四元交互体系Li~ ,Na~ //CO_3~(2-),B_4O_7~(2-)-H_2O 298K相关系的理论预测及实验研究

采用三元体系的溶解度数据 ,运用多元线性回归法拟合了 Li2 CO3(a) ,Na2 CO3(b) ,Li2 B4O7(c)的单盐参数、溶解平衡常数及有关的混合离子作用参数 .它们的值分别为 :β(0 )a =-1 .2 3 5 5 ,β(1)a =-2 .65 46,Ca=-0 .0 0 4660 7,β(0 )b =-3 .0 3 0 6,β(1)b =-3 .0 2 3 8,Cb=-0 .2 90 89,β(0 )c =-0 .2 93 0 4,β(1)c =2 .1 5 5 6,Cc=-0 .0 0 42 5 60 ,θL i,Na=1 .0 41 8,θB,C=-2 .63 0 5 ,ΨL i,Na,C=-0 .0 63 91 ,ΨL i,Na,B=0 .493 5 6,ΨL i,B,C=-0 .47842 ,ΨNa,B,C=0 .3 0 61 6,ln K(Li2 CO3) =-8.962 9,ln K(Na2 CO3· 1 0 H2 O) =3 .0 64 6,ln K(Li2 B4O7·3 H2 O) =-7.3 5 66,ln K(Na2 B4O7· 1 0 H2 O) =-7.4778.以盐的溶解平衡常数为判据 ,运用 Pitzer方程计算了四元体系 Li ,Na //CO2 -3,B4O2 -7-H2 O 2 98K时的溶解度 ,并采用等温溶解平衡法 ,对该体系 2 98K时溶解度进行了实验测定 ,同计算值相比 ,二者基本吻合     

Li+,Na+∥CO2-3,B4O2-7-H2O四元交互体系288K的相平衡

采用等温溶解平衡法对Li+,Na+∥CO2-3,B4O2-7-H2O四元体系进行288K相平衡研究.结果表明,该体系属简单共饱型,在288K等温溶解度相图中有二个共饱点,五条单变量曲线,平衡固相为Na2CO3@10H2O,Li2B4O7@3H2O,Na2B4O7@10H2O,Li2CO3.     

Li＋,Na＋∥,CO32－,B4O72－-H2O 四元交互体系288 K的相平衡

采用等温溶解平衡法对Li＋,Na＋∥,CO32－,B4O72－-H2O四元体系进行288 K相平衡研究.结果表明,该体系属简单共饱型，在288 K等温溶解度相图中有二个共饱点，五条单变量曲线，平衡固相为Na2CO3•10H2O， Li2B4O7•3H2O，Na2B4O7•10H2O, Li2CO3.     

Li~+,Na~+∥CO_3~(2-),B_4O_7~(2-)-H_2O四元交互体系288K的相平衡

采用等温溶解平衡法对Li~+,Na~+∥CO_3~2-,B_4O_7~2--H_2O四元体系进行288K相平衡研究.结果表明,该体系属简单共饱型,在288K等温溶解度相图中有二个共饱点,五条单变量曲线,平衡固相为Na2CO3·10H2O,Li2B4O7·3H2O,Na2B4O7·10H2O,Li2CO3.     

五元体系Li+,Na+//CO32-,So42-,B4O72-H2O 288 K介稳相平衡研究

采用等温蒸发法研究五元体系Li+,Na+//CO32-,SO42-,B4O72--H2O 288 K介稳相平衡关系,测定在288 K条件下的介稳平衡溶液中各组分的溶解度和溶液密度,根据实验数据绘制相应的介稳平衡相图及密度组成图.研究结果表明该五元体系介稳相平衡中有复盐Na3Li(SO4)2·6H2O生成,其介稳相图中有4个共饱点,9条单变量曲线,6个Li2CO3饱和的结晶区分别为LiBO2·8H2O,Na284O7·10H2O,Na2CO3·10H2O,Na2SO4,Li2O4·H2O和复盐Na3Li(SO4)2·6H2O.     

四元体系Na+,K+∥CO32-,B4O72--H2O 298K相平衡研究

采用等温溶解平衡法研究了四元体系Na^ ,D^ //CO3^2-,B4O7^2--H2O 298K时的相关系,该四元体系298K时的溶解度等温图含有5个相区：Na2B4O7.10H2O,K2B4O7.4H2O,Na2CO3.10H2O,K2CO3.3/2H2O和复盐Na2CO3.K2CO3.H2O,7条单变量曲线和3个共饱点,其中NaCO3.K2CO3.H2O K2CO3.3/2H2O K2B4O7.4H2O为相称共饱点,体系中发现了一种新的复盐：Na2CO3.K2CO3.H2O,这种复盐同时存在于含Na^ ,K^ //CO3^2-H2O三元体系的其它四元或高元体系中。     

一个新的三维超分子配位聚合物[Ni(pyridine-2-carboxylate)_2]_n·2nH_2O的水热合成及晶体结构

采用水热法合成了一个新的金属-有机配位聚合物[Ni(pyridine-2-carboxylate)2]n·2nH2O,对其进行元素分析、红外光谱和X射线单晶衍射测定.结构分析表明:该晶体属于三斜晶系,P-1空间群,晶胞参数a=5.128 4(6) nm,b=7.634 6(9) nm,c=9.229 5(11) nm,α=74.902(2)°,β=84.347(2)°,γ=71.442(2)°,V=330.70(7) nm3,化学式为C12H12NiN2O6,Mr=338.95,Dc=1.702 g/cm3,μ(Mo,Kα)=1.497 mm-1,F(000)=174,Z=1,R=0.033 3,wR=0.038 4((I＞2σ(I)).并且该配合物通过O-H...O和C-H...O氢键形成了三维超分子网状结构.     

Na+, K+//Cl-, B4O2-7-H2O四元体系273 K介稳相平衡

采用等温蒸发法研究了四元体系Na+, K+//Cl-, B4O2-7-H2O 273 K时的介稳相平衡与相图. 测定了该体系273 K平衡液相中各组分的溶解度及平衡液相的密度; 绘制了该体系的介稳相图. 该四元体系273 K相图由5条溶解度单变量线、4个结晶区及2个共饱和点组成. 体系无复盐或固溶体形成. 四个结晶区分别对应单盐NaCl、KCl、K2B4O7·4H2O 和Na2B4O7·10H2O. 共饱点E1处KCl、NaCl及Na2B4O7·10H2O三盐共饱和,所对应的平衡液相组成为w(Cl-)=29.15%, w(B4O2-7)=0.64%, w(K+)=5.97%, w(Na+)=15.55%; 共饱和点E2处盐KCl、Na2B4O7·10H2O和K2B4O7·4H2O的三盐共饱和, 所对应的平衡液相组成为w(Cl-)=22.84%, w(B4O2-7)=10.98%, w(K+)=28.01%, w(Na+)=1.53%. 同体系298 K时的稳定相图相比, 273 K时硼酸钠的结晶区变大, 而硼酸钾、氯化钠结晶区变小.     

五元交互体系Li+,Na+,K+//CO2-3,Cl--H2O在298.15 K的相平衡研究

针对西藏扎布耶盐湖卤水组成, 采用等温溶解平衡法研究了五元交互体系Li+, Na+, K+// CO2-3, Cl--H2O 于298.15 K时的相平衡, 并绘制了相图(空间立体图和Li2CO3饱和的投影图). 结果表明, 该五元体系相图含有7个结晶区、 13条单变量线和4个无变量点. 7个结晶区由6个单盐结晶区和1个复盐结晶区组成, 分别为LiCl*H2O, NaCl, KCl, Li2CO3, K2CO3*3/2H2O, Na2CO3*10H2O和NaKCO3*6H2O, 没有形成固溶体和天然碱(Na2CO3*NaHCO3*2H2O). 4个无变量点标记成K1, K2, K3和K4, 所对应的平衡固相盐分别是: Li2CO3+NaKCO3*6H2O+Na2CO3*10H2O+KCl, Li2CO3+NaKCO3*6H2O+K2CO3*3/2H2O+KCl, Li2CO3+NaCl+KCl+LiCl*H2O和Li2CO3+NaCl+Na2CO3*10H2O+KCl.     

苯并18－冠－6与M2[Pt(SCN)6](M=Na,K)配合物的合成、结构

合成了苯并18－冠－6(B18C6)与M2[Pt(SCN)6](M=Na,K)的配合物：{[Na (B18C6)]6[Pt(SCN)6]}[Pt(SCN)6](SCN)2(1),[K(B18C6)]2[Pt(SCN)6]·4H2O(2). 通过元素分析、红外光谱、单晶X射线衍射进行了表征.1为单斜晶系、空间群R3^-, a=b=1.9933(3)nm,c=2.9760(6)nm,α=β=90°,γ=120°,V=10.240(3)nm^3,Z=3, Dcalcd=1.564g/cm^3,F(000)=4908,R1=0.0535,wR2=0.1030.2为三斜晶纱、空间群 P1^-,a=1.1692(3)nm,b=1.1853(4)nm,c=1.2381(5)nm,α=61.419(5)°,β=80.757 (8)°,γ=89.003(5)°,V=1.4836(9)nm^3,Z=1,Dcalcd=1.476g/cm^3,F(000)=666, R1=0.0696,wR2=0.1346.1由{[Na(B18C6)]6[Pt(SCN)6]}^4+配阳离子、[Pt(SCN)6] ^2-配阴离子和SCN^-阴离子组成。相邻{[Na(B18C6)]6[Pt(SCN)6]}^4+通过Na-O键 形成三维网状结构。[Pt(SCN)6]^2-和SCN^-仅起平衡电荷的作用.2由两个[K (B18C6)]^+配阳离子和一个[Pt(SCN)6]^2-配阴离子组成。相邻[K(B18C6)]2[Pt (SCN)6]离子对通过K－O键形成一维链状结构。     

Thermal Decomposition of CF3C(O)O2NO2, CClF2C(O)O2NO2, CCl2FC(O)O2NO2, and CCl3C(O)O2NO2

Haloacetyl, peroxynitrates are intermediates in the atmospheric degradation of a number of haloethanes. In this work, thermal decomposition rate constants of CF₃C(O)O₂NO₂, CClF₂C(O)O₂NO₂, CCl₂FC(O)O₂NO₂, and CCl₃C(O)O₂NO₂ have been determined in a temperature controlled 420 l reaction chamber. Peroxynitrates (RO₂NO₂) were prepared in situ by photolysis of RH/Cl₂/O₂/NO₂/N₂ mixtures (R = CF₃CO, CClF₂CO, CCl₂FCO, and CCl₃CO). Thermal decomposition was initiated by addition of NO, and relative RO₂NO₂ concentrations were measured as a function of time by long-path IR absorption using an FTIR spectrometer. First-order decomposition rate constants were determined at atmospheric pressure (M = N₂) as a function of temperature and, in the case of CF₃C(O)O₂NO₂ and CCl₃C(O)O₂NO₂, also as a function of total pressure. Extrapolation of the measured rate constants to the temperatures and pressures of the upper troposphere yields thermal lifetimes of several thousands of years for all of these peroxynitrates. Thus, the chloro(fluoro)acetyl peroxynitrates may play a role as temporary reservoirs of Cl, their lifetimes in the upper troposphere being limited by their (unknown) photolysis rates. Results on the thermal decomposition of CClF₂CH₂O₂NO₂ and CCl₂FCH₂O₂NO₂ are also reported, showing that the atmospheric lifetimes of these peroxynitrates are very short in the lower troposphere and increase to a maximum of several days close to the tropopause. The ratio of the rate constants for the reactions of CF₃C(O)O₂ radicals with NO₂ and NO was determined to be 0.64 ± 0.13 (2σ) at 315 K and a total pressure of 1000 mbar (M = N₂). © 1994 John Wiley & Sons, Inc.     

Fe2P2O7(H2O)2

The compound diiron diphosphate dihydrate, Fe₂P₂O₇(H₂O)₂, was synthesized hydro­thermally and crystallizes in the monoclinic space group P2₁/n. The compound has a somewhat open framework made up of edge‐sharing iron(II) octahedra that form chains connected by five bridging diphosphates. The remaining octahedral site of each iron is occupied by coordinated water. The H atoms of the water molecules all point into a common channel.     

Thermodynamics of Cr2O3, FeCr2O4, ZnCr2O4, and CoCr2O4

High-temperature heat capacity measurements were obtained for Cr₂O₃, FeCr₂O₄, ZnCr₂O₄, and CoCr₂O₄ using a differential scanning calorimeter. These data were combined with previously available, overlapping heat capacity data at temperatures up to 400 K and fitted to 5-parameter Maier–Kelley C_p(T) equations. Expressions for molar entropy were then derived by suitable integration of the Maier–Kelley equations in combination with recent S^∘(298) evaluations. Finally, a database of high-temperature equilibrium measurements on the formation of these oxides was constructed and critically evaluated. Gibbs free energies of Cr₂O₃, FeCr₂O₄, and CoCr₂O₄ were referenced by averaging the most reliable results at reference temperatures of (1100, 1400, and 1373) K, respectively, while Gibbs free energies for ZnCr₂O₄ were referenced to the results of Jacob [K.T. Jacob, Thermochim. Acta 15 (1976) 79–87] at T = 1100 K. Thermodynamic extrapolations from the high-temperature reference points to T = 298.15 K by application of the heat capacity correlations gave Δ_fG^∘(298) = (−1049.96, −1339.40, −1428.35, and −1326.75) kJ · mol⁻¹ for Cr₂O₃, FeCr₂O₄, ZnCr₂O₄, and CoCr₂O₄, respectively.     

K2[Mo2O4(C2O4)2(H2O)2]·3H2O

The crystal and molecular structure of dipotassium di‐μ‐oxo‐bis[aqua(oxalato‐O¹,O²)oxomolybdenum(III)] trihydrate, K₂­[Mo₂O₄(C₂O₄)₂(H₂O)₂]·3H₂O, has been determined from X‐ray diffraction data. In the dimeric anion, which has approximate twofold symmetry, each Mo atom is in a distorted octahedral coordination, being bonded to one terminal oxo‐O atom, two bridging O atoms, two O atoms from the oxalato ligand and one from the water mol­ecule. Bond lengths trans to the multiple‐bonded terminal oxo ligand are larger than those in the cis position, confirming the trans influence as a generally valid rule.     

Kristallstruktur von LiHC2O4-H2O

LiHC₂O₄ · H₂O crystallizes in space group P 1 with a₀ = 4.99, b₀ = 6.16, c₀ = 3.45 Å; α₀ = 96.3°, β₀ = 98.0°, γ₀ = 80.4° and Z = 1. The crystal structure has been determined by direct methods. Refinement by least squares methods resulted to R₁ = 8,3%. In the structure the oxalate group is not planar. The angle between the two O? C? O planes is 2.9°.     

Ga2O3-La2O3-Yb2O3-Er2O3(HO2O3)体系光谱性质的研究

根据稀土离子能级的特点,对Ga2O3-La2O3-Yb2O3-Er2O3(HO2O3)体系的光谱性质进行了探讨,发现它们有二类发光性质:Stokes发光和反Stokes发光,研究了发光强度和发射波长与掺杂离子的依赖关系,观察到由能量的共振转移引起的荧光浓度猝灭现象,并取得了最大发光强度时的掺杂离子浓度和一些规律性结果.     

Die sechsgliedrigen Ringsysteme PIIISi2N2O, [PVSi2N2O]⊕ und PVSi2N2O

Compounds I-X of the sixmembered ring system PSi₂N₂O with phosphorus in different oxidation and bond numbers, collected in Schema 1, have been prepared for the first time and confirmed in their structure by elemental analysis as well as by infrared and¹H- and³¹P-spectroscopy.

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Mit Auszügen aus der DissertationK. P. Giesen, Techn. Univ. Braunschweig 1972.     

Studies on the System ZnO-V2O5-Fe2O3 Reactivity of ZnFe2O4 Towards ZnV2O6

Studies on the reactivity of ZnFe₂O₄ towards ZnV₂O₆ revealed that in the solid state the phases interact in a molar ratio of 1:3 to form a new compound, to which the molecular formula Zn₂FeV₃O₁₁ was assigned. The compound melts congruently at 825±5°C. This revised version was published online in July 2006 with corrections to the Cover Date.