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Exercise · Q24

Q.What role does sulfur play in the vulcanization of rubber, and why does vulcanized rubber not become sticky in hot weather the way raw rubber does?

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During vulcanization, sulfur atoms react with the residual C=C\text{C=C} double bonds present at every isoprene unit of NEIGHBOURING rubber chains, forming short chains of sulfur atoms -- disulfide or polysulfide bridges -- that covalently cross-link the chains together into a loosely connected three-dimensional network. Raw, un-cross-linked rubber becomes soft and tacky in hot weather because warming loosens the already-weak van der Waals attractions between its untethered chains, letting them flow and stick to surfaces they touch; the reactive double bonds along the chain also make the surface somewhat chemically 'grabby'. Once sulfur has cross-linked the chains and consumed many of those reactive double bonds, the chains are held in a fixed, covalently-bonded network that cannot flow or slide the way an uncross-linked chain can, and the surface's reactive sites are largely used up -- so vulca …

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