固相微萃取参数选择及其对有机锡分析的影响

固相微萃取是一种新型的、不断发展和完善的样品前处理方法，它与其它技术联用可对多种样品基体中挥发、半挥发性有机化合物进行测定。目前，该技术在毒性金属有机化合物中的应用很少。本文分析参数选择对固相微萃取的影响的同时，还对其在有机锡化合物分析中的应用作了综述。     

添加非金属元素Si对固体超强酸SO_4~(2-)/TiO_2的改性研究

采用共沉淀法引入Ｓｉ对ＳＯ２－４／ＴｉＯ２进行改性，制得了ＳＯ２－４／Ｔｉ－Ｓｉ－Ｏ系列固体超强酸，试样经ＩＲ、ＳＥＭ、ＸＲＤ表征和低温正戊烷异构化活性测试，发现超强酸中心是硫酸根离子与金属原子Ｔｉ结合形成的双配位螯合结构，在超强酸性的样品中ＴｉＯ２均呈锐钛矿晶型。引入Ｓｉ仅迟滞ＴｉＯ２晶化过程，控制Ｓｉ在ＳＯ２－４／Ｔｉ－Ｓｉ－Ｏ体系中的含量可以有效调节固体超强酸的酸性，并提高正戊烷异构化反应的选择性。     

Spectroscopic study of solid-state photoreaction in organic crystal: Photopolymerization of dimethyl ester of α,α′-dicyano-p-phenylenediacrylic acid and diethyl ester of p-phenylenediacrylic acid

Raman spectroscopy has been used to study solid-state photopolymerization reactions in dimethyl ester of α,α′-dicyano-p-phenylenediacrylic acid (p-CPAMe) and diethyl ester of p-phenylenediacrylic acid (p-PDAEt). The reactants and products were characterized by infrared and Raman spectroscopy. Excitation and emission spectra suggest that in p-CPAMe exciton–phonon coupling is strong, but in the other monomer it is very weak. Raman phonon spectroscopic study reveal that in both the samples the reaction mechanism is homogeneous in the initial stages. However, in the later stages the reaction becomes heterogeneous in p-PDAEt. In p-CPAMe the lattice becomes disordered with the progress of polymerization and finally becomes amorphous whereas in p-PDAEt the lattice remains highly ordered. © 1992 John Wiley & Sons, Inc.     

Grain boundary segregation diagrams of α-iron

Based on thermodynamic analysis of interfacial segregation, the segregation enthalpy H ^o of a solute I in a given matrix was found to depend linearly on two mutually independent terms reflecting the type of interface and the solid solubility limit X _infI ^sup* at temperature T and can be written as In this equation, the structural dependence of interfacial segregation is contained in H ^*() which corresponds to the extrapolated segregation enthalpy of a solute with unlimited solubility in the matrix. The product [Tln(X _infI ^sup* )] is essentially constant with temperature, and can therefore be obtained from data for maximum solid solubility, [Tln(X _infI ^sup* )]_max. The parameter v>0 represents the relationship between the activity a _infI ^sup* of a solute at the bulk solid solubility limit in a given matrix and X _infI ^sup* , a _infI ^sup* =(X _infI ^sup* ) ^v , and is characteristic for the matrix. Using recent experimental data for silicon, phosphorus, and carbon segregation at well-characterized grain boundaries in oriented bicrystals of -iron, the averaged value was determined. Values of H ^*() range from -8 kJ/mol (general grain boundaries) up to +8 kJ/mol (special grain boundaries). These values are discussed and used for a more precise and generalized construction of grain boundary segregation diagrams of -iron.     

Wet carbon-based solid acid/NaNO_3 as a mild and efficient reagent for nitration of aromatic compound under solvent free conditions

Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.     

离线超临界流体萃取和气相色谱/质谱联用对实验室内空气中气相有机污染物的测试

通过团体吸附剂富集，再用超临界ＣＯ２脱附后用气相色谱及质谱技术对实验室内空气中气相有机污染物进行了考察。文中对采样和萃取条件进行了优化，并与热脱附所得结果做了比较。结果表明在２２ＭＰａ，８０℃时，用甲醇改性的超临界ＣＯ２进行萃取的结果优于热脱附法。该法鉴定出气相有机污染物中５２个组分，占色谱峰总面积的９９．６％。     

A view and a review of the melting of alkali metal halide crystals

Summary A representational model, proposed to account for the physical changes that accompany the melting of alkali halides, was described in Part 1 [1]. The liquid is portrayed as undergoing continual dynamic structural reorganization of its constituent ions between individual small domains, zones of various regular, crystal-type arrays. These alternative arrangements are stabilized by the enthalpy of melting, which, in liquids, relaxes the restriction for solids that only the single, most stable, crystal structure can be present. The dynamic character of the melt accounts for its fluid character and the loss of long-range order [1, 2]. This model is extended here to consider the phase diagrams of binary, common ion, alkali halide mixtures comprehensively reviewed in [3]. Factors determining whether each of these yields a eutectic, or a solid solution, on cooling are discussed and several trends in the 70-phase diagrams are identified. Eutectic formation, involving maintenance of the liquid state below the melting points of the pure components, is ascribed to the participation, in an extended dynamic equilibrium, of additional domains having the regular structures characteristic of double salts. The known crystalline double binary halides [3], Li/Cs or Rb/F, Cl, Br or I, melt at temperatures well below those of the simpler pure component salts. It is concluded that the set/liq model for melting, proposed in [1, 2], accounts for some important properties of the phase diagrams presented in [3].     

H3PW12O40 and its cesium salts as pentane isomerization catalysts at ambient temperature

The activity of Mg−Al basic heterogeneous catalysts in the reactions of alcohols with ethylene oxide was studied. The kinetics of alcohol oxyethylation was examined. The kinetic equation of the reaction was determined and the structure of products was studied. The distribution coefficients of the oxyethylation reaction products were calculated. A comparison of the catalytic activity of Mg−Al hydroxides and products of their thermal treatment was made.     

The Glass Transition of Water and Aqueous Systems

After a brief introduction of the terms supercooling, amorphous solid state, glass transition and devitrification, the known ways of production of amorphous solid water are discussed. DSC experiments with quench cooled aqueous solutions show the phenomenon of glass transition and devitrification.This revised version was published online in November 2005 with corrections to the Cover Date.     

固相配位化学反应研究 L ⅩⅩⅢ.等温电导法研究醋酸锰和草酸的室温固相化学反应

本文利用等温电导法考察了醋酸锰和草酸的室温固相配位化学反应的制样方法对实验结果的影响，并获得了该反应的动力学参量。