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Question

The experimental values of colligative properties of many solutes in solution resembles calculated values of colligative properties.
However in some cases, the experimental values of colligative properties differ widely than those obtained by calculations. Such experimental values of colligative properties are known as abnormal values of colligative properties. The causes for abnormal values of colligative properties are:
(i) Dissociation of solute: It increases the colligative properties.
e.g.: Dissociation of KCl, NaCl etc. in H2O.
(ii) Association of solute: It decreases the colligative properties.
e.g.: Dimerisation of acetic acid in benzene.

Four different 100ml solutions are prepared by mixing 1 gram each of NaCl,(NH2)2CO,Na2SO4 and K4[Fe(CN)6] at a temperature T. Correct order of osmotic pressure is:

A
(NH2)2CO solution > NaCl solution > Na2SO4 solution > K4[Fe(CN)6] solution
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B
NaCl solution > Na2SO4 solution > (NH2)2CO solution > K4[Fe(CN)6] solution
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C
K4[Fe(CN)6] solution > Na2SO4 solution > NaCl solution > (NH2)2CO solution
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D
Na2SO4 solution > (NH2)2CO solution > NaCl solution > K4[Fe(CN)6] solution
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Solution

The correct option is B NaCl solution > Na2SO4 solution > (NH2)2CO solution > K4[Fe(CN)6] solution
NaCl solution
nNaCl = 158.5 in 100 ml
in 1000 ml = 1×1058.5 = 0.17
π=C×R×T×n
π=0.17×R×T×2
= 0.34RT

Na2SO4 solution
nNa2SO4 = 1142.04 in 100 ml
in 1000 ml = 1×10142.04 = 0.007
π=C×R×T×n
π=0.007×R×T×3
= 0.021RT

(NH2)2CO solution
n(NH2)2CO = 160 in 100 ml
in 1000 ml = 1×1060 = 0.016
π=C×R×T×n
π=0.016×R×T×1
= 0.016RT

K4[Fe(CN)6] solution
nK4[[Fe(CN)6] = 1368.35 in 100 ml
in 1000 ml = 1×10368.35 = 0.0027
π=C×R×T×n
π=0.0027×R×T×5
= 0.0027RT

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