2 .

SOLUTIONS [9 HOURS]
Solutions and types of solutions
Solution is a homogeneous mixture of two or more than two components. The solution of two
components is called Binary solution. In a solution, the component that is present in largest
quantity is known as Solvent and the one which is present in less quantity is Solute.
Solvent determines the physical state of a solution.
Types of Solutions

Expressing Concentration of a solution

Concentration of a solution is the amount of solute present in a given quantity of solvent or
solution.
Different methods to express concentration of a solution quantitatively are:

Ex. 10% aqueous solution of glucose means that 10g of sugar dissolved in 90g of water to
form 100g of solution.

25% by volume of ethyl alcohol means that 25 mL of ethyl alcohol dissolved in 75 mL of

water to form 100 mL of solution.
(iii) Mass by volume percentage (w/v): It is the mass of the solute dissolved in 100 mL of the
solution. This unit is commonly used in medicine and pharmacy.
(iv) Parts per million(ppm): It is the number of parts by mass of solute per million parts by
mass of solution. When the solute is present in very minute quantity concentration is
expressed in ppm.

The concentration of pollutants in water or atmosphere is often expressed in ppm.

(v) Mole fraction: It is the ratio of number of moles of one component to the total number of
moles of all the components present in the solution.

In a binary mixture, if the number of moles of A and B are nA and nB respectively,

Mole fraction of A = xA = nA/ nA + nB
Mole fraction of B = xB = nB / nA + nB
The sum of mole fractions of all the components in a solution is always unity.
(vi) Molarity(M) : It is the number of moles of solute present in one litre of solution.

= Mass of solute/Molar mass of solute

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Volume of solution in Litre
(vii) Molality (m) : It is the number of moles of solute present in 1000g or 1 kg of solvent.

= Mass of solute/Molar mass of solute

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Mass of solvent in kg
 SOLUBILITY
Solubility of a substance is the maximum amount that can be dissolved in a specific amount
of solvent at a particular temperature. Solubility depends on the nature of solute and
solvent, temperature and pressure.
Solubility of a solid in a liquid
A solute dissolves in a solvent if the intermolecular interactions are similar in both.
LIKE DISSOLVES LIKE means polar solute dissolves in polar solvents and non- polar
solute dissolves in non-polar solvents. Eg. Salt and sugar dissolves in water but not in
benzene where as naphthalene and anthracene dissolves in benzene whereas salt and
sugar do not.
Saturated solution- A solution in which no more solute can be dissolved at the same
temperature and pressure.
Solubility- is the amount of solute that can be dissolved in 100g of solvent at a given
temperature.
Solubility of a solid in liquid depends on:
[Link] of solute – Polar solute dissolves in polar solvents and non-polar solue dissolves in
non-polar solvents.
[Link] – If the dissolution of a solute in a given solvent is endothermic, then the
solubility increases with increase in temperature.
If the dissolution of a solute in a given solvent is exothermic, then the solubility of the solute
decreases with increase in temperature.
[Link] – Pressure does not have any significant effect on the solubility of solids in
liquids because solids and liquids are highly incompressible and unaffected by changes in
pressure.
Solubility of gas in a liquid depends on:
[Link] of gas and solvent – Easily liquifiable gases are more soluble in common solvents.
Eg- CO2 is more soluble in water than H2 and O2.
The gases which are capable of undergoing chemical reactions with water are more soluble
in water. Eg-HCl is more soluble in water and less soluble in benzene due to ionic nature.
[Link] of temperature – Solubility of gas in liquids DECREASES with rise in temperature
because dissolution of a gas in liquid is EXOTHERMIC in nature.
[Link] of pressure – Solubility of a gas in liquid increases with increase in pressure.
HENRY’S LAW – At constant temperature, solubility of a gas in liquid is directly proportional
to the pressure of the gas.
OR
Partial pressure of the gas in vapour phase is proportional to the mole fraction of the gas in
the solution.
If p is the partial pressure of the gas and x is the solubility in mole fraction, p = KH x where KH
is Henry’s constant.
[Link] is a function of nature of the gas.
[Link] the value of KH at a given pressure, lower the solubility of gas in the liquid.
[Link] KH value increases with increase in temperature, solubility decreases with increase in
temperature. (Aquatic species is more comfortable in cold water than warm water.)
Applications of Henry’s law
[Link] increase the solubility of CO2 in soft drinks and soda water, bottles are sealed under
high pressure.
[Link] high altitudes, atmospheric pressure is less. This leads to low concentration of oxygen
in the blood of mountain climbers. This low oxygen in blood causes climbers to become
weak and unable to think clearly.[ANOXIA]
[Link] cylinders carried by Scuba divers are filled with air diluted with Helium to minimize
the solubility of Nitrogen in the blood by decreasing its partial pressure to avoid the risk of
BENDS.
(Atmospheric pressure is more under water. Therefore more gases will be dissolved in blood
when scuba divers go under water. When they come back to the surface fast, dissolved gas
is released leading to the formation of bubbles in the blood. This results in blockage of
capillaries which causes acute pain and dangerous to life.)

Vapour pressure of liquid solutions

Pressure exerted by the vapours on the surface of the liquid at a given temperature is called
vapour pressure.(V.P).V.P of the liquid depends on:
[Link] of liquid – More volatile liquids will have higher V.P.
[Link] – V.P increases with increase in temperature.
Vapour Pressure of liquid-liquid solutions
Raoult’s law of binary solution- For a solution of volatile liquids, partial V.P of each
component in vapour phase is directly proportional to mole fraction of respective component
in solution phase at a given temperature.
Consider a binary solution of 2 volatile liquids 1&2..Let P total be the total V.P ,p1 and p2 be the
partial V.P, x1 and x2 be the mole fraction of components 1&2 respectively.
According to Raoult’s law, for component 1, p1 α x1
p1 = p10x x1 where p10 is the V.P of pure component 1.
For component 2, p2 α x2
p2 = p20 x x2 where p20 is the V.P of pure component 2.
According to Dalton’s law of partial pressures, Ptotal =p1 + p2
Substituting for p1 and p2 ,
Ptotal = p10 x1 + p20 x2
= p10(1-x2) +p20 x2
= p10 – p10x2 + p20x2
Ptotal = p10 + (p20-p10) x2 ----------------------------------------------(1)
Conclusions from (1) are:
[Link] V.P over the solution can be related to mole fraction of any one of the component.
2. Total V.P over the solution varies linearly with mole fraction of component 2.
[Link] on the V.P of pure components 1&2, total V.P over the solution decreases or
increases with increase in mole fraction of component 2.
Graph of V.P against mole fraction of an ideal solution

Raoult’s law is a special case of Henry’s law.

Vapour pressure of solutions of solids in liquids
Vapour pressure of solution is lower than that of pure solvent: When a non-volatile solid is
added to a solvent, a part of liquid surface is occupied by non-volatile solute particles.
Therefore evaporation take place from lesser surface area. Now particles will have less
tendency to escape into vapour phase, resulting in lowering of V.P.
Ideal and non-ideal solutions
Differences between ideal and non-ideal solutions

IDEAL SOLUTION NON-IDEAL SOLUTION

Obey Raoult’s law at all concentration and Does not obey Raoult’s law at all
temperature. concentration and temperature.
∆Hmix=0 ∆Hmix ≠ 0
∆ Vmix = 0 ∆ Vmix ≠ 0
A-A and B-B interaction is same as A-B A-A and B-B interaction is not same as A-B
interaction interaction
Eg: n-hexane and n-heptane, benzene and Eg: Ethanol and acetone, ethanol and
toluene, bromo benzene and chloro water, acetone and chloroform, HNO3 and
benzene H2O, HCl and H2O

NON-IDEAL SOLUTIONS
Vapour pressure of non- ideal solutions is higher or lower that what is expected from
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.
Differences between solution showing positive deviation and negative deviation
POSITIVE DEVIATION NEGATIVE DEVIATION
Partial V.P and total V.P is more than what Partial V.P and total V.P is less than what is
is expected from Raoult’s law. expected from Raoult’s law.
∆Hmix = Positive ∆Hmix = Negative
∆ Vmix = Positive ∆ Vmix = Negative
A-B interaction is weaker than A-A and B-B A-B interaction is stronger than A-A and B-B
interaction interaction.
Eg: Acetone- ethanol, water-ethanol, Eg: Acetone-aniline, acetone-chloroform,
acetone-CS2 water-HNO3,water-HCl.
For solutions with positive deviation, there is an intermediate composition at which V.P of the
solution is maximum and hence B.P is minimum. At this composition the solution distils at
constant temperature without change in composition. Such mixtures are called Azeotropic
composition. A solution with positive deviation form Minimum boiling azeotrope at a specific
composition. Eg: 95.5 % ethanol-4.5% water mixture form minimum boiling azeotrope.<
For solutions with negative deviation there is an intermediate composition at which V.P of
the solution is minimum and hence B.P is maximum. It is Maximum boiling azeotrope.
Eg: 68% HNO3-32% water mixture form maximum boiling azeotrope.
Azeotropes are the mixture of liquids which boil at constant temperature like pure liquid and
possess same composition of components in liquid phase and vapour phase. At this
composition it is not possible to separate the components by fractional distillation.
COLLIGATIVE PROPERTIES OF SOLUTIONS
Colligative properties are properties of dilute solutions of non-volatile solutes .Colligative
properties are the properties which depend on the number of solute particles and not on its
nature. Egs. are: Elevation in B.P, Depression in F.P, Relative lowering of V.P, Osmotic
pressure.
[Link] Lowering of Vapour Pressure
Vapour pressure of solution is less than that of pure solvent. According to Raoult’s law for a
solution of non-volatile solute, the relative lowering of V.P is equal to the mole fraction of
solute. p1 = p10 x1
The lowering of V.P of solvent(∆p1) = p10 – p1
= p10 – p10x1 = p10(1-x1) = p10 x2 -------------------1
∆p1 / p10 = (p10 – p1) /p10 = x2 = n2/n1 + n 2 where n1 and n2
∆𝑝1 𝑝10 − 𝑝1 𝑛2
0
= 0
= 𝑥2 = + 𝑛2
𝑝1 𝑝1 𝑛1

Are number of moles of solvent and solute respectively. For dilute solution. n2<< n1
Neglecting n2 in the denominator,
 p10 – p1 /p10 = W2/M2 x M1/W1 where w1 and w2 are the
masses and M1 and M2 are the molar masses of solvent and solute respectively. Knowing all
other quantities, molar mass of solute,M2 can be calculated.
Example:

[Link] in boiling point V.P of a liquid increases with increase in temp

.B.P of a liquid is the temperature at which it’s V.P becomes equal to atmospheric pressure.
V.P of a solvent decreases when a non- volatile solute is added to a solvent.

Thus the B.P of the solution is always higher than the B.P of the pure solvent.
Let Tb0 is the B.P of pure solvent and Tb is the B.P of solution. Increase in B.P ∆Tb=Tb-Tb0
Is known as elevation in B.P.
For dilute solution,∆Tb is directly proportional to the molal concentration of solute in the
[Link] ,∆Tb α m
,∆Tb = Kb m ---------1, where Kb is called Molal elevation constant
(Ebullioscopic constant).Unit of Kb is Kkgmol-1 .If w2g of solute of molar mass M2 is dissolved
in w1g of solvent, then molality, m =w2/M2 x 1000/w1
Substituting for m in 1, we get ,∆Tb = 1000 Kb w2 / M2 w1
M2 = 1000 Kb w2 / ∆Tb w1
Molal Elevation Constant (Kb) is the elevation in B.P caused by dissolving one mole of non-
volatile solute in one kg of solvent. SI unit of Kb is K kg mol-1
Example:1

Example :2
[Link] in Freezing point : Freezing point of a substance is the temperature at which
V.P of the substance in liquid phase is equal to the V.P in solid phase. A solution will freeze
when its V.P become equal to the V.P of pure solid solvent. Ding to Raoult’s law when a non-
volatile solute is added to a solvent,its V.P decreases and it would become equal to that of
solid solvent at lower temperature. Thus F.P of solvent decreases.

Let Tf0 is the F.P of pure solvent and Tf is the F.P when a non-volatile solute is dissolved in it.
The depression in F.P ∆ Tf = T0f - Tf
The depression in F.P of a dilute solution is directly proportional to the molality ‘m ‘ of the
solution. ∆ Tf α m
∆ Tf = Kf m -------------------------------- 1 where Kf is called Molal Depression
Constant or Cryoscopic constant.
Cryoscopic constant (Kf) is the depression in F.P produced by dissolving I mole of non-
volatile solute in I kg of solvent. SI unit of Kf is Kkgmol-1.
If w2 g of solute having molar mass M2, present on w1 g of solvent, produces the depression
in F.P ∆Tf , then substituting for molality m= w2 x1000/ M2 x w1 in equation 1
∆ Tf = Kf w2 1000/ M2 w1
M2 = 1000 Kf w2 / ∆Tf w1
Application of Depression in F.P.
[Link] the vehicles climbing high altitudes, because of low temperature, water in the radiator
will freeze. To avoid this, water mixed with ethylene glycol is used as coolant which can
survive upto -480c.
[Link] melt snow, NaCl or CaCl2 is added. It can retain liquid state upto -510c.
 OSMOSIS AND OSMOTIC PRESSURE

The passage of solvent from a solution of low concentration to a solution of high

concentration through a semipermeable membrane (SPM) is called osmosis.
Eg: 1. Shrivelling of raw mangoes pickled in brine.
2. Wilted flowers revive, when placed in fresh water.
[Link] cells collapse, when suspended in saline water.
Eg for SPM – Pig’s bladder, Parchment membrane, Cellophane etc.
The excess pressure that must be applied to the solution side to stop osmosis is called
osmotic pressure. It is denoted by π. Osmotic pressure is a colligative property. For dilute
solutions, osmotic pressure is proportional to Molarity,c of the solution at a given
temperature T.
π = CRT
π = n2RT / V where V is the volume of solution containing 1 mole of solute. If w2 g of solute
of molar mass M2 is present in the solution then n2 = w2/M2
π = w2RT/M2
M2 = w2RT/ π V
This method is used to determine molar masses of proteins, polymers and other
macromolecules. Magnitude of π is large even for very dilute solutions.
This method has advantage over

The solutions having same osmotic pressure at a given temperature is called ISOTONIC
SOLUTIONS. Out of two solutions with different osmotic pressure, the solution with higher
osmotic pressure is called HYPERTONIC SOLUTION and solution with lower osmotic
pressure is called HYPOTONIC SOLUTION.
0.9% (mass/volume) aqueous solution of NaCl is called normal saline solution and it is
isotonic with the fluid inside human RBC. During intravenous injections,t he medicine is
mixed with saline solution before injection. This prevents blood cell from shrinking or
bursting.
But if saline solution is less concentrated, that is Hypotonic with respect to human blood,
water will move into the cell causing it to swell and [Link] saline solution is more
concentrated, that is Hypertonic with respect to human blood, water will move out of the cell
causing it to shrink due to PLASMOLYSIS.
Examples for Osmosis
[Link] of raw mangoes to pickle when kept in salt solution
[Link] of wilted flowers and limped carrots.
[Link] movement from soil to root and subsequent movement to other part of plants.
[Link] of meat by salting and fruits by adding sugar.( water loses by osmosis from
bacteria and it will die.)
[Link] of tissues in people consuming more salt.
EDEMA – Swelling and puffiness produced because of water retention in the tissue cells
and intercellular spaces.
REVERSE OSMOSIS
The movement of solvent molecules from higher concentration to lower concentration
through SPM, when pressure more than osmotic pressure is applied to solution side is called
REVERSE OSMOSIS.
Application- Desalination of sea water.

Example for SPM – Cellulose acetate.

ABNORMAL MOLAR MASS
If we measure the colligative properties of electrolytic solutions, we find discrepancies
between observed and calculated values of colligative properties due to ASSOCIATION of
solute particles and DISSOCIATION of solute particles.
[Link] of solute particles- Ex- Dimerization of acetic acid and benzoic acid in benzene
due to Hydrogen bonding.

Due to association, number of molecules in the solution decreases, this results in decrease
in colligative properties.
[Link] of solute particles – Ex-Dissociation of electrolytes. During dissociation,
number of particles in the solution increases, colligative properties increases .As colligative
properties are inversely proportional to molar masses, molar mass calculated from colligative
properties will be less than their normal values.
Such molar masses that is either lower or higher than the expected value is called Abnormal
molar mass.
Van’t Hoff factor (i) – Significance- It gives the extend of association or dissociation of solute
particles. It is the ratio of normal molar mass to abnormal (Observed) molar mass.

Value of ’ i ‘ is - less than unity for association and greater than unity for dissociation. Value
is 1 for no association/ dissociation.
Value of ’ i’ for KCl, NaCl, K2SO4,MgSO4 are 2,2,3,2 respectively.
Inclusion of Van’t Hoff factor modifies the equation for colligative properties as:

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