Silica Group

Silica minerals - 12 percent of the Earth’s crust

Second to the feldspars in mineral abundance.
Free silica occurs in many crystalline forms
Quartz is by far the most commonly occurring form.
Tridymite, cristobalite, and the hydrous silica mineral opal
are uncommon, and vitreous (glassy) silica, coesite, and
stishovite have been reported from only a few localities.
Several other forms have been produced in the laboratory
but have not been found in nature.
 SiO2 Polymorphs
• -quartz: stable at atmospheric temp. upto 573oC
• -quartz: 573o-870oC
• -Tridymite: Unstable at atm. temp. – 117oC
• 1-Tridymite: 117o – 163oC, stable at 870oC
• 2-Tridymite: exist at 163oC, stable at 870o-1470oC
• -Cristobalite: exist at atm. Temp. 200o-275oC
• -Cristobalite: 200o – 275oC, stable at 1470oC
• Coesite: High pr. Phase- 38,000 atm, 450o-800oC
• Keatite: High pr.synthetic phase 330-1200 atm, 380o-585oC
• Stishovite: high density form of silica (4.3), syn. at 130,000 atm,
1200oC
• Lechatelierite: Silica glass: room temp. to 1000oC,
• Cryptocrystalline silica – chalcedony:
Crystallographic structures of the silica minerals - three-
dimensional arrays of linked tetrahedrons.
Each consisting of a silicon atom coordinated by four
oxygen atoms.
Tetrahedrons are usually quite regular.
Silicon-Oxygen bond distances are 1.61 ± 0.02 Å.
Principal differences are related to the geometry of the
tetrahedral linkages, which may cause small distortions
within the silica tetrahedrons.
High pressure forces silicon atoms to coordinate with six
oxygen atoms, producing nearly regular octahedrons in
the stishovite structure.
Structure of Quartz
Structure of Tridymite
Structure of
Cristobalite
 Symmetry and cell parameters of forms
of silica
Sl.No. Form System aÅ bÅ cÅ
1 -Quartz Trigonal 4.913 - 5.405
2 -Quartz Hexagonal 5.01 - 5.47
3 -Tridymite Orthorhombic 9.88 17.1 16.3
(pseudo-
hexagonal)
4 -Tridymite Hexagonal 5.03 - 8.22
5 -Cristobalite Tetragonal 4.97 - 6.92
(pseudo cubic)
6 -Cristobalite Isometric 7.13 - -
 Chemistry
• SiO2 - 100%,
• Quartz shows less range in chemical composition
• Commonly contains tens to hundreds of parts per million of
aluminum atoms substituting for silicon atoms, with charge
balance maintained by the incorporation of small atoms, such as
hydrogen, lithium, or sodium. Titanium, magnesium, or iron
atoms substituting for silicon atoms
• Anionic substitution (i.e., substitution for the negative ion,
oxygen) is limited because the linkage of the tetrahedrons is
disrupted.
• Small amount of inclusions: Li2O, Na2O, K2O, Al2O3, Fe2O3, MnO2,
TiO2
• Silica minerals are insoluble to sparingly soluble in strong acids
except hydrofluoric acid
Quartz crystals lack a centre of symmetry or planes of symmetry
and have one crystallographic axis (c) perpendicular to three polar
axes (a) that are 120° apart.
One end of a polar axis is different from its other end;
when mechanical stress is applied on such an axis, opposite
electrical charges develop on each end.
This leads to important applications in electronics as a frequency
control and in pressure gauges and other devices.
The lack of symmetry planes parallel to the vertical axis allows
quartz crystals to occur as two types:
left-handed or right-handed (enantiomorphism).
Polarized light is transmitted by a quartz crystal along the c-axis
direction, the plane is rotated in the direction of the handedness by
tens of degrees per millimetre, the amount depending on the
wavelength of the light. This property is used in optical instruments
such as monochromators.
 Solubility of silica minerals
Solubility of silica minerals in natural solutions and gases is of great importance. The
solubility of all silica minerals increases regularly with increasing temperature and
pressure except in the region of 340–550 °C and 0–600 bars, where retrograde
solubility occurs because of changes in the physical state of water.
The solubility of silica increases in the presence of anions such as OH- and CO2-3.
Quartz is the least soluble of the forms of silica at room temperature.
In pure water its solubility at 25 °C is about 6 parts per million, that of vitreous silica
being at least 10 times greater.
Silica dissolved in moving groundwater may partially fill hollow spheroids and
precipitate crystals to form geodes, or it may cement loose sand grains together to
form concretions and nodules or even entire sedimentary beds into sandstone,
which, when all pore space is eliminated by selective solution and nearby deposition
during metamorphism, form tough, pore-free quartzite
 Gases or solutions escaping from cooling igneous rocks or deep fractures
commonly are saturated with silica and other compounds that, as they cool,
precipitate quartz along their channel ways to form veins. It may be fine-grained (as
chalcedony), massive granular, or in coarse crystals as large as tens of tons. Most
natural colourless quartz crystals, “rock crystal,” were formed in this way.
The emergence of heated silica-bearing solutions onto the surface results in
rapid cooling and the loss of complexing anions. Rapid precipitation of fine-grained
silica results in formation of siliceous sinter or geyserite, as at Mammoth Hot Springs
in Yellowstone National Park in the western United States.
Quartz is mechanically resistant and relatively inert chemically during rock
weathering in temperate and cold climates. Thus, it becomes enriched in river, lake,
and beach sediments, which commonly contain more than one-half quartz by
weight. Some strata consist almost entirely of quartz over large lateral distances and
tens or hundreds of metres in thickness. Known as glass sands, these strata are
important economic sources of silica for glass and chemical industries. Quartz-
bearing strata are abundant in metamorphic terrains. The reincorporation of free
silica into complex silicates and the solution and redeposition of silica into veins is
characteristic of such terrains.
 Optical and Physical Properties
• The silica minerals when pure are colourless
and transparent and have a vitreous lustre.
They are nonconductors of electricity and are
diamagnetic. All are hard and strong and fail
by brittle fracture under an imposed stress.
 Origin and occurrence
Silicon and oxygen are the two most abundant elements in the
Earth’s crust,
Free silica (SiO2) appears as a mineral in crystallizing magma only
when the relative abundance of SiO2 exceeds that of all other
cations available to form silicates.
Silica minerals thus occur only in magmas containing more than
about 47 percent by weight of SiO2 and are incompatible with
minerals with low cation:silica ratios—such as olivine, nepheline, or
leucite.
Basaltic and alkalic igneous magmas, can crystallize only minor
amounts of silica minerals.
Gas released from such rocks can dissolve the silica components,
however, and later precipitate silica minerals upon cooling. The
amount of silica minerals crystallized from magma increases with
increasing silica content of magma, reaching 40 percent in some
granites and rhyolites.
 Uses
Quartz is the only natural silica mineral used in significant quantities;
The sand that is an essential ingredient of concrete and mortar is
largely quartz, as are the sandstone and quartzite used as building
stones. Crushed sandstone and quartzite are used for road and
railway construction, roofing granules, and riprap—erosion-control
linings of river channels. Quartz is hard (7 on the Mohs scale) and
resists fracture because it lacks easy cleavage. These properties,
combined with its ready availability, lead to its use as a sandpaper
abrasive and in sandblasting; for polishing and cutting glass, stone,
and metal; and for providing traction on stairs, streets, and rails.
Large amounts of relatively pure quartz are used in refractory
products, such as insulation and firebricks, foundry molds, and
electrical insulators, because of the combination of its high melting
temperatures, low coefficients of expansion, inertness of the high-
temperature forms of silica, and low costs.
• Relatively pure quartz is required in large tonnages as an ingredient
for glass and porcelain manufacture. High purity quartz is fused to
make premium grades of chemical and optical glass for which one
or more of its desirable properties of low thermal expansion, high-
shape stability, elasticity, low solubility, and transparency to various
kinds of light can justify the greatly increased costs involved. Fibres
of vitreous silica are essential for precision instruments, such as
balances, galvanometers, and gravimeters. Water glass, or sodium
silicate, various sols—very fine dispersions of solids in liquids—that
are used as hydrophobic (water-repelling) coatings, organic silicates
and silicones, silicon carbide, silicon metal, smelting flux, and
alloying in metallurgy.
• Quartz and its varieties have been used since antiquity as
semiprecious gems, ornamental stones, and collector’s items.
Precious opal, a hydrous form of silica, has been a gemstone since
Roman times.