The Cathode

The cathode is a tool shaped to conform to the desired cut in the workpiece. The tool is usually made from copper, steel, or alloy and insulated on the sides to give directed current lines. The tool is moved during electrolysis to maintain a constant small gap (about 0.25 mm) between the electrodes to reduce the voltage required. 

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As the anodes of the cathode-grounded tubes are cooled through the ceramic insulator, narrower insulators should lead to more heat transferable. For lower voltages, tube designs with twice the actual anode load are feasible. 

The primary goal of fixer desilvering is to remove silver from the fixer solution. This desilvering occurs at the cathode, and in good desilvering units, it is performed with an efficiency of well above 90%. 

If two redox electrodes both use an inert electrode material such as platinum, tlie cell EMF can be written down iimnediately. Thus, for the hydrogen/chlorine fiiel cell, which we represent by the cell Fl2(g) Pt FICl(m) Pt Cl2(g) and for which it is clear that the cathodic reaction is the reduction of CI2 as considered in section... 

Note that chemists tend to refer to positive ions as cations (attracted to the cathode m electrolysis) and negative ions as anions (attracted to an anode). In this section of the encyclopedia, the temis positive ion and negative ion will be used for the sake of clarity. 

It should be pointed out that external polarization differs from the unbiased (open circuit) case in that after application of, say, an anodic voltage only the oxidation reaction takes place on the metal, whereas the cathodic reaction (H — H2) occurs at the external counter-electrode. 

A process resulting in a decrease in touglmess or ductility of a metal due to absorjDtion of hydrogen. This atomic hydrogen can result, for instance, in the cathodic corrosion reaction or from cathodic protection. 

When the molten ionic hydrides are electrolysed, all yield hydrogen at the anode, the metal at the cathode. 

Sodium hydroxide is manufactured by electrolysis of concentrated aqueous sodium chloride the other product of the electrolysis, chlorine, is equally important and hence separation of anode and cathode products is necessary. This is achieved either by a diaphragm (for example in the Hooker electrolytic cell) or by using a mercury cathode which takes up the sodium formed at the cathode as an amalgam (the Kellner-Solvay ceW). The amalgam, after removal from the electrolyte cell, is treated with water to give sodium hydroxide and mercury. The mercury cell is more costly to operate but gives a purer product. 

The pure oxide is dissolved in molten cryolite in an iron bath lined with graphite which acts as the cathode (see Figure 7.1). The anode... 

Crude lead contains traces of a number of metals. The desilvering of lead is considered later under silver (Chapter 14). Other metallic impurities are removed by remelting under controlled conditions when arsenic and antimony form a scum of lead(II) arsenate and antimonate on the surface while copper forms an infusible alloy which also takes up any sulphur, and also appears on the surface. The removal of bismuth, a valuable by-product, from lead is accomplished by making the crude lead the anode in an electrolytic bath consisting of a solution of lead in fluorosilicic acid. Gelatin is added so that a smooth coherent deposit of lead is obtained on the pure lead cathode when the current is passed. The impurities here (i.e. all other metals) form a sludge in the electrolytic bath and are not deposited on the cathode. 

Hence sulphuric acid is used up and insoluble lead(II) sulphate deposited on both plates. This process maintains a potential difference between the two plates of about 2 V. If now a larger potential difference than this is applied externally to the cell (making the positive plate the anode) then the above overall reaction is reversed, so that lead dioxide is deposited on the anode, lead is deposited on the cathode, and sulphuric acid is re-formed. Hence in the electrolyte, we have ... 

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

Electrolysis of hydrochloric acid yields hydrogen at the cathode and oxygen at the anode from the dilute acid, but chlorine at the anode (of carbon) from the concentrated acid. Electrolysis of the concentrated acid is used on the large scale to recover chlorine. 

Corrosion problems are particularly important when two metals are in contact. The more reactive metal becomes the cathode of the cell and goes into solution when the cell is activated by an electrolyte. A typical cell is shown in Figure 13.7. When the metal in contact with iron is more reactive than iron itself, the iron is protected from corrosion. This is important when mechanical strength... 

Mercury is extensively used in various pieces of scientific apparatus, such as thermometers, barometers, high vacuum pumps, mercury lamps, standard cells (for example the Weston cell), and so on. The metal is used as the cathode in the Kellner-Solvay cell (p. 130). 

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. 

Solutions of nitric acid in 100% sulphuric acid have a high electrical conductivity. If nitric acid is converted into a cation in these solutions, then the migration of nitric acid to the cathode should be observed in electrolysis. This has been demonstrated to occur in oleum and, less conclusively, in concentrated acid, observations consistent with the formation of the nitronium ion, or the mono- or di-protonated forms of nitric acid. Conductimetric measurements confirm the quantitative conversion of nitric acid into nitronium ion in sulphuric acid. ... 

A gravimetric method in which the signal is the mass of an electrodeposit on the cathode or anode in an electrochemical cell. 

Also, by convention, potentiometric electrochemical cells are defined such that the indicator electrode is the cathode (right half-cell) and the reference electrode is the anode (left half-cell). 

Shorthand Notation for Electrochemical Cells Although Figure 11.5 provides a useful picture of an electrochemical cell, it does not provide a convenient representation. A more useful representation is a shorthand, or schematic, notation that uses symbols to indicate the different phases present in the electrochemical cell, as well as the composition of each phase. A vertical slash ( ) indicates a phase boundary where a potential develops, and a comma (,) separates species in the same phase, or two phases where no potential develops. Shorthand cell notations begin with the anode and continue to the cathode. The electrochemical cell in Figure 11.5, for example, is described in shorthand notation as... 

The cathodic reaction (the right-hand cell) is the reduction of Fe + to Fe +... 

In potentiometry, the concentration of analyte in the cathodic half-cell is generally unknown, and the measured cell potential is used to determine its concentration. Thus, if the potential for the cell in Figure 11.5 is measured at -1-1.50 V, and the concentration of Zn + remains at 0.0167 M, then the concentration of Ag+ is determined by making appropriate substitutions to equation 11.3... 

Equations 11.19-11.21 are defined for a potentiometric electrochemical cell in which the pH electrode is the cathode. In this case an increase in pH decreases the cell potential. Many pH meters are designed with the pH electrode as the anode so that an increase in pH increases the cell potential. The operational definition of pH then becomes... 

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