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Why do thiols have lower boiling points than corresponding alcohols?
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organosulfur compound
Examples of organosulfur compounds.
Thiols have lower boiling points than their corresponding alcohols primarily because of differences in hydrogen bonding.1
In alcohols, the strongly polarized O–H bond allows for the formation of relatively strong intermolecular hydrogen bonds, which significantly increase the energy required for the substance to transition into a gaseous state. In contrast, the S–H hydrogen bonding in thiols is much weaker. Because these intermolecular attractions are less effective at holding the molecules together, thiols are more volatile and exhibit lower boiling points than alcohols of similar structure.213