Mass Transfer
When the liquid phase and vapour phase of a binary system obeys Raoult's and Dalton's law respectively, the relative volatility is the ratio of

Vapour pressure of component A to the partial pressure of A
Vapour pressure of component A to that of component B
Vapour pressure of component A to the total pressure
Partial pressure of component A to the total pressure

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Mass Transfer
In case of steam distillation, the steam leaving the liquid is not completely saturated with distillate vapour, because

Mixing of steam with the material being vaporised is not so intimate as to result in equilibrium condition
Temperature is less
Saturated steam is used for steam distillation
Total pressure is less

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