Chemistry of solid state and silicate

Metallic bonds and metallic structure:-

Cupper , nickel , and iron are most commonly metals that known ,which it is good
conductor
Now we are talk about the solid state of substance
Cupper is most famous element in metals , and its high conductivity
As we say before in periodic table that is distinct with size , and we emphasize that
isn't considered as property
Now the free movement of electricity controls on the rule of solids state

The movement of electrons in the wire is very high in cupper ! why ?

Because cupper distinct with high density of electron cloud !
but in real , electrons is not remain at rest ! rather it continues
moves around the cupper atom ,but this happen in ideal case

But in real , electrons is continuous moving , so there will be

defects, means that may be there ions will removed and so on

Another point of view , the collection of atom whether it exist in

metal , … according to the size of atom ,
Suppose that if atom converted into Metal ion
(Cation ) will decrease the size , will if it converted
into non-metal (anion) its size will increase.

If the substance is crystalline ,whether atom or ions

will located at fixed position in form of specific
spatial shape
The Bravais lattice , exhibit particular 7 different 3-
dimenosnal space !
Which distinct with symmetry ! , whether complete
symmetrical or uncomplete symmetrical depend on
3 dimensional a,b,c , between them a particular angles , called Alpha, Beta ,Gama
Complete symmetrical means A=B=C , Alpha=Beta=Gama = 90 Degree Celsius
Triclinic system considered as incompletely , which considered as asymmetrical ,
alpha doesn't equal beta doesn't equal Gama , and a doesn't equal b doesn't equal
c

Face-centered Cubic unit cell: that occurs when the constituent particle at the
center of each face
Body-centered cubic unit cell : When the constituent particle at the Centre of the
body , is known as body-centered cubic unit cell
In fact , atoms is different in size , but we can simplify its shape in form of sphere
Closed-packed arrangement means that atoms accompany largest amount of
space , approximately occupies 74% of the total the space ! , because there is 26%
is still holes or empty as a follow
This empty spaces is called holes !

the spaces must be filled with low-size atom , to be able to join into this holes
What is the difference between cast iron and steel iron ?
Steel iron distinct from cast iron , in presence of carbon or manganese (small
atoms ) in holes ! , that's explain why steel iron doesn't exhibit elasticity or
movement, quite the opposite in case of Wrought iron
Because in case of wrought iron , the spaces isn't filled ,so it can formed into
different shapes
Holes (Close packed ) classified into two types
1-Tetrahedral hole

2-Octahedral hole

Tetrahedral is considered as central atom bonded to another 3 atoms ,like

pyramid shape

As it founded in methane or ammonia Diamond structure

Also diamond is tetrahedral, and its known as hardest element founded in the
earth! , with no electronegativity difference
Octahedral crystal structure is as a follows :-

Its phases appear in octahedron , it may appear in solution or solid

phase
Hybridization also lying under the scope of these crystal structure
Holes is arranged 2 Tetrahedral and 1 Octahedral
For every sphere in close-packed there will be one octahedral hole and two
tetrahedral holes !

There is a difference between anion and cation in close-packed arrangement

because anion will have high size than cation
Ionic compounds, such as NaCl , anion is chloride ,while cation is sodium
Chloride will causes close-packed arrangement , while cation will enter into the
holes ! , because positive ion size is lower
That subjected to limiting radius ratio
Silicon compose the earth crust in the form of silicate !
Oxide will causes close-packed arrangement ,while silicon cation will enter into the
holes !

Closed packed structure :-

1-Hexagonal closed packed
2-Cubic closed packed
Hexagonal closed packed : If the first sheet is
represented by A , and the second sheet
represented by B , repeating pattern of the close-
packed sheets is ABABAB , then the structure is
said to be

Cubic close-packed : Alternatively first sphere of

the third layer may be placed in a depression
such as Y , this sphere isn't exactly above the
spheres in first layer , so the pattern of sheets is
ABCABCABAC

Body-Centered cubic structure :While if there is not

close-packed, will occupy 68% from the total space,
hence there is 32% of empty spaces , so it less efficient
at filling the space than closed-packing
Which have coordination number of 8
There is another rule will explain crystal structure more , and it called limiting
radius ratio !
the crystal may be consist from metals (not charged)
And may be consist from non-metal (not charged) too
While in case of ionic crystal ,there is a specific organization in space called
prototype !
For example crystal structure of NaCl , any other molecules will lying under the
scope of NaCl type of structure !
ZnS is AX Type ( Zinc sulfide type of structure )
Is so important , because we will show it in the composing of silica
Take care , Silica ( SiO2) such as quartz or sand , while SiO4-4 Silicate is acidic radical

The presence of SiO2 or any compound which its chemical name is silica , but it
may exists in different crystal structures ! , which it will called polymorphism
The ability of the given chemical composition to crystallize in more than one form.
It will called polymorphism
Silica ( SiO2 ) is zinc sulfide type of structure ! Zinc blende and wurtzite
Limiting radius ratio tells us that the compound will appear in trigonal or
tetrahedral or square planar , and so on
Every structure has a different limiting radius ratio , which equal to M+ radius / A-
radius

Coordination number of closed-packed number of coordination number is 12

3 coordination number refers to planar triangle
6 coordination number refers to octahedral shapes
So limiting radius ratio will determine the structure or shape , the compound will
exist !

The percentage of covalent bond to the ionic bond !

Silicon and oxygen electron negativity difference is 1.7 , so it refers to 50% ionic
and 50% covalent !
but if electronegativity difference 0 means that 100% covalent or 0% ionic
From here we mention the idea of partially positive charge and partially negative
charge !
Hardest element founded in the world is called diamond , diamond is considered
as standard of hardness of any element I world ,then SiO2 Silica (sand ) appears !
Because we apply the this curve , we found that is considered as 50% ionic and
50% covalent , so if we apply limiting radius ration R+/R- will be founded as
tetrahedral
While if we apply covalent character will shows sp3 hybridization , but because it
not 100% as diamond ,which means that there is a percentage of covalent radical
and other is ionic
So in the 2 cases we can apply the 2 theories !
Ionic compounds Type of AX ( ZnS,NaCl,CsCl)
NaCl metallurgy is called halite
Stoichiometric is simplest ratio that compound can be written
Na Cl means 1 : 1 ! Stoichiometric ratio , but to know its crystal structure we must
apply limiting radius ratio , by R+/R- and it lying on the scope of octahedral , with
coordination number of 6
Every sodium cation is surrounded by 6 chloride anion , but we didn't respect the
size of ions , ( chloride must be bigger than sodium cation)
Close-packed is caused by chloride anion, while sodium is join into octahedral hole
Which means that there is 2 Tetrahedral hole is empty !
So it will called sodium chloride type of arrangement ( prototype ) as a model for
any arrangement similar to it !

ZnS , Zinc sulfide or Zn2+ bonded to S2- , is also ionic compound of type AX
When applying R+/R- we observed that limiting radius ration of zinc sulfide is
tetrahedral structure !
so Zinc is surroned by 4 sulphide , and sulphide is surroneded by 4 Zinc !
Close-packed is caused by sulfide.
So every Atom sphere is 2- Tetrahedral hole and 1 octahedral hole , but as we say
Zinc will enter inside the 1 of tetrahedral , so 50% of tetrahedral is filled , and
octahedral is completely empty !
What is the benefit of previous point ?
When we study the structure of silicate , we will observe that some ions join inside
tetrahedral hole and other in octahedral and so on !

Silicate is considered as polymer , polymer is also present in inorganic compounds

Silicate commonly known as polymerization compound , Silicon present in the
group 4 , besides it phosphorus and Sulfur and Chlorine
When we compare silicate with chlorate ?
We will found that silicate is polymer and get condensation in form of SiO2 to
simply it
But rather in the reality it founded in form of -SiO2-SiO2-SiO2-SiO2-SiO2

As the size of atoms is approximately equal to each other , As easy producing

covalent bond
Chlorine and oxygen size is similarly equal , so they may produce covalent pi-bond
as pi-bond appear , as high ability of attract molecules
As presence of sigma-bonds ,as the molecule will be more open or spread out!
Silicon and oxygen , its size not equal to each other , for this reason exhibit sigma
bonds only , and therefore spread out , and being inorganic polymer.
While in case of chlorate and hypochlorite, perchlorate exhibits pi-bonds , so it
can't spread out , and hard to compose polymer

Phosphorus is also can exhibit polymerization such happen in phosphate, but not
strongly polymerization such as silicon nor chlorate

Zinc sulfide type of structure there is type represent cubic-close packed , and
another represent hexagonal closed-packed
Cubic-close packed structure in zinc sulfide type of structure is called ZnS zinc
blende
While hexagonal close-packed structure is called wurtzite.
So it called zinc sulfide prototype
While Cesium chloride founded in the form of body-centered cubic due to its value
of limiting radius ratio , with a coordination number 8 ,means that every Casium
cation surrounded by eight chloride anions , take care this structure isn't close-
packed

Ionic compounds of the Type AX2(CaF2,TiO2)

Prototype of Calcium fluoride , and titanium dioxide , but it called fluorite in
metallurgy
Titanium dioxide is called rutile
Note that acidic radical of titanium is called titanate , TiO2 is called titania is
chemistry , such alumina Al2O3 , or Magnesia such as MgO
Calcium carbonate is called calcite in metallurgy
Coordination number of Calcium fluoride or fluorite : is 8 and 4 and this is called
8:4 arrangement
Calcium is surrounded by 8 fluroide , and fluoride is surrounded by 4 calcium
cation
Its crystal structure is very important !

And its coordination number must be obvious

Coordination number of rutile are six (6) and three (3) , means that each Ti+4ions
octahedrally surrounded by six O2- , and each O2- having three Ti+4
Silicon oxidation state usually is +4 , but there few cases such as titanium oxide
type of structure
mean that coordination number of +6 silicon may appear ! that may presence in
pressure of 40,000 atmospheric pressure of high pressure and attracted atom
together !
So it's very important in researches when silicon exist in hexa-coordinate

Layer Structure
Cadmium iodide , is very important in silicate , layer structure means that bond
within the layer is strong ,while between the layer the bond is weak vander vall
force holding sheet together !
as covalency increase as the stability of the bond increase , so we can apply also
limiting radius ratio !-

Ionic compound is distinct with electrostatic attraction between positive cation

and negative anion.
Na2CO3 melting point is 700 Degree Celsius due to electrostatic attraction force
While Sodium chloride when put it in water will solubilize ,while its melting point is
high
While covalency , means that hybridization of orbital as a result of convergence of
size, became covalent bond stronger !
but it may found in gaseous state , because every molecule founded in one
direction or 2 dimension ,but there is no 3 dimension such as diamond
N2 do be breaked required a high temperature due to non-polar covalent bond !
some people found that there is a bacteria had the ability to break this bond until
reaching nitrogen atom
As a covalency increase the bond strength increase !
while partially positive and partially negative , such HCL Covalent bond ! , but
when we break the bond , ionic character will appear in water
Covalent compounds dissolve in non-polar compounds such as , while ionic
compounds dissolve in polar solvent such as NaCl in water.
But must there is sufficient energy to break this bond in case of ionic compounds,
while chlorine gas to be break required a high-time , to reach to free radical

How does HCl ionize although it is a covalent compound?

Hydrogen chloride (HCl) is a covalent compound, but it ionizes in water to produce
H+ and Cl- ions. This is due to the polarity of the H-Cl bond, which results in a
partial positive charge on the hydrogen atom and a partial negative charge on the
chlorine atom
Difference between crystalline and amorphous
What is the difference between Amorphous solids and crystalline solids ?

Crystalline solids have regular arrangement of the constituent particles

While amorphous solids don't have any regular arrangement of the constituent
particle
One of most important example of amorphous is glass, because glass is produced
from the melting of silica
What is the difference between Quenching and Annealing ?
Quenching : involves rapid cooling of a metal to adjust the mechanical properties
of its original state
Annealing : is a heat process whereby a metal is heated to a specific temperature
and then allowed to cool slowly
Note : Process in chemistry means that there is chemical change ,while operation
means that there is only physical change takes place
We observed that in case of slowly heating process ( annealing ) gives sufficient
time for crystal to be formed !
While quenching means that will obtain less regular crystal structure
Usually Cement requires quenching process ,because cement is heated in 1450 C
to gives reactive substance ( that's why the crystal structure produced will not be
symmetrical exactly )
The more symmetrical of crystal structure ,the less reactivity of the substance will
obtained
For this reason amorphous substance is reactive than crystalline !
Symmetry has an inversely proportional with reactivity

Crystal : Any solid material in which the component atoms or ions are arranged in
a definite pattern , in which its dimension measured in Angstrom
Crystal : the spatial arrangement of atoms or ions in a definite pattern
There something called ionic crystal ( such as NaCl) Which it doesn't mean will
dissolve in water , because now we are talking about crystal structure in solid
phase not aqueous phase !
Any solution must be conductive , because there will be ions separated to each
other !
While in case of perfect crystalline solid structure is considered as neutral , and
there is no movement of ions !
In this case the crystalline solid will not be perfectly ordered arrangement , so it
considered in this case as conductive !
At absolute zero, crystals tends to have perfect ordered arrangement ,
in contrast when temperature increase, the chance of unoccupied of lattice site
with ion increases, This constitutes defect , means there is empty space or absence
one of the circles in the crystalline form.
Stoichiometry is the theoretical ratio between atoms of molecule, e.g. NaCl ,ZnS
In which stoichiometry ratio is 1 : 1
So the defects increases conductivity of crystal structure ! due to the movement of
ions or atoms !
Even defects occurs , the absence of specific ion must be compensated by another
ion to maintain electroneutrality !
Note that, the entry of electron in the crystal structure different than atom ,
because electron has more free movement , which increases conductivity
The movement of electrons required specific energy , if the energy is in the region
of visible of radiation , surely the color will appear
F-Center : is usually a position in a lattice where an anion , a negatively charged
ion is replaced by an electron
 Stoichiometric Defects
1-Schottky Defects 2-Frenkel Defects
Firstly Schottky Defects :-
Schottky Defects , is considered as a pair of holes in the crystal lattice due to one
positive ion and negative ion being absent from the crystal lattice
This defects tends to be formed in highly ionic compounds with high coordination
number
e.g. NaCl ,CsCl,KCl,KBr

2-Frenkel Defect
A "hole" may exist in the lattice because an ion occupies an interstitial position
rather than its correct lattice site , that's why we observed that positive ion
commonly to find in the interstitial position due to its small size.
We mention the difference between the cast iron and steel iron , which we say
that the steel iron distinct by presence of positive ion such as ( Manganese , silicon
) in the interstitial position , leads to give hardness and low elasticity to steel iron ,
the opposite case happen in the cast iron

The presence of positive ion in interstitial position leads to appear of polarizability

phenomena , due to difference in electron negativity between ions ! , and this
create another phenomena called dipole ! or covalent ! , so compounds with
Frenkel defects shows or exhibit some covalent properties
Note : Schottky Defect is easier to happen than Frenkel defect , so the energy
needed to form Schottky defect is lower than that to form Frenkel defect
Density of defect lattice should be lower than for a perfect lattice because of the
"holes" present.
Increasing of defects may lead to collapsing !
2.Non-Stoichiometric defects
Non-stoichiometric means that there is variable valency
If there is a hole of B- must compensated by electron , which means increases
conductivity , because electron exhibit more movement than Anion, as we say
that's subjected to rule of electroneutrality
2.1Metal Excess
Is an important term which describes non-stoichiometric defect , in which negative
ion is replaced by an electron

2.2Metal Deficiency
Metal deficiency require variable valency or oxidation state of the metal ,which
the positive ion is absent from its lattice site , and the charged are balanced by
adjacent metal ion having two charges instead of 1
e.g. FeO,FeS
but there is another possibility is to have an extra-negative ion in an interstitial
position and to balance the charges by means of extra-charge on an adjacent
metal ion

Semiconductors and Transistors

Most common practical examples are atoms which have four electrons in the
outer shell of their atoms
With a given sufficient energy ,some of the covalent bond break ,and electrons are
ejected or released from their normal site ,where electrical conduction takes place
By the migration of electrons one way , and the migration of positive holes in the
other , termed as intrinsic conduction

Silicates
Some important metallurgy names for compounds:-
Calcium carbonate :Calcite
Sodium chloride : Halite
Calcium fluoride : fluorite
ZnS : Zinc blende and wurtzite
Silicate considered as the basis of many industries e.g. cement , glass ,ceramic
Because silicate or silica is commonly founded in the earth crust !
Silicate shows close-packed from oxygen , and
Earth crust considered as oxide , and oxyanions.
Silicate or silica is close packed arrangement from oxygen , and holes (2
tetrahedral , and 1 octahedral )
The Silicon positive entry inside the holes , due to its low size !
Holes rule : every atom have 2 tetrahedral hole and 1 octahedral hole !
Silicate : is acidic radical , its chemical formula SiO4-4
Silica : is neutral compound SiO2
Polymorphism : the presence of compound with the same stoichiometric ratio in
more than crystal structure
Polymorphism is the basis of the cement compounds !!

Polymorphism of silica (SiO2)

Which exist in the nature in the form of quartz ! (mineralogical name )
Quartz ( sand ) its density is very important and commonly because it is equal
2.665 g/c.c (Important point ! )
Quartz is the first form of crystal structure of silica.
Quartz in the form of SiO2 to predict its crystal structure we must apply limiting
radius ratio ( which it exist in tetrahedral structure ) , it described by rule of
hybridization (sp3) covalent bond , while limiting radius ratio describe tetrahedral
by ionic form

Diamond is the most hardest compound present in the nature ! , because the
electronegativity difference between its atoms equal zero , due to Carbon-Carbon
bond exhibit 100% covalent bond
While in case of SiO2 electronegativity difference is 1.7 means 50% ionic and 50%
covalent.
So when we think with the point of view covalent nature of SiO2 , we will apply the
rules of MOT ( Molecular orbital theory , and hybridization ) gives sp3 tetrahedral
While in case of applying limiting radius ratio R+/R- give value represent to
tetrahedral structure too !
SiO2 exhibit partially positive charge and partially negative charge , due to
electronegativity difference
The three polymorphism of silica (SiO2) is (Alpha, beta) quartz , (Alpha, Beta)
tridymite , (Alpha, beta ) Cristobalite in different temperature
Must be keep in mind the degree of temperature that's suitable for forming any of
the previous crystal structure
There is high temperature form and high pressure form
High pressure form :-
Coesite : which it formed at 700 C , under a pressure of 40.000 atm
keatite : which it formed at a range of pressure between {Quartz , coesite
stishovite]
stishovite: Formed at a very high pressure
High temperature form is :-
Quartz
Tridymite
Cristobalite

Polymorphism of silica
 when we expose quartz to thermal heating , its volume will increase , for this
reason the density of Tridymite and cristobalite less dense than Quartz
Because the structure of SiO2 ( Quartz ) will be more open when the temperature is
increased !
The new form to be stable must be compensated by new ions to maintain its
volume!
Silica will melt in the degree of 1710 Degree Celsius, so it very hard to applied in
the industrial process , heaviest temperature , and heaviest industry is the industry
of cement ! , and we must think in the researches how to decrease it !
The relation between tridymite and cristobalite is the same relation between zinc
blende and wurtzite
There is another relation between Alpha Quartz and B-Quartz , is polarizing !
,because B-Quartz contains distortion bonds.
How to convert anything present in periodic table into oxy-compounds ?
Silicate minerals is called aluminosilicate clays (it represents to replacement of
silicon by aluminum )
Isomorphism : is the similarity of crystal structure for different compounds
e.g. replacement of silicon by aluminum in aluminosilicate
the only solution for analysis of clay ( aluminosilicate ) is melting with sodium
carbonate
sodium carbonate melts at 700 Degree Celsius, so atoms will get the ability of
movement

Silica or clay by melting with sodium carbonate will appear in solution phase ! , so
the atoms will be more movement , and easy to analyze by wet chemical analysis
such as semi-micro analysis
While solid-state is hard to analyze due to using of X-Ray ,etc ( expensive
instrumental )
Sodium silicate or waterglass is the only common soluble silicate !
(Na4 +4 )(SiO4-4)
HF is used in qualitative analysis to detect silicate ,since resultant silicon
tetrafluoride is hydrolyzed by water to silicic acid

Silicic acid formula Si(OH)4 or SiO2.2H2O silica gel

Hydrofluoric acid hard to deal with ! , experimentally very hard chemical reaction
to existence
While sodium silicate or waterglass method is more easier and more common in
any laboratories
Waterglass is used as binder
Cement is also used as binder , that's chemical substance, used for construction
that’s sets hardens and adheres to other materials to bind them together
Portland cement : is a fine powder produced by heating limestone and clay
minerals
Gipps : also can used as binder , but it's not strong binder !
What is the difference between Portland cement and regular cement ?
Cement is a powder that hardens when you add water. The most common
kind, Portland cement, is an ingredient in both concrete (a mixture of cement,
sand, and stone) and in mortar (a mix of cement, sand, and lime that's softer than
cement when it hardens

As binder low-strength , as the rocks' size increase

Such as Gipps ,or lime , they're weak binder ! , so the stones of the Baalbek temple
are distinguished by their large size, which depends on air leakage
As binder strength increase , as the rocks size decrease.

Crushed aggregate
 Silicate Lecture 8 Solid-State
Explanation :-
The silicate part is attached to much with structure, such as AX , AX2 , and we
know that the presence of silicate is important in earth crust , such as cement
industry , and glass , and ceramic , which these industries depends on silicate
And we talk about polymer, and we say that silicon-oxygen polymerization ,
As presence of sigma-bonds, as the molecule will be more open or spread out!
Silicon and oxygen , its size not equal to each other , for this reason exhibit sigma
bonds only , and therefore spread out , and being inorganic polymer.
While in case of chlorate and hypochlorite, perchlorate exhibits pi-bonds , so it
can't spread out , and hard to compose polymer
When we compare between chlorine-oxygen and silicon oxygen , chlorine-oxygen
doesn't exhibit polymer , which make molecule more shrinking ,similar to benzene
ring
Organic compounds , and benzene ring , more shrinking , except carbon-carbon
which its original is segma bonds , however it can spread !
Silicon-oxygen bond is segma and exhibit high strength , 50% ionic and 50%
covalent
But as we say phoshprous polymerization not high as strength of silicon-oxygen
Because electro negativity difference being very low !
Sulfur for this reason doesn't exhibit any polymerization ,and chlorine all its
compounds with oxygen ,same thing
As the size is approximately equal from two atoms , the overlapping became more
easily , for this reason chlorine-oxygen hard to polymerize , and exhibit bi-bond

Polymerization of silica , must be understand , and we must study from 2 books ,

not 1 one book ! , take care !
Silica : means SiO2 and neutral
Alumina is doesn't found too much in nature , so silica meaning similar to
magnesia , alumina , all the suffix considered as oxides !
Term silica , is defined in stoichiometric only , but silica as structure is complicated,
so it relates with polymorphism !
Polymorphism : is the presence of compound in different crystal structure
Compound there means silica
Polymorphism is the principle of cement chemistry !
every component will show different characteristics , such as desirable and non
desirable reactants in cement industry
Polymorphism of silica as we say before , while SiO2 means empirical formula
( only numbers ) and the equal of charges !
Charge appear only in radical or ion , while salt or oxides ,such as SO3 , it appears
covalent nature , and there is no structure solid , while empirical formula of it SO 3
SO32- is called sulphite , and will called oxyanions , or will be radical , or will be
acidic radical !

structure of silica is very important, because quartz is presence too much in our
nature , it main component of earth crust , and quartz can applied on ionic rule
and covalent rule , so it 50% ionic 50% covalent , so its structure will be
tetrahedral , tetrahedral is repeated too much , due to its stability , in the shape of
pyramidal , while skeleton will be tetrahedral , so we apply ionic rule ( limiting
radius ratio ) R+/R-
Quartz is very commonly presence in nature , quartz is presence on form of sand
,so it called the slip or silica slip , it also may called carbon slip , its form can't be
sufficient to judge on its structure
But the common nature is presence of quartz sand
If I have carbon – slip , and silica-slip , how did we can identify them ?
Depending on semi-micro analysis , we can add HCL , if there HCL we will add it ,
and see if there is effervescence and evolving of CO2 will be carbonate
There is low temperature form and high temperature form of quartz
( Must keep in your mind !)

Important numbers of densities different crystal structure of silica !(Keep in your

mind )
 Quartz density is 2.655 g/cm3.
 Tridymite density is 2.30 g/cm3
 Cristobalite density is 2.27g/cm3
So cristobalite is less density than quartz and less than tridymite, so it similar to
diamond tetrahedral , so tridymite and cristobalite structure is more opening ! due
to higher volume, due to higher temperature
So in 870 Degree Celsius will be
Density of granite is very high 3g/cm3
The new form to be stable must be compensated by new ions to maintain its
volume!, but the ion not necessary to be positive or negative , so it called foreign
ion !.
The stability of structure with foreign ion , is very important phenomena , because
there is structures don't stabilize without foreign ion , from these compounds is
tridymite and cristobalite ,so the foreign ion will introduced into edges to maintain
structure opening, reactivity , hardness is very important ! in solid-structure rule.
Tridymite presents a more complex picture ,the less dense structure of tridymite
and cristobalite are presumably maintained at high temperature by the thermal
movement of the atoms , and it is possible that they stabilized at lower
temperature by the inclusion of foreign atoms
Sometimes foreign ion is called glass-rate , zeolite is similar to sieving ,so it
maintain ions, because the ions size is higher , so and not pass through
Zeolite can be used in treatment of water , but zeolite idea is different than glass-
rate which inside it atoms or ions whatever it is inside the structure , so glass-rate
means inside the structure !
Cristobalite exist in some compounds , commonly more reactive than sand ( quartz
) , so if there is concrete , cristobalite fair us , because it may react ! ,so the stuff of
concrete must be inactive, or inert , cement only may be reactive , while sand must
be inert , because cement is like adhesive , hardness is come from stuff , such as
pure siliceous ,
And we say before , that as the strength of cementing substance ,the size of stone
is decreased
, so the concrete must be inactive.
Silica is infinite polymer three-dimensional , CO2 gas exhibit bi-bond , so is discrete
molecule ,but SiO2 has a high melting-solid
When we compare the relation between tridymite and cristobalite is like the
relation between tridymite and cristobalite is the same relation between zinc
blende and wurtzite.
The relation between alpha quartz and beta quartz
There is another relation between Alpha Quartz and B-Quartz , is polarizing !
,because Alpha-Quartz contains distortion bonds.
There is another relation between Alpha Quartz and B-Quartz , is polarizing !
,because B-Quartz contains distortion bonds.
The relation is that bond itself be dipole so it called distortion but not breaking !

The conversion from Quartz to tridymite it called

sluggish process !, involves breaking of Si-O-Si bonds
linking together.

The difference between alpha-beta quartz , and

difference between quartz and wurtzite (sluggish
process )
Suppose you being a chemist , whether sand or quartz or clay ,
There is difference between mud, and clay ?
Clay is distinct with that clay be a dried , while mud is distinct with presence of
water
Your think must be logical , also your think must read information, actually clay
minerals is the same components !
So it will have different particle size , thus will called colloid.
Clay is undesirable relative to building materials , because it swelling ,there is
layers in mountains from sand and clay
While clay is convert to colloid particles ,but the same compounds , the difference
only is the particle size !
If we want to analyze clay , we will use the method that we mention before ,
whether using HF or Sodium carbonate , to be in the solution form
Solution form is necessary in chemistry , nickel to convert nickelate , will use
sodium carbonate , platin also if we want to convert gold to aureate , we will use
too sodium carbonate
While HF is hard to treat with than sodium carbonate ,there some laboratory can
deal with HF , may cause excessive damage to skin !, so all precautions is taken
Sodium carbonate melts at 700 C , while it decompose in 1500 Degree Celsius
To convert silica to silicate will melt and convert into water-glass , which it called
sodium silicate ,as well as being used as binder.!
And we mention the hydrolysis reaction of SiF4 silicon tetrafluoride , so silicic acid
is formed , don't forget this reaction , and silica gel is commonly known as drying
agent
Silica gel is important in working in laboratory ,because silica gel change its color ,
so it commonly , also can used as catalyst
Types of polymerization
Silicic acid is polymerize or no ?
Silicic acid , as long as silicic acid give protons in water ( aqueous phase ) so , it
isn't polymerize
There is no polymerization in aqueous solution , except chromate and
dichromate !
for this reason silicic acid doesn't exhibit polymerization
While polymerization appear in solid , silicate formula is SiO4-4 , acidic radical , will
called discrete ! , when it presence in radical ( there is no polymerization ) !!
because SiO4-4 called discrete when there is no polymerization
So if there H+ means that that appear in solution , while if neutraility occur
minerals will compose !.
So now will talk about minerals contain discrete SiO4-4 not polymerized , so if there
zinc ,we want 2 moles of zinc to maintain electroneutrality
Berrilum ,etc. …
So SiO4-4 discrete ions may form zinc silicate or beryllium silicate , magnesium
silicate which they are minerals
Orthosilicate there in solid-state means mineral presence in discrete
e.g. Zinc, Beryllium , zirconium,Magensium
while close-packing is done as we say before by presence of negative ion ,and
cations which introduced through holes , (2 tetrahedral , 1 octahedral ).
Silicon coordination number is 4 , except stishovite , which that's presence at very
high pressure ,with a coordination number 6 , rutile structure
Aluminum is also important in silicate , because there is silicate compounds , and
others is called alumino-silicate, as important as silicate , because whole
compounds of clay is considered as alumino-silicate not pure silicate !
pure silicate is quartz or sand , because it doesn't accompany any charge and
called three dimensional silicate , similar to diamond
Alumino-silicate has a several structures , but there is a phenomena called
isomorphism replacement
Isomorphism replacement definition : The process of replacing one structural
cation for another of similar size
Size plays an important role in periodic table , also size there has an important role
in determining a lot of rules , as a result of similarity between size of Al 3+ and Si+4 ,
but there is different in charge , so must adjustment to maintain electrical
neutrality
There is a family of silicate , on of it called olivine
Aluminum may be 4,6 coordination number , which causes different minerals
There isa rock called , basalt rock , olefin compose also basalt rock
In orthosilicate (charged ) ,sharing of atoms , which it called vertices
Pyrosilicate is occur when one O atom of each SiO4 is shared with another SiO4
giving pyrosilicate ion Si2O76-

Compounds with discrete SiO4

Forsterite: Mg2SiO4
Zircon : ZrSiO4
Willemite : ZnSiO4
Phenacite : Be2SiO4
Crucible in the laboratory is manufactured from clay , while in high research they
depends on crucible manufactured from zircon , which have high ability to tolerate
elevated temperature
There is 2 types of sharing !
we know talk about charged silicate ! , so it want to neutralize
Vertices here is the name of atoms ,
There is a type of silicate called pyro silicate , in which oxygen atom is sharing
between 2 tetrahedral silicate ! , so its ion formula will be Si 2O72-
e.g. scandium silicate , and hemimorphite.
While if we have two oxygen atoms of every SiO4 are shared with SiO4 tetrahedral
resulting in closed rings or infinite chain [ 3 ring , or 6 ring or 12 ring ]
And commonly one is 12 membered- ring is emerald (beryl ) ,
Commonly example in 3 membered- ring s : Ca3(Si3O9) wollastonite.( which hasn't
any cemented property )
Burning of cement , making it hard to back again to its original !
If there oxygen sharing f every SiO4 , and atoms shared is called vertices
While there is another thing called infinite chains ( Chain silicate )

Chain silicate may be single-chain or double-chain

There is a another family of silicate in single-chain is called pyroxene , which is the
second compound compose basalt -rock
So basalt composed from pyroxene and olefin

Repeat unit mean that the triangle in the same direction, means that less number
in repeat unit in same direction
While 2 repeat units means that there is a different in direction
While in double-chain in amphibole which it considered as another family , most
commonly , that contain O-H
LiAlSIO3)2 , Spodumene , is also used in ceramic
While amphibole such as tremolite (double-chain ) you must practice on drawing
by less repeat unit as possible
Asbestos is undesirable environmentally , it considered as silica , it very harmful to
our lungs , so it
There is layer structure of silicate , we took before layer structure in solids-state .
don't forget such as CdI2
Chemistry of solid-state Last Lecture !
In the second term , you must know your group ( 4 or 5 ) , your article , and model
that will be executed.
You must realize that SiO4 isn't acceptable in report , so the report or researches
will refused ! , so SiO4 is important !
We say before sulfur excite electron to d-orbitals , but the hybridization is still sp 3 ,
not octahedral , take care !
Take care that silicate with cyclic , may be ( 3 membered ring , 6 membered ring ,
or 12 membered ring )
And the example of 12-membred ring was emerald or beryl
What is the types of silicate ?
1.Orthosilicate
2.Pyrosicliate
3.Cyclic Silicate
4.Chain silicate
5.Sheet silicate
6.Three dimensional silicate
the 2 books is important ,
relative to orthosilicate , and zircon ,willemite , and phenacite
in orthosicliate , most important is foresrite Mg,Fe Silicate , and may be occur
isomperishm replacement
zircon application is crucible
pyrosilicate : such as hemimorphite , scandium silicate , Sc2(Si2O7)
three membred ring , occurs in wollastonite
and wollastoniote is the result of burning cement , so it can't back again to cement
!
also the structure of emeraled or beryl is very important,
relative to formula of cyclic silicate SiO3 ( pyroxen ) , but In pyroxen is long chain ,
while in cyclic is closed !
and we say in pyroxene or chain silicate ,there is a lot of repeat unit , there is one
repeat unit or 2 repeat unit or 3 repat unit all in pyroxene
while 2 chain together will called amphibole
the chemistry is important in structure , while geologist do another role
the triangle , in pyrosilicate is one only ! , while in cyclcic is 2 , and chain may be 2
or 3
while in layer structure , also called sheet structure , is an important example for
aluminosilicate clay
Silicate with layer structure in page 818 , condensation may be 6 net , or 4: 8 net ,
the most important example is Egyptian blue(4:8 net )
4 : 6 : 8 net
We will take Egyptian blue 4: 8 net for easily study
While 4 : 6 : 12 is all forms that present in sheet silicate ,
But there another diagram of clay mineral -which drawn with another structure
Kaolin is important in manufacture of pottery , and porcelain
So there is different compounds than aluminium , so is isomorphism replacement ,
or layer silicate , will leak inside it another layers from aluminium hydroxide ,
Gybbsite , aluminium is 6 cordinated
There is different triangle , and opposite to each other , O and OH is , then the

rectangular within it the aluminum hydoride , then it surrounded by 6 OH , but

there 2 OH joined with O from silica .
Kaolinite in important of industry the cup of tea , kaolin pure is important in
France , also !
But in material building , clay in Aswan is important , because the water is
appear !
the clay which it be able to swelling , can't be used in building , so must be
substituted with clay able to swelling with normal sand
But clay able to swelling not in this picture , it also there is porcelain Chinese ,
Layers between structure is neutral not charged , ! is important thing in kaolin , so
it able to deformed ,while burned kaolin is different
There is another thing is called gibbsite Al(OH)3 there is something similar to it
magnesium hydroxide , and the same structure is observed
Also there is isomorphism repalcemnt in quarduble area , while magnesium and
aluminium is introduced in hexa area
Also there chlorite 3 layer not 2 layer
The rectangular of aluminium hydroxide or magnesium hydroxide , or ismorphous
repleacment , but in kaolin there is only 2 attached with OH of aluminium
hydroxide
While in three layer there is 2 upside and 2 downside
Also there is aluminum which it exist in recatanglur can be ismophorsm
repalcemtn with magnesium octahedral , while aluminum , silicon tetrahedral
isomprohism replacement
Silicon only rarely case in stishovite 6 coordination number.
So kaolin easy to deformation without breaking ( malleable ) because it neutral !
talc also is neutral

But if layer isn't neutral , so it will be charged , and it must netrailze by ion in the
center , so diffucilty of deformation ,
So it families of mica , or muscovite ,so it distinct with hardness as a result of
presence of charged ion between layers,
Chlorite also present in red sea .
It is very important to link between 2 books , not only 1 book
Now we want know the image and the name of minerals ..see page 820
In 823 page , we explain before ,the clay which able to swelling
Montmorillonite
The pure for of montmorillonite is bentonite used in petrol , to sewilling in specific
method ! .
There is 3 dimensional silicate , or framework sturcutre
We say before oxygen one is pyro , 2 oxygen cyclcic or pyroxene , 2-3 amphibole ,
while 3 only will be as clay mineral , 4 such as silica , while framework structure or
3 dimenosnal of silicate , means quartz , tridymite , crystoballite
-------- also tridymite and cristobalite is presence in page 105

Now we want to talk about lithosphere and hydrosphere

Close-packed atoms , Oxygen is very important 46.59%
Coordination number Must keep in your mind !

Vertices means that shared atoms ,

But there is zeolite with there is sharing of edges , not vertices !
, another important thing , that when we write 4 oxygen and 1 silicon is normal
silica such as orthosilicate , SiO44-
If number of oxygen to silicon decreases , the condensation occurs, Si2O7 , and
Si2O3 , but if O; SI is 5 not 4 , is important in cement industry and concrete
Such as Calcium silicate ,give hardening for concrete after 1 day only ! , due to
calcium silicate component O : Si
Tricalcium silicate , because there is free lime (CaO ) which makes it unstable
And it desirable for improve the reactions and burning !
By quenching is important to given't crystal structure
While annealing is used to be present of defects helps in activity
O : Si is higher means is possible to in 808 Page
Orthosilicate has another family called ..
811 page , and its structure in 818 is ..
Chondrite is important is considered as similar between magnesium hydorixde ,
and silicate , gives series of xy,xxy

Solid-solution is present in slag , Ca2MgSi2O7 Akermanite ( millite family )

Three-dimenosial silicate :-
Orthoclase ,Plagoclase

Feldspar is very important is aluminosilicate not pure silicate

There is orthoclase feldspar and plagioclase felspar
Plagioclase is the third compenent of basalt -rock
So basalt rock is composed of : plagioclase , oliefn , pyroxene
Sodium aluminium silicate , albite ( very famous )
Also there is Zeolite and ultramarine
Ultramarine is the last group of framework silicate

Coloured silicae used as pigments

While zeolite is similar to chromatography , and exchange of ions is occur
Lamellar zeolite (means layer zeolite )
 Assignment (1) Solid State Bravais lattice
Introduction
Bravais lattice refers to the 14 different 3-dimensonal configurations into which
atoms can be arranged in crystals.
The fine arrangement of crystals is may formed from ions or atoms ! or even it can
nanocrystal !
Unit Cell Definition : is the smallest group of symmetrically aligned atoms which
can be repeated in an array to make up entire crystal
Bravais lattice Definition : is an array of discrete points with an arrangement and
orientation that look exactly the same from any of the discrete points
14 types of Bravais lattice
7 types of Bravais lattice in 3-dimensonal space , which a,b, and c refers to
dimension of unit cell whereas 𝛂, 𝞫, and 𝝲 refers to corresponding angles in the
unit cells

1.Cubic Systems(Completely symmetrical )

a=b=c , 𝛂= 𝞫 =𝝲= 90C
3 possible types of cubic cell illustrated :-
Body-Centered : When the constituent particle at the Centre of the body , is
known as body-centered cubic unit cell
Face Centered : when the constituent particle at the center of each face
End-Centered : When the constituent particle present at the two opposite faces
Example : copper has a face-centered cubic structure.
2.Orthorhombic Systems:-
a≠b≠c
𝛂 = 𝞫 = 𝝲 = 90o
The four types of orthorhombic systems (simple, base centered, face-centered,
and body-centered orthorhombic cells) are illustrated below.

An example of a substance with a face-centered orthorhombic structure is barium

sulfate.
3.Tetragonal systems :-

a=b≠c

𝛂 = 𝞫 = 𝝲 = 90o

The two types of tetragonal systems are

A-simple tetragonal cells
B-body-centered tetragonal cells

E.g TiO2 (body-centered tetragonal )

Monoclinic system :-

Bravais lattices having monoclinic systems obey the following relations:

a≠b≠c

𝞫 = 𝝲 = 90o and 𝛂 ≠ 90o

The two possible types of monoclinic systems are primitive and base centered monoclinic cells,
as illustrated below.
Triclinic System(Completely unsymmetrical)
Exits only type of triclinic Bravais lattice which is primitive cell, it obeys following
relationship

a≠b≠c

𝛂 ≠ 𝞫 ≠ 𝝲 ≠ 90o

Example : K2Cr2O7 founded as simple triclinic structure

6.Rhomobhedral System

a=b=c

𝛂 = 𝞫 = 𝝲 ≠ 90o

Primitive rhombohedral cell is provided below

Example : Calcite or CaCO3 is made up of rhombohedral unit cells

7.Hexagonal System
a=b≠c

𝛂 = 𝞫 = 90o and 𝝲 = 120o

Simple hexagonal structure is the only type of hexagonal Bravais

Example : Zinc Oxide