Ideal Solution & Raoult's Law

Raoult's Law states that, for an ideal solution, the equilibrium partial
pressure of a component at a fixed temperature T equals the product
of its vapor pressure (when it is pure) and its mole fraction in the
liquid:
pA = POA xA
where
pA = equilibrium partial pressure of component-A in the gas at
temperature T
POA = vapor pressure of pure liquid A at temperature T
xA = liquid-phase mole fraction of component-A at temperature T
Note: The vapor pressure is a constant at constant temperature.
Hence, from the equation, we see that Raoult's Law predicts a linear

Daltons Law
Dalton's law states that the total pressure exerted by the mixture
of non-reactive gases is equal to the sum of the partial
pressures of individual gases.
Total pressure,

PT = pA + pB
= POA xA + POB xB
= POA xA + POB (1 - xA)
= xA (POA POB) + POB

If the vapor may be taken as an ideal gas then:

pA= PT yA

pB = PT yB

yA = pA/PT =

yB = pB/PT =

POA x A

POA x A POB x B

POB x B
POA x A POB x B

POA x A
POB x A (POA POB )

P OB x B
POA x B (POB POA )

POA

The constant-temperature phase

diagram for an ideal solution is
shown.
For a binary mixture of A and B;
pA = POAxA; pB = POBxB = POB (1 - xA)

POB

The partial pressures vary linearly

with xA. This is shown as pA vs. xA
and pB vs. xB
For an ideal gas mixture, the total
pressure is the sum of the partial
pressures.
Total pressure PT = pA + pB.

Relative Volatility
Distillation processes require a difference in volatilities of the
components. The greater the difference, the easier it is to separate
the components. A measure for this is termed the relative volatility.
Volatility of component-i: partial pressure of component-i divided by
mole fraction component-i in liquid
For a binary mixture of A and B, therefore:
Volatility of A = pA / xA

Volatility of B = pB / xB

where p is the partial pressure of the component and x is the liquid

mole fraction.
Relative volatility: the ratio of volatility of A (More Volatile Component
MVC) over volatility of B (Lower Volatile Component LVC):

Relative volatility is therefore a measure of separability of A and B.

Since xB = 1 - xA , we have:

Replace with pA = yAPT ; pB = ( 1 - yA )PT so as to express

everything in terms of the MVC:

Dropping subscript 'A' for more volatile component,

simplifying: we obtain the equation for relative volatility:

and

The larger the value of above 1.0,

the greater the degree of separability,
i.e. the easier the separation. Recall
that when a system has reached
equilibrium, no further separation can
take place.
The net transfer rate from vapor to
liquid is exactly balanced by the
transfer rate from liquid to vapor.
Separation by distillation is only
feasible within the region bounded by
the equilibrium curve and the 45 o
diagonal line.

From the equilibrium curves, we see that the greater the distance
between the equilibrium curve and the diagonal line (where y = x), the
greater the difference in liquid and vapor compositions and therefore
the easier the separation by distillation.

Flash Distillation

Distillate
vapor to total
condenser
Feed

V, yA, HV

F, zF, hF

Heating
source QH

Bottoms
liquid
B, xA, hB

FLASH (EQUILIBRIUM) DISTILLATION

This is defined as a single-stage continuous operation
where a vapor mixture is partially condensed or a liquid
mixture is partially vaporized. the vapour produced and the
residual liquid are in equilibrium and are then separated
and removed. The incoming fluid is first pressurized and
heated, and then fed through a reducing valve into the
flash drum. Because of the large pressure drop, part of the
fluid vaporizes extremely rapidly.

Feed
F, zF, hF

Distillate
vapour to
total
condenser
V, yA, HV

Heating
source QH
Bottoms
liquid
B, xA, hB

Flash can be seen as a distillation operation with only one

single-equilibrium stage. The flash operation stops when the
vapor and the liquid stream reach the equilibrium
compositions at the flash pressure and temperature. The
two streams obtained can be easily separated.
MATERIAL BALANCE EQUATIONS:
F = B + V;
FzF= BxA + VyA
ENERGY BALANCE EQUATION:
FhF + QH = BhB + VHv

Feed
F, zF, hF
Heating
source QH

Distillate
vapour to
total
condenser
V, yA, HV

Bottoms
liquid
B, xA, hB

Consider a binary mixture of A (MVC) and B (LVC). The feed is

preheated before entering the separator and flows through a
pressure-reducing valve to the separator where the separation
between the vapour and liquid takes place. The quantity of A
produced in the vapour (and in the liquid) depends on the
condition of the feed, i.e. how much of the feed is entering in
the vapour phase, which in turn is controlled by the extent of
heating. In other words, the degree of vaporization affects the
concentration (distribution) of A in the vapour phase and liquid
phase.

Feed
F, zF, hF

Distillate
vapour to
total
condenser
V, yA, HV

Heating
source QH

Bottoms
liquid
B, xA, hB

There is a relationship between the degree of heating

(vaporization) and mole fraction of A in the vapor and liquid (y
and x). This relationship is known as the Operating Line
Equation.
If no vaporization takes place, then the liquid leaving the
separator will have the same composition as the feed.
If total vaporization occurs, the vapour will also have the same
composition as the feed.

Feed
F, zF, hF

Distillate
vapour to
total
condenser
V, yA, HV

Heating
source QH

Bottoms
liquid
B, xA, hB

Define f : mole fraction of the feed that is vaporized

and withdrawn continuously as a vapor.
Therefore, for 1 mole of binary feed mixture, (1- f) is the
mole fraction of the feed that leaves continuously as a liquid.
Let
yA = mole fraction of A in vapor leaving
xA = mole fraction of A in liquid leaving
zF = mole fraction of A in feed entering

Feed
F, zF, hF
Heating
source QH

Distillate
vapour to
total
condenser
V, yA, HV

Bottoms
liquid
B, xA, hB

The distribution of A in the vapor and liquid phases (y A and xA)

depends on the amount of preheating that takes place. Based
on the definition of f, the greater the heating, the larger the
value of f which will be obtained.
If the feed is completely vaporized, then f = 1.0. Thus, f varies
from 0 (no vaporization) to 1 (total vaporization).
To see how yA and xA change as f changes, a material balance
is used to obtain an operating line equation, which relates the

From a material balance for 1 mole of feed then for the more
volatile component (A):
1. zF = f yA + (1 - f) xA
f yA = zF - (1 - f) xA
Re-arrange into:

1 f
zF
x

A
f
f

y A

From the above operating line equation, for a given value of

f and zF, there are certain values for yA and xA respectively.
The fraction f depends on the enthalpy of the feed and the
enthalpies of the vapour and liquid leaving the separator.
Dropping the subscripts gives the general operating line
equation

1 f
1
x

xF

f
f

 1 f
1
x

xF

f
f
For a given feed
condition
with
a
known value of f and
z F,
the
above
equation is a straight
line equation with
slope = -(1-f)/f and
intercept = zF / f.
y

If x = zF, and y = zF
(no separation), The
operating
line
crosses the point (xF,
xF) for all values of f.
This provides one
point
on
theoperating line on the equilibrium curve is
With zF known,
the
operating line. The
constructed. The Intersection between the operating line and
other point can be
the equilibrium curve yields the values for yA and xA. This is
obtained from the

 1 f
1
x

xF

f
f

:The above operating line can also be written as

B
F
x
A
zF

V
V

yA
Since

V
,
F

1 f
and

B
F

The energy balance is an independent equation, where the

only unknown is QH while hF, hB and Hv can be calculated or
read from an enthalpy-composition diagram for the
binary mixture.
F h F + QH = B h B + V H v
:For example
hF = xA CpA(T ) + xB CpB(T )

Analysis of Operating Line: Changes in Fraction

Vaporised
For a given feed composition, xF is fixed. When the
fraction of feed vaporized is changed, the mole fraction
MVC in the vapor and liquid products changes
accordingly.

f=0
no
vaporisatio
n
f=1
Complete
zF
vaporization

The Figure below shows how the temperature and mole fraction
change on a phase diagram.