Applied Electrochemistry

Cover Applied Electrochemistry
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In support of Le Blanc's theory it may be stated that tetravalent lead ions do exist, and they are therefore probably capable of forming by the electrolysis of lead sulphate solutions.
Liebenow's theory differs from Le Blanc's only as to the action of the peroxide electrode. According to this theory the lead peroxide goes into solution as doubly charged lead per- oxide ions, so that the peroxide plate is to be considered a reversible electrode with respect to the peroxide ions. On discharge, th
...e peroxide passes into the solution surrounding the peroxide plate, which is already saturated with respect to these ions. They then react with the hydrogen ions of the acid as follows : PbO 2 + 4 H+ = Pb + 2 H 2 O. (17) The lead ions then combine with the sulphate ions to form solid lead sulphate : Pb + Sl) 4 = PbSO 4 solid. (18) During charge, just the reverse reactions take place. The lead peroxide ions are deposited on the positive plate, and are replaced as they are used up by the solution of the sulphate from the electrode and its hydrolysis : Pb + 2 H 2 = Pb0 2 + 4 H+.

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