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 SOLUTIONS & COLLIGATIVE PROPERTIES

SOLUTIONS & COLLIGATIVE PROPERTIES

INTRODUCTION For example, common salt in water.

In normal life we rarely come across pure substances. Most
of these are mixtures containing two or more pure
substances. Their utility or importance in life depends on
their composition. The air around us is a mixture of gases
primarily oxygen and nitrogen; the water we drink contains
very small amounts of various salts dissolved in it. Our blood
is a mixture of different components. Alloys such as brass,
bronze, stainless steel, etc. are also mixtures. In this Unit,
we will consider mostly liquid solutions and their properties.
1. SOLUTIONS
1.1 Definition
A solution is a homogeneous mixture of two or more than
two components.
1.2 Classification
Solutions which contain two components in it are called
Binary Solutions.
Substances which are used to prepare a solution are called
as Components.
The component that is present in the largest quantity is
known as Solvent. Solvent determines the physical state in
which solution exists.
The other component present in lesser quantity in the
solution is termed as Solute.
Each component may be solid, liquid or in gaseous state.

1.3 Strength of Solutions

Mass of component in the sol.
Mass % of a component u 100
The amount of solute dissolved per unit solution or Total Mass of sol.
solvent is called Strength of solution. There are various 2. Volume percentage (%v/v):
methods of measuring strength of a solution. :
“It represents volume of a component in 100 mL of solution”
1. Mass Percentage (%w/w):
“It represents mass of a component present in 100 g of Vol. of component
Vol. % of a component = ×100
solution” Total vol. of solution
 SOLUTIONS & COLLIGATIVE PROPERTIES

3. Mass by volume percentage (%w/v): 8. Normality, N

“It represents mass of solute in grams present in 100 mL of It represents no. of equivalents of solute present in 1 L of
solution” solution.

Mass of solute in g No. of Equivalents of solute

Mass by vol. percent = u 100 Normality, N
Vol. of sol. in mL Vol. of sol. in L

4. Parts per Million (ppm)

Weight
No. of equivalents, eq
No. of parts of the component Equivalent weight (W / E)
Parts per Million u 106
Total no. of all the componens of sol.
M
E (z is the valency factor)
Concentration in parts per million can be expressed as mass z
to mass, volume to volume and mass to volume.
SOME IMPORTANT RELATIONSHIPS
5. Mole Fraction (x)
Dilution Law
“It represents the moles of a solute present in one mole of
solution” If a solution is diluted by adding solvent to it, then the
amount of solute remains constant and we can write:
No. of moles of the component
Mole fraction M1V1 = M2V2 and N1V1 = N2V2
Total no. of moles all the components
Molarity and Normality
For example, in a binary mixture, if the number of moles
of A and B are nA and nB respectively, the mole fraction Normality = z × Molarity
of A will be
IMPORTANT :
nA Mass %, ppm, mole fraction and molality are independent
xA
nA  n B of temperature, whereas molarity & normality are a
function of temperature. This is because volume depends
6. Molarity, M on temperature and the mass does not.
“It represents moles of solute present in 1 L of solution”
2. VAPOUR PRESSURE
Moles of solute
Molarity, M
Vol. of sol. in L 2.1 Definition

Units of Molarity are mol/L also represented by ‘M’ or Vapour pressure of a liquid/solution is the pressure exerted
‘Molar’. by the vapours in equilibrium with the liquid/solution at a
“Density of a solution is mass of the solution per unit particular temperature.
volume” Vapour pressure v escaping tendency
Mass of sol. 2.2 Vapour pressure of liquid solutions and
Density, d m/V
Vol. of sol. Raoult’s Law :

7. Molality, m
(Raoult’s law for volatile solutes)
“It represents moles of solute present per kg of solvent”
Raoult’s law states that for a solution of volatile liquids,
Moles of solute the partial vapour pressure of each component in the
Molality, m
Mass of solvent in kg solution is directly proportional to its mole fraction.
Consider a solution containing two volatile components
Units of molality are mol/kg which is also represented by
1and 2 with mole fractions x1 and x2 respectively. Suppose
‘m’ or ‘molal’.
SOLUTIONS & COLLIGATIVE PROPERTIES

at a particular temperature, their partial vapour pressures are In general

0 0
p1 and p2 and the vapour pressure in pure state are p and p .
1 2 pi = yi ptotal
Thus, according to Raoult’s Law, for component 1
2.3 Vapour pressures of solutions of solids in liquids
p1 v x1 and Raoult’s Law

and p1 = p10 x1 (Raoult’s law for non volatile solutes)

Similarly, for component 2 If a non-volatile solute is added to a solvent to give a
solution, the number of solvent molecules escaping from
p2 p02 x 2
the surface is correspondingly reduced, thus, the vapour
According to Dalton’s law of partial pressure, the total pressure is also reduced.
pressure (ptotal) over the solution phase in the container will
The decrease in the vapour pressure of solvent depends on
be the sum of the partial pressures of the components of
the quantity of non-volatile solute present in the solution,
the solution and is given as :
irrespective of its nature.
ptotal = p1 + p2
Raoult’s law in its general form can be stated as, for any
Substituting the values of p1 and p2, we get
solution the partial vapour pressure of each volatile
ptotal = x1 p10  x 2 p02 component in the solution is directly proportional to its
mole fraction.
(1  x 2 ) p10  x 2 p 02
In a binary solution, let us denote the solvent by 1 and solute
p  (p  p ) x 2
0 0 0 by 2. When the solute is non-volatile, only the solvent
1 2 1
molecules are present in vapour phase and contribute to
vapour pressure. Let p1 be the vapour pressure of the
solvent, x1 be its mole fraction, p10 be its vapour pressure
in the pure state. Then according to Raoult’s law

p1 D x 1

and p1 = x1 p10 = ptotal

The plot of vapour pressure and mole fraction of an

ideal solution at constant temperature. The dashed
line I and II represent the partial pressure of the
components. It can be seen from the plot that p1 and
p2 are directly proportional to x1 and x2, respectively.
The total vapour pressure is given by line marked III
in the figure.
Mole fraction in vapour phase
If y1 and y2 are the mole fractions of the components 1 and
2 respectively in the vapour phase then, using Dalton’s law If a solution obeys Raoult’s law for all concentrations,
of partial pressures: its vapour pressure would vary linearly from zero to
p1 = y1 ptotal the vapour pressure of the pure solvent.

p2 = y2 ptotal
 SOLUTIONS & COLLIGATIVE PROPERTIES

Solutions showing negative deviations from Raoult’s law :

2.4 Ideal and Non-ideal solutions
Ideal solutions :
An ideal solution is the solution in which each component
obeys Raoult’s law under all conditions of temperatures
and concentrations.
x Solvent-Solute(A-B) type of force is stronger than the other
two.
x The vapour pressure is lower than predicted by the law
x 'HMIXING < 0

Properties of Ideal solutions : x 'VMIXING< 0

x 'HMIXING = 0 For example,phenol and aniline, chloroform and acetone

etc
x 'VMIXING = 0

x Intermolecular attractive forces between the A-A and B-B

are nearly equal to those between A-B.

Eg. solution of benzene and toluene, Pressure composition curves for solution showing
solution of n-hexane and n-heptane negative deviation

Non – ideal solutions :

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

Solutions showing positive deviation from Raoult’s Law :

x Solvent-Solute(A-B) type of force is weaker than Solute-

Solute(B-B) & Solvent-Solvent(A-A) forces.

x The vapour pressure is higher than predicted by the law.

x 'HMIXING > 0

x 'VMIXING > 0

Eg. ethanol and acetone, carbon disulphide and acetone

Pressure composition curve for solution showing

positive deviation 2.5 Azeotropes

Azeotropes are binary mixtures having the same

composition in liquid and vapour phase and boil at a
constant temperature.

Minimum boiling azeotrope

The solutions which show a large positive deviation from

Raoult’s law form minimum boiling azeotrope at a specific
composition.

For example, ethanol-water mixture containing

approximately 95% of ethanol forms an azeotrope with
boiling point 351.15 K.
SOLUTIONS & COLLIGATIVE PROPERTIES
Boiling temperature - composition Diagram for solutions
showing large positive deviations.
(Minimum boiling azeotrope)
Maximum boiling azeotrope :
The solutions that show large negative deviation from
Raoult’s law form maximum boiling azeotrope at a specific
composition. Nitric acid and water mixture containing 68%
nitric acid forms an azeotrope with a boiling point of 393.5
K.
Boiling temperature - composition Diagram for solutions
showing large negative deviations.
(Maximum boiling azeotrope)
3. SOLUBILITY
3.1 Solubility of a solid in liquid
Solubility of a substance is its maximum amount that can
be dissolved in a specified amount of solvent.
Factors affecting the solubility of a solid in liquid :
1. Nature of solute and solvent :
Like dissolves like. For example, While sodium chloride
and sugar dissolve readily in water, naphthalene and
anthracene do not. On the other hand, naphthalene and
anthracene dissolve readily in benzene but sodium chloride
and sugar do not.
2. Temperature :
In a nearly saturated solution,
If ('solH > 0), the solubility increases with rise in
temperature and
If (' solH < 0) the solubility decreases with rise in
temperature.
Effect of pressure :
Does not have any significant effect as solids and liquids
are highly incompressible.
3.2 Henry’s law
Henry’s law states that at a constant temperature, the
solubility of a gas in a liquid is directly proportional to
the pressure of the gas.
The most commonly used form of Henry’s law states that
“the partial pressure of the gas in vapour phase (p) is
proportional to the mole fraction of the gas (x) in the
solution”. This is expressed as:
p = KH x
Here KH is the Henry’s law constant.
Characteristics of KH :
x KH is a function of the nature of the gas.
x Higher the value of KH at a given pressure, the lower is the
solubility of the gas in the liquid.
x KH values increase with increase of temperature indicating
that the solubility of gases increases with decrease of
temperature.
 SOLUTIONS & COLLIGATIVE PROPERTIES

Applications of Henry’s law Knowing that x2 = 1 – x1, equation reduces to

1. In the production of carbonated beverages.
'p1 x 2 p10
2. In the deep sea diving.
Equation can be wirtten as
3. For climbers or people at high altitudes.
Raoult’s Law as a special case of Henry’s Law 'p1 p10  p1
x2
p10 p10
According to Raoult’s law,
The expression on the left hand side of the equation as
pi = xi p i0 mentioned earlier is called relative lowring of vapour
pressure and is equal to the mole fraction of the solute. The
In the solution of a gas in a liquid, one of the components
above equation can be written as :
is so volatile that it exists as a gas. Its solubility according
to Henry’s law,
p10 -p1 n2 § n2 ·
p = KH x. ¨ since x 2 ¸
p10 n1 +n 2 © n1 +n 2 ¹
Thus, Raoult’s law becomes a special case of Henry’s law
Here n1 and n2 are the number of moles of solvent and solute
in which KH becomes equal to pi0 .
respectively present in the solution. For dilute solutions
n2 << n1, hence neglecting n2 in the denominator we have
4. COLLIGATIVE PROPERTIES
The properties that depend on the number of solute particles p10  p1 n2
irrespective of their nature relative to the total number of p10 n1
particles present in the solution are called colligative
properties.
p10  p1 w 2 u M1
There are four colligative properties: or p10 M 2 u w1
1. Relative Lowering of vapour Pressure
Here w1 and w2 are the masses and M1 and M2 are the molar
2. Elevation in Boiling Point masses of the solvent and solute respectively.
3. Depression in freezing point
4.2 Elevation in Boiling Point
4. Osmotic pressure
Boiling point of a liquid is the temperature at which the
4.1 Relative Lowering of vapour Pressure vapour pressure of the liquid becomes equal to the
atmospheric pressure.
When a non-volatile solute is added to a solvent, the vapour
pressure decreases. On addition of non-volatile solute the vapour pressure of
the solvent decreases and therefore, to boil the solution the
The lowering of vapour pressure w.r.t. the vapour
pressure of the pure solvent is called “Relative lowering required temperature will be higher. So, there will be a rise
in vapour pressure”. in the boiling point of the solution.

According to Raoult’s Law : The increase in boiling point 'Tb = T b – Tb0 where Tb0 is

p1 x1 p10 the boiling point of pure solvent and Tb is the boiling point
of solution is known as elevation of boiling point.
The reduction in the vapour pressure of solvent ('p1) is
Expression :
given as:
'Tb = Kb m
'p1 p10  p1 p10  p10 x1
Kb is called Boiling Point Elevation Constant or Molal
p10 (1  x1 ) Elevation Constant (Ebullioscopic Constant).
SOLUTIONS & COLLIGATIVE PROPERTIES

Calculation of molar mass of solute :

4.3 Depression in freezing point
w 2 / M2 1000 u w 2
m The freezing point of a substance may be defined as the
w1 /1000 M 2 u w1
temperature at which the vapour pressure of the substance
Substituting the value of molality in equation we get in its liquid phase is equal to its vapour pressure in the
solid phase.
K b u1000 u w 2 When a non-volatile solid is added to the solvent its vapour
'Tb
M 2 u w1 pressure decreases and now it would become equal to that
of solid solvent at lower temperature. Thus, the freezing
1000 u w 2 u K b point of the solvent decreases.
M2
'Tb u w1
'Tf = Tf0 – Tf where Tf0 is the freezing point of pure solvent
Kb : and Tf is its freezing point when non-volatile solute is
dissolved is known as depression in freezing point.
It is defined as the elevation in boiling point when the
molality of the solution is unity. Expression :
The unit of Kb is K kg mol–1 'Tf = Kf m
Determination of Kb : Kf is known as Freezing Point Depression Constant or
Molal Depression Constant or Cryoscopic Constant.
R u M1 u Tb2
Kb Calculation of molar mass of solute :
1000 u ' vap
w2 / M2
where: R = gas constant (8.314 JK/mol), m
w1 /1000
Tf = freezing temperature in K,

M1 = Molar mass of solvent in Kg/mol, Substituting this value of molality in equation we get :

'vapH = enthalpy of vapourisation of solvent in J/mol. K f u w 2 / M2

'Tf
w1 /1000

K f u w 2 u 1000
'Tf
M 2 u w1

K f u w 2 u 1000
M2
'Tf u w1

Kf :

It is defined as the depression in freezing point when the

molality of the solution is unity. The unit of Kf is K kg mol-1.

Determination of Kf :

The vapour pressure curve for solution lies below the R u M1 u Tf2
Kf
curve for pure water. The diagram shows that ' Tb 1000 u 'fus
denotes the elevation of boiling point of a solvent in
solution. where : R = gas constant (8.314 JK/mol),
Tf = freezing temperature in K,
 SOLUTIONS & COLLIGATIVE PROPERTIES

M1 = Molar mass of solvent in Kg/mol,

'fusH = enthalpy of fusion of solvent in J/kg

The excess pressure equal to osmotic pressure must

be applied on the solution to prevent osmosis.

Diagram showing 'Tf, depression of the freezing Expression :

point of a solvent in a solution.
For dilute solutions, osmotic pressure is proportional to
the molarity, C of the solution at a given temperature T.
4.4 Osmosis
Thus:
When a pure solvent and solution are kept with a semi- S= CRT
permeable membrane between them then the solvent
particles pass through the membrane from the solvent side Here S is the osmotic pressure and R is the gas constant.
to the solution side. This phenomenon is called “Osmosis”.
Calculation of molar mass :
The semi-permeable membrane is a membrane that allows
only small molecules to pass through and blocks the larger S (n 2 / V) RT
solute molecules.
Here V is volume of a solution in litres containing n2 moles
of solute. If w2 grams of solute, of molar mass, M2 is present
in the solution, then n2 = w2 / M2 and we can write,

w 2 RT
SV
M2

w 2 RT
or M2
SV

Isotonic solutions :

Two solutions having same osmotic pressure at a given

temperature are called isotonic solutions.

The solution with lower concentration or lower osmotic

Osmotic pressure :
pressure is known as “Hypotonic” with respect to more
The osmotic pressure of a solution is the excess pressure concentrated solution.
that must be applied to a solution to prevent osmosis, i.e.,
The solution with higher concentration or higher osmotic
to stop the passage of solvent molecules through a
pressure is known as “Hypertonic” with respect to dilute
semipermeable membrane into the solution.
solution.
 SOLUTIONS & COLLIGATIVE PROPERTIES

Reverse osmosis : Dissociation :

If a pressure larger than the osmotic pressure is applied to The number of particles will always increase due to
the solution side, the solvent will flow from the solution dissociation and hence i > 1.
into the pure solvent through the semi permeable membrane.
This phenomenon is called reverse osmosis. An o nA

Application : Initial particle = 1

Desalination of sea water : Final particles = 1 – D + nD

When pressure more than osmotic pressure is applied, pure i = 1 – D + nD

water is squeezed out of the sea water through the Modified Expressions :
membrane.
Relative lowering of vapour pressure of solvent,
4.5 Abnormal Molar Masses
p10  p1 n2
When the molecular mass of a substance determined by i.
p10 n1
studying any of the colligative properties comes out to be
different than the theoretically expected value, the substance Elevation of Boiling point 'Tb = i Kb m
is said to show abnormal molar mass.
Depression of Freezing point, 'Tf = i Kf m
Abnormal Molar Masses are observed:
Osmotic pressure of solution, S = i n2 RT/V
1. When the solute undergoes association in the solution.

2. When the solute undergoes dissociation in the solution. 5. VAPOUR PRESSURE

van’t Hoff Factor : On increasing the temperature of the liquid the escaping
To calculate extent of association or dissociation, van’t Hoff tendency of the molecules increases and the vapour
introduced a factor i, known as the van’t Hoff Factor. pressure increases.

Normal molar mass

i
Abnormal molar mass

Observed colligative property

i
Calculated colligative property

Total no. of moles of particles after association (dissociation) The distribution of molecular kinetic
No. of moles of particles before association (dissociation) energies in a liquid
Claussius-Clapeyron Equation
Association :
In p2/p1 = ('HVAP/R) (1/T1 – 1/T2)
Number of particles will always decrease due to association
therefore i < 1. where 'HVAP represents the enthalpy of vaporisation of
the liquid.
nA o An
6. THERMODYNAMICS OF DISSOLUTION
Let initial particles (ni) = 1
If the interactions grow stronger the process is exothermic
Final number( nf) = 1 – D + D/n and if they go weaker during the formation of solution
the process becomes endothermic. In general 'S is
van’t Hoff factor, i = nf/ni = 1 – D + D/n positive in dissolution process. If the mixing process is
spontaneous/natural then 'G has to be negative.
 SOLUTIONS & COLLIGATIVE PROPERTIES

6.1 Boiling Point Elevation

'GVAP = 0
Tb = 'HVAP/'SVAP
The non-volatile solute increases the randomness of the
The lower freezing point of a solution relative to that of a
solution phase and the entropy of the vapours remains
pure solvent is due to a difference in their entropies
the same. Due to this, 'SVAP decreases thus giving rise to
the boiling point. of fusion, 'Sfusion.

7. OSTWALD WALKER METHOD

The higher boiling point of a solution relative to that of a

pure solvent is due to a difference in their entropies This is a typical method to measure the relative lowering
of vapourization, 'Svap. in vapour pressure of a solution. Dry air is passed
successively through three systems: solution, pure solvent
and then a drying agent.
6.2 Freezing Point Depression
w1 and w2 represent the decrease in weight of the vessels
'GFUS = 0 and w3 represents the increase in weight of the third vessel
due to absorption.
Tf = 'HFUS/'SFUS
The entropy difference will increase in this case due to w1 v PSOLUTION w2 v P SOLVENT – P SOLUTION
the increase in the entropy of solution. This increase in (as the air was already saturated)
entropy will result in decrease of the freezing point
w3 v PSOLVENT
according to the above relation.
Using the above relations the relative lowering in vapour
pressure can be calculated.
SOLUTIONS & COLLIGATIVE PROPERTIES

IMPORTANT FORMULAE

In the formulae given below A represents solvent and B represents solute, also
MA = Molar mass of solvent MB = Molar mass of solute
WA = Mass of solvent VB = volume of solute
V = Volume of solution d = density of solution.

WB
1. Mass of percentage (w/w) = W  W u 100
A B

VB
Volume percentage (v/v) = V  V u100
A B

§w· WB u100
Mass by volume percentage ¨ v ¸
© ¹ V (mL)

WB
Parts per million (ppm) = W  W u10
6

A B

nA
2. Mole fraction of A, xA = n  n
A B

nB
mole fraction of B, xB = n  n
A B

xA + xB = 1

Moles of solute nB WB
3. Molarity (M) = Volume of solution in litre V( L) M B u V( L)

Moles of solute nB WB u 1000

4. Molality (m) = Mass of solvent in kg u 1000
WA M B u WA

Gram Equivalents of solute WB

5. Normality (N) = Volume of solution in litre GEM of solute u V( L)

GEM = Gram Equivalent Mass

6. Relationship between Molarity and Normality
The normality (N) and molarity (M) of a solution are related as follows :
Normality × Equivalent. mass (solute) = Molarity × Molar mass (solute)
 SOLUTIONS & COLLIGATIVE PROPERTIES

7. Relationship between Molarity and Mass percentage (p)

If p is the mass percentage and d is the density of the solution then
p u d u10
Molarity
Mol. mass (solute)

p u d u10
Normality
Eq. mass (solute)

8. Dilution formula : If the solution of some substance is diluted by adding solvent from volume V1 to volume V2, then

M1V1 = M2V2 Similarly, N1V1 = N2V2

9. Molarity of a mixture : If V1 mL of a solution of molarity M1 is mixed with another solution of same substance with volume
V2 and molarity M2, then molarity of the resulting mixture of solution (M) can be obtained as :

M1V1  M 2 V2
M
V1  V2

10. Raoult’s law for volatile solute. pA = p 0A x A and pB = p 0B x B

where pA and pB are partial vapour pressures of component ‘A’ and component ‘B’ in the solution. p 0A and p0B are vapour
pressures of pure components ‘A’ and ‘B’ respectively.

Total vapour pressure = p = pA + pB = p 0A x A  p B0 x B .

11. Raoult’s law for non-volatile solute.

pA0  p nB nB WB M A
xB u (For a dilute solution nB << nA)
p0A nA  nB nA M B WA

p 0A  p A
where xB is mole-fraction of solute and p 0A is relative lowering of vapour pressure.

12. Elevation in boiling point. 'Tb = Kb × m

K b u WB u 1000
MB
'Tb u WA

where, 'Tb Tb  Tb0

13. Depression in freezing point. 'Tf = Kf × m

K f u WB u 1000
MB
'Tf u WA

where, 'Tf Tf0  Tf

SOLUTIONS & COLLIGATIVE PROPERTIES

S).
14. Osmotic pressure (S
S= cRT where ‘c’ is molarity.
15. Van’t Hoff factor.

Normal molecular mass

i
Observed molecular mass

Observed colligative property

or i
Calculated colligative property

Total number of moles of particles after association / dissociation

or, i
Number of moles of particles before association / dissociation

Modified forms of colligative properties :

p0A  pA
(a) ix B (b) 'Tb = i Kbm
p0A

(c) 'Tf = iKfm (d) SV = inBRT

i 1
16. D wher D is degree of dissociation, ‘i’ is van’t Hoff factor, ‘n’ is number of ions produced per formula of the compound.
n 1

1 i
17. D
1
1
n

1 1
where D is degree of association, , n is the number of molecules of solute associate to form an associated molecule,  1.
n n
18. If i > 1, solute undergoes dissociation.
i < 1, solute undergoes association.
i = 1, neither association nor dissociation.

1
i , solute is dimer..
2
 F E B . 20 . 21 . 22

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