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(i) Laboratory method : In laboratory, H2O2 is prepared by Merck’s process. It is prepared by adding calculated amounts of sodium peroxide to ice cold dilute (20%) solution of H2SO4.
Na2O2 + H2SO4 → Na2SO4 + H2O2
(ii) By the action of sulphuric acid or phosphoric acid on hydrated barium peroxide BaO2.8H2O
(a) BaO2.8H2O + H2SO4 → BaSO4 ↓+ H2O2 + 8H2O
It must be noted that anhydrous barium peroxide does not react readily with sulphuric acid (because a coating of insoluble barium sulphate is formed on its surface which stops further action of the acid). Therefore, hydrated barium peroxide, BaO2.8H2O must be used.
(b) 3BaO2 + 2H3PO4 → Ba3(PO4)2 + 3H2O2
Ba3(PO4)2 + 3H2SO4 → 3BaSO4 + 2H3PO4
Phosphoric acid is preferred to H2SO4 because soluble impurities like barium persulphate (from BaO2.8H2O + H2SO4) tends to decompose H2O2 while H3PO4 acts as preservative (negative catalyst) for H2O2.
(iii) Industrial method: On a commercial scale, H2O2 can be prepared by the electrolysis of 50% H2SO4solution. In a cell, peroxy disulphuric acid is formed at the anode.
2H2SO4 ——————→ H2S2O8 (aq.) + H2(g)
Electrolysis Peroxy disulphuric acid
This is drawn off from the cell and hydrolysed with water to give H2O2.
H2S2O8 + 2H2O ——→ 2H2SO4 + H2O2 The resulting solution is distilled under reduced pressure when H2O2 gets distilled while H2SO4 with high boiling point, remains undistilled.
(iv) By redox process: Industrially H2O2 is prepared by the auto-oxidation of 2-alkylanthraquinols. The process involves a cycle of reactions. The net reaction is the catalytic union of and to give
The H2O2 formed (about 1%) is extracted with water and concentrated.
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