CHEMISTRY

SOLUTION
• Definition:
• Solution is a homogeneous mixture of two or more non-reacting
components.
• If there are two components, then the solution is said to be binary
solution.
• The component present in largest quantity is called solvent and the
other components are called solutes.
Types of Solute Solvent Examples
solutions
Gas Mixture of O2 and N2,
Gaseous Gas [Link] of
solutions Liquid Gas chloroform and N2

Solid Gas [Link] in N2

gas.

Gas Liquid O2 dissolved in water.

Liquid Ethanol dissolved in
solutions Liquid Liquid water.
Solid Liquid Glucose dissolved in
water, salt solution,
and sugar solution.

Gas Solid H2 in Pd.

Solid Sodium amalgam,
solutions Liquid Solid Zinc amalgam.
Solid Solid Cu dissolved in gold,
alloys (Brass,
bronze).
Terms to express the concentration of
solution
Molarity(M)
It is the number of moles of solute present per litre of solution.

Where = given mass of solute

w 1000
= molar mass of solute
M
V= volume of solution inB ml
mB  V
wB
mB
QUESTION

Calculate the molarity of a solution containing 5 g of NaOH in 450 mL

solution.
Molality (m)
It is the number of moles of solute present per 1000 g. of solvent.

w 1000
Where
m B of solvent.
is the given mass

mB  w A
wA
QUESTION

Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of

benzene.
Percentage:
It is the no of parts by mass or volume of solute or solvent present
in 100 parts by mass or volume of solution.
Mass / Mass percentage :

Mass/volume percentage :

wB
 100
wA  wB

wB
  100
V
Volume / Volume percentage:

vB
  100
V
MOLE FRACTION :

It is the ratio of number of moles of a particular component to the

total number of moles of all the components.
Let n
mole of solute is dissolved in
A
moles of solvent.
nB
Then

nA
A 
n A  nB
Where =mole fraction of solvent
n
B  B
= mole fraction of solute

n A  nB
A
B
PPM-Percentage-It is the no of parts by mass or volume of solute or
solvent present in parts by mass or volume of solution.

vB
ppm  10 6

v A  vB
wB
ppm   10 6

wA  wB
Relationship between molarity and density

x  d 10
M
mB
Where x is the mass percentage.
d is the density of the solution.
 Solubility:
• It is defined as maximum amount of solute dissolved in a
specified amount of solvent at a constant temperature.
(a)Solubility of solid in a liquid:
It depends upon the following factors.
• Nature of solute and solvent:
Like dissolves like, i.e polar solutes are dissolved in polar solvents
and non-polar solutes are dissolved in non-polar solvents.
Temperature:
• If the dissolution process is endothermic, then solubility increases
with increase in temperature.
• If the dissolution process is exothermic, then solubility decreases
with increase in temperature.
Pressure:
• Pressure has no effect on solubility of solid in liquid as solids are
incompressible.
 (b)Solubility of gas in liquid:
• Almost all gases are soluble in water and easily liquefiable gases
are more soluble.
• Solubility of gas in liquid is greatly affected by pressure as gases
are highly compressible and effect of pressure on this solubility is
given by Henry’s law.
Statement:
The solubility of a gas in a liquid is directly proportional to the
partial pressure of the gas.
Modified Henry’s law
The partial pressure of the gas in vapour
phase (p) is proportional to the mole fraction
of the gas (x) in the solution” and is
expressed as:
p = KH x
 Where KH is Henry’s constant which depends on nature of gas.
• Solubility of a gas in liquid decreases with increase in the value of
KH
Applications of Henry’s law

• To increase the solubility of CO2 in soft drinks and soda water, the
bottle is sealed under high pressure.
• 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, 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).
• 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.
Effect of Temperature
Solubility of gases in liquids decreases with rise in
temperature. When dissolved, the gas molecules are present
in liquid phase and the process of dissolution can be
considered similar to condensation and heat is evolved in
this process. We have learnt in the last Section that
dissolution process involves dynamic equilibrium and thus
must follow Le Chatelier’s Principle. As dissolution is an
exothermic process, the solubility should decrease with
increase of temperature.
If N2 gas is bubbled through water at 293 K, how
many millimoles of N2 gas would dissolve in
1litre of water? Assume that N2 exerts a partial
pressure of 0.987 bar. Given that Henry’s law
constant for N2 at 293 K is 76.48 kbar.
Evaporation:

• The process by which liquid molecules escape from its surface to

vapour state is called evaporation.
• It is a surface phenomenon.
• It causes cooling because the average kinetic energy of the remaining
molecules decreases.
Vapour pressure of a liquid
• If evaporation takes place in closed vessel equilibrium exists
between liquid and vapour. At equilibrium rate of evaporation is
equal to rate of condensation.
• The pressure exerted by the vapours when it is in equilibrium
with liquid at a given temperature is called vapour pressure.

Vapour pressure of solution:

• When a non-volatile solute is dissolved in a liquid, the vapor
pressure of the solution is less than the vapor pressure of pure
solvent.
 RAOULT ’S LAW FOR A SOLUTION
CONTAINING NON VOLATILE SOLUTE
STATEMENT
The vapour pressure of a solution
containing non volatile solute is directly
proportional to the mole fraction of the
solvent.
•Mathematically,
 
Ps X1
=> Ps = P0X1
Where P0 is the vapour pressure of pure solvent.
Ps is the vapour pressure of solution.
X1 is the mole fraction of solvent.
Let vapour pressure of solution is Ps
Mole fraction of solvent is XA
So according to this law
P  A
s

Ps  P0  A
Ps
0
 A
P
Ps
1 0  1  A
P
P 0
 P s
Where XB = mole 0
  B of solute
fraction
P
Po - Ps / Po = relative lowering in vapour pressure
Po – Ps = lowering in vapour pressure
 RAOULT ’S LAW FOR VOLATILE
COMPONENT
STATEMENT
For a solution containing volatile components ,
the partial vapour pressure of each component
is directly proportional to the mole fraction of
that component in solution.
PA α X A
PA  P X A
o
A
similarly PB α XB

PB  PBo X B
Then total pressure is

PA  P X A o
A

PB  P X B B
o

Ptotal  PA  PB
Ptotal  P X A  P X Bo
A B
o

Ptotal  P (1  X B )  P X B
o
A B
o

Ptotal  P  ( P  P ) X B
o
A B
o o
A
Partial pressure of the components in vapour
phase

PA  Ptotal y A
PB  Ptotal y B
Raoult’s law as a special case of Henry’s law

According to Raoult’s law

PP X o
According to Henry’s law

So whenP =K H then

X Raoult’s law becomes the special case of Henry
’s law. o
P KH
Ideal solutions
Solutions which obey Raoult’s law over the entire range of
concentration are called ideal solutions.
Characteristics-
• ∆mix V = 0 => Vsolute + Vsolvent = Vsolution
• ∆mixH = 0 i.e heat energy is neither released nor absorbed

•
PA  PAo X A
PB  PBo X B
A-A interaction & B-B interaction =A-B interaction
Vapour pressure and mole fraction graph
EXAMPLES OF IDEAL SOLUTION

Benzene & Toluene

n-Hexane & n-Heptane
Chloro benzene & Bromo benzene
CCl4 & SiCl4
Non Ideal solution

Solutions which do not obey Raoult’s law over the entire

range of concentration are called non ideal solutions.
Characteristics-
• ∆mix V ≠ 0
• ∆mixH ≠ 0
• A-A interaction & B-B interaction ≠A-B interaction
PA  PAO X A
PB  PBO X B
 Types of Non Ideal solution

• Non ideal solution showing +ve deviation from Raoult’s law

Characteristics-
• ∆mix V > 0 => Vsolute + Vsolvent < Vsolution
• ∆mixH > 0 i.e heat energy is absorbed.
• A-B interaction < A-A interaction & B-B interaction
• Ptotal > PA0XA + PB0XB

PA  PA0 X A
PB  PB0 X B
Vapour pressure and mole fraction graph
EXAMPLES OF NON IDEAL SOLUTION WITH
+ve DEVIATION

• Acetone & Ethanol, water & Ethanol, Acetone & CS2

• Consider a binary solution of acetone and ethanol. In ethanol there is
intermolecular H-bonding and in acetone there is dipole-dipole
interaction. When acetone is added to ethanol, acetone molecules
interact with ethanol molecules and occupy space between them. So
volume of solution increases and more no. of molecules vaporize. So
vapor pressure increases and solution shows positive deviation.
• Non ideal solution showing -ve deviation
Characteristics-
• ∆mix V < 0 => Vsolute + Vsolvent > Vsolution
• ∆mixH < 0 => Heat energy is released.
• A-B interaction > A-A interaction & B-B interaction

PA  PA0 X A
PB  P X B
B
0
Vapour pressure and mole fraction graph
EXAMPLES OF NON IDEAL SOLUTION WITH
-ve DEVIATION

• Acetone & chloroform, water & HNO3, water & HCl.

• Consider a binary solution of acetone and chloroform. In acetone
there is dipole-dipole interaction. When acetone is added to
chloroform, intermolecular H-bond is formed between them. So
attractive force become stronger and less no. of molecules vaporize.
Hence vapor pressure of solution decreases and solution shows
negative deviation.
Azeotropes:
• Azeotropes are the mixture of two liquids which
boil at constant temperature like a pure liquid
without undergoing any change in the
composition.
• Azeotropes are of two types.
Minimum boiling azeotropes:
• Azeotropes which show positive deviation from
Raoult’s law are known as minimum boiling
azeotrope.
• These azeotropes have lower boiling point than
both the components.
• Ex: Water (4.43%, 373K) & ethanol (95.57%,
351.3K) B.P of azeotrope= 350K.
Maximum boiling azeotropes:
• Azeotropes which show negative deviation
from Raoult’s law are known as maximum
boiling azeotrope.
• These azeotropes have higher boiling point
than both the components.
• Ex: Water (42%, 373K) & HNO3 (58%, 359K)
B.P of azeotrope= 393.5K.
Colligative properties
The properties of solutions which depend on
the numbers of solute particles and are
independent of their nature are called
colligative properties.
[Link] lowering in vapour pressure,
[Link] in boiling point
[Link] in freezing point
[Link] pressure.
[Link] LOWERING IN VAPOUR PRESSURE
•Let
  vapour pressure of pure solvent is p0
and vapour pressure of solution is ps
As vapour pressure of pure solvent is more than that of
solution, so p0 > ps
So lowering in vapour pressure(Δp) = p0 – ps
According to Raoult’s law , ps = p0x1
So, Δp = p0 – p0x1 = p0(1 - x1) = p0x2
where x2 is the mole fraction of solute.
=> = x2
where = Relative lowering in vapour pressure which is
equal to mole fraction of solute.
• So,
  =
For very dilute solutions, n1 > > > n2
=> = =

=> =
Where w2 is given mass of solute.
w1 is given mass of solvent.
M2 is molar mass of solute.
M1 is molar mass of solvent.
QUESTION
The vapour pressure of pure benzene at a
certain temperature is 0.850 bar. A non-
volatile solute weighing 0.5 g when added to
39.0 g of benzene, Vapour pressure of the
solution becomes 0.845 bar. What is the
molar mass of the solute?
[Link] IN BOILING POINT
• The temperature at which vapour pressure of liquid is
equal to the atmospheric pressure is called boiling
point.
• Boiling point of solution is more than the boiling
point of pure solvent because the vapour pressure of
solution is less than the vapour pressure of pure
solvent.
• The difference in the boiling point of solution and
pure solvent is called elevation in boiling point.
Let Tb0 is the boiling point of pure solvent.
Tb is the boiling point of solution.
So, Elevation in boiling point (ΔTb) = Tb – Tb0
• Experiment shows that the elevation in boiling
point is directly proportional to molality of the
solution.
So, ΔTb α m (molality)
=> ΔTb = Kbm
where Kb is the molal elevation constant or
Ebullioscopic constant.
• When m = 1moles per kg then ∆Tb = Kb.
• Molal elevation constant or Ebullioscopic
constant is defined as the elevation in boiling
point when molality of the solution is unity.
• Unit of Kb is [Link]-1
•  ΔTb = Kbm
=> ΔTb =

where w2 is given mass of solute.

M2 is molar mass of solute.
w1 is given mass of solvent.
QUESTION
Calculate the boiling point of a solution
prepared by dissolving 0.52g of glucose in
80.2g of water.(Kb is [Link]/mol)
(3)Depression in freezing point or Cryoscopy:
The temperature at which vapour pressure of liquid
is equal to the vapour pressure of solid is called
freezing point.
• Freezing point of solution is less than the freezing
point of pure solvent because the vapour pressure
of solution is less than the vapour pressure of pure
solvent.
• The difference in the freezing point of pure solvent
and solution is called depression in freezing point.
Let Tf0 is the freezing point of pure solvent.
Tf is the freezing point of solution.
So, Depression in freezing point (ΔTf) = Tf0 – Tf
Freezing point and v.p. graph
• Experiment shows that the depression in freezing point
is directly proportional to molality of the solution.
So, ΔTf α m (molality)
=> ΔTf = Kfm
where Kf is the molal depression constant or Cryoscopic
constant.
• When m = 1moles per kg then ∆Tf = Kf.
• Molal depression constant or Cryoscopic constant is
defined as the depression in freezing point when
molality of the solution is unity.
• Unit of Kf is [Link]-1
•  ΔTf = Kfm
=> ΔTf =

where w2 is given mass of solute.

M2 is molar mass of solute.
w1 is given mass of solvent.
QUESTION
45 g of ethylene glycol (C2H6O2) is mixed with 600 g of
water. Calculate
(a) the freezing point depression and (b) the freezing
point of the solution.
NOTE BELOW-
OSMOTIC PRESSURE

OSMOSIS
• The spontaneous flow of solvent molecule from pure solvent side to
solution side(from lower concentration to higher concentration)
through SPM is called osmosis.
OSMOTIC PRESSURE
• The pressure that just stops the flow of solvent is called osmotic
pressure of the solution.
• osmotic pressure is proportional to the molarity, C of the solution
at a given temperature T.
• Mathematically

Where V=Volume in Lit

  CRT
  nRT / V
  wB RT / M BV
M B  wB RT /  V
The osmotic pressure method has the advantage over other methods
• pressure measurement is around the room temperature.
• molarity of the solution is used instead of molality.
• As compared to other colligative properties, its magnitude is large
even for very dilute solutions.
• The technique of osmotic pressure for determination of molar mass of
solutes is particularly useful for biomolecules as they are generally not
stable at higher temperatures and polymers have poor solubility.
Isotonic solution
• Two solutions having same osmotic pressure at a given
temperature are called isotonic solutions.
• For example, the osmotic pressure associated with the
fluid inside the blood cell is equivalent to that of 0.9%
(mass/volume) sodium chloride solution, called normal
saline solution and it is safe to inject intravenously.
• On the other hand, if we place the cells in a solution
containing more than 0.9% (mass/volume) sodium
chloride, water will flow out of the cells and they would
shrink. Such a solution is called hypertonic.
• If the salt concentration is less than 0.9% (mass/volume),
the solution is said to be hypotonic. In this case, water
will flow into the cells if placed in this solution and they
would swell.
• People taking a lot of salt or salty food experience water retention in
tissue cells and intercellular spaces because of osmosis. The resulting
puffiness or swelling is called edema.
• Through the process of osmosis, a bacterium on salted meat or
candid fruit loses water, shrivels and dies.
• The preservation of meat by salting and of fruits by adding sugar
protects against bacterial action.
 Reverse Osmosis
•The flow of solvent molecules
from solution side to pure solvent
side by applying external pressure
more than osmotic pressure on
solution side is called Reverse
osmosis.
e.g. desalination of sea water.
Abnormal molar mass

• a molar mass that is either lower or higher than the expected or

normal value is called as abnormal molar mass.
• It is due to the association or dissociation of solute particles in
solution i.e. during association no of particles in solution decreases
and in case of dissociation no of particles in solution increases.
Van’t Hoff factor(i).

The ratio of experimental value of a colligative property to the

theoretical value is known as Van’t Hoff factor(i).
OR
The ratio of normal molar mass to the abnormal molar mass is known
as Van’t Hoff factor(i).
In dissociation
i 1

n 1
where α = degree of dissociation.
i= van't Hoff factor
n= no. of particles after dissociation.
In association
i 1
  1
n 1
where α = degree of association.
i= van't Hoff factor
1/n= no. of particles after association.
EXAMPLES OF van't Hoff's factor

• For NaCl it is 2
• For it is 3 Na2 SO4
• For it is 5
Al2 (SO4dimerisation
• For a substance undergoes
)3 is 0.5 and a substance
undergoes tetramerisation is 0.25.