Mass Transfer-I

Distillation
Lecture 3
Dr. Hemant Kumar
Department of Chemical Engineering
DDU Nadiad

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 Equilibrium
curve

Diagonal

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 Distribution diagram
• The vapor liquid
equilibrium can also be
shown on a distribution
diagram (x vs y*)
• Point P in the diagram
represents the tie line
DF for example
• Since the vapor is richer
in more volatile
component the curve
lies above 45o diagonal
line

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 Relative volatility:
The greater the distance between the equilibrium curve and
diagonal, the greater the difference in liquid and vapor
composition and easier the separation by distillation

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 Relative volatility
•One relative measure is called separability factor or relative
volatility α

“This is the ratio of the concentration ratio of A and B in one

phase to that in the other phase and is a measure of
separability”

•The value of α changes as x changes from 0 to 1

•If y*=x; except x=0 to x=1, α=1 and no separation is possible

•The larger the value of α above unity, the greater the degree
of separability

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 VLE at increased pressures

pt5> pt4> pt3 >pt2> pt1

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 Constant Temperature Equilibria

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 Constant Temperature Equilibria

•Upper curve is now x vs pt known as bubble point curve

•Lower curve is now dew point curve y* vs pt

•Now liquid solution of binary mixture at point W is heated at

constant temperature in closed vessel and pressure is reduced

•It will follow path w to R

•pB is the vapor pressure of pure B and pA is the vapor pressure

of pure component A

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 Ideal solutions- Raoult’s law
• Raoult's law is applicable to the mixtures whose vapors and
liquids are ideal
• Raoult's law:
For an ideal solution the equilibrium partial pressure p* of a
constituent at a fixed temperature equals the product of its
vapor pressure p when pure at this temperature and its mole
fraction in the liquid
and eqn (1)
• If the vapor pressure is also ideal, the total as well as partial
pressures are linear in x at a fixed temperature shown in
figure
eqn
(2)

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 Idea solutions- Raoult’s law

• The equilibrium vapor composition can be computed at this

temperature
• For Ex: the value of y* at point D on the figure equals the ratio
of the distances FG to EG

eqn (3)

eqn (4)

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 Idea solutions- Raoult’s law

Divide eqn (3)/(4)

Or

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 Idea solutions- Raoult’s law
Example 1: Compute the vapor-liquid equilibria (compute x ,
y* and α) at constant pressure of 1 std atm for mixtures
of n-heptane with n-octane, which may be expected to
form ideal solutions.
Find out: t-x-y and p-x-y diagram

Solution: step 1: at 1 atm find out boiling points of n-heptane

and n-octane. [use Antoine eqn to find b.pt. at 101.3kPa]
Step 2: in the boiling point range find out vapor pressures of
both components using Antoine equation
Step 3: use Raoult's law to find out partial pressure and total
pressures at these temperatures.

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 Idea solutions- Raoult’s law
For example: at one std atm pressure (760 mmHg) boiling
points of n-heptane and n-octane are 98.4 oC and 125.6 oC
respectively.
In between the boiling point range i.e. at 110 oC, vapor
pressures of n-heptane and n-octane are pA=1050 mmHg and
pB=484 mmHg (Note: vapor pressure will be provided
otherwise find with the help of Antoine eqn)

Step 4: Use Antoine eqn to generate the vapor pressure of both

components in the boiling point range of 98.4 oC and 125.6 oC
ln P sat (kPa)=A-[B/(T (Kelvin)+C)]
your answer in kPa has to be converted to mmHg (1 kPa = 7.5
mmHg)
Constants:
n- heptane: 13.8622 (A); 2910.26 (B); -56.718 (C)
n- Octane: 13.9346 (A); 3123.13(B); -63.515 (C)

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 Idea solutions- Raoult’s law
Use Raoult's law to calculate pt, x and y*

Rearranging the eqn gives:

x = 0.487 mole fraction of heptane in liquid

From eqn (3):

y*=0.674 mole fraction of heptane in vapor

Also α = pA/pB = 1050 mmHg/484 mm Hg = 2.17

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t oC pA (mm Hg) pB (mm Hg) x y* 𝞪=
(pA /pB)

100

ln P sat (kPa)=A-[B/(T (Kelvin)+C)]

n- heptane: 13.8622 (A); 2910.26 (B); -56.718 (C)
n- Octane: 13.9346 (A); 3123.13(B); -63.515 (C)

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 Idea solutions- Raoult’s law

Likewise generate the t-x-y and p-x-y data at different

temperature range

For ideal solutions the value of α does not vary considerably.

Therefore, avg. of all values is α =2.16

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 Idea solutions- Raoult’s law

Also with the help of α value, we can calculate y* values at

values of x ranging from 0 to 1

Rearranging eqn

Y* can be represented as

Since α=2.25,
This eqn can be used to generate x-y* data, in case α value is
known.
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 (a)
Positive deviations from ideality
(b)

(c)

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 Positive deviations from ideality
• A mixture whose total
pressure is greater than
computed from ideality is
said to show positive
deviations from ideality
• Most mixtures fall into this
category
• In these cases the partial
pressures of each
components are larger than
ideal as shown in figure

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 Positive deviations from ideality

• As the conc for each

component approaches
unity mole fraction, the
partial pressure for that
substance approach ideally
tangentially

• Raoult's law in other words

is nearly applicable to the
substance present in large
concentrations

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 Positive deviations from ideality: Minimum boiling mixtures
• When the positive deviations from ideality are sufficiently
large and the vapor pressure of the two components are not
too far apart
• In that case the total pressure curves at constant temp may
rise through a maximum at some concentration as shown in
fig (a) in the next slide
• The significance of this curve is seen by studying const.
pressure curve in fig (b) and (c)
• The liquid and vapor compositions are tangent at point L, the
point of azeotropizm at a given pressure indicating
“minimum boiling azeotrope”
• For all mixtures less than pt. L (point of azeotropizm) like pt.
C, the equilibrium vapor (E) is richer in more volatile
component than liquid (D)
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 Positive deviations from ideality
• For all mixtures richer than pt. L, like Point F: The equilibrium
vapor (G) is richer in less volatile component than liquid (H)
• A mixture of composition L gives rise to a vapor of
composition identical with the liquid and it consequently
boils at constant temperature and without change in
composition
Heating of mixture in the open pan:
• If solutions either D or H are boiled in an open vessel with
continuous escape of vapors
• The temperature and composition of the residual liquids in
each case move along the lower curve away from point L
• Towards K for a liquid at H, and toward J for one at D
• Solutions like these cant be separated by ordinary distillation
methods. Since at x=y*, α=1

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 Positive deviations from ideality
• The azeotropic composition as well as its boiling point
changes with pressure. Therefore, changing the pressure may
eliminate the azeotropizm

• Example: Ethanol water azeotropizm forms at 78.2 oC and

89.4 mole% ethanol
• Azeotropizm disappears at 70 mm Hg for this system

• other example of positive deviations

CS2 and aceton system

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 Partial liquid miscibility
• Some substance exhibit such large positive deviations from
ideality that they don’t dissolve completely in the liquid state
• Example: Isobutanol- water and phenol-water

Liquid phase:
• Curves through points C and E represents the solubility limits
of the constituents at relatively low temperatures
• Mixtures of compositions and temperature represented by
points within the central area such as point D form two
phases at equilibrium at C and E and line CE is a liquid tie line
• Mixtures in the regions on either side of the solubility limits
such as point F are homogeneous liquid
• Solubility ordinarily increases with increased temperatures,
therefore, central area consequently decreases in width

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 Partial liquid miscibility

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 Partial liquid miscibility
Broken lines:
• If pressure were high enough for vaporization not to occur,
the liquid-solubility curve would continue the broken lines
However at constant pressure
• At constant pressure under study vaporization will occur at
increased temp giving rise to VLE curves shown in the figure
• The homogenous liquid such as at point F, the VLE
phenomenon is normal and such a mixture will boil at point H
to give first bubble of vapor of composition J
• The same is true for any solution richer at pt. M greater or
equal to except that vapor is leaner in more volatile
component
• Any two phase liquid mixture ranging from K to M will boil at
the temperature of the line KM

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 Partial liquid miscibility
• And all these give rise to the same vapor composition L
• A liquid mixture of avg. composition L which produces a
vapor of the same composition is called a Heteroazeotrope
Distribution diagram:
• The corresponding distribution diagram is shown in fig b
• With tie line HJ at point (H, J)
• Solubility limits at the bubble pt. K and M
• In relatively few instances, azeotrope composition lies
outside the limits of solubility like as Methyl-ethyl
ketone-water & phenol-water

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 Thanks
Exercise : Practice example 7.1 (B K Dutta:
Principles of mass transfer and separation
processes)

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