Electrochemistry
Electrochemistry
Electrochemistry
* An electrochemical cell or a galvanic cell or voltaic cell is a device used to convert chemical energy
produced in a redox reaction into electrical energy.
* A redox reaction consists of two half reactions called oxidation half reaction and reduction half
reaction.
* Salt Bridge is a U-Shaped tube containing concentrated solution of an electrolyte like KCl, KNO3,
K2SO4, etc or solidified solution of such an electrolyte in agar-agar.
* Function of salt bridge is to complete the inner circuit by flow of ions and to maintain electrical
neutrality in the solution of half cells.
* In electrochemical cell the electrode on which oxidation takes place is called anode (or negative pole)
and electrode on which reduction takes place is called cathode (or positive pole).
REPRESENTATION OF CELL
Zn+Cu2 +
Zn2++Cu
If standard condition are used ie, temp=298K, concentration =1M, pressure=1atm, the electrode Potential
is called standard electrode Potential.
Need of a reference electrode:- Absolute value of electrode potential cannot be determined because
Oxidation or Reduction half life reaction cannot occur alone. Therefore a reference electrode is required.
ELECTROCHEMICAL SERIES:-
Conductivity decreases with dilution (decrease in concentration)-for both Strong and Weak electrolyte.
Reason – Number of ions per unit volume that carry the current in a solution decreases on dilution.
λ =K V.
For strong electrolyte Λ increases slowly with dilution because inter ionic
attraction decreases with dilution.
Reason- for weak electrolytes change in Λ with dilution is due to increase in the
number of ions, in total volume of solution that contains 1 mole of electrolytes.
Batteries
Overall Reaction = Zn(Hg) + HgO(s) ZnO(s) + Hg. (Concentration of ion does not change. )
Secondary Batteries
Discharging
Anode = Lead
During the reaction of cell concn of H2So4 decreases as sulphate and hydrogen ions are consumed to form
PbSO4 + H2O.
Recharging
Recharging reverses the flow of current resulting in the formation of Pb on anode and PbO 2 on cathode.
Anode = Cadmium
Electrolytes = KOH
Fuel cells
In the cell hydrogen and oxygen are bubbled through porous Carbon electrodes into concentrated
aqueous NaOH solution.
Corrosion
Chemistry of corrosion
At cathodic site = H+ + e- H
4H + O2 2H2O
Electrolysis
Electrolysis is the process of decomposition of an electrolyte by passage of electricity through its aqueous
solution or molten state.
Electrode connected to +ve pole of battery is anode and electrode connected to –ve is cathode.
Faradays Laws
1st law :- weight of any substance deposited at any electrode is proportional to quantity of electricity
passed.
W = ZQ
Q=It
2nd law :- When same quantity of electricity is passed through solution of different electrolytes the
weights of substance deposited are directly proportional to their chemical equivalents weights.
= 96500 Coulombs.
1/R = G (conductance)
... G = A/ l
K = 1/ (kappa) = conductivity.
K = G*/R
*If cations have higher reduction potential than water cation is liberated at cathode, otherwise H 2 is
liberated by reduction of water.
*If anion has higher oxidation potential than water anion is liberated at anode otherwise O 2 due to
oxidation of water.
Cathode Na++e- Na
Cl + Cl Cl 2
OR
OR
NET RESULT:- Copper deposited at cathode from solution Eqt. Amount of Cu from anode dissolve into
solution.
* Metals with- Eo values (negative reduction potential) can liberate hydrogen from Acids.
Since hydrogen will have greater tendency to get reduced (accept electron) metals lose electrons.
Example: - Zn, Mg, Ni can liberate hydrogen from HCl, H 2SO4 etc. but Cu & Ag etc can not.
A redox reaction is feasible only if species with lower reduction potential is oxidised ie, loses electrons.
Cu/ Cu2+=0.34V
= -0.76-(+0.34)
= -1.1 V Reaction not feasible.
Nernest Equation:
Equilibrium Constant From Nernst Equation