(Physical Chemistry) LIQUID SOLUTION

SOLUTIONS
EXERCISE # O-I
1. vapour pressure depends only on Temp.

2. vapour pressure depends only on Temp.

1
3. v.p. 
intermolecular force

4. vapour pressure remains constant with constant temp

1
6. v.p. 
force of attraction

7. at higher altitudes Patm < 1 atm boiling point decreases as Patm decreases
So if Patm < 1 atm B.P. < 100°C

8. Pext increases so B.P. also increases

9. Psolvent = P°solvent Xsolvent

10. PT = P°A XA + P°B XB

PT = (P°A – P°B)XA + P°B

1 4
13. PT = × 92 + × 31
5 5

PT = 43.2 mm of Hg
14. PT = P°A XA + P°B XB
84 = 70 × 0.8 + P°B × 0.2
P°B = 140 torr
18. for immiscible liquid
PT = P°A + P°B = 100 + 200 = 300 torr

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(Physical Chemistry) LIQUID SOLUTION
19. Colligative properties depends only on number of solute particles.

33.  = CRT

W
= = RT
Molar mass

1

Molar mass

34.  = CRT

 = 0.3 × 0.0821 × 298

 = 7.33 atm

35.  = CRT

7.4 = C × 0.0821 × 300

C = 0.3 mole/ L

1V1 + 2 V2
39. f =
V1 + V2

1.2 + 2.5
f = = 1.85 atm
2

40. only solvent particles can more through SPM. So non blue colour
formation

41. i = 1 + (n – 1)
i −1
(n – 1) =

i −1 1+ i −1
n= +1=
 
1
42. i=1+( – 1)
n


i=1–+
n

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(Physical Chemistry) LIQUID SOLUTION
43. 3A ––→ A3
1 1
i=1+( – 1) =
3 3

44. K2[Pt Cl6] i=3

47. vapour pressure will be maximum for the solution which have min. no. of particles

51. Tf  , Tf 
Tb  im
1
52. 1 = × 2 × RT = RT
2

2 = 2 × 0.5 × RT = RT
1 = 2 (isotonic)

Po − PS in
59. =
P o
in + N
2i
0.5 =
2i + 3

i = 1.5  1 +  = 1.5
  = 0.5
[C4(NH3)3Cl] Cl + AgNO3 ––→ AgCl
2 mole 2 × 0.5 = 1 mole
60. i = 1 + (n – 1)
3
4 = 1 + (n – 1)
4
n=5
So. C.N. = 5 and compound should
= Ba3 [Co(CN)5]2
62. C2H5Cl + C6H5OH is not ideal solution.
Ptheo. = 80 × 0.4 + 120 × 06
32 + 72 = 104 mm
Pobs < Ptheo.  –ve deviation

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(Physical Chemistry) LIQUID SOLUTION

63. max. boiling azeotrope is formed by the solution which show –ve deviation.

64. vmix < 0

V < 50 mL

65. H2SO4 + H2O  –ve deviation

66. for ideal solution

Vmix = 0 Hmix = 0
Smix > 0 Gmix < 0

68. H = +ve , S = +ve , G = –ve

69. Pobs = 580 torr

Ptheo = 300 × 0.4 + 800 × 0.6
= 120 + 480 = 600
Pobs < Ptheo.  –ve deviation CHCl3 + CH3COCH3

71. Pobc = 0.95 atm

Ptheo = 300 × 0.08 + 800 × 0.92

= 760 torr = 1 atm
Pobc < Ptheo
it will show –ve deviation

1
72. solubility of gas  Pressure 
T

73. P = KHX

KH  , X 
T  , KH 

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(Physical Chemistry) LIQUID SOLUTION
74. XP

5.3  10−4 593

=
C2 760

760
C2 = = 5.3 × 10–4 = 6.8 × 10–4 M
593

12.6 6.3
76. Total mass of HNO3 = 5000 × 1.5 × + 5000 × 1 × = 1260
100 100

1260
Moles of HNO3 = = 20
63
20
M= =2
10

98  1.8  10
77. M= = 18
98

nA 0.2 1
78. = =
n H2O 0.8 4

1000
m= = 13.9
4  18

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(Physical Chemistry) LIQUID SOLUTION
EXERCISE # S-I
2. Let The volume of 30% (W/w) H2SO4 and 70% (W/w) H2SO4 is 100 mL.

Total volume of solution = 0.2 L

Total mass of H2SO4 = 120 × 0.3 + 160 × 0.7
= 36 + 112 = 148 g
148
Mole of H2SO4 =
98
148
M= 98 = 7.55
0.2
148
98
M= × 1000 = 11.44
(280 − 148)

3. r.p. of H2O = 355 torr

PO2 = 760 – 355 = 405 torr

P'O2 = 2 × 405 = 810 torr
(as volume is halved)
Ptotal = v.p. of H2O + P'O2
= 355 + 810 = 1165 torr

4. PN1 = 1 – 0.3 = 0.7 atm

P'N2 = 3 × 0.7 = 2.1 atm

Ptotal = 2.1 + 0.3 = 2.4 atm

2 3
5. P= 100 +  300
4 5
1100
= = 220
5
o
7. P = PCH3OH XCH3OH

23
X CH3OH = = 0.24
96

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(Physical Chemistry) LIQUID SOLUTION
1 y A yB
9. = +
PT PAo PBo

0.35 0.65
= +
577 390
PT = 440 torr
PAo X A
yA =
Ptotal

0.35  440
XA = = 0.27
577

PAo  A
10. yA = = 0.5
PT

P°A × A = P°B × B
X A n A PBo 75 3
= = o = =
X B n B PA 200 8

3 8
XA = , XB =
11 11
3
mole % of A = × 100 = 27.3%
11

1 3
11. 550 = PAo  + PBo 
4 4

1 4
560 = PAo  + PBo 
5 5
P°B = 600 mm of Hg
P°A = 400 mm of Hg

1 3
12. 1=  PAo +  PBo …….(i)
4 4

1 = 0.2 × P°A + 0.2 × P°B + 0.6 × 0.8 …….(ii)

From (i) & (ii) P°B = 0.7 atm
P°A = 1.9 atm

Po − PS n
37. =
Po N

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(Physical Chemistry) LIQUID SOLUTION
760 − PS 2.4  7 / 164
=
PS 100 / 18
760
PS = = 746.2 mm Hg
1.018
38. moles of acid = moles of NaOH

200 × M = 125 × 0.1

M = 0.0625
DTf = i Kf x m
0.186 = i × 1.86 × 0.0625
i = 1.6
1.6 = 1 +    = 0.6
% dissociation = 60%
40. Solution of CHCl3 and ethyl methyl ketone shows negative deviation

41. Pexp = 90 mm Hg
1 3
PThe. = 100 × + 80 ×
4 4
= 85 mm Hg
Pexp. > PThe. , It shows +ve deviation.

42. P = KHX  P ×  nsolute

1 6.56  10−3
=  P = 7.62 bar
P 5  10−2
nN 2
43. P = KHX = KH ×
nH 2 O

nN 2
0.987 = 76.48 × 103 ×
1000 / 18

nN 2 = 0.717 m moles

44. X = KHP = 3.1 × 10–2 × 4

X = 12.4 × 10–2 m

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(Physical Chemistry) LIQUID SOLUTION
EXERCISE # O-II
PAo X A Po X
1. yA = = o A Ao
PT PA X A + PB X B

PAo X A
yA =
(PAo − PBo )X B + PBo

1 Po − Po Po 1
= A o B + Bo .
yA PA PA X A

1 Po 1 PBo − PAo
= Bo . +
X A PA yA PBo

2. Pext = 1000 torr

B.P. is The temp. when v.p. = Pext we have to check v.p. of solution at the given temp.
at 90°C
2 1 2200
PT = 1000 × + 200 × =
3 3 3
PT < Pext
At 100°C
2 1
PT = 1350 × + 300 × = 1000
3 3
PT < Pext
So B.P. is 100°C
3. x + y = 0.1
If y = 0 , x = 0.1 (0.1 mole KCl)
Tf = iKf m = 2 × 0.1 × 1.85 = 0.37
If x = 0 , y = 0.1 (0.1 mole KCl)
Tf = iKf m = 3 × 0.1 × 1.85 = 0.555
4. 4 kJ(aq) + HgCl2 (s) ––→ K2[HgI4](aq) + 2KCl(s)
ni 5 1 (LR) 0 0
nf 1 0 1 2
no. of particles initial = 5 × 2 = 10
no. of particles finally = 1 × 2 + 1 × 3 + 2 × 2 = 9
no. of particles are decreasing
Tb  , Tb 

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(Physical Chemistry) LIQUID SOLUTION
17. 2CH3COOH (CH3COOH)2

Initial 0.1 M 0
Eq. (0.1 – 2x) M xM
1
K=
(CH3COOH)2  =
x
= 24 =
5
Ans.
[CH 3COOH] 0.1 − 2x 2 2
0.1 −
24

17. 2CH3COOH (CH3COOH)2

Initial 0.1 M 0
Eqn. (0.1 – 2x) M xM
[CH 3COOH]
K=
[CH 3COOH]2

x x
Or 3.6 × 10–2 = 
(0.1 − 2 x) (0.1) 2
2

 x = 3.6 × 10–4

(CH3COOH)2  =
x x

[CH 3COOH] 0.1 – 2x 0.1

3.6 10 –4 9
= =
0.1 2500

18. 2CH3 COOH (CH3COOH)2

Eqn. (0.1 – 2x – y) M xM

 0.1 M

CH3COOH + H2O CH3COO– + H3O+

Eqn. (0.1 – 2x – y) M yM yM
 0.1 M

[CH 3COO − ][H 3O + ] y.y

Ka = or 2 × 10–5 =
[CH 3COOH] 0.1

 [H3O+] = y = 2 10 –6 M
and pH = – log (2 × 10–6)1/2 = 2.85

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(Physical Chemistry) LIQUID SOLUTION
EXERCISE # S-II
1. P = 180 XB + 90

PS = P°B XB + P°T XT = P°B XB + P°T (1 – XB)

= (P°B – P°T) XB + P°T
P°T = 90 mm Hg P°B – P°T = 180
P°B = 270 mm Hg
936
n C6H6 = = 12 , n C6H6 CH3 = 8
78
PT = P°B XB + P°T XT
12 8
= 270 × + 90 × = 330 mm Hg
20 20

PTo X T 36
yT = = = X1T
Ptotal 330

PBo X B 162
yB = = = X1B
Ptotal 330

162 36
P'total = 270 × + 90 × = 142.36
330 330

PBo X B 9.82
y'B = =
Ptotal 142.36

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(Physical Chemistry) LIQUID SOLUTION
EXERCISE # (JEE MAINS)
57. Due to presence of solute vapour pressure of solution will be less than V.P. of pure solvent. So,
vapour move from higher pressure to lower pressure.

58. If both solutions are isotonic

 Molarity of A = Molarity of B
0.73 / M A 1.65 / M B
× 1000 = × 1000
250 1000

MA 0.73
 = = 1.77 = 177 × 10–2
M B 0.25 1.65

So correct answer is 177.

60. Let mass of water initially present = x gm
 Mass of sucrose = (1000 – x) gm

 1000 − x 
 moles of sucrose =  
 342 

 1000 − x 
  1000 − x
 0.75 = 
342  x
 =
 x  1000 342  0.75
 
 1000 

 256.5 x = 106 – 1000x

 x = 795.86 gm
 moles of sucrose = 0.5969
New mass of H2O = a kg
0.5969
4= 1.86  a = 0.2775 kg
a

 ice separated = (795.86 – 277.5) = 518.3 gm

63. YA = 0.5  YB = 0.5

PA = PB = 0.4 atm

PA = PA0 X A

PA0 = 2

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(Physical Chemistry) LIQUID SOLUTION
64.  Dilute solution given:

P0 − PS n solute
~n
P0 solvent

P0 − P0 2 n solute
=n
P0 solvent

n
solvent 100
n
solute ~ = = 2.78mol
2 18  2

More accurate approach:

P 0 − PS n
solute
=n
PS solvent

P0 − P0 2 n
solute
0
= n
P 2 solvent

100
n
solute ~ n solvent = = 5.55 mol
18

65. [HCOOH] = 0.5 ml l–1

⇒ (0.5 ml × 1.05 g ml–1) HCOOH in 1L

⇒ 0.525 g HCOOH in 1L

(0.525 / 46)
m= mol [Assuming dilute solution]
1kg

Tf 0.0405  46
 Tf = iK f m  i = = = 1.9
k f m 1.86  0.525

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(Physical Chemistry) LIQUID SOLUTION
EXERCISE (JEE-ADVANCED)

21. PT = PA∘ XA + PB∘ XB

0.3 = PAo × 0.25 + PBo × 0.75
0.4 = PAo × 0.5 + PB∘ × 0.5
0.8 = PA∘ + PB∘
on solving eq
PAn (i) \& (ii)
PB∘ = 0.2
22. Number of ions present per formula unit of ionic salt = x
Van 't Hoff factor (i) = 0.9 × x + 0.1 × 1
(Assuming 90% dissociation)
∴ Relative lowering in vapour pressure = Mole fraction of solute

60−59.724 i×0.1
⇒ = 1800
60 +0.1
18

i × 0.1
⇒ 0.0046 =
100 + 0.1

(0.9x + 0.1) × 0.1

0.0046 ≈
100

⇒ 0.9x + 0.1 = 4.6

4.5
⇒x= =5
0.9

x=5

23. Mole of urea = 0.2

Weight of urea = 0.2 × 60 = 12 g
Weight of solvent = 1000 g
Weight of solution = 1012 g
1012
∴ Volume of solution = 1.012 = 1000ml

∵ 1000ml solution contain 0.2 mole

0.2×50
∴ 50ml solution contain = = 0.01
1000
0.06
Mole of urea in other solution = = 0.001
60

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(Physical Chemistry) LIQUID SOLUTION
0.01 + 0.001
∴ Concentration of solution =
300
1000
= 0.0366
∴ 𝜋 = CRT
= 0.0366 × 62 × 300
= 682

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