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Liquid Extraction
Liquid extraction produces separation of the constituents of a liquid solution by contact
with another insoluble liquid. If the components of the original solution distribute
differently between the two liquids, separation will result. The component balances will
be essentially identical to those for leaching, but there are two major differences that
complicate the calculations:
the carrier phase is a liquid, not a solid, so the physical separation techniques will
change, and
Two distinct phases develop, so the simplicity of uniform solution is lost.
Common applications of liquid extraction include: the separation and purification of lube
oils, separation of penicillin from fermentation broth, etc.
Extraction is driven by chemical differences, not by vapor pressure differences, and so
can be used in situations when distillation is impractical. For instance, it can be used to
separate materials with similar boiling points (so that distillation is impractical) or
mixtures containing temperature sensitive compounds.
Distillation and evaporation produce finished products; liquid extraction generally does
not. The products are still mixtures, although with new compositions, and these must be
separated to obtain final products. Secondary separation often requires distillation or
evaporation. The overall process cost thus must be considered when choosing extraction.
Extraction may become economical for dilute aqueous solutions when evaporation would
require vaporization of very large amounts of water.

Terminology
Certain terms are commonly used when describing extraction processes. The solution to
be extracted is called the feed; the liquid used in contacting is the solvent. The enriched
solvent product is the extract and the depleted feed is called the raffinate.
Extraction processes may be single stage, multistage crosscurrent, or countercurrent. Cocurrent extraction offers no advantages over a single stage (convince yourself of this!).
This class will primarily be concerned with countercurrent systems.

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Equilibrium
Extraction calculations require an understanding of ternary equilibrium. You probably
should refresh your memory on how ternary diagrams are read and used. I would
anticipate that you learned this in your material balance course.
One new term that may not be familiar is the plait point. This point is located near the top
of the two-phase envelope, at the inflection point. It represents a condition where the 3component mixture separates into two phases, but the phases have identical
compositions. (Compare this with an azeotropic mixture of liquid and vapor.)
There are two main classes of liquid-liquid equilibrium that occur in extraction. A Class
I system is the one I expect you are familiar with; it has one immiscible pair of
compounds and produces the familiar envelope. Class II mixtures have two pair of
immiscible compounds, and so the two-phase envelope crosses the triangular diagram
like a bridge. Class I mixtures are the most common and are preferable -- so if you can
pick a solvent to get a Class I, you usually want to do so. Classes can change with
temperature, so that is also a concern.

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Solvent Selection
One of the key decisions when designing an extraction process is the choice of the
solvent to be used. Issues include:
Selectivity -- compare the equilibrium ratio of solute in each phase
Distribution Coefficients -- y/x at equilibrium; large values preferable
Insolubility -- solvent should not be soluble in carrier liquid
Recoverability -- consider constraints (i.e. azeotropes)
Density -- must be different so that phases can be separated by settling
Interfacial Tension -- if too high, liquids will be difficult to mix
Chemical Reactivity -- solvent should be inert and stable
Viscosity, Vapor Pressure, Freezing Point -- low values make storage easier

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Safety -- toxicity, flammability

Cost

Calculations
As with the other separations we discuss, there are two primary calculations:
the number of stages needed to make a separation (extent)
the amount of solvent needed to make a separation (rate/capacity)
Since LL equilibrium is seldom available in algebraic form, the calculations tend to be
iterative or graphical. You have a choice of graphical approaches depending on the type
of equilibrium diagram you have available (or choose to construct):
A modified McCabe-Thiele approach can be used if y vs. x data is available. The
coordinates for the diagram are the mass fraction of solute in the extract phase and
the mass fraction in the raffinate for the other. The curve is typically concave
downward, begins at the origin and ends with the plait point composition.
When one has a convenient equilateral triangle diagram, construction can be done
directly on the triangle. Some authors refer to this as the Hunter-Nash method.
Rectangular equilibrium diagrams can be constructed. These look a lot like the
enthalpy-composition diagrams from distillation calculations or the "solid-free"
diagrams used in leaching.

Solvent-to-Feed Ratio
For a given feed mixture, required degree of extraction, operating pressure and
temperature, and choice of solvent, there is a minimum solvent-to-feed ratio which
corresponds to an infinite number of contact stages.
As with the other separations we have studied, this corresponds to a "pinch" between the
equilibrium and operating curves at the feed composition. Algebraically, this corresponds
to an extract phase in equilibrium with the entering feed. The pinch can also be found
graphically -- on a McCabe-Thiele type construction, minimum solvent ratio corresponds
to a pinch (curves intersecting) at the feed composition. During a triangular construction,
a feed pinch is represented by the operating line overlapping a tie-line and running
through the feed point.

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A theoretical upper limit or maximum solvent-to-feed ratio also can be determined. If you
visualize the ternary diagrams, you notice that if enough solvent is added, the equilibrium
curve is crossed and the single phase region is entered. Once this happens, it is
impossible to divide the mixture into different phases, hence no separation is achieved.
The maximum solvent-to-feed ratio is thus that which puts the mixture on the phase
boundary.

McCabe-Thiele Method
A modified McCabe-Thiele approach is probably the most straightforward graphical
technique for solving extraction problems. As always, the main constraint is the
equilibrium data. When the data is given in a tabular form, it isn't difficult to construct
the needed y (solute in the extract phase) vs. x (solute in the raffinate phase) diagram;
however, it is a bit of a chore to pull the points off of a ternary diagram. In the latter case,
it may sense to construct directly on the triangle.
Once you have the y vs. x plot, the component and material balances can be used to set
the endpoints of the operating curve. Interior points can be found by selecting an
intermediate value of x, and calculating the appropriate y (this typically is an iterative
calculation). You want to find enough interior points to be sure of the shape of the curve,
but shouldn't have to calculate too many of these points. The operating curve that results
will typically be curved. For extraction calculations, both the equilibrium and the
operating equations will be typically be curved.
Once the curves are available, they can be "stepped
off" into triangles, just as one would expect from
McCabe-Thiele.

Construction on Ternary Diagram

Construction on a ternary diagram is a little
messier. The diagrams are typically much more
crowded and so counting stages is more
complicated. You also typically need substantial
extra space on the side of the diagram; often you
want to tape a spare sheet of paper in place to get
the workspace. Pocket rulers end up being too
short, so make sure you have a longer (~ 2 ft) straightedge around.
The first step is to locate the known endpoints.
The fresh solvent point will typically lie on a side of the triangle (it has little or no
solute and minimal raffinate). If pure, the fresh solvent point will be at an apex.

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The feed point will lie on the solute-carrier axis; only rarely will the feed contain
solvent.
Products result from equilibrium stage separation, so both will lie on the phase
envelope. Often, only one of these is given in the problem statement.
The fundamental idea of all
constructions is that a single line
connects points made from "mixing" two
streams. The endpoints are thus
connected two different ways.
First, a segment is drawn connecting the
"entering" streams (La, Vb) and one
between the "leaving" streams (Lb, Va). These will intersect in the middle of the diagram
at a "mixing point", M. Since the two streams leaving an ideal stage, are in equilibrium,
this point is related to the equilibrium curve. Lever arm principles apply, so that the M
point splits the line segments proportionately to the solvent/feed ratio, so that

An "operating" point, P, is located by connecting the "sides" of the cascade: La to Va and

Lb to Vb. The P point can lie on either side of the triangle, depending on the slope of the
tie lines. (This is where that extra piece of paper comes in handy!) All possible operating
points must pass through the P point.

With the endpoints and the P point, the stages can be stepped off. Begin at the Va (extract
product) point. Trace down a tie- line to the raffinate side of the envelope; the intersection
will be at the composition of the stream leaving stage one, so this is the L 1 point. Next,
construct a line connecting L1 with P and extend the line back across to the extract side of
the diagram. This is an operating line, and the intersection is the V2 point. The triangle
that has been formed represents one ideal equilibrium stage.

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This procedure -- down a tie line, up an operating line -- is repeated until the feed point is
reached/passed. The total number of triangles created is the number of stages. Often the

construction gets crowded and may be hard to read.

Problems can be varied by changing the given information. You then will need to think
through the relationships (solvent/feed ratio, equilibrium tie-lines, operating lines, etc.)
and adapt the procedure.
Minimum solvent-to-feed is determined by extending the tie-line that runs through the
feed point until it intersects the segment connecting Vb and Lb. This intersection is the
point Pmin, an operating point at minimum S/F. The line is then extended back across the
envelope to the extract side. The intersection is the point Vmin, corresponding to the extract
product at minimum S/F. (Remember that a "pinch" on this type of diagram means that
the operating and equilibrium (tie-lines) overlap.) A mixing point "Mmin" can be
determined using the feed point, Vb, Lb, and Vmin, and the lever-arm rule will provide a
value for the S/F ratio.
Maximum solvent-to-feed is found by locating a point "Mmax" on the line connecting the
fresh solvent and the feed, at the point where it intersects the extract side of the envelope.
S/F is then calculated by lever arm.

Note on Tie Lines

Rarely do you have all the equilibrium tie
lines you want. It is thus good to know that
there is a fairly easy way of generating
additional lines.
To do this, you construct a "conjugate curve"
from the existing tie lines. Take each
endpoint and draw a line from its downward,
perpendicular to base of the triangle. The extensions from the raffinate side will intersect
those from the extract side, and each pair forms a point on the conjugate curve. The final
point is the plait point. When a new tie line is needed, one composition is chosen, a line is
traced down to the conjugate curve, and then back up to the envelope on the other side.
This is the other end of the tie line.

Construction on Rectangular Equilibrium Diagram

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Graphical solution can be readily done on rectangular equilibrium diagrams, but this
method will not be discussed here. This method is usually the first choice only if the
equilibrium data is already plotted in rectangular form.

References:
1.

McCabe, W.L. and J.C. Smith, Unit Operations of Chemical Engineering, 3rd Edition, McGraw-Hill, 1976.
pp. 619-637.

2.

McCabe, W.L., J.C. Smith, P. Herriot, Unit Operations of Chemical Engineering, 5th Edition, McGrawHill, 1993. pp. 623-641.

3.

Seader, J.D. and E.J. Henley, Separation Process Principles, John Wiley, 1998, pp. 436-438, 443-448.

4. Treybal, R.E., Mass-Transfer Operations, 3rd Edition, McGraw-Hill, 1987 (reissue). pp. 477553.
Copyright 1997, 1999, 2002, and 2003 by R.M. Price -- All Rights Reserved.