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Q.(a) Give one example of a solution showing positive deviation from Raoult's law. (1 mark)

(b) The vapour pressure of pure benzene at certain temperature is 0.850 bar. A non-volatile non-electrolyte solute weighing 0.5 g is added to 39 g of benzene. The vapour pressure of the solution is 0.845 bar. What is the molar mass of the solute added? (Given, molar mass of benzene = 78 g mol−1^{-1}) (2 marks) OR
(c) What are azeotropic mixtures? (1 mark)
(d) Calculate the mole fraction of ethylene glycol (C2H6O2C_2H_6O_2) in an aqueous solution containing 20% of ethylene glycol by mass. (2 marks)
Meghalaya MboseMBOSE Meghalaya Intermediate Board 2024Subjective· 3mImportance★★★★★
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(a) A classic positive-deviation pair is ethanol + acetone; (b) applying Raoult's-law relative-lowering-of-vapour-pressure to the given data gives a solute molar mass of about 169 g mol⁻¹.

(a) A solution showing positive deviation from Raoult's law

Positive deviation occurs when solute–solvent (A–B) interactions in the mixture are weaker than the pure-component (A–A and B–B) interactions, so molecules escape into the vapour phase more easily than Raoult's law predicts, and ΔmixH>0\Delta_{mix}H>0 (endothermic mixing), ΔmixV>0\Delta_{mix}V>0. A standard textbook example: ethanol + acetone (mixing partly breaks ethanol's hydrogen bonding) — other valid examples are acetone + carbon disulphide, or acetone + benzene.

(b) Molar mass of the solute

By Raoult's law, the relative lowering of vapour pressure of the solvent equals the mole fraction of solute:

p1∘−psp1∘=x2=n2n1+n2\dfrac{p_1^\circ - p_s}{p_1^\circ} = x_2 = \dfrac{n_2}{n_1+n_2}

Given: p1∘=0.850p_1^\circ = 0.850 bar, ps=0.845p_s = 0.845 bar, mass of benzene w1=39 gw_1=39\ g (M1=78 g mol−1M_1=78\ g\,mol^{-1}), mass of solute w2=0.5 gw_2=0.5\ g.

Moles of benzene: n1=3978=0.5 moln_1 = \dfrac{39}{78} = 0.5\ mol

Relative lowering: 0.850−0.8450.850=0.0050.850=5.88×10−3\dfrac{0.850-0.845}{0.850} = \dfrac{0.005}{0.850} = 5.88\times10^{-3}

Since the solute is dilute (n2≪n1n_2 \ll n_1), x2≈n2n1x_2 \approx \dfrac{n_2}{n_1}:

n2=x2×n1=5.88×10−3×0.5=2.94×10−3 moln_2 = x_2 \times n_1 = 5.88\times10^{-3} \times 0.5 = 2.94\times10^{-3}\ mol

M2=w2n2=0.52.94×10−3≈170 g mol−1M_2 = \dfrac{w_2}{n_2} = \dfrac{0.5}{2.94\times10^{-3}} \approx 170\ g\,mol^{-1}

(Solving the exact, non-approximated equation x2=n2/(n1+n2)x_2=n_2/(n_1+n_2) gives n2=2.96×10−3 moln_2 = 2.96\times10^{-3}\ mol and M2≈169 g mol−1M_2 \approx 169\ g\,mol^{-1} — the same answer to 3 significant figures.)

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