precision (R.S.D.) was 1.42% for 20 μg ml−1 standard solution of CO32− (n=10). The detection limit was 0.20 μg ml−1 CO32−. The method was evaluated by the injection of real natural water samples and an average recovery of 100.1% was obtained. The sampling rate was 30 samples h−1. The method is simple, feasible with satisfactory accuracy and precision and thus could be used for monitoring TIC in water. 相似文献
6.
The structure of a complex, disordered type A-B carbonate apatite (CAp) of approximate composition Ca10(PO4)6−y(CO3)x+(3/2)y(OH)2−2x, x-0.7, y-0.6, synthesized at 3 GPa, 1400°C has been determined using single-crystal X-ray diffraction and FTIR spectroscopy at room temperature and pressure. Crystal data are: hexagonal, space group P63/m, Z=1; a=9.5143(3), c=6.8821(2) Å, V=539.5 Å3, and R=0.025. There are three structural locations for the carbonate ion. The channel carbonate is mainly in the closed vertical configuration of the structure, with two of its oxygen atoms close to the c-axis (A1 carbonate; IR bands at 1541 and 1449 cm−1), but subordinate amounts are also located in an open vertical configuration (A2 carbonate; IR bands at 1563 and 1506 cm−1). The type B carbonate ion is located close to the sloping faces of the PO4 tetrahedron (IR bands at 1474 and 1406 cm−1), confirming earlier inferences from polarized IR spectra. 相似文献
7.
Nancy J. McMillan Russell S. Harmon Frank C. De Lucia Andrzej M. Miziolek 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1528-1536
Laser-induced breakdown spectroscopy (LIBS) provides an alternative chemical analytical technique that obviates the issues of sample preparation and sample destruction common to most laboratory-based analytical methods. This contribution explores the capability of LIBS analysis to identify carbonate and silicate minerals rapidly and accurately. Fifty-two mineral samples (18 carbonates, 9 pyroxenes and pyroxenoids, 6 amphiboles, 8 phyllosilicates, and 11 feldspars) were analyzed by LIBS. Two composite broadband spectra (averages of 10 shots each) were calculated for each sample to produce two databases each containing the composite LIBS spectra for the same 52 mineral samples. By using correlation coefficients resulting from the regression of the intensities of pairs of LIBS spectra, all 52 minerals were correctly identified in the database. If the LIBS spectra of each sample were compared to a database containing the other 51 minerals, 65% were identified as a mineral of similar composition from the same mineral family. The remaining minerals were misidentified for two reasons: 1) the mineral had high concentrations of an element not present in the database; and 2) the mineral was identified as a mineral with similar elemental composition from a different family. For instance, the Ca–Mg carbonate dolomite was misidentified as the Ca–Mg silicate diopside. This pilot study suggests that LIBS has promise in mineral identification and in situ analysis of minerals that record geological processes. 相似文献
8.
蟹,虾壳微观形貌与结构研究 总被引:6,自引:0,他引:6
用X射线衍射与扫描电镜研究了蟹壳,虾壳的形貌与微观结构,蟹壳中以方解石晶型存在的碳酸钙分布在网状结构的有机质中,网孔的尺寸约5~25μm有机基质脱去蛋白后留下的甲壳质呈片层状结构,它的重复距离为0.96nm。 相似文献
9.
A series of alkaline uranyl carbonates, M[UO2(CO3)3]·nH2O (M=Mg2, Ca2, Sr2, Ba2, Na2Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba2[UO2(CO3)3]·6H2O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO2)(CO3)3 clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90±0.02 Å.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces. 相似文献
10.
B. Movassagh M. M. Lakouraj A. Gholami 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1507-1511
Silver carbonate supported on celite (Ag 2 CO 3 /Celite) is used as a mild heterogeneous reagent for conversion of a variety of thioamides into their corresponding amides in acetonitrile at room temperature. 相似文献