The chemical reactions that occur at the electrodes during electrolytic conduction constitute electrolysis.

When liquid (molten) sodium chloride, for example, is electrolyzed, we find that the Na+ ion move toward the negative electrode and the Cl- ions move toward the positive electrode (Figure, 16,3) the reactions that take place at the electrodes are Positive electrode Negative electrode Na- + eNa oxidation reduction

In electrochemistry we assign the terms cathode and anode according to the chemical reaction that is taking place at the electrode. Reduction always takes place at the chatode and oxidation always taken place at the anode. Thus, in our electrolysis reaction above, we label the negative electrode the cathode and the positive electrode the anode. The net chemical change that takes place in the electrolytic cell is called the cell reaction. It is obtained by adding together the anode and cathode reactions in such a way that the same procedure that we used in the ion electron. Method of balancing oxidation-reduction reaction. Thus, in this case we must mulitiply the reduction half reaction by 2 get () () ( ) ()

() () ( ) () In this electrolytic cell, then, sodium is formed at the cathode and chlorine gas at the anode. This is one of the major sources of pure sodium metal and chlorine gas in the United States. The electrolysis of aqueous solutions of electrolytes is somewhat more complex because of ability of water to be oxidized as well reduced. The oxidation reaction for water is () ( ) ( )

And the reduction reaction takes the form () ( ) ( ) In acidic solutions another reaction that may take place is the reduction of H+, which is ( ) ( )

Reaction 16.3 is not, however, a major reaction in most dilute aqueous solutions that we shall consider. In aqueous solution, then we have the possible oxidation and reduction of the solvent in addition to the possible oxidation and reduction of the ions of the

solute. Whether the solute anion or water is going to be oxidized, or whether the solute cation or water is going to be reduced , depents on the relative ease of the two competing reactions, as well shall see in the next few examples. Electroplating. We have just seen how copper can be plated out on an electrode in an electrolysis cell. The plating out of the metal in this fashion is called electroplating. If we replaced the cathode in the cell in figure 16.5 with another metal, the surface of that metal will also become covered with a layer of pure copper when the current is appliec. Other metals can be electroplated as well as copper, which makes this process of great commercial importance. In the manufacturing of automobiles, for example, various parts, such as steel bumpers, are electroplated with chromium for beauty as well as for protection against corrosion. Michael faraday was the first to describe, in a quantitative fashion, the relationship that exists between the amount of current used and the extent of the chemical change that takes place at the electrodes during electrolysis. The extent of an electrolysis reactions is, of course, related to the number of moles of electrons lost or gained in the oxidation-reduction reactions, respectively. For example, in the reactions for the reduction of silver ion the silver metal,

1 mol of electrons reacts with 1 mol of silver ions to give 1 mol, or 107,87 g, of solid silver (the amoundt of silver deposited can be determined experimentally by weighing the cathode before and after the current is supplied to the cell). Thus, in this case, when 107,87 g of silver are deposited on the cathode, we know that 1 mol of electrons must have passed through the cell. The quantity of electricity that must be supplied to a cell in order for 1 mol of electrons to undergo reaction, has been know historically as faraday (F). In the above example, then, 1 F was supplied to produce the 107,78 g of silver, and it would take 2 F to produce 215,74 g of silver, and so on. Actually, the faraday is just another way of saying a mole of electrons. Another important unit is the coulomb (C). One coulomb is the quantity of charge that moves past any given point in a circuit when a current of 1 ampere (A) is supplied for 1 second (s). Thus, Experimentally, it is found that 1 F is equivalent to 96,487 coulombs, or 96,500 when rounded off to three significant figures. Thus, Experimentally, it is found that 1 F is equivalent to 96,487 coulombs, or 96.500 when rounded off to three significant figures. Thus, Lets look at some examples of how these concepts can be applied.

All the tripositive aquo ions of these elements are acidic, that of aluminium the least and that of tallium the most so. Thus aqueous solutions of their salts are appreciably hidrolyzed, and salts are appreciably hydrolysed, and salts of weak acids (e.g. carbonates and cyanides) cannot exist in contact with water. Nucklear magnetic resonance studies have shown that in acidic solution aluminium is present as the [Al(H2O)6]3+ ion as the acidity is decreased, polymeric hydrolysed spesies such as hydrated [Al2(OH2)]4 and [Al7(OH)16]5+ appear, then Al(OH)3 is precipitated, and finally, in alkaline solutions, aluminate anions such as [Al2(OH)6]3+, [Al(OH)4]- and polimeric species like [(HO)3AlOAl(OH)3]2- are formed. The chemistry of gallium is broadly similar to that of aluminium in this respect indium and thallium(III) hydroxides, howeve, are not amphoteric. Redox potential data show that Al3+ (aq) is much lest readily reduced than the other tripositive cations in aqueous solutions this doubtless arises partly from a more negative hydration free energy of the smaller Al3+ ion, but another important contributory factor is the increases in ionisation energies between aluminium and gallium, and and between indium and thallium there is relatively little variation is atomisation enthalpies, and the overall variation in E is therefore quite different from that in the two proceding groups of elements. Was discussed the influence of hydrogen ion concentration on the formation of iron (III) acetylacetone in aqueous solution and on the extraction of iron into organic solvents by acetylacetone. Since formation of the aluminium compound , [Al(acac)3], is an exactly analogous process, we shall not repeat the treatment here. We may however, note that 8-hydroxyquinoline (oxine) fro