Concentration Term

Chemical Classification
of Matter

Pure
Mixtures
Substances

Homogeneous Heterogeneous
Homogeneous Mixtures Heterogeneous Mixtures

 Uniform composition and  Non-uniform composition

properties. and properties.

 Number of phases = 1  Number of phases = 2 or more than 2

 Example : Solutions  Example : Colloids, Suspensions

Solutions

Solutions are homogeneous mixtures of two or more than two

components (solute and solvent) which are chemically non reacting.

Identification of Solvent AND SOLUTE

(1) (2)
Sugar Water Alcohol Water
Solid Liquid Liquid Liquid
50 gm 100 gm 50 gm 100 gm
Solute Solvent Solute Solvent
100 gm 50 gm 100 gm 50 gm
Solute Solvent Solvent Solute

Solvent is that component in solution whose physical state is the same

as that of the resulting solution while other component is called as
solute.
If the physical state of both component is same, then the component
in excess is known as solvent and other one is called as solute.
 On the basis of number of
components present in solution

Types of
solutions

On the basis of physical state

of solvents
On the basis of number of components present in solution

Binary : Two components (one solvent + one solute)

Ternary : Three components (one solvent + two solutes)

Quaternary : Four components (one solvent + three solutes)

On the basis of physical state of solvents

Gaseous Solutions : Solvent is in gaseous state.

Liquid Solutions : Solvent is in liquid state.

Solid Solutions : Solvent is in solid state.

On the basis of physical state of solvents
Solution (Solid in Solid)

Formed by mixing of two solid component Brass (Cu + Zn), German

Silver (Cu + Zn + Ni) Bronze (Cu + Sn)

Substitutional solid, Brass

Interstitial solid, Tungsten Carbide

Solution (liquid in liquid)

When one liquid dissolved into another liquid molecules of solvent

are accommodating molecules of solute.

Completely Miscible

Partially Miscible

Immiscible
Solution (solid in liquid)

The solubility of a solid in liquid at any temperature is define as

Maximum amount of solid (solute) in gram dissolved into 100 gm
of the liquid (solvent) at temperature.

Saturated Solution

Unsaturated Solution

Super Saturated Solution

 Some important definition

Dissolution

When a solid solute is added to the solvent, some solute dissolves and
its concentration increases in solution. This process is known as
dissolution

crystallisation

Some solute particles in solution collide with the solid solute particles
and get separated out of solution. This process is known as
crystallisation.
 Solubility

Maximum amount of solute which can be dissolved in a specified amount

of solvent at constant temperature is solubility.

Solubility is affected by -

 Nature of solute and solvent

 Temperature

 Pressure
Nature of Solute and Solvent

It is observed that polar solutes dissolve in polar solvents and non

polar solutes in nonpolar solvents.

In general, a solute dissolves in a solvent if the intermolecular

interactions are similar in the two or we may say like dissolves like.
 Temperature effect

1. In general if DHdiss > O Endothermic process

sgas  Temperature Ex- NaCl, KCl

2. In general if DHdiss < O Exothermic process

1
sgas  Ex- Na2CO3.H2O, Li2CO3
Temperature
 Effect of pressure

Pressure does not have any significant effect on solubility of solids

in liquids. It is so because solids and liquids are highly incompressible
and practically remain unaffected by changes in pressure.
CONDITION FOR SOLUBILITY

Solubility of ionic compound into polar solvent due to (H.E.)  L.E

Non-polar compound due to similar solute-solvent, solvent-solvent,

solute-solvent interaction.
Solubility of Gas in Liquid

In general all gases are solute in solvent in some extent.

Nature of gas and solvent

Effect of Temperature

Effect of Pressure
Solubility of Gas in Liquid
Solubility of Gases in Liquid
Henry's Law

The partial pressure of the gas in vapour phase (P) is

proportional to the mole fraction of the gas (𝜒) in the solution.

P = KH 𝝌

Here,

KH = Henry's Constant

𝝌 = Mole fraction or solubility

 P = KH 𝝌

Henry’s constant :

 Henry's Constant is not a universal constant.

 It depends on nature of gas and temperature.

 KH increases with increase in temperature therefore

solubility of gas decreases.

 Unit of KH = Unit of Pressure

Gas Temperature/K KH/kbar Gas Temperature/K KH/kbar
He 293 144.97 Argon 298 40.3
H2 293 69.16 CO2 298 1.67
N2 293 76.48 Formaldehyde 298 1.83 × 10-5
N2 303 88.84 Methane 298 0.413
O2 293 34.86 Vinyl chloride 298 0.611
Application of Henry's Law

 To increase solubility of CO2 in soft drinks

 Sea divers use air diluted with He to avoid a condition

known as ‘bends’ to cope up with high ‘P’ under water.

 At high altitudes, when partial pressure of O2 is less, it

leads to a condition known as ‘Anoxia’.
Limitation

 It is valid only for ideal behaviour of gas. As none of the gas

is ideal, this law may be applied at low pressure and high
temperature

 It gives better result when the solubility of gas in the liquid

is low.

 The gas should neither dissociate nor associate in the liquid.

 Example

The Henry's law constant for the solubility of nitrogen gas in water
at 298 K is 1 × 105 atm. The mole fraction of nitrogen in air is
0.8. Calculate the number of moles of nitrogen from air dissolved in
10 moles of water at 298 K and 5 atm pressure of air.

Solution

Ans. (4 × 10-4 moles)

 Example

The value of Henry’s law constant for some gases at 293 K is given
below. Arrange the gases in the increasing order of their solubility.
He : 144.97 kbar, H2 : 69.16 kbar,
N2 : 76.48 kbar, O2 : 34.86 kbar
(A) He < N2 < H2 < O2 (B) O2 < H2 < N2 < He
(C) H2 < N2 < O2 < He (D) He < O2 < N2 < H2

Solution

Ans. (A)
 Alternate Statement of Henry’s Law

 Solubility of a gas in liquid at given temperature is

directly proportional to pressure.

s  P

 The mass of a gas dissolved into a liquid at constant

temperature is proportional to pressure at gas

m  P
Variation of solubility of gas with pressure

s
P
Variation of solubility of some gases with equilibrium pressure

Oxygen

Nitrogen

s
Helium

P
Henry’s constant :
Important Points

Certain gases are highly soluble in water like NH3, HCl etc. and
certain gases are less soluble in water like O2, N2, He etc.

Increasing pressure increases solubility.

Increase in temperature decreases solubility.

Those gases which can react with solvent do not follow Henry's Law.
e.g. NH3 in water.

For real gases Henry's Law can only be applied at low pressure and
high temperature conditions.
 Limitations of Henry's Law

Henry’s law is valid only if

1. Pressure is low

2. Temperature is high

3. Gas Can’t React with Solvent

4. Henry’s law is applicable on only very dilute solution

5. Henry’s law is a special case of Roult’s law

 Example

If N2 gas is bubbled through water at 293 K, how many millimoles of N2

gas would dissolve in 1 L 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.

Solution

Ans : 0.716 mmol

 Example

Solubility of a specific non-volatile salt is 4 gm in 100 gm H2O at 25°. If

2 gm, 4 gm and 6 gm added to 100 gm water at 25°C in system x, y, z.
The order of V.P. is

Solution

Ans : y = z > x
 Example

INCORRECT statement is:

(A) (KH) O2 > (KH)H2 at T K
(B) Henry constant not applicable on HCl(g)
(C) KH , T 
(D) Henry law apply on very dilute solution.

Solution

Ans : (A)
 Example

Henry constant for solubility of N2 gas in H2O at 298 K is 105 atm.

The mole fraction of N2 in Air is 0.6 the number of mole of N2 from
air dissolved in 10 mole of H2O at 298 K and 5 atm is

Solution

Ans : 3 × 10–4
Ans :2.6 285
2.7 1.846 gm
 Vapour Pressure
 We have a container filled with pure substance at a constant
temperature.

 Initially evaporation takes place and molecules at the surface are

converting into vapours.
 If it is covered then vapours will start to exert pressure and condensation
also takes place.

 Rate of evaporation is same but rate of condensation increases.

 At given temperature, this is the maximum pressure exerted by vapours.

At dynamic equilibrium,
Rate of evaporation = Rate of condensation
Vapour Pressure

Dynamic equilibrium
established

Rate of evaporation

Rate
Time
Vapour Pressure of a Liquid

At a constant temperature, the pressure exerted by the vapours

of a liquid on its surface when they (liquid and its vapours) are in
equilibrium, is known as vapour pressure.

Vapour pressure of pure liquid is represented by " P° ".

H2O(l) ⇌ H2O(g) ; KP = PH° 2O

Factors affecting vapour pressure

(a) Nature of liquid

R O
H

Strong intermolecular force of attraction, Less vapour pressure

Weak intermolecular force of attraction, More vapour pressure

(b) Temperature

If temperature increases

Kinetic Energy of molecules / atoms increases

More particles will convert to gaseous phase as inter molecular

forces of attraction can now be overcomed.

Vapour pressure increases.

If temperature is increased, vapour pressure increases.

 Factors affecting vapour pressure

Effect of temperature on vapour pressure can be explained

For an equilibrium

A(ℓ) ⇌ A(g)

Kp = PA

Equilibrium constant = Vapour pressure of A.

Kp = P1 (at T = T1)
1

Kp = P2 (at T = T2)
2
 Factors affecting vapour pressure

Then, Vant Hoff’s equation can be shown as

K p2 ΔH 1 1
log = − ΔvapH > 0
K p1 2.303R T1 T2

P2 ΔH 1 1
∴ log = −
P1 2.303R T1 T2
 Note

1. Vapour pressure does not depend on amount of substance and surface

area.

2. More volatile liquid has lower Boiling point

Less volatile liquid has higher Boiling point

Evaporation vs. Boiling

 Bubbles can not form.

 It can take place at any temperature.

 Vapour Pressure < External Pressure

Evaporation
Evaporation vs. Boiling

 Bubbles can form and rise.

 It occurs at specific temperature(boiling point).

What happens to
vapour pressure
when we add two
miscible liquids
 According to Raoult's law

The Raoult’s law states that for a solution of volatile liquids, the
partial vapour pressure of each component of the solution is directly
proportional to its mole fraction present in solution.
 According to Raoult's law

PA α xA PA = PA∘ xA
PB α xB PB = PB° xB

PTotal = PA + PB

Where,
xA, xB → Mole fraction of A and B in liquid solution at equilibrium.
PA° , PB° → Vapour pressure of pure component 1 and 2 at the same
temperature.
PA, PB → Vapour pressure contribution of A and B respectively.

PTotal = PA + PB = PA° xA + PB° xB

In a given phase, sum of the mole fractions of all components = 1

xA + xB = 1
xA = 1 – xB
So, PTotal = xA PA° + (1 – xA) PB°

PS = PB° – xAPB° + xAPA°

PS = PB° + (PA° – PB° ) xA

Y = c + mx
Graph of Raoult's law
 P∘B

Vapour Pressure
P∘A

xA = 1 Mole Fraction xA = 0
xB = 0 xB = 1
 P∘B

Vapour Pressure
d

P∘A
c

xA = 1 a xA = 0
xB = 0 Mole Fraction xB = 1
 P∘B

Vapour Pressure
d

P∘A
c

xA = 1 a xA = 0
xB = 0 Mole Fraction xB = 1
 Example

Two liquid A and B are mixed to form an ideal solution. If one mole of
A and 4 moles of B are mixed then the total vapour pressure of
solution becomes 540 mm of Hg. If 1 moles of B is further added then
total vapour pressure of solution increases by 8 mm of Hg, Then find
the value of PA° & PB° .
(A) 348 mm, 420 mm (B) 600 mm, 400 mm
(C) 588 mm, 348 mm (D) 348 mm, 588 mm

Solution

Ans : (D)
 Example

Consider the graph of total vapour pressure (PS) for ideal solution of A
and B at Temperature (T) versus mole fraction of A (XA)

200

PS (mm Hg)

100

0 XA 1
Select the correct statement.
(A) Boiling point of pure A is more than B
(B) Vapour pressure of pure A at temperature T is 100 mm Hg
(C) Vapour pressure of pure B at temperature T is 200 mm Hg
(D) Boiling point of pure A is less than B
Solution

Ans : (D)
 Example

The following graph is plotted between the vapour pressures of two

volatile liquids against their respective mole fractions
PBo

Which of the following combinations are correct ?

(A) When xA = 1, P = PAo PAo

(B) When xB = 1, P > PAo

(C) When xA = 1, P < PAo
xA = 1 xB = 1
(D) When xB = 1, P > PBo xB = 0 xA = 0
X

Solution
Solution

Ans : (A,B)
 Example

32 g of methanol (Mw = 32) is added in 23g of ethanol (Mw = 46) to

form an ideal solution. If vapour pressure of CH3OH & C2H5OH in pure
state are 30 & 51 mm of Hg. Then Calculate
(1) Partial vapour pressure of CH3OH & C2H5OH.
(2) Total vapour pressure of solution.
(3) Mole fraction of methanol and ethanol in vapour phase

Solution
Ans : (1) 20mm, 17mm of Hg
(2) 37 mm of Hg
(3) Y(CH3OH) = 20/37
 Example

Two liquids A & B are mixed to form an ideal solution. The total vapour
pressure of solution is 235 – 135 x. Then find the value of p°A & p°B . If x
is the mole fraction of B in solution.

Solution

Ans : (1) p°A = 235 mm Hg

(2) p°B = 100 mm of H
 Calculation of yA & YB from Dalton’s law

Vapour phase
yA + yB = 1
Liquid phase
xA + xB = 1

Dalton’s law of partial pressure

Partial pressure of gas = Mole fraction in vapour phase (y) × Total

pressure of gas (pT )

pA = yA pT pB = yB pT
 Calculation of YA & YB from Dalton’s law

Combining Raoult’s law and Dalton’s law

xA p°A = yA pT

xB p°B = yB pT

xA p∘A
yA =
pT

xB p∘B
yB =
pT
In a liquid phase, sum of the mole fractions of all components = 1

x A + xB = 1

yA pT yB pT
+ = 1
p°A p°B

yA yB 1
+ =
p°A p°B pT
 yA yB 1
+ =
p°A p°B pT

p°B

p°A

0 1
Mole fraction of B
in vapour phase
 yA yB 1
+ =
p°A p°B pT

100% liquid
p°B

p°A

P 100% vapours

0 1
Mole fraction of B
Vapour Pressure V/S Vapour Composition

The V.P. of ideal solution always lie in between the V.P. of pure
components.

Below vapourous curve, the system will by 100 % vapour & above
liquidous and curve, 100% liquid. Both the physical states exists only
in between the curves.

At any composition, the physical state of system may be changed by

changing the pressure.

At any pressure in between pA° and pB°, the physical state of system
may be changed by changing the composition.
 Example

A solution has two liquids A and B and vapour pressures of A and B in

pure state are p°A = 80 atm and p°B = 120 atm. Then find out mole
fraction of A in vapour phase if initially equal moles of A and B are
taken.

Solution

Ans : 0.4
 Example

Ratio of vapour pressures of A and B in pure state is 1:2 and ratio of

moles of A and B is also 1:2, then find out mole fraction of A in vapour
phase.

Solution

Ans : 0.2
 Example

Calculate pT in following cases (given p°CH3OH = 60, p°C2H5OH = 80)

(1) 1 mol CH3OH & 1 mol C2H5OH
(2) 1 mol CH3OH & 3 mol C2H5OH
(3) 3 mol CH3OH & 1 mol C2H5OH

Solution

Ans : (1) 70 mm
(2) 75 mm
(3) 65 mm
Ans : 0.3 and 0.7
What happens when
a non-volatile solute
is added to a volatile
liquid ?
Non-volatile solute :
Glucose, Sugar, Urea, NaCl
etc.
What happens when a non-volatile solute is added to a
volatile liquid ?

It's vapour pressure decreases because less vapours are formed.

Less number of solvent particles are present at the surface of the

solution.
 Calculation of vapour pressure

For a non-volatile solute added to a solution, it’s vapour pressure is

given by Raoult’s law :

pS = p°A xA + p°B xB

p°B = 0

pS = p°A xA = p° xSolvent
 Calculation of vapour pressure

At constant temperature vapour pressure of solution containing non-

volatile solute is proportional to mole fraction of solvent.

p°A

pS

0 xA 1
 Solution

Ideal Non-Ideal

Positive Negative
Deviation Deviation
 Ideal solutions

Those solutions which obey Raoult's law over the entire range of
concentration are known as ideal solutions.

For Ideal Solutions :

A ••••• A B ••••• B A ••••• B

+ =
 Non-Ideal solutions

Those solutions which do not obey Raoult's law over the entire range
of concentration, then they are called non-ideal solutions.

For Positive Deviation :

A ••••• A B ••••• B A •••••••••• B

+ =
 Non-Ideal solutions

Those solutions which do not obey Raoult's law over the entire range
of concentration, then they are called non-ideal solutions.

For Negative Deviation :

A •••••••••• A B •••••••••• B A •••• B

+ =
 Difference between ideal and non ideal solutions

Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions
Vapour
ps = p∘A xA + p∘B xB ps > p∘A xA + p∘B xB ps < p∘A xA + p∘B xB
Pressure
 Difference between ideal and non ideal solutions

Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions

Zero Positive (+) Negative (–)

A + B = A-----B A + B = A-----B A + B = A-----B
10ml 10ml 20ml 10ml 10ml 20.2ml 10ml 10ml 19.8ml
DVmix

Intermolecular Intermolecular
Intermolecular distances are
distances increase. distances decreases.
same.
 Difference between ideal and non ideal solutions

Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions

Zero Positive Negative

(Endothermic) (Exothermic)
DHmix
No heat is absorbed or Heat is evolved as
Heat is absorbed as
evolved as a result of mixing. result of mixing. result of mixing.
 Difference between ideal and non ideal solutions

Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions

DGmix Negative (–) Negative (–) Negative (–)

 Difference between ideal and non ideal solutions

Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions

DSmix Positive (+) Positive (+) Positive (+)

Graph of ideal Solution

p°B

Vapour Pressure
p°A

xA = 1 Mole Fraction xA = 0
xB = 0 xB = 1
Examples of ideal Solution

(1) Benzene and toluene

(2) CCl4 and SiCl4

(3) n-hexane and n-heptane

(4) C2H5Br and C2H5Cl

Graph of non-ideal solutions with positive deviation

p°B

Vapour Pressure
p°A

xA = 1 Mole Fraction xA = 0
xB = 0 xB = 1
Examples of non-ideal solutions with positive deviation

(1) Ethanol and cyclohexane

(2) Ethanol and Water

(3) Ethanol and Acetone

(4) Methanol and H2O

(5) CCl4 and Benzene

(6) CCl4 and Toluene

(7) CCl4 and CHCl3

Graph of non-ideal solutions with negative deviation

p°B

Vapour Pressure
p°A

xA = 1 xA = 0
Mole Fraction
xB = 0 xB = 1
Examples of non-ideal solutions with negative deviation

(1) CHCl3 and CH3COCH3

(2) CHCl3 and C6H6

(3) CHCl3 and C2H5OC2H5

(4) CHCl3 and HNO3

(5) H2O and HCl

(6) H2O and HNO3

 Temperature v/s vapour composition

Boiling point of a liquid is the temperature at which the vapour pressure

of the liquid become equal to the atmospheric pressure.

Boiling point curves for ideal binary solution

(i) The boiling point of ideal solution always lie in between the boiling
points of pure liquids.

(ii) Below liquidous curve, the system in 100% liquid and above vaporous
curve, the system is 100% vapour. Both the physical states exists
only in between the curves.
(iii) At any composition, the physical state of system may be changed
by changing the temperature.

(iv) At any temperature in between TA° and TB° , the physical state of
system may be changed by changing the composition.
 100 % vapour
T°A

T
T°B

100 % liquid

0 Mole Fraction of B 1
 Distillation

It is the method of separation of liquids by converting them into vapors

(boiling).

(i) The separation of liquid by distillation occurs because at any T or P,

the composition of distillate or condensate is different than the
composition of original liquid.

(ii) With the elimination of vapor above the liquid, the boiling point of
residual liquid increases.

(iii) The boiling point of distillate is less than that of original liquid.
 Azeotropes

1. Some liquids on mixing, form azeotropes which are binary mixtures

having the same composition in liquid and vapour phase and boil at a
constant temperature, the liquid and vapour have the same
composition, and no further separation occurs.

2. Components form azeotrope can't be separated by fractional

distillation but can be separated by azeotropic distillation.
 Azeotropes

Ideal solutions never form azeotrope but non-ideal solution form

azeotrope.

3. There are two types of azeotropes :

A. Azeotropes showing positive deviation

(minimum boiling azeotrope)

B. Azeotropes showing negative deviation

(maximum boiling azeotrope)
A. Large positive deviation (minimum boiling azeotrope)

The solution of large positive deviation can not be seperated by

distillation because at composition 'x', the liquid & vapour composition
becomes identical. Such solution which can not be separated by
distillation are called azeotropic mixture or constant boiling solution.

At any composition less than X, traces of pure A may be obtained but

not pure B. Similarly at composition greater than X, traces of pure B
may be obtained but not pure A.
 L
T°A
L V
P P°B
V V T°B
L
L
PA
°

0 X 1 0 X 1
Mole Fraction of B Mole Fraction of B

Maximum Vapour Pressure Minimum Boiling Point

Minimum boiling point Azeotropic

% composition Boiling point

Mixture
of azeotrope (pressure = 1 atm)

Water-Ethanol 96 Ethanol 78.15° C

Pyridine-Water 57 Pyridine 92.60° C

Ethanol-Benzene 32.4 Ethanol 67.80° C

Acetic acid-Toluene 28 Acetic Acid 105.40° C

B. Large negative deviation (maximum boiling azeotrope)

T°A
PB
°

P L

L V T°B
PA
°
T

0.0 X 1.0 0.0 X 1.0

Mole Fraction of B Mole Fraction of B

Minimum Vapour Pressure Maximum Boiling Point

Maximum boiling point azeotrope

% composition Boiling point

Mixture
of azeotrope (pressure = 1 atm)

Nitric acid-Water 68% Nitric acid 125.5°C

Acetic acid-Pyridine 65% Pyridine 139.0°C

Chloroform-Acetone 80% Chloroform 65.0°C

Hydrogen chloride-
79.8% Water 108.6°C
Water
 Example
10 ml of liquid A (B.P. = 368K) and 10 mL of liquid B (B.P. = 415 K) are
mixed to obtain 19.92 ml of a constant boiling mixture then B.P. of the
solution is
(A) < 368 K (B) > 368 K but < 415 K
(C) > 415 K (D) Unpredictable

Solution

Ans : (_)
 Example

Among the following that forms an ideal solution ?

(A) Water and methanol (B) Acetone and ethanol
(C) Benzene and toluene (D) Water and HCl

Solution

Ans : (C)
 Example

The mixture of n-hexane and n-heptane is an example of

(A) Ideal solution
(B) Non-ideal solution
(C) Dilute solution
(D) None

Solution

Ans : (_)
 Example

An azeotropic mixture of two liquids boil at a lower temperature then

either of them when
(A) It is saturated.
(B) It does not deviate form Raoult’s low.
(C) It shows negative deviation from Raoult’s low.
(D) It shows positive deviation from Raoult’s low. `

Solution

Ans : (_)
 Example

Total vapour pressure of mixture of 1 mol of volatile component A

(PA° = 100 torr) and 3 mol of volatile component B (PB° = 60 torr) is 75
torr. What is correct :
(A) There is positive deviation from Raoult’s law.
(B) Boiling point has been lowered.
(C) Force of attraction between A and B is smaller than that between
A & A or B & B.
(D) All are correct.

Solution

Ans : (_)