Electrochemicalimpedancespectroscopy-ETHZürich.ppt

* * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * Polarization Resistance Whenever the potential of an electrode is forced away from its value at open circuit, that is referred to as polarizing the electrode. When an electrode is polarized, it can cause current to flow via electrochemical reactions that occur at the electrode surface. The amount of current is controlled by the kinetics of the reactions and the diffusion of reactants both towards and away from the electrode. In cells where an electrode undergoes uniform corrosion at open circuit, the open circuit potential is controlled by the equilibrium between two different electrochemical reactions. One of the reactions generates cathodic current and the other anodic current. The open circuit potential ends up at the potential where the cathodic and anodic currents are equal. It is referred to as a mixed potential. The value of the current for either of the reactions is known as the corrosion current. The Butler Volmer equation: For the polarization resistance of simple reactions at electrodes When there are two simple, kinetically controlled reactions occurring, the potential of the cell is related to the current by the following (known as the Butler-Volmer equation). I is the measured cell current in amps,Icorr is the corrosion current in amps,Eoc is the open circuit potential in volts,?a is the anodic Beta coefficient in volts/decade,?c is the cathodic Beta coefficient in volts/decade If we apply a small signal approximation (E-Eoc is small) to the buler Volmer equation, we get the following: which introduces a new parameter, Rp, the polarization resistance. As you might guess from its name, the polarization resistance behaves like a resistor. If the Tafel constants ?i are known, you can calculate the Icorr from Rp. The Icorr in turn can be used to calculate a corrosion rate. We will further discuss the Rp parameter when we discuss cel