Brilliant STUDY CENTRE LONG TERM -2022 (ONLINE CLASS NOTESD)

CHAPTER - 00
SOLUTIONS

Introduction
 Solutions are homogenous mixtures of two or more than two components.
 The component present usually in largest quantity and does not undergo a phase change is called
solute, which is denoted as 1, while the component present in small amount and undergo a phase
change is called solute, which is denoted as 2.
 Binary solution - solutions consists of two components only ie., one solute and one solvent.
 Physical state of solution = Physical state of solvent.
Types of Solutions
Depending upon the physical state of solvent taken, solutions are classified into 3 major types
1) Solid solutions
2) Liquid solutions
3) Gaseous solutions
Depending upon the physical state of solute added to a particular solvent, these three major types are
further classified into 3 types each so that there are 9 types of solutions.

Solution Solute Solvent Example

Solid Alloys
Solid solutions Liquid Solid Amalgam (compounds of Hg)
Gas Occluded H2 in Pd
Solid Glucose dissolved in water
Liquid solution Liquid Liquid Ethanol dissolved in water
Gas Oxygen dissolved in water

Solid Camphor in Nitrogen gas

Gaseous solutions Liquid Gas Chloroform mixed with N2 gas
Gas Mixture of O2 and N2

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Expressing Concentration of Solution (Concentration Techniques)

Concentration of a solution means the amount of solute in solution. The major concentration techniques
are
1. Mass Percentage (w/w)

Mass of one component

(w / w)   100
Totalmass of solution

10% (w/w) aqueous solution of glucose means 10 g glucose dissolved in 90 g water results in 100 g
of glucose solution.
This unit is commonly used in industrial chemical application.
eg : Commercial bleaching solution contains 3.62% (w/w) aqueous solution of sodium hypochlorite.
2. Volume Percentage (v/v)

Volume of one component

v / v × 100
Total volume of solution

10% (v/v) aqueous solution of ethanol means 10 ml of ethanol dissolved in water such that the total
volume of the solution is 100 ml.
This unit is also used in chemical industries
eg : A 35% (v/v) solution of ethylene glycol (anti-freeze) is used in cars for cooling the engine which
lowers the freezing point of water to 255.4 K (–17.60C)
3. Mass by Volume Percentage (w/v)

Mass of solute
w / v 100
Volume of solutionin mL

5% (w/v) aqueous solution of NaCl means 5g NaCl dissolved in enough water so that the final volume
of the solution is 100 ml.
This unit is used in medicine and pharmacy
4. Parts per million (ppm)
This unit is commonly used when the solute is present in trace quantities

Number of parts of the component

ppm  106
Totalnumber of parts of allcomponents of solution

The term ‘part’ may be mass or volume or both.

In terms of mass,

Mass of one component

ppm  102 10 4  mass% 104
Totalmassof solution

ie ppm = mass % × 104

1ppm  1mgL1  1gmL1

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eg : 1) The level of CO2 in atmosphere is 0.03% by mass ie., 300 ppm
2) A litre of sea water weighs 1030 g contains 6 × 10–3 g dissolved oxygen. Its concentration is
ppm is :

6 10 3
 106  5.8 ppm
1030
5. Strength(S)

Mass of solute(g)
S gL1
Volume of solution(L)

5gL–1 aqueous solution of NaCl means 5g NaCl is present in 1 L solution.

6. Mole Fraction (  )

Number of moles of the component


Totalnumber of moles of all the components

For a binary solution

n1 n2
1  and 1 
n1  n2 n1  n2

w1 / M1 w 2 / M2
OR 1  and 2 
w1 / M1  w 2 / M2 w1 / M1  w 2 / M2

Also 1   2  1
Generally, in a given solution sum of all the mole fraction is unity ie.,
1   2  ......  i  1
7. Molality (m)

Number of moles of solute n2 w2

m  
Mass of solvent inkg w1 M2 .w1

w 2 .1000
If w1 is in g, m  molkg1(m)
M2 . w1

x molal (x m) aqueous solution of NaOH means x mol NaOH dissolved in 1 kg water

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8. Molality (M)

Number of molesof solute n2 w

M   2
Volume of solutioninL V M2 .V

x Molar (x M) aqueous solution of NaOH means x mol NaOH present in 1 L solution

9. Normality (N)

Number of gram equivalents of solute ng  eq w

N   2
Volume of solutioninL V E2 . V

E2 = Equivalent mass of solute

w 2 .1000
If V is in mL, N  eqL1 (N)
E2 .V

x normal (x N) aqueous solution of H2SO4 means x g-equivalents of H2SO4 present in it solution.

NOTE :

N N
Seminormal= ; Decinormal= etc
2 10

10. Formality (F)

Number of formulaunits of solute

F
Volume of solutioninL

This unit is used when the solute is an ionic compound but the magnitude of molecular mass and
formula mass of ionic compound is same.

 F M

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Some Important Points & Shortcuts

1. dH2O  1gmL1

 1 g = 1 mL
1000 g = 1000 mL

 1kgH2 O  1L H2O

1000
 Number of moles of H2Oin1L OR 1kg   55.5moles
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2. Among the concentration technique ; v/v, w/v, ppm (in terms of volume), S, M, N & F are temperature
dependent because volume is included which changes with temperature.
3. 1 molar aqueous solution is more concentrated than 1 molal aqueous solution because less amount
of water is present in 1 molar solution.
But for solvents other than water, m and m are same or different depends upon the density of solvent
taken.
4. If mass % and density of solution (g mL–1) are given,

10  d  mass%
M
M2

5. Relation between m and 

1000 2
m
1M1

6. Relation between M and 

1000 d 2
M
1M1  2M2

7. Relation between m and M

1000M
M
1000 d  MM2

8. Relation between N and M

N = (n-factor) M
OR

neq  (n  factor)nmoles

Acidity of base
Basicity of acid
Number of electrons transferred per mole of oxidi sin gagent or reducing agent etc.
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9. Molarity Equation
a) Dilution Formula
M1V1 = M2V2
b) Reaction Formula

M1V1 M2 V2

n1 n2

Here n1 and n2 are the stoichiometric coefficients of reactants or products.

10. Normality Equation
For both dilution and reaction, normality equation is :
N1V1 = N2V2
ie., 1 equivalent of reactant A requires 1 equivalent of reactant B
1 equivalent of reactant A products 1 equivalent of product B
11. Molarity of a Mixture (Mmini)
a) Acid + Acid OR Base + Base OR Neutral +Neutral

M1V1  M2 V2
Mmix 
V1  V2

M1  M2
if V1 = V2 ; Mmini 
2
b) Acid + Base

M1V1  M2 V2
Mmix 
V1  V2

if V1 = V2,

M1  M2
Mmix 
2
12. Normality of a mixture (Nmini)
a) Acid + Acid OR Base + Base OR Neutral + Neutral

N1V1  N2 V2
Nmix 
V1  V2

If V1 = V2

N1  N2
Nmix 
2

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b) Acid + Base

N1V1  N2 V2
Nmix 
V1  V2

If V1 = V2

N1  N2
Nmix 
2
13. Relation connecting n-factor, M & N
n1M1V1 = n2M2V2 ...(1)
Since n represents n-factor
nM = N

 (1) becomes

N1V1 = N2V2
14. Primary Standards
The solutes can be directly converted into a standard solution, whose concentration is known as
called 10 standards.
eg : NaCl, Na2CO3, H2C2O4. 2H2O (oxalic acid) etc.
15. Secondary Standards
The solutes cannot converted into a standard solution directly are called 2o standards because of their
deliquescent and hydroscopic nature.
eg : NaOH, H2SO4, KMnO4 etc.
To determine the concentration of unknown solution, a method known as titration is applied.
LIQUID SOLUTIONS
Solubility
Solubility of a substance is its maximum amount that can be dissolved in a specified amount of
solvent at a specified temperature.
Solubility depends upon

1)
2)
Nature of solute
Nature of solvent  "Like dissolvesLike "
ie polar solutes dissolved
3) Temperature in polar solvents &
4) Pr essure non  polar solutes dissolved
innonpolar solvents

a) Solubility of a solid in a liquid

When a solid solute is added to the solvent, some solute dissolves and its concentration increases in
solution. This process is known as dissolution.

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Some solute particles in solution collide with solid solute particles and get separated out of solution.
This process is known as crystallisation.
An equilibrium is reached when the two processes occurs at the same rate.

 Solution
Solute + Solvent 
At this stage, the concentration of solute is solution will remain constant under the given conditions.
Such a solution in which no more solute can be dissolved at the same temperature and pressure (for
gases as solutes) is called a saturated solution.
An unsaturated solution is the one in which more solute can be dissolved at the same temperature.
Concentration of solute in saturated solution in its solubility.
Effect of Temperature
Consider the equilibrium

 Solution
Solute + Solvent 
This being a dynamic equilibrium, must follow Le Chattler’s principle.
Effect of temperature on the solubility of a solid in a liquid can be explained by the equation.

K2 H  T2  T1 
log     Van’t Hoff’s Equation
K1 2.303R  T 1T2 

K = Equilibrium constant
H  Enthalpy change

a) If in a nearly saturated solution, the dissolution process is endothermic ie., H  0

K2
log 0 Since T2 > T1
K1

K2
ie 1
K1

or K2 > K1

 As T  equilibrium constant K  ie., dissolution also increases.

b) If the dissolution process is exothermic ie., H  0

K2
log  0 since T > T & H   ve
K1 2 1

K2
log 1
K1

or K2 < K1

 As T  equilibrium constant K  ie., dissolution decreases.

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ii) Effect of Pressure
Pressure does not have any significant effect on the solubility of solids in liquids. It is so because
solids and liquids are highly incompressible.
b) Solubility of a gas in a liquid
i) Effect of pressure - Henry’s Law
“The partial pressure of the gas in vapour phase (P) is proportional to the mole fraction of the
gas (  ) in the solution”.

Pgas   gas
or
Pgas  K H gas . gas

KH is known as Henry’s law constant which is a function of the nature of gas and temperature.
1) At same temperature, different gases show different KH values
eg : KH (N2) = 76.48 kbar and KH(O2) = 34.86 kbar at the same temperature of 298 K
2) At different temperatures, same gas exhibit different KH values.
eg : KH(N2) = 76.48 kbar @ 293 K but 88.48 kbar @ 303 K.
Plot of P Vs 

P
Since K H  , as   K H  ie., a gas with low KH has more solubility at the given conditions.

eg : HCHO (KH at 298 K = 1.83 × 10–5) has more solubility in water than He (KH at 293 K = 144.97) in
water.
ii) Effect of Temperature
Since the dissolution of a gas in a liquid is same as that of condensation process (exo), as temperature
increases dissolution (  ) decreases always.
 The solubility of a gas increases with decrease of temperature. This is whey aquatic species are
more comfortable in cold water rather than warm waters.
NOTE
Henry’s law also takes the form

gas  K H gas . Pgas

1
unit of K H  unit of (pressure)

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Application of Henry’s Law

1) In soft drink and soda water industry - to increase the solubility of CO2 in soft drinks and soda water,
the bottle is seated under high pressure.
2) SCUBA (Self Contained Underwater Breathing Apparatus) divers experience high concentration of
dissolved gases while breathing air at high pressure under water. When the divers came towards the
surface, the pressure gradually decreases. This releases dissolved gases and lead to the formation
of bubbles of N2 in the blood. This blocks capillaries and creates a medical condition known as bends,
which are painful and dangerous to life.
To avoid bends, the toxic effect of high concentration of N2 in the blood the tanks used by scuba divers
are filled with air diluted with He.
In the cylinder ;
N2 > O2 > He
56.2% 32.1% 11.7%
3) At high altitude, the partial pressure of O2 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 altitude or climbers. Low
blood oxygen causes anoxia.
Limitations of Henry’s Law
Henry’s law is not valid if
1) the temperature is too low
2) the pressure is very high
3) gases reacts with solvent
4) gases undergo dissolution or association in solvent

eg : NH3  H2O   NH4  OH

 NH4OH 

 H3 O  Cl
HCl  H2O 

Liquid - Liquid Solutions

Vapour Pressure (VP)
VP of a liquid or a solution is the equilibrium pressure exerted by the vapours of a liquid or a solution at
a particular temperature.

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At equilibrium



H2 O(  ) 
 H2O( g) ; K p  PH2Og  VP

Since VP is the equilibrium constant in terms of pressure, VP changes with temperature only. Therefore
while reporting VP of a liquid or a solution we should report the temperature always.
Effect of Temperature on Vapour Pressure

P  H  T2  T1 
log  2      Clausius  Clapeyron Equation
 P1  2.303R  T1T2 

Since evaporation is endothermic, H  0(  ve) . As temperature increases from T1 to T2 (T2 > T1).

P 
log  2   0
 P1 

P2
1
P1

P2 > P1

ie., VP  with  in T

VP Vs T graph

More volatile liquid A has low B.P & vice versa.

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Vapour Pressure of Liquid - Liquid Solutions

Raoult’s Law (Francois Marte Raoult)
“For a solution of volatile liquids, the partial vapour pressure of each component of the solution is
directly proportional to its mole fraction present in solution”.
For component 1

P1  1 and

For component 2

P2  2

or P1  P10 1 and P2  P20 2

Here P10 and P20 are the respective V.P of pure components 1 and 2.

P1 and P2 are the respective V.P of components 1 and 2 in solution.

According to Dalton’s Law of Partial Pressures,

Total [Link],
PT = P1 + P2

ie., PT  P10 1  P20 2

= P10 (1  2 )  P20 2  P10  (P20  P10 )  2

ie.,
a) Total vapour pressure over the solution can be related to the mole fraction of any one component.
b) Total vapour pressure over the solution varies linearly with the mole fraction of component 2.
c) Depending on the vapour pressures of the pure components 1 and 2, total V.P over the solution
decreases or increases with the increase of the mole fraction of component 1.

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Plot of VP Vs 

P1  P10 1 & P2  P20  2

y  mx y  mx

Here component 1 is less volatile than the component 2. ie., P10  P20 .

Composition of a Solution
A) In solution phase ;

Composition = 1 &  2

B) In vapour phase
Composition = Y1 & Y2

According to Dalton’s law of partial pressure,

P10  PT . Yi

Pi
or Yi 
PT

For binary solution,

P1 P2
Y1  & Y2 
PT PT
P10 1 P20  2
or Y1  & Y2 
PT PT

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Verification of relation between X & Y

P1 P
Y1   i 1
PTotal PT
P10 1
or Y1 
P 1  P20 2
1
0

1 P10 1  P20  2 P20  2

or   1 
Y1 P10 1 P10 1

1 P0 (1   ) P0  P 0 
 1 2 0 1 ( 2  1  1 )  1  2 0 2 1
Y1 P1 1 P1 1

P20 P0 P0 P0
 1  0 2  1  20  0 2
P10
P1 1 P1 P1 1

1  P10  P20  P20 1

ie.,   
Y1  P10  P10 1

1 1
Vs
Y1 1 graph

1  P10  P20   P20  1

   
Y1  P10   P10  1
y c m x

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Raoult’s Law as a special case of Henry’s Law

According to Raoult’s Law

P10  P10 10 ...(1)

According to Henry’s Law

P10  K H i  10 ...(2)

 Raoult’s law is a special case of Henry’s law in which KHi  Pi

0

Vapour Pressure of Solution of Solids in Liquids - Raoult’s law in General Form

In pure liquids, the entire surface is occupied by the molecules of liquid.

If a non-volatile solute is added to a solvent to give a solution, the V.P of the solution is solely from
solvent alone.

 PS  P1  P2  P1 only because 2 is non volatile.

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In the solution, the surface has both solute and solvent molecules, thereby the fraction of the surface
covered by the solvent molecules get reduced. Consequently, the number of solvent molecules
escaping from the surface is corresponding reduced, thus the V.P is also reduced.

The decrease in the V.P of solvent depends on the quantity of non-volatile solute present in the solution
irrespective of its nature.

ie., P1  P10

 Lowering of VP  P1  P1  P1
0

 Raoult’s law in general form can be stated as : “For any solution the partial VP of each volatile
component in the solution is directly proportional to its mole fraction”.

 If the solute is non-volatile,

P1  1 only

ie., P1  P10  1

P1 Vs  1 Graph

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Types of Solutions Based on Raoult’s Law
Based on Raoult’s law solutions are classified into 2 types.
1. Ideal Solutions

 The solutions which obeys Raoult’s law over the entire range of concentration are called ideal
solutions.

 Two properties are

a) Enthalpy of mixing mi xH  0

b) Volume of mixing mix V  0 .

 At molecular level, the intermolecular attractive interactions will be of two types A-A and B-B,
whereas in solution, A-B interaction also be present. But A-B has same strength as that of A-A
and B-B interactions.

 Perfect ideal solutions are very rare but some solutions are nearly ideal.
egs : 1) n-hexane + n-heptane
2) Bromoethane + Chloroethane
3) Benzene + Toluene
4) Chlorobenzene + Bromobenzene etc.
2. Non-Ideal Solutions

 When a solution does not obey Raoult’s law over the entire range of concentrations, then it is
called a non-ideal solution.

 Two main properties are

a) mixH  0

b) mix V  0

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Type of Non-Ideal Solutions

Non ideal solutions with Non ideal solutions with

+ve deviation -ve deviation
1) VP is higher than that predicted by 1) VP is lower than that predicted by
Raoult's law Raoult's law

2) 2)

3) A-B interaction is weaker than A-A 3) A-B interaction is stronger than A-A and
and B-B interaction and A and B will B-B interaction and theescaping
easily escaped into Paseous phase tendency into vapour phase for A and B
decreases
4) VP Vs  graph ; 4) VP Vs  graph ;

5) Examples : 5) Examples :
a) Ethanol + water a) HNO3 + water
b) Acetone + CO2 b) HCl + water
c) Methanol + water c) Acetone + Chloroform
d) Acetone + benzene d) Phenol + Aniline
e) Toluene + CCl4 e) Acetic acid + Pyridine

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NOTE - Explanation for Examples

1. Acetone + Chloroform

Here the acetone - chloroform interaction is stronger than acetone-acetone as well as chloroform-
chloroform interactions. Therefore, this solution exhibit -ve deviation from ideal behaviour because the
strong interaction decreases the escaping tendency of two liquids which decreases the VP of solution.
2. Ethanol + Water
Here ethanol - ethanol and water - water interaction is already strong because it is a H-bond. Compared
to the individual H-bonding, the H-bonds formed between ethanol and water is not so strong which
increases the escaping tendency of these two liquids results in +ve deviation from ideal behaviour.
For solution of any types whether it is ideal or non-ideal,

Smix   ve (disorder increases)

Gmix   ve (dissolution is spontaneous)

Azeotropes

 These are the binary mixtures having the same composition in liquid and vapour phase and boils at a
constant temperature.

 It is not possible to separate the components by fractional distillation.

 Azeotropes are formed by solutions which does not obey Raoults law ie., non-ideal solutions.

 Azeotropes are classified into 2 types

a) Minimum boiling azeotropes
b) Maximum boiling azeotropes

Minimum Boiling Azeotropes Maximum Boiling Azeotropes

1) Formed by non-ideal solutions having +ve 1) Formed by non-ideal solutions having
deviation -ve deviation

2) They boils at a temperature lower than the 2) They boils at a temperature higher than
boiling points of individual liquids the boiling points of individual liquids
(minimum boiling) (maximum boiling)
3) Ethanol-water mixture - 95% by volume of 3) HNO3 - water mixture - 68% by volume of
ethanol forms azeotropes
HNO3 forms azeotropes

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Azeotropic Distillation
 Azeotropes cannot be repeated by fractional distillation due to constant boiling point.
 a) By adding a suitable chemical we can separate one of the component thereby separation of
components is possible.
b) By adding a third component called entrainers which decreases the VP of one of the component
thereby boiling point may differ, then we can perform fractional distillation  azeotropic distillation.
Colligative Properties (CP)
All the properties depend on the number of solute particles irrespective of this nature relative to the
total number of particles present in the solution are called colligative properties.
(Co = together ligare = to bind  Latin words)

W2
CP  n2 OR CP 
M2
Major CP are

1) Relative lowering of VP (RLVP) - P1 / P10

2) Elevation of Boiling point - Tb

3) Depression of freezing point - Tf

4) Osmotic pressure - 

RLVP ( P1P10 )
The VP of a solvent in solution (VP of solution in the case of a non-volatile solute) is less than that of
pure solvent.

ie., P1  P10

 Lowering of VP = P1  P1  P1
0

According to Raoult’s law, P1  P10 1

P1  P10  P10 1  P10 (1  1 )  P10 2

P1 P10  P1 n2
RLVP    2 
P10 P10 n1  n2

For dilute solutions n2 << n1

 n1  n2  n1 ;

P 10  P 1 n2
 
P 10 n1

Depends directly on n2, hence it is colligative property

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P10  Ps n2 w 2M1
   (Ps = P1)
P10 n1 M2 w 1

P10  Ps n2
But for all cases, 
P10
n1  n2

P10 n
or 0  1 1
P1  Ps n2

P10 n1 P10  P10  Ps n

ie., 0  1  ;  1
P1  Ps n2 P1  Ps
0
n2

P1 n1
ie., P0  P  n
1 s 2

P1  Ps n
or  2
Ps n1
Calculation of M2
For dilute solns,

P10  Ps wM
0
 2 1
P1 w 1M2

 P0   w 2M1 
M2   0 1  
 P1  Ps   w1 
Ostwald & Wacker Method
This method verifies experimentally the RLVP. The experimental set up is given as :

The solution chamber, solvent chamber and anh.CaCl2 guard tube are previously weighed.
Here, weight loss in solution chamber  P1

weight loss in solvent chamber  P10  P1

Weight loss in solvent chamber P0  P

  1 0 s
Total weight lossinboth chamber P1

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Total weight gain in CaCl2 tube ...(1)

We know that,

P10  Ps w 2M1
 ...(2)
P10 M2 w 1

From (1) & (2)

Weight lossin solvent chamber w 2M1


Total weight loss inboth chamber M2 w1

Total weight gain CaCl2 tube

Hence RLVP is verified

Elevation of Boiling Point ( Tb )

 BP of a liquid or a solution is the temperature at which its VP becomes equal to atmospheric pressure.
 At 1 atm, BP is called normal BP
Normal BP of H2O = 1000C
At 1 bar, BP is called standard BP
Standard BP of water = 99.60C
ie., 1 atm = 1.013 bar
 When a non-volatile solute is added to a volatile liquid the VP of the solvent in solution decreases. This
decrease in VP increases the BP of solution and the increase in BP is known as elevation of BP is
Tb .
If Tbo is the BP of pure solvent and Tb is the BP of solution,

Tb > Tb0

 Elevation of BP Tb  Tb  Tb
0

VP Vs T curve

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From the graph,

P1  Tb ...(1)

From RLVP

P1   2 ...(2)

 Tb  2

n2
Tb  k. 2 , where k = proportionality constant = k.
n1  n2

For dilute solution, n1  n2  n1

n2
 Tb  k.
n1

Since Tb proportional to n2, number of moles of solute, then Tb is a colligative property..

k.n2M1
Tb 
w1
Since k and M1 are constant, K.M1= constant = Kb known as molal elevation constant or elevation of
BP constant or ebullioscopic constant.

n2
 Tb  k b .  k b .m, molality of solution
w1

kb . w 2 .1000
OR Tb  M2 .w1

k b .w 2 .1000
OR Tb  Tb  Tb  k b .m 
0

M2 . w1

Experimental verification of Tb  Lansberger method

Ebullioscopic Constant, Kb ;
Kb is a property of solvents.

Tb K
Kb   1
 K kg mol1 or K m1
m kgmol
For a molal solution,

K b  Tb

 Kb is defined as the elevation of BP for a 1 molal solution.

Kb for H2O = 0.52 K kg mol–1

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Calculation of M2

K b .w 2 .1000
M2 
Tb .w1

Determination of Kb for a solvent

R =Universal gas constant

R(Tbo )2
Kb  Tbo  B.P of pure solvent
1000 v
 v  latent heat of vapourisation for unit mass of solvent   VH / M1

RM1 (Tbo )2 H
 Kb   v  VH  Molar heat of vapourisation
1000 vH M1
M1  Molar mass of solvent in g / mol

Depression of Freezing Point ( Tf )

 FP of a substance is defined as the temperature at which the vapour pressure of the substance in its
liquid phase is equal to its VP in solid phase. ie., at FP both liquid and solid form co exist.
 When a non-volatile solute is added to a solvent VP of solution decreases which decreases the FP of
solution and the decrease is known as depression of FP ( Tf ) .

If Tfo be the FP of pure solvent and Tf be that of solution, then

Tfo > Tf

 Depression of FP  Tf  Tf  Tf
o

VP Vs T curve

Similar to Tb , we can show that

k f . w 2 .1000
Tf  Tfo  Tf  k f .m 
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The proportionality constant kf is known as molal constant OR depression of FP constant OR cryoscopic
constant.
Kf is a property of solvent.

Tf
Kf   K kg mol1
m

For a 1 molal solution, k f  Tf  Kf is defined as depression of FP for a 1 molal solution.

K f of water  1.86 K kg mol1

Calculation of M2

K f . w 2 . 1000
M2 
Tf . w 1

Determination of Kf

 f  latent heat of fusion

R(T ) o 2
fH
Kb  f

1000  f M1
 f H  Molar heat of fusion

RM1 (Tfo )2
 Kf 
1000 v H

Experimental verification of Tf  Beckmann Method

Note :
 Rast Method
In Rast Method, the solvent used is camphor with a high Kf value of 40 K kg mol–1. By using this
solvent, Tf is obtained as a measurable value.

 Antifreeze solutions and use of NaCl & CaCl2 to remove ice from the roads are application of Tf .

4. Osmotic Pressure (  )
Osmosis
The flow of solvent from its higher concentration into lower concentration OR from dilute solution into
concentrated solution through a semi permeable membrane (SPM) is known as osmosis.
eg : 1) Raw mangoes sheivel when pickled in brine
2) Wilted flowers revive when placed in fresh water
3) Blood cells collapse when suspended in salini solution
4) Carrot become limb because of wake loss in atmosphere and can become firm when
placed in water
5) Water movement from soil into plant roots and subsequently into upper portions of the
plant.

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6) Preservation of meat by salting and of fruits by adding sugar protects against bacterial
action because bacterium on salted meat or candid fruit loses water sheivels and dies.
7) People taking of lot of salt or salty food experience water retention in tissue cells and
intercellular spaces. This results puffiness or swelling called Edema.
Semi-Permeable membranes (SPM)
SPM allows the passage of solvent molecules only.

Osmotic Pressure (  )

The minimum pressure that just stops the flow of solvent is called osmotic pressure (  ) solution.

We know that   hg ;   density of solution

g  9.8 ms 2

Experimentally it was found that

  C and   T

ie.,   CT

  CRT R  Gas constant

C = Concentration in terms of molarity
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n2RT
or  
V

Since   n2 ,  is a colligative property

w 2RT

M2 V

Calculation of M2

w 2RT
M2 
V
Advantages of Osmotic Pressure Measurement
1. This method is widely used for determine molar masses of proteins, polymers and other
macromolecules and the values are more accurate and large because this method is carried out at
room temperature. Otherwise, biomolecules becomes unstable at elevated and depressed
temperatures and polymers have poor solubility.
2. Taking molarity instead of molality
Isotonic solutions
Two solutions having same osmotic pressure a given temperature are called isotonic solutions.
When isotonic solutions are separated by SPM no osmotic occurs between them.
eg :  associated with fluid inside the blood cells is equivalent to that of 0.9% (w/v) NaCl solution.

 RBC and 0.9% w/v NaCl (normal saline) are isotonic  IV injection (Intravenous injection) uses
0.9% w/v normal saline solution.
For isotonic solutions,

1  2
C1RT = C2RT

ie., C 1  C2

n1 n2

v v
If volume is same, n1 = n2

w1 w 2

M1 M2
Hypertonic & Hypotonic Solutions
If two solutions have different osmotic pressure or different concentrations,
a) the one with high concentration is called hypertonic
b) the one with low concentration is called hypotonic

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Reverse Osmosis (RO)
The direction of osmosis can be reversed if a pressure larger than the osmotic is applied to the
solution side. That is, pure solvent flows out of the solution side. That is, pure solvent flows out of the
solution through SPM. This phenomenon is called RO.
RO is the main principle behind desalination of sea water

Usually SPM in desalination of sea water is a film of cellulose acetate.

Experimental verification of osmotic pressure is known as
1) Harteley & Berkely Method
2) Morse & Frazer Method
Abnormal Molar Masses
The molar mass of solute obtained from colligative properties ie., apparent molecular mass has a
magnitude that is either lower or higher than the expected or normal values. This abnormalities is
known as abnormal molar masses.
This abnormal molar masses is due to the association or dissociation of solutes in solvent.
i. Dissociation
Consider dissociation of KCl in water

KCl  K   Cl

No. of particle 1 2 (neglecting ionic int eractions)

Normal molar mass of KCl = 74.5 g

Abnormal (apparent OR observed)
molar mass of KCl = 37.25 g
As number of particles doubles, CP also doubles and molar mass become half because

CP  n2

1
OR CP  M
2

ii. Association
Consider the association (Dimerisation) of acetic acid in benzene


2CH3 COOH 
 (CH3 COOH)2
[Link] particles 2 1

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Normal molar mass of CH3COOH = 60 g
Abnormal molar mass of CH3COOH = 120 g
As the number of particles halved, CP also halved and molar mass become doubles because

CP  n2

1
OR CP  M
2

These abnormalities in molar mass of solute due to association or dissociation is known as abnormal
molar masses.
van’t Hoff’s Factor (i)
In order to account for abnormal molar masses of solute, van’t Hoff’s factor (i) is introduced by J.H.
van’t Hoff
i is defined as

Normal molar mass Observed Colligative Properties

i= =
Abnormal molar mass Calculated Colligative Property

Total no. of moles of particles after association


No. of moles of particlesbefore asso / disso

 Assuming 100% dissociation of solutes,

i for NaCl, KCl etc = 2
i for K2SO4, Na2SO4 etc = 3
i for K4[Fe(CN)6] = 5
For non-electrolytes such as glucose, sucrose, urea, alcohols etc i = 1
 Association of solute in solvent is represented as



nS 
 Sn
100% Dimerisation i = 1/2
100% Termerisation i = 1/3 etc
 100% association i = 1/n
A. Dissociation
 i>i
 A general dissociation of solute is represented as



An 
 nA
Initial moles 1 0
At equilibriummoles 1 n


(degree of dissociation)

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Total number of moles nT  1    n  1  (n  1) 

nT 1  (n  1) 
van’t Hoff factor i i
ni 1

i 1
ie., 
n 1
 Dissociation constant (Kd)

C 2
Kd 
1 
C = Concentration
  Degree of dissociation
B. Association
 i<1
 A general association of solute is represented as



nA 
 An
Initial moles n 0
At equilibrium moles n  n 

nT  n  n  

nT n  n    1 
i   1    ; i  1    1 
ni n n n 

i 1 1 i
ie.,  or 
1 1  1/ n
1
n
 Association Constant (Ka)

C 2
Ka 
1 
In general, the abnormalities of molar mass can be minimized by multiplying n2 with i. Therefore
modified CPs are

P10  Ps in2
1) RLVP 
P10
n1  in2

2) Tb Tb  ik b .m

3) Tf Tf  ik f .m

4)    iCRT

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Variation of CP with i

P10  Ps
1)  i 2 ; Ps  P10  i 2P10
P10

A s i  Ps 

2) Tb  ik bm ; Tb  Tb0  ik bm

A s i  Tb 

3) Tf  ik f m ; Tf0  Tf ik f m ; Tf  Tf0  ik f m

A s i  Tf 

4)   iCRT

i

As i  

1
 VP of solution (Ps) & Freezing point of solution (Tf) 
i
Osmotic pressure (  ) & Boiling point of solution (Tb) i
Isotonic Solutions & van’t Hoff’s Factor
For isotonic solutions

1  2

i1C1RT  i2C2RT ; i1C1  i2C2

n1 n
i1  i2 2 (Assume that volume of two solutions are equal)
V V

w1 w2
ie., i1 M  i2 M
1 2

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