Silicon forms a very large number of compounds containing heterocatenated anions and find

importance in the make up of minerals.

Silicates are: Simple silicate anion SiO44- (a)
Pyrisilicate or disilicate anion Si2O76- (b)

Simple silicate, Pyrosilicate

Portion of the infinite single chain
orthosilicate
(SiO3)n2n-

Portion of the infinite double chain or band

Portion of a sheet or layer
(Si4O11)n6n-
structure
(Si2O5)n2n-

Various Silicate Structures

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  Present in Olivine (Mg, Fe)2 SiO4 (an imp. constituent of basalt

 Na4SiO4 and K2SiO4 are also orthosilicates

Other minerals contaning orthosilicates are:

Phenacite (Be2 SiO4)
Willemite (Zn2SiO4) Si2O76-
SiO44-
Zircon (ZrSiO4) etc.
Minerals contg pyrosilicates are
not common.
The metal-oxygen bond in all silicates contains considerable covalent character just like Si- MnPb8(Si2O7)3 contains both
SiO44- and Si2O76- ions
oxygen bond contains considerable ionic character

Orthosilicates contain no Si-O-Si linkages such as are present in the disilicate, chain
silicates and the cyclic compounds
Although these can be formulated as Na4+ (SiO4)4- , Zr4+ (SiO4)4- , M2 2+ (SiO4)4- , as the more
electropositive metal (M2+ = Na+, Mg2+, Fe2+, Zn2+, Al3+ in chracter, it becomes more difficult
Metasilicate anion
to discern discrete silicon anions.
When M = Si, it becomes impossible and the result is SiO2. Thus the aluminosilicates are These are cyclic structures of general
usually treated as large covalent structures formula (SiO3)n2n- occurring in
BaTiSi3O9
Alternatively, silicates can be treated as closest packed arrays of oxide ions with Si4+ ions
Na2ZrSi3O9.H2O
fitting into the tetrahedral holes and other metal ions fitting into either tetrahedral holes or
Cu6Si6O18.6H2O
octahedral holes.
Be3Al2Si6O18

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 These are found in minerals called pyroxenes e.g. MgSiO3,
CaMg(SiO3)2 and LiAl(SiO3)2.

 In these chains, the silicon atoms share two of their four

tetrahedrally coordinated oxygen atoms with adjacent atoms as
shown,

If further sharing of oxygen atoms occurs by half of the silicon

atoms, a double chain or band structure is formed and is found in
Amphiboles.

 Amphiboles contain the (Si4O11)6- repeating unit as well as metal

and hydroxide ions e.g Na2Fe5(OH)2[Si4O11]2 (blue asbestos) and
(Mg, Fe)7(OH)2[Si4O11]2 (grey brown asbestos)

Further linkage by complete sharing of three oxygen atoms per

silicon results in layer or sheet structures, yielding an empirical
formula [Si2O5]2-

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 However, the interweaving the layers with Al(OH)3, or Mg(OH)2, the following mineral structures are
obtained:

1. A structure of repeated silicon layers bonded to aluminium layers with bridging - O – and –O(H)- , is
present in the china clay minerals, Al2(OH)4Si2O5

2. A structure of repeated pairs of silicon layers with aluminium layers between/bridged with – O - and
– O(H) – is present in pyrophyllite, Al2(OH)2Si4O10.

3. If the Al in the kaoline structure is replaced by Mg, the serpentine structure, Mg3(OH)4Si2O5 is formed.
The dimensions of Mg(OH)2 are slightly larger than those of the Si 2O5 sheet, so the composite layers
tend to curl. The fibres from the curled layers form white asbestos

Further substitution can occur with one out of four silicon atoms in each Si 4O10 unit replaced by
aluminium, and to compensate the charge, +1 cation is added, a variety of minerals is formed e.g.

KAl2(OH)2Si3AlO10 (White mica) Layers in these mica are held together by

KMg3(OH)2Si3AlO10 (Mg- mica) electrostatic interactions with the potassium ions
K(Mg,Fe)3(OH)2Si3AlO10 (Black mica)

Three classes of aluminosilicates framework minerals are of importance:

1. The feldspars with general formula : MAl2-xSi2+xO8
2. Zeolites : Mx/nn+ [AlxSiyO2x+2y]x-.zH2O
3. Ultramarines
The feldspars weather to form clays:

Zeolites are characterised by open structures that permit exchange of cations and water molecule

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Synthesis of Zeolites:

Lines represent oxygen bridges; intersections of lines show positions of the aluminium and
silicon atoms

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 Some natural and synthetic Zeolites:

Applications of natural and synthetic Zeolites:

1. As cation exchangers, since the ions can migrate freely through the open structure
2. Certain zeolites may behave as molecular sieves if the water adsorbed in the cavities is completely removed. Various
uncharged molecules such as CO2 , NH3 and organic compounds can be selectively adsorbed in the cavities depending
upon their size. Thus the zeolite framework behaves similarly to the clathrate cage.

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3. Zeolites may behave as acidic catalysts: The acidity may be of Bronsted type if hydrogen ions are exchanged for mobile
cations such as Na+ by washing with acid . If the zeolite is heated, water may then be eliminated from the Bronsted sites
leaving aluminium atoms coordinated to only three oxygen atoms, and these will act as Lewis acids:

Heterogenous catalysis by acidic zeolites:

(1) Zeolite rho :Na12Al12Si36O96. 44H2O

Conversion of methanol to methylamine

Zeolite ZSM-5 :Na3Al3Si93O192. 16H2O

(2)

Methylation of Toluene to form xylene

Linear p-xylene escapes the catalyst much more easily than the
o- and m-xylenes.

(3)
Zeolites may activate transition metal ions for redox catalysis e.g. Cu(II)/Cu(I) exchanged zeolite catalysise the high
temp. conversion of NOx to N2 and O2 :

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 Another class of aluminosilicates is Ultramarines

 They have open frameworks and intense colors

 Have “free” anions and no water in the cavities
 Utramarine blue contains radical anions, S3- and S2- . The dominant S3- provides blue color
 Utramarine green also contains both the anions but in comparable amounts
 Utramarine violet and pink also contain both the anions, but the color is suggested to be due
to S4 or S4-.

In all of the silicates, the sharing of oxygen atoms between

tetrahedra is by an apex only:

In no cases, edges or faces are shared

Another class of heterocatenation is the silicones, (R2SiO)n