Steric effects in electrode processes

The discharge of the lead citrate complex (PbL2−) on a mercury electrode covered by n-hexanol or n-heptanol molecules has been investigated by means of polarographic and chronocoulometric methods. The relation between the bulk surfactant concentration and the rate of the electrode reaction was examined. An average value of the steric factor r≠/ri equal to 4.0 ±0.2 was found for the cathodic electrode reaction occurring in aqueous solutions of sodium citrate containing aliphatic alcohols. The kinetic and mechanistic implications of an increase in the reactant size under such conditions are discussed.