Question 15

NUMERICALHARD

Vapour Pressure and Molar Volume of an Ideal Solution of Volatile Liquids A and B

Two volatile liquids A and B form an ideal solution. Consider a 5 molal solution of B in A inside a closed container having a total vapour pressure of 100 mm Hg100 \text{ mm Hg} at 300 K300 \text{ K}. The vapour pressure of pure A at 300 K300 \text{ K} is 105 mm Hg105 \text{ mm Hg}. Assume that A and B behave as ideal gases in the vapour phase.

Given: The gas constant R=0.08 L atm K−1 mol−1R = 0.08 \text{ L atm K}^{-1} \text{ mol}^{-1} Molar mass of A is 50 g mol−150 \text{ g mol}^{-1} Molar mass of B is 57 g mol−157 \text{ g mol}^{-1} Density of liquid B at 300 K300 \text{ K} is 0.5 g/mL0.5 \text{ g/mL} 1 atm=760 mm Hg1 \text{ atm} = 760 \text{ mm Hg}

At 300 K300 \text{ K}, the ratio of the molar volume of pure B in vapour phase to its molar volume in liquid phase is ____.

Correct Answer: 2000

Detailed Solution

  1. Determine mole fractions in solution: Molality (mm) = 5. Let mass of solvent A be 1000 g1000 \text{ g}. Moles of B (nBn_B) = 5. Moles of A (nAn_A) = 1000 g50 g/mol=20\frac{1000 \text{ g}}{50 \text{ g/mol}} = 20. Mole fraction of A (xAx_A) = 2020+5=0.8\frac{20}{20 + 5} = 0.8. Mole fraction of B (xBx_B) = 520+5=0.2\frac{5}{20 + 5} = 0.2.

  2. Find vapour pressure of pure B (PB∘P_B^\circ): Using Raoult's law: PT=PA∘xA+PB∘xBP_T = P_A^\circ x_A + P_B^\circ x_B 100=105(0.8)+PB∘(0.2)100 = 105(0.8) + P_B^\circ(0.2) 100=84+0.2PB∘100 = 84 + 0.2 P_B^\circ 16=0.2PB∘⇒PB∘=80 mm Hg16 = 0.2 P_B^\circ \Rightarrow P_B^\circ = 80 \text{ mm Hg}.

  3. Calculate molar volume of pure B in vapour phase (Vv,BV_{v,B}): Using ideal gas law: Vv,B=RTPB∘V_{v,B} = \frac{RT}{P_B^\circ} PB∘=80760 atmP_B^\circ = \frac{80}{760} \text{ atm} Vv,B=0.08×30080/760=24×76080=228 L/molV_{v,B} = \frac{0.08 \times 300}{80/760} = \frac{24 \times 760}{80} = 228 \text{ L/mol}.

  4. Calculate molar volume of pure B in liquid phase (Vl,BV_{l,B}): Vl,B=Molar massDensity=57 g/mol0.5 g/mL=114 mL/mol=0.114 L/molV_{l,B} = \frac{\text{Molar mass}}{\text{Density}} = \frac{57 \text{ g/mol}}{0.5 \text{ g/mL}} = 114 \text{ mL/mol} = 0.114 \text{ L/mol}.

  5. Calculate the ratio: Ratio = Vv,BVl,B=2280.114=2000\frac{V_{v,B}}{V_{l,B}} = \frac{228}{0.114} = 2000.

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