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This is all about linearity of the molecule and steric hindrance. Consider the linear structure of ethylene glycol versus the branched structure of propylene glycol. EG can "stack" more easily and therefore engage in more intermolecular bonding than PG. More attraction means more energy required to vaporize. On the other hand, 1,3 propane diol, ...


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When the vapor pressure equals the applied ambient pressure the liquid can form vapor in the bulk liquid hence "boiling". To accurately measure this care must be taken to mix the liquid well and to prevent overheating. At lower vapor pressures evaporation is only from the exposed surfaces.


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