Electrochemical studies of Tl(I) crown-ether complexes in nonaqueous media

Summary Complexation equilibria of the Tl(I) ion with 18-crown-6 and dibenzo-18-crown-6 were studied polarographically in 10 nonaqueous solvents. The stability of the complexes is strongly influenced by the nature of solvents and varies with their Lewis basicities. It has been found that the logK _s value (K _s is the stability constant of the complex) can be well described by empirical relation logK _s=a DN+b, whereDN stands for the Gutmann donor number anda andb mark the regression coefficient. Addition of the second explanatory parameter, the acceptor number, is not statistically significant. This result is in agreement with the predominant role of Tl(I) ion solvation.

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Elektrochemische Untersuchungen von Tl(I)-Kronenetherkomplexen in nichtwäßrigen Medien

Zusammenfassung Es wurden die Komplexierungsgleichgewichte des Tl(I)-Ions mit 18-Krone-6 und Dibenzo-18-krone-6 polarographisch in 10 nichtwäßrigen Lösungsmitteln untersucht. Die Stabilität der Komplexe wird sehr stark vom Solvens beeinflußt, wobei eine starke Abhängigkeit von der Lewis-Basizität beobachtet wird. Es wurde festgestellt, daß die logK _s-Werte (K _s ist die Komplexstabilitätskonstante) gut mit der empirischen Beziehung logK _s=a DN+b beschrieben werden können, wobeiDN die Gutmann'sche Donorzahl unda undb die Regressionskonstanten bedeuten. Hinzunahme der Akzeptorzahl als zweiten Parameter bleibt statistisch insignifikant. Dieses Ergebnis stimmt mit dem dominierenden Einfluß der Tl(I)-Ionensolvatation überein.

     

Chemical modification of silica surface by immobilization of functional groups for extractive concentration of metal ions

Increased utilization of mechanically stable synthetic matrices particularly silica gel as a solid support and its surface modification either by impregnation of organic ligands directly or covalent grafting through spacer unit for extractive concentration of trace elements are highlighted in the present article. Experimental evidences for existence of surface silanol and its chemical nature have explored the idea of silica surface modification. Recent methods of development in functionalized silica synthesis by attachment of various ligands or organic reagents to the silica surface and techniques of characterization of the modified surface have been reported. Analytical applications of various modified silica surfaces, in particular, adsorption of trace elements taking separation and preconcentration into account from complex synthetic mixture as well as natural water is presented.     

Momentum transfer in an agitated vessel with off-centred impellers

Momentum transfer was investigated in an unbaffled agitated vessel of inner diameter 0.3 m equipped with different off-centred impellers. The distribution of the shear rate on the tank wall as a function of the impeller type and Reynolds number was studied in the turbulent regime of the Newtonian liquid flow. The dependences of the averaged dimensionless shear rate, friction coefficient, and dissipated energy on the Reynolds number and eccentricity ratio were approximated using four-parameter equations. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Heterogeneous ECE Processes at Channel Electrodes: Analytical Solution for all Reaction Rate Constants and Different Diffusion Coefficients

An analytical solution is developed for heterogeneous ECE processes occurring at channel electrode surface for both laminar and turbulent flow. The solution explicitly links the behavior of ECE processes and the parameters. A simple expression of the effective number of electrons transferred, covering all the reaction rate constants and different diffusion coefficients of the reactant A and the intermediate product B, is obtained. Excellent agreement with previous numerical and analytical results is shown . Parametric studies illustrate the effects of diffusion coefficients, hydrodynamic factors and reaction rate constants on the effective number of electrons transferred and the currents.     

TiO2/P(VdF-HFP)杂化纤维微孔膜的制备及其电化学性能

用电纺法制备了TiO₂/P(VdF-HFP)(聚偏氟乙烯-六氟丙烯共聚物)杂化纤维微孔膜, 用SEM观察了杂化纤维微孔膜的形貌, 并测算了这类由超细纤维相互搭接而形成的微孔膜的孔隙率. 这种微孔膜吸附LiPF₆/EC-DMC-EMC(碳酸乙烯酯-二甲基碳酸酯-碳酸甲乙酯)电解质溶液后得到凝胶聚合物电解质膜. 用电化学方法测试了聚合物电解质膜的离子电导率、锂离子迁移数等参数, 并研究了TiO₂纳米晶的掺入对聚合物电解质电化学性能的影响. 结果表明, TiO₂的掺入降低了P(VdF-HFP)聚合物基体的结晶度, 改善了凝胶聚合物电解质的低温电化学性能.     

2-(8-羟基喹啉-5-磺酸-7-偶氮)-1,8-二羟基-3,6-萘二磺酸与牛血清白蛋白的相互作用

用平衡透析法和分光光度法研究了 2 (8 羟基喹啉 5 磺酸 7 偶氮 ) 1,8 二羟基 3,6 萘二磺酸与牛血清白蛋白 (BSA)在酸性溶液中的结合反应 ,认为 8Q5SAC与BSA之间的结合力是以静电引力为主的非共键作用力 ,并探讨了其结合模型。在 2 98K下 ,测得这一反应的最大结合数为 35～ 40 ,结合常数为 6 .1× 10 5L mol。还研究了溶液基本条件如酸度和离子强度等对 8Q5SAC与牛血清白蛋白分子复合物形成的影响 ,在pH =3.34条件下 ,标准工作曲线的线性范围为 0 .2 0～ 46 .90mg L。     

流通池光度滴定法应用—络合反应中的质子释放数测定

用具有流通池的分光光度计作测定装置,建立了由平衡移动法测定络合反应中质子释放数的新方法。方法简单、快速,仅用一个标准溶液,适于在变更pH值范围内金属离子不发生水解和没有其他副反应的体系。     

Shape analysis based critical Eotvos numbers for buoyancy induced partial detachment of oil drops from hydrophilic surfaces

Removal of oil drops from solid surfaces immersed in an aqueous medium is of interest in many applications. It has been shown that drop shape analysis can be used to predict conditions at which the stability limit of a lighter than water oil drop on a solid surface immersed in an aqueous bath is reached (Adv. Colloid Interface Sci. 98 (2002) 265). However the above analysis is restricted to cases where the contact angle made by the drop is below 90degrees and when the surface conditions result in a 'pinned' contact line. In this paper, it is shown that drop shape analysis can be used to predict the critical conditions at which drop stability limit is reached for drop contact angles of 90degrees and above, which is encountered with 'hydrophilic' surfaces. This critical condition can predict the occurrence of partial oil drop detachment, before complete removal due to 'roll-up', which occurs when the hydrophilic surface is adequately smooth which prevents 'pinning' of the contact line. The critical conditions at which partial drop detachment occurs can also be approximately predicted from simple force balances. It has been shown (Adv. Colloid Interface Sci. 98 (2002) 265) that for contact angles less than 90degrees, the critical limit based on shape analysis appears to resolve the differences that arise due to alternate expressions for capillary retention force. This paper shows that even for contact angles above 90degrees, the critical conditions predicted from the shape analysis resolves the differences in the predictions from the alternate force balances. Drop shape analysis used in this paper is based on the 'Arc-length' form of Young-Laplace or 'drop shape' equation, which is different from the 'Y vs X' form of the above equation that is used in Adv. Colloid Interface Sci. 98 (2002) 265. The above drop shape equation is solved by a fourth order Runge-Kutta technique and it is shown that for angles less than 90degrees, the two forms of the drop shape equation, predict almost identical values of the critical Eotvos number. This paper highlights the competing effects of interfacial tension lowering induced drop instability and 'roll-up', a term that is used to describe the retraction of the contact line of an oil drop on a surface, in being the primary c ause for drop detachment.     

Liquid-liquid extraction of copper (I) and copper (II) as ion-paired complexes with acyclic 2-thienyl-containing polythioether and triphenylmethane dye anion

Three acyclic polythioethers containing 2-thienyl units at both ends were synthesized and the effect of substituent on the extraction of copper(II) was studied. The methyl groups in the terminal thiophene ring have imparted an appreciable degree of increase in the percent extraction of copper(II), while the introduction of chlorine atoms into the 2-thienyl unit resulted in the reverse effect. Among the counter dye anions examined, tetrabromophenolphthalein ethylester was the best one for copper(II) extraction. The composition of extracted species was evaluated to be 122 (Cu(II)/polythioether/dye anion). Quantitative extraction of copper(I) was attained as complexes with various triphenylmethane dyes, i.e., bromocresol green, bromothymol blue, bromo-phenol blue and pyrogallol red. Copper(I) in organic phase was completely back-extracted with 2 mole/l sulfuric acid containing 10% hydrogen peroxide.     

考虑偏差值的中立型区间交叉效率研究

在不确定性环境下,当决策单元(DMU)的投入产出数据为区间数形式时,为解决决策单元之间既不是合作也不是竞争关系时的交叉评价问题,本文提出一种中立型区间交叉效率模型。从所有被评价者的角度出发解决评价权重的选取问题,以决策单元投入得分的平均偏差与产出得分的平均偏差之和最小化为目标,建立决策单元在最佳和最差两种生产状态下的中立型区间交叉效率模型。在本文提出的中立型模型视角下,DMU的投入得分平均偏差和产出得分平均偏差之和达到最小。算例结果表明该中立型区间交叉效率模型的有效性,解决了不确定性环境下的交叉评价问题,保证评价的客观公正,更加符合现实。