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

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
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

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

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