Mechanism and Kinetics of Thermal Dissociation of Inclusion Complex of Benzaldehyde with β-Cyclodextrin

The inclusion complex of benzaldehyde (BA) with β-cyclodextrin (β-CD) was prepared and was studied by thermal analysis and X-ray diffractometry. The composition of the complex was identified by TG and elemental analysis as β-CD·BA·9H₂O. TG and DSC studies showed that the thermal dissociation of β-CD·BA·9H₂O took place in three stages: dehydration in the range 70-120°C; dissociation of β-CD·BA in the range 235-270°C; and decomposition of β-CD above 280°C. The kinetics of dissociation of β-CD·BA in flowing dry nitrogen was studied by means of TG both at constant temperature and at linearly increasing temperature. The results showed that the dissociation of β-CD·BA was dominated by a one-dimensional random nucleation and subsequent growth process (A₂). The activation energy E was 124. 8 kJ mol^-1, and the pre-exponential factor A 5.04·10¹¹ min^-1. This revised version was published online in July 2006 with corrections to the Cover Date.     

仲碳伯胺萃淋树脂吸萃金的性能及机理

研究了仲碳伯胺（Ｎ１９２３）萃淋树脂吸萃金的机理，溶液酸效应、吸附等温线、吸附速率、盐析剂效应及柱操作条件的影响等，将该树脂用于矿样中金含量的测定，结果与７１７＾＃离子交换树脂吸附法一致，取得了较好的结果。     

OClO与OH反应机理的理论研究

用密度泛函B3LYP/-311+G~(* *)和级电子相关倒映 合簇CCSD(T)/6-311+G~(* *)方法研究了OClO与OH反应的微观机理，研究结果表明：该反应经过缔合、H转移 和离解等复杂过程，最终得到四种产物，分别为HOCl+O_2，HCl+O_3,ClO+HO_2和 HOClO_2,从能量上看，形成HOCl+O_2和HCl+O_3的通道更容易进行，而形成 ClO+HO_2的通首在动力学上是最不利的。     

Design and Theoretical Study of Nickel Catalysts for Syndiotactic Polyolefins

A nickel catalyst was nodeled with ligand L^2,[NH=CH-CH=CH-0]^-,which should have potential use as a syndiotactic plyolefin catalyst,and the reaction mechanism was studied by theoretical calculations using the density functinal method at the B3LYP/LANL2MB level.The mechanism involves the formation of the intermediate [NiL^2Me]^ ,in which the metal occupies a T-shaped geometry.This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L^2.The results show that both structures can lead to the desired product via similar reaction paths,A and B.Thus,the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-0 or trans to the Ni-N bond in the catalyst.The polymerization process thus favors the catalysis of syndiotactic polyolefins.The syndiotactic synthesis effects could also be enhanced by varations in the ligand substituents.From energy considerations,we can conclude that it is more favorable for the methyl ttrans-O position to form a complex than to occupy the trans-N position.From bond length considerations,it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position.     

添加剂对PVDF相转化过程及膜孔结构的影响

研究了PVP、PEG及LiCl 3种成孔添加剂下PVDF DMAc H2 O 添加剂体系的成膜机理 .无论那种添加剂的铸膜液相转换成膜过程中都存在凝胶分相和液液分相两种相变方式 ,在 30～ 6 0℃时凝胶分相在较低的非溶剂浓度下先于液液分相发生 ,LiCl作为添加剂较PEG、PVP对铸膜液有较强的致凝胶作用 ,成膜过程中凝胶分相段时间依PVP、PEG、LiCl的顺序延长 ,导致液液分相初始分相点处聚合物浓度增大 ,阻止了大孔结构的充分发展 .制得的膜依PVP、PEG、LiCl的顺序有效孔隙率和通量降低 ,结晶度升高 .以LiCl为添加剂制得的膜几乎不改变PVDF膜的疏水性 ,而以PVP或PEG为添加剂的膜隔水压差降低约 2 0kPa .     

THE POLYMERIZATION OF AROMATIC AND HETEROCYCLIC DINITRILES

This review is a concise survey about the works in our laboratory on the polymerization of aromatic and heterocyclic dinitriles, including the polymerization kinetics and mechanism, synthesis of heterocyclic dinitriles, the structure of polymers, and the correlation between the structures of dinitriles and polymerization rates and thermal performances of Polymers.     

改性生物凝胶对重金属离子的吸附性能研究

以桔子汁加工残渣为原料,制备钙型和氢型生物凝胶作为吸附剂,用于去除水溶液中的重金属离子.结果表明,上述凝胶在水溶液中稳定性较好,对重金属离子的吸附性能优良.钙型凝胶的吸附选择性顺序为:Fe3 ＞Pb2 ＞Cd2 ＞Zn2 ,饱和吸附容量分别为:Pb2 、Cd2 、Zn2 均为约1.1mmol/g、Fe3 为1.5mmol/g;氢型凝胶的吸附选择性顺序为:Pb2 ＞Zn2 ＞Cd2 .钙型凝胶对Fe3 的吸附行为明显不同于氢型凝胶,钙型凝胶以离子交换机理以及Fe3 与Ca2 之间的共沉淀作用为主;而氢型凝胶对Fe3 的吸附则以离子交换机理为主.     

尼龙1010非等温结晶动力学与机理研究

尼龙１０１０非等温结晶动力学与机理研究朱诚身，王经武，李卓美（郑州大学材料工程系郑州４５００５２）（中山大学高分子研究所广州５１０２７５）关键词尼龙１０１０，非等温结晶动力学，结晶机理，动力学结晶能力尼龙１０１０的结晶动力学，无论是等温还是非等温，研...     

芥子气模拟剂2-氯乙基乙基硫醚的光催化降解

利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚（2-CEES）在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S；少量小分子的羧酸、醚和砜；微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C－S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活.     

Redox behavior of V/MgO catalyst in H2S wet oxidation at room temperature

The room temperature wet catalytic oxidation was conducted in a batch reactor with V/MgO catalyst. The XRD study of the catalyst used indicated that V/MgO could not only oxidize H2S to sulfur selectively, but also prevent the sulfidation of metal oxide effectively at the room temperature. The XPS study indicated that the H2S oxidation with V/MgO could proceed by a redox mechanism (V⁵⁺↔ V⁴⁺) and that V³⁺ formation (V⁴⁺→ V³⁺), was responsible for the deactivation of V/MgO. This revised version was published online in June 2006 with corrections to the Cover Date.