CHM 271

PHASE EQUILIBRIUM
CHAPTER 6

6.1 Definition (Phases, Components, Phase rule, Degree

of Freedom)
6.2 One component system (H2O & CO2 systems)
6.3 Two component system (Raoult’s Law)
6.4 Colligative properties
6.4.1 Boiling point elevation
6.4.2 Freezing point depression
Mdm Nurul Amni Abdullah
Faculty of Applied Sciences
amni2468@uitm.edu.my
Definitions
• Phase
• Component
• Phase rule: Degree of freedom
1-component system
• Phase diagram of water (H2O)
• Phase diagram of carbon dioxide (CO2)
2-component system
• Raoult’s Law & Ideal Solutions
• Two completely miscible liquids
• Vapour pressure-composition Diagram
• Fractional distillation
• Non- ideal Solutions & Azeotropic system
• Two completely miscible solids

Colligative Properties
• Boiling Point Elevation
• Freezing Point Depression

2
 Lesson Outcomes:
At the end of this lesson, students will be able to :

• Identify phases and components

• Explain the water and CO2 phase diagram
• Explain the Raoult’s Law (Ideal & Deviations)
• Draw/Sketch the Vapor Pressure-composition & Boiling Point
composition phase diagram
• Solve quantitative problem relate to P°, Tb, Tf
• Explain Colligative properties

3
 Phase (p)
▪ Definition 1: Homogeneous regions of matter
▪ Definition 2 : A distinct homogeneous part that is in contact
with other parts but separated from them by a
distinguishable (well-defined) boundary.
▪ A system can exist in solid, liquid or gas phase or
furthermore can coexist in any combination of two phases,
even three-phase at once.

4
Cont…

▪ Gas or a gaseous mixture : single-phase

▪ Miscible liquid : single-phase
▪ Mixture of immiscible liquid : two-phase
▪ Immiscible liquid : an element with two allotropes and a mixture of
two different states of substance
▪ Substance that can coexist in three different states (solid, liquid and
gas) forms a three-phase system.

2-Phase (Binary phase) System

Solid phase - ice

Liquid phase - water

5
Component (c)

▪ Component : a chemically independent constituent of a system

▪ Number of components (c) : the minimum number of independent
species required to describe the composition of all phases
present in the system (the number of substance present)
▪ Examples:
▪ Ice & water= one component
▪ Water & ethanol= two component
▪ Water & CCl4= two component

6
 Number of phase and component
System Phase Number of Number of
phases components
Air(O2, CO2, N2 etc) Gas 1 many
Ice and water Solid-liquid 2 1
Water and vapour Liquid- gas 2 1
Ice and vapour Solid-gas 2 1
Ice,water and vapour Solid-liquid-gas 3 1
Water and ethanol Liquid 1 2
(miscible liq)
Water and CCl4 Liquid-liquid 2 2
(immiscible liq)
Iodine crystal and Solid-gas 2 1
iodine vapour
Rhombic sulfur and Solid-solid 2 1
monoclinic sulfur

7
Phase Changes
Least
Order

Greatest
Order 8
The Phase Diagram

Phase diagram
• shows the regions of pressure & temperature at which its various
phases are thermodynamically stable.
• shows the equilibrium pressure-temperature relationship among
different phases of a pure substance in a closed system.
• to predict physical state at specific temperature and pressure

Phase boundary
• a boundary between regions, shows the values of P and T at which
2 phases coexist in equilibrium.

9
 The Phase Diagram (in general)

Pressure/atm
✓area/ region = phase
✓line = set of
temperature and
pressure which 2 phase
on either side of line exist
Liquid in equilibrium
Solid
✓Triple point, O =
temperature and
O
Vapour pressure at which all 3
phases of a substance
coexist in equilibrium

- Temperature/oC

10
▪ The phase diagram for a substance A is shown. State the
physical state of A at the condition X, Y and Z

x
P liquid

solid y
O
z
vapour

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
11
 The Phase Diagram

Equilibrium can exist not only between the liquid and vapor phase
of a substance but also between the solid and liquid phases, and
the solid and gas phases of a substance.
12
Pressure
(atm)
water
C
B

ice

vapour

A
Temperature
(ºC)

13
 Gibbs Phase Rule

The phase rule

a general relation among the degree of freedom, f, the number of components, c
and the number of phases, p at equilibrium for a system of any composition.

f=c–p+2

Degree of freedom or Variance, f

the number of intensive variables that can be changed independently without
changing the number of phases in equilibrium. (intensive variables: temperature,
pressure, or concentration on the phase equilibrium as well as chemical
constituents equilibrium)

14
 Gibbs Phase Rule
f=c–p+2
f = degrees of freedom
The number of variables that can be changed independently
without changing the phase of a system
p = number of phases
The number of homogeneous and distinct parts of the system
separated mechanically by definite boundaries
c = number of components (chemical constituents that must be
specified in order to define all phases)
2 = Two intensive parameters (normally, temperature and pressure)

ONLY APPLIES TO SYSTEMS IN CHEMICAL EQUILIBRIUM!!

15
 The Phase Rule
General Rule:
• If you have equilibrium balance between reactants and products, the
number of components will be reduced by one.
• If you have equal amounts (concentrations) of products formed, the
number of components will also be reduced by one.

Example 1

NaCl(s) dissolved in H2O.

Available chemical constituents are 4.

+ –
Na , Cl , NaCl and H2O.

+ –
But Na and Cl have the same amount “equal neutrality” as NaCl, then c = 2 and
not 4.

16
 The Phase Rule

Example 2
CaCO3(s) CaO(s) + CO2(g)

Available chemical constituents are 3.

Is it correct to say c = 3 ?
Because of the equilibrium condition the number of independent
components is reduced by one.
Thus, c = 2 instead of 3.
Can you specify the number of phases for the reaction?
We have here three homogeneous, distinct parts of the system
separated by definite boundaries. Thus, p = 3.

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 The Phase Rule ( Water system)
How many components do you have?
Only one component which is H2O.
In the one-phase regions, one can vary
either the temperature, or the pressure, or
both (within limits) without crossing a phase
line.
These regions:
f=c–p+2
=1–1+2
= 2 degrees of freedom

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 The Phase Rule
Along a phase line we have two
phases in equilibrium with each other,
the number of phases = 2.
If we want to stay on a phase line, we
can't change the temperature and
pressure independently.

Along a phase line:

f=c–p+2
=1–2+2
= 1 degree of freedom.\

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 The Phase Rule
At the triple point there are three
phases in equilibrium, but there is only
one point on the diagram where we
can have three phases in equilibrium
with each other.

At the triple point:

f=c–p+2
=1–3+2
= 0 degrees of freedom.

20
 One-component phase equilibrium

For a one-component system (pure water)

f＝1－p＋2＝3－p，(C＝1）

f ≥0, p ≥1, 3≥p≥1

p＝1，f＝2 : bivariant

p＝2，f＝1 : univariant

p＝3，f＝0 : invariant
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One-Component System

▪ Single component system contains only one chemically

independent species.
▪ Examples:
▪ Water
▪ Carbon dioxide
Single component system (with its 3 phases)

22
 Triple Point & Critical Point

▪ Most of substances (e.g water) can exist in 3 phases

▪ Triple point : the temperature and pressure at which
the three phases (solid, liquid & vapour) of a
substance exist in equilibrium
▪ Critical point : the critical temperature and critical
pressure, at which it is impossible to liquefy a gas

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i) Phase Diagram of H2O
▪ The lines in H2O phase
diagram are same as CO2
phase diagram
▪ It’s only different at AB line
which the solid-liquid
boundary line for water
slopes to the left or has a
negative slope.
▪ Under normal condition
(25°C, 1 atm) –H2O is liquid
▪ At 1 atm, the phase changes
from solid to

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Cont. Phase Diagram of H2O

▪ Triple point A: below 1 atm, (at

0.01⁰C and 0.006 atm)
▪ Critical Point C: 374⁰C, 218
atm
▪ Freezing Point : 0 ⁰C, 1 atm
▪ Boiling point: 100⁰C , 1 atm
▪ Line AB slopes to the left
(negative slope) because m.p
and freezing point of liquid
water decreases with pressure
▪ If the pressure increases
above 1 atm, it will increase
the b.p & lower the m.p thus
favours the formation of liquid
due to ice is less dense than
liquid H2O
25
ii) Phase Diagram of CO2
Critical point
▪ A (-56.4⁰C, 5.1 atm) : the triple point
at which the 3 phases exist in
equilibrium
▪ B (31⁰C, 73 atm) : the critical point
at which CO2 gas cannot be
liquefied.
▪ AB – boiling point curve (the
variation of boiling temperatures with
pressure)
▪ Along AB, liquid CO2 is in
equilibrium with CO2 gas
Triple point
▪ AC – sublimation or deposition curve
(the variation of sublimation
temperatures with pressure)
▪ Along AC, solid CO2 is in equilibrium
with CO2 gas.

26
Cont…
▪ The triple point A of CO2 is above
atmospheric pressure (1 atm).
▪ It is impossible for solid CO2 to
melt at 1 atm.
▪ Instead solid CO2 (dry ice)
sublimes into gas
▪ AD – melting point or freezing
point line (the variation of melting
temperatures with pressure)
▪ Along AD, solid CO2 is in
equilibrium with liquid CO2

▪ AD slopes to the right (a positive slope)

▪ implies that the melting point (m.p) increases with
pressure due to solid CO2 is denser than liquid CO2

27
 Variation of Melting Point with Pressure
28
▪ An increase in pressure favours the formation of the denser phase

Variation of
m.p with
Pressure

solid liquid
(higher (higher
density phase) density phase)
 When the solid is the
denser phase
▪ The solid-liquid equilibrium line is
inclined to the right.
▪ At higher pressures, liquid is
converted to solid, the solid
becomes stable at temperatures
above the normal melting point OR
the melting point is raised by an
increase in pressure
▪ The behavior is shown by
substance like CO2

29
 When the liquid is the
denser phase
▪ The liquid-solid line is
inclined to the left
▪ An increase in pressure
favours the formation of liquid
from solid; i.e the melting
point is decreased by raising
the temperature
▪ Water behave this way as ice
is less dense than liquid
water.

30
 Two-Component System
▪ A mixture of two chemically independent species
▪ The mixture may be of
▪ homogeneous/miscible (a single phase)
▪ A mixture of N2 gas and H2 gas
▪ A solution of methanol in ethanol
▪ Alloy of copper in tin

▪ heterogeneous/immiscible (consists of two or more phases)

▪ Suspension of oil in water

F = c - p + 2 (Phase rule)
▪ When two components are present in a system, C = 2 and F=4-P.

31
Miscibility ▪ The ability of liquid mixture’s
components to mix with each other.
Miscibility

Miscible Partially miscible Immiscible

•liquids form a •results in a •liquids cannot mix
homogeneous distinguishable together at all
mixture, mix meniscus between the •the volume is the
completely to form liquids total volume of
a single phase •the volume is not liquids added
•Eg.: ethanol & identical to the original originally
water volume. •Eg.: oil & water,
•Eg.: hexanol & water water & hexane

32
The equilibrium vapor pressure : the vapor pressure measured when
a dynamic equilibrium exists between condensation and
evaporation

H 2 O (l ) H2O (g)

Dynamic Equilibrium

Rate of = Rate of
condensation evaporation

33
 Measurement of Vapor Pressure

Before Evaporation At Equilibrium

34
The boiling point is the temperature at which the (equilibrium)
vapor pressure of a liquid is equal to the external pressure.

The normal boiling point is the temperature at which a liquid boils

when the external pressure is 1 atm.

35
Critical temperature (Tc) : the temperature above which the gas
cannot be made to liquefy, no matter how great the applied
pressure.
Critical pressure (Pc) : the minimum pressure that must be applied
to bring about liquefaction at the critical temperature.

36
 Solution & Raoult’s Law
▪ A solution : a homogeneous mixture made up of solute
(s) in a solvent
▪ A solution made up of 2 liquid components may be
ideal or non-ideal
▪ Raoult’s Law : the law that classifies solutions as either
ideal or non-ideal

Ideal Solution Non-ideal Solution /Real

solution
1. methyl alcohol-water 1. ethanol – water
2. benzene-toluene 2. isopropylalcohol – water
3. methanol-ethanol 3. propanol – water
4. chloroform – ethanol
37
 Raoult’s Law
▪ Ideal solutions obey Raoult’s Law
▪ The law states that the partial vapor pressure of
component A is equal to the product of its mole
fraction in solution and the vapor pressure of pure
A. (similar for liquid B)

PA = XA.POA

PA = partial vapor pressure of component A in a solution

PoA = vapor pressure of pure component A
XA = mole fraction of component A (= nA/ntotal)
38
Therefore,
Total pressure = Vapor pressure of the
solution

PTotal = PA + PB

= XA.POA + XB.POB

Dalton’s Law
When The total pressure of a
mixture of ideal gases is
XB =O, P = XA.POA the sum of the partial
pressures of the gases
XA =O, P = XB.POB mixture

Note : The total mole fraction in a system is always

equal to 1 (XA + XB = 1)
39
 Ideal Solutions
▪ Ideal solutions are formed when the solute and solvent have
similar structures (eg. mixture of benzene & toluene)
▪ In a mixture of miscible liquids of A and B, there are 3 types of
intermolecular forces between the molecules which are the
attraction between A---A, B---B and A---B.
▪ In ideal solution, intermolecular attractions between like molecules
and unlike molecules are equal in strength.
▪ There is no change in the energy ( ∆Hsoln = 0) and volume of
solution ( ∆V = 0)

40
▪ Applying Dalton’s law of partial pressures,
partial pressure of a component=(mole fraction) x (total pressure)
▪ YA and YB represents mole fractions of component A and component B
in the vapour phase respectively
▪ P=PA +PB. Hence the mole fraction of component A in the vapour is
given:
YA= PA/P = PA/(PA+PB)
Similarly, the mole fraction of component B

41
 Vapour Pressure-Composition Curve
(Ideal Solution)
▪ Vapour is always rich in
the more volatile
component. PoB
▪ Blue line is the total
pressure against
composition for the
mixture. PoA

▪ Component B is more
volatile than A
O XB → 1
1 XA O

42
Vapour Pressure-Composition Curve
(Ideal Solution)
Vapor ▪ The figure shows the
pressure equilibrium between liquid and
vapor of an ideal solution, (eg.
Mix of benzene & toluene)
Liquid PoB
▪ Liquid is favorable at higher
pressure and vapor at lower
Liquid-Vapor pressure.
PoA ▪ The composition of the vapor
Vapor which is in equilibrium with a
C1 C2 liquid mixture of composition
C1 is given by C2.
O XB → 1
1 XA O
▪ P actual= P calculated

43
 Vapour Pressure-Composition Curve
(Benzene – Toluene mixture)
▪ When mole fraction of benzene
Vapor pressure
(atm) is at C1 in the solution, vapor
composition of benzene is
PoBenzen equivalent at point C2.
Liquid e

▪ As liquid composition of
Liquid-Vapor
benzene increases, its vapor
PoToluen
e
composition increases even
Vapor further.
C1 C2

O
XBenzene 1 ▪ An increase in benzene
→
composition, the composition of
toluene decrease.

44
 Boiling Point (b.p) – Composition
Curve
▪ The figure shows the equilibrium
(oC) between liquid and vapor of an
ideal solution(eg. Mix of benzene
110 and toluene)
vapor
V1
T1 ▪ B.p of benzene is lower than
toluene, as benzene is more
T2 V2 volatile than toluene.

V3 ▪ The diagram is upside-down

T3 liquid because the vapor phase is stable
80 at high temperature.
▪ Component that has higher vapor
pressure has lower b.p and vice
L1 L2 L3 100 versa.
% benzene
▪ The most volatile compound will
distillate first as it has lower b.p.

45
Fractional Distillation

▪ Distillation – a scientific
technique used to separate
components of a solution
mixture by boiling the solution
mixture first and then
condensing it into vapor.
▪ Fractional distillation – a
process of separating mixtures
of volatile components based
on difference in boiling point
▪ Eg:
- refining of petroleum to obtain
gasoline or petrol.

46
The first fraction collected
Fractional Distillation Apparatus
contains the most volatile A liquid mixture is placed in the round
component (lowest boiling bottom flask connected to
point). fractionating column that further
connected to condenser which allows
Later fractions are less volatile the vapour to cool and condense
liquids.

The least volatile (highest

boiling point) components
remain as a residue in the
distillation pot.

Boiling chips are

added to avoid
bumping
The vapor emerging from the
top of the column is condensed
Round bottom flask is
to a liquid in the water-cooled
heated using steam
condenser.
bath that allow
mixture to boil

47
❑ Repeating boiling and condensation ,pure benzene is obtained as
distillate or the condensate

Residue
Distillate

Pure liquid collected as Liquid that has higher

a result of boiling point and
condensation from remains as liquid after
distillation process the distillation

❑ This technique is a concept in fractional distillation process.

❑ 2 component can be separated using this method
❑ For example above: toluene is the residue
❑ If 3 component: fractional distillation produces
• First distillate
• Second distillate
• Residue

48
 Fractional Distillation

▪ Liquid composition of C1 is
boiled, the vapor given off
Constant pressure will have composition of D1
Boiling point/oC (richer in A).
Vapor ▪ This vapor condensed to
composition
TB give the liquid of composition
C2.
D1
▪ Liquid of C2 will in turn boils
D2 at lower temperature and
give out a vapor having D2
TA Liquid composition (richer in A).
composition
▪ Pure A will ultimately
C3 C2 C1 obtained by successively
distilling the fractions.
1 XA O

49
 Non- Ideal Solution
▪ At low concentrations of solute, most solutions show deviations
from ideality.
▪ Non-ideal solution can deviate from ideal behavior in two ways:
- positive deviation from Raoult’s Law
- negative deviation from Raoult’s Law
• The deviation of real gases from ideal gases behaviour is caused
by 2 factors
• i) existence of intermolecular forces of attraction between gas
molecules
• ii) the gas molecules occupy space i.e they have volume

50
 Deviation from Ideality
 Extreme deviations from ideality
 Result in maxima /minima in vapour-pressure diagrams
and temperature- composition diagrams

AZEOTROPES Means composition does

a – without not change during boiling
zeo- boil
Trops - change
Azeotropic mixture: Mixture of two miscible liquids that has a constant
boiling point and the vapour that exist in equilibrium with the liquid
has the same composition as the liquid
On heating an azeotropic mixture until it boils, the vapor liberated has
the same composition as the original liquid mixture 51
 Azeotropic System
▪ Liquid mixtures which deviate widely from ideality
cannot be separated completely by fractional
distillation.
▪ Azeotrope : a mixture with a constant boiling point
where the vapor is the same as the composition of
the liquid.
▪ Fractional distillation will yield one pure liquid
component and an azeotropic mixture.

52
 Azeotropic Mixtures

Components Normal boiling Normal boiling point of Mole

point/oC Azeotropes/oC fractions
Propanone 56.5 64.8 0.36
Trichloromethane 61.2 0.64
Benzene 80.1 67.9 0.46
Ethanol 78.5 0.54
Water 100 108.7 0.89
Hydrogen 83.8 0.11
chloride
Benzene 80.1 77.5 0.55
Cyclohexane 81.0 0.45
Carbon disulphide 46.2 65.0 0.60
Propanone 56.5 0.40

53
 ▪ Positive deviation:
- Attractive forces: A-B < A-A or B-B
- PT > Pcalculated using Raoult’s Law
- Volume of solution > volume of pure components
- ∆Hsoln is positive
- Eg.: water-ethanol mixture

Negative deviation:
- Attractive forces: A-B > A-A or B-B
- PT < Pcalculated using Raoult’s Law
- Volume of solution < volume of pure components
- ∆Hsoln is negative

* At low pressures & high temperatures, real gases approach ideal behaviour
54
54
 Positive Deviation
Vapour pressure is higher than ideal in
these mixtures means that the
molecules are easily breaking away
than they do in pure liquids.
That is because the intermolecular
forces between molecules of A and B
are
weaker than they are in the pure
liquids.
A-A ̴ B-B > A-B in which bond is
weaker.
So, the vapour pressure is higher than
predicted by Raoult’s Law
- Tendency of molecules to vaporize
is greater.
Boiling point is lower than its pure
component.
Negative Deviation
Vapour pressure is lower than ideal in
these mixtures means that the
molecules are not easily breaking
away than they do in pure liquids.
That is because the intermolecular
forces between molecules of A and B
are
greater than they are in the pure
liquids.
A-A ̴ B-B < A-B in which bond is
stronger.
So, the vapour pressure is lower than
predicted by Raoult’s Law
- Tendency of molecules to vaporize
is lower.
Boiling point is higher than its pure
component. 55
 Positive Deviation Negative Deviation

56

Negative deviations:
Positive deviations: • Preal < pideal and Treal > Tideal
• preal> pideal and Treal < Tideal • T-X curves curve upwards,
• T-X curves curve down, • may form maximum.
• may form minimum. Mixture at maximum: azeotrope (z)
Mixture at minimum: Fractional distillation:
• minimum-boiling azeotrope (z). • azeotrope left as liquid!
Fractional Distillation: • Azeotrope boils sharp
• azeotrope comes off top! 56
Cont...
Temperature Temperature
1) 2)

1) Positive deviation 2) Negative deviation

Total vapor pressure of a solution of 2 Total vapor pressure of a solution of 2
miscible liquids is higher than calculated miscible liquids is lower than calculated
using Raoult’s Law using Raoult’s Law

Boiling point is lower than its pure Boiling point is higher than its pure
component. component. 57
Cont... negative deviation
positive deviation

In the case of the positive deviation, the In the case of the negative deviation,
mixture with composition a1 is known as the mixture with composition a2 is
a minimum boiling point azeotropic known as a maximum boiling point
mixture. azeotropic mixture.

58
58
 Water - Alcohol System
▪ The figure shows a boiling point-composition graph for
water/alcohol system (eg. Water & ethanol).
(oC) ▪ Vapor at point E will
100
condensed to point F at
90 E around 90oC.
vapor ▪ The liquid at composition F
G
will boiled again and
F
produce vapor at
liquid composition G, and then
66
repeating the distillation
process until pure ethanol
20% % methanol obtained at its pure b.p
(66oC)
59
 (oC)

66 oC
liquid

75 oC

85 oC

90 vapor

95 oC

100
20% % methanol

The diagram shows a fractional distillation of water-ethanol with the temperature

scales decreased along the y-axis.
Ethanol is distillated at 66oC.

60
▪ Ethanol (boiling point = 78.5ºC) and water (boiling point = 100ºC)
form an azeotropic mixture with a composition of 95% water by
mass and a boiling point of 78ºC.
a) Sketch a boiling point –composition curve for the system
b) Explain what happens when a mixture containing 50% ethanol
by mass is distilled fractionally

61
62
 Eutectic System
(Two completely miscible solids)
▪ A eutectic or eutectic mixture : a mixture of two or
more phases at a composition that has the lowest
melting point. (a liquid mixture that freezes at
minimum temperature)
▪ It is where the phases simultaneously crystallize
from molten solution.
▪ The proper ratios of phases to obtain a eutectic is
identified by the eutectic point on a binary phase
diagram.
▪ The term comes from the Greek 'eutektos', meaning
'easily melted’.

63
 Eutectic System
▪ Eutectic point - the point on a phase diagram where the
maximum number of allowable phases are in equilibrium.
▪ When this point is reached, the temperature must remain
constant until one of the phases disappears. A eutectic is
an invariant point.
▪ A liquid with the eutectic composition freezes at a single
temperature, without previously depositing solid A or B.
▪ A solid with the eutectic composition melts, without
change of composition, at the lowest temperature of any
mixture.
▪ One technologically important eutectic is solder, which
has mass composition of about 67 % tin (Sn) & 33 % lead
(Pb) and melts at 183oC
64
• Eutectic phase diagram describes behavior of the alloys, two
components of which are completely soluble in liquid state and entirely
insoluble in solid state.
• This diagram has two liquid curves, starting from the freezing points of
the two metals and intersecting in a minimum point – eutectic point. 65
▪ When pure liquid of zinc is cooled, it
freezes at 419⁰C. Temperature
▪ An amount of Cd is added to zinc and 419ºC A
heated to turn to liquid.
321ºC
▪ When, it is cooled, it become solid and B
freeze at lower temperature than pure
zinc.
E
▪ Adding more Cd causes freezing point to
drop further until finally at 270⁰C 270ºC

▪ Pure Cd is freezes at 321⁰C %Cd

▪ When, zinc is added to Cd, freezing point will decrease. By adding
more zinc, the freezing point becomes lower and finally reach at
270⁰C
▪ The eutectic composition of Zn-Cd mixtures contains 17% Zn and
66
83% Cd.
 Cooling Curves

▪ A cooling curve is a line graph

that represents the change of
phase of matter, typically from a
gas to a solid or a liquid to a
solid.
▪ The independent variable (X-
axis) is time and the dependent
variable (Y-axis) is
temperature.

67
Cooling curve on Eutectic mixture
▪ Cooling process begins when the liquid
mixture is cooled from A to B
▪ Along AB is change in slope during
cooling. At B, the rate cooling becomes
slower.
▪ The process at point B.
▪ One of the components begins to
freeze/pptate from mixture
▪ Heat of fusion is released by the
component mixture
▪ B to C: mixture is cooled further until all
liquid freezes

▪ The minimum temperature at point C, all liquid crystallizes/ freezes to

form a eutectic mixture.
▪ DE represents the cooling of eutectic solid.
68
Cooling curve of Bi-Cd mixture at
various compositions
▪ Curve L and S, the slopes
change at point P and Q
respectively
▪ Due to the precipitate
form during cooling
process.
▪ Heat released from the
substance, the cooling
process slow down, the
slope declined.
▪ Heat release by
substance: heat of fusion

69
▪ First section of curve:
▪ Liquid is cooled and reaches
super cooled stage, before
freezing takes place.
▪ Plateau region:
▪ Freezing occur where the
temperature remains constant
until all liquid turn into solid
▪ At this point, the temperature
is freezing point for liquid and
melting point for solid
▪ Last section of curve:
▪ Solid is cooled to room
temperature

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 Colligative Properties
➢ Definition: Properties of solutions that depend only on the number of
dissolved solute particles in solution and not on their identity.

number of solute particles

number of solvent molecules

➢ Two types of colligative properties :

1) *colligative properties of electrolytes (Van’t Hoff factor= number
of discrete ions in a formula unit of the substance)
2) *colligative properties of non-electrolytes (Van’t hoff factor =1)
➢ Colligative properties of solution determines by the total number of
solute particles
➢ Electrolytes compound separate into two/more particles when it
dissolves. Ex: NaCl2 → Na+ and Cl-
* Not examinable/not covered in syllabus
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 Colligative Properties
▪ Effect of addition of solute to form a
solution:
1) stabilizes the solvent in the liquid
phase
2)lowers the solvent chemical potential
3)the solvent molecules have less
tendency to move to the gas or solid
phase.

▪ Result:
▪ Boiling point increases
▪ Freezing point decreases OR vice versa
Extension of vapor pressure concept:
Normal Boiling Point: BP of Substance @ 1atm
When solute is added, BP > Normal BP
Boiling point is elevated when solute inhibits solvent from escaping.

Elevation of B. pt.
Express by Boiling point
Elevation equation

B.P of liquid / solution: Temp when

VP= external pressure
75
 Boiling Point Elevation
▪ Boiling point elevation(∆Tb) is defined as the boiling
point of the solution(Tb) minus the boiling point of the
pure solvent(T°b):

∆Tb = Tb(solution) – T°b(solvent)

▪ Value of ∆Tb is proportional to the molality of the

solution, i.e

76
•This figure shows that the boiling point of the
solution is higher than that of water.
▪ Addition of a non-volatile solute to a solution raises the boiling
point of the solution above that of the pure solvent.
▪ This effect is because the solution’s vapor pressure is
lowered as described by Raoult’s law.
▪ The solution’s temperature must be raised to make the
solution’s vapor pressure equal to the atmospheric pressure.
▪ The amount that the temperature is elevated is determined by
the number of moles of solute dissolved in the solution.
▪ Adding non-volatile solute dilutes the concentration of the liquid
molecules and reduce the rate of evaporation.
▪ To compensate for this and re-attain equilibrium, boiling point
occurs at higher temperature.

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Boiling-Point Elevation
DTb = Tb – T b0
T b0 is the boiling point of
the pure solvent

T b is the boiling point of

the solution

Tb > T b0 DTb > 0

DTb = Kb m
m is the molality of the solution
(mol solute/ kg solvent)
Kb is the molal boiling-point
elevation constant (0C/m)
for a given solvent
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DTb = (Tb -Tb°) = Kb . m
Where, DTb = BP. Elevation
Tb = BP of solvent in solution
Tb° = BP of pure solvent
m = molality , kb = BP Constant

Some Boiling Point Elevation and Freezing Point Depression Constants

Normal bp (°C) Kb Normal fp (°C) Kf

Solvent pure solvent (°C/m) pure solvent (°C/m)

Water 100.00 +0.5121 0.0 1.86

Benzene 80.10 +2.53 5.50 4.90
Camphor 207 +5.611 179.75 39.7
Chloroform 61.70 +3.63 - 63.5 4.70
(CH3Cl)
80
Example:
For a 0.262 molal solution of sucrose in water, calculate the boiling point of
the solution.

▪ Calculate the boiling point elevation:

ΔTb = Kbm
Kb = 0.512 (from table above)
m = 0.262 molal
ΔTb = 0.512 x 0.262 = 0.134oC

▪ Calculate the boiling point of the solution:

Tb (solution) = normal boiling point + ΔTb
Tb (solution) = 100.00 + 0.134
= 100.134oC

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▪ Freezing point (Tf) of a pure solvent is lowered by the
addition of a solute which is insoluble in the solid solvent.
▪ Fewer molecules are available to freeze.
▪ Re-establishment of equilibrium achieved at a lower
temperature.
▪ Unlike boiling-point elevation, the solute is not restricted to
be nonvolatile. For example, methanol, a fairly volatile liquid
that boils at only 65°C, has sometimes been used as an
antifreeze in automobile radiators.

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 F.P-Temp when solid
began to appear in
▪ Normal Freezing Point: FP of Substance @ 1atm solution
▪ 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. 83
83
 ΔTf = Kf • m
Where
ΔTf = change in freezing point, (°C)
m = molality of solute, (mol/kg or m)
Kf = molal freezing point depression constant
for the solvent.

Freezing point of the solution = Tf solvent - ∆Tf

84
The figure shows that the freezing point of
the solution is lower than that of water.
85
Freezing-Point Depression
DTf = T 0f – Tf
T f0is the freezing point of
the pure solvent

T f is the freezing point of

the solution

T 0f > Tf DTf > 0

DTf = Kf m
m is the molality of the solution

Kf is the molal freezing-point

depression constant (0C/m)
for a given solvent
86
 Freezing Point Depression

Phase Diagram and the

lowering of the freezing point. DTf = Kf m

Where, DTf = FP depression

m = molality ,
kf = FP Constant

Generally freezing point depression is

used to determine the molar mass of an
unknown substance.
Derive an equation to find molar mass from
the equation above.

87