Lecture 1 - Phase Equilibrium

TOPIC 8 : PHASE EQUIBLIBRIA
8.1 - Single Component System

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Triple Point & Critical Point
8.2 - Two Component System
8.3 - Colligative Properties
Objective :
At the end of this lesson students should be able to:
(a)
Define phase and component.
(b)
Define triple point and critical point.
Phase Diagram H2O

Phase Diagram C2O
(c)
(d)
Sketch and explain the phase diagram of H2O

and CO2.
Explain the anomalous behaviour of H2O.
Describe the changes in phase with respect to
i. temperature (at constant pressure)
ii. pressure (at constant temperature).

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Definition
Example
Relationship
Phase Diagram H2O
Phase Diagram C2O
Exercise
Definitions
PHASE :
The phases of a system are parts of it which are
separated by a distinct boundary, such as solid, liquid
and gas.
Homogenous part of a system which is chemically and
physically uniform.

A two-phase system is one containing either

- a gas and a solid
- a gas and a liquid
- a solid and a liquid
- a solid and a solid
- two immiscible liquids
A three-phase system is one containing either

- a solid, a liquid, and a gas
- two immiscible liquids and a gas

Definitions
COMPONENT :
A component is a chemically independent constituent of a system. The
number of components in a system is the minimum number of independent
species necessary to define the composition of all the phases present in the
system.
The number of components in a phase system is the minimum number of
chemical entities needed to define all the phase of the system

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Definition
Example
Relationship
Phase Diagram H2O
Phase Diagram C2O
Example :

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Definition
Example
Relationship
Relationship between System, Phase & Component

System
Description
Mixture
of gases
Depend
types of
gases
Gases are well mixed.

We cannot see
the boundary between
the gases.
Two liquids
Do not mix
(oil-water)
We can see the boundary

between the two liquid,
Two liquids
well mixed
(alcohol-water)
We cannot see
the boundary of
the solution.

Phase Diagram H2O
Phase Diagram C2O

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Phase Diagram H2O
Phase Diagram C2O
Definitions
PHASE DIAGRAM :
A graphical plot of pressure vs temperature that shows
the conditions at which a substance exists as a solid,
liquid or gas in a one component system.
Shows the conditions under which equilibrium exists
between the different states of matter.
A typical phase diagram has three regions : solid, liquid
and gas. Each of these region is separated by their
boundary lines (i) solid/gas (ii) solid liquid and (iii) liquid
gas.

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Phase Diagram H2O
Phase Diagram C2O
Definitions
CRITICAL POINT :
At this point and above, it is not possible to liquefy a
gas however great the pressure is. Indeed the term
vapour should only be used below the critical point, as
it implies that it is possible to form a liquid.
TRIPLE POINT :
Triple point is an unique point at which the three lines
representing the solid/liquid, liquid/vapour and
solid/vapour equilibriums. It represents the conditions at
which all the three phases can co-exist in a stable
manner and each is at equilibrium with the other two.

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Phase Diagram H2O
Phase Diagram C2O
Definitions
CRITICAL TEMPERATURE :
The highest temperature at which a gas can
be liquefied.
CRITICAL PRESSURE :
The pressure required to liquefy a gas at the
critical temperature.

Phase & Component

Phase Diagram H2O
Curve Description
Explanation
Anomalous Behavior
Phase Diagram of H2O

Pressure ( atm )
8.1 - SINGLE
COMPONENT SYSTEM
Critical Point
1 atm
Phase Diagram C2O
Triple Point
0o C
100oC
Temperature ( oC)

Phase Diagram H2O

Curve Description
1 atm
Phase & Component

Curves in Phase Diagram of H2O

Pressure ( atm )
8.1 - SINGLE
COMPONENT SYSTEM
C
Critical Point
Explanation
Anomalous Behavior
Phase Diagram C2O
Triple Point
0o C
100oC
Temperature ( oC)
T-C: Represents the variation of boiling temperature with pessure

T-B: Represents the variation of melting temperature with pessure
T-A: Represents the variation of sublimation temperature with
pessure

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Explanation
At low temperatures and atmospheric pressure, the
stable phase is the solid (ice).

Phase Diagram H2O
Curve Description
Explanation
Anomalous Behavior
Phase Diagram C2O
At 1 atm, the temperature at which ice and water are at

equilibrium, is called the melting point ( 0C , 273.15 K).
The line separates the solid and liquid phases. As this
line is not vertical, the transition from solid to liquid
takes place at different temperatures under different
pressures.
At temperatures between 0C and 100C under 1
atmospheric pressure, the stable phase is liquid water.
At 100C, the line representing the equilibrium between
liquid and gas is reached and the temperature at which
boiling takes place under atmospheric pressure is the
boiling point. The boiling point varies as the pressure
varies.

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Phase Diagram H2O
Curve Description
Explanation
Anomalous Behavior of H2O

The phase diagram for water is not typical, the melting
temperature line , T-B , slopes to the left i.e. the melting
temperature decreases with pressure.
This is connected with the fact that ice is less dense than
water, while most solids are denser than their liquids.
Anomalous Behavior
Phase Diagram C2O
The melting curve or fusion curve of ice / water is very

special. It has a negative slope due to the fact that:
when ice melts, the molar volume decreases. Ice
actually melt at lower temperature, higher pressure.

Phase & Component

Phase Diagram H2O
Phase Diagram C2O
Curve Description
Phase Diagram of CO2

Pressure ( atm )
8.1 - SINGLE
COMPONENT SYSTEM
Critical Point
Explanation
Triple Point
Temperature ( oC)

Phase & Component

Phase Diagram H2O
Phase Diagram C2O
Curve Description
Curves in Phase Diagram of CO2

B
Pressure ( atm )
8.1 - SINGLE
COMPONENT SYSTEM
C
Critical oint
Explanation
Triple Point
A
Temperature ( oC)
T-C: Represents the variation of boiling temperature with pressure

T-B: Represents the variation of melting temperature with pessure
T-A: Represents the variation of sublimation temperature with
pressure

8.1 - SINGLE
COMPONENT SYSTEM
Phase & Component
Explaination
The phase diagram of carbon dioxide is more typical,
showing a rightward sloping melting temperature line.

Phase Diagram H2O
Phase Diagram C2O
Curve Description
Explanation
Triple point for carbon dioxide is -57C ( 216.4 K ) and 5.2

atm ( 516 kPa ). The triple point is above atmospheric
pressure, so that at atmospheric pressure carbon dioxide
sublimes, so dry ice, which is solid carbon dioxide, changes
directly from solid to gas.
At this pressure, the liquid phase is not stable, the solid
simply sublimes. Thus solid carbon dioxide is called dry ice,
because it does not go through a liquid state in its phase
transition at room pressure.
The critical temperature for carbon dioxide is 31.1C, and
the critical pressure is 73 atm. Above the critical temperature,
the fluid is called super-critical fluid.

1. Determine the stable phase of Carbon Dioxide at

a) 0.75 atm and -60 oC
b) 5.50 atm and -70 oC
2. What is the physical state of water under each of the following
conditions?
a) -5 oC and 1 atm
b) 100 oC and 1.3 atm
c) 110 oC and 0.8 atm

8.2 - TWO
COMPONENT SYSTEM
Objective :
[1][2]
Miscibility
Ideal Solution
(a)
State the miscibility of a liquid mixture:

i. miscible
ii. partially miscible
iii. immiscible.
(b)
State the properties of an ideal solution.
(c)
Define and apply Raoults law.
(d)
Explain the positive and negative deviations

from Raoults law for non-ideal solutions.
(e)
Sketch and interpret the following curves for a

mixture of two miscible liquids:
i. vapour pressure-composition
ii. boiling point-composition
Raoults Law
Non-ideal Solution
Azeotrope
Distilation

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Objective :
[1][2]
(f)
Define azeotropic mixture.

Determine the composition of azeotropic mixture
from a boiling point-composition diagram.
(g)
Explain the principles involved in simple and

fractional distillations of a binary mixture.
(h)
Determine the distillate and residue of a

distillation from the boiling point-composition diagram.
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Miscibility
Miscible
MISCIBLE
Partially Miscible
Immiscible
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Two
liquids are considered "miscible" or

mixable if shaking them together results in a
single liquid phase , with no meniscus visible
between layers of liquids.
Miscible refers to the property of various
liquids that allows them to be mixed together.
Example : Methanol & Water

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Miscible
Miscibility
PARTIALLY MISCIBLE :
Partially Miscible
Immiscible
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
When one liquid partially dissolves in the

other, the result is two solutions appearing
as two layers. These two liquids are
considered to be partially miscible
Example : Hexanol & Water

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Miscible
Partially Miscible
Immiscible
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Miscibility
IMMISCIBLE
:
IM
Two liquids are considered "immiscible" or

unmixable if shaking equal volumes of the
liquids together results in a meniscus visible
between two layers of liquid, the volumes of
the liquid layers are the same as the volumes
of liquids orginally added to the mixture.
Distilation
Immiscible refers to the property of various

liquids that if they cannot be mixed together.
Example : Oil & Water

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Diagram
Raoults Law
Properties Of an ideal Solution

A solution containing a mixture of liquid A and liquid B
is ideal solution if ,
Non-ideal Solution
Azeotrope
Distilation
the three different intermolecular forces A-A, B-B

and A-B, are of the same type and comparable in
strength and expect the molecules to intermingle
randomly into a solution.
there is no energy change in the formation of the
solution , Hsolution = 0.
the volume of the solution is the sum of the
volumes of the two liquids A and B, Vsolution = 0
Obeys the Raoults law.
Pactual = P measured (calculated)
The measured vapour pressure of the solution is
the same as that predicted by the Raoults Law.

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Diagram
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Vapour pressure & boiling point diagram

of an ideal Solution

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Calculation
Definition
Raoult's law states that the vapor pressure of each
component in an ideal solution is dependent on the
vapor pressure of the individual component and the
mole fraction of the component present in the solution.
Example Question
Non-ideal Solution
Azeotrope
Distilation
Once the components have reached equilibrium in the

solution, the total vapor pressure of the solution is:

8.2 - TWO
COMPONENT SYSTEM
[1][2][3]
Calculation
Miscibility
Ideal Solution
The partial pressure of a solvent over a solution, PA, is given
Raoults Law
by the vapour pressure of the pure solvent, PoA times the mole
Calculation
fraction of the solvent in the solution, XA:
Example Question
Non-ideal Solution
PA = XA PoA
Azeotrope
Distilation
In a solution containing only one solute, XA = 1 XB, where

XB is the mole fraction of the solute. The above equation can
be rewritten as ;
PA = (1 XB) PoA
PA = PoA XB PoA
Po P
= P = X Po

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Calculation
[1][2][3]
Solutions that contain more than one volatile components
Ideal Solution
Raoults Law
Calculation
Example Question
In many solutions such as benzene and carbon

tetrachloride, both solute and solvent have appreciable
tendencies to undergo evaporation.
Non-ideal Solution
Azeotrope
Distilation
In this case, the vapour will contain both solute and

solvent molecules, and the vapour pressure of the
solution will be the sum of the partial pressures exerted
by each component.
The partial pressure of any component above such a
mixture is also given by Raoults Law.

8.2 - TWO
COMPONENT SYSTEM
Miscibility
[1][2][3]
Calculation
Solutions that contain more than one volatile components
Ideal Solution
Raoults Law
Thus, the partial pressure of component A , PA is given by :
Calculation
Example Question
PA =
XAPOA
where :
PA = the vapour pressure of pure A
XA = the mole fraction of A in the solution
Non-ideal Solution
Azeotrope
Distilation
Similarly , the partial pressure of component B , PB is :

PB =
XBPOB
where :
PB = the vapour pressure of pure B
XB = the mole fraction of B in the solution
Finally , the total vapour pressure of a mixture of A and B is given by

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Calculation
Example Question
Non-ideal Solution
Azeotrope
Distilation
Calculation
Calculating the Vapour Pressure of a Solution of
two volatile components
Example :
A mixture containing 50.0 g of carbon tetrachloride,

CCl4 and 50.0 g of chloroform, CHCl3 was prepared.
At 50oC, the vapour pressure of pure CCl4 is 317 torr
and that of pure CHCl3 is 526 torr.
What is the vapour pressure of the mixture at 50 oC?
Solution

8.2 - TWO
COMPONENT SYSTEM
Calculating the Vapour Pressure of a Solution of

two Volatile Components
Miscibility
Ideal Solution
Raoults Law
Calculation
Example Question
Non-ideal Solution
Solution :
By using Raoults Law,
No of moles :
component A, CCl4 = 0.325 mol CCl4

component B, CHCl3 = 0.419 mol CHCl3
Mole fractions :
X CCl
= 0.437
(0.325 + 0.419)
Azeotrope
Distilation
0.325
X CHCl =
0.419
= 0.563
(0.325 + 0.419)
Partial pressure of each component above the solution :
PCCl = X CCl P0CCl

= (0.437)(317 torr) = 139 torr
PCHCl = X CHCl P0CHCl = (0.563)(526 torr) = 296 torr
Total vapour pressure :

8.2 - TWO
COMPONENT SYSTEM
Non-Ideal solution
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Positive Deviation
Actually, very few mixtures really obey

Raoults law. Usually, the measured vapour
pressure of the solution is either larger or
smaller than Raoults law.
Negative Deviation
Azeotrope
Distilation
If the vapour pressure of the solution is larger

than Raoults Law, the solution will shows
positive deviation
If the vapour pressure of the solution
issmaller than Raoults Law, the solution will
shows negative deviation

8.2 - TWO
COMPONENT SYSTEM
Non-Ideal solution : Positive Deviation
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Positive Deviation
Negative Deviation
Azeotrope
Distilation
Composition-vapour pressure curve for a solutions that

shows positive deviations from Raoults law

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Positive Deviation
Negative Deviation
Azeotrope
Distilation
Composition-vapour boiling temperature diagram for a

solutions that shows positive deviations from Raoults
law

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Positive Deviation
Negative Deviation

When the attractive forces between the solute and
solvent molecules are weaker than those between solute
molecules or between solvent molecules, (A-A , B-B > A-B)
neither the solute nor solvent particles are held as tightly in
the solution as they are in the pure substances.
The escaping tendency of each is therefore greater in the
solution than in the solute or solvent alone.
Azeotrope
Distilation
As a result, the partial pressures of both of them over the

solution are greater than that predicted by Raoults law.
Therefore, the solution has a larger vapour pressure than
expected and exhibit a positive deviation from Raoults law.

8.2 - TWO
COMPONENT SYSTEM
Non-Ideal solution : Negative Deviation
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Positive Deviation
Negative Deviation
Azeotrope
Distilation
Composition-vapour pressure curve for a solution that

shows negative deviations from Raoults law

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Positive Deviation
Negative Deviation
Azeotrope
Distilation
Composition-vapour boiling temperature diagram for a

solution that show negative deviations from Raoults law

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Positive Deviation

The opposite effect is produced when the solute-solvent
attractions are larger than the solute-solute and solventsolvent attractions (A-B > A-A , B-B).
Each substance is held more tightly in the presence of each
other than in their pure liquids.
Negative Deviation
Azeotrope
Distilation
As a result, their partial pressures over the solution are less

than Raoults law would predict and their solutions show
negative deviations.

8.2 - TWO
COMPONENT SYSTEM
Summary of solution properties

Ideal Solution
Non-Ideal Solution
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Positive deviation
Negative deviation

8.2 - TWO
COMPONENT SYSTEM
Azeotrope :
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
An azeotrope is a mixture with the same the

composition of a vapour and liquid and has
constant boiling point and cannot be
separated by distillation.
A solution that shows positive deviations from
Raoults law, exhibits a minimum-boiling
azeotrope and maximum-vapour pressure
azeotrope.
A solution that shows negative deviations
from Raoults law, exhibits a maximum-boiling
azeotrope and minimum-vapour pressure
azeotrope.

8.2 - TWO
COMPONENT SYSTEM
Distillation
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
A technique used for the separation of

components of a solution by boiling the
solution and then condensing its vapour.
Azeotrope
Distilation
Simple distillation
Simple distillation
Fractional distillation
Distillation binary mixture
Azeotropic mixture

8.2 - TWO
COMPONENT SYSTEM
Simple Distillation
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Simple distillation
Azeotropic mixture
Simple distillation is a procedure by which two

liquids with different boiling points can be
separated .
Simple distillation is effective only when
separating a volatile liquid from a nonvolatile
substance or when separating two liquids that
differ in boiling point by 50 degrees or more.
Simple distillation is carried out without any
column packing, In theory, simple distillation
involves as few as one theoretical plate .

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Simple distillation
Azeotropic mixture
Simple Distillation Apparatus

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Fractional Distillation
Fractional distillation is a method to separate
mixtures of liquids with boiling points that are
close to each other by repeated simple
distillation process.
Azeotrope
Distilation
Simple distillation
In fractional distillation, the vapors formed

from the boiling mixture rise into the
fractionating column where they condense on
the column's packing.
Azeotropic mixture
As vapors continue to rise through the

column, the liquid that has condensed will
revaporize.

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Simple distillation
Azeotropic mixture
Fractional Distillation Apparatus

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Simple distillation
Azeotropic mixture
Fractional distillation of binary mixture (A & B)

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Simple distillation
Azeotropic mixture
Fractional distillation of binary mixture (A & B)

A fractionating column produces the effect of many
successive boiling and condensation cycles
automatically.
The column sizes have a large surface area. The
liquid mixture boils and the vapour rises up the
column.
As the temperature drops, the vapour condenses,
the liquid (richer in A) drops back into the boiling flask
and the vapour (richer in B) moves up the column.
This happens many times as the vapour rises up the
tube.
A long enough column will result in a vapour of pure
B at the top of the column and eventually pure A left
in the boiling flask.

8.2 - TWO
COMPONENT SYSTEM
Composition of azeotropic mixture
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
There are some solutions that exhibit very large

deviations from ideality.
Azeotrope
Distilation
Simple distillation
Solutions exhibit positive deviations

from Raoults law
Solutions exhibit negative deviations
from Raoults law
Azeotropic mixture
As a result, they cannot be totally separated into

their components even by fractional distillation.

8.2 - TWO
COMPONENT SYSTEM
Solutions exhibit positive deviations

from Raoults law
Miscibility
Ideal Solution
Raoults Law
These solutions have a maximum in the vapour pressure

curve and hence a minimum in the boiling point. Diagram
such a solution has minimum-boiling azeotrope.
Non-ideal Solution
100
Distilation
Simple distillation
Temperature
Azeotrope
78.5
Azeotropic mixture
Azeotropic Composition
Xwater : 0.056, Xethanol : 0.944
Coressponding to 99% ethanol
100% ethanol
100% water
The boiling point diagram for water-ethanol mixture

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Distilation
Fractional Distillation ethanolwater mixture

Ethanol-water mixtures (obtained by fermentation of
sugar for example), are rich in water.
Fractional distillation is able to concentrate the alcohol
to, at best, azeotropic composition of approximately
95% by volume of ethanol.
Simple distillation
Azeotropic mixture
Once this composition has been achieved, the liquid

and vapour have the same composition, and no
additional fractionation takes place.

8.2 - TWO
COMPONENT SYSTEM
Solutions exhibit negative deviations

from Raoults law
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
These solution have a minimum in the vapour pressure curve

and hence a maximum in the boiling point diagram. A solution
with such a maximum boiling point is called a maximumboiling point azeotrope.
Distilation
Simple distillation
Azeotropic mixture
Temperature
Azeotrope
100
100% water
Azeotropic Composition
(31.8% water and 68.2% HNO3)
78.5
100% HNO3
The boiling point diagram for nitric acid-water mixtures

8.2 - TWO
COMPONENT SYSTEM
Miscibility
Ideal Solution
Raoults Law
Non-ideal Solution
Azeotrope
Fractional distilation nitric acidwater mixture

Fractional distillation is able to concentrate the nitric
acid. From the diagram, this azeotropic mixture can be
separating them into, at best, one pure component plus
a solution having the maximum boiling point (azeotropic
composition).
Distilation
Simple distillation
Azeotropic mixture
Fractional distillation is able to concentrate the nitric

acid.

8.3 - COLLIGATIVE
PROPERTIES
Colligative properties
Objective :
(a)
Define colligative properties.
(b)
Describe the colligative properties of a solution:

i.
ii.
iii.
iv.
(c)
lowering of vapour pressure

boiling point elevation
freezing point depression
osmotic pressure
Perform calculations on colligative properties of

a non-electrolyte solution containing non-volatile
solutes.

8.3 - COLLIGATIVE
PROPERTIES
Vapour pressure lowering
Freezing point depression
Boiling point elevation
Properties of solutions which depend on the
number of molecules present and not on the
kind of molecules.
Osmotic pressure
Four colligative properties are :

1. Vapour pressure lowering
2. Freezing point depression
3. Boiling point elevation
4. Osmotic pressure

8.3 - COLLIGATIVE
PROPERTIES
The effect of a nonvolatile solute on the phase

diagram for water.
Osmotic pressure
When a solute is added to pure solvent, the mole fraction

decreases. Addition of a solute at constant T and P lowers the
solvent chemical potential.

8.3 - COLLIGATIVE
PROPERTIES
Osmotic pressure

The change in vapor pressure where the solute is
less volatile than the solvent is regulated by
Raoult's law, which states that the pressure is
equal to the mole fraction of the solvent times the
vapor pressure of pure solvent: P=Xsolvent*P.
The change in the vapor pressure occurs when a
solute is added to a solvent.
If a nonvolatile solute (one that has no tendency

to escape from a solution) is dissolved in a liquid
solvent, the vapour pressure of the solvent is
lowered.

8.3 - COLLIGATIVE
PROPERTIES
Osmotic pressure

When a solute is added to the solvent, some of the solute
molecules occupy the space near the surface of the liquid, as
shown. When a solute is dissolved in a solvent, the number of
solvent molecules near the surface decreases, and the vapor
pressure of the solvent decreases.
It decreases the rate at which the solvent molecules in the liquid

can escape into the gas phase. As a result, the vapor pressure
of the solvent escaping from a solution should be smaller than
the vapor pressure of the pure solvent.
o
P<P

8.3 - COLLIGATIVE
PROPERTIES
Calculation vapour pressure lowering
Psolution = X solvent Psolvent

XA + XB = 1
Osmotic pressure
PA = (1 - X B )PA
- X P
PA = PA
B A
- P = X P
PA
B A
A
PA X B P

8.3 - COLLIGATIVE
PROPERTIES
Osmotic pressure
The vapour pressure of pure water at 26oC is

25.21 torr. What is the vapour pressure of a
solution which contains 20.0 g glucose,
C6H12O6 in 70 g water?
Solution
20.0 g
180.0 g mol
glucose 0.111 mol glucose
70.0 g
18.0 g mol
H 2 O 3.89 mol H 2 O

8.3 - COLLIGATIVE
PROPERTIES
Xwater :
3.89
0.111 3.89
0.972
Osmotic pressure
P = P X H 2O
= (25.21 torr) (0.972)
= 24.5 torr

8.3 - COLLIGATIVE
PROPERTIES
At the freezing point, solid and liquid are at equilibrium.

The temperature where the equilibrium occurs at a
pressure of 1.0 atm is called the normal freezing point.
Since at the freezing point, the solid and liquid have the
same vapour pressure and since the vapour pressure
is lower in the solution than in the pure liquid, it
requires a lower temperature to achieve equilibrium.

Osmotic pressure

8.3 - COLLIGATIVE
PROPERTIES
Calculation freezing point depression

The amount that the freezing point is lowered (the
freezing point depression) is shown on the diagram as
Tf.
Osmotic pressure
For dilute solutions, the decrease in freezing point

depends on the molality of the solute in the solution.
Tf = kf m
Where ;
Tf
= (freezing point of pure solvent) (freezing

point of solution)
Kf
= molal freezing point depression constant

8.3 - COLLIGATIVE
PROPERTIES
Osmotic pressure
Calculation freezing point depresion

How much glycol (1,2-ethanediol), C2H6O2 must be
added to 1.00 L of water so the solution does not freeze
above -20C?
kf (H2O) = 1.86C kg mol-1
Solution
Tf = kf m
since 1.0 L has a mass of 1.0 kg ,10.8 mol of ethylene

glycol
10.8 mol 62.1 g/mol = 670 g ethylene glycol.

8.3 - COLLIGATIVE
PROPERTIES
Because of the lowere vapor pressure, the boiling point

of a solution is elevated as compared to the pure
solvent.
This point is well illustrated in the Phase diagram for

water.
The change in boiling point (T) can be calculated in

the same way as the change in freezing point, except a
different constant is used.
Boiling point elevation measurements can be use

determine the molar mass of an unknown solute.

Osmotic pressure

8.3 - COLLIGATIVE
PROPERTIES
Calculation boiling point elevation

For dilute solutions, the increase in boiling point
depends on the molality of the solute in the solution.
Tb = kb m

Osmotic pressure
Where ;
Tb = boiling point of solvent boiling point of pure water
Kb = molal boiling point elevation constant
m = molality of solute = # moles solute / 1000 g solvent

8.3 - COLLIGATIVE
PROPERTIES
Calculation boiling point elevation

A sample of 1.20 g of a non-volatile organic compound is
dissolved in 60.0 g benzene. The BP of solution is 80.96C. BP
of pure benzene is 80.08C. What is the molar mass of the
solute ?

Osmotic pressure
Solution
T = 80.96 - 80.08 = 0.88C

8.3 - COLLIGATIVE
PROPERTIES
Osmotic pressure
Osmotic pressure
Osmosis is a process whereby a solvent passes
from a dilute into a more concentrated solution
through a semipermeable membrane, which
allows the passage of solvent molecules but
blocks the passage of solute molecules.
The presence of solute can cause pressure to be
exerted across a semipermeable membrane
according to an equation quite similar to the ideal
gas law.
The osmotic pressure () is the pressure that
must be applied to the solution to stop the influx of
solvent.

8.3 - COLLIGATIVE
PROPERTIES
Osmotic pressure
Formula calculation osmotic pressure
For solutions that are dilute, it can be shown that the

osmotic pressure is proportional to the molarity (M) of
the solute, and that the proportionality constant is RT,
where R is the gas constant and T is the absolute
temperature.
V = nRT
= MRT
where : = osmotic pressure
M = molarity
R = gas constant
T = absolute temperature
n = moles of solute
V = the volume of the solution

8.3 - COLLIGATIVE
PROPERTIES
Osmotic pressure
Example calculation osmotic pressure

What is the osmotic pressure at 0oC of an
aqueous solution containing 46.0 of glycerin
(C3H8O3) per liter?
Solution
46.0 g
92.0 g mol
glycerin 0.50 mol glycerin
= nRT
V
-1
(
0
.
50
mol)
(0.0821
L
atm
mol
K) (273 K)
=
1.00 L
= 11.21 atm

Exercise
Answer :
Exercise :
1. Describe the following systems according to the
number of component, the number of phase and the
type of phase. The symbols are: S solid, L liquid,
G - gas

Exercise
Answer :
2.
Analyse the phase diagram for carbon dioxide

and answer in what phase CO2 should exist at:
a) 60C and 6 atm
b) -60C and 2 atm
c) -45C and 10 atm
d) -57C and 5.2 atm

Exercise
Answer :
3.
A solution composed of 8.3 g of a non-volatile

substance dissolved in 1 mol of chloroform, CHCl3,
has a vapour pressure of 511 mmHg. The vapour
pressure of pure chloroform at this temperature is
526 mmHg.
Calculate:
a) the mole fraction of the solute,
b) the number of moles of the solute,
c) the molar mass of the solute.

Exercise
Answer :
Answer :
1. .

Exercise
Answer :
3.

Lecture 1 - Phase Equilibrium

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Lecture 1 - Phase Equilibrium

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TOPIC 8 : PHASE EQUIBLIBRIA

8.1 - Single Component System

8.2 - Two Component System

8.3 - Colligative Properties

Define phase and component.

Define triple point and critical point.

Phase Diagram H2O

Sketch and explain the phase diagram of H2O

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

A two-phase system is one containing either

A three-phase system is one containing either

8.3 - Colligative Properties

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

Relationship between System, Phase & Component

Gases are well mixed.

We can see the boundary

Triple Point & Critical Point

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

TOPIC 8 : PHASE EQUIBLIBRIA

Phase & Component

8.3 - Colligative Properties

Phase Diagram of H2O

8.2 - Two Component System

Phase Diagram C2O

TOPIC 8 : PHASE EQUIBLIBRIA

Phase Diagram H2O

Phase & Component

8.3 - Colligative Properties

Curves in Phase Diagram of H2O

8.2 - Two Component System

T-C: Represents the variation of boiling temperature with pessure

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

Triple Point & Critical Point

At 1 atm, the temperature at which ice and water are at

TOPIC 8 : PHASE EQUIBLIBRIA

8.2 - Two Component System

8.3 - Colligative Properties

Anomalous Behavior of H2O

The melting curve or fusion curve of ice / water is very

TOPIC 8 : PHASE EQUIBLIBRIA

Phase & Component

8.3 - Colligative Properties