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

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

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Mass Transfer
Steam distillation is not recommended to be used, if the

Material can not be distilled by indirect heating even under low pressure, because of the high boiling temperature
Azeotropic mixture is to be separated and the final product is miscible with water
Material to be distilled is thermally unstable or has the tendency to react with other components associated with it, at the boiling temperature
Liquids decompose, if distilled directly at atmospheric pressure

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