CHEMISTRY : IIT CORNER 1 Phase : 2 Solutions & C. P.

SOLUTIONS & COLLIGATIVE PROPERTIES : IIT CORNER

Illustration 1: One litre of sea water weighs 1030 g and contains about 6 × 10–3g of dissolved O2. Calculate the
concentration of dissolved oxygen in ppm.
Solution: Mass of O2 in mg = 6 × 10–3g × 103 mg/g = 6mg
Mass of O 2 in mg 6
ppm of O2 in 1030 g sea water = =
Mass of sea water in kg (1030 /1000)kg
6 × 1000
= = 5.8ppm
1030
Illustration 2: The vapour pressure of pure water at 37°C is 47.1 torr. What is the vapour pressure of an
aqueous solution at 37°C
37°C containing 20 g of glucose dissolved in 500 gm of water. Also
calculate vapour pressure lowering.
500
Solution: n H 2O = = 27.78 mol
18
20
n(glucose) = = 0.11 mol
180
n H 2O 27.78 27.78
X H 2O = = = = 0.996
n H2O + n (glu cose) 27.78 + 0.11 27.89
According to Raoult’s law,
PH 2O = PHo 2O X H 2 O = 47.1× 0.996 = 46.9 torr
PHo 2 O – PH2 O = 47.1 – 46.9 = 0.2 torr
Illustration 3: The vapour pressure of ethyl alcohol at 25°C is 59.2 torr. The vapour pressure of a solution of
urea in ethyl alcohol is 51.3 torr. What is the molality of the solution?
PAo – PA nB n Moles of solute
Solution: = X solute = = B =
PA o
n A + n B n A Moles of solvent
59.2 – 51.3 7.9
= X solute = = 0.1334
59.2 59.2
Moles of solute m mol m mol
Molality = = =
Mass of solvent in kg 1 kg 1000 g
1000
No. of mol of solvent in 1000 gm =
46
m mol m × 46
X solute = =
1000 / 46 1000
x × 1000
m = solute
M solvent
0.1334 ×1000
Molality = = 2.9 molal.
46
Illustration 4: Estimate the boiling point of a solution of 25.0g of urea NH2CONH2 plus 25.0g of thiourea
NH2CSNH2 in 500g of chloroform, CHCl3. The boiling point of pure chloroform is 61.2°C, Kb of
chloroform = 3.63 Km–1.
Solution: Molecular mass of urea, NH2CONH2
= 2 × amu N + 1amu C + 1amu O + 4 × amu H
= 2 × 14 + 12 + 16 +4 × 1 = 60 g/mol
Molecular mass of Thiourea, NH2CSNH2
= 2 × amu N + 1amu C + 1amu S + 4 × amu H
= 2 × 14 + 12 + 32 + 4 × 1 = 76 g/mol
Mass of urea 25.0g
Moles of urea = = = 0.42mol
Molecular mass of urea 60g / mol
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25.0
Moles of thiourea = = 0.33mol
76 g/mol
Moles of solute 0.75mol
Molality, m = = = 1.50m
Mass of solvent in kg (500g /1000g)kg
∆Tb = Tb – Tb0 = Kb⋅mm = 3.63 K m–1 × 1.50m = 5.44K = 5.445°C
Tb = 5.445°C + Tb0 = 5.445°C + 61.2°C = 66.645°C
Illustration 5: What is the percent by mass of iodine needed to reduce the freezing point of benzene to
3.5°C? The freezing point and cryoscopic constant of pure benzene are 5.5°C and 5.12 K/m
respectively.
Solution: ∆Tf = Tf0 – Tf = Kfm
5.5°C – 3.5°C = 5.12 K/m × m
2
m= = 0.39m
5.12
∴ Mass of iodine needed for 1000g of benzene = m × molecular mass of iodine I2
= 0.39 mol/kg × 254 g/mol = 99.06 g/kg
∴ 1000g + 99.06g solution contains 99.06g I2
99.06g ×100
100g solution contains = 9.01%
1099.06g
Illustration 6: A solution is prepared by dissolving 26.3g of CdSO4 in 1000g water. The depression in freezing
point of solution was found to be 0.284K. Calculate the Van’t Hoff factor. The cryoscopic
constant of water is 1.86K kg solvent mol–1- solute.
Solution: Molecular mass CdSO4 = 112.4 +32 + 4 × 16 = 208.4 g/mol
Mass CdSO 4
Molality CdSO4 =
Molecular mass CdSO 4 × Mass solvent in kg
26.3g
= = 0.216m
 1000 
(208.4g / mol) ×  kg 
 1000 
∆Tf 0.284K
∆Tf = iKfm or i = = = 1.21
K f m 1.86K / m × 0.126m
Illustration 7: Three particles of a solute, A, associate in benzene to form species A3. Calculate the freezing
point of 0.25
.25 molal solution. The degree of association of solute A is found to be 0.80. the
freezing point of benzene and its cryoscopic constant are 5.5°C and 5.12 Km–1 respectively.
Solution: 3A → A3
No. of moles dissolved 3 0
No. of moles after dissociation m(1–α) mα/3
Total moles present after dissociation
α  α  2α   3 − 2 × 0.8 
= m(1 − α ) + m = m 1 − α +  = m 1 −  = 0.25m  
3  3  3   3 
= 0.177m
∆Tf = Kfm or Tf0 – Tf = 5.12 Km–1 × 0.117 m = 0.6
Tf = Tf0 – 0.6°C = 5.5°C – 0.6°C = 4.9°C

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Solved Problems Objective
Problem 1 : The ratio of the value of any colligative property for KCl solution to that for sugar is nearly -----
times.
(A) 1 (B) 0.5 (C) 2 (D) 2.5
Exp. colligative property no.of particle furnished by KCl
Solution : iKCl= = =2
Normal colligative property no. of particles before dissociation
isugar = 1
Problem 2 : Osmotic pressure of blood is 7.65 atm at 310 K. An aqueous solution of glucose that will be
isotonic with blood is ----- wt/ vol.
(A) 5.41% (B) 3.54% (C) 4.53% (D) 53.4%
Solution: We know πV V = nRT for glucose and blood;
If isotonic, πglucose = πblood
W W
Thus, 7.65 × V = × 0.0821 × 310 ∴ = 54.1 g/ lit = 5.41 % (wt/vol)
180 V
Problem 3 : The Van’t Hoff factor for 0.1 M La (NO3)3 solution is found to be 2.74 the percentage dissociation
of the salt is
(A) 85% (B) 58% (C) 65.8% (D)56.8%
+3 −
Solution: La (NO3)3 ↽ ⇀ La + 2NO3
1–α α 3
3α
i = 1 + 3α
2.74 = 1 + 3α
α = 0.58, percentage dissociation = 58%
Problem 4 : Maximum freezing point will be for 1 molal solution of, assuming equal ionization in each case
(A) [Fe(H2O)6]Cl3 (B)[Fe(H2O)5Cl]Cl2 . H2O (C)[Fe(H2O)4Cl2]Cl . 2H2O (D)[Fe(H2O)3Cl3] . 3H2O
Solution: Larger the value of ‘i’
Smaller the f.p. (d) in a case of non electrolytes, i = 1
Problem 5 : Equal amounts of a solute are dissolved in equal amounts of two solvents A and B. The relative
lowering of vapour pressure for the solution A has twice the relative lowering of vapour
pressure for the solution B. If MA and MB are the molecular weights of solvents A and B
respectively, then for dilute solution of A and B, with solute.
MB
(A) MA = MB (B) M A = (C)MA = 4MB (D)MA = 2MB
2
 P o − Ps  n  P o − Ps  n
Solution:  P o  = N and  Po  = N
 A A  B B

 P − Ps 
o

 Po 
∴
 A = NB = w B MA MA
× = or
MA
= 2 ∴ MA = 2MB
 P − Ps 
o
NA MB w A MB MB
 Po 
 B
Problem 6 : The relationship between osmotic pressure at 273 K when 10 gm glucose (P1), 10 gm 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
n w
Solution: π = CRT = RT or π = RT
v M×v
1
πα
M
M. wt. of glucose, sucrose and urea in the order urea < glucose < sucrose
∴ π in the order urea > glucose > sucrose

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Problem 7: FeCl3 on reaction with K4(Fe(CN)6] in aqueous solution gives blue colour. These are separated by a
semi permeable membrane AB. Due to osmosis there is
0.01 M FeCl3

0.1 M K4 [Fe(CN)6]
Side X Side Y

(A) blue colour formation in side x (B)blue colour formation in side y

(C) blue colour formation in both sides (D)no blue colour formation
Solution: Due to osmosis, solvent (i.e., water) from y side migrates towards x side. Since solute (i.e.) FeCl3 is not
migrating, there is no blue colour formation.
formati
Problem 8: A weak electrolyte, AB, is 5% dissociated in aqueous solution. What is the freezing point of a 0.100
molal aqueous solution of AB? Kf for water is 1.86 deg/molal.
(A) –3.8°C (B)–0.1953°C (C)–1.7°C (D)– 0.78°C
5
Solution: Degree of dissociation, α, α AB = = 0.05
100
AB → A+ + B–
No. of moles dissolved m 0 0
No. of moles after dissociation m(1 – α) mα mα
After dissociation 0.1(1 – 0.05) 0.1 × 0.05 0.1 × 0.05
Total moles = 0.1 (1 – 0.05) + 0.1 × 0.05 + 0.1 × 0.05
∴ The net molality = 0.105 m = 0.095 + 0.005 + 0.005 = 0.105m
∆Tf = Kfm or Tf0 – Tf = 1.86 K/m × 0.105m = 0.1953 deg
Tf = 0°C – 0.1953 = –0.1953°C
Problem 9 : Calculate the boiling point of a one molar aqueous solution
(density = 1.04 g mL–11) of potassium chloride, Kb for water = 0.52 kg mol–1. Atomic masses of K =
39, Cl = 35.5
(A) 107.28°C (B)103.68°C (C)101.078°C (D)None of these
Solution: Volume of solution = 1000 ml
Mass of the solution = V × d = 1000 mL × 1.04 g/mL = 1040g
Amount of solute in 1000 mL solution = 1 M
= 1 M × Molecular Mass = 1M × 74.5g/mol = 74.5g
Mass of water = Mass of solution – Mass of KCl = 1040g – 74.5g = 965.5g
Moles of solute 1 mol
Molality of the solution = m = = = 1.0357
Mass of solvent in kg (965.5 /1000)kg
∆Tb = i .Kb.m
m = 2 × 0.52 K kg mol–1 × 1.0357 = 1.078°C
Boiling point of the solution = 100°C + 1.078°C = 101.078°C
101.078
Problem 10 : 20 g of a binary electrolyte (mol.wt. = 100) are dissolved in 500 g of water. The freezing point of
0.74°C, Kf = 1.86 K.molality–1. The degree of ionisation of the electrolyte is
the solution is –0.74°C,
(A) 50% (B) 75% (C) 100% (D) 0
1000 × K f × w 1000 × 1.86 × 20
Solution: ∆Tf = ∴ 0.74 = ⇒ M = 100
M×W M × 500
Normal mol.wt 100
Now, =1+α=
exp. mol.wt. 100
So, α = 0
Problem 11 : Y g of non - volatile organic substance of molecular mass M is dissolved in 250g benzene. Molal
elevation constant of benzene is Kb. Elevation in its boiling point is given by
M 4 K bY KY KY
(A) (B) (C) b (D) b
K bY M 4M M
1000 × K b × Y 4K b Y
Solution: ∆T = =
250 × M M

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Solved Problems Subjective
Problem 1 : The freezing point depression of a 0.109 M aq. solution of formic acid is –0.21°C. Calculate the
equilibrium constant for the reaction,
HCOOH (aq) H+ (aq) + HCOO– (aq)Kf for water = 1.86 kg mol–1 K
Solution : From question
∆Tf = 0.21°C
Molality of solution = 0.109 m
The reaction is
HCOOH (aq) H+(aq) + HCOO– (aq)
Initially moles C 0 0
Moles after dissociation (1–α)C
(1 αC αC
(1 − α) × C + α × C + α × C
i= = 1 + α, where α = degree of dissociation
1× C
As we know,
∆Tf = Kf × i × Cm
0.21 = 1.86 × (1+α) × 0.109 (in very dilute solution molarity and molality can be taken as same)
0.21
∴ 1+α = = 1.0358
1.86 × 0.109
or, α = 0.0358 = 0.036
∴ [HCOOH] = (1–α) × C = (1–0.036)
(1 × C = 0.964 ×C
[H ] = α × C = 0.036 × C, [HCOO ] = 0.036 ×C
+ –

[H + ][HCOO − ] 0.036 × C × 0.036 × C

Ka = = = 1.34 × 10–3 ×C mol lit–1
[HCOOH] 0.964 × C
= 1.34 × 10–3 × 0.109
Ka = 1.46 × 10–4
Problem 2 : The freezing point of a solution of acetic acid (mole fraction is 0.02) in benzene is 277.4 K. Acetic
acid exists partly as a dimer
2A A2. Calculate equilibrium constant for dimerisation. Freezing point of benzene is 278.4
K and (Kf for benzene is 5)
Solution: Let acetic acid = A
Benzene = B
Assume, α part of A forms dimer
2A A2
1 0 initially moles
1–α α/2
/2 moles after dimer is formed
(1 − α ) + α 2
∴i= = 1 – α/2
1
Mol. fraction of A = xA = 0.02
Mol. fraction of B = xB = 0.98
x 1000 0.02 1000
Molality of A in B = A × = × = 0.262 mol kg–1 of Benzene
mB XB 78 0.98
Since, ∆Tf = Kf × i × molality
278.4–277.4 = 5 × i × 0.262
or, 1 = 5 × i × 0.262
1
i= = 0.763
5 × 0.262
1– α/2 = 0.763 ⇒ α = 0.47
Hence the molality of A after dimer is formed = (1–α)(1 × initial molality
= (1 – 0.48) × initial molality = 0.52 × 0.262
α 0.48
Molality of A2 after dimer is formed = × molality = × 0.262 = 0.24 × 0.26 = 0.06288
2 2
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The equilibrium constant

Keq =
[ A 2 ] = 0.06288 = 3.39 kg mol–1
[ A ] (0.13624)2
2

Problem 3 : A milimolar solution of pottassium ferricyanide is 70% dissociated at 27°C. Find out the osmotic
pressure of the solution.
1
Solution: Given, concentration of solution = C = M = 10–3M
1000
K3[Fe(CN)6] → 3K+ + [Fe(CN)6]–3
Initially moles 1 0 0
Moles after dissociation 1-α 3α α
70
Where α = degree of dissociation = 70% = = 0.7
100
Total moles of after dissociation = (1–α)
(1 + 3α + α = 1+ 3α
1 + 3α
∴i=
1
i = 1+3α = 1+(3× 0.7) = 3.1
Since osmotic pressure
π = iCRT
∴ π = 3.1 × 10–3 × 0.0821 × 300= 0.31 × 3 × 0.0821 atm = 0.07635 atm
Problem 4 : If the solution of mercuric cyanide of strength 3 g / L has an osmotic pressure 0.3092 × 105 Nm–2
at 298 K, what is the apparent
apparent molecular weight and degree of dissociation of Hg(CN)2?
(Hg = 200.61, C = 12 , N = 14)
Solution: Let the apparent molecular weight = mo
n w 1 3 × 10−3 1
pressure = π = ×RT
RT = × × RT or, 0.3092 × 105 = × −3 × 8.314 × 298
v mo v mo 10
∴ mo = 240.2 × 10–3 kg
number of particles after dissociation no
normal
rmal mol. w t.
Since, =
number of particles before dissociation observed mol. wt.
∴ Hg(CN)2 Hg++ + 2CN–
1– α 2α
∴ Number of particles after dissociation = (1 – α) + α + 2α= 1 + 2α
−3
1 + 2α 252.61× 10
i.e., =
1 240.2 × 10 − 3
∴ α = 0.02457 or 2.4567 %
Problem 5 : If the apparent degree of ionization of KCl (KCl = 74.5 gm mol–11) in water at 290K is 0.86.
Calculate the mass of KCl which must be made up to 1 dm3 of aqueous solution so as to produce
the same osmotic pressure as the 4.0% solution of glucose at that temperature.
Solution : Due to ionization of KCl
KCl → K+ + Cl–
Initial moles 1 0 0
Moles after dissociation 1–α α α
∴ i=
(1 − α) + α + α
= 1+ α
1
From question, degree of ionization = α = 0.86
∴ i = 1+ 0.86 = 1.86
For Osmotic pressure of glucose,
For 4% glucose solution,
Weight of glucose = 40 gm
Volume of solution = V = 1L = 1dm3

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Molecular weight of glucose C6H12O6= m = 180
1
∴ πglucose = n × × RT, where πglucose = osmotic pressure of glucose
v
w 1 40 1
= × ×R×T= × × RT
m v 180 1
1 1 w 1 w1 1
Similarly, πKCl = i × n × × RT = 1.86 × n × ×RT= 1.86 × 1 × × RT = 1.86 × × ×RT
v v m1 v 74.5 1
As both solutions are isotonic
∴πKCl = πglucose
w1 40
1.86 × × RT = × RT
74.5 180
40 0.5
∴ W1 = × = 8.9 gm
180 m
Problem 6 : The freezing point of an aqueous solution of KCN containing
0.1892 mol kg–1 of solvent was found to be – 0.704°C. On adding 0.095 mol of Hg(CN)2, the
freezing point of the solution was found to be – 0.530°C. If the complex – formation takes place
according to the following equation.
Hg(CN)2 + nKCN Kn [Hg(CN)n+2].
What is the formula of the complex ?Kf(H2O) is 1.86 kg mol–1 K.
Solution: ∆Tf (KCN solution) = 0.704°C
molality of KCN solution = 0.1892
i = (1 + x)
∆Tf = Kf × m × i
∆Tf 0.704
i = (1 + x) = = = 2.0
K f × m 1.86 × 0.1892
This gives x = 1, indicating 100% ionization of KCN
∆Tf of the complex = 0.530
Molality of Hg(CN)2 = 0.095 mol kg–1
Kn [Hg(CN)n+2] nK+ + [Hg(CN)n+2]–
1 0 0 ….. initially moles
1– α nα α …..
.. moles after dissociation here
i = (1–α) + nα + α = 1+nα
1+n
∵α=1
∴ i = 1+ n
∆Tf = Kf × i × molality
0.503 = 1.86 × I × 0.095
i= 0.503 ≈ 3
1.86 × 0.095
1+ n = 3 or, n = 2
Hence, the complex is K2[Hg(CN)4]
Problem 7`: Ethylene dibromide (C2H4Br2) and 1,2–dibromopropane (C3H6Br2) forms a series of ideal solution
over the whole range of composition. At 85°C,
85 C, the vapour pressure of these pure liquids are 173
mmHg and 127mm Hg respectively.
10 gm of ethylene dibromide is dissolved in 80 gm of 1,2 – dibromo–propane.
dibromo Calculate the
partial pressures
essures of each components and the total pressure of the solution at 85°C.
85
Calculate the composition of vapour in equilibrium with the above solution and express as mole
fraction of ethylene dibromide
What would be the mole fraction of 1,2 dibromopropane
dibromopropane in solution with 50:50 mole mixture in
the vapour.
Solution: Let C2H4Br2 = A, ∴ mA = 24+4 + 160, where mA= molecular weight of A
mB = molecular weight of B and B is C3H6Br2 = mB = 36 + 6+ 160 = 202
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Moles of A, nA = w A = 10 = 0.053 Moles of B, nB = w B = 80 = 0.396
mA 188 mB 202
XB = nB = 0.396 = 0.882
nA + nB 0.053 + 0.396
∴ xA + xB = 1
∴ xA = 1 – 0.882= 0.118
a) We know, total pressure
PT = PA + PB Where PA, PB are partial pressures of A and B respectively.
= PAo ⋅ X A + PBo ⋅ X B , where PAo , PBo are partial pressures of pure component of A and B.
PT = 173 × 0.118 + 127 × 0.882= 20.42 + 112.014= 132.43mm Hg
Here partial pressure of A, PA = 20.42 mm Hg
Here partial pressure of B, PB = 112.014 mm Hg.
b) Mole fraction of ethylene dibromide in the vapour
partial pressure of A 20.42
YA = = = 0.154
Total pressure 132.43
c) In vapour phase
nA: nB = 50:50
∴YA = 0.5, YB = 0.5
Problem 8: Calculate the molecular weight of cellulose acetate if its 0.5% (wt./vol) solution in acetone
ac (sp. gr. =
0.9) shows an osmotic rise of 23 mm against pure acetone at 27°C.
Solution: 0.5% (wt. /vol) solution means 0.5 gm of cellulose acetate is dissolved in 100 ml solution.
Osmotic pressure = 23 mm of pure acetone
2.3 × 0.9
π = 2.3 Cm of pure acetone = cm of Hg = 0.1522 cm of Hg
13.6
0.1522
π = atm = 0.002 atm
76
Let the molecular weight of the cellulose acetate be M
0.5
Here, number of mole of cellulose acetate (n) =
M
Volume = v = 100 ml = 0.1 lit
R = 0.082 lit atm mol–1 K–1
–
, T = ( 27 + 273) = 300 K
n 0.5 1
Osmotic pressure (π) = ×RT ⇒ 0.002 = × × 0.0821 × 300 ∴ M = 61575
v M 0.1
Problem 9: 1kg of an aqueous solution of Sucrose is cooled and maintained at –4°C. – How much ice will be
–1
separated out if the molality of the solution is 0.75? Kf (H2O) = 1.86 Kg mol K.
Solution: Sucrose is a non–electrolyte,ence
electrolyte,ence i = 1
Molecular weight of sucrose (C12H22O11) = m = 342 gm mol–1
Molality of the solution = 0.75 m = 0.75 mol kg–1 solvent
= 0.75 × 342 gm Sucrose per kg solvent = 256.5 gm Sucrose per kg solvent
hence, weight of 1 molal solution = 1000 + 256.5 = 1256.5 gm
256.5
Sucrose present in 1 kg solution = × 1000 = 204.14 gm
1256.5
Weight of solvent (H2O) present in 1 kg solution = 1000–
1000 204.14 = 795.86 gm
w 1000
point f = Kf × i ×
Since depression in freezing point,∆T × , Where W = weight of solvent
m W
204.14 1000
w = weight of the solute or, 4 = 1.86 × 1 × ×
342 W
∴ W = 277.55 gm i.e., weight of solvent required to maintain this solution at – 4°C is
W = 277.55
Hence rest weight of H2O will convert into ice.
Hence amount of ice formed = 795.86 – 277.55 = 518.31 gm

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Problem 10: River water is found to contain 11.7% NaCl, 9.5% MgCl2, and 8.4%. NaHCO3 by weight of solution.
Calculate its normal boiling point assuming 90% ionization of NaCl, 70% ionization of MgCl2 and
50% ionization of NaHCO3 (Kb for water = 0.52)
11.7 9.5 8.4
Solution: nNaCl = = 0.2 n MgCl2 = = 0.1 n NaHCO3 = = 0.1
58.5 95 84
iNaCl = 1+ α = 1+ 0.9 = 1.9
i MgCl2 = 1 + 2α = 1+ 0.7 × 2 = 2.4
i NaHCO3 = 1+ 2α = 1+ 0.5 × 2 = 2.0
Weight of solvent = 100 – (11.7 + 9.5 + 8.4) = 70.4 g
(i NaCl × n NaCl + i MgCl2 × n MgCl2 + i NaHCO3 × n NaHCO3 ) × K b × 1000
∆Tb =
Weight of solvent
(1.9 × 0.2 + 2.4 × 0.1 + 2 × 0.1) × 0.52 × 1000
= = 5.94°C
70.4
∴ Boiling point of solution = 100 + 5.94 = 105.95°C
Problem 11: An aqueous solution containing 288 gm of a non–volalite non volalite compound having the stochiometric
composition CxH2xOx in 90 gm water boils at 101.24°C at 1.00 atmospheric pressure . What is the
molecular formula?
Kb(H2O) = 0.512 K mol–1 kg
Tb (H2O) = 100°C
Solution: Elevation in B.P. = 101.24 – 100 = 1.24°C
Since solute is non volatile
Since the elevation in boilingboilin point is
∆Tb = Kb × i × molality
w 1000
= Kb × 1× ×
m W
288 1000
1.24 = 0.512 × ×
m 90
∴ m = 1321.2 gm mol–1
m = mol.wt. of solute
molar mass of CxH2xOx = 12x + 1 × 2x + 16x = 30x
∴ 30x = 1321.2
∴ x = 44
Hence the molecular formula is = C44H88O44
Problem 12: A complex is represented as CoCl3.xNH3. Its 0.1 m solution in aqueous solution shows ∆Tf = 0.558°
Kf(H2O) = 1.86 mol–1 K and assume 100% ionization and co–ordination co ordination number of Co(III) is six .
What is the complex?
Solution: From question, molality of solution = Cm = 0.1
Depression in freezing point = ∆Tf = 0.558°C
Kf (H2O) = 1.86 kg mol–1 K–1
As we know that
∆Tf = Kf × i × m, Where i = Vant Hoff’s factor
0.558 = 1.86 × 0.1 × i
0.558
∴i= =3
0.186
or, i ≈ 3 indicates that complex ionize to form three ions since co−ordination no. is 6 hence x = 5
i.e., CoCl3.5NH3 → [Co(NH3)5Cl]++ + 2Cl–
↓ ↓
1 Cation 2 anions
So, the complex is [Co(NH3)5Cl]Cl2

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CHEMISTRY:
SECTION - I
LEVEL – I Objective Single Choice
1. At 40°C, the vapour pressure in torr of methanol and ethanol solution is P = 119x + 135
Where x is the mol. fraction of methanol. Hence:
(A) vapour pressure of pure methanol is 119 torr.
(B) vapour pressure of pure ethanol is 135 torr.
(C) vapour pressure of equimolar mixture of each is 127 mm
(D) mixture is completely immiscible
2. Consider following cases:
I : 2 M 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 ionizes 100%; which is/a true statement?
(A) both are isotonic (B) I is hypertonic (C) II is hypertonic (D) inadequate data
3. If PA is the vapour pressure of a pure liquid A and the mol fraction of A in the mixture of two liquids A and B is
x, the partial vapour pressure of A is:
x (1 − x)
(A) (1 – x)PA (B) xPA (C) PA (D) PA
(1 − x) X
4. When mercuricuric iodide is added to the aqueous solution of potassium iodide, the:
(A) freezing point is raised (B) freezing point is lowered
(C) freezing point does not change (D) boiling point does not change
5. 100 mL of liquid A was mixed with 25 mL of liquid B to give a non-ideal
ideal solution of A-B
A mixture. The volume of
this mixture would be
(A) 75 mL (B) either less or more than 125 mL
(C) close to 125 mL but not exceeding 125 mL (D) just more than 125 mL.
6. 0.01 M solution each of urea, common salt and Na2SO4 are taken. The ratio of depression of freezing point is
(A) 1:1:1 (B) 1:2:1 (C) 1:2:3 (D) 2:2:3
7. A X molal solution of a compound in benzene has mole fraction of solute equal to 0.2. The value of X is
(A) 14 (B) 3.2 (C) 1.4 (D) 2.
8. Mole fraction of the component A in vapour phase is x1 and mole fraction of component A in liquid mixture is
x2 ( p 0A = vapour pressure of pure A; pB0 = vapour pressure of pure
B), then total vapour pressure of the liquid mixture is :
p A0 x2 pA0 x1 pB0 x1 pB0 x2
(A) (B) (C) (D)
x1 x2 x2 x1
9. Nitrobenzene freezes at 278.98°C. 0.25 molal solution of a solute in nitrobenzene causes freezing point
depression of 2°C. K f for nitrobenzene is
(A) 2K m –1 (B) 4K m –1 (C) 8K m –1 (D) 12K m –1 .
10. The freezing point of 1 molal NaCl solution assuming NaCl to be 100% dissociated in water is
(A) –1.86°C (B) –3.72°C
3.72°C (C) + 1.86°C (D) + 3.72°C.
11. Which one of the following pairs of solution can we expect to be
be isotonic at the same temperature?
(A) 0.1 M urea and 0.1 M NaCl (B) 0.1 M urea and 0.2 M MgCl 2
(C) 0.1 M NaCl and 0.1 M Na 2SO 4 (D) 0.1 M Ca(NO3 )2 and 0.1 M Na 2SO 4
12. Vapour pressure of a solution of 5 g of a non-electrolyte
non electrolyte in 100 g of water at a particular temperature is 2985
N / m . The vapour pressure of pure water is 3000 N / m 2 , the molecular weight of the solute is
2

(A) 60 (B) 120 (C) 180 (D) 380.

13. 0.15 g of a substance dissolved in 15 g of a solvent boiled at a temperature higher by 0.216°C than that of the
pure solvent. Find out the molecular weight of the substance. ( K f for solvent is 2.16°C).
(A) 1.01 (B) 10.1 (C) 100 (D) 10.
14. A 5% solution of cane sugar (Mol. Wt. = 342) is isotonic with 1% solution of substance X. The molecular weight
of X is
(A) 17.12 (B) 68.4 (C) 34.2 (D) 136.2.
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15. The vapor pressure of a solvent decreased by 10 mm of Hg when a non-volatile volatile solute was added to the
solvent. The mole-fraction
fraction of solute in solution is 0.2. What would be the mole-fraction
mole fraction of solvent if decrease
in vapour pressure is 20 mm of Hg?
(A) 0.8 (B) 0.6 (C) 0.4 (D) 0.2.
16. An ideal solution was obtained by mixing methanol and ethanol. If the partial vapour pressure of methanol
and ethanol are 2.619 kPa and 4.556 kPa respectively, the composition of vapour (in terms of mole fraction)
will be
(A) 0.634 MeOH, 0.365 EtOH (B) 0.365 MeOH, 0.635 EtOH
(C) 0.574 MeOH, 0.326 EtOH (D) 0.173 MeOH, 0.827 EtOH.
17. Vapour pressure of CCl 4 at 25°C is 143 mm Hg. 0.5 gm of a non-volatile
non volatile solute (Mol. Wt. 65) is dissolved in
100 ml CCl 4 . Find the vapour pressure of the solution. (Density of CCl4 = 1.58 g / cm 3 ).
(A) 141.93 mm (B) 94.39 mm (C) 199.34 mm (D) 143.99 mm.
-1
18. The boiling point elevation constant for toluene is 3.32 K kg mol , the normal boiling point of toluene is
110.70C. The enthalpy of vaporization of toluene
tol would by nearly:
(A) 17.0 k Jmol-1 (B) 34.0 kJ mol-1 (C) 51.0 kJ mol-1 (D) 68.0 kJ mol-1
19. The molal elevation constant is the ratio of the elevation in B.P. to
(A) molarity (B) molality
(C) mole fraction of solute (D) mole fraction of solvent.
vent.
20. The osmotic pressure of a 5% solution of cane sugar at 150°C is (Mol. Wt. of cane sugar = 342)
(A) 4 atm. (B) 3.4 atm. (C) 5.07 atm. (D) 2.45 atm.
21. In a mixture A and B components show negative deviation as :
(A) ∆Vmix = +ve (B) ∆Hmix = -ve
(C) A – B interaction is weaker than A –A and B – B interaction (D) none
22. The freezing point of equimolal aqueous solution will be highest for
(A) C6 H 5 NH 3Cl (B) Ca(NO3 )2 (C) La(NO3 )3 (D) C6 H12 O6 (glucose).
0
23. Benzene and toluene form nearly ideal solutions. At 20 C, the vapour pressure of benzene is 75 torr and that
of toluene is 22 torr. The parial vapour pressure of benzene at 200C for a solution containing 78g of benzene
benz
and 46 g of toluene of torr is
(A) 50 (B) 25 (C) 37.5 (D) 53.5
24. The vapour pressure of pure liquid A is 0.80 atm. On mixing a non-volatile
non volatile B to A, its vapour pressure
becomes 0.6 atom. The mole fraction of B in the solution is
(A) 0.150 (B) 0.25 (C) 0.50 (D) 0.75
25. A dry air is passed through the solution, containing the 10 gm of solute and 90 gm of water and then it pass
through pure water. There is the depression in weight of solution wt. by 2.5 gm and of pure solvent by 0.05
gm. Calculate
alculate the molecular weight of solute
(A) 50 (B) 180 (C) 100 (D) 25

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 Phase :3 Solutions & C.P. 12 CHEMISTRY IIT CORNER
CHEMISTRY:
LEVEL - II More than one choice
1. 0
1 mol benzene (Pbenzene = 42 mm) and 2 mol toluene (Ptoluene 0
= 36mm) will have:
(A) total vapour pressure 38 mm
(B) mol fraction of vapours of benzene above liquid mixture is 7/19
(C) positive deviation from Raoult’s law (D) negative deviation from Raoult’s law
2. Which is/are correct statement(s)?
(A) when mixture is less volatile, there is positive deviation from Raoult’s law
(B) when mixture is more volatile, there is negative deviation from Raoult’s law
(C) when mixture is less volatile, there is negative deviation from Raoult’s law
(D) when mixture is more volatile, there is positive devation from Raoult’s law la
3. When a solute is added to a pure solvent, the
(A) vapour pressure of the solution becomes lower than that of the pure solvent
(B) rate of evaporation of the pure solvent is reduced
(C) solute does not affect the rate of condensation
(D) rate of evaporation
aporation of the solution is equal to the rate of condensation of the solution at a lower vapour
pressure than that in the case of the pure solvent
4. According to Raoult’s law the relative decrease in the solvent vapour pressure over the solution is equal to
(A) the mole fraction of the solvent (B) the mole fraction of the solute
(C) the number of moles of the solute
(D) i times the mole fraction of the solute which undergoes dissociation or association in the solvent
5. Which of the following statements
statements are correct for a binary solution which shows negative deviation from
Raoult’s law?
(A) The negative deviation from linearity diminishes and tends to zero as the concentration of the solution
component approaches unity
(B) When solutions form, their volumesvolumes are smaller than the sum of the volumes of their components
(C) Heat is released during the formation of the solution
(D) Heat is absorbed during the formation of the solution
6. A binary liquid (AB) shows positive deviation from Raoult’s law when
(A) p A > p 0A X liq
A
and p A > p0B X liq
B
A B-B > A-B
(B) Intermolecular forces: A-A,
(C) ∆Vmix > 0 (D) ∆Hmix > 0
7. The azeotropic solutions of two miscible liquids
(A) can be separated by simple distillation
(B) may show positive or negative deviation from Raoult’ law
(C) are supersaturated solutions
(D) behave like a single component and boil at a constant temperature
8. If P0 and Ps are the vapour pressures of the solvent and its solution respectively and N1 and N2 are the mole
fractions of the solvent and nd solute respectively, then
(A) PS = P0N2 (B) P0 – PS = P0N2 (C) PS = P0 N1 (D)(P0 – PS)/PS = N1/(N1 + N2)
9. Which of the following form ideal solution ?
(A) C6H5Cl — C6H5Br (B) C6H6 — C6H5CH3 (C) Hexane — Heptane (D) Ethanol + Cyclohexae
10. At constant temperature, the osmotic pressure of a solution is
(A) directly proportional to the concentration
(B) inversely proportional to the molecular weight of the solute
(C) directly proportional to the square of the concentration
(D) directly proportional
tional to the square root of the concentration
11. Ideal solution is formed when its components
(A) have zero heat of mixing (B) have zero volume change
(C) obey Raoult’s law (D) can be converted into gases
12. In the depression of freezing point experiment,
expe it is found that
(A) The vapour pressure of the solution is less than that of pure solvent
(B) The 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 ules solidify at the freezing point
13. The colligative properties of a solution are
1
(A) ∝ molality (B) ∝ =
molecular mass of the solute
(C) proportional to each other
(D) independent of the nature of the solute, i.e., electrolyte or non-electrolyte
non
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LEVEL - III Other Engg. Exams
1. Equimolar solution in the same solvent have
(A) same boiling point but different freezing point (B) Same freezing point but different boiling point
(C) Same boiling and same freezing points (D) Different boiling and different
ifferent freezing points.
2. The colligative properties of a solution depend on
(A) Nature of solute particles present in it (B) Nature of solvent used
(C) Number of solute particles present in it (D) Number of moles of solvent only.
3. Which of the following is not a colligative property
(A) Osmotic pressure (B) Elevation in B.P.
(C) Vapour Pressure (D) Depression in freezing point
4. An aqueous solution of methanol in water has vapour pressure
(A) equal to that of water (B)) Equal to that of methanol
(C) More than that of water (D) Less than that of water.
5. Benzene and toluene form nearly ideal solutions. At 200C, the vapour pressure of benzene is 75 torr and that
of toluene is 22 torr. The parial vapour pressure of benzene at 200C for a solution containg 78g of benzene
and 46 g of toluene of torr is
(A) 50 (B) 25 (C) 37.5 (D) 53.5
6. The vapour pressure lowering caused by the addition of 100 g of sucrose (molecular mass = 342) to 1000g of
water having the vapour pressure of pure water at 250C is 23.8 mm Hg.
(A) 1.25 mm Hg (B) 0.125 mm Hg (C) 1.15 mm Hg (D) 00.10 mm Hg
7. The vapour pressure of pure liquid A is 0.80 atm. On mixing a non-volatile non volatile B to A, its vapour pressure
becomes 0.6 atom. The mole fraction of B in the solution is
(A) 0.150 (B) 0.25 (C) 0.50 (D) 0.75
8. When a non-volatile
volatile solute is dissolved in a solvent, the relative lowering of vapour pressure is equal to
(A) Mole fraction of solute (B) Mole fraction of solvent
(C) Concentration n of the solute in grams per litre (D) Concentration of the solute in gram 100 ml.
9. The vapour pressure of water at 200C is 17.54 mm. When 20g of a non-ionic, ionic, substance is dissolved in 100 g
of water, the vapour pressure is lowered by 0.30 mm. What is is the molecular weight of the substances.
(A) 210.2 (B) 206.88 (C) 215.2 (D) 200.8
10. A dry air is passed through the solution, containing the 10 gm of solute and 90 gm of water and then it pass
through pure water. There is the depression in weight of solution wt. by 2.5 gm and of pure solvent by 0.05
gm. Calculate the molecular weight of solute
(A) 50 (B) 180 (C) 100 (D) 25
11. Which of the following liquid pairs shows a positive deviation from Raoult’s law
(A) Water –nitric acid (B) Benzene –methanol (C) Water-hydrochloric acid (D) Acetone-chloroform
12. A solution that obeys Raoult’s law is
(A) Normal (B) Molar (C) Ideal (D) Saturated
13. Liquids A and B form an ideal solution
(A) The enthalpy of mixing is zero
(B) The entropy of mixing is zero
(C) The free energy of mixing is zero
(D) The free energy as well as the entropy of mixing are each zero.
14. A solution of sucrose (molar mass = 342 g/mol) is prepared by dissolving 68.4g of it per litre of the solution,
what is its osmotic pressure (R = 0.082 lit. atm k-1 mol-1) at 273 k.
(A) 6.02 atm (B) 4.47 atm (C) 4.04 atm (D) 5.32 atm
15. If 20 g of a solute was dissolved in 500 ml of water and osmotic pressure of the solution was found to be 600
mm of Hg at 150C, the molecular weight of the solute is
(A) 1000 (B) 1200 (C) 1400 (D) 1800

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CHEMISTRY:
SECTION - II
LEVEL - I Subjective
1. At 37°C, the osmotic pressure of blood is 7.65 atm. How much glucose should be used per litre for an
intraveninous injection that is to have the same osmotic pressure as blood. [M2 = 180g mol–1)
2. An aqueous solution of sugar containing 9 gm per 50 ml of the solution is isotonic with an aqueous solution of
2.923 gm. NaCl per 100 ml. Calculate the molecular weight of sugar [Temperature = 300°K].
3. 1 g of monobasic acid when dissolved in 100 g of water lowers the freezing point by 0.168°C. 0.2 gm of the
same acid when dissolved and titrated required 15.1 ml of N/10 alkali. Calculate degree of dissociation of the
acid. (Kf for water is 1.86)
4. In a cold climate, water gets frozen causing damage to the radiator of a car. Ethylene glycol is used as an anti-
anti
freezing agent. Calculate the amount of ethylene glycol to be added to 4 kg of water to prevent it from
freezing at – 6°C.Kf for water = 1.86 kg mol–1 K.
5. 1.1 gm of CoCl3.6NH3 (mol weight = 267) was dissolved in 100 gm of water. The freezing point of the solution
was – 0.29°C. How many moles of the solute particles exist in solution for each mole of solute particles
introduced?
6. When a compound is dissolved in 1000gm of benzene, the freezing point of benzene is depressed by 1.28°K. If
the same amount of compound is dissolved in 1 kg of water, the freezing point of water was depressed by
1.4°K. If the compound completely dissociates in water but remains undissociated in benzene, calculate into
how many ions does a molecule dissociate in water. Kf for benzene = 5.12,Kf for water = 1.86
7. 0.02 m solution of CH3COOH is 3% dissociated at 25°C. Calculate freezing point and osmotic pressure of the
solution Kf for water = 1.86°C m–11.
8. When 36.0 g of a non-volatile
volatile solute having the empirical formula CH2O is dissolved in 1.20 kg of water, the
solution freezes at –0.93°C.
0.93°C. What is the molecular formula of the compound? (kf = 1.86).
9. The vapour pressures of two pure liquids A and B are 60 torr and 80 torr respectively. If the mole fraction of A
in an ideal solution with B, is 0.2 then what is the mole fraction of A in the vapour collected over the solution.
10. Calculate the amount
ount of ice that will separate out on cooling a solution containing 50g of ethylene glycol in
200g water to – 9.3°C (Kf for water = 1.86 K mol–1 kg).
LEVEL – II Subjective
1. The formula weight of an acid is 82.0. In a titration, 100 cm3 of solution of this acid containing 39.0g of this
acid per litre were completely neutralized by 95.0 cm3 of aqueous NaOH containing 40g of NaOH per litre.
What is the basicity of this acid?
2. At 25°C, 1 mole of A having a vapour pressure of 100 torr and 1 mol of B having a vapour pressure of 300 torr
were mixed. The vapour at equilibrium is removed, condensed and the condensate is heated back to 25°C.
The vapours now formed are again removed, recondensed and analysed. What is the mole fraction of A in
this condensate?
3. What weight of the non-volatile
volatile solute, urea (NH2 – CO – NH2) need to be dissolved in 100g of water, in order to
decrease the vapour pressure of water by 25%? What will be the molarity of the solution?
4. A solution containing 0.5216g of naphthalene (mol. wt. = 128.16) in 50 ml of CCl4 shows boiling point elevation
of 0.402° while a solution of 0.6216g of an unknown solute in the same weight of solvent gave a boiling point
elevation of 0.647°. Find the molecular mass of the unknown solute.
5. The pressure of the water vapour of a solution containing a non-volatile
non volatile solute is 2% below that of the vapour of
pure water. Determine the molality of the solution.
6. Two elements ‘A’ and ‘B’ form compounds having formulae AB2 and AB4. When dissolved in 20 g of benzene , 1 g
of AB2 lowers the freezing point by 2.3°C whreas 1 g of AB4 lowers the freezing point by 1.3°C. Calculate the
atomic weights of A and B. (Kf for benzene = 5.1°C m–1)
7. Benzene and toluene form an ideal solution. The vapour pressure
pressure of benzene and toluene are respectively 75
mm and 22 mm at 20°C. If the mole fractions of benzene and toluene in vapour are 0.63 and 0.37 respectively,
calculate the vapour pressure of the ideal mixture.
8. Calculate the molality and molarity of a solution
solution made by mixing equal volumes of 30% by weight of H2SO4
(density = 1.218 g/ml) and 70% by weight of H2SO4 (density = 1.610 g/ml).
9. At 25°C, 1 mol of a having a vapour pressure of 100 torr and 1 mol of B having a vapour pressure of 300 torr
were mixed. the vapour at equilibrium is removed, condensed and the condensate is heated back to 25°C. The
vapors now formed are again removed, recondensed and analyzed. What is the mole fraction of A this
condensate?
10. The freezing point depression of a 0.109 M aq. aq solution of formic acid is –0.21°C.
0.21°C. Calculate the equilibrium
constant for the reaction, HCOOH (aq) ↽ ⇀ H (aq) + HCOO (aq);Kf for water = 1.86 kg mol–1 K
+ –

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SECTION - III
A Matrix-Match Type
p q r s
This section contains 2 questions. Each question contains statements given in two column which
A p q r s
have to be matched. Statements (A, B, C, D) in Column I have to be matched with statements (p,
q, r, s) in Column II.. The answers to these questions have to be appropriately
appropriately bubbles as B p q r s

illustrated in the following example. C p q r s

If the correct matches are A–p, A–s, B–q,
q, B–r,
B C–p, C–q and D–s, s, then the correctly bubbled 4 × 4 p q r s
D
matrix should be as follows :
1. Match the following :
Column I Column II
(A) CCl4 + CHCl3 (p) Raoult’s law

(B) + H 2O (q) Nearly ideal solution

PA ∝ xA
(C) (r) Non-ideal solution with –ve
– deviation
(D)
PA < PA0 x A (s) Non-ideal
ideal solution with +ve deviation
2. Match the following :
Column I Column II
(A) CH3COOH in H2O (p)
Neither association nor dissociation
(B) CH3COOH in benzene (q)
When a non-volatile
volatile solute is added.
Polymer in water Molecular mass observed greater than molecular
(C) (r)
mass actual.
(D) Vapour pressure of a liquid decreases (s) ∆Tb(obs) > ∆Tb(calc.)
B Linked Comprehension Type
This section contains 4 paragraphs C1-3 , C4-66,C7-9 and C10-12. Based upon each paragraph, 3 multiple choice questions have to be
answered. Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.
C1––3 : Paragraph for Questions Nos. 1 to 3
According to Raoult’s law (which is applicable for a mixture of volatile liquids) the partial vapour pressure of a
liquid is directly proportional to mol fraction of that component. Further assuming ideal behaviour for
vapours and applying Dalton’s law we can write different equations as follows:
PA = PA0 x A , PB = PB0 x B PTotal = PA + PB = PA0 x A + PB0 x B = PB0 + (PA0 − PB0 )x A
Further mol fraction of a component in vapour phase is equal to the ratio of partial vapour pressure to total
vapour pressure of mixture.
The vapour pressure of two pure liquids A and B which form an ideal ideal solution are 300 and 500 torr
respectively at temperature T. A mixture of the vapours of A and B for which the mol fraction of A is 0.25 is
slowly compressed at temperature T.
1. The total pressure when first drop of condensate is formed will be
(A) 428 torr (B) 400 torr (C) 388 torr (D) 358 torr
2. The pressure when only the last bubble of vapour remains will be
(A) 350 torr (B) 375 torr (C) 525 torr (D) 450 torr
3. The mol fraction of B in the last bubble of vapour will be
(A) 0.16 (B) 0.84 (C) 0.20 (D) 0.80
C4––6 : Paragraph for Questions Nos. 4 to 6
Two liquids A and B form ideal solutions. At 300K, 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 more mole of B is added to this solution,
the vapour pressure of the solution increases
in by 10 mm of Hg.
4. The vapour pressure of pure A
(A) 400 mm of Hg (B) 700 mm of Hg (C) 600 mm of Hg (D) 800 mm of Hg
5. The vapour pressure of pure B.
(A) 800 mm of Hg (B) 600 mm of Hg (C) 400 mm of Hg (D) 700 mm of Hg
6. The mole of fraction
on A in vapour phase
(A) 0.25 (B) 0.18 (C) 0.75 (D) 0.45
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CHEMISTRY:
C6––8 : Paragraph for Questions Nos. 7 to 9
A solution of sucrose (molar mass = 342) has been prepared by dissolving 68.4g of sucrose in one kg of water.
Kf for water is 1.86 K kg mol–1 and vapour pressure of water at 298 K is 0.024 atm.
7. The vapour pressure of the solution at 298 K will be
(A) 0.230 atm (B) 0.233 atm (C) 0.236 atm (D) 0.0239 atm
8. The osmotic pressure of the solution at 298 K will be
(A) 4.29 atm (B) 4.49 atm (C) 4.69 atm (D) 4.89 atm
9. The freezing point of the solution will be
(A) –0.684°C (B) –0.342°C
0.342°C (C) –0.372°C (D) –0.186°C
C10–12
12 : Paragraph for Questions Nos. 10 to 12
Properties such as boiling point, freezing point and vapour pressure of a pure solvent change when solute
molecules are added to get homogeneous solution. These are called colligative properties. Applications of
colligative properties are very useful in day-to-day
day day life. One of its examples is the use of ethylene glycol and
water mixtures as anti-freezingg liquid in the radiator of automobiles.
A solution M is prepared by mixing ethanol and water. The mole fraction of ethanol in the mixture is 0.9
Given: Freezing point depression constant of water (K fwater ) = 1.86 K kg mol–1
Freezing pointt depression constant of ethanol (K ethanol
f ) = 2.0 K kg mol–1
Boiling point elevation constant of water (K water
b ) = 0.52 K kg mol–1
Boiling point elevation constant of ethanol (K ethanol
b ) = 1.2 K kg mol–1
Standard freezing point of water = 273K Standard freezing point of ethanol = 155.7 K
Standard boiling point of water = 373 K Standard boiling point of ethanol = 351.5 K
Vapour pressure of pure water = 32.8 mm Hg Vapour pressure of pure ethanol = 40 mm Hg
–1
Molecular weight of water = 18 g mol Molecular weight of ethanol = 46 g mol–1
In answering the following questions, consider the solutions to be ideal dilute solutions and solutes to be non-
non
volatile and non-dissociative.
10. The freezing point of the solution M is
(A) 268.7 K (B) 268.5 K (C) 234.2 K (D) 150.9 K
11. The vapour pressure of the solution M is
(A) 39.3 mm Hg (B) 36.0 mm Hg (C) 29.5 mm Hg (D) 28.8 mm Hg
12. Water is added to the solution M such that the mole fraction of water in the solution
soluti becomes 0.9 The boiling
point of this solution is
(A) 380.4 K (B) 376.2 K (C) 373.5 K (D) 354.7 K
C Assertion and Reasoning
This section contains 4 questions numbered 1 to 4. Each question contains STATEMENT-1
STATEMENT 1 (Assertion) and STATEMENT-2
STATEMENT
(Reason). Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is correct.
A) Statement – 1 is True, Statement – 2 is True; Statement – 2 is a correct explanation for Statement – 1.
(B)Statement – 1 is True, Statement – 2 is True; Statement – 2 is NOT a correct explanation for Statement – 1.
(C)Statement – 1 is True, Statement – 2 is False.
(D)Statement – 1 is False, Statement – 2 is True.
1. STATEMENT - 1 If a solution is heated such that keeping rest of all things unchanged volume is changed, then
it also brings changes to colligative properties related with it.
STATEMENT - 2 The molarity of sol’n
sol n changes on changing the volume of solution for same amount of solute.
2. STATEMENT – 1 The vapour pressure of a liquid is the equilibrium constant of liquid – vapour equilibrium at
the given temperature
STATEMENT – 2 The ratio of the lowering of vapour pressure of a solvent upon dissolution of a non-volatile
non
solute, to the vapour pressure of pure solvent increases with temperature.
3. STATEMENT – 1 Reverse osmosis is used to purify saline water.
STATEMENT – 2 Solvent molecules pass from concentrated to dilute solution through semipermeable
membrane if high pressure is applied on solution.
4. STATEMENT - 1 Azeotropic mixtures are formed only by non-ideal
non solutions
STATEMENT - 2 Boiling point of an azeotrope is either higher than both the components or lower than both
the compounents

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Previous IIT- JEE Problems Objective
1. An azeotropic solution of two liquids has boiling point lower than either of them when it. [1981]
(A) shows negative deviation from Raoult’s law (B) shows no deviation from Raoult’s law
(C) shows positive deviation from Raoult’s law (D) is saturated
2. For a dilute solution, Raoult’s law states that: [1985]
(A) the lowering of vapour pressure is equal to the mole fraction of solute
(B) the relative lowering of vapour pressure is equal to the mole fraction of solute
(C) the relative lowering of vapour pressure is proportional to the amount of solute in solution
solut
(D) the vapour pressure of the solution is equal to the mole fraction of solvent
3. When mercuric iodide is added to the aqueous solution of potassium iodide then [1987]
(A) freezing point is raised (B) freezing point is lowered
(C) freezing point does not change (D) boiling point does not change
4. Which of the following 0.1 M aqueous solution will have the lowest freezing point? [1989]
(A) Potassium sulphate (B) Sodium chloride (C) Urea (D) Glucose
5. The freezing point of equimolal aqueous solution
so will be highest for: [1990]
(A) C6H5NH3Cl (B) Ca(NO3)2 (C) La(NO3)3 (D) C6H12O6 (glucose)
6. 0.2 molal acid HX is 20% ionized in solution. Kf = 1.86 K molality–1. the freezing point of the solution is
(A) –0.45 (B) –0.90
0.90 (C) –0.31 (D) –0.53
7. The molecular weight of benzoic acid in benzene as determined by depression in freezing point method
corresponds to: [1996]
(A) ionization of benzoic acid (B) dimerization of benzoic acid
(C) trimerization of benzoic acid (D) salvation of benzoic acid
8. During depression of freezing point in a solution the following are in equilibrium [2003]
(A) liquid solvent, solid solvent (B) liquid solvent, solid solute
(C) liquid solute, solid solute (D) liquid solute, solid solvent
9. The elevation in boiling
oiling point of a solution of 13.44g of CuCl2 in 1 kg of water using the following information
will be (Molecular weight of CuCl2 = 134.4 and Kb = 0.52 K molal–1) [2005]
(A) 0.16 (B) 0.05 (C) 0.1 (D) 0.2
10. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g of benzene (Kf = 1.72 K kg mol–1), a freezing point
depression of 2K is observed. The Van’t Hoff factor (i) is [2007]
(A) 0.5 (B) 1 (C) 2 (D) 3
11. In the depression of freezing point experiment, it is found that the [1999]
(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 soute molecules solidify at the freezing point
(D) only solvent molecules solidify at the freezing point
Previous IIT- JEE Problems Subjective
1. What is the molarity and molality of a 13% solution (by weight) of sulphuric acid with a density of 1.02 g/ml?
To what volume should 100 ml of this acid be diluted in order to prepare a 1.5 N solution? [1978]
2. A bottle
tle of commercial sulphuric acid (density 1.787 g/ml) is labeled s 86 percent by weight. What is the
molarity of the acid. What volume of the acid has to be used to make 1 litre of 0.2 M H2SO4?[1979]
3. 0.5 gm of fuming H2SO4 (Oleum) is diluted with water. This solution is completely neutralized by 26.7 ml of
0.4 N NaOH. Find the percentage of free SO3 in the sample of oleum. [1980]
4. The vapour pressure of pure benzene is 639.7 mm of mercury and the vapour of a solution of a solute in
benzene at the same temperature is 631.9 mm of mercury. Calculate the molality of the solution.
[1981]
5. Two liquids A and B form 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. Hg. At the same temperature, if one more 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 state. [1982]

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6. An organic compound CxH2yOy was burnt with twice twice the amount of oxygen needed for complete combustion
to CO2 and H2O. The hot gases when cooled to 0°C and 1 atm pressure, measured 2.24 litres. The water
collected during cooling weighed 0.9g. The vapour pressure of pure water at 20°C is 17.5 mm Hg and is
lowered by 0.104 mm when 50 g of the organic compound are dissolved in 1000 g of water. Give the
molecular formula of the organic compound. [1983]
7. The vapour pressure of ethanol and methanol are 44.5 mm and 88.7 Hg respectively. An ideal solution is
formed at the same temperature by mixing 60g of ethanol with 40g of methanol. Calculate the total vapour
pressure of the solution and the mole fraction of methanol in the vapour. [1986]
8. The vapour pressure of a dilute aqueous solution of glucose (C6H12O6) is 750 mm of mercury at 373 K.
Calculate (i) molality and (ii) mole fraction of the solution. [1989]
9. The vapour pressure of pure benzene at a certain temperature is 640 mm Hg. A non-volatile
non non-electrolyte
solid weighing 2.175 g is 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? [1990]
10. The degree of dissociation of calcium nitrate in a dilute aqueous solution, containing 7.0g of the salt per 100
gm of water at 100°C 0°C is 70%. If the vapour pressure of water at 100°C is 760 mm, calculate the vapour
pressure of the solution. [1991]
11. Addition of 0.643 g of a compound to 50 ml of benzene (density: 0.879 g/ml.) lowers the freezing point from
5.51°C to 5.03°C. If Kf forr benzene is 5.12 K kg mol–1, calculate the molecular weight of the compound.
[1992]
12. What weight of the non-volatile
volatile solute, urea (NH2 – CO – NH2) needs to be dissolved in 100g of water, in
order to decrease the vapour pressure of water by 25%? What will will be the molality of the solution?
[1993]
–1
13. The molar volume of liquid benzene (density = 0.877 g mL ) increases by a factor of 2750 as it vaporizes at
20°C and that of liquid toluene (density = 0.867g mL–1) increases by a factor of 7720 at 20°C. A solutionsol of
benzene and toluene at 20°C has a vpour pressure of 46.0 Torr. Find the mole fraction of benzene in the
vapour above the solution. [1996]
14. volatile solution (that does not dissociate) is dissolved in 56.8 cm3 of benzene
A very small amount of a non-volatile
(density 0.889 g cm–3). At room temperature vapour pressure of this solution is 98.88 mm Hg while that of
benzene is 100 mm Hg. Find the molality of this solution. If the freezing temperature of this solution is 0.73
degree lower than that of benzene, what is the value of molar freezing point depression constant of
benzene? [1997]
15. A solution of a non volatile solute in water freezes at –0.30°C.
0.30°C. The vapour pressure of pure water at 298 K is
23.51 mm Hg and Kf for water is 1.86 K kg mol–1. Calculate the vapour pressure of this solution at 298 K.
[1998]
16. Nitrobenzene is formed as the major product along with a minor product in the reaction of benzene with a
hot mixture of nitric acid and sulphuric acid. The minor product consists of carbon : 42.86%, hydrogen :
2.40%, nitrogen: 16.67%, and oxygen: 38.07% (i) Calculate the empirical formula of the minor product. (ii)
When 5.5 g of the minor product is dissolved in 45g of benzene, the boiling point of the solution is 1.84°C
higher than that of pure benzene.
ene. Calculate the molar mass of the minor product and determine its molecular
and structural formula. (Molal boiling point elevation constant of benzene is 2.53 K kg mol–1).[1999]
17. To 500 cm3 of water, 3.0 × 10–3 kg of acetic acid is added. If 23% of 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 0.997 g cm–3, respectively.
[2000]
18. 1.22g of benzoic acid is dissolved in 100 g of acetone and 100 g of benzene separately. BoilingBoil point of the
solution in acetone increases by 0.17°C, while that in the benzene increases by 0.13°C; Kb for acetone and
benzene is 1.7 K kg mol–1 and 2.6 K kg mol–1. Find molecular weight of bzenoic acid in two cases and justify
your answer. [2004]
19. 75.2 g of C6H5OH (phenol) is dissolved in a solvent of Kf = 14. If the depression in freezing point is 7 K then find
the % of phenol that dimerises. [2006]

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ANSWERS
SECTION - I
Level - I Level - II Level - III
Single Choice More than one correct Other Engg. Exams
1. (B) 14. (B) 1. (A, B) 1. (C) 11. (B)
2. (A) 15. (C) 2. (C, D) 2. (C) 12. (C)
3. (B) 16. (B) 3. (A, B, C, D) 3. (C) 13. (A)
4. (A) 17. (A) 4. (B, D) 4. (C) 14. (B)
5. (B) 18. (B) 5. (A, B, C) 5. (A) 15. (B)
6. (C) 19. (B) 6. (A, B, C, D) 6. (B)
7. (B) 20. (C) 7. (B, D) 7. (B)
8. (A) 21. (B) 8. (B, C) 8. (A)
9. (C) 22. (D) 9. (A, B, C) 9. (B)
10. (B) 23. (A) 10. (A, B) 10. (C)
11. (D) 24. (B) 11. (A, B, C)
12. (C) 25. (C) 12. (A, D)
13. (C) 13. (A, B, C)

SECTION - II
Level – I Subjective
1. 54.18 g 2. 180.1239
3. 0.196 4. 804g
5. 4 6. 3
7. 0.504 atm 8. C2H4O2
9. χA = 0.16 torr 10. 38.71g
Level – II Subjective
1. 2 2. Xa = 0.1
3. 18.52 m 4. 95 g mol–1
5. 1.134 m 6. 25.5, 42.5
7. 39.65 mm of Hg 8. 11.4 m, 7.6 m
9. χA = 0.1 10. Ka = 1.5 × 10–4

SECTION – III
A B C
Matrix-Match Type Linked Comprehension Type Assertion and Reasoning
1. (A – p, q), 1. (A) 1. (D)
(B – s), 2. (D) 2. (C)
(C – p, q), 3. (B) 3. (A)
(D – r) 4. (A) 4. (B)
2. (A – s), 5. (B)
(B – r), 6. (C)
(C – p), 7. (D)
8. (D)
(D – q)
9. (C)
10. (D)
11. (B)
12. (B)

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SECTION – IV

Previous IIT-
IIT JEE Problems Objective

1. (C) 2. (B) 3. (A) 4. (A)

5. (D) 6. (A) 7. (B) 8. (A)
9. (A) 10. (A) 11. (A, D)

Previous IIT-
IIT JEE Problems Subjective
1. 1.38 M, 1.40m, 184 ml
2. 15.81 M; 12.65
3. 3.84%
4. 0.156 mole/kg
5. 400 mm of Hg, 600 mm ofHg
6. (CH2O)5 or C5H10O5
7. 66.17 mm, 0.65
8. 0.7053 mol/kg, 0.9868
9. 6525
10. 746.3 mm Hg
11. 156.056
12. 18.52 m
13. 0.73
14. 5.027 K molality–1
15. 23.44 mm Hg
16. 168 g, (C6H4(NO2)2, m-dinitrobenzene
dinitrobenzene
17. 0.228 K
18. 122, 224
19. 75%

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