Investigating interfacial parameters with platinum single crystal electrodes

The concepts of total and free charge of platinum single crystal electrodes are revised in this paper, together with the associated concepts of potential of zero total and free charge. Total charges can be measured from CO displacement method. Results on solution of different pH are described. A novel buffer composition is used to attain pH values close to neutrality while avoiding interferences from anion adsorption processes. Stress is made on the fact that free charges are not accessible through electrochemical measurement for systems at equilibrium since adsorption processes (hydrogen and hydroxyl) interfere with free charge determination. Still, a model is described that allows, under some assumptions, extract free charge values and the corresponding potential of zero free charge for Pt(111) electrodes. On the other hand, fast measurement outside equilibrium can separate free charges from adsorption processes based on their different time constant. In this way, the laser induced temperature jump experiment allows determination of the potential of maximum entropy, a magnitude that is intimately related with the potential of zero free charge. Values of the potential of maximum entropy as a function of pH are given for the different basal planes of platinum.