ORIENTATION OF MOLECULES OF ALIPHATIC-ALCOHOLS ADSORBED ON A MERCURY-ELECTRODE SURFACE - ANALYSIS OF STERIC FACTORS OF INHIBITED ELECTRODE-REACTIONS AND QUANTUM-CHEMICAL CALCULATIONS

The orientation of adsorbed aliphatic alcohols on mercury electrode su rface is discussed on the basis of literature data concerning steric f actors of electrochemical reactions inhibited by these alcohols and on quantum chemical calculations using the MOPAC program. Steric factors were evaluated from dependences of rate constants of electrochemical reactions of several model systems on alcohol concentration at total s urface coverage. Theoretical calculations were made for a single alcoh ol molecule interacting with a 28-atomic mercury cluster. These two se ts of data point to a vertical orientation of adsorbed alcohol molecul es, even at incomplete coverage of the electrode surface.