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STRUCTURE OF THE SILICATES
1.Approx. 90% of the mineral content
 of the earth’s crust is of silicates
 where Si-O bonding, coupled with
 different cations and anions, formed
 different minerals.
2.The fundamental unit on which the
 structures of all silicates are based
 consists of four O2- apices of a
 regular tetrahedron surrounding and
 coordinated by one Si4+ at its centre.
STRUCTURE OF THE SILICATES
3. The Si-O bond is partly ionic
   (generated due to attraction of opp.
   charged ions) and partly covalent.
   This tetrahedral groups can be linked
   with adjacent tetrahedral groupings
   through sharing of one or all four
   oxygen atoms (Polymerization).
4. The mean Si-O bond length is 1.62Å.
   Other cations near the oxygen atom
   of a Si-O bond also attract the
   oxygen and tend to lengthen the Si-0
   bond( greater co-ord no; longer bond
   length). The strength of the Si-O
   bond limits the range of the bond
   lengths from 1.60Å to 1.64Å
STRUCTURE OF THE
                 SILICATES
The bond length between Si atoms and the bridging
The bond length between Si atoms and the bridging
oxygen atoms (OBR) are on average longer by about
0.025Å compared with the Si-O bond length to the O nb.
[especially when SiO4 are linked in structures.
The OBR-Si-OBR bond angle is also shows slightly
smaller value when bridging oxygens are not involved.
This suggests that that the Si atoms are displaced
from the centres of the tetrahedra (awayfrom O BR) coz
of repulsive force between two Si atoms.
The aforesaid sharing of oxygens gave rise to diverse
structural configurations for silicates with various Si-O
ratios.
When tetrahedra are corner-linked, the Si-O bond angle
defines the orientation of the tetrahedra relative to one
another. This bond angle can vary between 1200 and 1800
depending on the local structural environment as well as
temp. and pressure. The bond angle of a strain-free Si-O-
Si bond is near 1400.
When Al substitutes Si in a tetrahedron, the [AlO4]
tetrahedra is slightly larger than a [SiO4] tetrahedra coz.
Al-O bond (1.75Å) is larger than the Si-O bond. When
SiO4and AlO4 are linked in a structure, this size
difference is accommodated by a change in the T-O-T
bond angle (T= tetrahedral cation)
SiO44- complex ion
• A group of ions that is so tightly bound together
  that they act like a single unit.

• Building block of silicate minerals

• 1 silicon ion + 4 oxygen ions
  arranged in a triangular pyramid

 • Electrical charge of -4
Silicate tetrahedron
SiO44-
Tetrahedron Viewing


                                                Top point




                                                  base

View from the top,   Flat base of tetrahedron   Side view
looking down.        facing you. Top point
Top point of         of tetrahedron pointing
tetrahedron          away from you.
facing you
Nesosilicates (island silicates)
SiO44- tetrahedron forms ionic bonds with cations such as Mg2+, Fe2+
  Example: Olivine
  Mg2SiO4 - Fosterite      Fe2SiO4 - Fayalite     (Mg, Fe)SiO4
                                                  Solid solution




      Mg2+ or Fe2+
Olivine: nesosilicate structure (island silicate)
                               View from the side (“wall” of structure)
Why Mg OR Fe?
• Same size
• Same electrical
charge



Peridot
Corner Sharing Base to Base
                 side view


    O2-


   Si4+




3-D Side View




                             © S. Brachfeld 2003
Inosilicicates: Single Chains (Pyroxene)
SiO3 Chain forms ionic bonds with cations above the tip
and below the base

                          Boxed region when view from



               How many Si
               How many O
                 2 Si
                 6O
                                      Yellow tetrahedron in front
                                     Gray behind and to the side
                                        Cation, forming ionic
            Stand here                  bond with tetrahedron
            look up the chain           chain
Corner Sharing Tip to Tip



            O2-


           Si4+




tesy of Donna Whitney, University of Minnesota Dept. Geology


                                     Face sharing
Assembling a Single Chain Silicate (Pyroxene)

Build xl in this direction




                                           © S. Brachfeld 2003
Pyroxene- Where’s the cleavage?
breaking at the molecular scale

 What human eyes
 see at the macro scale
                   90˚ cleavage




                                      © S. Brachfeld 2003
Double Chain Silicates (Amphibole)
PAIR of SiO4 chains that link by corner sharing in 2 directions
Amphibole formula is long: lots of space for small
   and medium cations




              Cations include Na+, K+, Ca2+, Mn2+,
              Fe2+, Mg2+, Fe3+, Al3+, Ti4+


Stand here
look up the chain
60˚-120˚ Cleavage in Double Chain Silicates (Amphibole)- (actually 56˚ - 124˚)
         breaking at the molecular scale
        What human eyes see
        at the macro scale
                                      120 ˚




                                                       © S. Brachfeld 2003
Nesosilicates: independent SiO4 tetrahedra

                           b




                                                 c




                           projection


      Olivine (100) view blue = M1 yellow = M2
Inosilicates: single chains- pyroxenes
   b




                                a sinβ




Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
Inosilicates: double chains- amphiboles


                                                             Hornblende:
                                                       (Ca, Na)2-3 (Mg, Fe, Al)5
                                                         [(Si,Al)8O22] (OH)2

                                                        M1-M3 are small sites

                                                          M4 is larger (Ca)

                                                          A-site is really big

                                                          Variety of sites →
                                                         great chemical range

    Hornblende (001) view dark blue = Si, Al purple = M1 rose = M2
light blue = M3 (all Mg, Fe) yellow ball = M4 (Ca) purple ball = A (Na)
                          little turquoise ball = H
Stishovite




Tectosilicates
                                                       Coesite




Low Quartz                                                   β- quartz
                                         α- quartz                       Liquid
                                                       Cristobalite
                                                 Tridymite




       001 Projection Crystal Class 32

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Silicate structure

  • 1. STRUCTURE OF THE SILICATES 1.Approx. 90% of the mineral content of the earth’s crust is of silicates where Si-O bonding, coupled with different cations and anions, formed different minerals. 2.The fundamental unit on which the structures of all silicates are based consists of four O2- apices of a regular tetrahedron surrounding and coordinated by one Si4+ at its centre.
  • 2. STRUCTURE OF THE SILICATES 3. The Si-O bond is partly ionic (generated due to attraction of opp. charged ions) and partly covalent. This tetrahedral groups can be linked with adjacent tetrahedral groupings through sharing of one or all four oxygen atoms (Polymerization). 4. The mean Si-O bond length is 1.62Å. Other cations near the oxygen atom of a Si-O bond also attract the oxygen and tend to lengthen the Si-0 bond( greater co-ord no; longer bond length). The strength of the Si-O bond limits the range of the bond lengths from 1.60Å to 1.64Å
  • 3. STRUCTURE OF THE SILICATES The bond length between Si atoms and the bridging The bond length between Si atoms and the bridging oxygen atoms (OBR) are on average longer by about 0.025Å compared with the Si-O bond length to the O nb. [especially when SiO4 are linked in structures. The OBR-Si-OBR bond angle is also shows slightly smaller value when bridging oxygens are not involved. This suggests that that the Si atoms are displaced from the centres of the tetrahedra (awayfrom O BR) coz of repulsive force between two Si atoms. The aforesaid sharing of oxygens gave rise to diverse structural configurations for silicates with various Si-O ratios.
  • 4. When tetrahedra are corner-linked, the Si-O bond angle defines the orientation of the tetrahedra relative to one another. This bond angle can vary between 1200 and 1800 depending on the local structural environment as well as temp. and pressure. The bond angle of a strain-free Si-O- Si bond is near 1400. When Al substitutes Si in a tetrahedron, the [AlO4] tetrahedra is slightly larger than a [SiO4] tetrahedra coz. Al-O bond (1.75Å) is larger than the Si-O bond. When SiO4and AlO4 are linked in a structure, this size difference is accommodated by a change in the T-O-T bond angle (T= tetrahedral cation)
  • 5. SiO44- complex ion • A group of ions that is so tightly bound together that they act like a single unit. • Building block of silicate minerals • 1 silicon ion + 4 oxygen ions arranged in a triangular pyramid • Electrical charge of -4
  • 6.
  • 8. Tetrahedron Viewing Top point base View from the top, Flat base of tetrahedron Side view looking down. facing you. Top point Top point of of tetrahedron pointing tetrahedron away from you. facing you
  • 9. Nesosilicates (island silicates) SiO44- tetrahedron forms ionic bonds with cations such as Mg2+, Fe2+ Example: Olivine Mg2SiO4 - Fosterite Fe2SiO4 - Fayalite (Mg, Fe)SiO4 Solid solution Mg2+ or Fe2+
  • 10. Olivine: nesosilicate structure (island silicate) View from the side (“wall” of structure) Why Mg OR Fe? • Same size • Same electrical charge Peridot
  • 11. Corner Sharing Base to Base side view O2- Si4+ 3-D Side View © S. Brachfeld 2003
  • 12. Inosilicicates: Single Chains (Pyroxene) SiO3 Chain forms ionic bonds with cations above the tip and below the base Boxed region when view from How many Si How many O 2 Si 6O Yellow tetrahedron in front Gray behind and to the side Cation, forming ionic Stand here bond with tetrahedron look up the chain chain
  • 13. Corner Sharing Tip to Tip O2- Si4+ tesy of Donna Whitney, University of Minnesota Dept. Geology Face sharing
  • 14. Assembling a Single Chain Silicate (Pyroxene) Build xl in this direction © S. Brachfeld 2003
  • 15. Pyroxene- Where’s the cleavage? breaking at the molecular scale What human eyes see at the macro scale 90˚ cleavage © S. Brachfeld 2003
  • 16. Double Chain Silicates (Amphibole) PAIR of SiO4 chains that link by corner sharing in 2 directions
  • 17. Amphibole formula is long: lots of space for small and medium cations Cations include Na+, K+, Ca2+, Mn2+, Fe2+, Mg2+, Fe3+, Al3+, Ti4+ Stand here look up the chain
  • 18. 60˚-120˚ Cleavage in Double Chain Silicates (Amphibole)- (actually 56˚ - 124˚) breaking at the molecular scale What human eyes see at the macro scale 120 ˚ © S. Brachfeld 2003
  • 19. Nesosilicates: independent SiO4 tetrahedra b c projection Olivine (100) view blue = M1 yellow = M2
  • 20. Inosilicates: single chains- pyroxenes b a sinβ Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
  • 21. Inosilicates: double chains- amphiboles Hornblende: (Ca, Na)2-3 (Mg, Fe, Al)5 [(Si,Al)8O22] (OH)2 M1-M3 are small sites M4 is larger (Ca) A-site is really big Variety of sites → great chemical range Hornblende (001) view dark blue = Si, Al purple = M1 rose = M2 light blue = M3 (all Mg, Fe) yellow ball = M4 (Ca) purple ball = A (Na) little turquoise ball = H
  • 22. Stishovite Tectosilicates Coesite Low Quartz β- quartz α- quartz Liquid Cristobalite Tridymite 001 Projection Crystal Class 32