Electrochemical reduction of acetone on mercury electrode in aqueous sulphuric acid solution

Electrochemical reduction of acetone in aqueous H₂SO₄ solution was studied on Hg electrode by galvanostatic, potentiodynamic and polarographic methods. Electrocapillary curves show that acetone molecule adsorbs to a monolayer at concentrations larger than 0·5 M in a potential range of 0 > V > ? 1·0 V (nhe). It orients with the positive end of the dipole toward electrode surface and extends an attractive interaction to its neighbours.Kinetics oberved by galvanostatic pulse method and polarography leads the following conclusions; (1) adsorbed acetone molecule undergoes elecrochemical reduction at potentials more negative than ?1·0 V (nhe), (2) reaction rate is the first and second order with respect to the amount of adsorbed acetone and proton activity, and (3) one electron transfer step determines the reaction rate (Tafel slope is 0·12 V). Reaction intermediate is concluded from the potentiodynamic study to be isopropanol radical, (CH₃)₂??OH, whose amount is proportional to that of adsorbed acetone and to a_H+. From the above results, the rate of the electrochemical reduction of acetone is H₂SO₄ solution is concluded as determined by the step, (CH₃)₂?OH(a) + H⁺ + e^? → (CH₃)₂CHOH.