Aromaticity in Group 14 homologues of the cyclopropenylium cation

The nature of the bonding and the aromaticity of the heavy Group 14 homologues of cyclopropenylium cations E₃H₃⁺ and E₂H₂E′H⁺ (E, E′=C–Pb) have been investigated systematically at the BP86/TZ2P DFT level by using several methods. Aromatic stabilization energies (ASE) were evaluated from the values obtained from energy decomposition analysis (EDA) of charged acyclic reference molecules. The EDA‐ASE results compare well with the extra cyclic resonance energy (ECRE) values given by the block localized wavefunction (BLW) method. Although all compounds investigated are Hückel 4n+2 π electron species, their ASEs indicate that the inclusion of Group 14 elements heavier than carbon reduces the aromaticity; the parent C₃H₃⁺ ion and Si₂H₂CH⁺ are the most aromatic, and Pb₃H₃⁺ is the least so. The higher energies for the cyclopropenium analogues reported in 1995 employed an isodesmic scheme, and are reinterpreted by using the BLW method. The decrease in the strength of both the π cyclic conjugation and the aromaticity in the order C?Si>Ge>Sn>Pb agrees reasonably well with the trends given by the refined nucleus‐independent chemical shift NICS(0)_πzz index.     

A facile "dispersion-decomposition" route to metal sulfide nanocrystals

In this paper, we demonstrate a simple and general "dispersion-decomposition" approach to the synthesis of metal sulfide nanocrystals with the assistance of alkylthiol. This is a direct heating process without precursor injection. By using inorganic metal salts and alkylthiol as the raw materials, high-quality Ag(2)S, Cu(2)S, PbS, Ni(3)S(4), CdS, and ZnS nanocrystals were successfully synthesized. The mechanism study shows that the reaction undergoes two steps. A key intermediate compound, metal thiolate, is generated first. It melts and disperses into the solvent at a relatively low temperature, and then it decomposes into metal sulfide as a single precursor upon heating. This method avoids using toxic phosphine agent and injection during the reaction process. The size and shape of the nanocrystal can be also controlled by the concentration of the reactant and ligands. Furthermore, the optical properties and assembly of the nanocrystals have also been studied. This report provides a facile, direct-heating "dispersion-decomposition" approach to synthesize metal sulfides nanocrystals that has potential for future large-scale synthesis.     

超级铝热剂Al/CuO前驱体的制备、表征、热分解机理及非等温分解反应动力学

以硝酸铜、无水乙醇、1,2-环氧丙烷和纳米铝粉为原料, 在超声振荡条件下, 采用溶胶-凝胶法制备了纳米复合含能材料——超级铝热剂Al/CuO的前驱体. 利用热重-差示扫描量热-傅里叶变换红外-质谱(TG- DSC-FTIR-MS)联用技术, 研究了纳米Al/CuO溶胶-凝胶前驱体的热行为和分解过程及机理. 利用不同升温速率下的TG-DTG分析, 研究了纳米超级铝热剂Al/CuO的溶胶-凝胶前驱体的热分解反应机理, 采用了6种动力学分析方法进行动力学参数计算, 得到前驱体分解反应的表观活化能、反应级数、频率因子等动力学参数, 纳米Al/CuO前驱体分解反应的动力学方程为: dα/dt=10^14.0×4α^3/4exp(-2.0×10⁴/T).     

High temperature normal phase liquid chromatography of aromatic hydrocarbons on bare zirconia

The normal phase HPLC behavior of a bare zirconia column was studied at temperatures up to 200 °C using a hexane mobile phase. The use of elevated column temperatures significantly decreased the retention of twenty five aromatic model compounds according to the van't Hoff equation (>30-fold decrease for some compounds). Large improvements in peak shape, efficiency (>2.2-fold), aromatic group-type selectivity, and column re-equilibration times (>5-fold) were obtained at elevated temperatures. The thermal decomposition of two polar nitrogen compounds (indole and carbazole) was observed in a hexane/dichloromethane mobile phase at temperatures greater than 100 °C. The first order decomposition of carbazole was studied in further detail.     

Thermal Decomposition Kinetics of Some Di‐ and Triorganotin(IV) Carboxylates Derived from para‐Nitrophenylethanoic Acid

Thermogravimetric (TG) investigations of organotin(IV) carboxylates with the general formula R_mSnL_4−m (where R=CH₃, C₂H₅, n‐C₄H₉, C₆H₅, cyclo‐C₆H₁₁, n‐C₈H₁₇, m=2, 3, and L=para‐nitrophenylethanoate anion) have been performed. Derivative thermogravimetry (DTG) and differential thermal analysis (DTA) techniques, Horowitz‐Metzger method and the fundamental thermodynamic relations are used to evaluate the thermokinetic parameters of each thermal degradation pattern. Results reveal that the thermal stability is functional to Sn C and Sn O bonds. In the case of R₂SnL₂, activation energy, reaction order and pre‐exponential factor associated with the bulk degradation processes increase as the alkane chain length increases. Hence, Oct₂SnL₂ is thermally more stable than Bu₂SnL₂, which in turn is more resistant to thermal dissociation than Et₂SnL₂. The same phenomenon is not observed for R₃SnL compounds because their degradation is highly irregular. Furthermore, R₂SnL₂ has larger values of kinetic parameters than those of corresponding triorganotin(IV) para‐nitrophenylethanotes. Thermodynamic parameters of these compounds also reinforce the above facts.     

Preparation,Characterization and Non‐isothermal Kinetics of the Dehydration Process of [Sm(p‐MOBA)3bath]2·4H2O

The new complex of [Sm(p‐MOBA)₃bath]₂·4H₂O (p‐MOBA, p‐methoxybenzoate; bath, 4,7‐diphenyl‐1,10‐phenanthroline) was synthesized and characterized by elemental analysis, molar conductance, IR, UV and XRD patterns. The thermal decomposition of the complex was studied under the non‐isothermal condition by TG‐DTG and IR techniques. The most probable mechanism function of the dehydration process was obtained from the analysis of DSC curves of the complex employing the double extrapolated method on the basis of integral isoconversional non‐linear (NL‐INT) and Tang‐Wanjun integral equations. The integral function of the mechanism was [1? (1?α)^1/2]^1/2 and the corresponding kinetic parameters (activation energy E and the pre‐exponential factor A) were obtained.     

A novel method to prepare metal oxide electrode:Spin-coating with thermal decomposition

In this work,we propose a new spin-coating method coupling with high thermal decomposition,to prepare the tin-antimony(Sn-Sb) oxide electrode.The character of the spin-coating electrode was compared with the dip-coating electrode through X-ray diffraction(XRD),scanning electron microscopy(SEM),accelerated life test,cyclic voltammetry,and electrolytic degradability. The results showed that the spin-coating electrode had a better defined crystal form,a smoother and more compact surface than that of the dip-coating electrode.Service time of the spin-coating electrode was determined to be longer than 15 h,and it was less than 2 min for the dip-coating electrode.Electrochemical characterization analysis showed that the electrolytic degradability of the spin-coating electrode is better than that of the dip-coating electrode.     

[Cu2(C2O4)(C12H8N2)2(C3H7NO)2](ClO4)2配合物的合成及其热分解

以邻菲罗啉、2,5二羟基-1,4-二噻烷和Cu(ClO4)2.6H2O为原料,合成了中心对称的双核配合物[Cu2(C2O4)(C12H,N2)2(C3 H7NO)2](ClO4)2(1).通过红外光谱、元素分析等分析测试手段对其进行了表征;借助TG-DTG技术在氮气气氛下研究了配合物的热分解情况,并根据热分析结果确定了...     

热红联用研究催化剂对PDADN-RDX改性双基推进剂热分解的影响

利用PDSC、TG和DSC -FTIR联用技术和加热裂解原位池红外技术研究了两种燃速催化剂对PDADN -RDX - CMDB推进剂热分解的影响,结果表明,推进剂的热行为有很大改变:分解温度降低、分解热增大、分解放热速率提高,主要组分的标志性官能团提前消失,主要气体产物提前出现,具有负生成热的气体放出量明显增加.初步阐...     

Cholesky decomposition of a positive semidefinite matrix with known kernel

The Cholesky decomposition of a symmetric positive semidefinite matrix A is a useful tool for solving the related consistent system of linear equations or evaluating the action of a generalized inverse, especially when A is relatively large and sparse. To use the Cholesky decomposition effectively, it is necessary to identify reliably the positions of zero rows or columns of the factors and to choose these positions so that the nonsingular submatrix of A of the maximal rank is reasonably conditioned. The point of this note is to show how to exploit information about the kernel of A to accomplish both tasks. The results are illustrated by numerical experiments.