ChE 3103
Mass Transfer I
Equilibrium Staged Separation
Vapor-Liquid Phase Equilibrium
Safat Anam
Lecturer
[Link] ChE, RUET
Objective of the Course
• Understanding equilibrium staged separation
processes
• Handling design and simulation problem of
equilibrium staged separation i.e.
– calculate column height and diameter based on
materials to be processed
– Deciding operating parameters for an existing column
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Text Book and Author
Phillip C Wankat is a Distinguished Professor in Chemical
Engineering and Engineering Education at Purdue
University
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Topics to be Discussed
Part A: Concept of Equilibrium Staged Separation, Distillation
1. Introduction to Equilibrium-Staged Separation
2. Vapor-Liquid Phase Separation
3. Flash Distillation
4. Introduction to Column Distillation
5. Column Distillation: Internal Stage-by-stage Balances
6. Advanced Binary Distillation: McCabe-Thiele and Lewis Analysis
7. Batch Distillation
8. Staged Column Design
Part B: Absorption & Stripping, Extraction
1. Absorption and Stripping
2. Immiscible Extraction
3. Extending McCabe-Thiele Analysis and the Kremser Equation to
Other Separations
4. Extraction of Partially Miscible Systems 4
Introduction
• Separations are crucial in chemical engineering
• The equilibrium stage concept is applicable when the process
can be constructed as a series of discrete stages in which the
two phases are contacted and then separated
• The two separated phases are assumed to be in equilibrium with
each other
• For example, in distillation, a vapor and a liquid are commonly
contacted on a metal plate with holes in it. Because of the
intimate contact between the two phases, solute can transfer
from one phase to another
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Equilibrium-Staged Separation
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Importance of Separation
Q: Why does chemical engineering require the study of separation
techniques?
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Some of the most common chemical
engineering separation methods
1. Flash distillation
2. Continuous column distillation
3. Batch distillation
4. Absorption
5. Stripping and
6. Extraction
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Vapor-Liquid Phase Equilibrium
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Concept of Equilibrium
Streams leaving a stage are in equilibrium.
Q: What do we mean by equilibrium?
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Concept of Equilibrium contd…
• In phase equilibrium, the rate at which each species is vaporizing, is equal
to the rate at which it is condensing.
• Although on a molecular scale nothing has stopped, on the macroscopic
scale, where we usually observe processes, there are no further changes in
temperature, pressure, or composition.
Equilibrium conditions can be conveniently subdivided into
thermal,
mechanical, and
chemical potential equilibrium
Tliq=Tvap
Pliq=Pvap
(Chemical Potential i)liq= (Chemical Potential i)vap
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Form and Sources of Equilibrium Data
1. Experimental data
Table
Graphical presentation
DePriester Chart
2. Simple models for VLE
Raoult’s law, Henry’s law constant
Activity Coefficient
3. Relative volatility
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Experimental Measurement Equipment
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Data Generation from Experimental Measurement
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Data Generation from Experimental
Measurement contd…
Very often only the composition of the most volatile component
(ethanol in this case) will be given.
The mole fraction of the less volatile component can be found
from the following equation.
Equilibrium depends on pressure.
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Degrees of Freedom (DOF)
We see in Table 2-1 that if pressure and temperature are set,
then there is only one possible vapor composition for ethanol,
yEtoh, and one possible liquid composition, xEtoh.
Thus we cannot arbitrarily set as many variables as we might
wish.
The number of variables that we can arbitrarily specify is
known as the degrees of freedom (DOF).
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Gibbs Phase Rule
For non-reacting systems the resulting Gibbs’ phase rule is -
where F = degrees of freedom,
C = number of components, and
P = number of phases.
For the binary system, C = 2 (ethanol and water) and P = 2 (vapor and liquid).
Thus, F=2−2+2=2
When pressure and temperature are set, all the degrees of freedom are used,
and at equilibrium all compositions are determined from the experiment.
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Graphical Representation of Binary VLE
Binary VLE data can be represented graphically in several ways.
The most convenient forms are
T-x-y
y-x, and
H-x-y diagrams.
These figures all represent the same data and can be converted from
one form to another.
The simplest such graph is the y vs. x graph. This diagram is also
called a McCabe-Thiele diagram when it is used for calculations.
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x-y Diagram
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T-x-y Diagram
Liquid and vapor in equilibrium
must be at the same T;
These streams will be
connected by a horizontal
isotherm as shown in the Figure
for xEtoh = 0.2.
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H-x-y Diagram (Ponchon-Savarit diagram)
The isotherms shown in H-x-y diagram show the change in enthalpy at constant T
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as weight fraction varies.
H-x-y Diagram: Drawing an Isotherm
Go vertically from the saturated liquid curve to the
auxiliary line. Then go horizontally to the saturated
vapor line.
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Isotherms from y-x and T-x-y Diagram
Isotherms on the enthalpy-composition diagram can also be
generated from the y-x and T-x-y diagrams.
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Azeotrope
Q: Definition of azeotrope?
The ethanol-water system shows an azeotrope, i.e., the liquid and vapor are of
exactly the same composition at a certain temperature. For ethanol, the
composition is -
(0.8943 mol fraction, at 78.15°C).
Q: What is minimum-boiling azeotrope?
The azeotrope boils at 78.15°C, which is less than the boiling point of
either pure ethanol (78.370C)
or pure water (1000C).
The azeotrope
location is a function
of pressure.
Below 70 mmHg no
azeotrope exists for
ethanol-water.
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Azeotrope contd…
Maximum-boiling azeotropes
It is rare and only the T-x-y diagram will look significantly different.
Azeotrope T is greater than
both of the pure component.
Example
HCl at a concentration of
20.2% and 79.8% water (by
mass)
BP of HCl = -850C
BP of Water = 1000C
Azeotrope T = 1100C
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Graphical mass balances for equilibrium systems
To determine the amount of liquid and vapor formed when a two-
phase mixture separates, mass balances are required.
A two-phase mixture at point A is allowed to separate into liquid at B
and vapor at C.
A,B,C are on the same isotherm.
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Graphical mass balances for equilibrium systems contd…
Lever-arm rule
The value of L/V can be used to determine the amounts of liquid
and vapor.
The seesaw is a convenient way to remember the form of the
lever-arm rule.
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Distribution Coefficient or K Value
K value depends on T, P and composition. But, in many cases, K is
independent of composition.
For light hydrocarbons, the approximate K values can be determined
from monographs prepared by DePriester.
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DePriester
Chart
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DePriester
Chart
contd…
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Boiling point from DePriester Chart
If only one component is present, then y=1.0 and x=1.0.
So, Ki = y/x = 1
This gives a simple way of determining the boiling T of a pure
compound at any P.
At BP, K=1. If P is specified, then a
straight line can be drawn through
these two points in DePriester Chart.
It will go through the BP in T axis.
Example: BP of iC4 when P = 150 kPa
is -1.50C. 31
Raoult's Law
Two major assumptions required to reduce VLE calculations to
Raoult's law are:
– The vapor phase is an ideal gas.
– The liquid phase is an ideal solution
Antoine equation
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Raoult's Law : Applicability
• It can be applied only to species for which a vapor pressure is
known, and this requires that the species be "subcritical," i.e.,
that the temperature of application be below the critical
temperature of the species.
• An important and useful feature of Raoult's law is that it is
valid for any species present at a mole fraction approaching
unity, provided only that the vapor phase is an ideal gas.
Chemical similarity of the constituent species is not here a
requirement.
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Henry’s Law
For a species present as a very dilute solute in the liquid phase,
that the partial pressure of the species in the vapor phase is
directly proportional to its liquid-phase mole fraction. Thus,
according to Henry's law -
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Liquid-phase activity coefficient
Non-idealities in the liquid phase are taken into account with a
liquid-phase activity coefficient, γi
γi = γi (T, P, concentration)
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Relative Volatility
• In order to separate a binary mixture using distillation process, there
must be a differences in volatilities of the components.
• For a binary mixture of A and B
Volatility of A = pA / xA Volatility
of B = pB / xB
where pi is the partial pressure of the component and xi is
the liquid mole fraction.
• Relative volatility is the ratio of volatility of A (MVC) over volatility of
B (LVC) and a measure of separability of A and B.
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Relative Volatility contd…
The K values are strongly dependent on T and thus vary greatly in
distillation column. Much of the T dependence is removed if the ratio of
K values is taken.
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Special Case: Constant Relative Volatility,
• If the value of is known and is
constant, we can use it to
obtain the equilibrium curve.
This can be done by
rearranging the equation for
relative volatility, to obtain the
function y = f(x) or x = f(y).
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