JEE (Adv.

)-Chemistry Solution & Colligative Properties

Marked Questions may have for Revision Questions.

PART - I : SUBJECTIVE QUESTIONS
Section (A) : Concentration terms (Revision of mole)

Commit to memory :
no. of moles of solute no. of moles of solute
Molarity = ; Molality = × 1000
volume of solution (in L) W(g) of solvent

molarity 1000
Molality = (where d is density of solution in g/ml)
1000d molarity m.wt.of solute

w m solute (g) n
% 100 ; xsolute = (where, n is moles of solute, N is moles of solvent)
w msolution (g) n N
xsolute + xsolvent = 1

A-1. Calculate the concentration of NaOH solution in g/ml which has the same molarity as that of a solution of HCl
of concentration 0.0365 g/ml.
A-2. The density of 2M solution of sodium sulphate (Na2SO4) is 1.284 g/ml. Calculate
(i) amount of Na2SO4 in % w/w
(ii) mole fraction of Na2SO4
(iii) molality of Na+ and SO42- ions.
A-3. Calculate the molality and molarity of a solution made by mixing equal volumes of 30% by weight of H2SO4
(density = 1.20 g/mL) and 70% by weight of H2SO4 (density = 1.60 g/mL).
Section (B) : General Introduction & types of solution
B-1. What are the characteristics of the supersaturated solution.
B-2. Why are some solution processes exothermic whereas others are endothermic ?
Section (C) : Vapour Pressure

Commit to memory :
* The partial pressure of vapours of X in equilibrium with X at a given temperature is called as its vapour
pressure. (X is given pure solid or pure liquid)

* A gas is said to be saturated with vapours of a liquid if the partial pressure of liquid vapours is equal to its
(saturated) vapour pressure.

* Partial pressure of vapours of X (pure solid or liquid) will remain equal to its vapour pressure till the vapours
of X are in equilibrium with X.

C-1._ Write the order of vapour pressure for the following

(i) n-C6H14
(ii) n-C7H16
(iii) n-C8H18
C-2. The vapour pressure of water at 80ºC is 355 torr. A 100 ml vessel contained water saturated oxygen at
80º C, the total gas pressure being 760 torr. The contents of the vessel were pumped into a 50.0 ml, vessel at
the same temperature. What were the partial pressures of oxygen and of water vapour and the total pressure
in the final equilibrium state ? Neglect the volume of any water which might condense.
JEE (Adv.)-Chemistry Solution & Colligative Properties
Section (D) : Solutions of Solid and Gases in Liquids

Commit to memory :

* Henry’s law : The solubility of gas in a liquid at a given temperature is directly proportional to its partial
pressure above liquid in which it is dissolved.
P = KHx(where x is mole fraction of unreacted, dissolved gas and P is its partial pressure above liquid.)
D-1. How many gm O2 gas will disolve in 100 gm water at 9 bar and 27°C? (KH = 40 Kbar)
D-2. If N2 gas is bubbled through water at 293 K, how many millimoles of N2 gas would dissolve in 1 litre of water,
if N2 exerts a partial pressure of 0.987 bar. Given that Henry's law constant for N2 at 293 K is 76.48 kbar.
Section (E) : Immiscible Liquids

Commit to memory :
If A and B are volatile immiscible liquids, then above their mixture.
* PT = PºA + PºB (PT = Total pressure above mixture of A and B, PºA = vapour pressure of A,
PºB = vapour pressure of B)

PAº nA
= n (nA and nB are moles of A and B in distillate)
PBº B

wA PA MA
(wA and wB are masses of A and B in distillate, MA and MB are molar masses of A and B)
wB PB MB

E-1. A mixture of an organic liquid A and water distilled under one atmospheric pressure at 99.2ºC. How many
grams of steam will be condensed to obtain 1.0 g of liquid A in the distillate ? (Vapour pressure of water at
E-2. Boiling point of a mixture of water and nitrobenzene is 99°C, the vapour pressure of water is 733 mm of Hg and
the atmospheric pressure is 760 mm of Hg. The molecular weight of nitrobenzene is 123. Find the ratio of
weights of the components of the distillate.
Section (F) : Completely miscible liquids : Raoult’s law

Commit to memory :
Statement of Raoult's law ( for volatile liq. mixture ): In solution of volatile liquids, the partial vapour
pressure of each component is directly proportional to its mole fraction in solution.
pA xA
pA = xAPAº ....... (1)
where pA = Partial vapour pressure of component A, x A = Mole fraction of component ‘A’ in solution,
PAº = Vapour pressure of pure component ‘A’ at given temperature

Hence PT = xAPAº + xBPBº ....... (2)

(PT = Total pressure of vapour above solution, PBº = vapour pressure of pure component 'B' at given
temperature.)
1 yA yB
Thus, P = o + o (for complete derivation, refer page no. 12 of sheet)
T PA PB
(yA = mole fraction of A in vapour phase above the solution and yB = mole fraction of B in vapour phase above
the solution)
F-1. Two liquids, A and B, form an ideal solution. At the specified temperature, the vapour pressure of pure A is 200
mm Hg while that of pure B is 75 mm Hg. If the vapour over the mixture consists of 50 mol percent A, what is
the mole percent A in the liquid ?
JEE (Adv.)-Chemistry Solution & Colligative Properties
F-2._ Liquids 'X' and 'Y' form an ideal solution. The vapour pressure of solution may be expressed as :
P[/cmHg] = (80 – 25x), where 'x' is the mole-fraction of liquid 'X' in the liquid solution at equilibrium. Calculate
the vapour pressures of pure liquids 'X' and 'Y'.
F-3. At 80oC, the vapour pressure of pure benzene is 753 mm Hg and of pure toluene 290 mm Hg. Calculate the
composition of a liquid in mole per cent which at 80oC is in equilibrium with the vapour containing 30 mole per
cent of benzene.
F-4._ Liquid 'R' and 'S" form an ideal solution. The mole-fraction of 'R' in liquid and vapour phases at equilibrium are
0.25 and 0.40, respectively. If the vapour pressure of solution is 0.50 bar, calculate PR0 and PS0

F-5. Two liquids A and B form an ideal solution. At 300 K, the vapour pressure of a solution containing 1 mole of A
and 3 moles of B is 550 mm of Hg. At the same temperature, if one mole of B is added to this solution, the
vapour pressure of the solution increases by 10 mm of Hg. Determine the vapour pressure of A and B in their
pure states.

Section (G) : Non-ideal Solutions

Commit to memory :

* +ve deviation –ve deviation

PT.exp > (xAPºA + xBPºB) PT.exp < (xAPºA + xBPºB)

(where PT.exp is experimental total pressure above mixture of volatile liquids A and B).

Hmix = +ve Hmix = –ve

Vmix = +ve Vmix = –ve

Smix = +ve Smix = +ve

Gmix = –ve Gmix = –ve

G-1. A non ideal solution was prepared by mixing 30 ml chloroform and 50 ml acetone. Comment on volume of
mixture.
G-2. Total vapour pressure of mixture of 1 mole of volatile component A (PºA = 100 mm Hg) and 3 mole of volatile
component B (PºB = 80 mm Hg) is 90 mm Hg. Find out nature of solution and sign of entropy of solution.

Section (H) : Degree of Ionisation/Dissociation for Weak Electrolytes

Commit to memory :

* For dissociation / association i = 1 + (n – 1)

(where n is total number of particles produced per solute particle after association / dissociation, i = vant
Hoff factor, = degree of dissociation / association.
Moles of solute particles after association / dissociation of X Observed value of colligative property
i= Moles of X without association / dissociation
= Theoretical value of that colligative property

Theoretical molar mass of solute

i = Observed molar mass of solute
JEE (Adv.)-Chemistry Solution & Colligative Properties
H-1. Complete the following table. (Use : i = 1 + (n – 1) )

Dissociation / association
Solute Degree of dissociation / association n i
reaction
NaCl 1
H2SO4 1
CH3COOH
0.2
(in water)
CH3COOH
0.5
(in benzene)
Glucose
KBr 0.8

A 3A A3 1

H-2. Calculate the percentage degree of dissociation of an electrolyte XY2 (Normal molar mass = 164) in water if
the observed molar mass by measuring elevation in boiling point is 65.6.

Section (I) : Relative lowering of vapour pressure

Commit to memory :

P º PS Pº Ps n
* RLVP = = xsolute ; Ps =
Pº N
(where Pº = vapour pressure of pure solvent, Ps = partial pressure of vapour above solution, n = dissolved
moles of solute, N = moles of solvent.)

Pº Ps msolute (g) Msolvent

Ps = × (where m = given mass in solution, M = molar mass.)
Msolute msolvent(g)

Pº Ps Msolvent
Ps = ( molality ) ×
1000
If solution is of single solute and it gets associated or dissociated;
Pº Ps i.n Pº Ps Msolvent
Ps = ; that is Ps = i × (molality) ×
N 1000

I-1._ The vapour pressure of pure liquid solvent A is 0.80 atm. When a nonvolatile substance B is added to the
solvent its vapour pressure drops to 0.60 atm. What is the mole fraction of component B in the solution?

I-2. The degree of dissociation of Ca(NO3)2 in a dilute aqueous solution containing 7 g salt per 100 g of water at
100ºC is 70%. If the vapour pressure of water at 100ºC is 760 mm of Hg, calculate the vapour pressure of the
solution.

I-3._ The vapour pressure of pure benzene at 30° C is 640 mm of Hg and the vapour pressure of a solution of a
solute in C6H6 at the same temperature is 624 mm of Hg. Calculate molality of solution.
JEE (Adv.)-Chemistry Solution & Colligative Properties
Section (J) : Elevation of Boiling Point & Depression of Freezing Point

Commit to memory :

* Tb = i × Kb × m (where Tb = elevation in boiling point of solution, Kb = ebullioscopic constant,

m = molality of single solute, Tb = boiling point of solvent (in K).
2 2
RTb M RTb
Kb = = (M = Molar mass of solvent)
1000 Hvap 1000 L vap
Tf = i × Kf × m (where Tf = depression in freezing point of solution, Kf = cryoscopic constant,
Tf = freezing point of solvent (in K).
2 2
RTf M RTf
Kf = =
1000 Hfusion 1000 L fusion

J-1. (a) A solution containing 0.5 g of naphthalene in 50 g CCl4 yield a boiling point elevation of 0.4 K, while a
solution of 0.6 g of an unknown solute in the same mass of the solvent gives a boiling point elevation of 0.65
K. Find the molar mass of the unknown solute.
(b) The boiling point of a solution of 0.1 g of a substance in 16 g of ether was found to be 0.100ºC higher that of
pure ether. What is the molecular mass of the substance. Kb(ether) = 2.16 K kg mol–1.
J-2. The amount of benzene that will separate out (in grams) if a solution containing 7.32 g of triphenylmethane in
1000 g of benzene is cooled to a temperature which is 0.2°C below the freezing point of benzene?
(Kf = 5.12 K-Kg/mol)
J-3. The boiling point of a solution of 5 g of sulphur in 100 g of carbon disulphide is 0.474ºC above that of pure
solvent. Determine the molecular formula of sulphur in this solvent. The boiling point of pure carbon disulphide
is 47ºC and its heat of vaporisation is 84 calories per gram.

J-4. Calculate the freezing point of a solution of a non-volatile solute in a unknown solvent of molar mass 30 g/
mole having mole fraction of solvent equal to 0.8. Given that latent heat of fusion of solid solvent = 2.7 kcal
mol–1, freezing point of solvent = 27°C and R = 2 cal mol–1 k–1.

Section (K) : Osmotic Pressure

Commit to memory :
n
* = CRT = RT (n = Total moles of solute particles in solution, V = Total volume of solution in L)
V
K-1. (a) Predict the osmotic pressure order for the following(assume salts are 100% dissociated).
I 0.1 M urea II 0.1 M NaCl
III 0.1 M Na2SO4 IV 0.1 M Na3PO4
(b) If equal volumes of all these solutions are mixed then calculate the osmotic pressure of the net
resultant solution obtained at 300K.
K-2. A solution containing 3.00 g of calcium nitrate in 100 c.c. of solution had an osmotic pressure of 11.2
atmosphere at 12° C. Calculate the degree of ionisation of calcium nitrate at this dilution and temperature.
K-3._ Calculate the osmotic pressure of a solution containing 18 gm glucose and 17.1 gm canesugar (C12H22O11)
per litre, at 27°C.
K-4. At 2ºC the osmotic pressure of a urea solution is found to be 500 mm of Hg. The solution is diluted and the
temperature is raised to 27ºC, when the osmotic pressure is found to be 109.09 mm of Hg. Determine the
extent of dilution.
JEE (Adv.)-Chemistry Solution & Colligative Properties

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : Concentration terms (Revision of mole)
A-1. Persons are medically considered to have lead poisoning if they have a concentration greater than 10 micrograms
of lead per decilitre of blood. Concentration in parts per billion is : (Given : Density of Blood = 1g/ml)
(A) 1000 (B) 100 (C) 10 (D) 1
Section (B) : General Introduction & types of solution
B-1. Which statement best explains the meaning of the phrase “like dissolves like “ ?
(A) A Solute will easily dissolve a solute of similar mass
(B) A solvent and solute with similar intermolecular forces will readily form a solution
(C) The only true solutions are formed when water dissolves a non-polar solute
(D) The only true solutions are formed when water dissolves a polar solute
B-2. An ionic compound that attracts atmospheric water so strongly that a hydrate is formed is said to be :
(A) Dilute (B) Hygroscopic (C) Immiscible (D) Miscible
Section (C) : Vapour Pressure
C-1. A liquid is kept in a closed vessel. If a glass plate (negligible mass) with a small hole is kept on top of the
liquid surface, then the vapour pressure of the liquid in the vessel is :
(A) More than what would be if the glass plate were removed
(B) Same as what would be if the glass plate were removed
(C) Less than what would be if the glass plate were removed
(D) Cannot be predicted
C-2. The vapour pressure of water depends upon :
(A) Surface area of container (B) Volume of container
(C) Temperature (D) All
C-3. Among the following substances, the lowest vapour pressure is exerted by :
(A) Water (B) Mercury
(C) Acetone (D) Ethanol
C-4. At higher altitudes, water boils at temperature < 100ºC because
(A) temperature of higher altitudes is low (B) atmospheric pressure is low
(C) the proportion of heavy water increases (D) atmospheric pressure becomes more.

Section (D) : Solutions of Solid and Gases in Liquids

D-1. The solubility of gases in liquids :
(A) increases with increase in pressure and temperature
(B) decreases with increase in pressure and temperature
(C) Increases with increase in pressure and decrease in temperature
(D) decreases with increase in pressure and increase in temperature
D-2. According to Henry’s law, the solubility of a gas in a given volume of liquid increases with increase in :
(A) Temperature (B) Pressure (C) Both (A) and (B) (D) None of these

D-3. Some of the following gases are soluble in water due to formation of their ions :
I : CO2 ; II : NH3 ; III : HCl ; IV : CH4 ; V : H2
Water insoluble gases can be :
(A) I, IV , V (B) I, V (C) I, II, III (D) IV, V

D-4. The solubility of N2(g) in water exposed to the atmosphere, when its partial pressure is 593 mm is
5.3 × 10–4 M. Its solubility at 760 mm and at the same temperature is :
(A) 4.1 × 10–4 M (B) 6.8 × 10–4 M (C) 1500 M (D) 2400 M
JEE (Adv.)-Chemistry Solution & Colligative Properties
Section (E) : Immiscible Liquids
E-1. When a liquid that is immiscible with water was steam distilled at 95.2ºC at a total pressure of 748 torr, the
distillate contained 1.25 g of the liquid per gram of water. The vapour pressure of water is 648 torr at 95.2ºC,
what is the molar mass of liquid?
(A) 7.975 g/mol (B) 166 g/mol (C) 145.8 g/mol (D) None of these
E-2.. If two liquids A (PºA =100 torr) and B (PºB = 200 torr) are completely immiscible with each other, each one will
behave independently of the other, are present in a closed vessel. The total vapour pressure of the system will
be:
(A) less than 100 torr (B) less than 200 torr
(C) between 100 to 200 torr (D) 300 torr

Section (F) : Completely miscible liquids : Raoult’s law

F-1. For a binary ideal liquid solution, the total pressure of the solution is given as :
(A) Ptotal = PºA + (PºA – PºB) XB (B) Ptotal = PºB + (PºA – PºB) XA
(C) Ptotal = PºB + (PºB – PºA) XA (D) Ptotal = PºB + (PºB – PºA) XB
F-2. Mole fraction of A vapours above the solution in mixture of A and B (XA = 0.4) will be
[Given : PA = 100 mm Hg and PB = 200 mm Hg]
(A) 0.4 (B) 0.8 (C) 0.25 (D) none of these

F-3. At 323 K, the vapour pressure in millimeters of mercury of a methanol-ethanol solution is represented by the
pA
equation p = 120 XA + 140, where XA is the mole fraction of methanol. Then the value of lim X is
xA 1 A

(A) 250 mm (B) 140 mm (C) 260 mm (D) 20 mm

F-4. Given at 350 K pA° = 300 torr and pB° = 800 torr, the composition of the mixture having a normal boiling point
of 350 K is :
(A) XA = 0.08 (B) XA = 0.06 (C) XA = 0.04 (D) XA = 0.02

F-5. Two liquids A and B have PºA and PºB in the ratio of 1 : 3 and the ratio of number of moles of A and B in liquid
phase are 1 : 3 then mole fraction of ‘A’ in vapour phase in equilibrium with the solution is equal to :
(A) 0.1 (B) 0.2 (C) 0.5 (D) 1.0
F-6. The vapour pressure of a pure liquid 'A' is 70 torr at 270C. It forms an ideal solution with another liquid B. The
mole fraction of B is 0.2 and total vapour pressure of the solution is 84 torr at 270C. The vapour pressure of
pure liquid B at 270C is
(A) 14 (B) 56 (C) 140 (D) 70

Section (G) : Non-ideal Solutions

G-1. The vapour pressure of the solution of two liquids A(pº = 80 mm) and B(pº = 120 mm) is found to be 100 mm
when xA = 0.4. The result shows that
(A) solution exhibits ideal behaviour
(B) solution shows positive deviations
(C) solution shows negative deviations
(D) solution will show positive deviations for lower concentration and negative deviations for higher
concentrations.

G-2. Consider a binary mixture of volatile liquids. If at XA = 0.4 the vapour pressure of solution is 580 torr then the
mixture could be (pAº = 300 torr, pB° = 800 torr) :
(A) CHCl3 – CH3COCH3 (B) C6H5Cl – C6H5Br
(C) C6H6 – C6H5CH3 (D) nC6H14 – nC7H16
JEE (Adv.)-Chemistry Solution & Colligative Properties
G-3. A solution of sulphuric acid in water exhibits :
(A) Negative deviations from Raoult’s law
(B) Positive deviations from Raoult’s law
(C) Ideal properties
(D) The applicability of Henry’s law
G-4. When KCl dissolves in water (assume endothermic dissolution), then :
(A) H = + ve, S = + ve, G = + ve
(B) H = + ve, S = – ve, G = – ve
(C) H = + ve, S = + ve, G = – ve
(D) H = – ve, S = – ve, G = + ve
G-5. The dissolving process is exothermic when :
(A) The energy released in solvation exceeds the energy used in breaking up solute-solute and solvent-
solvent interactions.
(B) The energy used in solvation exceeds the energy released in breaking up solute-solute and solvent-
solvent interactions.
(C) The energy released in solvation is about the same as the energy used in breaking up solute-solute and
solvent-solvent interactions.
(D) The energy used in solvation is about the same as the energy used in breaking up solute-solute and
solvent-solvent interactions.
G-6. Which of the following is less than zero for ideal solutions ?
(A) Hmix (B) Vmix (C) Gmix (D) Smix
Section (H) : Degree of Ionisation/Dissociation for Weak Electrolytes
H-1. One mole of a solute A is dissolved in a given volume of solvent. The association of the solute take place as
follows: nA An
If is the degree of association of A, the van’t Hoff factor i is expressed as:

1–
n
(A) i 1 – (B) i 1 (C) i = 1
(D) i = 1
n

H-2._ The Vant Hoff factor (i) for a dilute solution of K3[Fe(CN)6] is (Asuming 100% ionsation) :
(A) 10 (B) 4 (C) 5 (D) 0.25
H-3._ The value of observed and calcutated molecular wieght of silver nitrate are 92.64 and 170 respectively. The
degree of dissociation of silver nitrate is :
(A) 60% (B) 83.5 % (C) 46.7% (D) 60.23%
H-4. A complex containing K+, Pt(IV) and Cl¯ is 100% ionised giving i = 3. Thus, complex is :
(A) K2[PtCl4] (B) K2[PtCl6] (C) K3[PtCl5] (D) K[PtCl3]
Section (I) : Relative lowering of vapour pressure
I-1. One mole of non volatile solute is dissolved in two moles of water. The vapour pressure of the solution relative
to that of water is
2 1 1 3
(A) (B) (C) (D)
3 3 2 2
I-2. The vapour pressure of pure A is 10 torr and at the same temperature when 1 g of B is dissolved in 20
gm of A, its vapour pressure is reduced to 9.0 torr. If the molecular mass of A is 200 amu, then the
molecular mass of B is :
(A) 100 amu (B) 90 amu (C) 75 amu (D) 120 amu
I-3. The vapour pressure of pure benzene, C6H6 at 50°C is 268 Torr. How many moles of non-volatile solute per mol
of benzene is required to prepare a solution of benzene having a vapour pressure of 167 Torr at 50°C?
(A) 0.377 (B) 0.605 (C) 0.623 (D) 0.395
JEE (Adv.)-Chemistry Solution & Colligative Properties
I-4. If relative decrease in vapour pressure is 0.4 for a solution containing 1 mol NaCl in 3 mol H2O, NaCl is .... %
ionised.
(A) 60% (B) 50% (C) 100% (D) 40%
I-5. The vapour pressure of a solution of a non-volatile solute B in a solvent A is 95% of the vapour pressure of the
solvent at the same temperature. If the molecular weight of the solvent is 0.3 times the molecular weight of
the solute, what is the ratio of weight of solvent to solute.
(A) 0.15 (B) 5.7 (C) 0.2 (D) none of these
Section (J) : Elevation of Boiling Point & Depression of Freezing Point
J-1. At a constant temperature, S will be maximum for which of the following processes :
(A) Vaporisation of a pure solvent
(B) Vaporisation of solvent from a solution containing nonvolatile and nonelectrolytic solute in it
(C) Vaporisation of solvent from a solution containing nonvolatile but electrolytic solute in it
(D) Entropy change will be same in all the above cases
J-2. What should be the freezing point of aqueous solution containing 17 gm of C2H5OH in 1000 gm of water
(water Kƒ = 1.86 deg – kg mol–1) (Assumption : consider solute to be non volatile)
(A) – 0.69°C (B) – 0.34°C (C) 0.0°C (D) 0.34°C
J-3. A solute’S’ undergoes a reversible trimerization when dissolved in a certain solvent. The boiling point elevation
of its 0.1 molal solution was found to be identical to the boiling point elevation in case of a 0.08 molal solution
of a solute which neither undergoes association nor dissociation. To what percent had the solute ‘S’ undergone
trimerization?
(A) 30% (B) 40% (C) 50% (D) 60%
J-4. A complex of iron and cyanide ions is 100% ionised at 1m (molal). If its elevation in b.p. is 2.08. Then the
complex is (Kb = 0.52° mol–1 kg) :
(A) K3[Fe(CN)6] (B) Fe(CN)2 (C) K4[Fe(CN)6] (D) Fe(CN)4
J-5. PtCl4.6H2O can exist as a hydrated complex 1 molal aq. solution has depression in freezing point of 3.72°.
Assume 100% ionisation and Kf(H2O) = 1.86° mol–1 kg, then complex is -
(A) [Pt(H2O)6]Cl4 (B) [Pt(H2O)4Cl2]Cl2 . 2H2O
(C) [Pt(H2O)3Cl3]Cl . 3H2O (D) [Pt(H2O)2Cl4] . 4H2O
J-6. How many moles of sucrose should be dissolved in 500 g of water so as to get a solution which has a
difference of 104°C between boiling point and freezing point. (Kf = 1.86 K Kg mol–1, Kb = 0.52 K Kg mol–1)
(A) 1.68 (B) 3.36 (C) 8.40 (D) 0.840
J-7. Which of the following has been arranged in order of decreasing freezing point?
(A) 0.05 M KNO3 > 0.04 M CaCl2 > 0.140 M sugar > 0.075 M CuSO4
(B) 0.04 M BaCl2 > 0.140 M sucrose > 0.075 M CuSO4 > 0.05 M KNO3
(C) 0.075 M CuSO4 > 0.140 M sucrose > 0.04 M BaCl2 > 0.05 M KNO3
(D) 0.075 M CuSO4 > 0.05 M NaNO3 > 0.140 M sucrose > 0.04 M BaCl2
J-8. A solution of x moles of sucrose in 100 grams of water freezes at 0.2ºC. As ice separates the freezing point
goes down to – 0.25ºC. How many grams of ice would have separated?
(A) 18 grams (B) 20 grams (C) 25 grams (D) 23 grams
Section (K) : Osmotic Pressure
K-1. Select correct statement :
(A) Osmosis produced by semipermeable membrane.
(B) Desalination of sea-water is done by reverse osmosis
(C) Both are correct statements
(D) None is correct statement
K-2. The relationship between osmotic pressure at 273 K when 10 g glucose (P1) ,10 g urea (P2) and 10 g sucrose
(P3) are dissolved in 250 mL of water is :
(A) P1 > P2 > P3 (B) P3 > P1 > P2 (C) P2 > P1 > P3 (D) P2 > P3 > P1
JEE (Adv.)-Chemistry Solution & Colligative Properties

K-3. Osmotic pressure of blood is 7.40 atm at 27°C. Number of moles of glucose to be used per litre for an
intravenous injection that is to have the same osmotic pressure as blood is :
(A) 0.3 (B) 0.2 (C) 0.1 (D) 0.4

K-4._ Osmotic pressure of a sugar solution at 240C is 2.5 atmosphere. The concentration of the solution in mole per
litre is :
(A) 10.25 (B) 1.025 (C) 1025 (D) 0.1025

K-5. Osmotic pressure of a solution of glucose is 1.20 atm and that of a solution of cane sugar is 2.5 atm. The
osmotic pressure of the mixture containing equal volumes of the two solutions will be
(A) 2.5 atm (B) 3.7 atm (C) 1.85 atm (D) 1.3 atm.
K-6. Consider following cases :
I : 2M CH3COOH solution in benzene at 27°C where there is dimer formation to the extent of 100%
II : 0.5 M KCl aq. solution at 27°C, which ionises 100%
Which is/are true statements(s) :
(A) both are isotonic (B) I is hypertonic (C) II is hypotonic (D) none is correct

PART - III : MATCH THE COLUMN

1. Column – I Column – II
If at a particular temperature, the density of 18 M H2SO4 is 1.8 g cm –3. Then :
(A) Molality (p) 0.1
(B) % concentration by wt. of solute (q) 0.9
(C) mole fraction of H2SO4 (r) 500
(D) mole fraction of H2O (s) 98

2. Column – I Column – II
(A) Ethyl methyl ketone + CHCl3 (p) Smix. > 0
(B) Ethanol + hexane (q) Vmix. > 0
(C) C2H5Br + C2H5I (r) Hmix. < 0
(D) Acetone + Benzene (s) Maximum boiling azeotropes
(t) Minimum boiling azeotropes

3. Column – I Column – II
Assuming all the solutes are non volatile and all solutions are ideal and neglect the hydrolysis of cation and
anion.
(A) 10 ml 0.1 M KOH aqueous solution is added (p) Osmotic pressure of solution increases
to 10 ml 0.1 M HCl aqueous solution
(B) 10 ml 0.1 M KOH aqueous solution is added (q) Vapour pressure of solution increases
to 10 ml 0.1 M CH3COOH aqueous solution
(C) 10 ml 0.1 M HNO3 aqueous solution is added (r) Boiling point of solution increases
to 10 ml 0.1 M NH3 aqueous solution
(D) 10 ml 0.1 M HNO3 aqueous solution is added (s) Freezing point of solution increases
to 10 ml 0.1 M KOH aqueous solution
JEE (Adv.)-Chemistry Solution & Colligative Properties

Marked Questions may have for Revision Questions.

PART - I : ONLY ONE OPTION CORRECT TYPE
1. All of the water in a 0.20 M solution of NaCl was evaporated and a 0.150 mol of NaCl was obtained. What was
the original volume of the sample ?
(A) 30 mL (B) 333 mL (C) 750 mL (D) 1000 mL

2. The vapour pressure of water at 20°C is 17.54 mmHg. What will be the
vapour pressure of the water in the apparatus shown after the piston is
lowered, decreasing the volume of the gas above the liquid to one half
of its initial volume (assume temperature constant).
(A) 8.77 mmHg
(B) 17.54 mmHg
(C) 35.08 mmHg
(D) between 8.77 and 17.54 mmHg

3. A sample of air is saturated with benzene (vapor pressure = 100 mm Hg at 298 K) at 298K, 750mm Hg
pressure. If it is isothermally compressed to one third of its initial volume, the final pressure of the system is
(A) 2250 torr (B) 2150 torr (C) 2050 torr (D) 1950 torr

1
4. Consider two liquids A & B having pure vapour pressures PA & PB forming an ideal solution. The plot of X
A

1
v/s Y (where XA and YA are the mole fraction of liquid A in liquid and vapour phase respectively) is linear with
A
slope and Y intercepts respectively :

PºA (PAº PBº ) PºA (PBº PAº )

(A) and (B) and
PºB PBº PºB PBº

PºB (PAº PBº ) PºB (PBº PAº )

(C) and (D) and
PºA PBº PºA PBº

5. An ideal solution contains two volatile liquids A (pº = 100 torr) and B (pº = 200 torr). If mixture contain 1 mole
of A and 4 mole of B then total vapour pressure of the distillate is:
(A) 150 (B) 180
(C) 188.88 (D) 198.88
benzene
2200
6. Assuming the formation of an ideal solution, determine
the boiling point of a mixture containing 1560 g benzene 1800
Vapour 1350
(molar mass = 78) and 1125 g chlorobenzene (molar Pressure
chlorobenzene
1000
mass = 112.5) using the following against an external 540
pressure of 1000 Torr. 400
300
200
90 100 110 120
t(cº)
(A) 90ºC (B) 100ºC
(C) 110º (D) 120ºC
JEE (Adv.)-Chemistry Solution & Colligative Properties
7. Given P-x curve for a non-ideal liquid mixture (Fig.). Identify the correct T-x curve for the same mixture.

(A) (B) (C) (D)

8. If vapour pressures of pure liquids ‘A’ & ‘B’ are 300 and 800 torr respectively at 25°C. When these two liquids
are mixed at this temperature to form a solution in which mole percentage of ‘B’ is 92, then the total vapour
pressure is observed to be 0.95 atm. Which of the following is true for this solution.
(A) Vmix > 0 (B) Hmix < 0 (C) Vmix = 0 (D) Hmix = 0

9. The vapour pressure of two pure liquids A and B, that form an ideal solution are 100 and 900 torr respectively
at temperature T. This liquid solution of A and B is composed of 1 mole of A and 1 mole of B. What will be the
pressure, when 1 mole of mixture has been vapourized ?
(A) 800 torr (B) 500 torr (C) 300 torr (D) 400 torr

10. In the following aqueous solutions.

(A) 1 m sucrose (B) 1 m potassium ferricyanide and (C) 1 m potassium sulphate
maximum value of vapour pressure of solution is that of :
(A) A (B) B (C) C (D) equal

11. When only a little quantity of HgCl2(s) is added to excess KI(aq) to obtain a clear solution, which of the
following is true for this solution? (no volume change on mixing).
The reaction is 4KI(aq.) + HgCl2(s) — K2[HgI4] (aq.) + 2KCl (aq.)
(A) Its boiling and freezing points remain same (B) Its boiling point is lowered
(C) Its vapour pressure become lower (D) Its boiling point is raised
(E) Its freezing point is lowered.

12. FeCl3 on reaction with K4[Fe(CN)6] in aq. solution gives blue colour. These
are separated by a semipermeable membrane PQ as shown. Due to osmosis
there is-
(A) blue colour formation in side X
(B) blue colour formation in side Y
(C) blue colour formation in both of the sides X and Y
(D) no blue colour formation

13. Two beakers, one containing 20 ml of a 0.05 M aqueous solution of a non volatile, non electrolyte and the
other, the same volume of 0.03 M aqueous solution of NaCl, are placed side by side in a closed enclosure.
What are the volumes in the two beakers when equilibrium is attained ? Volume of the solution in the first and
second beaker are respectively.
(A) 21.8 ml and 18.2 mL (B) 18.2 mL and 21.8 mL
(C) 20 mL and 20 mL (D) 17.1 mL and 22.9 mL
JEE (Adv.)-Chemistry Solution & Colligative Properties

PART - II : NUMERICAL TYPE QUESTIONS

1. What volume of 98% sulphuric acid (in ml) should be mixed with water to obtain 200 mL of 15% solution of
sulphuric acid by weight ? Given density of H2O = 1.00 g cm –3, sulphuric acid (98%) = 1.88 g cm –3 and
sulphuric acid (15%) = 1.12 g cm –3.

2. Calculate the concentration of CO2 in a soft drink that is bottled with a partial pressure of CO2 of 4 atm over the
liquid at 25ºC. The Henry’s law constant for CO2 in water at 250C is 3.1 × 10–2 mol/litre–atm. Write answer
after multiplying by 100.

3. An ideal aqueous solution containing liquid A(M.Wt. = 128) 64% by weight has a vapour pressure of 145 mm
Hg. If the vapour pressure of A is x mm of Hg and that of water is 155 mm Hg at the same temperature. Then
find x/5. The solutions is ideal.

4. A and B form ideal solutions; at 50ºC, PAº is half PBº. A solution containing 0.2 mole of A and 0.8 mole of B
has a normal bolling point of 50ºC. Find 18 × PBº. (PBº is in atm)

5. Two liquids A and B are miscible over the whole range of composition and may be treated as ideal (obeying
Raoult’s law.) At 350 K the vapour pressure of pure A is 24.0 kPa and of pure B is 12.0 kPa. A mixture of 60%
A and 40% B is distilled at this temperature. A small amount of the distillate is collected and and redistilled
at 350 K; what is the mole percent of B in the second distillate ?

6. How many facts related to CHCl3 + ethylmethylketone solution are correct ?

(a) It shows negative derivation. (b) It forms maximum boiling azeotropic mixture
(c) S > 0 (d) G < 0
(e) Components can be separated by fractional distillation.

7. How many of the following solutions show negative deviation from Raoult's Law ?
Liquid A + Liquid B
(i) (CH3)2CO + CS2
(ii) CCl4 + C6H6
(iii) CCl4 + CHCl3
(iv) H2O + C2H5OH
(v) (C2H5)2O + (CH3)2CO
(vi) CH3COOH + C5H5N (pyridine)
(vii) C6H5NH2 + (CH3)2CO
(viii) C6H5Cl + C6H5Br
(ix) Cyclohexane + Ethanol

8. Determine i (vant-Hoff factor) for a tribasic acid H3A. Assuming first dissociation to be 100%, second disso-
ciation 50%, third dissociation 20%. (Round off your answer to nearest integer).

9. 0.1 mole XY2 is dissolved in 2L water, where it ionizes to give X2+ and Y22–. Observed osmotic pressure is 3
atm. Molar mass of X is 24 and Y is 32. Find Mobserved + 2i (where Mobserved is observed molar mass of XY2)
(Use R = 1/12 L-atm/mol.K and temperature is 87°C)

10. How many grams of sucrose (C12H22O11) must be dissolved in 90 g of water to produce a solution over which
the relative humidity is 80%? Assume the solution is ideal. Give your answer after dividing by 10.

11. 1.22 g of a monobasic acid is dissolved in 100 g of benzene. Boiling point of solution increases by 0.13ºC with
respect to pure benzene. Find the molecular mass of acid in benzene solvent (in u). Report your answer after
dividing it by 100 and Round it off to nearest integer. (Kb of benzene = 2.6 K kg mol–1).
JEE (Adv.)-Chemistry Solution & Colligative Properties
12._ At 27ºC, a 1.2% solution ( wt./vol.) of glucose is isotonic with 4.0 g/litre of solution of solute X. Find the molar
mass of X, if the molar mass of glucose is 180. (R = 0.082 L atm mol –1 K–1, Molar mass of glucose = 180 g/
mole)

13. 10 g of solute A and 20 g of solute B both are dissolved in 500 ml. of water. The solution has the same osmotic
pressure as 6.67 g of A and 30 g of B are dissolved in the same volume of water at the same temperature. If
the ratio of molar masses of A and B is x/y, find x + y.

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. We have 100 mL of 0.1 M KCl solution. To make it 0.2 M,
(A) evaporate 50 mL water (B) evaporate 50 mL solution
(C) add 0.1 mol KCl (D) add 0.01 mol KCl
2. The vapour pressure of a dilute solution of a solute is influenced by :
(A) Temperature of solution (B) Mole fraction of solute
(C) M.pt. of solute (D) Degree of dissociation of solute
3. According to Henry’s law, the partial pressure of gas (P g) is directly proportional to mole fraction of gas in
dissolved state , i.e., Pgas = KH . Xgas where KH is Henry’s constant. Which are correct ?
(A) KH is characteristic constant for a given gas–solvent system
(B) Higher is the value of KH , lower is solubility of gas for a given partial pressure of gas
(C) KH has temperature dependence
(D) KH increases with temperature

4. Select correct statements :

(A) Gases which have high value of van der Waals constant ‘a’ are easily liquefied
(B) Easily liquefiable gases are water soluble
(C) Gases which forms ions in a solvent are soluble in that solvent
(D) Under same conditions, NH3 has low solubility in water than that of CO2 .
5. Two liquids X and Y are perfectly immiscible. If X and Y have molecular masses in ratio 1 : 2, the total vapour
pressure of a mixture of X and Y prepared in weight ratio 2 : 3 should be (Px0 = 400 torr, Py0 = 200 torr)
(A) 600 torr (B) 400 torr
(C) 800 torr (D) 1000 torr

6. Which of the following is/are correct for an ideal binary solution of two volatile liquids (eg. benzene & toluene)?
(A) Its vapor is always richer in the more volatile component (compared to the liquid).
(B) The liquid will gradually become richer in the less volatile component if such a mixture is boiled (distilled).
(C) The PT (ie. the total pressure) above the solution will be the sum of the vapor pressures of the two pure
components.
(D) The boiling point of the solution will be less than the boiling points of the two components.

7. Which is/are true about ideal solutions ?

(A) The volume change on mixing is zero (B) The enthalpy of mixing is zero
(C) The entropy of mixing is zero (D) The enthalpy of mixing is negative

8. The diagram given below represents boiling point composition

diagram of solution of components A and B, which is/are incorrect
among the following?
(A) The solution shows negative deviation
(B) A-B-interactions are stronger than A-A and B-B
(C) The solution is ideal solution
(D) The solution shows positive deviation.
JEE (Adv.)-Chemistry Solution & Colligative Properties
9. Which is/are correct statement(s) ?
(A) When mixture is more volatile than both pure components, there is positive deviation from Raoult’s law
(B) When mixture is less volatile than both pure components, there is negative deviation from Raoult’s law
(C) Ethanol and water form ideal solution
(D) CHCl3 and water form ideal solution

10. At 35°C, the vapour pressure of CS2 is 512 mmHg, and of acetone is 344 mmHg. A solution of CS2 and
acetone in which the mole fraction of CS2 is 0.25, has a total vapour pressure of 600mmHg. Which of the
following statements is/are correct ?
(A) A mixture of 100 mL of acetone and 100 mL of CS2 has a volume of 200 mL
(B) When acetone and CS2 are mixed at 35°C, heat must be absorbed in order to produce a solution at 35°C.
(C) Process of mixing is exothermic
(D) Entropy of mixing is zero

11. In which of the following pairs of solutions will the values of the vant Hoff factor be the same?
(A) 0.05 M K4 [Fe(CN)6] and 0.10 M FeSO4
(B) 0.10 M K4[Fe(CN)6] and 0.05 M FeSO4 (NH4)2SO4. 6H2O
(C) 0.20 M NaCl and 0.10 M BaCl2
(D) 0.05 M FeSO4 (NH4)2SO4 . 6H2O and 0.02 M KCl . MgCl2 . 6H2O

12. 2 g of non-volatile hydrocarbon solute dissolved in 100 g of hypothetical organic solvent (molar mass = 50)
was found to lower vapour pressure from 75.50 to 75 mm of Hg at 20°C. Given that hydrocarbon contains 96%
of C. Then which of the following are true ?
(A) molecular wt of solute = 150 (B) molecular formula = C12H6
(C) molecular wt. of solute = 132 (D) molecular formula = C10H12

13. In the depression of freezing point experiment , it is found that the :

(A) Vapour pressure of the solution is less than that of pure solvent
(B) Vapour pressure of the solution is more than that of pure solvent
(C) Only solute molecules solidify at the freezing point
(D) Only solvent molecules solidify at the freezing point

14. Consider following solutions :

I : 1 M aqueous glucose solution II : 1M aqueous sodium chloride solution
III : 1M aqueous ammonium phosphate solution IV : 1M benzoic acid in benzene
Select correct statements for the above solutions :
(A) All are isotonic solutions (B) III is hypertonic of I, II and IV
(C) IV is hypotonic of I, II and III (D) II is hypotonic of III but hypertonic of I and IV

15. Which facts are true when we use van’t Hoff equation PV = nST for osmotic pressure P of dilute solutions?
(A) The equation is identical to that of ideal gas equation
(B) The solute particles in solution are analogous to the gas molecules and the solvent is analagous to the
empty space between the gas molecules
(C) Solute molecules are dispersed in the solvent the way the gas molecules are dispersed in empty space
(D) The equation is not identical to that of ideal gas equation
JEE (Adv.)-Chemistry Solution & Colligative Properties

PART - IV : COMPREHENSIONS
Read the following passage carefully and answer the questions.
Comprehension # 1

PA = x A PA & PB = x BPB

PT = x A PA + x BPB (Note : PA > PB ; A is more volatile than B)

Vapour pressure of mixtures of Benzene (C6H6 ) & toluene (C7H8) at 50ºC are given by PM = 179 XB + 92, where
XB is mole fraction of C6H6.

1. What is vapour pressure of pure liquids ?

(A) PB = 92 mm, PT = 179 mm (B) PB = 271 mm, PT = 92 mm

(C) PB = 180 mm, PT = 91 mm (D) none of these

2. Vapour pressure of liquid mixture obtained by mixing 936 g C6H6 & 736 g tolene is :
(A) 300 mm Hg (B) 250 mm Hg
(C) 199.4 mm Hg (D) 180.6 mm Hg

Comprehension # 2

Answer the questions (given below) which are based on the following
diagram.
Consider some facts about the above phase diagram :
Vapour pressure diagram for real solutions of two liquids A and B
that exhibit a positive deviation from Raoult’s law. The vapour
pressure of both A and B are greater than predicted by Raoult’s
law. The dashed lines represented the plots for ideal solutions.
JEE (Adv.)-Chemistry Solution & Colligative Properties
3. A : This is observed when A...B attractions are greater than average of A...A and B...B attraction:
B : Hmix = +ve, Vmix = +ve
C : Boiling point is smaller than expected such that vaporisation is increased
D : Mixture can form azeotropic mixture
Select correct facts
(A) A, B, C (B) B, C, D (C) A, C, D (D) A, B, C, D

4. Total vapour pressure of mixture of 1 mol of volatile component A (p° A = 100 mm Hg) and 3 mol of volatile
component B (p°B = 60 mm Hg) is 75 mm. For such case :
(A) There is positive deviation from Raoult’s law
(B) Boiling point has been lowered
(C) Force of attraction between A and B is smaller than that between A and A or between B and B.
(D) All the above statements are correct.

Comprehension # 3
An ideal solution is obtained by mixing a non-volatile solute B with a volatile solvent A (molar mass = 60). If the
mass ratio of A : B in solution is 10 : 1 and vapour pressure of pure A is 400 mm and vapour pressure decreases
by 4% on forming the above solution at 300K.
5. The mole fraction of solute in the solution is -
(A) 0.96 (B) 0.04 (C) 0.16 (D) 0.84
6. The molality the solution is -
36 25 36
(A) 1 (B) (C) (D)
25 36 25
7. The molar mass of B in the solution is -
(A) 1440 (B) 14400 (C) 4 (D) 144

(
JEE (Adv.)-Chemistry Solution & Colligative Properties

* Marked Questions may have more than one correct option.

PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)
1. The Henry's law constant for the solubility of N2 gas in water at 298 K is 1.0 × 105 atm. The mole fraction of
N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water of 298 K and 5 atm pressure
is : [JEE 2009, 3/160]
(A) 4 × 10–4 (B) 4.0 × 10–5 (C) 5.0 × 10–4 (D) 4.0 × 10–6
2. The freezing point (in ºC) of a solution containing 0.1 g of K3[Fe(CN)6] (Mol. Wt. 329) in 100 g of water
(Kf = 1.86 K kg mol–1) is : [JEE 2011, 3/180]
(A) – 2.3 × 10–2 (B) – 5.7 × 10–2 (C) – 5.7 × 10–3 (D) – 1.2 × 10–2
3. For a dilute solution containing 2.5 g of a non- volatile non- electrolyte solute in 100 g of water, the elevation
in boiling point at 1 atm pressure is 2ºC. Assuming concentration of solute is much lower than the concentration
of solvent, the vapour pressure (mm of Hg) of the solution is (take Kb = 0.76 K kg mol–1)[IIT 2012, 3/136]
(A) 724 (B) 740 (C) 736 (D)718
4.* Benzene and naphthalene form an ideal solution at room temperature. For this process, the true statement(s)
is (are) : [JEE(Advanced) 2013, 4/120]
(A) G is positive (B) Ssystem is positive (C) Ssurroundings = 0 (D) H = 0
5. MX2 dissociates into M2+ and X– ions in an aqueous solution, with a degree of dissociation ( ) of 0.5.
The ratio of the observed depression of freezing point of the aqueous solution to the value of the depression
of freezing point in the absence of ionic dissociation is [JEE(Advanced) 2014, 3/120]
6. If the freezing point of a 0.01 molal aqueous solution of a cobalt(III) chloride-ammonia complex (which
behaves as a strong electrolyte) is –0.0558ºC, the number of chloride(s) in the coordination sphere of the
complex is [Kf of water = 1.86 K kg mol–1] [JEE(Advanced) 2015 4/168]

7. Mixture(s) showing positive deviation from Raoult's law at 35°C is (are) [JEE-Adv. 2016]
(A) carbon tetrachloride + methanol (B) carbon disulphide + acetone
(C) benzene + toluene (D) phenol + aniline

8. For a solution formed by mixing liquids L and M, the vapour pressure of L plotted against the mole fraction
of M in solution is shown in the following figure, Here x L and xM represent mole fractions of L and M,
respectively, in the solution. the correct statement(s) applicable to this system is(are)

pL

1 xM 0
(A) Attractive intramolecular interactions between L–L in pure liquid L and M–M in pure liquid M are stronger
than those between L–M when mixed in solution
(B) The point Z represents vapour pressure of pure liquid M and Raoult's law is obeyed when
xL 0
(C) The point Z represents vapour pressure of pure liquid L and Raoult's law is obeyed when
xL 1
(D) The point Z represents vapour pressure of pure liquid M and Raoult's law is obeyed from
xL = 0 to xL = 1
JEE (Adv.)-Chemistry Solution & Colligative Properties
9. Pure water freezes at 273 K and 1 bar. The addition of 34.5 g of ethanol to 500 g of water changes the
f reezing poi nt of the solution. Use the f reez ing point depression constant of water as
2 K kg mol–1. The figures shown below represents plots of vapour pressure (V.P.) versus temperature (T).
[Molecular weight of ethanol is 46 g mol–1]
Among the following, the option representing change in the freezing point is - [JEE-Adv. 2017]

er
Wat 1 Water
l
1 h ano
(A) + Et (B)

V.P./bar

e
er

Ic
V.P./bar

Wat
e

Water+Ethan
Ic

ol

271 273 271 273

T/K T/K

1 er
Water Wat
ol
(C) (D) 1 Et h an
V.P./bar

ter+

V.P./bar
Ic

Wa

e
Ic
Water+Ethan
ol

270 273 270 273

T/K T/K
10. Liquids A and B form ideal solution over the entire range of composition. At temperature T, equimolar binary
solution of liquids A and B has vapour pressure 45 Torr. At the same temperature, a new solution of A
and B having mole fractions x A and xB, respectively, has vapour pressure of 22.5 Torr. The value of x A/
xB in the new solution is____. [JEE-Adv. 2018]
(Given that the vapour pressure of pure liquid A is 20 Torr at temperature T)

11. The plot given below shows P–T curves (where P is the pressure and T is the temperature) for two solvents
X and Y and isomolal solutions of NaCl in these solvents. NaCl completely dissociates in both the solvents.

1 2 3 4

760
Pressure (mmHg)

1. solvent X

2. solution of NaCl in solvent X

3. solvent Y

4. solution of NaCl in solvent Y

360
362

367
368

Temperature (K)
On addition of equal number of moles a non-volatile solute S in equal amount (in kg) of these solvents,
the elevation of boiling point of solvent X is three times that of solvent Y. Solute S is known to undergo
dimerization in these solvents. If the degree of dimerization is 0.7 in solvent Y, the degree of dimerization
in solvent X is ___. [JEE-Adv. 2018]
JEE (Adv.)-Chemistry Solution & Colligative Properties
12. On dissolving 0.5 g of a non-volatile non-ionic solute to 39 g of benzene, its vapor pressure decreases
from 650 mm Hg to 640 mm Hg. The depression of freezing point of benzene (in K) upon addition of the
solute is ______ [JEE-Adv. 2019]
(Given data : Molar mass and the molal freezing point depression constant of benzene are
78 g mol–1 and 5.12 K kg mol–1, respectively)

PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. If sodium sulphate is considered to be completely dissociated into cations and anions in aqueous solution,
the change in freezing point of water ( Tf), when 0.01 mole of sodium sulphate is dissolved in 1 kg of water,
is (Kf = 1.86 K kg mol–1) [AIEEE-2010, 4/144]
(1) 0.0372 K (2) 0.0558 K
(3) 0.0744 K (4) 0.0186 K
2. On mixing, heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid
components (heptane and octane) are 105 kPa and 45 kPa respectively. Vapour pressure of the solution
obtained by mixing 25.0 g of heptane and 35 g of octane will be (molar mass of heptane = 100 g mol –1 and of
octane = 114 g mol–1) [AIEEE-2010, 4/144]
(1) 72.0 kPa (2) 36.1 kPa
(3) 96.2 kPa (4) 144.5 kPa
3. Kf for water is 1.86 K kg mol–1. If your automobile radiator holds 1.0 kg of water, how may grams of ethylene
glycol (C2H6O2) must you add to get the freezing point of the solution lowered to –2.8ºC ?
(1) 72 g (2) 93 g
(3) 39 g (4) 27 g
4. Consider separate solution of 0.500 M C2H5OH(aq), 0.100 M Mg3(PO4)2(aq), 0.250 M KBr(aq) and
0.125 M Na3PO4(aq) at 25 C. Which statement is true about these solution, assuming all salts to be strong
electrolytes ? [AIEEE 2014, 4/120]
(1) They all have the same osmotic pressure.
(2) 0.100 M Mg3(PO4)2(aq) has the highest osmotic pressure.
(3) 0.125 M Na3PO4(aq) has the highest osmotic pressure.
(4) 0.500 M C2H5OH(aq) has the highest osmotic pressure.
5. The vapour pressure of acetone at 20ºC is 185 torr. When 1.2 g of a non-volatile substance was dissolved in
100 g of acetone at 20ºC, its vapour pressure was 183 torr. The molar mass (g mol –1) of the substance is:
[JEE(Main) 2015, 4/120]
(1) 32 (2) 64 (3) 128 (4) 488
6. An aqueous solution of a salt MX2 at certain temperature has a van't Hoff factor of 2. The degree of dissociation
for this solution of the salt is : [JEE (MAIN-2016-ONLINE]
(1) 0.50 (2) 0.80 (3) 0.67 (4) 0.33
7. The solubility of N2 in water at 300 K and 500 torr partial pressure is 0.01 g L –1. The solubility
(in g L–1) at 750 torr partial pressure is : [JEE (MAIN-2016-ONLINE]
(1) 0.02 (2) 0.005 (3) 0.015 (4) 0.0075

8. 18 g glucose (C6H12O6) is added to 178.2g at 100ºC water. The vapour pressure of water (in torr) for this aqueous
solution is : [JEE (MAIN)-2016]
(1) 759.0 (2) 7.6 (3) 76.0 (4) 752.4

9. The freezing point of benzene decreases by 0.45°C when 0.2 g of acetic acid is added to 20 g of benzene.
If acetic acid associates to form a dimer in benzene, percentage association of acetic acid in benzene will
be :- (Kf for benzene = 5.12 K kg mol–1) [JEE (MAIN)-2017]
(1) 64.6% (2) 80.4% (3) 74.6% (4) 94.6%
JEE (Adv.)-Chemistry Solution & Colligative Properties
10. 5 g of Na2SO4 was dissolved in x g of H2O. The change in freezing point was found to be 3.82°C. If Na2SO4
is 81.5% ionised, the value of x [JEE (MAIN-2017-ONLINE]
(Kf for water = 1.86°C kg mol ) is approximately.
–1

(Molar mass of S = 32 g mol–1 and that of Na = 23 g mol–1)

(1) 45 g (2) 65 g (3) 15 g (4) 25 g

11. A solution is prepared by mixing 8.5 g of CH2Cl2 and 11.95 g of CHCl3. If vapour pressure of CH2Cl2 and CHCl3
at 298 K are 415 and 200 mmHg respectively, the mole fraction of CHCl 3 in vapour form is: (Molar mass
of Cl = 35.5 g mol–1) [JEE (MAIN-2017-ONLINE]
(1) 0.486 (2) 0.325 (3) 0.162 (4) 0.675

12. For 1 molal aqueous solution of the following compounds, which one will show the highest freezing
point ? [JEE (MAIN)-2018]
(1) [Co(H2O)5Cl]Cl2.H2O (2) [Co(H2O)4Cl2]Cl.2H2O
(3) [Co(H2O)3Cl3].3H2O (4) [Co(H2O)6]Cl3

13. Two 5 molal solutions are prepared by dissolving a non-electrolyte non-volatile solute separately in the solvents
3
X and Y. The molecular weights of the solvents are MX and MY, respectively where MX = M . The relative
4 Y
lowering of vapour pressure of the solution in X is "m" times that of the solution in Y. Given that the number
of moles of solute is very small in comparison to that of solvent, the value of "m" is -
[JEE (MAIN-2018-ONLINE]

3 4 1 1
(1) (2) (3) (4)
4 3 2 4

14. The mass of a non-volatile, non-electrolyte solute (molar mass = 50 g mol –1) needed to be dissolved in 114
g octane to reduce its vapour pressure by 75%, is :- [JEE (MAIN-2018-ONLINE]
(1) 50 g (2) 37.5 g (3) 75 g (4) 150 g

15. Which one of the following statements regarding Henry's law is not correct ?
[JEE (MAIN-2019_JAN-ONLINE]
(1) The value of KH increases with increase of temperatrue and KH is function of the nature of the gas
(2) Higher the value of KH at a given pressure, higher is the solubility of the gas in the liquids.
(3) The partial pressure of the gas in vapour phase is proportional to the mole fraction of the gas in the solution.
(4) Different gases have different KH (Henry's law constant) values at the same temperature.

16. A solution containing 62 g ethylene glycol in 250 g water is cooled to –10°C. If Kf for water is 1.86 K kg
mol–1, the amount of water (in g) separated as ice is : [JEE (MAIN-2019_JAN-ONLINE]
(1) 32 (2) 48 (3) 16 (4) 64

17. The vapour pressures of pure liquids A and B are 400 and 600 mmHg, respectively at 298K. On mixing the
two liquids, the sum of their initial volumes is equal to the volume of the final mixture. The mole fraction of
liquid B is 0.5 in the mixture. The vapour pressure of the final solution, the mole fraction of components A
and B in vapour phase, respectively are- [JEE (MAIN-2019_April-ONLINE]
(1) 500 mmHg, 0.5, 0.5 (2) 450 mmHg, 0.4, 0.6
(3) 450 mmHg, 0.5, 0.5 (4) 500 mmHg, 0.4, 0.6
JEE (Adv.)-Chemistry Solution & Colligative Properties
18. For the solution of the gases w, x, y and z in water at 298K, the Henrys law constants (KH) are 0.5, 2,
35 and 40 kbar, respectively. The correct plot for the given data is :-
[JEE (MAIN-2019_April-ONLINE]

z
y z

partial partial y
pressure x w pressure

x
(1) (2)
w
(0,0) mole fraction (0,0) mole fraction
of water of water

z
partial partial
pressure pressure y
z
y x
(3) (4)
x
w w
(0,0) mole fraction (0,0) mole fraction
of water of water

19. At 35° C, the vapour pressure of CS2 is 512 mm Hg and that of acetone is 344 mm Hg. A solution of CS2
in acetone has a total vapour pressure of 600 mm Hg. The false statement amongst the following is :
[JEE (MAIN-2020_Jan-ONLINE]
(1) Heat must be absorbed in order to produce the solution at 35°C
(2) Raoult's law is not obeyed by this system
(3) A mixture of 100 mL CS2 and 100 mL acetone has a volume < 200 mL
(4) CS2 and acetone are less attracted to each other than to themselves.

20. Two open beakers one containing a solvent and the other containing a mixture of that solvent with a non volatile
solute are together sealed in a container. Over time : [JEE (MAIN-2020_Jan-ONLINE]
(1) the volume of the solution decreases and the volume of the solvent increases
(2) the volume of the solution and the solvent does not change
(3) the volume of the solution increases and the volume of the solvent decreases
(4) the volume of the solution does not change and the voluem of the solvent decreases
JEE (Adv.)-Chemistry Solution & Colligative Properties

ANSWER KEY
EXERCISE # 1
PART - I
A-1. 0.04 g/mL
A-2. (i) 22.12%, (ii) 0.035 (iii) Na+ = 4 m, SO42– = 2 m
A-3. Molality = 11.44 m, Molarity = 7.55 M
B-1. Some of the characteristics of supersaturated solution are given below
(i) If a crystal of solute is added to supersaturated solution, crystallisation occurs rapidly.
(ii) Supersaturated solutions contain more solute than they should have at a particular temperature.
B-2. The overall energy change associated with dissolution depends on the relative magnitude of the solute–solute
, solvent–solvent and solute–solvent interactions. The process is exothermic if the new interaction release
more energy than disrupting the old interactions requires, it is endothermic if opposite is true.
C-1. (i) > (ii) > (iii)

C-2. PO2 = 810 mm Hg, PH2O = 355 mm Hg , Ptotalal = 1165 mm Hg

D-1. 0.04 D-2. 0.716 mmol. E-1. 5.15 g

WW
E-2. = 3.973 F-1. 27.3 mole %
WN

F-2._ PX0 = 55 cmHg, PY0 = 80 cmHg F-3. 14.16 mole percent benzene

F-4._ PR0 = 0.8 bar, PS0 = 0.4 bar F-5. pA0 = 400 mm of Hg, pB0 = 600 mm of Hg
G-1. V < 80ml.
G-2. There is positive deviation from Raoult’s law, S > 0.

Dissociation / a ssociation
Solute De gre e of dissociation / a ssociation n i
H-1. re action
NaCl NaCl Na + + Cl – 1 2 2
H 2SO 4 H 2SO 4 2H + + SO 42– 1 3 3
CH3 COOH
CH 3COOH H + + CH3COO – 0.2 2 1.2
(in water)
CH3 COOH
2CH 3COOH (CH 3 COOH)2 0.5 0.5 0.75
(in benzene)
Glucose No association or dissociation No association or dissociation Not defined 1
KBr KBr K + + Br– 0.8 2 1.8
A 3A A3 1 0.33 0.33

H-2. 75% I-1._ 0.25 I-2. 746.2 mm of Hg I-3._ 0.32 m

J-1. (a) M = 94.52, (b) m = 135 J-2. 232 J-3. S8
J-4. 10.33°C K-1. (a) Urea < NaCl < Na2SO4 < Na3PO4 (b) 6.15 atm K-2. = 0.81
K-3. 3.69 atm K-4. Volume must have been made 5 times
JEE (Adv.)-Chemistry Solution & Colligative Properties
PART - II
A-1. (B) B-1. (B) B-2. (B) C-1. (B) C-2. (C) C-3. (B) C-4. (B)
D-1. (C) D-2. (B) D-3. (D) D-4. (B) E-1. (C) E-2. (D) F-1. (B)
F-2. (C) F-3. (C) F-4. (A) F-5. (A) F-6. (c) G-1. (C) G-2. (A)
G-3. (A) G-4. (C) G-5. (A) G-6. (C) H-1. (C) H-2. (B) H-3. (B)
H-4. (B) I-1. (A) I-2. (B) I-3. (B) I-4. (C) I-5. (B) J-1. (A)
J-2. (A) J-3. (A) J-4. (A) J-5. (C) J-6. (D) J-7. (A) J-8. (B)
K-1. (C) K-2. (C) K-3. (A) K-4. (D) K-5. (C) K-6. (A)

PART - III
1. (A) (r) ; (B) (s) ; (C) (q) ; (D) (p)
2. (A) – (p, s, r); (B) – (p, q, t); (C) – (p); (D) – (p, q, t)
3. (A) – q, s ; (B) – q, s ; (C) – q, s ; (D) – q, s
EXERCISE # 2
PART - I
1. (C) 2. (B) 3. (C) 4. (B) 5. (C) 6. (B) 7. (B)
8. (B) 9. (C) 10. (A) 11. (B) 12. (D) 13. (B)

PART - II
1. 18 2. 12 mol/litre. 3. 21 4. 20 5. 14 6. 4 (A,B,C,D)
7. 2 8. 3 9. 48 10. 43 11. 2 12. 60
13. 4

PART - III
1. (ABD) 2 . (ABD) 3. (ABCD) 4. (AC) 5. (A) 6. (AB)
7. (AB) 8. (ABC) 9. (AB) 10. (B) 11. (BD) 12. (AB)
13. (AD) 14. (BCD) 15. (ABC)

PART - IV
1. (B) 2. (C) 3. (B) 4. (D) 5. (B) 6. (C)
7. (D)

EXERCISE # 3
PART - I
1. (A) 2. (A) 3. (A) 4. (BCD) 5 . 2 6. 1 7. (AB)
8. (AC) 9. (D) 10. 19 11. 0.05 12. 0.97 to 1.06

PART - II
1. (2) 2. (1) 3. (2) 4. (1) 5. (2) 6. (1) 7. (3)
8. (4) 9. (4) 10. (1) 11. (2) 12. (3) 13. (1) 14. (4)
15. (2) 16. (4) 17. (4) 18. (3) 19. (3) 20. (3)