Synthesis and Structure of the New Ammonium Indium Phosphate (NH4)In(OH)PO4

A new ammonium indium phosphate (NH₄)In(OH)PO₄ was prepared by hydrothermal reaction in the In₂O₃-NH₄H₂PO₄-NH₃/OH system (T=200°C, autogenous pressure, 7 days). The formula (NH₄)In(OH)PO₄ was determined on the basis of chemical and thermal analysis (TG/DSC), X-ray powder diffraction and IR-spectroscopy. (NH₄)In(OH)PO₄ crystallizes in the tetragonal system with space group P4₃2₁2 (No. 96); a=9.4232(1) Å, c=11.1766(1) Å, V=992.45(2) ų; Z=8. The crystal structure was refined by the Rietveld method (R_w=6.35%, R_p=5.10%). The second-harmonic generation study confirmed that structure of (NH₄)In(OH)PO₄ does not have a center of symmetry. The cis-InO₄(OH)₂ octahedra form helical chains, parallel to the c-axis. The In-O-In bonds are nearly equidistant. The chains are interconnected by phosphate tetrahedra and create tunnels containing the NH₄⁺ ions along the c-axis. (NH₄)In(OH)PO₄ is isostructural with RbIn(OH)PO₄.     

两性离子流动相测定杂多酸中的磷酸根、氯离子和硫酸根

采用离子色谱法测定杂多酸中痕量阴离子。由于常规的淋洗液(如Na2CO3,NaOH)呈碱性,使杂多酸迅速分解生成磷酸根,致使测定结果偏高。实验通过在常规淋洗液中加入适量两性离子后,调节淋洗液的pH为中性,从而能准确测定杂多酸中磷酸根氯离子和硫酸根的含量值。经过比较分别用去离子水和流动相稀释的样品中磷酸根的测定结果,确定淋洗液的最佳条件为2.5mmol/LNa2CO3-9.0mmol/LCHES,在该条件下测定,快速、准确、灵敏,且有较好的灵敏度和重现性。     

磷酸酯甜菜碱两性表面活性剂的合成与性能

磷酸酯甜菜碱从皮肤溶出的氨基酸量少,脱脂低,毒性和刺激性低,易降解,是一类性能优良两性表面活性剂[1,2]。它的合成大多以长链卤烷或胺为原料,成本较高。本文以高级脂肪醇、氯乙醇以及二甲胺为原料、P2O5为磷酸化剂,合成了C12H25OCH2CH(OOCCH3)CH2N+(CH3)2CH2CH2OP(O)(O )(OH)磷酸酯甜菜碱。测定了表面张力、泡沫性能、钙皂分散力及增溶能力。1　合成十二烷基缩水甘油醚(Ⅰ)[2]　在500ml三颈烧瓶中加入月桂醇0 2mol,正已烷200ml和四丁基溴化铵0 01mol;在室温和强烈搅拌下加入50%的NaOH水溶液48g,滴加环氧氯丙烷0 4mol后升…     

冰点下降法测定正十六烷中TBP的活度系数

磷酸三正丁酯(TBP)是核燃料及多种稀有金属水冶过程中使用的重要萃取剂,Healy 等人用蒸气压法、Alcock 用溶解度法先后测定过它在一些溶剂中的活度系数,不同作者的数据分歧很大,测定的浓度范围一般也较小.高宏成等人用磷-32标记TBP 分配法在较大浓度范围内测定过TBP 在氯仿、四氯化碳、苯、正已烷等8～9种溶剂中的活度系数,     

Possible Mechanisms of Intercalation

Recent knowledge of the kinetics and intercalation mechanisms are summarized and accompanied by examples of intercalation reactions of water and ethanol into anhydrous vanadyl phosphate and redox intercalation of alkali metal cations into vanadyl phosphate dihydrate. Three possible mechanisms of intercalation are presented which are based on: (i) a concept of exfoliation of layers; (ii) the formation of stages and randomly stacked layers; (iii) co-existence of intercalated and non-intercalated parts of crystals of the host separated by an advancing phase boundary. The corresponding kinetic curves are ascribed to mechanisms (ii) and (iii).     

关于冷原子吸收法测定尿汞影响因素探讨

介绍了对尿汞快速测定法的改进，用消泡剂磷三丁酸消除尿中泡沫，并讨论了尿汞测定的最佳条件，本法的相对标准偏差为４．８－９．０％，回收率９４－１０１％。     

Preparation and Crystal Structure of Potassium Iron Hydrogen Phosphate,KFe3(HPO4)2(H2PO4)6 · 4 H2O

Single crystals of potassium iron hydrogen phosphate, KFe₃(HPO₄)₂(H₂PO₄)₆ · 4 H₂O, were prepared hydrothermally by heating a mixture of Fe₂O₃, H₃PO₄ and K₂CO₃ with a small amount of water. It crystallizes monoclinic, space group C2/c (N° 15 Int. Tab.) with Z = 4 and a = 1701(2), b = 960.4(5), c = 1750(1) pm, β = 90.88(7)°. The crystal structure was solved by using 1716 unique reflections F₀ > 4σ(F₀) with a final wR2 value of 0.126 (SHELXL-93). The main feature of the crystal structure are layers formed by PO₄-tetrahedra around the FeO₆-octahedra parallel to (001). K⁺ and H₂O molecules connect these layers. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), Charge Distribution (CHARDI) and the Madelung Part of Lattice Energy (MAPLE) are calculated for the title compound. The existence of hydrogen bonds is confirmed by these calculations.     

Zirconium-mediated conversion of homoallylic ethers into cyclopropane derivatives

Homoallylic ethers react with Cp₂ZrCl₂/2 n-BuLi reagent to afford cyclopropane derivatives. Cyclopropylcarbinyl-homoallyl rearrangements involving zirconium species are observed depending on the substrate structure.     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究 Ⅰ.B2O3含量的影响

 制备了不同B2O3含量（0～20％）的B2O3／TiO2－ZrO2固体酸催\r\n化剂，用XRD，FT－IR，N2吸附及NH3－TPD等方法测定了其结构、比表\r\n面积、孔分布和表面酸性．结果表明，当B2O3含量较低（≤5％）时，\r\n催化剂呈无定形态，样品中的B2O3主要以BO4结构存在．当B2O3含量较\r\n高（≥8％）时，催化剂中的TiO2－ZrO2以ZrTiO4晶相存在，分散于Ti\r\nO2－ZrO2表面的B2O3主要以玻璃体形式和BO3结构存在．随着B2O3含量\r\n的增加，催化剂的比表面积减小，孔径增大．300℃下的环己酮肟气相\r\nBeck－mann重排反应结果表明，随着B2O3含量的增加，己内酰胺的选择\r\n性逐渐增大，而己内酰胺的收率在B2O3含量为12％时达到最大值．讨论\r\n了B2O3／TiO2－ZrO2的催化性能与其表面酸性及孔径大小的关系．     

Crystal structure of sodium potassium zinc diphosphate NaKZnP2O7

Single crystals of NaKZnP₂O₇ were grown, and their crystal structure was determined by X-ray diffraction (space group P2₁/n, a = 12.585(5) Å, b = 7.277(5) Å, c = 7.428(5) Å, β = 90.00(5)°, Z = 4, 1916 F(hkl), R ₁ = 0.0461). The structure contains a 3D tetrahedral zinc phosphate framework with a system of intersecting channels running along the b and c axes. The sodium and potassium atoms are coordinated to six and seven oxygen atoms, respectively, and reside inside these channels; the potassium cations, which are larger than the sodium cations, are located at channel intersections.