Cathodic Decomposition

Vacuum Deposition-also vapor deposition or gas plating the deposition of metal coatings by means of precipitation (sometimes in vacuum) of metal vapor onto a treated surface. The vapor may be produced by thermal decomposition, cathode sputtering or evaporation of the molten metal in air or an inert gas. 

Figure 14 schematically shows that various situations are possible here. The semiconductor is stable against cathodic decomposition if the electrochemical potential level of the corresponding reaction lies in the conduction band and against anodic decomposition if it lies in the valence band. In both cases, if the whole potential change occurs in the semiconductor (band edge pinning at the surface), this level is inaccessible to the Fermi level of the semiconductor.t For example, in the case of Fig. 14a, the semiconductor is absolutely stable because the levels of both decomposition reactions lie outside the forbidden band. However, more frequent are the cases where the semiconductor is stable against only one type of decomposition cathodic (Fig. 14b) or anodic (Fig. 14c). Finally, if both levels Fdec, and Fjec.p He in the forbidden band (Fig. 14d) the semiconductor can, in principle, suffer decomposition both under anodic and cathodic polarization.

Electrocatalysis can modify the composition of the electrode surfaces and the nature of the electrolytic products. The perchlorate decomposition (cathodic production of chloride) on platinum catalysts is one of the examples [57] and the IrCT decomposition during the sodium chlorate production [58]. The electropolymerization of the organic substances is critically dependent on the type of the electronic/ionic conductors, electrolyte characteristics, and the electrolysis resident time of the monomer [59]. 

Electrolyte Overall decomposition Cathode half-equation Anode half-equation... 

Cell Volta.ge a.ndIts Components. The minimum voltage required for electrolysis to begin for a given set of cell conditions, such as an operational temperature of 95°C, is the sum of the cathodic and anodic reversible potentials and is known as the thermodynamic decomposition voltage, is related to the standard free energy change, AG°C, for the overall chemical reaction,... 

Fig. 7. Mercury cathode electroly2er and decomposer (11) 1, brine level 2, metal anodes 3, mercury cathode, flowing along baseplate 4, mercury pump 5, vertical decomposer 6, water feed to decomposer 7, graphite packing, promoting decomposition of sodium amalgam 8, caustic Hquor exit 9, denuded mercury 10, brine feed 11, brine exit 12, hydrogen exit from decomposer 13, chlorine gas space 14, chlorine exit 15, wash water.

Silver reduces the oxygen evolution potential at the anode, which reduces the rate of corrosion and decreases lead contamination of the cathode. Lead—antimony—silver alloy anodes are used for the production of thin copper foil for use in electronics. Lead—silver (2 wt %), lead—silver (1 wt %)—tin (1 wt %), and lead—antimony (6 wt %)—silver (1—2 wt %) alloys ate used as anodes in cathodic protection of steel pipes and stmctures in fresh, brackish, or seawater. The lead dioxide layer is not only conductive, but also resists decomposition in chloride environments. Silver-free alloys rapidly become passivated and scale badly in seawater. Silver is also added to the positive grids of lead—acid batteries in small amounts (0.005—0.05 wt %) to reduce the rate of corrosion. 

Fig. 5. Energy requirements of the HaH-Hfiroult cell (23—25). E, decomposition of alumina Eg, depolarization by carbon E, anode overvoltage E, counter electromotive force E, bath voltage drop E, bath bubble voltage F/, anode voltage drop Eg, cathode voltage drop E, external voltage drop ...

The cell is the basis of all electrolysis. The anode admits current into the electrolyte and the cathode serves as a means of exit for the electrical current. The electrical flow provides a definition for electrolysis the flow of current from the anode through the electrolyte and out of the cell through the cathode with ensuing decomposition of the electrolyte, with products being formed at the electrodes. 

Main cathode reaction Anodic water decomposition Two principal cathode by-products... 

The charge state of the cell must be maintained in operation to have a cell voltage of 0.9 to 1.2 V [6]. Overcharging the cell is to be avoided due to electrolytic decomposition of water and evolution of gas. The cell voltage should therefore not exceed 1.4 V. Cathodic protection stations should be operated so that the cell voltage lies in the desired range. 

Peroxodisulfuric acid, H2S2O8, is a colourless solid mp 65° (with decomposition). The acid is soluble in water in all proportions and its most important salts, (NH4)2S208 and K2S2O8, are also freely soluble. These salts are, in fact, easier to prepare than the acid and both are made on an industrial scale by anodic oxidation of the corresponding sulfates under carefully controlled conditions (high current density, T < 30°, bright Pt electrodes, protected cathode). The structure of the peroxo-disulfate ion [now preferably called hexaoxo-/r-peroxodisulfate(2-)]0 l is OaSOOSOa " with... 

Sulphates, silicates, carbonates, colloids and certain organic compounds act as inhibitors if evenly distributed, and sodium silicate has been used as such in certain media. Nitrates tend to promote corrosion, especially in acid soil waters, due to cathodic de-polarisation and to the formation of soluble nitrates. Alkaline soils can cause serious corrosion with the formation of alkali plumbites which decompose to give (red) lead monoxide. Organic acids and carbon dioxide from rotting vegetable matter or manure also have a strong corrosive action. This is probably the explanation of phenol corrosion , which is not caused by phenol, but thought to be caused by decomposition of jute or hessian in applied protective layers. ... 

It has been noted that the total current required to protect large structures can be substantial even in mildly corrosive environments. In seawater, for example, an initial current in the region of 200mA/m for bare steel might well be required in the North Sea. This is because the relatively high oxygen concentration and the tide and wave action all contribute to a facile cathodic reaction. Fortunately this current diminishes with time. The reason for this is the protective scale on the steel surface which forms during cathodic protection by decomposition of the seawater. 

Platinum Platinum-coated titanium is the most important anode material for impressed-current cathodic protection in seawater. In electrolysis cells, platinum is attacked if the current waveform varies, if oxygen and chlorine are evolved simultaneously, or if some organic substances are present Nevertheless, platinised titanium is employed in tinplate production in Japan s. Although ruthenium dioxide is the most usual coating for dimensionally stable anodes, platinum/iridium, also deposited by thermal decomposition of a metallo-organic paint, is used in sodium chlorate manufacture. Platinum/ruthenium, applied by an immersion process, is recommended for the cathodes of membrane electrolysis cells. ... 

Overpotential. It has been found by experiment that the decomposition voltage of an electrolyte varies with the nature of the electrodes employed for the electrolysis and is, in many instances, higher than that calculated from the difference of the reversible electrode potentials. The excess voltage over the calculated back e.m.f. is termed the overpotential. Overpotential may occur at the anode as well as at the cathode. The decomposition voltage ED is therefore ... 

For the electrolysis of a solution to be maintained, the potential applied to the electrodes of the cell (Eapp ) must overcome the decomposition potential of the electrolyte (ED) (which as shown above includes the back e.m.f. and also any overpotential effects), as well as the electrical resistance of the solution. Thus, Eapp must be equal to or greater than (ED + IR), where / is the electrolysis current, and R the cell resistance. As electrolysis proceeds, the concentration of the cation which is being deposited decreases, and consequently the cathode potential changes. 

In the common method of electro-gravimetric analysis, a potential slightly in excess of the decomposition potential of the electrolyte under investigation is applied, and the electrolysis allowed to proceed without further attention, except perhaps occasionally to increase the applied potential to keep the current at approximately the same value. This procedure, termed constant-current electrolysis, is (as explained in Section 12.4) of limited value for the separation of mixtures of metallic ions. The separation of the components of a mixture where the decomposition potentials are not widely separated may be effected by the application of controlled cathode potential electrolysis. An auxiliary standard electrode (which may be a saturated calomel electrode with the tip of the salt bridge very close to the cathode or working electrode) is inserted in the... 

It must be emphasised that in evaluating the limiting cathode potential to be applied in the separation of two given metals, simple calculation of the equilbrium potentials from the Nernst Equation is insufficient due account must be taken of any overpotential effects. If we carry out, for each metal, the procedure described in Section 12.2 for determination of decomposition potentials, but include a reference electrode (calomel electrode) in the circuit, then we can ascertain the value of the cathode potential for each current setting and plot the current-potential curves. Schematic current-cathode potential... 

Daniell cell 64 d.c. arc source 763, 771 Dead-stop end points 635 Decantation 119 Decomposition potential 504 Degreasing agent 80 Delves cup 788 Demasking agents 312, 334 Densitometers 231, 232 Depolariser anodic, 515 cathodic, 509... 

A thermal plasma system has been developed for the decomposition of methane. A schematic diagram of the experimental apparatus is shown in Fig. 1. The system consists primarily of D.C. plasma torch, plasma reactor and filter assembly. Plasma was discharged between a tungsten cathode and a copper anode using N2 gas. All the experiments were carried out at atmospheric pressure at 6 kW input electric power and N2 flow rate of 10 to 12 1/min. The feed gas (CH4) flow rates were varied from 3 to 15 1/min depending on the operating conditions, shown in Table. 1. 

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