Effect of the temperature on the electrochemical behaviour of aliphatic alcohols

The effect of temperature on the electrochemical behaviour of aliphatic alcohols on Pt is studied by the potential sweep method in the temperature range 15°–60° C. No changes in the mechanism of electrooxidation of primary alcohols are observed. In the current—potential curves of secondary alcohols a new maximum at about 0.9 V appears at higher temperatures connected probably with the oxidation of products of the destructive chemisorption in the double-layer region on anodic sweep. Unexpected electrochemical activity is found for tertiary alcohols at higher temperatures. The mechanism of electrooxidation of the latter compounds differs strongly from that of the two other types of alcohols, which is attributed to the lack of hydrogen at the α-C atom. Apparent activation energies are calculated in the different potential ranges.