芒硝与氯化钾生产硫酸钾的工艺研究

本文根据Ｋ＋，Ｎａ＋‖Ｃｌ￣－，ＳＯ－Ｈ＿２Ｏ四元相图，在对硫酸钠与氯化钾复分解反应进行分析及理论计算的基础上，提出闭合循环的二步法生产硫酸钾工艺流程。一段转化母液直接蒸发回收副产品氯化钠，无废物排出。根据所拟流程，进行了实验室试验，得到满意的结果     

Production of Potash and N-Mg Compound Fertilizer via Mineral Shoenite from Kunteyi Salt Lake: Phase Diagrams of Quaternary System(NH_4)_2SO_4-Mg SO_4-K_2SO_4-H_2O in the Isothermal Evaporation and Crystallization Process

Based on the requirement of the new technology for producing potassium sulfate and N-Mg compound fertilizer,boussingaultite,by the reaction of the mineral shoenite from Kunteyi Salt Lake,Qinghai province,and the industrial byproduct ammonium sulfate,the solubilities of the quaternary system (NH_4)_2SO_4-Mg SO_4-K_2SO_4-H_2O at 25.0oC in the isothermal evaporation and crystallization process were measured using the isothermal evaporation method,and the corresponding phase diagrams were plotted.According to the diagram,this system contains six saturation points and six solid phase fields of crystallization,which correspond to (K_(1-m),(NH_4)_m)_2SO_4,(NH_4)_2SO_4·Mg SO_4·6H_2O,K_2SO_4·Mg SO_4·6H_2O,Mg SO_4·6H_2O,(K_(1-n),(NH_4)_n)_2SO_4·Mg SO_4·6H_2O and Mg SO_4·7H_2O,respectively.By analyzing and calculating the isothermal evaporation and dissolution phase diagram of this quaternary system at 25.0oC,K_2SO_4 and (NH_4)_2SO_4·Mg SO_4·6H_2O can be separated via K_2SO_4·Mg SO_4·6H_2O and (NH_4)_2SO_4 as raw materials.Theoretical calculations about the proposed process were carried out and verified by experiment,which indicated that the yield of potassium sulfate was improved and the magnesium resources were fully utilized.     

Fe2+-Ti4+ charge transfer in stoichiometric Fe2+,Ti4+-minerals

Optical absorption spectra are presented for taramellite, traskite and neptunite, all of which have both Fe²⁺ and Ti⁴⁺ as major elements. The spectra of each of these minerals are dominated by a single, intense absorption band in the 415 to 460 nm region with 7000 to 9000 cm^?1 halfwidth. These transitions, assigned to Fe²⁺-Ti⁴⁺ intervalence charge transfer, showed little difference in intensity at 80 and 300 K and have molar absorptivities which range from ～100 to ～1300 M^?1 cm^?1. The Fe²⁺-Ti⁴⁺ absorptions in these standards generally compare well to other mineral spectra in which Fe²⁺ — Ti⁴⁺ intervalence absorption has previously been proposed with the exception of the most cited example, blue corundum.     

催化动力学光度法测定痕量金的研究

研究了在稀Ｈ２ＳＯ４介质中，痕量Ａｕ（Ⅲ）催化ＫＢｒＯ３     

Crystallization Kinetics of Potassium Sulphate in Aqueous System Mg~(2+),K~+//Cl,SO_4~(2-)-H_2O

正As an excellent chemical fertilizer,Potassium Sulphate(K2SO4)could provide both potassium and sulfur elements for crops.However,it is well known that potassium resource is very poor in China.To understand the Crystallization Kinetics(CK)of K2SO4could be conducive to utilize the limited potassium resource,promote the yield and purity of K2SO4.In this study saturated solution of potassium sulphate was prepared according to the phase diagram of Mg2+、     

Studies on the spin Hamiltonian parameters and local structure for Rh4+ and Ir4+ in TiO2

The spin Hamiltonian (SH) parameters (g factors g _x , g _y and g _z and the hyperfine structure constants A _x , A _y and A _z ) and local structure for the rhombic Rh⁴⁺ and Ir⁴⁺ centers in TiO₂ (rutile) are theoretically studied from the perturbation formulas of these parameters for a low spin (S = 1/2) d ⁵ ion under rhombically distorted octahedra. In the calculations, the ligand orbital and spin–orbit coupling contributions as well as the influence of the local lattice distortions are taken into account using the cluster approach. The local axial elongation ratios are found to be about 1.7 and 3 times, respectively, larger for the Rh⁴⁺ and Ir⁴⁺ centers than that (≈0.0075) for the host Ti⁴⁺ site in rutile, while the perpendicular distortion angles (≈−0.28° and −0.42°, respectively) are more than one order in magnitude smaller than the host value (≈−9.12°). This means that the impurity centers exhibit further elongations of the oxygen octahedra and much smaller perpendicular rhombic distortions as compared with those of the host Ti⁴⁺ site in TiO₂. The above local lattice distortions can be mainly ascribed to the substitution of the host Ti⁴⁺ by the nd ⁵ impurities, which may induce different physical and chemical properties for the metal–ligand clusters. In addition, the influence of the Jahn–Teller effect on the local structure may not be completely excluded. The calculated SH parameters show reasonable agreement with the observed values.     

娘子关泉域岩溶地下水SO_4~(2-),Ca~(2+),Mg~(2+)污染分析

分析了娘子关泉域岩溶地下水ＳＯ２－４,Ｃａ２＋,Ｍｇ２＋等组分含量增多的原因,并定量地探讨了ＳＯ２－４,Ｃａ２＋,Ｍｇ２＋的各种来源比例。研究表明,含水层中石膏溶解及硫化物氧化是造成ＳＯ２－４,Ｃａ２＋,Ｍｇ２＋高含量的主要原因,控制硫化物氧化水进入含水层,对水质改良有显著效果。     

The reaction MgCr2O4 + SiO2 = Cr2O3 + MgSiO3 and the free energy of formation of magnesiochromite (MgCr2O4)

Low-temperature heat capacity measurements for MgCr₂O₄ have only been performed down to 52 K, and the commonly quoted third-law entropy at 298 K (106 J K⁻¹ mol⁻¹) was obtained by empirical extrapolation of these measurements to 0 K without considering the magnetic or electronic ordering contributions to the entropy. Subsequent magnetic measurements at low temperature reveal that the Néel temperature, at which magnetic ordering of the Cr³⁺ ions in MgCr₂O₄ occurs, is at ∼15 K. Hence a substantial contribution to the entropy of MgCr₂O₄ has been missed. We have determined the position of the near-univariant reaction MgCr₂O₄+SiO₂=MgSiO₃+Cr₂O₃. The reaction, which has a small positive slope in P-T space, has been bracketed at 100 K intervals between 1273 and 1773 K by reversal experiments. The reaction is extremely sluggish, and lengthy run times with a flux (H₂O, BaO-B₂O₃ or K₂O-B₂O₃) are needed to produce tight reversal brackets. The results, combined with assessed thermodynamic data for Cr₂O₃, MgSiO₃ and SiO₂, give the entropy and enthalpy of formation of MgCr₂O₄ spinel. As expected, our experimental results are not in good agreement with the presently available thermodynamic data. We obtain Δ _f H ^∘ ₂₉₈=−1759.2±1.5 kJ mol⁻¹ and S ^∘ ₂₉₈=122.1±1.0 J K⁻¹ mol⁻¹ for MgCr₂O₄. This entropy is some 16 J K⁻¹ mol⁻¹ more than the calorimetrically determined value, and implies a value for the magnetic entropy of MgCr₂O₄ consistent with an effective spin quantum number (S') for Cr³⁺ of 1/2 rather than the theoretical 3/2, indicating, as in other spinels, spin quenching. Received: 9 May 1997 / Accepted: 28 July 1997     

交互四元体系Li~+,Mg~(2+)//SO_4~(2-),B_4O_7~(2-)-H_2O 288K时相平衡研究

采用等温溶解平衡法研究了288K时Li+,Mg2+//SO42-,B4O72--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+//SO42-,B4O27--H2O288K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。     

离子色谱法同时测定地质样品中氟氯磷硫

本文研究了离子色谱同时测定地质样品中F~-、Cl~-、PO_4~(3-)、SO_4~(2-)的前处理过程,选择了色谱测定最佳条件。在Na_2CO_3全熔的样品溶液中,加入(NH_4)_2CO_3使Si、Al随大多数金属离子同时沉淀;再用预处理柱除去熔剂引入的大量Na~+及CO_3~(2-)消除其干扰;并在流出液中补加相应试剂与淋洗液相匹配,实现了多种地质样品中F~-、Cl~-、PO_4~(3-)和SO_4~(2-)的测定。方法检出限(3s,μg/ml)分别为F~-0.05、Cl~-0.1、PO_4~(3-)0.3、SO_4~(2-)0.5。测定范围为F~-0.05—3μg/ml,Cl~-0.1—6μg/ml,PO_4~(3-)0.3 —30μg/ml,SO_4~(2-)0.5—30μg/ml。     

垃圾渗滤液污染场地NO_3~-、PO_4~(3-)和SO_4~(2-)对微生物活性的影响

通过实验研究垃圾渗滤液污染场地N、S、P和湿度等因素对微生物活性的影响.结果表明：同时添加N和P后,土壤和细砂中微生物活性分别在第7 天和第14 天达到最大值0.685和0.588,有机质质量分数分别降低了10.97%和22.1%,平均降解速率分别为0.405和0.190 mg/(kg·d);添加NO_3~-后,土壤和细砂中有机质质量分数分别减少了10.3%和28.9%;添加SO_4~(2-)后,土壤和细砂中有机质质量分数分别减少了8.87%和28.4%;另外,湿度为50%和60%时,土壤中微生物活性的最大值分别为0.259和0.266,有机质平均分解速率分别为0.195和0.305 mg/(kg·d).因此,N、S、P和湿度对地下环境中微生物的活性有重要影响.     

NH_4~+型斜发沸石对Zn~(2+)和Ag~+两种抗菌离子的离子交换热力学研究

通过液相离子交换试验研究了Zn2+和Ag+两种抗菌金属离子与NH4+型斜发沸石离子交换的热力学特征,绘制了Zn2+和Ag+的离子交换等温线,计算了不同条件下达到离子交换平衡时,NH4+型斜发沸石对Zn2+和Ag+的选择性校正系数Kc和交换平衡常数Ka,得出了ln Ka值与1/T之间的线性关系,导出了反应标准摩尔焓变(ΔrHθm)、反应标准摩尔Gibbs自由能变(ΔrGθm)和反应标准摩尔熵变(ΔrSθm)。结果表明:达到离子交换平衡时,NH4+型斜发沸石对Zn2+和Ag+的最大交换度分别为0.668和0.856,ΔrHθm分别为7.165 k J/mol和5.276 k J/mol,ΔrGθm0,ΔrSθm0,即该过程是吸热和熵增加反应,并且该反应在20℃能自动发生,升高温度有利于NH4+型斜发沸石交换Zn2+和Ag+;在相同条件下,NH4+型斜发沸石对Ag+的离子交换能力大于Zn2+。     

Die Kristallstruktur des Voltaits,K2Fe 5 2+ Fe 3 3+ Al[SO4]12·18H2O

Zusammenfassung Die Kristallstruktur von künstlichem Voltait, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂· ·18 H₂O, kubisch hexakisoktaedrisch,Fd3c–O _h ⁸,a ₀=27,254 ,Z-16, wurde mittels photographischer Röntgendaten bestimmt. Die Aufklärung der Struktur erfolgte mit Patterson- und Fouriermethoden unter Zuhilfenahme des multiplen isomorphen Ersatzes. Die Verfeinerung nach der Methode der kleinsten Quadrate ergab mit anisotropen Temperaturfaktoren für 726 beobachteteF _hkl R=0,033. Das Hauptmerkmal der Struktur ist ein 3dimensionales Gerüst aus [Fe³⁺O₆]-Oktaedern, [Fe ₅ ^6/2+ Fe ₁ ^6/3+ O₄(H₂O)₂]-Oktaedern und [K⁺O₁₂]-Polyedern, die durch SO₄-Tetraeder verknüpft werden. Hohlräume dieses Gerüstes werden von ungeordnet orientierten [Al(H₂O)₆]-Oktaedern eingenommen. Es wird gezeigt, daß Al als wesentlicher Bestandteil dieses Voltaits angesehen werden muß.

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The crystal structure of voltaite, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂·18H₂O

Summary The crystal structure of synthetic voltaite, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂· · 18 H₂O, cubic hexakis-octahedral, space groupFd3c–O _h ⁸,a ₀=27.254 ,Z=16, was determined from photographic X-ray data. The structure was solved by Patterson and Fourier-methods with the aid of multiple isomorphic substitution. Least squares refinement with anisotropic temperature factors resulted inR=0.033 for 726 observedF _hkl . The dominant structural feature is a continous framework composed of [Fe³⁺O₆]-octahedra, [Fe ₅ ^6/2+ Fe ₁ ^6/3+ O₄(H₂O)₂]-octahedra and [K⁺O₁₂]-polyhedra linked by SO₄-tetrahedra. The arrangement gives rise to cages occupied by disordered [Al(H₂O)₆]-octahedra. It is shown that Al must be considered to be a essential constituent of such voltaites.

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Mit 2 Abbildungen     

57Fe Mössbauer study on compositions of the series Fe3+TaO4-Fe2+Ta2O6

Fe⁵⁷ Mössbauer spectra were measured on compositions of the series Fe_1?x/3Ta_1+x/3O₄, 0≤x≤1. The spectra are characterized by mixed valencies of Fe²⁺ and Fe³⁺ ions for 0<x<1. Starting from x=0 with rutile structure, a trirutile structure forms towards x=1. Quadrupole splitting QS of Fe³⁺ is QS(Fe³⁺)≈0.55 mm/s and isomer shift IS is IS(Fe³⁺)≈0.40 mm/s (referred to Fe); both quantities exhibit minor variations along the series. The Fe²⁺ subspectra for x>0.5 were fitted using one symmetrical doublet; however, for x<0.5 two symmetrical doublets were necessary to describe these patterns. QS(Fe²⁺)=2.0–3.2 mm/s and IS(Fe²⁺)=0.90–1.15 mm/s for all compositions. In the case x<0.5, marked temperature dependent QS values appear to exist. This feature may be related to short range order effects and possibly also in part to intervalence electron transfer betwee Fe²⁺ and Fe³⁺ ions.     

Phase Equilibrium and Phase Diagram of the Ternary System(MgCl_2 + MgB_2O_4 + H_2O) at 288 and 298 K

正1 Introduction The brines with high concentrations of magnesium and boron resources are widely distributed in the Qaidam Basin of the Qinghai-Tibet plateau,China(ZhengTang,1988).Although some works on the ternary system     

Die Reaktion Phlogopit + Calcit + Quarz = Tremolit + Kalifeldspat + H2O + C2O

Hydrothermal experiments with mixtures of synthetic minerals have shown the reversibility of the reaction 5 phlogopite + 6 calcite + 24 quartz = 3 tremolite + 5 K-feldspar + 2 H₂O + 6 CO₂. In an isobaric T – diagram the equilibrium curve reaches a maximum at = 0,75. The P, T-values for this maximum are: 2 kb-523°; 4 kb-585°; 6 kb-625°; P±5%, T±10° C. These results give a first approximation of the P, T conditions responsible for a similar mineral reaction which has been recorded from natural metamorphic assemblages.

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Herrn Prof. H. G. F. Winkler danke ich für anregende Diskussionen, desgleichen Herrn Dr. D. Puhan für wichtige Hinweise und Mitteilung seiner exp. Daten. Herrn Prof. V. Trommsdorff und Herrn P. H. Thompson bin ich für petrographische Angaben zu Dank verpflichtet. Der Aufbau der Hydrothermalanlage und die Finanzierung der laufenden Untersuchungen wurde aus den Mitteln des Fonds zur Förderung der wissenschaftlichen Forschung ermöglicht. Für diese Unterstützung gilt daher mein besonderer Dank.     

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.     

Polarized electronic absorption spectra of Co2+ ions in the kieserite-type compounds CoSO4 · H2O and CoSeO4 · H2O

Polarized electronic absorption spectra of the kieserite-type compounds CoSO₄ · H₂O and CoSeO₄ · H₂O have been obtained at room temperature (spectral range 35 000-5000 cm^-1) and at liquid nitrogen temperature (visible spectral region), using microscope-spectrometric techniques. The spectra are interpreted and evaluated in terms of a tetragonal crystal field formalism for the d⁷ configuration, in regard to the pseudotetragonal elongation of the CoO₄(H₂O)₂ octahedra, known from previous X-ray structure investigations, employing the tetragonal parameters Dq, Dt, and Ds, and the Racah parameters B and C. The observed and calculated energy levels are in good agreement for the following parameter sets: CoSO₄ · H₂O: Dq=826, Dt=40, Ds=350, B=856, C=3580 cm^-1; CoSeO₄· H₂O: Dq=817, Dt=44, Ds=406, B=841, C=3490 cm^-1; corresponding ‘cubic’ crystal field strengths Dq_cub are 803 and 792 cm^-1, respectively. The values of Dq_(cub), Racah B and C are in the common range for Co²⁺ ions in (pseudo) octahedral fields of oxygen ligands, and their differences in CoSO₄· H₂O compared to CoSeO₄ · H₂O are consistent with somewhat different mean Co-O bond lengths and with a slightly higher covalent contribution to Co-O bonding in the selenate compound. The values found for the parameter Dt, which is directly correlated to the extent of tetragonal distortion, are much lower than expected from purely geometrical considerations, thus confirming a significantly higher position of H₂O ligands in the spectrochemical series compared to oxygen ligands belonging to SO₄ or SeO₄ groups.     

Experiments on the phase transition calcite+wollastonite+ +epidote=grossular-andraditess+CO2+H2O

The reaction 2 epidote+2 calcite+3 wollastonite3 grossular-andradite_ss+ 2 CO₂+1 H₂O has been explored by hydrothermal experiments at a total fluid pressure of 1000 bars. For a grossular-andradite_ss of andradite ₂₅ composition, the isobaric univariant curve passes through the points 458°C: X_CO2=0.00; 521°C: X_CO2=0.026; 523°C: X_CO2=0.052; 526°C: 0.088; 528°C: X_CO2=0.104. This curve intersects the isobaric univariant curve of the reaction calcite+quartz+[H₂O] wollastonite+CO₂+[H₂O] at the isobaric invariant point around 528°C and X_CO2=0.12. At higher values of X_CO2, this reaction is replaced by another one, namely: 2 epidote+5 calcite+3 quartz3 grossular-andradite_ss+5 CO₂+ 1 H₂O. It is demonstrated that both the reactions do actually take place during the metamorphism of calcareous rocks. The petrologic significance of contrasted sequence of reactions within this system observed by various workers is also discussed.     

东海陆架近岸区SO42-扩散通量的初步研究

研究化学物质的扩散通量对于了解沉积物和上覆水体之间物质的迁移、交换及其量的动态关系是很重要的。这方面的工作大体说来是从七十年代开始的东海陆架测区地处长江口外,地形比较开放,海底多属泥质或泥质粉砂区,部分地区下伏有残留砂,因此底质多样,且其中还居留着底栖动物,尤以多毛类为主。由于它们的活动可能对SO₄=通量有制约性的影响。为了研究陆架测区SO₄=通量的扩散移动特点及其量的各种关系本文依据SO₄=通量有制约性的影响。