Liquid-Liquid Equilibrium

Ternary System

Most practical situations involving liquid-liquid equilibrium involve

three or more components.

Our attention is with three component systems. In this process, a

solute is removed from a feed stream by contacting it with a solvent.

The solute is quite soluble in the solvent, while the other component

in the feed is less soluble.

 Liquid-Liquid Equilibrium
Terminology
Solute Component (1)
Original solvent Component (2)
Extractive solvent Component (3)
x1S, x2S and x3S are the composition of the three components in (solvent
rich phase) 1,2,3 respectively.
x1R, x2R and x3R are the composition of the Three components in the
(raffinate phase) 1,2,3 respectively.

Feed Raffinate-rich phase

(component +original solvent) (x1R1, x2R1 , x3R1)

solvent-rich phase
Extractive solvent (x1S1, x2S1 , x3S1)
 Liquid-Liquid Equilibrium

The solvent phase is rich in solvent and preferentially soaks up

component 1 (the solute), which we are trying to separate from the
other component in the feed (component 2, raffinate).
The raffinate phase is the liquid phase which is rich in the component
2 (raffinate) and from which the solute (component 1) is being
removed.
The original feed is usually a mixture of solute (component 1) and
raffinate (component 2).
The solvent-rich phase contains mostly solvent (component 3) and
solute (component 1) and only a small amount of raffinate (component
2)
The raffinate-rich phase contains mostly solute (component 1) and
raffinate (component 2), but also possibly some small amount of
solvent.
Liquid-Liquid Equilibrium
 Liquid-Liquid Equilibrium

Triangular Diagrams
Ternary systems are represented on two types of triangular diagrams:

1. Equilateral triangles
 Liquid-Liquid Equilibrium
2. Right Triangles
 Liquid-Liquid Equilibrium
Mixture
[50% Acetic + 20% H2O + 30%vinyl acetate]

(Solute)

Extractive
Original solvent
solvent
 Liquid-Liquid Equilibrium
b) Liquid-liquid Equilibrium tie lines (LLE Tie lines)

Different chemical systems give different types of triangular diagrams.

 Liquid-Liquid Equilibrium
The phase boundary, called the solubility line, is the solid line. Within
the two-phase region,
liquid-liquid equilibrium lines (the dashed lines) connect compositions
of the two phases that are in equilibrium with each other
The left side of the phase boundary gives the compositions of the
raffinate-rich liquid phase (xjR).

The right side of the phase boundary gives the compositions of the
solvent-rich liquid phase (xjS).
The LLE tie-lines and the equilibrium phase boundary are normally
found by laboratory experimentation.

A mixture that has an overall composition inside the two-phase region

will split into two liquid phases with compositions given at the two ends
of the LLE tie-line.
 Liquid-Liquid Equilibrium
A conjugate line can be used to
locate the tie-lines.
From point A on-the left phase
boundary, the other end of the
tie-line is found by drawing a
horizontal line to the conjugate
line.
A vertical line is then drawn from
the point M intersection to the
right phase boundary. The point M
of intersection of this line and
the right phase boundary (point
B in the figure) is the other end
of the tie-line.
 Liquid-Liquid Equilibrium
As the system becomes richer in solute, the tie-lines get shorter and
ultimately become just a point at the plait point P. Outside the two-
phase region, a single, homogeneous liquid phase exists.

Effect of Temperature on solubility

Usually, the solubility increases as the

temperature increases, for this reason,
most liquid-liquid extraction systems
operate at low temperatures and some
times even require refrigeration.
Pressure, on the other hand, has little
effect on solubility.
 Liquid-Liquid Equilibrium

if we specify only one concentration of one liquid phase, all the other
concentrations can be immediately determined from the phase diagram
For example, if we fix the concentration of component 1 in the
raffinate-rich phase (x1R), we can read from the diagram:

1. The concentration of component 3 in the raffinate-rich phase (x3R),

by using the left side of the solubility curve.

2. The concentrations of components 1 and 3 in the solvent-rich phase

that is in equilibrium with the raffinate-rich phase, by going to the other

end of the LLE tie-line. The concentrations x1S and x3S are read from

the right side of the solubility curve.

 Liquid-Liquid Equilibrium
Example: Thirty thousand kg/hr
of a ternary mixture of 19
weight percent isopropyl
alcohol (IPA), 41 weight
percent toluene, and 40
weight percent water are
fed into a, decanter
operating at 25C. the figure
gives the LLE data for the
system. Determine the
compositions and flow rates
of the two liquid streams
leaving the decanter.
 Liquid-Liquid Equilibrium
The overall compositions of the feed
(z1 = 19 percent and z2 = 40
percent) are located on the
diagram.
The compositions of the two liquid
phases are read off the diagram at
the two ends of the LLE tie-line.

The raffinate-rich phase is 14

percent IPA and 2 percent water
(the rest being toluene).

The solvent-rich phase is 23

percent IPA and 74 percent water.
 Liquid-Liquid Equilibrium
Total mass: 30000 = S + R

Water = (30000)(0.4) = S(0.74) + R(0.02)

Solving the last two equations simultaneously gives

S = 15833 kg/h
R = 14176 kg/h

IPA in = (30000)(0.19) = 5700 kg/h

IPA out = S(0.23) + R(0.14)
= (15833)(0.23) + (14176)(0.14) = 5625 kg/h

The difference is due to the accuracy of reading composition from the diagram
 Liquid-Liquid Extraction
In liquid-liquid extraction, a liquid of two or more components to be
separated is contacted with a second liquid phase, called the solvent,
which is immiscible or partially miscible with one or more components
of the liquid feed.

The simplest liquid-liquid extraction involves only a ternary system. The

feed consists of two miscible components, the carrier (C) and the
solute (A). Solvent (S) is a pure component. Components (C,S) are at
most only partially soluble in each other. Solute (A) is soluble in (C)
and completely or partially soluble in S.

During the extraction process, mass transfer of (A) from the feed to the
solvent occurs, with less transfer of (C) to the solvent, or (S) to the
feed.
 Liquid-Liquid Extraction
Liquid-liquid extraction is used to separate components in situations where:

1. Relative volatilities are quite close to unity ( < 1.1), making distillation
very costly. (Distillation requires tall towers due to the existence of
many trays, and high energy consumption because of high reflux
ratios.)

e.g. A mixture of benzene and cyclohexane. The normal boiling points of these organics
are 80.1C and 80.7C, respectively, making their separation by distillation impractical

2. Thermally sensitive components will not permit high enough

temperatures to produce a vapor-liquid system at reasonable pressures
(pressures greater than 10-50 mm Hg).
 Liquid-Liquid Extraction
EQUIPMENT
Different mechanical devices are used in liquid-liquid extraction such as:

1. The simplest is a mixer/settler, or decanter, in which the two liquid

phases are separated.

2. Plate towers, packed towers, and mechanically agitated mixers

(rotating disk contactors)

the number of stages tends to be much smaller than in distillation

columns. This is due to the larger settling times required for liquid-liquid
separation because of the small density differences between the liquid
phases.
Liquid-liquid extraction columns are sometimes operated in a pulsed
mode.
Liquid-Liquid Extraction

Extractor/stripper process.
 Liquid-Liquid Extraction
1. Mixer/ Settler

Mixing vessel with variable-speed Horizontal gravity-settling vessel.

turbine agitator
 Liquid-Liquid Extraction
2. Spray column
 Liquid-Liquid Extraction
3. Packed column

Feed
Extract

Single-section Two-section Dual solvent with

cascade cascade two-section cascade
Liquid-Liquid Extraction
Liquid-Liquid Extraction
 Liquid-Liquid Extraction
GRAPHICAL MIXING RULES
If we have two streams that contain three components and mix them together.
Let one of these streams be stream A with flow rate FA (kg/h) and composition
x1A, x2A and x3A (weight fractions of components 1,2, and 3), and let the other be
stream FB with corresponding composition x1B, x2B and x3B . The mixed stream
leaving the mixer will have a flow rate FM and composition x1M, x2M and x3M . A
flow diagram is as follows:

FA
x1A, x2A , x3A
FM
x1M, x2M , x3M
FB
x1B, x2B , x3B
 Liquid-Liquid Extraction

To determine the location of the mixture composition on a graph, since there are
three components, only two coordinates are needed to completely specify the
composition of any stream. We can use either right or equilateral triangular plots.
If we use right-triangular plot. locate point A with coordinates (x1A, x2A ) and point
B with coordinates (x1B, x2B). The point M with coordinates (x1M, x2M ) representing
the mixture will lie some place on the graph.
 Liquid-Liquid Extraction
After mixing point M is supposed to lie on a straight line joining the A
and B points. If we can show that the angles and in the figure are
equal, then M must lie on a straight line between A and B.

The total mass balance for the system is

(1)

Component balances for components 1 and 2 are

(2)

and (3)
 Liquid-Liquid Extraction

Rearranging these two equations, we obtain:

Solving for the ratio FAIFB, we have:

or
 Liquid-Liquid Extraction

These two ratios are the tangents of the angles and , hence, tan
= tan . Therefore, = , and we have proven that the line AMB is a
straight line.
The coordinates of the point M can be solved for analytically by using
equations (1), (2), and (3). Alternatively, M can be located graphically
where the distance from the point A to the point M divided by the
distance from the point M to the point B is equal to the ratio FB/FA.