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Vapor-Liquid Equilibrium Concepts

Vapour liquid equilibrium describes the static condition where the macroscopic properties of a system no longer change over time. Raoult's law states that the partial pressure of a component in a liquid mixture is equal to the mole fraction of that component times its vapor pressure as a pure component. Deviations from Raoult's law can be positive or negative. Dalton's law describes the total pressure of a system as the sum of the partial pressures of the individual components. Equilibrium diagrams like T-x-y, P-x-y diagrams graphically represent the vapor-liquid equilibrium at different temperatures and pressures. Fugacity is a concept used to study phase and chemical reaction equilibria and accounts for non-

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73 views15 pages

Vapor-Liquid Equilibrium Concepts

Vapour liquid equilibrium describes the static condition where the macroscopic properties of a system no longer change over time. Raoult's law states that the partial pressure of a component in a liquid mixture is equal to the mole fraction of that component times its vapor pressure as a pure component. Deviations from Raoult's law can be positive or negative. Dalton's law describes the total pressure of a system as the sum of the partial pressures of the individual components. Equilibrium diagrams like T-x-y, P-x-y diagrams graphically represent the vapor-liquid equilibrium at different temperatures and pressures. Fugacity is a concept used to study phase and chemical reaction equilibria and accounts for non-

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VAPOUR LIQUID

EQUILIBRIUM
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.

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