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Exercise · Q20

Q.Describe, with equations, the industrial preparation of hydrogen peroxide by

(a) the electrolytic oxidation of a bisulfate solution and
(b) the auto-oxidation of 2-ethylanthraquinol.
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  1. Electrolytic oxidation of bisulfate. A cold, concentrated solution of ammonium bisulfate (or sulfuric acid) is electrolysed using platinum electrodes. At the anode, the bisulfate ion is oxidised to peroxodisulfate:

    2HSO4−⟶S2O82−+2H++2e−2\text{HSO}_4^{-} \longrightarrow \text{S}_2\text{O}_8^{2-} + 2\text{H}^{+} + 2e^{-}

    The peroxodisulfuric acid/peroxodisulfate so formed is then hydrolysed -- carried out under reduced pressure, by distillation, to avoid decomposing the hydrogen peroxide product as soon as it forms:

    S2O82−+2H2O⟶2HSO4−+H2O2\text{S}_2\text{O}_8^{2-} + 2\text{H}_2\text{O} \longrightarrow 2\text{HSO}_4^{-} + \text{H}_2\text{O}_2

    The regenerated bisulfate can, in principle, be recycled back to the electrolytic step.
  2. Auto-oxidation of 2-ethylanthraquinol (the anthraquinone process). A solution of 2-ethylanthraquinol in a suitable organic solvent is agitated with a stream of air (or oxygen). The quinol is oxidised by the atmospheric oxygen to 2-ethylanthraquinone, and hydrogen peroxide is liberated into the solution in the same step:

    2-ethylanthraquinol+O2⟶2-ethylanthraquinone+H2O2\text{2-ethylanthraquinol} + \text{O}_2 \longrightarrow \text{2-ethylanthraquinone} + \text{H}_2\text{O}_2

    The hydrogen peroxide is then extracted from the solvent, and the 2-ethylanthraquinone left behind is catalytically reduced (using hydrogen gas over a palladium or nickel catalyst) back to the original 2-ethylanthraquinol, regenerating the starting material so the whole process can be run as a continuous cycle. This anthraquinone process is the dominant industrial route to hydrogen peroxide today.
    ✓Final answer

    1. 2HSO4−→S2O82−+2H++2e−2\text{HSO}_4^{-} \rightarrow \text{S}_2\text{O}_8^{2-} + 2\text{H}^{+} + 2e^{-} at the anode, then S2O82−+2H2O→2HSO4−+H2O2\text{S}_2\text{O}_8^{2-} + 2\text{H}_2\text{O} \rightarrow 2\text{HSO}_4^{-} + \text{H}_2\text{O}_2 on hydrolysis.
    2. 2-ethylanthraquinol is oxidised by air/O2 to 2-ethylanthraquinone while liberating H2O2\text{H}_2\text{O}_2; the quinone is then reduced back (H2/catalyst) to the quinol, so the cycle repeats continuously.

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