Gslides:

https://docs.google.com/presentation/d/10i9jk5ITlUfarVDGUoFoyUKU6cJPfkLB4p6L70iuSmg
/edit#slide=id.p

Red - comments from alex

INTRO final here:

https://docs.google.com/document/d/1tz3OeSnxZlDSLkuGbeTTJ5UNFGZS7axK4kVYmGPt_VU/edi
t

What are crystals?

how do we grow crystals from liquid to solid?
What is Alum? How is it formed?
What is recrystallization/ crystallization and growth - dapat mamention yung
nucleation chenez. Explain the mechanism/process/explanation behind the process
Discuss alum structure as in crystal structure
Solubility of alum in water at diff temperature - also include kung ano definition
ng solubility
Applications of alum

What are crystals?

A crystal is characterized by the orderly, repetitive arrangement in three
dimensions of the ions, atoms or molecules that make up the crystal

What are crystals?

A crystal is a solid material whose atoms are arranged in a highly ordered, and
periodic manner in three dimensions. [1]

Etymology:
The English word derives ultimately from Greek ???sta????(krystallos) meaning "ice"
[2]

Throughout time, people have collected crystals, treasured them, and even ascribed
magical powers to them. So much so that there is a science dedicated to the study
of them- mineralogy.

how do we grow crystals from liquid to solid? / What is recrystallization/

crystallization and growth

Crystallization is the process of forming a crystalline structure from a fluid or

from materials dissolved in a fluid.

Crystallization occurs in two major steps. The first is nucleation, the appearance
of a crystalline phase from either a supercooled liquid or a supersaturated
solvent. These act as centers of crystallization. It may occur spontaneously or may
be induced artificially. [3]

The second step is known as crystal growth, which is the increase in the size of
particles and leads to a crystal state. As soon as stable nuclei, i.e. particles
larger than the critical size, have been formed in a supersaturated or supercooled
system, they begin to grow into crystals of visible size.[3] Supersaturation is
one of the driving forces of crystallization

Recrystallization is The growth of new *mineral grains from pre-existing mineral

grains by the solid-state *diffusion of *ions in response to a change in
temperature, pressure, or composition of the rock system. [3.1 The formation of a
new, strain-free grain structure from that existing in cold-worked metal, usually
accomplished by heating. [3.2]

What is Alum? How is it formed?

Alum, any of a group of hydrated double salts, usually consisting of aluminum

sulfate, water of hydration, and the sulfate of another element. A whole series of
hydrated double salts results from the hydration of the sulfate of a singly charged
cation (e.g., K+) and the sulfate of any one of a number of triply charged cations
(e.g., Al3+). Aluminum sulfate can thus form alums with sulfates of the singly
charged cations of potassium, sodium, ammonium, cesium, and other elements and
compounds. In similar fashion, sulfates of the triply charged cations of iron,
chromium, manganese, cobalt, and other metals may take the place of aluminum
sulfate. The most important alums are potassium aluminum sulfate, ammonium aluminum
sulfate, and sodium aluminum sulfate. Potassium aluminum sulfate, also known as
potassium alum or potash alum, has a molecular formula of K2(SO4)�Al2(SO4)3�24H2O
or KAl(SO4)2�12H2O.

Alums can easily be produced by precipitation from an aqueous solution. In

producing potassium alum, for example, aluminum sulfate and potassium sulfate are
dissolved in water, and then upon evaporation the alum crystallizes out of the
solution. A more common production method is to treat bauxite ore with sulfuric
acid and then with potassium sulfate. Ammonium alum is produced by the evaporation
of a water solution containing ammonium sulfate and aluminum sulfate. It can also
be obtained by treating a mixture of aluminum sulfate and sulfuric acid with
ammonia. Alums occur naturally in various minerals. Potassium alum, for example, is
found in the minerals kalinite, alunite, and leucite, which can be treated with
sulfuric acid to obtain crystals of the alum. [4]

SEEDING

Probably the best method for inducing crystallization is to inoculate or seed a

supersaturated solution with small particles of the material to be crystallized.
Deliberate seeding is frequently employed in industrial crystallization to effect a
control over the product size and size distribution (section 7.5.5). Atmospheric
dust frequently contains particles of the crystalline product itself, especially in
industrial plants or in laboratories where quantities of the material have been
handled. Fortuitous seeding from this source can serve to prevent the
crystallization of thermodynamic unstable phases, e.g., hydrates or polymorphs,
that might otherwise appear (Ostwald�s rule of stages, section 5.7).
Seed crystals, however, do not necessarily have to consist of the material
being crystallized in order to be effective; isomorphous substances will frequently
induce crystallization. For example, phosphates will often nucleate solutions of
arsenates; sodium tetraborate decahydrate (borax) can nucleate sodium sulphate
decahydrate; phenol can nucleate m-cresol; and so on. The success of silver iodide,
as an artificial rain-maker, is generally attributed to the striking similarity of
the AgI and ice crystal lattices. However, there are many cases where lattice
similarity does not exist and undoubtedly other factors have to be considered.
Micro-organisms like Pseudomonas syringae, for example,
have been used commercially as ice nucleators in the snow-making process (Liao and
Ng, 1990). In laboratory and large-scale crystallizations the first sign of
nucleation often appears in one given region of the vessel, usually where there is
a local high degree of supersaturation, such as near a cooling surface or at the
surface of the liquid. On the other hand, it is not uncommon to find some
particular spot on the vessel wall or on the stirrer acting as a crystallization
centre. The most reasonable explanation of this phenomenon is that minute cracks
and crevices in the surface retain tiny crystals from a previous batch which seed
the system when it becomes supercooled. It is possible, of course, for some part of
a metal or glass surface to be in a condition in which it acts as a catalyst for
nucleation.
There are several reasons why the seed crystal size may be influential in
secondary nucleation. For example, large seeds generate more secondary nuclei in
agitated systems than do small seeds because of their greater contact probabilities
and collision energies. Indeed, very small crystals can follow the streamlines
within the turbulence eddies in vigorously agitated solutions, behaving essentially
as if they were suspended in a stagnant fluid, rarely coming into contact with the
agitator or other crystals. Other factors to consider are that crystals smaller
than about 10 pm probably grow much more slowly than do macrocrystals (section
6.2.7) and, as mentioned above, some damaged crystal fragments may not be capable
of growing at all. ). The secondary nucleation rate decreased with an increase in
the seed size or in the number of seeds of a given size. The latent period was
drastically reduced by decreasing the seed size, but
was relatively unaffected by the number of seeds added. [xyz]

** on supersaturation:
The induction period may therefore be considered as being made up of several parts.
For example, a certain �relaxation time�, t,, is required for this system to
achieve a quasi- steady-state distribution of molecular clusters. Time is also
required for the formation of a stable nucleus, tn, and then for the nucleus to
grow to a detectable size, tg. So the induction period, &, may be written.
In some systems, particularly at low supersaturation, another time lag may be
observed. To distinguish it from the induction period, defined above as the point
at which crystals are first detected in the system, the term �latent period� will
be used, and is defined here as the onset of a significant change in the system,
e.g. the occurrence of massive nucleation or some clear evidence of substantial
solution desupersaturation.

Solubility of alum in water at diff temperature

Table 1. Solubility table of potassium aluminum sulphate per 100g of water at
different temperatures
temperature(0C)
Solubility (g/100g)
temperature(0C)
solubility(g/100g)
0
3.0
40
11.7
10
4.0
60
24.8
20
5.9
80
71.0
30
8.4
100
-
Source: Mullin, J.W.. (2001). Crystallization (4th Edition). Elsevier.
https://app.knovel.com/hotlink/toc/id:kpCE00002P/crystallization-4th-
edition/crystallization-4th-edition

What is solubility
Solubility, degree to which a substance dissolves in a solvent to make a solution
(usually expressed as grams of solute per litre of solvent). Solubility of one
fluid (liquid or gas) in another may be complete (totally miscible; e.g., methanol
and water) or partial (oil and water dissolve only slightly). In general, �like
dissolves like� (e.g., aromatic hydrocarbons dissolve in each other but not in
water). Some separation methods (absorption, extraction) rely on differences in
solubility, expressed as the distribution coefficient (ratio of a material�s
solubilities in two solvents). Generally, solubilities of solids in liquids
increase with temperature and those of gases decrease with temperature and increase
with pressure. A solution in which no more solute can be dissolved at a given
temperature and pressure is said to be saturated (see saturation).[w]

Discuss structure of ALUM

Potassium aluminum sulfate is a member of a large class of solids known as alums;

its chemical formula is KAl(SO4)2�12H2O. The unit cell contains four K atoms, four
Al atoms, eight S atoms, 32 oxygen atoms
in the sulfate ions, and 48 water molecules. [78]
Applications of alum
It is commonly used in water purification, leather tanning, dyeing,[4] fireproof
textiles, and baking powder. It also has cosmetic uses as a deodorant, as an
aftershave treatment and as a styptic for minor bleeding from shaving

WATER PURIFICATION
The addition of inorganic coagulants such as aluminum sulfate (or alum) or iron
(III) salts such as iron(III) chloride cause several simultaneous chemical and
physical interactions on and among the particles. Within seconds, negative charges
on the particles are neutralized by inorganic coagulants. Also within seconds,
metal hydroxide precipitates of the iron and aluminium ions begin to form. These
precipitates combine into larger particles under natural processes such as Brownian
motion and through induced mixing which is sometimes referred to as flocculation.
The term most often used for the amorphous metal hydroxides is "floc." Large,
amorphous aluminum and iron (III) hydroxides adsorb and enmesh particles in
suspension and facilitate the removal of particles by subsequent processes of
sedimentation and filtration. [5]

Leather tanning
Tawing is a method that uses alum and aluminium salts, generally in conjunction
with other products such as egg yolk, flour, and other salts. The leather becomes
tawed by soaking in a warm potash alum and salts solution, between 20 and 30 �C.
The process increases the leather's pliability, stretchability, softness, and
quality.
Tawing is a method of tanning with aluminium salts (alum). It is a naturally-
occurring double salt, but which is also artificially produced. Tawing comes under
mineral tanning and is one of the oldest tanning processes. After tanning with
alum, the dried leather is stiff and firm. To make it softer, the leather is then
tumbled and greased.
Alum tanning makes the leather white and very water-sensitive. The tannins are
washable, making this leather much more sensitive than with chrome tanning which,
with a few exceptions such as for Sheepskin, has replaced alum tanning.[6]
DYEING
To achieve bright colours with natqural dyes, you need to mordant your wool, cotton
or silk beforehand. With the exception of woad and indigo, most natural dyes do not
adhere very well to the fibres and need the help of a mordant.

A mordant is a chemical binding agent that adheres well to both the fibres and to
the dye. The word comes from the Latin mordere, which means to bite.
Alum is a mordant

BAKING POWDER
Alum is used as the acidic component of some commercial baking powders.
DEODORANT
Lets begin by explaining the raw material of natural crystal deodorants. Natural
crystal deodorants are made from potassium alum, which is a naturally occurring
sulfate mineral which typically occurs as encrustations on rocks. It is derived
from the oxidation of sulfide minerals and potassium-bearing minerals; and appears
as a white to colorless translucent crystalline stone. When it is extracted from
the Earth large blocks of potassium alum crystal are shipped to crystal deodorant
manufacturers, where the blocks are then cut, shaped, polished and packaged to form
what we know as crystal deodorant. [7]
-What is ALUM?

Alum

Alternative Title: alumen

Alum, any of a group of hydrated double salts, usually consisting of aluminum
sulfate, water of hydration, and the sulfate of another element. A whole series of
hydrated double salts results from the hydration of the sulfate of a singly charged
cation (e.g., K+) and the sulfate of any one of a number of triply charged cations
(e.g., Al3+). Aluminum sulfate can thus form alums with sulfates of the singly
charged cations of potassium, sodium, ammonium, cesium, and other elements and
compounds. In similar fashion, sulfates of the triply charged cations of iron,
chromium, manganese, cobalt, and other metals may take the place of aluminum
sulfate. The most important alums are potassium aluminum sulfate, ammonium aluminum
sulfate, and sodium aluminum sulfate. Potassium aluminum sulfate, also known as
potassium alum or potash alum, has a molecular formula of K2(SO4)�Al2(SO4)3�24H2O
or KAl(SO4)2�12H2O.

Alums can easily be produced by precipitation from an aqueous solution. In

producing potassium alum, for example, aluminum sulfate and potassium sulfate are
dissolved in water, and then upon evaporation the alum crystallizes out of the
solution. A more common production method is to treat bauxite ore with sulfuric
acid and then with potassium sulfate. Ammonium alum is produced by the evaporation
of a water solution containing ammonium sulfate and aluminum sulfate. It can also
be obtained by treating a mixture of aluminum sulfate and sulfuric acid with
ammonia. Alums occur naturally in various minerals. Potassium alum, for example, is
found in the minerals kalinite, alunite, and leucite, which can be treated with
sulfuric acid to obtain crystals of the alum.

Most alums have an astringent and acid taste. They are colourless, odourless, and
exist as a white crystalline powder. Alums are generally soluble in hot water, and
they can be readily precipitated from aqueous solutions to form large octahedral
crystals.

Alums have many uses, but they have been partly supplanted by aluminum sulfate
itself, which is easily obtainable by treating bauxite ore with sulfuric acid. The
commercial uses of alums mainly stem from the hydrolysis of the aluminum ions,
which results in the precipitation of aluminum hydroxide. This chemical has various
industrial uses. Paper is sized, for example, by depositing aluminum hydroxide in
the interstices of the cellulose fibres. Aluminum hydroxide adsorbs suspended
particles from water and is thus a useful flocculating agent in water-purification
plants. When used as a mordant (binder) in dyeing, it fixes dye to cotton and other
fabrics, rendering the dye insoluble. Alums are also used in pickling, in baking
powder, in fire extinguishers, and as astringents in medicine. [x]

[x] https://www.britannica.com/science/alum

The alum structure (KAl(SO4)2�12H2O)

Potassium aluminum sulfate is a member of a large class of solids known as alums;
its
chemical formula is KAl(SO4)2�12H2O. It crystallizes in a cubic unit cell and
crystal den-
sity measurements show that Z = 4. The systematic absences 0kl (k Th 2n), h0l (l Th
2n), and The systematic absences 0kl (k ? 2n), h0l (l ? 2n), a
hk0 (h ? 2n) uniquely indicate the space group Pa-3. The general and special
positions for
this space group are:
Multiplicity Wyckoff lette rSite symmetr
Coordinates of
equivalent positions
24 d 1 (x, y, z) and 23 others
8 c 3 (x, x, x) and 7 others
4 b -3 (�, �, �), (�, 0, 0),
(0, �, 0), (0, 0, �)
4 a -3 (0, 0, 0), (0, �, �),
(�, 0, �), (�, �, 0)
The unit cell contains four K atoms, four Al atoms, eight S atoms, 32 oxygen atoms
in the sulfate ions, and 48 water molecules. It is best to consider first the atoms
that have
the lowest populations in the unit cell because their locations are more likely to
be more
highly defined by the symmetry of the crystal; here, these are the K and Al atoms.
The A
atoms must occupy either the Wyckoff positions a or b, which are the only ones with
mul
tiplicities of 4. For this space group, these positions have the same environment
and local
symmetry; they differ only in the choice of origin. Thus, we can choose to place
them o
either site; let us put them on the a-sites.
Having made this choice, the four K atoms, which also have a population of 4, must
reside on the b-sites. The eight S atoms cannot be located on the a- or b-sites,
because these
are now already occupied, and must reside on the Wyckoff c-sites. The locations of
th
eight S atoms, one of which is at the coordinates (x, x, x), depend on a free
parameter x that
we do not know. If x is approximately 0, however, then the S atoms would lie too
close to
the Al atoms; if x is approximately �, then the S atoms would lie too close to the
K atoms.
Therefore, x is likely to be about �, with the exact value depending on the
relative radii of
the Al and K atoms and how the sulfate groups are oriented in the unit cell (Figure
29.3).

There are several possible choices of sites for the 32 oxygen atoms in the sulfate
anions
and the 48 oxygen atoms in the water molecules. A likely arrangement for the
sulfate
oxygens is that 24 of them reside in general positions and 8 reside on Wyckoff
sites c, with
a different x parameter than the S atoms. The water molecules probably reside on
two di
ferent sets of general positions.
Finding exact locations of the sulfate oxygen atoms or the water molecules by trial
and
error is not necessary, however, because the Al, K, and S atoms carry most of the
electron
density in the crystal. As we will show in Chapter 32, their locations can be used
to calcu-
late phases for the reflections that will enable us to calculate the full electron
density map,
which very likely will reveal the locations of the oxygen atoms.
[y]

[y] Girolami, Gregory S.. (2016). X-Ray Crystallography. University Science Books.
Online version available at:

https://app.knovel.com/hotlink/toc/id:kpXRC00001/x-ray-crystallography/x-ray-
crystallography

More detailed structure of alum https://www.ionicviper.org/system/files/The

%20Structure%20and%20Color%20of%20Alums_student%20version.pdf

Alum is the common name for the hydrated salt of potassium aluminum sulfate. This
is called a �double salt� because it contains two different cations - in this
case, potassium and aluminum - that crystallize together in a single solid. The
alum crystal structure shown below contains aluminum (gray) and potassium (purple)
ions, as well as tetrahedral sulfate (SO4
2-) counterions.i The crystal is a hydrate, and the red atoms shown attached to
the metals indicate oxygens from the water molecules. (Hydrogens are not shown, for
simplicity.) As indicated in the figure, the metal atoms have an octahedral
coordination sphere, with a single metal ion surrounded by 6 water molecules. (The
site symmetry of the potassium atoms is somewhat distorted from a true octahedron.)
The formula for this compound is
KAl[SO4]2*12H2O. It is important to note that this compound is a salt, and so it
fully dissolves into individual ions in solution. Here, the octahedral coordination
of the metal ions depends on the crystal structure, unlike coordination compounds
that maintain the same coordination geometry in the solid and solution states.

It turns out that this particular crystal structure occurs in many compounds, which
are described as isomorphous crystals because they share the same (iso) structure
(morphos) despite having different compositions. The name �alum� is used to refer
to the specific crystal shown in figure 1, but it is also used as the name of the
family of compounds that have the same structure. We can write a general formula
for the alum crystals in this way:

[]
* 12H
O, where

is a metal with a +1 charge, and is a different metal with a +3 charge. The

structure shown in figure 1 is the potassium alum, and if the aluminum ions were
switched for chromium ions it would be called the chrome alum. Isomorphous crystals
are particularly interesting because they allow us to observe different metals
within the same chemical environment. As long as the ionic radii are similar and
the charges follow the pattern shown above, many different metals can be
substituted into the same crystal structure:[z]

METHO
Explain bakit inulit yung experiment sa bahay (kung mas maganda yung crystal na
kalalabasan)
Indicate experiment objectives
Include materials used
Include set up pictures
Duration of experiment
processes and reason behind the process?
expected result/appearance� explain why?

Objectives
The experiment aimed to grow an alum crystal
The experiment aimed to assess the physical appearance of the alum crystal after
growth.

Materials/equipment Used:
[INSERT IMAGES SA SLIDES]

[INSERT SET-UP IMAGES SA SLIDES]

INITIAL METHODOLOGY
150 g of alum was dissolved in 400 mL of distilled water while being heated at
2000�C.
A drop of red food coloring was added
The solution was filtered while hot
The solution was divided into two: The first batch was used for seed formation and
the second half was used for the crystal growth of pre-formed alum.

First Batch: Seed Formation

The beaker containing 200 mL of solution was covered with paper.
After 2 days, the liquid was transferred into a second beaker so that the crystals
formed at the bottom of the first beaker could be collected.
The best shaped crystal was chosen as a seed and was tied onto nylon string
The liquid obtained from the solution was reheated and the crystals collected were
added back into the solution so that they could be melted. Additional 20g of alum
was also added into the solution.
The solution was allowed to cool to room temperature. The seed crystal attached to
the string was then submerged into the solution.
The solution was covered and was left undisturbed for ____days.

The solution was covered because another way to force a solute to crystallize is by
evaporation of the solvent. When a saturated aqueous solution of a substance is
allowed to stand in an open container at room temperature, the water will slowly
evaporate forcing the solute in excess of the solubility to crystallize [x]

Second Batch: Growth of pre-formed alum

A portion of the alum source was obtained and used as seed crystal.
The crystal was submerged into the 200mL solution.
The solution was covered and left undisturbed for ___days.

METHODOLOGY AT HOME (include in report if mas maganda yung naform na crystal sa

bahay. Depends kung kay Yzra or kay Alex yung mas maganda yung growth)

Explanation for repeating the experiment at home:

RND
Show sample/final crystal
Discussion of appearance, reason for the appearance
Seed vs �tawas seed kuno�, effect on crystal produced (bakit mag kaiba yung
kalalabasan if ever)
Bakit small seed yung pinili (check yzra�s answer)
Sources of error
Recommendation?
Octahedral or FCC = explain bakit ganun yung shape
Sources of error
Relate sa theoretical solubility yung solubility ng solution na naproduce natin sa
experiment (wait for intro)
Possible source of error kung bakit hindi na-achieve ang expected appearance ay
baka dahil super saturated yung solution.
The solubility changes with temperature. Most substances are more soluble at higher
temperatures than at lower temperatures. When a solution saturated at a higher
temperature is cooled to a lower temperature, one of two things occur. Some of the
excess solid will crystallize out of the solution, forming crystals on the bottom
of the container, or, all the solid may remain in the solution. The cool solution,
where everything remains dissolved, will be supersaturated, that is, it contains
more solute than allowed by its solubility at that temperature. Supersaturated
solutions are unstable and will, in most cases, deposit the excess solute in
crystalline form when disturbed.[x]
Generally speaking, the degree of supersaturation must not be high, and in any case
the solution must never be allowed to approach the labile condition. The degree of
supersaturation should be kept as constant as possible to ensure a constant rate of
deposition of solute on the crystal seed. [y]
Single crystals are better grown by a cooling than by an evaporation process, as
supersaturation can then be much more closely controlled. [y]

Crystal appearance
The morphology of a crystal depends on the growth rates of the different
crystallographic faces. Some faces grow very fast and have little or no effect on
the growth form; the ones that have the most influence are the slow-growing faces.
The growth of a given face is governed by the crystal structure and defects on the
one hand, and by the environmental conditions on the other. [aaa]
According to the Bravais rule, the important faces governing the crystal morphology
are those with the highest reticular densities and the greatest interplanar
distances. Or in simpler terms, the slowest-growing and most influential faces are
the closest-packed and have the lowest Miller indices. The surface energy theories
of crystal growth (section 6.1.1) suggest that the equilibrium form should be such
that the crystal has a minimum total surface free energy per unit volume. [aaa]

Effect of Seeding
It is possible to remove the impurities from a crystalline mass by dissolving the
crystals in a small amount of fresh hot solvent and cooling the solution to produce
a fresh crop of purer crystals, provided that the impurities are more soluble in
the solvent than is the main product.

Shape of Potassium Alum

The ideal shape for alum crystals is octahedral. A well grown crystal should also
be clear and has smooth faces and sharp, well defined edges. [zzz]
Has a pronounced octahedron face group with Miller indices {111}