Crystallization

Dr. Muhammad Bilal K Niazi

POLYMORPHISM
A single substance may crystallise in more than one of seven crystal
systems, all of which differ in their lattice arrangement, and exhibit
not only different basic shapes but also different physical properties.
A substance capable of forming more than one different crystal is said
to exhibit polymorphism, and the different forms are called polymorphs.
Calcium carbonate, for example, has three polymorphscalcite
(hexagonal) aragonite (tetragonal), and vaterite (trigonal).
Although each polymorph is composed of the same single substance, it
constitutes a separate phase. Since only one polymorph is
thermodynamically stable at a specified temperature and pressure, all
the other polymorphs are potentially capable of being transformed
into the stable polymorph.
Phase Equilibria
Enantiotropic

Some polymorphic transformations are rapid and reversible and

polymorphs may be enantiotropic (interconvertible)
Monotropic (incapable of transformation)

Graphite and carbon, for example, are monotropic at ambient

temperature and pressure
Ammonium nitrate has five enantiotropic polymorphs over the
temperature range 255398 K
ONE-COMPONENT (OR UNARY) PHASE
DIAGRAMS
There are three externally controllable parameters that will affect phase structure

i.e. temperature, pressure, and composition and phase diagrams are constructed when

various combinations of these parameters are plotted against one another

Perhaps the simplest and easiest type of phase diagram to understand is that for a one-

component system, in which composition is held constant (i.e., the phase diagram is for
a pure substance); this means that pressure and temperature are the variables.

This one-component phase diagram (or unary phase diagram) [sometimes also called a

pressuretemperature (or PT) diagram] is represented as a two-dimensional plot of

pressure (ordinate, or vertical axis) versus temperature (abscissa, or horizontal axis)
Phase diagram of H2O
Phase diagram of H2O
Here it may be noted that regions for three different phases i.e. solid, liquid, and
vapor
Each of the phases will exist under equilibrium conditions over the temperature
pressure ranges of its corresponding area
The three curves shown on the plot (labeled aO, bO, and cO) are phase boundaries; at any
point on one of these curves, the two phases on either side of the curve are in
equilibrium (or coexist) with one another
Equilibrium between solid and vapor phases is along curve aO, likewise for the solid-
liquid, curve bO, and the liquidvapor, curve cO
Upon crossing a boundary (as temperature and/or pressure is altered), one phase
transforms to another. For example, at one atmosphere pressure, during heating the
solid phase transforms to the liquid phase (i.e., melting occurs) at the point labeled 2
The reverse transformation (liquid-to-solid, or solidification) takes place at the same
point upon cooling
At the intersection of the dashed line with the liquid-vapor phase boundary [point 3
(Figure 9.2), at 100 C] the liquid transforms to the vapor phase (or vaporizes) upon
heating
Triple Point
All three of the phase boundary curves intersect at a common point,
which is labeled O (and for this system, at a temperature of 273.16 K and
a pressure of 6.04 x 10-3 atm). This means that at this point only, all of
the solid, liquid, and vapor phases are simultaneously in equilibrium
with one another. Appropriately, this, and any other point on a PT
phase diagram where three phases are in equilibrium, is called a triple
point
Any deviation from this point by a change of temperature and/or
pressure will cause at least one of the phases to disappear
 SINGLE COMPONENT SYSTEM
The phase reactions exhibited by two enantiotropic forms, and , of the same substance
The point of intersection of the two vapour pressure curves is the transition point at which the
two forms can coexist in equilibrium at the specified temperature and pressure
The triple point at which vapour, liquid and solid can co-exist may be considered as the melting
point of the form
On slow heating,
solid changes into
solid and finally
melts with the reverse
process taking place
on slow cooling
The two curves
intersect at a
metastable triple point
where the liquid,
vapour, and a solid
can coexist in
metastable
equilibrium
SINGLE COMPONENT SYSTEM
The pressuretemperature curves for a monotropic substance for which the vapour
pressure curves of the and forms do not intersect
Hence there is no transition point
In this case, solid is the metastable form, and the metastable triple point is as
shown.
TWO-COMPONENT SYSTEMS
Temperature, pressure, and concentration can affect phase equilibria
in a two-component or binary system, although the effect of
pressure is usually negligible and data can be shown on a two-
dimensional temperatureconcentration plot
Three basic types of binary systemeutectics, solid solutions, and
systems with compound formation
The eutectic is the mixture of components that has the lowest
crystallisation temperature in the system
 TWO-COMPONENT
SYSTEMS
When a melt at X is cooled along XZ,
crystals, theoretically of pure B, will start to
be deposited at pointY.
On further cooling, more crystals of pure
component B will be deposited until, at the
eutectic point E, the system solidifies
completely.
At Z, the crystals C are of pure B and the
liquid L is a mixture of A and B where the
mass proportion of solid phase (crystal) to
liquid phase (residual melt) is given by ratio
of the lengths LZ to CZ; a relationship
known as the lever arm rule.
Mixtures represented by points above AE
perform in a similar way, although here the
crystals are of pure A
PHASE DIAGRAM FOR BINARY SYSTEM
where the liquidus represents the temperature at which mixtures of A and B begin to
crystallise on cooling and the solidus represents temperatures at which mixtures begin to
melt on heating
A melt at X begins to crystallise at Y and then at Z, the system consists of a mixture of
crystals of a composition represented by C and a liquid of composition represented by L.
where the ratio of crystals
to liquid is again given by
the lever arm rule.
The crystals do not,
however, consist of a single
pure component as in a
simple eutectic system but
are an intimate mixture of
components A and B
Must be heated and re-
crystallised, perhaps many
times, in order to achieve
further purification.
SOLUBILITY AND SATURATION
Supersaturation
A solution that is in thermodynamic equilibrium with the solid phase
of its solute at a given temperature is a saturated solution, and a
solution containing more dissolved solute than that given by the
equilibrium saturation value is said to be supersaturated. The degree of
supersaturation may be expressed by:

where c and c are the solution concentration and the equilibrium

saturation value respectively. The supersaturation ratio, S, and the
relative supersaturation, are then:
Crystal size and solubility
If very small solute particles are dispersed in a solution, the solute concentration
may exceed the normal equilibrium saturation value. The relationship
between particle size and solubility first applied to solidliquid systems
by OSTWALD may be expressed as

where cr is the solubility of particles of radius r, s the density of the solid, M

the relative molecular mass of the solute in solution, the interfacial
tension of the crystallization surface in contact with its solution and ni the
moles of ions formed from one mole of electrolyte. For a non-electrolyte, ni
=1
ASSIGNMENT
PROBLEM 1 :
At 293 K, a supersaturated solution of sucrose contains 2.45 kg
sucrose/kg water. If the equilibrium saturation value is 2.04
kg/kg water, what is the supersaturation ratio in terms of kg/kg
water and kg/kg solution
Solution
PROBLEM 2:
Compare the increase in solubility above the normal equilibrium
values of 1, 0.1 and 0.01 m particles of barium sulphate and
sucrose at 298 K. The relevant properties of these materials are:
SOLUTION:
Taking the gas constant, R as 8314 J/kmol K,