Distillation Design

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What are you going to learn in this chapter?

4.1 Vapor-Liquid Equilibrium Relations

4.2 Single-Stage Equilibrium Contact for Vapor-Liquid
System
4.3 Simple Distillation Methods
4.4 Distillation with reflux and McCabe-Thiele Method

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4.1 Vapor-Liquid Equilibrium Relations
4.1.1 Raoult’s Law

An ideal law, Raoult’s law, can be defined for vapor-liquid phases in

equilibrium (only ideal solution e.g. benzene-toluene, hexane-heptane etc.

p A  PA x A (1)

Where
pA is the partial pressure of component A in the vapor in Pa (atm)
PA is the vapor pressure of pure A in Pa (atm)
xA is the mole fraction of A in the liquid.

1  x A  xB in liquid:
Composition (2)
1  y A  y Bin vapor:
Composition (3)
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4.1.2 Boiling-Point Diagrams and xy Plots

Boiling-point diagram for system benzene (A)-toluene (B) at a total pressure

of 101.32 kPa.

Dew point is the temperature at which

the saturated vapour starts to condense.

Bubble-point is the temperature at

which the liquid starts to boil.

The difference between liquid and

vapour compositions is the basis for
distillation operations.

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4.1.2 Boiling-Point Diagrams and xy Plots

Boiling-point diagram for system benzene (A)-toluene (B) at a total pressure

of 101.32 kPa.

If we start with a cold liquid

composition is xA1 = 0.318 (xB1
= 0.682) and heat the mixture, it
will start to boil at 98ºC.
The first vapor composition in
equilibrium is yA1 = 0.532 (yB1 =
0.468).
Continue boiling, the
composition xA will move to the
left since yA is richer in A.

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4.1.2 Boiling-Point Diagrams and xy Plots

The boiling point diagram can be calculated from (1) the pure vapor-
pressure data in the table below and (2) the following equations:

p A  pB P
(4)

PA x A  PB (1  x A )  P
(5)
p A PA x A
yA  
P P (6)
Where
pA, pB are the partial pressure of component A and B in the vapor in Pa (atm)
PA , PB are the vapor pressure of pure A and pure B in Pa (atm)
P is total pressure in Pa (atm)
xA is the mole fraction of A in the liquid.
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4.1.2 Boiling-Point Diagrams and xy Plots

The boiling point diagram can be calculated from (1) the pure vapor-
pressure data in the table below and (2) the following equations:

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 Ex 4.1 Use of Raoult’s Law for Boiling-Point Diagram
Calculate the vapor and liquid compositions in equilibrium at 95ºC
(368.2K) for benzene-toluene using the vapor pressure from the
table 1 at 101.32 kPa.

Solution: At 95ºC from Table 1 for benzene, PA = 155.7 kPa and PB = 63.3
kPa. Substituting into Eq.(5) and solving,

PA x A  PB (1  x A )  P

155.7(xA) + 63.3(1-xA) = 101.32 kPa (760 mmHg)

Hence, xA= 0.411 and xB= 1 – xA = 1 - 0.411 = 0.589. Substituting into eqn.
(6),
p A PA x A 155.7(0.411)
yA    0.632
P P 101.32

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The boiling point diagram can be calculated from the pure vapor-pressure
data in the table below and the following equations:

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A common method of plotting the equilibrium data is shown in Fig. 2 where
yA is plotted versus xA for the benzene-toluene system. The 45º line is
given to show that yA is richer in component A than is xA.

Fig. 2 Equilibrium diagram for system benzene(A) – toluene(B) at 101.32

kPa (1atm).
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 4.1 Vapor-Liquid Equilibrium Relations
4.1.2 Boiling-Point Diagrams and xy Plots

Ideal boiling point diagram Minimum-boiling azeotrope Maximum-boiling azeotrope

An azeotrope is a mixture of two or more liquids in such a ratio that its

composition cannot be changed by simple distillation.
This occurs because, when an azeotrope is boiled, the resulting vapor has
the same ratio of constituents as the original mixture. 11
4.1 Vapor-Liquid Equilibrium Relations
4.1.2 Boiling-Point Diagrams and xy Plots

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4.2 Single-Stage Equilibrium Contact for Vapor-Liquid System
A single equilibrium stage is
- the two different phases are brought into intimate contact with each other.
- The mixing time is long enough and the components are essentially at
equilibrium in the two phases after separation.

V1 V2
Where
V1, V2 is a vapor
L0, L1is a liquid
L0 L1

Total mass balance: L0  V2  L1  V1  M

Mass A balance: L0 x A0  V2 y A 2  L1 x A1  V1 y A1  Mx AM

In case of constant molal overflow : V1 = V2 and L0 = L1 13

 Ex 4.2 Equilibrium Contact of Vapor-Liquid Mixture
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
contacted with 110 kg mol of a liquid at the 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.

Solution: The given values are V2 = 100 kg mol, yA2 = 0.40, L0=110 kg
mol , and xA0 = 0.30.

V1 V2
For constant molal overflow,
V2 = V1 and L0 = L1.

L0 L1

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 Material balance on component A,

L0 x A0  V2 y A 2  L1 x A1  V1 y A1  Mx AM

110 (0.30)  100(0.40) 110 x A1  100 y A1

To solve equation above, the equilibrium relation between yA1 and xA1 in
figure below must be used.
First, we assume that xA1 = 0.20 and substitute into equation above to
solve for yA1.

110 (0.30)  100(0.40) 110 (0.2)  100 y A1

Assuming that xA1 = 0.20 and solving yA1 = 0.51.

Next, assuming that xA1=0.40 and solving, yA1 = 0.29.
Next, assuming that xA1=0.40 and solving, yA1 = 0.29.
(These point are plotted on the graph.)
At the intersection of this line with the equilibrium curve, 15
y = 0.455 and x = 0.25. Answer
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4.3 Simple Distillation Methods

4.3.1 Introduction

Distillation is a method used to separate the components of liquid solution,

which depends upon the distribution of these various components between
a vapor and a liquid phase.

The vapor phase is created from the liquid phase by vaporization at the
boiling point.

Distillation is concerned with solution where all components are appreciably

volatile such as in ammonia-water or ethanol-water solutions, where both
components will be in the vapor phase.

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4.3.2 Relative Volatility of Vapor-Liquid Systems

Relative volatility( AB )
It is a measure of the differences in volatility between 2 components, and hence their boiling
points. It indicates how easy or difficult a particular separation will be.

yA / xA yA / xA
 AB  
y B / xB (1  y A )(1  x A )

Where αAB is the relative volatility of A with respect to B in the binary system.

P x PB xB
Raoult’s law: yA  A A yB 
P P
PA
 AB 
PB
 AB x A
yA 
1  ( AB  1) x A

when αAB is above 1.0, a separation is possible. 18

Ex 4.3 Using data from table 1 calculate the relative volatility for the
benzene-toluene system at 85ºC (358.2K) and 105ºC (378.2K)

Solution: At 85ºC, substituting into equation below for a system following

Raoutl’s law,
PA 116.9
 AB   2.54
PB 46.0

Similarly at 105ºC,
204.2
 2.38
86.0

The variation in α is about 7%. Answer

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