University of Leeds

School of Chemical and Process Engineering

Separation Processes
Distillation
CAPE 3301/5301M/5345M

Dr Xiaoan Mao
[email protected]
Main contents

• Vapor-liquid equilibria
• Single-stage operation – flash vaporization
• Differential, or simple, distillation
• Continuous rectification – binary systems
• Multistage tray towers
– McCabe and Thiele Method

• Non-ideal continuous distillation

• Multi-component mixture
• Azeotropic and extractive distillation
• Practical consideration of distillation column design

2
References:

• Mass transfer operation, Robert E. Treybal (3rd ed), Chapter 9 Distillation

• Transport processes and separation process principles (includes unit

operations), Christie John Geankoplis (4th ed), Chapter 11 Vapor-liquid
separation processes
• Separation process principles, J. D. Seader et al (3rd ed), Chapter 7
Distillation of binary mixtures

• Coulson and Richardson's Chemical Engineering

Volume 2 (5th ed), Chapter 11 Distillation (Knovel)
Volume 6 (4th ed), Chapter 11 Distillation (Knovel) - Design

3
What you will learn

1) Theories of distillation processes

2) Methods of distillation calculations
– Equilibrium
– Binary systems
• Batch
• Flash
• Rectification
– Multi-component systems
3) Design methods and consideration

4
Methods of teaching

1) Lectures, tutorials and self-study questions

2) A test (CAPE5301M only) – 10%, Week 19

3) End of semester examination

CAPE3301 CAPE5301M

50% of module mark 40% of module mark

5
Basic separation techniques

6
Basic separation techniques

Separation by phase addition or phase creation – If the feed mixture is

homogeneous, single phase solution (gas, liquid), a second immiscible phase must
often be created or added before separation of chemical species can be achieved. This
second phase is created by an energy-separating agent (ESA) and/or added as a mass-
separating agent (MSA).

Application of an energy-separating agent involves heat transfer to or from the

mixture to be separated. Alternatively, vapour may be created from a liquid phase by
reducing the pressure.

A mass-separating agent may be partially immiscible with one or more mixture

components and frequently is the constituent of highest concentration in the added
phase. Alternatively, the mass-separating agent may be miscible with a liquid feed
mixture, but may selectively alter partitioning of species between liquid and vapour
phases.

7
Basic separation techniques

8
Basic separation techniques

9
Basic separation techniques

Separation by phase addition or phase creation – When the feed mixture includes
species that differ widely in volatility, expressed as vapour-liquid equilibrium ratios (K
– values) – partial condensation or partial vaporization – may be adequate to achieve
the desired separation. Two phases are created when a vapour feed is partially
condensed by removing heat, and a liquid feed is partially vaporized by adding heat.
Alternatively, partial vaporization can be initiated by flash vaporization, by reducing
the feed pressure with a valve or turbine.
In both operations, after partitioning of species has occurred by interphase mass
transfer, the resulting vapour phase is enriched with respect to the species that are
more easily vaporized, while the liquid phase is enriched with respect to the less-
volatile species.

10
Basic separation techniques

Liquid-liquid extraction –using one or two solvents respectively, is widely used when
distillation is impractical, especially when the mixture to be separated is temperature-
sensitive and or more than 100 distillation stages would be required. When one
solvent is used, it selectively dissolves only one or a fraction of the components of the
feed mixture. Additional separation operations are generally required to recover, for
recycling, solvent from streams leaving the extraction operation.
Evaporation–is defined as the transfer of volatile components of a liquid into a gas by
heat transfer. Applications include humidification, air conditioning, and concentration
of aqueous solutions.
Crystallization–is carried out in some organic, and in almost all inorganic, chemical
plants where the desired product is a finely divided solid. Crystallization is a
purification step, so the conditions must be such that impurities do no precipitate with
the product. In solution crystallization the mixture, which includes a solvent, is cooled
and there is mass transfer of a solute from the liquid solution to a pure solid crystalline
phase.

11
Basic separation techniques

Liquid-solid extraction –leaching is used in the metallurgical, natural product, and

food industries. The major problem in leaching is to promote diffusion of the solute
out of the solid and into the liquid solvent. The most effective was of doing this is to
reduce the dimensions of the solid to the smallest feasible particle size. For large scale
applications, large open tanks are used in counter-current operation. The major
difference between solid-liquid and liquid-liquid centersaround the difficulty in
transporting the solid, or the solid slurry from stage to stage.

12
Basic separation techniques

Separation by barriers –The use of micro-porous and non-porous membranes as semi-

permeable barriers is rapidly gaining popularity in industrial separation processes for
application to difficult and highly selective separations. Membranes are usually
fabricated from natural fibres, synthetic polymers, ceramics or metals, but they may
also consist of liquid films. Solid membranes are fabricated into flat sheets, tubes,
hollow fibres or spiral-wound sheets.
Osmosis involves the transfer, by a concentration gradient, of a solvent through a
membrane into a mixture of solute and solvent. The membrane is almost non-
permeable to the solute. In reverse osmosis, transport of solvent in the opposite
direction is effected by imposing a pressure, higher than the osmotic pressure, on the
feed side. Using a non-porous membrane, reverse osmosis successfully desalts water.
Microporous membranes can be used in a manner similar to reverse osmosis to
selectively allow small solute molecules and/or solvents to pass through the
membrane and prevent large dissolved molecules and suspended solids from passing
through.
Microfiltration refers to the retention of molecules typically in the size range from
0.05 to 10 µm. Ultrafiltration refers to the range from 1 to 100 nm.

13
Basic separation techniques

Separation by solid agents –The solid, usually in the form of a granular material or
packing, acts as an inert support for a thin layer of absorbent, or alternatively, enters
directly into the separation operation by selective adsorption of, or chemical reaction
with, certain species in the feed mixture. The active separating agent eventually
becomes saturated with solute and must be regenerated or replaced periodically.
Adsorption is used to remove components present in low concentrations in non-
adsorbing solvents or gases and to separate the components in gas and liquid mixtures
by selective adsorption on solids, followed by desorption to regenerate the adsorbent.
Chromatography is a method for separating components of a feed gas or liquid
mixture by passing the feed through a bed of packing. The feed may be volatilized into
a carrier gas, and the bed may be a solid adsorbent (gas or liquid-solid
chromatography). Because of selective adsorption on the solid adsorbent surface of
absorption into the liquid absorbent, followed by desorption, the different
components of the feed mixture move through the bed at different rates, thus
effecting the separation.
Ion exchange resembles adsorption in that solid particles are used and regenerated.
However, a chemical reaction is involved. In water softening, an organic or inorganic
polymer in its sodium form removes calcium ions by a calcium-sodium exchange.

14
 Quiz

For each of the following binary mixtures, a separation operation is suggested. Explain
why the operation will or will not be successful.

a) Separation of air into oxygen-rich and nitrogen-rich products by distillation.

b) Separation of m-xylene from p-xylene by distillation.
c) Separation of benzene and cyclohexane by distillation.

Spend five minutes to work on the solutions

15
Quiz

For each of the following binary mixtures, a separation operation is suggested. Explain
why the operation will or will not be successful.

a) Separation of air into oxygen-rich and nitrogen-rich products by distillation.

The normal boiling points of the two components are sufficiently different that
they can be separated by distillation, but elevated pressure and temperatures are
required. At moderate to low production rates, they are usually separated at
lower cost by either adsorption or gas permeation through a membrane.

16
Quiz

For each of the following binary mixtures, a separation operation is suggested. Explain
why the operation will or will not be successful.

b) Separation of m-xylene from p-xylene by distillation.

The close normal boiling points make separation by distillation impractical.

However, their widely different melting points make crystallization the separation
method of choice.

17
Quiz

For each of the following binary mixtures, a separation operation is suggested. Explain
why the operation will or will not be successful.

c) Separation of benzene and cyclohexane by distillation.

The normal boiling points preclude a practical separation by distillation. Their

melting points are also close, making crystallization also impractical. The method
of choice is to use distillation in the presence of phenol (normal boiling point of
181.4 °C), which reduces the volatility of benzene, allowing nearly pure
cyclohexane to be obtained.

18
Distillation – an overview

19
An introduction to distillation

Throughout the 20th century, multistage distillation has been by far the most widely
used method for separating liquid mixtures of chemical components. Unfortunately,
distillation is a very energy intensive technique, especially when the relative volatility
of the components being separated is low (<1.5). The energy consumption for
distillation alone in the US for 1976 totalled nearly 3% of the entire national energy
consumption. Approximately two-thirds of the distillation energy was consumed by
petroleum refining, where distillation is widely used to separate crude oil into
petroleum fractions, light hydrocarbons and aromatic chemicals.

 Key operation in oil refining for large scale pure product production (can exceed 1
M bbl/day). The world’s largest refinery complex is in India with a production
capacity of 1.24 M bbl/day.
 Column diameters and height typically in the range of 0.3 –10 m and 3 –75 m,
respectively.
 Capable of providing constant product purity with variation in feed composition.
 Coupled with control systems and other separation units.

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 Distillation column

Chemical Boiling Point (°C) Melting Point (°C)

Simple distillation Benzene 80.1 5.5
https://www.youtube.com/watch?v=x-Bnq6UPdZo Toluene 110.6 -95.0 21
Distillation column: P&ID for Benzene Distillation

22
• A significant number of chemical engineering unit operations are concerned with the
problem of changing the compositions of solutions and mixtures through methods NOT
necessarily involving chemical reactions. Separations, including enrichment,
concentration, purification, refining and isolation, are important to chemical engineers.
• The mixing of chemicals to form a mixture is a spontaneous, natural process that is
accompanied by an increase in entropy and randomness. The inverse process, the
separation of that mixture into its constituent chemical species, is not a spontaneous
process; it requires an expenditure of energy.
• A general separation process is shown below. The feed mixture can be vapor, liquid or
solid, while the two products may differ in composition and phase state from each other,
as well as from the feed.

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 Distillation
Distillation is the most widely utilised industrial separation method.

Distillation involves multiple contacts between counter-currently flowing liquid and vapor
phases. Each contact consists of mixing the two phases to promote rapid partitioning of
species by mass transfer, followed by phase separation. The contacts are often made on
horizontal trays (referred to as stages) arranged in a vertical column. Vapor, while flowing up
the column, is increasingly enriched with respect to the more volatile species.
Correspondingly, liquid flowing down the column is increasingly enriched with respect to the
less volatile species. Feed to the distillation column enters on a tray somewhere between
the top and bottom trays, most often near the middle of the column. The portion of the
column above the feed entry is called the enriching or rectifying section; and that below is
the stripping section.

Feed vapor will move up the column; feed liquid will move down. Liquid is required for
making contacts with vapor above the feed tray, and vapor is required for making contacts
with liquid below the feed tray.

Normally, vapor from the top of the column is condensed in a condenser by cooling water or
a refrigerant to provide contacting liquid, called reflux. Similarly, liquid at the bottom of the
column passes through a reboiler, where it is heated by condensing steam or some other
heating medium to provide contacting vapor, called boil-up.
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 Equilibrium-stage processes

A large class of mass transfer devices consists of

assemblies of individual units, or stages, that are
interconnected so that the materials being
processed pass through each stage in turn. The two
streams move through the assembly either counter-
currently, co-currently, or cross-currently. In each
stage, they are brought into contact, mixed and
then separated. Such multistage systems are called
cascades. The counter-current arrangement is
normally preferred, because it generally results in a
higher degree of separation than the other two.

25
For mass transfer to take place, the streams entering each stage must not be equilibrium
with each other, for it is the deviation from equilibrium conditions that provides the driving
force for transfer. The leaving streams are usually not in equilibrium either but are much
closer to being so than the entering streams are.

To simplify the calculations for a cascade, the streams leaving each stage are often assumed
to be in equilibrium, which, by definitions, makes each stage ideal. A correction factor, or
efficiency factor, is applied later to account for any actual departures from equilibrium.

** Note –mass transfer separations are governed by transport (mass transfer limits the
rate of separation) and by equilibrium (thermodynamics limit the extent of separation).

26
The cascade shown consists of a series of single sections or stages with streams entering and
leaving only from the ends. Such cascades are used to recover components from a feed stream
but are not generally useful for making a sharp separation between two selected feed
components. To do this, it is best to provide a cascade consisting of two sections and the
counter-current cascade is often used. It consists of one section above the feed and one below.

27
 Material and energy balance for stages

When considering multistage systems as a whole, attention is focused on the streams passing
between the individual stages. An individual unit in a cascade normally receives two streams
from the two units adjacent to it (e.g. one from the stage above and the other from the stage
below, brings them into close contact, and delivers two streams respectively (e.g. one to the
stage above and one to the stage below).
The individual contact units in a cascade are numbered sequentially, starting from one end. If
we consider the stages are numbered from the bottom and up. A general stage in the system is
the nth stage, which is number n counting from the bottom. The stage immediately ahead of
stage n in the sequence is stage n-1 and that immediately following it is stage n+1.
To designate the streams pertaining to any one stage, all streams originating in that stage carry
the number of the unit as a subscript. Thus, for a two-component system, yn-1 is the mole
fraction of the lightest component (i.e. the one with the lowest boiling point) in the vapor
phase leaving stage n-1, and Ln is the molar flow rate of the L phase leaving the nth stage.

28
 Material and energy balance for stages

The total input of material to stage n is 𝐿𝑛+1 + 𝑉𝑛−1 units (mass or moles) per time and the
total output is 𝐿𝑛 + 𝑉𝑛 units per time. Since, under steady flow, there is neither accumulation
nor depletion, the input and the output are equal and the material balance can be written
as:

𝐿𝑛+1 + 𝑉𝑛−1 = 𝐿𝑛 + 𝑉𝑛

This equation is the total material balance for the stage.

Another balance can be written by equating input to output for component i giving the
component i balance:

𝐿𝑛+1 𝑥𝑖,𝑛+1 + 𝑉𝑛−1 𝑦𝑖,𝑛−1 = 𝐿𝑛 𝑥𝑖,𝑛 + 𝑉𝑛 𝑦𝑖,𝑛

Obviously, if all the component balances for a system were added up, the sum would be
equal to the total material balance.

29
 Material and energy balance for stages

In most equilibrium stage processes, the general energy balance can be simplified by
neglecting potential energy and kinetic energy. If, in addition, the process is workless and
adiabatic, a simple enthalpy balance applies:

𝐿𝑛+1 𝐻𝐿,𝑛+1 + 𝑉𝑛−1 𝐻𝑣,𝑛−1 + 𝑄𝑛 = 𝐿𝑛 𝐻𝐿,𝑛 + 𝑉𝑛 𝐻𝑣,𝑛

where 𝐻𝐿 and 𝐻𝑉 are the enthalpies per unit (mass or moles) of the L phase and V phase,
respectively, and 𝑄𝑛 is the heat added.

30
In distillation, a feed mixture of two or more components is separated into two or more
products, including, and often limited to, an overhead distillate and a bottom product, whose
compositions differ from that of the feed. Most often, the feed is a liquid or a vapor-liquid
mixture. The bottom product is always a liquid, but the distillate may be a liquid or a vapor or
both. The separation requires that: (1) a second phase be formed so that both liquid and vapor
phases are present and can contact each other; (2) the components have different volatilities
so that they will partition between the two phases to different extents and (3) the two phases
can be separated by gravity or other mechanical means.

31
 Worked example 1

A mixture of methanol and water containing 40 mol% of methanol is to be separated to give a

product of 90 mol% of methanol at the top, and a bottom product with 10 mol% of methanol.
The feed flow rate is 100 kmol/hr and the feed is heated so that it enters the column at its
boiling point.
It is required to find the top and bottom product flow rates.

32
 Worked example 1

A mixture of methanol and water containing 40 mol% of methanol is to be separated to give a

product of 90 mol% of methanol at the top, and a bottom product with 10 mol% of methanol.
The feed flow rate is 100 kmol/hr and the feed is heated so that it enters the column at its
boiling point.
It is required to find the top and bottom product flow rates.

Feed Distillate Bottom

Methanol 40% 40 90% 33.75 10% 6.25

Water 60% 60 10% 3.75 90% 56.25

Total 100% F=100 D=37.5 B=62.5

kmol/hr kmol/hr kmol/hr

0.9𝐷 + 0.1𝐵 = 40 9𝐷 + 𝐵 = 400

0.1𝐷 + 0.9𝐵 = 60 𝐷 + 9 400 − 9𝐷 = 600

33
Vapor-Liquid Equilibria

34
 Vapor-Liquid Equilibria

The chemical potential of liquids: To discuss the equilibrium properties of liquid mixtures we
need to know how the chemical potential of a liquid varies with its composition. To calculate
its value, we use the fact that, at equilibrium, the chemical potential of a substance present
as a vapor must be equal to its chemical potential in the liquid.
Phase boundaries: The phase diagram of a substance shows the regions of pressure and
temperature at which its various phases are thermodynamically stable. The lines separating
the regions, which are called phase boundaries, show the values of P and T at which two
phases co-exist in equilibrium

35
 Vapor-Liquid Equilibria

Consider a liquid sample of a pure substance in a closed vessel. The pressure of a vapor in
equilibrium with the liquid is called the vapor pressure of the substance. Therefore, the
liquid-vapor phase boundary in a phase diagram shows how the vapor pressure of the liquid
varies with temperature.

𝑃𝑡 = 𝑃𝐴𝑉

where
𝑃𝑡 = total pressure
𝑃𝐴𝑉 = vapor pressure of component A

Recall Dalton’s law: The pressure exerted by a mixture of perfect (intermolecular forces are
neglected) gases is the sum of the partial pressures of the gases. That is, if a certain amount
of H2 exerts 25 kPa when present alone in a container, and an amount of N2 exerts 80 kPa
when present alone in the same container at the same temperature, then the total pressure
when both gases are present is the sum of these two partial pressures, or 105 kPa.
𝑃𝑡 = 𝑝𝐴 + 𝑝𝐵 ⋯ ⋯
36
 Vapor-Liquid Equilibria

Next we define the partial pressure, 𝑝𝑖 , for a mixture of vapors A and B:

𝑝𝐴 = 𝑦𝐴 𝑃𝑡
𝑝𝐵 = 𝑦𝐵 𝑃𝑡

The partial pressure, 𝑝𝑖 , for a mixture of liquids A and B:

𝑝𝐴 = 𝑥𝐴 𝑃𝐴𝑉
𝑝𝐵 = 𝑥𝐵 𝑃𝐵𝑉

𝑃𝑡 : total pressure
𝑃𝐴𝑉 : vapor pressure of pure component A
𝑃𝐵𝑉 : vapor pressure of pure component B
𝑝𝐴 : partial pressure of A
𝑝𝐵 : partial pressure of B
𝑥𝐴 : mole fraction of A in liquid phase
𝑥𝐵 : mole fraction of B in liquid phase
𝑦𝐴 : mole fraction of A in vapor phase
𝑦𝐵 : mole fraction of B in vapor phase
37
 Vapor-Liquid Equilibria

Raoult’s Law: for an ideal solution, the equilibrium partial pressure 𝑝𝑖 of a constituent at a
fixed temperature equals the product of its vapor pressure 𝑃𝑖 when pure at this temperature
and its mole fraction in the liquid.

𝑝𝐴 = 𝑃𝐴𝑉 𝑥𝐴
𝑝𝐵 = 𝑃𝐵𝑉 (1 − 𝑥𝐴 )

In a two fluid mixture

𝑥𝐴 + 𝑥𝐵 = 1, and 𝑦𝐴 + 𝑦𝐵 = 1.

If the vapor phase is also ideal,

𝑃𝑡 = 𝑝𝐴 + 𝑝𝐵 = 𝑃𝐴𝑉 𝑥𝐴 + 𝑃𝐵𝑉 (1 − 𝑥𝐴 )

And the total as well as the partial pressures are linear in x at a fixed temperature.

38
Vapor-Liquid Equilibria

39
 Vapor-Liquid Equilibria

Henry’s law (Ideal-dilute solutions): William Henry found experimentally that, for real
solutions at low concentrations (low solubility), although the partial pressure of the solute is
proportional to its mole fraction, the constant of proportionality is not the vapor pressure of
the pure substance.

𝑝𝐴 = 𝑥𝐴 𝐾𝐴

In this expression 𝑥𝐴 is the mole fraction of the solute and 𝐾𝐴 is the proportionality factor
(with the dimensions of pressure) determined so that the plot of the partial pressure of A
against its mole fraction is tangent to the experimental curve at 𝑥𝐴 = 0.
Failure to follow Henry’s law over wide concentration ranges may be the result of chemical
interaction with the liquid or electrolytic dissociation, as is the case with water-ammonia, or
nonideality in the gas phase.

40
Vapor-Liquid Equilibria

41
 Vapor-Liquid Equilibria

Summary:
𝑝𝐴 = 𝑦𝐴 𝑃𝑡 𝑝𝐴 = 𝑥𝐴 𝑃𝐴𝑉
𝑝𝐵 = 𝑦𝐵 𝑃𝑡 𝑝𝐵 = 𝑥𝐵 𝑃𝐵𝑉

𝑃𝐴𝑉 𝑥𝐴 = 𝑃𝑡 𝑦𝐴 𝑥𝐴 + 𝑥𝐵 = 1
𝑃𝐵𝑉 𝑥𝐵 = 𝑃𝑡 𝑦𝐵 𝑦𝐴 + 𝑦𝐵 = 1

𝑃𝑡 = 𝑝𝐴 + 𝑝𝐵 = 𝑃𝐴𝑉 𝑥𝐴 + 𝑃𝐵𝑉 (1 − 𝑥𝐴 )

42
 Worked example 2 - Raoult’s Law

Calculate the vapor-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

• Calculate the liquid and vapor mole fractions for the more volatile component at 110 °C
• Calculate the relative volatility

Spend ten minutes to work out the solutions

43
 Worked example 2 - Raoult’s Law

Calculate the vapor-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

• Calculate the liquid and vapor mole fractions for the more volatile component at 110 °C
• Calculate the relative volatility

𝑃𝑡 = 𝑝𝐴 + 𝑝𝐵 = 𝑃𝐴𝑉 𝑥𝐴 + 𝑃𝐵𝑉 (1 − 𝑥𝐴 ) 𝑃𝐴𝑉 𝑥𝐴 = 𝑃𝑡 𝑦𝐴

𝑃𝑡 − 𝑃𝐵𝑉 760 − 484 𝑃𝐴𝑉 𝑥𝐴 1050 × 0.488

𝑥𝐴 = 𝑉 = = 0.488 𝑦𝐴 = = = 0.674
𝑃𝐴 − 𝑃𝐵𝑉 1050 − 484 𝑃𝑡 760
𝑦𝐴 𝑦𝐴 0.674
𝑥 𝑦𝐴 𝑥𝐵 𝑥𝐴 0.488
𝛼𝐴𝐵 = 𝑦𝐴 = = = = 2.169
𝐵 𝑦𝐵 𝑥𝐴 1 − 𝑦𝐴 1 − 0.674
𝑥𝐵 1 − 𝑥𝐴 1 − 0.488 44
 Worked example 2a - Raoult’s Law

Calculate the vapor-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

45
 Worked example 2a - Raoult’s Law

Calculate the vapor-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

T (°C) 𝑃𝐴 (mmHg) 𝑃𝐵 (mmHg) 𝑥𝐴 𝑦𝐴 𝛼

98.4 760 333 1.000 1.000 -
105 940 417 0.656 0.811 2.254
110 1050 484 0.488 0.674 2.169
115 1200 561 0.311 0.492 2.139
120 1350 650 0.157 0.279 2.077
125.6 1540 760 0.000 0.000 -

𝑃𝑡 − 𝑃𝐵𝑉
𝑃𝑡 = 𝑝𝐴 + 𝑝𝐵 = 𝑃𝐴𝑉 𝑥𝐴 + 𝑃𝐵𝑉 (1 − 𝑥𝐴 ) 𝑥𝐴 = 𝑉
𝑃𝐴 − 𝑃𝐵𝑉
𝑃𝐴𝑉 𝑥𝐴
𝑃𝐴𝑉 𝑥𝐴 = 𝑃𝑡 𝑦𝐴 𝑦𝐴 =
𝑃𝑡
𝑦𝐴 𝑦𝐴
𝑥 𝑦𝐴 𝑥𝐵 𝑥𝐴
𝛼𝐴𝐵 = 𝑦𝐴 = =
𝐵 𝑦𝐵 𝑥𝐴 1 − 𝑦𝐴
𝑥𝐵 1 − 𝑥𝐴 46
 Worked example 2a - Raoult’s Law

Calculate the vapor-liquid equilibria at constant pressure of 1 atm for mixtures of n-heptane
and n-octane, which may be expected to form ideal solutions.

130

125 Bubble points

Dew points
120
Temperature (°C)

115

110

105

100

95
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction

47
 Constant-Pressure Equilibria

The upper curve provides the temperature-vapor composition (t-y) relationship, the lower
that of the temperature-liquid composition (t-x). Liquid and vapor mixtures at equilibrium are
at the same temperature and pressure throughout, so that horizontal tie lines such as line DF
join equilibrium mixtures at D and F. There are an infinite number of such tie lines for this
diagram. A mixture on the lower curve, as at point D, is a saturated liquid; a mixture on the
upper curve, as at F, is a saturated vapor. A mixture at E is a two-phase mixture, consisting of a
liquid phase composition at D and a vapor phase composition at F in such proportions that the
average composition of the entire mixture is represented by E. The relative amounts of the
equilibrium phases are related to the segments of the tie line,

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐷 𝑙𝑖𝑛𝑒 𝐸𝐹
=
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐹 𝑙𝑖𝑛𝑒 𝐷𝐸

48
 Constant-Pressure Equilibria

Consider a solution at G at constant pressure. The solution is entirely liquid. If it is heated, the
first bubble of vapor forms at H and has the composition at J, richer in the more volatile
substance, and hence the lower curve is called the bubble-point-temperature curve. As more
of the mixture is vaporized, more of the vapor forms at the expense of the liquid, giving rise,
for example, to liquid L and its equilibrium vapor K, although the composition of the entire
mass is still the original as at G. The last drop of liquid vaporizes at M and has the composition
of N. Superheating the mixture follows the path MO. The mixture has vaporized has vaporized
over a temperature range from H to M.

49
 Constant-Pressure Equilibria

The vapor-liquid equilibrium compositions can also be shown on a distribution diagram (x vs

y). Point P on the diagram represents the tie line DF, for example. Since the vapor is richer in
the more volatile substance, the curve lies above the 45° diagonal line.

50