Metallized membrane electrodes

Gibbs TK, McCallum C, Pletcher D. 1977. The oxidation of carbon monoxide at platinum and gold metallized membrane electrodes. Electrochim Acta 22 525-530. 

Bergman I (1968) Metallized membrane electrode atmospheric oxygen monitoring and other applications. Nature 218 266 Blurton KF, Stetter JR (1978) A sensitive electrochemical detector for gas chromatography. J Chromatogr 155 35 5 Bonanos N (2001) Oxide-based protonic conductors point defects and transport properties. Solid State Ion 145 265-274... 

Opekar F (1989) Analytical applications of metallized membrane electrodes. Electrormrilysis 1 287-295 Opekar F, Stulik K (1999) Electrochemical sensors with solid polymer electrolytes. Aneil Chim Acta 385 151-162 Otagawa T, Zaromb S, Stetter JR (1985) Electrochemical oxidation of metheme in nonaqueous electrolytes at room temperature. J Electrochem Soc 132 2951-2957... 

J. Langmaier, F. Opekar, and V. Pacakova. Application of a metallized membrane electrode for the determination of gaseous sulfur compoimds after reductive pyrolysis. Talanta 34 453-459,1987. 

Fig. 14. The use of a metallized membrane electrode as an electrochemical filter to remove O2 so that smaller concentrations of CO2 can be determined.

The concept of the reversed fuel cell, as shown schematically, consists of two parts. One is the already discussed direct oxidation fuel cell. The other consists of an electrochemical cell consisting of a membrane electrode assembly where the anode comprises Pt/C (or related) catalysts and the cathode, various metal catalysts on carbon. The membrane used is the new proton-conducting PEM-type membrane we developed, which minimizes crossover. 

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. 

The relative measurement error in concentration, therefore, is determined by the magnitude of the error in measuring the cell s potential and by the charge of the analyte. Representative values are shown in Table 11.7 for ions with charges of+1 and +2, at a temperature of 25 °C. Accuracies of 1-5% for monovalent ions and 2-10% for divalent ions are typical. Although equation 11.22 was developed for membrane electrodes, it also applies to metallic electrodes of the first and second kind when z is replaced by n. 

Potentiometric electrodes are divided into two classes metallic electrodes and membrane electrodes. The smaller of these classes are the metallic electrodes. Electrodes of the first kind respond to the concentration of their cation in solution thus the potential of an Ag wire is determined by the concentration of Ag+ in solution. When another species is present in solution and in equilibrium with the metal ion, then the electrode s potential will respond to the concentration of that ion. Eor example, an Ag wire in contact with a solution of Ck will respond to the concentration of Ck since the relative concentrations of Ag+ and Ck are fixed by the solubility product for AgCl. Such electrodes are called electrodes of the second kind. 

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... 

Homogeneous polycrystalline membrane electrodes [see Fig. 2.10 (3)J. The relatively high electrical conductance of monoclinic / -Ag2S and its extremely low solubility product led to the development of halide and other metal ISEs with addition of silver sulphide. 

Yoon el al. [112] reported an all-solid-state sensor for blood analysis. The sensor consists of a set of ion-selective membranes for the measurement of H+, K+, Na+, Ca2+, and Cl. The metal electrodes were patterned on a ceramic substrate and covered with a layer of solvent-processible polyurethane (PU) membrane. However, the pH measurement was reported to suffer severe unstable drift due to the permeation of water vapor and carbon dioxide through the membrane to the membrane-electrode interface. For conducting polymer-modified electrodes, the adhesion of conducting polymer to the membrane has been improved by introducing an adhesion layer. For example, polypyrrole (PPy) to membrane adhesion is improved by using an adhesion layer, such as Nafion [60] or a composite of PPy and Nafion [117],... 

Electrodes based on solutions of cyclic polyethers in hydrocarbons show a selective response to alkali metal cations. The cyclic structure and physical dimensions of these compounds enable them to surround and replace the hydration shell of the cations and carry them into the membrane phase. Conduction occurs by diffusion of these charged complexes, which constitute a space charge within the membrane. Electrodes with a high selectivity for potassium over sodium (> 1000 1) have been produced. 

Two main groups of indicator electrodes are considered here. In one case, metal indicator electrodes that exhibit a potential difference as a consequence of a redox process occurring at the metal surface are examined. Later, ISEs that can respond to ionic species based on the principles of ion extraction across an active sensing membrane will be studied in detail. 

Although not strictly relevant to amperometric sensor technology, various metalloporphyrins [Co(III), Mn(III), Fe(III) Fig. 45] have been shown to sense anions potentiometrically with selectivity sequences dependent on the centrally bound metal (Amman et al., 1986 De et al., 1994). For example the anti-Hofmeister selectivity sequence SCN" > I" > CIO4 > N02 > Br > Cl- > NOJ was exhibited by PVC membrane electrodes containing [87]. 

The type of apparatus described here has been used by many workers since the early 1900s, but was not used much until the work of Devanathan and Stachurski emphasized its potential in the early 1960s. The principle is quite simple and is illustrated in Fig. 25. Two electrochemical cells are separated by a metallic membrane, which acts as the working electrode in each of the cells. 

The structure of a SPE cell is shown in Fig. 2.3. The basic unit of a SPE electrolyzer is an electrode membrane electrode (EME) structure that consists of the polymer membrane coated on either side with layers (typically several microns thick) of suitable catalyst materials acting as electrodes [43,49,50], with an electrolyzer module consisting of several such cells connected in series. The polymer membrane is highly acidic and hence acid resistant materials must be used in the structure fabrication noble metals like Pt, Ir, Rh, Ru or their oxides or alloys are generally used as electrode materials. Generally Pt and other noble metal alloys are used as cathodes, and Ir, Ir02, Rh, Pt, Rh-Pt, Pt-Ru etc. are used as anodes [43,46]. The EME is pressed from either side by porous, gas permeable plates that provide support to the EME and ensure... 

How analytical methods deal with interferences is one of the more ad hoc aspects of method validation. There is a variety of approaches to studying interference, from adding arbitrary amounts of a single interferent in the absence of the analyte to establish the response of the instrument to that species, to multivariate methods in which several interferents are added in a statistical protocol to reveal both main and interaction effects. The first question that needs to be answered is to what extent interferences are expected and how likely they are to affect the measurement. In testing blood for glucose by an enzyme electrode, other electroactive species that may be present are ascorbic acid (vitamin C), uric acid, and paracetamol (if this drug has been taken). However, electroactive metals (e.g., copper and silver) are unlikely to be present in blood in great quantities. Potentiometric membrane electrode sensors (ion selective electrodes), of which the pH electrode is the... 

Another explanation is that metal oxide electrodes behave like glass pH electrodes. The analogy, however, really does not work Glass membranes in pH electrodes connect a sample solution with a second, reference solution of known pH. The semiconductor electrode, on the other hand, is in contact with only a single solution. 

Redox potential pH Ionic activities Inert redox electrodes (Pt, Au, glassy carbon, etc.) pH-glass electrode pH-ISFET iridium oxide pH-sensor Electrodes of the first land and M" /M(Hg) electrodes) univalent cation-sensitive glass electrode (alkali metal ions, NHJ) solid membrane ion-selective electrodes (F, halide ions, heavy metal ions) polymer membrane electrodes (F, CN", alkali metal ions, alkaline earth metal ions)... 

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. 

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