Past exam of the medicine course of the University of Oxford / 1867 / First examination / Chemistry / 3

How is bleaching-powder made ? What are its chief properties ?

Bleaching powder is made by passing chlorine over slaked lime, exposing a large surface of the powder to the gas. The contemporary name “chlorinated lime” is more informative than treating it as pure calcium chloride. The 1867 British Pharmacopoeia (1867) describes this manufacture and a dull-white, partly water-soluble powder with bleaching and disinfecting properties.^[ref]

An idealized overall chemical equation isThe chlorine undergoes disproportionation: one part becomes chloride, with oxidation state $-1$, and another becomes hypochlorite, with oxidation state $+1$. Commercial bleaching powder contains residual calcium hydroxide, water and chlorine-bearing solid phases; the chemical equation is a useful composition balance, not a claim that the powder is one pure molecular substance or simply a fully characterized mechanical mixture. The old formula ${\mathrm{CaOCl}}_2$ is an abbreviated representation, not the formula of pure calcium hypochlorite, ${\mathrm{Ca}(\mathrm{OCl})}_2$.

Its chief properties follow from the hypochlorite chemistry. The aqueous extract is alkaline and oxidizing. The chemical equilibriumproduces hypochlorous acid on lowering the pH. Oxidation of coloured organic compounds can destroy the chromophores responsible for their colour. This is irreversible chemical alteration of a dye, rather than merely washing it away. The historical description that bleaching works through “nascent oxygen” is not a necessary modern mechanism: hypochlorous acid and related reactive chlorine species themselves react with substrates.

With sufficient hydrochloric acid, the hypochlorite and chloride can generate chlorine:This explains acid-induced gas evolution and why acidification is not an innocuous way to use a bleaching material. Exposure, moisture and heating can reduce the stored oxidizing strength. Its useful strength is measured as available chlorine, rather than inferred from the powder's total mass or its smell; inert material and residual lime do not provide the same bleaching capacity.