NAME: GAURAV S SINGH ROLL NO: 934 CLASS : BE-4 SUBJECT: E.M.C.

.C. SEMINAR ON OVER POTENTIAL AND PERFORMANCE OF CELL GUIDED BY: PROF V.V. MATHANE

 INTRODUCTION:
OVER VOLTAGE:Overpotential means that even though you have your electrodes at the "right" potential for a reaction to occur (according to the charts), the reaction doesn't necessarily take place to a noticable degree, and you have to go to a higher potential before anything happens.

Over potential is an electrochemical term which refers to the potential (voltage) difference between a half-reaction's thermodynamically determined reduction potential and the potential at which the red ox event is experimentally observed.
Overpotential is a potential that must be applied in an electrolytic cell in addition to the theoretical potential required to liberate a given substance at an electrode. The value depends on the electrode material and on the current density.

Expressed as: n=Ei-Erevv; where Ei=voltage impressed , Errevv=E reversible, Erevv=Ecathode-Eanode..

EXAMPLE: The most commonly cited example is the oxidation of water, where two molecules of H2O come together to make an O2. In order to get the reaction to happen, you have to go to a higher potential than expected. The effect is related to the rates (kinetics) of the reactions that are happening at the electrodes, so overpotentials are most commonly needed when two or more molecules have to take part in a reaction at an electrode.

Due to overpotential : An electrolytic cell's anode is more positive using more energy than thermodynamics require. An electrolytic cell's cathode is more negative using more energy than thermodynamics require. A galvanic cell's anode is less negative supplying less energy than thermodynamically possible. A galvanic cell's cathode is less positive supplying less energy than thermodynamically possible.

Activation over potential for the evolution of selected gases on various electrode materials at 25 C Material of the electrode Hydrogen Oxygen Chlorine

Platinum (platinized)
Palladium Gold Iron Platinum (shiny) Silver Nickel Graphite Lead Zinc Mercury

0.07 V
0.07 V 0.09 V 0.15 V 0.16 V 0.22 V 0.28 V 0.62 V 0.71 V 0.77 V 0.85 V

+0.77 V
+0.93 V +1.02 V +0.75 V +0.95 V +0.91 V +0.56 V +0.95 V +0.81 V

+0.08 V

+0.10 V

+0.12 V

 Varieties of over potential: Over potentials can be judged into three categories: activation, concentration, and resistance.

Activation over potential:

Depends on the activation energy of the redox event. Refers exclusively to the activation energy necessary to transfer an electron from an electrode to an electrolyte.

Reaction over potential : Related to chemical reactions that must formally precede electron transfer. The reaction over potential can be reduced or eliminated with the use of homogeneous or heterogeneous electro catalysts . Concentration over potential: All involve the depletion of charge-carriers at the electrode surface. The concentration of charge-carriers is depleted by the physical formation of a bubble. Caused by differences in concentration of the charge-carriers between bulk solution and on the electrode surface.

Bubble over potential: It is due to the evolution of gas at either the anode or cathode. This reduces the effective area for current and increases the local current density. Example would be the electrolysis of an aqueous sodium chloride solution Resistance over potential : Includes junction over potentials, cell design, surface polarization , other sources of counter electromotive forces .

Over voltage concerned with two basics reaction. 1.Cathodic reaction 2.Anodic reaction
o o o

1.CATHODIC REACTION: Deposition process Metal over voltage Hydrogen over voltage.

HYDROGEN OVER POTENTIAL: In most cases the difference between electrode potential arising from the passage of the current on hydrogen evolution and the potential of the equilibrium hydrogen under the same conditions is identified with activation polarization since concentration polarization is small here and may be disregarded. When hydrogen is evolved from alkaline solution ,concentration polarization must be lower owing to very high concentration of discharging particles.

 2.ANODIC REACTION:
Here main concern is oxygen over voltage.

OXYGEN OVER POTENTIAL:

The anodic evolution of oxygen is nearly an important as the cathodic hydrogen evolution reaction. The reaction
constituting the decomposition of water is;

2H2O=2H2+O2
The oxygen over potential represents a considerable fraction of the total over potential in a cell for electrolysis of water and affects the consumption of electric power in the industrial electrolytic production of hydrogen and oxygen.

 REFERENCE: 1.INTERNET 2.THEORETICAL ELECTROCHEMISTRY byL.ANTROPOV

3. CLASS DISCUSSION

THANK YOU