Crystallization

The general idea is to avoid too high a driving force because that will force crystals to
grow too rapidly. There must be time for the correct atom, ion, or molecule to find a
place in the crystal lattice where it can fit perfectly. Intense driving force may force an
impurity into the lattice. The following graph indicates an acceptable operating
region.

A concentration in solution that falls in the bluish region is below saturation, and no
crystals can form. 
The red/purple region indicates where the concentration in solution is higher than
saturation, and there is a driving force for deposition of crystals. The exact transition
to the yellow region cannot be measured; this line is indistinct and depends on the
conditions of the experiment. 
A concentration in the yellow region is far above saturation. Too much driving force
means that we can expect crystallization to be spontaneous and fast.

In the red/purple region, especially close to the lower line, nothing may happen unless
something such as nucleation sites or seed crystals initiates crystallization.
Crystallization
 

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, rather, this understanding must be combined with
laboratory practice to gain proficiency in this technique.

How to do a crystallization

To crystallize an impure, solid compound, add just enough hot solvent is added 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.
 DISTILLATION PRINCIPLES
Separation of components from a liquid mixture via distillation depends on the differences
in boiling points of the individual components. Also, depending on the concentrations of
the components present, the liquid mixture will have different boiling point characteristics.
Therefore, distillation processes depends on the vapour pressurecharacteristics of liquid
mixtures.

Vapour Pressure and Boiling

The vapour pressure of a liquid at a particular temperature is the equilibrium
pressureexerted by molecules leaving and entering the liquid surface. Here are some
important points regarding vapour pressure:

energy input raises vapour pressure

vapour pressure is related to boiling

a liquid is said to ‘boil’ when its vapour pressure equals the surrounding pressure

the ease with which a liquid boils depends on its volatility

liquids with high vapour pressures (volatile liquids) will boil at lower temperatures

the vapour pressure and hence the boiling point of a liquid mixture depends on
the relative amounts of the components in the mixture
distillation occurs because of the differences in the volatility of the components in
the liquid mixture

The Boiling Point Diagram

The boiling point diagram shows how the equilibrium compositions of the components in a
liquid mixture vary with temperature at a fixed pressure. Consider an example of a liquid
mixture containing 2 components (A and B) - a binary mixture. This has the following
boiling point diagram.

The boiling point of A is that at which the

mole fraction of A is 1. The boiling point of B
is that at which the mole fraction of A is 0. In
this example, A is the more volatile
component and therefore has a lower boiling
point than B. The upper curve in the diagram
is called the dew-point curve while the lower
one is called the bubble-point curve.

The dew-point is the temperature at

which the saturated vapour starts to
condense.

The bubble-point is the temperature at

which the liquid starts to boil.

The region above the dew-point curve shows

 the equilibrium composition of the superheated vapour while the region below the bubble-
point curve shows the equilibrium composition of the subcooled liquid.

For example, when a subcooled liquid with mole fraction of A=0.4 (point A) is heated, its
concentration remains constant until it reaches the bubble-point (point B), when it starts
to boil. The vapours evolved during the boiling has the equilibrium composition given by
point C, approximately 0.8 mole fraction A. This is approximately 50% richer in A than the
original liquid.

This difference between liquid and vapour compositions is the basis for
distillation operations.

Relative Volatility
Relative volatility is a measure of the differences in volatility between 2 components, and
hence their boiling points. It indicates how easy or difficult a particular separation will be.
The relative volatility of component ‘i’ with respect to component ‘j’ is defined as

yi = mole fraction of component ‘i’ in the vapour

xi = mole fraction of component ‘i’ in the liquid

Thus if the relative volatility between 2 components is very close to one,

it is an indication that they have very similar vapour pressure
characteristics. This means that they have very similar boiling points
and therefore, it will be difficult to separate the two components via
distillation.

METHODS of SEPARATING MIXTURES and purifying

substances

2.1 Simple Distillation

Distillation involves 2 stages and both

are physical state changes.

(1) The liquid or solution mixture

is boiled to vaporise the most volatile
component in the mixture (liquid ==>
gas). The ant-bumping granules give a
smoother boiling action.
(2) The vapour is cooled by cold water in the condenser to condense (gas ==>
liquid) it back to a liquid (the distillate) which is collected.

This can be used to purify water because the dissolved solids have a much higher
boiling point and will not evaporate with the steam, BUT it is too simple a method to
separate a mixture of liquids especially if the boiling points are relatively close.

2.2 Fractional Distillation

Fractional distillation involves
2 main stages and both are
physical state changes. It can
only work with liquids with
different boiling points.
However, this method only
works if all the liquids in the
mixture are miscible (e.g.
alcohol/water, crude oil etc.)
and do NOT separate out into
layers like oil/water.

(1) The liquid or solution

mixture is boiled to
vaporise the most volatile
component in the mixture
(liquid ==> gas). The ant-
bumping granules give a
smoother boiling action. 

(2) The vapour passes up through a fractionating column, where the separation
takes place (theory at the end). This column is not used in the simple distillation
described above.

(3) The vapour is cooled by cold water in the condenser

to condense (gas ==> liquid) it back to a liquid (the distillate) which is collected.

This can be used to separate alcohol from a fermented sugar solution.

It is used on a large scale to separate the components of crude oil, because the
different hydrocarbons have different boiling and condensation points (see oil).

FRACTIONAL DISTILLATION THEORY:

Imagine green liquid is a mixture of a blue liquid (boiling point 80 oC) and a yellow
liquid (boiling point 100oC), so we have a coloured diagram simulation of a
colourless alcohol and water mixture! As the vapour from the boiling mixture enters
the fractionating column it begins to cool and condense. The highest boiling or least
volatile liquid tends to condense more i.e. the yellow liquid (water). The lower
boiling more volatile blue liquid gets further up the column. Gradually up the column
the blue and yellow separate from each other so that yellow condenses back into
the flask and pure blue distils over to be collected. The 1st liquid, the lowest boiling
point, is called the 1st fraction and each liquid distils over when the top of the
column reaches its particular boiling point to give the 2nd, 3rd fraction etc.

To increase the separation efficiency of the tall fractionating column, it is

usually packed with glass beads, short glass tubes or glass rings etc. which greatly
increase the surface area for evaporation and condensation. 

In the distillation of crude oil the different fractions are condensed out at different

points in a huge fractionating column. At the top are the very low boiling fuel gases
like butane and at the bottom are the high boiling big molecules of waxes and tar.

2.3 Paper or Thin Layer Chromatography

   This method of
separation is used to
see what coloured
materials make up e.g.
a food dye analysis.

The material to be
separated e.g. a food
dye (6) is dissolved in
a solvent and carefully
spotted onto chromatography paper or a thin layer of a
white mineral material on a glass sheet.  Alongside it are
spotted known colours on a 'start line' (1-5).

The paper is carefully dipped into a solvent, which is absorbed into the paper and
rises up it. The solvent may be water or an organic liquid like an alcohol (e.g.
ethanol) or a hydrocarbon, so-called non-aqueous solvents. For accurate work the
distance moved by the solvent is marked on carefully with a pencil and the
distances moved by each 'centre' of the coloured spots is also measured. These
can be compared with known substances BUT if so, the identical paper and solvent
must be used (See Rf values below).

Due to different solubilities and different molecular 'adhesion' some colours move
more than others up the paper, so effecting the separation of the different coloured
molecules.

Any colour which horizontally matches another is likely to be the same molecule

i.e. red (1 and 6), brown (3 and 6) and blue (4 and 6) match, showing these three
are all in the food dye (6).

The distance a substance moves, compared to the distance the solvent front
moves (top of grey area on 2nd diagram) is called the reference or Rf value and
has a value of 0.0 (not moved - no good), to 1.0 (too soluble - no good either),
but Rf ratio values between 0.1 and 0.9 can be useful for analysis and identification.

Rf = distance moved by dissolved substance (solute) / distance moved by

solvent.

Some technical terms: The substances (solutes) to be analysed must dissolve in

the solvent, which is called the mobile phase because it moves. The paper or thin
layer of material on which the separation takes place is called the stationary or
immobile phase because it doesn't move.

It is possible to analyse colourless mixture if the components can be made

coloured e.g. protein can be broken down into amino acids and coloured
purple by a chemical reagent called Ninhydrin and many colourless organic
molecules fluoresce when ultra-violet light is shone on them. These are
called locating agents.

Thin layer chromatography (t.l.c) is where a layer of paste is thinly and evenly
spread on e.g. a glass plate. The paste consists of the solid immobile phase like
aluminium oxide dispersed in a liquid such as water. The plate is allowed to dry and
then used in the same way as paper chromatography.

Gas-liquid chromatography is described below

  

2.4 Three techniques used in a particular and separation and

purification procedure
2.4c
2.4a FILTRATION 2.4b EVAPORATION
CRYSTALLISATION
Filtration use a filter paper or fine porous
ceramic to separate a solid from a liquid. It
works because the tiny dissolved particles
are too small to be filtered BUT
any insoluble 'non-dissolved' solid
particles are too big to go through!

Evaporation means a liquid changing to a

gas or vapour. In separation, its removing
the liquid from a solution, usually to leave
a solid. It can be done quickly with gentle heating or left out to 'dry up' slowly. The
solid will almost certainly be less volatile than the solvent and will remain as a
crystalline residue.

Crystallisation can mean a liquid substance changing to its solid form.

However, the term usually means what happens when the liquid from a
solution has evaporated to a point beyond the solubility limit. Then solid
crystals will 'grow' out of the solution because the solution is too concentrated for all
the solid to remain dissolved at that temperature. Crystallisation is often done from
a hot concentrated solution, because most substance are more soluble the hotter
the liquid. Consequently on cooling a hot concentrated solution, crystals form as
the solubility gets less and less.

These separation methods are involved in e.g. (1) separation of a sand and salt
mixture or (2) salt preparations

(1) The sand/salt mixture is stirred with water to dissolve the salt. The sand is
filtered off and washed with pure water to remove remaining traces of salt
solution. The salt solution (filtrate) is carefully heated in a dish to evaporate
the water and eventually the salt crystals form. Here the solvent is water, but
other mixtures can be separated using the same sequence of procedures
using a different solvent. e.g. copper and sulphur can be separated using an
organic solvent like tetrachloromethane which will dissolve the sulphur
(hazardous chemical solvent).

(2a) When the water insoluble base (e.g. a metal oxide) is dissolved in an
acid, the excess solid base is filtered off and the filtrate solution heated to
evaporate the water to produce the salt crystals.

(2b) Two solutions of soluble substances are mixed and react to form an
insoluble salt. The insoluble salt is filtered off to separate it from the solution,
washed with pure water to remove any residual salt solution. The solid is
then removed from the filter paper and dried to give the pure dry insoluble
salt.

Some important words-phrases to do with the above procedures.

A solvent is a liquid that dissolves things.

The solute is the solid that dissolves in a solvent.

A solution is a mixture of a liquid with something dissolved in it.

The technique of solvent extraction involves using a liquid to dissolve a solid

to separate it from a mixture (e.g. in purifying salt in the experiment
described above.

A saturated solution is one in which no more substance will dissolve in the

liquid.

Soluble means the substance (gas, liquid or solid) dissolves in a liquid to

form a solution.

Insoluble a substance won't dissolve in a particular liquid.

Remember, a solid may dissolve in one liquid but not in another.

See how these methods are used in making salts

   

  2.5 Miscellaneous Separation Methods and

other apparatus uses
Separating Distillation, described  is used to
funnel separate miscible liquids that
dissolve in each other. If two
liquids do NOT mix, they form
two separate layers and are
known as immiscible liquids (e.g.
oil/water). This is illustrated in the
diagram on the left, where the
lower grey liquid will be more
dense than the upper layer of the
yellow liquid and shows how you
can separate these two liquids
using a separating funnel.
(particle picture on gas-liquid-solid page)

1. The mixture is put in the separating funnel with the

stopper on and the tap closed and the layers left to settle
out. 2. The stopper is removed, and the tap is opened so
that you can carefully run the lower grey layer off first into a
beaker. 3. This leaves behind the upper yellow layer liquid,
so separating the two immiscible liquids.
 MAGNET This can be used to separate iron from a mixture with
sulphur (see below). It is used in recycling to recover iron
and steel from domestic waster i.e. the 'rubbish' is on a
conveyer belt that passes a powerful magnet which pluck's
out magnetic materials.
GASES Methods of collecting gases are on a separate web page.
Includes the preparation of ammonia, carbon dioxide,
sulphur dioxide, hydrogen and a cracking experiment.
Use of U tube to
collect things in e.g.
condensing out
water in a
combustion
investigation

Burette and Their use is included in Salt Preparations and titrations with

pipette the Acids, Bases, Salts, pH page. A burette is used to
measure volumes accurately and a pipette is used to
 separate out an accurate volume of a solution from a bulk
container of the solution.
Decanting is the simplest possible way of separating a
liquid (pure or a solution) from an insoluble solid which has a
density greater than water (i.e. > 1.0 g/cm3). The solid-liquid
mixture is allowed to stand e.g. in a beaker, until all the solid
settles out to the bottom of the container. Then the liquid is
carefully poured off to leave the insoluble solid behind.
Decantation However it is inefficient e.g. a small amount of liquid is
always left in the solid residue and very fine solid particles
take some time to settle out and any disturbance of the
liquid can mix them in with the liquid being poured off. Wine
may be served in a decanter to leave the undesirable solids
behind - no good for bits of cork though, they float!
In its simplest form these techniques involve using a liquid
to dissolve a solid to separate it from a mixture.
The extraction of pure salt from a sand-salt mixture is a
simple example of the technique.
Solvent Extracti
on For more complex examples see the advanced level
chemistry page. ASA2 solute distribution between two
immiscible liquids, partition coefficient , calculations and
uses
Centrifuges and Centrifuges are devices or apparatus that can be used to
centrifuging separate insoluble materials (usually a solid) from a
liquid, where normal filtration does not work well e.g. a
suspension of very fine (tiny) solid particles. The
centrifuge consists of carriage or glass tube holder,
mounted on an electrically motor driven vertical axle. The
carriage holds the balanced glass tubes of equal
amounts of the solid-liquid mixture in each tube, all tubes
initially in a horizontal position before the motor is switched
on.  The tube carriage is rotated at high speed safely in
a fully enclosed container. Unbalanced tubes can break
with the extra vibration and this situation has a 'knock on'
effect, quite literally, as other tubes are likely to shatter with
the erratic high speed unbalanced motion. High velocity
glass fragments are not good for you! On rapid rotation of
the carriage the tubes whirl round horizontally and the
centrifugal force causes the more dense insoluble material
particles to move outwards, separating from the liquid. When
rotation ceases the solid particles end up at the 'bottom' of
the glass tubes with the liquid above. After the centrifuging
operation the liquid can be decanted off and the solid is left
at the bottom of the glass tube. You might be interested in
the solid, liquid or both products depending on the context.
Centrifuges come in all sizes and centrifuge technology has
many applications in the separation of mixtures and the
purification of materials.

If [ ] represents the glass tubes, the horizontal rotation

situation is shown below ..
 [solid/liquid] <== axle | carriage ==> [liquid\solid]

Uses-applications: In biology cells can be separated from

fluids. A waste 'sludge' can be treated e.g. removing toxic
solids from contaminated water from an industrial process.
Milk can be separated from whey. Edible oils, wines and
spirits can be cleaned or 'clarified' of solid impurities.
Expensive oils and other fluids used as lubricants in
machining metal parts in industry become contaminated with
tiny metal fragments. The larger pieces of metal are easily
removed by filtration or sedimentation (allowing to settle out)
but the very fine metal particles can only be removed by
using a centrifuge. This is likely to be a cheaper option than
buying more machine fluid AND reducing pollution since the
fluid is recycled leaving less waste to dispose of.

  

Sublimation (chemistry)
Previous (Subjective idealism)

Next (Sublime (philosophy))

Simple sublimation apparatus. Water, usually cold, is circulated in cold finger to allow the desired compound to be
deposited.
1 Cooling water in. 2 Cooling water out.3 Vacuum/gas line. 4 Sublimation chamber. 5 Sublimed material deposited on the
cold finger. 6 Crude material. 7External heating.
In chemistry, sublimation is the process by which a substance undergoes conversion from
the solid phase to the gas phase, without going through an intermediate liquid phase. Iodinecrystals and
solidified carbon dioxide are examples of substances that sublimate at room temperature and regular
atmospheric pressure. By contrast, at normal pressures, most chemical compounds
and elements possess three different states—solid, liquid, and gas—at different temperatures. In these
cases, the transition from the solid to the gaseous state requires an intermediate liquid state. [1] The
antonym (opposite process) of sublimation is called deposition. The formation of frost is an example of
meteorological deposition.

Contents

 [hide]

1 Examples of

sublimation

2 Principles of

sublimation

3 Uses

4 See also

5 Notes

6 References

7 Credits

Examples of sublimation
As mentioned above, carbon dioxide (CO2) is a common example of a chemical compound that
sublimates at atmospheric pressure—a block of solid CO2 (dry ice) at room temperature and one
atmosphere pressure will turn into gas without first becoming a liquid. Iodine is another substance that
visibly sublimates at room temperature. In contrast to CO 2, though, it is possible to obtain liquid iodine at
atmospheric pressure by heating it.

Snow and other water ices also sublimate, although more slowly, at below-freezing temperatures. This
phenomenon, used in freeze drying, allows a wet cloth to be hung outdoors in freezing weather and
retrieved later in a dry state. Naphthalene, a common ingredient in mothballs, also sublimes
slowly. Arsenic can also sublimate at high temperatures.

Some materials, such as zinc and cadmium, sublimate at low pressures. In high-vacuum applications, this

phenomenon may be problematic.
Principles of sublimation
Sublimation is a phase transition that occurs at temperatures and pressures below what is called the
"triple point" of the substance (see phase diagram). The process is an endothermic change—that is, a
change in which heat is absorbed by the system. The enthalpy of sublimation can be calculated as the
enthalpy of fusion plus the enthalpy of vaporization.

Uses
Sublimation is a technique used by chemists to purify compounds. Typically a solid is placed in a vessel
which is then heated under vacuum. Under this reduced pressure the solid volatilizes and condenses as a
purified compound on a cooled surface, leaving the non-volatile impurities behind. This cooled surface
often takes the form of a "cold finger" (shown in the diagram above). Once heating ceases and the
vacuum is released, the sublimed compound can be collected from the cooled surface. Usually this is
done using a sublimation apparatus.

Frost-free freezers are the result of having a fan and air circulation inside the freezer. The sub-zero
temperature combined with the air circulation that keeps the air arid, significantly accelerates the
sublimation process. This keeps freezer walls and shelves free of ice, although ice-cubes will continually
sublimate.

Dye sublimation is also often used in color printing on a variety of substrates, including paper. A small
heater is used to vaporize the solid dye material, which then solidifies upon the paper. As this type of
printer allows extremely fine control of the primary color ratios it is possible to obtain a good quality
picture even with relatively low printer resolution, as compared to other printer types of similar resolution.
Standard black and white laser printers are capable of printing on plain paper using a special "transfer
toner" containing sublimation dyes which can then be permanently heat transferred to T-shirts, hats,
mugs, metals, puzzles and other surfaces.

In alchemy, sublimation typically refers to the process by which a substance is heated to a vapor, then
immediately collects as sediment on the upper portion and neck of the heating medium (typically a retort
or alembic). It is one of the 12 core alchemical processes.

In the Fast-Freeze, Deep-Etch technique, samples (for example, tissue samples) are rapidly frozen in
liquid nitrogen and transferred to a vacuum device in which surface ice is sublimed. This effectively
etches the sample surface, revealing the preserved 3D structure of the hydrated material. A rotary
shadowed surface replica can then be obtained via electron microscopy.

Sublimation is also used to create freeze-dried substances, for example tea, soup or drugs in a process
called lyophilization, which consists of freezing a solution or suspension and heating it very slowly under
medium to highvacuum—specifically, a pressure lower than the vapor pressure of the solvent at its
melting point. This can be well below the melting point of water if there are organic solvents or salts in the
sample being freeze-dried. The resulting solid is usually much easier to dissolve or resuspend than one
that is produced from a liquid system, and the low temperatures involved cause less damage to sensitive
or reactive substances.

The dialysis process

The concept of dialysis, that is partition (separation) of substance between two solutions by use
of semipermeable membrane, is quite simple. Extracorporeal dialysis employs the artificial
kidney (dialyzer) as semipermeable membrane, while   Intracorporeal   dialysis employs the
peritoneal membrane.

Physical principles of dialysis

Diffusion, Ultrafiltration and Osmosis are the basic physical principles of dialysis. Diffusion is
the net directional movement of molecules occurring from a solution of higher concentration to a
solution of low concentration. Ultrafiltration is the movement of solvent across a semipermeable
membrane in response to a pressure difference applied across the membrane.If the solutes
dissolved in the solvent is small enough to permeate the membrane, they are dragged along with
the solvent and cross over to the other side, and this called Convection. Osmosisthe movement of
the solvent (e.g. water) from the side of low concentration to the side of higher concentration.