CHAPTER 5

PHASE EQUILIBRIUM
 Sub topic
— Raoult’s Law
— One component system
— Two component system
— Azeotropic mixture
— Fractional distillation

2
 DEFINITION
— PHASE
is defined as a homogenous part of heterogenous system
Eg: a glass of “Teh O ICE”
teh O – liquid
ice- solid

3
 DEFINITION
— Component
is the minimum number of different substances required
to describe the composition of all phases in the system.
Eg:
Air(O2 , N2, CO2…...) – many component
ice- water – one component
water – CCl4 – two component

4
 What is the Phase Diagram?
— is a diagram to visualize the phases where there is an
existence of equilibrium between phases as a function of
pressure and temperature.

— It shows the equilibrium pressure –temperature relationship

among the different phases of a given pure substance in a
closed system such as a sealed vessel

5
 ……cont Phase Diagram
— Uses - to predict physical state at specific temperature and
pressure

— Each part in phase diagram represent different things:

ü area/ region = phase
ü line = set of temperature and pressure which 2 phase on either side of
line exist in equilibrium
ü Triple point, O = condition of temperature and pressure at which all 3
phases of a substances coexist at equilibrium

Pressure
(atm)
solid liquid
O
vapour
Temperature
(ºC)
Example:

— The phase diagram for a substances A is shown. State the physical

state of A at the condition X, Y and Z

P x liquid

solid O y
z
vapour

T
Solution:

At condition x, compound A exist as solid and liquid in equilibrium

At condition y, liquid A and gas/ vapour A exist in equilibrium
At condition z, substances A exist as a solid only
 ….cont Phase Diagram
A C
Melting point

•
liquid

•
solid
Sublimation point

O
gas
• Boiling point

Triple point
B

8
 Pressure, atm
A C

P2 •
liquid P1T1 – solid ⇌gas
P3 •
P2T2 – solid ⇌liquid
solid

O
P3T3 - liquid⇌ gas

P1 • gas

B Temperature, °C
T1 T2 T3
9
 PHASE CHANGES
sublimation

melting boiling
SOLID LIQUID GAS

freezing condensation

deposition
10
 PHASE CHANGES

11
 Phase Diagram of
water, (H2O)

One Component
System
Phase Diagram of
Carbon Dioxide,
(CO2)

12
 Phase Diagram for CO2

13
 Phase diagram for H2O

14
Phase diagrams for CO2 and H2O

CO2 H2 O
(ice is less dense than liquid water)
Differences Between H2O and CO2
Characteristic water CO2

Effect of Melting point Melting point

pressure on decreasing increasing with
melting point with pressure pressure
increase increase

density water Solid CO2

more denser more denser
than Ice than liquid
CO2
16
 Triple Point
— is a point where all phases ( solid, liquid and gas) are present
in equilibrium

Triple point of water(0.01°C , 0.006 atm)

Triple point of CO2( -56.4°C, 5.11 atm)

17
 Boiling point
— A liquid boils at a temperature at which its
vapour pressure is equal to the pressure above its
surface.

— Normal boiling point ,

T = 100°C P = 1 atm = 760 mm Hg

18
19
 Critical Point
— For CO2 , P = 73.75 atm , T = 31 °C

— It means CO2 gas does not liquefy above this

point.

— Above the critical temperature and pressure, a

substance is referred to as a supercritical fluid.

20
 sublimation
— A solid changes directly to vapor without passing
through the liquid phase.

— A solid can sublime only at a temperature below

the triple point.

21
 Degree of Freedom , F
— is the number of intensive variables
( temperature and pressure) that can be independently
varied without changing the phase of a system.

P+F=C+2 where:
P = no. of phase
C = no. of component
F = degree of freedom

22
 Degree of Freedom
— For one component system;
so , C = 1
P+F=1+2
F=3-P

23
Example
— Calculate number degrees of freedom, F for every part below:
Pressure
(atm)
C
liquid B

O
solid vapour

A
Solution: Temperature
(ºC)

Area COB : P = 1 (liquid) Point O : P = 3 (liquid + solid + vapour)

F=3-P F=3-P
F=3–1=2 F=3–3=0

Line OC/OB/OA : P = 2 (liquid + solid)

F=3-P
F=3–2=1
 To determine degree of freedom
— For one phase
F = 3 –P
=3–1
F =2
System bivariant

25
 To determine degree of freedom
— For two phases,
F=3–2
F =1
System univariant

26
 To determine degree of freedom
— For three phases;
F = 3-3
F=0

System invariant

27
 Pass Year Exam – April 2006
— A pure substance A has a liquid vapour pressure of 320 mmHg at
125 ºC, 800 mm Hg at 150 ºC, and 60 mm Hg at the triple point,
85 ºC. The melting point of A decreases slightly as pressure
increases.
(7 marks)

28
 i) Sketch a labelled phase diagram for A.

Pressure, mmHg

800
760
liquid
320
solid
60
gas

85 125 150 Temperature, °C

29
 ii) What changes occur when, at a constant pressure of 320
mmHg, the temperature drops from 150 ºC to 100 ºC.

Answer:
vapour condenses to liquid

30
 2 Component
systems

Non-ideal
Ideal Solution
solution

Does not Obey to

Obey to Raoult’s Law
Raoult’s Law
31
 Ideal behaviour

An ideal solution which obey Raoult’s Law has the

following properties:
— The heat of solution is zero, there is no heat produced or released
during mixing.
— There is no volume change on mixing the two components.
— No change in solution temperature.
— No chemical interactions between the solute and solvent.
— The sum of the partial vapour pressures of A and B is exactly equal
to the total vapour pressure of the solution.
A------A ≈ B-----B » A---------B
— Intermolecular attractions between the molecules of solute and
solvents are equal.
32
 Examples of mixtures that would produce
ideal solutions are:

— n-hexane + n-heptane
— bromoethane + iodoethane
— benzene + methylbenzene(toluene)
— water + methanol
— benzene + carbon tetrachloride(CCl4)

33
34
 Intermolecular Force

SOLUTE SOLUTE
(A) (A)

SOLVENT
(B) SOLVENT
(B)

SOLVENT SOLUTE
(B) (A)
35
 The strength of intermolecular force
London
Dipole-induce dipole
Hydrogen bonding More
Ion-dipole stronger
Ionic

36
37 22 Nov 2013
 RAOULT’S LAW
— States that the partial vapor pressure of component A is
proportional to mole fraction of A in the solution times its pure
vapor pressure

PA = c A P !
A

PB = c B P !
B

38
Raoult's Law
— The French chemist Francois Raoult discovered the
law that mathematically describes the vapor
pressure lowering phenomenon.
— Raoult's law states that the vapor pressure of a
solution, PA, equals the mole fraction of the solvent,
XA , multiplied by the vapor pressure of the pure
solvent, PAo.
o
PA = c A x PA
...cont Raoult’s Law
— The vapour that exist in equilibrium with a mixture of two
liquids is a mixture of two vapour

— Total pressure of vapour above liquid mixture is the sum of

the partial pressures of two vapours
P mixture = PT = PA + PB
PA & PB = partial pressure
PT = (PAº.cA ) + (PBº.cB) Po = pure vapour pressure
c =mole fraction
— That’s is
PA = PAº.cA
PA = partial pressure of A in the ideal solution
PAº = vapour pressure of pure A
cA = mole fraction of A in the solution,
na
n = number of moles xA =
na + nb
— Similarly, for liquid B in the ideal solution
PB = PBº.cB
Example :

— At 80oC, the vapour pressure of pure benzene is 10.0 x

104Nm-2 and the vapour pressure of pure methylbenzene is
4.0 x 104Nm-2. An ideal solution contains 7.8 g of benzene
and 36.8 g of methylbenzene. Calculate
(a) the partial pressures of benzene and methylbenzene
(b) the total vapour pressure of the mixture
(Mr of benzene = 78, Mr of methylbenzene = 92)

Answer

(a) Pbenzene = 2 x 104 Nm-2

Pmethylbenzene = 3.2 x 104 Nm-2

(b) 5.2 x 104 Nm-2

Deviation Intermolecular DH examples
from force
Raoult’s law
Solution pure
Ideal equal equal zero Hexane +
heptanes

negative stronger weaker negative Water +

hydrogen

positive weaker stronger positive Benzene +

ethanol

42
 DALTON’S LAW
— The total vapour pressure is equal to the sum of the
partial vapour pressure at that composition

PT = PA + PB + ...........

43
 Vapour composition
— Vapour is always rich in the more volatile component
— Mole fraction of component A and B in the vapour is
given by;

PB
cB =
PT

44
 PHASE DIAGRAM OF TWO COMPONENT
( L – L system)

— Vapor pressure - composition diagram

— Boiling point – composition diagram

45
 What is Vapour pressure?

liquid ⇌ vapour
v is the pressure exerted by the molecule
that escape to the vapour phase.
— Once equilibrium between liquid and
vapour is reached, the number of molecules
per unit volume in the vapour does not
change with time.

— This means that the pressure exerted by the

vapour over the liquid remains constant.

— It depend on the strength of intermolecular

forces of the substances.
46
 Vapour pressure - composition diagram
For Ideal Solution
— A mixture of component X and Y

You must indicate this two matter:

— Component Y is more volatile
— Vapor pressure Y is greater than vapour pressure X

47
 Vapor pressure, atm

P°Y

0 1
Mole fraction Y

48
 Vapor pressure, atm

P°X

1 0
Mole fraction X

49
 Vapor pressure, atm

Total pressure P°Y

P°X

1 0
Mole fraction X

Mole fraction Y
50
 Boiling point – composition diagram
For Ideal Solution
— Before you sketch the diagram, you must indicate the
temperature of both component.

— Eg ; component Y – lower boiling point

— component X – higher boiling point

51
 Temperature, °C
vapor •

Vapor «liquid

Tie-shaped

• liquid

0 100
% component X

52
 Figure: Liquid-Vapour Composition Diagram of Toluene-
Carbon Tetrachloride

53
Non Ideal or Real solution
l Solutions that show a deviation from Raoult's law are called non-ideal
solutions or real solutions because they deviate from the expected
behavior.

l Most solution fall into this category

• Attractive forces: A-B < A-A or B-B (Escaping tendency higher)

Ø PA ¹ PAº.cA or PB ¹ PBº.cB

• Examples are
1. ethanol – water
2. isopropylalcohol – water
3. propanol – water
4. chloroform – ethanol.
 NON-IDEAL SOLUTION

(A) NEGATIVE DEVIATION (B) POSITIVE DEVIATION

55
Deviations from Raoult's law
— Deviations from Raoult's law can either be positive
or negative.
— A positive deviation means that there is a higher
than expected vapor pressure above the solution:
PA > PAoXA
— A negative deviation means that we find a lower
than expected vapor pressure for the solution:
PA < PAoXA
…cont..Deviations from Raoult's law

Deviation from Solution Obeying

Raoult’s Law Raoult’s Law
..cont: Deviations from Raoult's law

(a) Ideal solution (b) & (c) Non Ideal solution

…cont: Deviations from Raoult's law
We assumed that the solute did not interact with the
solvent at all.
NEGATIVE DEVIATIONS
If the solute is strongly held by the solvent,
the solution will show a negative deviation from
Raoult's law, because the solvent will find it more
difficult to escape from solution.

Heat of solution is negative, the mixing process is

exothermic ( DHsoln < 0)
…cont: Deviations from Raoult's law
POSITIVE DEVIATIONS

If the solute and solvent are not as tightly bound to each

other as they are to themselves,
then the solution will show a positive deviation from
Raoult's law because the solvent molecules will find it
easier to escape from solution into the gas phase.

Heat of solution is positive, the mixing process is

endothermic ( DHsoln > 0)
 Comparison between ideal and non-ideal solution
Ideal Non-ideal Non-ideal
(negative (Positive deviation)
deviation)
PA = PAº.cA PA < PAº.cA PA > PAº.cA

l. n-hexane + n-heptane l.Water + nitric acid l water + hexanol

l bromoethane + l HF + water l ethanol + kloroform (CHCl3)
Iodoethane l HCl + water l ethanol + toluene
l Benzene + l sulfuric acid +

methylbenzene methanoic acid

l Water + methanol l prpanon + kloroform

P P P

PºB PºB PºB P

P B
B
P PºA
PºA B PºA
PA
PA PA
0 XA 0 XA 0 XA
XB 0 XB 0 XB 0
Vapour pressure-composition diagram
vs boiling point diagram
— The ideal solution is rarely achieved. In practice, however, many
cases occur in which it is approximately reached
P B.p (ºC)
liqu
id
Vapour pressure.
(at constant T)

(at constant P)
Boiling point.
liquid

XA XA
XB XB
(a) Vapour pressure vs mole fraction (b) boiling point vs mole fraction

— Component with high vapour pressure means that its boiling point
is low. Therefore the vapour pressure versus mole fraction
curve/diagram is opposite to the boiling point vs mole fraction
Comparison between ideal and non-ideal solution

Ideal solution Non-ideal Non-ideal

(negative deviation) (Positive deviation)
b.p b.p b.p
Max b.p
r
pou va
va A

ur
r
ou po

po
p ur
va

va
liqu A vapour
id B id id B id
liqu liqu il qu
liquid

XA XA
XA Min b.p

P P P
liq
uid PºB
PºB
PºA PºA
vap
our
PB

0 XA 0 XA 0 XA
 Vapor pressure - composition diagram
For Non-Ideal Solution
— A mixture has positive deviation

100%A 100%B
64
 Vapor pressure - composition diagram
For Non-Ideal Solution
— A mixture has negative deviation

100%A 100%B
65
 Boiling point - Composition
curve (T-x)
Temperature-composition phase diagram is represented by a double
curve.
It is the opposite in the case of the Pressure-composition phase
diagram.
The lowest part of the curve corresponds to the pure liquid with the
highest vapor pressure “the one that vaporizes more easily”.

There are three type of boiling point-composition diagram for a liquid

mixture that contain 2 completely component:

üWithout maximum/minimum boiling point- obey Raoult’s

Law/deviate slightly
üMaximum boiling point- system show negative deviation from
Raoult’s Law. Eg Mixture HBr + H2O, HCl + H2O, CHCl3 +
CH3COCH3, HNO3 + H2O
üMinimum boiling point- system show positive deviation from
Raoult’s Law. Eg Benzene + ethanol, ethanol + H2O,
trichloromethane + ethanol
66
 Boiling point - composition diagram For
Non-Ideal Solution
Before you sketch the diagram, indicate this following;

— Temperature of first component (A)

— Temperature of second component(B)
— Temperature of azeotropic mixture
— Composition of azeotropic mixture

Azeotropic mixture is a mixture of liquids which

boils at a constant composition and thus the
composition cannot be changed by simple
distillation.

67
 For negative deviation
— Has max azeotropic temperature

Temperature, °C vapor • 102

vapor

liquid • 75

60 • liquid

100%B 100% A
70%A , 30%B
68
Negative deviations (T-x)
If the Pressure-composition curve

shows minimum for

negative deviation from Raoult’s law,
the Temperature-composition curve will

show a maximum.

69
 negative deviation – maximum boiling point

B.p (ºC) A B
our 121
vap
T2 T1
va
po
(at constant P)

100
Boiling point.

liquid ur
liq
uid
78

X2 X1 X3
100% 100%
H2 0 Azeotropic HNO3
68.2% HNO3
 For positive deviation
— Has minimum azeotropic temperature

Temperature, °C

80 • vapor
vapor
• 75

liquid liquid • 55

100%B 100% A
70%A , 30%B
71
 Positive deviations (T-x)
If the Pressure-composition curve

shows maximum for positive

deviation from Raoult’s law,
the Temperature-composition curve will

show a minimum.

72
 positive deviation – minimum boiling point

B.p (ºC)
A B

80 ºC va
po
(at constant P)
Boiling point.

T1 ur
apour
v 78.5 ºC
liqu
id T2
id
liqu

X1 X2 X4 X3
100% azeotropic 100%
benzene ethanol
 Liquid-Vapour Diagrams of 2 Different Azeotropic Mixtures;
A) Ethanol and Water B) Formic Acid and Water.

min boiling point max boiling point

74
 Fractional Distillation
— A procedure for separating mixtures of volatile components based on
difference in boiling point.

— Principle;
lower boiling point- distillate
higher boiling point - residue
Subject to fractional distillation
- 1st distillate – distill over which is at low T
- 2nd distillate – residue which is at high T

75
 Distillation Apparatus

76
 Principles of Fractional Distillation
for ideal solution

— Component A would
be a distillate (lower
boiling point)

— Component B would
be a residue

77
 Principles of Fractional Distillation
for non- ideal solution – negative deviation

boiling

T1
TA
TB
condensation

Area Y Area X

C3 C2 C1 70% A
78
 Principles of Fractional Distillation
for non- ideal solution – negative deviation
— Less than 70 % of A (area Y)
distillate = pure B (low T)
residue = azeotropic mixture (high T)

— More than 70% of A (area X)

distillate = pure A (low T)
residue = azeotropic mixture (high T)

79
…cont….. Non Ideal solution
-negative deviation
-max boiling point temperature of azeotropic

Subject to fractional distillation

B.p (ºC) A B - 1st distillate – distill over which is at low T
our
- 2nd distillate – residue which is at high T
vap 121
T2 T1
va
po
(at constant P)

100
Boiling point.

liquid ur
liq
uid
78 At composition X1 (Section B):
Distillate: Pure HNO3
Residue: Azeotropic Mixtures
X2 X1
At composition X2 (Section A):
100% 100%
H2 0 Azeotropic HNO3 Distillate: Pure H2O
68.2% HNO3
Residue: Azeotropic Mixtures
 Principles of Fractional Distillation
for non- ideal solution – positive deviation

TA

TB

Area X
Area Y

65% A
81
 Principles of Fractional Distillation
for non- ideal solution – positive deviation
— Less than 65 %A ( area Y)
distillate = azeotropic mixture (low T)
residue = pure B (high T)

— More than 65% A (area X)

distillate = azeotopic mixture (low T)
residue = pure A (high T)

82
 ..cont…..
Non Ideal solution
-positive deviation
-min boiling point temperature of azeotropic

B.p (ºC) Subject to fractional distillation

A B - 1st distillate – distill over which is at low T
vaporisation - 2nd distillate – residue which is at high T
80 ºC va
po
(at constant P)
Boiling point.

T1 ur
apour
v 78.5 ºC
liqu At composition X1 (Section A):
id T2
id Distillate: Azeotropic Mixtures
liqu
condensation Residue: Pure benzene

At composition X3 (Section B):

X1 X3
Distillate: Azeotropic Mixtures
100% azeotropic 100%
benzene ethanol Residue: Pure ethanol
Example :

— The boiling point of HBr and H2O are -67oC and 100oC
respectively. The azeotropic mixture contains 30% HBr and
70% H2O water boils at 126oC.
(a) Sketch the boiling point versus composition curve for this
system. Mark clearly the liquid and vapour curves on the
diagram and label the axes and also the boiling points.
(b) What type of deviation is shown by the mixture?
(c) Identify the components that are distilled over is a mixture
of 52% HBr and 48% H2O water undergoes fractional
distillation.
Answer:
(a)
(b) Negative type of deviation

(c) The distillate first distilled (distilled over) would be pure

HBr at boiling temperature of -67oC followed by the
azeotropic mixture which will distill at temperature of
126oC
 Pass Year Exam
Ethanol (boiling point 78.5ºC) and water form a constant boiling
mixture having a boiling point of 78.2ºC and a composition of
95.6% ethanol.

i) Define the term constant boiling point mixture.

ii) Sketch and label the boiling point-composition diagram for

ethanol and water system.

iii) An ethanol-water mixture shows positive deviations from

Raoult’s Law. Explain the phenomenon.
(8 marks)

86
 Answer Scheme
i) The mixture has identical composition of vapour and liquid
at one definite temperature.

ii)
Title ½
y-axis – temperature, unit ½, ½
x-axis – % composition of ethanol or water ½, ½
vapour & liquid curves ½, ½
Shape 1½
azeotropic temp (78.2 ºC) & composition (95.6 % ethanol)
1,1
b.p of 100 % ethanol (78.5 ºC) ½
b.p of 100% water (100 ºC) ½
87
 Answer Scheme (cont.)
Positive deviations mean
— the mixture has a higher total pressure than the vapour
pressures of either pure water or pure ethanol,

— higher escaping tendency from liquid phase to vapour

phase

— due to weaker intermolecular attractions

between ethanol and water than those existing in pure
components.

88
 Solid – Liquid System
(eutectic mixture)
— Two process involved;
1) freezing ( liquid → solid )
2) melting ( solid → liquid )

89
 Eutectic diagram
Temperature, °C
T1 X
Freezing point of
pure B, T2•
• A (l) + B (l)
• • Freezing point of
pure A ,T3
•
T4 •
B (s) + liquid • A(s) + liquid
T5 • • Eutectic temp.

A (s) + B (s) + eutectic

100% B 40% A 70% A 100% A

90
 Eutectic system

TmA = Freezing point of component A

TmB = Freezing point of component B
TE = Eutectic Temperature
E = Eutectic point
..cont: Eutectic system

Eutectic point
the point where
minimum
temperature required
to freeze the liquid
mixture.

Eutectic
temperature.

Eutectic mixture
is a liquid mixture that freezes at minimum temperature.
is a mixture of chemical compounds or elements that has a single
chemical composition that solidifies at a lower temperature
..cont: Eg: Eutectic system

• Solid present as separate phases (e.g ice and salt)

Temperature
X y
Melting point pure B
z liquid Ty
Melting point pure A

Solid A + Solid B +
liquid liquid
Eutectic point
Solid A + Solid B +
eutectic eutectic
Pure A Pure B
CZ Cy
Eutectic
composition Mole fraction
XA XB
Eg: Eutectic system

Two metals, S and R form a eutectic mixture

at 136oC with the eutectic composition of
45% S. The melting points of S and R are
365oC and 280oC respectively. Sketch a
eutectic diagram for the mixture of S and R
and label all the phases in the diagram.
 Cooling curve at 100% B
Temperature, °C
T1 B start freeze

B + liquid
T2 B completely freeze

100%B
Time (min)

95
 Cooling curve at point X –
add 40% A into B
A (l ) and B (l)
Temperature, °C
T1 B start freeze

T4
A start freeze

Eutectic temp,T5 A and B completely freeze

B(s) + liquid

Time (min)
96
 The graph below represents the freezing point of
the molten mixture of copper and silver.

Temperature, °C

P Z

100(Ag) Percentage copper by mass 100 (Cu)

97
 Physical properties of matter are categorized as
either Intensive or Extensive:

o Intensive - Properties that do not depend on the amount of

the matter present.

o Extensive - Properties that depend on the amount of matter

present.

98
 Melting/Freezing Point

Color
Odor

Intensive
Properties
Boiling Point
Density

Luster
How shiny a substance is.

99
 Length

Weight Mass
Extensive
Properties

Volume

100
 Colligative Properties
• Properties that depend only on the number of solute
particles in solution but not on the nature of the solute
particles.

• The solution must contain non-volatile solutes and

must be dilute because a dilute solution is most likely to
behave like an Ideal Solution.

101
 There are four types of colligative
properties
— Lowering of vapour pressure.
— Elevation of boiling point.
— Depression of freezing point.
— Osmotic pressure.

102
 (a) Vapour pressure lowering, DP
— the vapour pressure of a
solvent is reduced by the
presence of a nonvolatile
solute in the solvent.

— It because a nonvolatile
solute reduces the rate
of vaporization of the
solvent( see figure )

103
 — Solvent molecules have less tendency to leave a solution(B)
than a pure solvent(A).

— Therefore it is easier to change a pure solvent into vapour

than a solution into vapour.

104
 Raoult's Law
— can be used to calculate the vapour pressure of a solution.

105
 — When the solute is a nonvolatile solid, the vapour pressure is
zero, so the above equation reduces to

106
 — If the solution only contain one solute, X1 = 1- X2 , where X2
is the mole fraction of the solute.

— Therefore P1 = ( 1-X2)P°1
or P1 = P°1 –X2P°1
So that P°1 – P1 = DP = X2P°1

— So, vapour pressure lowering (DP) µ to mole fraction of

solute(X2)

107
— Total vapour pressure of solution,
P solution = PA + PB

— Remember, if B is non-volatile solute it has no vapour

pressure (non-volatile- non evaporate rapidly). Eg non-
volatile solute: sucrose, glucose,glycerol
So, PB = 0
P solution = PA + PB
= PAº.cA + PBº.cB
= PAº.cA + 0
= PAº.cA
Example : Powater = 0.5 atm)

— At 80oC, the vapour pressure of pure water is 0.5

atm. Determine the mass of sucrose, C12H22O11that
must be dissolved in 150 g of water at 80oC to
reduce the vapour pressure above the solution to
0.4 atm. (Psolution = 0.4 atm)
 PB = 0 because sucrose is non volatile

— Psolution = PA(water) + PB(sucrose)

= Pwater + o
0.4 = P0water X c water mol water = 150
18
= 0.5 X nwater = 8.3 mol
nwater + nsucrose

= 0.5 x 8.3
8.3 + nsucrose

n sucrose = ????
\m sucrose = n sucrose X RMM sucrose = ????
Answer: 709.65 g
 Practice:
Using Raoult’s law to find vapor pressure lowering

10.0 g of the paraffin C20H42, a non-volatile solute was

dissolved in 50.0 g of benzene, C6H6. At 53°C, the vapor
pressure of pure benzene is 300 torr.

— What is the vapor pressure of the solution at this

temperature?
Ans: 284 torr

111
 Estimate the relative molar mass
The vapor pressure of pure water at 25°C is 17.54 mmHg. When
114 g a compound A is dissolved in 1000g water, the vapor
pressure is lowered by 0.11 mmHg. Estimate the relative molar
mass of compound A.

Ans : 325.6 gmol-1

112
 • Boiling Point Elevation, DTb
• Freezing Point Depression, DTf

113
 • Boiling point elevation (DTb) is defined
as the boiling point of solution (Tb) minus the boiling point of
the pure solvent (T°b).

DTb = Tb - T°b

114
…..cont
ΔTb = imB. Kb
Where
ΔTb = change in boiling point of the solvent,(°C)
mB = molality of solute, (mol/kg or m)
Kb = molal boiling point elevation constant for
the solvent.

Boiling point of the solution = Tb solvent + ∆Tb

 • The extent of elevation is directly proportional to the
molality of the solution.

Substance (solvent) Kb
Benzene 2.53
camphor 5.95
carbon tetrachloride 5.03
Ethyl ether 2.02
Water 0.52

116
 The table below illustrates the meaning
of the van't Hoff factor (i):

Example
NaCl 2 ion ( i= 2)
CaCl2 3 ion ( i= 3)
Na2SO4 3 ion (i= 3)
AlCl3 4 ion (i= 4)

117
 The unit of molality
— Molality = moles of solute mol/kg
molal (m)
mass of solvent(kg)
= mass solute(g) / molar mass solute
mass(g) solvent / 1000

DTb = i.Kb x mass solute(g) x 1000

molar mass solute(gmol-1) x mass(g) solvent

So Tb solution = Tb pure solvent + DTb

Eg : Tb water =100 °C ; if DTb = 3.4 °C

Tb solution =100 + 3.4 = 103.4 °C

118
 Why Does Adding Salt Increase the
Boiling Point of Water?
— The reason why the boiling point rises when solute is added to a solvent has to
do with vapor pressure. A liquid boils when its vapor pressure is equal to that of
the atmosphere. Vapor pressure of a solution increases as it is heated. At
standard temperature and pressure, the vapor pressure of a solution is always
lower than that of a pure liquid, and thus a solution must reach a higher
temperature before it boils.

— The degree of boiling point elevation is dependent on the amount of solute

added to solution. The larger the number of salt molecules added to a given
volume of water, the greater the degree of boiling point elevation. According to
About.com, a person would have to add 230 grams of sodium chloride (table
salt) to a liter of water in order to increase its boiling point a mere 2 degrees
Celsius.

119
 Example

— How many grams of Al(NO3)3 must be added to 1.00

kg of water to raise the boiling point to 105.0°C?
Kb = 0.51°C/m
MW = 212.9962 g/mol
 Solution:

DTb = i.Kb x mass solute(g) x 1000

molar mass solute(gmol-1) x mass(g) solvent

i= 4 ion (Al(NO3)3)

DTb = 105 – 100 = 5oC

\5 = 4 x 0.51 x mass solute(g) x 1000

212.9962 x 1000
\ Mass solute = 5 x 212.9962 x 1000
4 x 0.51 x 1000

121 = 522.05 g
 Freezing Point Depression
• the presence of a non-volatile solute lowers the freezing
point of a solvent.

DTf = Tf° - Tf

Generally freezing point depression was a common method for

determining molar mass

122
….cont…

DTf = Tf ! - Tf
where Tf = freezing po i nt of the solution
Tf ! = freezing poin t of the pure solvent
DTf a m
DTf = kf . m
where kf = molal freezing poin t depression constant (C ! / m)
m = molality = concentration of the solute in unit of molal
no. of moles of solutes
=
mass of solvent (kg )
 • The extent of depression is directly proportional to the
molality of the solution:

Substance Kf
benzene 5.12
camphor 40.
carbon tetrachloride 30.
ethyl ether 1.79
water 1.86

124
…cont
ΔTf = imB.Kf
Where
ΔTf = change in freezing point, (°C)
mB = molality of solute, (mol/kg or m)
Kf = molal freezing point depression constant for
the solvent.

Freezing point of the solution = Tf solvent - ∆Tf

 — Molality = moles of solute The unit of molality
mol/kg
mass of solvent(kg) molal (m)
= mass solute(g) / molar mass solute
mass(g) solvent / 1000

DTf = iKf x mass solute(g) x 1000

molar mass solute(gmol-1) x mass solvent(g)

So Tf solution = Tf pure solvent - DTf

Eg : Tf water = 0 °C ; if DTf = 2.5 °C

Tf solution = 0 – 2.5 = - 2.5 °C

126
 Why does salt lower the freezing point of water?

— When salt is present, however, it upsets this process, as it

prevents the molecules from coming together. It is like
having a handful of weak magnets. They come together easily
if nothing is in between them, but if other things are present,
such as marbles, the magnets have a more difficult time
attracting one another.
— Water with salt in it has to be colder for it to solidify.
Lowering the temperature of water makes the molecules
move more slowly. In time, the molecules entering and
leaving the solid part of the water equal out again, as
everything is moving more slowly, and it is able to freeze.

127
Example :
Calculate the freezing point of a solution made from
22.0 g of octane (C8H18) dissolved in 148.0 g of
benzene (C6H6). Benzene freezes at 5.5 oC and its Kf
value is 5.12 oCm-1.
Solution:

DTf = Kf x molality
Tf solvent – Tf solution = 5.12 oc/m x molality
5.5oC ????

Molality of solution = moles of solute (C8H18)

mass of solvent (kg)
= 22.0 g / 114
148/1000 kg
= 0.193/0.148
= 1.304 molal
DTf = Kf x molality
Tf solvent – Tf solution = 5.12 oc/m x molality

5.5oC ????

\ 5.5oC - Tf solution = 5.12 x 1.304

= 6.677
\ Tf solution = 5.5oC – 6.677

= -1.177oC
 What is Osmosis?
Osmosis is process of solvent
molecules (fresh water) flow
from the dilute solution to
the concentrated solutions
via semi permeable
membrane due to different
concentration.

This movement continues until

it reaches an equilibrium which
is concentration of water is
equal at both side.

Semi permeable membrane

allow the water molecule to
pass through only.

131
 Osmotic pressure
The flow of solvent molecules through the
membrane can be stopped by applying external
pressure.

The pressure that just stops the flow of solvent

particles is the osmotic pressure, p

After applying external pressure, the level of

solution at both side become equal.

Osmotic pressure is a colligative property as it

only depends on the concentration of the
solution.

Experimental data shows that osmotic pressure

is directly proportional to the molarity (number of
moles of solute per litre of solution) of the
solution at a certain given temperature.

Two solutions which have the same osmotic

pressures at a given temperature are Isotonic
solutions.
132
 Osmotic pressure calculation
—

133
 Sample Problem
—

134
 Exercise
1) 9 g of nonelectrolyte solute was dissolved in enough water to produce
a 500 ml solution. The osmotic pressure was measured to be 1871.1 torr
at 300 K. Determine the molar mass of the solute. (Ans : 180.4 g/mol)

2) An aqueous solution with a volume of 100 ml and containing 0.122 g of

an unknown molecular compound has an osmotic pressure of 16.0 torr at
20 ⁰C. Determine the molar mass of the solute. (Ans : 1390 g/mol)

3) Calculate the osmotic pressure in mm Hg of a protein when 5.00 g of

the protein (molar mass = 235,000 g/mol) is used to prepare 100 ml of an
aqueous solution at 4⁰C. (Ans : 3.66 mmHg)

4) Determine the osmotic pressure in torr of a 0.0115 M glucose at body

temperature (37⁰C) ( Ans : 222.4 torr)

135