Phase Equilibria - Ternary System

PHASE EQUILIBRIA: TERNARY SYSTEM We aim for the solute (A) to be mostly in the extract stream.
• Equilibrium: a stage when chemical potential of any Raffinate: residual solute in this layer = xR, A
component present in the system stays steady with
time Distribution
• Phase Equilibria how the solute partitions itself = DA = yE, A / xR, A
o
o the study of the equilibrium which exists measure of affinity of solute
o
between or within the different states of 0 0
μ R- μ E chemical potential difference
matter, namely, solid, liquid, ang gas o DA = =
RT (R)(temperature)
o application of the principles of
thermodynamics to the study of the Liquid-liquid extraction (LLE)
equilibrium relationships within or between
phases, corresponding to homogeneous and Where
heterogeneous phase equilibria, respectively.
o E.g., equilibrium of a liquid and its saturated • Bioseparations
vapor, the equilibrium of water and ice at the • Nuclear (Uranium recovery)
melting point of ice, and the separation of a • Mining: nickel/cobalt; copper/iron
mixture of water and triethylamine into two • Perfumes, fragrances, and essential oils
immiscible layers, or phases, that differ in • Fine and specialty chemicals
density. • Oil sands: extract bitumen away from water
What is phase equilibrium in thermodynamic sense? Why
Phase equilibrium is the state of thermodynamic systems in • Temperature sensitive products

which the different phases of the substance having common • High purity requirements
boundary surfaces do not vary quantitively. • High-boiling point species in low quantity
• Need to separate by species type
Criteria of Phase Equilibria • Close-boiling points, but high solubility
difference
1. Temperature and the pressure of the phase should be
• Azeotrope-forming mixtures
equal.
2. The chemical potential of each component in each of Extractor types: 3 major steps required
the phases that is present are equal.
3. The global Gibb’s Free Energy is at minimum. (G = 0 at
equilibrium)
Ternary System: have three non-reactive components. In liquid

systems, the components may or may not be partially soluble.
Ternary Phase Diagram: represents the phase behavior of

mixtures containing three components in triangular diagram. A 1. Mixing / contacting
ternary phase diagram shows possible phases under equilibrium • Turbulent contact between liquid phases
according to the position of a mixture of three components at • Small droplet dispersion in a continuous
constant temperature and pressure. phase
Ternary Extraction • Which phase is dispersed?
• Mass-transfer between phases
• Limited by solute loading in solvent
2. Phase Separation
Raffinate • Reverse of above mixing step
Feed
• Drops come together and coalesce
EXTRACTOR • Relies on density difference
Extracting Extract 3. Collection of phases leaving the unit
solvent
• Split the raffinate from the extract
Main Aims
Solute: species we aim to recover (A) from the feed
• High recovery of solute overall (low xR and high yE)
Feed or “Feed Solvent”: one of the liquids in the system • Concentrated solute in extract (high yE)
(“carrier”)
How to achieve this?
Solvent: MSA (by convention: the “added” liquid)
• Cocurrent mixer-settlers
Extract: Solvent (not solute) mostly present in this layer.
• Cross-current mixer settlers
YE, A = concentration of A, the solute, in extract. • Counter-current mixer-settlers in series
• High interfacial area during mixing
• Reduce mass-transfer resistance
• Promote mass transfer: aim is to move solute in feed
o Molecular diffusion
o Eddy diffusion
Ternary Liquid-liquid Extraction is a method by which a • The vertices of the triangle, represent pure
compound is pulled from solvent A to solvent B where solvents components.
A & B are not miscible. • The bases represent zero composition (0%) lines for
components of the opposite vertex.
• Involves 1 solute, 2 solvents • In the diagram above, trichloroethane is (0%) on the
• The solute dissolves in solvent A and is extracted to water-acetone binary mixture base. It then increases
another solvent B, where the two solvents must be as indicated to 100% on the opposite vertex, which is
immiscible. Only the solute will dissolve on both a pure trichloroethane vertex.
solvents A & B. • Water is 0% on the Acetone-Trichloroethane binary
• Also known as partitioning mixture base. It then increases as indicated to 100%
on the opposite vertex, which is a pure Water vertex.
Who invented the liquid-liquid solvent extraction? Ridge • Similarly, Acetone increase from 0% on the Water-
National Laboratory Trichloroethane binary mixture base to 100% on the
opposite vertex.
• The composition of the binary mixture increases from
one pure component to another moving along the
base.
Consider a system of water, acetone, and trichloroethane with a

ternary liquid-liquid equilibrium as shown in the diagram.
• Water completely dissolves acetone; however, it is

complete immiscible in trichloroethane.
• That, Trichloroethane completely dissolves acetone,
but its is immiscible in water.
• Trichloroethane is used to extract acetone from water.
• Tie lines are lines that connect equilibrium points on
the miscibility boundary.
• A mixture with composition M in the two liquid phase

regions, will always split into two phases with
composition C1 for phase P1 and C2 for phase P2 on
the miscibility boundary (liquid-liquid equilibrium)
following the tie lines as indicated.
• Tie lines converge to the Plait Point, possible since the
two liquid components have the same composition.
• Composition on the Triangular diagram will be read by

reading composition of each component, using
composition lines that run parallel to the zero
composition line.
For LLE, the Ternary Triangular Diagram has two regions:
• A single liquid phase region, where all three

components are dissolved into a single phase.
• A two liquid phase region, where a mixture in that
composition space splits into two immiscible liquid
phases. For liquid-liquid extraction, the mixture needs
to be in the two phase region.
• The two regions are divided by the miscibility
boundary, which is the liquid-liquid equilibrium line.
•
Hittorf method is based on measurements of ion

concentration changes near the electrodes as a result of the
passage of current through an electrolyte.
The number of equivalents of electrolyte lost from any

compartment is directly proportional to the transport
number of the ion moving away from the compartment.
This is known as the HITTORF METHOD.
• Hittorf method has been generally employed for the

experimental determination of transference numbers
and involve measurement of changes of concentration
in the vicinity of the electrode.
• Hittorf method is used in electrolysis.
What is ion transport number (transference number)?
• It is the fraction of the total electrical current carried in

an electrolyte by given ionic specie. Difference in
number rises from differences in electrical mobility.
• Ratio of the electric current derived from the cation to
the total electric current.
• If the transference number is close to 1, it implies that
the ion conducting performance in the polymer
electrolyte is really accomplished by the cation.
How is transport number determined?
• It is determined by the Hittorf’s Method.

• During electrolysis, ions owing to solvation, transport
not only electric charge but also the solvent in their
solvation sheaths.

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PHASE EQUILIBRIA: TERNARY SYSTEM We aim for the solute (A) to be mostly in the extract stream.

What is phase equilibrium in thermodynamic sense? Why

Phase equilibrium is the state of thermodynamic systems in • Temperature sensitive products

Ternary System: have three non-reactive components. In liquid

Ternary Phase Diagram: represents the phase behavior of

Consider a system of water, acetone, and trichloroethane with a

• Water completely dissolves acetone; however, it is

• A mixture with composition M in the two liquid phase

• Composition on the Triangular diagram will be read by

For LLE, the Ternary Triangular Diagram has two regions:

• A single liquid phase region, where all three

Hittorf method is based on measurements of ion

The number of equivalents of electrolyte lost from any

This is known as the HITTORF METHOD.

• Hittorf method has been generally employed for the

What is ion transport number (transference number)?

• It is the fraction of the total electrical current carried in

How is transport number determined?

• It is determined by the Hittorf’s Method.

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