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Q.Why is chloroform kept in dark coloured bottles ?

CBSECBSE Class XII Board 2019Subjective· 1mImportance★★★★★
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Chloroform is stored in dark bottles because it undergoes slow oxidation in the presence of light and air to form phosgene (COCl₂), a highly toxic gas. The dark glass blocks UV/visible light, which catalyzes this free‑radical chain reaction.


The core idea: light‑catalysed decomposition

Chloroform (CHCl3\mathrm{CHCl_3}) is not inherently unstable, but it reacts with atmospheric oxygen when exposed to light (especially UV and blue wavelengths). The reaction is a free‑radical chain process:

  1. Initiation – Light energy breaks the weak C–H\mathrm{C–H} bond in chloroform, producing a trichloromethyl radical:

CHCl3→hν⋅CCl3+H⋅\mathrm{CHCl_3 \xrightarrow{h\nu} \cdot CCl_3 + H\cdot}

  1. Propagation – The radical reacts with oxygen:

⋅CCl3+O2→CCl3OO⋅\mathrm{\cdot CCl_3 + O_2 \rightarrow CCl_3OO\cdot}

This peroxy radical then abstracts a hydrogen from another chloroform molecule, forming a hydroperoxide and regenerating the ⋅CCl3\cdot\mathrm{CCl_3} radical:

CCl3OO⋅+CHCl3→CCl3OOH+⋅CCl3\mathrm{CCl_3OO\cdot + CHCl_3 \rightarrow CCl_3OOH + \cdot CCl_3}

  1. Decomposition – The hydroperoxide breaks down to yield phosgene (COCl2\mathrm{COCl_2}) and hydrogen chloride:

CCl3OOH→COCl2+HOCl\mathrm{CCl_3OOH \rightarrow COCl_2 + HOCl}

(Further reactions also produce HCl\mathrm{HCl}.)

Phosgene is a colourless, highly poisonous gas (used as a chemical weapon in WWI). Even trace amounts are dangerous.


Why a dark bottle helps

The bottle’s dark colour (usually amber or brown glass) absorbs the UV and blue wavelengths that would otherwise initiate the radical reaction. By cutting off the energy source, the chain reaction cannot start.

Watch out

A common mistake is to think chloroform decomposes spontaneously in light. It does not — it requires oxygen as well. If the bottle is completely filled (no air gap) and sealed, the risk is much lower. But in practice, some air always remains, so the dark bottle is the primary safeguard.


Additional precautions

  • Full bottles – Minimising the air space above the liquid reduces the oxygen available. …

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