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Several factors go into it. Usually, whatever has the weaker intermolecular forces will have the lower boiling point. For example, if comparing two molecules and one is capable of hydrogen bonding, that one will have the higher boiling point. If one is capable of dipole-dipole interactions and the other only has London dispersion then the former will have the higher boiling point. If two molecules being compared have the same possible intermolecular forces, the larger molecule has the higher boiling point.
Boiling point refers to the breaking of intermolecular forces that hold a substance together. The stronger the intermolecular force, the harder it is to boil a liquid/solid into a gaseous state. Hydrogen bonding is the strongest, followed by dipole-dipole, then london dispersion.
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