Stoichiometry
According to Raoult's law, "The vapor pressure exerted by component in a solution is proportional to the mole fraction of that component." Raoult's law is not applicable under the following assumption/condition.

The component molecules are non polar and are of almost equal size
In the formation of solution, chemical combination/molecular association between unlike molecules takes place
No component is concentrated at the surface of the solution
The attractive forces between like and unlike molecules are almost equal

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Stoichiometry
The boiling points for pure water and pure toluene are 100°C and 110.6°C respectively. Toluene and water are completely immiscible in each other. A well agitated equimolar mixture of toluene and water are prepared. If, at a total pressure of one standard atm. exerted by the vapours of water and toluene, the mole fraction of water Xw in the vapour phase satisfies

0.5 < Xw < 1.0
Xw = 1.0
0 < Xw < 0.5
Xw = 0.5

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