Unit 2 Solutions

Solutions are homogeneous mixtures of two or more than two components

Solvent:-Generally, the component that is present in the largest quantity is known as solvent.

Solvent determines the physical state in which solution exists.

Solute:-One or more components present in the solution other than solvent are called solutes.
Generally present in smaller quantity.

Binary solutions:-consisting of two components, Solvent and Solute.

Types of solution:-Depending upon physical state , solutions are categorized in 3 types.

Types of Solutions
 Expressing Concentration of Solutions

Mass percentage (w/w): Mass % of a component

For example, if a solution is described by 10% glucose in water by mass, it means that 10 g of glucose is
dissolved in 90 g of water resulting in a 100 g solution

Volume𝑜𝑓 𝑡h𝑒𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡h𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Volume percentage (V/V): Volume % of a component= × 100
𝑇𝑜𝑡𝑎𝑙 volume 𝑜𝑓 𝑡h𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
• For example, 10% ethanol solution in water means that 10 mL of ethanol is dissolved in water such that the
total volume of the solution is 100 mL.
• Solutions containing liquids are commonly expressed in this unit.
• For example, a 35% (v/v) solution of ethylene glycol, an antifreeze, is used in cars for cooling the engine

Mass by volume percentage (w/V)

commonly used in medicine and pharmacy. It is the mass of solute dissolved in 100 mL of the solution.
 Expressing Concentration of Solutions
Parts per million (ppm)=

• Concentration in ppm can also be expressed as mass to mass, volume to volume and mass to volume.
• A litre of sea water (which weighs 1030 g) contains about 6 × g of dissolved oxygen . Expressed as 5.8 ppm
of sea water.
• The concentration of pollutants in water or atmosphere is often expressed in terms of or ppm.

Mole fraction (x):- Number of moles of the component

Mole fraction of a component =
Total number of moles of all the components

in a binary mixture, if the number of moles of A and B are nA and nB respectively, the mole fraction
of A will be
In a given solution sum of all the mole fractions is unity, i.e.
 Expressing Concentration of Solutions
Molarity: Molarity (M) is defined as number of moles of solute dissolved in one litre of solution.

Its unit is

For example, 0.25 M solution of NaOH means that 0.25 mol of NaOH has been dissolved in one litre of its solution .

w=mass of solute in g, M= Molar mass of solute =volume of solution in millilitre

If density and mass percentage is given, then

 Expressing Concentration of Solutions
Molality: Molality (m) is defined as the number of moles of the solute per kilogram (kg) of the solvent.

Its unit is

For example, 1.00 m solution of KCl means that 1 mol (74.5 g) of KCl is dissolved in 1 kg of water.

w=mass of solute in g, M= Molar mass of solute =mass of solvent in g

Mass %, ppm, mole fraction and molality are independent of temperature, whereas molarity is a
function of temperature. This is because volume depends on temperature and the mass does not.
Practice Time:-
1. Calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 20% of C2H6O2 by mass.
Answer:- 20% of C2H6O2 by mass means 20 g of ethylene glycol and 80 g of water.

Molar mass of C2H6O2 = 12 × 2 + 1 × 6 + 16 × 2 = 62 .

Moles of C2H6O2 = 0.322 mol

Moles of water = = 4.444 mol

Mole fraction of water =1 – 0.068 = 0.932

2. Calculate the molarity of a solution containing 5 g of NaOH in 450 mL solution.
Answer:-
Given:- Mass of solute, w= 5g

Volume of solution, V=450 mL

Molar mass of solute(NaOH), M=40 g/mol

= 0.278 M

3. Calculate molality of 2.5 g of ethanoic acid (CH 3COOH) in 75 g of benzene.

Answer:-
Given:-Mass of solute=2.5 g
Mass of solvent=75 g
Molar mass of solute(CH3COOH)=63 g/mol
 Solubility:-
• Solubility of a substance is its maximum amount that can be dissolved in a specified amount of solvent
at a specified temperature.
• It depends upon the nature of solute and solvent as well as temperature and pressure.

Solubility of a Solid in a Liquid:-

• Polar solutes dissolve in polar solvents and non polar solutes in nonpolar solvents. In general, a solute
dissolves in a solvent if the intermolecular interactions are similar in the two or we may say like dissolves
like.
• E.g. 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.

• Dissolution :-When a solid solute is added to the solvent, some solute dissolves and its concentration increases
in solution. This process is known as dissolution.
• Crystallisation :-Some solute particles in solution collide with the solid solute particles and get separated out
of solution. This process is known as crystallisation.
 • At a state of dynamic equilibrium
Rate of dissolution= rate of crystallization
Solute + Solvent Solution
• Saturated solution:- solution in which no more solute can be dissolved at the given temperature and
pressure is called a saturated solution.
• The concentration of solute in saturated solution is referred as its solubility
• Unsaturated solution :- Solution in which more solute can be dissolved at the given temperature.
Effect of temperature
• As per Le Chateliers Principle, if in a saturated solution, the dissolution process is endothermic (Dsol H >
0), the solubility increases with rise in temperature and if it is exothermic (Dsol H < 0) the solubility
decreases.
Effect of pressure
• Pressure does not have any significant effect on solubility of solids in liquids. It is so because solids and liquids
are highly incompressible and practically remain unaffected by changes in pressure.
 Solubility of a Gas in a Liquid
Henry’s law:-The law states that at a constant temperature, the solubility of a gas in a liquid is directly
proportional to the partial pressure of the gas present above the surface of liquid or solution.

If we use the mole fraction of a gas in the solution as a measure of its solubility, then it can be said that the mole
fraction of gas in the solution is proportional to the partial pressure of the gas over the solution.

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” and is expressed as:
p = KH x slope of the line= p
• is the Henry’s law constant and function of the nature of the gas.
• Higher the value of at a given pressure, the lower is the solubility of the gas in the liquid x
• values increase with increase of temperature indicating that the solubility of gases decreases with increase of
temperature.
• It is due to this reason that aquatic species are more comfortable in cold waters rather than in warm waters
 Applications of Henry’s law:-
• To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure.

• Scuba divers must cope with high concentrations of dissolved gases while breathing air at high pressure
underwater. Increased pressure increases the solubility of atmospheric gases in blood. When the divers come
towards surface, the pressure gradually decreases. This releases the dissolved gases and leads to the formation of
bubbles of nitrogen in the blood. This blocks capillaries and creates a medical condition known as bends, which
are painful and dangerous to life. To avoid bends, as well as, the toxic effects of high concentrations of nitrogen
in the blood, the tanks used by scuba divers are filled with air diluted with helium

• 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. Low blood
oxygen causes climbers to become weak and unable to think clearly, symptoms of a condition known as anoxia.
Example If N2 gas is bubbled through water at 293 K, how many millimoles of N 2 gas would dissolve in 1 litre of
water? Assume that N2 exerts a partial pressure of 0.987 bar. Given that Henry’s law constant for N 2 at
293 K is 76.48 kbar.
Solution
The solubility of gas is related to the mole fraction in aqueous solution. The mole fraction of the gas in the
solution is calculated by applying Henry’s law. p = KH x

p (nitrogen) = 0.987 bar , KH = 76.48 kbar = 76480 bar

As 1 litre of water contains 55.5 mol of it, therefore if represents number of moles of in solution,

( in denominator is neglected as it is < < 55.5)

 Vapour Pressure of Liquid-Liquid Solutions

binary solution of two volatile liquids and denote the

two components as 1 and 2.
Partial vapour pressures
the mole fractions
Total vapour pressure at equilibrium

Raoult’s law :-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

Thus, for component 1 µ and p1 = = vapour pressure of pure component 1 at the same temperature.
for component 2 µ and = = vapour pressure of pure component 2 at the same temperature.

According to Dalton’s law of partial pressures, = +

=+
=+ Following conclusions can be drawn from the following equation-

+ =
(i) Total vapour pressure over the solution can be related to the mole fraction of

=( + any one component.

=+ (ii) Total vapour pressure over the solution varies linearly with the mole fraction

= of component 2.

= (iii) Depending on the vapour pressures of the pure components 1 and 2, total

Similarly = vapour pressure over the solution decreases or increases with the increase of

A plot of p1 or p2 versus the mole the mole fraction of component 2.

fractions x1 and x2 for a solution gives a
linear plot
The minimum value of ptotal is and the maximum value
assuming that component 1 is less volatile than component 2, i.e.,
<
 The composition of vapour phase of solution:-

The composition of vapour phase in equilibrium with the solution is determined by the partial
pressures of the components.

If and are the mole fractions of the components 1 and 2 respectively in the vapour phase
then, using Dalton’s law of partial pressures:
 Example

Vapour pressure of chloroform (CHCl3) and dichloromethane (CH2Cl2) at 298 K are 200 mm Hg and 415 mm Hg
respectively. (i) Calculate the vapour pressure of the solution prepared by mixing 25.5 g of CHCl 3 and 40 g of CH2Cl2 at
298 K and, (ii) mole fractions of each component in vapour phase.
Solution (i), Molar mass of CHCl3 = 119.5 g /mol , Molar mass of CH2Cl2 = 85 g /mol
Moles of = 0.213 mol , Moles of CH Cl =
2 2

Total number of moles = 0.213+0.47 = 0.683 mol

(component 1 is and component 2 is CH2Cl2
= mm Hg

(ii) Using we can calculate the mole fraction of the components in gas phase (y)
First use p1 = .5 mm Hg
= + =+ =62.4+285.5=347.9 mm Hg
 Raoult’s Law as a special case of Henry’s Law
Raoult’s Law Henry’s Law

Liquid-Liquid Solutions Gas in a Liquid Solutions

partial vapour pressure of each the partial pressure of the gas in vapour
component of the solution is directly phase (p) is proportional to the mole
proportional to its mole fraction present fraction of the gas (x) in the solution
in solution

. p = KH x

• If we compare the equations for Raoult’s law and Henry’s law, it can be seen that the partial pressure of
the volatile component or gas is directly proportional to its mole fraction in solution.
• Only the proportionality constant KH differs from .
• Thus, Raoult’s law becomes a special case of Henry’s law in which KH becomes equal to .
 Vapour Pressure of Solutions of Solids in Liquids
• Liquids at a given temperature vapourise and under equilibrium conditions
the pressure exerted by the vapours of the liquid over the liquid phase is
called vapour pressure

• If a non-volatile solute is added to a solvent to give a solution , the vapour

pressure of the solution is only from the solvent alone.
• This vapour pressure of the solution at a given temperature is found to be
• In a binary solution, let us denote the lower than the vapour pressure of the pure solvent at the same
solvent by 1 and solute by 2. temperature.
• According to Raoult’s law
• In such solution the number of solvent molecules escaping from the
surface is reduced, thus, the vapour pressure is also reduced.
 Ideal Solutions:-
• The solutions which obey Raoult’s law over the entire range of concentration are known as ideal solutions
p1 = , = , = +

• The enthalpy of mixing of the pure components to form the solution is zero and the volume of mixing is also zero,
i.e.,
• It means that no heat is absorbed or evolved when the components are mixed. Also, the volume of solution would
be equal to the sum of volumes of the two components

• At molecular level, consider two components A and B, in pure components, the intermolecular attractive
interactions will be of types A-A and B-B, whereas in the binary solutions in addition to these two interactions, A-
B type of interactions will also be present.
• If the intermolecular attractive forces between the A-A and B-B are nearly equal to those between A-B, this leads to
the formation of ideal solution.
• Nearly ideal solutions are solution of n-hexane and n-heptane, bromoethane and chloroethane, benzene and
toluene.
 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.
• The vapour pressure of non-ideal solution is either higher or lower than that predicted by Raoult’s law .If it is
higher, the solution exhibits positive deviation and if it is lower, it exhibits negative deviation from Raoult’s law.

solution which exhibits positive deviation Solution which exhibits negative deviation
• Vapour pressure is higher than that predicted by • Vapour pressure is lower than that predicted by
Raoult’s law Raoult’s law
• p1 , , + • p1 , , +

• A-B type of interactions <A-A and B-B type • A-B type of interactions > A-A and B-B type
interactions interactions

e.g.Mixture of ethanol and acetone, mixture of e.g.mixture of phenol and aniline, mixture of
carbon disulphide and acetone chloroform and acetone
 Positive Deviation Negative Deviation

0
𝑝0
2
𝑝2

0 0
𝑝1 𝑝1
 Azeotropes-
• Binary mixtures having the same composition in liquid and vapour phase and boil at a constant temperature are
known as azeotropes.
• It is not possible to separate the components azeotropes by fractional distillation.
• There are two types of azeotropes called minimum boiling azeotrope and maximum boiling azeotrope.
• The solutions which show a large positive deviation from Raoult’s law form minimum boiling azeotrope at a
specific composition . For example, 95% by volume of ethanol in water
• The solutions that show large negative deviation from Raoult’s law form maximum boiling azeotrope at a
specific composition. E.g.68% nitric acid and 32% water by mass, with a boiling point of 393.5 K.
 Colligative Properties
Properties depend on the number of solute particles irrespective of their nature relative to the total number
of particles present in the solution are called colligative properties

These are:
(1) Relative lowering of vapour pressure of the solvent
(2) Depression of freezing point of the solvent
(3) Elevation of boiling point of the solvent and
(4) osmotic pressure of the solution.
 Relative Lowering of Vapour Pressure:-

• The vapour pressure of a solvent in solution containing non-volatile solute is less than that of the pure solvent.
• Relation between vapour pressure of the solution, mole fraction and vapour pressure of the solvent, i.e., p1 =
• The reduction or lowering in the vapour pressure of solvent () is given as:
we know

= relative lowering of vapour pressure

• Here the number of moles of solvent and solute respectively present in the solution.
• For dilute solutions < < , hence neglecting in the denominator we have

Here w1 and w2 are the masses and M1 and

M2 are the molar masses
of the solvent and solute respectively.
Elevation of Boiling Point:-

• Vapour pressure of a liquid increases with increase of temperature.

• A liquid boils at the temperature at which its vapour pressure is equal to the atmospheric pressure.
• Vapour pressure of the solvent decreases in the presence of non-volatile solute.

• Thus, the boiling point of a solution is always higher than that of

the boiling point of the pure solvent in which the solution is
prepared, this is referred as Elevation of Boiling point
• It depends on the number of solute molecules rather than their
nature

The increase in boiling point is known as elevation in boiling

point.
Elevation of Boiling Point:-

For dilute solutions the elevation of boiling point (DTb) is directly proportional to the molal concentration of
the solute in a solution. Thus
or
m=molality =Boiling Point Elevation Constant or Molal Elevation Constant (Ebullioscopic Constant).
The unit of is K kg if m=1 then
=mass of solute in g, =mass of solvent in g, = Molar mass of solute in g/mol
 Depression of Freezing Point

• At the freezing point of a substance, the solid phase is in

dynamic equilibrium with the liquid phase.
• Thus, the freezing point of a substance is the temperature at
which the vapour pressure of the substance in its liquid
phase is equal to its vapour pressure in the solid phase.
• A solution will freeze when its vapour pressure equals the
vapour pressure of the pure solid solvent.
• When a non-volatile solid is added to the solvent its vapour
pressure decreases and now it would become equal to that
of solid solvent at lower temperature. Thus, the freezing The decrease in freezing point is known as
point of the solvent decreases. depression in freezing point.
 Depression of Freezing Point
depression of freezing point (DTf) for dilute solution is directly proportional to molality, m of the solution. Thus
or
m=molality =Freezing Point Depression Constant or Molal Depression Constant or Cryoscopic Constant
The unit of is K kg if m=1 then
=mass of solute in g, =mass of solvent in g, = Molar mass of solute in g/mol

The values of and , which depend upon the nature of the solvent, can be ascertained from the following relations
 Osmosis and Osmotic Pressure
• Raw mangoes shrivel when pickled in brine (salt water);
• Wilted flowers revive when placed in fresh water,
• Raisins (Kishamish) swell in water
• blood cells collapse when suspended in saline water,
semipermeable membranes (SPM):Membranes having network of sub-
microscopic holes or pores ,from which only small solvent molecules, like
water, can pass but the passage of bigger molecules like solute is hindered
are known as semipermeable membranes (SPM).e.g. pig’s bladder or
parchment or cellophane.

Osmosis :-The flow of solvent molecules through semipermeable

membrane from pure solvent to the solution or from the lower concentrated
solution to the higher concentrated solution is called osmosis.
 Osmotic pressure of the solution:-

The flow of the solvent from its side to solution side across a
semipermeable membrane can be stopped if some extra pressure is
applied on the solution. This pressure that just stops the flow of
solvent is called osmotic pressure of the solution.

The osmotic pressure of a solution is the excess pressure that

must be applied to a solution to prevent osmosis Fig.: The excess pressure equal to the
osmotic pressure must be applied on
the solution side to prevent osmosis
Osmotic pressure is a colligative property as it depends on the
number of solute molecules and not on their identity.
 Osmotic pressure of the solution

Osmotic pressure is proportional to the molarity, C of the solution at a given temperature T. Thus:
p =CRT  = osmotic pressure, R= gas constant, T= temperature in K, C=Molarity of the solution
V is volume of a solution in litres containing moles of solute.
= mass of solute in g, = Molar mass of solute in g/mol

This method is widely used to determine molar masses of proteins, polymers and other macromolecules.
The osmotic pressure method has the advantage over other methods because:
1. Osmotic pressure is measured around the room temperature and
2. Molarity of the solution is used instead of molality.
3. As compared to other colligative properties, its magnitude is large even for very dilute solutions.
4. Biomolecules are generally not stable at higher temperatures and polymers have poor solubility.
• Two solutions having same osmotic pressure at a given temperature are called isotonic solutions.
• When such solutions are separated by semipermeable membrane no osmosis occurs between them.
• Two solutions having different osmotic pressure at a given temperature, the one with lower osmotic pressure is
called hypotonic solution and another one with higher osmotic pressure is called hypertonic solution
• For example, the osmotic pressure associated with the fluid inside the blood cell is equivalent to that of 0.9%
(mass/ volume) sodium chloride solution, called normal saline solution and it is safe to inject intravenously.
• On the other hand, if we place the cells in a solution containing more than 0.9% (mass/volume) sodium chloride,
water will flow out of the cells and they would shrink. Such a solution is called hypertonic.
• If the salt concentration is less than 0.9% (mass/volume), the solution is said to be hypotonic. In this case, water
will flow into the cells if placed in this solution and they would swell.
 Phenomena explained on the basis of osmosis:-
• A raw mango placed in concentrated salt solution loses water via osmosis and shrivel into pickle.
• Wilted flowers revive when placed in fresh water.
• A carrot that has become limp because of water loss into the atmosphere can be placed into the water
making it firm once again. Water will move into its cells through osmosis.
• When placed in water containing less than 0.9% (mass/ volume) salt, blood cells swell due to flow of water
in them by osmosis.
• People taking a lot of salt or salty food experience water retention in tissue cells and intercellular spaces
because of osmosis. The resulting puffiness or swelling is called edema.
• Water movement from soil into plant roots and subsequently into upper portion of the plant is partly due
to osmosis.
• The preservation of meat by salting and of fruits by adding sugar protects against bacterial action. Through
the process of osmosis, a bacterium on salted meat or candid fruit loses water, shrivels and dies.
Reverse Osmosis and Water Purification:-

• The direction of osmosis can be reversed if a pressure larger than the osmotic pressure is applied to the
solution side.
• Flow of the pure solvent out of the solution through the semi permeable membrane is called reverse
osmosis and is of great practical utility.
• Reverse osmosis is used in desalination of sea water

When pressure more than osmotic pressure is applied, pure

water is squeezed out of the sea water through the membrane.

SPM:-A workable porous membrane is a film of cellulose

acetate placed over a suitable support.
Cellulose acetate is permeable to water but impermeable to
impurities and ions present in sea water.
Numerical based on colligative properties
0
relative lowering of vapour pressure
𝑝1 − 𝑝1 𝑤2 × 𝑀 1
=𝑥 2 =
𝑝01 𝑀 2 × 𝑤1

𝐾 𝑏 × 𝑤2 × 1000 0
Elevation of Boiling Point ∆ 𝑇 𝑏 =𝐾 𝑏 𝑚= 𝑇 𝑏=𝑇 𝑏 + ∆ 𝑇 𝑏
𝑀 2 ×𝑤1

𝐾 𝑓 ×𝑤2 ×1000 0
Depression of Freezing Point ∆ 𝑇 𝑓 =𝐾 𝑓 𝑚= 𝑇 𝑓 =𝑇 𝑓 − ∆ 𝑇 𝑓
𝑀 2 ×𝑤 1

𝑤2 𝑅 𝑇
Osmotic pressure 𝜋=
𝑀2 𝑉
 Example (Based on relative lowering of vapour pressure)

• The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile, non-electrolyte solid
weighing 0.5 g when added to 39.0 g of benzene (molar mass 78 g/mol). Vapour pressure of the solution, then, is
0.845 bar. What is the molar mass of the solid substance?
Solution
Given

Therefore, M2 = 170
Example (Based on Elevation of Boiling Point) Calculating boiling point

• 18 g of glucose, C6H12O6, is dissolved in 1 kg of water in a saucepan. At what temperature will

water boil at 1.013 bar? Kb for water is 0.52 K kg .

Solution

Given :- K kg
We know

or
Boiling point of water=373.15 K =
Boiling point of solution=373.15+0.052=373.202 K =100+0.052=
 Example (Based on Elevation of Boiling Point) Calculating molar mass of solute

• The boiling point of benzene is 353.23 K. When 1.80 g of a non-volatile solute was dissolved in 90 g of
benzene, the boiling point is raised to 354.11 K. Calculate the molar mass of the solute. Kb for benzene is
2.53 K kg

Solution
Given :- K kg

Molar mass of solute=

Example (Based on Depression of Freezing Point) Calculating freezing point of solution

• 45 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate (a) the freezing point depression
and (b) the freezing point of the solution. K kg
Solution Given :-
We know

or
freezing point depression= or
Freezing point of water=273.15 K =
Freezing point of solution=273.15 - 2.25= 270.9 K =0 – 2.25 =
 Example (Based on Depression of Freezing Point) Calculating molar mass of solute

• 1.80 g of a non-electrolyte solute dissolved in 90 g of benzene lowered the freezing point of benzene by
0.40 K. The freezing point depression constant of benzene is 5.12 K kg . Find the molar mass of the solute.

Solution
Given :- K kg ,

Molar mass of solute=

 Example (Based on Osmotic pressure)

• 200 of an aqueous solution of a protein contains 1.26 g of the protein. The osmotic pressure of such
a solution at 300 K is found to be 2.57 × bar. Calculate the molar mass of the protein.

Solution

Given:  = 2.57 × bar, V = 200 = 0.200 litre

T = 300 K R = 0.083
 Abnormal Molar Masses:-

• Molar mass that is either lower or higher than the expected or normal value is called as abnormal molar mass.
• E.g. Normal molar mass of KCl is 74.5 g/mol, but if measured by using colligative properties it comes 37.25 g/mol.
Actually one mole of KCl dissociate to give one mole each of ions i.e. 2 moles of particles (assuming 100 %
dissociation). As we know colligative properties are directly proportional to number of particles .Then for KCl will be
twice the normal value. And Molar mass is inversely proportional to the colligative properties. Therefore, the molar
mass calculated on the basis of this will be half the expected value
• E.g. Molecules of ethanoic acid (acetic acid, Normal molar mass 60 g/mol) dimerise in benzene due to hydrogen
bonding. In this case the number of particles is reduced to half due to dimerization and for ethanoic acid will be half
of the normal value. . Therefore ,the molar mass calculated on the basis of this will be twice(120 g/mol) the expected
value.(Assume that all the molecules associate)
 van’t Hoff factor (i):-

In 1880 van’t Hoff introduced a factor i, known as the van’t Hoff factor, to account for the extent of dissociation or
association
• Here abnormal molar mass is the
experimentally determined molar
mass and
• Calculated colligative properties
are obtained by assuming that the
In case of association, < 1 non-volatile solute is neither
associated nor dissociated
for dissociation , > 1
If no association no dissociation =1
For example, the value of for aqueous KCl solution is 2 (assuming 100 % dissociation), while the value for ethanoic
acid in benzene is 0.5 (Assume that all the molecules associate).
Modified equations for colligative properties after Inclusion of van’t Hoff factor :

0
𝑝1 − 𝑝1 𝑤 2 × 𝑀1
Relative lowering of vapour pressure of solvent =𝑖 𝑥 2 =𝑖
𝑝01 𝑀 2 ×𝑤1

𝐾 𝑏 ×𝑤 2 ×1000
Elevation of Boiling point, ∆ 𝑇 𝑏 =𝑖 𝐾 𝑏 𝑚=𝑖
𝑀 2 × 𝑤1

𝐾 𝑓 ×𝑤 2 × 1000
Depression of Freezing point ∆ 𝑇 𝑓 =𝑖 𝐾 𝑓 𝑚=𝑖
𝑀 2 × 𝑤1

Osmotic pressure of solution 𝑤2 𝑅 𝑇

𝜋 =𝑖
𝑀2 𝑉
Degree of association (α) and van’t Hoff factor ):-

Consider one association reaction at equilibrium

2 C6H5COOH (C6H5COOH)2
Initial no. of moles 1 0 if α is the degree of association n=2
At equilibrium 1
total number of moles of particles at equilibrium = 1
Degree of Dissociation (α) and van’t Hoff factor ):-

Consider dissociation reaction at equilibrium

Initial no. of moles 1 0 if α is the degree of dissociation

At equilibrium 1
total number of moles of particles at equilibrium = 1
Example:-2 g of benzoic acid (C6H5COOH) dissolved in 25 g of benzene shows a depression in freezing
point equal to 1.62 K. Molal depression constant for benzene is 4.9 K kg/mol. What is the percentage
association of acid if it forms dimer in solution?

Solution:-We have to find out degree of association (α) , for this first find out van’t Hoff factor )

Given:- = 4.9 K kg/mol and =122 g/mol put the values

it forms dimer i.e. n=2

degree of association =0.992 X100=99.2 %

Example:- 0.6 mL of acetic acid , having density 1.06 g/mL, is dissolved in 1 litre of water. The depression in
freezing point observed for this strength of acid was 0.0205°C. Calculate the van’t Hoff factor and the
dissociation constant of acid. = 1.86 K kg /mol
Solution:- First find out number of moles of acetic acid, for this find out mass of acetic acid =volume x density
mass of acetic acid=0.6 X 1.06= 0.636 g and molar mass of acetic acid = 60 g/ mol

( As density of water = 1 g/

As n=2,
Dissociation constant