Mass Transfer–I (PCMT 405 )

Module IV: Lecture # 2

Flash Distillation & Differential Distillation

Dr. Amitava Bandyopadhyay

Professor
Department of Chemical Engineering
University of Calcutta
 Learning Objectives
Students will be able to
1. Calculate the molar enthalpies of vapor mixture & liquid solution
2. Draw H-x-y diagram of a binary mixture
3. Draw x-y diagram from H-x-y diagram of a binary mixture
4. Determine the composition of a mixture using H-x-y diagram
5. Illustrate the Flash or Equilibrium distillation
6. Estimate the composition of products as well as enthalpy &
composition of products
7. Illustrate the differential or batch or the Rayleigh distillation
8. Derive & apply the Rayleigh equation
9. Solve the Rayleigh equation by different methods
10. Describe the experimental verification of the Rayleigh equation
11. Illustrate the steam distillation
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 Introduction: Types of Distillation

Figure 1. Types of distillation and

equipments

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Flash or Equilibrium Distillation
 Molar Enthalpies of Liquid & Vapor
● Change in composition is accompanied by a change in enthalpy.
● Enthalpy-concentration diagrams of V ⇔ L are useful in distillation.
Molar Enthalpy of Liquid
♣ Components are mixed at a reference temperature =T0 (K)
♣ Enthalpies of pure components = zero at T0 (reference temperature)
♣ Heat Effects at T0 : release of heat of solution = ∆HS (kJ/kmol)
♣ Mixture is heated at Temperature = T (K)
♣ Concentration of liquid = x (mole fraction)
♣ Molar enthalpy of the solution at temperature T can be calculated from
HL = C PS Mav (T − T0 ) + ∆HS ; (kJ/kmol)
♣ CPS = specific heat of solution (kJ/kg.K); Mav = average molecular weight of the solution
Molar Enthalpy of Vapor
⊗ Heat of mixing of vapor is negligible
⊗ Individual components are heated at T from T0 followed by vaporization & mixing of vapors
⊗ Vapor concentration = y (mole fraction)
⊗ Molar enthalpy of saturated vapor at temperature T can be calculated from
HV = yMA CPA (T − T0 ) + λA  + (1 − y ) MB CPB (T − T0 ) + λB  ; (kJ/kmol)
⊗ CPA & CPB = specific heats of pure liquids A & B (kJ/kg.K);
⊗ λA & λB = heats of vaporization of A & B at temperature T (kJ/kg)
⊗ MA & MB = molecular weight of A & B
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 Enthalpy-Concentration (H-x-y*) Diagram y or y*
x, y, HL & HV data for Methanol – Water system
x 1.0 0.90 0.80 0.60 0.20 0.10 0.05 0.01 0.0
y* or y 1.0 0.935 0.898 0.859 0.815 0.755 0.625 0.253 0.0
HL (kcal/kmol) 1300 1297 1294 1248 929 930 1083 1390 1530
HV (kcal/kmol) 8500 8722 8812 8916 9056 9259 9659 10,754 11,250

● Mixture tends to separate into

vapor
a liquid & a vapor phase at
equilibrium represented by W
& D on the TIE line through F
● Amounts of L & V can be
found from Lever-Arm Rule
Two-phase
● TIE line WD is represented by mixture
R on the x-y* equilibrium
curve
liquid

Figure 2. Enthalpy-concentration (H-x-y*) for CH3OH-H2O system

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Drawing x-y* diagram from H-x-y* diagram y or y*
STEP # 1: Draw the H-x-y* diagram. H-x-y*
vapor
STEP # 2: Draw 450 diagonal in a square drawn at the
bottom of the H-x-y* diagram with same
dimension for the horizontal axis.
STEP # 3: Draw several tie lines on the H-x-y* diagram
Two-phase
STEP # 4: Locating equilibrium points on x-y* diagram: mixture
Consider a tie line WD.
STEP # 5: Draw a vertical line from D (on the H-y*
curve) to 450 diagonal and locate Q on it.
STEP # 6: Move horizontally (left) from Q to locate the liquid
point of intersection of vertically downward
line drawn from W.
STEP # 7: Mark this point of intersection as R (a point
on the equilibrium curve).
STEP # 8: Follow the procedure identically for all other
tie lines drawn in STEP # 3 to locate other
Q
points of the equilibrium curve and join
them to produce the equilibrium curve (x-y*
x-y*
diagram).

Figure 3. Drawing x-y* diagram from H-x-y*

diagram for CH3OH-H2O system
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Mixture Composition from H-x-y* diagram y or y*
Let states (enthalpy, composition & amount) of 2 solutions represented by M & N
Solutions are mixed to produce another solution having its state represented by P
Material Balance: M+N=P (i) z may be x or y
Component “A” Balance: MzM + NzN = PzP (ii) [z = composition of A]
Enthalpy Balance: MHM + NHN = PHP (iii) [H = molar enthalpy]
Eliminating P : 12000
M zN − zP HN − HP H − HP HP − HM vapor
= = ⇒ N =
N zP − zM HP − HM zN − zP zP − zM 10000 N

HV, HL (kcal/kmol)
8000
From From Slope Slope
H-y* curve
(i) & (ii) (i) & (iii) of NP of PM 6000 H-x curve

M, P & N 4000 .
P
two-phase mixture
collinear
2000
Mixture represented by P:
M liquid

removing a part of it represented by M; 0

part of P left behind should have H & z 0.0 0.2 0.4 0.6 0.8 1.0
x, y*
represented by N
Figure 4. H-x-y* diagram for CH3OH-H2O system
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 Salient Points on Flash Distillation
● Separation of a volatile component from a liquid can be achieved by flash
distillation.
● Single-stage separation by vaporization.
● Operation is referred to as ”flash”- since MVC of a saturated liquid mixture
rapidly vaporizes upon entering a tank/drum which is at lower pressure &/or
higher temperature than the incoming fluid.
● If the feed is sub-cooled liquid then it should be heated to raise its temperature
& pressure before flashing into the tank.
● As the feed enters the flash drum, it impinges against an internal deflector plate
which promotes liquid-vapor saturation of the feed mixture.
● Sometimes the vapor is condensed wherein MVC as well as some LVC will
present. Thus flash distillation once is not effective in such cases. A series of
flash is needed to improve the quality of the MVC.
● In every general terms, an individual flash distillation unit may be seen as
analogous to single tray in a distillation column.

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 Flash or Equilibrium Distillation
● Feed is heated under
pressure in a preheater.
● Hot liquid is throttled &
“flashed” under reduced
pressure.
● Pressure is suitably adjusted.
● Baffles are used at top to
prevent entrainment of mist,
if any.

It is also called
Flash Vaporization
Figure 5. Schematic of Flash Distillation

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 Flash or Equilibrium Distillation y or y*
● Vapor fraction ( f ) of the feed depends upon the heat added in the still.
Material Balance: F = D + W 1.0
f = 0; no vaporization
D W W
or, 1 = + = f + ;
F F F
W 0.8
or, = 1 − f ; ...(1)  D = f , vapor fraction 

Compostion in the vapor, y

(x W, yD)
F F  yD
Material Component Balance: 0.6
xF F = yD D + xW W
.
D W  (x F, yF)
or, xF = yD   + xW   ; 0.4
f = 1; complete
vaporization
F D
or, xF = yD f + xW (1 − f ) slope = −
(1 − f ) = −  W 
D
(1 − f ) xF 0.2
f  
or, yD = − xW + ... (2)
f f x - y curve
 Eq(2) ⇒ f & xF known;  x = y line
 y & x ⇒ unknown  0.0
0.0 0.2 x W 0.4 0.6 0.8 1.0
 D W

( W D )
Compositon in the liquid, x
x , y ⇒ point on t he eqm. curve 
(1− f ) xF Figure 6. Typical calculation on Flash Distillation
Generalizing Eq (2): y = − x +
f f
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Flash Distillation: y or y*
CASE # 1: Estimating Equilibrium Composition of Products
Available: x-y data, F, xF, D or W
Follow the steps to find xW & yD W 
slope = −  
STEP # 1. Draw the equilibrium (x W , yD)  D 

Compostion in the vapor, y

yD
curve
STEP # 2. Draw the diagonal (x = y
line) .
(x F , x F)
STEP # 3. Locate feed point (xF, xF) on
the diagonal
STEP # 4. Draw operating line with a
slope  W 
−  x - y curve
D x = y line

STEP # 5. Intersection of this line with 0.0 0.2 xW 0.4 0.6 0.8 1.0
Compositon in the liquid, x
equilibrium curve gives xW &
yD (Figure 7). Figure 7. Estimation of equilibrium composition
of products

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Flash Distillation: y or y*
CASE # 2: Estimating enthalpy, composition & amount of products
[At Equilibrium]
Available: H-x-y , xF, F & Q
v
Follow the steps to find HV, HL, yD, xW, D & W
STEP # 1. Draw H-x-y diagram & x-y curve v
below it.
STEP # 2. Locate feed point F(xF, HF +Q/F)
STEP # 3. Draw a line by trial-&-error, passing
through F such that it will be a tie xF
line.
STEP # 4. Points of intersection of this line
with H-x-y curves gives enthalpy &
concentration of distillate &
residue (Figure 8).
STEP # 5. Use the expressions for finding W
&D
xF
[ xF F = yD D + xW W ] & slope = − D 
W
  Figure 8. Estimation of enthalpy,
composition & amount of products at
equilibrium 13
Flash Distillation: y or y*
CASE # 3: Estimating Composition of Products
Not at Equilibrium:
DW: On H-x-y diagram, a straight line through points of D(HD,
yD), W(HW, xW) & feed point (HF + Q/F, xF) is drawn (in upper
figure).
FM: single-stage operating line on x-y coordinates with
negative slope (–W/D) passing through compositions
representing points F (influent) & M (effluent) (lower figure).
At Equilibrium: Products represented by D' & W' (located on
a tie line: upper figure) & on x-y curve at N (lower figure).
Richest vapor (infinitesimal amount), corresponding to P at
the bubble point of the feed
Leanest liquid (infinitesimal amount), corresponding to T at
the dew point of the feed
Compositions of actual products will be between these
limits, depending on extent of feed vaporization & stage xF
efficiency.

Figure 9. Estimation of composition of products

in flash distillation xF
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 Flash Distillation: Enthalpy Balance
Material Balance: F = D +W (1)
Material Component Balance: xF F = yD D + xW W (2)
Material Enthalpy Balance: H F F + Q = H D D + HW W (3)
From Eqs (1) &(2) From Eqs (1) & (3)
xF ( D + W ) = yD D + xW W  Q
F  H F +  = H D D + HW W
or, xF D + xFW = yD D + xW W  F
or, xF D − yD D = xW W − xFW  Q
or, ( D + W )  H F +  = H D D + HW W
or, D ( xF − yD ) = W ( xW − xF )  F
W ( xF − y D ) ( y − xF ) Q
or, DH F + D − DH D = WHW − WH F − W
Q
or, = =− D
D ( xW − xF ) ( xW − xF ) F F
 Q   Q
or, D  H F + − H D  = W  HW − H F − 
 F   F
These expressions are useful  Q    Q 
H
 F +  − H H − H +
 D  F F 
W 
D
in understanding enthalpies F  =−  
& compositions of distillate or, =
D   Q    Q 
& residue w.r.t. feed. H − H
 W  F F  + H − H +
 W  F F 
     

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 Differential or Batch or
the Rayleigh Distillation
Differential or Batch or the Rayleigh Distillation
● Infinite number of flash vaporizations of a liquid with infinitesimal
portion of liquid were flashed each time ⇒ net result equivalent to a
differential distillation.
● Single-stage separation by vaporization.
● Most elementary form is differential distillation, in which a liquid is
charged to the still pot and heated to boiling.
● The method has a strong resemblance with laboratory distillation.
● Why “differential”?
● Vapour produced at any time is in equilibrium with the liquid from
which it is produced, but its composition changes continuously since
the liquid with which it is in equilibrium is constantly changing in
composition.
● Therefore, mathematical treatment of such distillation has to be
differential.

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 Salient Points on Batch Distillation
● Costlier compared to continuous counterpart.
● Chosen when it is not possible to run a continuous process due to limiting process
constraints, the need to distill other process streams or because the low frequency use of
distillation does not warrant a unit devoted solely to a specific product.
● A relatively efficient separation of two or more component may be accomplished
through batch distillation in a pot or tank.
● Although the purity of the distilled product varies throughout the course of batch
distillation, it is used in certain specific in industry.
● More than one product may be obtained.
● Binary mixture of EtOH – H2O yield high quality of EtOH initially. As the composition in
the still weakens w.r.t. EtOH, a second product may be recovered from top with reduced
concentration of EtOH. In this way it is not only possible to obtain two different qualities
of product but also to reduce the alcohol content in the still.
● Particularly useful for small quantities of multi-component organic mixture, since it is
possible to obtain different components at reasonable degrees of purity. The quantity
remaining in the still may be recharged next batch to improve the yield.
● Used largely for speciality chemicals, pharmaceuticals like antibiotics and other schedule
drugs manufactured in small quantities with very high cost.

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 Differential Distillation: Schematic view
vapor leaving still pot (y ) is in Vapor formed is continuously
equilibrium with perfectly mixed removed & condensed to
liquid in the still at any instant distillate; Richer in MVC;
Total Condensation: yD = xD
(single stage)

Residual unvaporized As distillation proceeds, the relative

bottoms are richer in LVC amount of volatile components’
composition of initial charge & distillate
decrease with time.

Figure 10. Schematic Layout of Differential distillation of a binary mixture

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 Developing the Rayleigh Equation
Consider
At any time liquid left in the still = L moles Binary Mixture
Composition of MVC in the still = x (m.f.) A (MVC) + B (LVC)
Composition of vapor leaving = y (m.f.)
Composition in the still changes with time as evaporation continues
Assume the following for deriving Rayleigh equation –
Original amount of liquid in the still = x.L
Moles (differential) of liquid vaporized = dL With respect to
Change in composition of liquid (m.f.) = (x – dx) MVC
Change in moles of liquid = (L – dL) y or y*
x
Amount of vapor produced & condensed = y.dL

Component-Material Balance:- of liquid in the still =  left in the still  + produced & condensed
original amount amount of liquid Amount of vapor
     
x.L = ( x − dx )( L − dL ) + y.dL F
dL
xF
dx
or, x.L = x.L − x.dL − L.dx + dx.dL + y.dL Integrating Eq(1) within limits ∫ L
= ∫ (y − x)
or, L.dx = ( y − x ) .dL 
dx.dL is ignored  W x
W
being very small  F
xF
dx
or,
dL
=
dx
...(1)
or, ln ∫
=
W x ( y − x )
...(2) Rayleigh Equation
L (y − x) W

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Analytical Solution of the Rayleigh Equation y or y*
Equation (2) can be analytically solved using the relative volatility of the MVC
xF xF
F dx dx
ln =
W x ∫ =∫
( y − x ) xW  αx    αx 
 −x  y =   
( )
W

 1 + (α − 1 ) x    1 + α − 1 x  
Different forms of solution of the above equation can be given as follows
 Fx  F ( 1 − xF )
ln  F  = α ln ... (3)
 WxW  W (1 − xW )
F  1  xF (1 − xW ) 1 − xW
ln =   ln + ln ...(4)
W  α − 1  xW (1 − xF ) 1 − xF
F  1   xF 1 − xF 
ln =  ln − α ln  ...(5)
W  α − 1   xW 1 − xW 
2
Limiting condition: for α = 2, F  xF  1 − xW  Knowing values of 3 parameters,
Eqs (3), (4) & (5) reduces to =    value of 4th one can be
W  xW  1 − xF  determined

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 Use of the Rayleigh Equation y or y*
Determining one of the five parameters using the solution of Rayleigh Equation
parameters are known
(e.g., α, F, W & xF )  Fx  F ( 1 − xF )
ln  F  = α ln ... (3)
W (1 − xW )
Four out of five

 WxW  trial-and-error
F  1  xF (1 − xW ) 1 − xW procedure
ln =   ln + ln ...(4)
W  α − 1  xW (1 − xF ) 1 − xF Remaining one (xW)
is obtained
F  1   xF 1 − xF 
ln =  ln − α ln  ...(5)
W  α − 1   xW 1 − xW 
xF F = yD D + xWW
Average composition
xF F − xWW
(yD) of distillate (D) or , yD =
D
For any two components in a differential distillation following relation exists
α  x , x = moles of A & B in the still at any time 
x A  xB   A B
=  ; x A0 , xB 0 = moles of A & B present initially in the still
x A0  xB 0  α = relative volatility of A w.r.t. B 
 
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Graphical Integration of the Rayleigh Equation y or y*
xF
F dx
ln =
W x ∫ (y − x)
9

8
xW1= 1st trial
xW2= 2nd trial
W
xW= 3rd trial (desired value)
● The integration requires that the 7

Values of 1/[y-x]
function [1/( y - x)] be evaluated 6 To estimate the area
at appropriate values of x. 5 under the curve

● It is a trial-and-error procedure. 4
● It involves guessing xW and then 3
determining if the above Eq is 2 xW2
xW
satisfied. xW1 xF
1
Calculation of values of 0
1/(y – x) 0.0 0.2 0.4 0.6 0.8 1.0
Values of x
x y y – x 1/(y – x)
Figure 11. Schematic showing the
graphical integration

23
 Numerical Integration of the Rayleigh Equation
Convenient method is Simpson’s 1/3rd rule, as described below
F
xF
dx From the plot estimate the values of f(x) as given below:
ln = ∫
W x (y − x)
;
f ( xw ) =
1
= say, P
Data given: F, xF, yD y − xW
W = F exp [ − A] ;
W

Assume a value for xW  x + xF  1

f w = = say, Q
xF xF
dx  2  y −  xw + xF 
A= ∫ f ( x )dx = ∫ ( y − x )
xW xW

 2 

1
f ( xF ) = = say, R
y − xF
A typical plot of f(x) vs x
F x −x   x + xF  
ln = A = F W  f ( xW ) + 4 f  W  + f ( x )
F 
W 6   2  
= ( xF − xW ) 6  × [P + 4Q + R ]

A W = F exp [ − A] W
xF F − xWW
yD = D=F-W
D
Check the error between yD given & yD obtained, if it
is within 5%, then xW assumed is acceptable, else
Figure 12. Batch distillation analysis guess another value till the error is within 5%

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Differential Distillation: Lab Set-up to verify the Rayleigh Equation
y or y* Example: CH3COOH + H2O mixture
xF
F dx
Rayleigh Equation: ln =
W x∫ ( y − x )
...(1)
W

 Assume a feed volume of 90 to 100 mL;

 Stop distillation, after collection of 30
to 35 mL of condensate;
 To measure the volume of Feed;
xW xD  To measure the volumes of Distillate &
Residue after distillation, ensuring
Residue Distillate complete condensation of vapor;
 To estimate xF, xW, xD of MVC from
Feed, Residue & Distillate respectively
Figure 13. Differential distillation: Laboratory  To determine F, W & D
Set up to verify the Rayleigh Equation  To calculate ln(F/W) [LHS of Eq (1)]
 To draw 1/(y - x) vs x curve
Boiling points: CH3COOH = 118 0C; H2O = 100 0C
 To locate xF & xW on the above curve
 To determine the area under the curve [RHS of Eq (1)]
 To study the values of RHS & LHS & hence the verification of the Rayleigh equation
25
 Steam Distillation
Basis of Steam Distillation
 Property of an immiscible liquid mixture
 For an immiscible mixture of A & B: mixture total vapor pressure = PvA + PvB at a
given Temp
 Bubble temperature of such a mixture < boiling point of either A or B

Steam distillation ⇒ a Separation process

 Live steam is blown through a liquid containing A (low volatility & solubility in
H2O)
 A vaporizes slowly (based on its vapor pressure at operating Temp) & leaves with
the steam
 A = target compound for recovery in a reasonably pure state
 Mixture may contain traces of non-volatile impurity or compound
 In some cases, steam distillation is similar to steam stripping

26
 Steam Distillation
 Feed containing A is steam distilled
 A has little miscibility with water
 Condensate has two layers which makes ease of
separation of desired product A
 Steam Coil: provided to meet the energy needs &
to avoid condensation of live steam
Applications:
 Separation of a high boiling material from solution.
Examples: decolorization/deodorization of
vegetable oils, recovery & purification of essential
oils
 Separation & purification of hazardous &
inflammable substances like turpentine
 Separation of thermally unstable substance from a
Figure 14. Schematic of Steam mixture
distillation  Separation of volatile impurities from waste water.
Examples: removal of NH3, VOCs (eg. halogenated
hydrocarbons) from waste water.

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 Summary
Following items have been discussed to meet the learning objectives
1. Calculation of molar enthalpies of vapor mixture & liquid solution
2. Method of drawing H-x-y diagram of a binary mixture
3. Method of drawing x-y diagram from H-x-y diagram of a binary mixture
4. Method of determination of composition of a mixture using H-x-y
diagram
5. Flash or Equilibrium distillation
6. Method of estimation of the composition of products as well as
enthalpy & composition of products
7. Differential or batch or the Rayleigh distillation
8. Derivation & application of the Rayleigh equation
9. Solving the Rayleigh equation by different methods
10. Experimental verification of the Rayleigh equation
11. Steam distillation

28
 References
● B.K.Dutta. Principles of Mass Transfer and Separation
Processes. 2nd Edition, Prentice Hall of India,2007. Chapter # 7
● R.E.Treybal. Mass Transfer Operations. 3rd Edition, McGraw Hill,
New Delhi, 1983.
● J.D. Seader & E.J. Henley. Separation Process Principles. 2nd
Edition. John Wiley & Sons, Inc. USA. 2006.
● A.Bandyopadhyay. Lecture Notes on Separation Process I /
Mass Transfer I; University of Calcutta. 2009 – 2024.

Thank You
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