PHASE EQUILIBRIA

References: Unit Operations of Chemical Engineering by

McCabe, Smith & Harriott, 7th Ed.
Principles of Transport Processes & Separation
Processes by Geankoplis, 1st Ed.

Prepared by: Ma. Junallie F. Pomperada, ChE, MEngr, PhDTM

Phase Equilibria
• Mass transfer ceases when an equilibrium between
the two phases is reached.

• The rate of mass transfer is directly proportional to

the driving force (which is a departure from
equilibrium condition).

• To be able to evaluate the rate of mass transfer, the

driving force has to be accurately determined which
in turn rely on the equilibria between phases.
Phase Equilibria
• In nearly all situations two phases are involved
except two solid phases.

• The controlling variables are the intensive properties

of temperature, pressure and concentration.

• Equilibrium data can be shown either in the form of

tables, equations and graphs.

• For most operations however, the pertinent

equilibrium relationships are shown graphically.
BASIS FOR PHASE
EQUILIBRIUM
I. Phase Rule

F = C - P + 2

where: F - number of degrees of freedom

C - number of components
P - number of phases
Degrees of Freedom or Variance

 number of independent intensive variables –

temperature, pressure and concentrations – that
must be fixed to define the equilibrium state of the
system

 If fewer than F variables are fixed, an infinite

number of states fits the assumption while if F is
too many, the system is overspecified.
Degrees of Freedom or Variance

 for a two-phase system, variance is equal to 2 which

is also equal to the number of components. If for
example, pressure is fixed, the liquid-phase
concentration can be changed independently, then
the gas-phase composition and temperature (for
liquid-gas equilibria) can be determined.

Refer to the text by McCabe for specific examples

on Gas Absorption , Distillation & Liquid Extraction.
II. Raoult’s Law

pA  PA xA
where: pA – partial pressure of A in the gas phase
xA – mole fraction of A in the liquid phase
PA – vapor pressure of pure A

Note: The Law holds for ideal solutions only

(system which have substances similar
to each other)
III. Henry’s Law

pA  HxA or y A  H ' xA

where: pA – partial pressure of A in the gas phase

xA – mole fraction of A in the liquid phase
H – Henry’s constant
H’ = H/P
P – total pressure
IV. K factor – Distribution Coefficient

• ratio of the mole fractions in the yie

vapor and liquid phases at Ki 
equilibrium xie

'
• If Raoult’s Law and Dalton’s Law Pi
hold then; Ki 
P
IV. K factor – Distribution Coefficient

• If Raoult’s Law holds then the ratio of the K

factors and relative volatility of the components
are the same
yi
xi K i Pi '
 ij    '
yj K j Pj
xj

• K factors are strongly temperature-dependent but

the relative values of K for two components
change only moderately
Sample Problem 1

The partial pressure of CO2 in air is 1.333 x 104

Pa and the total pressure is 1.1333 x105 Pa. The
gas phase is in equilibrium with the water
solution at 303K. What is the value of xA of CO2 in
equilibrium in the solution?

Note: Henry’s Law Constant for CO2 @ 303.2K = 0.186 x 104

Appendix A.3-18 pg 988, Geankoplis
H (atm/mole fraction) G
Sample Problem 2

At 303K the concentration of CO2 in water is 0.90

x 10-4 kg CO2/kg water. Using Henry’s Law
constant, what partial pressure of CO2 must be
kept in the gas to keep the CO2 from vaporizing
from the aqueous solution?

G
PHASE EQUILIBRIA OF
DIFFERENT PROCESSES
 GAS-LIQUID
EQUILIBRIA
A. Absorption
B. Desorption/Stripping
C. Distillation
c.1 differential distillation
c.2 flash distillation
c.3 open-steam batch distillation
c.4 Mc-Cabe Thiele Method
c.5 Ponchon-Savarit Method
LIQUID-LIQUID
EQUILIBRIA
EXTRACTION
LIQUID- SOLID
EQUILIBRIA
LEACHING
GAS-SOLID EQUILIBRIA
ADSORPTION
-END-