CHAPTER 1 – SOLUTIONS

Solution:
Homogeneous mixture of two or more substances in single phase.
e.g. Brass mixture of copper and zinc different from German silver (Copper, Zinc and Nickel)
The solution may be binary (if two components), ternary (if three component) or multinary (if more than three
components present).
• SOLUTE – The part of a solution that is being dissolved (usually the lesser amount)
• SOLVENT – The part of a solution that dissolves the solute (usually the greater amount)
• Solute + Solvent = Solution
• Saturated Solution: A solution which cannot dissolve any more of the solute at a particular
temperature.
S.No. Solute Solvent Example

1 Gas Gas Air

2 Gas Liquid Aerated water (CO2 + H2O)

3 Gas Solid Hydrogen in palladium

4 Liquid Liquid Alcohol in water, benzene in toluene

5 Liquid Solid Mercury in zinc amalgam

6 Liquid Gas CO2 dissolved in water

7 Solid Liquid Sugar in water, common salt in water

8 Solid Gas Smoke

9 Solid Solid Various alloys

Expression of concentration of solution

➢ Mass Percentage (w/w)
Mass of solute X 100
Percentage (w / w) =
Mass of solution
➢ Volume Percentage(V/V)
Volume of solution X 100
Percentage (V / V) =
Volume of solution

➢ Mass by Volume Percentage(w/V)

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 Mass of solute X 100
Percentage (w / V) =
Volume of solution

➢ Parts per million

Mass of solute X 106

Part Per Million(ppm) =
Mass of solution

➢ Mole Fraction

Number of moles of component

Mole fraction (X) =
Total number of moles of all components

nΑ XB = nB
XA = (n A + n Β )
(n A + n Β )

X A + XB = 1
Where nA = no. of moles of solvent , nB= no. of moles of solute
Sum of mole fractions of solute and solvent is equal to 1.

➢ Molarity
Moles of solute
Molarity =
Litres of solution

w 2 X 1000
M=
M2 X V
➢ Molality

w 2 X 1000
m=
M 2 X w1
Solubility
The maximum amount of a substance that can be dissolved in a specified amount of solvent is called its
solubility.
The solubility of a solute in a liquid depends upon the following factors:
(i) Nature of the solute
(ii) Nature of the solvent

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(iii) Temperature of the solution
(iv) Pressure (in case of gases)
Solubility of a solid in a liquid

Pressure has no significant effect on solubility of solid in liquid.

Effect of temperature: If in a saturated solution, the dissolution process is endothermic, the solubility should
increase with rise in temperature and if it is exothermic, the solubility should decrease according to Le
Chatelier’s principle.
Solubility of gas in a liquid
Henry’s Law
The effect of pressure on the solubility of a gas in a liquid is governed by Henry’s Law. It states that the
solubility of a gas in a liquid at a given temperature is directly proportional to the partial pressure of the gas
Mathematically, P = KHX
where P is the partial pressure of the gas; and X is the mole fraction of the gas in the solution and KH is Henry’s
Law constant.
• The value of Henry’s constant is different for different gases at
constant temperature.
• Solubility of gaseous solute is lower with higher values of KH
• This indicates that KH is a function of the nature of the gas.
• KH also change with change in temperature for all the gaseous
solutes.
• The KH values increase as temperature increases which means
the decrease in solubility of gaseous solute.

• Due to above reasons O2 will be dissolved more in cold water than in warm water. So aquatic
species are more comfortable in cold water than in hot water.

Applications of Henry’s law

1. To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure.
2. Oxygen dissolves into the blood at the lungs because the pressure of oxygen in the air is higher,
allowing it to dissolve into the bloodstream.
3. 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,

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 the toxic effects of high concentrations of nitrogen in the blood, the tanks used by scuba divers are
filled with air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen).
4. 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.

Liquid-Liquid solution
Pressure exerted by vapour of liquid at constant temperature and in equilibrium state is called Vapour
Pressure of liquid.

Boiling point: The temperature at which the vapour pressure of liquid is equal
to external pressure.
A liquid having high vapour pressure boils at low temperature. bp α 1/VP
Raoult’s Law
Raoult’s Law states that for a solution of volatile liquids, the partial vapour pressure of each component in the
solution is directly proportional to its mole fraction.

P1 = X1 P1
• X1 is the mole fraction of solvent A

• P1 - vapor pressure of pure A

• P1 – Partial vapour pressure of Solvent A in solution

The composition of vapour phase in equilibrium with the solution is determined by the partial pressures of the
components. If y1 and y2 are the mole fractions of the components 1 and 2 respectively in the vapour phase
then, using Dalton’s law of partial pressures:

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Raoult’s Law as a special case of Henry’s Law
According to Raoult’s law, the vapour pressure of a volatile component in a given solution is given by
P1 = X1 P1
In the solution of a gas in a liquid, one of the components is so volatile that it exists as a gas and we have
already seen that its solubility is given by Henry’s law which states that P = KHX
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 Thus, Raoult’s law becomes a special case of Henry’s law in which KH becomes equal to
P10.

Ideal & non-ideal solutions

Ideal solutions Non-ideal solutions
1. Ideal Solution - Solution which follows Raoults’ 1. Non-Ideal Solution - Solution which doesn’t follow
Law over all range of concentration Raoults’ Law over all concentration range.
2. Intermolecular attractive forces between A-A and 2. Intermolecular attractive forces between A-A and
B-B are same as those between A-B B-B are not same as those between A-B
3. Δ Hmix = 0 3. Δ Hmix ≠ 0
4. Δ Vmix = 0 4. Δ Vmix ≠ 0
Example: Example:
Benzene and Toluene H2O and ethanol
n-Hexane and n-heptane H2O and acetic acid
Bromoethane & chloroethane CHCl3 and CCl4

Types of Non-Ideal Solution

Solutions showing positive deviation from Raoults’ law Solutions showing negative deviation from
Raoults’ law
Attractive forces between A-A and B-B are stronger than Attractive forces between A-A and B-B are
A-B, leads to increase in vapour pressure. weaker than A-B, leads to decrease in vapour
pressure.
In Positive Deviation:
o
1. PA > PAo XA & PB >PB XA In Negative Deviation:
o
2. Δ Hmix > 0 1. PA <PAo XA & PB < Pb XB
3. Δ Vmix > 0 2. Δ Hmix < 0
Example: Cyclohexane and Ethanol 3. Δ Vmix < 0
H2O and ethanol Eg: Chloroform and Acetone
H2O and methanol H2O and acetic acid

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 CHCl3 and CCl4

Azeotropes
Binary mixtures having the same composition in liquid and vapour phase and boil at a constant temperature.
In such cases, it is not possible to separate the two components by fractional distillation.
Two types of Azeotropes
➢ Minimum boiling Azeotrope: Solutions which show a large positive deviation from Raoult’s law form
minimum boiling azeotrope at a specific composition.
e.g. Ethanol (95%) and water (5%) mixture
➢ Maximum boiling azeotrope: Solutions which show a large negative deviation from Raoult’s law form
maximum boiling azeotrope at a specific composition.
e.g. Nitric acid (68%) and water (32%)
Colligative properties
Colligative properties of solutions are those properties which depend only upon the number of solute particles
in the solution and not on their nature.

(i) Relative lowering in vapour pressure

The expression on the left-hand side of the equation is called relative lowering of vapour pressure and is equal
to the mole fraction of the solute.

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(P 0 - P ) n (P 0 - P ) n
1 1 2 1 1 2
0
= 0 =
P1 (n1 + n2 ) If n2 < n1 P1 n1

(P 0 - P ) w XM
1 1 2 1
0 =
P1 M 2 X w1
(ii) Elevation of boiling point
Elevation in BP (Tb –Tb◦) is proportional to molality of solution
∆Tb α m
∆ Tb = kb m
Kb =Boiling Point Elevation Constant or Molal Elevation Constant (Ebullioscopic Constant). The unit of Kb is

K kg mol-1.

(iii) Depression of freezing point

Depression in FP (Tf◦–Tf ) is proportional to molality of solution
∆Tf α m

∆ Tf = kf m
Kf = Molal Freezing point depression constant or Molal Depression Constant or Cryoscopic Constant. The unit
of Kf is K kg mol-1.

(iv) Osmotic pressure

Osmosis: If Semi-permeable membrane is placed between the solvent and solution, the solvent molecules will
flow through the membrane from pure solvent side to the solution side. This process of flow of the solvent is
called Osmosis.
Osmosis may be

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(i) Exosmosis It is outward flow of water or solvent from a cell through semipermeable membrane.
(ii) Endosmosis It is inward flow of water or solvent from a cell through a semipermeable membrane.
Osmotic Pressure: The Pressure that must be applied to the solution side to stop osmosis
π= CRT
where π = osmotic pressure C = molarity R = ideal gas constant T = Kelvin temperature

Osmotic pressure method is widely used to determine molar masses of proteins, polymers and other
macromolecules.
On the basis of osmotic pressure, solutions can be classified as:

Isotonic solution:
Two solutions are called isotonic if they exert the same osmotic pressure. These solutions have same molar
concentration. 0.91% solution of pure NaCl is isotonic with human RBC.
Hypertonic solution:
A solution is called hypertonic if its osmotic pressure is higher than that of the solution from which it is
separated by a semi-permeable membrane.
When a plant cell is placed in a hypertonic solution(0.91% solution of pure NaCl), the fluid from the plant cell
comes out and cell shrinks, this phenomenon is called plasmolysis.
Hypotonic solution:
A solution is called hypotonic if its osmotic pressure is lower than that of the solution from which it is
separated by a semipermeable membrane.

When a plant cell is placed in a hypotonic solution (less than0.91% solution of pure NaCl), the water will flow
into the cell and cell will swell.
Reverse osmosis:
When the external pressure applied on the solution is more than osmotic pressure, the solvent flows from the
solution to the pure solvent, which is called reverse osmosis. Desalination of sea water is done by reverse
osmosis.
Abnormal Molecular Masses:
Solute particles can undergo association or dissociation in the solvent. This results in increase or decrease no.
of solute particles, hence affects the values of colligative properties.

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The calculated molar mass will be thus higher or lower than the expected or normal value and is called as
Abnormal molar mass.
Colligative property ∝ 1 / MB
i.e., higher and lower values of molar mass is observed in case of association and dissociation respectively,
e.g., in benzene, acetic acid gets associated, so, its observed molecular mass is 120.Similarly KCI undergoes
dissociation in aqueous solution, so its observed molecular mass is 37.25.
These observed values are corrected by multiplying with van’t Hoff factor (i).
VANT HOFF FACTOR (i)
van’t Hoff factor gives the extent of dissociation or association of a solute.
i > 1 (For dissociation)
i < 1 (For association)
i = 1 (No association/dissociation – For non-electrolytic solutes)
Modified Colligative Properties

Degree of Dissociation (α) and van’t Hoff Factor (i):

Degree of Association (α) and van’t Hoff Factor (i):

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PERCENTAGE OF DISSOCIATION/ASSOCIATION
Percentage of dissociation or association = α x 100
DISSOCIATION CONSTANT (K)
Dissociation constant, K is given as

c = concentration α = degree of dissociation

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