KIL 2008 / KKEK 2158

Separation Processes 1

2 – Introduction to Distillation

Dr. Hanee Farzana Hizaddin

Department of Chemical Engineering
University of Malaya

hanee@um.edu.my
1
Learning outcomes
At the end of this class, you should be able to:

• Explain the thermodynamic concept governing distillation method

• Distinguish different types of distillation methods
• Perform single-stage equilibrium calculation
• Derive and apply Rayleigh equation

2
Distillation Method
• The most widely used separation process in the chemical industry

• An equilibrium stage operation

• A method for separating various components of a liquid solution by exploiting the

differences in their volatility (vapor pressure)

• A Unit Operation – i.e. a physical separation process and NOT a chemical reaction

• All components involved in the distillation are present in both vapor and liquid
phases

• When to use distillation?

• When the components are appreciably volatile e.g. ethanol-water, ammonia-water

solutions

• When the composition of the vapor phase will be different than the composition in
the liquid phase at equilibrium at the boiling point of the liquid

3
Two main methods of distillation
No Reflux

• Production of a vapor by boiling the

liquid mixture in a single stage and
condensing the vapor

• No liquid is allowed to return to the

still, i.e. no reflux

• Three important types of single-

stage distillation without reflux:

• Flash distillation
• Simple batch or differential
distillation
• Simple steam distillation

4
Two main methods of distillation

With Reflux

• Involves the return of part of the

condensate (in liquid phase) to the
still (i.e. reflux)

• The returning liquid is brought into

close contact with the rising vapors
on the way to the condenser

• Known as fractional distillation,

distillation with reflux, or
rectification

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Important Thermodynamic Fundamental Concepts for Distillation
Vapor Pressure
• According to Kinetic Theory, the molecules in a liquid are in a constant
state of thermal motion and some of these molecules are moving fast
enough to escape from the liquid forming a vapor above the liquid.
This vapour exerts a pressure on the surface of the liquid, i.e., vapor
pressure
• The vapour pressure of a liquid increases, generally exponentially,
with temperature
• As a liquid is heated, the vapour pressure of the liquid increases to the
point at which it just equals the applied pressure - usually atmospheric
pressure. The liquid now begins to bubble (boil)
• Liquids with high vapour pressures (volatile compounds / “light”
compounds) require relatively little energy (heat) to increase the vapor
pressure to match the applied (atmospheric) pressure, and thus, boil,
i.e. they have low boiling points
• Liquids with low vapour pressures (less volatile / “heavy” compounds)
require considerably more energy to increase the vapor pressure to
the point where it matches the applied pressure, thus, they have
relatively high boiling points
Boiling Point
• The Boiling Point is the temperature at which
internal vapor pressure of the liquid is equal to the
pressure exerted by its surroundings
• If the liquid is open to the atmosphere, the boiling
point is the temperature at which the internal vapor
pressure of the liquid becomes equal to atmospheric
pressure ( ̴760 mm Hg = 1 atm).
• The internal vapor pressure of a pure liquid rises
steadily as the temperature is increased until the
boiling point is reached.
• The temperature remains constant throughout the
boiling process of a pure liquid. At the boiling point,
the liquid and vapor are in equilibrium. If the
composition of each phase remains constant, the
temperature will remain constant
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Important Thermodynamic Fundamental Concepts for Distillation
Vapour pressure/ boiling point of Miscible Liquid mixtures

• Liquid and liquid mixtures

• Miscible and non miscible liquid mixtures
• Miscible liquid mixture is also called as solution

• Liquid compounds making a miscible liquid mixtures normally have different vapor pressures at a given
temperature

• The individual compounds in a mixture each exert its own pressure - called partial pressure

• The sum of the partial pressures equals to the total vapor pressure of the solution/mixture (Dalton’s
Law for ideal gas)
• Ptotal = PA + PB

• When the total pressure of a mixture (sum of the partial pressures) is equal to or greater than the
applied pressure, normally atmospheric pressure (760 mm Hg), the solution boils

• Solutions/mixtures have higher vapour pressure and lower boiling point than their constituent pure
liquids 7
Deviations from Raoult’s Law
• In a solution of two miscible liquids (A & B)

𝑃𝐴 = 𝑥𝐴 𝑃𝐴𝑠𝑎𝑡 𝑃𝐵 = 𝑥𝐵 𝑃𝐵𝑠𝑎𝑡

𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃𝐴 + 𝑃𝐵 = 𝑥𝐴 𝑃𝐴𝑠𝑎𝑡 + 𝑥𝐵 𝑃𝐵𝑠𝑎𝑡

• When the total pressure (sum of the partial

pressures) is equal to or greater than the applied
pressure the solution boils

• Solutions/ mixture may or may not follow the Raoult’s Law.

• Binary mixtures that follows the Raoult’s law are called ideal solution, where the attraction
between A and B molecules is the same as those for the pure components, i.e A-B=A-A & A-B.
Example: benzene/toluene mixture

• When the interaction of A and B molecules (A-B) is less than that between the molecules of pure
constituents (A-A, A-B), then vapour pressure of solution is now greater than the expected from
Raoult’s Law. (positive deviation). Example: benzene/ethyl alcohol mixture

• When the interaction of A and B molecules (A-B) is more than that between the molecules of pure
constituents (A-A, A-B), then vapour pressure of solution is now lesser than the expected from
Raoult’s Law. (negative deviation). Example: Chloroform/acetone mixture
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Boiling point diagram of an ideal solution
• B has the higher vapour pressure. Thus it will have the lower
boiling point.

• Composition of the liquid phase differ than the vapour phase

Saturated
vapor line • If you boil a liquid mixture, you would expect to find that the
Saturated
liquid line
more volatile substance escapes to form a vapour more easily
than the less volatile one.

• You would expect to find a higher proportion of B (the more

volatile component) in the vapour than in the liquid. You can
discover this composition by condensing the vapour and
analysing it. That would give you a point on the diagram.

• If B is more volatile than A, boiling point B < boiling point A • The difference between liquid and vapour compositions is
and PBsat >PAsat the basis for distillation operations.

• Then the number of moles of B in the vapor phase > number

of moles of B in the liquid phase
• yB>xB

• The result of this process is that when a mixture of two

miscible liquids with different boiling points is heated, the
vapor will have a different composition than the liquid, i.e. the
vapor is enriched in the more volatile (lower boiling)
component.
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Example 1 – Construct a boiling point diagram
The vapor pressure data are given below for the system hexane-octane.

a) Using Raoult’s law, calculate and plot the x-y data at a total pressure of 101.32 kPa

b) Plot the boiling point diagram

Vapor Pressure (kPa)

T (°C)
n-hexane (A) n-octane (B)
68.7 101.3 16.1
79.4 136.7 23.1
93.3 197.3 37.1
107.2 284.0 57.9
125.7 456.0 101.3

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Solution to Example 1
Vapor Pressure (kPa)
At temperature T, T (°C) n-hexane n-octane xA yA
(A) (B)
𝑃 = 𝑥𝐴 𝑃𝐴𝑠𝑎𝑡 + 𝑥𝐵 𝑃𝐵𝑠𝑎𝑡
68.7 101.3 16.1
𝑃 = 𝑥𝐴 𝑃𝐴𝑠𝑎𝑡 + 1 − 𝑥𝐴 𝑃𝐵𝑠𝑎𝑡 79.4 136.7 23.1
93.3 197.3 37.1
𝑃 − 𝑃𝐵𝑠𝑎𝑡 107.2 284.0 57.9
𝑥𝐴 =
𝑃𝐴𝑠𝑎𝑡 − 𝑃𝐵𝑠𝑎𝑡 125.7 456.0 101.3

and

𝑦𝐴 𝑃 = 𝑥𝐴 𝑃𝐴𝑠𝑎𝑡

𝑥𝐴 𝑃𝐴𝑠𝑎𝑡
𝑦𝐴 =
𝑃

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Single-stage Equilibrium Contact for Vapor-Liquid System
• A single-stage process is one in which two different phases are brought into intimate contact with each other
and then are separated
• During the time of contact, intimate mixing occurs and the various components diffuse and redistribute
themselves between the two phases
• If mixing time is long enough, the components are essentially at equilibrium between the two phases after
separation
• Thus, the process is considered a single equilibrium stage

V2 L1 • Total mass balance:

• The two entering phases, L0 and V2 of 𝐿0 + 𝑉2 = 𝐿1 + 𝑉1

known amount and compositions enter
the stage, mix and be at equilibrium • For a binary mixture of A and B,

• The two exit streams, L1 and V1 leave in 𝐿0 𝑥𝐴0 + 𝑉2 𝑦𝐴2 = 𝐿1 𝑥𝐴1 + 𝑉1 𝑦𝐴1
equilibrium with each other
No need for a balance on B (not an independent
equation since xA+xB = 1)
V1 L0
• To solve for xA1 and yA1,
• May assume constant molal overflow
• Need equilibrium relations between A and B
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Example 2 – Single stage equilibrium
A vapor at the dew point and 101.32 kPa containing a mole fraction of 0.40 benzene (A) and 0.60 toluene (B) and 100 kg
mol total is brought into contact with 110 kg mol of a liquid at a boiling point containing a mole fraction of 0.30 benzene
and 0.70 toluene. The two streams are contacted in a single stage, and the outlet streams leave in equilibrium with
each other. Assume *constant molal overflow. Calculate the amounts and compositions of the exit streams.

VLE data:

*constant molal overflow:

Vapor pressure (kPa)
• It means that for every mole of vapour
T (°C) xA yA condensed, 1 mole of liquid is vaporised.
Benzene (A) Toluene
• This does not happen in reality but it is an
(B)
acceptable approximation.
80.1 101.32 1.000 1.000 • It is based on negligible heat of mixing and
85 116.9 46.0 0.780 0.900 heat loss and on constant molar enthalpies.
90 135.5 54.0 0.581 0.777 • It means that while the liquid and vapour
compositions may change the overall
95 155.7 63.3 0.411 0.632
flowrate of each is constant through the
100 179.2 74.3 0.258 0.456 column
105 204.2 86.0 0.130 0.261 • In other words,
110.6 240.0 101.32 0 0 • Vin = Vout
• Lin = Lout

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Solution – Example 2
Use the material balance equation
V2 L1 𝐿0 𝑥𝐴0 + 𝑉2 𝑦𝐴2 = 𝐿1 𝑥𝐴1 + 𝑉1 𝑦𝐴1
𝑦𝐴2 𝑥𝐴1
Vapor pressure (kPa)
T (°C) xA yA
Benzene (A) Toluene
(B)
Assume constant molal overflow, 80.1 101.32 1.000 1.000
85 116.9 46.0 0.780 0.900
90 135.5 54.0 0.581 0.777
95 155.7 63.3 0.411 0.632
V1 L0 Substitute the known values
100 179.2 74.3 0.258 0.456
𝑦𝐴1 𝑥𝐴0 105 204.2 86.0 0.130 0.261
110.6 240.0 101.32 0 0

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Solution – Example 2
• Plot the x-y diagram for benzene (A) because analytical
expression that relates xA and yA is not available xy diagram
• Solve the material balance equation by trial and error: 1

0.9

0.8

0.7

0.6

0.5

yA
0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA

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Distillation with No Reflux – Flash Distillation
• A single stage distillation where a liquid mixture is partially vaporized
• Vapor is allowed to come to equilibrium with the liquid, and the
vapor and liquid phases are then separated
• This process can be done batch wise or continuously

• Example:
• A mixture of components A and B at a flow rate F mol/h flows
into the heater and is partially vaporized.
• The mixture then reaches equilibrium and is separated. Let xF, x
and y be the composition of component A in the mixture.

• A total material balance on A:

𝐹𝑥𝐹 = 𝑉𝑦 + 𝐿𝑥 Eq. (1)

• Since 𝐿 = 𝐹 − 𝑉,
𝐹𝑥𝐹 = 𝑉𝑦 + 𝐹 − 𝑉 𝑥 Eq. (2)

• Usually, the moles per hour of F, V, and L are known or specified.

Thus, the two unknowns are x and y.
• Need another relationship to solve for x and y …. i.e. the equilibrium
line (xy diagram)
• A convenient method is to plot Eq. 2 on the xy diagram
• The intersection of Eq. 2 and the xy diagram provides the solution

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Example 3: Flash Distillation
• A mixture of 50 mol% benzene and 50 mol%
toluene is subjected to flash distillation at a
separator pressure of 1 atm and temperature
95°C such that 40% of the feed will vaporize.

a) What are the compositions of the vapor and

liquid leaving the flash chamber?

b) What is the required feed temperature?

Heats of vaporization, λ and specific heats of the

liquid are:

Benzene: 𝜆 = 7 360 cal/mol; 𝐶𝑝 = 33 calΤmol.℃

Toluene: 𝜆 = 7 960 cal/mol; 𝐶𝑝 = 40 calΤmol.℃
17
Simple Batch or Differential Distillation
• Liquid is first charged to a heated kettle.
• The liquid is boiled slowly and the vapors are withdrawn as rapidly as they form to a condenser
• The condensed vapor (distillate) is collected
• The first vapor condensed will contain the most amount of the more volatile component (MVC) e.g. A
• As vaporization proceeds, the vaporized product contains less amount of A

Example
• L1 moles of components A and B with a composition of MVC A x1is placed
in the still.

• At any given time, there are L moles of liquid left in the still with MVC
composition x, and the composition of the vapor leaving in equilibrium is
y. A differential amount of dL is vaporized.

• The composition in the still pot changes with time.

• Assume a small amount of vapor dL is vaporized and the composition of

the liquid changes from x to x – dx and the amount of liquid from L to L –
dL

• Do a material balance on the MVC A to derive the Rayleigh equation

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Rayleigh equation - Derivation
Original amount of A = amount of A left in the liquid + amount of A vaporized

𝑥𝐿 = 𝑥 − 𝑑𝑥 𝐿 − 𝑑𝐿 + 𝑦𝑑𝐿

Expanding the RHS multiplication:

𝑥𝐿 = 𝑥𝐿 − 𝑥𝑑𝐿 − 𝐿𝑑𝑥 + 𝑑𝑥𝑑𝐿 + 𝑦𝑑𝐿

Neglecting the term dxdL (negligible because of the small value) and rearranging,

𝑑𝐿 𝑑𝑥
=
𝐿 𝑦−𝑥
Integrating,
𝑥1
𝐿1
𝑑𝐿 𝐿1 𝑥1
𝑑𝑥 𝐿1 𝑑𝑥
න = ln = න ln = න Rayleigh equation
𝐿2 𝐿 𝐿2 𝑥2 𝑦 − 𝑥 𝐿2 𝑥2 𝑦 − 𝑥

The average composition of total material distilled, yav, can be obtained by the material balance:

𝐿1 𝑥1 = 𝐿2 𝑥2 + 𝐿1 − 𝐿2 𝑦𝑎𝑣

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Rayleigh equation – Solution to the RHS
𝑥1
𝐿1 𝑑𝑥
How to solve the Rayleigh equation? ln = න
𝐿2 𝑥2 𝑦 − 𝑥

Option 3:
Option 1: Assume that Option 2: Assume that Graphical/numerical
K=y/x is constant α is constant integration

𝐾𝐴 𝑦𝐴 /𝑥𝐴 𝑦/𝑥 Given T-x-y data, integrate

𝐿1 𝑥1
𝑑𝑥 𝑥1
𝑑𝑥 𝛼𝐴𝐵 = =
𝐾𝐵 𝑦𝐵 /𝑥𝐵
=
1−𝑦 / 1−𝑥 numerically using the
ln = න =න trapezoid rule
𝐿2 𝑥2 𝑦 − 𝑥 𝑥2 𝑥 𝐾 − 1
𝛼𝑥
𝑦=
𝐿1 1 𝑥1 1+𝑥 𝛼−1
ln = ln
𝐿2 𝐾 − 1 𝑥2 𝑥1
𝐿1 𝑑𝑥
ln = න
𝐿2 𝑥2 𝑦 − 𝑥

𝑥1 −1
𝐿1 1+𝑥 𝛼−1
ln = න −𝑥 𝑑𝑥
𝐿2 𝑥2 𝛼𝑥

𝐿1 1 𝑥1 1 − 𝑥2
ln = ln + 𝛼 ln
𝐿2 𝛼 − 1 𝑥2 1 − 𝑥1
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Rayleigh equation – Derivation of alternative
• A simple alternative to the Rayleigh equation can be derived for an ideal mixture based on the relative volatility.
• Although the temperature in the still increases during a batch distillation, the relative volatility does not change much
and an average value can be used
𝑦𝐴 𝑥𝐴
= 𝛼𝐴𝐵
𝑦𝐵 𝑥𝐵
• If the mixture has LA mol of A and LB mol of B, the ratio LA/LB = xA/xB\
• When dL mol is vaporized, the change in A is yAdL or dLA, and the change in B is yBdL or dLB. Substituting these into the
above equation, we obtain

𝑑𝐿𝐴 /𝑑𝐿 𝑑𝐿𝐴 𝐿𝐴

= = 𝛼𝐴𝐵
𝑑𝐿𝐵 /𝑑𝐿 𝑑𝐿𝐵 𝐿𝐵
𝑑𝐿𝐴 𝑑𝐿𝐵
= 𝛼𝐴𝐵
𝐿𝐴 𝐿𝐵
Integrating between the limits L A0 and LA and LB0 and LB respectively,

𝐿𝐴 𝐿𝐵
𝑑𝐿𝐴 𝑑𝐿𝐵
න = 𝛼𝐴𝐵 න
𝐿𝐴0 𝐿𝐴 𝐿𝐵0 𝐿𝐵
1/𝛼𝐴𝐵
𝐿𝐴 𝐿𝐵 𝐿𝐵 𝐿𝐴
ln = 𝛼𝐴𝐵 ln OR =
𝐿𝐴0 𝐿𝐵0 𝐿𝐵0 𝐿𝐴0
21
Example 4 – Rayleigh equation
A mixture of 100 mol containing 50 mol % n-pentane and 50 mol % n-heptane is distilled under differential
conditions at 101.3 kPa until 40 mol is distilled. What is the average composition of the total vapor distilled and
the composition of the liquid left?

Equilibrium data is given below, where x and y are mole fractions of n-pentane

X y
1.000 1.000
0.867 0.984
0.594 0.925
0.398 0.836
0.254 0.701
0.145 0.521
0.059 0.271
0 0

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Example 4 – Solution
Given values are L1 = 100 mol, x1 = 0.50, L2 = 60 mol, and V (moles distilled) = 40 mol. Hence, L2 = 60 mol.
Substitute these values into the Rayleigh equation:

• We need to find x2, i.e. the composition of the liquid residue L2 at the end of the distillation.

x y 1/(y-x)

23
Example 3 – Solution
From the integration, x2= is where the numerical integration equals to .

To find the average composition of the vapor distilled, use the material balance equation

𝐿1 𝑥1 = 𝐿2 𝑥2 + 𝐿1 − 𝐿2 𝑦𝑎𝑣

24
Example 5 – Rayleigh Equation
100 moles of benzene (A) and toluene (B) mixture containing 50%
(mole) of benzene is subjected to a differential distillation at
atmospheric pressure until the composition of benzene in the
residue is 33%. Calculate the total moles of the mixture distilled.
Average relative volatility may be assumed as 2.16

25
Example 5 – Solution using Option 2
Using the average volatility, Option 2 can be used to solve the Rayleigh equation.

𝐿1 1 𝑥1 1 − 𝑥2
ln = ln + 𝛼 ln
𝐿2 𝛼 − 1 𝑥2 1 − 𝑥1

In this example, L1 = 100 mol, L2 is to be determined, x1=0.50, x2=0.33, α=2.16

26
Example 5 – Solution using Option 3
The x-y relationship can be obtained using the equilibrium relation by the equation:

𝛼𝑥
𝑦=
1+𝑥 𝛼−1

Calculate x-y for the region x=0.33 to x=0.50

x y 1/(y-x)
0.33
0.36
0.39
0.42
0.45
0.48
0.5

27
Example 5 – Solution using Option 3
Integrate the graph from x=0.33 to x=0.50

The area will be approximately

𝑥1
𝐿1 𝑑𝑥
ln = න =
𝐿2 𝑥2 𝑦 − 𝑥

100
ln =
𝐿2

𝐿2 = mol

Moles of mixture distilled = L1 - L2 =

28
 Simple steam distillation
• Steam distillation is a special type of distillation for
temperature sensitive materials like natural aromatic
compounds.
• Many organic compounds tend to decompose at high
temperatures. Separation by normal distillation would then not
be an option, so water or steam is introduced into the distillation
apparatus.
• By adding water or steam, the boiling points of the compounds
are depressed, allowing them to evaporate at lower
temperatures, preferably below the temperatures at which the
deterioration of the material becomes appreciable.
• This method is often used to separate a high-boiling component
from small amounts of non-volatile impurities.
• After distillation the vapors are condensed as usual, usually
yielding a two-phase system of water and the organic
compounds, which can be separated because they are
immiscible
• Conclusion: Steam is used to reduce the boiling point of a liquid
to be distilled
• When a mixture of two practically immiscible liquids are heated
to the vapor phase, each constituent independently exerts its
own vapor pressure as a function of temperature as if the other
constituent were not present.
• Consequently, the vapor pressure of the whole system increases.
Boiling begins when the sum of the partial pressures of the two
immiscible liquids just exceeds the atmospheric pressure.
• In this way, many organic compounds insoluble in water can be
purified at a temperature well below the point at which
decomposition occurs.
• For example, the boiling point of bromobenzene is 156 °C and
the boiling point of water is 100 °C, but a mixture of the two
boils at 95 °C. Thus, bromobenzene can be easily distilled at a
temperature 61 °C below its normal boiling point.
29
Simple steam distillation – Example
• Consider a mixture of water (A) and phenylamine (B). At atmospheric pressure,
• Boiling point of water: 100°C
• Boiling point of phenylamine: 184°C

• At 98°C, the vapor pressure of water and phenylamine are:

• PAsat = 94.30 kPa
• PBsat = 7.07 kPa

• The total vapor pressure of the mixture would be P = PAsat + PBsat = 101.37 kPa  close to Patm
• The mixture will boil when its vapor pressure equals the external pressure

• Thus, phenylamine can be separated through steam distillation at 98°C at Patm, well below its pure
component boiling temperature which is at 184 °C

30
Application of steam distillation – Example

https://simplesolutionsforthehome.wordpress.com/category/health-and-beauty/essential-oils/
31
References
• http://www.slideshare.net/zoraizhaiderzoraizhaider/distillation-
lecture?from_action=save
• http://facstaff.cbu.edu/rprice/lectures/distill.html#def
• http://www.chemguide.co.uk/physical/phaseeqia/immiscible.html

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