CHAPTER

2 Solution

Vapour Pressure  F1  F2  F
Ideal solution :  ⇒ DHsolution = 0
Pressure exerted by vapours over the liquid surface at VT= V1 + V2
equilibrium. Non-Ideal Solutions
T↑ ⇒ V.P.↑ (1) Solution showing +ve deviation :
Attractive Forces↑ ⇒ V.P. ↓ F < F1 or F2
Raoult’s Law VT > V1 + V2

(1) Volatile binary liquid mix: Q DHsolution > 0

Volatile liq. A B
Mole fraction XA / YA XB / YB ⇒ liq/vapour

V.P. of pure liq. PAº PBº

Binary liquid solution:
PAº
PBº

O XA 1
Fig.: A solution that shows +ve deviation from Raoult’s law
By Raoult’s law ⇒ PT = PAº XA + PBº XB = PA + PB ...(i)
(2) Solution showing -ve deviation:
By Dalton’s law ⇒ PA = YA PT...(ii)
⇒ F > F1 and F2
PB = YB PT ...(iii)
⇒ VT < (V1 + V2)
Ideal and Non-Ideal Solutions
⇒ DHsolution < 0
Ideal Solutions
Solution-A Solution-B
A.......A B.......B
F1 F2
V1 V2

A.......B
F
VT Fig.: A solution that shows -ve deviation from Raoult’s law
 Table: Deviation from Raoult’s Law where nB = mole of Non-volatile solute.

Negative i = Van’t Hoff’s factor.

Positive deviation Zero deviation
deviation
(DH = +ve) (DH = 0)
(DH = – ve) (2) Elevation in B.P. :

acetone + DTb = (Tb′ – Tb) = i. Kb × m.

(i) ethanol + cyclohexane benzene + toluene
chloroform
RTb2
where Kb =
acetone + carbon benzene + n-hexane + 1000 × lv
(ii)
disulphide chlorform n-heptane
where Tb = B.P. of pure solvent.
nitric acid + ehyl bromide +
(iii) acetone + benzene l = Latent heat of vapourization (per gm)
chloroform ethyl iodide

acetone + chlorobenzene + Kb = molal elevation constant

(iv) ethanol + acetone
aniline bromo benzene
M = Molar mass
water + nitric
(v) ethanol + water
acid  ∆H vap 
where lv =  
carbon tetrachloride + diethyl ether
 M 
(vi)
chloroform + chloroform

Azeotropic mixtures: Some liquids on mixing in a particular

composition form azeotropes which are binary mixture having
same composition in liquid and vapour phase and boil at a
constant temperature. Azeotropic mixture cannot be separated
by fracional distillation.
Types of Azeotropic Mixtures
(3) Depression in FP:
(i) Minimum boiling Azeotropic mixtures: The mixture
of two liquids whose boiling point is less than either DTf = Tf – Tf′ = i Kf × m
of the two pure components. They are formed by RTf2
where Kf =
non-ideal soluton showing positive deviation. For 1000´ f
example ethanol (95.5%) + water (4.5%) water boils at
Tf = f.p. of pure solvent
351.15 K.
Kf = molal depression constant
(ii) Maximum boiling Azeotropic mixtures: The mixture
of two liquids whose boiling point are more than lf = latent heat of fusion per gm.
either of the two pure components. They are formed
(4) Osmotic pressure:
Pext = Posmotic = 
by non-ideal solutions showing negative deviation. For
example HNO3 (68%) + water (32%) mixture boils at p ∝ (PAº – PA)
393.5 K. p = iC. R.T. Solution Solvent

Colligative Properties where p = osmotic pressure

Properties depends on relative no. of particles of non volatile
C = molarity (mole/lit)
solute in solution.
No. of particle of Colligative Sol. (1) Sol (2)
⇒
Non volatile solute Properties
If p1 = p2 Isotonic
(1) Relative lowering of V.P. :
PAº - PA nB n soln (1) hypertonic
=i  i B [For dilute solution] If pl > p2  n
PAº nA + nB nA sol (2) hypotonic

P9 Solutions 5
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 Table: Van’t Hoff factor for different Cases of solutes undergoing Ionisation and Association

Abnormal mol. wt.

Solute Example Ionisation/association (x degree) y* Van’t Hoff factor
(m1′)

Non-
urea, glucose, sucrose etc. none 1 1 normal mol.wt.
electrolyte

Ternary  2A+ + B2- m1

K2SO4, BaCl2 A 2 B  3 (1 + 2x)
electrolyte 1-x 2x x (1 + 2x )

 A3+ + 3B- m1

Electrolyte K3[Fe(CN)6], A3 B  4 (1 + 3x)
1-x x 3x (1 + 3x )

Associated 1  x 2− x 2m1

benzoic acid in benzene  A 2
2A  1 −  =  
Solute 1-x x /2 2  2  2  (2 - x )

1 1 2m1
forming dimer  A 2
A   x 2− x
(1-x ) 2 x /2 2 1 −  =  (2 - x )
 2  2 

é m1 ù
1 é æ1 ö ù ê ú
any solute  A n
nA  ê1 + çç -1÷÷ x ú ê æ 1 ö÷ ú
1-x x /n n êë çè n ÷ø úû ê 1 + ççç -1÷÷ x ú
êë è n ø úû

ml
1
 A n 1 x
forming polymer An A  1− x + x
(1-x) n x /n n n 1− x +
n

one mole of solute giving y  yB

A  m1
General y [1 + (y –1)x]
mol of products 1-x xy [1 + (y -1)x]

* number of products from one mole of solute

6 NEET-XII P10
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