They provide us with the knowledge of phase

composition and phase stability as a function of

temperature (T), pressure (P) and composition (C).

PHASE
EQUILIBRIUM

one of the most important sources of information

concerning the behavior of elements, compounds
and solutions.
COMPONENTS PHASE

PHASE RULE: DEGREE

OF FREEDOM
 1) The mixture of ice and water = have two •A chemically and
phase which is solid and liquid structurally homogeneous
portion of material
2) The mixture of oxygen gas and nitrogen gas •Separated with other parts
= have one phase which is gas phase (the of the system
system is homogen)

3) The mixture of oil and water = have 2 same

phase(liquid). Oil and water are not
homogen and have the boundaries to
separate both phase

4) CaCO3(s) CaO(s) + CO2(g)

= 3 phase (2 solid,1 gas)

•Determines the number of

independent variables needed
•Is the correlation between the PHASE
number of phase (P), components
(C), and degree of freedom
OR
 PHASE RULES

F = C – P +2
Degree of
freedom or the
number of
independent The number
variables of phase
2 variables
Number of (temperature
component and pressure)
 DEGREE OF FREEDOM (F)

The number of variables that may UNIVARIANT

be changed independently without
causing the appearance of a new
phase or disappearance of an TYPES
existing phase BIVARIANT

EXAMPLES

CaCO3(s) CaO(s) + CO2(g) Calculate the degree of freedom (F)

F = C – P +2 Means: only one The number of components is not

=2–3+2 variable, either always easy to determine at first
= 1 (univariant) temperature or pressure glance, and it may require careful
can be changed examination of the pyhsical
independently conditions of the system at
equilibrium
Standard phase diagram for water (H2O)

ONE COMPONENT
SYSTEM

Standard phase diagram for carbon dioxide

(CO2)
 H2 O
Standard phase diagram for one component system CO2

B Critical
point ???

What does it
means by:
1)AO curve
2)OB curve
3)OC curve
4)AOB curve
5)BOC curve
O 6)AOC curve

?????
Standard phase diagram for water (H2O) TA curve = known as melting point or
freezing point
Special
case !!!!! Represent the equilibrium between ice
and liquid

Has a negative slope

Water as the liquid is denser than the solid

(ice floats on water).

That means that an increase of pressure

favors the formation of liquid and that the
melting point of water falls with increasing
pressure.

According to Le Chatelier’s principle,

when pressure is applied, the reaction This unique properties of water is due to
shifts in the direction that can release the the network of hydrogen bonding in ice is
stress and cause ice to melt more extensive than in liquid
 LEARNING CHECK !!!!!

(d)
50

(c)
(b)

(a)
 LEARNING CHECK !!!!!

50
(a) (b) (c) (d) (e)
 The point O is the triple point for
Standard phase diagram for carbon dioxide CO2 (at 5.1 atm, -57o C). So, CO2
(CO2) solid can’t changed to liquid
form at 1 atm.
Critical point

Has a positive slope

So, its shows that the increases

of pressure, will increased the
melting point for CO2 solid

sublimation
 Raoult’s law – in
Two completely explaining the effect
miscible liquid – ideal, of non-volatile solute
non-ideal, positive on vapour pressure of
and negative solvent and its melting
deviation and boiling point

TWO COMPONENT
SYSTEM

Composition diagram
Eutectic system and vs boiling point
cooling curves composition for ideal,
non-ideal, negative n
positive deviation

Fractional distillation
and azeotropic
system
VAPOUR PRESSURE
 Vapour pressure When a liquid evaporates in a
increases with closed vessel, its gaseous
increasing temperature molecules formed above the
due to its KE liquid have high KE and exert a
vapour pressure.

The molecules collide with the

pinston and push the pinston
upward

sublimation

Microscopic equilibrium between gas and Microscopic equilibrium between gas and solid.
liquid. Note that the rate of evaporation of the Note that the rate of evaporation of the solid is
liquid is equal to the rate of condensation of equal to the rate of condensation of the gas.
the gas.
Volatile liquid is a liquid that can easily
evaporate at one atmospheric pressure and
room temperature

Molecules of volatile liq escape the liquid

phase into gaseous phase.(KE)

A volatile liquid has a strong tendency to

vapourize or evaporate into vapour, creating
high vapour pressure.

On contrary a less volatile liquid has low

vapour pressure because of lower tendency
to vapourize
 1
Types of Molecules: the types of molecules ethyl ether (C4H10O)
that make up a solid or liquid determine its Pvapor (25oC) = 520 torr
vapor pressure. If the intermolecular forces
between molecules are: ethyl alcohol (C2H6O)
Pvapor (25oC) = 75 torr
•relatively strong, the vapor pressure will
be relatively low.
Low
•relatively weak, the vapor pressure will be
Temperature
relatively high.

2
Temperature: at a higher
temperature, more molecules have
enough energy to escape from the
liquid or solid. At a lower temperature, High
fewer molecules have sufficient energy Temperature
to escape from the liquid or solid.
COMPLETELY MISCIBLE
LIQUID

RAOULT’S LAW
 Methanol and ethanol 3 types :
Liquid 1)Complete Miscible liquid
ether and 2)Half miscible liquid
solution in
water 3)Immiscible liquid
liquid
Oil and
Ideal solution- mostly involve the
water
substance that have similar
physicochemical properties. Ex:
MeOH/EtOH, benzene/toluene, n-
hexane/n-heptane
Complete Miscible liquid

• 2 types of complete miscible liquid which is ideal and non-ideal solution

• An ideal solution is a solution that obeys Raoult’s law and non-ideal solution
disobey.
•A solution is a ideal solution when: A A = A B

•The intermolecular attractions between the mixture of same molecule with the
the mixture of different molecule are equal.
•The volume of the mixture are the total volume of both liquid (volume of liquid
A add with volume of liquid B)
•No heat changes (no endo-exothermic process)
•Obeys Raoult’s law
 •Relationship between vapour pressure of a solvent and its mole fraction

•States the vapour pressure of the solute containing solution (PA) is equal to the
mole fraction of the solvent (XA) times the vapour pressure of the pure solvent
(Po A)
PA = XA Po A PT = PA + P B
@
Psolution = Xsolvent Po solvent Ptotal = XA PoA + XB PoB

EXAMPLE !!!!!

A solution is prepared by adding 2.0 mole of glucose Psolution = Xsolvent Po solvent

in 15.0 mole of water at 25 oC. The vapour pressure The mole fraction:
of pure water at 25 oC is 23.76 mmHg. Calculate the XA = nA / nt
vapour pressure of the solution at 25 oC = 15.0 /17.0= 0.88
Therefore,
Psolution = 0.88 x 23.76 mmHg
= 20.96 mmHg
 EXAMPLE !!!!!

At 25 oC the vapour pressure of pure benzene and toluene are 93.4 mmHg and
26.9 mmHg. If the mixture contains 60.0g of benzene and 40.0 g of toluene,
calculate the vapour pressure of this solution

PT = PA + P B
Calculate the number of moles for benzene and toluene:
@
n of benzene : PA + P B = 60/78 = 0.77 mole
Ptotal = XA PoA + XB PoB
n of toluene : PA + P B = 40/92 = 0.43 mole
 IDEAL SOLUTION
DIAGRAMS (RAOULT’S
LAW)

VAPOUR PRESSURE/ BOILING POINT/

COMPOSITION COMPOSITION
DIAGRAM DIAGRAM
There is actually no such thing as an ideal mixture! However, some liquid mixtures
get fairly close to being ideal. These are mixtures of two very closely similar
substances. Commonly quoted examples include:

•hexane and heptane

Pure mixture vapour pressure
•benzene and methylbenzene
•propan-1-ol and propan-2-ol Notice that the vapour pressure of pure B is higher than that of
pure A. That means that molecules B must break away more
easily than of A. B is the more volatile liquid.
Pure vapour pressure

Total vapour pressure of the

mixture
We'll start with the boiling points of pure A and B.B has VP BP
the higher vapour pressure. That means that it will have
the lower boiling point.

The diagram just shows what happens if

you boil a particular mixture of A and B.
Notice that the vapour over the top of the
boiling liquid has a composition which is
much richer in B - the more volatile
component.
 EXAMPLE !!!!!

Which vapour
sample rich at
this point?

composition
NON-IDEAL DIAGRAMS
• NEGATIVE DEVIATION
•POSITIVE DEVIATION
•Involves the intermolecular forces between molecules in solution are stronger
than those in pure liquid

•Therefore, vapour pressure of the solution is lower than vapour pressure of its
components or pure liquid.

•Example : A A B B
=

WEAKER THAN

A B

•SO,the molecules in the solution have lower tendency to escape into vapour
phase.

•Therefore the process is EXOTHERMIC

 Nitric acid and water form mixtures
in which particles break away to
form the vapour with much more
Azeotrope difficulty than in either of the pure
liquids.

That means that mixtures of nitric acid

and water can have boiling points higher
than either of the pure liquids because it
needs extra heat to break the stronger
attractions in the mixture.

In the case of mixtures of nitric acid and

water, there is a maximum boiling point of
120.5°C when the mixture contains 68% by
mass of nitric acid. That compares with the
boiling point of pure nitric acid at 86°C, and
water at 100°C.

Notice the much bigger difference this time

due to the presence of the new ionic
interactions
 USING THE DIAGRAM As the acid loses water, it becomes more
concentrated. Its concentration gradually
Distilling dilute nitric acid increases until it gets to 68% by mass of nitric
Start with a dilute solution of nitric acid acid. At that point, the vapour produced has
with a composition of C1and trace exactly the same concentration as the liquid,
because the two curves meet.
through what happens.

You produce a constant boiling mixture (or

azeotropic mixture or azeotrope). If you distil
dilute nitric acid, that's what you will eventually
be left with in the distillation flask. You can't
produce pure nitric acid from the dilute acid by
distilling it.

The vapour produced is richer in water than the

original acid. If you condense the vapour and
reboil it, the new vapour is even richer in water.
Fractional distillation of dilute nitric acid will
enable you to collect pure water from the top of
the fractionating column.
Distilling nitric acid more concentrated than 68% by mass
This time you are starting with a concentration C2 to the right of
the azeotropic mixture.
The vapour formed is richer in nitric acid. If
you condense and reboil this, you will get a
still richer vapour. If you continue to do this
all the way up the fractionating column, you
can get pure nitric acid out of the top.

As far as the liquid in the distillation flask is

concerned, it is gradually losing nitric acid. Its
concentration drifts down towards the
azeotropic composition. Once it reaches that,
there can't be any further change, because it
then boils to give a vapour with the same
composition as the liquid.

Distilling a nitric acid / water mixture containing

more than 68% by mass of nitric acid gives you
pure nitric acid from the top of the fractionating
column and the azeotropic mixture left in the
distillation flask.
Formed when the intermolecular forces between molecules in the mixture are
weaker than those in pure liquids.

A A = B B

STRONGER THAN

A B

The solution has a greater

Vapour pressure of the solution is higher tendency to evaporate or
than expected escape into vapour

The process is endothermic

A large positive deviation from Raoult's
Law produces a vapour pressure curve
with a maximum value at some
composition other than pure A or B.

If a mixture has a high vapour pressure it

means that it will have a low boiling point

The molecules are escaping easily and you

won't have to heat the mixture much to
overcome the intermolecular attractions
completely.

The implication of this is that the boiling

point / composition curve will have a
minimum value lower than the boiling
points of either A or B.
 USING THE DIAGRAM

Suppose you are going to distil a mixture of

ethanol and water with composition C1 as
shown on the next diagram. It will boil at a
temperature given by the liquid curve and
produce a vapour with composition C2.

When that vapour condenses it will, of

course, still have the composition C2. If you
reboil that, it will produce a new vapour
with composition C3.
 This particular mixture of ethanol and water
AZEOTROPE boils as if it were a pure liquid. It has a
constant boiling point, and the vapour
composition is exactly the same as the
liquid.

It is known as a constant boiling

mixture or an azeotropic mixture or
an azeotrope.

SUMMARISE

Distilling a mixture of ethanol containing

less than 95.6% of ethanol by mass lets
you collect:

• A distillate containing 95.6% of ethanol in

the collecting flask (provided you are
careful with the temperature control, and
the fractionating column is long enough

• Pure water in the boiling flask.

FRACTIONAL
DISTILLATION
Typical fractional distillation in the lab the thermometer bulb is
placed exactly at the outlet
to give the maximum from the fractionating
possible surface area for column
vapour to condense on

Some fractionating columns

have spikes of glass sticking
out from the sides which
serve the same purpose

In some cases, where you are collecting

a liquid with a very low boiling point,
you may need to surround the collecting
flask with a beaker of cold water or ice.
 Relating what happens in the fractionating column to the
phase diagram

Boil a mixture with composition C1.

Which compound
that rich at this
point? What phase?

Which compound
that rich at this
point? What phase

The vapour over the top of the boiling liquid

will be richer in the more volatile
component, and will have the composition
C2.
Which compound
that rich at this Each time the vapour condenses to a liquid,
point? What phase? this liquid will start to trickle back down the
column where it will be reboiled by up-coming
hot vapour. Each time this happens the new
vapour will be richer in the more volatile
component.

The aim is to balance the temperature of the

column so that by the time vapour reaches the
top after huge numbers of condensing and
reboiling operations, it consists only of the
more volatile component - in this case, B.

The boiling points of the two liquids. The closer

they are together, the longer the column has
to be.
what is the point of the packing in the column?

•To make the boiling-condensing-reboiling process as effective as

possible, it has to happen over and over again.

•By having a lot of surface area inside the column, you aim to have the
maximum possible contact between the liquid trickling down and the
hot vapour rising.

•If you didn't have the packing, the liquid would all be on the sides of the
condenser, while most of the vapour would be going up the middle and
never come into contact with it.
 •BOILING POINT ELEVATION
•FREEZING POINT DEPRESSION
 BOILING POINT : is the temperature at which its vapour pressure equals the
external pressure

Boiling point of WHY??

pure solvent
∆Tb = Tb - T ob Boiling point
solvent is
higher than
Boiling boiling point of
Boiling point point of solution
elevation solution

Molal (m) = mol solute ∆Tb is proportional to molality

Kg solvent of solute in the solution, so…. ∆Tb = Kb m

Molar mass of solute = Kb (gram solute) The molal boiling point

(∆Tb ) (kg solvent) elevation constant with unit
o
C/m or oC kg/mol
EXAMPLES:

What is the boiling point elevation when 11.4 g of ammonia (NH 3) is dissolved in 200.
g of water? Kb for water is 0.52 °C/m.

1) Determine molality of 11.4 g of ammonia in 200. g of water:

11.4 g / 17.031 g/mol = 0.6693676 mol

0.6693676 mol / 0.200 kg = 3.3468 m

2) Determine bp elevation:

Δt = Kb m
Δt = (0.52 °C/m) (3.3468 m)
Δt = 1.74 °C
 EXAMPLES:

Calculating Molecular Mass (Formula Weight) of Solute

1.15g of an unknown, nonvolatile compound raises the boiling point of 75.0g

benzene (C6H6) by 0.275oC. 
Calculate the molecular mass (formula weight) of the unknown compound.

Calculate the molality of solute particles: 

m = ΔTb ÷ Kb 
ΔTb = 0.275oC 
Kb = 2.53oCm-1 (from table above) 
m = 0.275 ÷ 2.53 = 0.109m

Calculate the moles of solute present: 

molality = moles solute ÷ kg solvent 
n(solute) = m x kg solvent = 0.109 x 75.0 x 10-3 = 8.175 x 10-3 mol

Calculate the molecular mass (formula weight) of the solute: 

n(solute) = mass(solute) ÷ MM(solute) 
MM(solute) = mass(solute) ÷ n(solute) = 1.15 ÷ 8.175 x 10-3 = 141 g/mol
FREEZING POINT DEPRESSION : is the temperature at which solid begins to appear in
liquid or solution

Boiling point of
∆Tf = T of - Tf solution
T of > T f
Boiling point of
pure solution

Molal (m) = mol solute ∆Tf is proportional to molality of

Kg solvent solute in the solution, so…. ∆Tf = Kf m

Molar mass of solute = Kf (gram solute)

(∆Tf ) (kg solvent)
 •the boiling point of the solvent in a solution
is higher than that of the pure solvent;

•the freezing point (melting point) of the

solvent in a solution is lower than that of
the pure solvent.
Learning check !!!!!!

Automobile antifreeze is ethylene glycol, C2H6O2. It is a non-electrolyte. If a radiator

contains 40.0% antifreeze and 60.0% water, by mass, what is the freezing point of the
solution in the radiator? The normal freezing point for water is 0.0 °C and Kf is 1.86 °C
mol/kg.

Find the molality of the solution. The mass of the solvent is 0.0600 kg and the
formula weight of the solute is 62.066 g/mol.
                                          
 
 
 

Use the freezing point depression formula