Dr. Jewel A.

Capunitan
Department of Chemical Engineering, CEAT - UPLB
2nd semester A.Y. 2015-2016
 process wherein two phases of different compositions
are brought into contact to initiate transfer of
components from one phase to the other
PHASE A PHASE B

-Mass -Mass
(species A) (species B)

under appropriate conditions, repeated contacting

and separation of phases can lead to an almost
complete separation of components.
Lab-scale distillation
Distillation column
Lab-scale solvent
extraction

Extraction column
 Physical Models
develop a model which reproduces the action of
operation

Equipment Knowledge
consider equipment operation

Empirical Method
test a proposed mathematical expression
 RATE OPERATIONS

EQUILIBRIUM STAGE MODELS

 Two streams are in continuous contact
Visualize carriers of property (mass, heat, momentum)
to arrive at an expression of rate of transfer between
the two streams
 Two streams or phases are brought into contact,
allowed to reach equilibrium then separated and
withdrawn, with the leaving streams in equilibrium

L EQUILIBRIUM L*
V* STAGE V

We will be studying EQUILIBRIUM STAGE MODELS in

this course.
 Phase equilibrium limitations
and rate of transfer obtainable in
a mass transfer operation can be
PHASE EQUILIBRIA used to calculate the required
size of the operating unit.

CALCULATION OF Specified product

NUMBER OF purity & recovery,
EQUILIBRIUM STAGES phase flow rates

CALCULATION OF
NUMBER OF ACTUAL Stage efficiency
STAGES

CALCULATION OF
PHYSICAL SIZE OF EACH Phase flow rates
ACTUAL STAGE
Concept of Equilibrium
condition for all combination of phases, wherein there is
zero net interchange of properties (e.g. mass, energy)

Description of a System
Phase may be defined as a physically distinct &
homogeneous portion of a system (solid, liquid, vapor/gas)
Description of a System
Variables in a system:
Intensive independent of the total quantity of the phase
(e.g. temperature, pressure, composition)
Extensive dependent of the total quantity of the phase
(e.g. volume)

Based on the number of components:

Binary 2 components
Ternary 3 components
Multicomponent - > 3 components
 J. Williard Gibbs: The equilibria between phases require
a balance of all potentials (T, P, chemical potential of
each component in each phase)
Chemical potential tendency of the chemical species to
leave the phase (instability)
The chemical potential of a particular species i in a
multicomponent system is identical in all phases at
physical equilibrium (at constant T & P) (J.W. Gibbs)

i i
(1) ( 2)
i
( 3)
... i
(N)
 In terms of fugacity (measurable quantity)

fi fi ... f i
(1) ( 2) ( 3) (N)
fi

Relationship between and f:

= +
 useful in predicting the number of intensive variables
that may be varied independently in an equilibrium
condition
If the number of variables in a system of several
components in equilibrium among several phase is
related to the number of equations relating them, the
result is:
F C P 2
Where: F = number of intensive variables that may be varied
independently
C = number of components
P = number of phases
EXAMPLES
1. Liquid water
2. Mixture of water and steam
3. V-L mixture of benzene and toluene

F C P 2
 also referred to as fractionation
or fractional distillation, it is the
most widely used separation
process in the chemical industry
separation technique that is
based on the differences in the
constituents volatility
applications:petroleum refining,
distillation of liquefied air,
alcohol distillation
fi V fi L
 Shows that the compositions in an equilibrium mixture
depend upon the total pressure of the system and
upon the vapor pressures of the components

PT y i Pi x i
s

PT = total pressure
yi = mole fraction of a in the vapor
PiS = vapor pressure of a at the equilibrium T
xi = mole fraction of a in the liquid
Applicability
Accurate only in predicting VLE for an ideal solution in
equilibrium with an ideal gas mixture (ideal systems)
Ideal solutions components with similar structures
and physical properties
Benzene-toluene, propane-butane, methanol-ethanol

Sources of Vapor Pressure Data, PiS

Graphically (Appendix D-1, Foust)

Antoines equation (constants found in Appendix D-2e)

APPENDIX D-1 (Foust, et al, 1980)
 Log VP = A B/(C + T)

Where: A, B, C = Antoines constants

(Appendix D-2e, Foust)
VP = vapor pressure, mmHg
T = temperature, oC

Ex: Determine the vapor pressure for n-hexane at 100oF.

 The vapor pressure of the solute in a very dilute
solution can be used in a Raoults Law formulation as a
constant over a significant range of concentrations

Pi Hi x i For dilute solutions only

Pi = PT yi
= partial pressure of component i in the vapor
Ha = Henrys Law constant
= experimentally measured (App. D-3, p. 734,
Foust 2nd ed.)
xi = mole fraction of component i in the liquid
 Ratio of equilibrium compositions
Relatively convenient in engineering calculations for
phase equilibrium
K-value experimentally determined constant

yi K i xi
Sources of Ki
Graphically (Appendix D-2, Foust; Fig. 13-14 of Perrys
Chem. Eng. Handbook, 7th ed.)
K equation (constants found in Table D-2d, Foust)
APPENDIX D-2a (Foust, et al, 1980)
K-value determination
by graphical means
(Perry, et al, 1997)
K-value determination
Table D-2d, Foust et.al.
K-value for ideal systems:

Pi S
Ki PT
Dependent on equilibrium T & P only

K-value for dilute systems:

Ki Hi
PT
SIDE NOTE: For LLE

KDi = distribution coefficient or LLE ratio

= xi1 / xi2
 Index of relative ease or difficulty of separation
Separation factor: ratio between equilibrium ratio
By convention, component a will be the more volatile
species in the solution
Ka
ab
Kb
ab 10,000 Almost perfect separation in a single stage
ab = 1.1 Almost perfect separation requires a hundred stages
RELATIVE VOLATILITY for non-ideal systems

ya (1 xa ) ab xa
ab ya
xa (1 ya ) 1 xa ( ab 1)

RELATIVE VOLATILITY for ideal systems

S
Pa
ab S
Pb
1. A mixture of butane and pentane is at equilibrium at
300 kPa pressure and 40oC. Calculate the
composition of the liquid and vapor phases using (a)
Raoults Law and (b) using experimental values of Ka.

2. What is the relative volatility of butane to pentane

at 40oC and 465 psia?

Antoines constants:
A B C
butane 6.83029 945.9 240.0
pentane 6.85221 1064.63 232.0
Read pp. 29-38, Foust, et.al.
Secure and bring copies of App. D-1 to App. D-2e, pp.
728-732, Foust et.al., 2nd ed.