Activity coefficients of electrolytes from the E.M.F. of liquid membrane cells. II - multicharged electrolyte solutions

The activity coefficients of Co(en)₃Cl₃ and K₂SO₄ were measured by means of a cell with ion-exchange liquid membranes following the method described in paper I. The results prove that this method is even more valuable with multicharged salts than with 1-1 electrolytes. The values obtained are precise and reliable down to dilution limits never before accessible, e.g., 4×10^–5 mol-kg^–1 in Co(en)₃Cl₃. High dilution levels are of particular importance when dealing with highly charged electrolytes since the trend at higher concentrations often leads to errors both in extrapolation to infinite dilution and in the absolute activity coefficients. As an application, the activity coefficients of [Co(en)₃]₂(SO₄)₃-suspected to be wrongly evaluated in past literature-were measured, and their values at low concentrations were actually lower than those quoted before.     

Chemical species produced in the reaction between ethanedial (glyoxal) and 5-amino-1,10-phenanthroline and their iron(II) complexes: preparation and some spectrometric studies

Chemical species obtained by reaction of 5-amino-1, 10-phenanthroline with ethanedial (glyoxal) are reported with regard to their preparation, chemical composition and spectrometric characterization (UV-visible, infrared and liquid secondary ion mass spectrometry). Products of the reaction are postulated to be a mixture of species with molecular weights of 339, 371,480 and 524 u. Chemical reactions leading to these products and possible structural formulas for each of these species are presented. The iron complexes of these ligands, because of their extremely low solubility in most solvents, find application as redox mediators when incorporated in carbon paste electrodes, particularly for sensing in continuous-flow systems.     

三唑螯合树脂分离富集催化光度法测定痕量金

研究了三唑螯合树脂 (AMTR)在盐酸介质中分离富集金 ,吸附的容量大 ,选择性高 ,无污染。同时研究了分离后在盐酸介质中 ,在抗坏血酸 (VC)存在下痕量金 催化溴酸钾氧化偶氮氯膦S褪色的指示反应及其动力学条件 ,据此建立测定痕量金 的新方法。方法的检出限为 4.16× 10 - 7g L ,测定范围为 0～ 70mg L ,用于样品的测定获得满意结果。     

Potentiometric pH response of membranes prepared with various aminated-poly (vinyl chloride) products

The preparation and potentiometric pH response properties of membranes formulated with various aminated-poly(vinyl chloride) (PVC-NH₂) products are described. Products containing secondary and/or primary amino functional groups are obtained by modifying PVC with mono- and/or diamines, respectively. Blank membranes prepared with either type of aminated-polymer exhibit nearly Nernstian potentiometric pH responses over different pH ranges. In general, membranes based on diamino products exhibit pH response over a wider range (5–10.5) than membranes formulated with monoamino products (<8.0). These potentiometric results are used to estimate the basicity of the various primary and secondary amino sites in the membrane phases.Dedicated to Professer W. Simon on the occasion of his 60th birthday     

Evaluation of a PVC‐Based Thionine‐Zeolite and Zeolite Free Membranes as Sensing Elements in Ion Selective Electrode

The construction and performance characteristics of thionine electrodes based on the ion‐pair complex thionine‐tungstophosphate and thionine‐mordenite zeolite embedded in a polyvinyl chloride (PVC) matrix is described. Thionine electrode based on the ion‐pair is used for the indirect determination of ascorbic acid by standard addition method.     

Increased electrochemical detector sensitivity by electrode surface modification

Summary Electrode surface modification by electrochemical pretreatment of glassy carbon electrodes was shown to enhance significantly the sensitivity of the electrodes for the detection of timolol and oxprenolol, but reduce slightly the sensitivity to prenalterol. This method may permit the detection of exprenolol and timolol with increased sensitivity, or may allow their detection at lower applied potentials than is presently possible. Electrode surface modification may prove to be a valuable aid to the detection of compounds that are considered to be outside the practical limits of electrochemical detection.     

Transport properties and electroanalytical response characteristics of drotaverine ion-selective sensors

The construction and electroanalytical response characteristics of poly(vinyl chloride) matrix ion-selective sensors (ISSs) for drotaverine hydrochloride are described. The membranes incorporate ion-association complexes of drotaverine with tetraphenylborate, picrate, tetraiodomercurate, tetraiodobismuthate, Reinecke salt, and heteropolycompounds of Keggin structure—molybdophosphoric acid, tungstophosphoric acid, molybdosiliconic acid and tungstosiliconic acid as electroactive materials for ionometric sensor controls. These ISSs have a linear response to drotaverine hydrochloride over the range 8×10^–6 to 5×10^–2 mol L^–1 with cationic slopes from 51 to 58 mV per concentration decade. These ISSs have a fast response time (up to 1 min), a low determination limit (down to 4.3×10^–6 mol L^–1), good stability (3–5 weeks), and reasonable selectivity. Permeabilities and ion fluxes through a membrane were calculated for major and interfering ions. Dependences of the transport properties of the membranes on the concentrations of the ion exchanger and near-membrane solution and their electrochemical characteristics are presented. The ISSs were used for direct potentiometry and potentiometric titration (sodium tetraphenylborate) of drotaverine hydrochloride. Results with mean accuracy of 99.1±1.0% of nominal were obtained which corresponded well to data obtained by use of high-performance liquid chromatography.     

Sol-gel-derived prussian blue-silicate amperometric glucose biosensor

A new type of inorganic biosensor is introduced. The sensor comprises glucose oxidase enzymes encapsulated in a sol-gel-derived Prussian blue-silicate hybrid network. Glucose is detected by the biocatalytic reduction of oxygen followed by catalytic reduction of hydrogen peroxide by the Prusian blue catalyst. The sol-gel silicate entails a rigid encapsulating matrix, the Prussian blue provides chemical catalysis and charge mediation from the reduction site to the supporting electrode, and the enzyme is responsible for the biocatalysis. The feasibility of a dual optical/electrochemical mode of analysis is also demonstrated.     

Influence of structural changes on the ion selectivities of magnesium ionophores based on malonic acid diamides

In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992     

Single‐Wall Carbon Nanotube Paste Electrodes: a Comparison with Carbon Paste,Platinum and Glassy Carbon Electrodes via Cyclic Voltammetric Data

A new carbon electrode material, obtained by mixing single wall carbon nanotubes (SWNTs) with a mineral oil binder is studied. Carbon nanotube pastes show the special properties of carbon nanotubes combined with the various advantages of composite electrodes such as a very low capacitance (background current) and the possibility of an easy preparation, modification and renewal. A better knowledge of the characteristics of electrode reactions at carbon nanotube paste (CNTP) electrodes was obtained studying the electron transfer rates of various redox couples under different pretreatment conditions. A critical comparison with carbon paste (CP), platinum (Pt) and glassy carbon (GC) electrodes was also carried out. Capacitance and resistance values were also calculated for all electrodes investigated. Both untreated and treated CNTP electrodes showed a low resistance while the capacitance was markedly reduced with CNTP electrodes previously treated with concentrated nitric acid. An electrochemical pretreatment on CNTP electrodes was developed which showed an excellent result towards two‐electron quinonic structure species. After this treatment the heterogeneous standard rate constants for p‐methylaminophenol sulfate (MAP) and dopamine resulted to be significantly higher (2.1×10^?2 cm/s and 2.0×10^?2 cm/s, respectively) than those obtained with the other electrodes studied. Reproducibility, stability and storage characteristics of CNTP electrodes were also reported.