CHAPTER 5-Phase Equilibrium PDF

CHAPTER 5
PHASE EQUILIBRIUM
Sub topic
 Roult’s Law
 One component system
 Two component system
 Azeotropic mixture
 Fractional distillation
2 chm431/Dr Noraini Hamzah 22 Nov 2013

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

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

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

Phase Diagram
A C
Melting point

liquid

solid
Sublimation point
O
gas
 Boiling point
Triple point
B

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
PHASE CHANGES
sublimation
melting boiling
SOLID LIQUID GAS
freezing condensation
deposition
PHASE CHANGES

Phase Diagram of
water, (H2O)
One Component
System
Phase Diagram of
Carbon Dioxide,
(CO2)

Phase Diagram of CO2

Phase diagram for water.

Exercise
Consider a sample of H2O at point O.
a) What phase (s) is (are) present?
b) If the temperature of sample were reduced at constant
pressure, what would happen?
c) How would you convert the sample to vapor without
changing the temperature?

Answer
a) O is the triple point: ice, liquid and water vapor are present
b) Sample will freezes completely.
c) Reduce the pressure to below the triple point value.

Perhaps to 4 mmHg

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
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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)

Boiling point
 A liquid boils at a temperature at which its vapor
pressure is equal to the pressure above its surface.
 Normal boiling point ,

T = 100C P = 1 atm = 760 mm Hg

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.

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.

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

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

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

 For two phases system,
F=3–2
F =1
System univariant

 For three phases system;
F = 3-3
F=0
System invariant

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)

i) Sketch a labelled phase diagram for A.
Pressure, mmHg
800
760
liquid
320
solid
60
gas
85 125 150
Temperature, C

ii) From the phase diagram, show how you
would estimate the boiling point.
 Answer
145 ºC at a pressure of 760 mm Hg

iii) 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

2 Component
systems
Non-ideal
Ideal Solution
solution
Obey to Raoult’s Law

Ideal behaviour
 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 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.

Examples of mixtures that would produce
ideal solutions are:
 n-hexane + n-heptane
 bromoethane + iodoethane
 benzene + methylbenzene(toluene)
 water + methanol
 benzene + carbon tetrachloride(CCl4)

Intermolecular Force
SOLUTE SOLUTE
(A) (A)
SOLVENT
SOLVENT
(B)
(B)
SOLVENT SOLUTE
(B) (A)
The strength of intermolecular force
London
dipole-induce dipole
Hydrogen bonding More
ion-dipole stronger
ionic

Deviations from Ideal Behavior

ROULT’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   A P 
A
PB   B P 
B

Deviation Intermolecular H 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

DALTON’S LAW
 The total vapor pressure is equal to the sum of the
partial vapor pressure at that composition
PT  PA  PB  ...........

Vapor composition
 Vapor is always rich in the more volatile component
 Mole fraction of component A and B in the vapor is given
by;
PA PB
A  B 
PT PT

PHASE DIAGRAM OF TWO COMPONENT
( L – L system)
 Vapor pressure - composition diagram
 Boiling point – composition diagram

What is Vapor pressure?
liquid ⇌ vapor
 Once equilibrium between liquid and

vapor is reached, the number of molecules
per unit volume in the vapor does not
change with time.
 This means that the pressure exerted by the

vapor over the liquid remains constant.
 It depend on the strength of intermolecular

forces of the substances.

Vapor 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 vapor pressure X

Vapor pressure, atm
PY
0 1
Mole fraction Y

Vapor pressure, atm
PX
1 0
Mole fraction X

Vapor pressure, atm
Total pressure PY
PX
1 0
Mole fraction X
Mole fraction Y
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

Temperature, C
vapor 
 liquid
0 100
% component X

Figure 2: Liquid-Vapour Composition Diagram of Toluene-
Carbon Tetrachloride

Non-ideal solution
NEGATIVE DEVIATION POSITIVE DEVIATION

(A) Positive Deviation from Raoult’s
Law.
 If the A-B attraction is weaker than A-A attraction and B-B
attraction, the partial pressure of both of them over the solution a
greater than predicted by Raoult’s Law.
 Heat of solution is positive, the mixing process is endothermic (
Hsoln > 0)
 Examples :
water + hexanol
Ethanol + kloroform (CHCl3)
Ethanol + toluene

(B) Negative deviation from Raoult’s
Law.
 If the A-B attraction is stronger than A-A attraction and B-B attraction, the
partial pressure of both of them over the solution a less than predicted by
Raoult’s Law.
 Heat of solution is negative, the mixing process is exothermic ( Hsoln <

0)
 Examples :
water + nitric acid(HNO3)
water + HF
water + HCl
sulfuric acid + methanoic acid
propanon + kloroform

For Non-Ideal Solution
 A mixture has positive deviation
100%A 100%B
For Non-Ideal Solution
 A mixture has negative deviation
100%A 100%B
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

For negative deviation
 Has max azeotropic temperature
Temperature, C vapor  102

vapor
liquid  75
60  liquid
100%B 100% A
70%A , 30%B
For positive deviation
 Has minimum azeotropic temperature
Temperature, C
80  vapor
vapor  75
liquid liquid  55
100%B 100% A
70%A , 30%B
Liquid-Vapour Diagrams of 2 Different Azeotropic
Mixtures;
A) Ethanol and Water B) Formic Acid and Water.

Pass year exam-April 2006
A solution is made up of two components A and B.
The pure vapour pressure of A is 375 torr and the
pure vapour pressure of B is 500 torr. The total
vapour pressure of the solution is larger than that
calculated by Raoult’s law.
 Does this solution shows positive or negative

deviation from ideal behaviour?
 Do you expect the heat of solution to be
endothermic or exothermic?
 Describe the interaction between molecules A and
B.
 Draw a plot of vapour pressure versus mole fraction
for this solution.
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

Distillation Apparatus

Principles of Fractional Distillation
for ideal solution
 Component A would
be a distillate (lower
boiling point)
 Component B would
be a residue

for non- ideal solution – negative deviation
boiling
T1
TA
TB
condensation
Area Y Area X
C3 C2 C1 70% A
for non- ideal solution – negative deviation
 Less than 70 % of A (area Y)
distillate = pure B
residue = azeotropic mixture
 More than 70% of A (area X)

distillate = pure A
residue = azeotropic mixture

for non- ideal solution – positive deviation
TA
TB
Area X
Area Y
65% A
for non- ideal solution – positive deviation
 Less than 65 %A ( area Y)
distillate = azeotropic mixture
residue = pure B
 More than 65% A (area X)

distillate = azeotopic mixture
residue = pure A

Pass year exam –April 2006
The normal boiling point of acetone is 56.1 oC, and that
of chloroform is 61.2 oC. At 1.0 atm, the azeotropic
mixture boils at 64.4 oC.
 What is meant by an azeotropic mixture?

 Does the mixture exhibits a maximum or a minimum boiling
azeotrope?
 Sketch a temperature-composition diagram phase diagram of
chloroform and acetone.
(5 marks)

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)

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
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.

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

Eutectic diagram
Temperature, C
T1 X
Freezing point of
pure B, T2
A (l) + B (l)

  Freezing point of
pure A ,T
T4   3
B (s) + liquid  A(s) + liquid

T5   Eutectic temp.
A (s) + B (s) + eutectic
100% B 40% A 70% A 100% A

Cooling curve at 100% B
Temperature, C
T1 B start freeze
B + liquid
T2 B completely freeze
Time (min)

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)
The graph below represents the freezing point of
the molten mixture of copper and silver.
Temperature, C
P Z
0 Percentage copper by mass 100

Pass Year Exam
i) What does the temperature at point X represent?
ii) Consider a molten mixture, containing equal masses of silver and
copper was allowed to cool down from a temperature at P. At
what temperature do the first crystals of solid appear?
iii) What is the percentage of silver in these first crystals?
iv) Explain what is meant by the term eutectic mixture at Y
(5 marks)

Answer scheme
i) Melting point of pure silver
ii) At Q
iii) 0 %
iv) Eutectic mixture at Y
 melts at a single defined temperature at Y
(½)
 and produces a liquid melt containing copper and silver
( 1)
 has the same composition as the solid
(½)
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.

Melting/Freezing Point
Color
Odor
Intensive
Properties
Boiling Point
Density
Luster
How shiny a substance is.

Length
Weight Mass
Extensive
Properties
Volume

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.

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

(a) Vapor pressure lowering, P
 the vapor 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 )

 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 vapor than

a solution into vapor.

Raoult's Law
 can be used to calculate the vapor pressure of a solution.

 When the solute is a nonvolatile solid, the vapor pressure is
zero, so the above equation reduces to

 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 = P = X2P1
 So, vapor pressure lowering (P)  to mole fraction of

solute(X2)

Practice:
Using Roult’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
 Calculate the vapor pressure lowering.

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

Boiling Point Elevation
Freezing Point Depression

 Boiling point elevation (Tb) is defined
as the boiling point of solution (Tb) minus the boiling point of
the pure solvent (Tb).
Tb = Tb - Tb

 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

 Molality = moles of solute
weight of solvent(kg)
= mass solute(g) / molar mass solute
mass(g) solvent / 1000
Tb = Kb x mass solute(g) x 1000

molar mass solute(gmol-1) x mass(g) solvent
So Tb solution = Tb pure solvent + Tb
Eg : Tb water =100 C ; if Tb = 3.4 C
Tb solution =100 + 3.4 = 103.4 C

The table below illustrates the meaning
of the van't Hoff factor:
Example
NaCl 2 ion ( i= 2)
CaCl2 3 ion ( i= 3)
Na2SO4 3 ion (i= 3)
AlCl3 4 ion (i= 4)

Freezing Point Depression
 the presence of a non-volatile solute lowers the freezing
point of a solvent.
Tf = Tf - Tf

 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

 Similarly :
Tf = Kf x mass solute(g) x 1000

molar mass solute(gmol-1) x mass solvent(g)
So Tf solution = Tf pure solvent - Tf
Eg : Tf water = 0 C ; if Tf = 2.5 C
Tf solution = 0 – 2.5 = - 2.5 C

Practice exercise :
Calculate the freezing point of a solution containing 0.600 kg
of chloroform, CHCl3 and 42.0 g of eucalyptol, C10H18O a
fragrant substance found in the leaves of eucalyptus trees.
Freezing point chloroform = -63.5 C . Kf chloroform =
4.62 C m-1
Ans : -65.6C

Practice exercise :
 Automotive antifreeze consists of ethylene glycol, C2H6O2 a
non-volatile electrolyte. Calculate the boiling point and
freezing point of a 25.0 % (mass/mass) solution of ethylene
glycol in water.
Ans : bp = 102.8C , fp = -10.0C

Using Colligative Propertives to
determine molar mass
 Ethanoic acid has a freezing point of 16.63C. On adding 2.50 g
of an organic solute to 40.0 of the acid, the freezing point was
lowered to 15.48C. Calculate the relative molar mass of the
solute. Kf for ethanoic acid is 3.90 Cm-1
Ans : 212 gmol-1

 A 7.85 g sample of compound with the empirical formula C5H4 is
dissolved in 301 g of benzene. The freezing point of the solution is
1.05C below that of pure benzene. What are the molar mass and
molecular formula of this compound?
Answer : 127.7 gmol-1 , C10H8

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CHAPTER 5

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 It shows the equilibrium pressure –temperature relationship

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b) Sample will freezes completely.

c) Reduce the pressure to below the triple point value.

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Effect of Melting point Melting point

density water Solid CO2

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

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

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 Normal boiling point ,

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 It means CO2 gas does not liquefy above this

 Above the critical temperature and pressure, a

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 A solid can sublime only at a temperature below

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Obey to Raoult’s Law

 The heat of solution is zero, there is no heat produced or released

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negative stronger weaker negative Water +

positive weaker stronger positive Benzene +

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 Vapor pressure - composition diagram

 Boiling point – composition diagram

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 Once equilibrium between liquid and

 This means that the pressure exerted by the

 It depend on the strength of intermolecular

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You must indicate this two matter:

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