POLARIZATION

At the equilibrium (non-polarized) state the rates of oxidation and reduction reactions proceeding at any electrode are equal. For example the ions of Cu are receiving electrons on the electrode surface and transfer from the electrolyte to the copper deposit. In parallel the same number of copper atoms give up their electrons and dissolve in the electrolyte. Reduction: Cu++ + 2e- = Cu

Oxidation: Cu = Cu++ + 2eThe processes produce two equal electric currents in opposite directions. The current passing through the electrode surface in the equilibrium (non-polarized) state at any direction is called exchange current.

ACTIVATION POLARIZATION
An ELECTROCHEMICAL REACTION proceeds through several successive steps. The reaction rate is controlled by the slowest step (rate-determining step) of the process.An energy barrier of should be overcome for proceeding the ratedetermining step of the process. The activation energy required for overcoming the barrier changes the ELECTRODE POTENTIAL.

Activation polarization is the overpotential (change of the electrode potential) caused by overcoming the energy barrier of the slowest step of the electrochemical reaction

Contd.
Common cause of cathodic activation polarization is the the reaction of HYDROGEN formation and evolution at the cathode surface: First step: reduction of the hydrogen ions resulted in formation of atomic hydrogen on the cathode surface. H+ + e- = H Second step: formation of molecules of gaseous hydrogen. 2H = H2 Third step: formation of hydrogen bubbles. H2 + H2 + H2 +H2 + ... = nH2 The cathode is polarized by the hydrogen atoms producing a film covering the cathode surface. The film affects the process kinetic: it slows down the reaction between the electrons and hydrogen ions dissolved in the electrolyte.

Contd.
The activation polarization overpotential may be calculated by the Tafel equation: act =-(RT/nF)ln(i/i0) = 2.3(RT/nF)log(i/i0) for cathodic activation polarization act = (RT/nF)ln(i/i0) = 2.3(RT/nF)log(i/i0) for anodic activation polarization Where R - gas constant R=8.3143 J/(mol*K); T - temperature, K; n - number of electrons transferred by one ion; F - Faraday constant F=96500 C/mol (C-coulombs); - electron transfer coefficient (0<<1); i - current density; i0 - current exchange density. The factor = 2.3(RT/nF) is called Tafel slope and then activation polarization: act = log(i/i0)

CONCENTRATION POLARIZATION
Concentration polarization of an electrode is a result of formation of a DIFFUSION LAYER adjacent to the electrode surface where there is a gradient of the ion concentration. DIFFUSION of the ions through the layers controls the electrochemical reaction (corrosion,electroplating). The electrode potential may be calculated according to the Nernst Equation:

E = E0 - (RT/nF)ln(Cion)
Where: E0 - Standard Electrode Potential, V; R - gas constant R=8.3143 J/(mol*K); T - temperature, K; n - number of electrons transferred by one ion; F - Faraday constant F=96500 C/mol (C-coulombs); Cion - molar activity (concentration) of ions

Contd.
The concentration within the diffusion layer changes from Cb (bulk concentration) to Cs (concentration at the electrode surface). Correspondingly the electrode potential changes within the diffusion layer: from Eb = E0 - (RT/nF)ln(Cb) to Es = E0 - (RT/nF)lnC(s) The difference between Es and Eb is called concentration overpotential, which is the measure of the concentration polarization: c = Es - Eb = (RT/nF)ln(Cs/Cb)