INTRODUCTION TO

SILICATES
Shubhabrata Paul
Reading resources…
 Introduction to Mineralogy
 WilliamD. Nesse
 Oxford University Press, 2000, 442 pages

 Mineralogy, 2 nd ed.
 Dexter Perkins, Prentice Hall, 2002
 Mineral Classification
 In most cases, minerals are grouped according to
the major “building block” in the chemical
structure.
 Silicates (SiO44-)
 Oxides (O22-)
 Sulfides (S2-)
 Sulfates (SO42- )
 Carbonates (CO32-)
 Halides (Cl1- , F1- Br1- )
 Native Elements (single element)
 Silicates

 CRUST MOSTLY Oxygen O and SilicoN Si

 27% of all known minerals are silicates
 40% of common minerals are silicates
 >90% minerals in the earth’s crust are silicates
 Silicon tetrahedron - The basic building
block of all silicates

 The Si-O bond – 50% covalent, 50% ionic

 C.N. = 4, e.v. = Z / CN = 1
 Four (4) oxygens in each tetrahedron, so total charge -4
O-coordination and Bond Strength of Other
Common Cations in Silicate Minerals
 Role of Al in Silicate Minerals

 Al+3 may occur in tetrahedral [4] (substituting for

Si+4) or octahedral [6] coordination

 Ionic radius of Al+3 = 0.39Å (4-fold); = 0.54Å (6-

fold) (Si+4=0.26Å)

 Ionic Al:O Radius Ratio (4-fold) =0.39/1.36=0.286

 Upper limit of tetrahedral coordination RR=0.225

 Ionic Al:O Radius Ratio (6-fold) = 0.388

 Upper limit of octahedral coordination RR=0.414
Nesosilicates Inosilicates
(double chain)

Sorosilicates

Cyclosilicates Phyllosilicates

Inosilicates
Tectosilicates
(single chain)
Silicate Classification
 Nesosilicate (Island Silicate)
 Corner oxygen is not shared with other SiO4-4 polyhedrons
 Thus, this group is often referred to as the island silicate
group. The basic structural unit is then SiO4-4.
 In this group the oxygens are shared with octahedral
groups that contain other cations like Mg, or Ca+2.
 Olivine is a good example: (Mg,Fe)2SiO4
 Other common rock forming nesosilicates are Garnet,
Zircon etc.
 Forms minerals with
 High density and hardness
 Poor cleavage
 Olivine group

 High temperature Fe-Mg silicate

 It is the first silicate mineral to
crystallize from a magmatic melt.
 Individual silicate linked together by
iron and magnesium ions
 Forms small, rounded crystals with no
cleavage

(Mg,Fe)2SiO4
 Olivine group
 2 end-members:
 Forsterite - Mg2SiO4

 Fayalite – Fe2SiO4

 Occurance:
 Mostly in mafic and
ultramafic igneous rocks
 PureFo is found in
metamorphic rocks
 Other commmon Nesosilicates - Garnet

 General composition: X3Y2(Si3O12)

 where the X sites contains large divalent cations, usually Ca, Fe,
Mg, or Mn+2, and the Y sites are occupied by smaller trivalent
cations, like Al and Fe+3
 Different end-members
 Pyrope Mg3Al2Si3O12 – deep red to black
 Almandine Fe3Al2Si3O12 – deep brownish red
 Spessartine Mn3Al2Si3O12 – brownish red to black
 Grossular Ca3Al2Si3O12 – yellow-green to brown
 Andradite Ca3Fe2Si3O12 – variable-yellow, green, brown, black
 Uvarovite Ca3Cr2Si3O12 – emerald green
 Mostly occurs in metammorphic rocks
 Other common Nesosilicates

 Zircon: ZrSiO4

 Al2SiO5 minerals are common

in aluminous metamorphic
rocks (meta-shales and meta-
mudstones) and sometimes
found in aluminous igneous
rocks
 Kyanite Same composition
 Sillimanite Different P, T
 Andalucite
 Sorosilicate (Double Island Silicates)
 If one of the corner oxygens is shared
with another tetrahedron, this gives rise
to the sorosilicate group.
 It is often referred to as the double
island group because there are two
linked tetrahedrons isolated from all
other tetrahedrons.
 In this case, the basic structural unit is
Si2O7-6.
 Example: Hemimorphite –
Zn4Si2O7(OH)2H2O
 Cyclosilicate (Ring Silicates)
 If two of the oxygens are
shared and the structure is
arranged in a ring
 The Si:O ratio is 1:3
 Rings containing 3 (Si3O9-6), 4
(Si4O12-8), or 5 (Si5O15-10) Si Si6O18-12
are possible, but only the
rings with 6 Si are at all
common
 Example: Beryl -
Be3Al2Si6O18
 Inosilicates (Single Chain Silicates)
 If two of the oxygens are shared
in a way to make long single
chains of linked SiO4 tetrahedra
 In this case, the basic structural unit
is SiO3-2
 This group is the basis for the
pyroxene group of minerals, like
the orthopyroxenes (Mg,Fe)SiO3
or the clinopyroxenes
Ca(Mg,Fe)SiO3
 Pyroxene
 Each silicon tetrahedron, the excess
negative charge is now only 2-, which
still requires insertion of cations in the
crystal structure.
 These cations are bonded to, and
serve to link, the chains, but these
bonds are weaker than those within
the chains.
 The single chain silicates have
cleavages parallel to the chains,
along two planes that meet at
approximately 90 degrees.
 Pyroxenes
 These have a general structural formula of XYZ2O6

 where X = Na+, Ca+2, Mn+2, Fe+2, or Mg+2 filling

octahedral sites called M2

 Y = Mn+2, Mg+2, Fe+2, Al+3, Cr+3 ot Ti+4 filling smaller

octahedral sites called M1

 Z = Si+4 or Al+3 in tetrahedral coordination.

 Pyroxenes
Clinopyroxenes
X Y
 Diopside Ca Mg Si2O6
 Hedenbergite Ca Fe2+ Si2O6
 Augite Ca (Mg, Fe2+) (Al, Fe3+, Ti) Si2O6
 Pigeonite (Mg,Fe2+, Ca) (Mg, Fe2+) (Al, Fe3+) Si2O6
 Aegirine Na Fe3+ Si2O6
 Jadeite Na Al Si2O6
 Spodumene Li Al Si2O6
Orthopyroxenes
Enstatite MgSiO3
Hypersthene (Mg, Fe)SiO3
Orthoferrosilite FeSiO3
Pyroxene “quad”

Clinopyroxenes

Orthopyroxenes
 Inosilicates (Double Chain Silicates)
 If two chains are linked together so that
each tetrahedral group shares 3 of its
oxygens, we can from double chains,
 The basic structural group being Si4O11-6
 W0-1X2Y5Z8O22(OH,F)2.
W = the large A site which may be vacant
or contain varying amounts of Na/Ca.
 X = Ca, Na, Fe+2or Mg;

 Y = Fe2+, Mg, Fe+3 or Al

 Z = Si and Al in the tetrahedra. The limit of

this substitution appears to be (Al2Si6).
 Amphibole
 Hornblende is the most
common mineral in the
amphibole group
 Cations serve to balance
charge and link the strongly
constructed double chains,
whose extra width causes the
cleavage planes to change
orientation and meet at
approximately 60 and 120
degrees, producing
hexagonal cross sections.
(Na,Ca)2(Mg,Al,Fe)5(Si,Al)8O22(OH)2
 Phyllosilicate (Sheet Silicate)

 3 oxygens from each

tetraheral are shared
 The basic structural group
being Si2O5-2
 A good example is biotite
K(Mg,Fe)3(AlSi3)O10(OH)
 Al is substituting for Si in one
of the tetrahedral groups
 Mica group
 Micas are the chief minerals of Biotite: K2(Mg,Fe)6Si3O10(OH)2
schist's and are also commonly
found in igneous rocks

 They form at lower temperatures

than the inosilicates (pyroxenes
and amphiboles) and are
frequently formed as
replacement minerals after
hydrothermal alteration

 Sheet structures that result in one

direction of perfect cleavage
Muscovite: K2Al4(Si6Al2O20)(OH,F)2
 Tectosilicate (Framework Silicates)
 All 4 oxygens are shared
 The basic structural group is SiO2
 The minerals quartz, cristobalite, and
tridymite all are based on this
structure.
 Sometimes, Si is replaced by Al and
allows for other ions to be found
coordinated in different arrangements
within the framework structure
 Thus, the feldspar and feldspathoid
minerals are also based on the
tectosilicate framework
 Quartz
 As visible crystals, Quartz is one of the
more common rock forming minerals.
 It occurs in siliceous igneous rocks,
metamorphic rocks and is the chief
constituent of sand.
 Because it is highly resistant to chemical
weathering, it is found in a wide variety
of sedimentary rocks.
 Covalent bonds exist between all
tetrahedral oxygen atoms.
 Quartz has no cleavage planes and
will break by conchoidal fracture
 Feldspad & Felspathoid group

 Coupled ionic substitution -

Al3+ replaces Si4+.
 This introduces a positive
charge deficiency
 Cations are introduced to
balance this charge deficiency
 This bond can be between calcium (Ca+2), sodium (Na+1) and
potassium (K+1), depending upon composition of the magma
and crystallization temperature.
 Introduction of these cations result in 2 sets of cleavege
 Feldspar group
 Three end-members:
 Orthoclase – KAlSi3O8
 Albite – NaAlSi3O8

 Anorthite – CaAl2Si2O8

 Alkali feldspar:
 Series
between KAlSi3O8
and NaAlSi3O8
 Plagioclase feldspar:
 Series
between CaAl2Si2O8
and NaAlSi3O8
 General composition
 For all silicates: XmYn (ZpOq)Wr
 X = 8 to12 fold coordination site
 K+, Rb+, Ba+2, Na+, Ca+2
 Y = 6 fold coordination site
 Al+3, Mg+2, Fe+2, Fe+3, Mn+2, Ti+4
 Z = 4 fold coordination site
 Al+3 or Si+3
 the ratio p:q depends on the degree of polymerization of
the silica (or alumina) tetrahedrons, or the silicate structural
type as discussed above.
 O = Oxygen
 W = hydroxyl (OH-1), can be substituted by Fl-1 , Cl-1
 The subscripts m, n, and r depend on the ratio of p to q and
are chosen to maintain charge balance.
Bowen’s reaction series
 Nonsilicate mineral groups
 Fluorite (left, calcium fluoride) and
halite (right, sodium chloride) are
members of the Halide mineral group.
The minerals in this group have, as part
of the chemical structure, an ion from
the halogen elements: Fl1- , Cl1- , I1- , or
Br1-

 Gypsum (calcium sulfate) is a member

of the sulfate group. The building
block for minerals in this group is the
sulfate ion, SO42- .
 The Carbonate Group
 Carbonates are minerals
found in exoskeletons of
marine organisms.
 Calcite (calcium

carbonate – CaCO3) is
the most important
carbonate mineral.
 It has a nearly perfect
rhomboid cleavage
 Nonsilicate Rock-forming
mineral groups
 Sulfates – minerals
containing the sulfate
ion

 Gypsum (Calcium
sulfate: CaSO4 –
2H2O. A product of
rapid evaporation of
ancient seas