growth of copper real (autosaved)
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Growth of Copper (II) SulphatePentahydrate
(CuSO4.5H2O) from Aqueous Solution.
Introduction
Crystals play an important role in modern technology and their importance in the field of
pharmaceutical, agriculture and materials science cannot be over emphasized. The physical
and chemical properties of crystals determine their uses. Usually crystal growth aims at
producing crystals with the desired quality for specific applications. There are several
techniques used to grow crystals but each techniques aims at producing a crystal with such
quality good enough to be used for the desired application. Crystal growth may be achieved
using simple cheap techniques or complex and relatively expensive methods. The growth rate
and crystal sizes also vary with the method used. Crystals may be produced in the solid, liquid
or vapour phase and usually involves a controlled or tailored phase transformation. Based on
the phase transformation process, crystal growth techniques are classified as solid growth,
vapour growth, melt growth and solution growth.
Solid Growth - Solid-to-Solid phase transformation Liquid Growth - Liquid to Solid phase transformation Vapour Growth - Vapour to Solid phase transformation
Crystals will grow from a melt much more rapidly than the will grow from the vapour phase
or from solution. This is simply because the density of the material in the melt is comparable
to that in the crystal, so the atoms or molecules are essentially there already to grow the
crystal. For vapour and solution growth, the density of the atoms or molecules in the mother
phase is much lower, and the growth rate depends on the rate at which they arrive at thesurface of the crystal. For the commercial growth of crystals, the faster the crystals of
acceptable quality can be grown the better. This is also true for non-commercial growth of
experimental crystals. So melt growth is the preferred method. However there are various
reasons why many crystals cannot be grown from the melt as we shall see below.
Crystal growth involves two successive processes referred to as nucleation and growth
respectively. Nucleation is a process whereby tiny fragments called seeds crystals are
produced, this usually occurs when components of a solution start to precipitate out, forming
nuclei which attract more precipitate. The seed crystal then forms the base upon which the
growth occurs. Nucleation can occur spontaneously mostly due to changes in pressure and
temperature in which case it is referred to as homogeneous or it can be induced or aided in
which case it is referred to as heterogeneous. The two processes involved in crystal grow i.e.
nucleation and growth will be discussed in more detail.
Nucleation
For a crystal to grow, a seed capable of maintaining a stable condition in a solution, melt or
vapour phase has to be produced first. Nucleation requires the formation of a 3d nucleus.
In this experiment Copper (II) Sulphate Pentahydrate was grown using the temperature
reduction method. This method is a sub-group of the solution growth methods. As mentionedabove, crystal growth from solution is a slow process and the method is mostly used for
materials which cannot be grown from a melt. Some materials decompose or sublime below
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their melting point and cannot be growth from melts. This is true for Copper (II) Sulphate
Pentahydrate, therefore solution growth is the most appropriate method to use.
Aim of Experiment.
The aim of the experiment is to grow a single crystal of Copper (II) Sulphate Pentahydrate
from an aqueous solution by temperature reduction method.
Theory
Growth of crystals from low temperature aqueous solution is controlled by the temperature
and concentration of the solution. Materials, which possess high solubility and whose
solubility is temperature dependent, can be grown easily by solution method. This method is
simpler and cheaper compared with other methods. But growth process is slow and it takes a
long time for crystallization. There are several methods in solution growth depending on thesolvents and the solubility of the solute. These include;
Temperature reduction method Isothermal evaporation method salting out
Copper (II) Sulphate Pentahydrate was grown by low temperature solution growth method. As
mentioned above, this method is applicable for materials with moderate to high solubility and
even more important is that the solubility should be highly temperature dependent. The
solubility of Copper (II) Sulphate Pentahydrate is very temperature dependent. At 0C the
solubility is about 250g/l of water and at 100C the solubility increases to more than 2000g/l
of water (see fig. 1).
Fig 1.The Solubility curve of Copper (II) SulphatePentahydrate in Water.
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This method is suitable to grow single crystals from starting materials which are either
unstable or undergo phase transformation under high temperatures. Copper (II) Sulphate
Pentahydrate as is a salt with a triclinic crystal structures, dehydrates at 150C and
decomposes at 650C. Other growth methods such as growth from melts, vapours or solid to
solid transformation will not be suitable to grow Copper (II) Sulphate Pentahydrate because
these other methods require much higher temperatures which may decompose or dehydrate
the material. The experiment was performed as follows;
Equipment
Fume hood, growth apparatus with control unit, bright lamp (e.g. cold-light lamp), drying
cabinet with temperature control, various beakers (3002000 ml) with appropriate
cover glasses (watch glasses), crystallizing dish, heating plate with magnetic rotation,
glass rod, thermometer (up to 80 C), filter paper with matching funnel, laboratorystand, clamps etc., nylon thread, latex gloves, lint-free paper towels, Teflon tweezers,
plastic tins for storage.
Chemical
1000g copper (II) sulphate pentahydrate, several litres of 18 Mcm H2O, detergents,
alcohol (e.g. isopropanol)
Procedure
The experiment was performed stepwise as follows:
Cleaning Preparation of growth apparatus Growth of seed crystals Preparation of saturated solution and the determination of saturation point. Growth of crystals End of growth, preparation of grown crystal, determination of growth rate End of Experiment.Cleaning
In order to avoid parasitic nucleation all the devices used in this experiment were freed from
all solid particles. This was achieved by thoroughly cleaning all the device parts as follows:
Flushing with soap water and rinsing with plenty of water Repeatedly rinsing with 18 Mcm H2O using a wash bottle Finally washing down with deionised water Dripping and drying in an oven at suitable temperaturesGrowth Apparatus Set-up and Preparation
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The outer vessel was filledwith water up to about 1-2 cm
below the aluminum ring. The
water level was tried to be
kept constant by replenishing
it from time to time.
The pump was started and thethermostat was set so the
water get a uniform
temperature of about 50C.
This is the growth
temperature.
The crystallizing vesselstogether with all the stirring
parts were thoroughly cleaned
initially with tab water then
with 18 Mcm H2O. The
vessels and the other parts
were then left to drain
The parts were rapidlyassembled to avoid dust from
getting into the vessel.
The growth apparatus used for this experiment is shown in the diagram below and it was
prepared a s follows:
Growth of Seed Crystals
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While the growth apparatus gets a uniform temperature a solution for the seed crystal was
prepared. The solution was prepared as follows:
30g of Copper (II) Sulphate Pentahydrate was mixed with 100ml of 18 Mcm H2O in a300ml cooking cup
The mixture was placed in a heating plate and heated to a temperature of about 50C andoccasional up to 60C to get all the Copper (II) Sulphate Pentahydrate into solution.
During the heating the solution was constantly stirred to help dissolution and keep a
uniform temperature throughout the solution.
The solution was then left to stay overnight at room temperature. The solution wascovered to prevent dust or other solid particles from getting inside as this might lead to
parasitic nucleation. The next day some seed crystals were formed.
The solution was filtered over the crystals into a crystallising dish The biggest of the seed crystal was selected to be used for the growth. A fishing line was tight around the seed crystal to enable it to be suspended in the growth
solution.
Preparation of Saturated solution and the determination of saturated point.
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The saturated solution was prepared in the following way:
A 3l flask , suction filter, and funnel were cleaned and heated (without the sealing cuffs)
to about 85C
A temperature of 50C was chosen as the growth temperature and the solubility Copper
(II) Pentahydrate at this temperature was determined using the solubility curves.
Based on this calculation, 0,657kg (per litre of water) of Copper (II) Pentahydrate is need
to make a saturated solution at 50C.
The mixture of the 0,657kg of Copper (II) pentahydrate and 1000ml of water was then
heated to about 60C on a heating plate with a Teflon stirrer. The cooking cup was
covered throughout the dissolution time.
A membrane pump was then used to filter the solution and the filtered solution was then
poured into the crystallising vessel in the growth apparatus.
The saturation point was determined by the streaking method using a crystal of lower quality.
The principle of the streaking method is shown schematically below.
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The test seed crystals and the attachment cord were clean with alcohol and briefly dipped in
deionised water to roughen the surface of the crystal. The crystal was then introduced into the
saturated solution and observed with a lamp from behind the growth apparatus. The
observation was to check for the three possible scenarios above. Alternatively the crystal was
left to stay in the saturated solution over night at the growth temperature. If the solution is not
saturated, the test crystal will dissolve, if the solution is over saturated, the test crystal will
grow and if the size does not change significantly, it means the solution has the right
saturation for this temperature. The test crystal did not show any significant change in size
after 24 hours and we assumed that the saturation point for the solution at the growth
temperature was reached.
Growth of Crystal
After being convinced that the saturation point of the growth solution is correct, the test
crystal was removed and replaced by the seed crystal. The seed crystal was also dipped in
deionised water to roughen the surface. Suspended on a nylon cord, the seed crystal was
slowly lowered into the saturated solution such that it was roughly in the middle of the vessel
with the saturated solution without touching the walls or bottom of the vessel.
After making sure that the seed crystals was in the desired position we proceeded with
temperature reduction. The switch was adjusted to the temperature reduction mode and the
temperature reducer was turned to position 1. The temperature was reduced at a 0,2
interval after every few days until the growth process was completed. At the end of the
growth period the growth apparatus was switched off and the crystal was left to stay in the
solution for more one night. This is to prevent thermal shock of the crystal. The crystal was
then removed and sprayed with a vanish coating to prevent it from absorbing moisture. The
crystal was measured and the growth rate was determined.
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Results and Discussions
The experiment lasted for four weeks in total. The first two days were used in the preparation
of the seed crystal, growth apparatus, growth solution and the determination of the saturationof the growth solution. The rest period was used for the growth. The diagrams below show
both the seed crystal and the grown crystal. The seed crystal has the dimension of 2,5cm by
3,5 cm and the grown crystal has the dimension of 4,5cm by 5,5cm.
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0
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0 10 20 30
Growth [cm]
Time [days]
short axis
long axis