气相色谱法研究配位化合物的热稳定性——ⅩⅢ.普鲁士蓝化合物的热分解及其加氢反应研究

普鲁士蓝化合物的热分解过程,可分为三个阶段:(1)脱水;(2)Fe³⁺还原至Fe²⁺;(3)C≡N^-键的断裂。H₂气中的热分解由于发生了一系列的加氢反应,分解产物及所对应的分解温度都不同于He气中的情况,其产物的种类增加,C≡N^-键的断裂温度降低。普鲁士蓝化合物中,CN^-呈典型的双端基配位,可看作是一种双金属配位的活化模型,与CN^-呈单端基配位的K₃[Fe(CN)₆]相比,C≡N^-键的活化程度增加,不仅断裂温度降低,且能发生更深度的加氢反应。     

A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

Some remarks on Prandtl system

The purpose of this paper is to correct some drawbacks in the proof of the well-known Boundary Layer Theory in Oleinik’s book. The Prandtl system for a nonstationary layer arising in an axially symmetric incopressible flow past a solid body is analyzed. This paper was supported by NSF of China (10571144), NSF for youth of Fujian province in China (2005J037) and NSF of Jimei University in China.     

SOURCE－TYPE SOLUTIONS OF A QUASILINEAR DEGENERATE PARABOLIC EQUATION WITH ABSORPTION

ＳＯＵＲＣＥ－ＴＹＰＥ ＳＯＬＵＴＩＯＮＳ ＯＦ Ａ ＱＵＡＳＩＬＩＮＥＡＲ ＤＥＧＥＮＥＲＡＴＥ ＰＡＲＡＢＯＬＩＣ ＥＱＵＡＴＩＯＮ ＷＩＴＨ ＡＢＳＯＲＰＴＩＯＮ￥ＺＨＡＯＪＵＮＮＩＮＧＡｂｓｔｒａｃｔ：Ｔｈｅｅｘｉｓｔｅｎｃｅａｎｄｎｏｎｅｘ...     

铈对纳米铁氧体粉末电磁学性质影响的研究

采用固相反应制备的Ce0 .2 5FeNiO3,FeNiO5,Fe3O4 ,Fe2 O34种纳米粉体 ,在 1～ 2 0 0 0MHz范围内进行了电磁学性质 (μ′,μ″ ,ε′,ε″)及吸波特性的比较研究。发现 4种纳米粉体的 μ′数据大小顺序为Ce0 .2 5FeNiO3>FeNiO5>Fe3O4 >Fe2 O3,μ″的变化幅度为Ce0 .2 5FeNiO3>Fe3O4 >FeNiO5>Fe2 O3。Ce0 .2 5FeNiO3的ε′和ε″的变化幅度大于其他几种纳米粉体。结果表明 ,加入稀土铈的铁氧体纳米粉体性能优于其他几种材料     

THE FIRST BOUNDARY VALUE PROBLEM FOR QUASILINEAR DEGENERATE PARABOLIC EQUATIONS OF SECOND ORDER IN SEVERAL SPACE VARIABLES

In this paper,we study the first boundary value problem for quasilinear equations ofthe formUnder certain conditions,the existence of generalized solutions in BV is proved by meansof the method of parabolic regularization.To do this,we need some estimates on the family{u_ε}of solutions of regularized problems and the most difficult step is to estimate|grad u_ε|L~(1+)In addition,some results on the uniqueness and stability of generalized solutions areestablished.     

Cooling curve thermal analysis,phase constitution,and solidification characteristics of cast Mg–5Gd–2Y–xNd–Zr alloys

Journal of Thermal Analysis and Calorimetry - Mg–RE alloys are high-strength magnesium alloys with great application potential. The solidification pathways and microstructure formation of...     

Uniqueness and stability of solutions for Cauchy problem of nonlinear diffusion equations

The uniqueness of solutions for Cauchy problem of the form $$\frac{{\partial u}}{{\partial t}} = \Delta A(u) + \sum\limits_{i = 1}^N {\frac{{\partial b^i (u)}}{{\partial x_i }} + c(u)} $$ is studied. It is proved that ifu ∈BVx and A(u) is strictly increasing, the solution is unique.     

A New Clathrate: Synthesis and Crystal Structure of the [36]ene-O6N8/THF (1:2) Clathrate

A new clathrate inclusion compound of 2,3:11,12:20,21:29,30-tetrabenzo-1,13,16,19,31,34-hexaoxa-5,6,8,9,23,24,26,27- octaaza-7,25-dithioketone-2,3:4,5:9,10:11,12:22,23:27,28:29,30-cyclo-[36]ene([ 36]eneO₆N₈), which contains THF, has been prepared and crystallizes in the monoclinic space group P2₁/n with a = 9.829(5)Å, b = 24.23(1)Å, c = 10.181(9)Å, = 92.93(5)-. Each unit cell contains two [36]ene-O₆N₈ molecules and four THF molecules. The [36]ene-O₆N₈ molecule lies on the crystallographic centre of symmetry and a pair of the THF molecules with half-chair conformation are located within rectangular channels formed by the macrocycle molecules.     

Selective Encapsulation and Chiral Induction of C60 and C70 Fullerenes by Axially Chiral Porous Aromatic Cages

Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host–guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R- PAC-2 , S- PAC-2 (with Br substituents) and R- PAC-3 , S- PAC-3 (with CH₃ substituents) enantiomers. PAC-2 , rather than PAC-3 , achieves fullerene encapsulation and selective binding of C₇₀ over C₆₀ in fullerene carbon soot. More significantly, the occurrence of chiral induction between R- PAC-2 , S- PAC-2 and fullerenes is confirmed by single-crystal X-ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face-to-face arene-fullerene interactions dominate C₇₀ selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene.