WELCOME

UNIT-2 SOLUTIONS

PART1

SUNILKUMAR
HSST CHEMISTRY
GOVT HSS FOR GIRLS
KANNIAKULANGARA
THIRUVANANTHAPURAM
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Mixtures:- A combination of two or more elements or

compouds in any proportion is called mixture

MIXTURE

Homogenous Mixture Heterogenous Mixture

The composition is same The composition is not same
throughout the sample throughout the sample

Example Example

Sugar in water Oil in water

Seawater Sand and water
Air
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Solutions
Solvent

the component
which is
Solute present in
The component largest quantity
other than
solvent

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Some Definitions
A solution is a
homogeneous mixture of 2
or more substances called
components.
A solution containing two
component is called binary
solution.
In solution ,the component
which is present in the largest
quantity is called solvent.
The components other than
solvent are called solutes
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Solute Solvent Example

Depending
Gas Gas Mixture of gases, Air
upon the
nature of Liquid Gas Water vapour in air,Mist
solute and Solid Gas Vapours of iodine in
air,Camphor in N2
solvent
SOLUTE- Gas Liquid CO2 dissolved in
water(aerated soft drink)
lesser Liquid Liquid Mixture of miscible liquids
amount (alcohol in water)
Solid Liquid Salt in water,Sugar in water
SOLVENT –
largest Gas Solid Solution of H2 in
Pd(occlusion)
quantity
Liquid Solid Hg in Zn,Hg in Au
Solute +
Solid Solid Homogenous mixture of
Solvent = two or more metals (alloys)
Solution ,Cu in Au ,Zn in Cu (Brass)
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Expressing Concentration

Mass percentage
Volume percentage
Mass by volume percentage
Parts per million
Mole Fraction (χ)
Molarity (M)
Molality (m)
Normality(N)
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Mass percentage
Mass percentage (w/w): The mass percentage of a
component in a solution is the mass of the component per
100gm of the solution
Mass % of a component
= Mass of the component in the solution ×100
Total mass of the solution
If WB is the mass of the solute and WA is the mass of the
solvent
Mass % of A = WA x100
WA+ W B

Mass % of B = WB x 100
WA+W B
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Volume percentage
The volume percentage of a component in
a solution is defined as the volume of the
component per 100 parts by volume of the
solution:

Volume % of a component =
Volume of the component ×100
Total volume of solution
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Mass by volume percentage

It is the mass of the solute
dissolved in 100 ml of the solution

Mass/volume percentage=
Mass of the component in solution X100
Total volume of the solution
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Parts per million(PPM)

When a solute is present in minute
amount ,the concentration is expressed
in parts per million (ppm).
It is defined as the mass of the solute
present per million parts by mass of
the solution.

PPM= Mass of the component ×106

Total mass of the solution
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Mole Fraction (χ)

It is the ratio of number of moles one component to the
total number of moles present in the solution .It is
denoted by ‘x’ .
If ‘nA’and ‘nB’are the number of moles of two
components ‘A’ and ‘B’ present in the solution.

Molefraction of A, XA = nA
nA+nB
Molefraction of B, XB = nB
XA+ XB=1 nA+ nB

Sum of the molefraction of all the components in a

solution is unity(1)
Note:- molefraction is independent of temperature
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Molarity(M)
It is number of moles of solute dissolved per
litre of the solution.It is represented by ‘M’
Morarity = Number of moles of solute
Volume of the solution in litre

Or Molarity = Number of moles of solute x1000

Volume of solution in mL

Unit mol/L or molL-1 or Molarity=Wx1000

or M
M x V(mL)
Note:- The molarity of a solution changes with temperature
due to change in volume of the solution
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Molality
It is the number of solute dissolved
per kg(1000gm) of solvent
Molality = Number of moles of solute
Weight of solvent in kg
Molality=Number of moles of solutex1000
Weight of solvent in gm
Or Molality=W1x1000 W2-weight of solvent
M1x W2 Unit mol/Kg or molkg-1
or m
Note:- Molality of solution does not change with
temperature .This is because mass of the solvent does not
change with change in temperature.Therefore molality is
considered better for expressing the concentration of
solution.
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Normality(N)
Equivalent mass of acid = Molecular mass
Basicity
Basicity is the number of H+ ions given to the solution

Equivalent mass of base = Molecular mass

Acidity
Acidity is the number of OH- given to solution
Normality is defined as the number of gram equivalent of
solute dissolved per litre of the solution .It is denoted by ‘N’
Normality(N) = Number of gram equivalent of solute
Volume of solution in litre

Or Normality= Mass of solute x 1000

Eq. mass of solute x Volume of solution in ml
or Normality = Wx1000
E x V (mL)
 Dilution Formula
If ‘V1’ml of a solution with molarity ‘M1’ is diluted to ‘V2’ ml,then
the molarity of the resulting solution ‘M2’ is given by

M1V1=M2V2

This is applicable to normality as well

N1V1 = N2V2

If ‘V1’ml of a solution with molarity ‘M1’ is added to ‘V2’ ml of

molarity ‘M2’ of the same substance,then the molarity of the
resulting solution
M = M1V1+ M2V2
V1+V2
 Problems
1. Calculate the molefraction of ethylene glycol (C2H6O2)
CCcccaa
in a solution containing 20% C2H6O2 by mass

20% by mass means 20gm of (C2H6O2) & 80gm of water

Number of moles of C2H6O2 = 20/62 =0.322 mol
Number of moles of H2O = 80/18 = 4.444 mol
X C2H6O2 = 0.322 = 0.067
0.322 + 4.444
Similally ,X H2O= 1- 0.067= 0.932
HW.Calculate the molefraction of benzene in solution
containing 30% by mass in carbon tetrachloride.
2.Calculate the mass percentage of benzene (C6H6) and
carbon tetrachloride (CCl4) if 22gm of benzene is
dissolved in 122 g of carbon tetrachloride
Mass% of C6H6 = 22 x100 = 15.28%
22+122
Mass % of CCl4 = 122 x100 = 84.72%
22+122
3.Calculate the molarity of a solution containing 5 gm of
NaOH in 450 ml of solution
Molarity = Wx1000 = 5x1000 = 0.278 mol/L or M
MxV 40x 450
HW.Calculate the molarity of each of the following
solutions(a) 30gm of Co(NO3)2.6H2O in 4.3 L of solution
(b) 30 mL of 0.5M H2SO4 diluted to 500mL.
4.Calculate the molality of 2.5g of ethanoic acid(CH3COOH) in
75 gm of benzene
Molality =W1x1000 = 2.5x1000 = 0.556 mol/kg
M1 x W 2 60x75
Hw.Calculate the mass of urea (NH2CONH2) required in making 2.5
kg of 0.25 molal aqueous solution
5.Calculate (a) molality (b) molarity and (c) molefraction of KI if the
density of 20% (mass/mass) aqueous KI is 1.202gmL-1.
(a) Molality =W1x1000 = 20x1000 =1.506mol/kg
M1 x W 2 166x80
(b) Molarity = W x1000 density = mass/volume
MxV 1.202 = 100/volume
Volume = 83.19 mL
Molarity = 20 x1000 = 1.44M
166X 83.19
No. of moles of KI = 20/166 = 0.120 mol X KI =0.12 = 0.026
No.of moles of H2O= 80/18 = 4.444 mol 0.12+ 4.444
Solubility of solid in Liquids
The maximum amount of solute dissolved in
a given amount of solvent to form a saturated
solution at a particular temperature is called
solubility
The solubility of a solid in liquids depends upon
1.Effect of temperature :- In a saturated solution there
is an equillibrium .Therefore according to Le-chatlier
principle,if the dissolution process is endothermic,the
solubility increases with increase in temperature.If the
dissolution process is endothermic ,the solubility
decreases with rise in temperature.
2.Effect of pressure:-Pressure has no significant
effect on solubility of solids in liquids.This is because
solids & liquids are nearly incompressible and remain
unaffected by change in pressure
Solubility of Gases in Liquids
The solubility of a gas in a liquid depends upon the
following factors.
(i)Nature of the gas (ii) Temperature (iii) Pressure
(i) Nature of the Gas :- Generally easily liquifiable
gases are more soluble.Thus gases like CO2,HCl,NH3
etc are more soluble in water than gases like H2,O2 etc.
(ii) Temperature:- With increase in temperature the
solubility of gases generally decreases.
Due to this factor aquatic species are more
comfortable in cold water than warm water
(iii) Pressure:- The effect of pressure on the solubility
of gas is given by Henry’s law.
It states that the solubility of gas in a liquid is directly
proportional to the pressure of the gas.
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Most commonly used form of Henry’s law states that the
molefraction of the gas in a solution (XB) is proportional
to the partial pressure of the gas in vapour phase
Partial pressure of the gas = KH .molefraction of the gas or
P = KH . X B
Where ‘ K H ‘ is Henry’s law constant
Higher the value of KH at a given
pressure, lower is the solubility
of gas in liquid.
molefraction of solute

The value of KH increases with increase of temperature 21

Applications of Henry’s Law
* Toincrease the solubility of CO2 in soft
drinks and sodawater,the bottle is sealed
at higher pressure
*A medical condition known as Anoxia
in people living at high altitudes or
climbers
*A condition known as Bends
(Decompression sickness) in
Scuba divers
o

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 Vapour pressure of a liquid
The pressure exerted by the vapour above the liquid
surface which is in equilibrium with the liquid at a given
temperature.The vapour pressure of a liquid depends on
two factors.
(i)Nature of the liquid:- Each liquid has a characteristic
vapour pressure.It depends upon the magnitude of intermolecular
forces.Weaker the intermolecular forces,greater is the vapour pressure.
(ii)Temperature:- The vapour pressure of a liquid increases with
increasein temperature.At higher temperature,molecules will have
larger kinetic energy,therefore larger number of molecules will
escape into vapour state.

When a small amount of a non -

volatile solute is added to solvent,the
vapour pressure of the solution is
found to be less than that of pure
solvent
Raoult’s law for binary solution of volatile liquid
When two volatile liquids of A and B are mixed to form a
solution,the vapour phase consists of vapours of each
components.The partial pressure of each component
depends on molefraction of the corresponding component.

If PA and PB are the partial vapour pressure of the liquids A

and B in a solution and A and B are the molefraction.
PA α A or PA = P°A.B PB α B or PB = P°B.B

Where P°A and P°B are the vapour pressure of pure

componets A and B respectively

Raoult’s law states that at a given

temperature ,for a solution of volatile liquids, the

partial vapour pressure of each component is

directly proportional to its molefraction

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 P0B
P = P A+ P B
tot al
0
P
Vapour pressure

xA=1 molefraction xA=0

xB=0 xB=1

According to Dalton’s law of partial pressure

Ptotal = PA+ PB = P0A .XA + P0B.XB

= P0A (1-XB ) + P0B.XB = P0A - P0A .XB+ P0B.XB
Ptotal = P0A + XB ( P0B-P0A)
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According to Raoult’s law, Ptotal = PA+ PB = P0A .XA + P0B.XB
If ‘B’ is non volatile solute ,Ps = P0A.XA , Ps α XA

For solutions containing non-volatile solute Raoult’s law may be

stated as at a given temperature,the vapour pressure of a
solution is directly proportional to molefraction of solvent only

A plot between the vapour pressure and the mole fraction of the
solvent is linear
 Ideal Solutions
The solutions which obey Raoult’s law over the
entire range of concentration are known as
ideal solutions.
The ideal solutions should have the following
characteristics
(i)It should obey Raoult’s law ie, PA = P0A .XA and
PB= P0B.XB
(ii)Heat change on mixing is zero ( ΔHmix = 0 ), since
there is no change in magnitude of the attractive forces in two
components the heat change on mixing is zero
(iii)Volume change on mixing is zero ΔVmix = 0

In ideal solution ,the volume of the solution is

the sum of the volumes of components before
mixing.
(iv)Substances forming an ideal solution have
similar structure
Eg.(i)Benzene and Toluene (ii) n-hexane &n-heptane
(iii)Chlorobenzene and bromobenzene (iv) C2H5Br & C2H5Cl
Note:- Most of the dilute solutions behaves as ideal solutions
The vapour pressure of the solution always lies b/w the vapour
pressure of the pure components

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Non-ideal solutions
The solution which do not obey Raoult’s law are called non-ideal
solutions.In non-ideal solutions,there is a change in volume and
heat when the two components are mixed.

(i) PA # P0A .XA and PB# P0B.XB

(ii) Δ Hmixing # 0

(iii) ΔVmixing # 0

The non-ideal solutions are further classified into two types

(i)Solution showing ‘+’deviation
(ii)Solution showing – ve deviation
(i)Solution showing ‘+’deviation
Consider a binary solution of two components A and B.If the
A-B interaction are weaker than A-A and B-B interactions,the escaping
tendency of A and B molecules from the solutions becomes more.As a
result the partial vapour pressure of each component is higher than
that expected from Raoult’s law.Therefore the total vapour pressure of
the solution is greater than the vapour pressure as expected according
to Raoult’s law.

PA > P0A .XA and PB > P0B.XB

>
The total vapour pressure of the solution Ps > PA+ PB
Here Δ Hmixing= + ve , ΔVmixing = + ve
Eg:(i) Ethyl alcohol & cyclohexane (ii) Acetone & Benzene
(iii) Acetone & Cabondisulphide(iv)Ethyl alcohol & water
(v) Acetone & Ethyl alcohol

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 Solution showing – ve deviation
Consider a binary solution of two components A and B .If the A-B interactions are
stronger than A-A and B-B interaction,the escaping tendency of A and B molecules
from the solution becomes less. As a result partial vapour pressure of each
component is less than that expected from Raoult’s law.Therefore the total vapour
pressure of the solution is lower than the vapour pressure as expected according to
Raoult’s law
PA < P0A .XA and PB < P0B.XB
The total vapour pressure of the solution Ps < PA+ PB
Here ΔHmixing= - ve , Δ Vmixing = - ve
Eg: (i) Acetone & chloroform (ii) Chloroform & HNO 3 (iii) H2O & HNO3 (iv) H2O & HNO3 (v) H2O & HCl
 Azeotrope (constant boiling mixtures)
The solution which boils at constant temperature and distilled over
completely at that temperature without any change in composition
are called azeotropes.These are of two types
(i)Minimum boiling azeotropes :- The solution which show positive
deviations from Raoult’s law are called minimum boiling
azeotropes,because they have a composition having minimum
boiling point.They have boiling points lower than either of the
components
Eg :- H2O (4.4%) & C2H5OH (95.6%)
B.P 1000C 78.60C Boiling point of azeotrope is 78.10C
(ii)Maximum boiling azeotrope :- The solution which show
negative deviations from Raoult’s law are called maximum boiling
azeotropes,because they have a composition having maximum
boiling point.They have boiling points higher than either of the
Components
.
Eg (i) H2O (80%) & HCl (20%)
B.P 1000C 20.20C Boiling point of azeotrope is 108.60C
 COLLIGATIVE PROPERTIES (Democratic properties)

The properties of a solution which depends only on the number of

moles of solute particles but not the nature of the solute are called
colligative properties.
The four important colligative properties are
(i)Relative lowering of vapour pressure (ii) Elevation of boiling point
(iii) Depression of freezing point (iv) Osmotic pressure
(i)Relative lowering of vapour pressure

The presence of a non-

volatile solute means
that fewer solvent
particles are at the
solution’s surface, so
less solvent evaporates.
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When a non-volatile solute is added to a solvent the vapour pressure
of the solution is lowered.This phenomenon is called lowering of
vapour pressure.
According to Raoult’s law, Ps = P0A .XA + P0B.X B

0 0
If ‘B’ is non-volatile , P B= 0 , Ps = P A XA But XA = 1-XB
0
(1-XB)
0A 0 0 0
Ps = P A , Ps = P - P A XB , P A – Ps = P A XB

B
(P - Ps) is the lowering of vapour pressure P A- Ps
0
A
0
=
0
P A
P0A–Ps = XB Represent the relative lowering of vapour pressure
P0 A
According to the above equation , the relative lowering of
vapour pressure depends only on the molefraction of the non-
volatile solute.So it is a colligative property
For very dilute solution , nB<< nA

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 (ii)Elevation of Boiling point
The boiling point of a liquid is defined as the temperature at which
the vapour pressure of a liquid becomes equal to the atmospheric
pressure.The vapour pressure of a solution is lower than that of
solvent, the solution has to be heated to a high temperature so as to
equalize its vapour pressure with the atmospheric pressure.Thus the
boiling point of the solution will be higher than that of the pure
solvent.The difference between the boiling points of the solution (T b )
and the solvent (T0b) is called the elevation of boiling point. Thus

ΔTb= Tb -T0b

Elevation boiling point is directly proportional

to molal concentration of the solute in a solution.

ΔTb α m ,ΔTb = Kb m where ‘Kb’ is called molal elevation constant

or boiling point elevation constant or molal ebullioscopic constant. 37
From the above equation it is clear that , the elevation
of boiling point depends upon the number of moles of
solute but does not depend upon the nature of the
solute. So it is a colligative property.
When molality ,m=1 , ΔTb = Kb
Hence molal elevation constant is defined as the
elevation in boiling point produced for 1 molal solution
(when one mole of non-volatile solute is dissolved per
kilogram(1000g) of solvent).Its unit is K kg mol-1 or K
molal-1
Calculation of molarmass of non-volatile solute

ΔTb = Kb m But Molality,m = WB.1000

MB . W A
ΔTb = Kb WB .1000
MB .WA
MB = Kb xWB x1000
ΔTb xWA
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 (ii)DEPRESSION OF FREEZING POINT
The freezing point of a substance is the temperature at which the
solid and liquid phase of the substance have same vapour
pressure.When a non-volatile solute is dissolved in a solvent,its
vapour pressure decreases.Since vapour pressure of the solution is
decreased ,it will become equal to that of the solid solvent at a lower
temperature.It is evident from the figure.

ΔTf = T0f -Tf

Tf0 -freezing point of pure solvent

Tf -freezing point of solution
Depression of freezing point is directly
proportional to molal concentration of
the solute in a solution.

ΔT α m ,ΔT = K m where ‘K ’ is called molal depression constant

f f f f
or freezing point depression constant or molal cryoscopic constant.
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From the above equation it is clear that , the depression
of freezing point depends upon the number of moles of
solute but does not depend upon the nature of the
solute. So it is a colligative property.
When molality ,m=1 , ΔT = K
f f
Hence molal depression constant is defined as the
depression of freezing point produced for 1 molal
solution.
(when one mole of non-volatile solute is dissolved per
kilogram(1000g) of solvent).Its unit is K kg mol-1 or K
molal-1
Calculation of molarmass of non-volatile solute

ΔTf = Kf m But Molality,m = WB.1000

MB . W A
ΔTf = Kf WB .1000
MB .WA MB = Kf xWB x1000

ΔTf xWA 40