NiFe2O4—ZnFe2O4尖晶石固溶体中的离子占位

在１＊１０＾５Ｐａ,１４００℃条件下实验合成了不同成分的Ｎｉ（１－ｘ）ＺｎｘＦｅ２Ｏ４尖晶石,并将部分尖晶石在１１００℃和１６１０℃条件下重新平衡。采用粉晶Ｘ射线衍射法测定了尖晶石的晶胞参数。将实测的尖晶石晶胞参数与理论计算值进行对比,结果发现,在温度小于１４００℃时Ｎｉ（１－ｘ）ＺｎｘＦｅ２Ｏ４尖晶石中的四面体主要由Ｚｎ＾２＋、Ｆｅ＾３＋占据,而八面体主要由Ｎｉ＾２＋、Ｆｅ＾３＋占据,但至少当温     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Li2B4O7—Na2B4O70H2O三元体系25℃相关系及物化性质实验

通过实验研究了Ｌｉ２Ｂ４Ｏ７－Ｎａ２Ｂ４Ｏ７－Ｈ２Ｏ三元体系２５℃相关 溶液的物化性质，其２５℃相图由二条溶解度曲线构成，分别对应于Ｌｉ２Ｂ４Ｏ７．３Ｈ２Ｏ、Ｎａ２Ｂ４Ｏ７．１０Ｈ２Ｏ相区，属简单共饱和型。简要讨论了该体系硼酸盐在水听溶解行为，并用经验公式描述了物有浓度的变化规律。     

Phase Equilibria in the Ternary Systems KBr–K2B4O7–H2O and KCl–K2B4O7–H2O at 373 K

According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide （KBr） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）,and those in the ternary system KCl-K2B4O7-H2O are potassium chloride （KCl） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）.Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.     

Crystal structure of yegorovite Na4[Si4O8(OH)4] · 7H2O

Doklady Earth Sciences - Using X-ray analysis, the crystal structure of yegorovite Na4[Si4O8(OH)4] · 7H2O, a newly-discovered mineral from the Lovozero alkaline complex (Kola Peninsula,...     

The MgCr2O4–MgFe2O4 solid solution series: effects of octahedrally coordinated Fe3+ on T–O bond lengths

The influence on the spinel structure of Fe³⁺ → Cr substitution was studied in flux-grown synthetic single crystals of the magnesiochromite–magnesioferrite (MgCr₂O₄–MgFe₂O₄) solid solution series. Samples were analysed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption and Mössbauer spectroscopy. With the exception of iron-poor samples (3–12 mol-% MgFe₂O₄), optical absorption and Mössbauer spectra show that iron occurs almost exclusively as trivalent Fe in the present samples. A very intense and broad absorption band at ca 7,800 cm^?1 dominates the optical absorption spectra of samples with higher Fe-contents. The appearance of this band is related to a distinct structural disorder of Fe³⁺ and a development of magnetic ordering as demonstrated by Mössbauer spectra. Profound composition-related changes are observed in the Mössbauer spectra, which are magnetically unsplit in the range 2–41 mol-% magnesioferrite, but become magnetically split in the range 59–100 mol-% magnesioferrite. Structural parameters a ₀ and M–O increase with magnesioferrite content and inversion degree, while u and T–O decrease. Our study confirms the previously reported (Lavina et al. 2002) influence of Fe³⁺ at the M site on T–O bond lengths in the spinel structure.     

Na2CO3-Na2B4O7-H2O三元体系288K相平衡研究

采用等温溶解平衡法研究了三元体系 Na2 CO3- Na2 B4 O7- H2 O 2 88K时的相平衡及平衡液相的主要物化性质 (密度 ,电导率 ,p H)。研究发现 :该三元体系为简单共饱和型 ,无复盐及固溶体形成 ,根据溶解度数据绘制出相图 ,相图中单变量曲线所对应的平衡固相分别为 :Na2 CO3· 10 H2 O,Na2 B4 O7· 10 H2 O。并简要讨论了物化性质的变化规律。     

交互四元体系Li+,Mg2+//SO2-4,B4O2-7-H2O 288 K时相平衡研究

采用等温溶解平衡法研究了288K时Li+, Mg2+//SO2-4, B4O2-7- H2O四元体系的固液相平衡关系,测定了该四元体系在288K时平衡液相的溶解度和密度.依据实验测定的平衡溶解度数据及对应的平衡固相,绘制了该四元体系的平衡相图及密度组成图.研究结果表明:交互四元体系Li+, Mg2+//SO2-4, B4O2-7- H2O 288K时平衡相图中有2个共饱点,5条单变量曲线,4个结晶区对应的平衡固相分别为Li2B4O7·3H2O,Li2SO4·H2O,MgB4O7·9H2O和MgSO4·7H2O.     

Solid-liquid Equilibria for the Quaternary NaCl–Na2SO4–Na2B4O7–H2O System at 348 K

正1 Introduction China has very abundant liquid mineral resources.Especially,the brine resources in the west of Sichuan Basin are pushed into the first place in China,whose K and B contents are unusually high.These rare liquid mineral resources have very good exploitation prospect(Lin,2001;2006).Generally speaking,phase equilibrium     

尖晶石型CoAl2O4纳米粉体的合成及表征

铝酸钴(CoAl2O4)是目前世界上最耐候、耐光、耐热、耐化学品的尖晶石型钴蓝颜料,为了解决传统钴蓝制备方法存在的能耗高、产品粒径分布不均匀、易团聚等问题,尝试采用柠檬酸盐凝胶法合成了尖晶石型CoAl2O4纳米粉体,对样品进行了TG-DSC、XRD、SEM等分析,考察了前驱体凝胶的热分解过程,以及煅烧温度对CoAl204晶化程度和粒度的影响．确定了钴蓝最佳合成条件为：n(Co^2 )／n(Al^3 )=1：3,柠檬酸与金属离子摩尔比为1：1,pH值约为6．5,煅烧温度为800℃．结果表明,采用柠檬酸盐凝胶法成功合成了平均粒径为60nm,粒度分布均匀的尖晶石型CoAl2O4纳米粉体,该法具有合成成本低、制备工艺简单、易操作等优点．     

ZnAl2O4晶体的生长基元与结晶形态

从负离子配位多面体生长基元模型出发，建立了ZnAl2O4晶体生长基元的数学模型，并通过对ZnAl2O4晶体生长基元稳定能的计算，讨论了ZnAl2O4晶体生长基元的结构，从而认为正八面体是其有利生长基元。     

稀土尖晶石ZnY2O4的软化学合成与表征

本文使用流变相反应法合成草酸盐先驱物,并通过热分解得到ZnY2O4稀土复合氧化物,使用TG,IR和XRD等分析方法研究了ZnY2O4的结构和合成机理,并通过Rietveld分析方法得到产物的结构为尖晶石相关相(图1,表1).     

Thermodynamic properties of tooeleite,Fe63+(As3+O3)4(SO4)(OH)4·4H2O

Tooeleite, nominally Fe₆³⁺(As³⁺O₃)₄(SO₄)(OH)₄·4H₂O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol⁻¹. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol⁻¹ K⁻¹. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol⁻¹. The log K_sp value, calculated for the reaction Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O + 16H⁺ = 6Fe³⁺ + 4H₃AsO₃ + SO₄²⁻ + 8H₂O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe³⁺ and As³⁺ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe²⁺ to Fe³⁺ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.     

298K时三元体系K^＋／CO3^2—,B4O7^2——H2O和Li^＋／CO3^2—,B4O7^2——H2O相关系

研究了二个三元体系Ｌｉ＋／ＣＯ２－３,Ｂ４Ｏ２－７Ｈ２Ｏ（１）和Ｋ＋／ＣＯ２－３,Ｂ４Ｏ２－７Ｈ２０（２）２９８Ｋ时的相平衡关系和平衡液相的物化性质（密度、折光密、粘度、电导率、ｐＨ值）。研究表明：这二个三元体系均属简单共饱型,无复盐或固溶体形成。体系（１）的两段溶解度曲线对应于无水Ｌｉ２ＣＯ３和Ｌｉ２Ｂ４Ｏ７·３Ｈ２Ｏ结晶区,体系（２）的两段溶解度曲线对应于Ｋ２ＣＯ３·３／２Ｈ２Ｏ和Ｋ２Ｂ４Ｏ７·４Ｈ２Ｏ结晶区。     

夏季长江口潮间带CH4、CO2和N2O通量特征

使用原位静态箱现场采样,对夏季(7月和8月)长江口崇明东滩湿地3种主要温室气体CO2、CH4和N2O的界面通量进行了同步观测.结果表明,夏季低潮滩是大气CH4的排放源(40.2 μg/(m2·h)),CO2和N2O的吸收汇(通量值分别为-86.3 mg/(m2·h),-27.6 μg/(m2·h)).7月和8月中潮滩是3种温室气体的排放源,CH4日平均排放速率达到6.56 mg/(m2·h),CO2为301 mg/(m2·h),N2O为69.9 μg/(m2·h).温度(气温和不同深度地温)、沉积物有机碳含量以及潮滩植被海三棱藨草和沉积物表层藻类的光合和呼吸是决定CH4、CO2、N2O产生、排放和吸收的主要因素.相关分析表明中潮滩气体排放通量与温度(气温和不同深度地温)呈显著正相关关系,但在低潮滩气体通量与温度的相关关系不明显.     

Hydrogen bonding in goldichite,KFe(SO4)2⋅4H2O: structure refinement

Mineralogy and Petrology - The crystal structure of goldichite KFe(SO4)2⋅4H2O was determined on a single crystal from the Baiyinchang copper deposit, Gansu, China. [P121/c1, a = 10.395(2), b...     

H2Pb2Fe4[（Te，S）O4]9·9H2O：东坪金矿的未定名碲酸盐矿物

东坪金矿是产于正长杂岩内接触带的特大型金矿床。矿石以富碲、少硫化物为特点。主要载金矿物为自然金和金、银碲化物。后包裹于黄铁矿为主的硫化物内,属于氰化法的“难溶金”,在表生条件下的氧化产物种类丰富的含金碲酸盐相中含量与自然金相当。