Silicates

➢ Silicates are alumino-silicates of magnesium, calcium, iron etc.

➢ Quartz, mica, feld spar and zeolites are important examples of silicates.
These are found in almost all rocks, clays and soils present in earth's crust.
➢ man-made silicates: Glass and cement

General properties of silicates

➢ various types
➢ all silicates are insoluble in water (Exception: Na2SiO3, water Soluble)
➢ Si-O bond in silicates is very strong. Si-O bond can be broken with strong
reagents like HF.
➢ Although Si-O bond is covalent, it has noticeable degree of ionic character.
(E.N. difference between O and Si is 3.5 - 1.8 = 1.7.)

Structure and types of silicates

➢ The structure of silicates has been found with the help of X-ray diffraction
techniques.
➢ basic building unit is tetrahedral SiO44-
➢ Tetrahedral shape of SiO44- ion is due to sp3 hybridization of Si-atom.

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➢ Depending on the way the tetrahedral units are linked, the silicates are
classified into the following types.

1. Ortho silicates (or Neso or Island silicates):

➢ simplest silicates which contain discrete SiO44- tetrahedral units.
➢ these ions do not share O-atoms with one another.

➢ The ortho silicate ion is the strong conjugate base of weak orthosilicic
acid as well as it will not persist in aqueous solutions. Hence in nature,
ortho silicate minerals are rare and only found with cations which form
highly insoluble salts.

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➢ The degree of polymerization is denoted by Oxygen to Silicon ratio
(O/Si). Greater the degree of polymerization, lower will be the O/Si ratio.
The values of O/Si for ortho silicates (least polymerized) = 4:1
➢ Examples of Ortho silicates:
i. Phenacite (also known as phenakite) - Be2SiO4
ii. Willemite - Zn2SiO4 - A minor silicate ore of zinc. Highly fluorescent
(green) under shortwave UV.
The Be2+ and Zn2+ ions are tetrahedrally surrounded by the oxygen
atoms of silicate.
iii. Olivine - (Fe/Mg)2SiO4 : Typically green in color. The cations are
octahedrally coordinated to the oxygen atoms of the silicate.
iv. Zircone - ZrSiO4 : The oldest mineral on Earth. The coordination
number of Zr4+ is 8.

2. Pyro silicate (or Soro silicate or disilicate):

➢ contain Si2O76- ions which are formed by joining two tetrahedral
SiO44- which share one oxygen atom at one corner (one oxygen is
removed while joining).

➢ The pyrosilicate ion is less basic than orthosilicate ion.

➢ There is only one mineral in nature containing pyrosilicate ion.
E.g. Thortveitite - Sc2Si2O7

3. Cyclic silicates:
➢ contain (SiO3)n2n- ions which are formed by linking three or more
tetrahedral SiO44- units cyclically. Each unit shares two oxygen atoms
with other units.

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E.g.
i. Benitoite - BaTi(SiO3)3 : containing three tetrahedra arranged cyclically
[Si3O9)6-].
ii. Beryl - Be3Al2(SiO3)6: containing six-silicate rings [Si6O18)12-]. It is an
aluminosilicate. Each aluminium is surrounded by 6 oxygen atoms
octahedrally. Well-known varieties of beryl include emerald and
aquamarine.

4. Chain silicates or pyroxenes:

➢ contain (SiO3)n2n- ions which are formed by linking ‘n’ number of
tetrahedral SiO44- units linearly. Each unit shares two oxygen atoms with
other units.

Examples of chain silicates:

i. Spodumene – LiAl(SiO3)2 - a pyroxene mineral consisting of lithium
aluminium inosilicate

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ii. Diopsite - CaMg(SiO3)2
iii. Wollastonite - Ca3(SiO3)3

5. Double chain silicates (or Amphiboles):

➢ General formula is (Si4O11)n6n- . There are two types of tetrahedra: those
sharing 3 vertices and those sharing only 2 vertices.

E.g.
i. Asbestos - These are noncombustible fibrous silicates. They have been
used for thermal insulation material, brake linings, construction material
and filters. These are carcinogenic amphiboles affecting the lungs. Hence
their applications are restricted nowadays.
ii. Tremolite - Ca2Mg5(Si4O11)2(OH)2
➢ The single and double chain silicates are collectively known as
Inosilicates.

6. Sheet or Phyllo or two dimensional (2-D) silicates:

➢ The general formula is (Si2O5)n2n- .
➢ Each SiO4 tetrahedron shares three oxygen atoms with others and thus
by forming two-dimensional sheets.
➢ These silicates can be cleaved easily just like graphite. The layers are
held together by weak van der Waal's forces.

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E.g.
i. Talc - Mg3Si4O10(OH)2: It is the main ingredient of soap stone. It is the
softest material with a smooth and greasy touch.
ii. Micas: General formula is X2Y4–6Z8O20(OH, F)4
Where X = K, Na, or Ca
Y = Al, Mg, or Fe
Z = Si or Al
E.g. Muscovite mica - KAl2(AlSi3O10)(F,OH)2 - split into thin layers
extremely easily and Lepidolite - KLi2Al(Al,Si)3O10(F,OH)2
iii. Clay: It is an aluminosilicate with sheet structure.
iv. Kaolinite - AlSiO5(OH)5

7. three dimensional (3-D) or tecto or Framework silicates:

➢ The general formula is (SiO2)n . All the oxygen atoms of SiO4 are shared
with other tetrahedra and thus by forming three-dimensional network.
➢ The values of O/Si for tecto silicates (most polymerized silicate) = 2:1.
➢ With increase in the degree of polymerization, there is decrease in the
charge per silicon atom as well as the basicity of silicate mineral. Indeed,
silica (SiO2) is an acidic oxide.
➢ The basic silicate minerals readily react with weak acids and undergo
weathering.

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➢ E.g. SiO2 - Quartz, Tridymite and Crystobalite - These are the
crystalline forms of silica.
➢ When SiO44- units are replaced by AlO45- units, three dimensional
aluminosilicates are formed. E.g. Feldspar, Zeolites, Ult etc.,

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