6.solution - Colligative Properties-1 PDF

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Summary
1. Osmotic Pressure:
(i) π = ρgh
Where, ρ = density of soln., h = equilibrium height.
(ii) Vant – Hoff Formula (For calculation of O.P)
π = CST
 C − mol / lit.

S = ideal soln. constant =π atm.  R − 0.082 lit.atm.mol −1k −1
 T − kelvin

= 8.314 J mol-1K-1 (exp value)
t
ne
= R (ideal gas) constant.
n
π = CRT = RT (just like ideal gas equation)
e.
V
Therefore C = total conc. Of all types of particles. =
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(n1 + n2 + n3 + ......)
C1 + C2 + C3 + ....... =
at
V
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Note: If V1 of C1 conc. + V2 mL of C2 conc. Are mixed.
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 C1V1 + C2V2   π 1V1 + π 2V2 

π =  RT ; π = 
 V1 + V2   RT 
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Types of solutions:
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(a) Isotonic solution – Two solutions having same O.P.

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π1 = π2
(b) Hyper tonic – If π1 > π2. ⟹ Ist solution is hypertonic solution w.r.t 2nd solution.
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(c) Hypotonic = IInd solution is hypotonic w.r.t. Ist solution.

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Abnormal Colligative Properties: (In case of association of dissociation) Vant Hoff correction
Factor(i):
exp/ observed / actual / abnormal value of colligative property
i=
Theoritical value of colligative property
exp/ observed no.of particles / conc. observed molality

=
Theoritical value of colligative property Theoritical molality
theoretical molar mass ( formula mass )

=
experimental / observed molar mass (apparent molar mass )
o i > 1 ⇒ dissociation.
i < 1 ⇒ dissociation.
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πexp.
o i= ∴ π = iCRT ⇒ π − (i1C1 + i2C2 + i3C3 ....) RT
πtheor .
Relation between i & a (degree of dissociation):
For electrolyte Ax . By ; Ax Bx (aq.) → xA y + → + yB x −
i = 1 + (n -1) α where, n = x + y.
Relation b/w degree of association β & i.
1 
nA → An . ; 1  − 1 β
i =+
n 
2. Relative Lowering of vapour Pressure (RLVP) :
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Vapour pressure: Psoln < P
Lowering VP = P – Ps = ∆P
e.
∆P
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Relative lowering in vapour pressure RLVP = =
P
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Raoult’s law: - (For non – volatile solutes)
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Experimentally relative lowering in V.P = mole fraction of the non volatile solute in solutions.
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P − Ps n
RLVP
= = X= solute
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P n+ N
P − Ps n P − Ps M
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= ; = (molality ) × ( M = molar mass of solvent )

P N P 1000
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If solute gets associated of dissociated

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P − Ps i.n P − Ps M
; i × (molality ) ×
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= =
P N P 1000
o According to Raoult’s law
(i) p1 = p10 X 1 where, X 1 is the mole fraction of the solvent (liquid) (ii) An alternate form →
p10 − p1
= X2
p10
∆P ∆P
o Ostwald – Walker Method: Experimental or lab determination of or
P Ps
Loss of wt of solution containers α Ps.
Loss of in wt ot solvent containers α (P - Ps.)

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gain in wt of dehydrating agent α P.

P − Ps loss in wt. of solvent P − Ps loss is wt. of solvent
= = ⇒
P loss in wt. of solution P gain is wt. dehydrating agent
3. Elevation In Boiling Point:

∆Tb =i × K b m
RTb2 RTb2 M
Kb = or Kb = ∴ ∆Lvap - is cal/gm or J/gm
1000 × Lvap 1000 × ∆H vap
R = 2 cal mol-1 K-1 or 8.314 J…..

Tb = b.p of liq (in kelvin) ; Kb = K kg mol-1.
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 ∆H vap 
∆H vap - molar enthalpy of vaporisation Lvap =  
e.
 M 
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4. Depression in Freezing point: at
i K f .m.
∴ ∆T f =×
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RT f2 RT f2 M
K f molar depression constant = =
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1000 × L fusion 1000 × ∆H fusion

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Raoult's Law for Binary (Ideal) Mixture Of Volatile Liquids:

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PA = X APA0 ∴ PB = X BPB0
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∴ A is more volatile than B

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∴ B.P of A < B. P. of B
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∴ According to Dalton’s law
PT =PA + PB = X APA0 + X BPB0
X A, = mole fraction of A in vapour above the liquid / solution.
X B, = mole fraction of B
PA = X APA0 = X A ' PT
PB = X B'PT = X BPB

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1 X A' X B'
= + .
PT PA0 PB0
Graphical Representation:
PA = X A PA0 & PB = X B PB0
PT X A PA0 + X B PB0
=
PT = X A PA0 + (1 − X A ) PB0 = ( PA0 − PB0 ) X A + PB0
(1 − X B ) PA0 + X B PB0 =
PT = ( PB0 − PA0 ) X B + PA0
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e.
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ldeal solutions {mixtures}:

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1. The mixtures which follow Raoul'ts law at all temp. & at all compositions will be known as
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ideal mixture / ideal

solution.
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2. Ideal solution will be obtained only when the forces of attraction b/w the liq. Molecules are
exactly of same
nature & almost of same magnitude
A--------A ⇒ A ------B,
B -------B
3. ∆H mix =
0
4. ∆Vmix =
0
5. ∆S mix =
+ve as for process to proceed

@aakashallen
6. ∆Gmix =
- ve
e.g. (1) Benzene + Toluene.

(2) Hexane + heptane.
(3) C2 H 5 Br + C2 H 5 I .
Non – Ideal Solutions: Which do not obey Raoult’s law

(a) Positive deviation: -
(i) PT .exp > ( X A PA0 + X B PB0 )
(ii)
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e.
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(iii) ∆H mix =
+ve energy absorbed (iv) ∆Vmix =
+ve ( 1L + 1L > 2L) (v) ∆Gmix =
-ve
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e.g. H2O + CH3OH.
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H2O + C2H5OH
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C2H5OH + hexane
C2H5OH + cyclohexane.
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CHCl3 + CCl4 → dipole dipole interaction becomes weak.

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(b) Negative deviation
(i) PT exp < x A P 0 + xB P 0 B
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(ii)
Strong of attraction.
(iii) ∆H mix =
−ve (iv) ∆Vmix =
−ve (1L +1L < 2L) (vi) ∆Gmix =
−ve
e.g. H2O + HCOOH

H2O + CH3COOH
H2O + HNO3
CHCl3 + CH3OCH3
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e.
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Immiscible Liquids:
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(i) Ptotal= PA + PB (ii)

= o
PA P=
A XA PA0 [Since, XA = 1]
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(iii)
= PB P=o
B XB PB0 [Since, XB = 1] (iv) Ptotal
= PAo + PB0
PA0 nA PA0 WA M B
(v) = (vi) =
PB0 nB PB0 M AWB
nA RT 0 nB RT
=PA0 = ; PB
V V

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B.P. of solution is less than the individual B.P.'s of both the liquids.
Henry Law:
This law deals with dissolution of gas in liquid i.e. mass of any gas dissolved in any solvent per
unit volume
is proportional to pressure of gas in equilibrium with liquid.
t
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mαp
m = kp
e.
weight of gas
m→
Volume of liquid
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at
K → Henry constant (in atm-1)
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P → Pressure of gas.
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@aakashallen
Practice Questions
1. 18 g of glucose (C6H1206) is added to 178.2 g of water. The vapour pressure of water (in torr) for this
aqueous solution is (2016)
(a) 76.0
(b) 752.4
(c) 759.0
(d) 7.6
2. The vapour pressure of acetone at 20°C is 185 torr. When 1.2 g of a non-volatile substance was
t
dissolved in 100g of acetone at 20°C, its vapour pressure was 183 Torr. The molar mass of the substance
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is (2015)
(a) 32
e.
(b) 64
(a) 128
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(b) 488
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3. Which of the following colligative properties can provide molar mass of proteins (or polymers or
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colloids) with greatest precision?
(a) osmotic pressure

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(b) elevation of boiling point

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(c) depression of freezing point

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(d) relative lowing of vapour pressure

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4. The Henry's law constant for the solubility of N2 gas in water at 298 K is 1.0 x 105 atm. The mole
fraction of N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water of 298 K
and 5 atm pressure is (2009)
(a) 4.0 x 10-4
(b) 4.0 x 10-5
(c) 5.0 x 10-4
(d) 4.0 x 10-6
5. A molal solution is one that contains one mole of a solute in (1986)

@aakashallen
(a) 1000 g of the solvent
(b) I L of the solvent
(c) I L of the solution
(d) 22.4 L of the solution
6. 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
t
ne
(d) the vapour pressure of the solution is equal to the mole fraction of solvent
e.
7. 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

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(b) shows no deviation from Raoult's law
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(c) shows positive deviation from Raoult's law

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(d) is saturated
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.le
8. The freezing point of benzene decreases by 0.45°C when 0.2 g of acetic acid is added to 20 g of
benzene. If acetic acid associates to form a dimer in benzene, percentage association of acetic acid in
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benzene will be (Kf for benzene = 5.12 K kg mol-1) (2017)

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(a) 64.6 %
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(b) 80.4%
(c) 74.6 %
(d) 94.6 %
9. Pure water freezes at 273 K and 1 bar. The addition of 34.5 g of ethanol to 500 g of water changes the
freezing point of the solution. Use the freezing point depression constant of water as 2 K kgmol-1. The
figures shown below represent plots of vapour pressure (V.P.) versus temperature (T). [Molecular
weight of ethanol is 46 g mol-1] (2017)
Among the following, the option representing change in the freezing point is

@aakashallen
t
ne
e.
iv
10. Consider separate solution of 0.500 M C2H50H (aq), 0.100 M Mg3(PO4 )2(aq), 0.250M KBr(aq) and
at
0.125 M Na3PO4(aq) at 25°C. Which statement is true about these solutions, assuming all salts to be
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strong electrolytes? (2014)
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(a) They all have the seine osmotic pressure
(b) 0.100 M Mg3(PO4)2(aq) has the highest osmotic pressure

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(c) 0.125 M Na3PO4(aq) has the highest osmotic pressure

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(d) 0.500 M C2H5OH (aq) has the highest osmotic pressure

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11. The freezing point (in° C) of solution containing 0.1 g of K3[Fe(CN)6] (mol. wt. 329) in 100 g of water
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(Kf = 1.86K kg mol-1) is (2011)
(a) - 2.3 x 10-2
(b) -5.7 x10-2
(c) -5.7 x 10-3
(d) -1.2 x 10-2
12. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50g of benzene (Kf = 1.72 K kg mol-1), a freezing
point depression of 2 K is observed. The vant Hoff factor (i) is (2007)
(a) 0.5

@aakashallen
(b) 1
(c) 2
(d) 3
13. The elevation in boiling point, when 13.44 g of freshly prepared CuCl2 are added to one kilogram of
water, is. [Some useful data, Kb = 0.52 K kg mol-1 , molecular weight of CuCl2 = 134.4 g]. (2005)
(a) 0.05
(b) 0.1
(c) 0.156
t
(d) 0.21
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e.
14. 0.004 M Na2SO4 is isotonic with 0.01 M glucose. Degree of dissociation of Na2SO4 is (2004)
(a) 75%
iv
at
(b) 50%
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(c) 25%
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(d) 85%
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15. During depression of freezing point in a solution the following are in equilibrium (2003)
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(a) liquid solvent, solid solvent

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(b) liquid solvent, solid solute

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(c) liquid solute, solid solute

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(d) liquid solute, solid solvent
16. The molecular weight of benzoic acid in benzene as determined by depression in freezing point
method corresponds to (1996)
(a) ionization of benzoic add
(b) dimerisation of benzoic acid
(c) trimerisation of benzoic add
(d) solvation of benzoic add

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17. The freezing point of equimolal aqueous solutions will be highest for (1990)
(a) C6H5NH3Cl (aniline hydrochloride)
(b) Ca(NO3)2
(c) Le(NO3)3
(d) C6H12O6 (glucose)
18. Which of the following 0.1 M aqueous solution will have the lowest freezing point? (1989)
(a) Potassium sulphate
t
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(b) Sodium chloride
(c) Urea
e.
(d) Glucose
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at
19. When mercuric iodide is added to the aqueous solution of potassium iodide (1987)
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(a) freezing point is raised

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(b) freezing point is lowered

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(c) freezing point does not change

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(d) boiling point does not change

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20.
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21.

@aakashallen
22.
t
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23.
e.
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at
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24. 2.56 g of sulfur in 100 g of CS2 has depression in freezing point of 0.01°C. Kr = 0.1°molal-1. Hence the
nc
atomicity of sulfur in CS2 is

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25.
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w
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26.

@aakashallen
27.
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e.
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at
28.
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29.
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w
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30.
@aakashallen
31.
32. The beans are cooked sooner in a pressure cooker, because
(a) boiling point increase with increasing pressure
(b) boiling point decrease with increasing pressure
(c) extra pressure of pressure cooker, softens the beans
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(d) internal energy is not lost while cooking in pressure cooker.
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e.
iv
33. at
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nc
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34.
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w
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35.
36.

@aakashallen
37.
38.
t
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e.
iv
at
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39.
nc
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.le
w
w
40.
w
41.
42.
@aakashallen
43.
t
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44.
e.
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at
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45.
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@aakashallen
Answer Key:
1. b 2b 3. a 4. a 5. a 6. b 7. c 8. d 9. a 10. a
11. a 12. a 13. c 14. a 15. a 16. b 17. d 18. a 19. a 20. b
21. d 22. b 23. b 24. d 25. c 26. c 27. c 28. a 29. b 30. d
31. b 32. a 33. d 34. a 35. d 36. a 37. a 38. a 39.a 40. d
41. d 42. d 43. b 44. c 45. c
“Detail solutions are mentioned in the content library”
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e.
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nc
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@aakashallen

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 C1V1 + C2V2   π 1V1 + π 2V2 

(a) Isotonic solution – Two solutions having same O.P.

(c) Hypotonic = IInd solution is hypotonic w.r.t. Ist solution.

exp/ observed no.of particles / conc. observed molality

theoretical molar mass ( formula mass )

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For electrolyte Ax . By ; Ax Bx (aq.) → xA y + → + yB x −

= ; = (molality ) × ( M = molar mass of solvent )

If solute gets associated of dissociated

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gain in wt of dehydrating agent α P.

3. Elevation In Boiling Point:

R = 2 cal mol-1 K-1 or 8.314 J…..

1000 × L fusion 1000 × ∆H fusion

Raoult's Law for Binary (Ideal) Mixture Of Volatile Liquids:

∴ A is more volatile than B

∴ According to Dalton’s law

PT =PA + PB = X APA0 + X BPB0

X A, = mole fraction of A in vapour above the liquid / solution.

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PA = X A PA0 & PB = X B PB0

PT = X A PA0 + (1 − X A ) PB0 = ( PA0 − PB0 ) X A + PB0

ldeal solutions {mixtures}:

ideal mixture / ideal

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e.g. (1) Benzene + Toluene.

Non – Ideal Solutions: Which do not obey Raoult’s law

(i) PT .exp > ( X A PA0 + X B PB0 )

CHCl3 + CCl4 → dipole dipole interaction becomes weak.

(b) Negative deviation

(i) PT exp < x A P 0 + xB P 0 B

e.g. H2O + HCOOH

(i) Ptotal= PA + PB (ii)

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colloids) with greatest precision?

(a) osmotic pressure

(b) elevation of boiling point

(c) depression of freezing point

(d) relative lowing of vapour pressure

(a) 4.0 x 10-4

(b) 4.0 x 10-5

(c) 5.0 x 10-4

(d) 4.0 x 10-6

5. A molal solution is one that contains one mole of a solute in (1986)

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(a) 1000 g of the solvent

(b) I L of the solvent

(c) I L of the solution

(d) 22.4 L of the solution

6. For a dilute solution, Raoult's law states that (1985)

(a) shows negative deviation from Raoult's law

(c) shows positive deviation from Raoult's law

benzene will be (Kf for benzene = 5.12 K kg mol-1) (2017)

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(a) They all have the seine osmotic pressure

(b) 0.100 M Mg3(PO4)2(aq) has the highest osmotic pressure

(c) 0.125 M Na3PO4(aq) has the highest osmotic pressure

(d) 0.500 M C2H5OH (aq) has the highest osmotic pressure

(Kf = 1.86K kg mol-1) is (2011)

(a) - 2.3 x 10-2

(b) -5.7 x10-2