SOLUTIONS

Solution:
A solution is a homogeneous mixture of two or more substances whose composition can be varied with certain limits.
• The substances making up the solution are called components of the solution.
• Solutions having two components are called binary solution, solution having three components are called ternary
solution while those having four components are called quaternary solution.
• A binary solution has two components – solute and solvent.
• Solute is the component present in lesser quantity while solvent is the component present in larger quantity.
• The solubility depends upon the interactions between the molecules of the pure components and between the
molecules of different components.
• If EA – A and EB – B are the energy between the molecules of the components A and B respectively and E A – B is the
energy between molecules of A and B, then the difference 2(EA – B) – (EA – A) + (EB – B ) will determine whether the
two components are miscible, partially miscible or completely miscible.

Concentration:
It is defined as the amount of solute present in the given quantity of the solution.

Mass Percentage:
The mass percentage of a component in a given solution is the mass of the component per 100 g of the solution.
Mass percentage of A = WA x 100
WA + WB
Volume Percentage:
It is defined as the volume of the component per 100 parts by volume of the solution.
Volume percentage of A = Volume of A x 100
Volume of A + Volume of B
Parts Per Million:
It is the parts of a component per million of the solution.
ppm A = Mass of A x 106
Mass of solution
Molarity (M):
It is the number of moles of the solute dissolved per litre of the solution.
Molarity = Moles of solute = Moles of solute x 1000
Volume of solution in litres Volume of solution in mL
Its unit is moles/litre.
Disadvantage: Molarity changes with temperature because of expansion or contraction of the liquid with temperature.

Molality (m):
It is the number of moles of the solute dissolved per kg of the solvent.
Molality = Moles of solute = Moles of solute x 1000
Weight of solvent in kg Weight of solvent in g
Its unit is moles/kg.

Mole Fraction (x):

It is the ratio of number of moles of one component to the total number of moles present in the solution.
Mole fraction of solute (xA) = nA
nA + nB
Mole fraction of solvent (xB) = nB
nA + nB

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also, xA + xB = 1
Mole fraction is independent of temperature.

Henry’s Law:
Henry’s law states that “the mass of a gas dissolved per unit volume of a solvent at a given temperature is proportional to
the pressure of the gas in equilibrium with the solution”.
If m is the mass of the gas dissolved per unit volume of the solvent and p is the equilibrium gas pressure, then
m α p or m = Kp
where K is the proportionality constant.

→ The solubility of gases decreases with increase of temperature. This is the reason that the aquatic species are more
comfortable in cold water than warm water.
→ To increase the solubility of CO2 in soft drinks and soda water, the bottles are sealed under high pressure.

Solubility:
Solubility is the maximum amount of solute that can be dissolved in a given quantity of solvent at a particular
temperature.
A saturated solution represents the limit of solute that can be dissolved in a given quantity of solvent at a given
temperature. Thus, the concentration of solute is maximum in a saturated solution.
• If the solute dissolves with absorption of heat (endothermic process), the solubility increases with rise in temperature.
• If the solute dissolves with evolution of heat (exothermic process), the solubility decreases with rise in temperature.

Vapour Pressure:
The pressure exerted by the vapours above the liquid surface in equilibrium with the liquid at a given temperature is
called vapour pressure.
Vapour pressure of a liquid depends upon –
Nature of the liquid:
The liquids which have weaker intermolecular forces, escape readily into vapour phase and therefore have greater vapour
pressure.
Temperature:
The vapour pressure of a liquid increases with the increase in temperature. With the rise in temperature, kinetic energy of
molecules increases and their tendency to go into the vapour phase increases.

Vapour pressure of Solution:

Evaporation is a surface phenomenon. In the case of solution, the non-volatile solute molecules also occupy certain
surface area. As a result, lesser number of solvent molecules will escape into vapours. Therefore, the vapour pressure of
the solution is less than that of pure solvent.

Raoult’s Law for Binary Solutions of Volatile Liquids:

“At a given temperature for a solution of volatile liquids, the partial vapour pressure of each component in solution is
equal to the product of the vapour pressure of the pure component and its mole fraction”.
pA = p˚A xA
Raoult’s Law for Binary Solution Containing Non-volatile solute:
When a non-volatile solute is added to a pure solvent, the vapour pressure of the solution will be the vapour pressure due
to solvent only.
Raoult’s law may be stated as “at a given temperature, the vapour pressure of a solution containing non-volatile solute is
directly proportional to the mole fraction of the solvent”.
p (solution) = p (pure solvent) x mole fraction of solvent
p = p˚A xA

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Rearranging, p / p˚A xA
or 1 – p = 1 – xA [subtracting each side from 1]
p˚A

or p˚A – p = xB or p˚solvent – psolution = xsolute

p˚A p˚solvent
where, p˚A – pA represents the lowering in vapour pressure
and p˚A – pA / p˚A represents the relative lowering in vapour pressure.
Raoult’s law may also be stated as “at a given temperature the relative lowering in vapour pressure of an ideal solution
containing the non-volatile solute is equal to the mole fraction of the solute”.

Raoult’s Law as a Special Case of Henry’s Law:

According to Raoult’s law, the vapour pressure of a volatile component in given solution is given by the relation –
pA = p˚A xA
In the case of a gas in a liquid, the gaseous component is volatile component. Its solubility is governed by Henry law is
given by the relation –
p = KH x [KH is Henry’s constant]
The comparison of equations for Raoult’s law and Henry’s law shows that the partial pressure of the volatile component
or gas is directly proportional to its mole fraction in solution. Only difference in the two expressions is the proportionality
constant p˚A in Raoult’s law and KH in Henry’s law. Therefore, Raoult’s law becomes a special case of Henry’s law in
which KH becomes equal to vapour pressure of the pure component.

Ideal Solutions:
• A solution which obeys Raoult’s law at all concentrations and at all temperatures is called an ideal solution.
• In these solutions, the intermolecular interactions between the components (A – B attractions) are of the same
magnitude as the intermolecular interactions in pure components (A – A and B – B attractions).
• For such solutions, pA = p˚A xA and pB = p˚B xB. The total pressure , p = pA + pB
• Since there is no change in magnitude of the attractive forces in the two components present, the heat change on
mixing is zero i.e. Δmixing H = 0.
• In ideal solutions, there is no change in volume on mixing i.e. Δmixing V = 0.
• Example of ideal solutions are – benzene and toluene and chlorobenzene and bromobenzene.

Graphical Representation of Behaviour of Ideal Solutions:

The vapour pressures of the components are linear
functions of their mole fractions.
(i) When xA = 1 i.e. the liquid is pure A then
pA = p˚A x 1 = p˚A
(ii) When xA = 0 i.e. the liquid is pure B then
pA = p˚A x 0 = 0
The total vapour pressure p, exerted by the solution as a
whole at any composition is given by the sum of partial
pressures i.e. p = pA + pB
= p˚A xA + p˚B xB

XA = 1 Mole fraction → XA = 0
XB = 0 XB = 1

Non-ideal Solutions:

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• The solutions which do not obey Raoult’s law are called non-ideal solutions.
• For such solutions, pA ≠ p˚A xA and pB ≠ p˚B xB
• Also for non-ideal solutions, Δmixing H ≠ 0 and Δmixing V ≠ 0

Types of Non-ideal Solutions:

Non-ideal solutions showing positive deviations from Raoult’s law :

If the A – B interactions in the solutions are weaker than the A – A and B – B interactions, then the escaping tendency of
A and B becomes more than from pure liquids. As a result, each component has a partial vapour pressure greater than
expected on the basis of Raoult’s law. This behaviour is known as positive deviation from Raoult’s law.
For such solutions, pA > p˚A xA and pB > p˚B xB
Example of such solutions are – Ethyl alcohol and water , Benzene and Acetone , Ethyl alcohol and Cyclohexane

Explanation for Positive Deviations:

In ethyl alcohol, the molecules are held together due to hydrogen bonding.
When cyclohexane is added to ethyl alcohol, the molecules of cyclohexane tend to occupy the spaces between ethyl
alcohol molecules. Consequently, some hydrogen bonds in alcohol molecules break and the attractive forces are
weakened. The escaping tendency of molecules increases and vapour pressure increases.
• For such solutions, ΔmixingH is positive because energy is required to break A – A or B – B attractive forces. So, the
dissolution process is endothermic.
• Because of the decrease in the magnitude of intermolecular forces in solutions, the molecules will be loosely held and
there will be increase in volume on mixing i.e. ΔmixingV is positive.

Non-ideal solutions showing negative deviations from Raoult’s law :

If the A – B interactions in the solutions are stronger than the A – A and B – B interactions, then the escaping tendency of
A and B becomes less than from pure liquids. As a result, each component has a partial vapour pressure lesser than
expected on the basis of Raoult’s law. This behaviour is known as negative deviation from Raoult’s law.
For such solutions, pA < p˚A xA and pB < p˚B xB
Example of such solutions are – Acetone and Chloroform , Water and Nitric acid

Explanations for Negative Deviations:

When acetone and chloroform are mixed, there are new attractive forces due to intermolecular hydrogen bonding. The
attractive forces become stronger and the escaping tendency of molecules decreases and the vapour pressure becomes
less.
• ΔmixingH is negative because energy is released due to increase in attractive forces. Dissolution process is exothermic.

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• Because of the increase in forces of attraction in the solution, the molecules will be held more tightly. There will be
decrease in volume on mixing i.e. ΔmixingV will be negative.

Azeotropes:
The solutions (liquid mixtures) which boil at constant temperature and can distil unchanged in composition
are called azeotropes or azeotropic mixtures.

Minimum boiling azeotropes:

The solutions which show positive deviations from Raoult’s law are also called minimum boiling azeotropes.
Maximum boiling azeotropes:
The solutions which show negative deviations from Raoult’s law are also called maximum boiling azeotropes.

Colligative Properties:
The properties of the solution which depend only on the number of solute particles but not on the nature of the solute are
called colligative properties.
Four important colligative properties are as given below –

Relative Lowering in Vapour Pressure:

For a solution containing non-volatile solute, the vapour pressure of the solution (p) is equal to the vapour pressure of the
solvent (pA). For such solutions the vapour pressure of the solution is always less than the vapour pressure of pure solvent.
Thus, p = pA = p˚A xA

or, p˚A – pA = xB
p˚A
Since relative lowering of vapour pressure is equal to the mole fraction of the solute, therefore it is a colligative property.

Determination of Molar Mass of a solute from Relative Lowering in Vapour Pressure:

A known mass of a solute is dissolved in a known quantity of solution and relative lowering in vapour pressure is
measured experimentally.
Now, Mole fraction of the solute, xB = nB = wB / MB
n A + nB wA + wB
MA MB
Since the law is applicable to the ideal solutions which are dilute, the molar concentration of the solute nB << nA . Hence
it can be neglected.
so, xB = wB / MB = wB x MA
wA / MA MB x wA

so, p˚A – pA = wB x MA or MB = wB MA
p˚A MB x wA wA x (p˚A – pA )
p˚A
Elevation in Boiling Point:
The boiling point of a liquid is the temperature at which its vapour
pressure becomes equal to the atmospheric pressure.
The boiling point of the solution is always higher than that of the
pure solvent. The difference in the boiling points of the solution (Tb)
and pure solvent (Tb˚) is called the elevation in boiling point.
Elevation in boiling point, ΔTb = Tb - Tb˚

Experimentally, ΔTb α m ΔTb

or ΔTb = Kb m
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where m is the molality of the solution and Kb is molal boiling
point elevation constant or molal boiling point constant or ebullioscopic constant.

If m = 1 then ΔTb = Kb
Molal elevation constant is defined as the elevation in boiling point for 1 molal solution i.e. a solution containing 1 mole
of solute dissolved in 1000 g of the solvent.
Since elevation in boiling point is directly proportional to the molal concentration of the solute (i.e. number of moles of
solute), therefore it is a colligative property.

Determination of Molar Mass of Solute from Elevation in Boiling Point Temperature:

To calculate the molar mass of an unknown non-volatile compound, a known amount of it is dissolved in a known mass
of solvent and the elevation in boiling point is determined.
Now, Molality (m) = Moles of solute x 1000 = wB x 1000
Weight of solvent in grams MB x wA

But ΔTb = Kb m = Kb x wB x 1000

MB x wA

or MB = Kb x wB x 1000
ΔTb x wA

Depression in Freezing Point:

The freezing point is the temperature at which the solid and the
liquid states of the substance have the same vapour pressure.
Freezing point of the solution is always lower than that of the
pure solvent. The difference in the freezing points of the solution (Tf)
and pure solvent (Tf˚) is called the depression in freezing point.
ΔTf = Tf˚ - Tf
Experimentally, ΔTf α m
or ΔTf = Kf m
where Kf is the molal freezing point depression constant or molal cryoscopic constant.
If m = 1 then ΔTf = Kf
Molal freezing point depression constant is defined as the depression in freezing point for 1 molal solution i.e. a solution
containing 1 mole of solute dissolved in 1000 g of solvent.
Since depression in freezing point is directly proportional to the molal concentration of the solute (i.e. number of moles of
solute), therefore it is a colligative property.

Determination of Molar Mass of Solute from Depression in Freezing Point Temperature:

To calculate the molar mass of an unknown non-volatile compound, a known mass of it dissolved in a known mass of a
solvent and depression in its freezing point (ΔTf) is determined.
Now, Molality (m) = Moles of solute x 1000 = wB x 1000
Weight of solvent in grams MB x wA

But ΔTf = Kf m = Kf x wB x 1000

MB x wA

or MB = Kf x wB x 1000
ΔTf x wA

Anti-freeze Solutions:
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Water is used in radiators of vehicles. If the vehicle is to be used in placed where the temperature is less than zero then
water would freeze in the radiator. To avoid this problem, certain substances are used in radiators so that water does not
freeze in low temperature in radiators. These are called anti-freeze solutions. Example – ethylene glycol.
Osmosis:
The phenomenon of the flow of solvent from pure solvent to the solution when separated by a semi-permeable membrane
is called osmosis.
Osmotic Pressure:
The excess pressure which must be applied to a solution to prevent the passage of solvent into it through a semi-
permeable membrane is called osmotic pressure. It is denoted by ‘π’ .

Van’t Hoff found that a dilute or ideal solution behaves like an ideal gas and the different laws are applicable to the dilute
solutions as well. He found that for dilute solutions, the osmotic pressure (π) is given as –
π = cRT
where c is the concentration of the solution, T is the temperature and R is the gas constant.
At a given temperature, π α c
Since osmotic pressure depends upon the molar concentration of solution, it is a colligative property.

Determination of Molar Mass from Osmotic Pressure:

According to Van’t Hoff equation, π = c R T = nB R T [concentration, c = n / V]
V
or π = wB R T or MB = wB R T
V MB V π
Hypertonic Solution:
If a solution has more osmotic pressure than some other solution, it is called hypertonic.
Hypotonic Solution:
If a solution has less osmotic pressure than other solution, it is called hypotonic.
Isotonic Solution:
Solutions having same osmotic pressure are called isotonic solutions.

NOTE: A 0.91% solution of sodium chloride (known as saline water) is isotonic with human blood cells. In this solution,
the blood cells neither swell nor shrink. Therefore, the medicines are mixed with saline water before being injected into
the veins.

Reverse Osmosis:
The process of movement of solvent from the solution to the pure solvent through a semi-permeable membrane by
applying excess pressure on the solution is called reverse osmosis.

Abnormal Molar Masses:

It is found that the molar masses calculated using various colligative properties do not agree with the theoretical values.
This discrepancy in molar mass is called abnormal molar mass.
To get accurate values of the molar masses followings conditions must be met –
(a) The solution must be dilute because in concentrated solution, the particles begin to interact with each other as well as
with the solvent. The solution becomes non-ideal.
(b) The solute must not associate or dissociate in solution. Due to association or dissociation, the number of molecules
changes resulting in change in the colligative property.

Association of Solute Particles:

• In non-polar solvents, the solute molecules undergo association i.e. two or more molecules exist in combination with
each other to form bigger molecules.
nA  An
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• Total number of molecules in solution becomes less and therefore, colligative properties will be lower.
• Since the colligative properties are inversely proportional to the molar mass of the solute, the molar mass will be
greater than the theoretical values.
2 CH3COOH  (CH3COOH)2
• The association of solute molecules in a solution is due to the hydrogen bonding between these molecules.

Dissociation of Solute Molecules:

• Molecules of certain substances dissociate or ionise in a solvent to give two or more particles.
A B  A+ + B –
• Total number of particles increases in solution and therefore, colligative properties will be large.
• Since the colligative properties are inversely proportional to the molar mass of the solute, the molar mass will be less
than the theoretical values.
K Cl  K+ + Cl –

Van’t Hofff Factor:

Van’t Hoff introduced a factor called Van’t Hoff factor, ‘i' to express the extent of association or dissociation of solutes
in solution.
It is the ratio of the normal and observed molar masses (abnormal molar mass) of the solute.

i = Normal molar mass = Observed value of colligative property

Observed molar mass Normal value of colligative property

In case of association, observed molar mass is more than the normal molar mass, so i < 1.
In case of dissociation, observed molar mass is less than the normal molar mass, so i > 1.
In case of no association or dissociation, i = 1.

Using Van’t Hoff factor, the modified colligative properties are as follows:
(i) Relative lowering vapour pressure, Δp = i x solute
(ii) Elevation in boiling point, ΔTb = i Kb m
(iii) Depression in freezing point, ΔTf = i Kf m
(iv) Osmotic pressure, π = icRT

Degree of Dissociation (α):

Degree of dissociation is defined as the fraction of total substance that undergoes dissociation into ions.

Degree of dissociation = Number of moles of substance dissociated

Total number of moles of the substance

Suppose a molecule of an electrolyte gives m ions after dissociation. If we start with 1 mole of the solute, and α is the
degree of dissociation, then at equilibrium:
Number of moles of solute left undissociated = 1–α
Number of moles of ions formed = mα
Total number of moles of particles = 1–α + mα

Van’t Hoff factor,

i = Observed number of moles of solute = 1–α + mα
Normal number of moles of solute 1

α = i – 1

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 m–1

Degree of Association (α):

Degree of association is defined as the fraction of total number of molecules which combine to form associated molecules.
Degree of dissociation = Number of moles of substance dissociated
Total number of moles of the substance

Suppose n molecules of the solute associate to form the associated molecule A n

nA  An

If we start with 1 mole of A and α is the degree of association, the concentration of the species after association is :
[A] = α / n
[A n] = (1 – α )

Total number of moles after association = 1 – α + α / n

Van’t Hoff factor,
i = Observed number of moles of solute = 1–α + α/n
Normal number of moles of solute 1

α = i – 1
1/n – 1

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