Metal ion-selective electrodes

The continuous flow method is still necessary when one must use probe methods which respond only relatively slowly to concentration changes. These include pH, Oj-sensitive electrodes, metal-ion selective electrodes,thermistors and thermocouples, " epr and nmr detection. Resonance Raman and absorption spectra have been recorded in a flowing sample a few seconds after mixing horseradish peroxidase and oxidants. In this way spectra of transients (eompounds I and II) can be recorded, and the effext of any photoreduction by the laser minimized. ... 

In this chapter, approaches to estimates of (1) the polyelectrolyte (electrostatic) effect, (2) the hydrophobicity/hydrophilicity effect, and (3) the multicoordination effect, specified for metal ion/polyelectrolyte systems are described. As weak acidic polyelectrolytes, polyacrylic acid, PAA, as well as polymethacrylic acid, PMA, are exemplified as an example of weak basic polyelectrolyte, poI y(/V-vinyI i m idazoIc), PVIm, is chosen all the chemical structures of the polymer ligands are illustrated in Figure 1. Precise poten-tiometric titration studies by the use of a glass electrode as well as respective metal ion selective electrodes have been performed for the complexation equilibrium analyses. All the equilibrium constants reported in this chapter were obtained at 298 K unless otherwise stated. 

Reference 9 gives a review of applications of atomic absorption spectrophotometry to biological samples. Tiiis technique is widely used for metal analysis in biological fluids and tissues, in environmental samples such as air and water, and in occupational health and safety areas. Routine applications of flame emission spectrometry to biological samples are generally limited to the alkali and alkaline earth metals. Ion-selective electrode measurements (Chapter 13) have largely replaced the flame emission measurements in the clinical chemistry laboratory. 

Complexometric titrations, e.g. titration of barium with EDTA, using a divalent metal ion selective electrode. 

There is a wide variety of ion-specific electrodes currently available and it would appear that new techniques will develop rapidly in the future. A promising area is the synthesis of series of cyclic polyethers by Pedersen (1967). These selectively bind alkali metal ions (Izatt et al, 1969). Such compounds hold promise for sensitive alkali-metal-ion-selective electrode membranes, and may well become the basis of some of the commercially available proprietary electrodes. 

When first developed, potentiometry was restricted to redox equilibria at metallic electrodes, limiting its application to a few ions. In 1906, Cremer discovered that a potential difference exists between the two sides of a thin glass membrane when opposite sides of the membrane are in contact with solutions containing different concentrations of H3O+. This discovery led to the development of the glass pH electrode in 1909. Other types of membranes also yield useful potentials. Kolthoff and Sanders, for example, showed in 1937 that pellets made from AgCl could be used to determine the concentration of Ag+. Electrodes based on membrane potentials are called ion-selective electrodes, and their continued development has extended potentiometry to a diverse array of analytes. 

The potential of the indicator electrode in a potentiometric electrochemical cell is proportional to the concentration of analyte. Two classes of indicator electrodes are used in potentiometry metallic electrodes, which are the subject of this section, and ion-selective electrodes, which are covered in the next section. 

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. 

National Institute of Standards and Technology (NIST). The NIST is the source of many of the standards used in chemical and physical analyses in the United States and throughout the world. The standards prepared and distributed by the NIST are used to caUbrate measurement systems and to provide a central basis for uniformity and accuracy of measurement. At present, over 1200 Standard Reference Materials (SRMs) are available and are described by the NIST (15). Included are many steels, nonferrous alloys, high purity metals, primary standards for use in volumetric analysis, microchemical standards, clinical laboratory standards, biological material certified for trace elements, environmental standards, trace element standards, ion-activity standards (for pH and ion-selective electrodes), freezing and melting point standards, colorimetry standards, optical standards, radioactivity standards, particle-size standards, and density standards. Certificates are issued with the standard reference materials showing values for the parameters that have been determined. 

Hardness can also be calculated by summation of the individually deterrnined alkaline earths by means of atomic absorption analysis. Basic samples must be acidified, and lanthanum chloride must be added to minimise interferences from phosphate, sulfate, and aluminum. An ion-selective electrode that utilizes ahquid ion exchanger is also available for hardness measurement however, this electrode is susceptible to interferences from other dissolved metal ions. 

Chlorine and fluorine in beryUium metal are isolated by pyrohydrolysis or by distUlation (21). Fluoride and chloride in the condensate are determined by ion-selective electrode or colorimetricaUy. 

Potentiometric Titrations. If one wishes to analyze electroactive analytes that are not ions or for which ion-selective electrodes are not available, two problems arise. First, the working electrodes, such as silver, platinum, mercury, etc, are not selective. Second, metallic electrodes may exhibit mixed potentials, which may arise from a variety of causes. For example, silver may exchange electrons with redox couples in solution, sense Ag" via electron exchange with the external circuit, or tarnish to produce pH-sensitive oxide sites or Ag2S sites that are sensitive to sulfide and haUde. On the other... 

The quaternary ammonium salts (QAS) are widely used as ionofores of ion-selective electrodes and extractants of metals halogenic anion complexes. The influence of the QASes nature with various methyl groups contents on the cadmium extraction from bromide media has been investigated. 

In electro-gravimetric analysis the element to be determined is deposited electroly tically upon a suitable electrode. Filtration is not required, and provided the experimental conditions are carefully controlled, the co-deposition of two metals can often be avoided. Although this procedure has to a large extent been superseded by potentiometric methods based upon the use of ion-selective electrodes (see Chapter 15), the method, when applicable has many advantages. The theory of the process is briefly discussed below in order to understand how and when it may be applied for a more detailed treatment see Refs 1-9. 

A novel development of the use of ion-selective electrodes is the incorporation of a very thin ion-selective membrane (C) into a modified metal oxide semiconductor field effect transistor (A) which is encased in a non-conducting shield (B) (Fig. 15.4). When the membrane is placed in contact with a test solution containing an appropriate ion, a potential is developed, and this potential affects the current flowing through the transistor between terminals Tt and T2. 

An example of a modem instrument of this type is the Coming Model 410 flame photometer. This model can incorporate a lineariser module which provides a direct concentration read-out for a range of clinical specimens. Flame photometers are still widely used especially for the determination of alkali metals in body fluids, but are now being replaced in clinical laboratories by ion-selective electrode procedures (see Section 15.7). 

Legin AV, Vlasov YG, Rudnitskaya AM, Bychkov EA (1996) Cross-sensitivity of chalcogenide glass sensors in solutions of heavy metal ions. Sens Actuators B 34 456 61 De Marco R, Shackleton J (1999) Cahbration of the Hg chalcogenide glass membrane ion-selective electrode in seawater media. Talanta 49 385-391... 

Pectins in the acidic form were dissolved either in pure water or in 0.1 M NaNOs and put to pH -7.2 by adding 0.05 M NaOH. Various amounts of metal ions were added to pectins solutions at two different concentrations, for 2 h under stirring at 25.0 0.1°C. Concentration of metal ions in solution at equilibrium was determined either by a potentiometric method using ion-selective electrodes for Cu2+ and Pb2+ or by a spectrophotometric method using tetramethylmurexide dye (Kwak Joshi, 1981) for Ni2+, Tsfi and Ca2+. 

Thus, the behavior of the selective membrane p N is completely equivalent to that of an electrode of metal N. Hence, membranes of this type are called ion-selective electrodes, and in the particular case discussed, the membrane is called an -selective electrode. Sometimes the term is extended to the entire left half of cell (23.5), which in addition to the membrane contains the standard solution and the reference electrode. 

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. 

Here the pure metal electrode represents the simplest ion-selective electrode, which according to the Nemst-Van t Hoff equation (cf., eqn. 2.39) yields a potential... 

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... 

Also of great interest is the so-called FIA scanning as a method for investigating, for instance, the influence of pH on the solvent extraction of metal dithizonates95 by controlled-potential continuous alteration of the pH of the carrier stream. Many other investigations can thus be made, such as the catalytic activity of enzymes and the influence of pH on ion-selective electrodes. 

Especially sensitive and selective potassium and some other ion-selective electrodes employ special complexing agents in their membranes, termed ionophores (discussed in detail on page 445). These substances, which often have cyclic structures, bind alkali metal ions and some other cations in complexes with widely varying stability constants. The membrane of an ion-selective electrode contains the salt of the determined cation with a hydrophobic anion (usually tetraphenylborate) and excess ionophore, so that the cation is mostly bound in the complex in the membrane. It can readily be demonstrated that the membrane potential obeys Eq. (6.3.3). In the presence of interferents, the selectivity coefficient is given approximately by the ratio of the stability constants of the complexes of the two ions with the ionophore. For the determination of potassium ions in the presence of interfering sodium ions, where the ionophore is the cyclic depsipeptide, valinomycin, the selectivity coefficient is Na+ 10"4, so that this electrode can be used to determine potassium ions in the presence of a 104-fold excess of sodium ions. 

The total metal concentration in a solution can be easily determined using methods such as atomic absorption spectroscopy (AAS) however, the bioavailability of different metal species likely varies. In addition, much of the original concentration may have speciated into insoluble precipitates. Therefore, the concentration of some bioavailable species may be extremely low, perhaps even within or below the nanomolar range.99 Ion-selective electrodes are useful for measuring the bioavailable concentration of a metal because they measure only the free, ionic species, which is often most prevalent.102... 

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