What is equilibrium?

At equilibrium no driving force for energy

or mass transfer .

Equilibrium is the static condition in

which no change occur in the
macroscopic properties of a system with
time

Raoults law
Raoults law states that the partial pressure is equal to product of vapor
pressure and mole fraction in liquid phase.

p1=x1.p10
Where,
p1-partial pressure of component
p10-vapour pressure of pure component
x1 -mole fraction of component in liquid phase

(a) a solution that shows positive deviation from

Raoult's law

(b) a solution that shows negative deviation from

Raoult's law.

Daltons law

Ptotal = p1+ p2
Where,
Ptotal -Total pressure
p1 ,p2 -Partial pressure of component.

Composition of liquid phase :

x1= p1/ p10
= partial pressure of component /vapour pressure of pure component

Composition in gaseous phase :

y 1= p1/ P

= partial pressure of component /total pressure

Raoults law becomes

yiP=xiPisat (i=1,2,3..n)
Where:
yi = Vapor-phase mole fraction.
xi = Liquid-phase mole fraction.
Pi = Vapor pressure of pure species i at the T of the system.
yi P = Partial pressure of species i.

VLE by Modified Raoults Law

yi P = xi i Pisat ( i= 1,2,..,N)
Where
i = Activity coefficient.

T-x-y diagram/boiling point diagram

Effect of pressure on VLE The high pressure

diagrams are above low pressure.

Equilibrium Diagram
Vapor composition is drawn against liquid comp at
constant pressure. Vapour is always rich in more
volatile component the curve lies above the diagonal
line.

Effect of varying pressure on equilibrium

diagram

P-x-y Diagram

Fugacity: It is derived from Latin, expressed as

fleetness or escaping tendency. It is used
to study extensively phase and chemical reaction
equilibrium.
G = RT ln f +
- Is an constant depends on temperature and nature
of gas.
fugacity has same units as pressure for an ideal gas.

Fugacity coefficient () :
Fugacity coefficient is defined as the ratio of fugacity
of component to its pressure.

=f/P
- Is the measure of non ideal behavior of the gas.

Activity(a):
It is defined as the fugacity of the existing condition
to the standard state fugacity

a=f/ fo
Activity coefficient :
It measure the extent to which real solution depart from
ideality.
ln=bx
ln=bx

Activity coefficient equations

Wohls three suffix equation

Margules equation
Van laar equation
Wilson equation
Non random two liquid (NRTL)equation
Universal quasi chemical (UNIQUAC)equation
Universal functional activity coefficient (UNIFAC)
method

Consistency test for VLE data

Using slope of ln curves

Using data at mid point
Redlich kister method
Using the coexistence equation
Using partial pressure data

Thank You