ELECTROCHEMISTRY
1. What is the effect of catalyst on:
(i) Gibbs energy (ΔG) and
(ii) activation energy of a reaction?
Answer:
(i) There will be no effect of catalyst on Gibbs .energy.
(ii) The catalyst provides an alternative pathway by decreasing the activation
energy of a reaction.
2. Two half cell reactions of an electrochemical cell are given below :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I), E° = + 1.51 V
Sn2+ (aq) → 4 Sn4+ (aq) + 2e–, E° = + 0.15 V
Construct the redox equation from the two half cell reactions and predict if this
reaction favours formation of reactants or product shown in the equation.
Answer:
The reactions can be represented at anode and at cathode in the following ways :
At anode (oxidation) :
Sn2+ → = Sn4+ (aq) + 2e– ] × 5 E° = + 0.15 V
At cathode (reduction) :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (I)] × 2 E° = + 1.51 V
The Net R × M = 2MnO–4(aq) + 16H+ + 5Sn2+ → 2Mn2+ + 5Sn4+ + 8H2O
Now E°cell = E°cathode – E°anode
= 1.51 – 0.15 = + 1.36 V
∴ Positive value of E°cell favours formation of product.
3. Given that the standard electrode potentials (E°) of metals are :
K+/K = -2.93 V, Ag+/Ag = 0.80 V, Cu2+/Cu = 0.34 V,
Mg2+/Mg = -2.37 V, Cr3+/Cr = -0.74 V, Fe2+/Fe = -0.44 V.
Arrange these metals in increasing order of their reducing power.
Answer:
Ag+/Ag < Cu2+/Cu < Fe2+/Fe < Cr3+/Cr < Mg2+/ Mg < K+/K
More negative the value of standard electrode potentials of metals is, more will
be the reducing power.
4. Under what conditions is E0cell = 0 and ΔrG0 = 0 ?
Solution: At the condition of equilibrium, E0cell = 0 and ΔrG0 = 0
5. What does the negative sign in the expression E0Zn2+ /Zn = – 0.76 V means?
Solution: It implies that Zn is more reactive than hydrogen or it is a stronger
reducing agent. In a cell containing zinc electrode and standard hydrogen
electrode present in two half cells, zinc will be oxidised to Zn 2+ ions while
H+ ions will get reduced to hydrogen.
6. Depict the galvanic cell in which the cell reaction is : Cu + 2Ag + → 2Ag +
Cu2+.
Solution: In the cell reaction: Cu + 2Ag+ → 2Ag + Cu2+
At anode : Cu → Cu2+ + 2e
At Cathode : 2 Ag+ + 2e → 2Ag
The representation of cell = Cu(s) | Cu2+(aq) || Ag+(aq) | Ag (s)
7. Consider a cell given below
Cu |Cu²+ || Cl- | Cl₂, Pt
Write the reactions that occur at anode and cathode.
Solution: The reaction taking place at the two electrodes are:
At anode : Cu(s) → Cu2+(aq) + 2e–
At cathode: Cl2 (g) + 2e– → 2 Cl–
8. The cell in which the following reaction occurs :
2Fe3+ (aq) + 2I– (aq) → 2Fe2+ (aq) + I2 (s) has E0cell = 0.236V at 298K. Calculate
the standard Gibbs energy and the equilibrium constant of the cell reaction.
(Antilog of 6.5 = 3.162 × 106; of 8.0 = 10 × 108; of 8.5 = 3.162 × 108)
Answer:
log KC = nE0 cell 0.0591=2×0.2360.0591 = 8
KC = antilog 8 = 1 × 108
ΔG° = -nFE0cell = -2 × 96500 × 0.236
= -45548 J/mol-1
= -45.548 kJ/mol-1
9. Determine the value of ΔG° for the following reaction :
Ni(s) + 2Ag+ (aq) → Ni2+ (aq) + 2Ag(s),
E° = 1.05 V
(1F = 96500 C mol-1)
Answer:
According to the formula
ΔG° = -nFE° = – 2 × 96500 ×1.05
or ΔG° = -202650 J mol-1 = -202.65 KJ mol-1
Now ΔG° ⇒ -202650 J Mol-1
