1

CHAPTER 3
BY
ChM. DR HAIRUL AMANI
BINTI
ABDUL HAMID

CHM476 Physical Chemistry

 2

LEARNING OUTCOME
At the end of this topic, you will be able to:
a) Define phases, components and degree of
freedom.
b) Draw and explain one component phase
diagram of Ice-water-vapour system and CO2
system
c) Explain Raoult’s law and able to differentiate
ideal solution from solutions which deviate
from Raoult’s law – positive and
negative deviation.
 3

d) Explain the effect of volatile and non-

volatile solute on vapour pressure and able to
do calculations involved. (colligative
properties)
e) Able to draw vapour pressure composition
diagram and boiling point composition
diagram.
f) Explain fractional distillation and azeotropic
system using diagrams drawn in (e).
g) Explain the eutectic system and able to draw
the eutectic diagrams by the use of cooling
curves
 4

CONTENTS
• PHASE
• COMPONENT
• DEGREE OF FREEDOM
• ONE COMPONENT SYSTEM:
*H2O SYSTEM, CO2 SYSTEM
• TWO COMPONENT SYSTEMS
• RAOULT’S LAW
• COLLIGATIVE PROPERTIES
• DEVIATIONS FROM RAOULT’S LAW
 5

PHASE ‘P’
• Any homogeneous part of a system having all
physical and chemical properties the same
throughout.
• Separated from other parts of the system by a
distinct boundary
• Physically and chemically different from other
parts of the same system
• Mechanically separable from other parts of the
system
• A system may consist of one or more phases
 6

PHASE CHANGES
 7

DEFINITIONS
• Boiling point – liquid boils at the temperature where
the vapor pressure of the liquid equals to the external
pressure or the prevailing atmospheric pressure
• Normal boiling point – the boiling point of the liquid
at 1 atm , that is the temperature at which the vapor
pressure of the liquid is equal to an external pressure of
1 atm.
• Melting point – the temperature at which the liquid
and solid states have the same vapor pressure.
• Normal melting point or freezing point – the
temperature at which solid and the liquid have the same
vapor pressure under conditions when the pressure on
the sample is 1 atm.
 8

ONE PHASE SYSTEM

• No boundary between substances

example:
g-g system: Oxygen and nitrogen
l-l system: water and ethanol (miscible liquid)
solution of NaCl in water.
s-s system: a crystal of a substance –
gemstone, ice
 9

TWO PHASE SYSTEMS

Two substances with a boundary separating
them

Example:
l-l : water and oil
l-g: water and water vapour
s-g: ice and water vapour
s-l: ice and water
 10

WATER: 3 PHASE SYSTEM

Water Boundary
vapour s-v

Boundary Ice cube

l-v

Water Boundary
l-s
 11

THREE PHASE SYSTEM

Three substances with boundaries separating
each other

Example: s-l-g: ice-water-water vapour system

 12

COMPONENT ‘C’
The least number of independently variable
constituents which must be specified so that
composition of each and every phase is described.

Example:
1. Water + ethanol – miscible liquids P =1, C = 2
2. Water + oil – immiscible liquids P=2, C = 2
3. Water + ice + water vapour P = 3, C = 1
 13

DEGREE OF FREEDOM ‘F’

The smallest number of independent variables
of components (temperature, pressure,
concentration) which must be specified to
define completely the remaining variables of
the system

Example:
At triple point F=0, where temperature and
pressure are fixed.
 14

PHASE RULE

P+F=C+2
F=C–P+2

More components, more degree of freedom

More phases involved, less degree of
freedom
 15

F=C–P+2
In one-component system, C = 1
F = 3-P

When P = 1
F= 3-1 = 2 (bivariant system)

When P = 2
F = 3 – 2 = 1 (univariant system)

When P = 3
F = 3-3 = 0 (invariant system)
 16

ONE COMPONENT SYSTEM

Represented by -
temperature-pressure
phase diagram

16
 17

PHASE DIAGRAM OF H2O

 18

PHASE DIAGRAM OF H2O

218

0.06
atm

Triple pt

374

Normal fpt Normal bpt

 19

PHASE BOUNDARIES
(ON THE LINE)
1. 2 different phases co-exist in
equilibrium at various pressures
and temperatures.

2. On any point of these lines F = 1

(univariant)
(P = 2, C = 1 → F = C + 2 – P = 1)

3. i) Liquid- vapour boundary

(vapour pressure curve)
ii) Solid – vapour boundary
(sublimation curve)
iii) Solid – liquid boundary
(fusion curve – negative slope)
 20

WITHIN AREAS

1. Only 1 phase exist

2. At any point within

these areas F = 2
(bivariant)
( P= 1, C = 1
F = C + 2 –P = 2 )
 21

IMPORTANT POINTS

1. Critical point
- End point of a liquid-
vapour boundary
- beyond this point, liquid
phase is no longer
distinguishable from
the vapour phase
- Tc = 374.3 oC (647.3 K)
Pc = 218 atm
 22

IMPORTANT POINTS
2. Triple point
- solid, liquid and vapour
co-exist in equilibrium
- F = 0 (invariant)
(P = 3, C = 1,
F = C + 2 – P = 0)
- Temperature and
pressure are fixed
- Tt = 0.0098 oC,
Pt = 0.006 atm
 23

IMPORTANT POINTS
3. Normal boiling point
- on the vapour-pressure
curve (liquid-vapour curve)
- the temperature at P = 1 atm.
- Tb = 100 oC (373.15 K)
4. Normal freezing point
- on the fusion curve
- the temperature at P = 1 atm
- Tf = 0 oC (273.15 K)
 24

SPECIAL FEATURES
1. Solid-liquid boundary – negative
slope
-Melting point of ice decreases as
external pressure increases
- density of ice is less than density of
water : volume of water increases
as it freezes.

2. Triple point is below 1 atm.

- when ice is heated it melting at
normal mpt 273.15 K.
 25

PHASE DIAGRAM OF CO2

 26

PHASE DIAGRAM OF CO2

 27

PHASE BOUNDARIES
1. Liquid-gas boundary
- vapour pressure curve (liquid-gas curve)
- Bpt of substance as external pressure
2. Solid-vapour boundary
- sublimation curve (solid-gas curve)
- normal sublimation temp = -78 oC (194.7K)
3. Solid-liquid boundary
- fusion curve
- positive slope mpt of dry ice increases as vapour
pressure increases
 28

IMPORTANT POINTS

1. Triple point
Tt = -56.6 oC (216.8 K) Pt = 5.1 atm

2. Critical Point
Tc = 31.2 oC (304.2 K) Pc = 72.8 atm
 29

SPECIAL FEATURES
1. Solid-liquid boundary line – has a positive slope.
- mpt of dry ice increases as external pressure
increases
- dry ice is more dense than liquid CO2
- volume decreases as it freezes
2. Triple point lies above 1 atm.
- liquid CO2 exist only at pressures ≥5.1 atm (Pt)
- sublimes when heated at atm pressure
- has no normal mpt and bpt.
 30

TWO COMPONENT SYSTEM

 31

SATURATED VAPOUR PRESSURE

(I) (II) (III)

(I) Evaporation - VP above liquid increases

(II) Condensation - molecules in the vapour reenter the liquid

(III) Dynamic equilibrium - Rate of evaporation = rate of condensation

- saturated vapour pressure or vp of a liquid. – given by Raoult’s Law
- depends on nature of liquid and temperature
 32

RAOULT’S LAW
The partial vapour pressure of a component in a mixture is
equal to the vapour pressure of the pure component at
that temperature multiplied by its mole fraction in the
mixture.
PA = XA PoA
PA = Partial pressure of solvent A
XA = Mole fraction of solvent A
PoA = Vapour Pressure of pure solvent A.
- Applicable when there are more than one component in a
liquid solution.
• Only ideal solutions obey Raoult’s law.
 33

TYPES OF SOLUTION
1. Solution with volatile solute
2. Solution with non-volatile solute

33
 34

TYPES OF SOLUTION
1. Solution with volatile solute
Both solute (B) and solvent(A) contribute to
total vapour pressure of solution

Pt = PA + PB
 35

VP OF SOLUTION WITH VOLATILE

SOLUTE

PA = XA PoA PB = XB PoB
XA = nA XB = nB
n A + nB nA + nB

Pt = XA PoA + X B PoB

Pt = PA + PB
 36

WHEN A MORE VOLATILE THAN B

- Liquid A has higher vp than liquid B.
- Vapour in equilibrium with ideal solution of 2
volatile components has higher mole fraction of
A than is found in solution.

- PA = XA PT XA = mole fraction of A in vapour

- XA = PA
PT
 37

EXERCISE
Pentane C5H12 and hexane C6H14, both
form an ideal solution. The vapour
pressure of pentane and hexane is 420
mmHg and 102 mmHg respectively at
20oC. What is the vapour pressure of a
solution containing 10.0 g of pentane and
10.0 g of hexane at this temperature?
What is the mole fraction of pentane in the
vapour above the solution?
 38

n C5H12 = 10.0 g n C6H14 = 10.0 g

72 g mol-1 86 g mol-1
= 0.14 mol = 0.12 mol

X C5H12 = 0.14 mol X C6H14 = 1 – 0.54

0.14 mol + 0.12 = 0.46
= 0.54
P C5H12 = 0.54 x 420 mmHg P C6H14 = 0.46 x 102
mmHg
= 226.8 mmHg = 46.9 mmHg
P solution = 226.8 + 46.9
= 273.7 mmHg
 39

Composition (mole fraction) of pentane in the

vapour:

X C5H12 (in vapour) = P C5H12 / P solution

= 226.8 / 273.7
= 0.83
 40

TYPES OF SOLUTION
2. Solution with non-volatile solute
Vapour pressure above the solution is due to partial
pressure of solvent only.
- non-volatile solute has no tendency to escape from
solution to vapour phase
- causes number of solvent molecules per unit
volume at surface to be less
- lowers the escaping tendency of solvent molecules
to space above liquid.
- lowers the vapour pressure of solvent
 41

SOLUTION WITH NON-VOLATILE SOLUTE

PT = PA
 42

42 Colligative Properties
Dissolving solute in pure liquid will change all physical
properties of liquid such as density, vapor pressure,
boiling point, freezing point and osmotic pressure.

Colligative Properties are properties of a liquid that

change when a solute is added.

The magnitude of the change depends on the number of

solute particles in the solution, NOT on the identity of
the solute particles.
 43

43
Vapor Pressure Lowering
• Nonvolatile solute have no tendency to escape from solution into vapor
phase
• It reduces the number of solvent molecules per unit volume at the surface
, - lowers the escaping tendency of the solvent molecules to the space
above the liquid
• Presence of a non-volatile solute - fewer solvent particles are at the
solution’s surface, so less solvent evaporates!
 44

PHASE DIAGRAM FOR PURE WATER/ AQUEOUS

SOLUTION CONTAINING NON VOLATILE SOLUTE
 45

• ∆Tf and ∆Tb depends on molality of solution

• The higher the concentration of the nonvolatile
solute, the greater is the value of ∆T.
• When a solution boils or freezes, only the solvent
vaporizes or freezes while the solute remains in
solution.
• Therefore, the boiling point and freezing point of
a solution are not constant as they are for pure
solvent.
 46

RAOULT’S LAW AND COLLIGATIVE

PROPERTIES
1. Vapour Pressure Lowering P
- depressed vapour pressure due to presence
of non volatile solute
PT = PA XA + XB = 1 XA = 1 - XB

PA = XA PoA
= (1 - XB) PoA
= PoA - XBPoA
XBPoA = PoA –PA = P (vapour pressure lowering)
 47

EXERCISE
Calculate the vapour pressure lowering of water
when 5.67 g of glucose, C6H12O6 is dissolved in
25.2 g of water at 25 oC. The vapour pressure
of water at 25 oC is 23.8 mmHg.
n C6H12 O6 = 5.67 g/180 g mol-1 = 0.0315 mol
nH2O = 25.2 g/18 g mol-1 = 1.4 mol
X C6H12 O6 = 0.0315 / (0.0315 + 1.4) = 0.0220
P = X C6H12 O6 x PH2O
= 0.0220 x 23.8
= 0.524 mmHg
 48

2. Boiling Point Elevation

• Boiling occurs when the vapor pressure of the
liquid becomes equal to the pressure of the
environment or external pressure.
• When a nonvolatile solute is added to a volatile
solvent
1. The vapor pressure of the solvent is lowered. Thus
the solution must be heated to a higher
temperature than the boiling point of the pure
solvent to reach the external vapor pressure of 1
atm in order for boiling to occur.
2. The presence of nonvolatile solute elevates the
boiling point of the solvent.
 49

Boiling point elevation Tb

- boiling occurs when vp of liquid = external vp
- presence of non-volatile solute
a) lower the vp of solvent
solvent need to be heated to higher temp than
bpt of pure solvent to reach external vp (1 atm)
b) elevates the bpt of solvent
Kb = Molal Bpt constant
Tb = Kb m m = molality
= mole of solute
mass of solvent (kg)
 50

3.Freezing Point Depression

 Normal Freezing Point: FP of Substance at 1atm
 When solute is added, FP < Normal FP
 FP is depressed when solute inhibits solvent from crystallizing.

When solution freezes the solid form is almost

always pure.

Solute particles does not fit into the crystal

lattice of the solvent because of the differences
in size. The solute essentially remains in
solution and blocks other solvent from fitting into
the crystal lattice during the freezing process.
 51

Freezing Point Depression Tf

- mpt is the temperature when vp (s) = vp (l)
- presence of non volatile solute:
a) solution will freeze at a temperature lower the
fpt of pure solvent – solvent in solution has a
lower vp than that of pure solvent.
b) Freezing will only occur when the vp of solid =
vp of liquid and since vp has been lowered, the
fpt also will be lower.
Kf = Molal Fpt constant
m = molality
Tf = Kfm
52
53
54
 55

TWO COMPONENT SYSTEMS

Represented by phase diagrams:
1. Temperature (boiling/freezing point) –
composition diagram (constant pressure
2. Pressure –composition diagram
(constant temperature)

55
 56

TWO COMPONENT SYSTEMS

PHASE DIAGRAM
56

• Phase diagram for two component systems may be

represented by temperature-composition (constant
pressure) or pressure-composition (constant temperature).

384 torr 384 torr

P (Total)
P (Benzene)
133 torr 133 torr

P (Toluene)

0 X Benzene 1
1 X Toluene 0
 57

VAPOUR PRESURE OF IDEAL

SOLUTION OF TWO LIQUIDS
57

• The vapor pressure above a solution varies with

temperature and composition of the solution.

• The change with composition, for ideal solution

is controlled by Raoult’s law.

• Both component A and B are volatile and

contribute to the vapor pressure of the solution.
 58

VAPOUR PRESURE OF IDEAL

SOLUTION OF TWO LIQUIDS
58

PA = XAPOA

• XA = Mole fraction of A = nA /(nA + nB)

• POA = the vapor pressure of pure A
• PA = The vapor pressure of A in
• solution

PB = XBPOB
• Ptotal = Psolution = PA + PB
= XAPOA + XBPOB
 59

IDEAL SOLUTIONS
• Two completely miscible liquids
• Components are structurally similar and
held together by similar intermolecular
forces (same type and same strength)
• Hsolution = 0
• Obeys Raoult’s law.
PA = XA PoA

Pt = PA + PB

59
 60

VAPOUR PRESSURE – COMPOSITION DIAGRAM FOR

COMPONENT A
70

Vapour
Pressure
At fixed
Temp

0 XA 1
 61

VAPOUR PRESSURE – COMPOSITION DIAGRAM FOR

COMPONENT B

Vapour
Pressure
40
At fixed
Temp

1 Xb 0
 62

IDEAL SOLUTION:
VAPOUR PRESSURE – COMPOSITION DIAGRAM

70

Vapour
Pressure
At fixed 40
Temp

0 XA 1
 63

NON-IDEALSOLUTION:
DEVIATIONS FROM RAOULT’S LAW

Two types of deviations:

1. Negative Deviation
2. Positive Deviation.
 64

NEGATIVE DEVIATION
70
Vapour
Pressure
At fixed 40

Temp

0 XA 1
 65

NEGATIVE DEVIATION
• PT < PT ideal solution
• Minimum vapour pressure
• Less tendency for molecules to escape into
vapour phase from solution
• Stronger attractive forces between solute and
solvent molecules in solution than those in pure
liquids
• ∆Hsolution = negative
 66

NEGATIVE DEVIATION
70
Vapour
Pressure
At fixed 40
Temp

0 XA 1
 67

POSITIVE DEVIATION

70

Vapour
Pressure
40
At fixed
Temp

0 XA 1
 68

POSITIVE DEVIATION
- PT > PT ideal solution
- Maximum vapour pressure
- Molecules having greater tendency to escape
from solution than from pure liquid
- Weaker attractive forces between solute and solvent
molecules in solution than those in pure liquids
- ∆Hsolution = positive,
- The two liquids unable to mix completely –
increase in volume of mixture solution
 69

POSITIVE DEVIATION

PT 70
Vapour
Pressure
At fixed
40
Temp

0 XA 1
 70

Phase diagram for two components

system – ideal solution
Pressure – composition Boiling point –
Diagram (constant T) composition Diagram
(constant P)
T
P
Vapour
Liquid

Liquid
Vapour
XA XA
 71

Bpt composition diagram

• High pressure – low bpt
• Max vp – min bpt
• Min vp – max bpt
• Fractional distillation to separate components of
mixture.
 72

Fractional Distillation of Ideal

Solution

Temp/
oC Vapour
Bpt B

T1

Liquid
T2
Bpt A

0 %A 100
 73

Fractional Distillation of Ideal solution

 74

Fractional Distillation
• Obtain by repeating the process of boiling-
condensing-boiling process until pure A and
pure B could be obtained from the mixtures.
• Repeating process done in a single operation
using fractionating column/tower.
• Fractionating column may consist of glass
beads, raschiq rings or using bubble cap
column.
 75

Fractional Distillation Set

 76

Fractionating tower
 77

Bubble-cap column
 78

MIN VP CORRESPOND TO MAX BPT

70

40

0 XA 1
 79

Bpt – composition diagram with a

maximum
Temp/ Vapour
oC

Bpt of Azeotropic
mixture

Bpt A

Bpt B

Liquid

0 %A 100
 80

Maximum bpt
 81

MAX VP CORRESPONDING TO MIN BPT

70

40

XA 1
 82

Minimum bpt
 83

Exercise
Liquid A dissolves completely in water. The
vapour pressure of an aqueous solution of A
(mole fraction 0.28) is 26.0 mmHg at 20oC. The
vapour pressure of liquid A and water at this
temperature is 43.5 mmHg and 17.5 mmHg
respectively. Is the aqueous solution of A ideal
or non-ideal?
 84

Answer:
PA = XAPoA = 0.28 x 43.5 mmHg = 12.18 mmHg
Pwater = XwaterPowater = 0.72 x 17.5 mmHg = 12.6
mmHg.
Psolution (calculated) = 12.18 + 12.6 = 24.8 mmHg
Psolution(actual) = 26.0mmHg , Psolution (calculated)=
24.8

Psolution(actual) > Psolution (calculated)

Aqueous solution is non-ideal. It shows positive

deviation from Raoult’s Law.
 85

Exercise:
The high solubility of ethanol, C2H5OH in water
is due to the formation of hydrogen bonds
between the molecules. An aqueous solution of
ethanol, prepared by dissolving 0.10 mol ethanol
in 0.36 mol water, was fractionally distilled. The
distillate was distilled at 78.2oC and the mole
fraction of ethanol in the distilllate was 0.994.
The normal boiling point of ethanol is 78.5oC.
What are the products of distillation? Explain
your answer.
86
 87

TWO COMPONENTS SYSTEM:

TWO COMPLETELY IMMISCIBLE SOLIDS (L – S
DIAGRAM)
• A single liquid melt from two immiscible solids is
cooled – solid is formed
• Temperature at which solid is formed – freezing pt
- dependent on composition of mixtures
• At eutectic point – three phases in equilibrium:
solid A, Solid B and liquid, and is invariant at fixed
pressure
• Cooling curves are used to construct phase
diagram of eutectic mixtures.

87
 88

TWO COMPONENTS SYSTEM:

TWO COMPLETELY IMMISCIBLE SOLIDS (L – S
DIAGRAM)
• eutectic mixture
A mixture of two or more substances
with melting point lower than that for any other
mixture of the same substances.

• A mixture of substances having a melting point

lower than that of any of its components; the
composition at the eutectic point
 89

TWO COMPONENTS SYSTEM:

TWO COMPLETELY IMMISCIBLE SOLIDS (L – S
DIAGRAM)
• A eutectic system
is a mixture of chemical compounds or elements
that has a single chemical composition that solidifies
at a lower temperature than any other composition.
This composition is known as the eutectic
composition and the temperature is known as the
eutectic temperature.

On a phase diagram the intersection of the eutectic

temperature and the eutectic composition gives the
eutectic point.
 90

PHASE DIAGRAM

Mpt
Mpt Liquid A pure
pure A +B B

Solid B +
Solid A + Liquid
Liquid mixture
Eutectic mixture Eutectic
point
temperature
Solid A + Solid B

0 B
%B
Eutectic composition
 91

COOLING CURVES
i) 100% A
ii) 80% A
iii) 60% A
iv) 50% A
v) 40% A
vi) 0%A
 92

COOLING CURVES VS PHASE DIAGRAM

 93

TUTORIAL QUESTIONS

93
 94

94
 95

95
 96

96
 97

What is the vapor pressure of water above a sucrose (MW=342.3 g/mol)

solution prepared by dissolving 158.0 g of sucrose in 641.6 g of water at
25 ºC? The vapor pressure of pure water at 25 ºC is 23.76 mmHg.

n sucrose = (158.0 g)/(342.3 g/mol) = 0.462 mol

n water = (641.6 g)/(18 g/mol) = 35.6 mol

n water 35.6
X water = = = 0.987
(n water)+ (n sucrose) 35.6 + 0.462

Pwater = Xwater Pwater = (0.987)(23.76 mm Hg)

= 23.5 mm Hg

Psolution = Pwater
 98

Calculate the vapour pressure lowering of water when

5.67 g of glucose, C6H12O6 is dissolved in 25.2 g of
water at 25 oC. The vapour pressure of water at 25 oC
is 23.8 mmHg.

n C6H12 O6 = 5.67 g nH2O = 25.2 g

180 g mol-1 18g mol-1
= 0.0315 mol = 1. 4 mol

X C6H12 O6 = 0.0315 = 0.0220

(0.0315 + 1. 4)

P = X C6H12 O6 x PH2O
= 0.0220 x 23.8
= 0.524 mmHg
 99

Q1: Calculate the lowering of the vapor pressure of water at 20 0C

by the addition of 54.1 g of mannitol (MW=182.2 g/mol) per
1000g of water . The vapor pressure of water at this
temperature is 17.54 torr. The experimental value is 0.0922
torr.

Q2: The vapor pressure of a solution containing 13 g of a non

volatile solute in 100 g of water at 28 0C is 27.371 torr. Calculate
the molecular weight of solute assuming that solution is ideal.
The vapor pressure of water at this temperature is 28.065 torr.

Q3: A solution was prepared by adding 20 g of urea to 125 g of

water at 25 0C , a temperature at which pure water has a vapor
pressure of 23.76 torr. The observed vapor pressure of the
solution was found to be 22.67 torr. Calculate the molar mass of
urea.
 100

Q1 : What is the mole fraction of glycine in an

aqueous solution of molality 0.140 mol kg-1 ?

Q2 : A solution was prepared by dissolving 18 g of

glucose in 150 g of water. The resulting solution
was found to be have a boiling point of 100.34 0C.
Calculate the molar mass of glucose given the
molal boiling point constant for water is 0.51 0C kg
mol-1.
 101

Q1 : What mass of ethylene glycol, C2H6O2, the main

component of antifreeze must be added to 10 dm3 of
water to produce a solution for use in car radiator that
freezes at -23.3 0C. Assume density of water is 1 gm-3.
The molal freezing point of water is 1.86 0C mol kg-1.

Q2 : If 68.4 g of sucrose (MW = 342 g/mole) is dissolved

in 1000 g of water:
a) What is the vapor pressure at 20 0C.
b) What is the freezing point?
The vapor pressure of water at 20 0C is 17.363 torr. The
molal boiling freezing point of water is 1.86 0C kg mol-1.