Selectivity, cation potentiometric

The influence of factor series to electrode characteristics has been established. Dependency of the potential of ISE from concentration of defined substance is linear in interval of concentration l lO - l lO mol/1 at the pH 2,0-6,5. Slopping of the graduated graph form 55-56 mV/pC for single-chai ge cation. Potentiometric factors of the selectivity K,, ISE for alkaloids of Papaver Somnifemm has been determined. 

Fig. 6. Transport selectivity and potentiometric selectivity of a Ca2 selective neutral carrier membrane (3 wt.% carrier 10, 65 wt.% o-nitrophenyl-octyl ether, 32wt.% polyvinyl chloride). Experimental selectivity coefficients KCaNa obtained with (16) and (18), respectively, as a function of the cationic concentration m (in moles/liter).

B6. Baum, G., Organic cation-selective electrode Potentiometric determination of acetylcholine activity. Anal. Lett. 3, 105-111 (1970). 

PPy is known to exhibit anionic or cationic potentiometric responses depending on the doping ion. PPy films doped with mobile inorganic anions show anionic sensitivity, while PPy films doped with anions of low mobility such as sulfate, large organic anions, or polyanions show cationic sensitivity. This bifunctionality of ionic and redox sensitivity makes PPy apphcable as an all-sohd-state, ion-selective electrode. All-solid-state, potentiometric PPy sensors were developed for potassium and sodium sensing, which showed better response time, selectivity and most importantly long-term stabihty than the coated wire electrode [130]. 

The sufficient selectivity to a principal component is the most important condition determining the possibility of ion-selective electrodes (ISEs) practical appliances. In this work, the relationship between the potentiometric selectivity of alkylammonium-selective electrodes and factors such as the nature of plasticizer, ion-exchanger and substitution degree of cationic nitrogen atoms of the principal and foreign ions, is discussed. 

ION-SELECTIVE ELECTRODES REVERSIBLE TO PHYSIOLOGICALLY ACTIVE AMINE CATIONS THE MAIN WAYS FOR CONTROLLING POTENTIOMETRIC SELECTIVITY... 

Electrochemical analytical techniques are a class of titration methods which in turn can be subdivided into potentiometric titrations using ion-selective electrodes and polarographic methods. Polarographic methods are based on the suppression of the overpotential associated with oxygen or other species in the polarographic cell caused by surfactants or on the effect of surfactants on the capacitance of the electrode. One example of this latter case is the method based on the interference of anionic surfactants with cationic surfactants, or vice versa, on the capacitance of a mercury drop electrode. This interference can be used in the one-phase titration of sulfates without indicator to determine the endpoint... 

By now a large number of ion-selective substances are known. They are used for the potentiometric concentration determination of practically all kinds of cations and anions. Numerous publications and monographs of the last two decades are concerned with ion-selective electrodes. 

Among potentiometric methods of analysis that are important for ecological applications, the one most widely used is that of pH measurements with an indicator electrode whose potential is a function of the hydrogen ion concentration. More recently, ion-selective electrodes reversible to other cations such as those of heavy metals have become available. 

Applications Potentiometry finds widespread use for direct and selective measurement of analyte concentrations, mainly in routine analyses, and for endpoint determinations of titrations. Direct potentiometric measurements provide a rapid and convenient method for determining the activity of a variety of cations and anions. The most frequently determined ion in water is the hydrogen ion (pH measurement). Ion chromatography combined with potentiometric detection techniques using ISEs allows the selective quantification of selected analytes, even in complex matrices. The sensitivity of the electrodes allows sub-ppm concentrations to be measured. 

Particular cases are potassium selective potentiometric sensors based on cobalt [41] and nickel [38, 42] hexacyanoferrates. As mentioned, these hexacyanoferrates possess quite satisfactory redox activity with sodium as counter-cation [18]. According to the two possible mechanisms of such redox activity (either sodium ions penetrate the lattice or charge compensation occurs due to entrapment of anions) there is no thermodynamic background for selectivity of these sensors. In these cases electroactive films seem to operate as smart materials similar to conductive polymers in electronic noses. 

Selig reported a potentiometric titration method for the analysis of procaine and some other organic cations precipitated by tetraphenylborate [67]. The development of ion selective coated-wire electrodes, and their application in the titration of procaine and other pharmaceutically important substances, was reported [68]. 

The direct potentiometric determination (using a cation-selective membrane electrode) of procaine and some physiologically active amines in pharmaceuticals has been reported [70]. The sensing membrane was formed from PVC plasticized with dibutyl phthalate, and contained 0.1 mM trioctyloxybenzene-sulfonic acid in dibutyl phthalate. The reference solution was a mixture of 1 mM solution of the organic base and hydrochloric acid. Response was found to be linear over a wide concentration range, and the method was highly selective. 

Fig. 4. Transport selectivity Kjj and potentiometric selectivity Kj j of a Na+-selective neutral carrier membrane using ligand 11. Experimental coefficients fCNaM obtained with (2) and (11) respectively given for different cations M. Membrane composition 32wt.% polyvinyl chloride, 65 wt.% dibutyl sebacate, 3wt.% carrier //. Thickness of membrane = 100 p.m. Current density approx. 0.1 p.Amm 2.

By running a potentiometric precipitation titration, we can determine both the compositions of the precipitate and its solubility product. Various cation- and anion-selective electrodes as well as metal (or metal amalgam) electrodes work as indicator electrodes. For example, Coetzee and Martin [23] determined the solubility products of metal fluorides in AN, using a fluoride ion-selective LaF3 single-crystal membrane electrode. Nakamura et al. [2] also determined the solubility product of sodium fluoride in AN and PC, using a fluoride ion-sensitive polymer membrane electrode, which was prepared by chemically bonding the phthalocyanin cobalt complex to polyacrylamide (PAA). The polymer membrane electrode was durable and responded in Nernstian ways to F and CN in solvents like AN and PC. 

Table 5), and several are now being used, or are potentially useful, for measuring key ocean elements. The most common use of direct potentiometry (as compared with potentiometric titrations) is for measurement of pH (Culberson, 1981). Most other cation electrodes are subject to some degree of interference from other major ions. Electrodes for sodium, potassium, calcium, and magnesium have been used successfully. Copper, cadmium, and lead electrodes in seawater have been tested, with variable success. Anion-selective electrodes for chloride, bromide, fluoride, sulfate, sulfide, and silver ions have also been tested but have not yet found wide application. 

Traditionally, potentiometric sensors are distinguished by the membrane material. Glass electrodes are very well established especially in the detection of H+. However, fine-tuning of the potentiometric response of this type of membrane is chemically difficult. Solid-state membranes such as silver halides or metal sulphides are also well established for a number of cations and anions [25,26]. Their LOD is ideally a direct function of the solubility product of the materials [27], but it is often limited by dissolution of impurities [28-30]. Polymeric membrane-based ISEs are a group of the most versatile and widespread potentiometric sensors. Their versatility is based on the possibility of chemical tuning because the selectivity is based on the extraction of an ion into a polymer and its complexation with a receptor that can be chemically designed. Most research has been done on polymer-based ISEs and the remainder of this work will focus on this sensor type. 

EPMEs based on carbon paste modified with antibiotics vancomycin, teicoplanin and teicoplanin modified with acetonitrile are proposed for the determination of d-2-HGA [47]. The proposed electrodes can be used reliably for enantiopurity tests of d-2-HGA using direct potentiometric method of analysis. The linear concentration ranges recorded for EPMEs are 10 7-10 3, 10 7-10 2 and 10 6-10 2 mol/L with detection limits of 1.00 x 10 8, 1.00 x 10 8 and 1.00 x 10 7 mol/L for the vancomycin, teicoplanin and teicoplanin modified with acetonitrile-based EPME, respectively. The selectivity was determined over l-2-HGA, creatine, creatinine and some inorganic cations. The proposed EPMEs were applied for the assay of d-2-HGA in urine samples. The duration of one analysis is 10 min, including the calibration of the instrument and the determination of the amount of d-2-HGA in the urine sample. 

Use of the potential of a galvanic cell to measure the concentration of an electroactive species developed later than a number of other electrochemical methods. In part this was because a rational relation between the electrode potential and the concentration of an electroactive species required the development of thermodynamics, and in particular its application to electrochemical phenomena. The work of J. Willard Gibbs1 in the 1870s provided the foundation for the Nemst equation.2 The latter provides a quantitative relationship between potential and the ratio of concentrations for a redox couple [ox l[red ), and is the basis for potentiometry and potentiometric titrations.3 The utility of potentiometric measurements for the characterization of ionic solutions was established with the invention of the glass electrode in 1909 for a selective potentiometric response to hydronium ion concentrations.4 Another milestone in the development of potentiometric measurements was the introduction of the hydrogen electrode for the measurement of hydronium ion concentrations 5 one of many important contributions by Professor Joel Hildebrand. Subsequent development of special glass formulations has made possible electrodes that are selective to different monovalent cations.6"8 The idea is so attractive that intense effort has led to the development of electrodes that are selective for many cations and anions, as well as several gas- and bioselective electrodes.9 The use of these electrodes and the potentiometric measurement of pH continue to be among the most important applications of electrochemistry. 

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