“Oil and water

just don’t mix.”

lubility of a Liquid in a Liquid
Mole Balance
I II
T P
Ni = Ni + Ni
I I II II
Ni = xi Ni + xi Ni
NI
xi I LIQUID I o
Equilibrium Relationship
xi
N II f iI = f iII
xi II LIQUID II
xiI γ iI = xiIIγ iII
lubility of a Liquid in a Liquid
T-x Diagram: 2,6-dimethyl pyridine-
water system

tie line
lubility of a Liquid in a Liquid
T-x Diagram: methyl ethyl ketone-
water system
T-x Diagram: perfluoro-n-heptane in
various solvents
Measurement of Liquid-
Liquid Equilibrium
hy do two liquid phases separate?
CONCEPT: The equilibrium criterion for a closed system at constant
T and P is that the Gibbs free energy of the system be a minimum.
hy do two liquid phases separate?
d 2G > 0 phase stability criterion

CONDITION FOR UPPER CONSOLUTE TEMPERATURE

 ∂ 2G   = 0 for some value of x1 at T=Tuc
  
 ∂x 2  > 0 for all values of x1 at T >Tuc
 1 T ,P
CONDITION FOR LOWER CONSOLUTE TEMPERATURE

 ∂ 2G   = 0 for some value of x1 at T=Tlc

  
 ∂x 2  > 0 for all values of x1 at T <Tlc
 1 T ,P

A
For a Margules mixture Tuc =
2R
 TERNARY SYSTEMS
Triangular Diagram
IK-Acetone-Water System at 298.15 K

plait point
binodal curve

tie line
tone-Water-1,1,2-trichloroethane System
TERNARY SYSTEMS Triangular
Diagram
ASSIGNMENT
Problem 11.2-4
11.2-12
11.2-14
11.2-15
ases in Thermodynamic Equilibrium
T P T P T P

VAPOR GAS LIQUID

LIQUID LIQUID LIQUID

Binary mixtures
G i I = G i II
Basis of analysis:
f i I = f i II
putational skills you must have gained so
Vapor-Liquid Equilibria
Compute conditions of VLE and develop x-y, T-x-y, and P-x-y
diagrams for ideal mixtures and for non-ideal mixtures (using activity
coefficient models).
Predict low-pressure VLE when no experimental data are
available.
Do bubble point, dew point, and partial vaporization calculations for
both ideal and non-ideal systems.
Solubility of a gas in a Liquid
Compute the solubility of a gas in a liquid

Solubility of a liquid in a Liquid

Compute the compositions when two partially miscible liquids are
mixed
NSIDER>>> isobutane (1) – furfural (2) mixture
T = 37.8oC P = 5 bar
vap 
P  T = 37.8  C  = 4.956 bar
1  
vap 
P  T = 37.8  C  = 0.005 bar
2  

x I = 0.1128 x II = 0.9284 → γ I = 8.375 γ II = 1.018

1 1 1 1
x I = 0.8872 x II = 0.0716 → γ I = 1.030 γ II = 12.77
2 1 2 2

phase I
Question>>>
Without changing the temperature, is it possible to form a phase II
vapor phase that is in equilibrium with the 2 liquid phases?
CONCEPT: a liquid mixture will vaporize when its total
vapor pressure equals the imposed pressure.

What is then the bubble-point pressure of the system

and the composition of the vapor that forms?
Phase behavior of isobutane-furfural
mixture at 37.8oC
Question>>>
Say, you are doing vapor liquid-equilibrium calculations.
When should you be concerned about the possible
existence of liquid-liquid equilibrium?

Answer>>>
When results of the calculation of vapor pressure as a
function of mole fraction would show an unusual maximum
and local minimum, you should undertake a liquid-liquid
phase equilibrium calculation.
se behavior of ethanol-n-hexane system
Phase behavior of ethanol-n-
hexane system heterogeneous
at P = 0.133 bar azeotrope
VLLE CALCULATIONS
Stepwise

( x i γ i ) I fiL = ( x i γ i ) II fiL = y i P
A
B

Simultaneous
THREE-PHASE FLASH PROBLEMS

Simultaneous equations:
equilibrium equations for all species Degree of Freedom?
mass balance equations
ASSIGNMENT
Problem 11.3-1
11.3-2
11.3-4
11.3-5
11.3-16
Partitioning of a Solute Among
Two Coexisting Liquid Phases

mixture with add solvent shake solute partitions

solute

The two liquids are completely immiscible!

e Distribution Coefficient
concentrat ion of solute in phase I
K=
concentrat ion of solute in phase II

xI γ II
Kx = 1 = 1
x II γI
1 1

COMPLICATIONS
1. presence of undissolved solute
2. the two liquids are partially miscible
erimental Determination of K
Octanol-Water partition Coefficient
for Species i
concentrat ion of i in O − rich phase
K=
concentrat ion of i in W − rich phase

CO C O γW
KOW ,i = i = i
CW C W γO
i i

Sometimes used as a measure of hydrophobicity.

ASSIGNMENT
Problem 11.4-1
11.4-2
11.4-4