Structures and Chemistry of silicate Silicates are classified on the basis of Si-O polymerism The culprit: the [SiO 4 ] 4 - tetrahedron
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1 Structures and Chemistry of silicate by: Seyed mohsen hoseini zade
2 Structures and Chemistry of silicate Silicates are classified on the basis of Si-O polymerism The culprit: the [SiO 4 ] 4 - tetrahedron
3 Structures and Chemistry of silicate Silicates are classified on the basis of Si-O polymerism [SiO 4 ] 4- Independent tetrahedra Nesosilicates Examples: olivine garnet [Si 2 O 7 ] 6- Double tetrahedra Sorosilicates Examples: lawsonite n[sio 3 ] 2- n = 3, 4, 6 Cyclosilicates Examples: benitoite BaTi[Si 3 O 9 ] axinite Ca 3 Al 2 BO 3 [Si beryl Be 3 Al 2 [Si 6 O 18 ] [Si 4 O 12 ]OH
4 Structures and Chemistry of silicate Silicates are classified on the basis of Si-O polymerism [SiO 3 ] 2- single chains Inosilicates [Si 4 O 11 ] 4- Double tetrahedra pryoxenes pyroxenoids amphiboles
5 Structures and Chemistry of silicate Silicates are classified on the basis of Si-O polymerism [Si 2 O 5 ] 2- Sheets of tetrahedra micas talc clay minerals serpentine Phyllosilicates
6 Structures and Chemistry of silicate Silicates are classified on the basis of Si-O polymerism low-quartz [SiO 2 ] 3-D frameworks of tetrahedra: fully polymerized quartz and the silica minerals feldspars feldspathoids zeolites Tectosilicates
7 Structures and Chemistry of silicate Nesosilicates: independent SiO 4 tetrahedra
8 Nesosilicates: independent SiO 4 tetrahedra b c projection Olivine (100) view blue = M1 yellow = M2
9 Nesosilicates: independent SiO 4 tetrahedra b c perspective Olivine (100) view blue = M1 yellow = M2
10 Nesosilicates: independent SiO 4 tetrahedra b M1 in rows and share edges a M2 form layers in a-c that share corners Some M2 and M1 share edges Olivine (001) view blue = M1 yellow = M2
11 Nesosilicates: independent SiO 4 tetrahedra b c M1 and M2 as polyhedra Olivine (100) view blue = M1 yellow = M2
12 Nesosilicates: independent SiO 4 tetrahedra Olivine Occurrences: Principally in mafic and ultramafic igneous and meta- igneous rocks Fayalite in meta-ironstones and in some alkalic granitoids Forsterite in some siliceous dolomitic marbles Monticellite CaMgSiO 4 Ca M2 (larger ion, larger site) High grade metamorphic siliceous carbonates
13 Nesosilicates: independent SiO 4 tetrahedra Garnet: A 2+ 3 B 3+ 2 [SiO 4 ] 3 Pyralspites - B = Al Pyrope: Mg 3 Al 2 [SiO 4 ] 3 Almandine: Fe 3 Al 2 [SiO 4 ] 3 Spessartine: Mn 3 Al 2 [SiO 4 ] 3 Ugrandites - A = Ca Uvarovite: Ca 3 Cr 2 [SiO 4 ] 3 Grossularite: Ca 3 Al 2 [SiO 4 ] 3 Andradite: Ca 3 Fe 2 [SiO 4 ] 3 Occurrence: Mostly metamorphic Some high-al igneous Also in some mantle peridotites Garnet (001) view blue = Si purple = A turquoise = B
14 Nesosilicates: independent SiO 4 tetrahedra Garnet: A 2+ 3 B 3+ 2 [SiO 4 ] 3 a 1 a 3 a 2 Pyralspites - B = Al Pyrope: Mg 3 Al 2 [SiO 4 ] 3 Almandine: Fe 3 Al 2 [SiO 4 ] 3 Spessartine: Mn 3 Al 2 [SiO 4 ] 3 Ugrandites - A = Ca Uvarovite: Ca 3 Cr 2 [SiO 4 ] 3 Grossularite: Ca 3 Al 2 [SiO 4 ] 3 Andradite: Ca 3 Fe 2 [SiO 4 ] 3 Occurrence: Mostly metamorphic Pyralspites in meta-shales Ugrandites in meta-carbonates Some high-al igneous Also in some mantle peridotites Garnet (001) view blue = Si purple = A turquoise = B
15 Inosilicates: single chains- pyroxenes b Diopside: CaMg [Si 2 O 6 ] a sin sin Where are the Si-O-Si-O chains?? Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
16 Inosilicates: single chains- pyroxenes b a sin sin Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
17 Inosilicates: single chains- pyroxenes b a sin sin Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
18 Inosilicates: single chains- pyroxenes b a sin sin Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
19 Inosilicates: single chains- pyroxenes b a sin sin Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
20 Inosilicates: single chains- pyroxenes b a sin sin Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
21 Inosilicates: single chains- pyroxenes Perspective view Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
22 Inosilicates: single chains- pyroxenes IV slab SiO 4 as polygons (and larger area) VI slab IV slab a sin sin VI slab IV slab VI slab b IV slab Diopside (001) view blue = Si purple = M1 (Mg) yellow = M2 (Ca)
23 Inosilicates: single chains- pyroxenes M1 octahedron
24 Inosilicates: single chains- pyroxenes M1 octahedron
25 Inosilicates: single chains- pyroxenes (+) M1 octahedron (+) type by convention
26 Inosilicates: single chains- pyroxenes (-) M1 octahedron This is a (-) type
27 Inosilicates: single chains- pyroxenes T M1 T Creates an I-beam like unit in the structure.
28 Inosilicates: single chains- pyroxenes T (+) M1 T Creates an I-beam like unit in the structure
29 Inosilicates: single chains- pyroxenes (+) (+) (+) The pyroxene structure is then composed of alternating I-beams Clinopyroxenes have all I-beams oriented the same: all are (+) in this orientation (+) (+) Note that M1 sites are smaller than M2 sites, since they are at the apices of the tetrahedral chains
30 Inosilicates: single chains- pyroxenes (+) (+) (+) The pyroxene structure is then composed of alternation I-beams Clinopyroxenes have all I-beams oriented the same: all are (+) in this orientation (+) (+)
31 Inosilicates: single chains- pyroxenes Tetrehedra and M1 octahedra share tetrahedral apical oxygen atoms
32 Inosilicates: single chains- pyroxenes (+) M2 c The tetrahedral chain above the M1s is thus offset from that below (+) M1 a The M2 slabs have a similar effect (+) M2 The result is a monoclinic unit cell, hence clinopyroxenes
33 Inosilicates: single chains- pyroxenes (-) M1 c Orthopyroxenes have alternating (+) and (-) I-beams (+) M2 (+) M1 (-) M2 a the offsets thus compensate and result in an orthorhombic unit cell This also explains the double a cell dimension and why orthopyroxenes have {210} cleavages instead of {110) as in clinopyroxenes (although both are at 90 o )
34 Pyroxene Chemistry The general pyroxene formula: Where W 1-P (X,Y) 1+P Z 2 O 6 W = Ca Na X = Mg Fe 2+ Mn Ni Li Y = Al Fe 3+ Cr Ti Z = Si Al Anhydrous so high-temperature or dry conditions favor pyroxenes over amphiboles
35 Pyroxene Chemistry The pyroxene quadrilateral and opx-cpx solvus Coexisting opx + cpx in many rocks (pigeonite only in volcanics) Wollastonite orthopyroxenes pigeonite 1200 o C Diopside clinopyroxenes Hedenbergite Solvus 1000 o C 800 o C Enstatite pigeonite orthopyroxenes Ferrosilite (Mg,Fe) 2 Si 2 O 6 Ca(Mg,Fe)Si 2 O 6
36 Pyroxene Chemistry Non-quad pyroxenes Jadeite NaAlSi 2 O 6 Aegirine NaFe 3+ Si 2 O Ca / (Ca + Na) Omphacite aegirineaugite Spodumene: LiAlSi 2 O Diopside-Hedenbergite Augite Ca(Mg,Fe)Si 2 O 6 Ca-Tschermack s molecule CaAl2SiO 6
37 Ideal pyroxene chains with 5.2 A repeat (2 tetrahedra) become distorted as other cations occupy VI sites Pyroxenoids 17.4 A 5.2 A 7.1 A 12.5 A Pyroxene 2-tet repeat Wollastonite (Ca M1) 3-tet repeat Rhodonite MnSiO 3 5-tet repeat Pyroxmangite (Mn, Fe)SiO 3 7-tet repeat
38 Inosilicates: double chains- amphiboles b Tremolite: Ca 2 Mg 5 [Si 8 O 22 ] (OH) 2 a sin sin Tremolite (001) view blue = Si purple = M1 rose = M2 gray = M3 (all Mg) yellow = M4 (Ca)
39 Inosilicates: double chains- amphiboles b Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (OH) 2 a sin sin 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
40 Inosilicates: double chains- amphiboles Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (OH) 2 Same I-beam architecture, but the I-beams are fatter (double chains) Hornblende (001) view dark blue = Si, Al purple = M1 rose = M2 light blue = M3 (all Mg, Fe)
41 Inosilicates: double chains- amphiboles a sin sin (+) (+) (+) b (+) (+) Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (OH) 2 Same I-beam architecture, but the I-beams are fatter (double chains) All are (+) on clinoamphiboles and alternate in orthoamphiboles 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
42 Inosilicates: double chains- amphiboles Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (OH) 2 M1-M3 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
43 Inosilicates: double chains- amphiboles Hornblende: (Ca, Na) 2-3 (Mg, Fe, Al) 5 [(Si,Al) 8 O 22 ] (OH) 2 (OH) is in center of tetrahedral ring where O is a part of M1 and M3 octahedra (OH) 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
44 Amphibole Chemistry See handout for more information General formula: W 0-1 X 2 Y 5 [Z 8 O 22 ] (OH, F, Cl) 2 W = Na K X = Ca Na Mg Fe 2+ (Mn Li) Y = Mg Fe 2+ Mn Al Fe 3+ Z = Si Al 3+ Ti Again, the great variety of sites and sizes a great chemical range, and hence a broad stability range The hydrous nature implies an upper temperature stability limit
45 Amphibole Chemistry Ca-Mg-Fe Amphibole quadrilateral (good analogy with pyroxenes) Tremolite Ca 2 Mg 5 Si 8 O 22 (OH) 2 Actinolite Ferroactinolite Ca 2 Fe 5 Si 8 O 22 (OH) 2 Anthophyllite Mg 7 Si 8 O 22 (OH) 2 Orthoamphiboles Cummingtonite-grunerite Clinoamphiboles Fe 7 Si 8 O 22 (OH) 2 Al and Na tend to stabilize the orthorhombic form in low-ca amphiboles, so anthophyllite gedrite orthorhombic series extends to Fe-rich gedrite in more Na-Al-rich compositions
46 a Inosilicates Pyroxenes and amphiboles are very similar: Clinopyroxene a Both have chains of SiO 4 tetrahedra Orthopyroxene Clinoamphibole The chains are connected into stylized I-beams by M octahedra High-Ca monoclinic forms have all the T-O-T T offsets in the same direction Low-Ca orthorhombic forms have alternating (+) and (-) offsets Orthoamphibole
47 pyroxene Inosilicates amphibole a b Cleavage angles can be interpreted in terms of weak bonds in M2 sites (around I-beams instead of through them) Narrow single-chain I-beams 90 o cleavages in pyroxenes while wider double- chain I-beams o cleavages in amphiboles
48 Phyllosilicates SiO 4 tetrahedra polymerized into 2-D sheets: [Si 2 O 5 ] Apical O s are unpolymerized and are bonded to other constituents
49 Phyllosilicates Tetrahedral layers are bonded to octahedral layers (OH) pairs are located in center of T rings where no apical O
50 Phyllosilicates Octahedral layers can be understood by analogy with hydroxides Brucite: Mg(OH) 2 c Layers of octahedral Mg in coordination with (OH) Large spacing along c due to weak van der waals bonds
51 Phyllosilicates a 2 a 1 Gibbsite: Al(OH) 3 Layers of octahedral Al in coordination with (OH) Al 3+ means that only 2/3 of the VI sites may be occupied for charge-balance reasons Brucite-type type layers may be called trioctahedral and gibbsite-type type dioctahedral
52 Phyllosilicates Kaolinite: Al 2 [Si 2 O 5 ] (OH) 4 T-layers and diocathedral (Al 3+ ) layers Yellow = (OH) (OH) at center of T-rings and fill base of VI layer weak van der Waals bonds between T-O groups T O - T O - T O vdw vdw
53 Phyllosilicates Serpentine: Mg 3 [Si 2 O 5 ] (OH) 4 T-layers and triocathedral (Mg 2 + ) layers Yellow = (OH) (OH) at center of T-rings and fill base of VI layer weak van der Waals bonds between T-O groups T O - T O - T O vdw vdw
54 Serpentine Antigorite maintains a sheet-like form by alternating segments of opposite curvature Chrysotile does not do this and tends to roll into tubes Octahedra are a bit larger than tetrahedral match, so they cause bending of the T-O layers (after Klein and Hurlbut, 1999).
55 Serpentine Veblen and Busek, 1979, Science 206, Nagby and Faust (1956) Am. Mineralogist 41, S = serpentine T = talc The rolled tubes in chrysotile resolves the apparent paradox of asbestosform sheet silicates
56 Phyllosilicates Pyrophyllite: Al 2 [Si 4 O 10 ] (OH) 2 Yellow = (OH) T-layer - diocathedral (Al 3+ ) layer - T-layer weak van der Waals bonds between T - O - T groups T O T - T O T - T O T vdw vdw
57 Phyllosilicates Talc: Mg 3 [Si 4 O 10 ] (OH) 2 Yellow = (OH) T-layer - triocathedral (Mg 2+ ) layer - T-layer weak van der Waals bonds between T - O - T groups T O T - T O T - T O T vdw vdw
58 Phyllosilicates Muscovite: K Al 2 [Si 3 AlO 10 ] (OH) 2 (coupled K - Al T-layer - diocathedral (Al 3 + ) layer - T-layer - K K between T - O - T groups is stronger than vdw Al IV IV ) T O T K T O T K T O T
59 Phyllosilicates Phlogopite: K Mg 3 [Si 3 AlO 10 ] (OH) 2 T-layer - triocathedral (Mg 2 + ) layer - T-layer - K K between T - O - T groups is stronger than vdw T O T K T O T K T O T
60 Phyllosilicates A Summary of Phyllosilicate Structures Fig Klein and Hurlbut Manual of Mineralogy, John Wiley & Sons
61 Phyllosilicates Chlorite: (Mg, Fe) 3 [(Si, Al) = T - O - T - (brucite) [(Si, Al) 4 O 10 ] (OH) 2 (Mg, Fe) 3 (OH) 6 (brucite) - T - O - T - (brucite) - T - O - T - Very hydrated (OH) 8, so low-temperature stability (low-t metamorphism and alteration of mafics as cool)
62 Fig. 6, Veblen et al (1977) Science 198 AAAS anthophyllite jimthompsonite chesterite HRTEM image of anthophyllite (left) with typical double-chain width Jimthompsonite (center) has triple-chains Chesterite is an ordered alternation of double- and triple-chains
63 Biopyriboles Fig. 7, Veblen et al (1977) Science 198 AAAS Disordered structures show 4-chain widths and even a 7-chain width Obscures the distinction between pyroxenes, amphiboles, and micas (hence the term biopyriboles: biotite-pyroxene-amphibole)
64 Pressure (GPa) Tectosilicates Stishovite Coesite quartz - quartz Cristobalite Tridymite Liquid After Swamy and Saxena (1994) J. Geophys. Res., 99, 11,787-11, Temperature o C
65 Tectosilicates Stishovite Low Quartz Coesite - quartz - quartz Cristobalite Tridymite Liquid 001 Projection Crystal Class 32
66 High Quartz at 581 o C Tectosilicates Stishovite Coesite - quartz - quartz Cristobalite Tridymite Liquid 001 Projection Crystal Class 622
67 Tectosilicates Stishovite Cristobalite Coesite - quartz - quartz Cristobalite Tridymite Liquid 001 Projection Cubic Structure
68 Tectosilicates Stishovite Stishovite Coesite - quartz - quartz Cristobalite Tridymite Liquid High pressure Si Si VI
69 Tectosilicates Low Quartz Stishovite Si IV Si VI
70 Tectosilicates Feldspars Substitute Al 3+ for Si 4+ allows Na + or K + to be added Substitute two Al 3+ for Si 4+ allows Ca 2+ to be added Albite: NaAlSi 3 O 8
71 Thanks a lot for your attention
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