盐类和温度对非离子型表面活性剂溶液粘度的影响

研究在各种盐类存在下,温度对非离子表面活性剂(OP类)溶液粘度的影响,发现相对粘度的对数值与1/T呈线性关系,从直线的斜率可得活化自由能ΔG′。由热力学关系式可计算粘性流体的活化焓ΔII′和活化熵ΔS′。用所得热力学函数对胶束型态的转化进行了讨论。     

The characterization of silica microparticles by electrophoretic mobility measurements

Summary Electrophoretic mobility measurements in the pH 2‐10 range are described for several commercial HPLC silica microparticles and a laboratory-produced product. The content of metal impurities for the silicas was also determined by AAS. An acidic/hydrothermal treatment was used to generate a more homogenous surface for some of the silicas. The zero points of charge (zpc) for both a native and a treated silica plus several commercial HPLC silicas were compared. The electrophoretic mobility method may be useful in predicting the utility of certain types of silica supports for chromatographic separations.     

聚N—异丙基丙烯酰胺溶液的温度依赖关系

用自由基聚合法合成了聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡＡＭ）样品，用乌氏粘度计考查了该聚合物的四氢呋喃（ＴＨＦ）溶液和水溶液的粘度与温度的依赖关系。发现ＰＮＩＰＡＡＭ－ＴＨＦ体系的特性粘数随温度升高而增大，ＰＮＩＰＡＡＭ－Ｈ２Ｏ体系的特性粘数－温度曲线表现出较为复杂的变化规律。并用实验确定的特性粘数对合成样品的分子量进行了表征Ｍｎ＝８．４４×１０＾５ｇ·ｍｏｌ＾－１。     

Influence of the Excited States of Atomic Nitrogen N(<Superscript>2</Superscript>D), N(<Superscript>2</Superscript>P) and N(R) on the Transport Properties of Nitrogen. Part II: Nitrogen Plasma Properties

In this paper, the calculated values of the viscosity and thermal conductivity of nitrogen plasma are presented taking into account five (e, N, N⁺, N₂ and N₂⁺) or eight (e, N(⁴S), N(²P), N(²D), N(R), N⁺, N₂ and N₂⁺) species. The calculations are based on the supposition that the temperature dependent probability of occupation of the states is given by the Boltzmann factor. The domain for which the calculations are performed, is for p = 1 and 10 atm in the temperature range from 5,000 K to 15,000 K. Classical collision integrals are used in calculating the transport coefficients and we have introduced new averaged collision integrals where the weight associated at each interacting species pair is the probable collision frequency. The influence of the collision integral values and energy transfer between two different species is studied. These results are compared which those of published theoretical studies.     

粘度法研究高分子溶液行为的实验改进(Ⅱ)

高分子在粘度计毛细管管壁上的吸附不仅会导致毛细管有效管径减小，而且可以导致毛细管界面性质发生显著改变，具体表现为测定高分子溶液流过时间t之前和之后纯溶剂的流过时间t0和t0′与高分子溶液流过时间t对浓度作图外推到浓度为零时的值t0^*并不一致。不同温度时聚乙烯吡咯烷酮（PVP）水溶液粘度测定结果表明，当吸附讷发子显著改变了毛细管界面性质时，需要将高分子溶液粘度测定方法由t/t0′改为t/t0^*。经过改进的粘度测定方法不仅更加普适合理，而且更加简单有效。     

On-line testing of gas chromatographic columns with a programmable computing integrator

Summary A program is described which calculates the number of effective plates and the coating efficiency over the entire range of a test chromatogram. The peak widths at half height are derived by assuming a Gaussian peak shape. The interpolated peak width at k=4 is used for computing a standardized number of effective plates. Plate height, column permeability, overall performance and a novel parameter called sampling efficiency are calculated from 5 other figures — i. e. carrier gas code, pressure drop, column length, column temperature and particle size.Dedicated to Dr. Leslie S. Ettre for his 60th birthday.     

Interactions between gelatin and sodium dodecyl sulphate: binding isotherm and solution properties

The interaction between sodium dodecyl sulphate (SDS) and gelatin was studied at pH 4.5 and 6.5 where the gelatin is positively charged (i.e.p. 8). At pH 4.5 a SDS/gelatin concentration range was found where gelatin precipitates. At pH 6.5 the SDS-gelatin complex remains soluble although three SDS concentration domains were distinguished where the SDS-gelatin complex had very different affinities for the solvent. Below C₁ the complex was highly surface active but other measurements (viscosity, potentiometry, protons uptake) did not reveal any particular consequence of binding. Between C₁ and C₂ the molecular size decreased (viscosity lowering) upon charge neutralization and collapse about small SDS aggregates (17 SDS molecules per gelatin molecule). Above C₂ a cooperative binding mechanism lead to the formation of SDS aggregates; the complex stretched out and turned strongly hydrophilic (the viscosity increases, low surface activity). At saturation one gelatin molecule bound about 200 SDS molecules. Above the overlap concentration (about 3 wt%) SDS aggregates formed between several gelatin molecules, the viscosity increased continuously with SDS concentration and the binding ratio was lower than in dilute gelatin solutions. A very good correspondence was found between the different analytical data including turbidity, viscosity, surface tension, protons uptake and direct potentiometric SDS binding measurements.     

New integrated measurement protocol using capillary electrophoresis instrumentation for the determination of viscosity, conductivity and absorbance of ionic liquid-molecular solvent mixtures

The low vapor pressure and the versatility of the physico-chemical properties of ionic liquids make them really attractive as an alternative for conventional molecular solvents. The knowledge of their physico-chemical properties (viscosity, conductivity, miscibility with organic solvents and anion-cation interactions) has appeared mandatory for better targeting their applications, although it is generally still lacking or incomplete.This work promotes capillary electrophoresis instrumentation as an integrated apparatus for measurement of viscosity, conductivity and absorbance of pure ionic liquids and ionic liquid-molecular solvent mixtures. Compared to current conventional techniques, the assets of this instrumentation for this purpose are the combined availability of a pressure delivery system, power supply, diode array absorbance detector and thermoregulation device, allowing unattended, automatic and easy operation, involving minimum sample handling. Most importantly, the required sample volume can be reduced to about 50 μL, making this protocol very cost-effective. A protocol was optimized with respect to time, sample consumption and data reliability for the determination of these physico-chemical parameters. Ionic liquids selected for method development and validation differed in the nature of their cation (butyl- and ethyl-methylimidazolium) and anion (trifluoromethanesulfonate and bis(trifluoromethanesulfonyl)imide). Various molecular solvents were mixed with these ionic liquids (acetonitrile, methanol, dimethylformamide and trifluoroethanol) and the same physico-chemical properties were determined by optimized methods. The knowledge of these data should be of great support in various application areas, including the development of new separation media for capillary electrophoresis and chromatographic techniques.     

Shear and NMR experiments of materials with flow behaviour depending on the deformation history

Oxide ceramic masses react to simple shearing with hardening (peptisation: increase in the shear stress with the shear deformation). In the present study the correlation between the increase in the shear stress and the porosity, agglomeration processes and the type of flow are analysed. For this purpose oxide ceramic masses are tested in a shear device especially developed for pastes and analysed by rheometric experiments, NMR methods and particle size analysis. The results support the hypothesis that structural changes (hardening, increase in the mean porosity) of the material during the peptisation mainly depend on the magnitude and not on the kind of the energy input and thus of the type of flow. The fraction of bound (more generally, the immobilised) water increases with the shear displacement. Also crushing of primary particles could be observed. Both the crushing of solid particles causing an increased solid surface and the formation of a three-dimensional gel structure are microscopic effects capable of resulting in the binding or retaining water. On a macroscopic scale these phenomena cause hardening. Magnetic resonance imaging visualises flow-induced agglomerates, which form owing to the shear flow and increase the porosity averaged over the whole sample. After the shear experiment rolls of paste can be seen which indicate that the general assumption of a plane shear flow in the shear device is not warrantable. Received: 19 July 2001 Accepted: 25 October 2001