Chapter 3 Crystal growth
CHAPTER 3
CRYSTAL GROWTH
3.1 INTRODUCTION
Crystallization is a separation and purification technique employed to
produce a wide variety of materials. Crystallization may be defined as a phase
change in which a crystalline product is obtained from a solution. A solution is
a mixture of two or more species that form a homogenous single phase.
Solutions are normally thought of in terms of liquids; however, solutions may
include solids suspension. Typically, the term solution has come to mean a
liquid solution consisting a solvent, which is a liquid, and a solute, which is a
solid, at the conditions of interest. The solution to be ready for crystallization
must be supersaturated. A solution in which the solute concentration exceeds
the equilibrium (saturated) solute concentration at a given temperature is
known as a supersaturated solution [1]. There are four main methods to generate
supersaturation that are the following:
• Temperature change (mainly cooling),
• Evaporation of solvent,
• Chemical reaction, and
• Changing the solvent composition (e.g. salting out).
The Ostwald - Miers diagram shown in Fig. 3.1 illustrates the basis of
all methods of solution growth. The solid line represents a section of the curve
for the solute / solvent system. The upper dashed line is referred to as the
super-solubility line and denotes the temperatures and concentration where
spontaneous nucleation occurs [2]. The diagram can be evaluated on the basis of
three zones:
• The stable (unsaturated) zone where crystallization is impossible.
• The Meta stable (supersaturated) zone where spontaneous nucleation is
improbable but a crystal located in this zone will grow.
• The unstable or labile (supersaturated) zone where spontaneous nucleation is
probable and so the growth.
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Chapter 3 Crystal growth
Crystallization from solution can be thought of as a two step process.
The first step is the phase separation, (or birth), of a new crystals. The second is
the growth of these crystals to larger size. These two processes are known as
nucleation
and
crystal
growth,
respectively.
Analysis
of
industrial
crystallization processes requires knowledge of both nucleation and crystal
growth.
The birth of new crystals, which is called nucleation, refers to the
beginning of the phase separation process. The solute molecules have formed
the smallest sized particles possible under the conditions present. The next
stage of the crystallization process is for these nuclei to grow larger by the
addition of solute molecules from the supersaturated solution. This part of the
crystallization process is known as crystal growth. Crystal growth, along with
nucleation, controls the final particle size distribution obtained in the system. In
addition, the conditions and rate of crystal growth have a significant impact on
the product purity and the crystal habit. An understanding of the crystal growth
theory and experimental techniques for examining crystal growth from solution
are important and very useful in the development of industrial crystallization
processes. The many proposed mechanisms of crystal growth may broadly be
discussed under a few general headings [2-5]:
• Surface energy theories
• Adsorption layer theories
• Kinematic theories
• Diffusion - reaction theories
• Birth and spread models
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Chapter 3 Crystal growth
Figure 3.1 - Ostwald-Miers diagram for a solute/solvent system [2].
3.2 THE THREE-STEP-MODEL
Modeling of crystal growth in solution crystallization is often done by
the Two- Step-Model. The Two-Step-model describes the crystal growth as a
superposition of two resistances: bulk diffusion through the mass transfer
boundary layer, i.e. diffusion step, and incorporation of growth unites into the
crystal lattice, i.e. integration step [2-5]. The overall growth rate is expressed as:
The Two-Step-Model is totally ignoring the effect of heat transfer on the
crystal growth kinetics. In the literature there is little evidence for the effects of
heat transfer on the crystal growth kinetics in the case of crystallization from
solution. Matsuoka and Garside[8] give an approach describing the combined
heat and mass transfer in crystal growth processes. The so called Three-Step-
~ 57 ~
Chapter 3 Crystal growth
model of combined mass and heat transfer takes the above mentioned effects
into account
[6-8]
. A mass transfer coefficient is defined which includes a
dimensionless temperature increment at the phase boundary constituted by the
temperature effect of the liberated crystallization heat and the convective heat
transfer. For simplicity the transport processes occurring during growth will be
described in terms of the simple film theory. This has the advantage that the
resulting equations can be easily solved and the predictions do not differ
significantly from those derived using the boundary layer theory
[9,10]
.
Conditions in the fluid adjacent to the growing crystal surface are illustrated in
Fig. 3.2. The mass transfer step can be presented by the equation:
where Ci* and Cb* are the saturation concentrations evaluated at the
interface and bulk temperatures, respectively. The effect of bulk flow,
important at high mass fluxes, is neglected in Eq. 3.4. It is also assumed that
the temperature difference (Ti - Tb) is sufficiently small for the solubility curve
to be assumed linear over this temperature range. A heat balance relating heat
evolution to convective transfer gives:
~ 58 ~
Chapter 3 Crystal growth
Where βd is defined by Matsuoka and Garside
[8]
as a dimensionless number
for the temperature increase at the crystal surface and therefore as measure of
the heat effect on growth kinetics.
Figure 3.2 - Concentration and temperature profiles to the crystal surface
as assumed in the simple film theory [6].
The analogy between mass transfer and heat transfer is given by [11]:
The general expression for the overall growth rate can be obtained by
combining Eqs. 3.1, 3.2 and 3.6:
Matsuoka and Garside
[8]
give a limit βd must be > 10 -2, for values
below which the influence of the heat transfer on the crystal growth kinetics
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Chapter 3 Crystal growth
can be neglected. The dissolution process is, on the contrary, quite frequently
described only by use of the diffusion step. What is not true since there is
definitely a surface disintegration step[12,13]. In other words dissolution is the
100 % opposite of crystal growth. However, a justification for the model
assumption that dissolution can be seen as just diffusion controlled is due to
experimental results which show a linear dependence on the concentration
difference (under saturation). Furthermore, the dissolution process is happening
according to literature much faster (4 to 6 times) than the crystal growth
process so that a possible surface reaction resistance is here difficult to observe
[12,13]
. The assumption that the dissolution of crystals involves the sole diffusion
step is therefore, in many cases valid:
Two methods, the differential and integration method are mainly used
for the measurements of the growth rates in fluidized bed experiments
[14]
. In
this study the differential method was used. In the differential method, the
crystallization is seeded by adding a few grams of crystals with a known sieve
aperture into a supersaturated solution. The seed crystals grow in the
supersaturated solution. Since the amount of crystals is small, it is assumed that
the concentration of the solution does not change during the growth. The other
assumptions are as follows:
• The number of seed crystals put into the crystallizer is equal to the number of
crystals taken out from the crystallizer.
• There is no crystal loss, an assumption which is always valid for an
experienced experiment.
• The shape factor of the growing crystals is considered to be the same.
This assumption is not always true especially in the case of surface
nucleation. In this case, growth values are thought of as average values. If the
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Chapter 3 Crystal growth
amount of the crystals put into the crystallizer is M1 and the amount of the
crystals taken out from the crystallizer is M2, they can be related to the size of
the crystals L as shown in the following equations[15]:
where L1 and L2 are the characteristic size of the crystals input and the
output, respectively. The overall linear growth rate G (m/s) is defined as the
rate of change of characteristic size:
The expression for the growth rate in terms of size of the seed crystals and the
weight of the crystals can be given by:
G and RG are related to each other as follows:
where β1 and α1 are surface and volume shape factors, respectively. M1
and M2 are experimentally obtained. The growth rate, RG, and the dissolution
rate, RD, are calculated from Eq. 3.16 by knowing L1 and t.
3.3 CRYSTAL GROWTH TECHNIQUES
The mathematical models are based on the Navier-Stokes equations and
the heat & mass transport equations in the 2D and 3D approximations. Special
models are available for crystallization phenomena and chemical reactions.
The mathematical aspects of the models used for the analysis of bulk
crystal growth are described in the literature
calculations
[16-19]
[16-31]
. The global heat transfer
are the basis for a detailed analysis of flows, mass transfer,
and crystallization. Usually, the view-factor (surface-to-surface) method is
applied to simulate radiative heat exchange; a heat transport conservation
~ 61 ~
Chapter 3 Crystal growth
equation is used to predict the temperature distribution. To simulate radiative
heat transfer in semitransparent media, we apply an original model based on a
combination of the ray-tracing and discrete ordinate approach [30,31].
The moving grid approach is used to find the geometry of the
melt/crystal interface. The grid is reconstructed after each step of finding the
crystallization front.

MELT GROWTH METHODS
This method is the most basic. A gas is cooled until it becomes a liquid,
which is then cooled further until it becomes a solid. Polycrystalline solids are
typically produced by this method unless special techniques are employed. In
any case, the temperature must be controlled carefully. Large crystals can be
grown rapidly from the liquid elements using a popular method invented in
1918 by the Polish scientist Jan Czochralski and called crystal pulling.



Horizontal Boat Growth Methods

Horizontal Gradient Freezing (HGF) method

Horizontal Bridgman (HB) method

Horizontal Zone Melting (HZM) method
Vertical Boat Growth Methods

Vertical Bridgman (VB) method

Vertical Gradient Freezing (VGF) method

Vertical Zone Melting (VZM) method
Pulling Methods

Czochralski (CZ) method

Liquid Encapsulated Czochralski (LEC) method

Kyropolous and Liquid Encapsulated Kyropolous (LEK)
methods

Floating Zone (FZ) Method

Other Methods

Shaped Crystal Growth Method

Heat Exchange Method (HEM)
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Chapter 3 Crystal growth

SOLUTION GROWTH METHODS

Simple Solution Growth Method

Traveling Heater Method (THM)

Solute Solution Diffusion (SSD) Method

Solvent Evaporation (SE) Method

Temperature Difference Method under Controlled Vapor
Pressure (TDM-CVP)



Hydrothermal Synthesis Method
VAPOR PHASE GROWTH METHOD

Direct Synthesis (DS) Method

Physical Vapor Transport (PVT) Method

Open tube method

Closed tube method

Chemical Vapor Transport (CVT) Method

Solid Phase Reaction (Solid State Re-crystallization)
MODIFICATION OF CRYSTAL GROWTH METHODS

In-Situ Synthesis

Vapor Pressure Control

Magnetic Field Application

Accelerated Crucible Rotation Technique (ACRT)
3.3.1 Solvent evaporation (SE) method for solid crystal growth
It is often necessary to remove solvent from a solution to recover either
a solid or a high-boiling liquid. There are several ways to do this.
3.3.1.1 Distillation
Simple distillation can be used to remove solvent. Distillation works
well if the solution is composed of a solid and a low-boiling solvent, or if the
solution is composed of a high-boiling liquid and a low-boiling solvent (with
boiling point differences greater than 100°). Advantages of distillation are that
the solvent can be collected and recycled and that no vapors are released into
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Chapter 3 Crystal growth
the atmosphere. A disadvantage is that it can take a long time. Simple
distillation is process covered on the next section.
Method 1 - Open-Dish evaporation
Solvent can be evaporated by placing the solution in an open container
(an Erlenmeyer, evaporating dish, beaker, and vial). The container is set on a
heat source (steam bath, hot plate, heating mantle, sand bath) and the solvent
boiled off. (If the solvent is water, use a heat source other than a steam bath.)
The problem with open-dish evaporation is that the solvent is released
into the air. Open-dish evaporation should always be done in a hood if the
solvent is anything other than water. Even in a hood, however, vapors are
released into somebody’s air. If the solvent is a hazardous compound (for
instance, methylene chloride), it is probably better to choose another method of
solvent removal.
Method 2 - Reduced-Pressure evaporation
You can accomplish evaporation from a solution quickly by placing it in
a side-arm flask, sealing the flask, and then applying vacuum. Under vacuum reduced pressure - liquids vaporize and boil off at lower temperatures;
effectively, the solvents come off a lot faster when under vacuum than at
atmospheric pressure.
In the Organic Chemistry Teaching Labs, a small (25 or 50 mL) side-arm flask
fitted with a rubber stopper is used to strip off small (5-10 mL) amounts of
solvent. As a vacuum source, we use the VacuuBrand systems. Details follow.
Procedure for crystal growth

Put the solution in a 25 or 50 mL side-arm flask. Do not fill the flask
more than one-third full, since the evaporation causes the solvent to
froth and bubble up and out of the flask.

A boiling chip is not necessary, but can be helpful, especially if not plan
to hold and swirl the flask during the process.

Stopper the flask with a black stopper. (Corks do not give a good seal.)

Clamp the flask to a ring stand to prevent it from falling over.
~ 64 ~
Chapter 3 Crystal growth

Connect the flask with vacuum tubing to the VacuuBrand vacuum
source. Do NOT use Tygon tubing.

Have ready a small dish containing warm water.

Turn on the vacuum.

The solution will bubble and froth, especially when you first turn on the
vacuum.

The flask will become cool as the solvent evaporates - place it in the
warm water bath to speed up the evaporation.

Remove the flask from the clamp and hold it in your hand and
constantly swirl it during the process both to prevent bumping and to
increase the surface area to speed up the process.

First turn off the vacuum source connection at your lab bench,

Disconnect the flask from the vacuum tubing.
Method 3 - Rotary evaporators
Rotary evaporators, or roto-vaps, are standard equipment in most
organic chemistry research labs. These evaporators are designed to remove
solvent rapidly from solutions.
Procedure

The motor in the roto-vap turns the flask rapidly, providing a greater
surface from which evaporation can occur, thus speeding up the process.
Cooling coils in the roto-vap condense the vapors and drop them into a
collection flask so that they can be recycled or properly disposed. The
roto-vap is connected to a vacuum source, again, this speed up the
evaporation process.

There are three tubing outlets on the roto-vap, one for a vacuum source
and two for the cooling coils. Use vacuum tubing to connect the outlet
that evacuates the roto-vap chamber to the vacuum source. Use a piece
of Tygon tubing to connect one cooling coil outlet to the cold water
~ 65 ~
Chapter 3 Crystal growth
faucet, and use another piece of Tygon tubing to connect the other
cooling coil outlet to the drain

Place the solution to be evaporated in a round bottom flask, then connect
the flask to the roto-vap. Do not fill the flask more than about one-third
full.

Use a joint clamp to secure the flask to the apparatus. Make sure the
cool water to the cooling coils is turned on.

Turn on the motor so that the flask rotates.

Usually the flask containing the solution to be evaporated is warmed by
a water bath.

Make sure the vent at the top of the cooling coils is closed.

Turn the vacuum outlet on the vacuum system on.

As the solvent evaporates, you may notice a lot of frothing and bubbling
in the evaporating flask. If it starts bubbling out of the flask, you can
open the vent a little to release some of the pressure.

The (unwanted) solvent condenses on the cooling coils and drips down
into the collection flask.

When the solvent has evaporated, turn off the motor that turns the flask
and turn the vacuum outlet to close.

Slowly open the vent to release the pressure in the roto-vap chamber.

Remove the flask from the roto-vap.
In current research work all methods were used but crystal growth from method
3 - Rotary Evaporators are used for further research work.
3.3.2 Distillation and reflux under heat
A process in which a liquid or vapour mixture of two or more
substances is separated into its component fractions of desired purity, by the
application and removal of heat.
Distillation is based on the fact that the vapour of a boiling mixture will
be richer in the components that have lower boiling points.
~ 66 ~
Chapter 3 Crystal growth
Therefore, when this vapour is cooled and condensed, the condensate
will contain more volatile components. At the same time, the original mixture
will contain more of the less volatile material.
Distillation columns are designed to achieve this separation efficiently.
Although many people have a fair idea what “distillation” means, the important
aspects that seem to be missed from the manufacturing point of view are that:
 Distillation is the most common separation technique
 It consumes enormous amounts of energy, both in terms of cooling and
heating requirements
 It can contribute to more than 50% of plant operating costs
To achieve this improvement, a thorough understanding of distillation
principles and how distillation systems are designed is essential.
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 pressure characteristics of liquid mixtures.
The vapour pressure of a liquid at a particular temperature is the equilibrium
pressure exerted 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
~ 67 ~
Chapter 3 Crystal growth
 distillation occurs because of the differences in the volatility of the
components in the liquid mixture
3.3.2.1 The boiling point diagram
The boiling point diagram shows in figure 3.3 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.
Figure 3.3 - The boiling point diagram
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 sub cooled liquid. For example, when a sub
cooled 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 have 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. Heating under
~ 68 ~
Chapter 3 Crystal growth
reflux enables a mixture including volatile materials to be heated for a long
time without loss of solvent. The system is designed to keep materials in the
flask - it follows, therefore, that any apparatus attached to the top of the
condenser is redundant.
Many organic reactions are quite slow and need heating to achieve a
reasonable reaction rate. However, most organic chemicals are quite volatile,
and if heated they will evaporate and be lost. The solution to this problem is to
heat the reaction mixture under reflux. This involves having the reaction
mixture in a flask which is attached to a vertical, open Liebig condenser. Never
attempt to stopper the Liebig condenser. This is quite a popular idea among
students "to stop the vapour escaping". If you attempt to heat sealed glass
apparatus it may explode! There should be no problem with vapour escaping as it hits the cold surface of the condenser it will condense and drip back in to
the flask. The use of a hot water bath may be safer and prevent overheating, but
will limit the reaction temperature to 100 ºC.
3.4 MATERIAL AND METHOD
[1] Materials
The
ligand
which
is
a
p- dimethylaminobenzaldehyde and
Schiff
base
obtained
from
o-phenylenediamine were used. The
stock solutions of FeCl3, NiCl2and CuCl2 were prepared.
[2] Preparation of schiff base
p-dimethylaminobenzaldehyde (1.4919 gm 0.1 mol) solution in ethanol
and o-phenylenediamine (1.0814 gm 0.1 mol) solution in hot water were taken
in round bottomed flask, 50 ml absolute ethanol was added and the mixture was
refluxed for 3 hour. The refluxed mixture was put in ice bath, then orange
coloured precipitate was obtained. It was suctioned filtered and washed with
distilled water. Schiff base obtained was dried and kept in vacuum desiccators.
The pure Schiff base was recrystallized from absolute ethanol
~ 69 ~
Chapter 3 Crystal growth
[3] Preparation of crystals
The crystals were prepared by mixing Schiff base (0.1mol) in hot
ethanol solution to (0.1mol) metal chloride salt solution prepared in distilled
water. The schiff base solution was added slowly with continuous stirring to
metal solution. It was refluxed for 2 hours and after refluxation, the mixture
was heated for 10 minutes till the contents was reduced to half. Then the metal
crystals precipitated out after being cooled. The precipitate
was filtered and
washed with the distilled water. All complexes were dried and kept in vacuum
desiccators.
3.5 CHEMISTRY OF CRYSTAL GROWTH
All chemicals used were of reagent grade. Their standard solutions were
prepared by using doubly distilled CO2 free water. Metal salt were standardized
by complexometric EDTA titration method conductivity water is used
throughout the experimental work. Digital µ 361 pH meter with readability +
0.001 with combined glass calomel electrode have been used for pH metric
study. Stoichiometrically 1:1:1 concentration of M1, M2, L1 and L2 were
maintained in the solution. Metal ligand mixtures of following compositions
were prepared for titration keeping total volume 50ml in each case (µ=0.2 M
NaClO4). The concentration of ligand and metal solution were checked by pH
metric titration against 0.2 N carbonate free sodium hydroxide solution.
The following sets were prepared for titration.
(A)
Known amount of HClO4.
(B)
Free HClO4 + known amount of ligand L1.
(C)
Free HClO4 + known amount of ligand L2.
(D)
Free HClO4 + known amount of ligand L1 + known amount
of metal [M1] (Binary).
(E)
Free HClO4 + known amount of ligand L2 + known amount of metal
[M1] (Binary).
(F)
Free HClO4 + known amount of ligand L1 + known amount of
metal [M2] (Binary).
~ 70 ~
Chapter 3 Crystal growth
(G)
Free HClO4 + known amount of ligand L2 + known amount of metal
[M2] (Binary).
(H)
Free HClO4 + known amount of ligand L1 + known amount of ligand
L2 + known amount of metal [M1] (Ternary).
(I)
Free HClO4 + known amount of ligand L1 + known amount of ligand
L2+ known amount of metal [M2] (Ternary).
(J)
Free HClO4 + known amount of ligand L1 + known amount of ligand
L2+ known amount of metal [M1] + known amount of metal [M2]
(Quaternary) .
(i)
M1 L1or L2 and M2L1or L2 → 1:1 Binary mixtures.
(ii)
M1L1L2 and M2L1L2 → 1:1:1 ternary mixtures.
where M1, M2 are CuII, NiII,FeIII as required
L1= o-Phenylenediamine
L2= p-dimethyleaminobenzaldehyde
Crystals of ternary mixtures M1L1L2 and M2L1L2 were used for further work.
3.6 SYSTEM USED
Instrument Name: All glass double distillation unit, with borosilicate
boiler, borosilicate condenser & Quartz Electric Heater, Vertical type.
Figure 3.4 - Photograph of Working of Rotary Reflux Distillation Setup
~ 71 ~
Chapter 3 Crystal growth
Specification:
Table 3.1 – Specification of Crystal Growth Apparatus
Dist. Water o/p capacity
1.5 lt/hr
230-250 volts
Electrical requirement
Single Phase 1.5x2 Kw
Quartz heater
Cooling water consumption
100 lt/hr
Biological Activity
Pyrogen free
pH
6.9 – 7
Conductivity S/cm
< 1X 10-6
Distillate Temp
65-75 C
The boiler is made of high purity quartz and the condenser is of
borosilicate/quartz material. The built in heater provides of minimum loss of
heat and production of material. The unit is mounted on powder coated metal
stand with electrical connections and is easy to dismantle and assemble the
unit. Fiber glass insulated wire and silicon rubber boot resist high temperature.
Spares for this unit:
1. Borosilicate boiler with water leveler 1.5 lt.
2. Condenser 1.5 lt.
3. Quartz new type heater B-34 complete unit.
4. Flasks – Boling, round bottom, short neck with interchangeable joint.
Capacity – 250 ml and Approx Height – 140 mm
All apparatus were used have high quality and Pore size of about 90 –
150 microns. All apparatus have excellent resistant to chemical attack. All
apparatus are incorporating them are mainly design for the application of
vacuum or for passage of gases at relatively low pressure. In all cases the
differential pressure must not exceed 100 KN/m2 (15 psi). All apparatus are
particularly suited for drying to constant weight. All apparatus at room
~ 72 ~
Chapter 3 Crystal growth
temperature can be placed directly 150 C, although customary practice is to
dry at 110C. It is advisable that rate of heating should not be more than
2C/min. This prevents internal strains caused by excessive temperature
differences between the surrounding glass vessel and the sintered disk, which
can lead to fracture of apparatus.
3.7 CRYSTALS SPECIFICATION
Photographs and Dimensions of all crystals were measured at Laljibhai
Chaturbhai Institute of Technology (LCIT), Mehsana. All apparatus were used
have high quality with 5 MP cameras.
Crystal of Cu(II) with O-Phenylenediamine and p-dimethyleaminobenzaldehyde
ligand
Figure 3.5 - Photograph of Crystal Cu(II)
A: Photograph of crystal in bulk form
B: Photograph of crystal in single form
Size: 0.80 mm length and 0.35 mm width
~ 73 ~
Chapter 3 Crystal growth
Crystal of Ni(II) with O-Phenylenediamine and p-dimethyleaminobenzaldehyde
ligand
Figure 3.6 - Photograph of Crystal Ni(II)
A: Photograph of crystal in bulk form
B: Photograph of crystal in single form
Size: 0.68 mm length and 0.47 mm width
Crystal of Fe(III) with O-Phenylenediamine and p-dimethyleaminobenzaldehyde
ligand
Figure 3.7 - Photograph of Crystal Fe(III)
A: Photograph of crystal in bulk form
B: Photograph of crystal in single form
Size: 2.57 mm length and 1.30 mm width
~ 74 ~
Chapter 3 Crystal growth
REFERENCE
1.
Karpinski, P.H. “Crystallization as a Mass Transfer Phenomenon”
Chem. Eng. Sci., 35, 2321-2324 (1980).
2.
Mullin, J.W. “Crystallization (3rd ed.)” Butterworth Heinemann, (1993).
3.
Myerson, A.S.“Handbook of Industrial Crystallization” Butterworth
Heinemann, (2002).
4.
Ohara, M. and Reid, R.C. “Modelling Crystal Growth Rates from
Solution”
Prentice-Hall, Englewood Cliffs, (1973).
5.
Nyvlt, J., Sohnel, O., Matuchova, M. and Broul, M. “The Kinetics of
Industrail Crystallization (1st ed.)” Elsevier Science Publishing
Company, Inc., (1985).
6.
Kubota, N., Yokota, M. and Mullin, J.W. “Kinetic Models for the
Crystal Growth from Aqueous Solution in the Presence of Impurities–
Steady and Unsteady State Impurity Actions” Proceeding of the 13th
Symposium on Industrial Crystallization, B. Biscans and N. Gabas,
Eds., Toulouse, France, 111-116 (1996).
7.
Dunning, W.J. and Albon, N.“The Kinetics of Crystal Growth of
Sucrose from Aqueous Solution, in: Growth and Perfection of Crystals”
Wiley, 446-457 (1958).
~ 75 ~
Chapter 3 Crystal growth
8.
Matsuoka, M. and Garside, J. “Non-Isothermal Effectiveness Factors
and the Role of Heat Transfer in Crystal Growth from Solutions and
Melts”
Chem. Eng. Sci., 46, 183-192 (1991).
9.
Garside, J., Mersmann, A. and Nyvlt, J. “Measurments of Crystal
Growth Rates (1st ed.)” European Federation of Chemical Engineering,
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