Redox Reactions

Question

Why do the following reactions proceed differently?

Pb3O4 +8HCl --->3PbCl2 +Cl2 +4H2O
Pb3O4 +4HNO3 --->2Pb(NO3)2 +PbO2 +2H2O

Answer

Pb3O4 is a stoichiometric mixture of 2 mol of PbO and 1 mol of PbO2. In PbO and PbO2 the oxidation state of lead is +2 and +4 respectively. PbOthus behaves as an oxidising agent and therefore can oxidise Cl- ion of HCl into chlorine. Also, PbO being basic in nature, therefore the reaction
Pb3O4 + 8HCl → 3PbCl2 + Cl2 + 4H2O
can be split into two reactions namely:
(a) Acid-base reaction
     2PbO + 4HCl  →  2PbCl2 + 2H2O
(b) Redox reaction
 +4          -1          +2    0
PbO2 + 4HCl → PbCl2 + Cl2 +2H2O
Since HNO3 itself is in oxidant, therefore, the reaction between PbO2 and HNO3 is not possible. However, the acid-base reaction occurs between PbO and HNO3 as:
2PbO + 4HNO3 → 2Pb(NO3)2 + 2H2O
                                       (acid-base reaction).
It is the passive nature of PbO2 against HNO3 that makes the reaction different from the one that follows with HCl.

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