新的聚合物支载硼氢负离子还原剂系统研究 3: 聚合物支载还原剂III

硼氢化钠的低分子还原系统研究很多,但其聚合物支载还原剂相对来说就很少,而且仅以强碱型阴离子交换树脂来制备的聚合物试剂。为了寻找用途更广泛的、新的聚合物支载还原剂,我们进行了硼氢负离子的聚合物还原系统的研究;发现能用弱酸型阳离子交换树脂制备出新的聚合物支载还原剂。前文报道了用NaBH_4的水溶液和阴离子交换树脂     

羧酸铜催化反应的研究——Ⅰ.羧酸铜催化醛肟转变为睛

本文报道了在多种羧酸铜催化下,醛肟在含有氰基的溶剂中(如CH_3CN、CH_3OCH_2CH_2CN等),均可脱水转变成相应的腈。反应条件温和,产率较高。具有不同空间和电性效应取代基的羧酸铜对反应的产率影响不大。实验中还发现溶剂乙腈参与了上述反应。     

铁(III)卟啉催化β-胡萝卜素分解动力学研究

使用BeckmannDU-8B紫外可见分光光度计研究了以氯合四－间三甲苯基卟啉铁（Ⅲ）（FeTMPCl）为催化剂，间氯过氧化苯甲酸（mCPBA）为氧化剂，咪唑（I_m）、2－甲基咪唑（MeI_m）、2－乙基－4－甲基咪唑（EMI_m）为轴向配体，催化β-胡萝卜素（β－cte）氧化分解为维生素A的动力学规律，提出了反应机理，研究了温度、催化剂浓度、氧化剂浓度及轴向配体对反应速率的影响，应用Gauss－Newton－Marquardt方法求得各基元反应的有关动力学参数．     

Kinetics and mechanism of thermal decomposition of hydroxylammonium nitrate

The kinetics of thermal decomposition of melted hydroxylammonium nitrate have been investigated by the rate of heat production in the temperature range 84.8–120.9°C. The decomposition proceeds with autocatalysis and up to 60 % of conversion the rate of the process increases proportionally to the square of the degree of decomposition. The initial rate is proportional to the square of the concentration of HNO₃ formed due to dissociation of the salt. The activation energy of this process is 15.3±1.8 kcal/mol. It is suggested that the initial stage the process proceeds via interaction between N₂O₃ and NH₃OH⁺, whereas the subsequent acceleration is due to oxidation of NH₃OH⁺ by nitrogen oxides formed as well as by nitrous acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1897–1901, November, 1993.     

碳酸盐前驱物制备Y2O3超细粉及透明陶瓷

以Y(NO3)3和NH4HCO3为原料,通过向Y(NO3)3溶液中滴加NH4HCO3的方式制备了化学组成为Y2(CO3)3·2H2O的先驱沉淀物。研究了先驱沉淀物煅烧过程中的物相变化。先驱沉淀物1100℃煅烧4h后得到了平均粒径为60nm的无团聚Y2O3超细粉体。所得粉体不添加任何添加剂,在1700℃下真空烧结4h得到了透明Y2O3陶瓷。     

Kinetic spectrophotometric determination of trace manganese (II) with dahlia violet in nonionic microemulsion medium

A new catalytic kinetic spectrophotometric method has been developed for the determination of trace amount of manganese (II) in nonionic microemulsion medium. The method is based on the catalytic effect of manganese (II) on the oxidation of dahlia violet by potassium periodate with nitrilotriacetic acid as an activitor in the presence of nonionic microemulsion. Under the optimum conditions, the calibration graph is linear in the range of 0.0004-0.0056 μg ml⁻¹ of manganese (II) at 580 nm. The detection limit achieved is 3.75×10⁻⁵ μg ml⁻¹. Manganese (II) in foodstuff samples was determined with satisfactory results.     

离子交换-双氧水氧化法制备纳米CeO2晶体

以99.995% Ce(NO₃)₃和强碱性阴离子交换树脂为原料，采用离子交换-双氧水氧化法合成制备出纳米CeO₂晶体。并就离子交换反应中的Ce³⁺浓度、树脂加入速度和离子交换温度及H₂O₂加入速度等条件对CeO₂粒径的影响进行了探讨，得出了离子交换-双氧水氧化法制备纳米CeO₂晶体的最佳工艺条件。FTIR、TEM分析表明，离子交换法无需对合成的Ce(OH)₃溶胶进行洗涤即可去除NO₃^-、CO₃^2-等阴离子杂质，并用H₂O₂将该溶胶氧化，经真空干燥可制得粒径分布均匀，平均晶粒尺寸约3 nm，高纯度的CeO₂粉体。     

Determination and fractionation of sulphur in a contaminated dredged sediment

Conversion of sulphur compounds in reduced, contaminated sediments that are brought in upland conditions may largely affect the potential mobility of heavy metal contaminants. We applied selected methods for the determination of total sulphur and sulphur fractions in a contaminated sediment in the reduced state and after gradual drying and oxidation during 1 month. Dry ashing, followed by ion chromatographic detection, was reliable for the determination of total sulphur. Good recoveries were obtained in both reference samples and spiked samples. Total sulphur was 14.5±0.6 g kg⁻¹ relative to dry sediment. Wet chemical methods that involve the determination of acid-volatile, Zn–HCl-reducible, chromium-reducible, acetone-soluble and HI-reducible sulphur were used to estimate specific sulphur forms. Results for acetone-soluble sulphur were to high and not consistent with results for other fractions. Major part of sulphur in the sediment (90%) was inorganic. Sulphides were converted partially to sulphate and to intermediary oxidised sulphur compounds upon oxidation of the sediment. The results suggested that the intermediary oxidised sulphur pool in the reduced sediment (2.5 g kg⁻¹) mainly consisted of pyrite, that was not converted during drying and oxidation. No significant changes in organic sulphur were detected.     

Copolymerization of butadiene and styrene with a gadolinium tricarboxylate catalyst

Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)₃: R = CH₃, CH₂Cl, CHCl₂, CCl₃, and CF₃], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)₃—(i—Bu)₃Al—Et₂AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)₃: CF₃ > CCl₃ > CHCl₂ > CH₂Cl ～ CH₃. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI₃)₃- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ～ 14.5 mol %) by ¹³C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)₂ and Co(acac)₃-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.     

CVD Reactions of TiCl4 with Ammonia： a Quantum Chemical Study

Based on density functional calculations, the mechanism and the energetic course of the chemical vapor deposition （CVD） reaction of TiCl4 with NH3 were studied at the level of B3LYP with 6-311g（d） basis set. Furthermore, the polymerization processes of dimerization, trimerization and tetramerization were investigated. The calculation results indicate that the formation of polymers is favored at the elimination reaction. On the basis of the calculated energetics, a possible mechanism of the reduction reaction has been proposed.