Purification in a chemical context is the physical

separation of a chemical substance of interest from

foreign or contaminating substances. purification, in
chemistry, separation of a substance into its components
and the removal of impurities. There are a large number
of important applications in fields such as medicine and
manufacturing The following list of chemical purification
methods should not be considered exhaustive.
.Affinity purification is used to purify proteins by retaining
them on a column through their affinity
to antibodies, enzymes or receptors which have been
immobilised on the column.
Filtration is a mechanical
Methodtoseparate solids from liquids or gases by passing
the feed stream through a porous sheet such as a cloth or
membrane, which retains the solids and allows the liquid
to pass through.
Centrifugation is a process in which light particles are
revolved over high speed with the help of electric
motor so that the fine particles which do not settle at
bottom would settle down.
Evaporation is used to remove volatile liquids from
non-volatile solutes which cannot be done through
filtration due to the small size of the substances.
Liquidliquid extraction removes an impurity or
recovers a desired product by dissolving the crude

material in a solvent in which other components of

the feed material aresoluble.
Crystallization separates a product from a liquid feed
stream, often in extremely pure form, by cooling the
feed stream or adding precipitants which lower
the solubility of the desired product so that it
forms crystals. The pure solid crystals are then
separated from the remaining liquor by filtration or
centrifugation.
Recrystallization: In analytical and synthetic
chemistry work, purchased reagents of doubtful
purity may be recrystallized, e.g. dissolved in a very
pure solvent, and then crystallized, and the crystals
recovered, in order to improve and/or verify their
purity.
Adsorption removes a soluble impurity from a feed
stream by trapping it on the surface of a solid
material such as activated carbon which forms
strong non-covalent chemical bonds with the
impurity. Chromatography employs adsorption and
desorption on a packed bed of a solid to purify
multiple components of a single feed stream.
Smelting is used to produce metals from raw ore, and
involves adding chemicals to the ore and heating it
up to the melting point of the metal.
Refining is used primarily in the petroleum industry,
whereby crude oil is heated and separated into

stages according to the condensation points of the

various elements.
Distillation, widely used in petroleum refining and in
purification of ethanol separates volatile liquids on
the basis of their relative volatilities.
Water purification combines a number of methods to
produce potable or drinking water.
Downstream processing refers to purification of
chemicals, pharmaceuticals and food ingredients
produced by fermentation or synthesized by plant and
animal tissues, for example antibiotics, citric
acid, vitamin E, and insulin.
Fractionation refers to a purification strategy in which
some relatively inefficient purification method is
repeatedly applied to isolate the desired substance in
progressively greater purity.
Electrolysis refers to the breakdown of substances
using an electric current. This removes impurities in
a substance that an electric current is run

SEPARATION PROCESS
In chemistry and chemical engineering, a separation
process, or a separation technique, or simply a
separation, is a method to achieve any mass transfer
phenomenon that converts a mixture of substances into
two or more distinct product mixtures (which may be
referred to as fractions),[1] at least one of which is

enriched in one or more of the mixture's constituents. In

some cases, a separation may fully divide the mixture
into its pure constituents. Separations are carried out
based on differences in chemical properties, or physical
properties such as size, shape, mass, density, or chemical
affinity, between the constituents of a mixture, and are
often classified according to the particular differences
they use to achieve separation. Usually there is only
physical movement, no substantial chemical modification.
In the case that no single difference can be used to
accomplish a desired separation, multiple operations will
often be performed in combination to achieve the desired
end.
Barring a few exceptions, almost every element or
compound is naturally found in an impure state. Often
these impure raw materials must be separated into
their purified components before they can be put to
productive use, making separation techniques essential
for the modern industrial economy. In some cases,
these separations require total purification, as in the
electrolysis refining of bauxite ore for aluminum metal,
but a good example of an incomplete separation
technique is oil refining. Crude oil occurs naturally as a
mixture of various hydrocarbons and impurities. The
refining process splits this mixture into other, more
valuable mixtures such as natural gas, gasoline and
chemical feedstocks, none of which are pure
substances, but each of which must be separated from
the raw crude. In both of these cases, a series of

separations is necessary to obtain the desired end

products. In the case of oil refining, crude is subjected
to a long series of individual distillation steps, each of
which produces a different product or intermediate.
The purpose of a separation may be analytical, i.e. to

help analyze components in the original mixture

without any attempt to save the fractions, or may be
preparative, i.e. to "prepare" fractions or samples of
the components that can be saved. The separation can
be done on a small scale, effectively a laboratory scale
for analytical or preparative purposes, or on a large
scale, effectively an industrial scale for preparative
purposes, or on some intermediate scale.

Basic concepts of separations

This section is concerned with separations of the
smallest subdivisions of matter, such as atoms,
molecules, and minute particles (sand, minerals,
bacteria, etc.). Such processes start with a sample in a
mixed state (composed of more than one substance)
and transform it into new samples, each of whichin
the ideal caseconsists of a single substance.
Separation methods, then, can be defined
as processesthat change the relative amounts of

substances in a mixture. In chemical methods, one may

start with a completely homogeneous mixture (a
solution) or a heterogeneous sample (e.g., solid plus
liquid); in the act of separation, some particles are
either partially or totally removed from the sample.

Reasons for making separations

There are two general reasons for performing
separations on mixtures. First, the mixture may contain
some substance that should be isolated from the rest of
the mixture: this process of isolating and thus removing
substances considered to be contaminants is called
purification. For example, in the manufacture
of synthetic drugs, mixtures containing variable
proportions of several compounds usually arise. The
removal of the desired drug from the rest of the
mixture is important if the product is to have uniform
potency and is to be free of other components that
may be dangerous to the body.
The second reason for performing separations is to

alter the composition of a sample so that one or more

of the components can be analyzed. For example, the
analysis ofair pollutants to assess the quality of the air
is of great interest, yet many of the pollutants are at a
concentration too low for direct analysis, even with the
most sensitive devices. Pollutants can be collected by
passing samples of air through a tube containing an
adsorbent material. By this process the pollutants are
concentrated to a level such that straightforward

analysis and monitoring can take place. In a second

example, several impurities in a sample
may interfere with the analysis of the substance of
primary interest. Thus, in the analysis of trace
concentrations of metals in rivers, organic substances
can cause erroneous results. These interferences must
be removed prior to the analysis. Several techniques
for removing interferences are discussed in analysis:
Interference removal.

CRYSTALLIZATION AND PRECIPITATION

The most common method of purifying solid organic
compounds is by recrystallization. In this technique, an
impure solid compound is dissolved in a solvent and
then allowed to slowly crystallize out as the solution
cools. As the compound crystallizes from the solution,
the molecules of the other compounds dissolved in
solution are excluded from the growing crystal lattice,
giving a pure solid. Crystallization is the (natural or
artificial) process of formation of solid crystals
precipitating from a solution, melt or more
rarelydeposited directly from a gas. Crystallization is
also a chemical solidliquid separation technique, in
which mass transfer of a solute from the liquid solution
to a pure solid crystalline phase occurs. In chemical
engineering crystallization occurs in a crystallizer.
Crystallization is therefore an aspect of precipitation,
obtained through a variation of the solubility conditions
of the solute in the solvent, as compared to
precipitation due to chemical reaction.

Crystallization of a solid is not the same as precipitation

of a solid. In crystallization, there is a slow, selective
formation of the crystal framework resulting in a pure
compound. In precipitation, there is a rapid formation
of a solid from a solution that usually produces an
amorphous solid containing many trapped impurities
within the solid's crystal framework. For this reason,
experimental procedures that produce a solid product
by precipitation always include a final recrystallization
step to give the pure compound.
The process of recrystallization relies on the property
that for most compounds, as the temperature of a
solvent increases, the solubility of the compound in
that solvent also increases. For example, much more
table sugar can be dissolved in very hot water (just
below the boiling point) than in water at room
temperature. What will happen if a concentrated
solution of hot water and sugar is allowed to cool to
room temperature? As the temperature of the solution
decreases, the solubility of the sugar in the water also
decreases, and the sugar molecules will begin to
crystallize out of the solution. (This is how rock candy is
made.) This is the basic process that goes on in the
recrystallization of a solid.
Crystallization is a technique that has long been used

in the purification of substances. Often, when a solid

substance (single compound) is placed in a liquid, it
dissolves. Upon adding more of the solid, a point
eventually is reached beyond which no further solid

dissolves, and the solution is said to be saturated with

the solid compound. The concentration of the saturated
solution depends on the temperature, in most cases a
higher temperature resulting in a higher concentration .
These phenomena can be employed as a means of

effecting separation and purification. Thus, if a solution

saturated at some temperature is cooled, the dissolved
component begins to separate from the solution and
continues to do so until the solution again becomes
saturated at the lower temperature. Because the
solubilities of two solid compounds in a particular
solvent generally differ, it often is possible to find
conditions such that the solution is saturated with only
one of the components of a mixture. When such a
solution cools, part of the less soluble substance
crystallizes alone, while the more soluble components
remain dissolved.
Crystallization, the process of solidifying from solution,
is highly complex. Seed particles, or nuclei, form in the
solution, and other molecules then deposit on these
solid surfaces. The particles eventually become large
enough to fall to the bottom of the container. In order
to achieve a high purity in the crystallized solid, it is
necessary that this precipitation take place slowly. If
solidification is rapid, impurities can be entrapped in
the solid matrix. Entrapment of foreign material can be
minimized if the individual crystals are kept small. It is
sometimes necessary to add a seed crystal to the
solution in order to begin the crystallization process:

the seed crystal provides a solid surface on which

further crystallization can take place.
The term precipitation sometimes is differentiated from
crystallization by restricting it to processes in which an
insoluble compound is formed in the solution by a
chemical reaction. It often happens that several
substances are precipitated by a given reaction. To
achieve separation in such cases, it is necessary to
control the concentration of the precipitating agent, so
that the solubility of only one substance is exceeded.
Alternatively, a second agent can be added to the
solution to form stable, soluble products with one or
more components in order to suppress their
participation in the precipitation reaction. Such
compounds, often used in the separation of metal ions,
are called masking agents.
Precipitation was used for many years as a standard
method for separation and analysis of metals. It has
now been replaced, however, by selective and sensitive
instrumental methods that directly analyze many
metals in aqueous solutions.
Crystallization is a technique which chemists use to purify
solid compounds. It is one of the fundamental procedures
each chemist must master to become proficient in the
laboratory. Crystallization is based on the principles of
solubility: compounds (solutes) tend to be more soluble in
hot liquids (solvents) than they are in cold liquids. If a

saturated hot solution is allowed to cool, the solute is no

longer soluble in the solvent and forms crystals of pure
compound. Impurities are excluded from the growing
crystals and the pure solid crystals can be separated from
the dissolved impurities by filtration.
This simplified scientific description of crystallization does
not give a realistic picture of how the process is
accomplished in the laboratory. Rather, successful
crystallization relies on a blend of science and art; its
success depends more on experimentation, observation,
imagination, and skill than on mathematical and physical
predictions. Understanding the process of crystallization
in itself will not make a student a master crystallizer; this
understanding must be combined with laboratory practice
to gain proficiency in this technique.

The steps in the recrystallization

of a compound aRE:
Find a suitable solvent for the recrystallization;
Dissolve the impure solid in a minimum volume of
hot solvent;
Remove any insoluble impurities by filtration;

 Slowly cool the hot solution to crystallize the desired

compound from the solution;

Filter the solution to isolate the purified solid

compound.

Choosing a solvent
The first consideration in purifying a solid by
recrystallization is to find a suitable solvent. There are
four important properties that you should look for in a
good solvent for recrystallization.
The compound should be very soluble at the boiling
point of the solvent and only sparingly soluble in
the solvent at room temperature. This difference in
solubility at hot versus cold temperatures is
essential for the recrystallization process. If the
compound is insoluble in the chosen solvent at high
temperatures, then it will not dissolve. If the
compound is very soluble in the solvent at room
temperature, then getting the compound to
crystallize in pure form from solution is difficult. For
example, water is an excellent solvent for the
recrystallization of benzoic acid. At 10C only 2.1 g
of benzoic acid dissolves in 1 liter of water, while at
95 C the solubility is 68 g/L.
The unwanted impurities should be either very
soluble in the solvent at room temperature or
insoluble in the hot solvent. This way, after the
impure solid is dissolved in the hot solvent, any
undissolved impurities can be removed by
filtration. After the solution cools and the desired

compound crystallizes out, any remaining soluble

impurities will remain dissolved in the solvent.
The solvent should not react with the compound
being purified. The desired compound may be lost
during recrystallization if the solvent reacts with
the compound.
The solvent should be volatile enough to be easily
removed from the solvent after the compound has
crystallized. This allows for easy and rapid drying of
the solid compound after it has been isolated from
the solution.
Finding a solvent with the desired properties is a
search done by trial and error. First, test the solubility
of tiny samples of the compound in test tubes with a
variety of different solvents (water, ethanol,
methanol, ethyl acetate, diethyl ether, hexane,
toluene, etc.) at room temperature. If the compound
dissolves in the solvent at room temperature, then
that solvent is unsuitable for recrystallization. If the
compound is insoluble in the solvent at room
temperature, then the mixture is heated to the
solvent's boiling point to determine if the solid will
dissolve at high temperature, and then cooled to see
whether it crystallizes from the solution at room
temperature.

Dissolving the solid

Once a suitable solvent is selected, place the impure
solid in an Erlenmeyer flask and add a small volume
of hot solvent to the flask. Erlenmeyer flasks are
preferred over beakers for recrystallization because
the conical shape of an Erlenmeyer flask decreases
the amount of solvent lost to evaporation during
heating, prevents the formation of a crust around the
sides of the glass, and makes it easier to swirl the hot
solution while dissolving the solid without splashing it
out of the flask.
Keep the solution in the Erlenmeyer flask warm on a
hot plate or in a water bath, and add small volumes of
hot solvent to the flask until all of the solid just
dissolves. Swirl the solution between additions of
solvent and break up any lumps with a stirring rod or
spatula. Occasionally there will be impurities present
in the solid that are insoluble in the chosen solvent
even at high temperature. If subsequent additions of
solvent to the solution do not seem to dissolve any of
the remaining solid, stop adding solvent to the
solution (as this will decrease the percent recovery of
the desired compound) and filter or decant the hot
solution to remove the insoluble impurities.

Using decolorizing carbon

Colored impurities are sometimes difficult to remove
from solid mixtures. These colored impurities, often
due to the presence of polar or polymeric compounds,
can cause a colorless organic solid to have a tint of
color even after recrystallization. Decolorizing or
activated carbon is used to remove the colored

impurities from the sample. Decolorizing carbon is

very finely divided carbon that provides high surface
area to adsorb the colored impurities.
Very little decolorizing carbon is needed to remove
the colored impurities from a solution. You must be
judicious in your use of decolorizing carbon: if too
much is used, it can adsorb the desired compound
from the solution as well as the colored impurities.
After the impure solid sample is dissolved in hot
solvent, a small amount of decolorizing carbon, about
the size of a pea, is added to the hot solution. This
must be done carefully to avoid a surge of boiling
from the hot solution. The solution is stirred and
heated for a few minutes and then filtered hot to
remove the decolorizing carbon. The resulting filtrate
should be colorless and the recrystallization process
continues as before.

Crystallizing the solid

After the insoluble impurities have been removed,
cover the flask containing the hot filtrate with a watch
glass and set it aside undisturbed to cool slowly to
room temperature. As the solution cools, the solubility
of the dissolved compound will decrease and the solid
will begin to crystallize from the solution. After the
flask has cooled to room temperature, it may be
placed in an ice bath to increase the yield of solid. Do
not rapidly cool the hot solution by placing the flask in
an ice bath before it has cooled to room temperaturethis will result in a rapid precipitation of the solid in an
impure form because of trapped impurities.

Sometimes the dissolved compound fails to crystallize

from the solution on cooling. If this happens,
crystallization can be induced by various methods.
One way to induce crystallization is by scratching the
inner wall of the Erlenmeyer flask with a glass stirring
rod. This is believed to release very small particles of
glass which act as nuclei for crystal growth. Another
method of inducing crystallization is to add a small
crystal of the desired compound, called a seed
crystal, to the solution. Again, this seed crystal acts
as a template on which the dissolved solid will begin
crystallizing. If neither of these two techniques results
in crystallization, the compound was probably
dissolved in too much hot solvent. If you believe that
you may have too much solvent for the amount of
dissolved compound, reheat the solution to boiling,
boil off or distill some of the solvent, and then allow
the solution to cool to room temperature again to
effect crystallization.

Isolating the solid by suction filtration

Once the compound has completely precipitated from
the solution, it is separated from the remaining
solution (also called the mother liquor) by filtration.
Typically this is done by vacuum or suction filtration
using a Bchner funnel. Line the bottom of the
Bchner or Hirsch funnel with a piece of filter paper
that is large enough to cover the holes in the bottom
plate of the funnel without curling up on the sides of
the funnel. Place a neoprene adapter on the stem of
the funnel and insert it in the top of a filter flask (a
thick-walled Erlenmeyer flask with a side-arm) that
has been securely clamped to a ringstand.

Using a piece of thick-walled vacuum tubing, connect

the side-arm of the filter flask to a water aspirator.
Turn the water to the aspirator on full force to create a
vacuum through the system. If necessary, carefully
adjust the piece of filter paper so that it covers all of
the holes in the funnel, and then dampen it with a
small volume of cold solvent; this will create a better
seal between the filter paper and the plate in the
funnel, preventing any solid from getting under the
filter paper and passing through the funnel. Slowly
pour the recrystallization solution into the funnel and
allow the suction to pull the mother liquor through.
Rinse the Erlenmeyer flask with a small volume of
cold recrystallization solvent to remove any remaining
solid. Add this solvent to the funnel and then wash
the solid in the funnel, called the filter cake or
residue, with a few milliliters of fresh, cold
recrystallization solvent to remove any remaining
mother liquor and dissolved impurities.
Leave the aspirator on for a few minutes and allow air
to pass through the crystals to dry them. After pulling
air through the crystals for a brief time, remove the
vacuum from the system by disconnecting the
vacuum tubing from the aspirator before turning the
water off. If you turn the aspirator water off first,
water can be sucked into the filter flask and may
contaminate the product. The filter cake is removed
from the funnel by carefully prying it from the filter
using a spatula. The cake of crystals will still be
slightly wet with solvent and should be allowed to dry
thoroughly before measuring the weight or melting
point of the solid material.

What
Crystallization

Happens

During

To crystallize an impure, solid compound, add just

enough hot solvent to it to completely dissolve it. The
flask then contains a hot solution, in which solute
molecules - both the desired compound and
impurities - move freely among the hot solvent
molecules. As the solution cools, the solvent can no
longer hold all of the solute molecules, and they begin
to leave the solution and form solid crystals. During
this cooling, each solute molecule in turn approaches
a growing crystal and rests on the crystal surface. If
the geometry of the molecule fits that of the crystal, it
will be more likely to remain on the crystal than it is
to go back into the solution. Therefore, each growing
crystal consists of only one type of molecule, the
solute. After the solution has come to room
temperature, it is carefully set in an ice bath to
complete the crystallization process. The chilled
solution is then filtered to isolate the pure crystals
and the crystals are rinsed with chilled solvent.
This first series of diagrams shows what happens if
you let a crystallization proceed slowly: first by
setting the flask at room temperature undisturbed
until crystals form, and then carefully on ice. The red
bar to the right of each image is a thermometer, to
indicate the temperature. The yellow triangles are an
impurity in the hot solution of orange hexagons. If the
solution is allowed to cool slowly, the impurities may
attach briefly to the growing crystal lattice, but they
soon leave as a compound with a more suitable
geometry comes in to take their place. Suitable

hexagons stay more readily in the growing lattice, and

eventually pure crystals of orange hexagons are
formed.

Crystallization in nature

Snowflakes are a very well known example, where

subtle differences incrystal growth conditions result in
different geometries.

Crystallized honey
There are many examples of natural process that
involve crystallization.

Geological time scale process examples include:

Natural
(mineral)
also gemstone);

crystal

formation

(see

Stalactite/stalagmite, rings formation.

Usual time scale process examples include:
Snow flakes formation;
Honey crystallization (nearly all types of honey
crystallize).
Artificial methods

Crystallization Process
For crystallization to occur from a solution it must
be supersaturated. This means that the solution has
to contain more solute entities (molecules or ions)
dissolved than it would contain under the equilibrium
(saturated solution). This can be achieved by various
methods, with (1) solution cooling, (2) addition of a
second solvent to reduce the solubility of the solute
(technique known as antisolvent or drown-out), (3)
chemical reaction and (4) change in pH being the
most common methods used in industrial practice.
Other methods, such as solvent evaporation, can also
be used. The spherical crystallization has some
advantages (flowability and bioavailability) for the
formulation of pharmaceutical drugs
Crystal production[edit]

From a material industry perspective:

Macroscopic crystal production: for supply the
demand of natural-like crystals with methods that
"accelerate time-scale" for massive production
and/or perfection.
Ionic crystal production;
Covalent crystal production.
Tiny size crystals:
Powder, sand and smaller sizes: using methods for
powder
and controlled
(nanotechnology
fruits) forms.
Mass-production: on chemical industry, like saltpowder production.
Sample production: small production of tiny
crystals for material characterization. Controlled
recrystallization is an important method to supply
unusual crystals, that are needed to reveal the
molecular structure and nuclear forces inside a
typical molecule of a crystal. Many techniques,
like X-ray crystallography and NMR spectroscopy,
are widely used in chemistry and biochemistry to
determine the structures of an immense variety of
molecules, including inorganic compounds and biomacromolecules.
Thin film production.
Purification[edit]

See also: Recrystallization (chemistry)

Used to improve (obtaining very pure substance)
and/or verify their purity.
Crystallization separates a product from a liquid
feedstream, often in extremely pure form, by cooling
the feedstream or adding precipitants which lower the
solubility of the desired product so that it forms
crystals.
Well formed crystals are expected to be pure because
each molecule or ion must fit perfectly into the lattice
as it leaves the solution. Impurities would normally
not fit as well in the lattice, and thus remain in
solution preferentially. Hence, molecular recognition is
the principle of purification in crystallization.
However, there are instances when impurities
incorporate into the lattice, hence, decreasing the
level of purity of the final crystal product. Also, in
some cases, the solvent may incorporate into the
lattice forming a solvate. In addition, the solvent may
be 'trapped' (in liquid state) within the crystal formed,
and this phenomenon is known as "inclusion".
Typical equipment
Equipment for
crystallization.

the main

industrial

processes

for

Tank crystallizers. Tank crystallization is an old

method still used in some specialized cases.
Saturated solutions, in tank crystallization, are
allowed to cool in open tanks. After a period of time
the mother liquor is drained and the crystals

removed. Nucleation and size of crystals are

difficult to control. Typically, labor costs are very
high.
Thermodynamic view
Low-temperature SEMmagnification series for a snow
crystal. The
crystals are captured, stored, and sputter
coated with platinum at cryo-temperatures for imaging.
The nature of a crystallization process is governed by
both thermodynamic and kinetic factors, which can
make it highly variable and difficult to control. Factors
such as impurity level, mixing regime, vessel design,
and cooling profile can have a major impact on the
size, number, and shape of crystals produced.
Now put yourself in the place of a molecule within a
pure and perfect crystal, being heated by an external
source. At some sharply defined temperature, the
complicated architecture of the crystal collapses to
that of a liquid. Textbook thermodynamics says that
melting occurs because theentropy, S, gain in your
system by spatial randomization of the molecules has
overcome the enthalpy, H, loss due to breaking the
crystal packing forces:

This rule suffers no exceptions when the temperature

is rising. By the same token, on cooling the melt, at
the very same temperature the bell should ring again,
and molecules should click back into the very same

crystalline form. The entropy decrease due to the

ordering of molecules within the system is
overcompensated by the thermal randomization of
the surroundings, due to the release of the heat of
fusion; the entropy of the universe increases.
But liquids that behave in this way on cooling are the
exception rather than the rule; in spite of the second
principle of thermodynamics, crystallization usually
occurs at lower temperatures (supercooling). This can
only mean that a crystal is more easily destroyed than
it is formed. Similarly, it is usually much easier to
dissolve a perfect crystal in a solvent than to grow
again a good crystal from the resulting solution. The
nucleation and growth of a crystal are under kinetic,
rather than thermodynamic, control.
Crystallization dynamics
As mentioned above, a crystal is formed following a
well-defined pattern, or structure, dictated by forces
acting at the molecular level. As a consequence,
during its formation process the crystal is in an
environment where the solute concentration reaches
a
certain
critical
value,
before
changing
status. Solid formation,
impossible
below
the solubility threshold
at
the
given temperature and pressure conditions, may then
take place at a concentration higher than the
theoretical solubility level. The difference between the
actual value of the solute concentration at the
crystallization limit and the theoretical (static)
solubility threshold is called supersaturation and is a
fundamental factor in crystallization dynamics.
Supersaturation is the driving force for both the initial

nucleation step and the following crystal growth, both

of which could not occur in saturated or
undersaturated conditions.

Nucleation
Nucleation is the initiation of a phase change in a small
region, such as the formation of a solid crystal from a
liquid solution. It is a consequence of rapid local
fluctuations on a molecular scale in a homogeneous
phase that is in a state of metastable equilibrium. Total
nucleation is the sum effect of two categories of
nucleation primary and secondary.
Primary nucleation
Primary nucleation is the initial formation of a crystal
where there are no other crystals present or where, if
there are crystals present in the system, they do not
have any influence on the process. This can occur in
two conditions. The first is homogeneous nucleation,
which is nucleation that is not influenced in any way by
solids. These solids include the walls of the crystallizer
vessel and particles of any foreign substance. The
second category, then, is heterogeneous nucleation.
This occurs when solid particles of foreign substances
cause an increase in the rate of nucleation that would
otherwise not be seen without the existence of these
foreign particles. Homogeneous nucleation rarely
occurs in practice due to the high energy necessary to
begin nucleation without a solid surface to catalyse the
nucleation.

Primary
nucleation
(both
homogeneous
and
heterogeneous) has been modelled with the following:
[1]

B is the number of nuclei formed per unit volume

per unit time.
N is the number of nuclei per unit volume.
kn is a rate constant.
c is the instantaneous solute concentration.
c* is the solute concentration at saturation.
(cc*) is also known as supersaturation.
n is an empirical exponent that can be as large as
10, but generally ranges between 3 and 4.
Secondary nucleation
Secondary nucleation is the formation of nuclei
attributable to the influence of the existing
microscopic crystals in the magma. [2] The first type of
known secondary crystallization is attributable to fluid
shear, the other due to collisions between already
existing crystals with either a solid surface of the
crystallizer or with other crystals themselves. Fluid
shear nucleation occurs when liquid travels across a
Crystal at a high speed, sweeping away nuclei that
would otherwise be incorporated into a Crystal,
causing the swept-away nuclei to become new

crystals. Contact nucleation has been found to be the

most effective and common method for nucleation.
The benefits include the following [2]
Low kinetic order and rate-proportional to
supersaturation, allowing easy control without
unstable operation.
Occurs at low supersaturation, where growth rate is
optimum for good quality.
Low necessary energy at which crystals strike
avoids the breaking of existing crystals into new
crystals.
The quantitative fundamentals have already been
isolated and are being incorporated into practice.
The following model, although somewhat simplified, is
often used to model secondary nucleation:[1]

k1 is a rate constant.
MT is the suspension density.
j is an empirical exponent that can range up to 1.5,
but is generally 1.
b is an empirical exponent that can range up to 5,
but is generally 2.

Crystal growth
Crystal growth
Once the first small crystal, the nucleus, forms it acts
as a convergence point (if unstable due to
supersaturation) for molecules of solute touching or
adjacent to the crystal so that it increases its own
dimension in successive layers. The pattern of growth
resembles the rings of an onion, as shown in the
picture, where each colour indicates the same mass
of solute; this mass creates increasingly thin layers
due to the increasing surface area of the growing
crystal. The supersaturated solute mass the original
nucleus may capture in a time unit is called
the growth rate expressed in kg/(m2*h), and is a
constant specific to the process. Growth rate is
influenced by several physical factors, such as surface
tension of solution, pressure, temperature, relative
crystal velocity in the solution, Reynolds number, and
so forth.
The main values to control are therefore:

 Supersaturation value, as an index of the quantity

of solute available for the growth of the crystal;
Total crystal surface in unit fluid mass, as an index
of the capability of the solute to fix onto the
crystal;
Retention time, as an index of the probability of a
molecule of solute to come into contact with an
existing crystal;
Flow pattern, again as an index of the probability of
a molecule of solute to come into contact with an
existing crystal (higher in laminar flow, lower
in turbulent flow, but the reverse applies to the
probability of contact).
The first value is a consequence of the physical
characteristics of the solution, while the others define
a difference between a well- and poorly designed
crystallizer.
Crystal size distribution
The appearance and size range of a crystalline
product is extremely important in crystallization. If
further processing of the crystals is desired, large
crystals with uniform size are important for washing,
filtering, transportation, and storage. The importance
lies in the fact that large crystals are easier to filter
out of a solution than small crystals. Also, larger
crystals have a smaller surface area to volume ratio,
leading to a higher purity. This higher purity is due to
less retention of mother liquor which contains
impurities, and a smaller loss of yield when the

crystals are washed to remove the mother liquor. The

theoretical crystal size distribution can be estimated
as a function of operating conditions with a fairly
complicated mathematical process called population
balance theory (using population balance equations).
Main crystallization processes[edit]
The main factors influencing solubility are, as we saw
above:
Concentration
Temperature
So we may identify two main families of crystallization
processes:
Cooling crystallization
Evaporative crystallization
This division is not really clear-cut, since hybrid
systems
exist,
where
cooling
is
performed
through evaporation, thus obtaining at the same time
a concentration of the solution.
A crystallization process often referred to in chemical
engineering is the fractional crystallization. This is not
a different process, rather a special application of one
(or both) of the above.
Cooling crystallization
Application

Most chemical compounds, dissolved in most

solvents, show the so-called direct solubility that is,
the solubility threshold increases with temperature.

Solubility of the system Na2SO4 H2O

So, whenever the conditions are favourable, crystal
formation results from simply cooling the solution.
Here cooling is a relative term: austenite crystals in a
steel form well above 1000 C. An example of this
crystallization process is the production of Glauber's
salt, a crystalline form of sodium sulfate. In the
diagram, where equilibrium temperature is on the xaxis and equilibrium concentration (as mass percent
of solute in saturated solution) in y-axis, it is clear
that sulfate solubility quickly decreases below
32.5 C. Assuming a saturated solution at 30 C, by
cooling it to 0 C (note that this is possible thanks to
the freezing-point depression), the precipitation of a
mass of sulfate occurs corresponding to the change in
solubility from 29% (equilibrium value at 30 C) to
approximately 4.5% (at 0 C) actually a larger
crystal
mass
is
precipitated,
since
sulfate
entrains hydration water, and this has the side effect
of increasing the final concentration.
There are of course limitation in the use of cooling
crystallization:

 Many solutes precipitate in hydrate form at low

temperatures: in the previous example this is
acceptable, and even useful, but it may be
detrimental when, for example, the mass of water
of hydration to reach a stable hydrate
crystallization form is more than the available
water: a single block of hydrate solute will be
formed this occurs in the case of calcium
chloride);
Maximum supersaturation will take place in the
coldest points. These may be the heat exchanger
tubes which are sensitive to scaling, and heat
exchange may be greatly reduced or discontinued;
A decrease in temperature usually implies an
increase of the viscosity of a solution. Too high a
viscosity may give hydraulic problems, and
the laminar flow thus created may affect the
crystallization dynamics.
It is of course not applicable to compounds
having reverse solubility, a term to indicate that
solubility increases with temperature decrease (an
example occurs with sodium sulfate where
solubility is reversed above 32.5 C).
Cooling crystallizers
Vertical cooling crystallizer in a beet sugar factory
The simplest cooling crystallizers are tanks provided
with a mixer for internal circulation, where
temperature decrease is obtained by heat exchange
with an intermediate fluid circulating in a jacket.

These simple machines are used in batch processes,

as in processing of pharmaceuticals and are prone to
scaling. Batch processes normally provide a relatively
variable quality of product along the batch.
The Swenson-Walker crystallizer
is
a
model,
specifically conceived by Swenson Co. around 1920,
having a semicylindric horizontal hollow trough in
which a hollow screw conveyor or some hollow discs,
in which a refrigerating fluid is circulated, plunge
during rotation on a longitudinal axis. The
refrigerating fluid is sometimes also circulated in a
jacket around the trough. Crystals precipitate on the
cold surfaces of the screw/discs, from which they are
removed by scrapers and settle on the bottom of the
trough. The screw, if provided, pushes the slurry
towards a discharge port.
A common practice is to cool the solutions by flash
evaporation: when a liquid at a given T 0 temperature
is transferred in a chamber at a pressure P 1 such that
the liquid saturation temperature T1 at P1 is lower
than T0, the liquid will release heat according to the
temperature difference and a quantity of solvent,
whose total latent heat of vaporization equals the
difference in enthalpy. In simple words, the liquid is
cooled by evaporating a part of it.
In the sugar industry vertical cooling crystallizers are
used
to
exhaust
the molasses in
the
last
crystallization stage downstream of vacuum pans,
prior to centrifugation. The massecuite enters the
crystallizers at the top, and cooling water is pumped
through pipes in counterflow.

Evaporative crystallization
Another option is to obtain, at an approximately
constant temperature, the precipitation of the crystals
by increasing the solute concentration above the
solubility threshold. To obtain this, the solute/solvent
mass ratio is increased using the technique
of evaporation. This process is of course insensitive to
change in temperature (as long as hydration state
remains unchanged).
All considerations on control of crystallization
parameters are the same as for the cooling models.
Evaporative crystallizers
Most industrial crystallizers are of the evaporative
type,
such
as
the
very
large sodium
chloride and sucrose units,
whose
production
accounts for more than 50% of the total world
production of crystals. The most common type is
the forced circulation (FC) model (see evaporator). A
pumping device (a pump or an axial flow mixer) keeps
the
crystal slurry in
homogeneous suspension throughout
the
tank,
including the exchange surfaces; by controlling
pump flow, control of the contact time of the crystal
mass with the supersaturated solution is achieved,
together with reasonable velocities at the exchange
surfaces. The Oslo, mentioned above, is a refining of
the evaporative forced circulation crystallizer, now
equipped with a large crystals settling zone to
increase the retention time (usually low in the FC) and
to roughly separate heavy slurry zones from clear
liquid.

DTB crystallizer

DTB Crystallizer

Schematic of DTB
Whichever the form of the crystallizer, to achieve an
effective process control it is important to control the
retention time and the crystal mass, to obtain the
optimum conditions in terms of crystal specific
surface and the fastest possible growth. This is

achieved by a separation to put it simply of the

crystals from the liquid mass, in order to manage the
two flows in a different way. The practical way is to
perform a gravity settling to be able to extract (and
possibly recycle separately) the (almost) clear liquid,
while managing the mass flow around the crystallizer
to obtain a precise slurry density elsewhere. A typical
example is the DTB (Draft Tube and Baffle)
crystallizer, an idea of Richard Chisum Bennett (a
Swenson engineer and later President of Swenson) at
the end of the 1950s. The DTB crystallizer (see
images) has an internal circulator, typically an axial
flow mixer yellow pushing upwards in a draft tube
while outside the crystallizer there is a settling area in
an annulus; in it the exhaust solution moves upwards
at a very low velocity, so that large crystals settle
and return to the main circulation while only the
fines, below a given grain size are extracted and
eventually destroyed by increasing or decreasing
temperature, thus creating additional supersaturation.
A quasi-perfect control of all parameters is achieved.
This crystallizer, and the derivative models (Krystal,
CSC, etc.) could be the ultimate solution if not for a
major limitation in the evaporative capacity, due to
the limited diameter of the vapour head and the
relatively low external circulation not allowing large
amounts of energy to be supplied to the system.