Elemental cathode

As discussed above, Pt is the reference electrode material for H2 evolution since it is the most active elemental cathode. H2 is formed on Pt with a Tafel slope of 30-40 mV, the lowest ever observed for this reaction. Its cost makes this metal unsuitable for routine applications. In fact, cathode materials traditionally used in technology have long been iron or mild steel in acidic solution and Ni in (strongly) alkaline solution. Steel can also be used in moderately basic solution. 

In alkaline electrolyzers, Ni is the only elemental cathode that can be used. It is generally considered as a fairly good electrocatalyst, but in facts it exhibits two shortcomings (i) its activity decreases with time [cf. the AVtterm in Equation (7.16)] especially under conditions of intermittent electrolysis and (ii) shutdown of industrial cells (for maintenance) leads to Ni dissolution at the cathode since this electrode is driven to more positive potentials by short-circuit with the anode. These shortcomings can be alleviated if Ni cathodes are activated, that is, if they are coated with a thin layer of more active and more stable materials. Activation has been attempted with a variety of materials from sulfides to oxides, from alloys to intermetallic compounds. 

In the case of an anay of band electrodes or interdigitated electrode structures, the width of each single electrode element and the gap between the electrode elements must be considered carefully in the sensor design. Interactions between electrode elements and their effects on the transient response to a potential step perturbation will directly affect the overall sensor output. When an interdigitated electrode structure is used, chemical cross-talk among the reactants and products in both electrode elements (cathode and anode) may occur, which will then influence the sensor output [3], Therefore, the relative location of the sensing elements is also an essential consideration. 

This is a monoelemental method and it requires a tight calibration per element and a different source for each one. There are however, di- or tri-atomic cathodes available. 

L. radius, ray) Radium was discovered in 1898 by Mme. Curie in the pitchblende or uraninite of North Bohemia, where it occurs. There is about 1 g of radium in 7 tons of pitchblende. The element was isolated in 1911 by Mme. Curie and Debierne by the electrolysis of a solution of pure radium chloride, employing a mercury cathode on distillation in an atmosphere of hydrogen this amalgam yielded the pure metal. 

Fig. 10. Dow diaphragm ceU (a) Six-ceU series, (b) Internal ceU parts a, cathode elements b, cathode pocket elements c, copper spring cHps d, perforated steel backplate e, brine inlet f, chlorine oudet g, copper backplate h, titanium backplate i, anode element.

Current is fed into the electrolyzer by means of anodic and cathodic end elements. The anodic compartment of each cell is joined to an independent brine feed tank by means of flanged connections. Chlorine gas leaves each cell from the top, passing through the brine feed tank and then to the cell room collection system. Hydrogen leaves from the top of the cathodic compartment of each cell the cell Hquor leaves the cathodic compartment from the bottom through an adjustable level connection. 

The HU-type cells are offered to cover the 30—150-kA range. All of the different cell types are equipped with cathodes and anodes of identical height and width. The only difference between the various models is the number of anode—cathode elements and consequently the length of the cell. Table 11 hsts the characteristics of the various HU cells. 

Eig. 19. CME monopolar electrolyzer a, membrane b, cathode element c, half-cathode element d, current distributor e. Teflon tube f, CI2 + depleted brine manifold g, conductor rod h, CI2 + depleted brine outlet nozzle i, base frame j, recycled NaOH manifold k, recycled NaOH inlet nozzle 1, gasket (the gasket-to-element ratio is quite small) m, tie rod n, anode element o, H2 + NaOH manifold p, end plate, q, under cell bus bar (simplifies piping... 

Aqueous Corrosion. Several studies have demonstrated that ion implantation may be used to modify either the local or generalized aqueous corrosion behavior of metals and alloys (119,121). In these early studies metallic systems have been doped with suitable elements in order to systematically modify the nature and rate of the anodic and/or cathodic half-ceU reactions which control the rate of corrosion. 

Lead Telluride. Lead teUuride [1314-91 -6] PbTe, forms white cubic crystals, mol wt 334.79, sp gr 8.16, and has a hardness of 3 on the Mohs scale. It is very slightly soluble in water, melts at 917°C, and is prepared by melting lead and tellurium together. Lead teUuride has semiconductive and photoconductive properties. It is used in pyrometry, in heat-sensing instmments such as bolometers and infrared spectroscopes (see Infrared technology AND RAMAN SPECTROSCOPY), and in thermoelectric elements to convert heat directly to electricity (33,34,83). Lead teUuride is also used in catalysts for oxygen reduction in fuel ceUs (qv) (84), as cathodes in primary batteries with lithium anodes (85), in electrical contacts for vacuum switches (86), in lead-ion selective electrodes (87), in tunable lasers (qv) (88), and in thermistors (89). 

Tungsten with the addition of as much as 5% thoria is used for thermionic emission cathode wires and as filaments for vibration-resistant incandescent lamps. Tungsten—rhenium alloys are employed as heating elements and thermocouples. Tantalum and niobium form continuous soHd solutions with tungsten. Iron and nickel are used as ahoy agents for specialized appHcations. 

Another approach for the production of phosphine is an aqueous electrolytic process, whereby nascent hydrogen reacts with elemental phosphoms (70). Phosphine is produced at the cathode. 

Use of glow-discharge and the related, but geometrically distinct, hoUow-cathode sources involves plasma-induced sputtering and excitation (93). Such sources are commonly employed as sources of resonance-line emission in atomic absorption spectroscopy. The analyte is vaporized in a flame at 2000—3400 K. Absorption of the plasma source light in the flame indicates the presence and amount of specific elements (86). 

In this process, uranium metal is electrodeposited at the cathode, while plutonium and other transuranium elements remain in the molten salt as trichlorides. Plutonium is reduced in a second step at a metallic cathode to produce Cd—Pu intermetallics. The refined plutonium and uranium metals can then be refabricated into metallic fuel (137). 

Monitors. Cathode ray tube (CRT) monitors ate a key element of electronic prepress systems, providing an electronic canvas for the operator. They may also be used to judge general adequacy of color in a process called soft proofing. 

For quantitative analysis, the resolution of the spectral analyzer must be significantly narrower than the absorption lines, which are - 0.002 nm at 400 nm for Af = 50 amu at 2500°C (eq. 4). This is unachievable with most spectrophotometers. Instead, narrow-line sources specific for each element are employed. These are usually hoUow-cathode lamps, in which a cylindrical cathode composed of (or lined with) the element of interest is bombarded with inert gas cations produced in a discharge. Atoms sputtered from the cathode are excited by coUisions in the lamp atmosphere and then decay, emitting very narrow characteristic lines. More recendy semiconductor diode arrays have been used for AAS (168) (see Semiconductors). 

Another process, which also generates elemental sulfur as a by-product, has been patented by Envirotech Research Center in Salt Lake City (29). In the Electroslurry process, a ball mill finely grinds a chalcopyrite concentrate, which reacts with an acidic copper sulfate solution for iron removal. The Hquor is electrolyzed and the iron is oxidized to the ferric form. This latter step leaches copper from the copper sulfide for deposition on the cathode. Elemental sulfur is recovered at the same time. 

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