ELECTROCHEMISTRY

PART 2
Dr. Ashima Srivastava
Dept of Chemistry
JSSATE, NOIDA
 CLASSWORK

• Sketch an electrochemical cell with Copper and Silver as electrodes dipped in their respective ion
solutions.
• Represent it with proper cell notations.
• Write down the chemical reactions
 NUMERICALS BASED ON NERNST EQUATION

If the concentrations of Fe2+ and Fe3+ are equal, what should be the concentration of Ag+ ions
to have zero voltage for a galvanic cell made up of Ag+∣Ag and Fe3+∣Fe2+ electrodes. Also,
calculate the equilibrium constant at 25oC for the following cell reaction:
Fe2+ + Ag+ → Fe3+ + Ag
Given that
EAg+/Ag=0.799V,
E Fe3+/Fe2+ = 0.771V.
(iv) To find out the pH of the solution
Example 5: Calculate the pH of the cell:
Pt, H2(g) (1atm)/H+//Ag+(1.0M)/Ag(s)
Given Ecell = 0.9V at 298K
E° Ag+/Ag = +0.80V
To find out the concentration of one of the ionic species in a cell if the concentration of the other species
is known
 QUESTIONS FOR PRACTICE

The Cu2+ ion concentration in a copper-silver electrochemical cell is 0.1M.

If Eo(Ag+/Ag) = 0.8V, Eo(Cu2+/Cu) = 0.34V, and Cell potential (at 25oC) = 0.422V, find the
silver ion concentration.
 BATTERIES

The term battery is used to represent the arrangement of two or more electrochemical cells
connected in series that can be used as a source of direct current.
Theoretically, the basis of the electrochemical cell is any redox reaction.
The redox reaction used should give the arrangement which fulfills the following requirements:
It should be light and compact.

Its voltage should not vary appreciably during its use.

It should provide power for a longer period
It should be rechargeable if possible.
 TYPES OF BATTERIES

Batteries can be classified into two categories, namely; primary battery or primary cells and secondary
battery or secondary cells.
Primary battery
This type of battery become dead over a period of time and the chemical reaction stops. They cannot
be recharged or reused.
Examples: Dry cell, Mercury cell.
Secondary battery
This type of battery can be recharged by passing direct current through them and can be used again and
again.
Examples: Lead storage battery, Nickel-cadmium storage battery.
 SECONDARY BATTERY: LEAD STORAGE BATTERY

It is the most frequently used battery in automobiles. It is a secondary battery.

It consists of a number of (3-6) electrochemical cells connected in series to get a 6-12V battery.
In each cell anode is made up of spongy metallic lead (Pb);
cathode is a grid of lead packed with lead dioxide (PbO2) and
electrolyte is dilute aqueous solution of sulphuric acid (38% by mass) having a density of 1.3 gm/ml.
SCHEMATIC DIAGRAM: LEAD STORAGE BATTERY
 WORKING OF BATTERY
(DISCHARGING OF BATTERY)
The reactions taking place during working are:

Anode Pb(s)
−
+ SO 4
2-
(aq) → PbSO4(s) + 2e

Cathode PbO2(s) + SO42-(aq) + 4H+ + 2e−→ PbSO4(s) + 2H2O(l)

Net reaction Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
During the working of the cell, the concentration of H2SO4 decreases as sulphate ions are consumed to form
PbSO4, as a result the density of the solution also decreases. The condition of the battery can be easily checked
by measuring the density of the solution.
 RECHARGING THE BATTERY

It can be recharged by connecting it to the external source of direct current. It reverses the flow of the electrons
resulting in the deposition of lead on anode and PbO2 on cathode.

During recharging the cell behaves as electrolytic cell. The recharging reactions are:

Cathode PbSO4(s) + 2e−→ Pb(s) + SO42-(aq)

Anode PbSO4(s) + 2H2O(l) → PbO2(s) + SO42-(aq) + 4H+ + 2e−

Net reaction
2PbSO4(s) + 2H2O(l) →Pb(s) + PbO2(s) + 2H2SO4(aq)
Applications: Motive power in cars, trucks, forklifts, construction equipment, recreational water
craft, standby/backup systems.

Advantages: low cost, long life cycle, and ability to withstand mistreatment. They also perform well in
high and low temperatures.

Disadvantage: Recycling causes environmental hazards.

RELATIONSHIP OF ECELL WITH ΔG, ΔH AND ΔS
The EMF of Pb/PbCl2 /KCl (M)Hg2Cl2(s)/Hg is 0.5357 V at 25°C and increase with temperature by
1.45×10-4 VK-1 . Calculate ∆H, ∆S and ∆G.
∆G = -103390 J = -103.39 KJ
∆H = -95.05 KJ/mol
∆S = 27.98 JK-1 mol-1
The EMF of the cell Cd,CdCl2 .2.5 H2O (saturated)lI AgCl(s), Ag in which the cell reaction is Cd
(s) + 2AgCl (s)+ H2O → CdCl2 .2.5 H2O (saturated) + 2Ag(s) is 0.6753V at 25°C and 0.6915V at 0
°C. Calculate ∆H, ∆S and ∆G for the cell reaction at 25°C.
∆G = -130332.9 J = -130.33 KJ
∆H = -167.7 KJ/mol
∆S = -125.064 JK-1 mol-1