On the Seventieth Birthday of J. Japaridze

Russian Journal of Electrochemistry -     

Electrical Double Layer at a Liquid Pb–Ga Electrode in Propylene Carbonate Solutions

Differential-capacitance curves and potentials of zero charge are obtained for a liquid Pb–Ga electrode in propylene carbonate (PC) solutions of surface-inactive electrolyte LiBF₄and 0.1 M solutions of LiBr and LiI. In PC and water, double-layer parameters of Pb–Ga differ from those of Ga. The lyophilicity of Pb–Ga in respect to PC is lower than that of Ga and coincides with that of Hg.     

High precision delta(17)O isotope measurements of oxygen from silicates and other oxides: method and applications

The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd.     

Structure of Electrical Double Layer on Liquid Pb–Ga Alloy in Aqueous Electrolytes

A new electrode, which is a liquid Pb–Ga alloy (0.06 at. % Pb), is developed and studied. It is shown that the alloy's double-layer characteristics dramatically differ from characteristics of a Ga electrode and are practically identical to characteristics of a Pb electrode. Hence, the Pb–Ga electrode in fact models electrochemical properties of a liquid Pb electrode. It is established that the metallic capacitance of the Pb–Ga electrode occupies an intermediate position between values of metallic capacitance of Ga and Hg electrodes, provided the metal–water chemisorption interaction is absent and the electrode charge is fixed. Hydrophilicity of the Pb–Ga electrode is substantially lower than hydrophilicity of a Ga electrode and coincides with hydrophilicity of an Hg electrode. It is shown that In–Ga, Cd–Ga, and Pb–Ga electrodes have close values of the electrochemical work function, and the chemisorption potential drop of the solvent in them increases in the series Pb–Ga < In–Ga < Cd–Ga with decreasing distance of closest approach of water molecules to the ionic core of the metal. The absorbability of anions at the Pb–Ga electrode increases in the series BF^– ₄= SO^2– ₄< Cl^–< Br^–< I^–.     

Electrical Double Layer Structure in Surface-Inactive Electrolytes on a Liquid Cd–Ga Electrode in Methanol and Propylene Carbonate

Differential capacitance curves and potentials of zero charge are obtained for liquid Cd–Ga electrodes in methanol and propylene carbonate solutions of a surface-inactive electrolyte. It is found that double-layer characteristics of the Cd–Ga electrode differ from those of a Ga electrode both in nonaqueous solutions and in water. The lyophilic nature of the Cd–Ga electrode, relative to methanol and propylene carbonate, is shown to approach that of the In–Ga electrode. In the absence of a metal–solvent chemisorption interaction, the difference between reciprocal metallic capacitances for Cd–Ga and Hg electrodes is independent of the solvent nature. The chemisorption interaction between the solvents and Cd–Ga, Ga, and In–Ga electrodes increases with the solvents' donor number.     

泥沙输运模拟综述——现状及其发展趋势

随着流体力学中数值方法的飞速发展,计算模型已经成为研究流体运动,泥沙输运和不同环境(诸如河流,湖泊及沿海地区)中相应污染物归趋过程等方面非常有吸引力的工具,在过去的30多年里,发展了许多计算水动力学/泥沙输运模型.文章追溯当前具有代表性的(一维、二维、三维)模型的发展历程,描述他们各自的特点,优势及局限,力图作为对模型方面感兴趣读者的第一指南,同时也为大家讨论模型的局限性,未来的发展趋势和研究需求方面搭建一个平台.给出了模型的表达,时空特性,水动力学和沉积物的耦合方式,处理非恒定流,推移质和悬移质,泥沙交换过程,泥沙类型(粘性或非粘性)及非均匀泥沙输运的能力.总结了不同模型的应用实例,读者可以运用这些例子作为研究模型设置,模型率定及模型验证的参考.给出了选择泥沙输运模型应遵循的原则,模型输入及率定方面存在的问题及改进的途径.探讨了现有水动力学/泥沙输运模型在处理复杂湍流,泥沙携带,流动与输沙耦合,非均匀泥沙,离散和扩散系数,河岸来沙处理等方面的局限性及改进的方向.最后,对基于多相流思想的泥沙输运模型及其它一些交叉性问题作了评述与展望.     

The influence of crystallographic inhomogeneity of a polycrystalline electrode surface on the behavior of the electric double-layer

The specific features of the electric double-layer structure at polycrystalline electrodes in the absence of specific ion adsorption have been examined for two different models: Model I and Model II. In the case of Model I each of the faces showing on the surface of a polycrystalline electrode retains its own Helmholtz and diffuse double layers. In the case of Model II the faces retain only their own Helmholtz layer, whereas the diffuse layer is common to the entire electrode surface. The difference of zero charge potentials of the faces is defined both by their dissimilar hydrophilic properties and by different work functions. The experimental data available at present on the electric double-layer structure at polycrystalline electrodes for which the potentials of zero charge of the faces differ significantly are described by Model I.     

同步荧光光谱法测定石油中的晕苯

用苯做溶剂对原油样品进行逐级稀释,恒波长同步荧光法对原油样品中晕苯进行定性、定量分析。分别从溶剂选择、波长差、狭缝宽度等参数对其测定的光谱条件进行优化。实验结果表明：用苯为溶剂、Δλ=6nm,狭缝宽度为2.5nm,为原油样品中晕苯的最佳测试条件。所建立方法测定晕苯的线性范围为0.5—100μg/mL,校准曲线的相关系数r大于0.99,相对标准偏差小于3%（n=5）。该法分析快速、准确,对石化工厂中对原油样品中晕苯的快速检测具有一定的应用价值。     

Interpreting early land management through compound specific stable isotope analyses of archaeological soils

Compound specific stable isotope analyses of managed soils using isotope ratio mass spectrometry have been undertaken as a means of determining early land use practices. delta (15)N amino acid signals demonstrate differences between manured grassland, unmanured grassland and continuous cereal cultivation under long-term experimental land use control conditions, with delta (15)N in hydrophobic amino acids providing the most distinctive signals. Analysis of early modern/medieval and of Bronze age anthropogenic soils from Orkney demonstrates that such signals are retained in archaeological contexts. delta (13)C analyses of n- alkanoic acid components of the fossil, Bronze Age, anthropogenic soils suggest a major terrestrial input to these soils, with uniform composition of formation materials. Surficial soils demonstrate the assimilation of isotopically lighter carbon, providing a means of assessing the mobility of the n- alkanoic acids within soils and sediments. Copyright 1999 John Wiley & Sons, Ltd.     

Uniaxial exchange flows of two Bingham fluids in a cylindrical duct

Buoyancy driven flows of two Bingham fluids in an inclined ductare considered, providing a simplified model for many oilfieldcementing processes. The flows studied are near-uniaxial andstratified, with the heavy fluid moving down the incline, displacingthe lighter fluid upwards. Existence and uniqueness resultsare obtained for quite general flows and for those which satisfyan axial flow rate constraint. Parametric dependence of thesolutions on the axial pressure gradient is studied. Flows whichsatisfy a zero net axial flow constraint result from an axialpressure gradient which minimizes the viscous dissipation, butnot the plastic dissipation. A regularization method is usedto compute solutions to these problems for (more or less) arbitraryfluid-fluid interfaces and duct-cross sections. Examples relatedto a number of practical applications are presented.