Two Component Systems

(A+B)
• When two components are present in a system, C = 2, so
F = 4 – P. ( 4 equivalent to 𝑥𝐴 , 𝑥𝐵 , P and T)
• If the temperature (or the pressure) is constant, the remaining
variance is
F’ = 3 – P.
• F’ indicates that one of the degrees of freedom has been
discarded (T or P).
• In this case, the number of degrees of freedom for one phase
system (P=1) are the pressure and the composition (mole
fraction of 𝑥𝐴 only since 𝑥𝐵 can be deduced).

1
1- Vapor pressure diagrams
•
2phasef
The partial vapor pressure of the components of an ideal solution
of two volatile liquids are related to the composition (𝑥) of the
liquid mixture by Raoult’s Law:

XA
𝒑𝑨 = 𝒙𝑨 𝒑∗𝑨 and 𝒑𝑩 = 𝒙𝑩 𝒑∗𝑩
the total pressure “p” is
𝒑 = 𝒑𝑨 + 𝒑𝑩 = 𝒙𝑨 𝒑∗𝑨 + 𝒙𝑩 𝒑∗𝑩 = 𝒙𝑨 𝒑∗𝑨 + (𝟏 − 𝒙𝑨 ) 𝒑∗𝑩
𝒑 = 𝒙𝑨 𝒑∗𝑨 + 𝒑∗𝑩 − 𝒙𝑨 𝒑∗𝑩
LIK s 0

𝒑 = 𝒑∗𝑩 + 𝒑∗𝑨 − 𝒑∗𝑩 𝒙𝑨 (Eq.1)

This expression shows that the total vapor pressure (at a fixed
temperature) changes linearly with the composition from 𝑝𝐵∗ to 𝑝𝐴∗ as
𝑥𝐴 changes from 0 to 1 (figure below).
2
 P P Pt PS ya

Bf
The variation of the total
vapour pressure of a binary
mixture with the mole fraction
of A in the liquid when
Raoult's law is obeyed (ideal
solution).
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3
1-a-The composition of the vapour
• The compositions of the liquid and vapor that are in mutual
equilibrium are not necessarily the same. The more volatile the
component, the higher amount of that substance should be in the
vapor.

O
• The composition of the vapour in equilibrium with a binary
mixture is calculated by using Dalton’s law. E
• 𝑦𝐴 and 𝑦𝐵 are the mole fractions (compositions) of A and B in the
vapour.

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𝑦𝐴 =
𝑝𝐴
𝑝
𝑦𝐵 =
𝑝𝐵
𝑝
Replace 𝑝𝐴 by 𝑥𝐴 𝑝𝐴∗ and 𝑝 as in slide 2,

𝒙𝑨 𝒑∗𝑨
𝒚𝑨 = and 𝒚𝑩 = 𝟏 − 𝒚𝑨 (Eq.2)
𝒑∗𝑩 +(𝒑∗𝑨 −𝒑∗𝑩 )𝒙𝑨

4
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 it
• Equation 1 (slide 2) shows how the total vapour pressure of the
mixture varies with the composition of the liquid (𝑥𝐴 ).

• When combine equations 1 and 2 we can relate the total vapour

pressure (p) to the composition of the vapour (𝑦𝐴 ), using the
following equation 3:

𝒑∗𝑨 𝒑∗𝑩
𝒑= (Eq. 3)
𝒑∗𝑨 + 𝒑∗𝑩 −𝒑∗𝑨 𝒚𝑨

𝒑 𝒑∗𝑩
pg
𝑝𝐴∗ =
𝑝𝐴∗
0ppg.p
when 𝒚𝑨 is zero

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5
 ME
• Pressure Vs. composition Diagram obtained using the liquid composition curve ( Eq.1
obtained by Raoult’s law) and the vapour composition curve (Eq.3 obtained by Dalton’s law)
• A point between the two lines corresponds to both liquid and vapour being present; outside
that region there is only one phase present.
• 𝑧
The mole fraction of A is denoted 𝐴 .
• XA is the liquid fraction in the equilibrium liquid-vapour.
• XB is the liquid fraction in the equilibrium liquid-vapour.
6
 The general scheme of interpretation of a pressure
composition diagram.

7
1-b-Interpretation of diagrams
• The pressure vs. mole fraction phase diagram shows the dependence of both vapor and liquid
composition upon mole fraction when pressure is varied.
• A richer interpretation of the phase diagram is obtained if we interpret the horizontal axis as
showing the overall composition, 𝑧𝐴 , of the system.
• All the points down to the solid diagonal line in the graph correspond to a system that contains
only a liquid phase.
• All points below the lower curve correspond to a system that contains only a vapour.
• Points that lie between the two lines correspond to a system in which there are two phases
present, one a liquid and the other a vapour.

8
• To make use of the phase diagram, consider the effect of lowering the pressure
on a liquid mixture of overall composition a, so the state of the system moves
down the vertical line that passes through a. This vertical line is called an
isopleth.

isopleth q

The vertical line through a is called an

isopleth (a line of constant composition
of the entire system).
9
1-c- The lever rule
A point in the two-phase area of a phase diagram indicates not only
qualitatively that both liquid and vapor are present, but represents
quantitatively the relative amounts of each. To find the relative amounts
of two phases α and β that are in equilibrium, we measure the distances lα
and lβ along the horizontal tie line, and then use the lever rule.
.
print
The lever rule, the distances 𝒍 and 𝒍
𝜶 𝜷
are used to find the proportions of the
amounts of phases  (such as liquid) and
𝜷 (such as vapor) present at
we equilibrium. wit
𝒏𝜶 𝒍𝜷
𝒏𝜶 𝒍𝜶 = 𝒏𝜷 𝒍𝜷 𝒐𝒓 =
𝒏𝜷 𝒍𝜶
Where 𝑛𝛼 is the amount of phase a and
𝑛𝛽 is the amount of phase b
(compositions).
10
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(a) A liquid in a container exists in equilibrium with its vapour. The phase diagram shows the
compositions of the two phases and their abundances (by the lever rule).
(b) When the pressure is changed by drawing out a piston, the compositions of the phases adjust as
shown by the tie line in the phase diagram.
(c) When the piston is pulled so far out that all the liquid has vaporized and only the vapour is
present, the pressure falls as the piston is withdrawn and the point on the phase diagram moves
into the one-phase region.

11
 2- Temperature-composition diagrams
Bats
• To discuss distillation we need a temperature-composition diagram
instead of a pressure-composition diagram.
• A phase diagram in which the boundaries show the composition of the
phases that are in equilibrium at various temperatures.
• An example is given below. Note that the liquid phase now lies in the
lower part of the diagram.

This is a temperature-composition
diagram corresponding to an ideal
mixture with the component A more
volatile than component B. Successive
T boilings and condensations of a liquid
originally of composition a, lead to a
condensate that is pure A. The
separation technique is called
fractional distillation.
12 b 00
What happens when a liquid of composition 𝒂𝟏 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 𝑎2′ . The vapour is richer in the
more volatile component A (the component with the lower boiling
point). From the location of 𝑎2 , we can state the vapour's
composition at the boiling point, and from the location of the tie
line joining 𝑎2 and 𝑎2′ we can read off the boiling temperature (𝑇2
) of the original liquid mixture.
booth

13
2-a-The distillation of mixtures

• In a simple distillation the vapor is withdrawn and condensed.

This technique is used to separate a volatile liquid from a non-
volatile solute or solid.
• In a fractional distillation, the boiling and condensation cycle is
repeated successively. This technique is used to separate volatile
liquids.
• The region between the lines in the previous diagram is a two-
phase region.
• The regions outside the phase lines correspond to a single phase.
• The efficiency of a fractionating column is expressed in terms of
the number of theoretical plates, the number of effective
vaporization and condensation steps that are required to achieve a
condensate of given composition from a given distillate.
14
 gided The number of theoretical plates
is the number of steps needed to

00 bring about a specified degree

of separation of two
components in a mixture. The
two systems shown correspond to
(a) 3, (b) 5 theoretical plates.

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p

15 composition
2-b-Azeotropes
• Although many liquids have temperature-composition phase diagrams resembling the ideal
version, (slide 12) a number of important liquids deviate from ideality.
• If a maximum occurs in the phase diagram, favorable interactions between A and B
molecules stabilize the liquid.
• If a minimum occurs in the phase diagram, unfavorable interactions between A and B
molecules de-stabilize the liquid.
• An azeotrope is a mixture of two (or more) miscible liquids that when boiled produce the same
composition in the vapor phase.

A high-boiling azeotrope A low-boiling azeotrope.

16
not ideal
2-c-Immiscible liquids

• Let’s consider the distillation of two

immiscible liquids, such as octane
and water.

• The system can be considered as the

joint distillation of the separated
components.
The distillation of (a) two
• Total vapor pressure 𝑝 = 𝑝𝐴∗ + 𝑝𝐵∗ immiscible liquids can be
regarded as (b) the joint
distillation of the separated
• Mixture boils when p = 1 atm, and components, and boiling
boils at a lower temperature than occurs when the sum of the
either component would alone. partial pressures equals the
17
external pressure (1 atm).