CHAPT ER 6

PHASE EQUILIBRIUM
 CONTENTS:

2 1 Definitions & Concepts

▹ Phases
▹ Components
▹ Gibbs Phase rule: Degree of Freedom
2 One-component system
▹ Phase diagram of water system
▹ Phase diagram CO2 system
3 Two-component system
▹ Ideal mixture vs Non-ideal Mixture
▹ Raoult’s Law
▹ Vapour Pressure Lowering: The effect of non-volatile solute on vapour pressure
of solvent, melting and boiling point
 CONTENTS:

3 ▹ Two completely miscible liquids- ideal, positive and negative deviation from
Raoult’s Law
▹ Vapour pressure-composition diagram versus boiling point-composition
diagram for ideal, negative and positive deviation of solutions
▹ Fractional distillation and azeotropic system
▹ Two completely miscible solids – eutectic system and cooling curves
4. Colligative properties
▹ Boiling point elevation
▹ Freezing point depression
 Lesson Outcomes:
4
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
 Phase (p)
5
 Definition1: 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.
 Gas or a gaseous mixture : single phase
 Miscible liquid : single phase
 ▹ Mixture of immiscible liquid : two-phase
6 ▹ 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 Phases
Solid phase - ice
Liquid phase - water
 ONE PHASE SYSTEM
7
▹ No boundary between substances.

▹ Example:
▹ g-g system: Oxygen and nitrogen
▹ l-l system: water and ethanol (miscible liquid)
▹ s-s system:gemstone
 TWO PHASE SYSTEM
8
▹ Two substances with a boundary separating them.
▹ Example:
▹ l-l system: water and oil
▹ l-g system: water and water vapour
▹ s-g system: ice and water vapour
▹ s-l system: ice and water
 THREE PHASE SYSTEM
9

▹ Three substances with

boundaries separating
each other.
Example:
▹ s-l-g system: ice-water-
water vapour system
 Components (c)
10
▹ 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
 Number of phase and component

System Phase Number of Number of

11 phase components

Air(O2, CO2, N2) 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 (miscible liq) Liquid 1 2
Water and CCl4 (immiscible liq) Liquid-liquid 2 2
Iodine crystal and iodine vapour Solid-gas 2 1
Rhombic sulfur and monoclinic sulfur Solid-solid 2 1
 Phase Changes
12
 The Phase Diagram
13 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.
 The Phase Diagram (in general)
14 ✓ area/ region = phase

✓line = set of temperature and

pressure which 2 phase on
either side of line exist in
equilibrium

✓Triple point, O = temperature

and pressure at which all 3
phases of a substance coexist
in equilibrium
 The Phase Diagram
15

▹ Equilibrium can exist not only between the liquid and vapour
phase of a substance but also between the solid and liquid phases,
and the solid and gas phases of a substance.
 Example 1
16
▹ The phase diagram for a substance A is shown. State the
physical state of A at the condition X, Y and Z

x ➢ At condition x: compound
P liquid A exist as solid and liquid
solid O y in equilibrium
z ➢ At condition y: liquid A and gas/
vapour vapour A exist in equilibrium
➢ At condition z: substances A
T
exist as a solid only
 Gibbs Phase Rule
17
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)
18
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!!
 The Phase Rule
19
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.
But Na+ and Cl– have the same amount “equal neutrality” as NaCl, then
c = 2 and not 4. Na+, Cl–, NaCl and H2O
 Example 2
20
▹ 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.
 The Phase Rule ( Water system)
21 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
 ▹ Along a phase line we have two
phases in equilibrium with each
22 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.
 ▹ At the triple point there
23 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.
 One-component phase equilibrium
24
▹ 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
 One-component System
25
▹ Single component system contains only one chemically
independent species.
▹ Examples:
 Water
Single component system (with
 Carbon dioxide
its 3 phases)
26 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
 Phase Diagram of H2O
27
▹ 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 liquid
 Phase Diagram of H2O
28 ▹ 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
 Example 3
29
Consider a sample of H2O at point A.
▹ What phase (s) is (are) present?
A is the triple point: ice, liquid and water vapor
are present.
▹ If the temperature of sample were reduced
at constant pressure, what would happen?
Sample will freezes completely
▹ How would you convert the sample to vapor
without changing the temperature?
Reduce the pressure to below the triple point
value.
 Phase Diagram of CO2
30 ▹ A (-56.4⁰C, 5.11 atm) : the triple point at
which the 3 phases exist in equilibrium
▹ B (31.1⁰C, 72.8 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
▹ AC – sublimation or deposition curve (the
variation of sublimation temperatures
with pressure)
▹ Along AC, solid CO2 is in equilibrium with
CO2 gas.
 Phase Diagram of CO2
31 ▹ 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
 Example3
32
▹ Refer to the phase diagram of carbon dioxide (CO2) below :

i) Identify the temperature and

pressure of points O and C (2 marks)

ii) Explain the variation of OD line

(solid-liquid boundary line) with
pressure. (3 marks)
33
ANSWER

▹ i)O : T = - 57 °C , P = 5.1 atm

B : T = 31 °C , P = 73 atm / 72.8 atm

▹ ii)OD slopes to the right (a positive slope)

Melting point increases with pressure
Solid CO2 is denser than liquid CO2
 Variation of Melting Point with Pressure
34
▹ An increase in pressure favours the formation of the more
dense phase

Variation of
m.p with Pressure

solid (more liquid (more

dense phase) dense phase)
 The solid is the more dense phase
35
▹ 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
When the solid is the more
▹ The behaviour is shown by
dense phase, an increase in
substance like CO2
pressure converts liquid to
solid and the melting point
increases.
 The liquid is the more dense phase
36
▹ 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
If the liquid is the more
▹ Water behave this way as ice dense phase, an increase in
is less dense than liquid pressure converts solid to liquid
water. and the melting point decreases
 Differences between H2O and CO2

37
Characteristic Water CO2
Effect of Melting point Melting point
pressure on decreasing increasing with
melting with pressure pressure
point increase increase
Density water Solid CO2
more denser more denser
than Ice than liquid
CO2
 Two-Component System
38
▹ 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
 Miscibility
39
▹ The ability of liquid mixture’s components to mix with each
other.
Miscible Partially Immiscible
miscible
liquids form a ▪ results in a •liquids cannot mix
homogeneous distinguishable together at all
mixture, mix meniscus between the •the volume is
completely to liquids the total volume
form a ▪ the volume is not of liquids added
single phase identical to the originally
original volume.
 Solution & Raoult’s Law
40
▹ 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
 Raoult’s Law
41
▹ 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 = X A .P o A
▹ PA = partial vapor pressure of component A in a solution
▹ Po A = vapor pressure of pure component A
▹ XA = mole fraction of component A (= n A/n total)
 Therefore :
42 Total pressure =Vapor pressure of the solution
P Total = PA + PB
= X A.P o A + X B.P o B

When Dalton’s Law

XB =O, P = XA.POA The total pressure of a
XA =O, P = XB.POB mixture of ideal gases is
the sum of the partial
pressures of the gases
Note : The total mole fraction in a system is always mixture
equal to 1 (XA + XB = 1)
 Ideal Solutions
43
▹ 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 ( ∆H soln = 0) and volume of
solution ( ∆V = 0)
 Cont…..
44
▹ 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
 Example 4
45 At 40 °C, the vapour pressure of heptane and octane are 92.0
mmHg and 31.0 mmHg, respectively. The mixture of heptane
and octane forms an ideal solution. A mixture of heptane-
octane containing 35% heptane is placed in a closed vessel.
▹ From the above situation, predict the more volatile
component.
▹ Calculate the total pressure of the vapour formed.
▹ Calculate the vapour composition of octane in equilibrium of
the solution.
 Answer
46
 Example 5
47 Mixture of ethanol and methanol forms an ideal solution. At
20˚C, vapour pressure of ethanol and methanol are 44.5
mmHg and 88.7 mmHg, respectively. A solution containing 5.0
mol of ethanol and 1.0 mol of methanol is allowed to vaporize
in a closed vessel until equilibrium is reached.
a) Determine the component that is more volatile.
b) Calculate the total vapour pressure in mmHg of the
solution
 Answer
48 a) Methanol

b) X ethanol = n ethanol / n total

= 5 mol / (5 mol + 3 mol)
= 0.625
Xmethanol = 1 – 0.625 = 0.375 mol
 Answer
49
 Vapour Pressure-Composition Curve
50 (Ideal Solution)
▹ Vapour is always
rich in the more
volatile component.
▹ Blue line is the total
pressure against
composition for the
mixture.
▹ Component B is
more volatile than A
 Vapour Pressure-Composition Curve
51 (Ideal Solution)
▹ Liquid is favorable at higher
pressure and vapour at lower
pressure.
▹ The composition of the vapor
which is in equilibrium with a
liquid mixture of composition C1
is given by C2.
▹ P actual= P calculated

The figure shows the equilibrium between liquid and

vapour of an ideal solution, eg. Mix of benzene & toluene
 Vapour Pressure-Composition Curve
(Toluene-benzene mixture)
52 ▹ When mole fraction of benzene
is at C1 in the solution, vapour
composition of benzene is
equivalent at point C2
▹ As liquid composition of
benzene increases, its vapour
composition increases even
further.
▹ An increase in benzene
composition, the composition of
toluene decrease.
 Boiling Point (b.p)– Composition Curve
53 ▹ B.p of benzene is lower than
toluene, as benzene is more
volatile than toluene.
▹ The diagram is upside-down
because the vapor phase is stable
at high temperature.
▹ Component that has higher vapor
pressure has lower b.p and vice
versa.
The figure shows the equilibrium
▹ The most volatile compound will between liquid and vapour of an ideal
solution (eg. Mix of benzene and
distillate first as it has lower b.p. toluene)
 Fractional Distillation
54 ▹ 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.
 Fractional Distillation
55

A liquid mixture is
placed in the round
bottom flask
connected to
fractionating
column that further
connected to
condenser which
allows the vapour to
cool and condense
 Fractional Distillation
56
Distillate

Residue
Pure liquid collected Liquid that has higher
as 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
▹ If 3 component: fractional distillation produces
1. First distillate
2. Second distillate
3. Residue
 Fractional Distillation
57 ▹ Liquid composition of C1 is
boiled, the vapor given off will
have composition of D1 (richer in
A).
▹ This vapor condensed to give the
liquid of composition C2.
▹ Liquid of C2 will in turn boils at
lower temperature and give out a
vapor having D2 composition
(richer in A).
▹ Pure A will ultimately obtained by
successively distilling the
fractions.
 Water - Alcohol System
58
▹ Vapour at point E will condensed
to point F at around 90oC.
▹ The liquid at composition F will
boiled again and produce vapor at
composition G, and then
repeating the distillation process
until pure ethanol obtained at it’s
Boiling point-composition
pure b.p (66oC) graph for water/alcohol
system (eg. Water &
ethanol)
 Non- Ideal Solution
▹ At low concentrations of solute, most solutions show
59
deviations from ideality.
▹ Non-ideal solution can deviate from ideal behavior in two
ways:
1. positive deviation from Raoult’s Law
2. 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
 Deviation from Ideality
60 ▹ Extreme deviations from ideality
▹ Result in maxima /minima in vapour-pressure diagrams and
temperature- composition diagrams

➢ 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
 Non- Ideal Solution
61
 Non- Ideal Solution
62 POSITIVE DEVIATION 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.
 Azeotropic System
63
▹ Liquid mixtures which deviate widely from ideality
cannot be separated completely by fractional
distillation.
▹ Azeotrope : a mixture with a constant boiling point
where the vapour is the same as the composition
of the liquid.
▹ Fractional distillation will yield one pure liquid
component and an azeotropic mixture.
 Azeotropic System
64
Positive deviation Negative deviation

the mixture with composition a1 is known as a the mixture with composition a2 is known as a
minimum boiling point azeotropic mixture. maximum boiling point azeotropic mixture
 Example6
65
A mixture containing two liquids U and V produces a boiling
point at 97˚C with the composition of 69 % V. the boiling
point for U and V are 85 ˚C and 70 ˚C.
a) Sketch the boiling point – composition diagram for the
system. Label all points and curve on the diagram.
b) With the aid of your sketch, identify the type of deviation
and the distillate when the mixture with 52 % of U is
distilled by fractional distillation.
 Answer
66

b) Negative deviation
Distillate = U
 Example7
67
Ethanol (boiling point = 78.5⁰C) and water (boiling
point = 100⁰C) form an azeotropic mixture with a composition
of 95% ethanol by mass and a boiling point of 78⁰C.
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
 Answer
68 a)
 Summary of negative & positive non ideal
solution
69
 Eutectic System (Two completely miscible solids)
70
▹ 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’.
 Eutectic System (Two completely miscible solids)
71
▹ 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.
 ➢ Eutectic phase diagram
72 describes behaviour 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.
 Example: (Zinc- Cadmium)
73 ▹ When pure liquid of zinc is cooled, it freezes at
419⁰C.
▹ An amount of Cd is added to zinc and heated to
turn to liquid.
▹ When, it is cooled, it become solid and freeze at
lower temperature than pure zinc.
▹ Adding more Cd causes freezing point to drop
further until finally at 270⁰C
➢ Pure Cd is freezes at 321⁰C
➢ 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 83% Cd.
 Example8
74 The melting point of X is 232 °C and Y is 327 °C. The eutectic
temperature is 183 °C and the composition of eutectic
mixture is 63 % X.
a) Define eutectic mixture.
b) Sketch a eutectic diagram for the mixture of X and Y. Label
all phases in the diagram.
c) A mixture containing 35% X is cooled from 350 °C the room
temperature. Predict the component that will be
crystallized from the mixture before reaching the eutectic
point.
 Answer
75 a) Eutectic mixture- it is liquid mixture that solidifies (freezes)
at a minimum temperature
b) o
Temperature( C)

327
Molten
Liquid
232
E Solid Y +
183
Molten
Solid X + Solid X + Solid Y
Molten
0% Composition of Y

E = Eutectic point 63% of X and 37% of Y

c) Y
 Example9
76 A mixture of antimony, Sb and lead, Pb forms a eutectic
mixture with the composition of 16.8 % Sb at 252oC. Melting
point of pure Sb and Pb are 630oC and 327oC, respectively.
a) Construct a eutectic diagram for the Sb – Pb mixture.
Label all phases and significant points.
b) Propose the metal that will freeze first when a mixture of
30 % Pb is cooled.
 Answer
77
a)
b) Antimony (Sb)
 Cooling Curves
78
▹ 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.
 Cooling curve: on eutectic mixture
79 ▹ 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.
▹ At point B:
i. One of the components begins to freeze from mixture
ii. 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.
 Colligative Properties
80
▹ Definition: Properties of solutions that depend only on the
number of dissolved solute particles in solution and not on
their identity.
▹ Effect of addition of solute to form a solution:
a) stabilizes the solvent in the liquid phase
b) lowers the solvent chemical potential
c) the solvent molecules have less tendency to move to the gas or
solid phase.
▹ Result:
a) Boiling point increases
b) Freezing point decreases OR vice versa
 Normal Boiling Process
81
▹ Normal Boiling Point: BP of Substance @ 1atm
▹ When solute is added, BP > Normal BP
▹ Boiling point is elevated when solute inhibits solvent from
escaping.
 Boiling Point Elevation
82
▹ 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. That is,
83

This figure shows that the boiling point of the solution is

higher than that of water.
 Boiling Point Elevation
84
▹ 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 vapour
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.
 Boiling Point Elevation
85

➢ 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
 Example10
86 For a 0.262 molal solution of sucrose in water, calculate the
boiling point of the solution.
▹ Calculate the boiling point elevation:
K b = 0.512 , m = 0.262 molal
ΔT b =K b m
ΔT b = 0.512 x 0.262 = 0.134oC
▹ Calculate the boiling point of the solution:
T b (solution) = normal boiling point + ΔT b
= 100.00 + 0.134 = 100.134oC
 Freezing Point Depression
87
▹ 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.
 Freezing Point Depression
88
▹ Normal Freezing Point: FP of Substance @ 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.
 Freezing Point Depression
89
 Freezing Point Depression
90

The figure shows that the freezing point of the solution is lower than that of water.
 Freezing Point Depression
91
 Example11
92 What mass of ethylene glycol (EG) (C2H6O2) must be
added to 37.8 g of water to give a Tf of 0.150°C?
ΔTf = Kf • mB