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Marinel Subu

Why does tetrachloromethane have a higher boiling point than trichloromethane?

London dispersion forces (LDF) are present in all molecules, whether polar or non-polar. Molecules also exhibiting dipole-dipole interactions (in addition to the LDF) must have stronger forces of attraction than those molecules which exhibit only LDF.

Then, why does tetrachloromethane (carbon tetrachloride), which is a non-polar molecule exhibiting only London dispersion forces, have a higher boiling point ($\pu{77 ^\circ C}$) than trichloromethane (chloroform) ($\pu{61 ^\circ C}$) which is a polar molecule, exhibiting dipole-dipole interactions?

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