UNIT 1 1

SOLUTIONS
Solutions:
• A solution is a homogenous mixture of two or more chemically non-reacting substances
whose composition can be varied continuously up to the limit of solubility.
• Solvent: the component in the solution that is present in larger quantity
(Substance/component in which dissolution take place)
• Solute: One or more components present in solution other than solvent (substance that
dissolves).

Characteristics of Solution:
I. A solution is a homogenous mixture of two or more substances.
II. The particles of solute in a solution cannot be seen by naked eyes.
III. A solution does not allow beam of light to scatter.
IV. A solution is stable.
V. A solute cannot be separated from solution by normal mechanical means.
VI. A solution has only one phase determined by phase of solvent.

Binary Solution: the solution consisting of two components.

Types of Binary Solutions

Type of solution Solute Solvent Common Examples
Gas Gas Mixture of Oxygen and Nitrogen gas
Gaseous Solution Liquid Gas Chloroform mixed with Nitrogen gas
Solid Gas Camphor in Nitrogen gas
Gas Liquid Oxygen dissolved in water
Liquid Solution Liquid Liquid Ethanol dissolved in water
Solid Liquid Glucose dissolved in water
Gas Solid Solution of hydrogen in palladium
Solid Solution Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold

Concentration of Solution: is deKined as amount of solute dissolved in a known quantity of

solvent.

Qualitative expression of concentration

Dilute Solution: Relatively very small quantity of solute
Concentrated solution: relatively very large quantity of solute

Quantitative expression of concentration:

1. Mass percentage (w / w): the number of parts by mass of a component (solute) per
hundred parts by mass of solution.

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑀𝑎𝑠𝑠 % 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 = × 100
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
• x% by mass means 100g of solution contain x g of solute and (100 – x) g of solvent.
Example:
• 10% glucose in water means 10g of glucose is dissolved in 90g of water resulting 100g of
solution.
 UNIT 1 2
SOLUTIONS
• Commercial bleaching solution contain 3.62 mass percentage of sodium hypochlorite in
water
2. Volume percentage (V / V): number of parts by volume of solute per 100 parts by volume
of solution.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

𝑉𝑜𝑙𝑢𝑚𝑒 % 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 = × 100
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Example:
• 10% ethanol: 10ml of ethanol dissolved in water such that total volume of the solution is
100ml.
• 35% (v/v) ethylene glycol, antifreeze, is used in cars for cooling the engine.
3. Mass volume percentage (w / V): Mass of solute dissolved in 100ml of the solution

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

𝑚𝑎𝑠𝑠/𝑉𝑜𝑙𝑢𝑚𝑒 % = × 100
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

4. Parts per million (ppm): Part of solute present per million parts of the solution.

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡

𝑝𝑝𝑚 = × 10!
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Example:
• A liter of sea water (1030g) contains about 6 × 10"# g of dissolved oxygen, such a small
quantity expressed as 5.8 g per 10! g (5.8ppm) of sea water.
• The concentration of pollutants in in water and atmosphere often expressed in terms of
µg𝑚𝑙 "$ or ppm.

5. Mole fraction: mole fraction of any component in a solution is the ratio of the number of
moles of that component to the total number of moles of all component present in the
solution. Denoted by “x”

%&'()* ,- ',.)/ ,- 01) 2,'3,4)40

𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝜒 = 5,06. 4&'()* ,- ',.)/ ,- 6.. 2,'3,4)40/ 74 01) /,.&07,4

• In a binary mixture of A and B, 𝑛8 and, 𝑛9 are number of moles of A and B,

𝒏𝑨 𝒏𝑩
𝑴𝒐𝒍𝒆 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 𝒐𝒇 𝑨, 𝒙𝑨 = 𝒏𝑨 < 𝒏𝑩
𝑴𝒐𝒍𝒆 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 𝒐𝒇 𝑨, 𝒙𝑩 = 𝒏𝑨 < 𝒏𝑩

• For a solution containing “i ” number of components, we have

𝒏𝒊 𝒏𝒊
𝒙𝒊 = =
𝒏𝟏 + 𝒏𝟐 + … … . . + 𝒏𝒊 ∑ 𝒏𝒊

• In a solution sum of all the mole fraction is unity,

𝑥$ + 𝑥A + … … … … . . +𝑥7 = 1
 UNIT 1 3
SOLUTIONS
6. Molarity (M): number of moles of solute dissolved in 1 liter (1 cubic decimeter) of
solution.
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠 × 1000 𝑚𝑙 𝐿"$
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦, 𝑀 = =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑒𝑟 𝑚𝑜𝑙. 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑛. 𝑖𝑛 𝑚𝑙

For example, 0.25 mol L-1 (0.25M) solution of NaOH means that 0.25 mol of NaOH has been
dissolved in one liter (1 dm3)

7. Molality (m): the number of moles of solute per kilogram (kg) of the solvent
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠 × 1000𝑔𝑟𝑎𝑚𝑠 𝐾𝑔"$
𝑀𝑜𝑙𝑎𝑙𝑖𝑡𝑦, 𝑚 = =
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑘𝑔 𝑚𝑜𝑙. 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 × 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠

For example, 1.00mol kg-1 (0r 1.00m) solution of KCl means that 1 mol (74.5g) of KCl is dissolved
in 1 kg of water.

8. Normality (N): Number of gram equivalents of solute present in one liter of the solution.

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑟𝑎𝑚 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦, 𝑁 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝐿𝑖𝑡𝑟𝑒
𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠 × 1000 𝑚𝑙 𝐿"$
=
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 × 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑛. 𝑖𝑛 𝑚𝑙

9. Strength of solution: Amount of substance in grams per litre. Or amount of substance in

gram moles liter-1.

𝑆𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑠𝑜𝑙𝑛. = 𝑁𝑜𝑟𝑎𝑚𝑎𝑙𝑖𝑡𝑦 × 𝐸𝑞𝑛𝑡. 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 = 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 × 𝑀𝑜𝑙. 𝑊𝑡. 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

Molality and mole fraction are independent of temperature, because they depend solely on
mass. In contrast, molarity, normality, and strength (concentration) depend on both mass
and volume and therefore can change with temperature.

Solubility:
• Solubility of a substance is its maximum amount of that can be dissolved in a speciKic
amount of solvent at a speciKic temperature.
• Depends on Nature of solute, solvent, temperature and pressure.

Solubility of solid in liquid: “Like dissolves like”

• Polar solutes dissolve in polar solvent
E.g.: NaCl and Sugar Dissolve in water
• Non-polar solutes dissolve in non-polar solvents
E.g.: Naphthalene and anthracene dissolve in benzene

Dissolution: when solid solute added to the solvent, some solute dissolves and its concentration
increases in solution.

Crystallization: some solute particles in solution collide with solid solute particles and get
separated out of the solution.
 UNIT 1 4
SOLUTIONS

Condition at which the number solute particle going into the solution will be equal to solute
particle separating out and state of dynamic equilibrium is reached

Solute + Solvent ⇌ Solution

At this stage the concentration of solute remains constant under given condition of temperature
and pressure. Such a solution in which no more solute can be dissolved at the same temperature
and pressure, is called saturated solution.

An unsaturated solution in which more solutes can be dissolved at the same temperature.

(Activity: prepare a saturated solution of NaCl)

Effect of temperature on the solubility of solid in a liquid (explained by Le Chatelier Principle)

If in a nearly saturated solution,

The dissolution process is endothermic (Dsol H > 0), the solubility should increase in rise in
temperature.

(Activity: Show the dissolution of copper sulphate in 100ml water with and without heating)

The dissolution process is exothermic (Dsol H < 0), the solubility should decrease in rise
temperature.

(Activity: Show the dissolution of NaOH in in 100ml water by cooling).

Effect of pressure on the solubility of solid in a liquid

Pressure does not have significant effect on the solubility of solid in liquid, because solids and liquids
are highly incompressible and practically unaffected by change in pressure.

Solubility of a gas in a liquid

Depends on following factors:
• Nature of the gas and liquid: Solubility of substance depends on polarity of solute and
solvent. E.g., Bromine soluble in CCl4 or CS2 than in water.
• Effect of temperature:
o Solubility of gas decreases with rise in temperature. (Obeys Le Chatelier principle)
o Dissolution of gases is exothermic, or heat is evolved.
o When dissolution is exothermic solubility decreases with increase of temperature.
• Effect of Pressure: Solubility of gases in liquid increases with increase of pressure.
o Rise in pressure increases the number of particles per unit volume over the solution
and also the rate at which the gaseous particles are striking the surface of solution
to enter it.
o The solubility of the gas will increase until a new equilibrium is reached resulting in
an increase in pressure of gas above the solution and thus its solubility increases.
Henry’s Law:
• The solubility of agas in a liquid is directly proportional to the partial pressure of the gas
present above the surface of the liquid or solution.
 UNIT 1 5
SOLUTIONS
• The partial pressure of the gas in vapor phase (p) is proportional to the mole fraction of
the gas (X)in the solution.
p = KH x
• KH, is the Henry’s law constant
• Different gases having different values of KH at same temperature.
• Higher the value of KH at a given pressure, the lower is the solubility of the gas in the
liquid.
• Value of KH increases with increase of temperature and the solubility decreases.
• Aquatic species are more comfortable in cold water due to higher dissolution of oxygen in
cold.

Examples:
• To increase the solubility of CO2 in the soft drinks and soda water, the bottle is sealed
under high pressure.
• Air pressure increases on going deep down under water, and the solubility of air we
breathe, in the blood increases. The air we breathe contain 78% Nitrogen, 21% Oxygen,
and rest contain carbon dioxide and other gases. But the exhaled air contains same
quantity of nitrogen and other gases, with 13 – 16% of oxygen and 4% of carbon dioxide.
The air tank of the scuba divers Killed with normal atmospheric air and the solubility of
atmospheric gases increases while going deep down under water. While the divers come
towards the surface, the pressure gradually decreases, the dissolved gases start releasing.
This leads to the formation of bubbles in blood. This blocks capillaries and create a
medical condition called “bends”, which are painful and dangerous to life. To avoid bends
and toxic effect of high concentration of nitrogen in blood, the air tanks are Killed with air
diluted with helium (11.7% He, 56.2% N2, and 32.1% O2).
• At high altitude the partial pressure of oxygen is less than that at the ground level. This
leads to the low concentration of oxygen in the blood and tissues.

Liquid in liquid solution: “Like dissolves like”

• Polar solutes miscible in polar solvent
E.g.: alcohol in water
• Non-polar solutes miscible in non-polar solvents
E.g.: toluene miscible in benzene

Miscibility of two liquids depends upon following factors:

• Liquids which are chemically similar are miscible in all proportion.
• Hydrogen bonding or dipole-dipole interaction between molecules of two liquids.
Molecular size of liquids which are miscible are approximately the same size.
 UNIT 1 6
SOLUTIONS

Vapor pressure: When a liquid is in equilibrium with vapors, the pressure exerted by the vapor
molecule on the walls of the container or on the surface of the liquid.

Effect of temperature on Vapor pressure:

Liquid ⇌ Vapour, ∆𝐻 > 0
• Vapor pressure increases with increase of temperature (Follows Le Chatelier principle).

Effect of Nature of Liquid on vapor pressure:

• Liquids with weak intermolecular interactions form vapor phase easily and have high vapor
pressure.
• Liquids which have strong molecular interaction do not vaporize easily and have low vapor
pressure.

Raoult’s law: “for any solution the partial vapour pressure of each volatile component in the
solution is directly proportional to its mole fraction”.

For a solution of volatile liquids, the partial vapor pressure of each component of the solution is
directly proportional to its mole fraction present in solution.
Thus, for component 1,
𝑝$ ∝ 𝑥$ or 𝑝$ = 𝐾 𝑥$

For pure liquid 𝑥$ = 1 and 𝐾 = 𝑝$, 𝑝$, is the vapor pressure of the pure component 1 at
same temperature.

Therefore, for component 1

𝑝$ = 𝑝$, 𝑥$

Similarly, for component 2

𝑝A = 𝑝A, 𝑥A
𝑝A, is the vapor pressure of the pure component 2 at same temperature.

Dalton’s law of partial pressure: The total pressure (𝑝5,06. ) over the solution phase in the
container will be the sum of the partial pressure of the components of the solution.
𝑝!"#$% = 𝑝& + 𝑝'

𝑝5,06. = 𝑝$, 𝑥$ + 𝑝A, 𝑥A = (1 - 𝑥A ) 𝑝$, + 𝑝A, 𝑥A = 𝑝$, + (𝑝A, − 𝑝$, ) 𝑥A

𝒑𝑻𝒐𝒕𝒂𝒍 = 𝒑𝒐𝟏 + (𝒑𝒐𝟐 − 𝒑𝒐𝟏 )𝒙𝟐

• Total vapor pressure over the solution can be related to the mole fraction of any one of the
components. ( 𝑝$ ∝ 𝑥$ or 𝑝A ∝ 𝑥A )
• Total vapor pressure over the solution varies linearly with the mole fraction of component
2. ( 𝑝5,06. = 𝑝$, + (𝑝A, − 𝑝$, ) 𝑥A )
• Depending on the vapor pressures of pure components 1 and 2, total pressure over the
solution decreases or increases with the increase of the mole fraction of component 1.
 UNIT 1 7
SOLUTIONS
A plot for Vapour pressures, 𝑝$ & 𝑝A v/s mole fractions 𝑥$ & 𝑥A gives a linear plot.

• When 𝑝5,06. = 𝑝A, the total vapor pressure over the solution is equal to the partial vapour
pressure of pure component 2. And same as when 𝑝5,06. = 𝑝$, .
• The maximum value of 𝑝5,06. is 𝑝A, and the minimum value is 𝑝$, from the graph. And we
can assume that component 2 is more volatile than component 1, 𝑝A, > 𝑝$, .

I. Raoult’s law is applicable only if two components are completely miscible and forms
homogenous solution.
II. Solutions that obey Raoult’s law are called ideal solution.
III. In case of ideal solutions, the vapor phase is richer in the more volatile component, i.e., the
one having relatively greater vapor pressure.
IV. Depending on the vapor pressure of pure components, the total vapor pressure over the
solution may increase or decrease with mole fraction of a component.

The composition of vapour phase which is in equilibrium with the solution:

• 𝑦$ & 𝑦A the mole fractions of component 1 and 2 at vapour phase, then the Dalton’s law can
be explained as,
𝑝$ = 𝑦$ 𝑝𝑇𝑜𝑡𝑎𝑙
𝑝A = 𝑦A 𝑝𝑇𝑜𝑡𝑎𝑙
In general,
𝑝7 = 𝑦7 𝑝𝑇𝑜𝑡𝑎𝑙

𝒑𝟏
𝒚𝟏 =
𝒑𝑻𝒐𝒕𝒂𝒍
𝒑𝟐
𝒚𝟐 =
𝒑𝑻𝒐𝒕𝒂𝒍

Vapor pressure of Solid in Liquid solution:

If a non-volatile solute is added to a solvent to give a solution,
• The vapour pressure of the solution solely from the solvent alone.
• The vapour pressure of the solution at a given temperature is found to be lower than the
vapour pressure of the pure solvent at the same temperature.
• In the solution the surface has both volatile solvent and non-volatile solute; there by
fraction of the surface covered by the solvent molecule gets reduced.
 UNIT 1 8
SOLUTIONS
• The number of solvent molecules escaping from the surface is correspondingly reduced,
thus the vapour pressure is also reduced.
• The decrease in the vapour pressure of solvent depends on the quantity of non-volatile
solute present in the solution, irrespective of its nature.

Thus, according to Raoult’s law, “At a given temperature, the vapor pressure of a solution
containing non-volatile solute is directly proportional to the mole fraction of the solvent”.
𝑝/,.&07,4 ∝ 𝑥/,.B)40
,
𝑝/,.&07,4 = 𝑝/,.B)40 𝑥/,.B)40
,
𝑝/,.B)40 = Vapor pressure of pure solvent at that temperature.

For a binary solution a solute 2 is added to solvent 1 with vapor pressure 𝑝$ and mole fraction 𝑥$ .
𝑝$, is the vapour pressure of solvent at its pure state. Then, according to Raoult’s law,

𝑝$ ∝ 𝑥$
𝑝$ = 𝑝$, 𝑥$
For solid in liquid solution the plot for the vapor pressure v/s mole fraction of solvent is linear

Liquid in liquid solutions can be classiKied into Ideal and Non-ideal solutions.

1. Ideal Solutions:
• The solutions which obey Raoult’s law over the entire range of concentration.
• The enthalpy of mixing of pure components to form solutions is zero. i.e., ∆𝒎𝒊𝒙 𝑯 = 𝟎
• No heat absorbed or evolved when the components are mixed.
• The volume of mixing is also zero. i.e., ∆𝒎𝒊𝒙 𝑽 = 𝟎
• The volume of solution would be equal to the sum of the volumes of two components. Thus
if two liquids are mixed in any proportion to give an ideal solution, there is no change in
volume.

For example: a binary solution of two component A and B, if the intermolecular interaction A-B in
solution is equal to the interaction between A-A and B-B, leads to the formation of ideal solution.
e.g.: solution of n-hexane and n-heptane, bromoethane and chloroethane, benzene and toluene
show nearly ideal behavior.
Other examples: ethyl bromide + ethyl iodide, CCl4 + SiCl4, n-butyl chloride + n-butyl bromide
 UNIT 1 9
SOLUTIONS
2. Non-ideal Solutions:
• Solutions does not obey Raolut’s law over the entire range of concentration.
• The vapour pressure of the solution is either higher or lower than that predicted by
Raoult’s law.

𝑝$ ≠ 𝑝$, 𝑥$ and 𝑝A ≠ 𝑝A, 𝑥A

i. The solution exhibits positive deviation: If the vapour pressure of the solution is higher
than that predicted by Raoult’s law, i.e. A-B interaction is weaker than A-A and B-B
interactions. This will increase the vapour pressure of the solution therefore A and B escapes
easily.
• Endothermic dissolution, ∆𝒎𝒊𝒙 𝑯 > 𝟎
• Volume increases on mixing, ∆𝒎𝒊𝒙 𝑽 > 𝟎

𝑝$ > 𝑝$, 𝑥$ and 𝑝A > 𝑝A, 𝑥A therefore, 𝑝$ + 𝑝A > 𝑝$, 𝑥$ + 𝑝A, 𝑥A

Example: mixture of ethanol and acetone. In pure ethanol molecules are hydrogen bonded. On
adding acetone, the acetone gets in between ethanol and break some hydrogen bonds between
ethanol molecule. Due to weakening of the interaction, solution shows positive deviation.
Other examples: water + methanol, cyclohexane + ethanol, CCl4 + Toluene.

ii. The solution exhibits negative deviation: If the vapour pressure of of the solution is lower
than that predicted by Raoult’s law. i.e., the A-A and B-B interactions are weaker than A-B
and leads to decrease in vapour pressure.
• Exothermic dissolution, ∆𝒎𝒊𝒙 𝑯 < 𝟎
• Volume decreases on mixing, ∆𝒎𝒊𝒙 𝑽 < 𝟎

𝑝$ < 𝑝$, 𝑥$ and 𝑝A < 𝑝A, 𝑥A therefore, 𝑝$ + 𝑝A < 𝑝$, 𝑥$ + 𝑝A, 𝑥A

Example:
1. mixture of phenol and aniline. The intermolecular hydrogen bonding between phenolic proton
and lone pair nitrogen in aniline is stronger than the intermolecular hydrogen bonding in similar
molecules (phenol and aniline).
2. chloroform and acetone, Methanol + Acetic acid, water + HNO3, Acetone + Chloroform.
 UNIT 1 10
SOLUTIONS
Azeotropes or Azeotropic mixtures:
• Binary mixtures having the same composition in liquid and vapour phase and boil at
constant temperature.
• Not possible separate the components by fractional distillation.
• Minimum boiling Azeotrope: Solution which show a large positive deviation from
Raoult’s law at a speciKic composition.
o Example: Ethanol - water mixture (obtained by fermentation of sugars) on
fractional distillation gives a solution containing approximately 95% by volume of
ethanol. The liquid and vapour have the same composition, and no further
separation occurs.

• Maximum boiling Azeotrope: Solutions that show large negative deviation from Raoult’s
law at a speciKic composition.
o Example: Nitric acid and water, have approximate composition, 68% nitric acid and
32% water by mass, with boiling point 393.5K.

Colligative Properties:
• Properties connected with decrease of vapour pressure.
o E.g., vapour pressure of solution decreases when a non-volatile solute added to a
volatile solvent.
• Properties depends on the number of solute particles irrespective of the nature relative to
the total number of particles present in the solution.

1. Relative lowering of Vapour pressure:

• Vapour pressure of the solution is less than that of the pure solvent
• Lowering of vapour pressure depends only on the concentration of the solute particle and
independent of their identity.
𝑝$ = 𝑝$, 𝑥$
• The reduction in vapour pressure of the solvent (∆𝑝$ )

∆𝑝$ = 𝑝$, − 𝑝$ = 𝑝$, − 𝑝$, 𝑥$ = 𝑝$, (1 − 𝑥$ )

∆𝒑𝟏 = 𝒑𝒐𝟏 𝒙𝟐

∆"! "!" $ "! &#

= 𝑥# = =
"!" "!" &! ' &#

(n2: Number of moles of solute and n1: number of moles of solvent, and n2 << n1)

𝒑𝒐𝟏 " 𝒑𝟏 𝒏𝟐 𝒘𝟐 × 𝑴𝟏 𝒎 × 𝑴𝟏
= = =
𝒑𝒐𝟏 𝒏𝟏 𝑴𝟐 × 𝒘𝟏 𝟏𝟎𝟎𝟎
 UNIT 1 11
SOLUTIONS
2. Elevation of Boiling point:
• Presence of non-volatile solute in the solution decreases the vapour pressure, there by
increases the boiling point to achieve the vapour pressure pure solvent.

E.g., the vapour pressure of an aqueous solution of sucrose is less than 1.013bar at
373.15K. In order to make the solution boil, its vapour pressure must be increased to
1.013bar by raising the temperature. Thus, the boiling point of the solution always higher
than that of the pure solvent.

• 𝑇(F the boiling point of pure solvent, and 𝑇( the boiling point of the solution when non-
volatile solute dissolved. Thus,

𝑻𝒉𝒆 𝑬𝒍𝒆𝒗𝒂𝒕𝒊𝒐𝒏 𝒊𝒏 𝑩𝒐𝒊𝒍𝒊𝒏𝒈 𝒑𝒐𝒊𝒏𝒕 ∆𝑻𝒃 = 𝑻𝒃 − 𝑻𝟎𝒃

• Experiments show that for dilute solutions the elevation in B.P ∆𝑻𝒃 is directly proportional
to the molal concentration (Molality in Kg mol -1) of the solute in the solution.
∆𝑻𝒃 ∝ 𝒎

∆𝑻𝒃 = 𝑲𝒃 𝒎

• 𝑲𝒃 is called the Boiling point Elevation constant or Molal Elevation constant

(Ebullioscopic Constant). The unit of 𝑲𝒃 is K Kg mol-1

𝒘𝟐 / 𝑴𝟐 𝟏𝟎𝟎𝟎 × 𝒘𝟐
𝒎= 𝒘𝟏 /𝟏𝟎𝟎𝟎
= 𝑴𝟐 × 𝒘𝟏

𝟏𝟎𝟎𝟎 × 𝒘𝟐
∆𝑻𝒃 = 𝑲𝒃
𝑴𝟐 × 𝒘𝟏

𝟏𝟎𝟎𝟎 × 𝒘𝟐
𝑴𝟐 = 𝑲𝒃
∆𝑻𝒃 × 𝒘𝟏

• 𝑴𝟐 is the molar mass of the solute in gram mol-1, 𝒘𝟏 is the weight of solvent in grams 𝒘𝟐
is the weight of solute in grams.
 UNIT 1 12
SOLUTIONS
3. Depression in Freezing point:
• Freezing point: the temperature at which the vapour pressure of the substance in liquid
phase is equal to its vapour pressure in the solid phase.
• A solution will freeze when its vapour pressure equal to the vapour pressure of pure
solvent.

• According to Raoult’s law when a non-volatile solute added to the solvent its vapour
pressure decreases and the solution will freeze at lower temperature than the pure solvent.
• 𝑇-F be the freezing point of pure solvent, and 𝑇- the freezing point of the solution when
non-volatile solute dissolved. Thus,

𝑻𝒉𝒆 𝑫𝒆𝒑𝒓𝒆𝒔𝒔𝒊𝒐𝒏 𝒊𝒏 𝑭𝒓𝒆𝒆𝒛𝒊𝒏𝒈 𝒑𝒐𝒊𝒏𝒕 ∆𝑻𝒇 = 𝑻𝟎𝒇 − 𝑻𝒇

• The depression in freezing point is directly proportional to the molality

∆𝑻𝒇 ∝ 𝒎

∆𝑻𝒇 = 𝑲𝒇 𝒎
• 𝑲𝒇 is known as the Freezing point depression constant or molal Depression Constant
or Cryoscopic Constant. The unit of 𝑲𝒇 is K Kg mol-1

𝟏𝟎𝟎𝟎 × 𝒘𝟐
𝒎=
𝑴𝟐 × 𝒘𝟏

𝟏𝟎𝟎𝟎 × 𝒘𝟐
∆𝑻𝒇 = 𝑲𝒇
𝑴𝟐 × 𝒘𝟏

𝟏𝟎𝟎𝟎 × 𝒘𝟐
𝑴𝟐 = 𝑲𝒇
∆𝑻𝒇 × 𝒘𝟏

• The values of 𝑲𝒇 and 𝑲𝒃 depend upon the nature of solvent.

𝑹 × 𝑴𝟏 × 𝑻𝟐𝒇
𝑲𝒇 =
𝟏𝟎𝟎𝟎 × ∆𝒇𝒖𝒔 𝑯
 UNIT 1 13
SOLUTIONS
𝑹 × 𝑴𝟏 × 𝑻𝟐𝒃
𝑲𝒃 =
𝟏𝟎𝟎𝟎 × ∆𝒗𝒂𝒑 𝑯

• R is the gas constant, 𝑴𝟏 molar mass of solvent, 𝑻𝒇 and 𝑻𝒃 denote the freezing point and
boiling point of solvent, ∆𝒇𝒖𝒔 𝑯 and ∆𝒗𝒂𝒑 𝑯 represent enthalpies of fusion and vaporization
of solvent.

Osmosis:
• The process of Klow of pure solvent molecule to the solution through a semi permeable
membrane. (Spontaneous Klow of solvent molecule from lower concentration to the
higher concentration of soln.).
• The Klow will continue till the equilibrium is attained.

Osmotic Pressure ( P ):
• The pressure that just stops the Klow of solvent to the soln.
• Osmotic pressure is the excess pressure that must be applied to a solution to prevent
(osmosis) passage of solvent molecule into solution through a semipermeable membrane.
• Or the hydrostatic pressure built up on the solution which just stop the osmosis.
• Osmotic pressure depends on concentration of soln. or the number of solute molecules.
• Osmotic pressure P is proportional to the molarity C of the solution at a given temperature
T.
P=CRT (R is the gas constant = 0.083 L bar mol-1 K-1)

𝑛A
Π= 𝑅𝑇
𝑉
𝑤A 𝑅𝑇
ΠV=
𝑀A

𝒘𝟐 𝑹𝑻
𝑴𝟐 =
𝚷𝐕

Osmotic pressure of mixture of two solution:

• When two solutions of the same substance of volumes V$ and VA having osmotic pressure
Π$ and ΠA are mixed, the resultant osmotic pressure, ΠO can be calculated as,

Π$ V$ + ΠA VA = ΠO (V$ + VA )

• When n$ and nA are the number of moles of two different solutes present in volume V$ and
VA then the osmotic pressure of the mixture is given by

:# ;! :$ ;! (:# > :$ );!

Π = Π$ + ΠA =
(=# >=$ )
+ (=# >=$ )
= (=# >=$ )

• Isotonic Solutions: Two solutions having same osmotic pressure at a given temperature.
Π$ = ΠA
C$ 𝑅𝑇 = CA 𝑅𝑇
C$ = CA
 UNIT 1 14
SOLUTIONS
o When isotonic solutions are separated by semipermeable membrane no osmosis
occur between them
• Hypertonic solution: Two solutions in which one solution having higher concentration. Or
one solution having higher osmotic pressure than the other.
• Hypotonic Solution: Two solutions in which one solution having lower concentration than
the other. Or a solution having lower osmotic pressure relative to some other solutions

Example: the osmotic pressure associated with the Kluid inside the blood cell is equivalent to that
of 0.9% (mass/volume) NaCl solution, called normal saline solution and it is safe to inject
intravenously. If we place the cell in a solution containing more than 0.9% mass/volume NaCl,
water will Klow out of the cell and they would shrink. Such solution is hypertonic. If the NaCl
concentration is less than 0.9% mass/volume, the solution is hypotonic. In this case, water will
Klow into the cell if placed in this solution and they would swell.

Reverse Osmosis:
• If a pressure larger than the osmotic pressure applied to the solution, the pure solvent
Klows out of the solution through semi permeable membrane.

Example: Desalination of sea water: a workable porous membrane made up of cellulose

acetate, which is permeable to water but impermeable to impurities and ions present in sea
water.

• Abnormal Molar masses: The difference in the observed and calculated molar masses of a
solute is due to the association or dissociation of the solute molecules in solution.
• Molar mass that is either lower or higher than the expected or normal value is called
abnormal molar mass.

• Association of solute particle: the formation of larger particle or molecule by the union of
two or more molecules.
𝑛𝑋 → (𝑋)4
o As a result, total number of molecules in solution become less than initially
dissolved in the solution and colligative property will have lower value.
o As the molar mass is inversely proportional to the colligative property, the molar
mass of solute will be greater than that of theoretical value.
o Example: the molar mass of acetic acid ion benzene, as determined from freezing
point depression, is 118 instead of 60. Molecules of acetic acid exist as dimers
(CH3COOH)2 when dissolved in benzene.

• Dissociation of solute molecule: More numbers of particle in solution due to ionization

𝐴𝐵 → 𝐴< + 𝐵"
o Dissociation results in an increase in the total number of particles, and therefore the
value of colligative properties of such solutions will be higher.
o Molecular mass will be less than the theoretical value.
o In a solution in which when there is dissociation of solute into ions (e.g.: 𝐾𝐶𝑙 ⇌
𝐾 < + 𝐶𝑙 " ), the experimentally determined molar mass is always lower than the
true value.

• Van’t Hoff introduced van’t Hoff facor to account for the extend of dissociation or
association.
 UNIT 1 15
SOLUTIONS

𝑁𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦

𝑖= =
𝐴𝑏𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦

𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 𝑜𝑟 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

𝑖=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 𝑜𝑟 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

Applying van’t Hoff factor on colligative properties.

𝒑𝟎𝟏 $ 𝒑𝟏 𝒏𝟐
I. Relative lowering of vapour pressure =𝒊
𝒑𝟎𝟏 𝒏𝟏

II. Elevation in Boiling point ∆𝑻𝒃 = 𝒊 𝑲𝒃 𝒎

III. Depression in Freezing point ∆𝑻𝒇 = 𝒊 𝑲𝒇 𝒎

𝒏𝟐 𝑹 𝑻
IV. Osmotic Pressure of Solution 𝚷 =𝒊
𝑽

Van’t Hoff’s factor and degree of dissociation:

• The fraction of total number of molecules which dissociates in solution into simple ions or
molecules is called degree of dissociation.
• Van’t Hoff’s Factor for dissociation of molecules

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

𝑖=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑏𝑒𝑓𝑜𝑟𝑒 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
• Calculation of i
Let solute be AxBy type

𝐴P 𝐵Q → 𝑥𝐴 Q< + 𝑦𝐵 P"
Initial no. of moles 1 0 0
After dissociation 1-a xa ya

Total number of solute particles = (1 - a) + xa + ya = 1 - a + a(x+y)

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

𝑖=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑏𝑒𝑓𝑜𝑟𝑒 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

𝟏 − a + a(𝒙 + 𝒚)
𝑽𝒂𝒏′𝒕 𝑯𝒐𝒇𝒇′𝒔 𝑭𝒂𝒄𝒕𝒐𝒓, 𝒊 = = 𝟏 − a + a(𝒙 + 𝒚)
𝟏

x + y = n, then
𝟏 − a + 𝒏a
𝑽𝒂𝒏′𝒕 𝑯𝒐𝒇𝒇′𝒔 𝑭𝒂𝒄𝒕𝒐𝒓, 𝒊 = = 𝟏 + 𝒏a − a = 𝟏 + a (𝒏 − 𝟏)
𝟏

𝑽𝒂𝒏′𝒕 𝑯𝒐𝒇𝒇′𝒔 𝑭𝒂𝒄𝒕𝒐𝒓, 𝒊 = 𝟏 + a (𝒏 − 𝟏)

 UNIT 1 16
SOLUTIONS
𝒊 − 𝟏
𝒅𝒆𝒈𝒓𝒆𝒆 𝒐𝒇 𝒅𝒊𝒔𝒔𝒐𝒄𝒊𝒂𝒕𝒊𝒐𝒏, a =
𝒏− 𝟏
Example:
• 𝑲𝟒 [𝑭𝒆(𝑪𝑵)𝟔 ] → 𝟒𝑲< + [𝑭𝒆(𝑪𝑵)𝟔 ]" , if a = 50%, Find out vant hoff’s factor i.
Ans: 𝑖 = 𝟏 − a + a(𝒙 + 𝒚) , x = 4, y = 1
𝑖 = 𝟏 − 𝟎. 𝟓 + 𝟎. 𝟓(𝟒 + 𝟏) = 𝟎. 𝟓 + 𝟐. 𝟓 = 𝟑

Number of
particles Abnormal
Solute type Ionization Van’t Hoff factor (i)
in soln. molecular mass
(n)
Non-electrolyte 1 1 M normal
Binary AB type
𝐴𝐵 ⇋ 𝐴& + 𝐵' M normal
NaCl, KCl, NaOH, 2 1 + 𝛼
1− 𝛼 𝛼 𝛼 1 + 𝛼
NH4OH
𝐴𝐵( ⇋ 𝐴(& + 2𝐵'
Ternary AB2 1− 𝛼 𝛼 2𝛼
3 M normal
(CaCl2, BaCl2) or
1 + 2𝛼
A2B type Na2SO4 𝐴( 𝐵 ⇋ 2𝐴& + 𝐵(' 1 + 2𝛼
3
1− 𝛼 2𝛼 𝛼

𝐴) 𝐵 ⇋ 3𝐴& + 𝐵)'
4
Quaternary A3B 1− 𝛼 3𝛼 𝛼
or AB3 M normal
)& ' 1 + 3𝛼
AlCl3, FeCl3, 𝐴𝐵) ⇋ 𝐴 + 3𝐵 1 + 3𝛼
K3[Fe (CN)6] 1− 𝛼 𝛼 3𝛼
4
Association of
solutes
𝑛𝐴 ⇋ 𝐴* 1 1 M normal
𝛼 1 − (1 − )𝛼 1
Benzoic acid 1− 𝛼 𝑛 𝑛 1 − (1 − 𝑛 ) 𝛼
𝑛
dimerizes into
Benzene

Van’t Hoff’s factor and degree of association:

• The fraction of total number of molecules of the substance which is present as associated
molecules is known as degree of association.
• Van’t Hoff’s factor for association of molecules

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

𝑖=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

• Calculation of i
𝑛𝐴 → (𝐴)4
Initial no. of moles 1 0
After association 1-a a/n
 UNIT 1 17
SOLUTIONS
Total number of solute particles = (1 - a) + a /n

𝜶
𝟏 − a +𝒏 𝜶
𝑽𝒂𝒏′𝒕 𝑯𝒐𝒇𝒇′𝒔 𝑭𝒂𝒄𝒕𝒐𝒓, 𝒊 = = 𝟏 − a +
𝟏 𝒏

The value of Van’t Hoff’s factor i < 1, association of solute particles in the solution, the
molecular weight is more than the normal, (weak electrolyte)

The value of Van’t Hoff’s factor i > 1, dissociation of solute particles in the solution, the
molecular weight is less than normal (strong electrolyte)

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