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Chapter-02: Solution
A homogenous mixture of two or more substances whose composition may be altered within a
certain limit is called Solution. The component present in excess and whose physical state is
the same as that of solution is known as Solvent.. The other component present in smaller
amounts is termed as Solute.

Note: Binary Solution in which water is solvent is called aqueous solution w

while
hile solution in which solvent
is a liquid other than water such as benzene, CCl4 etc. are called non aqueous solutions.

Types of solution

Concentration of solution: It is the amount of solute present in a particular amount of solvent

or solution.

Methods
hods of expressing concentration of solution:
1) Mass percentage method (w/w)

It is defined as the mass of solute (in gm) dissolved per 100 gm of solution.
20% CaCO3solution (w/w) means 20gm of CaCO3 is present in 100gm of
solution.(100g solution contain 20g of CaCO3)
2) Volume percentage method (v/v)
It is defined as the volume of a solute present in 100 cm³ of solution.
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10% ethanol(v/v) means 10 cm³ of ethanol dissolved in 100 cm³ of solution.

Note: Mass/Volume percent method (w/v)

This method is used commonly in medicine & pharmacy. It is a mass of solute dissolved in 100
cm³ of solution.
3) Parts per million and parts per billion: This method is used when solute is present in
traces or less amount.

4) Molarity: It is the number of mole

moless of solute dissolved in 1 Ltr. solution at a particular
temperature. Its unit is mol/L.

* Note:
1 I Ltr 1000 ml

2 I Ltr 1 dm³

3 1 M of sugar one mole of sugar or 342gm of sugar is dissolved in ILtr. of

solution means solution.

4 semi Molar M/2

5 Molar 1M

6 Deci Molar M/10

7 Centi Molar M/100

8 MilliMolar M/1000

9 Bi-Molar 2M

** Note: Molarity involves volume which is temperature dependent, hence Molarity

of solution change with temperature.

*** Note:
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5) Molality: It is the number of moles of solute dissolved in 1 Kg of solvent. Since mass is

independent of temperature. Hence Molality of a solution does not change with
temperature. Its unit is mol/Kg.

6) Mole Fraction (✘): The mole fraction of a particular component in a solution is the ratio of
no. of moles of that component to the total no. of moles of all the component present in
the solution.

Mole fraction is the dimensionless quantity and temperature independent.

For binary solution made up of two component A & B

Henry’s Law: The partial

artial pressure of a gas in vapor phase is proportional to the mole
fraction of the gas in the solution.
P α ✘

P = KH ✘ Where KH is Henry's constant.

1. Note: This law defines Solubility of gas in liquid.

2. At given pressure the solubility of gas is inversely proportional to the value of
KH.

3. KH is different for different gases.

4. KH for gases increases with increase with temperature indicating that the
solubility
ity of gas decreases with increase in temperature.

Application of Henry's Law:

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1. To increase the solubility of carbon dioxide in soft drink, the bottles are sealed under
high pressure
2. To minimize the painful impact deep sea divers during decompression use compressed
air diluted with helium.
3. Henry's law explains the supply of inhaled oxygen to tissues when air is inhaled it
combined with hemoglobin of blood in lungs to form Oxyhaemoglobin and in lungs the
partial pressure of oxygen is high. partial pressure of oxygen is low in tissues Hance
oxygen is released from oxyhaemoglobin and is utilised by us.
4. The pressure of oxygen decreases in air on going up the mountain at very high altitude
partial pressure of oxygen is much less than that of the ground level, therefore people
living at high altitudes or climbers have low concentration of oxygen in blood and tissues
which leads to weakness and loss in clarity of thinking and cause disease call Anoxia

Limitations of Henry's law

1. The pressure of the gas is not too high
2. Temperature in is not too low
3. It is applicable two ideal gases only
4. The law is not applicable to those gases which undergo a chemical change in solution
for example law cannot be applied to ammonia which reacts with the water to form
ammonium hydroxide
5. The law cannot be apply to gases which dissociate into Ions in solution for example it
cannot be applied to HCl gas which dissociates into H⁺ ions Cl⁻ ions in the solution.

Question: Why aqueous species like fish feel more comfortable in lakes in winter than in summer
Ans: Aqueous species need dissolved oxygen for breathing as solubility of gases decreases with
increase in temperature less oxygen is available in summer in the lakes.Hence they feel more
comfortable in winter when solubility of oxygen is higher.

Solubility of solid in liquid: Solubility of a substance at a given temperature is defined as the

amount of solid that dissolved in 100 gm of solvent to form a saturated solution.

Note: With increase in temperature solubility of solute

1. Increases if its dissolution process is endothermic.
2. Decreases if its dissolution process is exothermic.

Vapour Pressure: The pressure exerted by the vapour of a liquid at a particular temperature in
a state of dynamic equilibrium is called vapour pressure of the liquid at equilibrium.

Note: If a non volatile solute is added to the solvent to give solution vapour pressure of the
solution is decreased. This phenomena is called Lowering of vapour pressure.

Raoult’s Law for non volatile solute: According to this law relative lowering of vapour
pressure for a binary solution containing a nonvolatile solute and a volatile solvent at a particular
temperature is equal to the mole fraction of the solute.
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Where P⁰ is vapour pressure of pure solvent and P is vapour pressure of solution.

Raoult’s Law for Binary solution of volatile liquid: for a solution of volatile liquids the partial
vapour pressure of each component in the solution at a particular temperature is directly
proportional to its mole fraction.
PA α ✘A

PA = P⁰A ✘A
Where PA = partial pressure of component in solution
P⁰A = vapour pressure of component in pure state.
Similarly
PB α ✘B

PB = P⁰B ✘B
Where PB = partial pressure of component in solution
P⁰B = vapour pressure of component in pure state.
Note: Partial vapour pressure is the vapour pressure of a component in solution
Total vapour pressure (P) exerted by vapour above the solution is the sum of P A and PB as
required by Dalton’s law of partial pressure.

Since P⁰A and P⁰B are constant at given temperature equation 1 and 2 reveal that total
pressure P is a linear function of ✘A (or ✘B). This means the plot between P versus ✘A or P

versus ✘B should be straight line.

e.
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Composition of the Vapour phase of solution : Let YA and YB represent the mole fractions of
component A and B respectively in vapour phase in solution.

On the basis of Raoult’s law liquid

liquid-liquid solutions can be classified into Ideal and Non Ideal
solution:
Ideal solution: Solutions obeying Raoult’s Law
over the entire range of concentration at all
temperature and during formation of which no
change in volume and enthalpy takes place .
△ HMixing = 0 △ VMixing = 0
In order to form an ideal solution, the
component must possess identical molecular
forces. They must be similar in structure and
polarity. Two liquids A and B can form ideal
solutions only when A - B intermolecular
interm
forces are similar to A-A A and B-B
intermolecular forces, example: solution of
benzene and Toluene, solution of n-Hexane
n
and n-Heptane,, solution of Chloro-ethane
Chloro and
Bromo-ethane. Solution of Chloro-benzene
Chloro
and Bromo-benzene,
benzene, solution of Carbon Tetrachloride and Silicon Tetrachloride etc.
Non-Ideal solution: Solutions
ons do not obey Raoult’s Law are called non
non-Ideal
Ideal solutions

Two liquids A and B form Non-ideal

ideal solution when the forces of attraction between A-B
A
molecules are different from the forces between AA-A and B-B molecules.
They are of two types:
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Non-Ideal solution showing +ve

solution of Ethanol and Water, sol
CarbonTetrachloride and Toluene,solution of CarbonTetrachloride
solution of Ethanol and cyclo
cyclo-hexane etc.
deviation from Raoult’s Law: A
solution is said to show +ve
deviation from Raoult’s Law when at
any composition Its vapour pressure
is higher than that given by Raoult’s
Law. +ve deviation is shown by
those liquid pairs for which A-BA
molecular
olecular interaction forces are
weaker than A-A A and B-B
B molecular
interaction forces. For such
solutions △ HMixing > 0(+ve) and
△ VMixing
> 0(+ve). Example:
solution of Ethanol and n-Hexane,
n
Solution of Benzene and Acetone,
solution
ution of Acetone and Ethanol, solution
and Benzene,

Non-Ideal
Ideal solution showing -ve
deviation from Raoult’s Law: A
solution is said to show -ve
deviation
viation from Raoult’s Law when
at any composition Its vapour
pressure is lower than that given by
Raoult’s Law. -ve ve deviation is
shown by those liquid pairs for
which A-B B molecular interaction
forces are stronger than A-A
A and B-
B molecular interaction forces.
forc For
such solutions △ HMixing < 0(-ve)
and △ VMixing < 0(-ve).
0( Example:
solution of Water and HCl, solution
of Chloroform and diethyl ether, solution of Acetone and Aniline, solution of Water and
Nitric acid, solution of Chloroform and Nitric acid etc.
Raoult’s Law as a special case of Henry's Law: According to Henry’s Law P = KH ✘ and

or Binary solution of volatile liquid PA = P⁰A ✘A.

according to Raoult’s Law for
If we compare both the equations then the partial pressure of the volatile component is i directly
proportional to its mole fraction in its solution. Only the proportionality constant K H differs from
P⁰A then Raoult’s Law becomes a special case of Henry’s Law in which K H becomes equal to
P⁰A.
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Sl No Ideal Solution Non-Ideal

Ideal Solution

1 The Interaction between the components The Interaction between the components are
are similar to those in the pure components different from those of the pure components

2 There is no volume change and enthalpy Change in volume and enthalpy takes place
change on mixing the components. on mixing the components.
I.e. △ HMixing = 0 △ VMixing = 0

3 Each component obeys Raoult’s law at all They do not obey Raoult’s law. They show
temperatures and concentrations. i.e. +ve and -ve
ve deviation from Raoult’s law. i.e.
PA = P⁰A ✘A AND PB = P⁰B ✘B

4 They do not form Azeotropes

Azeotropes. They form Azeotropes.

Azeotropes: A solution of completely miscible liquids which distills without change in

composition at a particular temperature is called Azeotropes or azeotropic mixture.
They are of two types-
1. Minimum boiling Azeotropes: This type of mixture is formed by those non-ideal
non solutions
which show +ve deviation from Raoult’s law and at a certain comp composition
osition have higher
vapour pressure thanhan of more volatile components e.g. solution of water and ethyl
alcohol, solution of chloroform and ethanol.
2. Maximum boiling Azeotropes: This type of mixture is formed by those non-ideal
non solutions
which show -ve e deviation from Raoult’s law; e.g. solution of water and hydrochloric
hydroch acid,
solution of water and nitric acid.
Note: 1. Components
nts of a azeotropic mixture can
cannot
not separated through fractional distillation
2. The mixture containing 95.4% alcohol and 4.6% water is called rectified spirit

Colligative properties:. (from Latin Co means together and ligare means to link) The properties of
solution which depend upon number of solute particles present in a definite amount of solvent
but not on chemical nature of solute are called colligative properties. The important colligative
properties of solutions are:
1. Relative lowering of vapour pressure :
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2. Elevation of boiling point : The temperature at which the equilibrium vapour pressure of a
liquid becomes equal to the atmospheric pressure is called Boiling point of the liquid.
l
When a Non volatile solute is dissolved in a solvent its boiling point of solution formed
is raised, Hence boiling point of solution is always higher than the boiling point of pure
solvent in which solution is prepared.

Let T⁰b be the boiling point of pure solvent and Tb

be the boiling point of solution. The increase in
boiling point △ Tb = Tb - T⁰b is known as
elevation of boiling point.

Elevation in Boiling Point α molality

△ Tb α m, △ Tb = Kb m
where Kb = Ebullioscopic constant.

Kb is also called boiling point elevation constant

or molal elevation constant. Its unit is Kelvin Kg
mole⁻ ¹ (k.kg mol⁻ ¹).
Kb may be defined as elevation of boiling point produced on dissolving 1 mole of a
substance in 1000g of solvent.

Note: Sometimes value ue of Kb is given for 100g of the solvent. In such cases this constant is 10
times the value of the molal elevation constant.

3. Depression of freezing point: freezing point of a substance is the temperature at which

the solid and liquid phase of a substance coexist. It is defined as the temperature at
which its solid and liquid phase have the same vapour pressure. When a nonvolatile
solute is dissolved in solvent, the freezing point of the solution formed is decreased.
Hence the freezing point of a solution is always lower than that of the freezing point of
pure solvent in which solution is
prepared.
Let T⁰f be the freezing point of pure
solvent and Tf be its freezing when non
volatile solute is dissolved in it.The
decrease in freezing point
△ Tf = T⁰f - Tf is known as depression in
freezing point. Depression in freezing
Point α molality
△ Tf α m, △ Tf = Kf m
where Kf = Cryoscopic constant.

Kf is also called freezing point depression

constant or molal depression constant. Its unit is Kelvin Kg mole⁻ ¹ (k.kg mol⁻ ¹).
Kf may be defined as depression in freezing point produced on dissolving 1 mole of a
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substance in 1000g of solvent.

Note: Kb for Water =0.52 Kf for water =1.86

Application of depression of freezing point:

1. Antifreeze solution
solution- Water is used in radiators of vehicles as a cooling liquid. If the
vehicle is used at the high altitudes where the temperature is sub zero water would
freeze in the radiator. To avoid this difficulty a solution of ethylene glycol in water
wa is used
in radiators. This solution has a freezing point lower than zero. Freezing point can be
lowered to the desired extent by changing the concentration with proper ratio of ethylene
glycol and water. It is possible to protect the automotive cooling system to temperature
up to -40 degree Celsius
2. Cleaning of ice from the road on the hills: Salts such as NaCl or Calcium chloride are
scattered on icy roads at higher altitudes. This helps in melting the ice as low as the
outdoor temperature is above the lowest freezing point of salt-water water mixture. NaCl can
melt ice at a temperature as low as -21 degree Celsius.. Calcium chloride is effective in
melting the ice as low as -55 degree Celsius.

4. Osmotic pressure (ℼ) : The spontaneous flow of solvent through a semi permeable
membrane (SPM) from a pure solvent to a solution or form a dilute solution to a
concentrated solution is called osmosis ( in greek means PUSH).
The osmotic pressure of a solution at a particular temperature may be defined as hydro-
hydro
static pressure
ssure which builds up, when a solution is separated from solvent by a SPM and
which is just sufficient to stop osmosis.
or
osmotic pressure may be defined as external pressure which should be applied to the
solution in order to stop the phenomenon of osmosis.

Slno Diffusion Osmosis

1 It involves the free mixing of solution without Involve use of SPM

SPM

2 Both solvent and solute molecules move In osmosis only solvent molecules move
directly into each other. Thus it is a bilateral through SPM.
process.

3 Shown by solution as well as gases. Shown by solution only

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4 Can neither be stopped nor reversed It can be stopped or reversed by applying

external pressure.

Semi-permeable
permeable membrane [SPM]: There are few membrane through which small solvent
molecules like water can pass but passage of bigger molecules like solute is hindered such
membranes are called semi-permeable
permeable membrane. Animal bladder is natural semi-permeable
semi
membrane and cellophane is an artificial or synthetic semi
semi-permeable
permeable membrane.
membrane

NOTE :
1. The solutions which have the same osmotic pressure at a given temperature are called isotonic
solutions. Such a solution possesses the same molar concentration.

When a solution has higher osmotic pressure as compared to another solution, it is known as a
hypertonic solution while the solution having lower osmotic pressure is a hypotonic solution.
2. 0.91% solution of pure NaCl (called normal saline solution) is isotonic with human RBC, hence
this solution is safe to inject intravenously as RBC nei
neither swell nor shrink.
3. The shrinking of cells on account of exoexo-osmosis
osmosis is called plasmolysis. (crenation/ shriveling).
4. The swelling of cells in a hypotonic solution is called hemolysis (brusting) of the cell.
5. In an isotonic solution the flow of water in aand
nd out of the cell is happening at the same rate.
6. When the membrane permits the solvent molecules to come out through the membrane it is
called exosmosis and when the membrane permits the solvent molecules to enter inside, it is
called endosmosis.
7. The pressure
sure developed inside the cell due to inflow of water is referred to as turgor.
8. The roots of plants possess cells in which the cell sap is quite concentrated. Therefore plants and
trees absorb water from the soil through osmosis and push it up to its various vario parts such as
stems, leaves etc.
9. Preservation of meat by salting and of fruits adding sugar protects against bacterial action.
Through the process of osmosis a bacterium on salted meat or candid fruit loses water shrivels
and dies.
10. People taking a lot of salt or salty food, experience water retention in tissue cells and intercellular
spaces because of osmosis. This results in swelling or puffiness and this disease is called
Edema.
11. Raw mangoes when placed in concentrated solution of common salt lose wat water
er through osmosis
and ultimately shrivel into pickel.
12. Wilted flowers revive and regain their freshness when placed in fresh water because of osmosis.
Carrots get limped due to loss of water to the atmosphere, however when placed in ware, water
flows into them due to osmosis and they become firm again.

Reverse Osmosis and water purification: The natural process of osmosis can be reversed if
a pressure greater than osmotic pressure is
applied on the more concentrated solution
by using pressure greater thantha osmotic
pressure on more concentrated solution
side, pure solvent is forced to move from
more concentrated solution to dilute
solution through semi-permeable
membrane. The phenomenon is called
reverse osmosis. This is used in
desalination of seawater..
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Note:
Why osmotic pressure is considered to be one of the most suitable methods:
Other methods cannot not be used because.
1. The changes observed in these properties are very small. On the other hand these changes can
be easily measured by osmotic pressure.
2. Elevation in boiling point method for biomolecules such as proteins is not suitable because these
molecules are not stable at higher temperature whereas the advantage of the osmotic pressure is
that it can be measured at room temperature.
3. The osmotic pressure method has the advantage that it uses molarities instead of molalities.

Abnormal molar mass: When experimentally observed molar mass of a substance determined
on the basis of colligative property is found to be different from the normal value expected
exp from
its chemical formula. The observed molar mass is referred as abnormal molar mass. The cause
of obtaining abnormal molar mass is that colligative property depends only upon number numbe of
particles of solute in the solution. Since the molar mass of so solute
lute is inversely proportional to a
colligative Property the observed molar mass is also inversel
inversely
y proportional to the no. of particles
of solute in the solution, i.e.

Discrepancies (deviation) in determination of molar mass can occur when molecules of solute s
either dissociates or associates in solution. In case of association the no. of particles of solute
decrease in solution. Consequently observed value of colligative property decreases and a
higher value of molar mass is obtained. While in case of sol solute
ute undergoes dissociation in
solution. the no. of particles of solute increases, consequently observed value of colligative
property increases and lower value of molar mass is obtained.

Note: Acetic acid, benzoic acid etc when dissolve in benzene exist as dimer association generally takes
place in nonaqueous solvents, because in aqueous solution the high dielectric constant of water helps in
dissociation of associated molecules.

Vant’s Hoff factor(i): The ratio of observed (experimental) value of collig

colligative
ative property to the
normal value (calculated) of same colligative property is termed as Vant’s Hoff factor.

Note:
1. When solute undergoes association in solution ‘i’ is lesser than 1.
2. When solute undergoes dissociation in solution ‘i’ is greater than 11.
3. If observed colligative property is lesser than calculated value or observed molar mass is greater
than calculated molar mass (or ‘i’ is lesser than 1) there is association.
4. If observed colligative property is greater than calculated value or observed molar mass is lesser
than calculated molar mass (or ‘i’ is greater than 1) there is dissociation.
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The inclusion of Vant’s Hoff factor modifies the equation of colligative properties:

Note:
1. Degree of dissociation - is defined as the fraction of the total substance that undergoes
dissociation

2. Degree of association - is defined as the fraction of the total substance which exists in form of
associated molecules.