分散电极的制备及其分散差电池的电动势

物质超细化后除产生强烈的量子尺寸效应和宏观量子遂道效应外,还将产生强烈的表面效应和体积效应等。这些效应可改变其的电化学性质。早在1982年Plieth[1]就发现了金属颗粒的粒度对电极电势有影响,随后又在理论和实验方面做了许多工作[2,3]。后来人们又不断发现,组成电极的粉末     

双层修饰玻碳电极测定在大分子污染物存在下的痕量铜(Ⅱ)

应用选择性渗透的2-巯基乙磺酸(MES)自组装单层膜和纳米金阵列双层修饰玻碳电极,用溶出伏安法测定了在大分子污染物存在下的痕量Cu(Ⅱ)。纳米金阵列的修饰显著提高了玻碳电极的分析性能,而自发吸附的选择性渗透单层膜则有效阻止了电极表面被共存的大分子污染。方法校正曲线的斜率为0.13±0.016μA/10-9,LOD为0.137×10-9,且具有较大的线性范围。用此方法测定冶金废水中Cu2 含量,结果与AAS接近,方法具有实际应用价值。     

Minimizing Activity and Liquid Junction Errors In Direct Potentiometry By Using the Optimal Standard Solution

Abstract

In quantitative analysis by direct potentioroetry. e.g. when using ion-selective electrodes, situations arise where corrections appear necessary to account Tor activity coefficient and liquid junction potential effects. It is shown here that one can select an optimal composition for the standard or reference solution and thereby achieve two goals simultaneously: to reduce the error terms to a minimum and to eliminate the necessity of any corrective calculations.     

Flow-Injection Analysis of Chloride in Milk with a Dialyzer and a Coated Tubular Inorganic Chloride-Selective Electrode

Abstract

A rapid and reliable automated procedure for the direct measurement of the chloride content in milk is described. The method is based on the principles of the flow-injection technique; a dialyzer is used to eliminate interferences and the dialyzed chloride is measured with a coated tubular chloride-selective electrode. With this system potential change caused by the interference of casein is obviated, giving a stable baseline. Results obtained for chloride in milk at a sampling rate of 120 samples per hour compared well with data obtained by the standard Volhard titration method. With 30-μl samples a working range of 250–5000 mg/1 chloride is covered with a coefficient of variation of better than 0.50%.     

Development of Disposable Carbon Nanofibers Electrodes Supported on Filters

The purpose of this work is to develop simple and reproducible ways to fabricate carbon nanofibers (CNFs) electrodes. Disposable CNFs electrodes were fabricated after filtering CNFs through polytetrafluoroethylene filters (PTFE), using directly as electrodes these filters with the CNFs film. The electrochemical behaviour of CNFs/PTFE electrodes were tested with ferrocenemethanol and tris(2,2′‐bypyridyl)dichlororuthenium(II) (Ru(bipy)₃²⁺). As a proof of concept of the analytical usefulness of the CNFs/PFTE electrodes, the study of vitamin B₁₂ was carried out. Multivariate calibrate has been successfully used to determine vitamin B₁₂ in a complex medium with vitamins B₁ and B₆ as interferents.     

Modulating the Enantiodiscrimination Features of Inherently Chiral Selectors by Molecular Design: A HPLC and Voltammetry Study Case with Atropisomeric 2,2’-Biindole-Based Monomers and Oligomer Films

A family of inherently chiral electroactive selectors based on the 2,2’-biindole atropisomeric scaffold, of easy synthesis and modulable functional properties, is studied in cascade in two enantioselection contexts. They are at first investigated as probes in enantioselective HPLC, studying molecular structure and temperature effects, and achieving very efficient semipreparative enantioseparation. The enantiomers thus obtained, of remarkable chiroptical features (optical rotation as well as circular dichroism), are successfully applied as selectors in chiral voltammetry in different media for discrimination of the enantiomers of chiral electroactive probes, either by conversion into enantiopure electroactive electrode surfaces by electrooligomerization on glassy carbon substrate (the two monomers with shorter alkyl chains), or as chiral additive in achiral ionic liquid (the monomer with longest alkyl chains). Discrimination is conveniently and reproducibly achieved in terms of significant potential differences for the two enantiomers, specularly inverting either probe or selector configuration. In one case successful discrimination is also observed with the two probe enantiomers concurrently present, either as racemate or with enantiomeric excesses, neatly accounted for by the peak current ratios.     

Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes

A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott–Schottky or Gouy–Chapman–Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments.     

Device for aeration and mixing of cell and organelle suspensions during NMR experiments

A device for aeration and mixing of cell or organelle suspensions in a vertical bore NMR magnet is described. Multiple external sensors (e.g., ion-selective electrodes) may be immersed in the suspension within the bore of the magnet. The sensors are positioned to avoid noise due to contact with gas bubbles and proximity to the probe head. The required sample volume is minimised. The modular design of components permits the use of the device in magnets of various internal dimensions, or with probe heads of different sample tube diameter, by modification of the simpler components of the assembly.     

New Cyclodextrin-Based Ion-Selective Electrodes for Determining Activity Coefficients of Biologically Important Onium Ions

Ion-selective electrodes (ISEs), apart from fluoride, calcium, and a few others, have not often been used to obtain thermodynamic information on electrolytes. Here, novel cyclodextrin-based ISEs are used to determine activity coefficients of some onium chlorides in aqueous solution. Cyclodextrins, rendered lipophilic by alkylation, have been incorporated into polymeric membranes and used as ionophores in ISEs for sensing the substituted ammonium (onium) ions, choline, acetylcholine, and acetyl--methylcholine. Potentiometric measurements using these cyclodextrin-based ISEs allow the determination of ratios of activity coefficients in solutions. Choosing one solution as reference and using a theoretical model (e.g., Pitzer equations), it is possible to evaluate activity coefficients of individual solutions. Results for choline chloride compare well with limited data in the literature. This is the first time, that ISEs have been used to measure activity coefficients of biologically important ions.     

The non-integer cyclovoltammetric electron-exchange numbers of reversible redox reactions of adsorbates

Allowing for the interfacial potential distribution it can be shown that the apparent faradaic electron number, n_app, of ad-layers of chemically modified electrodes and the surface redox valency, n, relating to the slope of the peak potential/pH response [Huck (2002) J Solid State Electrochem 6:534] are at least identical, having the same thermodynamic origin. n_app is calculated from the cyclovoltammetric (CV) peak areas above the interpolated base line. At for proton-coupled surface redox reactions, the influence of the potential drop of the diffuse double layer disappears because the capacitor of the corresponding equivalent circuit becomes shortened by proton transfer, whereby the otherwise non-integer n_app or n values now approach the integer electron numbers, n, of the Nernst equation.