Lakshya JEE Advanced (2025)

ABHEDYA
Chemistry Solutions
Exercise -1 (c) 45 torr (d) All are possible
(Parikshit)
5. Calculate solubility of a saturated solution of Ag2CrO4 if
SINGLE CORRECT TYPE QUESTIONS boiling point of its saturated solution is 373K at a pressure
1. A very small amount of non-volatile solute (that does not of 760 mm of Hg.
dissociate) is dissolved is 56.8 cm3 of benzene (density (1 + 1.35 × 10− 5 )
0.889 g cm–3). At room temperature, vapour pressure of this
(a) 2.5 × 10–4 M
solution is 100 mm Hg while that of benzene is 102 mm Hg.
(b) 7.5 × 10–4 M
If the freezing temperature of this solution is 1.3 degree
lower than that of benzene, then what is the value of molal (c) 5.4 × 10–7 M
freezing point depression constant of benzene? (d) 1.8 × 10–7 M
(a) 5.07 deg/molal (b) 1.3 deg/molal MULTIPLE CORRECT TYPE QUESTIONS
(c) 3.9 deg/molal (d) 4.97 deg/molal 6. Consider the following vapour pressure composition graph.
2. Using the following information determine the boiling Hence
point of a mixture containing 1560 gm benzene and 1125 gm X
chlorobenzene, when the external pressure is 1000 torr. Ps
Assume the solution is ideal. PA Y V.P.
Given: Molar mass of benzene = 78 V.P.
Molar mass of chlorobenzene = 112.5 PB Z

Temperature Vapour pressure Vapour pressure

XAA == 01
X S XX
A A= 0
=1
(0°C) of benzene (torr) of chlorobenzene
(torr) (a) V.P. of A = SZ
80 750 120 (b) V.P. of B = ZY
(c) V.P. of B = SY
90 1000 200
(d) V.P. of solution at X = SZ + SY
100 1350 300
7. The diagram given below represents boiling point
110 1800 400
composition diagram of solution of component A and B,
120 2200 540 which is/are incorrect among the following?
°
(a) 120 °C (b) 110 °C TA

(c) 100 °C (d) 90 °C TB°

3. Pressure over ideal binary liquid mixture containing 10 moles T (K)

each of liquid A and B is gradually decreased isothermally.
If PA° = 200 mm Hg and PB° = 100 mm Hg, find the pressure
at which half of the liquid is converted into vapour. XB
(a) 150 mm Hg (a) The solution shows negative deviation.
(b) 166.5 mm Hg (b) A-B-interactions are stronger than A-A and B-B.
(c) 133 mm Hg (c) The solution is an ideal solution.
(d) 141.4 mm Hg (d) The solution shows positive deviation.
4. The vapour pressure of benzene, toluene and xylene are 80 8. For the given electrolyte AxBy, the degree of dissociation
torr, 20 torr and 10 torr respectively at 25°C. Then which of ‘α’ of can be given as
the following is possible value of vapour pressure of equimolar i −1
binary/ternery solution of these at same temperature? (a) α = (b) i = (1 – α) + xα + yα
Assuming all forming an ideal solution with each other.
( x + y − 1)
110 1− i
(c) α = (d) None of these
(a)
3
torr (b) 50 torr (1 − x − y )

1
 9. A liquid mixture having composition corresponding to 12. A weak monoprotic acid (molar mass 180) aqueous
point Z in the figure shown is subjected to distillation at solution of 0.18% w/v at 300 K has observed osmotic
constant pressure. pressure 0.369 atm. What should be its Van't Hoff
factor (i)? (R = 0.082 L-atm/K mole)
(a) 1.2 (b) 1.5
(c) 1 (d) 0.5
13. What is observed molar mass (in g/mol) of weak monoprotic
acid in solution in above question?
(a) 270 (b) 180
(c) 120 (d) 90
Which of the following statement is/are correct about the
process regarding point Z? 14. If equal volume of 0.01 M NaOH is added in the solution of
above weak acid solution, then what will be new observed
(a) The composition of distillate differs from the mixture.
osmotic pressure at same temperature? Neglect the
(b) The boiling point goes on changing. hydrolysis, dissociation of water and any volume contraction
(c) The mixture has lowest vapour pressure than that for or expansion. Assume 100% dissociation of the salt formed.
any other composition.
(a) 0.246 atm (b) 0.369 atm
(d) Composition of an azeotrope alters on changing the
external pressure. (c) 0.123 atm (d) 0.492 atm
10. Two solutions S1 and S2 containing 0.1 M NaCl(aq.) and 0.08 Comprehension (Q. 15 to 16): The composition of vapour over
M BaCl2(aq.) are separated by a semipermeable membrane. a binary ideal solution is determined by the composition of the
Which among the following statements is/are correct? liquid. XA and YA are the mole fractions of ‘A’ in the liquid and
(a) S1 and S2 are isotonic. vapour at equilibrium, respectively.
(b) S1 is hypertonic and S2 is hypotonic. 15. The value of XA for which (YA – XA) is maximum is
(c) S1 is hypotonic and S2 is hypertonic.
(d) Osmosis will take place from S1 to S2. PAo .PBo – PAo PAo .PBo – PBo
(a) (b)
11. 1 mole of a non-volatile solid is dissolved in 200 moles PAo – PBo PAo – PBo
of water. The solution is taken to a temperature TK
(lower than the freezing point of solution) to cause ice PAo .PBo – PBo PAo .PBo – PAo
(c) (d)
formation. After removal of ice, the remaining solution is PAo PBo
taken to 373 K where vapour pressure is observed to be 740 16. The vapour pressure of solution at this composition is
mm of Hg. Identify the correct option.
[Given data: Kf (H2O) = 2 K kg mol–1 and normal boiling (a) PAo . PBo (b) (PAo – PBo )
point of H2O = 373 K.]
(a) 163 moles of ice will be formed. (c) (PAo + PBo ) (d) 0.5(PAo + PBo )
2000 Comprehension (Q. 17 to 19): The experimental values of
(b) F.P. of final solution = 273 – K.
37 × 18 colligative properties of many solutes in solution resembles
(c) Freezing point of original solution should be − 10 °C. calculated values of colligative properties.
18 However in same cases, the experimental value of colligative
(d) Relative lowering of vapour pressure of final solution property differ widely than those obtained by calculation. Such
1 experimental values of colligative properties are known as
will be .
201 Abnormal values of colligative property. Cause for abnormal
values of colligative properties are:
COMPREHENSION BASED QUESTIONS (i) Dissociation of solute: It increases the value of colligative
Comprehension (Q. 12 to 14): Colligative properties i.e., the properties. e.g.: Dissociation of KCl, NaCl etc. in H2O.
properties of solution which depend upon the number of particles (ii) Association of solute: It decreases the value of colligative
present in solution are osmotic pressure, depression in freezing properties. e.g.: Dimerisation of acetic acid in benzene
point, elevation in boiling point and lowering in vapour pressure. 17. If degree of dissociation of an electrolyte A2B3 is 25% in a
Experimental values of colligative properties for electrolytes solvent, then
are always higher than those obtained theoretically because (a) Normal boiling point = Experimental boiling point
electrolytes dissociate to furnish more ions in solution. On the other
(b) Normal freezing point < Experimental freezing point
hand, experimentally obtained values of colligative properties for
associating nature of solute are lower than those obtained theoretically. (c) Normal osmotic pressure = (1/2) Experimental osmotic
The ratio of experimental colligative properties value to theoretical pressure
colligative properties value is called as van't Hoff factor. (d) Normal molecular weight = Experimental molecular

2
 weight D. Acetone + Benzene s. Maximum boiling
18. 4 different 100 mL solutions are prepared by mixing 1 gram azeotrope
each of NaCl, (NH2)2CO, Na2SO4 and K4[Fe(CN)6] at
t. Minimum boiling
temperature T. Correct order of osmotic pressure is
azeotrope
(a) (NH2)2CO solution > NaCl solution > Na2SO4 solution
> K4[Fe(CN)6] solution (a) A→ p ; B→ p, q, t; C→ p; D→ q, t
(b) NaCl solution > Na2SO4 solution > (NH2)2CO solution (b) A→ p, s,; B→ q, t; C→ p; D→ p, q,
> K4 [Fe(CN)6] solution (c) A→ p, r; B→ q, t; C→ p; D→ p, q, t
(c) K4[Fe(CN)6] solution > Na2SO4 solution > NaCl (d) A→ p, s, r; B→ p, q, t; C→ p; D→ p, q, t
solution (NH2)2CO solution
(d) Na2SO4 solution > (NH2)2CO solution > NaCl 22.
solution > K4 [Fe(CN)6] solution Column-I Column-II
19. One mole l2 (solid) is added in 1 M, 1 litre Kl solution. Then (Solute, degree of (van't Hoff
(a) Osmotic pressure of solution increases ionisation) factor)
(b) Freezing point of solution increases A. K2SO4 ; α = 0.85 p. 3.7
(c) Relative lowering in vapour pressure decreases
B. SnCl2 ; α = 0.7 q. 4.0
(d) No change in boiling point of solution
C. Al(NO3)3 ; α = 0.9 r. 2.7
MATCH THE COLUMN TYPE QUESTIONS D. Fe2(SO4)3 ; α = 0.75 s. 2.4
20. Assuming all the solutes are non-volatile and all solutions
are ideal and neglect the hydrolysis of cation and anion. (a) A→ r; B→ s; C→ p; D→ q
Column-I Column-II (b) A→ p; B→ s; C→ r; D→ q
A. 10 mL of 0.1 M NaOH p. Osmotic pressure (c) A→ s; B→ r; C→ p; D→ q
aqueous solution is mixed of solution
(d) A→ q; B→ r; C→ p; D→ s
with 10 mL of 0.1 M HCl decreases
aqueous solution
INTEGER TYPE QUESTIONS
B. 10 mL of 0.1 M NaOH q. Vapour pressure
aqueous solution is added to of solution 23. Equimolar mixture of A and B form an ideal solution
10 mL of 0.1 M CH3COOH increases at 300 K. The vapour of this solution is condensed
aqueous solution in 2nd container and temperature is maintained at
300 K. The vapour of 2nd container is condensed into 3rd
C. 10 mL of 0.1 M HCl r. Boiling point of container and temperature is maintained at 300 K. If total
aqueous solution is added solution decreases
vapour pressure of solution in 3rd container is x mm Hg,
to 10 mL of 0.1 M NH3
aqueous solution x
the value of is [P°A, and P°B at 300 K are 100 mm Hg
9
D. 10 mL of 0.1 M HCl s. Freezing point of and 200 mm Hg respectively.]
aqueous solution is added solution increases
to 10 mL of 0.1 M KOH 24. A non-volatile solute P is present in 500 mL solution and
aqueous solution molarity is found to be 1 M. A sample of 5 mL of this
solution is taken in another container and further 0.4 g of
(a) A→ q, r, s; B→ p, q, r, s; C→ p, q, r; D→ p, r, s
P is added and volume is increased by adding water such
(b) A→ p, q; B→ q, r, s; C→ p, r, s; D→ p, q, r, s
that final volume becomes 10 L. If molarity of diluted
(c) A→ p, q, r, s; B→ p, q, r, s; C→ p, q, r, s; D→ p, q, r, s
solution is 10–3 M, the molar mass of solute P (in g/mol)
(d) A→ p, q, r; B→ p, q, s; C→ p, q, r, s; D→ p, q,
is _________ .
21. 25. A solution comprising 0.1 mol of naphthalene and 0.6 mol
Column-I Column-II of benzene is cooled until some solid benzene freezes out.
The solution is then decanted off from solid and warmed to
A. Acetone + CHCl3 p. ∆Smix. > 0 353 K, where its vapour pressure is found to be 608 torr. The
B. Ethanol + Water q. ∆Vmix. > 0 freezing and normal boiling points of benzene are 278.5 K
C. C2H5Br + C2H5l r. ∆Hmix. < 0 and 353 K respectively. The amount of benzene that freezes
out due to cooling is x g. The value of 5x is _________ .

3
 26. A solution containing compound 'X' in water and a solution This solution is passed through different distillation stages
containing glucose in water were put in a closed system. and at a particular stage, it is found that the mole fraction
By doing this, some water vapour was removed from one 4
of A in vapour phase is . The total vapour pressure of
solution and got condensed in the other. It is found that when 7
both the solutions were at equilibrium vapour pressure, one solution at this stage of distillation is ______ (in mm Hg).
solution contains 10% (w/w) of 'X' and the other 5% (w/w) 29. The mole fraction, x of a solute in an ideal saturated
glucose. The molar mass (in g/mol) of 'X' is
− ∆H  1 1 
solution in a solvent is given by log10x = × − 
27. Safrole is contained in oil of sassafras and was once used to 2.303R  T T0 
flavour root beer. A 2.4 mg sample of safrole was dissolved
in 100.0 mg of diphenyl ether. The solution has a freezing where DHf and T0 are the molar heat of fusion and the
of 25.64oC. The freezing point of pure diphenyl ether is freezing point of the solute. The melting point of
26.84oC and the freezing-point-depression constant Kf, is phenanthrene is 100°C and the latent heat of fusion is
8.00oC/m. The molecular mass (in g/mol) of safrole is 24.3 cal g –1 . Calculate x, (the ideal solubility) of
phenanthrene (C14H10) in benzene at 25°C.
NUMERICAL TYPE QUESTIONS 30. Mixture of two liquids A and B is placed in cylinder
(UPTO TWO DECIMAL PLACE) containing piston. Piston is pulled out isothermally so that
28. A binary solution of A and B is ideal. If total vapour volume of liquid decreases but that of vapour increases.
pressure of this solution is represented as When negligibly small amount of liquid was remaining,
the mole fraction of A in vapour is 0.4. Given PA° = 0.4 atm
PS (in mm Hg) = 100 – 50 XB
and P B° = 1.2 atm at the experimental temperature.
Here, PS ⇒ Total vapour pressure Calculate the total pressure (in atm) at which the liquid
XB ⇒ Mole fraction of B in liquid state has almost evaporated. (Assume ideal behaviour).

4
 Exercise -2 ether is allowed to separate, what quantity of iodine (in mg)
(PW Challengers) remains in the water layer?
(Answer upto three decimal place)
NUMERICAL TYPE QUESTIONS (b) What quantity of iodine (in mg) remains in the water layer
(ANSWER UPTO ONE DECIMAL PLACE) if only 3 mL of ether is used?
1. The molecular weight of a newly synthesized organic (Answer upto three decimal place)
compound was determined by the method of isothermal (c) How much iodine (in mg) is left in the water layer if the
distillation. In this procedure two solutions, each in an open extraction in (b) is followed by a second extraction, again
calibrated vial, are placed side by side in a closed chamber. using 3 mL of ether?  (Answer upto four decimal place)
One of the solutions contained 9.3 mg of the new compound, 5. (a) A liquid mixture of benzene and toluene is composed of
the other 13.2 mg of azobenzene (MW = 182). Both were 1 mol of benzene and 1 mol of toluene. If the pressure over
dissolved in portions of the same solvent. During a period the mixture at 300 K is reduced, at what pressure (in mm
of 3 days of equilibration, solvent distilled from one vial Hg) does the first vapour form?
into the other until the same partial pressure of solvent was (Answer upto two decimal place)
reached in the two vials. At this point the distillation of
(b) What is the mole fraction of benzene in the first trace of vapour
solvent stopped. Neither of the solutes distilled at all. The formed. (Answer upto two decimal place)
volume of the two solutions at equilibrium were then read
(c) If the pressure is reduced further, at what pressure
on the calibration marks of the vials. The solution containing
(in mm Hg) does the last trace of liquid disappear?
the new compound occupied 1.72 mL and the azobenzene
(Answer upto two decimal place)
solution occupied 1.02 mL. What is the molecular weight
(d) What is the mole fraction of Toluene in the last trace of
(in g/mol) of the new compound? The mass of solvent in
liquid? (Answer upto two decimal place)
solution may be assumed to be proportional to the volume
of the solution. Given: PT° = 32.05 mm Hg, PB° = 103 mm Hg

2. The freezing point of an aqueous saturated solution of I2 is

–0.0024°C. More than this can dissolve in an KI solution INTEGER TYPE QUESTIONS
because of the following equilibrium:
6. In water at 20°C, the Henry’s law constant for oxygen is
I2(aq) + I–(aq)_______ 
 _______I3–(aq) 4.6 × 104 atm, and for nitrogen it is 8.2 × 104 atm, where
0.1 M KI solution dissolves 12.5 g/L of I2. the concentration are expressed as mole fractions. If we
(a) Calculate the equilibrium constant K C for the above are to prepare 99 mole % pure oxygen from air (successive
equilibrium. treatments by partially dissolving in water and then all the
(b) Also calculate the freezing point (in K) of the resulting gas is removed under vacuum the water), how many cycles
solution. Assume molarity to be equal to molality and also would be necessary to achieve this result?
assume that conc. of I2 in all saturated solution is same. 7. When cells of the skeletal vacuole of a frog wee placed in
[Kf for water = 1.86 K kg mol– 1] series of NaCl solution of different concentrations at 6°C, it
was observed microscopically that they remained unchanged
NUMERICAL TYPE QUESTIONS in x% NaCl solution, it shrank in more concentrated solution
and swells in more dilute solutions. Water freezes from the
3. Two solutions of non-volatile solutes A and B are prepared.
x% salt solution at –0.40°C. If the osmotic pressure of the
The molar mass ratio, M A = 1 . Both are prepared as 5% cell cytoplasm at 6°C is ‘y’× 0.0821 atm, then the value of
MB 3 ‘y’ is (Kf = 1.86 K mol–1 kg)
solutions by weight in water. Calculate the ratio of the
(∆Tf ) A 8. Consider the following arrangements, in which a solution
freezing point depressions, of the solutions. If the containing 20 g of haemoglobin in 1 dm3 of the solution is
(∆Tf ) B
two solutions are mixed to prepare two new solution S1 and placed in right compartment and pure water is placed in left
S2, the mixing ratio being 2 : 3 and 3 : 2 by volume for S1 compartment, separated by SPM. At equilibrium, the height
(∆Tf )S1 of liquid in the right compartment is 74.5 mm in excess of
and S2 respectively what would be the value of ? that in the left compartment. The temperature of the system
(∆Tf )S2 is maintained at 298K. The number of millimoles in 320 g
(Answer upto two decimal place) of haemoglobin is (Given: The density of final solution is
4. (a) The solubility of iodine per unit volume is 200 times greater 1.013 g/ml, g = 10 m/s2, R = 0.08 L-atm / K-mol)
in ether than in water at a particular temperature. If an
aqueous solution of iodine, 30 mL in volume and containing
2.0 mg of iodine, is shaken with 30 mL of ether and the

5
SINGLE CHOICE TYPE QUESTIONS (a) 0.6 atm (b) 0.8 atm
(c) 0.77 atm (d) 0.9 atm
9. A dilute solution contains m mol of solute A in 1 kg of
a solvent with molal elevation constant K b; The solute 1
12. The pressure at which th of the total amount (by mol) of
 A2. What is correct
dimerises in solution as 2A  3
expression for the equilibrium constant for this dimer liquid solution taken initially, will be present in the vapour
formation? (DTb is the elevation in boiling point for the form, is
given solution) (a) 0.283 (b) 0.791
(c) 0.600 (d) 0.652
K b (K b m + ∆Tb ) K b (K b m + ∆Tb )
(a) K = 2 (b) K = 13. The minimum pressure for the existence of liquid solution is
(2∆Tb + K b m) (∆Tb + K b m) 2 (a) 0.6 atm (b) 0.8 atm
K b (K b m + ∆Tb ) K b (K b m − ∆Tb ) (c) 0.77 atm (d) 0.9 atm
(c) K = (d) K =
(∆Tb − 2K b m) 2 (2∆Tb − K b m) 2

10. The partial molar volumes of propanone (CH3COCH3)

and butanone (CH3COCH2CH3 ) in a mixture in which
mole fraction of propanone is 0.4 are 75 cm3 mol–1 and
80 cm3 mol–1. Thus, the total volume of solution of total
mass 1 kg, is
(a) 1175 cm3 (b) 1000 cm3
(c) 1200 cm3 (d) 972 cm3

COMPREHENSION BASED QUESTIONS

Comprehension (for question 11 to 13)10 mole of liquid ‘A’ and
20 mole of liquid ‘B’ is mixed in a cylindrical vessel containing a
piston arrangement. Initially a pressure of 2 atm is maintained on the
solution. Now, the piston is raised slowly and isothermally. Assume
ideal behaviour of solution and A and B are completely miscible.
PA° = 0.6 atm and PB° = 0.9 atm
11. The pressure below which the evaporation of liquid solution
will start, is

6
 Exercise -3 (PYQ’s) Multiple Correct
9. For a solution formed by mixing liquids L and M, the vapor pressure
of L plotted against the mole fraction of M the solution is shown
Expressing Concentrations of Solutions
in the following figure. Here ꭓL and ꭓM represent mole fractions
of L and M, respectively, in the solution. The correct statement(s)
Single Correct
applicable to this system is (are)
1. A molal solution is one that contains one mole of a solute in C-18.07 W-20.51 UA-40.05 PC-21.38 (JEE Adv. 2017)
(IIT JEE 1986)
(a) 1000 g of the solvent (b) 1 L of the solvent
Z
(c) 1 L of the solution (d) 22.4 L of the solution
PL
Numerical/Integer Types
2. The mole fraction of urea in an aqueous urea solution containing
900 g of water is 0.05. If the density of the solution is 1.2 g cm³,
then molarity of urea solution is .......... 1 XM 0

(Given data: Molar masses of urea and water are 60 g mol and –1
(a) The point Z represents vapor pressure of pure liquid M and
18 g mol–1, respectively) Raoult's law is obeyed from xL = 0 to xL = 1
C-17.05 W-70.35 UA-12.61 (JEE Adv. 2019) (b) Attractive intermolecular interactions between L-L in pure
liquid L and M-M in pure liquid M are stronger than those
Subjective between L-M when mixed in solution
3. What weight of the non-volatile solute urea (NH2–CO–NH2) needs (c) The point Z represents vapor pressure of pure liquid M and
to be dissolved in 100 g of water, in order to decrease the vapour Raoult's law is obeyed when xL → 0
pressure of water by 25%? What will be the molality of the solution? (d) The point Z represents vapor pressure of pure liquid L and
(IIT JEE 1993) Raoult's law is obeyed when xL → 1
4. The vapour pressure of a dilute aqueous solution of glucose 10. Mixture(s) showing positive deviation from Raoult's law at 35°C is
(C6H12O6) is 750 mm of mercury at 373 K. Calculate (i) molality (are) C-13.58 W-43.07 UA-27.81 PC-15.54 (JEE Adv. 2016)
and (ii) mole fraction of the solute. (IIT JEE 1989) (a) carbon tetrachloride + methanol
5. What is the molarity and molality of a 13% solution (by weight) (b) carbon disulphide + acetone
of sulphuric acid with a density of 1.02 g/mL ? To what volume (c) benzene + toluene
should 100 mL of this solution be diluted in order to prepare a 1.5 N (d) phenol + aniline
solution? (IIT JEE 1978)
11. Benzene and naphthalene form an ideal solution at room temperature.
Vapour Pressure of Liquid Solutions & Ideal and For this process, the true statement(s) is (are)
C-17.39 W-60.89 UA-21.72 (JEE Adv. 2013)
Non-Ideal Solutions (a) ΔG is positive
Single Correct (b) ΔSsystem is positive

6. The vapour pressure of acetone at 20°C is 185 torr. When 1.2 g of (c) ΔSsurroundings = 0
a non-volatile substance was dissolved in 100 g of acetone at 20°C, (d) ΔH = 0
its vapour pressure was 183 Torr. The molar mass of the substance
is (JEE Adv. 2015) Numerical/Integer Types
(a) 32 (b) 64 (c) 128 (d) 488 12. Liquids A and B form an ideal solution for all compositions of A and
7. For a dilute solution, Raoult's law states that (IIT JEE 1985) B at 25°C. Two such solutions with 0.25 and 0.50 mole fractions
of A have the total vapor pressures of 0.3 and 0.4 bar, respectively.
(a) the lowering of vapour pressure is equal to the mole fraction What is the vapor pressure of pure liquid B in bar?
of solute C-41.71 W-48.28 UA-10.01 (JEE Adv. 2020)
(b) the relative lowering of vapour pressure is equal to the mole
fraction of solute 13. Liquids A and B form an ideal solution over the entire range of
composition. At temperature T, equimolar binary solution of liquids
(c) the relative lowering of vapour pressure is proportional to the
A and B has vapour pressure 45 torr. At the same temperature, a new
amount of solute in solution
solution of A and B having mole fractions xA and xB, respectively, has
(d) the vapour pressure of the solution is equal to the mole fraction vapour pressure of 22.5 torr. The value of xA/xB in the new solution is
of solvent
(Given that the vapour pressure of pure liquid A is 20 Torr at
8. An azeotropic solution of two liquids has boiling point lower than temperature T) C-26.64 W-58.59 UA-14.77 (JEE Adv. 2018)
either of them when it (IIT JEE 1981)
(a) shows negative deviation from Raoult's law Subjective
(b) shows no deviation from Raoult's law 14. Following statement is true only under some specific conditions.
(c) shows positive deviation from Raoult's law Write the condition for it.
(d) is saturated “Two volatile and miscible liquids can be separated by fractional
distillation into pure components.” (IIT JEE 1984)

7
 15. The vapour pressure of two miscible liquids A and B are 300 and 22. For a dilute solution containing 2.5 g of a non-volatile non-
500 mm of Hg respectively. In a flask 10 moles of A is mixed electrolyte solute in 100 g of water, the elevation in boiling point
with 12 moles of B. However, as soon as B is added, A starts at 1 atm pressure is 2°C. Assuming concentration of solute is much
polymerising into a completely insoluble solid. The polymerisation lower than the concentration of solvent, the vapour pressure (mm
follows first-order kinetics. After 100 min, 0.525 mole of a solute of Hg) of the solution is (take Kb = 0.76 K kgmol–1).
is dissolved which arrests the polymerisation completely. The final C-11.14 W-28.46 UA-60.4 (IIT JEE 2012)
vapour pressure of the solution is 400 mm of Hg. Estimate the rate (a) 724 (b) 740 (c) 736 (d) 718
constant of the polymerisation reaction. Assume negligible volume
change on mixing and polymerisation and ideal behaviour for the 23. The freezing point ( in °C) of solution containing 0.1 g of K3
final solution. (IIT JEE 2001) [Fe(CN)6] (mol. wt. 329) in 100 g of water (Kf = 1.86 K kg mol–1)
is (IIT JEE 2011)
16. The molar volume of liquid benzene (density = 0.877 g/mL)
increases by a factor of 2750 as it vaporises at 20°C and that of (a) –2.3×10–2 (b) –5.7×10–2
liquid toluene (density = 0.867 g mL–1) increases by a factor of 7720 (c) –5.7×10 –3
(d) –1.2×10–2
at 20°C. A solution of benzene and toluene at 20°C has a vapour
24. The Henry's law constant for the solubility of N2 gas in water at
pressure of 45.0 torr. Find the mole fraction of benzene in the vapour
298 K is 1.0×105 atm. The mole fraction of N2 in air is 0.8. The
above the solution. (IIT JEE 1996)
number of moles of N2 from air dissolved in 10 moles of water of
17. The vapour pressure of ethanol and methanol are 44.5 and 88.7 mm 298 K and 5 atm pressure is (IIT JEE 2009)
Hg respectively. An ideal solution is formed at the same temperature (a) 4.0×10–4 (b) 4.0×10–5
by the mixing 60 g of ethanol with 40 g of methanol. Calculate
the total vapour pressure of the solution and the mole fraction of (c) 5.0×10–4 (d) 4.0×10–6
methanol in the vapour. (IIT JEE 1986) 25. When 20 g of naphthoic acid (C11 H8 O2) is dissolved in 50 g of
18. An organic compound (CxH2yOy) was burnt with twice the amount benzene (Kf = 1.72 K kg mol–1), a freezing point depression of 2 K
of oxygen needed for complete combustion to CO2 and H2O. The is observed. The Van't Hoff factor (i) is (IIT JEE 2007)
hot gases when cooled to 0°C and 1 atm pressure, measured 2.24 (a) 0.5 (b) 1 (c) 2 (d) 3
L. The water collected during cooling weight 0.9 g. The vapour 26. The elevation in boiling point, when 13.44 g of freshly prepared
pressure of pure water at 20°C is 17.5 mm Hg and is lowered by CuCl2 are added to one kilogram of water, is. [Some useful data,
0.104 mm when 50 g of the organic compound are dissolved in 1000 Kb = 0.52 K kg mol–1, molecular weight of CuCl2 = 134.4 g].
g of water. Give the molecular formula of the organic compound. (IIT JEE 2005)
(IIT JEE 1983)
(a) 0.05 (b) 0.1 (c) 0.16 (d) 0.21
19. Two liquids A and B form an ideal solution. At 300 K, the vapour
27. 0.004 M Na2SO4 is isotonic with 0.01 M glucose. Degree of
pressure of a solution containing 1 mole of A and 3 moles of B is
dissociation of Na2SO4 is (IIT JEE 2004)
550 mm of Hg. At the same temperature, if one more mole of B is
added to this solution, the vapour pressure of the solution increases (a) 75% (b) 50% (c) 25% (d) 85%
by 10 mm of Hg. Determine the vapour pressure of A and B in their 28. During depression of freezing point in a solution the following are
pure states. (IIT JEE 1982) in equilibrium (IIT JEE 2003)
20. The vapour pressure of pure benzene is 639.70 mm of Hg and (a) liquid solvent, solid solvent
the vapour pressure of solution of a solute in benzene at the same (b) liquid solvent, solid solute
temperature is 631.9 mm of Hg. Calculate the molality of the
(c) liquid solute, solid solute
solution. (IIT JEE 1981)
(d) liquid solute, solid solvent
Colligative Properties and Abnormal Molar Masses 29. The molecular weight of benzoic acid in benzene as determined by
depression in freezing point method corresponds to
Single Correct (IIT JEE 1996)
21. Pure water freezes at 273 K and 1 bar. The addition of 34.5 g of (a) ionisation of benzoic acid
ethanol to 500 g of water changes the freezing point of the solution. (b) dimerisation of benzoic acid
Use the freezing point depression constant of water as 2 K kgmol–1. (c) trimerisation of benzoic acid
The figures shown below represent plots of vapour pressure (V.P.)
(d) solvation of benzoic acid
versus temperature (T). [Molecular weight of ethanol is 46 g mol–1]
30. The freezing point of equimolal aqueous solutions will be highest
Among the following, the option representing change in the freezing for (IIT JEE 1990)
point is C-42.99 W-32.02 UA-24.99 (JEE Adv. 2017)
(a) C6H5NH3 Cl (aniline hydrochloride)
(a) (b)
Water Water (b) Ca(NO3)2
1 1 (c) La(NO3)3
V.P./bar

V.P./bar

Ice Ice
Water+Ethanol Water+Ethanol (d) C6H12O6 (glucose)

270 273 T/K 271 273 T/K

31. Which of the following 0.1 M aqueous solution will have the lowest
freezing point? (IIT JEE 1989)
(c) (d) Water (a) Potassium sulphate
Water
Ice 1 Ice (b) Sodium chloride
1
V.P./bar
V.P./bar

(c) Urea
Water+Ethanol Water+Ethanol
(d) Glucose
270 273 T/K 271 273 T/K

8
 32. When mercuric iodide is added to the aqueous solution of potassium 36. The freezing point of the solution M is (IIT JEE 2008)
iodide (IIT JEE 1987) (a) 268.7 K (b) 268.5 K (c) 234.2 K (d) 150.9 K
(a) freezing point is raised
37. The vapour pressure of the solution M is (IIT JEE 2008)
(b) freezing point is lowered
(a) 39.3 mm Hg (b) 36.0 mm Hg
(c) freezing point does not change
(c) 29.5 mm Hg (d) 28.8 mm Hg
(d) boiling point does not change
38. Water is added to the solution M such that the mole fraction of water
Multiple Correct in the solution becomes 0.9. The boiling point of this solution is
33. In the depression of freezing point experiment, it is found that the (IIT JEE 2008)
(IIT JEE 1999) (a) 380.4 K (b) 376.2 K (c) 375.5 K (d) 354.7 K
(a) vapour pressure of the solution is less than that of pure solvent
Numerical/Integer Types
(b) vapour pressure of the solution is more than that of pure solvent
(c) only solute molecules solidify at the freezing point 39. 50 mL of 0.2 molal urea solution (density = 1.012 g mL–1 at 300 K) is
mixed with 250 mL of a solution containing 0.06 g of urea. Both the
(d) only solvent molecules solidify at the freezing point
solutions were prepared in the same solvent. The osmotic pressure
Comprehension/Passage Based (in Torr) of the resulting solution at 300 K is __.
Passage-I [Use : Molar mass of urea = 60 g mol –1 ; gas constant,
R = 62 L Torr K–1 mol–1; Assume, ΔmixH = 0, ΔmixV = 0]
The boiling point of water in a 0.1 molal silver nitrate solution
(solution A) is x°C. To this solution A, an equal volume of 0.1 molal C-6.84 W-66.77 UA-26.39 (JEE Adv. 2023)
aqueous barium chloride solution is added to make a new solution 40. An aqueous solution is prepared by dissolving 0.1 mol of an ionic
B. The difference in the boiling points of water in the two solutions salt in 1.8 kg of water at 35 °C. The salt remains 90% dissociated
A and B is y × 10–2 °C. in the solution. The vapour pressure of the solution is 59.724 mm
(Assume: Densities of the solutions A and B are the same as that of of Hg. Vapor pressure of water at 35 °C is 60.000 mm of Hg. The
water and the soluble salts dissociate completely. number of ions present per formula unit of the ionic salt is ......
Use: Molal elevation constant (Ebullioscopic constant). C-9.58 W-12.26 UA-78.16 (JEE Adv. 2022)
Kb = 0.5 K kg mol–1; Boiling point of pure water as 100°C.) 41. On dissolving 0.5 g of a non-volatile, non-ionic solute to 39 g
34. The value of x is ___.C-19.32 W-63.3 UA-17.38 (JEE Adv. 2021) of benzene, its vapour pressure decreases from 650 mm Hg to
640 mm Hg. The depression of freezing point of benzene (in K)
35. The value of |y| is ______.
upon addition of the solute is .........
C-5.34 W-74.47 UA-20.19 (JEE Adv. 2021)
(Given data: Molar mass and the molal freezing point depression
Passage-II
constant of benzene are 78 g mol–1 and 5.12 K kg mol–1, respectively).
Properties such as boiling point, freezing point and vapour pressure C-24 W-56 UA-20 (JEE Adv. 2019)
of a pure solvent change when solute molecules are added to get
42. The plot given below shows p-T curves (where p is the pressure and
homogeneous solution. These are called colligative properties.
T is the temperature) for two solvents X and Y and is molal solution
Applications of colligative properties are very useful in day-to-day
of NaCl in these solvents. NaCl completely dissociates in both the
life.
solvents.
One of its examples is the use of ethylene glycol and water mixture
1 2 3 4
as anti-freezing liquid in the radiator of automobiles.
A solution M is prepared by mixing ethanol and water. The mole
760
fraction of ethanol in the mixture is 0.9.
Pressure (mm Hg)

Given, freezing point depression constant of water

1. Solvent X
(Kfwater) = 1.86 K kg mol–1 2. Solution of NaCl in solvent X
Freezing point depression constant of ethanol 3. Solvent Y
4. Solution of NaCl in solvent Y
(Kfethanol) = 2.0 K kg mol–1
Boiling point elevation constant of water
360
362

367
368

(Kbwater) = 0.52 K kg mol–1

Boiling point elevation constant of ethanol Temperature (K)
(Kbethanol) = 1.2 K kg mol–1 On addition of equal number of moles of a non-volatile solute S in
Standard freezing point of water = 273 K equal amount (in kg) of these solvents, the elevation of boiling point
Standard freezing point of ethanol = 155.7 K of solvent X is three times that of solvent Y. Solute S is known to
Standard boiling point of water = 373 K undergo dimerisation in these solvents. If the degree of dimerisation
is 0.7 in solvent Y, the degree of dimerisation in solvent X is
Standard boiling point of ethanol = 351.5 K
C-5.08 W-73.81 UA-21.11 (JEE Adv. 2018)
Vapor pressure of pure water = 32.8 mm Hg
43. If the freezing point of a 0.01 molal aqueous solution of a cobalt (III)
Vapor pressure of pure ethanol = 40 mm Hg
chloride-ammonia complex (which behaves as a strong electrolyte)
Molecular weight of water = 18 g mol–1 is –0.0558°C, the number of chloride(s) in the coordination sphere
Molecular weight of ethanol = 46 g mol–1 of the complex is
In answering the following questions, consider the solutions to [Kf of water = 1.86 K kg mol–1] (JEE Adv. 2015)
be ideal dilute solutions and solutes to be non-volatile and non-
dissociative.

9
 44. MX2 dissociates into M2+ and X–ions in an aqueous solution, 50. Nitrobenzene is formed as the major product along with a minor
with a degree of dissociation (α) of 0.5. The ratio of the observed product in the reaction of benzene with a hot mixture of nitric acid
depression of freezing point of the aqueous solution to the value of and sulphuric acid. The minor product consists of carbon: 42.86%,
the depression of freezing point in the absence of ionic dissociation hydrogen : 2.40%, nitrogen : 16.67% and oxygen : 38.07%,
is C-58.1 W-35.21 UA-6.69 (JEE Adv. 2014) (i) Calculate the empirical formula of the minor product.
Fill in the Blanks (ii) When 5.5 g of the minor product is dissolved in 45 g of benzene,
the boiling point of the solution is 1.84° C higher than that of
45. Given that ΔTf is the depression in freezing point of the solvent
pure benzene. Calculate the molar mass of the minor product then
in a solution of a non-volatile solute of molality, m, the quantity
determine its molecular and structural formula. (Molal boiling point
limm→0 (ΔTf /m) is equal to …… (IIT JEE 1994)
elevation constant of benzene is 2.53 K kg mol–1).(IIT JEE 1999)
Subjective 51. A solution of a non-volatile solute in water freezes at –0.30°C. The
46. 75.2 g of C6H5OH (phenol) is dissolved in a solvent of Kf = 14. If vapor pressure of pure water at 298 K is 23.51 mm Hg and Kf for
the depression in freezing point is 7 K, then find the percentage of water is 1.86 K kg mol–1. Calculate the vapor pressure of this solution
phenol that dimerises. (IIT JEE 2006) at 298 K. (IIT JEE 1998)

47. 1.22 g C6H5COOH is added into two solvents and data of ΔTb and 52. Addition of 0.643 g of a compound to 50 mL of benzene (density:
Kb are given as : 0.879 g/mL ) lowers the freezing point from 5.51°C to 5.03°C. If Kf
for benzene is 5.12, calculate the molecular weight of the compound.
(i) In 100 g CH3COCH3 ΔTb = 0.17, Kb = 1.7 K kg/mol (IIT JEE 1992)
(ii) ln 100 g benzene, ΔTb = 0.13 and Kb = 2.6 K kg/mol 53. The degree of dissociation of Ca(NO3)2 in a dilute aqueous solution,
Find out the molecular weight of C6H5COOH in both the cases and containing 7.0 g of the salt per 100 g of water at 100°C is 70%. If
interpret the result. (IIT JEE 2004) the vapor-pressure of water at
48. Consider the three solvents of identical molar masses. Match their 100°C is 760 mm, calculate the vapor pressure of the solution.
boiling point with their Kb values (IIT JEE 2003) (IIT JEE 1991)
54. The vapour pressure of pure benzene at a certain temperature is 640
Solvents Boiling point Kb values mm Hg. A non-volatile, non-electrolyte solid weighing 2.175 g is
X 100°C 0.92 added to 39.0 g of benzene. The vapour pressure of the solution is
600 mm Hg What is the molecular weight of the solid substance
Y 27°C 0.63 (IIT JEE 1990)
Z 283°C 0.53
49. To 500 cm of water, 3.0×10 kg of acetic acid is added. If 23% of
3 –3

acetic acid is dissociated, what will be the depression in freezing

point? Kf and density of water are 1.86 K kg–1 mol–1 and 0.997g
cm–3, respectively.  (IIT JEE 2000)

10
 Answer Key (Abhedya)

Exercise -1 (Parikshit)
1. (a) 2. (c) 3. (d) 4. (d) 5. (a) 6. (a, c, d) 7. (a, b, c) 8. (a, b, c) 9. (c, d) 10. (c, d)
11. (a, c) 12. (b) 13. (c) 14. (a) 15. (b) 16. (a) 17. (c) 18. (b) 19. (d) 20. (c)
21. (d) 22. (a) 23. [20] 24. [80] 25. [78] 26. [380] 27. [160] 28. [71.42] 29. [0.23] 30. [0.67]

Exercise -2 (PW Challengers)

1. [76.0] 2. (a) 707.2 (b) 272.6 3. 0.82 4. (a) 0.010 mg I2, (b) 0.095 mg I2, (c) 0.0045 mg I2
5.  (a) 67.52, (b) XB = 0.24, (c) P = 49.01 mm Hg, (d) XT = 0.76, 6. [10] 7. [60] 8. [5] 9. (d)
10. (a) 11. (b) 12. (b) 13. (c)

Exercise -3 (PYQ's)
1. (a) 2. [2.98] 6. (b) 7. (b) 8. (c) 9. (b,d) 10. (a,b) 11. (b, c, d) 12. [0.20] 13. [19]
21. (a) 22. (a) 23. (a) 24. (a) 25. (a) 26. (c) 27. (a) 28. (a) 29. (b)
30. (d) 31. (a) 32. (a) 33. (a,d) 34. [100.1] 35. [2.5] 36. (d) 37. (b) 38. (b) 39. [682]
40. [5] 41. [1.02] 42. [0.05] 43. [1] 44. [2] 45. Kf

11