SROFF S. R.

ROTARY INSTITUTE OF
CHEMICAL TECHNOLOGY
 Name : Digpalsinh Chauhan
 Enroll no. : 140990105009
 Sub : MTO-ll
 Topic : VLE & Differential distillation
Contents
 Vapor liquid equilibrium (VLE)
 Differential distillation & material balance
Vapor liquid equilibrium
 Under given set of conditions, the equilibrium vapour composition
is related to the liquid composition , it is called vapour liquid
equilibrium.
 Basic data for distillation are the equilibrium existing between the
vapour liquid phases of a system under consideration.
 The equilibrium in vapour liquid system is governed by phase
rule.
F= C–P+2
here phases = 2 and components = 2
 The degrees of freedom (F) =2 so for distillation there are four
variables : Temperature , Pressure , Liquid composition & Vapour
composition.
 Two of these four quantities need to be fixed to define the system
in equilibrium.
 Vapor liquid equilibrium
 Constant pressure vapour liquid equilibrium
 If the boiling temperature is plotted versus the liquid composition
x, we get the ‘bubble point curve’. A plot of the temperature
versus y* , the equilibrium vapour composition, gives the ‘dew
point curve’.
 The bubble and dew point curves for binary mixture of A and B
at 1 atm total pressure are shown in fig. Both the liquid and
vapour phase concentrations of A (the more volatile) are plotted
along the horizontal axis and the temperature is plotted along
the vertical axis.
 The equilibrium diagram is shown in the T-x- y* diagram in which
x is plotted along the horizontal axis and y* along the vertical
axis.
Diagram for cyclo-
pentane & benzene
system at 1 atm
Vapor liquid equilibrium

 Fig. (b) show the equilibrium diagram on the x-y plane.

 It can be obtained directly by plotting the experimental data.
 It can also be drawn from the bubble point and dew point curve.
Vapor liquid equilibrium
 Constant temperature vapour liquid equilibrium

 Equilibrium data can be also collected from at constant

temperature by plotting P- x,y* diagram.
 The region below the curve PB – V – E| – PA represent the
superheated vapour , the region above the PB – L – E – PA
represent the subcooled liquid.
 The equilibrium composition corresponding to the tie line LV is
represent by the point QP on the x-y diagram.
Diagram for
dichloromethane & 1,2
dichloroethane system
at 40oC
Differential distillation
In this type of distillation technique, a known quantity of a
liquid mixture is charged into a jacketed kettle or still. The jacket
is provided for heating the liquid mass in the still with the help of
heating medium such as steam.
The charge is boiled slowly, the vapours formed is
withdrawn and fed to a condenser where it is liquified and
collected in a receiver as a distillate. In the early stage of
distillation, the vapour, so the distillate, leaving the still is rich in
the more volatile component and as the distillation proceeds the
liquid in the still becomes lean with respect to the more volatile
component. The composition of the less volatile component
thereby increases and hence the boiling point increases.
The product from such units can be collected in several
receivers, called cuts, to give the products of various purities over
 Differential distillation
the length of distillation period. The distillation is continued till the
boiling point of the liquid reaches a predetermined value and the
content of the still is finally removed as residual liquid containing
majority of the less volatile component.
Differential distillation
 Material balance
Let F be the kmol of a liquid mixture (A+B) containing xf mole
fraction of A which is charged to a distillation still.
Let D be kmol of distillate and W be kmol of residual liquid in
the still which are obtained at the end of operation.
Let yDavg and xw be the mole fraction of A in distillate and
bottom residual liquid.
Let L be kmol of liquid left in the still at any time during course
of distillation and let x be the mole fraction of A in the liquid.
Let a very small amount dD kmol of distillate of composition y
in equilibrium with the liquid is vaporised. Then, the composition
and the quantity of liquid decreases from x to x-dx and L to L-
dL, respectively.
Differential distillation

 Then the overall material balance at any time is

L = L – dL + dD
dL = dD
Material balance of component A gives
Lx = (L – dL) ( x – dx) + y dD
Lx = Lx – L dx – x dL + dL dx + y dD
here dL dx being very small can be neglected.
0 = -L dx – x dL + y dD
0 = -L dx – x dL + y dL
L dx = (y-x) dL
Differential distillation
dL dx

L yx
Integrating the above equation between the limits:
when, L= F , x=xf
and when, L=W, x=xw
F xf
dL dx
W
 L
 
xw y  x
xf
F dx
ln  
W xw y  x
Differential distillation
F = initial moles in the still/kettle,
W= moles left in the still. xf and xw are the initial and final
composition of the liquid respectively.
The above final equation is known as the Rayleigh equation.