Selective Electrodes ISE

An example is described here for the measurement of fluoride ions in solution. The fluoride electrode uses a LaF3 single crystal membrane and an internal reference, bonded into an epoxy body. The crystal is an ionic conductor in which only fluoride ions are mobile. When the membrane is in contact with a fluoride solution, an electrode potential develops across the membrane. This potential, which depends on the level of free fluoride ions in solution, is measured against an external constant reference potential with a digital pH/mv meter or specific ion meter. The measured potential corresponding to the level of fluoride ions in solution is described by the Nernst equation  

E = measured electrode potential E0 = reference potential (a constant) 

The level of fluoride, A, is the activity or effective concentration of free fluoride ions in solution. The total fluoride concentration, C, may include some bound or complexed ions as well as free ions. The electrode responds only to the free ions, whose concentration is  

The fluoride activity is related to free fluoride concentration by the activity coefficient r  

Ionic activity coefficients are variable and largely depend on total ionic strength. Ionic strength is defined as  

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If metallic electrodes were the only useful class of indicator electrodes, potentiometry would be of limited applicability. The discovery, in 1906, that a thin glass membrane develops a potential, called a membrane potential, when opposite sides of the membrane are in contact with solutions of different pH led to the eventual development of a whole new class of indicator electrodes called ion-selective electrodes (ISEs). following the discovery of the glass pH electrode, ion-selective electrodes have been developed for a wide range of ions. Membrane electrodes also have been developed that respond to the concentration of molecular analytes by using a chemical reaction to generate an ion that can be monitored with an ion-selective electrode. The development of new membrane electrodes continues to be an active area of research. 

In some systems, known as continuous-flow analy2ers, the reaction develops as the sample —reagent mixture flows through a conduit held at constant temperature. In such systems, the reaction cuvettes are replaced by optical reading stations called flow cells. In most analy2ers, whether of discrete- or continuous-flow type, deterrnination of electrolyte tests, eg, sodium and potassium levels, is done by a separate unit using the technique of ion-selective electrodes (ISE) rather than optical detection. 

Low sulfate selectivity of the ion-selective electrodes (ISE) based on lipophilic quaternary ammonium salts (QAS) is usually explained by unfavorable ratio of sulfate hydration and solvation energies. We have been shown that another reason does exist as well namely, low efficiency of sulfate-QAS cation interaction caused by steric hindrance for simultaneous approach of two QAS cations, containing four long-chain hydrocarbon substituents, to sulfate ion. 

Many double-charged anions, such as sulfate, hydrophosphate, oxalate etc., are highly widespread in natural sources and at the same time lack any convenient technique for their determination. Therefore, development of ion-selective electrodes (ISEs), responsive to these anions, is of great practical importance. However, for a long time all attempts directed toward creation of such electrodes were unsuccessful (except for carbonate ISEs based on trifluoroacetylbenzene derivatives), and only in recent years this field has shown significant progress. 

Ion-selective electrodes (ISEs) with ionophore-based membranes allow for quantification of a large number of analytes in various matrixes. Tailoring of the composition of the membranes to comply with the analytical task, requires advanced theory of membrane response. Most of theoretical descriptions include nonrealistic extra-thermodynamic assumptions, in the first place it is assumed that some kind of species strongly predominate in membranes. Ideally, a rigorous theory of ISE response should be based on strict thermodynamics. However, real ISE membranes are too complex. Therefore, known attempts aimed at rigorous thermodynamic description of ISEs proved to be fraritless. 

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. 

Despite the fact that a great lot of ion-selective electrodes (ISEs) with liquid and film polymeric membranes for the determination of physiologically active amines (PhAA) has been described, the factors responsible for their selectivity have not yet been studied sufficiently. In this work, the influence of plasticizer and ion-exchanger nature on the selectivity of ISEs reversible to PhAA cations of various stmctures has been discussed. 

The slightly soluble ion pair was used as electrode-active substance in a plastered membrane of an ion-selective electrode (ISE) for these alkaloids. 

The equipment required for direct potentiometric measurements includes an ion-selective electrode (ISE), a reference electrode, and a potential-measuring device (a pH/millivolt meter that can read 0.2mV or better) (Figure 5-1). Conventional voltmeters cannot be used because only very small currents are allowed to be drawn. The ion-selective electrode is an indicator electrode capable of selectively measuring the activity of a particular ionic species. Such electrodes exhibit a fast response and a wide linear range, are not affected by color or turbidity, are not... 

A significant development in the methodology of potentiometry that paved the way for its utility in bioanalysis was the discovery of the ion selective electrode (ISE). Conceptually, the ISE involves the measurement of a membrane potential. The response of the electrochemical cell is therefore based on an interaction between the membrane and the analyte that alters the potential across the membrane. The selectivity of the potential response to the analyte depends on the specificity of the membrane interaction for the analyte. 

The worldwide prevalence of ion-selective electrodes (ISE s) in clinical analyzers is a consequence of a major research effort which spanned more than two decades. The... 

Electrochemistry voltammetry, anodic stripping (ASV), cathodic stripping (CSV), polarography, differential pulse polarography (DPP), ion selective electrode (ISE)... 

There are also RMs which are prepared for a specific application and are used for validation of relevant methods. Cobbaert et al. (1999) made use of Ion Selective Electrode (ISE)-protein-based materials when evaluating a procedure which used an electrode with an enzyme-linked biosensor to determine glucose and lactate in blood. Chance et al. (1999) are involved with the diagnosis of inherited disorders in newborn children and they prepared a series of reference materials consisting of blood spotted onto filter paper and dried, from which amino-acids can be eluted and... 

Other studies involved the measurements of the SHG response from ion selective electrodes (ISE) [105,106] but one of the difficulties lies in the reabsorption of the SH signal generated at the interface in the bulk of one phase as the active species transfer. 

Electrodes which only respond to certain free (not bound) measured ions are called ion-selective electrodes (ISE). The term is now usually applied to all potentiometric measuring electrodes that are capable of providing data concerning the concentration or activity of... 

Together with active metal electrodes, the membrane electrodes represent the best known ion-selective electrodes (ISEs) however, the membrane type has the advantages of insensitivity to redox agents and surface poisons. As the... 

Fig. 5.20 shows the instrument with the addition of the ion-selective electrode (ISE) module, which performs Na, K and C02 analyses (240 samples or 720 tests per hour) as requested and without interruption of the other analyses. The sample for electrolyte determination is also placed on the sample tray and a third probe aspirates diluted sample from the reaction tray for processing by the ISE module. Finally, the Technicon SRA-2000 system is a computer-controlled network of the subsystems SMAC II and RA-1000. 

The history of ion-selective electrodes (ISEs) [1] starts from the discovery of the pH response of thin film glass membranes by Cremer in 1906, thus making ISEs the oldest class of chemical sensors. They still are superior over other sensor types in a variety... 

Fig. 18a.l. Schematic diagram of a potentiometric cell with an ion-selective electrode (ISE) as the indicator electrode. EM is the electrical potential of the sensing membrane and IFS the internal filling solution. 

These measure the potential difference between the transducing electrode and a reference electrode under conditions of zero current. Three types of potentiometric detectors are commonly employed ion-selective electrodes (ISE), gas-sensing electrodes and field effect transistors (FET). 

To understand the basics of ion-selective electrodes (ISEs), and relate the activities of analyte ions to the emf from an ISE by using the Nernst equation. 

The pH electrode (and its less sophisticated parent, the glass electrode) are the most commonly encountered forms of ion-selective electrodes (ISEs). Such an electrode is best defined as an electrode having a nemstian response to a single ion in solution where, by nemstian , we again mean that the Nemst equation is obeyed. The pH electrode is an ion-selective electrode since it only responds to protons in solution (with the occasional exception of cations of the alkali and alkaline-earth metals, as discussed below). 

We then described how ion-selective electrodes (ISEs) function by means of generating an emf that is related to the activity of a single ion. The simplest ISEs are glass electrodes for pH determination, and the related pH combination electrodes. Other solid-state ISEs, such as the fluoride electrode, function in the same way. 

Consider the case in which the solubility of silver chloride is being measured by using a silver ion-selective electrode (ISE). The ISE is immersed in a solution... 

We saw earlier in Section 3.5.2.2 how the selectivity of an ion-selective electrode (ISE) can be occasionally problematic, e.g. the activity of fluoride ion when determined by a fluoride ISE can be significantly in error if the solution also contains sufficient hydroxide ion to raise the pH above about 8. 

Ion-selective electrode (ISE) In potentiometry, an electrode having a nemstian response to one ion, ideally to the exclusion of others. 

In potentiometry with ion-selective electrodes (ISE), as a rule, it is the electromotive force of a cell such as the following that is measured. 

As has been shown over the last fifteen years, the membrane systems of ion-selective electrodes (ISEs) approach specificity under certain conditions. 

An important advance in ion-selective electrodes (ISEs) and related systems was based on the concept of polymeric liquid membranes developed by Eisenman [122]. The principle of this approach was to incorporate an organic compound as the ionophore into a polyvinyl chloride membrane... 

ION-SELECTIVE ELECTRODES (ISEs) AND ION-SENSITIVE FIELD-EFFECT TRANSISTORS (ISFETs)... 

Elemental fluorine, which is a member of the halogen family, is a pale yellow-green, irritating gas with a sharp odour and atomic mass of 18.998. Fluorine is chemically most reactive of all the elements and does not therefore occur naturally in the free state. In combination it comprises 0.065% of the earth s crust, being the 13th element in abundance [1], and is an inevitable part of the biosphere and human life. The term fluorine is, in this report, used to denote the element in any of its forms and fluoride to denote free inorganic fluoride to which a fluoride ion-selective electrode (ISE) responds. 

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