LLE Calculations

For two liquid phases at equilibrium

the fugacity of each component in
the phases must be equal.
For the binary case shown:

x1 1 = x1 1
(1 x1 ) 2 = (1 x1 ) 2
are the two relationships that
govern the partitioning of species
1 and 2 between the two phases.

CHEE 311

Lecture 30

Binary LLE Separations

The equivalent of a VLE flash calculation can be carried out on
liquid-liquid systems.

Feed

@ T, P

L, x1, x2

z1, z2

L, x1, x2

Given:

T, P and the overall composition of the system

F, z1, z2

Find:

L, x1, x2
L, x1, x2

CHEE 311

Lecture 30

Binary LLE Separations - Governing Eqn

Solving these problems requires a series of material balances:
Using a unit feed as our basis, an overall material balance yields:
(A)

F = 1 = L + L

A material balance on component 1 give us:

z1(1) =

x1 L

(B)

x1 L

Substituting for L from A into equation B:

(C)

z1 = x1 L + x1 (1 L )
An analogous material balance on component 2, yields:

z2 =

x 2 L

(D)

x 2 (1 L )

We have two equations (C,D) and three unknowns (L, x1 and x1).
We need an equilibrium relationship between xi and xi
CHEE 311

Lecture 30

Binary LLE Separations - Governing Eqn

Our LLE expression is:

x i i = x i i

or

1 1
x1 =
1

(14.74)

x 2

and

x 2 2
=
2

(E)

The governing equation we require to solve the problem is

generated from a final material balance on one of the liquid phases:
(F)
x + x = 1
1

Substituting equations C, D, E into the material balance F gives us

the final equation:

1
2
z1 ( )
z2 ( )
1
2
+
=1

1 + L 1 1 + L 1
1

CHEE 311

Lecture 30

Solving Binary LLE Separation Problems

Given:

T, P,F, z1, z2

Find:

L, x1, x2
L, x1, x2

The solution procedure follows that of binary VLE flash calculations

very closely.
You can immediately solve for x1 and x1 using the LLE
relationships
Or
You can solve the governing equation by iteration, starting
with estimates of x1 and x1 to determine activity coefficients,
and refining these estimates and L by successive
substitution.

1
2
z1 ( )
z2 ( )
1
2
+
=1

1 + L 1 1 + L 1
1

CHEE 311

Lecture 30

Vapour-Liquid-Liquid Equilibrium (VLLE)

In some cases we observe
VLLE, in which three
phases exist at
equilibrium.
F=2-+C
=2-3+2=1
Therefore, at a given P,
all intensive variables
are fixed, and we have
a single point on a binary
Tx,x,y diagram

CHEE 311

Lecture 30

Vapour-Liquid-Liquid Equilibrium (VLLE)

At a given T, we can
create Px,x,y diagrams
if we have a good
activity coefficient
model.
Note the weak
dependence of the
liquid phase
compositions on the
system pressure.

CHEE 311

Lecture 30