Solutions

CHEMISTRY CREST SOLUTIONS
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Perfect homogeneous mixture of two or more substances whose composition can be varied within
certain limits is called true solution.
A binary solution contains only two components called solute and solvent.
Solute:The component present in lesser proportions in a solution is called solute
Solvent : The component present in larger proportions in a solution is called solvent
Solute and solvent can be separated by simple physical methods like crystallization , adsorption and
distillation.
Classification of solutions :
1) Based on nature of solvent:
(a) If the solvent is H
2
O, it is called aqueous solution
(b) If the solvent is any organic solvent (Other than H
2
O i.e., C
6
H
6
, ether ,CCl
4
), it is called
non aqueous solution.
(c) If the solvent is alcohol, it is called alcoholic solution

2) Based on physical State of solvent:
(a) Gaseous solutions Solvent Gas Gas in gas : Air
Solute s/l/g Liq in gas: Water vapour
Solid in gas : Camphor in air

(b) Liquid Solutions Solvent Liq. Solid in liq : Sugar in H
2
O
Solute s/ l /g Liq. In liq : Alcohol in H
2
O
Gas in liq : Soda water (CO
2
in H
2
O)

(c) Solid solutions Solvent Solid Solid in solid : Alloys
Solute s/ l /g Liq. In solid : Amalgams
Gas in solid : Occlusion of H
2
on Pd



(3) Amount of Solute in definite amount of solvent:
Dilute solution: A solution having relatively less amount of solute dissolved in solvent is called
dilute solution
Concentrated solution: A solution having relatively more amount of solute dissolved in solvent is
called concentrated solution.

(4) Amount of solute present in solution:
Unsaturated: Solution containing less amount of solute dissolved in solvent than required for its
saturation at a given temperature.
Saturated : A solution having maximum amount of solute dissolved in solvent required for its
saturated at a given temperature.
If, in a saturated solution, some amount of solute is dissolved, then there exists dynamic equilibrium
between dissolved and undissolved solute particles.
Super saturated: A solution having more amount of solute dissolved in solvent than
required for its saturation at a given temperature.
Eg: Hypo and Alum form super saturated solutions
It is a meta stable solution.

METHODS OF EXPRESSING CONCENTRATION:

CONCENTRATION :
Amount of solute present in certain amount of solution is called Concentration.
Concentration can be expressed in different ways. Methods used to express concentration are as follows:
(1) Weight fraction (2) Weight percent (3) Volume fraction (4) Volume percent
(5) Solubility (6) Parts per million (ppm) (7) Molarity (8) Formality
(9) Normality (10) Molality (11) Mole fraction

1) WEIGHT FRACTION OF SOLUTE:
Amount of solute (in gram) present in 1 gm of solution is called weight fraction of solute.

weight of solute weight of solute
weight fraction of solute
weight of solution weight of solute+weight of solvent
= =

w
w W
=
+

2) WEIGHT PERCENT OF SOLUTE:
Amount of solute (in gram) present in 100 gm of solution is called weight percent of solute.

weight of solute
weight percent of solute 100
weight of solution
=
weight. fraction of solute 100 =
100
w
w W
=
+



3) VOLUME FRACTION OF SOLUTE:
Volume of solute (in ml) present in 1 ml of solution is called volume fraction of solute.
.

volumeof solute
volume percent of solute
volumeof solution
=

v
v V
=
+

4) VOLUME PERCENT OF SOLUTE:
Volume of solute (in ml) present in 100 ml of solution is called volume percent of solute .

volumeof solute
volume percent of solute 100
volumeof solution
=
= volumefraction of solute 100
100
v
v V
=
+

Weight fraction, weight percent, volume fraction and volume percent have no units since they are ratios.

Note:
x% solution (w/w) means x gram of solute is present in 100 gram of solution.
x% solution (w/v) means x gram of solute is present in 100 ml of solution.
x% solution (v/v) means x ml of solute is present in 100 ml of solution
x% solution (v/w) means x ml of solute is present in 100 gm of solution

5) SOLUBILITY:

The amount of solute (in gram) present in 100 gm of solvent is called solubility at a given temperature.
It is represented by s.

weight of solute
100
weight of solvent
s =

100
w
s
W
=
It has no units since it is a ratio.

Factors affecting solubility of :
(I) Solid in liquid
(II) Gas in liquid

(I) Solubility of solid in liquid :
It depends on the following
(a) Nature of solute
(b) Nature of solvent


These two factors can be explained by a saying, Like dissolves like
Polar solutes (ionic) dissolve in polar solvents ( )
2 3 2
H O, liq.NH , liq.H S.......

Non polar solutes (organic) dissolve in non polar solvents (ether, C
6
H
6
, CCl
4
)

Dissolution occurs only when

c)Temperature:
Acc to Le Chateliers Principle:
If the dissolution process is endothermic, solubility increases with increase in temperature
Eg: NaCl, NaNO , KCl, KNO
3 3

If the dissolution process is exothermic, solubility decreases with increase in temperature
Eg: ( )
4 2 3 2 3 2
3
Ce SO ,Li CO ,Na CO .H O
Solubility does not increase or decrease continuously with temperature.
Eg :
( )
4 3
NH NO formto form
Hydrate to another hydrate
2 2 2 2 2 2
CaCl .6H O CaCl .4H O CaCl .2H O
Hydrate to anhydrous
2 3 2 2 3
Na CO .10H O Na CO

Solubility curves :
When solubilities are plotted against temperature, the curves obtained are called solubility curves

d)Pressure:
Pressure does not have any significant effect on solubility of solid in liquid. It is because, solids and
liquids are highly incompressible

(II) Solubility of gas in liquid :
a)Nature of gas and the solvent :
Depends on chemical similarity between gas and solvent

b)Pressure:
Henry gave a quantitative relation between pressure and solubility of a gas in a liquid in the form of
Henrys law.
Henrys Law:
Acc to Henrys law, at a constant temperature, the solubility of a gas in a liquid is directly proportional
to the pressure of the gas which is in equilibrium with the liquid
s p or m p



Acc to Dalton,

When a mixture of gases are simultaneously in equilibrium with the liquid at a particulat temperature,
Solubility of a gas in liquid (s) partial pressure of gas
If mole fraction of a gas in the solution is taken as a measure of its solubility in the solution , then
mole fraction of gas in the solution is proportional to the partial pressure of the gas over the solution.

Henryslaw: (Modified)
p
A A

( p
A
= Partial Pressure of a gas in vapour state ,
A
=Mole fraction or Solubility of that gas in
solution)

H
p k
A A
.---- Henrys law
Where K
H
is Henrys law constant. Depends on nature of the gas, nature of the solvent and
temperature.
units = atm or bar or k bar
Greater the value of K
H
at a given pressure, lower is the solubility of the gas in the liquid.
K
H
values increase with increase in temperature indicating that the solubility of gases
decreases with increase of temperature.
If a graph is plotted between partial pressure of the gas and mole fraction of the gas in solution, then we
get a straight line passing through the origin

Applications of Henrys law :
Eg:
(1) Solubility of CO
2
in soda water and sot drinks is increased by sealing the bottle under high
pressure. When the bottle is opened to air, partial pressure of CO
2
above the solution decreases. Due to
this, solubility decreases and hence CO
2
bubbles out
(2) Scuba divers ( deep sea divers ) must cope up with high concentrations of dissolved gases
high pressure underwater. Increased pressure increases the solubility of atmospheric gases in
blood. When divers come up to surface, pressure gradually decreases. This releases dissolved
gases and leads to the formation of bubbles of nitrogen in the blood, which blocks capillaries and
creates a medical condition known as bends or Decompression sickness. To avoid this, scuba divers
use cylinders filled with 11.7% helium, 56.2% nitrogen and 32.1% oxygen
3)At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low
concentrations of oxygen in the blood and tissues of people living at high altitudes or climbers,
which causes climbers to become weak and unable to think clearly, leading to a condition known as
anoxia.



Limitations of Henrys law
a) P must be low and T must be high i.e., gas must be ideal gas
b) Gas must not undergo:
i) Association
ii) Dissociation
( ) ( )
( )
HCl aq HCl
g
HCl
aq
H Cl
aq
+
+
+

iii) Compound formation with solvent
Eg:
( )
NH H O NH OH
2 4 3 g
+
NH OH NH +OH
4 4
+

Effect of Temperature :
Solubility of gases in liquids generally decreases with rise in temperature as dissolution is exothermic.

6) CONCENTRATION IN PPM:

The mass of a component present in million parts (10
6
parts) by mass of solution is known as parts per
million.

6
Mass of that component
ppmof a component = 10
Mass of thesolution

7) MOLARITY:

No. of gram moles of solute present in 1 litre(dm
3
) of solution at a given temperature is called
Molarity.
It is denoted by M.

( )
( )
No.of grammoles of solute n
M=
Volumeof solution (in lit.) V

But,

weight
gram mole=
gram molecular weight

( )
weight of solute 1
M =
gram molecular weight of solute Volume of solution in lit.

(or)

( )
weight of solute 1000
M =
gram molecular weight of solute Volume of solution in ml

( ) Molaritygrammolecular weight of solutevolumeof solution in ml.
weight of solute=
1000



( )
no.of milli moles of solute
M =
Volume of solution in ml

From this, Molarity can also be defined as the no. of milli moles of solute present in 1 ml. of
solution at a given temperature

When strength of solution is given, molarity can be calculated using the formula

strength of solution in g/lit
M=
grammolecular weight of solute

Mass of solute in g
Strength of solution in g/lit =
volume of the solution in lit

When percentage strength of solution(w/v) is given, molarity can be calculated using the formula

%strength of solution (w/v) x 10
M=

When % strength of solution(w/w) and density (or) specific gravity of solution are given, molarity
can be calculated using the formula

( ) %strength of solution(w/w) density or specificgravity of solution 10
M=

When volume strength of H
2
O
2
is given, molarity can be calculated using the formula
Volume strength = M 11.2
Volume of oxygen liberated in ml at S.T.P by the decomposition of 1 ml of H
2
O
2
is called volume
strength of H
2
O
2

Units: Gram mole / litre

Molar or 1 M solution:
If 1 mole of solute is present in 1 litre of solution, it is called Molar or 1M solution.
Eg: If 98 grams of sulphuric acid is present in one litre of solution, it is called molar or 1M H
2
SO
4

solution.
Deci molar or 0.1M solution:
If 0.1 mole of solute is present 1 litre of solution, it is called Deci molar or 0.1M solution.
Semi molar or 0.5M Solution:
If 0.5 mole of solute is present 1 litre of solution, it is called Semi molar or 0.5M Solution
Centi molar or 0.01 M Solution:
If 0.01 mole of solute is present 1 litre of solution, it is called Centi molar or 0.01 M Solution

Effect of Temperature:
Molarity changes with temperature due to contraction or expansion of liquids.
When temperature is increased, volume of the solution increases. Hence molarity of the solution
decreases.



FORMALITY:
In case of ionic compounds, it is not proper to use the term molecular weight but it is proper to use the
term formula weight since they contain ions but not molecules.
Similarly, to express the concentration of ionic substances, the term formality is used instead of
molarity.
No. of gram formula weights of solute present in 1 litre of solution at a given temperature is called
Formality.
It is denoted by F.

( )
No.of gramformula weights of solute
F=
Volumeof solution(in lit.) V

( )
weight of solute 1
F =
gram formula weight of solute Volume of solution in lit.

(or)

( )
F =
gram formula weight of solute Volume of solution in ml

Formality also changes with temperature.

EQUIVALENT WEIGHTS :

a) Equivalent weights of Acids:

Equivalent weight of an acid is the ratio of molecular weight of acid to its basicity
Equivalent weight of acid =
molecular weight of acid
Basicity

(or)
Equivalent weight of an acid is defined as that weight of the acid in grams which releases one mole of
H
+
ions.

Basicity:
No. of replaceable hydrogen atoms present in a molecule of acid is called basicity.
Based on basicity, acids can be classified into different types.

Monobasic acids:
Acids whose basicity is one are called monobasic acids.

HCl: No. of replaceable hydrogen atoms is 1 basicity is 1.
Hence, Equivalent weight =
36.5
36.5
1
=
HPO
3
(Meta phosphoric acid) :
O
HO P O =

No. of replaceable hydrogen atoms 1 basicity is 1.
Hence equivalent weight =
80
80
1
=


H PO
3 2
( Hypo phosphorous acid) :-
O
HO P H
H

|

No. of replaceable hydrogen atoms 1 basicity is 1.
Hence equivalent weight =
66
66
1
=
Dibasic acids:
Acids whose basicity is 2 are called diabasic acids.
H
2
SO
4
(Sulphuric acid)
O
H O S O H
O

No. of replaceable hydrogen atoms 2.
Therefore basicity is 2. Hence equivalent weight =
98
49
2
=
H PO
3 3
(Phosphorous acid) :-
O
HO P OH
H

|

Therefore basicity is 2. Hence equivalent weight =
82
41
2
=
Tribasic acids:
Acids whose basicity is 3 are called tribasic acids.

4
H PO
3
( Phosphoric acid):-
O
HO P OH
|
OH

No. of replaceable hydrogen atoms 3

basicity -3. Equivalent weight =
98
32.6
3
=
Tetra basic acid:
Acids whose basicity is 4 are called tetra basic acids.
EDTA : Ethylene diamine tetra acetic acid
HO C H C
2

HO C H C
2

N H C CH N
2 2

CH C OH
2

CH C OH
2

O
O
O
O


292
73
4
=



H
4
P
2
O
7
(Pyrophosphoric acid) :

O O
HO P O P OH
| |
OH OH

No. of replaceable H atoms = 4
178
44.5
4
=

b) Equivalent weights of bases:
Equivalent weight of base is the ratio of molecular weight of base to its acidity.
Equivalent weight of base =
molecular weight of base
acidity

(or)
Equivalent weight of a base is defined as the weight of base in grams which accepts one mole of
H
+
ions.

Acidity:
No. of replaceable hydroxyl
( )
OH
groups present in a molecule of base is called acidity.

Based on acidity, bases can be classified into different types.

Mono acidic base:
Bases whose acidity is 1 are called mono acidic acids.
NaOH : No. of replaceable Hydroxyl groups 1.
acidity 1.
Equivalent weight of NaOH =
40
40
1
=

Di acidic base:
Bases whose acidity is 2 are called di acidic bases.
( ) Ca OH
2
: No. of replaceable OH
groups is 2.
acidity 2.
Equivalent weight of ( ) Ca OH
2
=
74
37
2
=

Tri acidic base:
Bases whose acidity is 3 are called tri acidic bases.
( )
3
Al OH No. of replaceable OH
groups is 3.
acidity is 3.
Equivalent weight of ( )
3
Al OH =
78
26
3
=



c) Equivalent weights of salts:
Equivalent weight of salt is the ratio of formula wt. of salt to total number of +ve or ve charges present
in it.
Equivalent weight of salt =
( )
Formula weight of salt
Total no.of +ve or -vecharges

(or)
Equivalent of weight of the salt is defined as weight of salt formed when one gram equivalent of acid
reacts with one gram equivalent of base.
a)
( )
1 , 1 NaCl Na Cl
+

Equivalent weight of NaCl =
58.5
58.5
1
=
b)
( )
2
2 3 3
2 , 1 Na CO Na CO
+

Equivalent weight of
2 3
106
53
2
Na CO = =

d) Equivalent weight of metals/non metals:
Equivalent weight of a metal or non metal is the ratio of atomic weight of metal/non metal to its valency.

Atomic weight
Equivalent weight of metal/non metal =
Valency

Equivalent weight of Na =
23
23
1
=
Equivalent weight of F =
19
19
1
=
Equivalent weight of O=
16
8
2
=

e) Equivalent weight of oxidant (or) oxidising agent:
Oxidant or oxidizing agent is the specie
that undergoes reduction or
oxidizes other species or
gains e or
shows decrease in oxidation state.
Equivalent weight of oxidant is the ratio of molecular weight of oxidant to the total no. of e gained or
decrease in oxidation state.
Equivalent weight of oxidant =
( )
Molecular weight of oxidant
Total no.of egained or decreasein oxidation number

Eg:
4
KMnO in acid medium.
( )
4 2 4 2 4 4 2
2KMnO +3H SO K SO +2MnSO +3H O+5 0
2 158 gram of
4
KMnO 5 16 gram of O.
? 8 gram of O.


4
2 158 8
KMnO 31.6
5 16

= =
(or)

4 4
KMnO MnSO
Mn : 7 2 + +
5 units decrease in oxidation state
Equivalent weight of KMnO
4
=
158
31.6
5
=
4
is strongly basic medium
( )
4 2 4 2
2KMnO +2KOH 2K MnO +H O+ 0
2 158 gram of
4
KMnO 16gramof O
? 8gramof O
4
158
KMnO 158
1
= = (or)

4 2 4
KMnO K MnO
Mn : +7 6 +
1 unit decrease in oxidation state
4
=
158
158
1
=
4
in neutral medium or weakly basic medium
( )
4 2 2
2KMnO +H O 2KOH+2MnO +3 0
2 158 gram of KMnO
4
3 16 gram of O
? 8 gram of O
Equivalent of weight of KMnO
4
=
8 2 158
52.6
3 16

=
(or)

4 2
KMnO MnO

+7 4 +
3 units decrease in oxidation state
4
158
KMnO 52.6
3
= =
2 2 7
K Cr O in acidic medium

( ) ( )
2 2 7 2 4 2 4 2
K Cr O K SO +Cr SO +4H O+3 0
294 gram of
2 2 7
K Cr O gives 316 gram of O
? 8 gram of O
Equivalent weight
2 2 7
294 8
K Cr O 49
3 16
= =

( )
2 2 7 4
3
K Cr O Cr SO

( ) ( ) 2 6 2 3 + +
6 units decrease in oxidation states
2 2 7
294
K Cr O 49
6
= =


f) Equivalent weight of reducing agent or reductant:
Reducing agent or reductant is a species
that undergoes oxidation or
reduces other species or
looses e or
shows increase in oxidation state.
Equivalent weight of reductant is the ratio of molecular weight of reductant to the total no. of e lost or
increase on oxidation state.
Equivalent weight reductant =
( )
Molecular weight of reductant
No.of lost or increasein oxidationstate e

Mohrs salt:

( )
4 4 4 2
2
FeSO . NH SO .6H O (

2+ 3+
Fe Fe
1 unit increase in oxidation state
Equivalent weight of Mohrs salt =
392
392
1
=
Oxalic acid:
( )
2 2 4 2
2 4 2
H C O 2H O
C O 2CO

( ) ( ) 2 3 2 4 + +
2 units increase in oxidation state
Equivalent weight of oxalic acid =
126
63
2
=

Sodium thio sulphate:
2 2 3 2 4 6
Na S O Na S O
( ) ( ) 2 2 2 2.5 + +
1 units increase in oxidation state
Equivalent weight of Sodium thiosulphate =
158
158
1
=

8) NORMALITY:

No. of gram equivalents of solute present in 1 litre of solution at a given temperature is called
Normality. It is represented by N.

( )
No.of gramequivalentsof solute
N=
volumeof solution inlit.

But,
No. of gram equivalents =
weight
gram equivalent weight



( )
weight of solute 1
N=
gramequivalent weight of solute volumeof solution inlit.

( )
N=
gramequivalent weight of solute volumeof solution inlit.

( ) Normalitygramequivalent weight of solutevolumeof solution in ml.
weight of solute=
1000

( )
No.of milli equivalents of solute
N=
volumeof solution in ml.

From this, Normality can also be defined as the no. of milli equivalent of solute present in 1 ml. of
solution at a given temperature.

When strength of solution is given, normality can be calculated using the formula

strength of solution in g/lit
N=
gramequivalent weight of solute

Mass of solute in g
Strength of solution in g/lit =
volume of the solution in lit

When % strength of solution(w/v) is given, normality can be calculated using the formula

weight %of solution ( / )10
N=
gramequivalent weight of solute
w v

When percentage strength of solution(w/w) and density or specific gravity of the solution are given,
normality can be calculated using the formula.

( ) %strength of solution(w/w)densityor specificgravity of solution10
N=
gramequivalent weightof solute

When volume strength of H
2
O
2
is given, normality can be calculated using the formula.
Volume strength = N 5.6
`
Units: Gram equivalent / litre.

Normal (or) 1 N solution:
If 1 gram equivalent of solute is present in 1 litre of solution, it is called Normal or 1N solution.
Deci normal (or) 0.1 N solution:
If 0.1 gram equivalents of solute is present in 1 litre of solution, it is called deci normal (or) 0.1N
solution.
Semi Normal (or) 0.5 N Solution:
If 0.5 gram equivalents of solute is present in 1 litre of solution, it is called semi normal (or) 0.5N
Solution
Centi normal (or) 0.01 N Solution:
If 0.01 gram equivalents of solute is present in 1 litre of solution, it is called Centi normal (or) 0.01 N
Solution


Effect of Temperature:
Normality changes with temperature due to contraction or expansion of liquids.
Normality decreases with increase in temperature because volume of the solution increases with increase
in temperature.

RELATION BETWEEN MOLARITY & NORMALITY:

Weight of solute 1000
Normality gram equivalent weight of solute volume of solution(in ml)

=
Molarity
grammolecular weight of solute volume of solution(in ml)

N grammolecular weight of solute
=
M gram equivalent weight of solute

N x gram equivalent weight of solute = M gram molecular weight of solute

For acids : Normality = Molarity basicity
For bases : Normality = Molarity acidity
For salts : Normality = Molarity total no. of +ve (or) ve charges
For oxidants or reductants : Normality = Molarity change in oxidation state.
In general,
Normality = Molarity x n factor

RELATIONS USED IN VOLUMETRIC ANALYSIS :

Dilution Law for Molar Solutions:
(i) This law is useful to calculate molarity of the resultant solution obtained on dilution of a standard
solution.
Solution whose concentration is exactly known is called standard solution
1 1 2 2
MV =M V
Where,

1
M = Molarity of solution before dilution,
1
V = Volume of solution before dilution

2
M = Molarity of solution after dilution,
2
V = Volume of solution after dilution

(ii) This law can also be used to calculate the volume of water to be added to get a solution of
required concentration from a solution of known Concentration (or) Standard Solution.

1 1 2 2
MV =M V

1 1
2
2
M V
V =
M

Volume of water to be added =
2 1
V V
(or) Simply,
Volume of water to be added ( )
1 2
2 1 1
2
M M
V V V
M
| |
=
|
\



Dilution law for normal solutions:

(i) This is useful to calculate normality of solution obtained on dilution of a standard solution.

1 1 2 2
N V = N V
Where N
1
and V
1
are the normality and volume of the solution before dilution.
N
2
and V
2
are the normality and volume of the solution after dilution.

(ii)This law can also be used to calculate the volume of water to be added to get a solution of
required concentration from standard solution.

1 1 2 2
N V = N V
Volume of water to be added = V
2
V
1

(or) Simply,
Volume of water to be added ( )
2 1
V -V =
1 2
1
2
N N
V
N
| |
|
\

Rule of Molarity:

1 1 2 2
1 2
M V M V
n n
=
Where, M
1
V
1
and n
1
are the molarity, volume and no. of moles of a reactant
M
2
, V
2
and n
2
are the molarity, volume and no. of moles of another reactant.

Rule of Normality:

1 1 2 2
N V = N V
Where N
1
and V
1
are the normality and volume of a reactant. N
1
and V
2
are normality and volume of
another reactant.

Note : Substances always react in 1 : 1 equivalents ratio. They may or may not react in 1 : 1 mole ratio

CALCULATION OF CONCENTRATION OF THE MIXTURES:

a) (i) When two acidic or basic solutions are mixed: (of the same solute), molarity of the
resultant solution can be calculated using the formula
1 1 2 2
1 2
M V +M V
M=
V +V

(or)

1 1 2 2 3 3
MV +M V =M V

(ii) When two acidic or basic solutions are mixed (same or different solutes), normality of the
resultant solution can be calculated using the formula.

1 1 2 2
1 2
N V +N V
N=
V +V

(or)

1 1 2 2 3 3
N V +N V = N V



b) When acidic and basic solutions are mixed:

Let N
a
be the normality of acid.V
b
be the volume of acid
N
b
be the normality of base,V
b
be the volume of base

Case 1: If
a a b b
N V = N V , Solution is neutral in nature.
Case 2: If
a a b b
N V N V > , Solution is acidic in nature.
Normality of the resultant solution can be calculated using the formula,

a a b b
a b
N V N V
N=
V +V

Case 3: If
b b a a
N V > N V , Solution is basic in nature.
Normality of the resultant solution can be calculated using the formula,

b b a a
a b
N V - N V
N=
V +V

c) If the weight of either acid or base is known, its equivalent weight or vice versa can be
calculated using the formula
( )
weight
= Normalityvolumeof solution in lit.
Equivalent weight

MOLALITY:

No. of gram moles of solute present in 1 kg of solvent is called Molality.
It is represented by m.

( )
No.of grammoles of solute
m=
weight of solvent in kg

But,
gram mole =
weight
grammolecular weight

( )
weight of solute 1
m
grammolecular weight of solute weight of solvent in kg
=

( )
m
grammolecular weight of solute weight of solvent ingram
=

( ) m grammolecular weight of solute weight of solvent ingram
weight of solute
1000

=

When solubility is given,

10
m
s
=



When weight percent of solution(w/w) is given,

( )
( )
weight percent of solution 1000
m
gram molecular weight of solute 100
x
x
=

Units : mole / Kg

Molal or 1m Solution:
If one mole of solute is present in 1 kg of solvent, it is called molal or 1 m solution.

Deci molal or 0.1m solution: If 0.1 mole of solute is present in 1 kg of solvent, it is called molal or
0.1m solution.

Effect of Temperature :
Molality is independent of temperature because it is expressed in terms of weights (as there is no volume
term in molality expression)

RELATION BETWEEN MOLARITY AND MOLALITY:

M=Molarity
Grammolecular weight of solute Volumeof solution(in ml)
=

m=Molality
Grammolecular weight of solute weight of solvent( in gm)
=

Molarity weight of solvent
Molality Volumeof solution
=
(or)

'
1000 M
m
1000 d MM
=

where M= Molecular weight of solute

MOLE FRACTION: ( )

Mole fraction of a particular component is the ratio of no. of moles of that component to the total no. of
moles of all the components present in the solution.
It is represented by

No.of moles of that component
Molefraction of a component
Total no.of moles of all thecomponents
=

A binary solution consists of only two components called solute and solvent.

No. of moles of solute =
weight of solute

w
n
m
=


No. of moles of solvent =
weight of solvent
grammolecular weight of solvent

W
N
M
=
Mole fraction of solute =
No.of moles of solute
No.of moles of solute +No.of moles of solvent

solute
n+N
n
=

/ w m
w W
m M
=
+

Mole fraction of sovent =
No.of moles of solvent
No.of moles of solute +No.of moles of solvent

solvent
n+N
N
=

/ W M
w W
m M
=
+

Sum of the mole fractions of all the components present in a solution is 1.
Mole percent = Mole fraction 100
Mole fraction is a ratio. So it has no units.
Mole fraction is independent of temperature because the quantities of solute and solvent
are expressed in terms of weight.

RELATION BETWEEN MOLE FRACTION AND MOLALITY:

Mole fraction of solute =
n
n N +
.(1)
Mole fraction of solvent =
N
n N +
..(2)

Dividing 1
st
equation by 2
nd
,

Mole fraction of solute
Mole fraction of solvent
n w M
N m W
= =

Where w = wt. of solute, m = Mol. Wt. of solute ,W = wt. of solvent, M = Mol. Of solvent

Multiplying by
1000
M
on both sides.



1000 1000 n w M
n M m W M
=

1000 n
N M
= Molality
(or)

Molefraction of solute 1000
Molality
Molefraction of solvent M''
= (M is Mol. wt of solvent)

(or)

molality
Molefraction of solute
1000
molality+
'' M
=
| |
|
\

(M is Mol. wt of solvent)

RELATION BETWEEN MOLARITY AND MOLE FRACTION

1000 d
A
A A A B
x x
M
M M

=
+

M be the molarity of a solution

A
and
b
are the molefractions of A and B
If M
A
and M
B
be the molar masses of A and B and d density of solution



Vapour Pressure :

Evaporation & Condensation :
The transformation of liquid into vapour is called vapourisation.

The number of molecules escaping from the liquid surface in unit time is known as rate of evaporation.
Rate of evaporation depends on,
(i) Nature of Liquid (ii) Surface Area
(iii) Temperature (iv) Flow of air over the surface

The transformation of vapour molecules with lower K.E back to liquid state is known as
Condensation.
The number of molecules of vapour condensing into liquid in unit time is known as rate of
condensation.
When a volatile liquid is taken in a closed vessel, after some time, the rate of evaporation becomes
equal to rate of condensation i. e., liquid-vapour equilibrium is attained. This equilibrium is dynamic in
nature
Vapour pressure:
Pressure exerted by molecules of vapour over the surface of liquid when both liquid and vapour are in
equilibrium with each other is called vapour pressure of liquid.
Vapour pressure is independent of surface area.
Factors affecting vapour pressure :
(a) Nature of liquid :

1
V.P volatility
Intermolecular attractions

(b) Temperature :
V.P varies exponentially with temperature
V. P increases with increase in temperature until T
c
of the liquid is reached
At a particular temperature, V.P. becomes equal to atm P. It is called Boiling point of the liquid

Boiling Point:
The temperature at which vapour pressure of a liquid becomes equal to Atmospheric pressure.
Volatile liquids have high Vapour Pressure and low Boiling Point.

1
V.P
B.P



B.P atmospheric or external pressure
(a) B.P of H
2
O at 760 mm of Hg = 100
0
C
(b) B.P of H
2
O at higher altitude < 100
0
C (as atmospheric pressure decreases)
(c) B.P of H
2
O in a pressure cooker >100
0
C (as pressure inside the cooker is more)

Clausius Clapeyron Equation:
Clausius and Clapeyron have theoretically derived a relationship between the vapour pressure and the
temperature of the liquid.
P =
/
.
V
H RT
e

(where, P = Vapour pressure, - constant,
V
H =Enthalpy of vapourisation , R Gas constant,
T = Temp.)
Taking log on both sides,
ln P = ln
V
H
RT

2.303 log P = 2.303 log
V
H
RT

1
log log .
2.303
V
H
P
R T

=

log p vs 1/T graph is a straight line with negative slope.

1
1
log log
2.303
V
H
P
RT

=

2
2
log log
2.303
V
H
P
RT

=

Therefore,

( )
2
1 1 2
1 1
log
2.303
V
H P
P R T T
| |
=
|
\



Raoults law:

I) For a solution containing a volatile liquid solvent and a non-volatile solid solute.
V.P of pure solvent =
0
P
V.P of solution = P
vapour pressure of the solution at a given temperature is less than the vapour pressure of the
pure solvent at a particulartemperature. P
0
> P
Reason : In a pure solvent, surface is occupied only by volatile solvent moplecules. But, in a solution,
the surface occupied by volatile solvent as well as non volatile solute molecules. Due to this,the number
of molecules of solvent present on surface are relatively less in solution than that of pure solvent as
some solvent molecules on the surface are replaced by solute molecules. As a result, rate of
evaporation decreses and V. P decreases
V. P
1
conc. of solute particles

B. P conc. of solute particles
P
0
P is lowering of vapour pressure and

0
0
P P
P
is relative lowering of vapour pressure

When a non-volatile solute is added, P
0
P increases

0
P P conc. of solute particles

0
P , P and P
0
P increase with increase in temperature

0
0
P P
P
is independent of temperature

Deriving Raoults law:

Acc to Raoults law, vapour pressure of a solution containing a non volatile solute is directly proportional
to the molefraction of solvent

A
P

.
A
P K =
For 1( 0
A B
= = . i.e., when there is no solute)
P = K
P = P
0

Then,
K = P
0

0
.
A
P P =



0
0
P
P
1 1
A
A
P
P
=
=

From this, Raoults law can be defined as

The relative lowering of vapour pressure of a dilute solution containing a non-volatile solute is equal to
mole fraction of solute

0
0
P
P
P n
n N
=
+

For a very dilute solution :

n N << .
Neglecting n in denominator,

0
0
P
P
P n
N
=
(Condensed or reduced or simplified form of Raoults law).
For a dilute or concentrated solution:

0
0
B
P P n
P n N
= =
+

0
0
1
P n N N
P P n n
+
= = +

0
0
0 0
0
1
P N
P P n
P P P N
P P n
=
+
=

0
P N
P P n
=

Multiplying by
''
1000
M
on the both sides.



II) For a solution continuing only two volatile liquids :

a) Liquid Phase:
Consider a binary solution of two volatile liquids 1 and 2.
When taken in a closed vessel, both the components would evaporate and an equilibrium would be
established between vapour phase and the liquid phase.
Acc to Raoults law, for a solution of volatile liquids, the partial vapour pressure of each component in
the solution is directly proportional to its mole fraction.

1 1
P

0
1 1 1
. P p =

2 2
P
0
2 2 2
. P p =
Acc . to Dalton, the total pressure over the solution will be the sum of the partial pressures of the
components of the solution
P
total
= P
1
+ P
2

( )
0 0
tot 1 1 2 1
P 1 P P = +
(or)

( )
0 0
tot 1 2 2 2
P 1 P P = +

Vapour Phase:
y
1
and y
2
are the mole fractions of the components 1 and 2 in vapour phase
According to Dalton,
P.P = MF P
total

P y P
total i i
=

P y P
1 1 total
P
1
y
1
P
total
=
=

0
P
2 2
y
2 0 0
P P
1 1 2 2

=
+



Condensation of vapours of solution:

'
x
1 1
'
x
2 2
y
y
=
=

''
x '
1 1
''
x '
2 2
y
y
=
=

When vapours of a solution containing liquids 1 and 2 is condensed, the composition of liquids 1
and 2 in the condensate I remains same .
When the vapours over condensate I can again recondense and the composition of 1 and 2 in
condensate II remains same as it was in vapour phase over condensate I
As the process goes on, vapour becomes richer and richer with more volatile component.

Colligative properties:

Properties that depend on the number of solute particles irrespective of their nature are called colligative
properties
Co means together, Ligare means to bind.
Colligative properties are
(a) Relative lowering of vapour pressure
(b) Depression in freezing point
( )
f
T
(c) Elevation in Boiling point ( )
b
T
(d) Osmotic pressure ( )
Magnitude of CP
1
Molar mass of solute particles

Magnitude of CP Concof soluteparticles
Elevation in B.P ( )
b
T :
When a non volatile solute is added to a volatile solvent, V.P. of solution decreases
( )
0
P P >
B.P of solution increases
( )
0
b b
T T >

Reason :

Since V.P. of solution is smaller than v.p. of pure solvent at any temp, to make it equal to P
ext
,we
temp. of solution has to be increases by greater amount in comparision to pure solvent.

This increase in the boiling point is known as elevation in boiling point.


Elevation in boiling point (T
b
) is directly proportional to the molality of the solution.
T m
b

T K m
b b
=
K
b
- Molal elevation constant or B.P elevation constant or Ebullioscopic constant.
K
b
is specific for a solvent.

( ) ( )
2 2
0
1000
1000
''
o
R T R T
b b
K
b
H L
V V
M
= =
| |
|
|
\

L
v
is latent heat of vapourisation per gm. of solvent H
V
is Enthalpy of vapourisation per mole of
solvent
If m = 1,
T K
b b
=

From this, Molal elevation constant can be defined as the elevation in boiling point produced when
molality of solution is unity
. T K m
b b
=
1000
'
w
T K x
b b
M W
=

. 1000
'
.
b
b
K w
M
T W
( If K
b
is given per 1000 gm. of solvent)
If K
b
is given per 100 gm. of solvent, then

. 100
'
K w
b
M
T W
b



Depression in F.P
( )
f
T :
Temprature at which vapour pressure of solid becomes equal to v.p of liquid is called freezing point of
liquid or melting point of solid.
At freezing pt or below it only solvent molecules will freeze but not solute molecules (solid will be of
pure solvent)
When a non volatile solute is added to a volatile solvent, V.P. of solution decreases
( )
0
P P >
F.P of solution decreases
( )
0
f f
T T <

This decrease in the freezing point is known as depression in freezing point.

o
f
T T T
f
=

Depression in freezing point (T
f
) is directly proportional to the molality of the solution.
T m
f

T K m
f f
=
K
f
- Molal depression constant or F.P depression constant or Cryoscopic constant.
K
f
is specific for a solvent

2 2
0
1000
1000
''
o
R T R T
f f
K
f
H L
f f
M
| | | |
| |
\ \
= =
| |
|
|
\

L
f
is latent heat of fusion per gm. of solvent, H
f
is Enthalpy of fusion per mole of solvent
If m = 1
T K
f f
=

From this, Molal depression constant can be defined as the depression in freezing point produced when
molality of solution is unity


. T K m
f f
=
1000
'
w
T K x
f f
M W
=

1
. 1000
.
f
f
K w
M
T W
( If K
f
is given per 1000 gm. of solvent)
If K
f
is given per 100 gm. of solvent, then

. 100
'
K w
f
M
T W
f

Osmotic pressure ( )
Osmosis :
The net spontaneous flow of solvent molecules from solvent to solution or from a less concentrated
solution to a more concentrated solution through a semi permeable membrane is called osmosis
A membrane which allows solvent molecules to pass through but not solute particles is called semi
permeable membrane
When membrane allows solvent molecules to come out through it , it is exosmosis
When membrane allows solvent molecules to enter inside , it is endosmosis.
Osmotic pressure :
Minimim pressure which must be applied on the solution to prevent flow of solvent into solution
through the semi permeable membrane is called osmotic pressure
Reverse Osmosis:
If a pressure higher than osmotic pressure is applied on the solution, the solvent flows from
solution into pure solvent. This process is called reverse osmosis.
Eg : Desalination of water
Vant Hoff equation ;

Vant Hoff Boyles law:
1
V
or C

(at conc. T)
Vant Hoff Charles law :

T (at conc. V)

T
V
V T

CT
V ST =

CST =

(S = 0.0828 lit atm/mole K, can be taken as almost equal to R = 0.0821 lit atm/mole K)

For n moles: V nRT =



n
RT
V
=

/ ' w M
RT
V
=
Or CRT =
Isotonic solutions (or) Iso osmotic solutions :
Solutions having same osmotic pressure or same vapour pressure are called Isotonic solutions (or)
Iso osmotic solutions

1 2
= (or)
1 2
C =C
Hypertonic solution :
A solution having higher osmotic pressure than the other is said to hypertonic solution
( )
1 2 1 2
or C >C >
Hypotonic solution :
A solution having lesser osmotic pressure than the other is said to hypotonic solution
( )
1 2 1 2
or C C < <
Advantages of :
(a) Usage of Molarity instead of molality.
(b) Calculation of P at room temperature.
(c) Large magnitude even with very dilute solution
Used for calculation of molar masses of protiens , polymers and macro molecules etc.

Abnormal Molar Masses:
Molar mass values higher or lower than expected are called abnormal molar masses.
In order to explain this, Vant Hoff proposed a factor called Vant Hoff factor( i)
Vant Hoff factor(i)
=
No.ofparticles after associ i ( )dissoci i n
No.of particles beforeassoci i ( )dissoci i n
at on or at o
at on or at o

=
observed magnitude of colligative property
Actual magnitude of colligative property

=
M
normal
M
observed

Cases:
If 1 i = , then there will be no association/dissociation
1 i > , then dissociation.
1 i <
,
then association



Modified forms of Colligative properties:
1)
0
0
RLVP
B
P P
i
P

=
2) Elevation in B.P.
b b
T i K m =
3) Depression in F.P
f f
T i K m =
4) Osmotic pressure iC.RT =

Abnormal molar masses are due to
1) Molecular Association
2) Molecular dissociation

Molecular Association:
Leads to decrease in no. of particles
Magnitude of colligative properties are decreased
Molar mass is increased
Magnitude of CP
1
Molar mass of solute particles

Eg:
( )
O
C H
6 6
2CH C OH CH COOH
3 3
2

No. of particles is halved (If association is 100%)
Magnitude of colligative properties are halved
Molar mass is doubled
M
Actual (or) Theoretical
- 60
M
Exptl (or) observed
- 120

Calculation of degree of Association:
Degree of association( ) : Fraction of the total substance which exists in the form of associated
molecules
Degree of association =
No.of moles associ d
Total no.of moles taken
ate

( ) nA A
n

Before 1 -

1 / n
After
1 + / n


i =
at on or at o
at on or at o

i =
1 / 1
1 1
1
n
n

+ | |
=
|
\

1 i
1
1
n

1
1
nor
obs
M n
M n
| |
=
|

\

1
obs nor
obs
M M n
M n
| |
=
|

\

Molecular dissociation:
Leads to increases in no. of particles
Magnitude of CP increases
Molar mass is decreased
Magnitude of CP
1
Molar mass of soluteparticles

Eg:
2
H O
NaCl Na Cl
+
+
No. of particles is doubled ( If 100% dissociation)
Mag. of C.P also doubled
Molar mass is halved

actual /Theoratical
M : 58.5

exptl /observed
M : 29.25

Calculation of degree of dissociation:
Degree of dissociation( ) : Fraction of the total substance that undergoes dissociation .

Degree of dissociation =
No.of moles dissoci d
Total no.of moles taken
ate

A nX
Before 1 -

-

1 n


After
1 n +

i =
at on or at o
at on or at o

( )
1
1 1
1
n
i n

+
= = +

1
1
i
n
| |
=
|
\

( )
.
1
1
nor obs
obs
M M
M n
| |
=
|
|
\

Ideal and Non-ideal solutions:

Ideal solutions Non-Ideal solutions
1) Obey Raoults law at Do not obey Raoults law
all concentrations
and temperatures
+ve deviation from -ve deviation from
Raoults law Raoults law

2) Molecular interaction
& A B A A B B = & A B A A B B < & A B A A B B >

3) Total vapour pressure
P P P
total A B
= + P P P
total A B
> + P P P
total A B
< +

4) Boiling point
- B.P will be less than B.P. will be greater than expected
expected

(Min boiling azeotrope) (Max boiling azeotrope)
B.P. of mix will be B.P. of mix will be more than either
Less than either A or B A or B

5) V V V
mix A B
= + ( )
mix mix A B
V ve V V V = + > + ( )
mix mix A B
V ve V V V = < +


6) 0 H
mix
= H ve
mix
=+ (Endothermic)
mix
H ve = (Exothermic)
7) S
mix
= + ve S
mix
= +ve S
mix
= +ve

8) G
mix
= ve
Gmix
= ve G
mix
= ve

Examples :

Benzene + Toulene Ethanol + CS
2
Phenol + Acetone
Chloroethane + Bromoethane Acetone + CS
2
HCl + H
2
O
Ethyl bromide + Ethyl chloride Acetone+Benzene HNO
3
+H
2
O
Chlorobenzene + Bromobenene Methylalcohol+H
2
O Acetone+Aniline
Ethyl alcohol+H
2
O CH
3
COOH+Pyridine
Chloroform + CCl
4
Benzene + CHCl
3

Benzene+ CCl
4
Chloroform + Ether
Toluene + CCl
4

Azeotropic mixture :
A liquid mixture , having a definite composition, boils like a pure liquid and distills over in the same
composition is called constant boiling mixture or azeotropic mixture or azeotrope
These are formed by non ideal solutions.

Solutions

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CHEMISTRY CREST SOLUTIONS

visit us at www.chemistrycrest.com Page 1

groups present in a molecule of base is called acidity.

Normality gram equivalent weight of solute volume of solution(in ml)

grammolecular weight of solute volume of solution(in ml)

is relative lowering of vapour pressure

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