2 Distillation PDF

Mass Transfer (ChE - 392)
2-Distillation
Saeed GUL, Dr.Techn, M.Sc. Engg.

Professor
Department of Chemical Engineering,

University of Engineering & Technology Peshawar, PAKISTAN
Introduction
 Distillation is the technique of preferential separation of the

more volatile component(s) from the less volatile ones in a feed
solution by partial vaporization of the feed followed by
condensation.
 The vapor produced is richer in the more volatile component(s).
The distribution of the components in the two phases is
governed by the vapor–liquid equilibrium relationship.
 Only partial separation of the components can be achieved in
this way.
 In order to have a larger degree of separation, multistage
contact between the vapor and the liquid phases is arranged in
a suitable device called a ‘distillation column
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Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Introduction
 Distillation is the most widely used separation process in the

chemical industry.
 It is normally used to separate liquid mixtures into two or
more vapor or liquid products with different compositions.
 Distillation is an equilibrium stage operation. In each stage, a
vapor phase is contacted with a liquid phase and mass is
transferred from vapor to liquid and from liquid to vapor.
 The less volatile, "heavy" or "high boiling", components
concentrate in the liquid phase; the more volatile, "light",
components concentrate in the vapor.
 By using multiple stages in series with recycle, separation can
be accomplished.
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Introduction
 The vertical cylindrical column provides, in a compact form
and with the minimum of ground requirements, a large
number of separate stages of vaporization and condensation.
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Introduction
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VAPOUR–LIQUID EQUILIBRIUM
 The composition of the vapor in

equilibrium with a liquid of
given composition is determined
experimentally using an
equilibrium still
 The results are conveniently
shown on a temperature–
composition diagram
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Vapor composition as a function of liquid
composition at constant pressure
For distillation purposes it is more convenient to plot y against
x at a constant pressure, since the majority of industrial
distillations take place at substantially constant pressure.
Positive Azeotrope Negative Azeotrope
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Dalton’s Law
The partial pressure PA of component A in a mixture of vapors is
the pressure that would be exerted by component A at the
same temperature, if present in the same volumetric
concentration as in the mixture.
By Dalton’s law of partial pressures,
P = ΣPA
that is the total pressure is equal to the summation of the partial
pressures. Since in an ideal gas or vapor the partial pressure is
proportional to the mole fraction of the constituent, then:
PA = yAP
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Raoult’s Law
Raoult's Law describes the behavior of vapors above a mixture of
liquids; in an ideal scenario the partial pressure of each component
present in the mixture is equal to its pure vapor pressure multiplied by
its mole fraction in solution.
For an ideal mixture, the partial pressure is related to the concentration
in the liquid phase by Raoult’s law which may be written as:
PA = P◦AxA
where P◦A is the vapor pressure of pure A at the same temperature.
This relation is usually found to be true only for high values of xA, or
correspondingly low values of xB, although mixtures of organic isomers
and some hydrocarbons follow the law closely.
For low values of xA, a linear relation between PA and xA again exists,
although the proportionality factor is Henry’s constant H, and not the
vapor pressure P0A of the pure material.
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For a liquid solute A in a solvent liquid B, Henry’s law takes
the form: PA = HxA
If the mixture follows Raoult’s law, then the vapour pressure of
a mixture may be obtained graphically from a knowledge of
the vapour pressure of the two components.
OA represents the partial pressure
PA of A in a mixture, and CB the
partial pressure of B, with the total
pressure being shown by the line
BA. In a mixture of composition D,
the partial pressure PA is given by
DE, PB by DF, and the total pressure
P by DG
Figure : Partial pressures of ideal mixtures
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Applications of Raoult’s & Dalton’s Law
Over the range OC the mixture

follows Henry’s law, and over BA
it follows Raoult’s law
Although most mixtures show

wide divergences from ideality,
one of the laws is usually
followed at very high and very
low concentrations.
Figure : Partial pressures of non-ideal mixtures
If the mixture follows Raoult’s law, then the values of yA for

various values of xA may be calculated from a knowledge of the
vapor pressures of the two components at various temperatures
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Applications of Raoult’s & Dalton’s Law
If the mixture follows Raoult’s law, then the values of yA for
various values of xA may be calculated from a knowledge of the
vapor pressures of the two components at various temperatures
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Example 11.1
The vapour pressures of n-heptane and toluene at 373 K are
106 and 73.7 kN/m2 respectively. What are the mole fractions
of n-heptane in the vapour and in the liquid phase at 373 K if
the total pressure is 101.3 kN/m2?
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Relative volatility
The relationship between the composition of the vapor yA and

of the liquid xA in equilibrium may also be expressed in a way,
which is particularly useful in distillation calculations. If the
ratio of the partial pressure to the mole fraction in the liquid is
defined as the volatility, then:
The ratio of these two volatilities is known as the relative

volatility α given by:
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Relative volatility
Substituting PyA for PA, and PyB for PB:
or
This gives a relation between the ratio of A and B in the vapor to

that in the liquid and is useful in the calculation of plate
enrichment
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Relative volatility
Since with a binary mixture yB = 1 − yA, and xB = 1 − xA then:
Use for constructing

Equilibrium curve
This relation enables the composition of the vapor to be

calculated for any desired value of x, if α is known. For
separation to be achieved, α must not equal 1 and, considering
the more volatile component, as α increases above unity, y
increases and the separation becomes much easier
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Relative volatility
From the definition of the volatility of a component, it is seen

that for an ideal system the volatility is numerically equal to the
vapor pressure of the pure component. Thus
the relative volatility α may be expressed as:
This also follows by applying equation 11.1 from which

PA/PB = yA/yB, so that:
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Relative volatility
Whilst α does vary somewhat with temperature, it remains
remarkably steady for many systems, and a few values to
illustrate this point are given in Table
It may be seen that α increases as the temperature falls, so that

it is sometimes worthwhile reducing the boiling point by
operating at reduced pressure.
FRANK points out, this is valid if the relative volatilities at the top
and bottom of the column differ by less than 15 per cent.
If they differ by more than this amount, the equilibrium curve
must be constructed incrementally by calculating the relative
volatility at several points along the column
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Relative volatility
The figure shows several

equilibrium curves with
Increasing the pressure or different values of the
temperature, decreases the relative volatility. Note that
relative volatility. Q1is high the greater the value of α,
temperature/pressure while the greater is the
it decreases towards Q4 separation area
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METHODS OF DISTILLATION
TWO COMPONENT MIXTURES
Three main methods are used in distillation practice:
 Differential distillation.
 Flash or equilibrium distillation
 Rectification.
Of these, rectification is much the most important, and it differs

from the other two methods in that part of the vapor is
condensed and returned as liquid to the still, whereas, in the
other methods, all the vapor is either removed as such, or is
condensed as product
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Differential Distillation
Batch distillation without reflux is often called differential

distillation. Because there is no reflux, the vapor product is in
equilibrium with the liquid residue in the tank at any given time.
In this process the

vapor formed on boiling
the liquid is removed at
once from the system.
As this process consists
of only a single stage, a
complete separation is So ,XO
impossible unless the
relative volatility is
infinite.
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Since the vapor produced is richer in the more volatile component

than the liquid, it follows that the liquid remaining becomes steadily
weaker in this component, with the result that the composition of
the product progressively alters.
Thus, whilst the vapor formed over a short period is in equilibrium

with the liquid, the total vapor formed is not in equilibrium with the
residual liquid.
At the end of the process the liquid which has not been vaporized is
removed as the bottom product. The analysis of this process was first
proposed by RAYLEIGH
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Modelling Differential Distillation
If S is the number of moles of material in the still,

x is the mole fraction of component A
dS, is the amount which is vaporized, containing a mole fraction y of A
The rate of depletion of liquid is equal to the rate of distillate output:

Initial Amount in Still = Amount Vaporized + Amount left in Still
S = dS + (S - dS)
xS = ydS + (x - dx)(S - dS)
xS = ydS + xS – xdS – Sdx + dxdS
Neglecting the term dxdS: xS = ydS + xS – xdS – Sdx + dxdS
Sdx = ydS – xdS

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Modelling Differential Distillation
Sdx = ydS − xdS Numerical integration
dS ( y − x) = Sdx
dS  dx 
=  
S  y−x
1/(y – x)
• •
Rayleigh equation x,final x xinitial
The integral on the right-hand side of this equation may be solved

graphically if the equilibrium relationship between y and x is available.
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In some cases a direct integration is possible Thus, if over the

range concerned the equilibrium relationship is a straight line of
the form y = mx + c, then:
𝑆𝑆 𝑥𝑥 𝑑𝑑𝑑𝑑 𝑆𝑆 𝑥𝑥 𝑑𝑑𝑑𝑑
𝑙𝑙𝑙𝑙 =∫𝑥𝑥 𝑙𝑙𝑙𝑙 =∫𝑥𝑥
𝑆𝑆0 0 𝑚𝑚𝑚𝑚+𝑐𝑐−𝑥𝑥 𝑆𝑆0 0 𝑚𝑚𝑚𝑚−𝑥𝑥+𝑐𝑐
𝑆𝑆 𝑥𝑥 𝑑𝑑𝑑𝑑
𝑙𝑙𝑙𝑙 =∫𝑥𝑥
𝑆𝑆0 0 𝑥𝑥(𝑚𝑚−1)+𝑐𝑐
𝑆𝑆 1 𝑥𝑥 (𝑚𝑚−1)𝑑𝑑𝑑𝑑
Multiplying and Divided by (m-1) 𝑙𝑙𝑙𝑙 = ∫
𝑆𝑆0 𝑚𝑚−1 𝑥𝑥0 𝑥𝑥(𝑚𝑚−1)+𝑐𝑐
𝑆𝑆 1 𝑥𝑥
𝑙𝑙𝑙𝑙 = 𝑙𝑙𝑙𝑙 𝑚𝑚 − 1 𝑥𝑥 + 𝑐𝑐 𝑥𝑥0
𝑆𝑆0 𝑚𝑚−1
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𝑆𝑆 1 𝑥𝑥
𝑙𝑙𝑙𝑙 = 𝑙𝑙𝑙𝑙 𝑚𝑚 − 1 𝑥𝑥 + 𝑐𝑐 𝑥𝑥0
𝑆𝑆 1
𝑙𝑙𝑙𝑙 = [⌊ln(𝑚𝑚 − 1)𝑥𝑥 + 𝑐𝑐⌋ - [𝑙𝑙𝑙𝑙 𝑚𝑚 − 1 𝑥𝑥0 + 𝑐𝑐]]
𝑆𝑆 1 𝑚𝑚−1 𝑥𝑥+𝑐𝑐]
𝑙𝑙𝑙𝑙 = 𝑙𝑙𝑙𝑙
𝑆𝑆0 𝑚𝑚−1 𝑚𝑚−1 𝑥𝑥0+𝑐𝑐]
1
𝑆𝑆 𝑚𝑚−1 𝑥𝑥+𝑐𝑐] 𝑚𝑚−1
𝑙𝑙𝑙𝑙 =𝑙𝑙𝑙𝑙
𝑆𝑆0 𝑚𝑚−1 𝑥𝑥0+𝑐𝑐]
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1 1
𝑆𝑆 𝑚𝑚−1 𝑥𝑥+𝑐𝑐] 𝑚𝑚−1 𝑆𝑆 𝑚𝑚−1 𝑥𝑥+𝑐𝑐] 𝑚𝑚−1
𝑙𝑙𝑙𝑙 =𝑙𝑙𝑙𝑙 =
𝑆𝑆0 𝑚𝑚−1 𝑥𝑥0+𝑐𝑐] 𝑆𝑆0 𝑚𝑚−1 𝑥𝑥0+𝑐𝑐]
𝑆𝑆 𝑚𝑚−1 𝑥𝑥 𝑚𝑚−1 +𝑐𝑐] 𝑆𝑆 𝑚𝑚−1 mx + c − x

= =
𝑆𝑆0 𝑥𝑥0 𝑚𝑚−1 +𝑐𝑐] 𝑆𝑆0 mx0 + c − x0
𝑆𝑆 𝑚𝑚−1 y−x
=
𝑆𝑆0 y0 − x0
From this equation the amount of liquid to be distilled in order to
obtain a liquid of given concentration in the still may be calculated,
and from this the average composition of the distillate may be
found by a mass balance.
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Alternatively, if the relative volatility is assumed constant over
the range concerned, then y = αx/(1 + (α − 1)x), may be
substituted in equation:
This leads to the solution:

This image cannot currently be displayed.
As this process consists of only a single stage, a complete separation

is impossible unless the relative volatility is infinite.
Application is restricted to conditions where a preliminary separation
is to be followed by a more rigorous distillation, where high purities
are not required, or where the mixture is very easily separated
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Flash or Equilibrium Distillation
Flash or equilibrium distillation,
frequently carried out as a
continuous process, consists of
vaporizing a definite fraction of the
liquid feed in such a way that the
vapor evolved is in equilibrium
with the residual liquid
The feed is usually pumped through a fired heater and enters the still
through a valve where the pressure is reduced.
The still is essentially a separator in which the liquid and vapor
produced by the reduction in pressure have sufficient time to reach
equilibrium.
The vapor is removed from the top of the separator and is then
usually condensed, while the liquid leaves from the bottom.
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Modelling Flash or equilibrium distillation
In a typical pipe still where, for example, a crude oil might enter at
440 K and at about 900 kN/m2, and leave at 520 K and 400 kN/m2,
some 15 per cent may be vaporized in the process.
The vapor and liquid streams may contain many components in such
an application, although the process may be analyzed simply for a
binary mixture of A and B as follows:
If F = moles per unit time of feed of mole fraction xf of A,
V = moles per unit time of vapor formed with y the mole fraction of A
S = moles per unit time of liquid with x the mole fraction of A,
then an overall mass balance gives:

F=V+S
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Modelling Flash or equilibrium distillation
and for the more volatile component:
This is an "operating line" equation -- plotted on a graph whose

coordinates are vapor composition vs. liquid composition, it
yields a straight line. To plot the line, you only need to know the
fraction vaporized (to get the slope) and the feed composition
(to get the intercept).
Slope of the line =
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Example 11.6
An equimolar mixture of benzene and toluene is subjected to
flash distillation at 100 kN/m2 in the separator. Using the
equilibrium data given in Figure 11.9, determine the composition
of the liquid and vapor leaving the separator when the feed is 25
per cent vaporized. For this condition, the boiling point diagram
in Figure 11.10 may be used to determine the temperature of the
exit liquid stream.
The fractional vaporization = V/F = f (say)
The slope of equation is:
When f = 0.25, the slope is therefore:
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Example 11.6
and the construction is made as shown in Figure to give
x = 0.42 and y = 0.63.
From the boiling point diagram, in Figure the liquid temperature
when x = 0.42 is seen to be 366.5 K.
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Example Flash Distillation
An equimolar mixture of benzene and toluene is subjected to flash

distillation at a pressure of 1 bar in the separator. Determine the
compositions (in mole fraction benzene) of the liquid and vapour
leaving the separator when the feed is 25% vaporized.
 Estimate the temperature in the separator.
 What are the concentrations in the vapour and liquid, and the
separator temperature, the feed is:
 0% vapourised
 50% vapourised
 75% vapourised
 100% vapourised ?
Plot the operating lines for each of these cases and discuss how the
operating lines change as f changes.
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Equilibrium data for benzene-toluene system at 1 bar is given in the Table below
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The operating line equation is as follows, with f = 0.25 (25% of feed is vaporized) and
xF = 0.50 (equimolar mixture, MVC = benzene)
Flash distillation operating line
Locate the first point ( x = xF = 0.50, y = xF = 0.50 ) on the 45o diagonal.
Locate the second point using the operating line equation.
Plot the operating line by joining the 2 points. Intersection between the operating
line and equilibrium curve gives the solution for xB and yD.
From graph - this is shown as

case (b) - we have:
xB = 0.44, yD = 0.66
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The separator temperature can be estimate by interpolation or
determined from the equilibrium phase diagram. As shown in the
Figure, this is approximately 92.4 oC.
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The same calculations can be repeated for the other scenarios and
the results are tabulated in the following Table:
We can see from the results that there is a trade-off between

quantity and concentration: the higher the fraction of feed vaporized
(i.e. the larger the vapor product), the lower the mole fraction MVC
in the vapor.
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Example Differential Distillation
A liquid feed consisting of 1200 gmoles of mixture containing 30%
naphthalene and 70% dipropylene glycol is differentially distilled at
100 mm Hg pressure and final distillate contains 55% of the feed
solution. The VLE data are:
x 8.4 11.6 28.0 50.6 68.7 80.6 88
y 22.3 41.1 62.9 74.8 80.2 84.4 88
 determine the amount of distillate

 determine the concentration of naphthalene in residue and distillate
Calculations:
F = 1200 gmol
F=D+W
D = 0.55 x 1200 = 660 gmol
Amount of distillate, D = 660 gmol
W = 1200 - 660 = 540 gmol
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From Rayleigh's equation
xW is calculated from the graphical method, for which the integral

term is the above equation is balanced:
ln (F/W) = ln (1200/540) = 0.7985
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The area of 0.7985 is obtained for xW = 0.07
F xF = D yD,avg + W xW
660 x yD,avg = 1200 x 0.3 - 540 x 0.07
yD,avg = 0.4882
Concentration of naphthalene in residue = 7%
Concentration of naphthalene in distillate = 48.82%
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Rectification
The fractionating process
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Number of plates required in a
distillation column
In order to develop a method for the design of distillation units to
give the desired fractionation, it is necessary, in the first instance
 To develop an approach which enables the necessary number of
trays to be calculated.
 The heat and material flows over the trays, the condenser, and the
reboiler must be established.
 Thermodynamic data are required to establish how much mass
transfer is needed to establish equilibrium between the streams
leaving each tray.
 The required diameter of the column will be dictated by the
necessity to accommodate the desired flowrates, to operate within
the available drop in pressure, while at the same time effecting the
desired degree of mixing of the streams on each tray.
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Balance over a Plate
Four streams of are involved:

plate n receives liquid Ln+1 from
plate n + 1 above, and vapor Vn−1
from plate n − 1 below
Plate n supplies liquid Ln to plate

n − 1, and vapor Vn to plate n + 1.
The action of the plate is to bring

about mixing so that the vapor Vn,
of composition yn, approaches
equilibrium with the liquid Ln, of
composition xn . Material balance over a plate
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Heat balance over a plate
A heat balance across plate n may be written as:
 This equation is difficult to handle for the majority of mixtures,

and some simplifying assumptions are usually made. Thus:
 with good lagging, the heat losses will be small and may be
neglected
 for an ideal system the heat of mixing is zero. For such
mixtures, the molar heat of vaporization may be taken as
constant and independent of the composition.
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Heat Balance over a Plate
• Thus, one mole of vapor Vn−1 on condensing releases

sufficient heat to liberate one mole of vapor Vn.
• It follows that Vn = Vn−1, so that the molar vapor flow is
constant up the column unless material enters or is
withdrawn from the section.
• The temperature change from one plate to the next will be
small, and HLn may be taken as equal to HLn+1.
Applying these simplifications to the equation, it is seen that

Ln = Ln+1, so that the moles of liquid reflux are also constant in
this section of the column. Thus Vn and Ln are constant over
the rectifying section, and Vm and Lm are constant over the
stripping section.
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Heat Balance over a Plate
 For these conditions there are two basic methods for

determining the number of plates required. The first is due to
SOREL and later modified by LEWIS, and the second is due to
MCCABE and THIELE. The Lewis method will be used here for
binary systems, (Although it can be used for calculations
involving multi-component mixtures) .This method is also the
basis of modern computerized methods.
 The McCabe–Thiele method is particularly important since it
introduces the idea of the operating line which is an important
common concept in multistage operations.
 When the molar heat of vaporization varies appreciably and the
heat of mixing is no longer negligible, these methods have to be
modified, and alternative techniques are available for this.
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Calculation of number of plates
using the Lewis–Sorel method
material balance above plate n,

indicated by the loop I
balance for the MVC gives:
Since the molar liquid overflow

is constant, Ln+1 may be replaced
by Ln and:
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Similarly, a material balance for
the total streams and for the
more volatile component from
the bottom to above plate m, as
indicated by the loop II and
noting that Lm = Lm+1 gives:
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Example 11.7
A mixture of benzene and toluene containing 40 mole per cent
benzene is to be separated to give a product containing 90 mole
per cent benzene at the top, and a bottom product containing
not more than 10 mole per cent benzene. The feed enters the
column at its boiling point, and the vapor leaving the column
which is condensed but not cooled, provides reflux and product.
It is proposed to operate the unit with a reflux ratio of 3
kmol/kmol product. It is required to find the number of
theoretical plates needed and the position of entry for the feed.
The equilibrium diagram at 100 kN/m2 is shown in Figure
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Thus, the top operating line from equation 11.35 is:
Since the feed is all liquid at its boiling point, this will all run down
as increased reflux to the plate below.
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The composition xt of the liquid on the top plate is found
from the equilibrium curve and, since it is in equilibrium with
vapor of composition, yt = 0.90, xt = 0.79.
This last value of composition is sufficiently near to that of the

feed for the feed to be introduced on plate (t − 3). For the lower
part of the column, the operating line equation (ii) will be used.
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This liquid xt−7 is slightly weaker than the minimum required

and it may be withdrawn as the bottom product. Thus, xt−7 will
correspond to the reboiler, and there will be seven plates in the
column.
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The method of McCabe and Thiele
McCABE and THIELE pointed out that, since these equations

represent straight lines connecting yn with xn+1 and ym with xm+1,
they can be drawn on the same diagram as the equilibrium curve
to give a simple graphical solution for the number of stages
required.
If xn+1 = xd in equation , then:
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and this equation represents a line passing through the point

yn = xn+1 = xd. If xn+1 is put equal to zero, then yn = Dxd/Vn, giving a
second easily determined point.
The top operating line is
therefore drawn through two
points of coordinates (xd, xd )
and (0, (Dxd/Vn)).
For the bottom operating line,
Equation
if xm+1 = xw, then:
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Since Vm = Lm − W, it follows that ym = xw. Thus the bottom

operating line passes through the point C, that is (xw, xw), and
has a slope Lm/Vm. When the two operating lines have been
drawn in, the number of stages required may be found by
drawing steps between the operating line and the equilibrium
curve
Limitations of McCabe & Thiele Method
The method does have limitations, however, and should not be
employed when the relative volatility is less than 1.3 or greater
than 5, when the reflux ratio is less than 1.1 times the
minimum, or when more than twenty-five theoretical trays are
required. In these circumstances, the Ponchon–Savarit method
should be used.
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Example 11.8. The McCabe-Thiele Method
Example 11.7 is now

worked using this method.
Thus, with a feed
composition, xf = 0.4, the
top composition, xd is to
have a value of 0.9 and
the bottom composition,
xw is to be 0.10. The reflux
ratio, Ln/D = 3.
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Plate Efficiency
The number of ideal stages required for a desired separation may
be calculated by one of the methods discussed previously, although
in practice more trays are required than ideal stages
The ratio n/np of the number of ideal stages n to the number of
actual trays np represents the overall efficiency E of the column,
which may be 30–100 %
The main reason for loss in efficiency is that the kinetics for the
rate of approach to equilibrium, and the flow pattern on the plate,
may not permit an equilibrium between the vapor and liquid to be
attained
The proportion of liquid and vapor, and the physical properties of
the mixtures on the trays, will vary up the column, and conditions
on individual trays must be examined (suggested by MURPHREE)
60
13 February 2019 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Plate Efficiency
For a single ideal tray, the vapor
leaving is in equilibrium with the
liquid leaving, and the ratio of the
actual change in composition
achieved to that which would
occur if equilibrium between yn
and xn were attained is known as
the Murphree plate efficiency EM
the plate efficiency expressed in
vapor and liquid terms is given by:
where ye is the composition of the vapor that would be in equilibrium

with the liquid of composition xn actually leaving the plate
61
13 February 2019 Dr. Saeed GUL, Department of Chemical Engineering, UET Peshawar, Pakistan
Flow through feed plate for various
feed conditions
Flow through feed plate for various feed conditions: (a) feed cold
liquid; (b) feed saturated liquid; (c) feed partially vaporized; (d) feed
saturated vapor; (e) feed superheated vapor.
13 February 2019 62
The “q”
All five of the feed types can be characterized by the use of a

single factor, denoted by q and defined as:
the moles of liquid flow in the stripping section that result from
the introduction of each mole of feed.
Then q has the following numerical limits for the various
conditions:
Cold feed, q > 1
 Feed at bubble point (saturated liquid), q = 1
 Feed partially vapor, 0 < q < 1
 Feed at dew point (saturated vapor), q = 0
 Feed superheated vapor q < 0
13 February 2019 63
Calculation of q
If the feed is a mixture of liquid and vapor, q is the fraction that is
liquid. Such a feed may be produced by an equilibrium flash
operation, so q = 1 - f,
where f is the fraction of the original stream vaporized in the flash.
The value of q for cold-liquid feed is found from the equation
C PL (Tb − TF )
q = 1+
λ
C PV (TF − Td )
For superheated vapor the equation is q = −
λ
where cpL , cpv = specific heats of liquid and vapor, respectively
TF = temperature of feed
Tb ,Td = bubble point and dew point of feed, respectively
λ = heat of vaporization
13 February 2019 64
Slope of q-Line
13 February 2019 65
Equation of q-Line
If the two operating lines intersect at a point with coordinates
(xq, yq ), then from equations of operating lines:
Vnyq = Lnxq + Dxd
and: Vmyq = Lmxq − Wxw F
or: yq(Vm − Vn) = (Lm − Ln)xq − (Dxd + Wxw) Vn
n
A material balance over the feed plate gives: Lm
F + Ln + Vm = Lm + Vn Vm
or: Vm − Vn = Lm − Ln − F
A material balance of the more volatile component over the
whole column gives:
Fxf = Dxd + Wxw
13 February 2019 66
Equation of q-Line
Thus, from equation

yq(Vm − Vn) = (Lm − Ln)xq − (Dxd + Wxw)
Fxf = Dxd + Wxw
This equation is commonly known as the equation of the q-line.
13 February 2019 67
Limiting Cases
Frequently, when analyzing or designing a process, it is useful to
look at limiting cases to assess the possible values of process
parameters.
In distillation analysis, separation of a pair of components can be
improved by increasing the number of stages while holding reflux
constant, or by increasing the reflux flow for a given number of
stages.
This tradeoff sets up two limiting cases:
 Total Reflux (minimum ideal stages)
 Minimum Reflux (infinite ideal stages)
13 February 2019 68
Limiting Cases
The design tradeoff between reflux and stages is the standard
economic optimization problem chemical engineers always
face -- balancing capital costs (the number of trays to be built)
vs. the operating cost (the amount of reflux to be recirculate).
A good design will operate near a cost optimum reflux ratio
13 February 2019 69
The importance of the reflux ratio
Influence on the number of plates required
The ratio Ln/D, that is the ratio of the top overflow to the quantity of
product, is denoted by R, and this enables the equation of the
operating line to be expressed in another way, which is often more
convenient. Thus, introducing R in equation
If R is known, the top line is most easily drawn by joining point A (xd, xd )
to B (0, xd/(R + 1)). This will avoid the calculation of the actual flow rates
Ln and Vn, when the number of plates only is to be estimated.
13 February 2019 70
Total Reflux
The total reflux condition represents
operation with no product removal.
All the overhead vapor is condensed
and returned as reflux.
Consequently, the reflux ratio (L/D)
is infinite. This, in turn, makes the
operating lines the 45 degree With
the operating lines on the diagonal.
 The operating lines are as far as they can get from the
equilibrium curve,
 so if the number of plates are stepped off using the diagonal
and the equilibrium curve,
 the number of theoretical stages will be a minimum.
13 February 2019 71
The number of plates at total reflux.
Fenske’s method
The Fenske Equation is a method for determining the minimum
number of trays required for a given separation. The Fenske
equation applies to distillation systems with constant relative
volatility
d = Distillate
s = Bottom
If the relative volatility varies through a column because of

temperature effects, it is possible to use a geometric mean value
of the relative volatility and the Fenske equation to get an
approximate value for the number of stages.
13 February 2019 72
Minimum Reflux
Minimum Reflux
The minimum reflux condition
represents the theoretical
opposite of total reflux -- an
infinite number of ideal
separation stages. In this case, the
intersection of the operating lines
lies on the equilibrium curve
itself. Thus, the distance between
the equilibrium curve and the
operating lines is at its minimum, the stepping triangles become
very small, there is no gap between the equilibrium curve and
the intersection point, so you cannot step past the feed point.
13 February 2019 73
Minimum Reflux
reduction in R will eventually bring

the operating line to AE, where an
infinite number of stages is needed
to pass from xd to xf . These
conditions are known as minimum
reflux
Two important deductions may be

made. Firstly that the minimum
number of plates is required for a
given separation at conditions of
total reflux, and secondly that there
is a minimum reflux ratio below which it is impossible to obtain the desired
enrichment, however many plates are used.
13 February 2019 74
Minimum Reflux
Figure represents conditions

where the q-line is vertical,
and the point E lies on the
equilibrium curve and has co-
ordinates (xf , yf ). The slope of
the line AE is then given by:
13 February 2019 75
Minimum Reflux
If the q-line is horizontal as
shown in Figure 11.18, the
enrichment line for minimum
reflux is given by AC, where C
has coordinates (xc, yc). Thus:
13 February 2019 76
Underwood Method for calculating
Minimum Reflux ratio
For ideal mixtures, or where over the concentration range
concerned the relative volatility may be taken as constant, Rm
may be obtained analytically from the physical properties of
the system as discussed by UNDERWOOD
Under conditions of minimum

reflux, a column has to have an
infinite number of plates
13 February 2019 77
Example 11.9
For the separation of a mixture of benzene and toluene,
considered in Example 11.7, xd = 0.9, xw = 0.1, and xf = 0.4. If the
mean volatility of benzene relative to toluene is 2.4, what is the
number of plates required at total reflux?
Solution
The number of plates at total reflux is given by:
Thus the number of theoretical plates in the column is 4, a

value which is independent of the feed composition
13 February 2019 78
Example 11.9
If the feed is liquid at its boiling point, then the minimum reflux
ratio Rm is given by:
Using the graphical construction with yf = 0.61, the value of Rm is:
13 February 2019 79
Selection of economic reflux ratio
The cost of a distillation unit includes
the capital cost of the column
determined largely by the number
and diameter of the plates,
and the operating costs, determined

by the steam and cooling water
requirements.
The depreciation charges may be

taken as a percentage of the capital
cost, and the two together taken as
the overall charges.
13 February 2019 80
The reduction in the required number of plates as R is
increased beyond Rm will tend to reduce the cost of the
column. For a column separating a benzene–toluene mixture,
for example, where xf = 0.79, xd = 0.99 and xw = 0.01, the
numbers of theoretical plates as given by the McCabe–Thiele
method for various values of R are given as follows. The
minimum reflux ratio for this case is 0.81.
Thus, an increase in R, at values near Rm, gives a marked

reduction in the number of plates, although at higher values
of R, further increases have little effect on the number of
plates
13 February 2019 81
Increasing the reflux ratio from Rm therefore affects the
capital and operating costs of a column as follows:
 The capital cost initially falls since the number of plates falls
off rapidly at this stage.
 The capital cost rises at high values of R, since there is then
only a very small reduction in the number of plates, although
the diameter, and hence the area, continually increases
because the vapor load becomes greater. The associated
condenser and reboiler will also be larger and hence more
expensive.
There is no simple relation between Rm and the optimum value,
although practical values are generally 1.1–1.5 times the
minimum
13 February 2019 82
Multiple feeds and side streams
In general, a side stream is defined as

any product stream other than the
overhead product and the residue
such as the streams S’, S”, and S’” in
Figure .
In a similar way, F1 and F2 are
separate feed streams to the column.
Side streams are most often removed
with multi-component systems,
although they may be used with
binary mixtures.
13 February 2019 83
Multiple feeds and side streams
A binary system is now considered,

with one side stream, as shown in
Figure. S represents the rate of
removal of the side stream and xs its
composition.
Assuming constant molar overflow,
then for the part of the column above
the side stream the operating line is
given by:
13 February 2019 84
Multiple feeds and sidestreams
Balances for the part of the tower

above a plate between the feed plate
and the sides tream give:
Since the side stream is normally

removed as a liquid, Ls = (Ln − S)
and Vs = Vn.
13 February 2019 85
Multiple feeds and sidestreams
13 February 2019 86
Batch distillation with rectification
In many instances processes are carried out in

batches, and it is more convenient to distil
each batch separately. In these cases the whole
of a batch is run into the boiler of the still and,
on heating, the vapor is passed into a
fractionation column. As with continuous
distillation, the composition of the top product
depends on:
 the still composition,
 the number of plates in the column
 and on the reflux ratio used
When the still is operating, since the top
product will be relatively rich in the more
volatile component, the liquid remaining in the
still will become steadily weaker in this
component.
13 February 2019 87
Batch distillation with rectification
OMB: Vj+1 = Lj + D
V1, y1 CMB: Vj+1yj+1 = Ljxj + DxD
L0, x0 D, xD • both are time-dependent
stage 1 • either D or xD (or both) change over the
y1 = x0 = xD course of the distillation
y1 ≠ K / xW From Constant Molar Overflow
stage j
assumption: Vj+1 = Vj and Lj = Lj-1
Vj+1, yj+1 Lj, xj
stage N operating line equation:

y = (L/V) x + (1 - (L/V)) xD
VN+1, xN+1 LN, xN y = x = xD slope = L/V
• actually a family of operating lines, since
time 0: F, xF L/V or xD (or both) change over the course
time t: W, xW of the distillation
• therefore the operating line moves on
still pot, with heater the M-T diagram
stage N+1
Choice of operating methods
Constant reflux ratio (variable xD) Constant distillate composition
(variable R)
•xD •xD
•
•
•
•
distillation must end distillation must end

when (or before) xD,avg = xF when (or before) R = ∞ (L/V = 1)
Easy to monitor and control. Harder to monitor and control (need to detect
xD on-stream and adjust R accordingly).
Multistage batch distillation with constant R
Given F, xF, xW,final, R and N,
find Dtotal, xD,avg 1
For N = 2 (incl. • •xD,1
1. For an arbitrary set of xD values, reboiler) 2•
draw a series of parallel operating 1
lines, each with slope R/(R+1) • •xD,2
2
2. Step off N stages on each 1 •
operating line to find its • •xD,3
corresponding xW
2
3. Perform numerical •
1• •xD,4
integration:
plot 1/(xD-xW) vs xW
limits: xF, xW,final 2•
4. Calculate Wfinal using Rayleigh

equation
xW,4 xW,3 xW,2 xW,1
5. Solve mass balances for
Dtotal and xD,avg
Factors Affecting Distillation Column Operation
Vapor Flow Conditions

Adverse vapor flow conditions can cause:
 Entrainment
 Weeping/dumping
 Flooding
 Foaming
13 February 2019 91
Entrainment
Entrainment refers to the liquid carried by vapor up to the
tray above and is again caused by high vapor flow rates. It
is detrimental because tray efficiency is reduced: lower
volatile material is carried to a plate holding liquid of
higher volatility. It could also contaminate high purity
distillate. Excessive entrainment can lead to flooding.
13 February 2019 92
Weeping/Dumping
This phenomenon is caused by low vapour flow. The
pressure exerted by the vapour is insufficient to hold up the
liquid on the tray. Therefore, liquid starts to leak through
perforations. Excessive weeping will lead to dumping. That is
the liquid on all trays will crash (dump) through to the base
of the column (via a domino effect) and the column will have
to be re-started. Weeping is indicated by a sharp pressure
drop in the column and reduced separation efficiency.
13 February 2019 93
Flooding
Flooding is brought about by excessive vapor flow, causing
liquid to be entrained in the vapor up the column. The
increased pressure from excessive vapor also backs up the
liquid in the downcomer, causing an increase in liquid holdup
on the plate above. Depending on the degree of flooding, the
maximum capacity of the column may be severely reduced.
Flooding is detected by sharp increases in column differential
pressure and significant decrease in separation efficiency.
13 February 2019 94
Foaming
Foaming refers to the expansion of liquid due to passage of

vapor or gas. Although it provides high interfacial liquid-
vapor contact, excessive foaming often leads to liquid
buildup on trays. In some cases, foaming may be so bad that
the foam mixes with liquid on the tray above. Whether
foaming will occur depends primarily on physical properties
of the liquid mixtures, but is sometimes due to tray designs
and condition. Whatever the cause, separation efficiency is
always reduced.
13 February 2019 95
Problem
A mixture of water and ethyl alcohol containing 0.16 mole fraction
alcohol is continuously distilled in a plate fractionating column to
give a product containing 0.77 mole fraction alcohol and a waste of
0.02 mole fraction alcohol. It is proposed to withdraw 25 per cent of
the alcohol in the entering stream as a side stream containing 0.50
mole fraction of alcohol. Determine the number of theoretical plates
required and the plate from which the side stream should be
withdrawn if the feed is liquor at its boiling point and a reflux ratio of
2 is used.
Solution
Taking 100 kmol of feed to the column as a basis, 16 kmol of alcohol
enter, and 25 percent, that is 4 kmol, are to be removed in the side
stream. As the side-stream composition is to be 0.5, that stream
contains 8 kmol
13 February 2019 96
13 February 2019 97
The slope of the operating line is always L/V and thus the slope in
each part of the column can now be calculated. The top operating
line passes through the point (xd, xd) and has a slope of (27.10/40.65)
= 0.67. This is shown in Figure 11b and it applies until xs = 0.50 where
the slope becomes (19.10/40.65) = 0.47. The operating line in the
bottom of the column applies from xf = 0.16 and passes through the
point (xw, xw) with a slope of (119.10/40.65) = 2.92.
13 February 2019 98
The steps corresponding
to the theoretical plates
may be drawn in as
shown, and 8 plates
are required with the
side stream being
withdrawn from the
fourth plate from the top
13 February 2019 99
PROBLEM 11.5
A continuous fractionating column, operating at atmospheric
pressure, is to be designed to separate a mixture containing 15.67
per cent CS2 and 84.33 per cent CCl4 into an overhead product
containing 91 per cent CS2 and a waste of 97.3 per cent CCl4 all by
mass. A plate efficiency of 70 per cent and a reflux of 3.16
kmol/kmol of product may be assumed. Using the
following data, determine the number of plates required.
The feed enters at 290 K with a specific heat capacity of 1.7 kJ/kg K
and a boiling point of 336 K. The latent heats of CS2 and CCl4 are
25.9 kJ/kmol.
13 February 2019 100

Solution
First convert all compositions into Mole Fraction
In this problem, the feed is not at its boiling-point so the slope of

the q-line must be determined in order to locate the intersection
of the operating lines. q is defined as the heat required to
vaporise 1 kmol of feed/molar latent heat of feed:
C PL (Tb − TF )
OR q = 1+
λ
where λ is the molar latent heat. Hfs is the enthalpy of 1 kmol of
feed at its boiling-point, and Hf is the enthalpy of 1 kmol of feed.
The feed composition is 27.4 per cent CS2 and 72.6 per cent CCl4 so
that the mean molecular mass of the feed is given by:
The intercept of the q-line on the x-axis is shown from equation

11.46 to be xf / q or:

Thus the q-line is drawn through (xf,
xf) and (0.196, 0) as shown in Figure.
As the reflux ratio is given as 3.16,
the top operating line may be drawn
through (xd, xd) and (0, xd/4.16).
The lower operating line is drawn by
joining the intersection of the top
operating line and the q-line with
the point (xw, xw).
The theoretical plates may be
stepped off as shown and 9
theoretical plates are shown.
If the plate efficiency is 70 per cent,
the number of actual plates = (9/0.7) = 12.85,
Thus: 13 plates are required
PROBLEM
A batch fractionation is carried out in a small column which has the
separating power of 6 theoretical plates. The mixture consists of
benzene and toluene containing 0.60 mole fraction of benzene. A
distillate is required, of constant composition, of 0.98 mole fraction
benzene, and the operation is discontinued when 83 per cent of the
benzene charged has been removed as distillate. Estimate the reflux
ratio needed at the start and finish of the distillation, if the relative
volatility of benzene to toluene is 2.46

The equilibrium data are calculated from the relative volatility by the
equation:
If a constant product is to be obtained from a batch still, the reflux

ratio must be constantly increased. Initially S1 kmol of liquor are in
the still with a composition xs1 of the MVC and a reflux ratio of R1 is
required to give the desired product composition xd.
When S2 kmol remain in the still of composition xs2, the reflux ratio
has increased to R2 when the amount of product is D kmol.

In this problem, xs1 = 0.6 and xd = 0.98 and there are 6 theoretical
plates in the column. It remains, by using the equilibrium data, to
determine values of xs2 for selected reflux ratios. This is done
graphically by choosing an intercept on the y-axis, calculating R,
drawing in the resulting operating line, and stepping off in the
normal way 6 theoretical plates and finding the still composition
xs2.

Conditions For Varying Overflow In
Non-ideal Binary Systems
 For a non-ideal system, where the molar latent heat is no
longer constant and where there is a substantial heat of
mixing, the calculations become much more tedious.
 For binary mixtures of this kind a graphical model has been
developed by RUHEMANN, PONCHON, and SAVARIT, based
on the use of an enthalpy-composition chart.
 It is necessary to construct an enthalpy-composition
diagram for particular binary system over a temperature
range covering the two-phase vapor-liquid region at the
pressure of the distillation.

The following data are needed:
 Heat capacity as a function of temperature, composition
and pressure.
 Heat of mixing and dilution as a function of temperature
and composition.
 Latent heats of vaporization as a function of composition
and pressure or temperature.
 Bubble-point temperature as a function of composition and
pressure.

A typical enthalpy–composition or H−x chart
is shown in Figure (Upper), where the upper
curve V is the dew-point curve, and the
lower curve L the boiling-point curve.
The use of this diagram is based on the
geometrical properties, as illustrated in Figure
(Lower)
If m is the mass, x the composition and H the
enthalpy per unit mass, then the addition of
two phases A and B to give phase C is
governed by:

Similarly, if an amount Q of heat is added to
a mass mA of a phase, the increase in
enthalpy from HA to HC will be given by:
The addition of two phases A and B is

shown on the diagram by point C on the
straight line joining the two phases.
The difference (A − B) is found by a point C

on the extension of the line AB.

 If, a phase represented by C in the
region between the dew-point and
boiling-point curves is considered, then
this phase will divide into two phases A
and B at the ends of a tie line through
the point C,so that:
 The H − x chart, therefore, enables the effect of adding two

phases, with or without the addition of heat, to be determined
geometrically.
 The diagram may be drawn for unit mass or for one mole of
material, although as a constant molar reflux does not now apply,
it is more convenient to use unit mass as the basis.
Thus, working with unit mass of product, the mass of the
individual streams as proportions of the product are calculated.
Figure 11.26 represents a continuous
distillation unit.
In this analysis, the quantities in the
streams V of rising vapor and L of reflux
are given in mass units, such as kg/s, and
the composition of the streams as mass
fractions, x referring to the liquid and y to
the vapor streams as usual.
The plates are numbered from the bottom
upwards, subscript n indicating the
rectifying and m the stripping section.

HV and HL represent the enthalpy per unit mass of a vapour and
liquid stream respectively.
QC is the heat removed in the condenser. In
this case no cooling of product is considered.
QB is the heat added in the boiler.
The following relationships are then
obtained by taking material and heat
balances:

We get

and and
We get
The last equation represents any operating line relating the

composition of the vapor yn rising from a plate to the composition of
the liquid reflux entering the plate, or alternatively it represents the
relation between the composition of the vapor and liquid streams
between any two plates.
From equation
it may be seen that all such operating lines pass through a common
pole N of coordinates xd and Hd.
A stream N may be defined with mass

equal to the difference between the
vapor and liquid streams between two
plates, of composition xd and of
enthalpy Hd.
The three quantities Vn , Ln+1, and N

are then on a straight line passing
through N, as shown in Figure

Below the feed plate a similar series of equations for material and
heat balances may be written as:

The last Equation represents any operating line below the feed plate,
and it shows that all such lines pass through a common pole M of
coordinates xw and Hw. As with the rectifying section, a stream M may
be defined by mass Lm +1 − Vm, composition xw and enthalpy Hw. Thus:
F=M+N
and: F x f = Mxw + Nxd
It therefore follows that phases F, M, and N are on a straight line on
the H − x chart, as shown in Figure
Determination of the number of plates
on the H − x diagram
The determination of the number
of plates necessary for a desired
separation is shown in Figure. The
position of the feed (F, xf) is shown
at F on the boiling line and the
pole N is located as (xd, H’d), where:
Pole M is located as on the extension of NF cutting the ordinate at xw in M

The condition of the vapor leaving the top plate is shown at V7 on the
dew-point curve with abscissa xd. The condition of the liquid on the top
plate is then found by drawing the tie line T7 from V7 to L7 on the boiling
curve. The condition V6 of the vapor on the second plate is found, from
equation 11.77, by drawing L7N to cut the dew-point
curve on V6. L6 is then found on the tie line T6.
Determination of the number of plates
on the H − x diagram
 The conditions of vapor and liquid
V5, V4, V3 and L5, L4 are found in the
same way. Tie line T3 gives L3, which
has the same composition as the feed.
 V2 is then found using the line MFV2, as
this represents the vapor on the top
plate of the stripping section.
 L2, L1 and V1 are then found by a
similar construction.
 L1 has the required composition of the
bottoms, xw.
 Alternatively, calculations may start
with the feed condition and proceed up
and down the column.
Enthalpy-concentration diagram
The enthalpy-concentration diagram requires the following data
at a constant pressure:
1. Heat capacity of the liquid as a function of temperature, composition, and
pressure.
2. Heat of solution as a function of temperature and composition.
3. Latent heats of vaporization as a function of composition and pressure or

temperature.
4. Boiling point as a function of pressure, composition and temperature.
The diagram at a given constant pressure is based on arbitrary

reference states of liquid and temperature, which is usually taken
as the boiling point of the lower boiling component A.
The saturated liquid enthalpy is
(1)
• The saturated vapor enthalpy is
(2)
(3)
(4)
Example: Enthalpy-concentration plot for
benzene-toluene
Prepare an enthalpy concentration Plot for benzene-toluene at 1
atm pressure. Equilibrium and physical property data are given.
benzene-toluene
Solution:
Choose a reference temperature of T0=80.1°C so that the liquid enthalpy of
pure benzene (xA=1) at the boiling point is zero.
For the first point: Select pure toluene (xA=0).
For liquid toluene at the boiling point of 110.6°C
= 0+(1- 0)(167.5)(110.6- 80.1) = 5109 kJ/kmol

For the saturated vapor enthalpy of pure toluene, first need to calculate
ΔHVB at T0=80.1°C:
=167.5(110.6 -80.1) 33330 +138.2(110.6- 80.1) = 34224 kJ/kmol

Hence, at yA = 0,
= 0 + (1-0) [34224+138.2(110.6-80.1)] = 38439 kJ/kmol

benzene-toluene
For pure benzene, xA = yA = 1, T = T0=80.1°C,
Hx = 0
=1[30820+96.3(80.1-80.1)] + 0
= 30820 kJ/kmol
Selecting xA = 0.5, the boiling point Tb = 92°C and the dew point for yA = 0.5
is Td = 98.8°C from the T-x-y plot.
= 0.5(138.2)(92-80.1)+(1-0.5)(167.5)(92-80.1)
= 1819 kJ/kmol
= 0.5 [30820 + 96.3 (98.8-80.1)] + (1-0.5) [34224 + 138.2 (98.8-80.1)]

= 34714 kJ/kmol
benzene-toluene
Tb Td Hx Hy
xA yA
(°C) (°C) (KJ/Kmol) (KJ/Kmol)
110.6 110.6 0 0 5109 38439
106.5 109.5 0.1 0.1 4345 37823
103 107 0.2 0.2 3702 37035
98.5 104.5 0.3 0.3 2920 36268
95 102 0.4 0.4 2321 35522
92 98.8 0.5 0.5 1819 34715
89 95.2 0.6 0.6 1334 33889
87 92 0.7 0.7 1014 33137
84 89 0.8 0.8 581.8 32432
82.5 85 0.9 0.9 338.7 31653
80.1 80.1 1 1 0 30820
Enthalpy-concentration plot for benzene-toluene
mixture at 1 atm.
Enthalpy-concentration plot
45000
Enthalpy of mixture, H or h, (KJ/kmol mixture)
40000
H vs yA, (saturated vapor)
35000
30000
25000
20000
15000
10000
5000 H vs xA, (saturated liquid)
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction benzene, xA or yA
The tie line represents the enthalpies and composition of the liquid and
vapor phases in equilibrium.
Procedure to determine the number of
theoretical plates
The procedure to determine the number of theoretical plates is
summarized below.
1. Locate the feed enthalpy and composition
2. Locate xD and xW
3. Locate ΔD by computation of Q’ or for a specific reflux ratio as R = L0/D
4. The line ΔD, F is extended to x = xW and thus locates ΔW whose

coordinates can be used to calculate QR.
5. The number of theoretical plates is then determined by application of the

straight line relationship on the H-x-y diagram and the equilibrium data of
the y-x diagram.
Locate the feed enthalpy and
composition.
Composition given in question
description. Feed enthalpy can either F
be calculated or provided as part of

the question.
 Mark the spot on the H-x diagram.
xW xD
Locate xD and xW
Compute the composition of
the distillate and bottom
product using knowledge of
stoichiometry.
13 February 2019 Dr. Saeed GUL, Department of Chemical 131

Engineering, UET Peshawar, Pakistan
Locate ΔD by computation of Q’ or for ΔD
a specific reflux ratio as R = L0/D.

When using 𝑄𝑄 ′ to locate the point ΔD,
you need the enthalpy of the distillate
(need thermodynamics knowledge on how F
to compute enthalpy; hint you need
temperature and composition)
Or if I like you guys enough I will
provide that information :-D
xW xD
Next you will need the condenser duty
and the distillate flowrate. Distillate
flowrate can be calculated using mass
balance and condenser duty can be
calculated using the formulae:

Locate ΔW by computation of 𝑸𝑸𝒓𝒓 and ΔD
join the points ΔD, 𝑸𝑸𝒓𝒓 and F .

When using 𝑸𝑸𝒓𝒓 to locate the point ΔW,
you need the enthalpy of the bottoms
(need thermodynamics knowledge on how F
to compute enthalpy; hint you need
temperature and composition)
ΔW
Or if I like you guys enough I will
provide that information :-D
xW xD
Next you will need the reboiler duty and
the bottoms flowrate. bottoms flowrate
can be calculated using mass balance and
reboiler duty can be calculated using the
formulae:
𝑸𝑸𝒓𝒓 = HxB – qr / B

ΔD
The number of theoretical plates is then

determined by application of the straight line
relationship on the H-x-y diagram and the
equilibrium data of the y-x diagram.
1. First a vertical line is drawn from point ΔD to F
the Bubble point curve on the x-y diagram.
2. Second draw a horizontal line from that point ΔW
to the dew point curve on the x-y diagram.
3. A third line horizontally from the dew point xW xD
curve of the x-y diagram to the bubble point
curve on the H-x diagram, is drawn
4. Join this point with the ΔD point

5. Now draw a vertical from the new point
obtained on the Dew curve of the H-x diagram
to the bubble curve of the x-y diagram.
6. Repeat steps from 2-5 until the line crosses
the angular line connect the feed , bottom and
distillate point.
ΔD
1. If the line coming from the dew point curve of
the x-y diagram crosses the feed point or lands on
the feed point in the H-x diagram then the number
of points before that represent the no of trays
before the feed tray. In this case the no of trays
before feed tray is 3 F
2. Now from the point on the bubble line on the H-

x diagram (that passes or lands on the point where ΔW
the feed enters, draw a line connecting that ΔW
with the dew curve on the H-x diagram. xW
xD
3. Drop a vertical from there touching the bubble
point on the x-y curve.
4. Join this point horizontally with the dew point
curve on the x-y diagram and from there draw a
vertical line joining the bubble point curve on the
H-x diagram.
5. From this point draw a straight line connecting
both ΔW a point on the dew line of the H-x
diagram.
6. Repeat Steps 3-5 until the line passes the ΔW point

ΔD
No of plates for the column are:
3 plates in the rectifying section

1 feed plate
F
5 plates in the striping section
Hence a total of 8 plates plus one ΔW
reboiler.
xW
xD
So total no of plates for the
distillation column is 9.

Example
A liquid mixture of benzene-toluene is to be distilled in a fractionating
tower at 101.3 kPa pressure. The feed of 100 kmol/h is liquid,
containing 45 mol % benzene and 55 mol % toluene, and enters at
54.4°C. A distillate containing 95 mol % benzene and 5 mol % toluene
and a bottoms containing 10 mol % benzene and 90 mol % toluene are
to be obtained. The reflux ratio is 1.755. The average heat capacity of
the feed is 159 kJ/(kmol.K) and the average latent heat is 32099
kJ/kmol. Determine the number of theoretical stages needed.
Example
Solution:
F = 100 kg mol/h, xF = 0.45, xD = 0.95, xB = 0.10,
D = 41.2 kg mol/h, B = 58.8 kmol/h R = 1.5Rm = 1.5 (1.17) = 1.755,
The feed enters at 54.5°C so q = 1.195.
The flows at the top of the tower are calculated as follows.
R = L/D = 1.755; L = 1.755D = 1.755(41.2) = 72.3;
V1 = L+D = 72.3+41.2 = 113.5
The latent heats of vaporization of benzene and toluene at the reference

temperature of 80.1°C are
ΔHVA = ΔHVAb = 30820 kJ/kmol ΔHVB = 34224 KJ/Kmol

Example
The saturation temperature (dew point) at the top of the tower for
y1=xD= 0.95 is 82.3°C.
Hy1 = 0.95 [30820+96.3(82.3-80.1)] + (1-0.95) [34224+138.2(82.3-80.1)]
= 31206 kJ/kmol
The boiling point of the distillate D is obtained as 81.1°C.
HxD = 0.95(138.2)(81.1-80.1) + (1-0.95)(167.5)(81.1-80.1)
= 139 kJ/kmol
The condenser duty is obtained from Eq.
qc =113.5(31206)-72.3(139)-41.2(139)=3526100KJ/h
Example
For xB = 0.10, HxB = 4350 from the Figure in slide 9.
The feed is at 54.5°C, using Eq. (1), we have
HF = 0.45(138.2)(54.5-80.1) + (1-0.45)(167.5)(54.5-80.1) = -3929 kJ/kg mol
For qr
qr = 41.2(139) + 58.8(4350) + 3526100 - 100(-3929) = 4180500 kJ/h

Q” = HxB – qr / B = 435 - 4180500/58.8 = - 66747 kJ/kmol
In the H-x-y diagram, draw the line from ΔD (xD=0.95, Q’=85724) through
(xF=0.45, HF=-3929) to intersect xB=0.10 gives Q” = - 66747 kJ/kmol from ΔB.
The number of theoretical plates is then determined by application of the

straight line relationship on the H-x-y diagram and the equilibrium data of the
y-x diagram.
ΔD
(y2, Hy2)
11 10 9 8 7 6 5 4 3 2 1
(x , H x )
1 1
ΔB
11 plates, or 10 plates plus 1 reboiler
are needed.
The feed is at plate 6.

Dr. Saeed GUL, Department of Chemical
The importance of the reflux ratio
(Total Reflux)
Any change in the reflux ratio R
will therefore modify the slope of
the operating line and, this will
alter the number of plates
required for a given separation as
shown in Figure
If no product is withdrawn from
the still, that is D = 0, then the
column is said to operate under
conditions of total reflux and the
top operating line has its
maximum slope of unity, and
coincides with the line x = y.

PROBLEM
A continuous fractionating column is required to separate a mixture
containing 0.695 mole fraction n-heptane (C7H16) and 0.305 mole
fraction n-octane (C8H18) into products of 99 mole per cent purity.
The column is to operate at 101.3 kN/m2 with a vapour velocity of
0.6 m/s. The feed is all liquid at its boiling-point, and this is supplied
to the column at 1.25 kg/s. The boiling-point at the top of the
column may be taken as 372 K, and the equilibrium data are:
Determine the minimum reflux ratio required. What diameter

column would be required if the reflux used were twice the
minimum possible?

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Mass Transfer (ChE - 392)

Saeed GUL, Dr.Techn, M.Sc. Engg.

Department of Chemical Engineering,

 Distillation is the technique of preferential separation of the

 Distillation is the most widely used separation process in the

 The composition of the vapor in

Over the range OC the mixture

Although most mixtures show

If the mixture follows Raoult’s law, then the values of yA for

The relationship between the composition of the vapor yA and

The ratio of these two volatilities is known as the relative

This gives a relation between the ratio of A and B in the vapor to

Use for constructing

This relation enables the composition of the vapor to be

From the definition of the volatility of a component, it is seen

This also follows by applying equation 11.1 from which

It may be seen that α increases as the temperature falls, so that

The figure shows several

Three main methods are used in distillation practice:

 Flash or equilibrium distillation

Of these, rectification is much the most important, and it differs

Batch distillation without reflux is often called differential

In this process the

Since the vapor produced is richer in the more volatile component

Thus, whilst the vapor formed over a short period is in equilibrium

If S is the number of moles of material in the still,

The rate of depletion of liquid is equal to the rate of distillate output:

xS = ydS + xS – xdS – Sdx + dxdS

Neglecting the term dxdS: xS = ydS + xS – xdS – Sdx + dxdS

Sdx = ydS – xdS

Rayleigh equation x,final x xinitial

The integral on the right-hand side of this equation may be solved

In some cases a direct integration is possible Thus, if over the

𝑆𝑆 𝑚𝑚−1 𝑥𝑥 𝑚𝑚−1 +𝑐𝑐] 𝑆𝑆 𝑚𝑚−1 mx + c − x

This leads to the solution:

As this process consists of only a single stage, a complete separation

then an overall mass balance gives:

This is an "operating line" equation -- plotted on a graph whose

When f = 0.25, the slope is therefore:

An equimolar mixture of benzene and toluene is subjected to flash

From graph - this is shown as

We can see from the results that there is a trade-off between

 determine the amount of distillate

xW is calculated from the graphical method, for which the integral

The area of 0.7985 is obtained for xW = 0.07

660 x yD,avg = 1200 x 0.3 - 540 x 0.07

Concentration of naphthalene in residue = 7%

Concentration of naphthalene in distillate = 48.82%

Four streams of are involved:

Plate n supplies liquid Ln to plate

The action of the plate is to bring

 This equation is difficult to handle for the majority of mixtures,

• Thus, one mole of vapor Vn−1 on condensing releases

Applying these simplifications to the equation, it is seen that

 For these conditions there are two basic methods for

material balance above plate n,

balance for the MVC gives:

Since the molar liquid overflow

This last value of composition is sufficiently near to that of the

This liquid xt−7 is slightly weaker than the minimum required

McCABE and THIELE pointed out that, since these equations

and this equation represents a line passing through the point

Since Vm = Lm − W, it follows that ym = xw. Thus the bottom