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A system of greater disorder of molecules is more probable. The disorder of molecules is reflected by the entropy of the system.A liquid vapourises to form a more disordered gas.When a solute is present, there is additional contribution to the entropy of the liquid due to increased randomness.As the entropy of solution is higher than that of pure liquid, there is weaker tendency to form the gas.Thus, a solute (non-volatile) lowers the vapour pressure of a liquid, and hence a higher boiling point of the solution. Similarly, the greater randomness of the solution opposes the tendency to freeze.In consequence, a lower the temperature must be reached for achieving the equilibrium between the solid (frozen solvent) and the solution.Elevation of B.Pt.(DeltaT_b) and depression of F.Pt.(DeltaT_f) of a solution are the colligative properties which depend only on the concentration of particles of the solute, not their identify.For dilute solutions. DeltaT_b and DeltaT_f are proportional to the molality of the solute in the solution. DeltaT_b=K_bm , K_b=Ebullioscopic constant=(RT_(b)^(@^(2))M)/(1000 DeltaH_(vap)) And DeltaT_f=K_fm , K_f=Cryoscopic constant=(RT_(f)^(@^(2))M)/(1000 DeltaH_(fus)) (M=molecular mass of the sovent) The values of K_b and K_f do depend on the properties of the solvent.For liquids, (DeltaH_(vap))/T_b^@ is almost constant. [Troutan's Rule, this constant for most of the unassociated liquids (not having any strong bonding like Hydrogen bonding in the liquid state ) is equal to 90 J//"mol".] For solutes undergoing changes of molecular state is solution (ionization or association), the observed DeltaT values differ from the calculated ones using the above relations In such situations, the relationships are modified as DeltaT_b=i K_bm, DeltaT_f=i K_fm where i=Van't Hoff factor, greater than unity for ionization and smaller than unity for association of the solute molecules. A mixture of two Immiscible liquids at a constant pressure of 1 atm boils at a temperature

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equal to the NORMAL boiling point of more volatile liquid
equal to the mean of the normal boiling point of the TWO liquids
greater than the normal boiling point of either of the liquid
smaller than the normal boiling point of either of the liquid

Solution :The vapour PRESSURE of a mixture of two IMMISCIBLE liquids is the sum of their vapour pressures in the pure states, independent of their relative amounts.Hence, B.Pt. of the mixture will be less than that of either of the liquids, remaining CONSTANT throughout.


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