Identify the overall oxidation reaction that occurs in lead storage cell during discharge.

Identify the overall oxidation reaction that occurs in lead storage cell during discharge.
  1. $\mathrm{Pb}_{(\mathrm{aq})}^{++}+\mathrm{SO}_{4(\mathrm{sq})}^{--} \longrightarrow \mathrm{PbSO}_{4(\mathrm{~s})}$
  2. $\mathrm{PbSO}_{4(\mathrm{~s})}+2 \mathrm{H}_2 \mathrm{O}_{(0)} \longrightarrow \mathrm{PbO}_{2(\mathrm{~s})}+4\mathrm{H}_{(\mathrm{aq})}^{+} +\mathrm{SO}_{4(\mathrm{xq})}^{--}+2 \mathrm{e}^{-}$
  3. $\mathrm{Pb}_{(8)}+\mathrm{SO}_{4(\mathrm{aq})}^{--} \longrightarrow \mathrm{PbSO}_{4(\mathrm{~s})}+2 \mathrm{e}^{-}$
  4. $\quad \mathrm{PbSO}_{4(\mathrm{~s})}+2 \mathrm{e}^{-} \longrightarrow \mathrm{Pb}_{(\mathrm{s})}+\mathrm{SO}_{4(\mathrm{mp})}^{--}$

Solution

When the lead storage cell provides current (i.e., during discharge), spongy lead ( $\mathrm{Pb}$ ) is oxidised to $\mathrm{Pb}^{2+}$ ions and negative charge accumulates on lead plates. The $\mathrm{Pb}^{2+}$ ions so formed combine with $\mathrm{SO}_4^{2-}$ ions from $\mathrm{H}_2 \mathrm{SO}_4$ to form insoluble $\mathrm{PbSO}_4$. The overall oxidation is the sum of these two processes. $\begin{aligned} & \mathrm{Pb}_{(\mathrm{s})} \longrightarrow \mathrm{Pb}_{(\text {(4) }}^{2+}+2 \mathrm{e}^{-} \quad \text { (oxidation) } \\ & \mathrm{Pb}_{(\text {(aq) }}^{2+}+\mathrm{SO}_{4(\text { (4) })}^{2-} \longrightarrow \mathrm{PbSO}_{4(\mathrm{~s})} \quad \text { (precipitation) } \\ & \hline \mathrm{Pb}_{(\mathrm{s})}+\mathrm{SO}_{4(\text { (aq) }}^{2-} \longrightarrow \mathrm{PbSO}_{4(\mathrm{~s})}+2 \mathrm{e}^{-} \end{aligned}$ (Overall oxidation)

Asked in: MHT CET 2023 (13 May Shift 1)

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