UNIT OPERATIONS

What is a "Unit Operation"

A unit operation is any part of potentially multiple-step process which can be considered to
have a single function. Examples of unit operations include:

Separation Processes

Purification Processes

Mixing Processes

Reaction Processes

Power Generation Processes

Heat Exchangers

In general the ductwork between the processes is not explicitly included, though a single pipe
can be analyzed for purposes of determining friction loss, heat losses, pressure drop, and so
on.
Large processes are broken into unit operations in order to make them easier to analyze. The
key thing to remember about them is that the conservation laws apply not only to the process
as a whole but also to each individual unit operation.
Separation Processes
There are a large number of types of separation processes, including distillation, extraction,
absorption, membrane filtration, and so on. Each of these can also be used for purification, to
varying degrees.
Separation by Flashing
A mixture of two liquids or a liquid and vapor can be separated by passing it to a flash drum
at a fixed temperature and pressure. The mixture is allowed to reach equilibrium (or near it),

and then the vapor exits the top and the liquid exits the bottom of the drum. This separates the
components somewhat, provided that the temperature is chosen between the boiling
temperatures of the components of the mixture at the pressure of the drum. The degree of
separation depends on the composition of the mixture, the concentrations of the species in the
mixture, and the temperature and pressure. Having data such as fugacity data or even vapor
pressures for simple modelling like Raoult's Law is invaluable when choosing the operating
conditions.
When a solution boils, the resulting gas is still a mixture, but the gaseous mixture will in
general have more of the lower-boiling compound than the higher-boiling compound.
Therefore, a higher-boiling compound can be separated from the lower-boiling compound by
simply allowing part of the solution to boil and part to remain as liquid.
Distillation
Distillation, like flashing, is a process which is generally used to separate a mixture of two or
more liquids based on their boiling points. However, what happens in a distillation column is
essentially a series of flashes, which are connected with recycle loops. The liquid from each
tray comes to equilibrium (ideally) with the vapor, and the vapor rises up to the next tray and
the liquid falls to the tray beneath it. Each tray has a different temperature because a reboiler
on the bottom and a condenser at the top maintain a temperature gradient across the column
(in certain separation setups one of these components is omitted).
Distillation is an unit operation, in which two constituent is separated by different boiling
point.
The net result is, like flashing, more of the lower-boiling compound(s) will exit at the top of
the column, and more of the higher-boiling compound(s) will fall to the bottoms. Since
distillation is multiple flashes in a row, it is typically more effective than a single flash,
although the latter may be sufficient depending on the purpose. Distillation columns are
standard for many types of separations because it is relatively inexpensive for its efficacy.
Distillation has a limit, however: non-ideal mixtures can form azeotropes. An azeotrope is a
point at which when the solution boils, the vapor has the same composition as the liquid.
Therefore no further separation can be done without another method or without using some
special tricks.

Two examples of distillation processes are petroleum distillation and the production of
alcoholic beverages. In the first case, oil is separated into its many components, with the
lightest at the top and the heaviest on the bottom. In the latter, the gas is enriched in ethanol,
which is later recondensed.
Gravitational Separation
Gravitational separation takes advantage of the well-known effect of density differences:
something that is less dense will float on something that is more dense. Therefore, if two
immiscible liquids have significantly different densities, they can be separated by simply
letting them settle, then draining the denser liquid out the bottom. Note that the key word here
is immiscible; if the liquids are soluble in each other, then it is impossible to separate them by
this method.
This method can also be used to separate out solids from a liquid mixture, but again the solids
must not be soluble in the liquid (or must be less soluble than they are as present in the
solution).
Extraction
Extraction is the general practice of taking something dissolved in one liquid and forcing it to
become dissolved in another liquid. This is done by taking advantage of the relative
solubility of a compound between two liquids. For example, caffeine must be extracted from
coffee beans or tea leaves in order to be used in beverages such as coffee or soda. The
common method for doing this is to use supercritical carbon dioxide, which is able to
dissolve caffeine as if it were a liquid. Then, in order to take the caffeine out, the temperature
is lowered (lowering the "solubility" in carbon dioxide) and water is injected. The system is
then allowed to reach equilibrium. Since caffeine is more soluble in water than it is in carbon
dioxide, the majority of it goes into the water.
Extraction is also used for purification, if some solution is contaminated with a pollutant, the
pollutant can be extracted with another, clean stream. Even if it is not very soluble, it will still
extract some of the pollutant.
Another type of extraction is acid-base extraction, which is useful for moving a basic or
acidic compound from a polar solvent (such as water) to a non-polar one. Often, the ionized

form of the acid or base is soluble in a polar solvent, but the non-ionized form is not as
soluble. The reverse is true for the non-ionized form. Therefore, in order to manipulate where
the majority of the compound will end up, we alter the pH of the solution by adding acid or
base.
For example, suppose you wanted to extract Fluoride (F-) from water into benzene. First, you
would add acid, because when a strong acid is added to the solution it undergoes the
following reaction with fluoride, which is practically irreversible:
The hydrogen fluoride is more soluble in benzene than fluoride itself, so it would move into
the benzene. The benzene and water fluoride solutions could then be separated by density
since they're immiscible.
The term absorption is a generalization of extraction that can involve different phases (gasliquid instead of liquid-liquid). However, the ideas are still the same.
Membrane Filtration
A membrane is any barrier which allows one substance to pass through it more than another.
There are two general types of membrane separators: those which separate based on the size
of the molecules and those which separate based on diffusivity.
An example of the first type of membrane separator is your everyday vacuum cleaner.
Vacuum cleaners work by taking in air laden with dust from your carpet. A filter inside the
vacuum then traps the dust particles (which are relatively large) and allows the air to pass
through it (since air particles are relatively small). A larger-scale operation that works on the
same principle is called a fabric filter or "Baghouse", which is used in air pollution control
or other applications where a solid must be removed from a gas.
Some fancy membranes exist which are able to separate hydrogen from a gaseous mixture by
size. These membranes have very small pores which allow hydrogen (the smallest possible
molecule, by molecular weight) to pass through by convection, but other molecules cannot
pass through the pores and must resort to diffusion (which is comparatively slow). Hence a
purified hydrogen mixture results on the other side.

Membranes can separate substances by their diffusivity as well, for example water may
diffuse through a certain type of filter faster than ethanol, so if such a filter existed it could be
used to enrich the original solution with ethanol.
Purification Methods
In order to bring any product to market, it is necessary to purify it adequately. Without
purification, people could get sick from eating foods, side-reactions could occur in industry
which would cause safety concerns, or a scientist's research could be invalidated. Fortunately
there are several methods used to purify things. The separation processes mentioned above
are often used for this purpose, as are the following two processes:
Adsorption
Not to be confused with absorption, adsorption is a process which separates components by
their relative adhesiveness to a surface. An adsorption column is essentially a pipe filled with
a certain material. When the contaminant flows by, it will bind to the material, and in this
way the fluid flowing by is cleaned.
A major disadvantage to this method is that the material will always have a saturation point
after which no more contaminant can latch on to it. At this point cleaning stops and therefore
the spent material must be replaced by new material.
Recrystallization
Recrystallization is the purification of substances by taking advantage of changes in solubility
with respect to temperature.We take advantage of this by dissolving an impure compound and
then lowering the temperature slowly. The solubility of most solid substances increases with
temperature , so decreasing the temperature will cause the solubility of both the impurities
and the substance to be purified to decrease. However, since there is likely much more of the
impure substance present than impurities, the impure substance will crystallize out long
before the impurities will. Therefore, as long as the temperature is not lowered too quickly,
the impure substance will crystallize out in a purer form, while most impurities will remain in
solution.

A disadvantage to this method is that it takes a long time to perform, but it is often the most
effective method for obtaining a pure sample of a product.

Heat Exchangers
In general, a heat exchanger is a device which is used to facilitate the exchange of heat
between two mixtures, from the hotter one to the cooler one. Heat exchangers very often
involve steam because steam is very good at carrying heat by convection, and it also has a
high heat capacity so it won't change temperature as much as another working fluid would. In
addition, though steam can be expensive to produce, it is likely to be less expensive than
other working fluids since it comes from water.
Tubular Heat Exchangers
A tubular heat exchanger is essentially a jacket around a pipe. The working fluid (often
steam) enters the jacket on one side of the heat exchanger and leaves on the other side. Inside
the pipe is the mixture which you want to heat or cool. Heat is exchanged through the walls
of the device in accordance to the second law of thermodynamics, which requires that heat
flow from higher to lower temperatures. Therefore, if it is desired to cool off the fluid in the
pipe, the working fluid must be cooler than the fluid in the pipe.
Heat exchangers work because heat naturally flows from higher temperature to lower
temperatures. Therefore if a hot fluid and a cold fluid are separated by a heat conducting
surface heat can be transferred from the hot fluid to the cold fluid.
Tubular heat exchangers can be set up in two ways: co-current or counter-current. In a cocurrent setup, the working fluid and the fluid in the pipe enter on the same side of the heat
exchanger. This setup is somewhat inefficient because as heat is exchanged, the temperature
of the working fluid will approach that of the fluid in the pipe. The closer the two
temperatures become, the less heat can be exchanged. Worse, if the temperatures become
equal somewhere in the middle of the heat exchanger, the remaining length is wasted because
the two fluids are at thermal equilibrium (no heat is released).

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 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.

Equilibrium

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.

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

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 HunterNash 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.
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 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.

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 L1 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.

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 it 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

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.

Leaching

Leaching is the preferential solution of one or more compounds from a solid mixture by
contact with a liquid solvent. The solvent partially dissolves the solid material so that the
desired solute can be carried away.
Typical users include:

the metals industry for removing mineral from ores (acid solvents)

the sugar industry for removing sugar from beets (water is solvent)

the oilseeds industry for removing oil from soybeans, etc. (hexane or
similar organic solvents)

The basic concepts of leaching also apply in the environment, where materials
can be leached out by rainwater and carried into the groundwater supply. A
simple, everyday example of a leaching process is making your morning coffee.
Liquid-Solid Equilibrium

Liquid-solid phase equilibrium is important in understanding leaching, crystallization, and

adsorption. Diffusion through solids is slow, even through pores in the substance, and so
equilibrium is harder to achieve.
Separation of a solid phase from a liquid phase is done by sedimentation, filtration, or
centrifugation. Complete separation is essentially impossible, so must deal with some degree
of liquid entrainment on any "wet" solid phase.
Principles

Leaching can be batch, semibatch, or continuous. It usually operates at an elevated

temperature to increase the solubility of the solute in the solvent. Calculations involve three
component (solid, solvent, solute) systems.
Feed to a leaching system typically is solid, consisting of basically insoluble carrier material
and a (usually desirable) soluble compound. The feed usually must be prepared by grinding

or chopping. It is then mixed with a liquid solvent. The desired material dissolves (to some
extent) and so leaves when the liquid is drawn off as overflow. The solids are then removed
as underflow. The underflow is wet, and so some of the solvent/solute mixture is carried out
here as well.
Flow through a leaching system may be crosscurrent or countercurrent.
Modeling Assumptions

Modeling a leaching system requires several assumptions to make the system "ideal".
The solubility of solute may have an upper bound, limiting how much solute the solvent may
hold. Ideally, the carrier will not dissolve, and so will not be present in the overflow. This is a
generally safe assumption, although allowance should be made for entrainment of solid
flakes, etc., in the overflow from the first stage.
Mixing of the solid and the solvent is critical. Typically, "perfect mixing" is assumed, as is
the idea of an equilibrium stage (the solid and liquid phases on each stage are in equilibrium).
These assumptions imply that all the liquid within the stage has the same composition and so
the overflow and the liquid carried in the underflow are identical. This is known as the
uniform solution assumption and will result in a linear equilibrium curve.
One also needs to determine how much liquid leaves entrained with the solids in the
underflow. The simplest option is the assumption of constant solution underflow which
means that every stage has the same, fixed ratio of solution to solid in the underflow stream.
Like the equimolar overflow assumption in distillation, this will produce a linear operating
curve. The first stage is again problematic, since it must "wet" the solid (fill pores, etc.) and
so will typically pick up more liquid than subsequent stages.
More generally, the amount of solution in the underflow depends on the properties of the
solution, which are dependent on its composition. The amount of solute present seems to
effect the "stickiness" of the solution. As a result, "draining data" is typically collected. This
relates the solution/solid ratio to the composition of the solution and is used to determine the
nature of the operating curve.
Operating Equations
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As has become customary in this course, we develop the operating equations from the
balances describing the system. The steady state material balance over any stage in a
countercurrent flow system is written as:
Following McCabe et al. (1993), V is used for the liquid solvent phase and L for
the entrained liquid phase. The subscripts indicate the stage in which the stream

originates, with a used for the fresh feed and b for the final product. Similarly,
the component balance is:

The operating equation is obtained by rearranging the component balance:

which can be shown to run through the points (x a, ya) and (xb, yb).

In some circumstances, it may be useful to use the total material balance to eliminate Vn+1
from the equation:

In the general operating case, the density and viscosity of the solution change with the solute
concentration and the mass retained by the solid phase changes from tank to tank.
Consequently, the ratio of entrained liquid to solution varies from stage to stage. In this case,
the operating curve is not linear.
In the special case of constant solution underflow, the mass retained by the solid does not
depend on the concentration and the operating line is linear after the first stage.
Calculations

Two main types of calculations are usually performed:

1. The extent of leaching is determined, usually by balance calculations.
Efficiency depends on contact timen and the liquid-solid separation
efficacy. The limit on extent is imposed by equilibrium constraints.
2. The number of stages required to reduce the solute content to a specified
value is determined. As with distillation, the relationship between the
equilibrium and operating lines will be used to determine the number of
stages.
Solution techniques are algebraic or graphical. Graphical solutions may be set up
using the actual compositions or on a "solid-free" basis.

Leaching calculations are almost always based on the principle that the solid will not dissolve
into the solvent. Thus, the concentrations x of solute in the solvent entrained in the slurry and
y of the solute in the solvent liquid phase can be expressed on a solid free basis without
significantly changing the calculation. The equilibrium behavior of the system establishes key
behaviors.
Begin with the assumptions that each stage has enough contact time that the system can reach
equilibrium, that there is enough solvent present in each stage to allow equilibrium removal
of solute from solvent, and that the solute will not absorb on the solvent. The uniform
solution assumption then applies, and the equilibrium x-y curve will be a straight line, xe=ye.

Two subsets of the uniform solution case should be noted. In the first, the solute is infinitely
soluble in the solvent. In this case, all values of x and y from 0.0 to 1.0 may be obtained. In
the second case, the solubility is limited to some maximum value, xs. The x-y diagram will be
a straight line, but will not go all the way from 0 to 1. Instead, at xs it will become vertical.
If the conditions (contact time, adequate solvent mass, no adsorption) that determine uniform
solution do not hold, the x-y diagram may be curved (often, it will look like that used in
distillation).
Constant Solution Underflow

In the case of constant solution underflow, both the equilibrium and operating curves are
linear and it is possible to solve for the number of stages directly. The general solution is
developed using the Kremser Equation is:
For leaching, the equilibrium line is x e=ye, so the equation becomes:
To use this, you need to make sure that La=Ln (that the flow of liquid entrained
with the solid is the same entering and leaving the first stage -- constant solution
underflow is specified starting with the first stage) or calculate the first stage
separately.
Variable Solution Underflow

If solution underflow is not constant, the operating equation for leaching is not linear. In this
case, an approach similar to the McCabe-Thiele method for distillation columns can be used.
1. Use system component balances to determine x a and xb.
2. Construct operating curve. In general, the operating curve will not
intersect the equilibrium curve as it did for distillation.
o

Select an xn somewhere in the middle. This gives an equivalent L n.

Use Ln and a material balance to obtain Vn+1.

Find yn+1 by a component balance

Plot (xn, yn+1) as a point on the operating curve.

Repeat as needed to obtain the full operating curve. Often a single

point is adequate.

3. Operating stages may then be stepped off as triangles between the

operating and equilibrium curves in the same fashion as was used for
distillation. Normally, you start with the dilute product composition.
Solid-Free Calculations

Another approach to solving these problems uses a graphical method similar to the PonchonSavarit method for distillation columns; however, a composition-composition diagram is used
for construction rather than an enthalpy-composition diagram. The method assumes that all

streams are a mix of solid and solution and that the ratio of solid to solution can be
calculated.
The working plot is constructed using modified compositions. Define a to be the mass (or
concentration) of solute, b the mass of solid (zero for an insoluble carrier), and s the mass of
solvent, then calculate:
mass solute/mass solution, and mass insoluble/mass solution
and plot Y vs. X. Since there are two phases (overflow and underflow), there will
be two curves.

The upper curve will be a line if solution underflow is constant. The lower curve will collapse
to the X axis (Y=0) when the carrier is completely insoluble. The curves are connected by tielines, based on the relationship between the phases. If the uniform solution condition holds so
that xe=ye, these will be vertical; if not, they will be slanted and must be determined.
Generally speaking, the equilibrium data must be obtained experimentally.
Once the composition diagram is constructed, a "J point" may be determined. This is useful in
some, but not all problems. J is defined as the in terms of the total amount of solute entering
(or leaving, they're equal at steady state):
or
Graphically, J is the intersection of the line connecting V a with Lb and that
connecting Vb and La. The J point is not used in the actual construction of stages;
it can be used for lever arm calculations.

The "P point" is used in the constructions. It is given by the equations:

or
P represents the "net flow" of material through the system, so that
Effectively, this point pretends that there are mixers on either end of the
leaching process, combining both the L and V flows into a single stream. This is
thus a fictitious value, and one coordinate must be negative.

Operating lines are constructed by connecting an L point with the P point. The intersection
with the axis will be the V point for the next stage.
Begin construction at Va point. First trace upward to the equilibrium curve along a tie line
(remember!, the tie lines are vertical for when the uniform solution conditions hold). This
will be the L1 point. Next construct a line by connecting L1 to P. The V2 point will lie at the
intersection of this line and the X-axis (the operating curve). Trace up a tie line to L2,
construct a line to find V3, etc. Continue to alternate between the tie lines and constructed
operating lines until the Vb point has been passed. The number of triangles formed will
correspond to the number of leaching stages required.