Lecture Two - Phase Equilibrium II

Two-Component Systems
Phase diagrams of binary mixtures
Phase rule: F = C - P + 2
for binary mixtures , C = 2

T, P, and composition(concentration) can vary

For example , if vapor pressure is constant

Condensed phase rule ; P + F = 3

Three possibilities (as before):

• P = 1 … F = 2 (bivariant phase field)

• P = 2 … F = 1 (univariant phase curve)

• P = 3 … F = 0 (invariant phase point)

Such a solid/liquid system with the gas phase absent is called a condensed system.
The experimental measurements of temperature and concentration in condensed
systems are usually carried out under constant atmospheric pressure.

The phase rule takes the form ; F' = C – P + 1 (The Reduced Phase rule) , where F'
gives the remaining degrees of freedom of the system. The reduced phase rule is
more convenient to apply to solid/liquid two-component condensed system. Since
the only variables for two-component solid/liquid systems are temperature and
composition, the phase diagrams for such systems consist of Temperature-
Concentration graphs (TC graphs).

1
 Two-Component Systems (Binary Systems)
 Mixture of Two Miscible Liquids
 Ideal Solutions and Raoult’s Law
 Deviation from Raoult’s Law, Non-ideal Solutions

Liquid in liquid: 3 types :

1) Complete Miscible liquid, (water and ethanol)
2) Partially miscible liquid , (ether and water)
3) Immiscible liquid, (CCl4 and water)

2
 Two-Component Systems – Mixture of Two Miscible Liquids

Two types of complete miscible liquid (mixtures of two volatile liquids in a

closed system) 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 ideal when:

 Ideal solution will be formed when the components have similar molecular
interaction before and after mixing.

 No heat changes (no endo-exothermic process)

 Obeys Raoult’s law
Examples: (MeOH/EtOH) , or ( benzene/toluene),
or ( n-hexane/n-heptane),or propan-1-ol and propan-2-ol

RAOULT'S LAW AND IDEAL MIXTURES OF LIQUIDS

Raoult’s law: states that the partial vapour pressure of a component in a mixture is equal
to the vapour pressure of the pure component at that temperature multiplied by its mole
fraction in the mixture.

Raoult's Law only works for ideal mixtures.

A mixture of liquids A and B,

Partial pressure of A: PA = χAP°A

Partial pressure of B: PB = χBP°B

The Po values are the vapour pressures of A and B if they were on their own as pure liquids.
3
xA and xB are the mole fractions of A and B

You calculate mole fraction using, for example:

In a binary solution : 𝑋𝐴 + 𝑋𝐵 = 1

(Dalton,s Law of Partial Pressures), The total vapour pressure of the mixture, PT

PT = PA + PB
PT = X A PA° + X B PB°

PT = X A PA° + (1 − X A )PB° Rearrangement

PT = PB° + X A (PA° − PB° )

The total vapor pressure over the solution is thus a linear function of xA with
intercept equal to PB° and slope equal to (PA° − PB° ) .

The slope can be positive or negative depending upon the relative magnitudes of
(PA° and PB° )

Composition of the vapour, 𝐘𝐀 𝐚𝐧𝐝 𝐘𝐁

The compositions of the liquid and vapour that are in mutual equilibrium are not necessarily
the same. The vapour should be richer in the more volatile component. Composition of the
vapor phase is obtained using the Dalton’s law of partial pressure. If 𝑌𝐴 𝑎𝑛𝑑 𝑌𝐵 are the mole
fractions of the liquids A and B in the vapor phase, then,From Dalton’s law, the mole fractions
in vapor phase are: 𝑌𝐴 𝑎𝑛𝑑 𝑌𝐵

𝑃 𝑃
𝑌𝐴 = 𝑃𝐴 and 𝑌𝐵 = 𝑃𝐵
𝑇 𝑇

𝑌𝐴 + 𝑌𝐵 = 𝟏

4
Example-1
The vapour pressure of pure liquid A at 300 K is 1150Torr and that of

pure liquid B is 780 Torr. These two compounds form ideal liquid and gaseous mixtures.
Consider the equilibrium composition of a mixture in which the mole fraction of B in the vapour

is 𝑌𝐵 =0.650.

a- Calculate the total pressure of the vapour and

b- What is the composition of the liquid mixture.
Answer;

a- Calculate the total pressure of the vapour

PT = PA + PB
PT = XA PA° + XB PB° Raoult′ s Law

? ? ?

the composition of the liquid mixture (X A and X B ???

PA° = 1150 Torr ; PB° = 780𝑇𝑜𝑟𝑟

𝑌𝐵 = 0.65 & 𝑌𝐴 + 𝑌𝐵 = 1 and 𝑌𝐴 = 0.35

𝑃𝐴 𝑃
𝑌𝐴 =
𝑃𝑇
: 𝑃𝑇 = 𝑌 𝐴 ----1
𝐴

𝑃𝐵 𝑃
𝑌𝐵 =
𝑃𝑇
: 𝑃𝑇 = 𝑌 𝐵 -----2
𝐵

𝑃𝐴 𝑃𝐵 𝑌𝐴 𝑃𝐴
= -------3 or =
𝑌𝐴 𝑌𝐵 𝑌𝐵 𝑃𝐵

𝑌𝐴 XA P°A
= ----4
𝑌𝐵 XB P°B

1−0.65 1150 𝑇𝑜𝑟𝑟 XA

= (1−XA )780Torr
0.65

5
XA = 0.267 and XB = 1 − 0.2675 = 0.733

PT = XA PA° + XB PB°

= 0.267 × 1150 𝑇𝑜𝑟𝑟 + 0.733 × 780 𝑇𝑜𝑟𝑟 = 878 𝑇𝑜𝑟𝑟

-------------------------------------------------------

Example-2 : The vapour pressure at 88°C of pure benzene is 957 Torr and that of
pure Toluene is 379.5 Torr .

a- What is the total pressure of above a liquid mixture?

( 𝑋𝑏𝑒𝑛𝑧𝑒𝑛𝑒 = 𝟎. 𝟔𝟓𝟗)

b- What is the composition of the vapour?

Answer; a- total pressure of above a liquid mixture?

PT = X A PA° + X B PB°
= 0.659 × 957 𝑇𝑜𝑟𝑟 + 0.341 × 379.5 𝑇𝑜𝑟𝑟 = 760 𝑇𝑜𝑟𝑟

b-What is the composition of the vapour?

𝑃𝐴 XA P°A 957𝑇𝑜𝑟𝑟 𝑥0.659
𝑌𝐴 = 𝑃 = = = 0.829
𝑇 𝑃𝑇 760 𝑇𝑜𝑟𝑟

𝑌𝐴 + 𝑌𝐵 = 𝟏 YB = 1 − 0.829 = 0.171

Problem

At 25 ℃ 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. Answer ; 𝑷𝑻 = 69.54 mmHg

6
 Phase diagrams of binary s ystems

1-Vapour pressure/composition diagram(ideal solution)

Ideal Solution or mixture.

 attraction between pure A–A or B–B (𝐛𝐞𝐟𝐨𝐫𝐞 𝐦𝐢𝐱𝐢𝐧𝐠) = attraction

between A–B (after mixing)
 The tendency of the molecules of A and B in the mixture to change from
liquid phase to the vapour phase is almost equal to that in pure A and
pure B
 Obeys Raoult’s law,

PT = X A PA° + X B PB° Raoult′ s Law

 No enthalpy change(∆𝐻 𝑚𝑖𝑥𝑖𝑛𝑔 = 0)and No volume change after
mixing
Example: MeOH/EtOH, or benzene/toluene, or n-hexane/n-heptane

7
fig.-1: Vapour pressure/composition diagram(ideal solution)
Notice that the vapor pressure of pure A is higher than that of pure B. That means that
molecules must break away more easily from the surface of A than of B. A is the more
volatile liquid. To get the total vapor pressure of the mixture, you need to add the values for A and
B together at each composition. The net effect of that is to give you a straight line as shown in
the diagram.

Deviation from Raoult’s Law – Non-ideal solutions

1-Positive Deviation from Raoult’s Law
The vapour pressure of the mixture is greater than that predicted by the Raoult’s
Law.

PT > PA + PB
PT > X A PA° + X B PB°

Examples : mixture of
a- CCl4 and CH3OH
b- CS2 and CH3COCH3
c- Cyclohexane and ethanol

8
Example; mixture of cyclohexane and ethanol
Before mixing

cyclohexane –A and ethanol-B

Vander Waals force between (A-A, molecule) hydrogen bond between (B-B, molecule)

 After mixing ; The introduction of cyclohexane inhibits the formation of

some of the hydrogen bonds. the molecules in the mixture has a greater tendency
to escape into vapour phase.
This leads to +ve deviation (a vapour pressure greater than that predicted by
Raoult’s Law). PT > PA + PB
PT > X A PA° + X B PB°

 The average intermolecular attraction between a molecule of A and a

molecule of B (after mixing) is weaker than the average of that between two
A molecules in pure A and that between two B molecules in pure B(before
mixing).

 The process is endothermic

9
 =========================================
2-Negative Deviation from Raoult’s Law
The vapour pressure of the mixture is lower than that predicted by the Raoult’s
Law.

PT < PA + PB
PT < XA PA° + XB PB°

 The average intermolecular attraction between a molecule of A and a molecule of B in

mixture(after mixing) are stronger than the average of that between two A molecules in
pure A and that between two B molecules in pure B (before mixing).

 Interaction between A–B (after mixing) > interaction between A–A or B–

B (𝒃𝒆𝒇𝒐𝒓𝒆 𝒎𝒊𝒙𝒊𝒏𝒈 )
 Therefore, vapour pressure of the mixture is lower than vapour pressure of its
components or pure liquid, so, the molecules in the mixture have lower tendency to escape
into vapour phase. This leads to -ve deviation.

 Therefore the process is EXOTHERMIC

10
 Example:
1- mixture of Nitric acid and water or

2- mixture of Propanone and Trichloromethane

Propanone Trichloromethane

[ dipole-dipole,between A–A dipole-dipole, between B-B ] before mixing

After mixing

Hydrogen bond can be formed in a mixture of trichloromethane and propanone.

This leads to -ve deviation (a v.p. lower than that predicted by the Raoult’s Law).

11
Table-1: Ideal and non-ideal solutions

Ideal solutions Non-ideal solutions

Positive deviation from Negative deviation
Raoult's law from Raoult's law
1. Obey Raoult's law at 1. Do not obey 1. Do not obey
every range of Raoult's law. Raoult's law.
concentration.
2. neither heat 2. 2. Exothermic
is evolved Endothermic dissolution; heat is
nor absorbed dissolution; heat is evolved.
during dissolution. absorbed.
3.

i.e.,

4. 4. attractive force 4. attractive force

interactions should be should be weaker should be greater
same, i.e., 'A' and 'B' than and attr than and attr
are identical in shape, active forces. 'A' and 'B' active forces. 'A' and 'B'
size and character. have different shape, have different shape,
size and character. size and character.
5. Escaping tendency 5. 'A' and 'B' escape 5. Escaping tendency
of 'A' and 'B' should be easily showing higher of both components 'A'
same in pure liquids and vapour pressure than and 'B' is lowered
in the solution. the expected value. showing lower vapour
pressure than expected
ideally.

12
Graphical representation of ideal and non-ideal solutions

2-Temperature Composition Diagrams

The temperature–composition diagram corresponding to an ideal mixture with the
component A more volatile than component B. Successive boiling and
condensations of a liquid originally of composition a1 lead to a condensate that is
pure A. The separation technique is called fractional distillation

To discuss fractional distillation we need a temperature-composition diagram .Such a

diagram shows composition at different temperatures at a constant pressure (typically 1 atm).

As in figure-1 :Temperature composition diagram

The region between the lines is a two-phase region with F' = 1. The

regions outside the phase lines correspond to a single phase and F' = 2

(the temperature and composition are both independently variable).

13
THEORY OF FRACTIONAL DISTILLATION

• Consider what happens when a liquid of composition a1 in Fig. -1 is

heated. It boils when the temperature reaches T2. Then the liquid has
composition a2 (the same as a1) and the vapour (which is present only as
a trace) has composition a′2. The vapour is richer in the more volatile
component A (the component with the lower boiling point).

• The vapor formed is condensed to yield a distillate of composition a3. If this

distillate is again heated to boiling, the phase diagram shows that this
mixture boils at T3 and yields a vapour of composition a′3 , which is even
richer in the more volatile component A. By repeating several times this
process of collecting the vapor, condensing it to get a new distillate and
heating the new distillate to its boiling point, finally vapor containing only
pure A is obtained. The residual liquid obtained at any stage is richer in B
and after several repetitions, a residual liquid containing only pure B is
obtained. Thus, we see that by the process of fractional distillation, it is
possible to separate the two constituents of an ideal binary liquid mixture.

Pure A is obtained in
the final distillate

Pure B is obtained in
the final residue

A is the more volatile

A

14
The efficiency of a fractionating column is expressed in terms of the number of
effective vaporization and condensation steps that are required to achieve a
condensate of given composition from a given distillate (three cycles, in fig.-1) .

In a simple distillation, the vapor is withdrawn and condensed. In fractional

distillation, the boiling and condensation cycle is repeated successively .

The laboratory set-up of fractional distillation

An ideal solution can be separated completely by fractional distillation.

In fractional distillation, the boiling and condensation cycle is repeated

successively. This technique is used to separate volatile liquids.

The boiling points of the two liquids. The closer they are
together, the longer the column has to be.

15
Glass beads to give the
maximum possible surface
area for vapour to condense

Simple Distillation

Simple distillation is a procedure by which two liquids with different boiling

points can be separated and can be used effectively to separate liquids that
have at least fifty degrees difference in their boiling points.

Fractional Distillation of Crude oil, A fractionating tower

Fractional distillation is used in oil refineries to separate crude oil into
hydrocarbons, which have different carbon numbers, boiling points and
applications. Some of the isolated products include gasoline, diesel, oils and
waxes. This method is also used in chemical plants, natural gas processing and
cryogenic air separation plants.

16
Fractional Distillation columns in a petroleum refinery

17
Fractional Distillation of Non-ideal Mixtures
(Azeotropes)

What is an Azeotropes mixture?

• They are binary mixtures having the same composition in liquid and
vapour phase and boil at a constant temperature.

• In such a case it is not possible to separate the components by fractional

distillation. There are two types of azeotropes: minimum boiling
azeotrope and maximum boiling azeotrope

It means liquid mixtures which distil without any change in composition are
called Azeotropes or Azeotropic mixtures.

1- High-boiling azeotrope, or maximum boiling azeotropes

A maximum in the phase diagram may occur when the favorable interactions
between A and B molecules reduce the vapor pressure of the mixture below
the ideal value – the A-B interactions stabilize the liquid – GE is negative.

Solution showing negative deviation from Raoult’s law form maximum boiling
azeotropes

Interaction between A – B > interaction between A – A or B – B

 The intermolecular forces between molecules in mixture (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.
 SO,the molecules in the solution have lower tendency to escape into
vapour phase.
 Therefore the process is EXOTHERMIC

18
Examples: trichloromethane-propanone, nitric acid-water mixtures.

Example : nitric acid/water

One example of azeotrope formation is nitric acid/water, 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, it needs extra heat to break the
stronger attractions in the mixture.

When the azeotropic composition has been reached, distillation cannot separate the
two liquids because the condensate has the same composition as the azeotropic
liquid. It has a constant boiling point, and the vapor composition is exactly the
same as the liquid. It is known as a constant boiling mixture or an azeotropic
mixture or an azeotrope.

19
2-Low-boiling azeotrope ( minimum boiling azeotrope)
 A minimum in the phase diagram may occur when the unfavorable
interactions between A and B molecules. For such mixtures GE is positive
(less favorable mixing than ideal)
 when the intermolecular forces between molecules in the mixture are weaker
than those in pure liquids, Vapour pressure of the solution is higher than
expected, The solution has a greater tendency to evaporate or escape into
vapour

Examples: dioxane-water and ethanol-water mixtures.

Solution shows positive deviation from Raoult’s form minimum boiling azeotrope

The ethanol-water system exhibits a minimum in its boiling point – composition

diagram and hence forms an azeotrope. The normal boiling points of the pure
components are : ethanol 78.5℃ and water 100℃. The azeotrope boils at 78.2℃
and has 96.5% by mass of ethanol. In general, a positive azeotrope boils at a lower
temperature than any other ratio of its constituents.

20
Two component systems (partially miscible liquids)
( A temperature-composition diagrams for system that consists of
pairs of partially miscible liquids)
 Critical solution temperatures

1-Upper Critical Temperature

 The upper critical solution temperature , Tuc, is the highest

temperature at which phase separation occurs.

Examples :

1- Phenol and water

 These liquids are partially miscible in each other.
 At certain ratios the liquids are completely miscible and at others they are
immiscible.
 As the diagram indicates, at low and high percentages of phenol, (Water and
phenol mix completely, forming a single liquid phase).
 However, at intermediate compositions and below the Critical Solution
temperature (CST), mixtures of phenol and water separate into two liquid
phases.
 Point "h" in the figure is the Critical Solution Temperature (CST=66.8⁰C),
 The maximum temperature at which the two-phase region exists is
termed the critical solution temperature (CST). In this case, the solubility
curve exhibits a maximum at the “critical solution temperature” is called
upper critical temperature.

21
  It is found that above Critical Solution Temperature (CST=66.8⁰C), the 2
liquids will become miscible in all proportions, the liquid mixture is
homogeneous, and one-phase liquid system is formed.
 At any temperature below the critical solution temperature, the composition
for the 2 layers of liquids in equilibrium state is constant and does not
depend on the relative amount of these 2 phases.
 For the phenol-water system, the CST is 66.8°C and the composition at the
CST is 66% by mass of water.
 Some other liquid pairs behaving like phenol-water system are given below
with their CST values and the percentage of the first component being given
in bracket.

(a) Methanol-Cyclohexane (49°C ; 29)

(b) Hexane-Aniline (59.6°C ; 52)
(c) Carbon disulphide-Methanol (49.5°C, 80)

Temperature-composition diagram for the system consisting of water and

phenol (pressure is constant)

binodal curve :- is the curve that separates two phase area from one
phase area

22
2- nitrobenzene and hexane mixture

As the diagram at right indicates, at low and high percentages of nitrobenzene,

hexane and nitrobenzene mix completely, forming a single liquid phase.
however, at intermediate compositions (and below the critical temperature)
mixtures of nitrobenzene and hexane separate into two liquid phases. Point
(Tuc) in the figure is the critical point. Above the critical temperature,
nitrobenzene and hexane are miscible in all proportions where all the
interactions between unlike and like molecules will disappears, homogenize the
mixture and one phase liquid result.
2-Lower Critical Temperature
The lower critical solution temperature , Tlc,( 18.5°C)
is the lowest temperature at which phase separation occurs. For triethylamine and
water, the system is partially miscible, 2 phases above Tlc, and single phase
below (they are mixed completely in all proportions).
Below this temp there is 1 phase; At lower temp. the two components form a
weak complex , but the weak complex have disrupted as the temp. increases thus
leading to partial miscibility and they form two phases.
The temperature–composition diagram for water and triethylamine. This system
shows a lower critical temperature at 292K.

23
 3- Some systems have both Tuc and Tlc, with a famous example
being nicotine in water, where Tuc=210℃ and Tlc= 61℃

The temperature–composition diagram for water and nicotine, which has both upper
and lower critical temperatures.

24