Solution - I

Session objectives
 Introduction
 Solubility
 Henry’s law
 Different concentration terms
 Vapour pressure
 Raoult’s law and its modification
 Relative lowering of vapour pressure
 Ideal solutions and non-ideal solutions
 Maximum and minimum boiling solutions
Introduction
Solute: Component of solution present in smaller amount.
Solvent: Component of solution present in the larger amount.

Solution: a homogenous mixture of two or more substances.

Solubility
Maximum amount of solute in grams which can be dissolved in a given amount
of solvent (generally 100 g) to form a saturated solution at that particular
temperature is known as its solubility

For solids
 Solubility of ionic compounds in water
generally increases with increase in
temperature.

For gases
 The solubility of gases in water decreases
with increase in temperature.
 Solubility tends to zero at the boiling
point of water.
Effect of pressure on solubility of gases

 Increase in pressure of the gas above the solution

increases the solubility of the gas in the solution.

More dilute solution More concentrated solution

Henry’s law
Solubility of a gas in a liquid is proportional to the pressure of the
gas over the solution.

C = kP C: molar concentration, P: pressure,

k: temperature-dependent constant

Carbonated cold drink is an

application of Henry’s law.
Different concentration terms
moles of solute (mol)
Molarity (M) 
volume of solution (L)

moles of solute
Molality (m) 
Weight of solvent (inkg)

Molarity of a solution changes with temperature due

to accompanied change in volume of the solution.

ni x1=mole fraction of solvent

Mole fraction(x) 
 ni x2=mole fraction of solute
Illustrative Example
Determine the molality of a solution prepared
by dissolving 75 g of Ba(NO3)2(s) in 374 g of water at 25oC.

Solution:

Molar mass of Ba(NO3)2 = 261

75 g
Number of moles of Ba(NO3 )2 
261 g mol-1
 0.287 mole
0.287 mole
Molality =  0.767 m
0.374 kg
Illustrative Example
Calculate the molality of 1 molar solution of NaOH given density of
solution is 1.04 gram/ml.

Solution:
1 molar solution means 1 mole of solute present per
litre of solution.

Therefore, mass of 1 litre solution = 1000 x 1.04

= 1040 gram

Mass of solute = 1 x 40 = 40g

Therefore, mass of solvent 1040 – 40 = 1000g

1
m= ×1000 = 1 molal solution.
1000
Different concentration terms

Mass of solute w
% by mass = ×100 = %
Mass of solution W

Volume of solute v
% by volume 
Volume of solution
 100  %
V

mass of solute
Parts per million (ppm) = ×106
mass of solution
Illustrative Example
Calculate the concentration of 1 molal solution of NaOH in terms
of percentage by mass.

Solution:

1 molal solution means 1 mole (or 40g) NaOH present in 1000g

of solvent.

Total mass of solution = 1000 + 40 = 1040g

Therefore, 1040g solution contains 40g NaOH

40
Therefore, 100g solution contains   100
1040

= 3.84% by mass.
Different Concentration terms
Relation between Molarity (M) and molality (m)

md
M M2  Molar mass of solute
MM2
1 d  density of solution
103
Relation between molality(m) and mol-fraction (x2) of solute

m
x2 =
103
m+
M1
Where M1 = Molar mass of the solvent

mM1
x2 
mM1  103
Illustrative Example
Calculate the molality and mole fraction of the solute in aqueous solution
containing 3.0 g of urea
(molecular mass = 60) in 250 g of water.

Solution:

Mass of solute 1000

Molality  
Molecular mass of solute mass of solvent in gram

3
  1000  0.2
60  250
Moles of urea 3 / 60
Mole fraction of urea =   0.00359
Total moles 3 250

60 18

Mole fraction of water = 1 – 0.00359 = 0.996

Illustrative Example
Calculate the mol fraction of ethanol and water in a sample of
rectified spirit which contains 95% of ethanol by mass.

Solution:
95% of ethanol by mass means 95 g ethanol present in 100 g of
solution.
Hence, mass of water = 100 – 95 = 5 g

95
Moles of C2H5OH = = 2.07 moles
46
5
Moles of water(H2O)= = 0.28mol
18
0.28
Mole fraction of C2H5OH = = 0.88
0.28 + 2.07

Mole fraction of water = 1 – 0.88 = 0.12

Vapour pressure of solution

Liquid molecules evaporate

from the surface

Vapourised molecules condensed

vapour pressure of pure to liquid
liquid

Both processes reach equilibrium

Po=Pressure exerted by the vapour
above the liquid surface at eqm.
Factors affecting Vapour Pressure
Nature of liquid:
More volatile liquids exert more
pressure on the liquid surface.

Temperature:
Increase in temperature
increases vapour pressure.

Vapour pressure  Temperature

Presence of a solute
Due to presence of volatile and non-volatile solute,
vapour pressure of solution decreases.
Vapor Pressure of Solution

Some of the solute particles

will be near the surface.

Block solvent molecules

from entering the gas phase.

Less no. of molecules per

unit surface area are
involved in equilibrium.
Raoult’s law for non-volatile solute

For highly dilute solutions

ps=x1po
po=vapour pressure of pure
liquid
x1=mol. fraction of solvent
ps=vapour pressure of
solution
Raoult’s law for non-volatile solute

Applicable for ideal solution

Hmix  0 Vmix  0

Here, solute-solute and solvent-solvent interaction exactly

equal in magnitude with solute-solvent interaction.
Relative lowering of vapour pressure
From Raoult’s law,

ps
ps  xsolvent po , o
 1  xsolute
p

ps
xsolute  1   Relative lowering of v.p,
po
o
p  ps po  ps
 o
 xsolute
po p

po  ps n n moles of solute
 N moles of solvent
po nN

po  ps n
 when n  10%
po N
Modification (two volatile liquids)
According to Raoult’s law,for two
volatile miscible liquids

ps  pA o x A  pBo xB
 pA  pB    (1)

xA  xB  1

pA Partial vapour pressure of A.

xA Mol fraction of A in liquid phase.

Modification (two volatile liquids)
According to Raoult’s law,for two
volatile miscible liquids

ps  pA o x A  pBo xB
 pA  pB    (1)

xA  xB  1

pA Partial vapour pressure of A.

xA Mol fraction of A in liquid phase.

Modification (two volatile liquids)
Illustrative Example
Vapour pressure of liquids A and B at a particular temperature are 120 mm and
180 mm of Hg. If 2 moles of A and 3 moles of B are mixed to form an ideal
solution, what would be the vapour pressure of the solution?

Solution :

pAo  120 mmHg pBo  180 mmHg

nA  2 mol nB  3mol.

2 3
xA  xB 
5 5

pS  pA o x A  pBo xB

2 3
 120   180 
5 5
 48  108  156
Illustrative Problem
At 40oC, the vapour pressure in torr of methyl
alcohol-ethyl alcohol solution is represented by
P = 119Xm + 135 where Xm is the mole fraction
of methyl alcohol. What are the vapour pressures
of pure methyl alcohol & ethyl alcohol ?
Solution
o
P = pm xm + pEoxE
o
= pm xm + pEo 1 - xm 


o
= pm 
- pEo xm + poE

Comparing it with
p  119xm  135
pEo  135
o
pm  pEo  119
pom  119  135  245 torr
Illustrative Problem
6g of urea is disolved in 90g water at 25oC ? What is vapour
pressure of sol. If vapour pressure of water is 40mmHg.
Solution
ps = po x solvent

nsolvent
Xsolvent =
ntotal

90/18
=
90/18 + 6/60

5
  0.980
5  .1
ps = 0.980 x 40 = 39.2 mm Hg
Modification (two volatile liquids)
From Dalton’s law of partial pressure

pA = y Aps - - - (2)

yA=mol. fraction of A in vapour phase

ps=vapour pressure of solution.

From (2)

pA
yA 
pS
pA o x A

pA o x A  pBo xB
Modification (two volatile liquids)

1 pA o x A  pBo xB

yA pA o x A
pBo (1  x A )
1 o
x A  xB  1
pA x A

pBo pBo
1 o

pA x A pA o

1 pBo pBo
 1 o  o
yA pA x A pA
Illustrative Problem
An unknown compound is immiscible
with water. It is steam distilled at 98.0oC
and P = 737 Torr.poH20 = 707 torr at
98.0oC. This distillate was 75% by weight of water.
Calculate the molecular weight of the unknown
 Solution
Using Dalton’s law of partial pressure
Ptotal = 737 torr PoH2O = 707 torr

Pounknown = 737 – 707 = 30 torr.

If water = 100 g the unknown = 75.0 g

Pounknown nunknown 75
o
   18
P H2O nH2O M  100
30 75  18

707 m  100
m  318.15 gmol
Non-ideal solution
Solute-solvent interaction are different than solute-solute and solvent solvent in non ideal
solutions.

These do not obey Raoult’s Law.

For non ideal solutions H  0 and V  0
Non ideal solution
 For solution showing positive
deviation from Raoult's law.
H  0 and V  0
Ps >Pideal
 For solution showing negative deviation
from Raoult's law.
H  0 and V  0
Ps  Pideal
Azeotropic mixtures

Liquid mixtures which distil without any change in

composition are called Azeotropes or Azeotropic mixtures.

Solution showing positive deviation from Raoult’s form

minimum boiling azeotrope

Interaction between A–B < interaction between A–A or

B–B
Azeotropic mixtures

Liquid mixtures which distil without any change in

composition are called Azeotropes or Azeotropic mixtures.

Solution showing positive deviation from Raoult’s form

minimum boiling azeotrope

Interaction between A–B < interaction between A–A or

B–B
Azeotropic mixtures
Solution showing negative deviation from Raoult’s law form
maximum boiling azeotropes
Interaction between A – B > interaction between A – A or B – B