09章_可逆电池的电动势及其应用.ppt

Dynamics electrochemistry Dynamics electrochemistry A Tafel plot is used to measure the exchange current density (given by the extrapolated intercept at ( = 0) and the transfer coefficient (from the slope). Dynamics electrochemistry In a simple model of the Nernst diffusion layer there is a linear variation in concentration between the bulk and the outer Helmholtz plane; the thickness of the layer depends strongly on the state of flow of the fluid. Dynamics electrochemistry Dynamics electrochemistry The change of potential with time and the resulting current/potential curve in a linear-sweep voltammeter experiment. The limiting value of the current density is proportional to the concentration of electro active species (for instance, [Ox]) in solution. Dynamics electrochemistry Dynamics electrochemistry A differential pulse polarography experiment. (a) The potential is swept linearly as a mercury droplet grows on the end of a capillary dipping into the sample, and then pulsed as shown by the green line. The resulting current is shown as the black line, and is sampled at the two points shown. (b) The data output is obtained as the difference of the currents at the two sampled points. Dynamics electrochemistry Dynamics electrochemistry (a) The change of potential with time and (b) the resulting current/potential curve in a cyclic voltammetry experiment. Dynamics electrochemistry (a) When a non-reversible step in a reaction mechanism has time to occur, the cyclic voltammogram may not show the reverse oxidation or reduction peak. (b) However, if the rate of sweep is increased, the return step may be caused to occur before the irreversible step has had time to intervene, and a typical reversible voltammogram is obtained. Equilibrium electrochemistry The salt bridge, essentially an inverted U-tube full of concentrated salt solution in a jelly, has two opposing liquid junction potentials which almost cancel. Equilibrium electrochemistry Equilibrium electrochemist