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(Ahrens) Mineral Physics PDF
(Ahrens) Mineral Physics PDF
ISBN o-87590-852-7
ISSN 1080-305X
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Preface
Thomas .I. Ahrens vii
Index 349
PREFACE
Vii
~- ~-------
Mineral Formula Crystal Space structure z a B Y Unit Cell Molar Density Ref.
Formula
Weight System Group Type (4 (“! (“) Vol (K3) Vol (cm3) (calc)(h4g/m3)
Single Oxides
Hemhxkie
cuprite cuzo 143.079 Cub. Pdm Cuprite 2 4.2696 17.833 23.439 6.104 25
Monoxides Group
Periclase NsO 40.312 Cub. F&n Halite 4 4.211 74.67 11.244 3.585 93
WUStite Fe0 71.848 Cub. F&n Halite 4 4.3108 80.11 12.062 5.956 61
Lime CaO 56.079 Cub. F&n Halite 4 4.1684 111.32 16.762. 3.346 235
Bunsenite NiO 74.709 Cub. F&m Halite 4 4.446 72.43 10.906 6.850 235
Munganosite MnO 70.937 Cub. Fm%m Halite 4 4.8105 87.88 13.223 5.365 195
Tenorite cue 79.539 Mono.C2lc Tencrite 4 4.6837 3.4226 5.1288 99.54 8 1.080 12.209 6.515 11
Montroydite HgO 216.589 Orth. Prima Montroydite 4 6.612 5.20 3.531 128.51 19.350 11.193 12
Zincite ZnO 81.369 Hex. P63mc Wurtzite 2 3.2427 5.1948 47.306 14.246 5,712 189
Bromellite Be0 25.012 Hex. P63nu: Wurtzite 2 2.6984 4.2770 26.970 a.122 3.080 189
sesquioxide Group
Corundum -41203 101.961 Trig. R3C 6 4.7589 12.9912 254.80 25.517 3.986 157
Hematite Fe203 159.692 Trig. R% Corundum 6 5.038 13.772 302.72 30.388 5.255 23
Eskolaite Cr203 151.990 Trig. R% Corundum 6 4.9607 13.599 289.92 29.093 5.224 157
Kureliunite v203 149.882 Trig. R% Corundum 6 4.952 14.002 297.36 29.850 5.021 157
Bixbyite Mnz03 157.905 Cub. la7 Bixbyite 16 9.4146 834.46 31.412 5.027 75
Avicennite T1203 456.738 Cub. 1ClS Bixbyite 16 10.543 1171.9 44.115 10.353 167
Claudetite AS203 197.841 Mono. P21ln Claudetite 4 7.99 4.65 9.12 78.3 331.8 49.961 3.960 176
Arsenolite AS203 197.841 Cub. F&m Arsenolite 16 11.0744 1358.19 51.127 3.870 177
Senurmontite SW3 291 A98 Cub. F&m Arsenolite 16 11.1519 1386.9 52.208 5.583 217
Valentinite Sb203 291.498 Chth. Vulentinite 4 4.911 12.464 5.412 331.27 49.881 5.844 216
Dioxide Group
Brookite TiO2 79.890 Orth. Ph Brookite 8 9.184 5.447 5.145 257.38 19.377 4.123 17
Anatase TiO2 79.890 Ten. Mtlamd Anatase 4 3.7842 9.5146 136.25 20.156 3.895 105
Rutile Ti02 79.890 Tetr. P42/mnm Rutile 2 4.5845 2.9533 62.07 18.693 4.2743 204
Cassiterite SnO2 150.69 Tetr. P42/mnm Rutile 2 4.737 3.185 71.47 21.523 7.001 15
Stishovite SiO2 60.086 Tea P4dmnm Rutile 2 4.1790 2.6651 46.54 14.017 4.287 20
Pyrolusite MnO2 86.94 Ten. P42/mnm Rutile 2 4.3% 2.871 55.48 86.937 5.203 121
Baddeleyite m2 123.22 Mono.P;?t/c Baddeleyite 4 5.1454 5.2075 5.3107 99.23 140.45 21.149 5.826 208
Uianinite UOZ 270.03 Cub. F&m Fluorite 4 5.4682 163.51 24.620 10.968 126
Thoriunite Th02 264.04 Cub. F&m Fluorite 4 5.5997 175.59 26.439 9.987 227
Multiple Oxides
Chry~Yl BeAl& 126.97 Orth. Prunb Oiivine 4 4.424 9.396 5.471 227.42 34.244 3.708 96
Spin.51Group
Spine1 M&Q 142.27 Cub. F&m Spinet 8 8.0832 528.14 39.762 3.578 61
Hercynite FeA120.t 173.81 Cub. F&m Spinet 8 8.1558 542.50 40.843 4.256 99
Magnesiofenite MgFezQ 200.00 Cub. F&m- Spine1 8 8.360 584.28 43.989 4.547 100
Mugnesiochromite M&r204 192.30 Cub. F&m Spine1 8 8.333 578.63 43.564 4.414 100
Magnetite FeFe204 231.54 Cub. Fcdm Spine1 8 8.394 591.43 44.528 5.200 100
Jacobsite MnFe204 230.63 Cub. k’&m Spine1 8 8.5110 616.51 46.416 4.969 100
Chnnnite FeCr204 223.84 Cub. F&m Spine1 8 8.3794 588.31 44.293 5.054 100
-
Ulvwspinel TiFe204 223.59 Cub. F&m Spinet 8 8.536 62 1.96 46.826 4.775 106
Table 1. Crystallographic Properties of Minerals (continued).
Mineral Fotmula Crystal Space StNCtUE z 0 Y Unit Cell Molar Density Ref.
Formula
Weight System Group ‘be (A) (“) Vol (A3) Vol (cm3) (calc)(Mg/m3)
Tilanale Group
Ihnenite FeTiOs 151.75 Trig. R? Ilmenite 6 5.0884 14.0855 315.84 3 1.705 4.786 229
Pyrophanite MnTiO3 150.84 Trig. Rs Ilmenite 6 5.137 14.283 326.41 32.766 4.603 235
Perovskite CaTi 135.98 Orth. Pbnm Perovskite 4 5.3670 5.4439 7.6438 223.33 33.63 4.044 113
Armalcolite Mg.@esTiS% 215.88 Otth. Bbmm Pseudobrookite 4 9.7762 10.0214 3.7485 367.25 55.298 3.904 230
Pseudobrookite FeaTi 239.59 Orth. Bbmm Pscudobrookite 4 9.747 9.947 3.717 361.12 54.375 4.406 3
Tungstates and Molybdnks
Ferberite FeW04 303.70 Mono. PZ/c Fe&rite 2 4.730 5.703 4.952 90.0 133.58 40.228 7.549 225
Huebnerite MnW04 302.79 Mono.P2/c Ferberite 2 4.8238 5.7504 4.9901 91.18 138.39 4 1.676 7.265 231
Scheelite CaWO4 287.93 Tetr. 141/a Scheelite 4 5.243 11.376 312.72 47.087 6.115 114
Powellitc CaMoO4 200.02 Tetr. 141/a Scheelite 4 5.23 11.44 301.07 45.333 4.412 101
Stolzite Pbwo4 455.04 Tetr. 141/a Scheelite 4 5.46 12.05 359.23 54.091 8.412 101
Wulfenite PbMoO4 367.12 Tctr. 141/a Scheelite 4 5.435 12.11 357.72 53.864 6.816 101
Hydroxides
Gibbsite WW3 78.00 Mono.P2t/n Gibbsite 8 8.684 5.078 9.736 9454 427.98 32.222 2.421 188
Diaspore AID 59.99 Orth. Pbnm 4 4.401 9.421 2.845 117.96 17.862 3.377 34
Bochmite APOW 59.99 Orth. Amam Boehmite 4 3.693 12.221 2.865 129.30 19.507 3.075 98
Brucitc MgWh 58.33 Trig. !%I Brucite 1 3.124 4.766 40.75 24.524 2.377 243
Goethite FeO(OH) 88.85 Or&. Pbnm Gocthite 4 4.587 9.937 3.015 137.43 20.693 4.294 65
Lepidoehrosite FeO(OH) 88.85 orth. cmczt Boehmite 4 3.08 12.50 3.87 148.99 22.435 3.961 43
Carhonotes
Magnesite M&03 84.32 Trig. R% Calcite 6 4.6328 15.0129 279.05 28.012 3.010 54
Smithsonite zatco3 125.38 Trig. R% Calcite 6 4.6526 15.0257 281.68 28.276 4.434 54
Siderite FeCQ 115.86 Trig. R% Calcite 6 4.6916 15.3796 293.17 29.429 3.937 54
Rhodochrositc MnCOs 114.95 Trig. R% Calcite 6 4.7682 15.6354 307.86 30.904 3.720 54
Otavite CdCOj 172.41 Trig. R% Calcite 6 4.923 16.287 341.85 34.316 5.024 26
Calcite CaC03 100.09 Trig. R?c Calcite 6 4.9896 17.0610 367.85 36.9257 2.7106 54
Vaterite CaC03 100.09 Hex. P63hmc Vaterite 12 7.151 16.937 750.07 37.647 2.659 146
Dolomite CaMgKQh 184.41 Trig. d Dolomite 3 4.8069 16.0034 320.24 64.293 2.868 182
Ankerite c*dco3)2 215.95 Trig. RT Dolomite 3 4.830 16.167 326.63 65.516 3.293 21
Aragonite CaC03 100.09 orth. Pmcn Aragonite 4 4.9614 7.9671 5.7404 226.91 34.166 2.930 51
Strontianite SrC03 147.63 Orth. Pmcn Aranonite
Y
4 5.090 8.358 5.997 255.13 38.416 3.843 51
Cerussite Pbco3 267.20 Orth. Pmcn Araaonite 4 5.180 8.492 6.134 269.83 40.629 6.577 191
Witherite BaC03 197.39 orth. Pmcn Aragonite 4 5.3126 8.8958 6.4284 303.81 45.745 4.314 51
Amrite Cu3@H)2(C03)2 344.65 Mon0.P2~/c Amrite 2 5.0109 5.8485 10.345 92.43 302.90 91.219 3.778 245
Malachite Cuz@H)zC% 221.10 Mono.P2t/a Malachite 4 9.502 11.974 3.240 98.75 364.35 54.862 4.030 244
Nitrates
Soda Niter Nd% 85.00 Trig. R% Calcite 6 5.0708 16.818 374.51 37.594 2.261 198
Niter KNOs 101.11 or&l. Pmcn Aragonite 4 5.4119 9.1567 6.5189 323.05 48.643 2.079 159
Berates
Borax Na2B40s(OH)4.8HaO 381.37 Mono. C2/c 11.885 10.654 12.206 106.62 1480.97 223.00 1.710 128
Table 1. Crystallographic Properties of Minerals (continued). P
Gypsum CaS042H20 172.17 Mono.lZ/a GypSlUll 4 5.670 15.201 6.533 118.60 494.37 74.440 2.313 46
Alunite* KAk@0dz(0Hki 414.21 Trig. RTm Alunite 3 7.020 17.223 735.04 147.572 2.807 145
Jamsite* KFes(S0dz(‘W6 500.81 Trig. RTm Alunite 3 7.304 17.268 797.80 160.172 3.127 112
Antleritc CU3(S04)(OW4 354.71 orth. Prima Antlerite 4 8.244 6.043 11.987 597.19 89.920 2.959 91 $
Thenarditc NqSO4 142.04 Orth. F&ii Thenardite 8 9.829 12.302 5.868 709.54 53.419 2.659 90 z
Arcanite K2SG4 114.21 Orb. Pmcn Arcanite 4 5.763 10.071 7.476 433.90 65.335
2.661 142 m
Epsomite MgS047HzO 246.48 orth. P212121 Epsomite 4 11.846 12.002 6.859 975.18 146.838
1.678 36 F
v1
Phosphates
Hydroxyspatite Cag(PO&OH 502.32 Hex. P63lm Apatite 2 9.424 6.879 529.09 159.334 3.153 214
Fluorapatite WPWsF 504.31 Hex. P63/m Apatite 2 9.361 6.884 523.09 157.527 3.201 215
Chlorapatite Ca#O&CI 520.77 Hex. P63im Apatite 2 9.628 6.764 543.01 163.527 3.185 137
Monazitc ccPo4 235.09 Mono.P2t/n Monazite 4 6.71 7.04 6.46 104.0 298.7 44.98 5.23 76
Xenotime ym4 183.88 Tetr. I4tlomd Ziicon 4 6.878 6.036 285.54 43.00 4.277 123
Whitlockite W~~~dWQh 2133. Trig. R3c Wbitlockite 3 10.330 37.103 3428.8 688.386 3.099 38
Triphylite LiFcPOq 157.76 Grth. Pmnb Olivine 4 10.334 6.010 4.693 291.47 43.888 3.595 237
Lithiophyllite LiMnP0.j 156.85 Orth. Pmnb Olivine 4 6.05 10.32 4.71 294.07 44.280 3.542 101
Amblygonite* LiAI(F,OH)POd 146.9 Tric. Pi Amblygonite 2 5.18 7.15 5.04 112.11 97.78 67.88 160.20 48.242 3.045 16
AugeIite* AMOW3W 199.9 Mono.C2/m Augelitc 4 13.124 7.988 5.066 112.42 490.95 73.924 2.705 101
Berlinite Am4 121.95 Trig. P3t21 Qu== 3 4.943 10.974 232.21 46.620 2.616 206
Orthosillcates
Garner Group
403.15 Cub. l&d Garnet 8 11.452 1501.9 113.08 3.565 8
Almandine 497.16 Cub. I&d Garnet 8 11.531 1533.2 115.43 4.312 8
Spessartine 495.03 Cub. In% Garnet 8 11.612 1565.7 117.88 4.199 161
Grossular 403.15 Cub. IaTd Garnet 8 11.845 1661.9 125.12 3.600 161
Andradite 508.19 Cub. IaTd Garnet 8 12.058 1753.2 13 1.99 3.850 161
Uvarovite 500.48 Cub. IaTd Garnet 8 11.988 1722.8 129.71 3.859 161
Olivine Group
Forsterite MgzSiQ 140.70 orth. Pbw?z Olivine 4 4.7534 10.1902 5.9783 289.58 43.603 3.221 69
Fayalite FqSiO4 203.77 Orth. Pbnm Olivine 4 4.8195 10.4788 6.0873 307.42 46.290 4.402 69
Tephroitc MnzSi04 201.96 Orth. Pbnm Olivine 4 4.9023 10.5964 6.2567 325.02 48.939 4.121 69
Liebenbergite Ni2Si04 209.50 Ortb. Ptnm Olivine 4 4.726 10.118 5.913 282.75 42.574 4.921 124
Ca-olivine Ca2Si04 172.24 Orth. Phm Olivine 4 5.078 11.225 6.760 385.32 58.020 2.969 50
Co-olivine CqSiO4 209.95 Orth. Pbmn Olivine 4 4.7811 10.2998 6.0004 295.49 44.493 4.719 32
Monticellite CaMgSiOd 156.48 orth. Pbnm Olivine 4 4.822 11.108 6.382 341 .x4 51.412 3.040 165
Kirschsteinite CaFeSi 188.01 Orth. Pbnm Olivine 4 4.844 10.577 6.146 314.89 47.415 3.965 32
Table 1. Crystallographic Properties of Minerals (continued).
Mineral Formula Crystal Space Stlucture z a Y Unit Cell Molar Density Ref.
Fonnula
Weight System Group Type (A) 8, (“1 Vol (A3) Vol (cm3) (calc)(Mg/m3)
Zircon Group
Zircon ZrSiO4 183.30 Tetr. Irlllumd Zircon 4 6.6042 5.9796 260.80 39.270 4.668 95
Hafnon HfSi04 210.51 Tetr. 14~lumd Zircon 4 6.5125 5.9632 257.60 38.787 6.916 212
Thorite* ThSiO4 324.1 Tetr. 14tlumd Zircon 4 7.1328 6.3188 321.48 48.401 6.696 222
Coffinhe’ USi 330.2 Tetr. 14@zd Zircon 4 6.995 6.236 305.13 45.945 7.185 115
Wilhife Group
Phenacite BezSi04 110.10 Trig. R7 Wiilemite 18 12.472 8.252 1111.6 37.197 2.960 241
Willemite ZnzSiO4 222.82 Trig. RI Willemite 18 13.971 9.334 1577.8 52.195 4.221 207
Eucryptite LiAlSIO4 126.00 Trig. Rj Willemite 18 13.473 9.001 1415.0 41.341 2.661 97
Ahminosilicate Group
Andalusite Al2SiOS 162.05 Orth. Pnnm Andalusite 4 7.7980 7.9031 5.5566 342.44 51.564 3.1426 233
Sillimanite AlzSi05 162.05 Orth. Pbam Sillimanite 4 1.4883 1.6808 5.7774 332.29 50.035 3.2386 233
Kyanite A12SiO5 162.05 Tric. PI Kyanite 4 1.1262 7.8520 5.5741 89.99 101.11 106.03 293.72 44.221 3.6640 233
Topaz Al$i04(OH,E)2 182.0 Orth. Pbnm Topaz 4 4.6651 8.8381 8.3984 346.21 52.140 3.492 242
Humite Group
Norbergite* Mg3Si04F2 203.0 Orth. fhm Norbergite 4 4.7104 10.2718 8.7476 423.25 63.13 3.186 13
Chondrodite* MgstSiOdzF2 343 .I Monof2tlb Chondrodite 2 4.7284 10.2539 7.8404 109.06 359.30 108.20 3.158 74
Humite* MmMW3Fz 484.4 Oh. fhm Hurnite 4 4.7408 10.2580 20.8526 1014.09 152.70 3.159 183
Clinohumite* MgdSQhFz 624.1 Mono. f&lb Clinohumite 2 4.7441 10.2501 13.6635 100.786 652.68 196.55 3.259 186
Staurolite* Ee.+ALtaSixO&OH)2 1704. Mono. c2/m Staurolite 1 7.8713 16.6204 5.6560 90.0 139.94 445.67 3.823 209
Other Ortbosilicotes
Titanite CaBSi 196.06 Mo~o.~?$/Q Titanite 4 7.069 8.122 6.566 370.23 55.748 3.517 213
Datolite CaBSiOd(OH) 159.94 Mono.f&lc Datolite 4 4.832 7.608 9.636 90.40 354.23 53.338 2.999 63
Gadolinite* BE$eB2SizOto 604.5 Mono f&/a Datolite 2 lO.ooo 7.565 4.786 90.31 360.69 108.62 5.565 148
Chloritoid* FeA12Si05(OH)z 251.9 Tric. Pi Chioritoid 4 9.46 5.50 9.15 97.05 101.56 90.10 462.72 69.674 3.616 88
Sapphirine* MgwWit.502o 690.0 Mono.fZ& Sapphirine 4 11.266 14.401 9.929 125.46 1312.11 197.57 3.493 149
Prehnite* Ca2Ai(Al,Si3)0to(OH)2 412.391 Orth. fxm Prehnite 2 4.646 5.483 18.486 470.91 141.82 2.908 170
Pumpelleyite C~(Mg~eAl)AlaSi~~O~42(0H)r~l915.1 Mono.CZlm Pumpelieyite 1 8.831 5.894 19.10 97.53 985.6 593.6 3.226 172
Axinite HFeCa&BSbOra 570.12 Tric. fi Axinite 2 1.151 9.199 8.959 91.8 98.14 77.30 569.61 171.54 3.324 220
Sorosiiicates & Cyciosiiicates
Epidote Group
Zoisite Cafil&Otz(OH) 454.36 ortb. funa Zoisite 4 16.212 5.559 10.036 904.41 136.19 3.336 52
Clinozoisite Ca2Al$Si3012(OH) 454.36 Mono. Pztlm Epidote 2 8.819 5.583 10.155 115.50 454.36 136.83 3.321 52
Hancockite* Ca(Rh,Sr)FeAl2Si30r~(OH) 590.6 Mono.f21/m Epidote 2 8.96 5.67 10.30 114.4 416.5 143.5 4.12 53
Allanite* CaBE(Al,Fe)$i30t2(0H) 565.2 Mono.f2t/m Epidote 2 8.927 5.761 10.150 114.77 413.97 142.74 3.96 53
Epidote* Ca~FeAl#i30t2(0H) 454.4 Mono.f 2t/m Epidote 2 8.8877 5.6275 10.1517 115.383 458.73 138.15 3.465 70
Melilite Group
Melilite* CaNaAlSizq 258.2 Ten. fa21rn Meiilite 2 7.6344 5.0513 294.41 88.662 2.912 134
Gehlenite* Ca;?AlAiSi@ 214.2 Tetr. fZ21m Melilite 2 7.7113 5.0860 302.91 91.220 3.006 135
Akerrnanite Ca2MgSi207 212.64 Tetr. fZ2lrn Meiiiite 2 7.835 5.010 307.55 92.6 19 2.944 116
Olher Sorosilicates and Cyclosilictaes
Lawsonite CaAizSiz07(OH)$I20 314.24 orth. ccmm Lawsonite 4 8.795 5.841 13.142 615.82 101 .I6 3.088 19
BUYi Be3Ai2SieOtx 537.51 Hex. P6lmmc Beryl 2 9.2086 9.1900 614.89 203.24 2.645 152
Cordierite’ MgzA4SisOts 584.97 orth. ccmm Betyl 4 17.079 9.730 9.356 1554.77 234.11 2.499 45
Table 1. Crystallographic Properties of Minerals (continued). m
Mineral Formula Crystal Space structure 2 a Y Unit Cell Molar Density Ref.
Fotmula
Weight System Group Type (A) (S, (“) Vol (A3) Vol (cm3) (calc)(Mg/m3)
Tourmaline* NaFe~Al&S~0~7(0H)~ 1043.3 Trig. R3m Tounnaline 3 15.992 7.190 1592.5 319.7 3.263 66
Vesuvianite* CatgFezMgAltoSitsqo(OH,F)s2935. Tetr. P4/nnc Vesuvianite 2 15.533 11.778 2841.8 421.9 3.429 6
Chain Sillfates
EnstotifelFerrosilite Group
EIlStatik f+ww6 200.79 Oh. Pbca Orthopyroxene 8 18.227 8.819 5.179 832.49 62.676 3.204 197
Ferrosilite Fe#i& 263.86 Orth. Pbca Orthopyroxene 8 18.427 9.076 5.237 875.85 65.941 4.002 197
Clinoenstatite MgzSizOs 200.79 Mono. P2tlc Clinoenstatite 4 9.626 8.825 5.188 108.33 418.36 62.994 3.188 150
Clinoferrosilite Pe2Si206 263.86 Mono.P&lc Clinoenstatitc 4 9.7085 9.0872 5.2284 108.43 437.60 65.892 4.005 33
Clinopyroxme Group
Diopside CaMgSi& 216.56 Mono. C2Ic Clincpymxene 4 9.746 8.899 5.251 105.63 438.58 66.039 3.279 39
Hedenbergitc CaPeSi 248.10 Mono.CVc Clinopyroxene 4 9.845 9.024 5.245 104.70 450.72 67.867 3.656 39
Jade& Ntilsi206 202.14 Mono. C2lc Clinopyroxene 4 9.423 8.564 5.223 107.56 401.85 60.508 3.341 39
Acmite NaFeSizOs 23 1.08 Mono. n/c Clinopyroxene 4 9.658 8.795 5.294 107.42 429.06 64.606 3.516 44
Cosmochlnr NaCrsi206 227.15 Mono.CZlc Clinopyroxene 4 9.579 8.722 5.261 107.37 419.98 63.239 3.592 39
Spodumene LiAlSi206 186.09 Mono.CUc Clinopymxene 4 9.461 8.395 5.218 110.09 389.15 58.596 3.176 39
Ca-Tschennaks CaAlAlSiOs 218.20 Mono. CL/c Clinopyroxene 4 9.609 8.652 5.274 106.06 421.35 63.445 3.438 164
Pyroxenoid Group
Wollastonite CajSi3Og 348.49 Tric. Ci 4 10.104 11.054 7.305 99.53 100.56 83.44 788.04 118.66 2.937 163
Bustamite* GaPe.dSi309 358.6 Tric. Ii Bustantite 4 9.994 10.946 7.231 99.30 100.56 83.29 764.30 115.09 3.116 163
Rho&mite MqSisOts 655.11 Tric. Pi Rhodonite 2 7.616 11.851 6.701 92.55 94.35 105.67 579.84 174.62 3.752 155
Pyroxmangite Mn7Si70a 917.16 Tric. Pi Pyroxmangite 2 6.721 7.603 17.455 113.18 82.27 94.13 812.31 244.63 3.749 155
Aenigmatite’ Na@5TiTiSkOzo 867.5 Tric. Pi Aenigmatite 2 10.406 10.813 8.926 104.93 96.87 125.32 744.52 224.21 3.869 40
Pectolitc’ HNaCa&Q 332.4 Tric. Pi Pectolite 2 7.980 7.023 7.018 90.54 95.14 102.55 382.20 115.10 2.888 163
Petalite LiAlS&Ote 306.26 Mono.PUa Petalite 2 11.737 5.171 7.630 112.54 427.71 128.80 2.318 219
Amphibole Group
Gedrite* Na,s(Mg$ez)A12Si,jO22(OH)2 853.23 Orth. Prima Orthoamphibole 4 18.531 17.741 5.249 1725.65 259.8 3.184 169
Anthophyltite* C%sFez)Sis022(OH)2 843.94 orth. Pm Onhoamphibole 4 18.560 18.013 5.2818 1765.8 265.9 3.111 58
Cummingtonite* ~MgsFez)SisOzz(OH)2 843.94 Mono. C2lm Amphibole 2 9.51 18.19 5.33 101.92 902.14 271.7 3.14 60
Tremolite* ~a,~C@WWzz(OH)z 823.90 Mono Calm Amphibole 2 9.863 18.048 5.285 104.79 909.60 273.9 3.01 92
Pargas&* NaCa2FeMg,tAl#i&22(OH)2 864.72 Mono.CZ/m Amphibole 2 9.910 18.022 5.312 105.78 912.% 274.9 3.165 185
Glaucophane* Naz(FeMaAlrSisOn~OH~~ 789.44 Mono.C2/m Amphibole 2 9.541 17.740 5.295 103.67 870.8 262.2 3.135 168
Sheet Slllctaes
Talcand Pyrophyllite
Talc &s%OldOH)z 379.65 Tric. Ci Talc 2 5.290 9.173 9.460 90.46 98.68 90.09 453.77 136.654 2.776 175
Pyrophyllite A12Who@H)2 360.31 Tric. Ci Talc 2 5.160 8.966 9.347 91.18 100.46 89.64 425.16 128.036 2.814 125
Trioclohedral Mica Group
An&e* KFe3(AlSi@t0(OH)2 511.9 Mono. (X/m 1M 2 5.386 9.324 10.268 100.63 506.82 152.63 3.215 94
Phlogopite* KMgfi&OldOH)2 417.3 Mono.C2/m IM 2 5.308 9.190 10.155 100.08 487.69 146.87 2.872 94
Lepidolite* KAlLi2AISi30t0(OH)2 385.2 Mono.C2/c =41 4 5.209 9.053 20.185 99.125 939.82 141.52 2.124 192
Lepidolite* KAU&AISi30tdOH)2 385.2 Mono. C2Ic 2M2 4 9.04 5.22 20.21 99.58 940.38 141.60 2.791 193
LepidolW KAlLifiISi3Oto(OH)2 385.2 Mono.C2lm 1M 2 5.20 9.01 10.09 99.28 466.6 140.5 2.825 194
Ziiwaldite* K(AlFeLi)AlSi3Otu(OH)2 434.1 Mono.CZ/m 1M 2 5.296 9.140 10.096 100.83 480.0 144.55 2.986 82
Table 1. Crystallographic Properties of Minerals (continued).
FomntlaCrystal Space structure z a Y Unit Ceii Molar Density Ref.
Mineral Formula
Weight System Group Type (4 (“) VoI (A3) Vol (cm3) (calc)(Mg/m3)
Chlorite Group
Chlorite* 555.8 Mono.C2/m Chlorite-IIb2 2 5.327 9.227 14.327 96.81 699.24 210.57 2.640 109
Chlorite* 555.8 Tric. Ci Chlorite-IIW 2 5.325 9.234 14.358 90.33 97.38 90.00 700.14 210.85 2.636 108
clay Group
NWXite 258.16 Mono.Cc Nacrite 4 8.909 5.156 15.697 113.70 658.95 99.221 2.602 24
Dickite 258.16 Mono.Cc Dickite 4 5.178 8.937 14.738 103.82 662.27 99.721 2.588 22
Kaoiinite 258.16 Tric. PI Kaolinite 2 5.1554 8.9448 7.4048 91.700 104.862 89.822 329.89 99.347 2.599 22
Amesite* 278.7 Tric. Cl Amesite 4 5.319 9.208 14.060 90.01 90.27 89.96 688.61 103.69 2.778 86
Lizardite* 277.1 Trig. P31m Lizardite IT 1 5.332 7.233 178.09 107.26 2.625 144
Tektosiiicates
Silica Group
Qu- SiO2 60.085 Trig. f322l 3 4.1934 5.4052 113.01 22.688 2.648 127
Coesite SiO2 60.085 Mono.C2/c Coesite 16 7.1464 12.3796 7.1829 120.283 548.76 20.657 2.909 210
Tridymite SiO2 60.085 Mono.Cc Tridymite 48 18.494 4.991 25.832 117.75 2110.2 26.478 2.269 ill
Cristobaiite SiO2 60.085 Tar. f4t2t2 Cristobalite 4 4.978 6.948 172.17 25.925 2.318 173
Stisbovite SiO2 60.085 Tetr. W&nm Rutiie 2 4.1790 2.6651 46.54 14.017 4.287 20
Feldspar Group
Sanidine KAISi& 278.33 Mono.CZm Sanidine 4 8.595 13.028 7.179 115.94 722.48 108.788 2.558 199
orthoclase KAISi30s 278.33 Mono.CZlm Sanidine 4 8.561 12.996 7.192 116.01 719.13 108.283 2.571 47
Micro&e KAiSisOs 278.33 Tric. Ci Sanidine 4 8.560 l2.%4 7.215 90.65 115.83 87.70 720.07 108.425 2.561 31
High Aibite NaAiSigOs 262.23 Tric. Ci Albite 4 8.161 12.875 7.110 93.53 116.46 90.24 667.12 100.452 2.610 234
Low Aibite NaAiSi& 262.23 Tric. Ci Albite 4 8.142 12.785 7.159 94.19 116.61 87.68 664.48 loo.054 2.621 89
Anorthite CaAI&Os 278.36 Tric. Pi Anorthite 8 8.173 12.869 14.165 93.11 115.91 91.261 1336.35 100.610 2.165 228
Ceisian BaAi2Si2Os 375.47 Mono.I;?/c Anorthite 8 8.627 13.045 14.408 115.22 1466.90 110.440 3.4cm 158
Fekispathoid Group
Leucite KAiSizOe 218.25 Tetr. I4tla Leucite lb 13.09 13.75 2356. 88.69 2.461 139
Kaisilite KAiSi04 158.17 Hex. P63 NepheIine 2 5.16 8.69 200.4 60.34 2.621 178
Nepheiine KNa@J&tOts 584.33 Hex. P63 Nepheiine 2 9.993 8.374 724.19 218.09 2.679 64
Meionite* Ct&&jSi&&@ 932.9 Tetr. P42/n Scapolite 2 12.194 7.557 1123.7 338.40 2.757 131
Marialitef NaqAI,jSi,jO~Cl 863.5 Ten. P42ln Scapoiite 2 12.059 7.587 1103.3 332.26 2.599 132
Zeolite Group
AnaIcime* NatsAIt&20g~i 6H2O 3526.1 Tetr. I4llacd Analcime 1 13.721 13.735 2585.8 1557.4 2.264 138
Chabazite’ Ca$i&sOw i3HzO 1030.9 Trig. R%I Chabazite 1 13.803 15.075 2487.2 499.4 2.065 37
Mordenite* KsAi&~Oga24H20 3620.4 Ortb. Cmcm Mordenite 1 18.167 20.611 7.529 2819.2 1698.0 2.132 153
CIinoptiioIite* KNa$J+Ai&+&~24H20 2750.0 Mono.C2/m Heuiandite 1 17.633 17.941 7.400 116.39 2097.1 1263.O 2.177 211
Heulandite’ Ca4Kdh%&n26H20 2827.7 Mono. CZm Heuiandite 1 17.715 17.831 7.430 115.93 2132.2 1284.3 2.221 4
Thomsonite* NaCa2AisSis02cbH20 671.8 Chth Pncn Thomsonite 4 13.089 13.047 13.218 2257.3 339.9 2.373 5
Table 1. Crystallographic Properties of Minerals (continued). 00
Harmotome* Ba$a,5Al$itt03~12H20 1466.7 Mono. P21/m Phillipsite 1 9.879 14.139 8.693 124.8 996.9 600.5 2.443 184
Phillipsite* K2.5Cal.gAlgSit0032.12H20 1291.5 Mono. P21/m Phillipsite 1 9.865 14.300 8.668 124.2 1011.3 609.1
Laumontite* CaA1$%401~4H~O 470.44 Mono Am Laumontite 4 7.549 14.740 2.120 184 z1
13.072 90. 90. 111.9 1349.6 203.2 2.315 202
Natrolite* NazA12Si30te2H20 380.23 Orth. Fdd2 Natrolite 8 18.326 18.652 6.601 2256.3 169.87 2.238 174 E
Sodalite* NqA13Si301~CI 484.6 Cub. Pii3n Sodahte 2 8.870 697.86 210.16 2.306 133 X
StiIbite* Nal,3Ca4.~AIleSi2C,072~34H~02968. Mono. C2lm Stilbite 1 13.64 18.24 11.27 128.0 2210. 1331. 2.23 71 ii
ScoIecite* CaAl~Si30te~3H20 392.34 Mono Fd Natrolite 8 18.508 18.981 6.527 90.61 2292.8 172.62
Gonnardite* Na&qAlgSitt0~12H~O 1626.04 Tetr. hi2d 2.273 107 P
Natrolite 1 13.21 6.622 1155.6 696.00
Edingtonite* Ba2A14SisO2e8H20 997.22 Tetr. PTi2lm Edingtonite 1 9.581 6.526 599.06 360.81 2.336
2.764 141
140 2
Gismondine* Ca&IsSia032.16Hfl 1401.09 Mono. P21la Gismondine 1 10.024 10.626 9.832 92.40 1024.3 630.21 2.223 226 8
Garronite* NaCa&I,jSireG3~13H~O 1312.12 Tetr. lzm2 Gismondine 1 9.9266 10.3031 1015.24 611.48 2.146 9 m
Merlinoite+ K&afilgSi~0~24H20 2620.81 olth. Immm Merlinoite 1 14.116 14.229 9.946 1982.28 1193.92 2.195 72 3
Ferrierite* NgKMgAl$%3t@Zl8H20 2614.2 Mono.P2rla Fenierite 1 18.886 14.182 7.470 90.0 2000.8 1205.1 2.169 79 2
Fetrierite+ In
NaKMgfil7Si2gQzlBH20 2590.3 Orth. lmmm Ferrierite I 19.236 14.162 7.527 90.0 2050.5 1235.0
Faujasite, NqCaAl.&0~16H20 1090.9 Cub. F&n Sodalite 16 24.74 15142. 570.02 1.914 18
2.097 80 F
Ericnite* MgNaKZCa2AlgSi~707~18H202683.1 Hex. P63lmmc Erionite I 13.252 14.810 2252.4 1356.6 I .978 201 rA
Cancrinite* Car,~Na&leSi,@~~l.6C02 1008.5 Hex. P63 Cancrinite I 12.590 5.117 702.4 423.05 2.383 81
Pollucite* CsAISi#s 312.06 Cub. la?d Analcime 16 13.682 2561.2 96.41 3.237 156
Brewsterite* SrAlfiis01~5H20 656.17 Mono. P21lm Brewsterite 2 6.767 17.455 7.729 94.40 910.2 274.12 2.394 10
High Pressure Silicates
Phase B Group
Phase B Ww-%%KW2 741.09 Mono. P21/c PhsB 4 10.588 14.097 10.073 104.10 1458.4 219.567 3.380 59
Anhydrous B MmSidh 864.78 Orth. Pmcb AnhB 2 5.868 14.178 10.048 835.96 25 1.749 3.435 59
Superhydrous B bmWhdOW4 619.40 Chth. Pnnm PhsB 2 5.0894 13.968 8.6956 618.16 186.159 3.327 166
MgSiO+roup
MgSiOg-perovskite MgSi03 100.40 Grth. Pbnm Perovskite 4 4.7754 4.9292 6.8969 162.35 24.445 4.107 103
MgSiO+lmenite MgSiO3 100.40 Trig. RJ Ilmenite 6 4.7284 13.5591 262.54 26.354 3.810 102
MgSiOs-garnet MgSi03 100.40 Tetr. 141/a Garnet 32 11.501 11.480 1518.5 28.581 3.513 7
Wadsleyiie Group
Wadsleyite MgzSiO4 140.71 orth. Imma Wadsleyite 8 5.6983 11.4380 8.2566 538.14 40.515 3.4729 104
I%-Co$SiO4 CqSiO4 209.95 Ortb. fmma Wadsleyite 8 5.753 11.524 8.340 552.92 41.628 5.044 151
Silicate Spine1 Group
rM8zSQ Mg#iO, 140.71 Cub. F&m Spine1 8 8.0449 524.56 39.493 3.563 196
y-Fez%04 FezSiO4 203.78 Cub. F&m Spine1 8 8.234 558.26 42.030 4.848 236
y-Ni2SiO4 NizSi04 209.95 Cub. Fa.h Spine1 8 8.138 538.96 40.511 5.174 236
*02SiO4 CqSiO4 209.50 Cub. f%%n Spine1 8 8.044 520.49 39.187 5.346 151
Silica Group
Coesite SiO2 60.085 Mono. C2lc Coesite 16 7.1464 12.3796 7.1829 120.283 548.76 20.657 2.909 210
Stishovite SiO2 60.085 Tetr. P4dmnm Kutile 2 4.1790 2.6651 46.54 14.017 4.287 20
Halides
Halite N&l 58.443 Cub. Fmh Halite 4 5.638 179.22 26.985 2.166 235
Sylvite KCI 74.555 Cub. F&n Halite 4 6.291 248.98 37.490 1.989 235
Villiaumite NtiF 41.988 Cub. Fdm Halite 4 4.614 98.23 14.791 2.839 235
Carobbiite KF 58.100 Cub. Far% Halite 4 5.34 152.3 22.93 2.53 235
Table 1. Crystallographic Properties of Minerals (continued).
Mineral Formula Crystal Space Structure Z a Y Unit Cell Molar Density Ref.
Formula
Weight System Group Type (A) (“1 Vol (K3) Vol (cm3) (calc)(h4g/m3)
Fluorite CaFz 78.077 Cub. Fdm Fluorite 4 5.460 162.77 24.509 3.186 232
Frankdicksonite BaF2 175.34 Cub. Fm%r Fluorite 4 6.1964 237.91 35.824 4.894 180
Sellaite MtPz 62.309 Tetr. P42/mnm Rut& 2 4.660 3.078 66.84 20.129 3.096 101
CdOIllel HszCh 472.09 Tetr. 14/mmm Calomel 2 4.45 10.89 215.65 64.94 1.269 101
Cryolite Na3AIFs 209.95 Mono. P21/n Cryolite 2 5.40 5.60 1.78 90.18 101
Neighbceite NaMgF3 104.30 orth. Pcmn Perovskite 4 5.363 7.676 5.503 226.54 34.11 3.058 101
Chlorargyrite AgCl 143.32 Cub. F&m Halite 4 5.556 171.51 25.83 5.550 101
Iodyrite AsI 234.17 Hex. P63mc Wurtzite 2 4.58 7.49 136.06 40.98 5.730 101
Nantokite CUCI 98.99 Cub. Fz3m 4 5.418 159.04 23.95 4.134 101
Sulfides
Pyrrhotite Fe7% 647.44 Trig. P3t Pyrrhotite 3 6.8613 17.062 696.84 139.90 4.628 62
Pyrite FeSz 119.98 Cub. Pa3 Pyrite 4 5.418 159.04 23.95 5.010 29
Cattierhe Cd2 123.06 Cub. Pd Pyrite 4 5.5385 169.89 25.582 4.811 162
Vaesite NiSz 122.84 Cub. Pd Pyrite 4 5.6865 183.88 27.688 4.437 162
Marcasite Fe& 119.98 orth. Pnnm Marcasite 2 4.436 5.414 3.381 81.20 24.45 4.906 30
Troilite FeS 89.911 Hex. PT2c Troilite 12 5.963 11.754 361.95 18.167 4.839 117
Smythite (kWgS11 855.3 Trig RTm Smythite 1 3.4651 34.34 357.08 215.07 3.977 221
Chalcopyrite CuFeS2 183.51 Tetr. lji2d Chalcopyrite 4 5.289 10.423 291.57 43.903 4.180 84
Cubanite CuFezS3 271.43 Orth. Pcmn Cubanite 4 6.467 11.117 6.231 447.97 67.453 4.024 218
Covelllite cus 95.60 Hex. Pbglmmc Covellite 6 3.7938 16.341 203.68 20.447 4.676 56
Chalcocite cu2s 159.14 Mono.PZt/c Chaicccite 48 15.246 11.884 13.494 116.35 2190.9 27.491 5.789 51
Tetrahedrite Cut2FeZnSb& 1660.5 Cub. Ia33m Tetmhedrite 2 10.364 1113.2 335.25 4.953 179
Bon& CusFeS4 501.80 Orth. Pbca Bomite 16 10.950 21.862 10.950 2521.3 98.676 5.085 122
Enargite Cu3AsS4 393.80 Orth. Pmt12~ Enargite 2 7.407 6.436 6.154 296.63 89.329 4.408 2
Niccolite Ni4s 133.63 Hex. Ptqlmmc NiAs 2 3.619 5.035 57.11 17.199 7.770 240
Cobaltite CoAsS 165.92 Onh. PcaZl Cobaltite 4 5.582 5.582 5.582 173.93 26.189 6.335 71
Sphalerite zns 91.434 Cub. F;i3m Sphalerite 4 5.4053 157.93 23.780 4.097 239
Wurtzite(2H) zns 97.434 Hex P6pc Wurtzite 2 3.822-l 6.2607 79.23 23.860 4.084 119
Greenockite CdS 144.464 Hex P63mc Wurtzite 2 4.1348 6.7490 99.93 30.093 4.801 235
Pentlandite NisFe& 773.5 Cub. F&-m IT&e 4 10.044 1013.26 152.571 5.069 87
Alabandite MnS 87.02 Cub. F&m Halite 4 5.214 141.I5 21.344 4.076 224
Galena PbS 239.25 Cub. F&m Halite 4 5.9315 208.69 31.423 7.614 160
Clausthalite PbSe 286.15 Cub. Fdm I talite 4 6.1213 229.37 34.537 8.285 160
Altaite PbTe 334.79 Cub. F&m Halite 4 6.4541 268.85 40.482 8.270 160
MolyMenite(2H) Md2 160.07 Hex P63lmmc Molybdenite 2 3.1602 12.294 106.33 32.021 4.999 28
Tungstenite ws2 247.92 Hex P63/mmc Molybdenite- -2H2 3.1532 12.323 105.77 31.853 7.785 203
Acantbite h.s 247.80 Mono.PZl/c Acanthite 4 4.231 6.930 9.526 125.48 227.45 34.248 7.236 190
Argentite AgzS 247.80 Cub. lm3m Argentite 2 4.86 114.79 34.569 7.168 41
Proustite AgsAsSj 494.72 Trig. R3c Proustite 6 10.82 8.69 881.06 88.44 5.594 55
Pyrargyritc has% 541.55 Trig. R3c Proustite 6 Il.01 8.72 920.42 92.39 5.861 55
Cinnabar HgS 232.65 Trig. P&‘l Cinnabar 3 4.145 9.496 14i.29 28.361 x.202 14
Metacinnabar H@ 232.65 Cub. Fq3m Sphalerite 4 5.8717 202.44 30.482 7.633 13
Coloradoitc HgTe 328.19 Cub. F;i3m Sphalerite 4 6.440 267.09 40.217 8.161 223
Stibnite SW3 339.69 Orth. Prima Stibnite 4 11.302 3.8341 11.222 486.28 73.222 4.639 143
Orpiment As2S3 246.04 Mono. P21/n orpiment 4 11.475 9.571 4.256 90.68 467.68 70.422 3.494 154
Table 1. Crystallographic Properties of Minerals (continued). E
n
MiIlemI Formula Crystal Space StNCtUR z iJ Y Unit CeII Molar Density Ref.
Formula
Weight System Group 5~ (4 8, P) Vol (A3) Vol (cm3) (calc)(Mg/m3)
-
Re&ar AsS 106.99 Mono.PZl/n Realgar 16 9.325 13.571 6.587 106.38 799.15 30. IO7 3.554 154
Bismuthinite Bi$$ 514.15 Orth. Pmcn Stibnite 4 3.981 11.147 11.305 501.67 75.539 6.806 110
Hazelwoodite Ni& 240.26 Trig. R32 Hazelwoodite 4.0718 89.459 89.459 89.459 67.50 40.655 5.910 171 6
COOperitc PtS 227.15 Tetr. P4~mmc Cooperite 2 3.465 6.104 13.29 22.070 10.292
Vysotskite PdS 138.46 Tetr. P42/m Cooperite 8 6.429 6.611 273.25 20.572 6.731 35
27 $:
X
Millerhe NiS 90.77 Trig. R3m Milkrite 9 9.6190 3.1499 252.4 16.891 5.374 181 .-
ijn”
Linneaite t&s4 305.06 Cub. F&n Spine1 8 9.406 832.2 62.652 4.869 120
Polydymite Ni& 304.39 Cub. Fd%n Spine1 8 9.489 854.4 64.326 4.132 49 ?
Violarite FeNi$$ 301.52 Cub. F&m Spine1 8 9.465 847.93 63.839 4.723 49
49 2
Greigite Fe& 295.80 Cub. F&m Spine1 8 9.875 %2.97 72.499 4.080 238 bl
Da&reel&e FeCrts,1 288.10 Cub. F&m Spine1 8 9.995 998.50 75.175 3.832 205 iz
Loellingite FeAs2 205.69 orth. Pnnm Loellingite 2 5.3001 5.9838 2.8821 91.41 21.521 7.412 136
Arsenopjrite FeAsS 162.83 Mono.C2l/d Arsenopyrite 8 6.546 9.451 5.649 89.94 349.48 26.312 6.189 68
Native Elements
Diamond C 12.011 Cub. Fdh Dimmnd 8 3.56679 45.38 3.4163 3.5158 235
Graphite C 12.011 Hex. Pbj/mmc Graphite 4 2.456 6.696 34.98 5.261 2.281 235
Silicon Si 28.086 Cub. Fdh Diamond 8 5.43070 160.16 12.058 2.329 235
Sulfur(a) S 32.064 Orth. Fd&i Sulfur 128 10.467 12.870 24.493 3299.5 15.443 2.076 235
SUWP) S 32.064 Mono. P2t Sulfur 48 10.926 10.885 10.790 95.92 1276.41 16.016 2.002 78
Kamacite Fe 55.847 Cub /m& a-hm 2 2.8665 23.55 7.093 7.873 235
Taenite FeNi 114.557 Cub Ft&n Taenite 32 7.168 368.29 13.864 8.263 235
Nickel Ni 58.710 Cub. F&n FCC 4 3.52387 43.76 6.590 8.910 235
Copper CU 63.540 Cub. Fn&n FCC 4 3.61496 41.2A 7.113 8.932 235
Arsenic AS 14.922 Trig. Rsrn Arsenic 18 3.7598 10.5475 129.12 4.321 17.340 200
Tin Stl 118.690 Tetr. f4tlamd Tin 4 5.8197 3.17488 107.54 16.194 7.329 235
Ruthenium Ru 101.070 Hex. P63/mmc HCP 2 2.7056 4.2803 27.14 8.172 12.368 85
Rhodium Rb 102.905 Cub. F&m FCC 4 3.8031 55.01 8.283 12.424 235
Palladium Pd 106.40 Cub. Fmh FCC 4 3.8898 60.16 9.059 11.746 235
Silver 43 107.87 Cub. F&m FCC 4 4.0862 68.23 10.273 17.500 235
Antimony Sb 121.75 Trig. RTm Arsenic 6 4.3083 Il.2743 180.06 18.075 6.736 235
Tellurium Te 127.60 Trig. P3t21 Selenium 3 4.456 5.921 101.82 20.441 6.242
Iridium Ir 192.20 Cub. F&m FCC 4 3.8394 56.60 8.522 22.553 235
Osmium OS 190.20 Hex. P63/mmc HCP 2 2.7352 4.3190 27.98 8.427 22.570 235
Platinum Pt 195.09 Cub. F&m FCC 4 3.9231 60.38 9.092 21.458 235
Gold AU 196.967 Cub. F&m FCC 4 4.07825 67.83 10.214 19.285 235
Lead Fb 207.190 Cub. Fm% FCC 4 4.9505 121.32 18.268 11.342 235
Bi 208.980 Trig. R%n Arsenic 6 4.54590 11.86225 212.29 21.311 9.806 235
SMYTH AND MCCORMICK 11
Acknmvledgements.The authors thank Stephen J. Guggenheim National Science Foundation Grant EAR 91-05391 and U.S. Dept.
(University of Illinois) and two anonymous reviewers for con- of Energy Office of Basic Energy Sciences.
structive criticism of the manuscript. This work was supported by
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SMYTH AND MCCORMICK 17
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Thermodynamic Properties of Minerals
Alexandra Navrotsky
Cp=3nR[1+klT-1+k2T-2+k3T-31+
A + BT + C p (disordering) (3)
L
500
400
liquid
G
300
0 Tm
E
+ 200
0" 100
0 t
4 0 400 600 1200 1600 2000
Fig. 2. Enthalpy and heat capacity in CaMgSi206. a glass-forming system,data from [21].
161,Berman [5], JANAF [18], and Fei et al. [9j for such where i is taken over the oxide componentsof the glassor
equations. liquid [22, 331. The partial molar heat capacitiesof the
In glass-forming systems, seeFig. 2. the heat capacity oxide componentsin glassesand melts, CpV,are given in
of the glass from room temperatureto the glasstransition
is not very different from that of the crystalline phase. Table 3.
For CaMgSi206 Cp, glass= 170 J/mol*K at 298 K, 256
3. MOLAR VOLUME, ENTROPY, ENTHALPY OF
J/mol=K at 1000 K; Cl,, crystal = 167J/mobK at 298 K,
FORMATION
249 J/mol*K at 1000 K [213. At Tg, the viscosity
decreases,and the volume and heat capacity increase, Table 4 lists enthalpiesand entropiesof formation of
reflecting the onset of configurational rearrangementsin selected minerals from the elements and the oxides at
the liquid [27]. The heat capacity of the liquid is severaltemperatures. Theserefer to the reaction
generally larger than that of the glass (see Table 2) and,
except for cases with strong structural rearrangements
(such as coordination number changes),heat capacitiesof aA + bB + CC + “/2 02 = AaBbCcOn (3
liquids dependonly weakly on temperature.
For multicomponent glasses and liquids with and
compositions relevant to magmatic processes, heat
capacities can, to a useful approximation, be given as a do] + bBOm +cCOn=AaBbCcOn (6)
sum of terms depending on the mole fractions of oxide
components, i.e., partial molar heat capacities are respectively, where A, B, C are different elements (e.g.
relatively independentof composition. Then Ca, Al, Si), 0 is oxygen, and referencestatesare the most
stableform of the elementsor oxidesat the temperaturein
Cp = CXi Cp (4) question. The free energy of formation is then given by
i
Glass/291 LiquidL22,28,33I
298 K 400K IOOOK 1500K
SiO2 44.04 52.39 70.56 82.6
Ti02 44.92 58.76 84.40 109.2
CaMgSi206 (diopside) -3200.5 t51 -585.2f51 -3209.61311 -579.3t311 -l42.6[51 -5.1m -155.6[31] -9.4 (311
NaAlSi 308 (high albite) -3924.2L311 -730.61311 -3925.8[311 -735.31311 -146.9B11 39.0151 -156.0[31] 24.9 prl
KAlSi 308 (sanidine) -3959.6J311 -737.5L311 -3962.1 1311 -744.1 1311 -208.0[311 36.1 f51 222.9 t311 12.3 1311
CaA12Si2Og (anorthite) -4228.7 I51 -756.7 I51 -4239.4(331] -764.61311 -96.5 prl 28.7 151 -lOO.9(311 21.4(311
Mg 3N 2Si30 12 (pyrope) -6286.5151 -1176.315] -6317.0(31] -1211.3(311 -74.2[311 -l9.9[51 -79.2pI1 -4.0 (311
Mg2AlqSi5Olg (cordierite) -915g.7151 -1702.0L51 -9200.313’1 -1750.71311 -50.8 [311 55.2[51 -67.0pi1 23.9[3311
Ca3Al2Si3012 (grossular) -6632.9151 -1214.4151 -6649.7L311 -J214.41311 -3J9.8[311 -33.3L51 337.9 (311 -43.01311
NAVROTSKY 23
A+;Oz=AO, (7) 3)
:6)
:41
and
(andalusite) A@,ox,298= -1.1 kJ/mol; for MgSi03 Fig. 3. Gibbs free energy for oxidation-reduction
equilibria, per mole of 02, data from [4, 18,311.
(enstatite) A%, ox,298= -35.6 kJ/mol, and for CaSi03
(wollastonite) AH;: ox,298 = -89.4 kJ/mol. Entropies of
formation of ternary oxides from binary componentsare
generally small in magnitude (-10 to +lO J/mol*K) unless and the following balance of enthalpy, entropy, and
volume terms is reached
major order-disorderoccurs.
4. ENTHALPY AND ENTROPY OF PHASE
TRANSFORMATION AND MELTING
AG(P,T)=O=AH;-TAS;+
P
s1 atm
AV(P, T) dP (10)
a AH and AS are values at I atm near 1000 K, AV is AV”298, for all listings in table, a = olivine, /I = spinelloid or wadsleyite, y=
spinel, px = pyrox-ene, il = ilmenite, gt = garnet, pv = perovskite, q = quartz, co = coesite, st = stishovite
PEROVSKITE
M”S03.7
CaGe03.4
PYROXENOID
-
OLIVINE + QUARTZ 600 1000 1400
1473 K-
PV
15
P (GPa)
11
-I 373 K
14 I 1 1 I
0.2 0.2 0.6 1.0 PX
0.6
Fe/(Fe+Mg) Fe/(Fe+Mg)
10 I I 1 I
1000 1500 2000 2500 3000 3500
Temperature W)
30
PV + PER
19
15 P (GPa)&, / [
P (GPa) SP(y)
\
11 a+y
18
OL(a)
7
lk
i”o’o0 15’00 20’00 25’00 30’00 35’00
Fe/(Fe+Mg) Temperature W)
Fig. 6. Phase relations in Mg2SiO&Fe#i04 as a Fig. 7. Phase relations in MgO-Si02 at high P and T.
function of pressure[lo]. (a) Mg2SiOq composition, (b) MgSi03 composition, [9].
NAVROTSKY 27
TEMPERATURE (K)
Fig. 8. Equilibrium phase relations in H20. Compiled Acknowledgments. I thank Rebecca Lange and Elena
from various sources [ 141. Petrovicova for help with tables and figures.
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28 THERMODYNAMICS
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Navrotsky, Scanning calorimetric
Thermal Expansion
Yingwei Fei
thermal expansion coefficient may be used 931 are also recommended as data sources.
The pressure effect on the thermal expansion coefficient
a(T) = a0 + a,T + azT-* (3) may be described by the Anderson-Griineisen parameter
(4)9
where a,, a,, and a, (5 0) are constants determined by
fitting the experimental data. The measured volume
above room temperature can be well reproduced by
a(C T)/a(T)= ME WVf (7)
I 1
T
v(Tj = vT,k?Xp 4WT (4) pressure can be calculated from equation (7) and the third
TI order Birch-Murnaghan equation of state,
Oxides
aA120a, corundum a 293-2298 K 7.3 0.0758 0.1191 -0.0603 PI
c 293-2298 K 8.3 0.0773 0.1743 0.0000 PI
I’ 293-2298 K 23.0 0.2276 0.4198 -0.0897 PI
FBI 31
TABLE 1. (continued)
Hydrous minerals
AlOOH, boehmite a loo-530 K 9.7 -0.0048 3.4000 0.0000 r71
b loo-530 K 25.3 -0.0232 9.2000 0.0000 [71
c loo-530 K 0.7 0.0005 0.2000 0.0000 [71
V loo-530 K 35.7 -0.0275 12.8000 0.0000 [71
32 THERMAL EXPANSION
TABLE 1. (continued)
TABLE 1. (continued)
Silicates
Akermanite, Ca2MgSi20T a 293-693K 10.7 0.1065 0.0000 0.0000 1311
c 293-693K 5.9 0.0346 0.8280 0.0000 [311
V 293-693 K 27.1 0.2453 0.8700 0.0000 1311
Andalusite, A12SiOs a 298-1273 K 12.5 0.1223 0.0963 0.0000 [971
b 298-1273 K 8.1 0.0753 0.1918 0.0000 [971
c 298-1273 K 2.3 0.0233 0.0000 0.0000 1971
V 298-1273 K 22.8 0.2181 0.3261 0.0000 [971
Beryl, Be,A12Sib0,8 a 298-1073 K 2.6 0.0260 0.0000 0.0000 [581
c 298-1073 K -2.9 -0.0290 0.0000 0.0000 [581
V 298-1073 K 2.3 0.0230 0.0000 0.0000 [581
Calcium silicates
Ca3Si207, rankinite V 293-1473 K 33.1 0.2883 1.4106 0.0000 [751
p-Ca2Si04 V 293-1473 K 31.4 0.4601 0.0158 -1.3157 1751
Ca,SiOs V 293-1273 K 25.7 0.1852 2.4073 0.0000 r751
Cancrinite a 298-673
K 7.0 0.0034 2.2150 0.0000 1751
c 298-673
K 16.1 0.0328 4.2629 0.0000 1751
V 298-673 K 29.9 0.0364 8.7589 0.0000 1751
Cordierite
Mg2At4SisO18 (hexagonal) a 298-873 K 2.2 0.0220 0.0000 0.0000 [351
c 298-873
K -1.8 -0.0180 0.0000 0.0000 1351
V 298-873 K 2.6 0.0260 0.0000 0.0000 [35, cf. 671b
f%Eucryptite, LiAlSi04 a 296-920 K 8.6 0.0860 0.0000 o.oooo rw
c 296-920 K -18.4 -0.1840 0.0000 0.0000 [Ml
V 296-920 K -1.2 -0.0120 0.0000 0.0000 WI
Feldspars
Celsian, BaAi2Si208 V 293-673 K 8.7 0.0605 0.8692 0.0000 [751
High Albite, NaAlSi$18 u 297-1378 K 9.6 0.0716 0.8114 0.0000 WI
b 297-1378 K 6.6 0.0656 0.0000 0.0000 WI
c 297-1378 K 5.2 0.0523 0.0000 0.0000 PI
34 THERMAL EXPANSION
TABLE 1. (continued)
TABLE 1. (continued)
Nephelines
PkdGd~SiQ a 293-1073 K 11.1 0.0512 1.9931 0.0000 1751
c 293-1073 K 8.3 0.0665 0.5544 0.0000 [751
v 293-1073 K 31.3 0.1889 4.1498 0.0000 [751
a 293-1073 K 19.5 0.1952 -0.0211 0.0000 [751
c 293-1073 K 19.8 0.2627 -2.1428 0.0000 [751
v 293-1073 K 58.5 0.6515 -2.2071 0.0000 [751
Olivines
CaMgo.dh.diO4 a 298-1068 K 6.4 0.0855 0.1308 -0.2331 WI
monticellite b 298-1068 K 7.4 0.0965 0.1806 -0.2575 1451
c 298-1068 K 10.3 0.1235 0.4236 -0.2891 1451
v 298-1068 K 24.2 0.3114 0.6733 -0.8133 r451
CaMn(MgZn)Si04 n 298-1073 K 6.5 0.0976 0.2233 -0.3605 1451
glaucochroite b 2981073 K 6.4 0.0953 0.2091 -0.3536 r451
c 298-1073 K 7.2 0.1055 0.2783 -0.3852 1451
v 298-1073 K 20.3 0.3007 0.7192 -1.1080 [451
Mg2Si04, forsterite (I 303-1173 K 6.6 0.0663 0.3898 -0.0918 WI
b 303-1173 K 9.9 0.1201 0.2882 -0.2696 WI
c 303-1173 K 9.8 0.1172 0.0649 -0.1929 F361
v 303-1173 K 26.4 0.3034 0.7422 -0.5381
Mg2Si04, forsterite v 296-1293 K 30.6 0.2635 1.4036 0.0000 E;
Mg2Si04, forsterite v 298-1273 K 28.2 0.3407 0.8674 -0.7545 [541
Mg2Si04, forsterite v 300-1300 K 27.3 0.2854 1.0080 -0.3842 1401
Mn2Si04, tephroite a 298-1123 K 5.8 0.0397 0.5249 0.0621 1611
b 298-1123 K 8.8 0.1042 0.2744 -0.2188 WI
c 298-1123 K 8.0 0.0807 0.3370 -0.0853 1611
v 298-1123 K 22.6 0.2307 1.0740 -0.2898 WI
Ni2Si04, Ni-olivine n 298-1173 K 9.5 0.1049 0.2093 -0.1409 [451
b 298-1173 K 8.9 0.0990 0.1746 -0.1387 [451
c 298-1173 K 9.0 0.1004 0.1827 -0.1396 r451
v 298-1173 K 27.3 0.3036 0.5598 -0.4204 [451
Fe,SiO,, fayalite a 298-1123 K 5.5 0.1050 0.0602 -0.4958 WI
b 298-1123 K 7.9 0.0819 0.1629 -0.0694 WI
c 298-1123 K 9.9 0.1526 -0.1217 -0.4594 WI
V 298-1123 K 26.1 0.2386 1.1530 -0.0518 [91,76,27]
@kde&SiO4 a 297-983 K 6.1 0.0610 0.0000 0.0000 P31
hortonolite b 297-983 K 9.6 0.0960 0.0000 0.0000 P31
c 297-983 K 9.7 0.0975 0.0000 0.0000 [I31
v 297-983 K 25.5 0.2557 0.0000 0.0000 1131
Mgo.7&.l&no.diO~ (I 296-1173 K 9.2 0.0916 0.0000 0.0000 ]271
hortnolite b 296-1173 K 11.1 0.1109 0.0000 0.0000 1271
c 296-1173 K 14.6 0.1456 0.0000 0.0000 1271
V 296-1173 K 35.0 0.3504 0.0000 0.0000 [27, cf. 791
Perovskite
MgSiOs a 77-298 K 8.4 0.0840 0.0000 0.0000 1711
b 77-298 K 0.0 o.oooo 0.0000 0.0000 [711
36 THERMAL, EXPANSION
TABLE 1. (continued)
TABLE 1. (continued)
TABLE 1. (continued)
Si02 group
Coesite V 293-1273 K 6.9 0.0597 0.7697 -0.1231 1751
Crisfobalite, low a 301-491 K 19.5 0.1950 0.0000 o.oooo 1631
c 301-491 K 52.7 0.5270 o.oooo 0.0000 1631
V 301-491 K 91.7 0.9170 0.0000 0.0000 F31
Cristobalite, high V 673-1473 K 6.0 0.0600 0.0000 0.0000 E751d
a-Quartz V 298-773 K 24.3 0.1417 9.6581 -1.6973 [lle
B-Quartz V 848-1373 K 0.0 0.0000 o.oooo 0.0000 PI
V 1473-1673 K -4.4 -0.0440 0.0000 0.0000 PI
Stishovite a 291-873 K 7.8 0.0758 0.0656 0.0000 1391
c 291-873 K 0.9 0.0060 0.6553 -0.1500 [391
v 291-873 K 16.4 0.1574 0.7886 -0.1500 1391
Stishovite a 300-693 K 7.5 0.0750 0.0000 0.0000 PI
c 300-693 K 3.8 0.0380 0.0000 0.0000 PI
V 300-693 K 18.6 0.1860 0.0000 0.0000 P81
Spodumene, a-LiAlSi20h v 293-1073 K 11.0 0.0758 1.1542 0.0000 1751
Topaz, A12Si04(F,0H)2 a 293-1273 K 4.6 0.0316 0.4698 0.0000 1751
b 293-1273 K 3.6 0.0245 0.3795 0.0000 E751
c 293-1273 K 6.3 0.0485 0.4924 0.0000 1751
v 293-1273 K 14.8 0.1098 1.2700 0.0000 [751
Wadsleyite (p-phase) a 293-1073 K 6.0 0.085 1 0.1388 -0.2662 WI
Mg2Si0, b 293-1073 K 5.6 0.0791 0.1165 -0.2487 PI
c 293-1073 K 9.3 0.1196 0.3884 -0.3412 P91
V 293-1073 K 20.9 0.2893 0.5772 -0.8903 WI
Zircon, ZrSi04 a 293-1293 K 3.4 0.0340 0.0000 0.0000 161
c 293-1293 K 5.6 0.0560 0.0000 0.0000 Fl
V 293-1293 K 12.3 0.1230 0.0000 0.0000 [6, cf. 821
Perovskites
BaZrO,, perovskite V 293-873 K 20.6 0.2060 0.0000 0.0000 w41
CaGeOs, perovskite a 295-520 K 13.8 0.1380 0.0000 0.0000 [501
b 295-520 K 6.8 0.0680 0.0000 0.0000 r501
c 295520 K 10.5 0.1050 0.0000 0.0000 1501
v 295-520 K 31.1 0.3110 o.oooo 0.0000 WI
a 520-673 K 12.1 0.1210 0.0000 0.0000 1501
b 520-673 K 12.1 0.1210 0.0000 0.0000 r501
c 520-673 K 10.5 0.1050 0.0000 0.0000 [501
V 520-673 K 35.0 0.3500 o.oooo o.oooo [501
NaMgO,, perovskite a 298-873 K 40.4 0.4040 0.0000 o.oooo PO51
b 298-873 K 15.3 0.15300 o.oooo 0.0000 w51
c 298-873 K 30.6 0.3060 0.0000 0.0000 r 1051
V 288-873 K 88.0 0.8800 0.0000 o.oooo 11051
NaMgOs, cubic V 1038-1173 K 94.9 0.9490 0.0000 o.oooo PO51
ScAlOs, perovskite u 293-973 K 10.0 0.1000 0.0000 0.0000 [321
b 293-973 K 7.0 0.0700 0.0000 0.0000 1321
c 293-973 K 10.0 0.1000 0.0000 0.0000 r321
FE1 39
TABLE 1. (continued)
TABLE 3~. Partial Molar Volume and Mean Thermal TABLE 3b. Partial Molar Volume and Mean Thermal
Expansion Coefficient of Oxide Components [46] Expansion Coefficient of Oxide Components
in Al-Free Melts [ 1l]
vi, 1573
a Data were derived from density measurements of 30 melts in a Data were derived from density measurements of 12 melts in
the system CaO-FeO-Fe203-SiO, [16,57]. Units are in cc/mole the system Na,O-FeO-Fe203-Si02 [ 171 and ferric-ferrous
and l/K. relations (471. Units are in cc/mole and l/K.
FE1 41
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44 THERMAL EXPANSION
Jay D. Bass
Table 1. (continued)
Material Subscript ij in modulus cij (GPa) ITS G Refer-
MgTm” 11 44 12 GPa GPa ences
SrO 5.009 170 55.6 46 87.3 58.1 46, 116
UOz, Uraninite 10.97 389 59.7 119 209 83 35
Spine1 Structured Oxides
Fe&, 5.206 275 95.5 104 161.0 91.4 47
Magnetite 270 98.7 108 162.0 91.2 47
FeCr204, Chromi te 5.09 322 117 144 203.3 104.9 47
M&04, 3.578 282 154 154 196.7 108.3 46, 24
Spine1 3.578 282.9 154.8 155.4 197.9 108.5 152
Mg0.2.6AlaOs 3.619 298.6 157.6 153.7 202.0 115.3 106
Mg0.3.5AlzOs 3.63 300.5 158.6 153.7 202.6 116.4 126
312 157 168 216.0 114.8 46
303 156 158 206.3 114.7 46
Mgo.75Feo.3sA11.9o04, 3.826 269.5 143.5 163.3 198.7 97 130
Pleonaste
FeA1204, Hercyni te 4.280 266.0 133.5 182.5 210.3 84.5 130
7-MgaSiOd, Ringwoodite 3.559 327 126 112 184 119 144
Ni$SiOd 5.351 366 106 155 226 106 13
MgAMh 4.389 300 126 118 179 110 140
Sulphides
Fe&, Pyrite 5.016 361 105.2 33.6 142.7 125.7 108
402 114 -44 104.7 149.7 47
PbS, Galena 7.597 127 23 24.4 58.6 31.9 47
ZnS, Sphalerite 4.088 102 44.6 64.6 77.1 31.5 47
Binary Halides
BaFz, Frankdicksonite 4.886 90.7 25.3 41.0 57.8 25.1 46
CaFz, Fluorite 3.181 165 33.9 47 86.3 42.4 46
NaCl, Halite 2.163 49.1 12.8 12.8 24.9 14.7 46
KCl, Sylvite 1.987 40.5 6.27 6.9 18.1 9.4 46
Garnets
Pyrope PY), 3.567 296.2 91.6 111.1 172.8 92.0 85
~gdWMh2 3.563 295 90 117 177 89 67
Grossular,(Gres) 3.602 321.7 104.6 91.2 168.4 108.9 11
CasAlsSisOr2
Uvarovite (Uv) 3.850 304 84 91 162 92 10
Ca3CrzSi3012
Spessartite (Spsa) 4.195 309.5 95.2 113.5 178.8 96.3 11
MnsAlaSiaOr2
Hibschite 3.13 187 63.9 57 100 64.3 86
Ca3A12(Si04)1.74(H404)1.28
Andradite (Anss) 3.836 289 85 92 157 90 10
CasFet3SisOra
AwoGmAlmd’y3 3.775 281.2 87.9 80.4 147.3 92.7 5
~mJ’y2&m23Sp~ 3.741 310.2 99.5 100.4 170.4 101.6 84
Ah&dhSpllA& 4.131 306.7 94.9 111.9 176.8 95.9 5
Ahd’mGr&h 4.160 306.2 92.7 112.5 177.0 94.3 111
PyrsAlmrsAnd4Uvs 3.705 296.6 91.6 108.5 171.2 92.6 121
PYdhdh 3.839 301.4 94.3 110.0 173.6 94.9 136
48 ELA!377CITY
Table 1. (continued)
A1203, Sapphire, 3.999 495 497 146 160 115 -23 251.7 162.5 46
Corundum 3.982 497 501 146.8 162 116 -21.9 253.5 163.2 83
AIP04, (cE) 2.620 64.0 85.8 43.2 7.2 9.6 -12.4 29.3 33.0 25
Berlinite, (cD) 69.8 87.1 42.2 10.6 14.9 13.4 33.9 32.7 32
CaCOz, Calcite 2.712 144 84.0 33.5 53.9 51.1 -20.5 73.3 32.0 46
Cr203, Eskolaite 5.21 374 362 159 148 175 -19 234.0 123.2 1, 46
FeaOs, Hematite 5.254 206.6 91.0 69
MgCOs, Magnesite 3.009 259 156 54.8 75.6 58.8 -19.0 114.0 68.0 46, 50
NaNOs, Nitratine 2.260 54.6 34.9 11.3 18.9 19.3 7.5 28.2 12.0 46
Ag&%, 5.59 59.5 39.8 9.97 31.7 29.6 0.18 36.8 11.0 47
Proustite
SiOn, a-Quartz 2.648 86.6 106.1 57.8 6.7 12.6 -17.8 37.8 44.3 46
cE 2.648 86.74 107.2 57.9 6.98 11.9 -17.9 37.8 44.4 46
CD 2.648 86.47 107.2 58.0 6.25 11.9 -18.1 37.5 44.5 46
Tourmaline, 3.100 305.0 176.4 64.8 108 51 -6 127.2 81.5 87
(Na)(Mg,Fe+2,Fe+3,A1,Li)sA1s(B0s)s(Sis0~s)(OH,F)~
Dolomite, 3.795 205 113 39.8 71.0 57.4 -19.5 13.7 94.9 45.7 46, 50
CaMg(CO3)a
Phenacite 2.960 341.9 391.0 91.4 148.0 136.0 0.1 3.5 212.8 98.9 148
BezSiOa
MgSiOs 3.795 472 382 106 168 70 -27 24 212 132 141
Ilmenite structure
50 ELA!XIClTY
Other Silicates
Wadsleyite, 3.474 360 383 273 112 118 98 75 110 105 174 114 105
@-MgzSiOd
AlzSiOs
Andalusite 3.145 233.4 289.0 380.1 99.5 87.8 112.3 97.7 116.2 81.4 162 99.1 126
Sillimanite 3.241 287.3 231.9 388.4 122.4 80.7 89.3 158.6 83.4 94.7 170.8 91.5 126
Sulphates, Sulphides, Carbonates
Sulphur 2.065 24 20.5 48.3 4.3 8.7 7.6 13.3 17.1 15.9 19.1 6.7 46
14.2 12.7 18.3 8.27 4.3 4.4 3.0 3.1 8.0 7.2 5.3 46
BaS04, 4.473 89.0 81.0 107 12.0 28.1 26.9 47.9 31.7 29.8 55.0 22.8 46
Barite 95.1 83.7 110.6 11.8 29.0 27.7 51.3 33.6 32.8 58.2 23.2 45
CaS04, 2.963 93.8 185 112 32.5 26.5 9.3 16.5 15.2 31.7 54.9 29.3 46
Anhydrite
SrS04, Celestite 3.972 104 106 129 13.5 27.9 26.6 77 60 62 81.8 21.5 46
Na2S04, 2.663 80.4 105 67.4 14.8 18.0 23.6 29.8 25.6 16.8 43.4 22.3 46
Thenardite
CaC03, Aragonite 2.930 160 87.2 84.8 41.3 25.6 42.7 37.3 1.7 15.7 46.9 38.5 46
Other Minerals
Chrysoberyl, 3.72 527.7 438.7 465.8 144.4 145.8 151.8 125 111 128 240 160 133
Al2 Be04
Danburite, 2.99 131 198 211 64.0 59.8 74.9 50 64 34 91.7 64.2 46
CaBzSizOa
Datolite, 3.05 215 155 110 37.1 50.3 78.5 44 50 41 80.4 53.6 46
CaBS&040H
Staurolite, 3.79 343 185 147 46 70 92 67 61 128 128.2 57.5 46
(Fe,Mg)2(A1,Fe3+)OsSiOs(0,0H)2
Topaz 3.563 281 349 294 108 132 131 125 84 88 167.4 114.8 46
Alz(F,OH)2Si04
Natrolite, 2.25 72.2 65.7 138 19.7 24.1 41.1 29.6 25.6 36.9 48.9 27.4 47
Table 9. (continued)
Acknowledgments: This work was supported in part by the NSF under grant no. EAR-90-18676.
The review of O.L. Anderson is appreciated.
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Elastic Constants of Mantle Minerals at High Temperature
T (K) Cl1 Cl2 c44 c.9 T (K) Cl1 Cl2 c44 c.5
300 299.0 96.4 157.1 101.3 300 296.6 108.5 91.6 94.0
f0.7 f0.6 f0.3 f0.2 f1.5 Al.4 f0.2 fl.O
400 292.9 97.0 155.8 98.0 350 294.6 107.6 91.2 93.5
500 296.9 97.6 154.3 94.6 400 292.7 106.9 90.8 92.9
600 280.6 98.0 152.8 91.3 450 291.0 106.5 90.4 92.3
700 274.5 98.4 151.3 88.0 500 289.2 105.9 90.0 91.7
800 268.2 98.5 149.7 84.8 _ 550 287.3 105.2 89.6 91.1
900 261.9 98.6 148.1 81.7 600 285.5 104.6 89.1 90.5
1000 255.7 98.7 146.5 78.5 650 283.8 104.2 88.7 89.8
1100 249.5 98.6 144.8 75.5 700 282.1 103.7 88.3 89.2
1200 243.3 98.4 143.1 72.5 750 280.3 103.2 87.8 88.6
1300 237.2 98.1 141.3 69.6 800 278.5 102.6 87.4 88.0
1400 231.0 97.6 139.5 66.7 850 276.7 102.1 86.9 87.3
1500 224.9 97.1 137.9 63.9 900 274.8 101.5 86.5 86.7
1600 219.0 96.4 136.2 61.3 950 273.1 101.0 86.0 86.1
1700 213.4 95.7 134.7 58.9 1000 271.2 100.3 85.5 85.5
1800 208.2 95.0 133.1 56.6 f2.0 f1.9 f0.2 f1.4
f1.2 Al.2 f0.5 f0.2
cs = (W)(C11- C12).
cs = (1/2)(G1- Gz). tAfter Suzuki & Anderson [65].
t From Isaak et al. [34].
Table 5. MgAlz04:
Measured single-crystal Table 7. KCl: Measured single-crystal
elastic modulit (GPa) from 300 to 1000 K elastic modulit (GPa) from 300 to 850 K
(max. measured value of T/O: 1.20) (max. measured value of T/O: 4.42)
300 292.2 168.7 156.5 61.8 300 40.1 6.6 6.35 16.7
55.2 f5.2 fl.O f0.3 f0.4 f0.5 f0.02 f0.3
350 290.1 167.2 155.0 61.5 350 38.4 6.8 6.28 15.8
400 288.6 166.3 155.3 61.1 400 36.9 7.0 6.21 15.0
450 286.2 164.8 154.4 60.7 450 35.4 7.1 6.15 14.1
500 284.4 163.7 153.6 60.3 500 33.8 7.2 6.11 13.3
550 282.8 162.8 152.9 60.0 550 32.3 7.3 6.05 12.5
600 281.1 161.9 152.2 59.6 600 31.1 7.5 5.96 11.8
650 297.1 160.8 151.5 59.1 650 29.7 7.7 5.87 11.0
700 277.2 159.8 150.7 58.7 700 28.2 7.7 5.79 10.2
750 275.3 158.8 149.9 58.2 750 26.6 7.7 5.69 9.5
800 273.3 157.7 149.2 57.8 800 25.2 7.8 5.57 8.7
850 271.1 156.5 148.5 57.3 850 23.5 7.7 5.57 7.9
900 269.2 155.5 147.7 56.9 f0.5 f0.5 f0.02 f0.4
950 267.3 154.4 146.9 56.4
cs = (W)(G1- Gz).
1000 266.0 154.0 146.1 56.0
t After Yamamoto & Anderson [76].
f6.5 f6.5 f1.3 f0.4
cs = (1/2)(G1-G2).
t After Cynn [19].
Table 9. MgzSi04: Measured single-crystal elastic modulit (GPa) from 300 to 1700 K
(max. measured value of T/O: 2.1)
300 330.0 200.0 236.0 67.2 81.5 81.2 72.1 68.0 66.2
f0.7 f0.4 f0.6 fO.l f0.2 f0.2 f0.4 zto.5 zto.5
400 326.3 197.2 233.1 65.9 80.1 79.6 71.6 67.0 65.2
500 322.4 194.2 230.1 64.4 78.7 78.0 71.1 66.1 64.0
600 318.6 191.2 226.8 63.0 77.2 76.3 70.4 65.1 62.9
700 314.5 188.0 223.6 61.6 75.8 74.6 69.7 64.3 61.8
800 310.3 184.8 220.3 60.1 74.3 73.0 69.1 63.3 60.7
900 306.3 181.5 216.9 58.8 72.8 71.3 68.3 62.5 59.4
1000 302.0 178.3 213.5 57.4 71.3 69.6 67.8 61.5 58.4
1100 297.4 175.1 209.8 56.1 69.9 67.9 67.2 60.5 57.3
1200 292.8 171.8 206.1 54.7 68.3 66.2 66.6 59.4 56.3
1300 288.3 168.7 202.7 53.3 66.9 64.6 66.0 58.5 55.3
1400 283.8 165.1 199.2 51.9 65.4 62.9 65.2 57.6 54.2
1500 279.1 162.2 195.5 50.6 64.0 61.4 64.6 56.7 53.2
1600 274.4 159.0 192.0 49.3 62.5 59.9 64.0 55.8 52.1
1700 269.8 155.6 188.2 48.0 61.0 58.4 63.3 54.9 51.0
fl.1 f0.8 Al.0 f0.2 f0.2 f0.3 f0.7 f0.9 f0.8
Table 10. Olivine FogoFalo: Measured elastic modulit (GPa) from 300 to 1500 K
(max. measured value of T/O: 2.26)
T (K) Cl1 c22 c33 c44 cs5 C66 c23 c31 Cl2
300 320.6 197.1 234.2 63.72 77.6 78.29 74.8 71.2 69.8
f0.4 f0.3 f0.5 f0.05 fO.l f0.08 f0.3 f0.4 f0.2
400 316.8 194.1 231.0 62.37 76.3 76.61 74.4 70.3 68.6
500 313.0 190.9 227.6 61.05 74.9 74.97 73.7 69.3 67.4
600 309.0 187.7 224.1 59.73 73.6 73.33 73.0 68.3 66.2
700 305.0 184.6 220.6 58.45 72.3 71.73 72.3 67.2 65.0
800 300.7 181.5 217.2 57.23 71.0 70.17 71.6 66.1 63.6
900 297.0 178.3 214.3 55.91 69.9 68.59 71.2 66.0 62.8
1000 293.1 175.3 210.4 54.68 68.5 67.07 70.3 64.7 61.8
1100 289.0 172.3 206.6 53.47 67.1 65.53 69.4 63.4 60.5
1200 285.1 169.2 202.9 52.28 65.8 64.01 68.6 62.4 59.4
1300 280.9 166.1 199.3 51.06 64.5 62.51 67.8 61.4 58.2
1400 276.6 163.0 195.6 49.83 63.2 61.02 67.0 60.5 57.2
f0.5 f0.4 f0.7 f0.07 f0.2 fO.ll f0.5 f0.5 f0.4
1500 272.0 159.8 192.1 48.57 62.2 59.52 66.4 59.8 56.2
Table 11. Fe#iOa: Measured single-crystal elastic modulit (GPa) from 300 to
700 K (max. measured value of T/O: 1.41)
300 266.9 173.5 239.1 32.4 46.7 57.3 97.9 98.7 95.1
f1.9 fl.1 f1.4 fO.l f0.1 fO.l f1.2 f1.6 f1.5
350 264.5 171.8 237.0 31.9 46.2 56.3 97.7 98.2 94.3
400 262.2 170.1 234.7 31.7 46.0 55.3 97.4 97.7 93.4
450 260.7 168.4 232.4 31.4 45.8 54.5 97.2 97.5 92.8
500 258.8 166.6 229.9 31.4 45.8 53.7 96.8 97.0 91.9
550 257.0 164.9 227.5 31.4 45.7 52.9 96.5 96.6 91.0
600 255.0 162.8 225.1 31.5 45.6 52.3 96.0 96.1 90.0
650 252.8 160.9 222.7 31.5 45.6 51.6 95.4 95.5 88.9
700 251.0 159.0 220.5 31.6 45.5 51.0 94.8 94.9 87.7
f2.2 f1.3 f1.6 f0.1 fO.l f0.2 f1.3 f1.8 f1.7
Table 12. MnzSi04: Measured single-crystal elastic modulit (GPa) from 300 to
700 K (max. measured value of T/O: 1.28)
300 258.3 165.5 206.7 45.3 55.6 57.8 91.7 95.2 87.1
f1.9 f1.0 f1.3 fO.l f0.2 f0.2 fl.O f1.5 Al.3
400 254.8 162.7 203.9 44.4 54.4 56.4 90.6 93.8 85.5
500 251.3 159.8 201.0 89.5 92.3 83.8 43.4 53.2 55.1
600 247.8 157.0 198.2 42.5 52.0 53.7 88.3 90.9 82.2
700 244.3 154.2 195.3 41.5 51.8 52.4 87.2 89.4 80.6
f2.4 f1.3 f1.7 f0.1 f0.2 f0.2 f1.3 f1.9 f1.6
Table 13. Co2SiO4: Measured single-crystal elastic modulit (GPa) from 300 to
700 K (max. measured value of T/O: 1.25)
300 307.7 194.7 234.1 46.7 63.9 64.8 103.2 105.0 101.6
Al.2 f0.7 f0.9 fO.l f0.1 f0.1 f0.7 fl.O f0.8
400 304.0 192.6 230.7 46.2 62.9 63.8 101.8 103.6 99.8
500 301.1 190.5 227.4 45.7 61.9 62.8 100.5 102.3 97.9
600 297.8 188.8 224.0 45.2 60.8 61.8 99.1 100.9 96.1
700 294.5 186.2 220.6 44.7 59.8 60.8 97.8 99.6 94.3
f1.7 f1.2 51.4 50.1 fO.l f0.2 fl.1 51.3 f1.3
tAfter Sumino [58].
ANDERSON AND ISAAK 69
Table 15. MgO: Thermal expansivity, specific heat, isotropic elastic constantst and velocitiesf
T at ciJ* Y cv IcT
K g/A 10-‘/K [ia Gta J/W) J/(gK) GPa lcr$s kr$s
100 3.602 0.63 165.7 132.0 0.194 1.59 0.194 165.6 9.80 6.13
200 3.597 2.24 164.6 130.3 0.662 1.55 0.658 163.5 9.78 6.10
300 3.585 3.12 163.9 131.8 0.928 1.54 0.915 161.6 9.73 6.06
f0.005 f0.06 f0.6 f0.5 f0.03 f0.6 f0.01 dLo.01
400 3.573 3.57 162.3 129.4 1.061 1.53 1.048 158.9 9.68 6.02
500 3.559 3.84 160.7 126.9 1.130 1.53 1.098 156.1 9.63 5.97
600 3.545 4.02 158.9 124.4 1.173 1.54 1.131 153.2 0.57 5.92
700 3.531 4.14 157.1 121.8 1.204 1.53 1.153 150.4 9.51 5.87
800 3.516 4.26 155.1 119.2 1.227 1.53 1.166 147.4 9.45 5.82
900 3.501 4.38 153.1 116.7 1.246 1.54 1.175 144.3 9.39 5.77
1000 3.486 4.47 151.1 114.1 1.262 1.54 1.181 141.4 9.33 5.72
1100 3.470 4.56 148.9 111.5 1.276 1.53 1.185 138.3 9.26 5.67
1200 3.454 4.65 146.7 109.0 1.289 1.53 1.188 135.1 9.19 5.62
1300 3.438 4.71 144.4 106.4 1.301 1.52 1.190 132.1 9.13 5.56
1400 3.422 4.80 142.0 103.8 1.312 1.52 1.191 128.1 9.05 5.51
1500 3.405 4.89 139.7 101.3 1.323 1.52 1.191 125.7 8.98 5.46
1600 3.388 4.98 137.3 99.0 1.334 1.51 1.191 122.5 8.92 5.41
1700 3.371 5.04 134.9 96.7 1.346 1.50 1.193 119.6 8.85 5.36
1800 3.354 5.13 132.7 94.5 1.358 1.50 1.193 116.6 8.78 5.31
f0.007 fO.10 fl.1 f1.6 f0.03 fl.1 f0.04 f0.05
$Computed from Table 1; tS uzuki [64]; ‘Garvin et al. [25].
70 HIGH T ELASTICITY OF MANTLE MINERALS
Table 16. AlsOs: Thermal expansivity, specific heat, isotropic mod& and velocities1
T P fft KS G Cp* 7 Cv KT vp u,
300 3.982 1.62 253.6 163.0 0.779 1.32 0.774 252.0 10.88 6.40
f0.009 f0.03 f1.7 f2.8 f0.03 f1.7 f0.05 f0.06
400 3.975 1.99 252.6 161.1 0.943 1.34 0.933 249.9 10.84 6.37
500 3.966 2.23 250.9 158.8 1.040 1.36 1.024 247.1 10.80 6.33
600 3.957 2.40 248.6 156.6 1.103 1.37 1.082 243.8 10.75 6.29
700 3.947 2.51 246.6 154.2 1.148 1.36 1.121 240.8 10.70 6.25
800 3.937 2.59 244.4 151.9 1.180 1.36 1.148 237.7 10.65 6.21
900 3.927 2.66 242.4 149.5 1.205 1.36 1.167 234.8 10.61 6.17
1000 3.916 2.73 240.0 147.1 1.223 1.37 1.179 231.4 10.55 6.13
1100 3.906 2.80 237.8 144.6 1.244 1.37 1.194 228.2 10.50 6.09
1200 3.894 2.88 235.2 142.2 1.257 1.38 1.199 224.5 10.44 6.04
1300 3.883 2.96 232.6 139.7 1.267 1.40 1.203 220.8 10.39 6.00
1400 3.872 3.03 230.0 137.2 1.277 1.41 1.205 217.1 10.33 5.95
1500 3.860 3.09 228.1 134.8 1.286 1.42 1.207 214.0 10.28 5.91
1600 3.848 3.15 225.9 133.5 1.296 1.43 1.209 210.7 10.23 5.86
1700 3.835 3.20 224.8 131.2 1.306 1.43 1.212 207.5 10.17 5.82
1800 3.823 3.25 221.8 127.5 1.318 1.43 1.216 204.7 10.12 5.78
f0.009 f0.06 f2.3 f4.8 f0.03 f2.2 f0.009 fO.ll
$Computed from Table 14; t White t Roberts [75]; *F urukawa et al. [24]; Dimensions as in Table 15.
Table 17. MgA1204: Thermal expansivity, specific heat, isotropic modulit and velocities*
T P at KS G C$ 7 Cv KT up v.,
300 3.576 2.11 209.9 108.2 0.819 1.51 0.811 207.9 9.95 5.50
f0.005 f0.04 f5.2 f2.5 f0.05 f5.2 f0.09 f0.06
350 3.572 2.18 208.2 107.7 0.899 1.41 0.889 205.9 9.92 5.49
400 3.568 2.25 207.1 107.2 0.963 1.36 0.952 204.6 9.91 5.48
450 3.564 2.32 205.3 106.6 1.014 1.32 1.001 202.5 9.87 5.47
500 3.560 2.38 203.9 106.0 1.055 1.30 1.039 200.8 9.85 5.46
550 3.555 2.45 202.8 105.5 1.088 1.28 1.069 199.4 9.83 5.45
600 3.551 2.51 201.6 104.9 1.115 1.28 1.094 197.8 9.81 5.45
650 3.547 2.57 200.3 104.3 1.139 1.28 1.115 196.1 9.78 5.42
700 3.542 2.63 199.0 103.6 1.160 1.27 1.133 194.4 9.76 5.41
750 3.537 2.69 197.7 103.0 1.179 1.27 1.149 192.7 9.73 5.40
800 3.532 2.74 196.2 102.4 1.180 1.27 1.164 190.9 9.71 5.38
850 3.528 2.80 194.7 101.8 1.213 1.27 1.178 189.0 9.68 5.37
900 3.523 2.85 193.4 101.1 1.229 1.27 1.190 187.3 9.65 5.36
950 3.518 2.90 192.0 100.5 1.243 1.27 1.201 185.5 9.63 5.34
1000 3.512 2.94 191.3 99.8 1.253 1.28 1.208 184.4 9.61 5.33
f0.005 f0.06 f6.5 f2.7 f0.05 f6.3 fO.ll f0.07
$Computed from Table 5; +Touloukian et al. [69]; *Robie et al. [48]; Dimensions as in Table 15.
ANDERSON AND ISAAK 71
Table 18. MgzSiOa: Thermal expansivity, specific heat, isotropic moduh .t and velocities 3
T P KS G CP* Y cv KT ‘UP V,
3.222 2.72 128.6 81.6 0.840 1.29 0.831 127.3 8.58 5.03
f0.007 f0.05 f0.4 f0.3 f0.02 f0.4 fO.O1 Ito.
400 3.213 3.03 127.1 80.3 0.990 1.21 0.976 125.2 8.54 5.00
500 3.203 3.22 125.4 78.9 1.068 1.18 1.048 123.1 8.48 4.96
600 3.192 3.36 123.7 77.4 1.119 1.17 1.093 120.8 8.43 4.93
700 3.181 3.48 121.9 76.0 1.156 1.16 1.124 118.6 8.38 4.89
800 3.170 3.59 120.2 74.5 1.186 1.15 1.148 116.3 8.32 4.85
900 3.159 3.70 118.3 73.1 1.211 1.15 1.167 114.0 8.27 4.81
1000 3.147 3.81 116.6 71.6 1.235 1.14 1.183 111.7 8.21 4.77
1100 3.135 3.92 114.8 70.1 1.256 1.14 1.197 109.4 8.15 4.73
1200 3.122 4.05 112.9 68.6 1.277 1.15 1.210 106.9 8.09 4.69
1300 3.109 4.16 111.1 67.1 1.296 1.15 1.220 104.6 8.03 4.65
1400 3.096 4.27 109.2 65.6 1.315 1.15 1.231 102.2 7.97 4.60
1500 3.083 4.39 107.5 64.1 1.334 1.15 1.240 99.9 7.91 4.56
1600 3.069 4.50 105.6 62.7 1.352 1.15 1.249 97.6 7.85 4.52
1700 3.055 4.62 103.7 61.2 1.370 1.14 1.257 95.2 7.79 4.48
f0.008 f0.08 f0.5 f0.3 f0.02 f0.5 f0.02 f0.01
$Computed from Table 9; t K ajiyoshi [38]; *Barin & Knacke [15]; Dimensions as in Table 15.
Table 19. Olivine FoseFals: Thermal expansivity, specific heat, isotropic mod& and velocities 3
T P CN~ KS G Cp' 7 Cv KT up V,
300 3.353 2.66 129.3 78.1 0.816 1.25 0.808 128.0 8.34 4.83
f0.004 f0.05 f0.3 f0.2 f0.02 f0.3 fO.O1 fO.O1
400 3.343 2.99 127.7 76.8 0.957 1.19 0.944 125.9 8.29 4.79
500 3.333 3.21 125.9 75.3 1.032 1.17 1.013 123.6 8.24 4.75
600 3.322 3.35 124.1 73.9 1.080 1.16 1.055 121.2 8.19 4.72
700 3.311 3.46 122.2 72.5 1.112 1.14 1.086 118.2 8.13 4.68
800 3.299 3.55 120.3 71.2 1.145 1.13 1.109 116.6 8.07 4.65
900 3.287 3.64 118.9 69.8 1.171 1.12 1.129 114.7 8.03 4.61
1000 3.275 3.71 117.0 68.5 1.194 1.11 1.147 112.1 7.97 4.57
1100 3.263 3.79 115.1 67.1 1.216 1.10 1.163 110.0 7.92 4.54
1200 3.251 3.86 113.2 65.8 1.236 1.09 1.177 107.8 7.86 4.50
1300 3.238 3.93 111.4 64.4 1.256 1.08 1.191 105.6 7.81 4.60
1400 3.225 4.00 109.6 63.1 1.275 1.07 1.203 103.4 7.75 4.22
1500 3.212 4.07 107.8 61.7 1.294 1.06 1.216 101.3 7.69 4.38
f0.004 f0.08 f0.5 f0.3 f0.02 f0.5 fO.O1 f0.01
$Computed from Table 10; tS uzuki [64]; *Barin & Knacke [15]; Dimensions as in Table 15.
Table 20. FezSi04: Thermal expansivity, specific heat, isotropic modulit and velocities4
T P fft KS G C,+ y Cv KT up
300 4.400 2.61 138.0 51.0 0.673 1.21 0.667 136.7 6.84 3.40
f0.009 f0.05 f0.8 f0.5 f0.03 f0.8 f0.02 f0.02
400 4.388 2.74 135.9 49.7 0.746 1.18 0.736 134.1 6.79 3.37
500 4.375 3.00 134.0 48.8 0.793 1.16 0.779 131.7 6.74 3.34
600 4.362 3.12 131.8 48.0 0.830 1.13 0.813 129.0 6.70 3.32
700 4.348 3.22 129.3 47.4 0.863 1.11 0.842 126.1 6.65 3.30
f0.009 f0.06 f0.9 f0.4 f0.03 f0.8 f0.02 f0.02
$Computed from Table 11; tS uzuki et al. [67]; *Watanabe [72]; Dimensions as in Table 15.
Table 21. MnsSiOe: Thermal expansivity, specific heat, isotropic modulil and velocitiest
300 4.129 2.27 128.9 54.5 0.666 1.06 0.661 128.0 6.99 3.634
f0.005 f0.05 f0.6 f0.3 f0.03 f0.6 fO.O1 f0.009
400 4.119 2.57 127.0 53.5 0.736 1.08 0.728 125.6 6.94 3.604
500 4.108 2.77 125.0 52.5 0.781 1.08 0.770 123.1 6.89 3.573
600 4.096 2.91 123.0 51.4 0.818 1.07 0.803 120.8 6.84 3.543
700 4.084 3.03 121.1 50.4 0.850 1.06 0.831 118.4 6.79 3.512
f0.005 1tO.06 f0.8 f0.3 f0.03 f0.8 f0.02 f0.011
$Computed from Table 12; t Ok ajima et al. [46]; *Barin & Knacke [15]; Dimensions as in Table 15.
Table 22. CosSiOa: Thermal expansivity, specific heat, isotropic moduh .t and velocities $
IComputed from Table 13; t ( assume MnsSiOa); *Watanabe [72]; Dimensions as in Table 15.
Table 23. MnO: Thermal expansivity, specific heat, isotropic modulit and velocitiesz
T P CY~ KS G Cp* 7 Cv KT I+ V,
300 5.378 3.46 149.0 68.3 0.632 1.51 0.623 146.7 6.68 3.57
fO.OO1 f0.07 f2.6 f1.5 f0.04 f2.5 f0.05 f0.04
350 5.369 3.58 148.0 67.6 0.653 1.51 0.641 145.2 6.66 3.55
400 5.359 3.68 146.9 66.7 0.669 1.51 0.655 143.7 6.63 3.53
450 5.349 3.77 145.8 65.6 0.682 1.51 0.665 142.2 6.60 3.50
500 5.339 3.85 144.8 64.4 0.692 1.51 0.673 140.7 6.57 3.47
fO.OO1 ho.08 f2.6 f1.6 f0.04 f2.5 f0.05 f0.04
SComputed from Table 6; tSuzuki et al. [66]; *B arin & Knacke [15]; Dimensions as in Table 15.
Table. 24. CaO: Thermal expansivity, specific heat, isotropic modulit and velocitiest
300 3.349 3.04 112.0 80.59 0.752 1.35 0.743 110.6 8.094 4.905
fO.OO1 *to.06 fO.l f0.02 zto.03 50.1 *to.002 fO.OO1
400 3.338 3.47 110.5 79.15 0.834 1.36 0.819 108.5 8.045 4.869
500 3.327 3.67 109.1 77.71 0.880 1.37 0.858 106.4 7.996 4.834
600 3.314 3.81 107.6 76.22 0.904 1.37 0.877 104.3 7.946 4.796
700 3.301 3.92 106.2 74.76 0.921 1.37 0.888 102.3 7.897 4.759
800 3.288 4.01 104.7 73.33 0.933 1.37 0.894 100.3 7.848 4.723
900 3.275 4.08 103.3 71.90 0.943 1.36 0.898 98.4 7.799 4.686
1000 3.262 4.14 101.7 70.40 0.952 1.36 0.901 96.3 7.745 4.646
1100 3.248 4.20 100.2 68.99 0.959 1.35 0.903 94.3 7.693 4.609
1200 3.234 4.26 98.7 67.56 0.965 1.35 0.903 92.3 7.640 4.571
f0.002 f0.09 f0.2 f0.08 f0.03 f0.3 f0.006 f0.003
IComputed from Table 2; t Oda et al. [43]; ‘G arvin et al. [25]; Dimensions as in Table 15.
Table 25. Grossular garnet: Thermal expansivity, specific heat, isotropic modulit and velocitiesf
T P cryi KS G Cp* y Cv KT vp v,
300 3.597 1.92 167.8 106.9 0.736 1.22 0.730 166.6 9.29 5.453
zlzO.006 f0.05 f0.7 f0.2 f0.03 f0.7 fO.O1 f0.006
400 3.589 2.28 166.2 105.7 .0.865 1.22 0.855 164.4 9.25 5.427
500 3.581 2.49 164.9 104.5 0.945 1.21 0.931 162.5 9.22 5.401
600 3.571 2.61 163.3 103.1 0.995 1.20 0.977 160.3 9.18 5.373
700 3.562 2.71 161.6 101.8 1.028 1.19 1.006 158.1 9.14 5.346
800 3.552 2.78 160.3 100.5 1.052 1.19 1.025 156.2 9.10 5.318
900 3.542 2.83 158.9 99.1 1.072 1.19 1.041 154.3 9.06 5.289
1000 3.532 2.88 157.5 97.7 1.092 1.18 1.056 152.3 9.03 5.259
1100 3.522 2.92 156.2 96.4 1.113 1.16 1.073 150.6 8.99 5.230
1200 3.512 2.97 154.4 94.9 1.139 1.14 1.095 148.3 8.94 5.198
1300 3.501 3.00 152.6 93.4 1.170 1.12 1.121 146.2 8.90 5.165
f0.006 f0.07 f1.2 f0.2 *0.03 f1.2 f0.02 f0.008
$Computed from Table 4; t1 saak et al. [36]; *Krupka et al. [39]; Dimensions as in Table 15.
Table 26. Pyrope-rich garnet: Thermal expansivity, specific heat, isotropic modulij and velocities1
T P at KS G Cp* y CV KT vp v,
300 3.705 2.36 171.2 92.6 0.726 1.50 0.718 169.4 8.92 5.00
zto.005 50.04 f0.8 f0.4 f0.03 f0.8 &to.02 zto.01
400 3.696 2.64 168.9 91.6 0.902 1.34 0.889 166.5 8.87 4.98
500 3.686 2.80 167.0 90.6 0.981 1.29 0.964 164.0 8.84 4.96
600 3.675 2.90 164.9 89.7 1.032 1.26 1.010 161.4 8.80 4.94
700 3.664 2.97 163.2 88.7 1.067 1.24 1.040 159.1 8.76 4.92
800 3.653 3.03 161.3 87.6 1.088 1.23 1.057 156.6 8.72 4.90
900 3.642 3.07 159.3 86.5 1.104 1.22 1.068 154.1 8.68 4.87
1000 3.631 3.11 157.3 85.5 1.116 1.21 1.076 151.6 8.64 4.85
AO.005 f0.06 fl.1 f0.6 f0.02 Al.1 40.03 f0.02
$Computed from Table 3; tb uzuki & Anderson [65]; * idem; Dimensions as in Table 15.
74 HIGH T ELA!JTICITY OF MANTLE MINERALS
Table 27. NaCl: Thermal expansivity, specific heat, isotropic elastic modulit and velocitiesl
300 2.159 11.8 25.3 14.71 0.868 1.59 0.822 24.0 4.56 2.610
f0.005 f0.2 f0.3 50.08 f0.04 f0.3 f0.02 &0.008
350 2.146 12.2 24.8 14.27 0.883 1.60 0.826 23.2 4.52 2.579
400 2.132 12.7 24.2 13.81 0.897 1.61 0.829 22.4 4.47 2.545
450 2.118 13.2 23.7 13.39 0.910 1.62 0.830 21.6 4.43 2.514
500 2.104 13.7 23.2 12.96 0.923 1.64 0.830 20.8 4.39 2.482
550 2.089 14.3 22.5 12.53 0.937 1.64 0.830 19.9 4.33 2.449
600 2.074 14.8 21.7 12.11 0.950 1.63 0.830 19.0 4.27 2.416
650 2.059 15.4 21.1 11.68 0.964 1.63 0.829 18.1 4.22 2.382
700 2.043 16.0 20.5 11.25 0.979 1.63 0.828 17.3 4.17 2.346
750 2.026 16.6 19.8 10.80 0.997 1.63 0.829 16.5 4.11 2.309
f0.006 f0.3 f0.3 fO.ll f0.04 f0.3 f0.02 f0.012
$Computed from Table 8; tEnck & Dommel [22]; *St&l AZ Prophet [57]; Dimensions as in Table 15.
Table 28. KCI: Thermal expansivity, specific heat, isotropic elastic modulit and velocities3
T P at KS G Cg 7 Cv KT up v,
300 1.982 11.0 17.8 9.47 0.689 1.44 0.657 17.0 3.92 2.19
f0.005 f0.2 f0.4 f1.03 f0.04 f0.3 f0.09 f0.12
350 1.971 11.3 17.3 9.18 0.701 1.42 0.664 16.4 3.88 2.16
400 1.959 11.7 17.0 8.91 0.713 1.42 0.669 15.9 3.84 2.13
450 1.948 12.1 16.6 8.64 0.724 1.42 0.672 15.4 3.80 2.11
500 1.935 12.6 16.1 8.39 0.735 1.43 0.674 14.7 3.75 2.08
550 1.923 13.2 15.7 8.13 0.745 1.44 0.675 14.2 3.71 2.06
600 1.910 13.7 15.4 7.85 0.756 1.45 0.676 13.7 3.68 2.03
650 1.897 14.2 15.0 7.57 0.767 1.46 0.676 13.2 3.64 2.00
700 1.883 14.7 14.5 7.29 0.778 1.46 0.677 12.6 3.59 1.97
750 1.869 15.2 14.0 6.98 0.791 1.44 0.679 12.0 3.53 1.93
800 1.855 15.7 13.6 6.67 0.806 1.43 0.683 11.5 3.48 1.90
850 1.840 16.2 12.0 6.41 0.823 1.39 0.691 10.9 3.42 1.87
f0.005 f0.2 f0.4 f0.13 f0.04 f0.3 f0.03 f0.02
$Computed from Table 7; tEnck et al. [23]; *Stull & Prophet [57]; Dimensions as in Table 15.
ANDERSON AND ISAAK 75
u (bT--6s)
T 0 6s 6T r
7
Y ~KT APTH
K K MPa/K GPa
300 1034 0.235 3.30 5.71 5.71 1.82 1.60 4.08 0.00
400 1029 0.237 3.16 5.16 5.16 1.49 1.52 4.98 0.45
500 1022 0.239 3.20 5.03 6.27 1.35 1.46 5.53 0.98
600 1015 0.240 3.31 5.08 6.09 1.29 1.42 5.85 1.55
700 1008 0.241 3.43 5.17 6.05 1.28 1.40 6.03 2.15
800 1001 0.243 3.55 5.29 6.06 1.28 1.38 6.15 2.76
900 994 0.244 3.62 5.37 6.08 1.28 1.36 6.24 1.43
1000 986 0.246 3.66 5.42 6.09 1.29 1.36 6.30 4.01
1100 979 0.247 3.65 5.42 6.07 1.29 1.36 6.40 4.64
1200 971 0.248 3.60 5.39 6.03 1.30 1.37 6.45 5.93
1300 963 0.250 3.51 5.32 5.98 1.29 1.38 6.52 5.93
1400 955 0.251 3.39 5.22 5.93 1.30 1.40 6.57 6.59
1500 947 0.253 3.24 5.08 5.87 1.30 1.43 6.62 7.24
1600 939 0.255 3.06 4.92 5.80 1.30 1.47 6.64 7.91
1700 932 0.257 2.85 4.73 5.74 1.32 1.52 6.64 8.57
1800 924 0.259 2.60 4.50 5.66 1.32 1.58 6.66 9.24
Calculated from Tables 14 & 16.
lb -6,)
T 0 Is 6.S 6T r v QKT APTH
7
300 945 0.183 2.83
5.26 5.73 1.57 1.40 5.04 0.00
400 937 0.185 2.79
4.83 5.34 1.33 1.40 5.67 0.54
500 928 0.188 2.81
4.69 5.17 1.23 1.38 6.00 1.12
600 920 0.190 2.86
4.67 5.08 1.18 1.37 6.16 1.73
700 911 0.192 2.92 4.70 5.05 1.16 1.35 6.23 2.35
800 902 0.194 2.98 4.74 5.03 1.15 1.34 6.28 2.98
900 894 0.196 3.04 4.78 5.02 1.13 1.32 6.32 3.61
1000 885 0.198 3.12 4.84 5.05 1.12 1.31 6.32 4.24
1100 875 0.200 3.21 4.92 5.08 1.12 1.30 6.31 4.87
1200 806 0.202 3.30 4.99 5.09 1.11 1.28 6.28 5.50
1300 857 0.204 3.41 5.08 5.10 1.10 1.26 6.22 6.12
1400 847 0.206 3.47 5.12 5.04 1.09 1.24 6.19 6.74
1500 838 0.208 3.50 5.13 4.92 1.07 1.22 6.16 7.36
1600 828 0.209 3.46 5.07 4.75 1.07 1.21 6.13 7.97
1700 820 0.211 3.36 4.95 4.56 1.06 1.20 6.03 8.58
1800 811 0.212 3.12 4.66 4.34 1.03 1.23 6.00 9.20
Calculated from Tables 1 dc 15. Dimensions as in Table 29.
Table 31. CaO: Dimensionless parameters, Debye temperatures and thermal pressure
300 671 0.210 4.15 6.19 6.00 1.51 1.24 3.36 0.00
400 666 0.211 3.75 5.54 5.38 1.31 1.24 3.73 0.36
500 660 0.212 3.60 5.27 5.13 1.22 1.23 3.90 0.74
600 654 0.213 3.54 5.14 5.01 1.17 1.23 3.98 1.13
700 649 0.215 3.52 5.07 4.99 1.13 1.23 4.01 1.53
800 643 0.216 3.53 5.03 4.95 1.10 1.23 4.02 2.34
900 637 0.218 3.55 5.01 4.93 1.07 1.22 4.01 2.34
1000 631 0.219 3.58 5.00 4.94 1.05 1.22 3.99 2.54
1100 625 0.220 3.62 5.01 4.96 1.03 1.22 3.96 3.13
1200 619 0.221 3.65 5.01 4.99 1.01 1.22 3.93 3.53
Calculated from Tables 2 & 24. Dimensions as in Table 29.
300 824 0.237 4.64 6.30 6.09 1.36 1.22 3.21 0.00
400 820 0.238 3.93 5.36 5.27 1.17 1.23 3.74 0.36
500 816 0.239 3.64 4.98 4.97 1.11 1.24 4.03 0.75
600 811 0.239 3.49 4.80 4.87 1.08 1.25 4.18 1.16
700 806 0.240 3.41 4.70 4.84 1.08 1.26 4.28 1.57
800 801 0.241 3.35 4.64 4.86 1.08 1.27 4.34 1.98
900 796 0.242 3.31 4.60 4.90 1.08 1.28 4.36 2.40
1000 791 0.243 3.29 4.58 4.96 1.09 1.29 4.38 2.83
1100 786 0.244 3.27 4.57 5.03 1.11 1.30 4.41 3.25
1200 780 0.245 3.26 4.57 5.11 1.15 1.31 4.40 3.69
1300 715 0.246 3.25 4.58 5.20 1.18 1.32 4.38 5.40
Calculated from Tables 4 & 25. Dimensions as in Table 29.
(b-i-k.)
T 0 t7 6s 6, r Y ~KT APT,
-i
300 779 0.271 4.81 6.27 4.29 0.97 0.88 4.00 0.00
350 777 0.271 4.52 5.90 4.07 1.00 0.89 4.25 0.21
400 775 0.270 4.36 5.70 3.96 1.00 0.90 4.40 0.42
450 773 0.270 4.24 5.55 3.90 1.00 0.92 4.51 0.65
500 771 0.270 4.16 5.46 3.86 1.00 0.93 4.59 0.87
550 769 0.270 4.11 5.41 3.86 1.02 0.94 4.64 1.10
600 767 0.270 4.07 5.35 3.86 1.04 0.96 4.68 1.34
650 765 0.270 4.05 5.34 3.88 1.04 0.97 4.69 1.57
700 764 0.270 4.01 5.30 3.89 1.04 0.98 4.72 1.81
750 761 0.270 4.00 5.29 3.92 1.05 1.00 4.74 2.04
800 759 0.270 3.98 5.28 3.94 1.06 1.01 4.74 2.28
850 757 0.270 3.98 5.29 3.98 1.07 1.02 4.74 2.52
900 755 0.270 3.98 5.30 4.02 1.09 1.04 4.73 2.75
950 753 0.270 3.97 5.30 4.06 1.10 1.05 4.73 2.99
1000 751 0.270 3.97 5.32 4.10 1.11 1.06 4.71 3.23
Calculated from Tables 3 & 26. Dimensions as in Table 29.
ANDERSON AND ISAAK 77
T 0 u (6T-6s) u
6s ST r
7 ~KT APT,
300 763 0.238 4.45 5.94 6.07 1.16 1.20 3.46 0.00
400 757 0.239 4.20 5.58 5.66 1.14 1.21 3.80 0.36
500 751 0.240 4.15 5.49 5.54 1.14 1.20 3.97 0.75
600 744 0.241 4.15 5.48 5.50 1.14 1.20 4.07 1.16
700 738 0.242 4.16 5.49 5.46 1.15 1.20 4.13 1.57
800 731 0.243 4.13 5.47 5.45 1.17 1.18 4.18 1.98
900 724 0.244 4.08 5.46 5.44 1.20 1.20 4.22 2.40
1000 718 0.245 4.05 5.47 5.45 1.25 1.22 4.26 2.83
1100 711 0.246 4.00 5.46 5.43 1.28 1.20 4.31 3.25
1200 704 0.248 4.02 5.49 5.38 1.28 1.21 4.33 3.69
1300 697 0.249 3.97 5.44 5.32 1.28 1.20 4.36 4.13
1400 689 0.250 3.90 5.37 5.24 1.28 1.21 4.37 4.50
1500 682 0.251 3.92 5.38 5.22 1.27 1.23 4.39 5.07
1600 674 0.252 3.93 5.40 5.19 1.28 1.19 4.40 5.43
1700 668 0.254 3.96 5.42 5.16 1.28 1.20 4.39 5.87
Calculated from Tables 9 & 18. Dimensions as in Table 29.
(6T-6S)
T 0 u 6s 6T r u Cd--T APTH
-7
300 731 0.249 5.24 6.59 6.56 1.07 1.17 3.37 0.00
400 725 0.250 4.70 5.95 5.92 1.03 1.17 3.76 0.36
500 719 0.251 4.46 5.65 5.63 1.02 1.17 3.97 0.75
600 713 0.252 4.33 5.51 5.50 1.02 1.18 4.05 1.15
700 706 0.252 4.25 5.44 5.42 1.04 1.18 4.11 1.56
800 700 0.253 4.21 5.40 5.38 1.06 1.18 4.14 1.97
900 699 0.255 4.16 5.36 5.36 1.07 1.18 4.18 2.38
1000 688 0.255 4.14 5.36 5.35 1.10 1.18 4.17 2.80
1100 681 0.256 4.13 5.37 5.35 1.13 1.18 4.17 3.22
1200 675 0.257 4.12 5.38 5.36 1.16 1.18 4.16 3.63
1300 669 0.258 4.07 5.35 5.32 1.18 1.18 4.15 4.05
1400 662 0.259 4.10 5.41 5.39 1.23 1.19 4.14 4.46
1500 665 0.260 4.10 5.43 5.41 1.26 1.19 4.13 4.88
Calculated from Tables 10 & 19. Dimensions as in Table 29.
78 HIGH T ELASTICITY OF MANTLE MINERALS
T u (h-b) v
0 6s ST r 7 QKT APTH
300 511 0.336 5.99 7.34 9.34 1.12 1.54 3.56 0.00
400 506 0.337 5.56 6.85 7.49 1.09 1.33 3.82 0.37
500 501 0.338 5.35 6.62 6.02 1.09 1.09 3.95 0.76
600 497 0.338 5.24 6.50 4.69 1.11 0.85 4.02 1.16
700 494 0.338 5.18 6.45 3.43 1.14 0.60 4.06 1.56
Calculated from Tables 11 & 20. Dimensions as in Table 29.
300 535 0.315 6.66 8.19 8.43 1.44 1.19 2.90 0.00
400 530 0.315 5.95 7.35 7.57 1.30 1.19 3.23 0.31
500 525 0.316 5.61 6.96 7.17 1.25 1.19 3.41 0.64
600 520 0.317 5.43 6.76 6.97 1.24 1.19 3.52 0.99
700 515 0.317 5.31 6.63 6.84 1.25 1.20 3.59 1.34
Calculated from Tables 12 & 21. Dimensions as in Table 29.
300 551 0.317 5.81 7.32 5.51 1.35 0.96 3.34 0.00
400 548 0.316 5.19 6.56 4.91 1.27 0.96 3.72 0.35
500 545 0.316 4.88 6.19 4.62 1.23 0.96 3.94 0.74
600 541 0.316 4.71 6.01 4.46 1.22 0.96 4.07 1.14
700 538 0.316 4.60 5.88 4.35 1.21 0.96 4.16 1.55
Calculated from Tables 13 dc 22. Dimensions as in Table 29.
Table 39. MnO: Dimensionless parameters, Debye temperatures and thermal pressure
300 534 0.301 4.14 5.96 8.33 1.20 1.56 5.07 0.00
350 531 0.302 4.03 5.82 8.14 1.18 1.57 5.20 0.26
400 527 0.303 3.94 5.71 8.01 1.17 1.57 5.29 0.52
450 523 0.305 3.88 5.64 7.95 1.16 1.57 5.36 0.79
500 519 0.307 3.83 5.58 7.94 1.16 1.58 5.41 1.05
Calculated from Tables 6 & 23. Dimensions as in Table 29.
ANDERSON AND ISAAK 79
(6,-b) v
T 0 tT 6s ST r 7 ~KT A~TH
300 862 0.280 6.03 7.73 5.30 1.12 0.90 4.38 0.00
400 858 0.279 5.72 7.36 5.01 1.20 0.90 4.60 0.45
500 854 0.279 5.49 7.07 4.78 1.22 0.90 4.79 0.92
600 850 0.278 5.27 6.82 4.59 1.21 0.90 4.97 1.41
700 845 0.278 5.10 6.62 4.43 1.20 0.90 5.11 1.91
800 840 0.278 4.96 6.47 4.30 1.19 0.90 5.24 2.43
900 835 0.277 4.85 6.35 4.20 1.18 0.90 5.33 2.96
1000 830 0.278 4.74 6.24 4.11 1.17 0.90 5.43 3.49
Calculated from Tables 5 & 17. Dimensions as in Table 29.
Table 41. NaCl: Dimensionless parameters, Debye temperature and thermal pressure
T 0 I7 (6T-b)
6s 6T r
7
v ~KT APTH
300 304 0.256 3.47 5.56 5.05 1.32 1.29 2.82 0.00
350 300 0.258 3.56 5.62 5.00 1.29 1.26 2.83 0.14
400 296 0.260 3.65 5.69 4.95 1.27 1.23 2.84 0.28
450 291 0.262 3.72 5.74 4.90 1.25 1.20 2.86 0.43
500 287 0.264 3.80 5.82 4.86 1.24 1.18 2.86 0.57
550 283 0.265 3.91 5.95 4.83 1.25 1.16 2.84 0.71
600 278 0.265 4.03 6.10 4.79 1.27 1.13 2.81 0.85
650 274 0.266 4.14 6.24 4.77 1.29 1.11 2.78 0.99
700 269 0.268 4.23 6.37 4.76 1.31 1.10 2.77 1.13
750 264 0.270 4.34 6.53 4.76 1.35 1.08 2.73 1.27
Calculated from Tables 8 & 27. Dimensions as in Table 29.
Table 42. KCl: Dimensionless parameters, Debye temperature and thermal pressure
300 230 0.274 3.77 5.84 4.66 1.34 1.17 1.87 0.00
350 227 0.275 3.86 5.88 4.77 1.34 1.17 1.86 0.09
400 224 0.277 3.92 5.88 4.86 1.32 1.17 1.86 0.19
450 221 0.278 3.97 5.88 4.93 1.30 1.17 1.86 0.28
500 218 0.278 4.02 5.88 4.97 1.28 1.17 1.86 0.37
550 214 0.279 4.05 5.87 5.02 1.26 1.17 1.87 0.47
600 211 0.282 4.06 5.84 5.10 1.23 1.18 1.88 0.56
650 208 0.284 4.09 5.83 5.19 1.21 1.18 1.88 0.65
700 204 0.285 4.18 5.90 5.30 1.23 1.18 1.86 0.75
750 200 0.286 4.27 5.98 5.44 1.25 1.18 1.83 0.84
800 196 0.289 4.34 6.04 5.61 1.27 1.19 1.81 0.93
850 192 0.288 4.50 6.19 5.76 1.33 1.19 1.77 1.02
Calculated from Tables 7 & 28. Dimensions as in Table 29.
80 HIGH T ELASTICITY OF MANTLE MINERALS
The appropriate equations used in preparing the ta- Mie-Griineisen equation of state).
bles are presented in Section 2. The various corre- A well-known thermodynamic identity is that the
lations between the thermoelsstic constants are pre- temperature derivative of the pressure at constant V is
sented in Anderson et al. [13] and reviewed in Sec- exactly equal to CYKT by means of calculus definitions,
tion 3. The mineral data are set forth in Section 4. so that
Theory appropriate to the high temperature trends of
the data is presented in Section 5. Extrapolation equa-
tions are reviewed in Section 6.
3. EQUATIONS USED IN TABLED VALUES where l+~ is the thermal pressure. Thus (YI<T is the
OF PHYSICAL PROPERTIES slope for the PTH versus T curve at constant V.
Using (6) for an isochore,
Once the elastic constants have been determined
over a wide range in T, the four dimensionless ther-
moelastic parameters at each T are computed [7] using PTH = (YKT dT, (7)
J
the following nomenclature:
which is equivalent to the statement that
CXKS (YIiT
-/x-z- (1)
PCP PCV
PTH =
afhv,
21,
p’
(11) (87/8T),
the
has an important
Mie-Griineisen formulation
effect on the validity
of the thermal
of
pres-
which is of interest in seismic tomography calculations sure.
[l, 20, 371. We also list values of the adiabatic Pois- The acoustic version of 0, 8,, shows that miner-
son’s ratio u given by als with higher density have higher values of 0,,. We
know that when the average mass is constant from
3Ks - 2G material to material, the value of 8,, rises as the 4/3
IY= 6Ks+2G’
(12) power of the density [2]. We would therefore expect
that O,, for perovskite will be high, in the neighbor-
4. SOME CORRELATIONS FOUND FOR
hood of that found for AlzOs.
PROPERTIES IN THE TABLES
The value of O,, for perovskite at ambient condi-
tions calculated by (5) is 1094 K. The values vr, = 10.94
This section deals with relationships between the
km/s, v, = 6.69 km/s, and ps = 4.108 g/cm3 used in
thermoelastic dimensionless parameters. The equation
the calculation are given by Yeganeh-Haeri et al. [78].
showing the relationship between ST - 6s and 7 is [lo]:
O,, for corundum is 1033 K, and pc = 3.981. This
similarity in values of 8,, and pc suggests that the
measured thermal pressure of corundum could be used
sT-a =7{l+K%L+G%]) as a guide for that of perovskite at mantle tempera-
s . (13) tures and pressures. The expected variation of O,,
(1+ a7TbT)
with T for perovskite is shown in Figure 1, where O,,
If the relative increase in (Y with T nearly compen- of perovskite is compared to that of forsterite and per-
sates for the relative decrease of 7 with T taking into iclase.
account the change in the denominator of (13), then
we may expect that 6~ - 6s is close in value to 7. Debye Temperature (four minerals)
Since the rate of change of 7 with T is seldom the 1200 1 I
same as the rate of change of (Y with T, we see that
ST -6s = 7 may be an approximation
limited range of temperatures,
valid only over a
usually near and above 1100 ~
--
perovskite
El
P=O
0. --- 1
In some thermodynamics manipulations, the approx-
imation 6T-6s = 7 is useful. In Tables 29-42, we show
the variation of (6~ - 6s) /7 with T/O for our fourteen
minerals. Thus an empirically determined approxima-
tion where actual high-temperature data are lacking
is
6, - 6s = 7. (14
Another significant correlation found for most min- Goto et al. [26], which are based on the VRH scheme.
erals is The errors indicated in Tables 15-28 for KS and G
are propagated by standard error techniques in which
r=bT, (15) two sources of error are considered. These errors in-
which allows one to calculate G for KT in high tem- clude both the uncertainty with which the midpoints
perature ranges where G is not known. It immedi- of the upper and lower bounds of KS and G are known
ately follows from (15) that, because G is less than and the difference between the midpoints and the up-
KS, I@WT) p 1 must be smaller than I(dKs/aT)pI. per bounds.
We couple thermal expansion CYand heat capacity
5. PRESENTATION OF MINERAL DATA Cp (at constant P) data with KS and G and calculate
the values for several other thermoelsstic quantities
We tabulate the adiabatic single-crystal elastic mod- given in Tables 15-42. We assume LY is accurate to
uli (Cij) for 14 minerals in Tables 1 to 14 starting 2% (unless specified otherwise in the original reference
at 300 K and proceeding in intervals of either 50’ or from which the a! data are obtained) and rigorously
lOOoK. The errors indicated at selected temperatures propagate errors to p, Cv, KT, up, and vI at high and
in Tables l-14 are those listed in the original refer- low temperatures in Tables 15-28. The uncertainty in
ences. The Cij data for thirteen of the fourteen miner- the dimensionless quantities 6s) 6T, I?, and v should be
als in Tables 1-14 were retrieved by the already defined taken as 5% or more, since the values of these parame-
RUS method (either rectangular parallelepipeds or res- ters can depend somewhat on the order of polynomial
onant spheres). The tabulated errors in the Cij from fit used when determining the T derivatives.
these thirteen minerals are the standard deviations de-
termined from the difference of each measured modal
frequency with that modal frequency value calculated 5a. MgO
from the final set of Cij. Thus the listed uncertainties Prior to the work of Isaak et al. [34], high T data on
reflect how consistent the frequency data are in provid- the elastic moduli of single-crystal MgO were available
ing Cij values for a particular specimen. The MnO Cij up to 1300 K. Spetzler [55] used an ultrasonic pulse-
data and their uncertainties are not from RUS mea- echo method to obtain ambient P data at 300 and
surements, but are those recommended by Pacalo and 800 K and provides a table listing T derivatives of elas-
Graham [47] from a weighted linear regression analyses ticity at these two temperatures. Sumino et al. [63],
together with the Pacalo and Graham [47] temperature using the rectangular parallelepiped resonance (RPR)
derivatives. method, extended the T range for which data were
The isotropic adiabatic bulk KS and shear G mod- available up to 1300 K. Isaak et al. [34] (RPR) and
uli computed from the Cij in Tables l-14 are included Zouboulis and Grimsditch [80] (Brillouin scattering)
in Tables 15-28. For minerals with cubic crystal sym- report Cij data for MgO UP to 1800 and 1900 K, re-
metry, I<s is given by (1/3)(Cii + 2Crz). We use the spectively.
Hashin-Shtrikman (HS) [29,30,73] scheme to compute We list the Cij values as reported by Isaak et al. [34]
G for cubic minerals (MgO, MgAlzOd, MnO, CaO, in Table 1 and note that an alternative source for
garnet, and NaCl) and both KS and G for minerals high T data can be found in Zouboulis and Grims-
with orthorhombic symmetry ([Mg, Fe, Mn, Co]zSiO.+). ditch [80]. In their Table 2, Zouboulis and Grims-
Very small variations (typically 5 0.1 GPa) between ditch [80] report (711(T), &(T), and the combined
our tabulated values of I<s and G for the orthorhom- moduli (Crr + Crz + 2644)/2 and (Cir - &)/2 ver-
bit minerals and the values found in the original ref- sus T. However, there is more scatter (especially in
erences are due to the differences in KS (or G) that the Cd4 modulus) in the data of Zouboulis and Grims-
result when using the HS and Voigt-Reuss-Hill (VRH) ditch [80] than in the data of Isaak et al. [34]. We find
schemes. However, the HS scheme usually provides excellent agreement in (dC~/dT)p values when com-
significantly narrower bounds and is preferred. The paring the results of Spetzler [55], Sumino et al. [63],
values in the tables are the averages of the upper and and Isaak et al. [34] in their T range of overlap. The
lower bounds found with the HS scheme. We use the high T (i.e., T > 1400 K) Zouboulis and Grimsditch
VRH scheme to determine the isotropic G for KC1 be- [80] data have T dependence nearly identical to that
cause of difficulties in interpreting the HS upper and of the Isaak et al. [34] data up to 1800 K.
lower bounds (see Section g. below). For corundum The values of the dimensionless parameters, 6s, ST,
(AlzOs) we use the KS and G values tabulated by I’, and Y, in Table 30 are found using sixth order poly-
ANDERSON AND ISAAK 83
nomial fits to the KS, KT, G, up, and v# results as pyrope, 1.2%; less than 0.5% almandine or spessartine)
done by Isaak et al. [34]. We find very little difference to 1350 K. Table 4 is constructed using the KS, Cs,
in the value of these dimensionless parameters, other and Cd4 of Isaak et al. [36] as primary data. Cir and
than a slightly less rapid decrease when T > 1500 K, Crz and their errors are calculated from these primary
when a lower order of fit, such as 3, is used. data. The Cij values in Table 4 are plotted by Isaak
et al. [36], but not explicitly tabulated in their presen-
5b. CaO tation. We follow Isaak et al. [36] in the order of fit
used to calculate the T derivatives for the dimension-
The appropriate thermoelastic quantities for CaO
less parameters. The parameters bs and & are found
[43] are listed in Tables 2, 24, and 31. Oda et al. [43]
using first order fits to the KS and KT data. Second
used the resonant sphere technique (RST) to reach
order fits were applied to the G data to obtain I’ and
1200 K. We include the o data of Okajima [45] as
to the I+, and v, values to obtain V. Isaak et al. [36]
tabulated by Oda et al. [43] in our Table 24. The di-
also provide new cx data for grossular-rich garnet and
mensionless parameters in Table 31 are obtained from
point out the possibility that the Skinner [51] thermal
a second order polynomial fit of the I<s, KT, G, up,
expansion values for garnets may be low.
and v, [43].
5e. Spine1 (MgAl~O4)
5c. Pyrope-Rich Garnet Cynn [19] provides Cij for single-crystal MgAlz04
Suzuki and Anderson [65] provide Cij for pyrope- over the range 298-999 K at irregular intervals of T.
rich garnet over the temperature range 298-993 K at There are data [19] up to 1060 K, but a sudden change
irregular intervals of T. The specimen used by Suzuki in the slope of the data near 1000 K is attributed to
and Anderson [65] is a single-crystal natural garnet the effect of cation disordering. We use the KS, Cs,
with composition: pyrope, 72.6%; almandine, 15.7%; and C44 values from 298-999 K given by Cynn [19] as
uvarovite, 6.1; androdite, 4.3%; spessartine, 0.7%; and the primary data source and interpolate to obtain the
grossular, 0.6%. We use the KS, Crr, and CJ~ values Cij in Table 5 at regular 50°K increments of T. Errors
given by Suzuki and Anderson [65] (see their Table 1) in Table 5 are either those given by Cynn [19] or are
as the primary data source and interpolate to obtain propagated from the errors in KS, C’s, and C44. The
these moduli given in Table 3 at 100°K increments of uncertainty in p at 300 K (Table 17) is assumed since
T. The C’44 value at 638 K given by Suzuki and An- it is not reported by Cynn [19]. The uncertainties in
derson [65] seems unusually low and is excluded in our the Cij for MgA1204 are large relative to most other
fit for interpolating. All errors in Table 3 are either resonance data; thus we present the dimensionless pa-
those given by Suzuki and Anderson [65] (i.e., errors rameters in Table 40 based on linear fits of KS, KT,
for KS, Cir, C,,) or are propagated from the errors in G, vr,, and v6 with T.
KS, Cr1, and Cd4 (i.e:, errors in Ciz and Cs). We ex-
trapolate (linear in ii’s and Cir; quadratic in C&a) the 5f. MnO
Suzuki and Anderson [65] Cij data over seven degrees Pacalo and Graham [47] present new data on MnO
to include the 1000 K values in Table 3. The dimen- from 273-473 K. We construct Table 6 using the Cij
sionless parameters 6s and ST (Table 33) are found and (X’ij/dT)p values recommended by Pacalo and
by a linear fit of the KS and KT values in Table 26. Graham [47] (see their Table 10) for MnO. For C44 we
We find that G and v, have noticeable curvature, so use a second order polynomial to interpolate at inter-
that second order fits are preferred when calculating vals of 50°K where the nonzero value of (8”Cij/dT2)p
F and V. It is worth noting that v tends to increase is found in Table 6 of Pacalo and Graham [47]. The
gradually from about 0.88 to 1.06 over the 300-1000 K recommended first temperature derivatives are based
range when second order fits to v, and vr versus T are on both ultrasonic pulse-echo [47] and resonant [62]
used. If first order fits are assumed, v is constant with measurements. For minerals of cubic symmetry there
a value of 0.97 over the 300-1000 K range in T. Ther- are only two independent moduli among KS, &I, and
mal expansion cx data on pyrope-rich garnet are also Ciz. The recommended values for KS, Cir, and Ciz
provided in the Suzuki and Anderson [65] paper. in Table 10 of Pacalo and Graham [47] are not self-
consistent. We take Cl1 and Cl2 from Pacalo and
5d. Grossular Garnet Graham [47] as the primary data and use these to
Isaak et al. [36] provide elasticity data for near end- compute KS for Table 23. Thus a small difference ap-
member grossular (grossular, 96.5%; andradite, 1.6%; pears between the 300 K value for KS in our Table 23
84 HIGH T ELASTICITY OF MANTLE MINERALS
(149.0 f 2.6 GPa) and that given by Pacalo and Gra- al. [77] is -0.012 GPa/K. The Yamamoto et al. [77]
ham [47] (150.6f 2.5 GPa). The values at 500 K in our results tend to favor those of Spetzler et al. [56], who
Table 6 require an extrapolation of 27°K beyond the obtained elasticity data to 800 K for NaCl. Spetzler
maximum T measured, but are below the Nkel tem- et al. [56] find (i?Ks/aT)p to be -0.011 GPa/K from
perature (522 K for MnO). Temperature derivatives 300-800 K. The Yamamoto et al. [77] data are out to
of KS, KT, C, up, and v, are done with a linear fit a slightly lower maximum temperature than Spetzler
in T when calculating the dimensionless parameters in et al. [56], but contain a much denser set of tabulated
Table 39. Cij values.
We interpolate the Crr, Clz, and C’44 found in Ta-
5g. KC1 ble 2 of Yamamoto et al. [77] to regular intervals of
Table 7 shows Cij for KC1 where we use the Ya- 50°K for our primary elasticity data source in Table 8.
mamoto and Anderson [76] data to interpolate at even The uncertainty in the density of the specimen used by
intervals of 100°K. The Crr, Ciz, and Cd4 [76] are Yamamoto et al. [77] is assumed to be 0.005 gm/cm3
taken as the primary data from which C’s and KS at 300 K (Table 27), since this is not provided by Ya-
(Table 28) and their errors are derived. In determining mamoto et al. We calculate the dimensionless param-
the isotropic shear modulus G we used the VRH rather eters in Table 41 using a second order fit in T to the
than the HS scheme. When attempting to use the HS KS, I<T, G, up, and v, values in Table 27, and note
scheme [30], we found that the resulting upper bound that this results in 6T at 300 K having a value near 5.6
for G is less than the lower bound for temperatures rather than 5.3 as indicated by Yamamoto et al. [77].
in the range of 300-450 K. We are unable to resolve We also find that above 600 K, ST increases gradu-
this difficulty. This seemingly contradictory result is ally from 6.1 to 6.5, rather than having a value nearer
likely related to the fact that the shear modulus C’s 5.8-5.9 in this temperature range. These differences
is very near to the value of the bulk modulus KS at are due to the difference in method used to calculate
the lower temperatures. In any case we must defer to the T derivatives. We fit the data over the T range
the VRH scheme for this material and note that there of measurement to a polynomial; Yamamoto et al. [77]
are relatively wide bounds on G (thus also on up and find T derivatives by taking a finite difference between
v,), especially so at lower temperatures. Statistical two adjacent data points.
analysis indicates that a second order polynomial fit
of KS, G, up, and v, is warranted when determining 5i. MgaSiO4
the T derivatives, whereas a linear fit of KT with T is Following the work of Sumino et al. [61] to 670 K and
adequate. Suzuki et al. [68] to 1200 K, the MgzSiOd (forsterite)
data of Isaak et al. [35] to 1700 K extend the T limit for
5h. NaCl which elasticity data are available. Prior to bhese stud-
Yamamoto et al. [77] report elasticity data from 294- ies the available data were limited to T near ambient
766 K for NaCl. Elasticity data up to the melting [27, 401. There is general agreement between the data
temperature of 1077 K for NaCl [31] were obtained where they overlap. Sumino et al. [61] provide schemes
with the composite oscillator method. To find accu- for extrapolating that are generally confirmed by the
rate Cij results with the composite oscillator requires higher temperature measurements of Suzuki et al. [68]
that the resonant frequencies of quartz and silica rods and Isaak et al. [35] (See Figures 3 and 5). We con-
that are coupled to the NaCl specimen be known in struct Table 9 from the Cij reported by Isaak et al. [35].
order to reduce the NaCl data. We also note that the The thermal expansion results of Kajiyoshi [38] are
experimental arrangement of Hunter and Siegel [31] used (see our Table 18) to calculate the thermoelastic
requires a large volume to be heated when increas- properties of MgsSiOd (see Isaak et al. [35] for a com-
ing temperature. For these reasons we prefer the data parison of the Kajiyoshi [38] values of a with other
of Yamamoto et al. [77], but emphasize that Hunter values in the literature). Isaak et al. [35] used the
and Siegel [31] report data 300’K higher in T than VRH scheme to calculate isotropic KS and G moduli,
do Yamamoto et al. [77]. There are relatively small whereas Table 18 lists KS and G obtained from the
but measurable differences in the T dependence of the HS averaging scheme. There is only a small difference
elastic moduli between these two data sets where they (5 0.1 GPa) between the two approaches. Isaak et
overlap. For instance, from 300-700 K the average al. [35] show that fits of the KS, KT, G, v~, and us
value of (aKs/BT)p from Hunter and Siegel [31] is data with T imply that third order polynomials are
-0.015 GPa/K, whereas that found by Yamamoto et appropriate to describe the data. Thus we use third
ANDERSON AND ISAAK 85
order fits for all T derivatives required to determine alite (see Graham et al. [28], Isaak and Anderson [33],
dimensionless parameters in Table 34. There are some and Wang et al. [71]). As an example of the effect
small differences in the 6s, 6~, and I between our Ta- of uncertainties in the derivative values, Graham et
ble 34 and Table 5 of Isaak et al. [35] due to different al. [28] report (llKs/dT)p = -0.030 GPa/K, whereas
methods used in calculating the T derivatives. Isaak Sumino [58] reports -0.0205 GPa/K. The reasons for
et al. [35] used the interval between the two neighbor- these types of discrepancies are under investigation.
ing points to calculate the derivative at a particular T; At present, we defer to the data of Sumino [58] since
here we apply polynomial fits over the whole temper- they involve a significantly wider range in T (up to
ature range from which the derivatives are obtained. 673 K) than the maximum temperature of 313 K used
The present approach produces smoother variations in by Graham et al. [28]. However, no compelling rea-
6s, 6~, I, and v with T. sons exist to suggest that the Sumino [58] fayalite data
should be preferred over those of Graham et al. [28].
5j. Olivine (F~Fa~o) From Figure 2 of Sumino [58] it is clear that KS
Isaak [32] reports data to 1400 and 1500 K, respec- is linear in T, whereas G requires a higher order T
tively, on two natural olivine samples with composi- dependence (at least a fourth order polynomial). In
tions of Fos2.iFar.r and Fos0.sFas.a. Previously avail- calculating the dimensionless parameters for fayalite
able T data on the elasticity of iron-bearing minerals in Table 36 we use linear fits in T for KS and KT
were limited to temperatures near ambient [40]. We in- and fourth order fits for G, vr, , and v,. Sumino [58]
clude the Cij for Foss.sFas,s (referred to here as olivine attributes the strong nonlinear behavior of the shear
FoaeFais) in Table 10. There are some differences be- modulus to influences of the antiferromagnetic to para-
tween the Cij of the two olivines reported by Isaak [32] magnetic transition, even though this transition occurs
that do not appear to be due to fayalite content. The at a much lower temperature (65 K).
differences are small, but caution should be used when Sumino [58] a 1so reports elasticity data on single-
interpolating between specimens with small differences crystal Mn$SiOa and CosSiO4 at 300 and 673 K. Sum-
in chemistry. The uncertainties in KS and G (and in ino [58] indicates that all the Cij of Mn#iOr and
all properties that depend on KS and G) are somewhat Co2SiO4 are linearly dependent on T with the excep-
smaller in Table 19 than found in Isaak [32] for these tion of Cad for Co$jiO4. We construct Tables 12 and
quantities. Isaak [32] estimated the uncertainty by 13, which show values of Cij at incremental tempera-
simply adding the uncertainty with which the HS aver- tures of lOOoK for MnzSi04 and CozSi04, using the
age value is known to the distance between the average Cij and the (dCij/aT)p given by Sumino [58] in his
value and the HS high value. Here we square both the Tables 4a,b. We assume a linear T dependence of the
uncertainty of the HS average and the distance from Co$SiOh Cd4 modulus in constructing Table 13 since
the HS average to the HS high value, add the squares, the presence of nonlinearity in this modulus is asserted
and take the root. We use linear fits in T to the KS, by Sumino [58] but no quantitative result is provided.
KT, G, up, and v, data when obtaining the dimension- As with FesSiOh, we must perform a small extrapola-
less parameters 6s, 6~, I’, and v. We start our olivine tion outside of the maximum T measured in order to
tables by interpolating the T = 296 and 350 K data include the T = 700 K values in the tables for Mn$SiOa
of Isaak [32] to 300 K. This shift in starting T causes and Co$SiO4. When calculating the dimensionless pa-
minor differences in the T derivatives; hence the slight rameters all T derivatives are assumed linear in T (see
differences between 65, 6~, and I in Table 35 and in Figure 2 in Sumino [58]).
Table 6b of Isaak [32].
51. Corundum (AlaOs)
5k. Fe#iO,, Mn#iO~, CosSiOd The C, (Table 14), I<s, and G (Table 16) for AlaOs
Sumino [58] presents T data from 25’-4OO’C (398- are those found in Goto et al. [26]. The KS and G
673 K) on the elasticity of single-crystal FezSiOa (fay- given by Goto et al. [26] are found by the the Voigt-
alite). We interpolate the Sumino [58] fayalite data Reuss-Hill averaging scheme. Full account is made of
(see his Table 3, specimen TA) so as to provide C;j the difference between the Hill (averaged VRH) val-
from 300-700 K in regular 50’K intervals in Table 11. ues for KS and G and the Voigt (upper bound) values
A small extrapolation over 27’K is required to extend when assigning errors to KS, G, and other isotropic
the values represented in Table 3 to 700 K. It should quantities derived from them. This accounts for larger
be noted that there are questions regarding the values errors being assigned to the G values in our Table 14
of some of the Cij and some of the T derivatives of fay- than are found in Table 2 of Goto et al. [26]. Appar-
86 HIGH T ELASTICITY OF MANTLE MINERALS
ently Goto et al. [26] assigned errors in G that include number; and p is the number of atoms in each cell (or
only the uncertainty in the Hill average itself, but do molecule). The first term on the right is the zero point
not consider the difference from the Hill average to vibrational energy EZV given by
the upper (or lower) bound. We interpolate the Cij,
KS, G, and p provided at 296 and 350 K to start our
Tables 14 and 16 at 300 K. E zv = :EhWj. (17)
j=l
We use (Y from White and Roberts [75] rather than
the cu preferred by Goto et al. [26], i.e., those from
Note that, unlike the last term in (16), there is no
Wachtman et al. [70].
T in EZV. This term arose by summing the allowed
We use a third order polynomial fit to determine
quantum state levels to find the energy of each normal
the T derivatives for each of KS, KT, G, vP, and v,
mode, according to the Hamiltonian [42].
required for the dimensionless parameters shown in Ta-
We replace w with y, the dimensionless frequency,
ble 29. This order of fit seems appropriate from a sta-
so that
tistical consideration, i.e., an F, test [18]. Thus, the
SS, ST, and u found in our Table 29 for AlsOs may
differ somewhat at a particular T from those given by (18)
Goto et al. [26] in their Tables 4 and 5. The Goto
et al. [26] 6s, 6T, and v values are calculated from Thus (16) can be given in terms of the thermal energy
derivatives found by using a finite interval from the
two nearest data points. Thus, we find considerably dvzB = Ezv + dmz, W-9
more scatter in the Goto et al. [26] 6s and ST values
than in Table 29. where
3pN 3pN
6. THEORETICAL BASIS FOR OBSERVED dTH = kT c en (1 - emyj) = kT c dTHj, (20)
PROPERTIES AT HIGH TEMPERATURE j=l j=l
Most, but not quite all, of the high temperature dTH is the energy arising from temperature excita-
properties of the solids reported here are consistent tion, called the thermal energy. Ezv is not affected
with the high temperature limit of the quasiharmonic by T, as shown in (17). Thus dTH --$ 0 as T --+ 0.
approximation of the statistical formulation of the free However, dvzs -+ EZV as T + 0, and EZV is a non-
energy. zero number. Ezv is sufficiently small that for most
numerical evaluations it could be dropped, but it is
6a. The Helmholtz Free Energy useful to keep this term in dvrB for algebraic manip-
The expression for the Helmboltz energy for an in- ulations done lat>:r on.
sulator is [41] The expression for the Helmholtz energy for an in-
sulator is thus
A = EST +-km,
A = EST + Ezv + dTH. (21)
where electronic and magnetic effects are ignored. EST
is the potential of a static lattice at absolute zero, and We need to divide (21) into temperature-dependent
dvrB is the vibrational energy due to motion of the and nontemperature-dependent parts, so we use
atoms as each is constrained to vibrate around a lattice
point. A = ET=O + dTH, (22)
The statistical mechanical definition of the vibra- where
tional contribution to the Helmholtz energy arising
from 3pN independent oscillators is ET=o=EsT+Ezv. (23)
dvrB = i3EhWj +kT3E!n(l-e-‘ui”T), (16) Dividing (21) into its vibrational and nonvibrational
j=l j=l parts, we define
Comparing (29) with (20), we see that By replacing the last logarithmic term above with its
argument, which is valid for low values of yj, we find
that
PTH= $cYjdTHj. (30)
3
en (1 - eWyj) 2: en yj - f yj.
(36)
The specific heat is formed by applying - (a/aT), to
(25), yielding Thus the high-temperature representation of (20) is
88 HIGH T ELASTICITY OF MANTLE MINERALS
Aht=Es~+Ezv+kT(Cenyj-~Cyj). (38)
j j -
‘?‘ht = Y(T+m) = - (44
We see that the last term above just cancels the zero
temperature energy given by (17), so that
which is independent of T. The data on y is found in
3pN
Tables 15-28.
Aht = EST + kT c (en hwj - en kT). (39) We see that there is an approximate trend for y to
j=l
be independent of T at high T. For these solids when
This can be simplified by defining an average frequency dy/dT is not zero, it is also true that CV does not
a, given by obey the Dulong and Petit limit. Thus departures
from quasiharmonic theory in CV create a departure
en v = -J-C hwj, from the quasiharmonic theory of 7. Above T = 8,
3pN the departure from (dy/dT), = 0 is slight, however.
in which case (20) becomes Applying the operator -(a/W), to (38), we find
the high T pressure, Pht , which by using (44) becomes
ATH = 3pNT ( en IiiZ - en kT) . (41)
6d. Thermodynamic Properties in the High T Pht(T, V) = P(0, V) + y7ht T. (45)
Limit of the Quasiharmonic Approximation
At high T, .4 includes only the static potential and
the thermal energy in the quasiharmonic approxima- Thus the thermal pressure is
tion. Using the equation U = -l/T’ ((BA/T)/aT),,
we find the high temperature internal energy to be PTH = -3pR
v -f’ht T.
cific heat.
We see that the quasiharmonic theory
allows for
Cc” = 3pR. (43) PTH to be virtually linear in T: at the highest mea-
sured T, aT II 0.05. But 7ht is not, as we shall see,
Equation (43) is known as the Dulong and Petit limit. exactly independent of T, though close to it. Thus
Thus the high temperature quasiharmonic approxima- there are counter effects in T, and the 1 - aT term
tion leads to the classical limit in specific heats. If at is often obscured. Thus to a very good approximation
high T the experimentally determined CV is not paral- PTH is proportional to T under the quasiharmonic ap-
lel to the T axis, we must conclude that the quasihar- proximation.
manic approximation is not adequate for this property, The thermal pressure relative to T = 8 for T > 0
and anharmonic terms must be added to A. is given by
From Figures 14-26, where the data for specific heat
versus T are listed, we see that for several solids of APTH = PTH (T, fi) - PTH (6 b) . (47)
interest to geophysicists (dCv/8T)~ = 0 at high T.
This is true for MgO, CaO, and A1203 and NaCl, but As shown in Tables 15-28, we see that APTH is indeed
not for olivine, garnets, spinel, or KCl. We must con- linear with T (for T/O0 > 1). (See also Figure 2).
ANDERSON AND ISAAK 89
ar-4
( )
-
fw v
= -$$7& - Qhl). (50)
Fig. 2. APT, versus T/O, for nine minerals show-
For q ht = 1, (aK~/tlT)v vanishes, so the determi-
ing: 1) APT, is linear in T/00; and 2) the slope
nation of (50) ordinarily yields a small quantity. To
of the APTH - T/O0 line decreases as pc/(M/p) de-
obtain the isobaric derivative, (aK~/aT)p, we use the
creases. Values of pc/(M/p) in ascending order (l-9)
calculus expression:
are: 0.195, 0.178, 0.176, 0.160, 0.160, 0.151, 0.119,
0.073, and 0.053. 00 is the acoustic 0 at T = 300 K.
(fi!$),= (s)v-&-T(=$)T. (51)
This means that for the thermal pressure property, the Thus at high T, along an isobar,
qua&harmonic approximation appears quite adequate
up to relative temperatures of T/C& x 2.0. This range = -3 -f,,t(l-qht)-(Yli.T
covers values of T/O0 for the mantle of the earth. The
linearity of PTH with T is not unique to silicates and
alkali halides; it is also found for gold (see Figure 10
(52)
of Anderson et al. [12]).
The term on the far right of (49) is the thermal bulk
The slope of the APTH - T curve from (47) is em-
modulus, KTH. Using (48) in (52), we have
pirically a constant. Since PTH = s CYKT dT, then we
can define an average value of CXKT, CYKT, good for T
above 0, such that (qth - 1) - d(T .
T
6f. Entropy and CV& in Cv , but even so, this effect does not appear in prop-
Applying the operator (a/X!‘), to (38), the entropy erties that are controlled by the volume derivatives of
is found A as described above. Further, we also showed that
there is no evidence of anharmonic effects in PTH be-
Sht = -3pR( Cn kT - en Foss+ 1). (54) cause it is linear in T. Thus (aP/aT)v should be es-
sentially independent of anharmonicity. If (BP/BT),
The entropy increases with en T in the quasiharmonic is independent of T, then (Y is controlled by (57), a
approximation at high T. In contrast, CV is indepen- strictly quasiharmonic equation.
dent of T in this approximation at high T, aa shown
by (43). 6h. & and q From the Quasiharmonic Theory
We note that if P is linear in T, then (t3P/BT)v From the definition of 6T, (3), and using (51), (52)
is independent of T. From experiments, however, we and (53), we find
find that CYKT is independent of T (or approximately
so) only at T above 0. The functional form of (YKT .
ST = (qht - 1) +
resembles a Cv curve. T
Applying the operator (d/aT), to the pressure given
by (45), we have for isochores, The above equation tells us that 6T should be virtu-
ally independent of T at high T. This is demonstrated
in Tables 29-43, which show that roughly speaking,
(+7)h’ = -3PR-h = -@Yht
(M,p) PO(1 - cm (55) 6, is parallel to the T axis. We also note that if
V
(BKTI ~P)T = Kh is virtually independent of T, and
Equation (55) is to be compared to (48). The actual the experimental evidence is in favor of this, 6~ at high
measured (YKT will have more structure than (YKT T should be slightly higher than Kh, providing q > 1.
We derived a relationship between three important
determined from PTH. Nevertheless to a fair approx-
dimensionless thermoelastic constants at high T. The
imation CYKT is parallel to the T axis for T > 8, as
Tables 29-42 show. above equation can be expressed as
=bT-K’+l- (59)
which is close to, and for some solids exactly equal to,
for the P = 0 isobar and where a = (13Kp/dT),, 6i. Summary of the Quasiharmonic Approxi-
given by (53). We note that (57) results from the mation Effects Upon Physical Properties
quasiharmonic approximation. The data presented here strongly suggest that the
Examination of (57) shows that at high T we may quasiharmonic approximation is valid for the follow-
expect IY to increase with T at high T even under the ing properties at least up to T = 20: P, KT, CYKT,
quasiharmonic approximation. This steady increase of (Y, and all the respective volume derivatives of these
(Y with T at high T does not necessarily require the four properties. They also suggest that the quasihar-
assumption of additional anharmonic terms in A be- manic approximation may or may not be valid for Cv
yond the quasiharmonic high T approximation, (41). and entropy for temperatures up to T = 28. This
It arises because the denominator in (57) has a term means that equations of state should not be corrected
that decreases with T even in the qua&harmonic ap- for anharmonic effects for pressures and temperatures
proximation. We saw some evidence of anharmonicity corresponding to mantle conditions. For an explana-
ANDERSON AND ISAAK 91
tion of why P, KT, (YKT and Q do not require anhar- could be used to find KS vs. T, because V is a func-
manic correction, while at the same time Cv and S tion of T. Anderson [3] used (61) in a more conve-
may require anharmonic correction, see Anderson et nient form, which follows when 6s is independent of
al. [13]. T. Along isobars,
Ks(T)[ 1,
=yq-$rq
KS0 CP(T)
(60)
dependence of KS upon a(T) and p(T).
Combining (1) and (2), we have
proximately constant. Sumino et al. [61] and Sumino Integrating (65) with respect to T
et al. [63], respectively, used (60) to extrapolate KS
from 700 to 2100 K (forsterite) and 1300 to 3100 K
KS(T) - Ks(To) = - / F dT.
(MgO). We emphasize that reliable extrapolations us-
ing (60) require that CYbe known at high T and the
assumption that 7 is constant. Assuming now that the product 6~7 is independent of
T at high T, and taking V = Vc(l+ aT), we find to a
7c. Extrapolations for KS Using 6s Constant very good approximation [54]
With T
Anderson and Nafe [9] pointed out that if bs is in- KS(T) - Ks(To) = -e [H(T) - H(To)]
dependent of T along isobars, then
where H(T) = s Cp dT is the enthalpy. used for one extrapolation and an equation involving
Equation (67) sh ows that KS(T) should be linear in linearity in Poisson’s ratio is also used
H(T). This was proven experimentally for three min-
erals for 300 < T < 1200 K by Soga et al. [54], and (T - To). (6%
for the same three minerals for 300 < T < 1800 K by
Anderson [5]. The term a(T - To)/2 is of little con- Both extrapolation equations give reasonably good re-
sequence in the calculation and can be ignored. An-
derson [5] used (67) t o extrapolate the velocities of
sound from 0 to the melting point. Equation (67) is
very useful because a(T) is not needed to find KS(T), Sumno et al. 119771
and there is much enthalpy data published listing H -. Exlrapolauon (Eq 60)
__ Exlraplation (Eq fiZj
to temperatures about or greater than 2500 K.
sured values of KS up to 1700 K, and their values are 0 400 800 1200 1600 2000
also plotted in Figure 3. Equations (62) and (63) gave -r (K)
good results for extrapolations, since the actual mea-
Fig. 3. Observed and extrapolated values of I<s ver-
sured values are quite close to the extrapolated ones.
sus T for forsterite. Experimental (plotted symbols):
However, Figure 3 illustrates the point that (60) is not
Isaak et al. [35]; Sumino et al. [61]. Extrapolations
a good extrapolation formula, at least for forsterite.
by Sumino et al. [61]: (s) using Equation (60) where
Sumino et al. [63] measured the elastic constants of
600 K is the reference T; (b) using Equation (62); and
MgO from 80 to 1300 K. They used equation (60) to
(c) using Equation (67). Two extrapolations made by
extrapolate values of KS above the maximum mea-
Sumino et al. [61] are confirmed to within 2% out to
surement (1300 K) up to 3000 K. This is shown in
1700 K by the measurements of Isaak et al. [35].
Figure 4, in which the measured values of KS [35] up
to 1800 K are also plotted. It is clear that the extrap-
olation formula given by (60) is reasonably successful 170, I
in the case of MgO. 60
1 50
7e. Extrapolation T
of G to High
Soga and Anderson [52] measured Ii’ and G for MgO 21 40
and Alz03 up to 1200 K and found that G was linear
in T above 800 K. They [53] later measured G and
(3
-1 30
KS up to 1100 K for MgaSiO4 and MgSiOs and also
found linearity for G and I(s. They used the empirical
formula
G(T) = Go -
dG
dT
(>I P To
(T - To) (68)
‘::::MgO_\__I
100'
0
'
500
'
1000
'
1500
'
2000
'
2500
'
3000
to estimate shear velocities up to 2500 K. T (K)
Sumino et al. [61] measured G for forsterite up to Fig. 4. Observed and extrapolated values of ICs ver-
400°C and reported extrapolated values from 700 K sus T for MgO. Experimental (plotted symbols): Isaak
to 2200 K. Isaak et al. [35] measured G up to 1700 K. et al. [34]; Sumino et al. [63]. Extrapolation by Sumino
These results are plotted in Figure 5. Equation (68) is et al. [63] using Equation (60).
ANDERSON AND ISAAK 93
160
pzisjiq
,c3_ 150
xm
- Extrapolated (Sumino et al. [1977])
140 6, at low T \
\
\
$:‘,:oy
\
4.2 - 130
200 600 1000 1400 1800
4-,'..'..""...",""
0 500 1000 1500 2000 Temperature (K)
T (K) Fig. 7. Observed and extrapolated values of I<s vs. T
Fig. 6. Observed and extrapolated values of vP and for grossular garnet. Experimental points shown with
v, versus T for forsterite. Experimental (plotted sym- symbols [36]. Extrapolations: TSl refers to first order
bols): Sumino et al. [61] up to 700 K; Isaak et al. [35] Taylor expansion using lower temperature data; long
up to 1700 K. Extrapolations by Sumino et al. [61] are dashed line using Equation (62) with low temperature
from 700 to 2200 K and are confirmed to within 1.5% value of 6s; short dashed line using Equation (62) with
at 1700 K by the measurements of Isaak et al. [35]. high temperature values of 6~.
94 HIGH T ELASTICITY OF MANTLE MINERALS
110
7g. The Importance of Using High T Values of
Gfossular (GGD) 6sandI’
Isaak et al. [36] reported ICS and G for grossular
105 garnet up to 1350 K, measuring 6s and F over a wide
T range. Figures 7 and 8 show the extrapolations pre-
sented by them up to 2000 K, with 4 methods. They
100 tried both a first order polynomial and a second or-
der polynomial. The fits were marginally successful,
as shown in Figures 7 and 8. They also found Equa-
tions (62) and (63) t o b e a much better representation
2 95
of G(T) provided that the exponents, 6~ and I?, are
4% the average high temperature values, and not the low
temperature values of I’ (T < 0). Therefore we rec-
u 90
ommend Equation (62) for extrapolations of KS and
Equation (63) f or extrapolations of G, provided that
a5 values of 6s and F measured above 8 are used in the
equations. If enthalpy data are available, we recom-
mend (67) for extrapolations of KS.
a0 Acknowledgements. The authors thank former mem-
bers of the mineral physics laboratory who contributed to
the data bank published here, including M. Kumazawa,
75
I. Ohno, Y. Sumino, I. Suzuki, S. Yamamoto, T. Goto,
200 600 1000 1400 1800 H. Oda, S. Ota, and H. Cynn. We acknowledge with
Temperature (K) thanks the works of E. K. Graham, N. Saga, R. Lieber-
mann, H. Spetzler, D. L. Weidner, J. Bass, I. Jackson, and
M. Manghnani that affected our research programs. Sung
Fig. 8. Observed and extrapolated values of G (GPa) Kim of Azusa Pacific University provided much help in the
versus T for grossular garnet. Experimental points statistical analysis required to arrive at values for the vari-
shown with symbols [36]. Extrapolations: TSl and ous dimensionless parameters. The salary of one of us was
TS2 refer to first and second order Taylor expansions provided by grants from the LLNL-IGPP branch under the
using low T data; long dashed lines using Equation (63) auspices of the Department of Energy under contract W-
with low T values of F; short dashed lines using Equa- 7405-ENG 48. Support for Mr. Kim was provided by the
tion (63) with high temperature value of I’. Office of Naval Research through Grant no. N90014-93-
10544. IGPP contribution no. 3849.
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ANDERSON AND ISAAK 97
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Static Compression Measurements of Equations of State
Elise Knittle
A= 2dsintI (1)
Sample
where A is the wavelength of the incoming x-ray, 28 is the
zl anglebetweenthe diffracted x-ray beamand the transmitted
beam, and d is the d-spacing or the distance between the
diffracting set of atomic planesin the crystal. The diffracted
x-rays, either Laue spots for single crystal samples or
diffracted cones of radiation for powdered samples, are
detectedby a solid state detector or on film. The set of d-
spacings for a crystal is used to determine the lattice
parametersand thus the volume of the crystallographicunit
Cylinder cell as a function of pressure. The relationship between d-
Sample
L 2cm
spacings and lattice parameters for the various lattice
symmetries are given in most standard texts on x-ray
diffraction [e.g., 361.
Pressurein the diamondcell is usually measuredusing the
ruby fluorescence technique [20, 128, 1291. Here, the RI
fl - and R2 fluorescence bands of ruby, at zero-pressure
wavelengthsof 694.24 nm and 692.92 nm, are excited with
blue or green laser light (typically He:Cd or Ar-ion lasers
are used). These fluorescence bands have a strong
Lever Arm wavelength shift as a function of pressure. This shift has
0 been calibrated using simultaneous x-ray diffraction
measurementson metals whoseequationsof state(pressure-
volume relation) are independentlyknown from shock-wave
measurements(seeChapter on Shock-waveMeasurements).
Therefore, the accuracy of the pressure measured in the
diamond cell is ultimately determined by the accuracy of
measurementsof shock-waveequationsof state. In addition
to average pressure measurements, ruby can be finely
Fig. la. The Mao-Bell-type diamond cell capable of dispersedin the sample (fluorescencemeasurementscan be
generating pressures up to 550 GPa. The diamonds are obtained for ruby grains less than 1 pm in diameter), thus
glued onto half-cylinders of tungsten carbide which are enabling pressure gradients to be accurately determined
mountedin a piston and cylinder madeof hardenedtool steel within diamondcell samples.
(shown here in a cutaway view at the top). The diamonds Becausediamondsare transparentand allow optical access
can be translationally aligned by means of set screws and to the sample, other methods for measuring equations of
tilted with respect to each other by rocking the WC half- state are possible. For example, the changesin the volume
cylinders. The piston and cylinder are placedin a lever arm of the sample chamber as a function of pressure can be
assembly (bottom) designed to advance the piston within directly measured [cf., 1393, or changes in the sample
the cylinder, apply force uniformly to the sample held dimensions with pressure may be directly measured [cf.,
between the diamonds, and exert a minimum amount of 1431. Additionally, accurate adiabatic moduli and their
torque on the piston. derivatives may be obtainedusing Brillouin spectroscopyin
conjunction with the diamond cell (see the chapter on
Elasticity).
100 STATIC COMPRESSION
FWD
Wood [85].
One of the most widely used high-pressure,large-volume
devices for equation of state measurementsis the piston-
cylinder (Figure 4a), where the pressure is applied
Plate uniaxially by a piston on a sampleembeddedin a pressure
f f medium and contained by the cylinder. As the sample is
1 cm compressed its volume decreases, and by careful
measurement of the resulting piston displacement as a
function of pressure, the P-V equation of state can be
determined. The routine pressure limit of the piston-
cylinder at room temperatureis betweenabout 3 and 5 GPa.
Other types of high-pressure, large-volume devices
utilizing opposedanvils for equationof state measurements
are Bridgman anvils and the Drickamer press. In these
devices, two tungsten carbide anvils are driven together to
uniaxially compress a sample contained within a large
retaining ring which acts as a gasket. If all or a portion of
the retaining ring is madeof a material transparentto x-rays
(suchas B or Be), diffraction measurementscan be madeon
a sample held at high pressures. The pressurelimit of the
Bridgman-anvil press is about lo-12 GPa at room
temperature, and the limit of the Drickamer press is about
30-35 GPa.
Holeto DiamondBack Boltsfor pressure A second family of large-volume apparatuses is the
andOpticAccess Application multi-anvil press. Rather than uniaxially compressingthe
sample, these devices compress simultaneously from
several directions. Such instruments are more difficult to
Fig. lb. Merrill-Bassett-type diamond-anvil cell shown in use than a piston-cylinder, as the anvils must be carefully
schematic from both side (top) and top views (bottom). alignedand synchronizedto compressthe sampleuniformly
This device can be usedto generatepressuresof - 30 GPa. and thus prevent failure of the anvils; however, much
The single-crystal diamonds are glued on flat, circular higher pressurescan be attained in multi-anvil devices. A
backing plates typically made of hardenedsteel, tungsten number of designs exist for multi-anvil pressesof which
carbide or copper-beryllium alloy. Holes or slits in the the ones most commonly used for equation of state
backing plates provide optical accessto the sample, which measurements are the tetrahedral-anvil and cubic-anvil
is contained between the diamondsin a metal gasket. The presses(Figure 4b), and multiple-stagesystems.
backing platesare held in place in recessesin larger steelor In tetrahedral and cubic-anvil presses,as their names
inconel plates by means of set screws, and also allow the imply, the samplesare typically contained within either a
diamonds to be translationally aligned relative to one tetrahedronor a cube composedof oxides, with the sample
another. Alignment pins ensurethat the the top and bottom occupying a cylindrical cavity inside the cube or
halvesof the cell are correctly oriented. Pressureis applied tetrahedron. The sample assembly, which varies in
by sequentiallyturning the three bolts which compressthe complexity dependingon the experiment, is compressedby
top and bottom plates together. four hydraulic rams in the caseof the tetrahedral press, or
six hydraulic rams for the cubic press. As illustrated in
Figure 4c for a cubic-anvil press, in-situ x-ray diffraction
KNITTLE 101
f = 1/2[(V/V&‘3 -11
xl = 3/2(K()f - 4)
This equation is successful in describing the equation of mineral or native element. Oxides, sulfides, halides and
state of a material at extremely high compressionsand is hydrides were included which are useful as mineral
being used with increasingfrequency in static compression analogues,either due to structural similarities to minerals,
studies. or to provide the systematics of the behavior of a given
structural type. Specifically not included are data for non-
4. EXPLANATION OF THE TABLE mineral III-V compoundsand other non-naturally occurring
semiconductors. All the KOTand KOT’ data listed are for
The Table lists the isothermal bulk moduli (KoT) and the structure of the common room-temperature,
pressurederivatives (dKo~/dl’=K& for minerals, mineral atmospheric-pressure phase, except where noted. In
analogues and chemical elements studied using static particular, the structures of the high pressure phasesare
compression techniques (i.e. x-ray diffraction, piston explicitly given, as are the specific structure for solids with
displacementmeasurementsor direct volume measurements more than one polymorph at ambient conditions. It should
at high pressures). All the data reported is from the be noted that entries with no errors simply reflect that error
literature from 1966 to the present: static compressiondata bars were not reportedin the original references.
from before 1966can be found in the previousHandbookof The silicate minerals are categorized following Deer,
Physical Constants. Not every entry in the Table is a Howie and Zussman’s An Introduction to the Rock-
KNll-TLE 103
Feedthrough
l-l I l-l
edium
X-Rays
5cm Assembly
V 2%
Fig. 4a. A piston-cylinder apparatus shown in cross- Fig. 46 A cubic-anvil press in which six, synchronized
section. Here, a uniaxial force is used to advancea piston rams are used to compress a cubic sample. The rams are
into a cylinder, compressing a pressure medium and thus usually made of steel with tungsten carbide or sintered
applying hydrostatic or quasi-hydrostatic pressure to a diamond tips. The sample geometries can vary from
sample contained within the medium. The piston and relatively simple, with the sample assemblyembeddedin a
cylinder are usually made of tungsten carbide and the cube of pressuremedium which is directly compressedby
maximum routine pressurelimit of this device is 5 GPa at the rams, to a sample contained in a second, cubic,
room temperature. The feedthroughinto the cylinder gives pressure-intensifying set of anvils (a multi-anvil press).
a way of monitoring the sampleenvironment. For example, Electrical leadscan be brought in between the rams of the
electricalleadscan be introducedinto the sampleto measure pressto heat the sample,monitor temperatureand pressure,
temperature or as a pressure gauge. Another use of the and measure pressure-induced changes in electrical
feedthrough is to provide current to a resistance heater conductivity. In addition, by using a low-atomic weight
surrounding the sample (not shown). Equation of state pressure medium such as B or Be, x-ray diffraction
measurementscan be made in this device by determining measurements can be obtained on samples held at high
the piston displacement as a function of pressure. (From pressures.(From [215]).
12151).
Forming Minerals [38]. The data for high-pressurephases (Fez@) and magnetite(Fe304) are listed with the oxides.
are given in the same category as for the low-pressure Also, measurementsare not given which clearly seemed
phase. For example, the bulk moduli for perovskite- to be incorrect, based on comparison with other static
structured silicates are given with the data for the compression measurements, ultrasonic data or Brillouin
pyroxenes, which have the same stoichiometry, under the spectroscopic results. Finally, I note that a range of
“Chain Silicates” category. materials have been statically compressedwith the primary
The data for the iron polymorphs and iron alloys which motivation being to characterizethe pressureat which phase
are important as possible core constituents are listed in a transitions occur. Such studies often do not report either
separatecategory (“Iron and Iron Alloys”). Therefore, iron bulk moduli or the numerical static compressiondata, and
sulfides, Fet-,O, iron hydride, and iron-silicon, iron-nickel are accordingly not included in the Table (an example of
and iron-cobalt alloys are found in this portion of the Table, this type of study are several static compressionrest&s for
while more oxidized iron minerals such as hematite Ge).
104 STATIC COMPRESSION
Framework Silicates:
Si02 2.65 36.4 AZ0.5 6.3 rk 0.4 PC, ND, P 5 2.5 GPa, 98
Quartz M EOS
Chain silicates:
CaMgSiO4 3.05 113 rf: 3 4 (assumed) DAC, scXRD, P < 6.2 186
Monticellite GPa, B-M EOS
Sheet silicates:
KAWi3OloO-02 2.80 61.4 f 4.0 6.9 I!I 1.4 DAC, pXRD, P < 18 49
Muscovite GPa, B-M EOS
GeO;? 4.23 39.1 f 0.4 2.2 AI 0.5 PC, ND, P I 2.5 GPa, 98
(quartz structure) M EOS
Carbon-Bearing Minerals:
BaS 4.25 55.1 + 1.4 5.5 (assumed) DAC, pXRD, P I 6.5 211
GPa, B-M EOS
ErS 8.38 101.5 + 1.0 5.4 * 0.2 see ref., P < 3 GPa, 89
1sqPV fit
ThS 9.56 145 & 6 5.4 + 0.1 DAC, pXRD, P I45 160
GPa, M EOS
Halides:
CsBr 4.44 19.1 * 0.9 5.0 f 0.1 DAC, pXRD, P < 53 103
GPa, B-M EOS
CSI 4.51 13.3 f 2.3 5.9 ?I 0.9 DAC, pXRD, P < 61 101
GPa, B-M EOS
122 STATIC COMPRESSION
Cd 4.51 13.5 Ik 0.2 5.45 _+0.06 DAC, pXRD, P _< 100 137
GPa, V EOS
BaC12 3.87 69.8 IL 0.5 1.40 I!I 0.05 DAC, XRD, O<P<lO 107
GPa, B-M EOS
Group I Elements:
K 0.86 3.10 f 0.01 3.91 f 0.01 see ref., P < 0.7 GPa, 99
M EOS
Group II Elements:
Transition Metals:
Group IV Elements:
Group V Elements:
Group VI Elements:
Noble Gases:
>0.18 0.082
GPa:
0.21
130 STATIC COMPRESSION
1.65 1.41
(77 W (at 77 K) (at 8;;K)
2.82 1.58
(110 K) (at 110 K) (at :i”oK)
Xe 3.78 5.18 + 0.32 GPa 5.48 f 0.24 DAC, XRD, P I 32 15
(solid) (0 K) (0 K) (0 K) GPa, B-M EOS
3.41 1.48
(159 K) (at 159 K) (at 1”;: K)
Lantbanides:
Actinides:
Fe 8.30 164.8 f 3.6 5.33 f 0.09 DAC, XRD, P < 300 132
E VW ph= GPa, B-M EOS
132 STATIC COMPRESSION
Feo.8Nio.2 8.37 171.8 zk 2.2 4.95 + 0.09 DAC, XRD, P < 260 132
E (hcp) phase GPa, B-M EOS
Ices:
NH3 0.86 7.56 + 0.06 5.29 + 0.03 DAC, XRD, 3<P<56 161
GPa, B-M EOS
Hydrides:
Amorphous Materials:
Si02 glass 2.21 37.0 lk 5.5 -5.6 + 6.2 DAC, length-change 143
measurements, P 110
GPa, B-M EOS
Acknowledgements. This work was supported by NSF and the have been completed without the help of Quentin Williams.
W.M. Keck Foundation. I thank T.J. Ahrens and an anonymous Institute of Tectonics (Mineral Physics Lab) contribution
reviewer for helpful comments. I’m sure references were number 208.
missed, for which I apologize in advance. This paper could not
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Shock Wave Data for Minerals
Nitrogen plus 1:1 N2+02 0.945 1.83 0.11 1.26 0.03 2.235 3.785 2 Cl791
OxygenC
Nitric Oxidee NO 1.263 3.76 0.06 0.98 0.02 2.01 3.245 2 7 [I791
Ammonia’ NH3 0.715 2.45 0.19 1.34 0.04 1.01 7.566 2 12 [83,121,140]/
u591
Carbon
MonoxideC co 0.807 1.54 __ 1.40 __ 1.692 2.471 2
2.59 0.04 0.974 0.010 2.471 5.608 3
1.3 0.3 1.21 0.04 5.608 7.92 4 t1501
TABLE 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued)
Carbon:
$
Copper cu 7.90 3.39 0.04 -0.06 0.08 0 0.646 1 3
2.29 0.06 1.90 0.03 0.627 2.969 2 18 [56,121,127,134, s
1361 z
Iron-Silicon FelTSi 7.641 3.87 0.04 1.67 0.02 0.984 3.568 2 37 [42,121]
Iron-Silicon Fe7Si 7.49 4.01 0.06 1.71 0.04 0.975 2.291 2 3 Wll
Iron-Silicon Fe3Si
(see Suessite)
TABLE 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued)
Carbides:
Moissanite Sic 2.333 2.3 0.3 1.84 0.12 2.048 3.444 4 10 [121,127,136]
Tantalum TaC 12.626 3.32 0.09 1.49 0.05 0.887 2.619 2 20 Cl211
Carbide
Tantalum TaC 14.110 4.34 0.05 1.36 0.03 0.435 3.76 2 21 [121,152]
Carbide
TABLE 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued)
Sulfides:
Halides:
5
TABLE 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) E
Sample error lower upper References I E
Mineral Formula Density Co ACo S error DP UP Phase* NO. of Temp. Refs.
(Mg/m3) (kmhec) (kmhec) AS (kmkec) (kndsec) Data B
L
Halite NaCl 0.989 0.74 0.09 1.470 0.018 2.53 6.02 2 5
3.9 -- 0.9 -- 6.02 6.6 3 2
-17.0 -- 4.1 __ 6.6 6.7 4 2 [lo61
Halite NaCl 1.427 1.56 0.12 1.49 0.03 2.29 5.66 5
5.6 -- 0.8 _- 5.66 6 2
-5.1 -- 2.5 -- 6 6.11 2 [lo61
Halite NaCl 2.159 3.60 0.09 1.17 0.18 0.00 0.647 1 28
3.41 0.03 1.42 0.03 0.646 1.7 2a 113
4.35 0.09 0.88 0.04 1.7 2.5 3a 109
2.43 0.07 1.66 0.02 2.5 3.75 4a 95
4.4 0.3 1.11 0.08 3.73 4.356 3b 43
3.5 0.3 1.33 0.05 4.324 6.52 4b 8
19 -1 __ 6.52 6.8 3c 2
3.8 i.2 1.18 0.02 6.8 11.05 4c 3 [32,73,84,106,
121,213] /[48,
103, 107, 176,
1771
Cryolite Na3 AlFg 2.96 4.70 0.10 0.89 0.09 0.71 1.57 2
3.76 0.12 1.44 0.04 1.57 3.8 4 U861
Oxides:
Water, Icei Hz0 0.35 0.080 0.18 1.40 0.03 2.76 6.75 2 5 [411
Water, Icei H20 0.60 0.83 0.16 1.40 0.03 2.57 6.2 2 5 [411
Water, Icei H20 0.915 4.05 0.05 -1.89 0.16 0.045 0.858 1 7
1.43 0.11 1.48 0.03 0.858 5.67 2 9 [41,75,1141
Water, Ice” H20 0.999 1.47 0.04 1.93 0.06 0.00 0.97 1 14
1.70 0.06 1.71 0.03 0.9 2.53 2 58
2.64 0.07 1.270 0.008 2.479 32.42 4 25 [19,29,116,121,
140.157.167.
2131217; 2251 /
[87,119] &
H
Seawater (mixture) 1.03 1.69 0.08 1.73 0.10 0.31 1.11 2 3
2.07 0.09 1.38 0.03 1.11 4.76 4 4 [2101
Bromellite Be0 2.454 3.5 0.3 1.92 0.12 1.799 3.356 2 6 [120,121]
Periclase MgO 3.00 3.10 0.14 1.88 0.06 1.259 3.362 2 13 [56,121,127]
Corundum A1203 3.92 8.71 0.05 0.716 0.017 0.37 5.5 2 6 [I521
Corundum A1203 4.00 9.52 0.04 0.955 0.008 1.02 8.28 2 4 [I521
Pyrolusite Mnf402 4.318 3.77 0.14 1.46 0.07 0.769 3.263 2 16 [47,121,217]
TABLE 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued)
Argutite GeO;? 6.277 9.51 0.12 0.29 0.11 0.15 2.57 2 6 W’l
Cerianite (Ce+4,Th)02 1.133 0.2 0.3 1.20 0.07 1.925 5.437 2 7 w11
Uraninite uo2 4.306 0.12 0.11 1.51 0.04 0.88 3.855 4 15 Wll
Hydroxides:
Aragonite CaCO3 2.928 5.82 0.11 0.78 0.12 0.11 1.83 2 12 WOI
Sulfates:
Mascagnite WLh‘Q 1.73 3.71 0.14 1.34 0.12 0.2 1.87 2 5 [991
Borates:
Silica
Polymorphs:
Porous Quartz SiO2 1.15 0.41 0.09 1.40 0.03 1.52 5.28 2 15 [188,2071
Porous Quartz SiO2 1.43 0.87 0.09 1.38 0.03 0.65 5.08 2 30 [ 188,207]
Silicic Acid H4Si04 0.55 -0.09 0.11 1.27 0.02 3.51 6.59 4 5 w31
Silicic Acid HaSi 0.65 -0.01 0.03 1.275 0.006 2.94 5.93 4 6 Cl881
Silicic Acid H4Si04 0.80 0.78 0.03 I.05 0.02 0.68 1.98 2 3
0.33 0.04 1.261 0.009 1.98 5.71 4 7 [1881
TABLE 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued) 5
Mullite A6Si2013 2.668 2.30 0.13 1.65 0.04 1.935 4.077 2 13 [121,127]
Pyroxenes:
Enstatite Ma- 2.714 2.70 0.11 1.31 0.04 1.901 3.258 2 5 [47,121,217]
&06
Molten cmgsi206 2.61 3.30 0.12 1.44 0.08 0.73 2.24 2 5 w331
Diopside”
Jadeite Na(A1 Fe+3)- 3.335 6.41 0.06 1.30 0.08 0.00 1.005 2a 3
f&6 6.57 0.10 1.09 0.07 0.986 1.94 2b 8
7.44 0.12 0.64 0.04 1.94 3.434 4 8 [47,121,135,
2171
Feldspars:
Oligoclase (NaAlSi3- 2.635 7.6 0.3 -1.5 1.2 0.195 0.3 1 13 Cl61
08)75(c~12-
Si208h9.5 -
(KAlSi3-
08h.5
Anorthite h&%208 2.769 3.17 0.16 1.45 0.04 2.911 4.338 2 3 [96] / [173,174]
Glasses:
Quartz Glass SiO2 1.15 0.09 0.2 1.51 0.06 3.07 5.21 4 4 UW
TABLE 1. Shock Wave Equation of State of Minerals and Related Materials of the Solar System (continued)
Quartz Glass SiO2 2.2 0.4 0.5 1.73 0.12 3.61 4.84 4 6 [911
Quartz Glass SiO2 2.204 5.83 0.03 -2.33 0.17 0.00 0.306 1 7
5.264 0.019 -0.114 0.014 0.306 2.106 3 32
3.40 0.08 0.78 0.03 2.063 2.742 2 20
0.80 0.08 1.70 0.02 2.703 5.175 4a 61
3.1 0.2 1.196 0.014 5.175 23.64 4b 3 [101,118,121,
127,129,163,
217,222] /
[104,117,118,
175, 1771
Aluminum 2024 Al’ 2.788 5.356 0.011 1.305 0.005 0.00 5.962 2 325 [56,90,121,134.
136,166,213,
217,224,226] I
[1651
Molybdenum MO 1.277 -0.03 0.06 1.25 0.03 0.678 4.05 2 5 I2091
Molybdenum MO 1.72 -0.39 0.10 1.40 0.03 3.02 5.01 2 4 GO91
Molybdenum MO 2.55 -0.12 0.05 1.473 0.013 0.654 6.51 2 10 PO91
Molybdenum MO 2.914 -0.16 0.04 1.538 0.012 0.65 6.3 2 10 12091
Molybdenum MO 4.435 0.04 0.02 1.735 0.008 0.62 5.66 2 8 PO91
Molybdenum MO 5.59 0.30 0.06 1.90 0.02 0.3 5.25 2 13 [2091
Notes:
a Starting temperature5K
b Starting temperature20K
c Starting temperature75-86K
d Starting temperature1llK
e Starting temperature122K
f Starting temperature148K; compressedgas
g Starting temperature165K
h Starting temperature196K
i Starting temperature203-230K
j Starting temperature258-263K
k Starting temperature273-298K
t Starting temperature3OOK;compressedgas
m Starting temperature1673K
n Starting temperature1773K
O Starting temperature1923K
P 5% cobalt
q raw data not provided
r with impurities
s compositionin weight percentoxides
172 SHOCK WAVE DATA FOR MINERALS
(1) us=co+sup
P 1 = PO (Us-uo)/(Us-u1)
Pl - PO = Po(Ul-uo)Q-Js-uo) (2)
As further discussed in several review articles on
El - Eo = 0’1 + Po>(l/po-l/p 1)/2 = l/2 (ul - ud2 (3)
shock compression [22,.59,136], and a recent book [40],
where p, u, P, and E are density, particle velocity, shock
pressure, and internal energy per unit mass and, as
indicated in Fig. 1, the subscripts o and 1 refer to the state
in front of and behind the shock front, respectively. In
Table 1, shock velocity and particle velocity are
designated as Us and ul. Thus for a single shock UP = u 1.
In the case of multiple shocks, the values of U, and us
given in the Table are for the final (highest pressure)
shock state. Equations (l)-(3) are often called the
Rankine-Hugoniot equations. It should be understood that
in this section pressure is used in place of stress in the
indicated wave propagation direction. In actuality, stress
in the wave propagation direction is specified by Eq. (2).
A detailed derivation of Eqs. (l), (2), and (3) is given in
Duvall and Fowles [70]. Equation (3) also indicates that
the material achieves an increase in internal energy (per
unit mass) which is exactly equal to the kinetic energy per
unit mass.
In the simplest case, when a single shock state is FIG. 2. Pressure-volume compression curves. For
achieved via a shock front, the Rankine-Hugoniot isentrope and isotherm, the thermodynamic path coincides
equations involve six variables (Us, ul, po, ~1, El - Eo, with the locus of states, whereas for shock, the
and Pl); thus, measuring three, usually Us, uI, and po, thermodynamic path is a straight line to point PI,Vl, on
determines the shock state variables p 1, El-E, and Pl. the Hugoniot curve, which is the locus of shock states.
AHRENS AND JOHNSON 173
Hugoniot data for minerals and other condensed media The analogous bulk modulus along the Hugoniot is:
may be described over varying ranges of pressure and
density in terms of a linear relation of shock and particle KH = -V @P/?lv)~. (11)
velocity in Table 1. This table was assembled using the
Microsoft Excel, version 3.0, (Redmond, WA 1993) The isentrope and the Hugoniot and isentropic bulk
program and the least-square fits to the shock wave data modulus arc related via:
with standard errors were derived by using the LINEST
function. The equations employed for line slopes and
intercepts are identical to those given in Bevington [46] KS = KH + KH 77 / (I- q,]
(Eq. 6-9, p. 104; Eq. 6-21, p. 114 for errors in slopes; and W)
Eq. 6-22, p. 114 for errors in intercepts). - [PH-ps] [Y+l-q, o-Gl+-*)I
The Us-Up data for a wide range of minerals are
given in Table 1. Here Co is the shock velocity at
Here we assume a volume dependence of the Gruneisen
infinitesimally small particle velocity, or the ambient parameter
pressure bulk sound velocity which is given by
Y= V (JPlJE)v = yo (V/Vo)q, (13)
co=dGG (5)
where
where KS is the isentropic bulk modulus,
KS = -V (dP/dV)s in the absence of strength effect (see q=dLnyld!nVandq’=denqJtin V (14)
Sect. 3).. Upon substituting Eq. 4 into Eq. 2, and denoting
the shock pressure as PH, this is given by: y. is the Griineisen parameter under standard pressure
and temperatures and is given by
PH = PoUp (Co + S Up) (6)
Yo = a KT V&v = a KsVo/Cp, (15)
Thus, from the form of Eq. 6, shock pressure is given as
the sum of a linear and quadratic term in particle velocity, where a is the the thermal expansion coefficient, KT is
based on the data of Table 1. A pressure-volume relation the isothermal bulk modulus and Cp and Cv are the
can be obtained by combining Eq. 6 with Eq. 1 to yield: specific heat at constant pressure and volume. We note
that the Ps and PH can be related by assuming the Mie-
PH = PO co2 “‘1/(1-sqj2 (7) Griineisen relation
where
PH - PS = + @H-E& (16)
Tl=l -v/vo=up/LJs. (8)
if y is independent of temperature, where EH = El-E0 is
Eq. 7 is often called the “shock wave equation of state” given by Eq. 3 and Es is given by
since it defines a curve in the pressure-volume plane.
The isentropic pressure can be written (e.g. V
[93,98,17l])by an expression analogous to Eq. 7 as a Es = - jP,dV. (17)
series vo
Because the Grtineisen ratio relates the isentropic
Ps = po co2 (11+ 2sTl2 + .*.), (9) pressure, Ps, and bulk modulus, KS, to the Hugoniot
pressure, PH, and Hugoniot bulk modulus, KH, it is a key
which upon differentiation yield the isentropic bulk equation of state parameter.
modulus The shock-velocity particle relation of Table 1 can be
used to calculate the shock pressure when two objects
impact. If (A) the flyer plate and (B) the target are known
KS = p. Co2 (1 + (4S-1) 17+ ...) (10) and expressed in the form of Eq. (7), the particle velocity
174 SHOCK WAVE DATA FOR MINERALS
That is;
and
In the caseof a phasechange, the pressurealong the initial volume, and Vb = V, compressedvolume. For the
isentrope P, at the volume Vl corresponding to a calculation of postshock temperatures Ti = TH , the
Hugoniot state(Pl,V 1) is given by Hugoniot temperature,Va = VH, the volume of the shock
state, and Vb = Voof, the postshock volume
Vl corresponding to the postshock temperature. For shock
?(Voo-V1)=-v\PdV++?P1-Ps)+QR (23) compressionto a volume V, P, is first obtained by using
Eq. 23; then T,, the isentropiccompressiontemperatureat
where the left-hand side is the Rankine-Hugoniot energy, volume V, may be calculated by using Eq. 24. Finally,
and the first and secondterms on the right representthe usingEq. 16, the shocktemperatureTH is given by
gain in the internal energy along the paths 1 and 2 of Fig.
2 Here Voo is the specific volume of the initial material
and V. the specific volume of the shock-induced high- (25)
pressurephase,or the intrinsic volume of the sampleif the
initial state is distended. Also ETR is the energy of
transition to the high-pressurephaseat STP. In the case It is useful to carry out both postshock and shock
of no phasechange,ETR = 0. For zero initial porosity temperature measurements as they provide
V 00 = vo* The unknown parameter in Eq. 23 is P,, complementary information for the thermal equation of
which is implicit in the first integral term on the right- state, that is, y, as well as Cv. Minerals for which shock
hand side and explicit in the second term. The second temperatureshave been measured(usually via radiative
term is obtainedby using the definition of the Gruneisen techniques)are so indicatedin Table 1.
parameter (Eq. 13) to calculate the change in energy In the case of molecular fluids such as water, a
associatedwith the pressuredifference (Pl-Ps) at constant formulation basedon the nearconstancyof Cp at constant
volume. pressureis used[4 1,167].
Although there have been few data collected,
4. SHOCK TEMPERATURES postshock temperaturesare very sensitive to the models
which specify y and its volume dependence,in the caseof
For many condensed media, the Mie-Gruneisen the Gruneisenequationof state [49,164,1651. In contrast,
equation of state,basedon a finite-difference formulation the absolutevaluesof shock temperaturesare sensitiveto
of the Gruneisen parameter (Eq. 16), can be used to the phase transition energy ETR of Eq. 23, whereas the
describe shock and postshock temperatures. The slope of the TH vs. pressure curve is sensitive to the
temperaturealong the isentrope [224] is given by specific heat.
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Electrical Properties of Minerals and Melts
Electrical properties of minerals and melts aid in the which to start a search, rather than as a source of absolute
interpretation of geophysical probes of the Earth’s internal values.
electrical structure (see Hermance, Section 1-12). In Recent previous compilations of data on electrical
addition, electrical conductivities and dielectric constants properties of rocks are given in references [17-19, 421.
of minerals are used in studies of mineral structure, Electrical properties of elements, minerals, and rocks at
electronic and ionic transport processes, defect chemistry, room temperature and 1 bar pressure, and of aqueous
and other mineral physical properties. This article fluids are treated by Olhoeft in Section 3-8 of this series
contains data and references to electrical properties of and in [42].
minerals and related materials at elevated temperature Electrical parameters. The electrical conductivity cr
and 1 bar pressure, and at elevated temperature and and the dielectric permittivity E relate an electrical
elevated pressure. Electrical properties of materials can stimulus and response through Maxwell’s relations. In
be very sensitive to minor chemical impurities and linear systems it can be shown that
variations. Cracks and other macroscopic defects, and
microscopic defects such as voids, inclusions, twins, etc. JT = GE + r&L’& (1)
in specimens can complicate the achievement of reliable
measurements. As a result, for a given electrical property where JT is the total current density, E is the electric field
of a mineral, there are often a wide range of reported gradient, and t is time. The first term on the right hand
values, sometimes differing by as much as several orders side of equation (1) is called the conduction current and
of magnitude. We have striven to provide reliable data the second term is the displacement current. For a time
for each material listed. Because minor element content varying electrical field of the form E = E, exp (iot)
and experimental conditions are known to strongly affect equation (1) becomes
electrical properties, we have attempted, where possible,
to tabulate both chemical composition and experimental JT = (a + ime) E. exp (icut) (2)
conditions for each measurement. Certain previous
compendia of mineral electrical properties have preferred in which i = J-1 and o = angular frequency. A total
to give only ranges of values for a given mineral [ 17-191. complex conductivity may be defined as
The data and tables presented here may best be used as a 1
guide to the literature or as a source of references from crT=oT+i<=o+i6.xz (3)
transition from extrinsic (impurity dominated) to intrinsic The electrical conductivity of a material is the sum of
conductivity. Each region is then described by an the conduction of each charge carrier (or defect) type
expressionof the form of equation (10). However, more acting in parallel
precise,and mechanisticallymore meaningful parameters
are derived if the entire data set is simultaneouslyfit to a 0 = Z Oi = Z Ciqjpi (13)
single expressionof the form
in which ci is the concentration of the ith type of charge
d = bol exp(-El/kT) + cro2exp(-E2/kT) (11) carrier, qi is its effective charge, and pi is its mobility (in
m2 V-l see-l). In general, all defects are presentin some
In the data tables that follow, experimentaldata that have amount in every crystal and each contributes to the total
been fit simultaneously to multiple linear segments are conductivity. Usually only one or two types of defects
indicated by braces. dominate under a given set of thermodynamicconditions.
The effect of pressure on conductivity can be The concentrationsof the defect speciesare governed by
characterized by the inclusion of an activation volume chemical reactions that lead to the production or
term Vo so that consumption of each defect type. For example, the
removal of a positively-charged ion from its normal site
u+ PVo resulting in the formation of a vacancyplus an interstitial
d = b. exp(-F)
ion (formation of a Frenkel defect) can be written as
in which U is the activation internal energy. The
activation volume is often interpreted as indicating the A;=V;+A; (14)
volume of the mobile species,but care should be taken
when making this interpretation. When available, For such a reaction, we can write equationsfor chemical
activation volumes are given in the tables, but more equilibrium constantsin the usualmanner
commonly measurements at elevated pressures are rvk I rqi
parameterized isobarically as functions of temperature K= (15)
using equation (10) or (11). In experiments at high [A;1
pressure it is difficult to control all thermodynamic in which K is the equilibrium constant and square
parameters. The values in Table 5 and 6 are the best brackets indicate site fractions. the Gibbs free energy
currently available. We expect that many of these values AGOfor this reaction is given by
will be revised as experimentalmethodsimprove.
Point Defects and Conductivity. The electrical AGo = -RT ln K (16)
conductivity of materialsis determinedby the point defect
chemistry. Point defects are imperfections in the crystal in which R is the gas constantand T is temperature.
lattice and the types of point defects possible are Reactions involving oxygen from the surroundings
substitutions, vacancies, interstitial ions, electrons, and are of particular importance in oxide materials. For
electron holes (electron deficiencies in the valence band example,the reaction
commonly termed ‘holes’). Kroger-Vink notation [23,24]
was developed to describe the type of defect and its 02, = l/2 02(g) + VG + 2e’
effective charge relative to a normal lattice site. Incthis
notation, eachdefect is given a symbol of the form A , in describesthe reaction of oxygen on a normal lattice site to
which the main symbol A indicates the species oB the release an oxygen molecule to the environment, leaving
defect (atom, electron, hole, or vacancy), the subscript B an oxygen vacancy and two electrons behind. Thus the
indicatesthe type of site (normal lattice site of a particular mineral stoichiometry dependson the chemical potential
atom type or an interstitial site), and the superscript c of oxygen (or the oxygen fugacity fo2) in the surrounding
indicates the net effective charge of the defect relative to atmosphere. In MgO, the reaction which incorporates
the normally occupancy of that lattice (dots indicate oxygen from the surroundings and forms a magnesium
positive relative charge, slashes indicate negative vacancyis written
charges). Tables 1 and 2 give thesedefinitions and show
as an example the defect species in nonstoichiometric l/2 02 = v;g + 2h’ + 0;
(Mg,Fe)O. Note how defects causedby aliovalent ions in
different valencestatesare written using this notation. Thus, in principle, the magnesiumvacancyconcentration
188 ELECTRICAL PROPERTIES OF MINERALS
Table 1 . Definitions of defect species (Kroger-Vink) constraint means that the temperature, the pressure, the
notation. oxygen fugacity, and the Mg:Fe ratio in the solid must all
be specified. Thus, the conductivity will have the general
Symbol Meaning form
Main symbol Element or Atomic symbol
species of defect e (electron) Oi = (To exp(-E/kT) (F&g)m fG2n (19)
h (hole)
V (vacancy) in which F& is the fraction of Fe on Mg sites and n and
m are cons Pants arising from the defect reaction
Subscript Site Normal Lattice Site stoichiometries. For a four-component system such as
(Atomic symbol) olivine (Mg,Fe)$iOq an additional constraint must be
I (Interstitial) specified; in olivine the most frequently specified
constraint is the silica activity aSlo2 (or equivalently the
Superscript Charge relative x (zero) enstatite activity aEn), so that the most general
to normal lattice ’ (negative) conductivity relation would have the form
site .
(positive)
Oi = 00 exp(-E/kT) (F&g)m fGzn aSi& ... .. (20)
IC
CJ 120-723
120-723
-7.7
1 1.04
7.9
0.91
.Oll
1 100 - 2.4 x lOlo Hz AC [461
Chlorides,
single crystal, synthetic
AgCl 0 373-728 7.0 0.90 [281
KC1 823-1041 8.30 2.06
LiCl 793-879 9.70 1.65
NaCl 723-1073 8.0 1.90
tJT 625-823 4.02 0.83 [331
823-1000 10.76 1.89
RbCl 823-990 8.48 2.12 LW
TIC1 293-700 5.40 0.79
Table 3. (continued)
Material Form Temperature log A1 EI “1 Comments References
of range u in eV fo2 in
equation K S/m, T atm
in K
Halides, continued:
Fluorides
single crystal, synthetic
KF (3 973-l 119 9.48 2.35 DC P81
LiF 993-1115 9.60 2.20
NaF 1123-1265 8.18 2.25
Oxides:
Aluminum oxide, Al203 10 kHz AC, DC [431
single crystal (sapphire) u 1573-1998 5.60 2.97 fez= 16 Pa
1573-1873 3.96 2.62 fo2= 1 Pa
1898-1998 11.71 5.5 fa=lPa
1573-1873 5.01 2.84 fm = 10m5Pa
1898-1998 13.01 5.8 fo2 = 10m5Pa
Calcium oxide, CaO 1000-1400 10.83 3.5 DC, 1.59 kHz AC [611
single crystal
2.68 2.11
320 ppm Fe u 1473-1773 fm- 1W3- 10-4Pa
7.48 3.68
2.68 2.11
1473-1773 fez- lo- 1 Pa
1 6.57 3.49 1
2.68 2.11
fo2 - 1 MPa
5.94 3.08
Table 3. High temperature electrical conductivities of minerals (continued)
Spinel, Fe-Mg-Al
Fe2+Feg 53+Al 1504 873-1673 6.44 0.39 co:co;! = 0.003 [391
Fe2+Fe 1’03+Al 1’04 873- 1673 7.74 0.25
Fe2+Fe1’53+A1204 873- 1673 7.84 0.23
Feo.2g2%xx7sFtz3% 873-1673 7.52 0.18
Feg 5 +Mgg 5Fez3+04 873-1673 7.74 0.18
Feo’7s2+Mgo 25Fez3+04 873- 1673 7.86 0.15
Feo:2a2+Mgo:7sPeo.s3+A11504 873- 1673 6.52 0.39
Feo.5 +Mgo.&+AQ 873-1673 7.41 0.28
Fe0.752+Mgo.25Fe1.53+A10.504 873-1673 7.75 0.22
Wustite, Fel-x0
x = 0.1039 - 0.1095 tST 1173-1573 8.062 0.161 Constant thermoelectric 161
x=0.0884- 0.0967 1173-1573 8.025 0.163 potential
x=0.0706 - 0.0817 1173-1573 7.967 0.167
x=0.0566 - 0.0706 1173-1573 7.899 0.168
x=0.0494- 0.0593 1173-1573 7.869 0.182
Silicates:
Cordierite,
Mgi.giFe0.o8Mno.oiA13.95Si5.oi
0 473- 1173 3.1 0.75 Impedance spectroscopy 1491
1 VW 473-l 173 -0.35 0.85
Feldspar, polycrystalline 1- 10kHzACinair 134,351
Albite, Grisons, France 0 673- 1173 0.15 0.86
Ndlsi$$.j
Albite, Mewry, France, 673-l 173 0.23 0.86
ko2Nao 98AlSi308,
Albite, synthetic (disordered) 673-1173 0.08 0.72
NaAlSi3 Og
Anorthite, synthetic, 0 673-l 173 -0.20 0.87
CaAl&Og,
TYBURCZY AND FISLER 193
0
3
Table 3. (continued)
Table 5. High pressureelectrical conductivity of minerals given in the form o = o. exp (-E/kT).
Ni2SiO4 773-l 100 1.0 1.38 x 10-l 0.56 Piston-cylinder, 1.6 kHz AC guard [691
1loo-1273 1.0 7.94 x 108 2.71 ring, Ni/NiO buffer
Dreiser Weiher, Germany 640847 1.0 6.24 x 10-l 0.43 Piston-cylinder, 1.6 kHz AC, guard [71 $
hm7Fv.6Wo3o.7 ring, natural paragenesis
Clinopyroxene, synthetic, 9
polycrystalline E
Diopside, CaMgSi206 746-1064 1.0 1.24 x lo2 1.28 Piston-cylinder, 1.6 kHz AC, guard [71 %
ring E
Spinel, 1122-1518 2.05 7.24 x lo5 1.98 Piston-cylinder WI z
?I-MmGeQ Impedance spectroscopy
Fcd
ERGAN buffered
Table 6. Electrical conductivity of (Fe,Mg)zSiOq olivine Table 7. Real relative dielectric permittivity K’ (1 MHz)
and spine1 (y-form) at room temperature (295 K) and and temperature derivatives for for&rite Mg2SiO4 over
pressures to 20 GPa. Values are given for the constants in the range 293 K to 1273 K [3].
the expression axp = rso exp[mx + (B, + bx)P], where x
is mole per cent Fe, P is pressure in GPa [26,27]. Valid Crystallographic lc’ l/K’ (&cXlT)
in the range 50 5 x 5 100. K-l
Orientation 293 K
Mineral log (z. m Bo b,
o. in (x in GPa-1 (x in mole
S/m mole % % Fe (loco 6.97 f 0.21 1.22&0.14x lOti
Fe) GPa- I (010) 7.7 1 f 0.24 1.69 f 0.12 x 1O-4
(001) 7.11 f 0.21 1.24 f 0.20 x 104
olivine - 10.42 0.125 2.0651x lo- 4.20 x 1O-4
Temperature, ‘C
Melt type 1200 1250 1300 1350 1400 1450 1500 1550
Nephelinite (C- 195) 0.59 0.91 1.15 1.27 1.35 1.43 1.48
Basanite (C-90) 0.41 0.73 1.03 1.27 1.36 1.45 1.49
Tholeiitic olivine basalt (C-50) 042 0.76 0.93 1.06 1.16 1.25
Olivine tholeiite (C-2 14) 0.48 0.67 0.82 0.96 1.06 1.17 1.25
Tholeiite (C-8) 0.36 0.56 0.71 0.85 0.95 1.07 1.15
Tholeiite (70- 15) 0.41 0.65 0.84 1.00 1.11 1.20 1.27
Tholeiite (PG- 16) 0.39 0.58 0.75 0.91 1.02 1.12 1.20 1.26
Quartz tholeiite (HT- 1) 0.16 0.40 0.59 0.76 0.90 1.01
Hawaiite (C-42) 0.62 0.77 0.88 1.00 1.11 1.21 1.27
Alkali olivine basalt (C-222) 0.48 0.66 0.81 0.95 1.05 1.15 1.23
Alkali olivine basalt (C-70) 0.53 0.69 0.82 0.95 1.04 1.16 1.22
Alkali olivine basalt (BCR-2) 0.30 0.46 0.60 0.73 0.83 0.92 1.00 1.07
Mugearite (C-2 10) 0.49 0.59 0.69 0.78 0.85 0.96 1.00
Andesite (HA) 0.39 0.48 0.56 0.64 0.71 0.79 0.86 0.92
Andesite (VC-4W) 0.34 0.42 0.50 0.58 0.65 0.71
Latite (V-3 1) 0.48 0.57 0.64 0.71 0.77 0.83 0.88 0.91
Trachyte (C- 128) 0.75 0.81 0.87 0.93 0.97 1.02 1.04
Rhyodacite (HR- 1) 0.46 0.52 0.60 0.66 0.72 0.76 0.81
Rhyolite obsidian (YRO) 0.41 0.47 0.53 0.58 0.62 0.67 0.71 0.74
Table 9. Electrical conductivity of naturally occurring silicate melts at elevated pressures over the
temperature range 1200-14OO“C, parameters for tits to the equation log 0 = log o. - (Ea + PAVo)/2.3kT
16%651.
. -I
I I I 1 .I I I I
-??O -16 -12 -8 -4 0
Log(fO,, MPa)
Figure 1. Calculated point defect model, plotted as log of the defect concentration versus log of oxygen fugacity, for
Fog0 olivine at 1473 K [l 11. Vertical dotted lines representstability rangeof olivine.
MgO: 40 ppm Al
1300°C
, &
-1300%
-7 -1 1
-3
-3.5
-4
-4.5
-5
-5.5
II I1l,,,l,,,l,,,l,,,l,,,I,,,-
-6
5.2 5.4 5.6 5.8 6 6.2 6.4 6.6 6.8
1 d/T (K-l)
Figure 3. Log conductivity versus T-1 for f& - 10m3to 10m4.bar for MgO containing 400 ppm Al. Solid line is total
conductivity, which is the sum of ionic conductivity (dashed-dot line) and the electronic conductivity (dashed line) [54,
551. -
-2.5
San Carlos Olivine Electrical Conductivity
T= 1473 K
-3
. . .
. .
. . /
. . #
. (
>: .
I . ’ . .
-3.5 / / . .
d . .
e/ . .
. .
. .
. .
-4 . .
. .
. .
.
I I I I I I I I I I I,, , , l , , , ( l , , , , l , , , , l ( , , , 1
-4.5
-8 -7 -6 -5 -4 -3 -2 -1 0
Log fo2 (Pa)
Figure 4. Log conductivity versus log fo2 for San Carlos olivine @go) illustrating that total conductivity is given by the
sum of the two mechanisms (dashed lines) with differing oxygen fugacity dependences [68].
1 I @ 8 ‘I’ 8 1 I’ r ’ , 8 ’ ’ , 8 ’ 8
Olivine Electrical Conductivity
-5
-6
6 8 10 12 14 16 18
104/T (K-l)
Figure 5. Log conductivity versus T-l at 1 GPa for olivines of different compositions. Solid buffer assemblages
controlling fo2 are given in parentheses; solid lines are QFM, dashed lines at IW. Data are from [7, 691. San Carlos
olivine at 1 bar (self-buffered at QFM) is shown for comparison. [68].
3
.-
.->
-4
5
s -6
-12
0.5 1 1.5 2 2.5 3 3.5
103/T (K-l)
Figure 6. Log conductivity versus T1 for some halides. Data from [28, 331. The low temperature conductivity of NaCl
and NaBr is impurity controlled. Conductivities for KC1 and RbCl coincide.
I I I I I I
-’ : Feldspar and Feldspathoid
: Electrical Conductivity
-2 :
NaAlSiO
-3 : NaAISi3G8
: NaAISi308 (nat.)
-4 : CaAlzSiz08
- Adularia (nat.)
-5 :
I I I I I I I I
-8 -
6 7 8 9 10 11 12 13 14 15
104/T (K-l)
Figure 7. Log conductivity versus T-l for feldspars and feldpathoids. All lines refer to intrinsic regime. Lines labeled by
formula only are synthetic samples; those labeled ‘nat’ are natural samples. Data from [34, 351.
10 I’ 1 I ’ I ’ * @ r II 8 8 8 1, 8 8 * II 2 I’,’ 11 ’
6 - Feo.9s0
4 -
2 -
0 - bMgo,,Fe 0.17 0 (QFW
-2 1
-4 -
-6 1
-8
5 6 7 8 9 10 11 12
104/T (K-l)
Figure 8. Log conductivity versus T1 for some binary oxides. Data from [6,61,63,70]. Oxygen buffers are shown in
parentheses where appropriate.
206 ELECTRICAL PROPERTIES OF MINERALS
Saturation Line
1O-6
I I I I I I I I I I I I I I
Figure 9. High pressure electrical conductivity of supercritical H20 versus density [13].
Acknowledgements. We thank Lee Hirsch, Jeff Roberts, Tom for errors rests with the authors. This work was supportedby
Shankland,and Al Duba for helpful reviews. The responsibility the National ScienceFoundation.
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on synthetic pyroxenes MgSiO,- 399-403,199o.
Viscosity and Anelasticity of Melts.
Donald B. Dingwell
2. CLASSES OF EXPERIMENTS
3. GEOMETRIES
[ 11, 251 for times greater than the relaxation time of the
The most widely used example of controlled strain rate melt. Equation 6 is known as Trouton’s rule.
and measured stress is the rotational (Couette) method (see Absolute shear viscosities in the range lo9 - IO1 1Pa s
Figure 5). Ryan and Blevins [34] provide a description of can be determined using micropenetration techniques (see
the physics of Couette viscometry. The strain rate is Figure 5). This involves determining the rate at which an
212 VISCOSITY AND ANELASTICITY OF MELTS
2rtmgh5
qs(Pas>=
3V Fh/Gt (27r h3 + V) (8)
qs (Pa s) = m ’ h2
3V 6h/6t . (9)
6. CALCULATION SCHEMES
Abyssol Ol~v~ne Tholellle (13OO’C)
A number of empirical calculation schemes for the
viscosity of silicate glass melts have been around for
several decades [37] but calculation methods for geological
melts are a more recent phenomenon. Bottinga and Weill
[3] produced a method for the estimation of melt viscosities
L I I I I
0 10 4(
Prt?ssi?eohbor
I 3o ’
Figure 6. Viscosity as a function of pressure for various 1
I I
12.0 I
‘. CLA
‘z
;d
11.6
,
.
rheology in silicate melts. The onset of non-Newtonian
3 rheology has been extensively investigated [47, 481. The
onset of non-Newtonian rheology for four geological melts
(a rhyolite, an andesite, a basalt and a nephelinite) is
illustrated in Figure 8. The low-strain-rate limit of
Newtonian viscosity is seen below strain rates of 10e4
whereas shear thinning (a decrease in viscosity with
increasing shear rate) sets in at higher strain rate. The onset
t I
-. of non-Newtonian rheology occurs approximately 3 log10
NEP
..
units of time “above” the relaxation time of each silicate
-.
: melt approximated from the Maxwell relation. A
11.2 L . normalization of the data for several compositions and at
I I I I I I I several temperatures is illustrated in Figure 9 where the
-5 -4 -3 -2 -1 viscosities are normalized to the low-strain-rate limiting
log,, STRAIN RATE (s-0
value of Newtonian viscosity and the strain rate of the
experiment is normalized to the relaxation frequency (the
Figure 8. Shear viscosities of Little Glass Mountain inverse of the relaxation time), calculated from the Maxwell
rhyolite (LGM), Crater Lake andesite (CLA), Hawaiian relation for each melt. The composition-dependence of the
‘holeiite (HTl3) and nephelinite (NFP) composition melts onset of non-Newtonian rheology can be removed in large
a function of applied strain-rate. With increasingstrain- part through this normalization. The success of this
e the onset of non-Newtonian (strain-rate dependent) normalization indicates that the onset of non-Newtonian
lravior is observed. The arrows indicate the calculated melt rheology in silicate melts can be easily estimated
rxation strain-rate for thesemelts. Redrawn from Webb using values for the Newtonian viscosity and the shear
1 Dingwell (1990b). modulus.
216 VISCOSITY AND ANELASTICITY OF MELTS
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The viscosity of synthetic and Viscosity of glassy Na20-B203- The onset of non-Newtonian rheo-
nntural silicate melts and glasses at Si02 system, J. Non-Cryst. Solid. logy of silicate melts, Phys.
high temperatures and at I bar , 95, 1031-1038, 1987. Chem Mineral., 17, 125-l 32,
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17864, 563pp.. 1987. flow in soda-lime-silica glass at Non-Newtonian rheology of ig-
35. Sato, H. and M.H. Manghnani, forming and annealing tempe- neous melts at high stresses and
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Virgo, Pressure dependence of the Chem., 156, 24.5-257, 1926. viscosity of sanidine liquid at high
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Viscosity of the Outer Core
R. A. Secco
Estimates of outer core viscosity span 14 orders of variations, and polar motion can all be accurately
magnitude. This wide range of values may be partially measured, the outer core viscosity estimates inferred from
explained by the difference in type of viscosity, molecular these measurements, ranging from 10-l to 10” poises,
viscosity (a rheological property of the material) vis-a-vis suffer from long observation times which can introduce
a modified or eddy viscosity (a property of the motion), large uncertainties from additional energy sources and/or
inferred from the various observational and theoretical sinks affecting the observed phenomenon. It must be
methods [24]. The motion associated with eddy viscosity noted, however, that time independent factors that affect
implies the possibility of non-viscous dissipative mechan- seismic wave amplitudes such as scattering, geometrical
isms such as ohmic dissipation. Molecular viscosity is spreading, radial and lateral inhomogeneities will be
separated into nearly equal components of shear viscosity, embodied in derived attenuation values. Confirmation of
q,, and bulk or volume viscosity, q,, depending on the any observation of inner core oscillation has not yet been
type of strain involved [ 14,151. 1, is a measure of made and therefore any so-derived viscosity estimate from
resistance to isochoric flow in a shear field whereas q” is geodetic observation or theory must be admitted with
a measure of resistance to volumetric flow in a 3-dimensi- caution. Other methods of outer core viscosity estimation
onal compressional field. In cases where outer core are from extrapolations launched from experimental data
viscosity estimates are based on observations of the at low (relative to core) pressures and temperatures using
attenuation of longitudinal waves, both TJ, and Q play various theories of liquid metals and from geomagnetic
significant roles but only 17,is important for damping field observations at Earth’s surface. Both of these suffer
whole Earth torsional mode oscillation and 11,for damping from large extrapolations and from the lack of any
radial mode oscillation [4]. experimental viscosity data on liquid Fe at pressures of
The majority of estimates of outer core viscosity is even a few kilobars. Most of the experimental data on
based on whole Earth geodetic and seismological observa- liquid Fe and liquid Fe-N& Fe-S, Fe-O and Fe-Si alloys is
tions. In terms of the observation times required by a found in the metallurgical literature and they are all
particular method, studies of p-wave attenuation benefit restricted to measurements at a pressure of 1 atm.
from their short periods (seconds) and all 7 studies cited The data and references are presented in 9 tables.
in Table 2 give upper bound viscosity values within a very Tables 1 and 2 are viscosity estimates based on geodetic
confined range of lo*-10’ poises. While long period and seismological studies, respectively. Tables 3 and 4
(minutes to years) geodetic phenomena, such as the radial are viscosity estimates from geomagnetic and liquid metal
and torsional modes of free oscillation, length of day theory studies, respectively. A brief description of the
method used for each estimate or measurement is also
R. A. Secco, Department of Geophysics, University of Western
given. Values of kinematic viscosity, v, reported in some
Ontario, London, Canada N6A 5B7 references have been converted to dynamic viscosity, 7,
by v = q/p, using a value of 10 g/cm’ for p, the density.
Mineral Physics and Crystallography The data in Tables l-4 are graphically presented in Figure
A Handbook of Physical Constants 1. Table 5 contains experimental shear viscosity data for
AGU Reference Shelf 2
Copyright 1995 by the American Geophysical Union. 218
SECCO 219
Sato and Espinosa (1967) 0.35 - 4.7 x 10” “Torsional free oscillations of whole Earth
Molodenskiy (1981) 2 lo7 “Forced nutation of the Earth (value for MCB)
Neuberg et al (1990) <3.3 x lo5 “Viscous damping only for nearly diurnal free
wobble (tidal measurements)
Bondi and Lyttleton (1948) <lo’* ‘Theoretically required for secular deceleration of
core by viscous coupling
Won and Kuo (1973) > 10-l ‘Theoretical evaluation of decay time of inner
core oscillation (value for ICB)
Toomre (1974) <lo” ‘18.6 year principal core nutation (value for
MCB)
Aldridge and Lumb (1987) 2.9 x lo7 ‘Decay of inertial waves in outer core
’ theory
” observation
220 VISCOSITY OF THE OUTER CORE
Sato and Espinosa (1965, 1967) 8.6 x lo’* Multiply reflected s-waves at mantle/core boundary.
Anderson and Hart (1978) 1.4 x IO’ Attenuation of body waves and checked against
radial mode Q data
Schloessin and Jacobs (1980) 2x lo5 Decay of free dynamo action during polarity transitions
Officer (1986) 2x IOX Value predicts correct order of magnitude of external field
and westward drift
SECCO 221
TABLE 4. Dynamic Viscosity Estimates of Outer Core from Theories of Liquid Metals
Bullard (1949) lo-2 From experimental values for liquid metals at STP
Clans (1972) 3.7-18.5 x IO-* Andrade formula for melting point viscosity
(value for ICB)
Leppaluoto (1972) l-5 x 10-l For a pure Fe outer core, from significant
structure theory of liquids (value for MCB)
Bukowinski and Knopoff (1976) >lO’ For a pure Fe outer core, from band structure
calculations
Schloessin and Jacobs (1980) 3.4 x lo* From experimental values for liquid Fe and
Andrade’s pressure effect on viscosity
Anderson (1980) lo’- lo4 Two structure state theory extrapolated to core
pressures
Svendsen et al (1989) 2.5 x lo-* Liquid state model fitted to high pressure melting
data on Fe
OUTER CORE VISCOSITY pure liquid Fe and Tables 6-9 contain experimental shear
viscosity data for liquid Fe alloys, all measured by the
A
f A oscillating crucible method. The viscosities in Tables 6-9
are presented as either dynamic or kinematic viscosities,
t as in the reference, because of insufficient density data for
4 i
SEISMOLOGY
: many of the alloy compositions.
f A
A
GEODESY
GEOMAGNETISM THEoRY
Fig.1. The common logarithm of dynamic viscosity (poises)
of the outer core plotted as a function of method used for its
Method determination.
222 VISCOSITY OF THE OUTER CORE
Reference T(“C) 1536 1550 1600 1650 1700 1750 1800 1850
Barfield and
Kitchener (1955) 7.60” 6.79’ 6.41 5.89’ 5.70 5.48’ 5.31 5.22
’ interpolated
’ extrapolated
Viscosity
Reference Composition Temperature Dynamic Kinematic
wt% Ni (“(3 (centipoises) (millistokes)
Adachi et al
(1973) 4.9 1516 6.11
1550 5.91
1604 5.69
1633 5.54
1665 5.36
TABLE 6 (continued)
Viscosity
Reference Composition Temperature Dynamic Kinematic
wt% Ni CC) (centipoises) (millistokes)
--___.- -- ~-
Arkharov et al
(1978) 0.52 1600 8.48
1.04 8.28
1.49 8.15
1.99 8.13
2.46 7.98
Viscosity
Reference Composition Temperature Dynamic Kinematic
wt% s 3 (“C) (centipoises) (millistokes)
Barfield and
Kitchener (1955) 1.16 1529 7.00
(+0.02 wt%C) 1600 6.45
1700 5.84
1800 5.41
Vostryakov et al
(1964) 0.39 1600 6.00
4.70 6.61
8.51 6.41
18.56 3.43
224 VISCOSITY OF THE OUTER CORE
TABLE 8. Experimental Data of Shear Dynamic Viscosity of Liquid Fe-O Alloys at 1 atm
Nakanishi et al
(1967) 0.012 1600 5.02
0.046 5.43
0.071 5.40
0.072 5.39
Viscosity
Reference Composition Temperature Dynamic Kinematic
wt% Si (“C) (centipoises) (millistokes)
TABLE 9 (continued)
Viscosity
Reference Composition Temperature Dynamic Kinematic
wt% Si (“C) (centipoises) (millistokes)
Acknowledgements. I gratefully acknowledge helpful discussions with H.H. Schloessin and L. Mansinha, comments
in reviews by D.L. Anderson and an anonymous reviewer, as well as financial support by the Natural Sciences and
Engineering Research Council of Canada.
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the Complex Eigen-frequency of the 38. Steinberg, J., Tyagi, S. and Lord, Jr., A.E. Pub.House, Tucson, 388 pp., 1978.
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Models of Mantle Viscosity
Scott D. King
ICE-l, was developed by Peltier and Andrews [40]. A surface, c is the radius at the core, 6pim is the density
summary of ice sheetmodels is provided by Peltier [39]. contrast at a depth r of spherical harmonic degree 1 and
Lambeck and co-workers have used far field absolute order m, and Gl(r,q(r)) is the geoid responsekernel.
sealevel changes,rather than the rebound histories at sites The density perturbations (6plm) are determined by
near formerly-glaciated regions [26, 321. They reason that seismic velocity perturbation models from seismic
relative sea level variations far from ice margins are less tomographic inversions and/or tectonic plate and slab
influenced by poorly-constrained ice models. The models from boundary layer theory and deep earthquake
difference between Nakada and Lambeck’s models based locations in subduction zones. To transform seismic
on relative sea level variations in the Pacific, and models velocity anomaliesinto density anomalies,we assumethat
based on Fennoscandianand Canadian Uplift could be changesin seismic velocity can be mappedinto changesin
interpreted as reflecting lateral variations in upper mantle temperature and do not represent changesin composition.
viscosity. Seismic velocity variations can be written in terms of
Table 1 compares a number of recently published elastic moduli for which the limited experimental
viscosity models from post-glacial rebound with geoid and information places reasonablebounds. Thus, the density
plate velocity studies compiled by Hager [14]. Becauseof perturbations in equation 3 can be written as
the limited power in the post-glacial rebound data set,
rebound models are usually reported in very simple
parameterizations. The models still range from the nearly-
uniform viscosity (Haskallian) model PT to strongly
layered models NL and HRPA (seeTable 1). where 6p/6vs is a velocity to density ratio and 6vslm is the
Another constraint on mantle viscosity comes from seismic velocity perturbation model.
modeling the geoid and dynamic topography of the surface A simple, two-layer viscosity model, with an increasein
and core mantle boundary, using the pattern of density viscosity of a factor of ten at 670 km depth or 1200 km
anomalies inferred from seismic tomography [ 11, 16, 17, depth, explains the longest wavelength geoid from the
l&23,49,50,51]. From early seismic tomography, it has inferred densitiesin the lower mantle [ 11, 181. This model
been observed that long-wavelength (i.e., spherical is different from the two end-member, post-glacial
harmonic degree 1 = 2,3) geoid lows are associatedwith rebound models. The differences between the models
long-wavelength, fast (presumably denser) regions in the from post glacial rebound and the geoid models have led
lower mantle [9]. In a static Earth, this is opposite of what to spirited debates,but until now no consensusmodel.
one predicts; geoid highs should correspond to mass The velocities of the Earth’s plates are the surface
excesses(Figure 2a). As shown by Pekris [36] (and others manifestations of convective flow in the mantle. Hager
since), a mass anomaly will drive flow that deforms the and O’Connell’smodel [15] showed that densities from the
surface and core mantle boundary (Figure 2b or 2c). The cooling of oceanplates and subducting slabsalone provide
resulting geoid is a combination of both internal (Figure the necessary buoyancy force to drive plates at the
2a) and boundary mass anomalies (Figure 2b or 2c) and observed velocities. Ricard et al. [50, 511, Ricard and
can be positive or negative, depending on the viscosity Vigny [47], Forte and Peltier [lo], and Forte et al. [12]
structure (compare Figure 2a + 2b versus 2a + 2~). used observed plate velocities to deduce the radial
The equations of motion of an incompressible self- viscosity structure of the mantle. Plate velocities constrain
gravitating spherical shell are presented in Richards and the absolute value of the viscosity of the mantle; the geoid
Hager [54] and Ricard et al. [50]. Theseequationscan be doesnot. The plate velocity data does not have the depth
solved by a separation of variables (assuming a radially- resolution of the geoid, becausea low viscosity zone can
stratified viscosity). The resulting ODE’s can be solved effectively decouple the plates from flow in the deep
for responsefunctions (kernels) which de nd only on the interior.
viscosity structure. The geoid (SVp” m, can then be In all of the studies discussed,the final viscosity model
calculated by convolving the response functions with a is dependentupon another model. In post-glacial rebound
distribution of density contrastsas follows studies, this is a model of the ice sheet.,which is only
crudely known. In the case of the geoid, it is the seismic
velocity models (see equations 3 and 4). Most seismic
tomographic inversions do not report formal uncertainties
(which are difficult to perform and, because of the
where y is the gravitational constant, a is the radius at the difficulty in defining sources of error may have little
230 MODELS OF MANTLE VISCOSITY
Model %m 77lm
Pa s) (pa s)
aPeltier and Tnsbingham [41] model, based on global sea level variations, with emphasis on near-field
sites.
bMitrovica and Peltier [29] model, based on the assumption that the gravity anomaly over Hudson Bay is
totally due to delayed rebound.
‘Lambeck. Johnston and Nakada [26] model 2. based on European sea level variations with emphasis on
relative variations in sites away from the ice margins.
eLambeck and Nakada [25] model for Australia, based on sea level variations with emphasis on relative
variations in sites spanning the continental margin.
fNakada and Lambeck [32] model for Oceanic response, based on sea level variations, with emphasis on
relative variations as a function of island size.
gRicard and Vigny [47] model from the Geoid and Plate velocities. Parentheses on (h) indicate the
thickness of the high viscosity lid.
hHager and Richards [la] model for relative mantle viscosity from the Geoid, calibrated for Plate
velocities and Advected heat flux [14]. An additional layer, from 400 km to 670 km depth has a
viscosity of 6 x 1020 Pa s.
iA modification of model HRGP that has an asthenospheric viscosity higher by a factor of 10, as might be
expected for Shield regions.
KING 231
500
r
,-me
I
.-_---.
I
.--
the Laurentide ice sheet suggeststhat this subset of the IO-2 lo“ loo IO’
relative sea level (RSL) data should be sensitive to the
viscosity at greater depths than other data subsets [30]. Relative Viscosity
They conclude that the preference of a uniform viscosity Fig. 4. Three representative 1-D viscosity models from
in the lower mantle of 1021 Pa s from other studies [e.g., Ricard et al. [51] from Monte Carlo inversion using geoid
2, 4, 5, 421 is more appropriately interpreted as a and plate velocities. The viscosities in this lot are scaled
constraint on the uppermost part of the lower mantle (i.e., by a characteristic mantle viscosity (rl= 102P Pa s).
KING 233
viscosity model is consistentwith recent post-glacial uplift rebound, plate velocity and geoid predictions. Using
analysesand mineral physics. perturbation theory on a 2-D Cartesian problem, Richards
and Hager [55] suggestedthis effect would be small for
3. COMPARISON long-wavelength structures in the lower mantle. Ritzler
and Jacobi [56], however, suggest that, because radial
The viscosity model from Forte et al. [12] - determined viscosity models underpredict the geoid compared to their
by inversion using the plate velocity data, the viscosity lateral viscosity equivalants, neglecting lateral viscosity
models from King and Masters [23] - determined by variations leads to errors in the magnitude of radial
inversion using the geoid data, and the viscosity model viscosity jumps as much as a factor of two. Zhang and
from Ricard et al. [51] - using a Monte Carlo inversion of Christensen [68] also find that the effects of lateral
geoid and plate velocity data - are remarkably similar. viscosity variations are significant, especially when the
Furthermore, the results of the post-glacial uplift inversion radial viscosity is stratified. Ricard et al. [52] showed that
by Mitrovica and Peltier [30] and the experimental data, as a model with lateral viscosity variations between
discussedby Panalli [46], seem compatible with these continental and oceanic asthenosphereis consistent with
observations. Upon considering both the uncertainty in the the observedglobal rotation of the lithosphere with respect
internal densitiesand surface loads and the uncertaintiesin to the hot spot reference frame (i.e., the degree 1 toroidal
the viscosity models themselves,it appearsthat the results component of plate velocities). A number of
from the different observationsare compatible. However, investigations addressing lateral viscosity variations are
if the transition zone is Ca rich, as suggestedby some [1], currently underway.
Karato’s 1211 results on the strength of garnet are
incompatible with this new model. Mantle models with a
hard transition zone appear compatible with observations
w. Acknowledgments. The author aeknowkdgessupport Erom
NSF grant EAR-91 17406. Thanks to R. O’Connell, A. Forte, and
4. LATERAL VISCOSITY VARIATIONS Y. Ricard for providing theses, reprints, and preprints. Thanks
also to the numerous anonymous reviewers whose comments
An area of increasing interest is the role of lateral helped improve this manuscript. Special thanks to Kathy
variations in viscosity and their effect on post-glacial Kincade for help in preparing this manuscript.
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Plastic Rheology of Crystals
J. P. Poirier
AH@)+PAV*
i = i0 fQZm 0” exp (- RT ) (1)
large strains in a stable manner by the so-called temperature), dislocations tend to remain straight in the
superplastic deformation , which may occur infine-grained deep troughs along the dense rows, and the thermally
materials. Non-Newtonian creep, with n 2 3, on the other activated, stress-assisted step of passing over the hill
hand, is potentially unstable and strain-induced structural between one row of atoms and the next (lattice friction), is
changesor strain heatingmay causeshearlocalization. the controlling process. Creep is then said to be glide-
Phase transformations strongly interact with plastic controlled. If the potential hills are so low, that slip
deformation; the resultant transformation plasticity [45] between localized obstaclesis easier than overcoming the
appears, in creep experiments, as an important transient obstacles, dislocations wait in front of the obstacle until
enhancementof the creeprate during transformation(or as a they can circumvent it by climbing out of their slip planes
stress drop in the case of deformation at constant strain- and glide until they meet the next obstacle. As climb of
rate). Localized phasetransformation under non-hydrostatic edge dislocations out of their slip plane is controlled by
stressesmay causeshearfaulting instabilities [7,30]. diffusion of point defects to or from the dislocations,
climb-controlled creep is rate-limited by thermally
2. PHYSICAL MECHANISMS activateddiffusion and can only occur at high temperatures;
also, the activation energy does not depend on stress. In
Plastic deformation is the macroscopicresult of transport climb-controlled creep as in glide-controlled creep, the
of matter on a microscopic scale, resulting from the strain is still due to dislocation glide, only the controlling
motion of defects: point defects, dislocations, or grain- processesof the strain rate differ. In general, dislocation
boundaries.Applied shearstressprovides the driving force creepis grain sizeindependent.
for the motion of defects and the rate of motion usually If one makes the reasonableassumptionthat, in steady-
increaseswith temperature.Deformation at low temperature statedeformation, the averagedistancebetweendislocations
U/T, c 0.3) is due to glide of dislocations on is determined by their long-range stress field, which
crystallographicslip planesin the direction of their Burgers balancesthe applied stress 6, the dislocation density p is
vector; plastic deformation occurs when the shear stress then proportional to cr2. The difference between the
resolved on the slip plane in the slip direction is equal to rheological equation for glide-controlled and climb-
the critical resolved shear stress (CRSS), characteristicof controlled creep essentially comes from the physics
the slip system. Deformation at high temperature, in most underlying the expressionof the velocity.
cases, involves diffusion of point defects (usually i) In glide-controlled creep (Figure 2a), to move by one
vacancies);it may also dependon the interaction of several Burgers vector, a dislocation must locally nucleatepairs of
kinds of defects : e.g., in dislocation creep controlled by kinks over the potential hill; sideways migration of the
vacancy diffusion or diffusion creep accommodated by kinks then brings the dislocation to the next low-energy
grain-boundarysliding (see[45] for a review). trough. Nucleation and migration of the kinks are
In general, the shear strain rate is given by a transport thermally activated processes;the applied stress helps in
equation, and is equal to the density of carriers of overcoming the energy barrier and the activation energy
deformation times the strength of the carriers times their decreasesby an amount equal to the work done by the
velocity. In the most frequent case of deformation by stress. In most cases, the dependenceof the activation
motion of dislocations, the shear strain-rate i obeys energy on stress can be assumedto be linear: AH (0) =
Orowans equation : AHo - Bo.
orientation of the samples with respect to the stress axis ii) At higher temperatures,during the incubation period,
(Table 1). clusters of water moleculesprecipitate into water bubbles;
Observationsof experimentally deformed crystals using the elastic strain aroundthe bubblesis relievedby punched-
transmission electron microscopy [ll, 36, 9, 181support out dislocation loops, which expand by climb and act as
the following mechanisms: sources, thus increasing the dislocation density; plastic
i) At low temperatures, low water fugacity, and high yield occurs suddenlywith a stressdrop (yield point) for an
strain rate, deformation is controlled by lattice friction, the applied stress high enoughto make massivemultiplication
density of grown-in dislocations is very small, the of dislocations possible. FitzGerald et al. [18] also point
dislocationsare straight and their mobility is low; quartz is out the role of microfractures in the nucleation of
then very strong. dislocations.
Fo92 Various 1430- 1650 5 - 150 co2/H2 = 0.1 f(o) 525 1311
F“92 <ill> 1500- 1600 10 - 40 cog2 = 0.43 3.5 523 1131
Fo92 <llO> 1400- 1600 10 - 60 cogH2 = 0.43 3.7 523 [I31
Foloo uo11 1550-1650 8 - 60 cog2 = 0.33 3.5 564 [I41
Woo ill11 1500- 1680 3 - 30 I--WA 2.9 667 WI
Fo90 r1011 1250- 1400 100 CO7JH2 = 2.3 536 [321
Fo90 [loll 1250 - 1400 100 CO2/H2 = 0.25 536 [321
Fo90 UOll 1250 - 1400 100
f”2
= 10e6 Pa 448 [321
Foloo nm 1400-1650 10 - 100 H2/cO2 2.6 460 [101
Woo w11 1400 - 1600 20 - 100 WC02 3.6 573 WI
Foloo [0111 1500 - 1600 30 - 100 WC02 2.7 598 WI
POIRIER 243
Orientation Buffer i0 n m Q i
of stressaxis (0 inMPa) Wmol)
(pseudo-cubic)
After [2]. 1200°C< T c 1525‘C ; 10-12<fo2 c lo3 atm. , buffer: opx (Mgo.9Feo.lSi03)or mw (Mg0.7Fe0.30)
c =e’oonfo m expC-Q$T)
Flow law: [loll2 .- -1 -1 .- 1 -1 -1
opx: E = 6 1 + d 2 ; [lOl]mw: E =d, +d2 ; [Oil] opx: 6 = ; 1+i2
.- 1 -1 -1 1 -1 -1 1 -1 1
[oll]mW: E =d, +i2 ; [llO]opx: d = i,+[i2‘ +t?, I ; [llO] mw: d‘ =i 1 +i,-
3.2. Olivine creep (of the order of 500 kJ/mol) does not tally with that
Olivine (Mg, Fe)zSiO4, the dominant mineral of the for diffusion of the slower species:oxygen or silicon (about
upper mantle, has an orthorhombic lattice and a slightly 335 kJ/mol). One should however note that climb of
distorted hexagonal close-packed oxygen sublattice.The dislocations should be controlled by multicomponent
common slip systems are: at low temperature (lOO)[OOl], d.$%sion of all the species,rather than by diffusion of the
correspondingto slip on the basalplane of the hcp oxygen slowest speciesalone [231.
sublattice in the a direction; and at high temperature The thermodynamic state of olivine with fixed Fe/Mg
(OlO)[lOO] (prism plane of the hcp sublattice in the c ratio is not entirely determinedwhen T, P and fo2 are fixed,
direction), with cross-slip on other prism planes such as
(001) and (011). the activity of one component (orthopyroxene or
High temperature creep of single crystals in various magnesio&istite) must also be specified. Bai et al [21
orientations obeys a power-law creep equationwith n = 3.5 performed systematic experiments on olivine buffered
(Table 2), apparently compatible with dislocation creep against orthopyroxene or magnesiowiistite for various
controlled by climb of edge dislocations. Examination of orientations as a function of temperature, stress, and
deformed samples by transmission electron microscopy oxygen fugacity. The results (Table 3) show wide
suggestthat creep can be controlled by climb and/or glide, variations in activation energy and fo2 dependence
according to the orientation [ 15, 211. However, when according to the experimental conditions: two or three
climb-control would be expected,the activation energy for power law equations are needed to describe
244 PLASTIC RHEOLOGY OF CRYSTALS
Crystal T n m Q Ref
i0
(“c> (cr inMPa) W/ml)
Enstatite (En99) 1350 - 1450 4.6 x 1011 3.8 0 750 Buffered by olivine r371
2.1 x 1015 11 I,
Enstatite (En96) 1350 - 1450 3.9 0 880 [371
Diopside 1000 - 1050 4.3 284 P = 5-15 kbar, in talc Ul
Diopside
Slip on (100) 1020 - 1137 4.9 x lo3 8.1 742 Ar 10% HZ-~% H20 [491
1, II
1137 - 1321 7.1 x 10-23 8.8 85 [491
,I 11
Slip on (110) 1020 - 1130 4.1 x 1O-4 6.5 442 [491
7.0 x 10-l* 6.0 !I 11 r491
1130 - 1321 48
Hedenbcrgite 900 - 1100 1.2 x lo* 3.6 526 P = 10 kbar [331
phenomenologically the creep behavior over the whole In orthoenstatite, the glissile dislocations with Burgers
range of experimental conditions, suggestingthat different vector [OOl] can dissociate on (100) [52]. During high-
mechanisms have to be considered. The stress exponent, temperature deformation, the shear stress can favor the
however, is equal to 3.5 in all cases(which, incidentally, is nucleation of very fine lamella of clinoenstatite on (100)
a confirmation of its limited usefulnessas a criterion for planes; calcium present as a minor ion in enstatite can
the determination of the physical mechanism of creep). diffuse to the clinoenstatite, thus forming thin lamella: of
Examination of deformed samples by the oxidation- calcic clinopyroxene [26], which might be confused with
decoration technique [3] shows that different dislocation stacking faults. High-temperaturecreep of (Mg, Fe)2Si2@
structures parallel the changesin power-law equationsand enstatite obeys a power law (Table 4); it does not seem to
confirms that several rate-controlling mechanisms may be be sensitiveto oxygen fugacity but the creep-rateincreases
operatingin different experimentalconditions. with increasingiron and aluminum content [37].
As in the case of quartz, water-related defects increase Mechanical twinning, primarily on the (100) plane in the
olivine plasticity . For single crystals of olivine treated in a [OOl] direction, is the dominant deformation mode for
hydrous environment at 1300°C under a hydrostatic clinopyroxenes at low temperatures [33]. At high
pressure of 300 MPa, and subsequently deformed in the temperature, crystals oriented in such a way that twinning
same conditions at a constant strain rate of 10m5s1,the is impossible deform by power-law creep (Table 4). In
flow stressis reducedby a factor of 1.5 to 2.5, with respect experiments on high-temperature creep of pure diopside,
to that of crystals treated in a dry environment [381. Ratteron and Jaoul [49] report a drastic decrease in
Samplesdeformed under wet conditions and examined in activation energy by a factor of almost ten above a critical
transmission electron microscopy exhibited evidence of temperature about 200°C below the melting point. The
enhancedclimb of dislocations(dislocationwalls, etc.). crystals then becomemuch more creep-resistantthan would
be expectedfrom the extrapolatedlower-temperaturecreep
3.3. Pyroxenes law. Examination of the deformed samplesby transmission
Although orthopyroxene Mg2Si206 (enstatite) and electron microscopy [ 131showed that aboveand below the
clinopyroxene MgCaSi& (diopside) are also important critical temperature deformation took place primarily by
minerals of the upper mantle, their plastic properties have (1 lo] 1/2<1 IO> slip, with no detectable occurrence of
been much less studied than those of olivine. The easiest climb. Deformation is therefore probably glide-controlled,
slip system of orthorhombic enstatite as well as of which accountsfor the high value of the stressexponent(n
monoclinic diopside is (lOO)[OOl], with dislocation glide = 8). Above the critical temperature, the dislocations were
on the planesof the layers of chains of Si04 tetrahedra,and pinned by tiny glassy globules (~10 nm), resulting from
in the direction of the chains. incipient partial melting well below the currently accepted
POWER 245
BaTi <l lO> 0.75 - 0.92 Argon -38 3.6 469 30 [41
KNbO3 <llO> 0.84 - 0.99 Argon -43 3.7 415 38 r51
KTa03 <llO> 0.87 - 0.99 Argon -11 1 292 21 [51
CaTi <l lO> 0.67 - 0.78 Air -39 2.5 274 15 [531
CaTi <loo> 0.67 - 0.78 Air -37 3.3 444 24 [531
NaNbO3 <lOO> 0.70 - 0.98 Air -92 5.3 192 14 [531
melting point of diopside. The fluid droplets may high pressures and, there is as yet no high-temperature
effectively act as obstaclesto dislocation slip, thus causing creep apparatus operating at these pressures; the only
the observedhardening. information we have so far on the plastic properties of the
silicate high-pressurephasescomes from experiments that
3.4. High-Pressure Mantle Minerals were performed at room temperature, either on the
Despite their importance for the rheology of the metastable phases at ambient pressure or in-situ in a
transition zone and the lower mantle, there is no diamond-anvil cell. There is also qualitative information
information on the plasticity of the high-pressure mantle extracted from the examination of dislocation structures of
minerals in the relevant conditions of temperature and the phasesby transmission electron microscopy. Finally,
pressure. The essential high-pressure phases are experiments on isostructural compounds presumably
(Mg,Fe)#iO4 P-phaseand y-spinel, and majorite garnet in belonging to isomechanicalgroups may provide some basis
the transition zone, and (Mg,Fe)Si03 perovskite and for speculation.
(Mg,Fe)O magnesiowtistitein the lower mantle. Karat0 et al. [251 performed microhardness tests on
Magnesiowiistite has the NaCl stucture and is stable at metastable MgSiO3 perovskite single crystals at room
ambient pressure.There havebeennumerousinvestigations temperature; they found a high value of the Vickers
on the plastic properties of the MgO end-member hardness(Hv= 18 GPa), higher than for olivine or enstatite.
(magnesiaor periclase),which is easily deformable even at MeadeandJeanloz[42] estimatedthe yield strengthat room
low temperatures, on the six{ 110) planes in the cl 10~ temperature of polycrystalline olivine, perovskite and y-
directions. There are however no experiments at very high spinel, prepared in a laser-heateddiamond-anvil cell, from
temperatures in controlled oxygen partial pressure the pressuregradient in the cell. They found that at room
conditions; experiments at about 0.5Tm, in air or vacuum temperatureperovskite was stronger than spine1or olivine.
are compatible with climb-controlled dislocation creep, However, it should be emphasizedthat the yield strength of
with n = 4 and Q = 400 kJ/mol [8]. Wiistite Fefwx 0, the crystalsdependson the critical resolvedshearstress(CRSS)
other end-member, is always non-stoichiometric and Fe- of the available slip systems; the dependence on
deficient; recent high-temperature creep experiments temperature of the CRSS may differ considerably for the
performed at various controlled oxygen fugacities [24] give various slip systems of one mineral (let alone for the slip
results (n = 4.8, -0.02 c m c 0.11, Q = 290 kJ/mol) systems of different minerals), so that the dominant slip
compatible with dislocation creep controlled by the system at room temperature may not be the same at high
diffusion of oxygen-related point defects whose nature temperature,and the ranking of minerals according to their
varies with temperature. There are good reasonsto believe yield strengths at room temperature cannot be assumedto
that deformation of magnesiowiistite at lower mantle remain the sameat high temperature.
conditions is not very difficult: crystals formed by Although transmission electron microscopy of phases
decomposition of olivine at high pressure in a diamond- deformed at high temperature, in their stability field, does
anvil cell contain a high density of dislocations[47]. not provide quantitative information on their strength, it
All phasesother than magnesiowiistiteare stable only at does at least provide reliable qualitative information on the
246 PLASTIC RHEOLOGY OF CRYSTALS
dislocation structures, density, and dissociationfrom which reasonableto assumethat the slip systemsare the sameas
educated guesseson the deformability can be attempted. in other perovskites, but crystals of perovskite structure
Thus, in natural y-spine1 (ringwoodite) formed at high certainly do not constitute an isomechanicalgroup [S, 531,
temperature in shocked meteorites, stacking faults and probably due to the fact that the distortions and the
dislocations similar to those found in MgA1204 spine1are dislocationcore structuresare different: creepparameterscan
observed [39]. There is also evidencefor the (lll)cllO> be very different even for apparently similar perovskites
slip system as in MgA1204 1121,and dislocationsare very (Table 5). Therefore, the successof the analogueapproach
straight, pointing to glide control of the deformation. to try elucidating the plastic properties of MgSi03 at high
There is no information on the plasticity or dislocation temperature is contingent on the existence of a good
structures of MgSi03 perovskite at high temperature; it is analogue(yet to be identified) of MgSi03 perovskite.
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Phase Diagrams of Earth-Forming Minerals
Dean C. Presnall
The purpose of this compilation is to present a selected For several of the mineral groups, only representative
and compact set of phase diagrams for the major Earth- phase diagrams are shown. (2) The presentation of more
forming minerals and to show the present state of knowl- complex phase diagrams that show mutual stability
edge concerning the effect of pressure on the individual relationships among the various minerals and mineral
mineral stabilities and their high-pressure transformation groups has been minimized. (3) Many subsolidus phase
products. The phase diagrams are arranged as follows: diagrams important to metamorphic petrology and
thermobarometry are excluded. Reviews of these
Figure subsolidus phase relationships and thermodynamic data for
Silica 1 calculating the phase diagrams have been presented
Feldspars 2-7 elsewhere [13, 50, 70, 122, 1541. Other useful reviews and
Pyroxenes 8-13 compilations of phase diagrams are Lindsley [96] for
Olivine 14-16 oxides, Gilbert et al. [60] and Huckenholz et al. [74] for
Garnet 17-20 amphiboles, Liu and Bassett [104] for elements, oxides,
Iron-titanium oxides 21-23 and silicates at high pressures, and Phase Diagrams for
Pargasite 24 Cerumists [129-1371. It will be noted that some diagrams
Serpentine 25 are in weight percent and others are in mole percent; they
Phlogopite 25 have usually been left as originally published. Minor
Iron 26-27 drafting errors and topological imperfections that were
found on a few of the original diagrams have been
The compilation has been compressed in three ways. (1) corrected in the redrafted diagrams shown here.
Pressure, GPa
5 10 15
Pressure, GPa Fig. 2. Isopleth for the composition, NaAlSigOs [12, 16,
331. The albite = jadeite + quartz reaction shown by Bell
Fig. 1. Phase relationships for SiO2. Numbers beside
and Roseboom [12] and in this figure is about 0.1 GPa
curves refer to the following sources: 1 - [178]; 2 - [168]; 3 higher than the curve of Boettcher and Wyllie [22]. The
- [160]; 4 - [4]. The melting curve is from Jackson [77] at ,latter passes through the “consensus” value of 1.63 GPa,
pressures below 4 GPa, from Kanzaki [83] at pressures 600°C for this reaction [81]. Also, the quartz-coesite curve
between 4 and 7 GPa, and from Zhang et al. [178] at
shown by Bell and Roseboom [12] and in this figure is
pressures above 7 GPa. The temperature of the high
about 0.4 GPa higher at 1300°C than the pressure given by
quartz-low quartz-coesite invariant point is from Mirwald a linear extrapolation of the curve of Bohlen and Boettcher
and Massonne [ 1131. The quartz-coesite transition is from [24], which is shown in Figure 1. The curve of Bohlen and
Bohlen and Boettcher [24] but note that their curve lies
Boettcher would intersect the albite = jadeite + quartz
toward the low-pressure side of the range of curves by
curve at about 1300°C rather than the jadeite + quartz
others [5, 23, 31, 62, 89, 1131. The high quartz-low quartz
(coesite) = liquid curve. At about lOOO”C, Liu [loll
curve is from Yoder [172]. Boundaries for the tridymite
synthesized NaAlSigOg in the hollandite structure at
and cristobalite fields are from Tuttle and Bowen [164]
pressures from 21 to 24 GPa, and a mixture of NaAlSi04
except that the cristobalite-high quartz-liquid invariant
(CaFezOa-type structure) + stishovite above 24 GPa.
point has been shifted to 0.7 GPa to accomodate the data of
Jadeite, NaAlSi206; Coesite, SiO2.
Jackson [77]. Silica has been synthesized in the FezN
structure at 35-40 GPa, T>lOOO”C by Liu et al. [105], and
at 35 GPa, 500-1000°C by Togaya [162]. However,
Tsuchida and Yagi [ 1631 reported a reversible transition
‘“““I’
between stishovite and the CaC12 structure at 80-100 GPa
and T> 1000°C.
Leucite + Liquid
High Sanidine
IIOO-
I I I I I I I I _
0 I 2 3 4
Pressure, GPa
Fig. 4. Isopleth for the composition, KAlSi30s [93, 1491. At 12 GPa, 900°C Ringwood et al. [144]
synthesized KAlSi3Os in the hollandite structure. In experiments from 8-10 GPa and 700”-lOOO”C, Kinomura
et al. [88] synthesized the assemblage K2Si409 (wadeite-type structure) + kyanite (A12Si05) + coesite (SiO2)
from the composition KAlSi30s; and they synthesized the hollandite structure of KAlSi3Os at 9OO”C, 12 GPa,
and at 700°C 11 and 11.5 GPa.
An
CaAlzSizOe
Ab Or
NaAISi,OB Mole percent KAISi,O,
Fig. 5. Compositions of coexisting alkali feldspar and plagioclase at 0.1 GPa and temperatures from 800 to
9OO”C, as indicated [49]. Note that the phase boundary is essentially isothermal except in the Ab-rich portion
of the diagram. Many others have discussed ternary feldspar geothermometry [lo, 39, 54, 58, 63, 66, 75, 80,
139, 142, 151-153, 1651 and ternary feldspar phase relationships [68, 121, 156, 164, 1751. An, anorthite; Ab,
albite; Or, orthoclase.
PRESNALL 251
1800 I I I 1 I I 1 I I
I
1700-
Liquid t Corundum _
1600 -
Liquid +
Corundum
I I I I I I I I I
7001 60 70 80 9gaA, si o
IO 20 30 40 50
NaAlSi308 Mole Percent 2 28
Anorthite
Albite
Fig. 6. Temperature-composition sections for the join NaAlSigOs (albite) - CaA12Si208 (anorthite) under
anhydrous conditions at 1 atm [26, 1171, 1 GPa, 2 GPa [33, 941, and under H20-saturated conditions at 0.5
GPa [79, 1751.
252 PHASE DIAGRAMS
130(
Liquid
120(
Leucite t Liquid
/
I lO(
Feldspar + Liquid
lOO( Feldspar
Liquid t Vapor
/ /
70(
t
Orthoclase tVapo
Vapor
/
2 Feldspars + Vapor
60(
50( II
Na*lSi,Or 20 30 40
Weight
50 60
percent
\
70 80 90
KAISi,O,
Fig. 7. Temperature-composition sections for the join NaAlSigOg (albite) - KAlSi308 (orthoclase) under
anhydrous conditions at 1 atm [148], and under HZO-saturated conditions at 0.2 GPa [29] and 0.5 GPa [ 119,
1751. Ab, albite; Liq, liquid; V, vapor. Locations of dashed lines are inferred.
PRFBNALL 253
Orthoenstatite
Protoenstatite
5 IO 15 20 25
Pressure, GPa
Fig. 8. Isopleth for the composition MgSi03 [7, 9, 35, 45, 56, 57, 65, 76, 92, 127, 140, 1691. For additional
data at pressures above 15 GPa, see also Sawamoto [147]. Not shown is a singular point at about 0.13 GPa
below which enstatite melts incongruently to forsterite + liquid [45]. Position of dashed curve is inferred. For
additional data on melting temperatures up to 58 GPa, see Zerr and Boehler [ 1771.
1601
I atm 20 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’
II?Gt II + CaSi03Pv
CM _
CaSiL3Pv
-. C;x + Gt
0
$ 14 -.
Di
+ _
a CaSi03 Pv
.‘CPX
IO -_
Pen + Di
I 1
3p 5c I
Di
60Casio
-3
Mole percent Casio,
\ Oen + Di
‘Oen
Fig. 12. Pressure-composition section for the system
I I I I I I I I’
u Oen + Di
\
Mole percenl
Fig. 13. Orthopyroxene + augite, orthopyroxene + augite + pigeonite, and pigeonite + augite equilibria at 1
atm and 500-1300°C [95]. Phase relationships to the right of the forbidden zone boundary are metastable
relative to augite + olivine + silica. Lindsley [95] has presented three other similar diagrams at 0.5, 1, and 1.5
GPa. Lindsley and Andersen [97] should be consulted for correction procedures required before plotting
pyroxenes on these diagrams for geothermometry. En, enstatite (MgSi03); Fs, ferrosilite (FeSiO3); Di,
diopside (CaMgSi206); Hd, hedenbergite (CaFeSi206).
Periclase + Liquid
2500 1
Anhydrous
ite
ie
Spine1
Forsterite
1 /I:
/ / Spine1 \ ]
-L I / I
5
Pressme, G Pa
Fig. 14. Isopleth for the composition Mg2SiOd [48, 57, 1411. Additional studies of the melting relationships
are Ohtani and Kumazawa [126] and Kato and Kumazawa [84-861. Locations of dashed lines are inferred.
2000
Llquld
t
Pyrope
iti
E I400
c OLIVINE
1300-
1000 I
I /
I200 - 0 I 2 3 ;essure, 5 6 7 8 9 IO
GPo
Mg,?,o, IO 20 30 40 50 60 70 80 90 Fe,S,O, Fig. 17. Isopleth for Mg3A12Si3012, pyrope garnet. Phase
Weight percent
relationships at pressures less than 5 GPa are from Boyd
Fig. 15. Phase relationships for the system Mg2Si04 and England [32]. The melting curve at 5 GPa and above
(forsterite) - FezSiO4 (fayalite) in equilibrium with Fe at 1 is from Ohtani et al. [125]. Liu [99] reported that pyrope
atm [27]. Locations of dashed lines are inferred. transforms to perovskite + corundum at about 30 GPa, 200-
800°C. Liu [loo] subsequently revised this result and
found that pyrope transforms to the ilmenite structure at
, I , , , , , , ,
PvtMw I1 1 /&j-Pv+Mw+St
/&LPv+Mw+St
about 24-25 GPa, lOOO”-14OO”C, and that ilmenite then
25- transforms to perovskite at about 30 GPa. Locations of
dashed lines are inferred.
SP
I- PV
Pv + Gt
\ P\
\ Gt 1
Al:o,
Gt
\
\
\
Fig. 16. Pressure-composition sections for the join Mole percent AI,O, ” -
Mg2Si04-Fe2Si04 at various temperatures. Phase Fig. 18. Pressure-composition section for the join MgSiOj-
relationships above 21 GPa are from Ito and Takahashi Al203 at 1000 and 1650°C [57, 821. For additional data
[76] and those below 21 GPa are from Akaogi et al. [3]. along the boundary between the garnet and clinopyroxene
Other references [51, 87, 1571 give additional data and + garnet fields at 1OOO”C,see Akaogi and Akimoto [2]. At
discussion of these phase relationships. Pv, perovskite 1100 and 1600°C for pressures between 2 and 6.5 GPa, the
(MgSiOg-FeSiO3 solid solution); Mw, magnesiowiistite A1203 content of pyroxene in equilibrium with garnet
(MgO-Fe0 solid solution); St, stishovite (SiO2); Sp, spinel; increases with decreasing pressure to at least 15 mole
Mod Sp, modified spinel; 01, olivine. percent [30, 341.
PRESNALL 257
A’,03
Corundum
Fig. 19. The system CaSi03-MgSi03-Al203 at 12OO”C,3 GPa [30]. Co, corundum; Di, diopside; Ca-Gt, Ca-
garnet; Mg-Gt, Mg-garnet; Wo, wollastonite; En, enstatite; CaAl$i06, Ca-Tschermak’s molecule.
Pyrope
+- Grossular,
GPa
GPa
Fig. 20. Compositions (unsmoothed) of coexisting garnet (Gt), Ca-rich pyroxene (Cpx), and Ca-poor
pyroxene (Opx or Cpx) at various pressures and temperatures [69]. Labels of the type, 9, 2000, indicate
pressure (GPa) followed by temperature (“C). Pyrope, Mg3Al$Si3012; Grossular, Ca3A12Si3012.
258 PHASE DIAGRAMS
I /I
L.IQUID Fe
--I”- .-
i’
AIR
..-.- -
- - py(f=JF.. “J ,cB
-.
)-
n!
(u 1200 -‘-‘~ \, /
2 k-/-l., 7. -.--pJ
y- lDrlhl + \A/iicTlrc
u
“+IaJ t -.-.- -.- .-.-
.-.-.-
800- CY-IRON + WkTlTE .-.-.- ,p-.-
__.-.-
-.- ,$!L- -
.-.-.- ,p?-. -
.~ _-_-_-I pL.- -.- ,6’1.-
600--‘-.- .-.-. -. - lC24- ,o-14-.-
,@C.-
-.-.- - .-.__. -.-.-.-.- ,g?-., - .-,Cj-E- .- -
I-.-.- (/!L.--.-.-.-.-.- -.-ic3L. - .- ,0-l” .- -
Cl!- IRON + MAGNETITE -.- -
I 1 1 -L- -I I I lC20-. -
Fe 0.1 0.3 Fe0 23 24 25 26 27 FesO, 29 Fe,O,
Weight % Oxygen
Fig. 21. Temperature-composition section for the system Fe-O at 1 atm [46,47, 64, 120, 1381. Light dash-dot
lines are oxygen isobars in atm.
PREBNALL 259
Rutile
TiOo
1300°c
One atm
1 * .
Fig. 22. The system TiOz-FeO-FqO3 at 13OO”C, 1 atm [161]. Light dashed lines are oxygen isobars labeled
in log oxygen fugacity units (atm). Psb, pseudobrookite (FezTiOs); Fpb, ferropseudobrookite (FeTi205); Ilm,
ilmenite (FeTiOs); Hem, hematite (FezOg); Usp, ulvospinel (FezTi04); Mt, magnetite (Fe304); Wiis, wiistite
(Fed3
260 PHASE DIAGRAMS
o”-1: i
k
0-
-:
-2c )
Temperature, “C
Fig. 23. Temperature-oxygen fugacity (&) grid for coexisting magnetite-ulvospinel solid solution and
ilmenite-hematite solid solution pairs [ 1551. Lines with labels of the type, I-70, indicate mole % ilmenite in
the ilmenite (FeTiOs) - hematite (Fe203) solid solution. Lines with labels of the type, U-70, indicate mole %
ulvospinel in the ulvospinel (Fe2Ti04) - magnetite (Fe304) solid solution. Mt, magnetite; Usp, ulvospinel;
Ilm, ilmenite; Hem, hematite.
PRESNALL 261
Pa-out
/ I
400 800 1000 1200 IL IO
Temperature”C
6000 -
CM IOC
I I
100 200 300
Pressure, GPO
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160. Suito, K., Phase relations of pure stishovite transition by in-situ X- 178. Zhang, J., R. C. Liebermann, T.
Mg2SiO4 up to 200 kilobars, in ray measurements, Tectonophys., Gasparik, C. T. Herzberg, and Y.
High-Pressure Research, edited by 35, 259-270, 1976. Fei, Melting and subsolidus
M. H. Manghnani and S. 169. Yamamoto, K., and S. Akimoto, relations of SiO2 at 9-14 GPa, J.
Akimoto, pp. 255-266, Academic The system MgO-Si02-H20 at Geophys. Res., 98, 19,785-
Press, 1977. high pressures and temperatures - 19,793, 1993.
161. Taylor, R. W., Phase equilibria in Stability field for hydroxyl-chon- 179. Zou, G., P. M. Bell, and H. K.
the system FeO-Fe203-Ti02 at drodite, hydroxy-clinohumite and Mao, Application of the solid-he-
13OO”C, Am. Mineral., 49, 1016- 10 A-phase, Am. J. Sci., 277, lium pressure medium in a study of
1030, 1964. 288-312, 1977. the CI-E Fe transition under hydro-
162. Togaya, M., High pressure 170. Yang, H.-Y., Crystallization of static pressure, Carnegie Inst.
generation and phase iron-free pigeonite in the system Washington Year Book 80, 272-
transformations of SiO2 and anorthite-diopside-enstatite- 274, 1981.
Diffusion Data for Silicate Minerals, Glasses, and Liquids
John B. Brady
J. B. Brady, Department of Geology, Smith College, North- where x (m) is distance and the n2 terms L: (moles
ampton, MA 01063 of i/m.J.s) are “phenomenological diffusion coeffi-
cients” [36]. Because each component of the system
Mineral Physics and Crystallography may move in response to a gradient in the chemical
A Handbook of Physical Constants potential of any other component, the complexity of
AGU Reference Shelf 2 describing diffusion in multicomponent systems rises
Copyright 1995 by the American Geophysical Union. 269
270 DIFFUSION DATA
Ji =-Di
for the single phase in which the diffusion occurs
reduces the number of independent gradients to (n- 1)
and the number of diffusion coefficients to (n-1)2. relates the instantaneous flux Ji (moles of i/m2s) of
Second, Onsager [ 132, 1331 showed that if the component i to the one-dimensional gradient of the
forces, fluxes, components, and reference frame are concentration of i, dCi/dx (moles of i/m4), and
properly chosen, the matrix of coefficients relating the defines the diffusion coefficient Di (m2/s). However,
forces and fluxes is symmetrical unless the experiment attains a steady state, time (t) is
also a variable and a continuity equation (Fick’s
Second Law)
L; = L;: , (3
BoundaryConditions Solution
Thin-film Solution
Ci + CO for Ix]> 0 as t + 0
} (y)=&exp[&) where cx=lL”(Ci -CO)dx (10)
c, 3.00 for x = 0 as t + 0
cases such as (12) and (13), the fractional extent of as silicate minerals, glasses, and liquids.
completion of homogenization by diffusion is propor- If Ci does change significantly in the experiment
tional to a. These fi relations provide impor- and Di is a function of Ci, observed compositional
tant tests that experimental data must pass if diffusion profiles might not match the shape of those predicted
is asserted as the rate-controlling process. They also by (9)-(13). In such cases the Di calculated with
provide simple approximations to the limits of these equations will be at best a compositional
diffusion when applying measured diffusion “average” and equation (8) should be considered.
coefficients to specific problems [ 1471. Experiments in which composition does change
significantly are often termed “interdiffusion” or
4. DIFFUSION COEFFICIENTS “chemical diffusion” experiments. A commonly-used
analytical solution to (8), for the same boundary
In general, one must assume that Di is a function of conditions as for equation (1 1), was obtained by
Ci. Therefore, equations (9)-( 13) may be used with Matano [122] using the Boltzmann [8] substitution
confidence only if Ci does not change appreciably (x=x/& 1:
during the experiment. This is accomplished either
(a) by using a measurement technique (typically
involving radioactive tracers) that can detect very
small changes in Ci, or (b) by using diffusional
exchange of stable isotopes of the same element that
leave the element concentration unchanged. Equation (14) can be evaluated numerically or graphi -
Approach (a) yields a “tracer diffusion coefficient” for tally from a plot of (Ci - CO)/(Cl - CO) versus x,
the element that is specific to the bulk composition where the point x = 0 (the Matano interface) is
studied. Approach (b) yields a “self-diffusion coeffi - selected such that
cient” for the isotopically doped element that is also
specific to the bulk chemical composition. Both
approaches generally ignore the opposite or exchange (15)
flux that must occur in dominantly ionic phases such
272 DIFFUSION DATA
0.0 1.0
(4
s 0.8
u
s
u ; 0.6
3 x
3 0.4
9
-1.5 1.0
g 0.2
-2.0 0.0
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1,
x/L
X2
Figure 1. Graphical solutions to equation (9). (A) The “thin film” solution of equation (10) is
shown with a=1 for various values of fi (labels on lines). Plotting ln(Ci - CO) as a function of
x2 at any time yields a straight line of slope -l/(4Dit). (B) The “finite pair” solution of equation
(12) is shown for h/L=O.4 and various values of Dt/L2 (labels on curves). Plotting (Ci -CO)/(Cl -
CO) as a function of x/L normalizes all casesto a single dimensionless graph. The initial boundary
between the two phases is marked by a dashed vertical line.
[32, p.230-2341. For binary, cation exchange independent fluxes and, therefore, the “tracer”
between ionic crystals, the Matano interface is the diffusion coefficients of Cu and Zn can be determined
original boundary between the two crystals. Diffu- in addition to the interdiffusion coefficient DCuZnm,.
sion experiments that follow the Boltzmann-Matano A similar analysis for binary cation interdiffusion
approach have the advantage of determining Di as a (AZ w BZ where AZ represents Al”Z;’ and BZ
function of Ci and the disadvantage of risking the represents BzbZ,“) in appreciably ionic materials such
complications of multicomponent diffusion, for as silicate minerals yields [5, 112, 113, lo]:
which neither (8) nor (14) is correct.
Darken [35] and Hartley and Crank [83] showed
1 +
that for electrically neutral species, the binary (AtiB)
interdiffusion coefficients (D,,-, ) obtained in a
Boltzmann-Matano type experiment and the tracer dif- I[
fusion coefficients ( Da and D*,) for the interdiffus ing
speciesare related by (17)
D AB-, (N,Di + NADIR) which requires vacancy diffusion if a#b. If a=b, then
=
( 17) simplifies to
Ii
where N A is the mole fraction and YAthe molar activ- (Daz)( Diz )
ity coefficient of component A. Darken developed his D AB-, =
analysis in response to the experiments of Smigelskas (NA,D;Z + NBZD;Z) I +
which duplicates the sample preparation, heating to AH (J/mole) is the “activation energy.” D, and AH
the temperature of the experiment, quenching (after have significance in the atomic theory of diffusion
“zero time” at temperature), and data analysis of the [see 32, 1211and may be related for groups of similar
other diffusion experiments, commonly reveals materials [162, 82, 1061.
sources of systematic errors. Diffusion data are listed in terms of AH and log D,
These and other important features of diffusion and their uncertainties. In many cases data were
experiments are described in Ryerson [141]. converted to the units &I, m2/s) and form (log D,) of
this compilation. Logarithms are listed to 3 decimal
7. DATA TABLE places for accurate conversion, even though the
original data may not warrant such precision. No
Due to space limitations, the data included in this attempt was made to reevaluate the data, the fit, or the
compilation have been restricted to comparatively uncertainties given (or omitted) in the original papers.
recent experimental measurements of diffusion coeffi- Also listed are the conditions of the experiment as
cients for silicate minerals, glasses, and liquids. appropriate including the temperature range, pressure
Many good, older data have been left out, but can be range, oxygen fugacity, and sample geometry.
found by following the trail of references in the recent Extrapolation of the data using (20) to conditions
papers that are included. Older data may also be outside of the experimental range is not advisable.
found by consulting the compilations of Freer [56, However, for ease of comparison log D is listed for a
571, Hofmann [86], Askill [2], and Harrop [81]. uniform temperature of 800°C (1200°C for the glasses
Some good data also exist for important non-silicate and liquids), even though this temperature may be
minerals such as apatite [ 157, 23, 451 and magnetite- outside of the experimental range. Use these
titanomagnetite [65, 136,591, but the silicate minerals tabulated log D numbers with caution.
offered the clearest boundary for this paper. Finally, a sample “closure temperature” (T,) has
Almost all of the data listed are for tracer or self- been calculated for the silicate mineral diffusion data.
diffusion. Interdiffusion (chemical diffusion) exper- The closure temperature given is a solution of the
iments involving minerals are not numerous and Dodson [38] equation
interdiffusion data sets do not lend themselves to
compact presentation. Interdiffusion data for silicate
liquids and glassesare more abundant, but are not in-
cluded [see 156, 3, 41. Neither are non-isothermal
(Soret) diffusion data [see 1081. Diffusion data listed
for silicate glasses and liquids have been further for a sphere of radius a=O.l mm and a cooling rate
restricted to bulk compositions that may be classified (dT/dt) of 5 K/Ma. The example closure temperatures
as either basalt or rhyolite. were included because of the importance of closure
Because diffusion is thermally activated, temperatures in the application of diffusion data to
coefficients for diffusion by a single mechanism at petrologic [107] and geochronologic [123, Chap. 51
different temperatures may be described by an problems. Note that other closure temperatures
Arrhenius equation would be calculated for different crystal sizes, cooling
rates, and boundary conditions.
D = D, exp (20)
Acknowledgments. This paper was improved by help-
and fit by a straight line on a graph of log D (m2/s) as ful comments on earlier versions of the manuscript by
a function of l/T (K-i) [147, Chap. 21. Log D, D. J. Cherniak, R. A. Cooper, R. Freer, J. Ganguly, B. J.
(m2/s) is the intercept of the line on the log D axis Giletti, S. J. Kozak, E. B. Watson, and an anonymous
(l/T = 0). AHl(2.303.R) is the slope of the line reviewer. N. Vondell provided considerable help with the
where R is the gas constant (8.3143 J/mole.K) and library work.
Mineral, Glass, Orienta- Diffusing Temperature P 0, 4 log D, (or D) log D ‘IT,” Experiment/Comments Ref.
or Liquid tion Component Range (“C) (MPa) (MPa) (kJ/mole) (m*/s) 8oo”c (“C)
E
4
YWI
u
Mineral, Glass, Orienta- Diffusing Temperature P 02 ma log D, (or D) log D ‘IT,” Experiment/Comments Ref. 7
or Liquid tion Component Range (“C) (MPa) (MPa) (kJ/mole) (m2/s) 800°C (“C)
[l@l ?
2
[loll
Mineral, Glass, Orienta- Diffusing Temperature P O2 4 log Do (or D) log D “T,” Experiment/Comments Ref.
or Liquid tion Component Range (“C) (MPa) (MPa) (kJ/mole) (m*/s) 800°C (“C)
I
nepheline powder 104.6(+10.5) -12.229 -17.3 199 Exchange with CO*, spherical [27]
model, bulk analysis
1’2”‘:’
phlogopite powder 373 Degassing into water, bulk t621
(Ann4) (see paper analysis, cylindrical model, 671
for camp.) (AV,zO m3/mole)
biotite (An& powder 281 Degassing into water, bulk [771
(see paper for analysis, cylindrical model
camp. reference) (AV =1.4~10-~ m3/mole)
biotite powder 88 Exchange with 41KC1 solu- F371
on, bulk analysis & ion
‘80 650-800
“wet”
100,20
NO
uB/ 172 (+25) -1l.OOO(f1.322) -19.4
c
2000 NO
“wet”
180 650-800 100 UB/ 239 (k8) -7.523 (f0.452) -19.1 t
“wet” NO m
4oAr 750-900 100 UBo r 268.2 (k7.1) -5.620 (f0.506) -18.7 t
“wet” NO
F
c 4
Sr 800 200 uB/ D=lxlO-*’
“wet” NO L
Y4
ii
Mineral, Glass, Orienta- Diffusing Temperature P O2 4 log Do (or D) log D ‘IT,” Experiment/Comments Ref. u
or Liquid tion Component Range (“C) (MPa) (MPa) (kllmole) (m2/s) 800°C (“C) ii
“wet”
1180 0.1 w, 1 I
=I@‘4
m, sectioning, Ion
I
probe, Rutherford backscatter,
olivine sintered 59Fe 1130 0.1 lo-to- n.d. n.d. log D59i+ = -10.143 + 0.2 [851 9
Wd%o-Faloo~ powder 10-12 ,
/ 404
act + 2.705 [Fe/(Fe+Mg)] j!
olivine //c-axis Ni 1149-1234 evac. UB 193 (f10) -8.959 (f0.36) -18.4 Thin Ni film, microprobe G'61
(Fo93.7Fa6.3) tube profile, anisotropy found
olivine (Fo,,Fas> //c-axis Fe-Mg 1125-1200 0.1 lo-l3 243 -5.759 -17.6 432 Microprobe profile, D varies [I41
fayalite powder (couple) interdiffusion w/direction, composition, fo2
olivine (Fa,,Te, )- //c-axis Fe-Mg 900-1100 evac. UB 208.5(+18.8) Do= 1.5(*0.3) Microprobe profile, D also ~1241
divine Fo91Fa9) (couple) interdiffusion tube +9.1 x [Mg/ x10-4) - 1.1x varies with direction and P
Wg+Fe)l [Mg/(Mg+Fe)] (AV a=5,5~10-~m~/mole)
olivine(MgzSi04) //c-axis Co-Mg 1150-1300 0.1 air 196 -8.690 -18.2 ! 403 Microprobe profile, D’s [l-m
- (Co2 SiO.+) (couple) interdiffusion 1300- 1400 526 2.288 -23.3 78 1 extrapolated to pure Fo
forsterite - //c-axis Ni-Mg 1200-1450 0.1 air 414 to 444 -1.652 -21.8 702 Microprobe profile, other [1261
liebensbergite (couple) interdiffusion interdiffusion coefficients [128]
grossularite C&9 isotropic ‘80 1050 800 UB n.d. D=2.5~10-~~ Exchange with t80-enriched [581
Fe.1 Ah$hPd 850 200 nd. D=4.8xlO-2’ water, ion probe profiles
almandine isotropic ‘80 8001000 100 UB 301 (+46) ,-8.222 (*0.740) -22.9 725 Exchange with ‘*O-enriched I311
(Al67SP2xAns b2) water, ion probe profiles
ww isotropic 25Mg 750-900 200 uB/ 239 (*16) -8.009 -19.6 5 14 Thin 25Mg0 film, ion probe [341
E’m%GrdJrI ) MH profiles
AlmsoPYPzo - isotropic Fe 1300-1480 2900- UBI 275.43 -7.194 -20.6 / 588 ! Calculated from interdiffusion VOI
Spess94Almg (couple) 4300 GrPC (rt36.49) experiments using model,
(AV,=5.6~10-~ m3/mole)
AlmzoPYPzo - isotropic Mg 13001480 2900- UB/ 284.52 -6.959 -20.8 604 Calculated from interdiffusion WI
Spessa4Alm6 (couple) 4300 GrPC (T37.55) experiments, (AV, =
5.6(f2.9)x10e6 m3/mole)
AlmsoPYPzo - isotropic Mn 1300-1480 2900- UB/ 253.44 -7.292 -19.6 526 Calculated from interdiffusion m
Spessa4Alm6 (couple) 4300 GrPC (k37.19) experiments, (AV, =
5.3(+3.0)x10-6 m3/mole)
almandine isotropic 86Sr 800- 1000 100 UB 205 (+17) -12.000(&0.602) -22.0 616 Exchange with %r water [311
b’%SPd% pY2 ) solution, ion probe profiles
almandine isotropic 145w 800-1000 100 UB 184 (+29) -12.523(*0.602) -21.5 ! 562 Exchange with 145Nd water 1311
b%SP2dnd’Y2) solution, ion probe profiles
wope powder tslSm 1300-1500 3000 UB/ 140 -11.585 -18.4 321 Exchange with silicate melt, WI
GTPC autoradiography, “sphere”
almandine isotropic 167ET 800- 1000 100 UB 230 (f38) -10.301(?0.763) -21.5 605 Exchange with 167Er water [311
@l&Pd@Y2) solution, ion probe profiles
AlmsoPYPzo - isotropic Fe-Mn 1300- 1480 4000 UBI 224.3 - 10.086 -21.0 57 1 Microprobe profiles, model [411
Spess94Alm6 (couple) interdiffusion GrPC (k20.5) fits of alm-rich composition
Mineral, Glass, Orienta- Diffusing Temperature P O2 =a log D, (or D) log D “Tc” Experiment/Comments Ref.
or Liquid tion Component Range (“C) (MPa) (MPa) (kJ/mole) (m2/s) 1200°C (“C)
Zircon dissolution,
Mineral, Glass, Orienta- Diffusing Temperature P 0, aa log Do (or D) log D “Tc” Experiment/Comments Ref.
or Liquid tion Component Range (“C) (MPa) (MPa) @J/mole) (m*/s) 1200°C (“C)
rhyolite glass and Ce 875-1100 0.1 air 490.4 2.72 (f0.99) -14.7 Thin film, serial sectioning by [91]
(dehydrated) NM melt (f23.9) etching, counting surface
rhyolite glass and Eu 700-1050 0.1 air 288.7 (k5.0) -3.11 (0.22) -13.3 Thin film, serial sectioning by [91]
(dehydrated) NM melt etching, counting surface
rhyolite (obsidian) melt 6% LREE 1000-1400 800 UB/ 251.5(*42.3) -4.638 (k1.436) -13.6 Monazite dissolution, [1381
Lake County, OR water GrPC microprobe profiles
rhyolite (obsidian) melt 1% LREE 1000-1400 800 UB/ 510.9(+59.0) 3.362 (f0.629) -14.8 , Monazite dissolution, [1381
Lake County, OR water GrPC microprobe profiles
rhyolite (obsidian) glass Hz0 400-850 0.1 Nz 103@5) -14.59 (f1.59) -18.2 Dehydration in Nz, FTIR [1661
Mono Craters profile, equilibrium model
rhyolite (obsidian) glass H20 510-980 0.1 air 46.48 -10.90 (+0.56) -12.5 Dehydration in air, bulk 1931
New Mexico (fl 1.40) weight loss, low water
rhyolite (obsidian) melt with 14CGz 800-1100 1000 UBI 75(?21) -7.187 -9.9 Thin film of Na2 14C03, B- 11551
Lake County, OR 8% water GrPC track profiles of cross section
basalt melt 6Li 1300-1400 0.1 air 115.5 -5.125 -9.2 Thin film of 6LiC1, ion probe [116]
(alkali) profile of cross section
basalt melt 0 1160-1360 0.1 IW to 215.9 -2.439 -10.1 Oxidation/reduction of bead, [1601
Goose Island co2 (f13.4) thermo-gravimetric balance
basalt (alkali melt 0 1280-1400 400 UB/ 293(+29) -0.790 (k2.5 1) -11.2 Reduction by graphite, bulk ]401
olivine) BC GrPC Fe0 analysis by titration
basalt (alkali melt 0 1280-1450 1200 UBI 360(+_25) 1.450 (t0.081) -11.3 Reduction by graphite, bulk ]401
olivine) BC GrPC Fe0 analysis by titration
basalt (alkali melt 0 1350-1450 2000 uB/ 297 (+59) -0.770 (k1.87) -11.3 Reduction by graphite, bulk ]401
olivine) BC GrPC Fe0 analysis by titration
basalt (tholeiite) melt 0 1300-1450 1200 uB/ 213 (k17) -3.010 (YkO.59) -10.6 Reduction by graphite, bulk [401
1921 Kilauea GrPC Fe0 analysis by titration
basalt (FeTi) melt ‘80 1320-1500 0.1 Co2 251 (+29) -2.854 -11.8 Exchange with tsO-selected [I51
Galapagos ‘3202 gas, bulk analysis of sphere
“basalt” (Fe-free) melt Ar 1300-1450 looo- 113.2 (k7.5) -6.140 (kO.068) -10.2 [ Method not described r391’
(synthetic) 3000
basalt (“alkali”) melt 24Na 1300-1400 0.1 air 163 (+13) -4.02 (f0.46) -9.8 Thin film, serial sectioning by [116]
Tenerife grinding, counting surface
basalt (tholeiite) melt 45Ca 1260-1440 0.1 air 184.1 -4.272 -10.8 Thin film, B-track profiles of [891
1921 Kilauea cross-section on film
“basalt” (Fe-free) melt 45Ca ilOO-14cKl 0.1 UB 106.3 -6.301 -10.1 Thin film of 45CaCl, B-track [152] ’
(synthetic) profiles of cross section
“basalt” (Fe-free) melt 45Ca 1100-1400 1000 UB 141.0 -5.284 -10.3 Thin film of 45CaCl, B-track [152] 1
(synthetic) --I
“basalt” (Fe-free) melt 45Ca 1100-1400 2000 UB 208.4 -3.211 -10.6 Thin film of 45CaCl, B-track t15211
(synthetic) profiles of cross section I
Mineral, Glass, Orienta- Diffusing Temperature P O2 fia log D, (or D) log D “Tc” Experiment/Comments Ref.
or Liquid tion Component Range (“C) (MPa) (MPa) (kJ/mole) (m2/s) 1200°C (“C)
T
basalt (“alkali”) melt 46Sc 1300-1400 0.1 air
Tenerife
basalt (“alkali”) melt 54Mn 1300-1400 0.1 air
Tenerife
basalt (“alkali”) melt 59Fe 1300-1400 0.1 air
Tenerife
basalt (tholeiite) melt 6OCo 1260-1440 0.1 air
1921 Kilauea
basalt (“alkali”) melt 6OCo 1300-1400 0.1 air
Tenerife
basalt (tholeiite) melt *%r 1260-1440 0.1 air
1921 Kilauea 1
basalt (“alkali”) 1 melt sSSr 1 1300-1400 0.1 air
Tenerife
basalt (tholeiite) melt 133& 1260-1440 0.1 air
1921 Kilauea
basalt (“alkali”) melt 133& 1300-1400 0.1 air
Tenerife
basalt (“alkali”) melt ‘Ts 1300-1400 0.1 air hin film, serial sectionin
Tenerife
basalt (tholeiite) melt ‘=Eu, 1320-1440 0.1 air
ul3/
GrPC profiles of cross section,
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290 DIFFUSION DATA
Q. Williams
Fig. 1. The normal modesof vibration of an SiO4-tetrahedra.Within isolated tetrahedra, all vibrations are
Raman-active, while only the v3 and v4 vibrations are active in the infrared. However, environments with
non-tetrahedral symmetries frequently produce infrared activity of the VI and v2 vibrations in silicate
minerals[modified from [121and [1811.
have contributed major insight into the characterizationof motion produces a change in the polarizability of a
different types of vibrational modes in complex crystals: material, then the vibration is Raman active. Notably,
the precise equations and means by which such while the induceddipole is a vector, the polarizability is a
calculationsare carried out have beenreviewed elsewhere secondrank tensor, and it is the symmetric properties of
13, 91. this tensor which allow the prediction of which families
Whether a given vibrational motion is of modes will be active when observed along different
spectroscopicallyactive underinfrared or Ramanexcitation crystallographicdirections.Thus, both Ramanand infrared
is governed by selection rules associated with a given activities are governedby interactionsof the electric field
crystal structure. These selection rules are primarily of the incoming light with vibrationally producedchanges
governed by the symmetry of the unit cell, and the in the charge distribution of the molecule or unit cell.
differing propertiesof Raman andinfrared activity. Infrared Yet, despite Raman active vibrations depending on
activity is produced when a changein the dipole moment changes in the polarizability tensor and infrared active
of the unit cell occurs during the vibration. It is this vibrations being generated by changes in the dipole
change in the electric field associatedwith the unit cell moment, the two sets of vibrations are not always
which interacts with the electric field of the incident mutually exclusive: for non-centrosymmetric molecules
photons. Because of this dependence on vibrational (or unit cells), some vibrations can be both Raman and
changes in the charge distribution, highly symmetric infrared-active. Finally, the intensities of different
vibrations are often inactive or weak in infrared spectra: vibrations in the two different types of spectroscopymay
for example, within isolated tetrahedra, both the be related to the magnitudeof the changesproducedin the
symmetric stretching and symmetric bending vibrations dipole moment or polarizability tensor in a given
shown in Figure 1 are infrared-inactive. vibration.
The physical origin of Raman scattering may be It is the relation of the change in the polarizability
viewed from a simple classical perspective in which the tensorand shifts in the dipole moment to the symmetry of
electric field associatedwith the incident light interacts the lattice which enables different vibrations to be
with the vibrating crystal. In particular, this interaction associated with different symmetry species, as well as
occurs through the polarizability of the material: that is, with possible crystallographic directionality for the
its ability to produce an induceddipole in an electric field. infrared and Raman modes. The way in which this
It is the oscillations in the polarizability produced by characterization of vibrational mode symmetries is
vibrations which causeRaman scattering: if a vibrational conductedis through an applicationof group theory called
294 INFRARED, RAMAN AND OPTRXL SPECTROSCOPY
factor group analysis. This is a meansof utilizing the site parallel to the wavevector of the incoming light can be
symmetries of atoms in the primitive unit cell of a crystal subject to an additional electrostatic restoring force
(as given, for example, in The International Tables of X- producedby the differing displacementsof planesof ions
ray Crystallography), coupled with character tablesof the relative to one another, an effect not generatedby shear.
site symmetry and crystal symmetry group, and Such transverseand longitudinal modesare thus separated
correlation tables between different symmetry groups to from one another by long-rangeCoulombic interactionsin
determine the number, activity, and symmetry of infrared the crystal [3,6].
and Raman vibrations of a crystal. Character tables for In practice, reflection spectra generally have broad
different symmetriesare given in many texts (for example, flattened peaks, with the lowest frequency onset of high
5), and correlation tablesare given in [73 and [8]: the latter reflectivity of a peak correspondingapproximately to the
text provides a number of worked examples of factor transverseoptic frequency,while the higher frequencydrop
group analysisapplied to mineralsand inorganic crystals. in reflectivity of a peak is near the frequency of the
Infrared spectra may be presentedfrom two different longitudinal optic vibration. These data are generally
experimentalconfigurations: absorption(or transmission), inverted for TO andLO frequenciesandoscillator strengths
or reflection. Sampleabsorbanceis dimensionless,and is (a measureof the intensity of the reflection of the band)
definedas using one of two types of analyses:Kramers-Kronig, or
an iterative classical dispersion analysis. Such analyses,
A = -log(&), (2) describedin [ 171and elsewhere,are designedto model the
extreme changesin the optical constants(expressedas the
where / is the intensity of light transmitted through the frequency dependentand complex index of refraction or
sample, and I, is the intensity of light transmitted dielectric constant) occurring over the frequency range of
through a non-absorbing reference material. Frequently, an optically active vibration.
such data are reported as per cent transmittance,which is For many minerals, the types of vibrational modes
simply the ratio I/I0 multiplied by 100 (note that may be divided into two loose categories: internal and
vibrational peaks are negative features in transmittance lattice modes. Internal modes are vibrations which can be
plots and positive features in absorbance).Becauseof the associated with those of a molecular unit, shifted (and
intensity of many of the absorptions in rock-forming possibly split) by interaction with the crystalline
minerals (greater than -2 p,rn thicknesses in the mid- environment in which the molecular unit is bonded: the
infrared (>-4OO cm-‘) often render samples effectively vibrations of the silica tetrahedra shown in Figure 1 are
opaque), such absorbanceor transmission data are often typical examplesof the types of motions which give rise
generated from suspensions of powdered minerals or to internal modes. Such internal modes are typically
glasseswithin matrices with indices of refraction which associated with the most strongly bonded units in a
approximate those of minerals. Typical examplesof such crystal, and thus with the highestfrequency vibrations of a
matrices are pressedsalts (typically KBr, KI or CsI) and given material. We note also that even the simple picture
hydrocarbons(for example,Nujol (paraffin oil) or teflon). of molecular vibrations is often complicated by the
While relative absorption intensities and locations can presenceof interacting molecular units within a crystal.
often be accurately determined using these techniques For example, it is difficult to associatedifferent bands in
(highly polarizablecrystals can presentdifficulties: seepp. feldspars with stretching vibrations of distinct A104 or
183-188 of [7]), absolute absorption intensity is SiO4 tetrahedra: becauseof the interlinking tetrahedra, a
compromisedand orientation information is lost. silica symmetric stretching vibration such as is shown in
A secondmeansby which infrared spectraare measured Figure 1 will involve a stretching motion of the adjoining
is through measurementof reflection spectra. Reflection A104 tetrahedra,and vibrations of thesetwo speciesmust
spectra of crystals sample two components of each be viewed as coupledwithin suchstructures.
vibrational modes: transverseoptic and longitudinal optic Lattice modes comprise both a range of (often
modes, while absorption spectroscopy ideally samples comparatively low-frequency) vibrations not readily
only the transverse modes. That there are two types of describable in terms of molecular units, and so-called
modes in reflection is becauseeach vibrational motion external modes. External modes are those which involve
may be described either with atomic displacements motions of a molecular unit against its surrounding
oriented parallel (longitudinal modes) and perpendicular lattice: for example,displacementsof the Si04 tetrahedra
(transverse modes) to the wavevector of the incoming against their surrounding magnesium polyhedra in
light. Those with their atomic displacements oriented forsterite would constitute an external motion of the
WILLIAMS 295
tetrahedral unit. Typically, such lattice modes are of Figure 3 shows representativevibrational frequencies
critical importance in controlling the heat capacity of of different functional, or molecular-like groupings, in
minerals at moderate temperatures (of order less than mineral spectra. In the case of many minerals with
-1000 K). As it is the thermal excitation of vibrational complex structures, normal modes involving motions of
modeswhich producesthe temperaturedependenceof the the entire lattice, or coupled vibrations of different
lattice heat capacity, considerableeffort hasbeen devoted functional groups may occur, and theseare not included in
to designing methods to extract thermochemical Figure 3. As expectedfrom Equation 1, there is a general
parameters such as the heat capacity and the Grtlneisen decreasein frequency with decreasesin bond strength for
parameter(the ratio of thermal pressureto thermal energy different isoelectronicand isostructural groupings,such as
per unit volume) from vibrational spectraat ambient and occurs in the P04-Si04-A104 sequenceof tetrahedral
high pressures [13]. A fundamental limitation on such anions.
techniqueslies in that infrared and Raman spectraaccess While both infrared and Raman spectroscopyrepresent
only vibrations which have the periodicity of the unit cell useful techniquesfor characterizingbondingenvironments,
(that is, effects of dispersionare ignored). vibrational mode frequencies and the molecular species
RepresentativeRaman spectraof quartz and calcite are present within minerals, infrared spectroscopyhas been
shown in Figure 2, along with a powder infrared extensively utilized as a quantitative technique for
absorption spectrum of quartz and an unpolarizedinfrared determining the concentration and speciation of volatile
reflectance spectraof calcite. The factor group analysisof components within samples. Specific examples include
quartz predicts 16 total optically active vibrations, with the determination of the dissolved molecular water and
four being Raman-active (A1 symmetry type), four being hydroxyl content of glassesand crystals, the amount of
infrared-active (A2 symmetry), and eight being both dissolved CO2 relative to COs2- groups, and the amount
Raman and infrared-active (E symmetry: doubly of impurities within crystals such as diamond and a range
degenerate). For calcite, such an analysis predicts five of semiconductors. Such determinations depend on an
Ramanactive vibrations (lAl, and four doubly degenerate application of the Beer-Lambert Law, in which the
Es symmetry modes) and eight infrared-active vibrations amount of absorption is assumedto be proportional to the
(3Azu and 5 doubly degenerateE,). Two features are number of absorbing species present in the sampled
immediately apparent from these spectra: first, the region. This may be expressedas
differencesbetweenthe vibrations of the silicategroup and
those of the carbonategroup are immediately apparent:in c = (M . A)/@. d. E), (3)
the infrared, the asymmetric stretching and out-of-plane
bendingvibrations of the carbonategroup are presentnear in which c is the weight fraction of a dissolvedspecies,M
1410 and 870 cm-l, while the strongest high frequency is the molecular weight of the dissolvedmaterial, A is the
vibrations in quartz lie near 1100 cm-l (the asymmetric absorbanceof a diagnosticband of the dissolvedspecies,p
stretches of the silica tetrahedra) and 680-820 cm-l is the density of the matrix in which the species is
(correspondingto Si-0-Si bending vibrations). Moreover, suspended,d is the path length through the sample,and E
the LO-TO splitting of the asymmetric stretching is the molar absorption coefficient of the suspended
vibration of the carbonate group is clearly visible in the species, with units of length2/mole. It is the
reflectance spectrum. Within the Raman spectrum, the determination of this last parameter on which the
most intense vibration of calcite is the symmetric quantitativeapplicationof Equation3 depends:typically, a
stretching vibration of the carbonategroup at -1080 cm-l, non-vibrational meansof analysis is used to quantify the
while that within quartz is predominantly a displacement amount of dissolved specieswithin a sequenceof samples
of the bridging oxygens between tetrahedraat 464 cm-l. in order to calibrate the value of E. Severalcomplications
At lower frequency (below 400 cm-‘), the spectrum of the exist in the straightforward application of Equation 3:
carbonate has Raman bands associated with external first, the extinction coefficient canbe frequency-dependent,
vibrations of the carbonate group relative to stationary in that the amount of absorption can depend on the
calcium ions. At lower frequencies than are shown in structural environment in which a given speciesoccurs.
Figure 2 in the infrared spectrum, both lattice-type Second,for someapplicationsa more appropriatemeasure
vibrations of the calcium ions relative to the carbonate of the number of speciespresent is not the amplitude of
groups and displacementsof the carbonategroups and the absorption, but rather the integrated intensity underneath
calcium ions both against and parallel to one another an absorptionband (see[21] for a mineralogically-oriented
OCCIE. discussionof eachof theseeffects in hydratedspecies).
CaC03:
SiO2: 465 cm-l
Raman Calcite
Quartz Si-0-Si
Raman
symmetric
stretch
:03-symmetric
1089 cm-1 stretch
Lattice modes
Lattice modes
Si04-asymmetric
stretch Si-0-Si 207 128 284 cm-1
bend
1083 cm-1 807 cm-1 /
CO3-asymmetric In-plane 155 cm-l
stretch bend i
I 1 1
1435 cm-1 713 cm-1
Powder
Infrared
LO TO
Infrared.
Reflectance
Out-of-plane
Fig. 2. Infrared and Raman spectraof SiO2-quartzand CaC03-calcite. The infrared spectrumof quartz is an
absorptionspectrum from powderedmaterial, while that of calcite is an unpolarized reflectance spectrum
from a singlecrystal. Both Ramanspectraare from single crystal samplesusing 514.5 nm excitation.
WILLIAMS 297
t In-Plane’ Hydroxides
bends , , O-H Bends O-H Bends
Asymmetric Stretches SZ. Out-oLG!ne Wane Carbonates
ketches Bends Bends
Stretches
-Bends/Stretches SiOg-octahedra
Polymerized
Silica Networks I
Inosilicates Elm’ V
& Non-Bridging 0 bends bends
Orthosilicates t I II
v3 Vl l---r+
Sulfates I
HH
v4 v2
Orthophosphates I v3 Iv
II...I...I,..I,.,l,,.I,,. 11ml1.1
Fig. 3. Approximate frequency rangeof common vibrations of silicates, oxides and other functional groups
within minerals. For tetrahedral species,the mode designationsare identical to those shown in Figure 1.
Most of the spectralrangesare derived Tom [3]; that for octahedralsilicon is from [24].
Energy
bZ /x AZ AZ
X 05
I Q M
c-v
M -o- -0 o- --o-M-O- ->
Y Y
-e3 Y
,O
I
BI % P a
0 P 0
I
d,Y dYz 7 d x2
Fig. 4. The effect of octahedralcoordination on the different d-orbitals of a transition metal cation (labelled
M). The surfacesof the d-orbitals representcontours of constantprobability that an electron lies within the
boundaries.The re ulsive effect producedby close proximity of the negatively chargedoxygen cations to
the dx2-v2 and dzf orbitals separatesthese in energy from the d,,, d,, and dxz orbitals by an amount
referred to as the crystal field splitting energy (also as 10 Dq or 4).
oriented towards the anions, lie at higher energy than the coordinated cations, thus producing a net preference of
remaining three orbitals becauseof the larger repulsive many transition metal ions for octahedral sites. For
interactions between the dx2-y2 and dz2 orbitals and their comparison, characteristic cohesive energies of divalent
neighboring anions. Thus, optical absorption may be transition metal ions octahedrally coordinatedby oxygen
producedby excitation of electronsinto andbetweenthese are on the order of 3000-4000Id/mole [4, 15, 163.
separated,or crystal-field split, energylevels, the energetic Furthermore, as each orbital can contain two electrons
separationbetween which is often referred to as 10 Dq or of opposite spins, two possible configurations are
A Such crystal-field effects are observed within possible for octahedrally coordinated cations containing
c£s containing such transition metal ions as Fe2+, between three and eight d-electrons: high spin
Fe3+, Mn2+, Ti3+, Cg+, and is associatedwith both the configurations, in which the energy required to pair two
colors and fluorescent properties of a range of minerals, electronswithin an orbital is greater than the crystal field
gems and laser crystals, including forsteritic olivines splitting energy, and electronsenter into the higher energy
(peridot: Mg2SiO4 with Fe2+), ruby (Al203 with C2+) unoccupieddx2-v2 and dz2 orbitals (eg states) rather than
and both silicate and aluminate garnets (which may pairing in the lower energy three-fold t2g states. For
contain a range of transition elements). The preferential comparison, electrons in low spin configurations fully
occupation of the lower energy levels produces a net occupy the t2g states before entering the eg levels.
crystal field stabilization energy (CFSE) which Among major transition elements,iron essentiallyalways
contributes to the thermochemicalenergeticsof transition occurs in the high spin configuration in minerals: this is
metal-bearingcrystals. The characteristicmagnitudeof the simply a consequenceof the energy required to pair spins
CFSE for Fe2+ (d6 configuration) in octahedral in divalent iron being larger than the crystal field
coordination in minerals is between about 40 and 60 stabilization energy. Estimates of the spin-pairing energy
Id/mole; that for octahedralC2+ (d3) is generallybetween in iron-bearing minerals are poorly constrained, but
200 and 275 M/mole. Characteristic octahedral CFSE representativevaluesfor this quantity are generallygreater
values for other transition metal cations with unpaired d- than 100 Id/mole at ambient pressure. Historically, the
electrons generally lie in between these extremes; high spin to low spin transition of iron in crystalline
tetrahedrally coordinated cations typically have CFS silicates has been frequently invoked as a possible high
energies between -30 and -70% that of octahedrally pressurephenomena.Essentiallyno experimentalevidence
WILLIAMS 299
and quantum mechanical selection rules. For example, 500 1000 1500
non-centrosymmetric environments (e.g. tetrahedrally Wavelength (nm)
coordinated cations) generally produce more intense
absorptions.The primary selectionrules are related to spin
multiplicity (involving conservation of the number of Fig. 5. Polarized crystal field absorption spectra of
unpaired electrons between the ground and excited state) Fe2SiO4-fayalite in three different crystallographic
and to conservation of parity (or, transitions being only orientations, combined with an interpretation of the
allowed between orbitals which differ in the symmetry of observed transitions in terms of the Ml and M2 cation
their wavefunction: the Laporte selection rule). These sites of Fe2+ in olivine [from 41. The dotted spectrum is
selectionrules may be relaxed through a range of effects taken parallel to the b-axis of this phase, the dashedline
which include orbital interactions, vibrational and parallel to c, and the solid line parallel to a. As the Ml
magneticperturbations,and lack of a centrosymmetricion and M2 sites are each distorted from perfect octahedral
site, producing both weak spin-forbidden and Laporte- symmetry, additional splitting beyond that shown in
forbidden transitions. Indeed, such crystal field bandsare Figure 4 occurs for the d-orbitals of iron ions within
frequently orders of magnitude less intense than the fayalite: this is shown in the insets. Short arrows in
vibrational bandsdiscussedabove. insets representelectrons occupying each d-orbital (Fe2+
Inter-valence,chargetransfer, and valenceto conduction has six d-electrons). The sharp bandsabove 20,000 cm-’
band transitions are all terms used to describeabsorption are generatedby spin-forbiddentransitions.
mechanismsof similar origins: the transfer of electrons
between ions in non-metals via an input of energy in the
300 INFRARED, RAMAN AND OPTICAL SPECTROSCOPY
form of a photon. The term inter-valence transition is frequently small), and represents the intercept of a plot of
generally used to describe processes associated with the the log of the conductivity and the inverse of temperature.
transfer of an electron between transition metal ions, Absorptions generated by such cation-anion charge
especially those which are able to adopt multiple valence delocalization processes are common in ore minerals such
states in minerals, such as Fe (+2,+3) and Ti (+3,+4). as sulfides and arsenides, and produce the opacity or deep
Characteristically, these bands occur in the visible region red color in the visible of many such minerals.
of the spectrum, and are most intense in those minerals Furthermore, they also induce effective opacity of most
which have large quantities of transition metals, and
relatively short metal-metal distances. As such, these
transitions produce the coloration of many iron and
! Charge-Trmsfer
iron/titanium-rich oxides and hydroxides. and Band-Gap
Charge transfer transitions not only occur between
transition metal ions, but also occur in excitation of 1.0
silicates in the far ultraviolet. The role of pressure (in conductivity of mantle materials naturally incorporates
most cases)is to decreasethe energy at which such band- both a frequency-dependent absorption coefficient and
gap related absorptionsoccur (that is, it becomeseasierto index of refraction of the material, as well as the black- or
delocalize electrons as the distance between ions greybody emission of Equation 5 [23]. Figure 6 shows
decreases).It is generally believed that among relevant representative values of emitted intensity for a range of
deepEarth constituentsonly relatively iron-rich materials temperatures,along with the wavelengthrangeof different
(such as FeO) will have absorption edgeswhich decrease absorption mechanismsoccurring in minerals relevant to
to zero energy and metallize over the pressure and the Earth’s upper mantle. Among lower mantle minerals,
temperature interval of the Earth’s mantle. However, the no optical absorption data have been reported for silicate
effect of a lower energy absorption edge in compressed perovskite; however, the absorptionof magnesiowiistiteat
magnesiowiistite (MgxFel-,O) may have a significant both ambient and high pressures has been well-
effect on the electrical conductivity of the deepmantle, in characterized [14]. Not shown in Figure 6 are the grain
addition to producing an absoluteimpediment to radiative boundary scattering effects which may also act to reduce
thermal conductivity at thesedepths. radiative conductivity over a broad frequency range.
This effect is illustrated in Figure 6; the intensity of Clearly, given the wavelength rangesover which crystal-
radiative thermal emission is described by the Planck field absorptions (which broaden in width at high
function, temperatures)andcharge-transferbandsoccur in transition-
metal bearing minerals, radiative conductivity is unlikely
I(v) = 2mhc2v5(exp[hvlkr] - 1)-l (5) to provide a rapid mechanismof heat transport within the
deep Earth. Thus, the optical properties of mantle
in which the emitted intensity, I, is a function of minerals play a passive but seminal role in the thermal
frequency (v). e representsthe emissivity of the material and tectonic evolution of the planet: were radiative
(assumedto be unity in the caseof a blackbody, and to lie conductivity an efficient meansof heat transport through
at a wavelength-independentvalue between zero and one the deep Earth, thermal convection (and its geochemical
for a greybody), and c, h, k and T are the speedof light, and geodynamicconsequences) would not be necessitated.
Plan&s constant, Boltzmann’s constant and temperature,
respectively. Figure 6 shows representative values of Acknowledgments. I thank the NSF for support, and
emitted intensity for a range of temperatures,along with an anonymous reviewer, T.J. Ahrens and E. Knittle for
absorption mechanismsof minerals relevant to the Earth’s helpful comments. This is contribution #207 of the
upper and lower mantle. The actual radiative thermal Institute of Tectonics at UCSC.
REFERENCES
1. Ashcroft, N.W., and D. Mermin, University Press, New York, Infrared and Raman Selection
Solid-State Physics, 826 pp., 1970. Rules for Molecular and Lattice
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Philadelphia, 1976. Applications of Group Theory, Method, 222 pp., Wiley-
2. Berry, F.J., and D.J. Vaughan 2nd Ed., 386 pp,, Wiley- Interscience,New York, 1972.
(eds.), Chemical Bonding and Interscience,New York, 1971. 9. Ghatak, A.K. and L.S. Kothari,
Spectroscopy in Mineral 6. Decius, J.C. and R.M. Hexter, An Introduction to Lattice
Chemistry, 325 pp., Chapman Molecular Vibrations in Crystals, Dynamics, 234 pp., Addison
and Hall, London, 1985. 391 pp., McGraw-Hill, New Wesley, New York, 1972.
3. Born, M. and K. Huang, The York, 1977. 10. Harvey, A.B. (Ed.), Chemical
Dynamical Theory of Crystal 7. Farmer, V.C. (Ed.), The Infrared Applications of Nonlinear Raman
Lattices, 420 pp., Oxford Press, Spectra of Minerals, 589 pp., Spectroscopy, 383 pp., Academic
New York, 1954. Mineralogical Society, London, Press, San Diego, Calif., 1981.
4. Burns, R.G., Mineralogical 1974. 11. Hawthorne, F.C., (Ed.) Reviews
Applica-tions of Crystal Field 8. Fateley, W.G., F.R. Dollish, in Mineralogy, Vol. 18,
Theory, 224 pp., Cambridge N.T. McDevitt and F.F. Bentley, Spectroscopic methods in
302 INFRARED, RAMAN AND OPTICAL SPECTROSCOPY
mineralogy and geology, 698 Wiley, New York, 1976. quantitative laser Raman
PP.. Min. Sot. Am., 15. Marfunin, A.S., Spectroscopy, spectroscopyfor the study of fluid
Washington, D.C., 1988. Luminescence and Radiation inclusions, Geochim. Cosmo-
3rd Ed., 1072 pp., Hemisphere, Centers in Minerals, 352 pp., chim. Acta., 52, 979-988, 1988.
Washington, D.C., 1992. Springer-Verlag, New York, 21. Paterson, M., The determination
24. Williams, Q., R. Jeanloz and P. 1979. of hydroxyl by infrared absorption
McMillan, Vibrational spectrum 16. McClure, D.S., Electronic spectra in quartz, silicate glasses and
of MgSi03 -perovskite: Zero of moleculesand ions in crystals. similar materials, Bull. Mineral.,
pressure Raman and infrared Part II. Spectra of ions in 105, 20-29, 1982.
spectra to 27 GPa, J. Geophys. crystals, Solid State Phys., 9, 22. Solymar, L. and D. Walsh,
Res., 92, 8116-8128, 1987. 399-525, 1959. Lectures on the Electrical
12. Hcrzberg, G., Molecular Specfra 17. McMillan, P.F. and A.M. Properties of Materials, 5th Ed.,
and Molecular Structure: II. Hofmeister, Infrared and Raman 482 pp., Oxford Univ. Press,
Infrared and Raman Spectra of Spectroscopy,Rev. Mineral., 18, New York, 1992.
Polyatomic Molecules, 632 pp., 99-159, 1988. 23. Siegel, R. and J.R. Howell,
Van Nostrand Reinhold, New 18. Nakamoto, K., Infrared and Thermal Radiation Heat Transfer,
York, 1945. Raman Spectra of Inorganic and 3rd Ed., 1072 pp., Hemisphere,
13. Kieffer, S.W., Heat capacity and Coor-dination Compounds, 4th Washington, D.C., 1992.
entropy: Systematic relations to edition, 484 pp., Wiley- 24. Williams, Q., R. Jeanloz and P.
lattice vibrations, Rev. Mineral., Interscience,New York, 1986. McMillan, Vibrational spectrum
14,65-126, 1985. 19. Nassau, K., The Physics and of MgSi03-perovskite: Zero
14. Mao, H.K., Charge transfer Chemistry of Color: The Fifteen pressure Raman and infrared
processesat high pressure,in The Causes of Color, 454 pp., J. spectra to 27 GPa. J. Geophys.
Physics and Chemistry of Wiley, New York, 1983. Res., 92, 8116-8128, 1987.
Minerals and Rocks, edited by 20. Pasteris, J.D., B. Wopenka and
R.G.J. Strens, pp. 573-581, J. J.C. Seitz, Practical aspects of
Nuclear Magnetic Resonance Spectroscopy of Silicates and Oxides
in Geochemistry and Geophysics
Jonathan F. Stebbins
is lost in MAS may prove to be useful in characterizing cesses, such as diffusion, viscous flow, and displacive
anisotropic materials. phase transitions, the fundamental rate may be within
Quantitative local structural information on minerals this range.
and melts is important to many problems in geochem-
istry and geophysics.NMR has proven to be very useful 1.1. Definitions
in this area. A secondnearly uniqueutiliiy of NMR, that The chemical shift 6 is the perturbation in the reso-
is just beginning to be applied in the geosciences, is in nant (Larmor) frequency v of a nuclide in a particular
studying dynamics at the time scale of seconds to chemicalenvironment, causedby screeningof the external
nanoseconds. For many geochemically interesting pro- magnetic field by the surroundingelectrons.6 is genemlly
STEBBINS 305
TABLE 2. NMR parameters for some nuclides of interest in geochemistry: quadrupolar nuclides. See Table
1 for notes.
TABLE 2 (continued)
electric field gradient, often summarizedby the nuclear among number of Al neighbors, bond angles,and 6 have
quadrupolarcoupling constant QCC=e2qQ/h. Here, eQ is beendevelopedthat allow rather preciseestimatesof 6 for
the nuclear quadrupolar moment, and eq is the principle tectosilicate structures 1343.A few correlationshave been
componentof the electric field gradientat the site of inter- developed for Si04 groups in general that allow estima-
est. The full description of the quadrupolarinteraction re- tion of 6 for most silicate structures [56,118]. Similar ap-
quires the electric field gradient tensor and its orientation proacheshavebeentaken for SiO6 groups[47,146].
relative to the structure. The deviation from cylindrical Structures correlations have been usedto derive im-
symmetry of this tensor is given by the asymmetry pa- portant constraints on Al/Si ordering in a number of min-
rameter n, which varies from 0 to 1. In liquids with suffi- erals. The greatestefforts havebeenon synthetic zeolites,
ciently rapid isotropic rotation of molecules,the field gra- because of their tremendous technological importance
dient and the quadrupolar interaction averageto zero and [34,72]. In geochemistry, the most important examples
Gire is observed. In MAS NMR, the central l/2 to -l/2 have been in determining the ordering state in feldspars
transition remains shifted and broadenedby a secondorder [64,102,103,120,127,169], other tectosilicates
quadrupolar interaction; in DAS NMR, Siso is shifted by [12,53,95,104,117,148], cordierite [107] and sheet sili-
the isotropic averageof the secondorder quadmpolarinter- cates [5,20,52,60,74,112,160]. In severalcases,discrep-
action, but is not broadened. anciesin thermodynamicdatathat had beententatively as-
cribed to underestimatesof the entropy of disorderedsyn-
2. APPLICATIONS TO CRYSTALLINE thetic phaseshavebeendisplacedto other parts of the data
SILICATES AND OXIDES baseby findings of nearly completeorder, suchas for sil-
limanite [59,140] and prehnite [139]. For a few systems,
2.1. 29S i careful combinationof NMR spectroscopywith calorimet-
Isotropic chemical shifts for 29Si and CSA data are ric observation has provided new insights and details of
listed in Tables 3 through 5. In silicates,the largesteffect the energetic control and consequencesof Si/Al disorder
of structure on chemical shift is that of coordinationnum- [17,53,103,1063.
ber. Thus, 6 for SiO6 groups is in the rangeof about -180 Very recently, 29Si MAS NMR has begun to be ap-
to -220 ppm relative to tetramethyl silane (TMS), and is plied to high pressure mantle phases that contain SiO6
in nearly all cases between about -65 and -120 ppm for groups. In MgSiOg ilmenite and perovskite, and p-
SiO4 groups. Signals near to -150 ppm are probably Mg2SiO4, Mg./Si disorder hasnot beendetected[63,146],
from SiO5 groups [58,166]. but both Mg/Si and WA1 disorder are significant in ma-
The secondmost important effect is that of the number jorite and majorite-pyrope solid solutions, as shown in
and identity of first cation neighbors.If bridging oxygens Figure 2 [101,146].
are consideredas thosesharedwith tetrahedralSi or Al (or
B or P) neighbors, and non-bridging oxygens to be those 2.2. 27A 1
shared with larger and/or lower charged M cations, an NMR studiesof 27Al in minerals have beenreviewed
Si04 site can be labeled as Q”, where n designatesthe recently [66], and data are listed in Tables6 and 7. Most
number of bridging oxygens(and Q standsfor quaternary). early studies of this nuclide were of single crystals, with
For a fixed M cation type, decreasingn by one tends to complete determinations of quadrupolar coupling con-
increase 6 by about 10 ppm to less negative, higher fre- stants, asymmetry parameters, and electric field gradient
quencies. Each Q” speciesthus has a distinct, but some- tensors, but without precise isotropic chemical shifts.
what overlapping range of 6. In a similar fashion, the The quadrupolar parameters have been shown to be
substitution of tetrahedral Al for a tetrahedralSi neighbor roughly correlated with the extent of distortion of the Al
tends to increase 6 by about 5 ppm. As a result, 29Si site for both octahedral and tetrahedral geometries [43].
MAS NMR spectra of aluminosilicates often have mul- Single-crystal work on MgAl204 spine1allowed quantifi-
tiple, partially overlapping peaks for Si sites with vary- cation of octahedralandtetrahedralAl site occupanciesand
ing numbers m of Al neighbors [Q”(mAl)]. This effect is ordering state [ 141.
particularly obvious and well-exploited in tectosilicates, As for 29Si isotropic shifts for 27Al in oxides (now
where it has often provided the key to unraveling quite determined most commonly by high resolution MAS
complex Al/Si ordering patterns. The bond anglebetween NMR) are most strongly influenced by coordination
tetrahedrahasa relatedeffect, againbest calibratedfor tec- number. 6 values for Al04 groups fall roughly in the
tosilicates. Increasing the mean Si-O-T angle systemati- range of 50 to 90 ppm relative to aqUeOUS fi@20)(j3+,
cally decreases8. A numberof semi-empiricalcorrelations and for Al06 groups in the range of -10 to 15 ppm.
308 NMR OF SILICATES AND OXIDES
TABLE 3. 29SiNMR data for Q”, Q’, and Q2 sitesin crystalline silicates.
mineral CSAb
(s)=synthetic nominal formula 4soa -611 422 433 ref.
Q” sites:
chondrodite MgdSQh(OKF)2 6oc [781
forsterite(s) MgzSiO4 61.9 38.8d 55.3 95.4 [78,159]
(s) Li2SiOq 64.9 L'81
monticellite(s) CaMgSiOq 66 44 60 94 W81
6) NaHgSiO4 66.4 b'81
6) Na2H2Si04.8.5H20 67.8 [781
majorite garnet(s)g Mg4SiV1Si1V3012e 68 to 90f [101,1461
6) Ba2SiO4 70.3 [781
6) cKa2Si04 70.3 [781
afwillite Ca3(HSi04)2.2H20 71.3,73.3 [341
lamite(s) P-Ca2SiOq 71.4 1781
PyropeW Mg3A1$G3012e 72.0 UOll
Ca-olivine(s) Y-CaTSi 73.5 [781
6) Ca3SiOg 69 to 75h [78,124]
(9 CaNaHSi04 j3.5 [781
phenacite Be2SiOq 74.2 [781
rutile ~1% SiO2 in Ti02 77.2 u391
titanite CaTiSiOg 79.6 11181
andalusite A12Si05 79.8 45 78 116 [78,128]
kyanite A12Si05 82.3,83.2 50 79 120 [118,128]
zircon ZrSi04 81.6 [781
piemontiteg ~a2(Al,MnPeh 81.9 11181
(Si207)(Si04)OH
grossular Ca3A12(SiO& 83.4 WI
topaz Al$i04(0H,F)2 85.6 [781
Q’ sites..
6) Na6si207 68.4 WI
(s) Ligsi207 72.4 r341
gehlenite(s) Ca2A12Si07 72.5 122 74 20 WI
akennanite(s) Ca2MgSi207 73.7 134 84 1 WI
m&bite(s) Ca3Si207 74.5,76.0 [781
hemimorphite ZnqSi207(OH)2.H20 77.9 [781
6) p-Mg2SiO4 79.0 11461
lawsonite CaA1$$07(OH).H20 81 123 92 28 [I281
6) a-Y2Si207 81.6,83.5 r341
6) a-La2Si207 83.2 [781
6) Ca&O7(OH)6 82.6 109 109 35 [34,461
STEBBINS 309
TABLE 3 (continued)
mineral CSAb
(s)=synlhetic nominal formula -&ma -611 422 433 ref.
piemontiteg Ca2W,MnPe)3 86.4,90.4 UW
(Si207)(Si04)OH
(9 In2Si207 87.7 E'81
6) p-Y2Si207 92.9 [781
thortveitite SqSi207 95.3 [781
zunyiteg A113Si502($OH)14F4Cli 91.2,96.9 U181
Q2 sites..
(s) LizSiOg 74.5 c781
w Na2SiO3 76.8 18 59 156 [78,136]
6) BaSi03 80 29 71 140 W81
(s) SrSi0-j 85 30 71 154 W81
orthoenstatite MkZSi206 82c L7781
clincenstatite(s) %X&206 81.8,84.2 4oi 73 132 [56,128]
diopside CaMgSi206 84.8 31 73 148 [118,128]
omphacite (Ca,Na)(Mg,Al)Si$I& 85.4 [1181
spodumene LiAlSi206 91.4 53 81 142 ill81
jadeite NaAlSi206 91.8 1-W
pyroxenephase(s)g NaMgg.SSiV1g.SSiIV206 92.1,97.6 w61
alamosite Pb12Si12036 84.1,86.5, WI
94.3
prehniteg Ca2A12Si301o(OH)2 84.6k u391
tchermakitic Ca2(Mg4Al)(AlSi70&- 83.4,87.4 [181
amphibole(s)g KW2
triple-chain N~2W&kQ tdW2 85.3 WI
phase(s)g
SC-Fpargasite(s) NaCa2MgqScSigA12022- 86m N31
(Q2+Q3) F2
tremoliteg Ca2MMWh1)2(OW2 87.2 50 77 137 [18,1281
hillebrandite(s) Ca$i03(0H)2 86.3 [781
pectolite(s) Ca2NaHSi309 86.3 [781
foshagite(s) CaqWMOW2 84.8,86.4 [781
xonotlite(s)g Ca6Si6017@Hh 86.8 [781
walstromite phase CagSi309 73.8,78.5, WI
79.0
wollastonite Ca3Si309 87.6,91.7l 24 85 158 Cl181
P-wollastonite(s) P-Ca3Si309 89.0 1781
TABLE 3 (continued)
mineral CSAb
(s)=synthetic nominal formula -&ma -611 422 433 ref.
Q2 sites, rings:
ps-wollastonite(s) a-CajSi309 83.5 0'81
6) W-W4012 87.5 63 63 141 ]71,781
tourmaline Na(Mg,Li,A1)3AlgSi6018- 88.1 U181
@03h@KF)4i
6) Ba7Si702I.lOBaCl2 92.5 1341
benitoite BaTiSis 94.2 [781
wadeitephase(s)g K2SiV1SiIV309 95.0 W61
mineral
(s)=synthetic nominal formula -hoa ordering ref.
state”
ej sites, layer aluminosilicates:
margarite CaA12(A12Si201o)(OH)2 15.5 4 C'81
phlogopite KMg3AlSi301o(F,OH)2 84 to 87 5 WJW
phlogopite(s)e KMg3AlSi301o(OH)2 83.2,87.0t,90.7 3 Lm
palygorskite MgAlSi401o(OH)2~4H20 84.9,91.7,96.8 [341
beidellite Nao.3A12(Alo.3Si2.701o) 88,94 [341
(OW2
muscovite KAl~SiAl~O~~(OH)~ 89,85?,81 [I 121
illitee KA12SiA1301o(OH)$ 91m Km
lepidolite KLi2Al(AlSi301o)(F,OH)2 89m V81
dickite A4Si&o(OHh 90.9 [341
kaolin& Aldi4Oio(OH)8 91.50 [781
endellite A4S4Olo(OHho~8H20 93.1 F’81
pyrophyllite AWWAotOHh 94.0 [112,118]
montmorillonite (Al,Mg)2S401o(OH)2.4HZO 93.7 WI
sepiolite Mg&j015(OH)2.2H20 92,95,98 WI
hectorite (Mg,Li)2.7Na0.3S401otOHh 95.3 WI
.4H20
TABLE 4 (continued)
mineral
(s)=syntbetic nominal formula -6isoa ordering ref.
state”
Q4. silica polymorphs:
q- SiO2 107.4” [118,126]
coesite SiO2 108.1,113.9 W61
cristobalite SiO2 108.5 [118,126]
tridymite SiO2 109.3-l 14.ow W61
@, feldspars:
low albitee NaAlSijOg 92.3,96.9,104.3 [103,127]
high albitee NaAlSigOg 91 to 112X [1691
microclinee KAlSi-jOg 95.6,97.6,100.6 [103,1271
sanidinee Ko.6Nao.4AlSi308 97,101m WI
anorthitee CaAl2Si2Og 82.7,84.7,89.3x WOI
a.northitee CaAl2Si208(disordered) 82.5 to 104Sx [1021
@, feldspathoids:
carnegieite(s) NaAlSiO4 82.2 D481
scdalite Na8Al&jO2&12 84.9 [1181
nephelinee Na3KAk+i40t& 85.1+,88.4 11481
kalsilite(s)e KAlSi04 88.8 H481
cancrinite Na8Al&i6024CO3 86.3 [1181
scapolitee Na4Al$i9024Cl- 92.6,106.2y [1171
Ca4Al&jO24CO3
analcite NaAlSi206.&0 91.6,96.8t,l02.0 3 r951
leucite KAlsi206 78.7 to 106.72 3 1951
Q4, zeolites:
thomsonite NaCa2AlgSi5020.6H20 86.4,89.0,91.7 [1181
scolectite CaAl2Si3010.3HZO 86.4,88.8,95.7 UN
natrolite Na2Al2Si3010.2H20 87.7t,95.4 U181
gmelinite N~Al2Si4012.6H20 92.0,97.2t,102.5 VI
chabazite CaAl2Si4012.6H2O 94.0,99.4?,104.8 WI
stilbite CaAl$Gi701g.7H20 98,101.5t,108 L'21
harmotone BaA1&016.6H20 95,98.6,102.6,108 1721
heulandite CaAl2Si7018.6H20 95.0 to 108.0aa 11181
@, others:
cordierite Mg2&Si5018 (ordered) 79,100t 4 w71
cordierite Mg2Ak&Olg (disordered) 79 to 112aa 1 r1071
petalite LiAlSi4010 87c [781
STEBBINS 313
TABLE 4 (continued)
mineral
(s)=synthetic nominal formula -hoa ordering ref.
danburite 89 WI
prehnite 98.6 4 D391
belyle 102.3 u191
Kleddelite 100.6 m
zunyite 128.5 4 U181
TABLE 5. 29Si NMR data for SiO6 and SiOs sites in crystalline silicates. Data for end-member
compositions only. SeeTable 3 for notes.
mineral
(s)=synthetic nominal formula -6. a ref.
SiO6, known structures:
thaumasite 179.6bb [48,1391
ilmenite phase(s) 181.0cc 0461
stishovite(s) 191.3 U461
perovskitephase(s) 191.7= WI
perovskitephase(s) 194.5 11461
pyroxenephase(s)g 194.7= 11461
majorite gamet(s)g 197.6dd [101,146]
wadeitephase(s)g 203.1 U461
6) 214.0, 217.0 IX81
6) 22oc Cl581
Si’”
Si”’
Fig. 2. 29Si MAS spectrum for a high pressure, MgSiOg garnet. The multiplicity of tetrahedral sites re-
sults from partial disorderamong six-coordinatedSi and Mg neighbors[ 1011.Black dot marks spinning side
band.
TABLE 6. 27Al NMR data A104 sites in crystalline silicatesand oxides. Data for a number of clay minerals,
synthetic zeolites,sheetsilicates,andphosphateshavebeenexcludedfor brevity.
Q’ sites:
(9 KA102.1SH20 5.0 0.25 81 [921
Q2 sites:
(9 KA102.H20 6.5 0.6 83 WI
6) a-BaA1204.2H20 3.4 0.5 81 WI
I, 5.1 0.9 80 [921
STEBBINS 3 15
TABLE 6 (continued)
@ sites, feldspars:
albitee NaAlSi308 3.29 0.62 63.0 [43,64,73,103,169
microclinee KAlSi30s 3.22 0.21 60.9 [43,64,73,103,169
anorthite, OziO CaA12Si208 8.5 0.66 62,55c [133lw41
ozoo 7.4 0.76
OOiO 6.8 0.65
mOO0 6.3 0.88
mOi0 5.5 0.42
mzO0 4.90 0.75
4.4 0.53
mzi0 2.6 0.66
@ sites, feldspathoids:
sodalitee Na8Al&j024Cl2 0.94 0.32 62.9 P’3961
nepheline Na3KAk&0t(jf 61.0,63.5 153,731
kalsilite(s)e KAlSi04 61.7 [531
scapolitee NaqAl3Si9024Cl-CaqA16Si6024C03 58.0c 11171
analcite NaAlSi&*H20 59.4 [731
leucite KAlSi$Qj 6 1,61j,69~ mw
316 NMR OF SILICATES AND OXIDES
TABLE 6 (continued)
Q4 sites, zeolites:
thomsonite 62.7 [731
scolectite 62.5,66.4 [731
natrolite 1.66 0.50 64.0 [43,731
gmelinite 59.9 [731
chabazite 59.4 r731
mordenite 55.8 r731
gismondite 56.4 [731
Ca-aluminates:
6) ca3&06, Al( 1) 8.69 0.32 79.5 WI
11 ” , Al(2) 0.54 78.25
9.30 WI
6) CanAll4033, Al(l) 9.7 0.40 85.9 W31
11 11 7442) 3.8 0.70 80.2 11231
6) Ca4A16013 2.4 0.95 80.3 [911
6) Ca4A16013~3H20 1.8 0.5 78 [911
,, 5.4 0.45 79 [911
6) CaA120qh 2.5-4.3 0.2-1.0 81.2-86.2 W31
6) CaA1407, Al(l) 6.25 0.88 75.5 W31
II II 9.55 0.82 69.5
, AV) W31
6) CaAIV1~AIVAllV~O~~9Q” 2.0 4 65 [911
TABLE 7. 27A1 NMR data for A105 and A106 sites in crystalline silicates and oxides. Data for a variety of
synthetic zeolites, sheetsilicates,andphosphateshavebeenexcludedfor brevity. SeeTable 6 for notes.
A105 sites:
A106 sites:
TABLE 7 (continued)
Ca-aluminates:
6) 2.4 10.2 W31
6) 0.71 0.09 12.36 11231
6) 1.8 10.20 W31
6) 1.5 =a 9 E911
<l 4-l 16 1911
ethingite(s) 0.36 0.19 13.10 WI
6) 1.7 11.80 W31
Al05 groups in a few known structureshave S values of almost negligible in many minerals at high magnetic
about 35 to 40 ppm. The more subtle effects of bond an- fields. Determination of Sisofrom MAS spectra can be
le and secondneighbor identity are similar to those for done in some casesby detailed analysisof spinning side-
49Si [2,66,88]. bands for the satellite transitions [55,79], by collection of
Many MAS NMR studies of 27A1of solids have re- spectraat more than one magnetic field [73,103], and, for
ported only peak positions, which are generallyshifted to sites with relatively large QCC (quadrupolar coupling
frequencieslower than &so by the secondorder quadrupo- constant) values, by fitting of quadrupolar line shapes
lar interaction. Quadrupolar shifts can be as large as 20 or [34]. Quadrupolar effects can broadenpeaksto the extent
more ppm for data collected at relatively low magnetic of being inadequatelynarrowed by MAS, or even lost en-
fields and/or for siteswith large field gradients,but canbe tirely becauseof instrumental dead time. MAS studiesat
STEBBINS 3 19
2.3. l’0
Although 170 can be observedat natural abundancein
liquids and in highly symmetrical sites in crystalline ox-
ides [6], applications to silicateshave generallybeenlim-
L
ited by the necessityof working on isotopically enriched
samples. The data assembledin Table 8 have been ob- 14oov
tained at high magnetic fields by the fitting of MAS,
DAS spectra, or static spectra. For some materials, the
latter can be quite informative, but neglect of chemical
shift anisotropycan lead to discrepancies[ 1311. 250 0 -150
The most obvious effect on 170 spectra of silicates
with tetrahedral Si is the distinction betweenbridging and Fig. 3. 27Al MAS spectrafor MgAl204 spine1quenched
non-bridging oxygens.The former generally have much from the two temperaturesshown. Featuresother than the
larger QCC values. Indeed, QCC is well correlated with two labeledpeaksare s inning side bands.The increasein
the electronegativity of the neighborcationsand thus with the intensity of the Al1B peak indicatesan increasein dis-
the covalent character of the M-O bonds order with temperature[86].
[ 115,152,153,154]. Isotropic chemical shifts for non-
bridging oxygensvary widely (over 1000ppm) depending
on the nature and number of the coordinatingcations.For
group II oxides and both bridging and non-bridging oxy- made to borate and borosilicate glasses [ 11,155,170].
gens in silicates, there are good correlations between in- Recently, similar effects on 6iso have been detected for
creasing cation size and decreasedshielding (higher fre- 23Na in silicates [53,103] as well as aluminofluoride
quencies or larger chemical shifts) [153,154]. CP MAS minerals [24]. Studies of other nuclides in silicates and
NMR has been shown to work well for enhancingsignals oxides are too numerousto mention in detail, but havere-
from oxygensnear to protons [ 1571. cently included 9Be, 13C, 19F, 25Mg, 31P, 35Cl, 39K,
DAS and DOR spectrahaverecentl beenshown to be 45Sc, 47Ti, 51V, 89Y, 93Nb, l19Sn, 129Xe, and *07Pb.
remarkably effective for resolving 170 NMR peaks for
structurally similar but crystallographically distinct sites 2.5. Dynamics in Crystalline Phases
in silicates [89]. In oxides and silcates, dynamical studieshaveconcen-
trated on the mechanismsand rates of diffusion of both
2.4. Other Nuclides cations (especially7Li+ and 23Na+)and anions(especially
NMR studiesof a variety of other nuclei in solid geo- 19F-), and on phasetransitions in materialswith abundant
logical materials have provided important structural in- nuclides of high Larmor frequency (e.g. 7Li, 19F,23Na,
formation [61]. The large differencesbetweenelectric field 27Al, 93Nb) [8,109,136,1381. The first of these reports
gradientsfor three- and four-coordinatedboron, for exam- extensive work on perovskite-structured oxides. Most of
ple, allow these sites to be easily distinguished by l1B these studies have been done at relatively low magnetic
NMR. Many applications of this relationship, as well as fields and consist primarily of relaxation time measure-
the effect of coordination number on &so, have been ments. As such, quantification of results often requires
320 NMR OF SILICATES AND OXIDES
TABLE 8. 170 NMR data for crystalline oxides and silicates.Somedata for synthetic zeolites, as well as oxysalts
and oxide superconductorsare excludedfor brevity. In silicates,“BO” signifiesbridging oxygen, “NBO” non-bridging
oxygen.
aluminum oxides:
corundum(s) CX-Al2O3,OA4 site 2.17 0.55 75C [13,156]
6) y-Al2O3, OA4 site 1.8 73C [1561
6) ~~-Al203, OA4 site 1.6 73C 11561
6) &Al2O3, OA4 site 1.6 72c [I561
6) t%Al2O3, OA4 site 1.2 72c [1561
II , OA13 site 4.0 0.6 79c [1561
p-alumina(s) 11A1203.Na20 c2.2 76c 161
STEBBINS 321
TABLE 8 (continued)
hydronides:
boehmite(s) AlO( OA4 site 1.15 0.13 7o.oc [125,1561
,, 11 A120H site 5.0 0.5 4oc U561
bayerite(s) Al(OH);, Al2OH site 6.0 0.3 4oc WI
brucite Mg(W2 6.8 0.0 25g [I571
orthosilicates:
forsterite(s) Mg2Si04, NBO 3.3h 72i if391
t, 11 2.8h 64i
, NBO WI
0 II 49i
,NBO 3.oh WY
htrnite(s) Ca2SiO4, NBO 2.9h 134i 1891
I, 2.7h 12gi
, NBO F391
II 122i
, NBO 2.P P391
I, 2.gh 122i
. NBO 1891
chain silicates:
diopside(s) caMgsi206, NBO 2.83 0.13 86i E391
9, 11 2.74 0.00 64
, NBO 1891
9, 11 0.36 69’
,BO 4.39 WI
clinoenstatite(s) Mg2si&j, NBO 2.9h 57i F391
I, II
, NBO 3.6h 61i [891
11 $9
,I-0 3.6h 59’ WI
I, 8, 4.2h 62’
, NBO WI
I, ,, 7oi
,BO 5.lh [891
11 ,*
,BO 5.2h 7oi WI
wollastonite(s) Ca3Si309, NBO 2.3h 115i WI
11 II , NBO 2.6h 114i if391
11 I,
, NBO 2.2h 107i P391
11 11 97’
, NBO 2.0h E391
It I,
, NBO 2.9h 103i [891
0 11
, NBO 2.6h 88i WI
I, 11 4.8h 75’
,BO F391
II 11
,BO 4.8h 75i WI
II 11 4.7h 67’
,BO [891
ps-wollastonite a-Casio+, NBO 2.1 0.1 94c r1531
11 ,, , NBO 2.3 0.1 91c [I531
11 9,
,BO 3.8 0.2 75c r1531
(s) a-SrSiOgj, NBO 2.1 0.1 10gc u531
19 II , NBO 2.2 0.1 105c u531
I, I,
,BO 4.1 0.4 80c [I531
322 NMR OF SILICATES AND OXIDES
TABLE 8 (continued)
framework silicates:
cristobalite(s) SiO2 5.3 0.13 4ok u311
Na-A zeolite(s) (seereference),Si-O-Al, BO 3.2 0.2 32= U521
Na-Y zeolite(s) (seereference),Si-O-Al, BO 3.1 0.2 31c U521
*a II , Si-O-Al, BO 4.6 0.1 44c 11521
complex models. In a few recent, high resolution studies information obtainableby diffraction methods.Becauseof
of silicates, the direct observation of exchangeamong the wide and continuous rangesof compositions studied,
multiple sites in a crystal offers the possibility of sim- and the frequent model-dependentnature of the structural
pler, more direct interpretations. Alkali cation dynamics conclusions, I have tabulated only a few 29Si MAS data
have beenstudied in a number of framework silicates,for on glasseswith the stoichiometry of end-member crys-
example [57,144], and can have an important influence talline phases(Table 9). Other recent reviews do include
even in ortho- and chain-silicates[38]. Structural and dy- some tabulations [34], as well as extensivediscussionof
namical changesoccurring during displacivephasetransi- silicate, oxide, borate, and non-oxide glasses
tions in silica polymorphs and their aluminum phosphate [lO,l l,29,61,62,145].These contain information on stud-
analogs have been explored in some detail [99,130,131]. ies of nuclides not included here, especially llB, 19F,
23Na9and 31P.
3. APPLICATIONS TO GLASSES,
AMORPHOUS SOLIDS, AND MELTS 3.1. 29S i
The relatively clear relationshipsbetween&so and Q
Techniquessuch as NMR becomeparticularly impor- speciesin crystalline silicates has led to a number of at-
tant when the absenceof long-range structure limits the tempts to quantify their abundancein glasses.Separate
STEBBINS 323
82.3 17 1701
80.1 13 [701
Notesfor Table 9:
Uncertainties are generallyat least 0.5 ppm in peakpositionsand widths.
*Partially resolvedshoulder
peaks for each Q speciesare often partially resolved in modynamic mixing models for these systemshave been
MAS spectra for alkali silicate glasses(Figure 4). Quanti- based on NMR data [9,77]. In a few favorable cases,
tative interpretations have usually dependedon assump- static spectra can permit quantification of Q species in
tions of Gaussian line shapeand curve fitting, but inter- glasses with fewer curve fitting assumptions than for
pretations have converged as data improves MAS spectra, becauseof the contrasts in chemical shift
[26,28,32,5 1,134,135]. It is now clear that speciation is anisotropy [9,32,134].
more disorderedthan requiredby simplestoichiometry,but In binary silicate glasses of alkaline earths, and in
more orderedthan predictedby random mixing of bridging aluminosilicate glasses,peaks for Q speciesare usually
and non-bridging oxygens [94,135]. A number of ther- unresolvedin MAS spectrabecauseof greateroverall dis-
324 NMR OF SILICATES AND OXIDES
3.2. 27Al
12 CPa
As in crystalline materials, interpretation of NMR
spectra of quadrupolar nuclides in glassesis complicated
by second-orderquadrupolarbroadening(possiblyleading
to signal loss from highly distorted sites). It may be im-
possible to distinguish theseeffects from thosecausedby
I bar
disordered distribution of sites, although again, studiesat
-80 -la, -160 -203
varying magnetic fields can be useful. Fitting of spinning
Fig. 4. 29Si MAS spectra for Na2Si409 glasses side bands,when theseare observable,can againbe useful
quenchedfrom liquids at 12 GPa and at 1 bar pressures. in determining isotropic chemical shifts [79,129]. Careful
Signalsfrom Si with different coordination numbers,and quantification of intensities is essential in determining
from different tetrahedralspecies,are labeled[166]. Black whether all Al hasbeendetected[651.
dots mark spinning sidebands. The most dramatic findings from 27Al MAS NMR in
glasseshas beenthe clear detectionof five and six coordi-
nated Al in a variety of compositions, including those in
the Si02-A1203 binary [105,110,113] and in some
order and variety of first neighbor cation arrangements, phosphorus-richglasses[27] and boroaluminates[ 15,971.
making quantitativederivation of speciationhighly model- In the CaO - Al203 - SiO2 ternary, non-tetrahedralAl is
dependent.Studieshaveincludedextensivework on alkali abundant only in compositions close to the Si02-A1203
and alkaline earth aluminosilicates [35,65,98] and Ca, join [ 1141.In carefully quantified studiesof glasscompo-
Mg silicates [70,94]. The narrowing of NMR peaks as sitions with M+l20/A1203 or M+*O/A1203 I 1.0, it
Al/Si is increasedto 1 suggeststhat some Si-Al ordering has been shown that high coordinatedAl is undetectable
occurs, probably becauseof at least partial “aluminum and thus comprises less than a few percent of the total Al
avoidance” [943.For pure Si02 glass,bond angledistribu- [65,98]. However, high-coordinateAl hasbeendetectedin
tions have been derived using empirical correlations be- only slightly peraluminousglassesnear to the MgA1204-
tween 6 and bond angles [44,94,98]. Si02 join [831.
One approachto determining the effect of temperature
on liquid structure is to quench liquids at varying rates to 3.3. 170
produce glasseswith different “fictive” or glasstransition As in crystals, the primary distinction among 0 sites
temperatures (Tg). This approachhas been usedto show detectedby NMR of glassesis that betweenbridging and
that Q speciesdistributions, as well as overall disorder in non-bridging oxygens(Figure 5). Static spectracan some-
bond angles, do indeedbecomemore randomwith increas- times be more informative than MAS data. Systematic
ing T [9,1353. compositional effects on the chemicalshifts for NBO sites
Studiesof alkali silicate glassesquenchedfrom liquids have been noted [61], as have pressureeffects on 0 site
at pressuresto 12 GPa have shown the presenceof six co- distribution [ 1651.Very recently, it hasbeendemonstrated
ordinated Si (Figure 4), and for the first time demonstrated that 170 DAS NMR can accurately quantify bond angles
the existence of five coordinated Si [147,166,167]. The and oxygen site distributions [36].
latter has now also been detected at low abundance
(~0.1%) in glasses formed at 1 bar pressure[137]. High 3.4. Water in Glass
coordinate Si has not been observed in NaAlSigOg or Both static “wideline” and high speed1H MAS studies
SiO2 glassesquenchedfrom liquids at high P [150,166]. have detected and quantified OH- and molecular Hz0
Six-coordinatedSi has alsobeenreported in alkali silicate [30,68]. 2H NMR has distinguishedamong water species
glassescontaining large amounts of P205 [25,27]. in glasses,as well, and has provided some dynamical in-
STEBBINS 325
formation [31]. In hydrous NaAlSigO8 glass,23Na 27A1, 3.5. Silicate and Aluminate Liquids
and 29Si MAS and CP MAS spectra were interpreted as In ionic and partially ionic liquids suchas silicates(at
indicating that OH is bound soley to Na with the possibil- least at high silica contents), flow requiresthe breakingof
ity of protonated bridging oxygens [67,69], whereas in the strongest bonds in the system (Si-0). As a result, at
hydrous binary alkali silicate glasses[85,139] and in SiO2 high temperatures where viscosities are low, silicate
[373, 29Si NMR has clearly shown the presence of species are short lived, with all cations and anions ex-
SiOH groups. llB, 170, 23Na, 27A1, and 29Si NMR changingrapidly amongavailablesites.Under thesecondi-
have been usedin severalstudiesof the interaction of sili- tions, therefore, in situ, high temperature NMR reveals
cate glasseswith water at ambient to hydrothermalcondi- only single 170, 23Na, 27A1, and 29Si peaks, for which
tions at a range of pH’s [16,139,168,169]. orientational effects that lead to broadeningin a solid, in-
cluding chemical shift anisotropy and quadrupolar cou-
plings, are fully averaged [38,81,121,142,149,1511.The
1 averagepeak position can still give structural information
however, since it is a quantitative weighted meanover all
species present. This approach has shown, for example,
that when aluminum oxides, aluminates, and fluorides
melt, the meanAl coordination number decreases[40,81].
A multi-nuclear high T NMR study of alkali aluminosili-
943 ‘C cate liquids has detectedsystematictempemtureeffects on
averagedchemicalshifts that can be interpretedin terms of
structural changes[ 1421.Studieshave now been made to
---iAL temperaturesgreater than 2 100° C, and have includedsys-
tematic work on the effects of composition on the struc-
ture and dynamics in the CaO-A1203-Si02 system
121,841.
At lower temperatures,incomplete exchangeand aver-
aging occurs, and, in favorable cases,NMR line shapes
can be analyzedto measurethe rates of exchange.The rate
of exchangeof Si among various anionic species,and that
of 0 between bridging and non-bridging sites, are funda-
mentally tied to diffusion and viscous flow. In K2Si4O9
liquid, for example (Figure 5) simulations of high tem-
perature 170 and 29Si line shapesgives results that can
be used to accurately predict the viscosity, assuminga
simple Eyring model for flow [38,145]. 2-D exchange
NMR spectroscopy just above the glass transition also
suggeststhat exchangeamong Q speciesis of key impor-
tance in flow even in the very high viscosity range [39].
A series of relaxation time measurementshas shown that
Si dynamics are greatly affected by the transition from
glass to liquid, and that the interaction of alkali cation
with the network can also be detected[38,75,76].
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Mijssbauer Spectroscopy of Minerals
Catherine McCammon
Quadrupoie Magnetic
barenudeus Isomershift splitting splitting
~~~~
0 Ah
Fig. 1. Illustration of hyperfine interactions for s7Fe nuclei, showing the nuclear energy level diagram for
(1) a bare nucleus, (2) electric monopole interaction (isomer shift), (3) electric quadrupole interaction
(quadrupole splitting), and (4) magnetic dipole interaction (hyperfine magnetic splitting). Each interaction is
shown individually, accompanied by the resulting Mossbauer spectrum.
0.98
.-5
%
‘E 0.96
2
,m
I- 0.94
0.921 , , , j
-4.0 -2.0 0.0 2.0 4.0
Velocity (mm/s)
Fig. 2. Mossbauer spectrum of orthopyroxene with composition Fe0.8Mg0,Si03 showing two quadrupole
doublets, one corresponding to Fe2+ in the Ml site (45% of total area) and one corresponding to Fe2+ in the
M2 site (55% of total area).
334 MdSSBAUER SPECTROSCOPY
only. For more complete information on specific dependenceof hyperfine parameterson composition. The
minerals, one should consult resources such as the relative areas of subspectra can be used as a rough
Minerals Handbook published by the Mossbauer Effect approximation to relative abundance,e.g. [973, but note
Data Center (see Table 3). Minerals are listed by name that site proportions often vary betweendifferent samples
except when part of a larger structure group, e.g. of the same mineral. For example, the amount of Fe3+
Fe3A12Si30i2 is listed under garnet, not almandine. may depend strongly on foa conditions, and the
Chemical compositions are given exactly as reported by distribution of iron cations between different
the authors (even if the resulting compositions are not crystallographic sites may be a function of thermal
electrostatically neutral). Data for differing compositions history. Most spectrawere fitted to Lorentzian lineshapes;
are provided for the major mineral groups to illustrate the the few exceptionsare noted in the tables.
Isomer shift (8) mm s-l Energy difference betweensourceand absorbernuclei resulting from effects
including differences in valence state, spin state and coordination of
absorber atoms. Experimentally one observesa single line shifted from a
referencezero point by the isomer shift plus the second-orderDoppler shift
(SOD), a small thermal shift due to atomic vibrations.
Centre shift (CS) mms -1 The experimentalshift of the centroid of a Mossbauerspectrum from a zero
referencepoint. The contribution from the SOD is similar in most standard
materials, so for purposesof comparison the isomer shift is often taken to
be equalto the centre shift.
Quadrupolesplitting mm s-l Splitting of the energy levels causedby interaction between the nuclear
(mQ) quadrupolar moment and an electric field gradient at the nucleus, and de-
pends on the valence and spin state of the absorber atoms, as well as the
coordination and degree of distortion of the crystallographic site.
Experimentally one observesa doublet in s7Feand l 19Snspectrawith com-
ponentsof equal intensity and linewidth in the ideal random absorbercase.
The quadrupole splitting is given by the energy separation between
components.
Hyperfine magneticfield Tesla Interaction of the dipole moment of the nucleus and a hyperfine magnetic
8 field causesa splitting of the nuclear energy levels, resulting in six peaks
for 57Fespectrain the simplest case.For an ideal random absorberwith no
quadrupoleinteraction the linewidths of the peaks are equal with intensity
ratio 3:2:1:1:2:3. The separation of peaks 1 and 6 is proportional to the
magnitudeof the hyperfine magneticfield.
Line width (0 mm s-l Full width at half maximum of the peak height. Peaks can be broadened
beyond the natural line width by effects due to equipment(vibrational, geo-
metrical, thermal, and electronic problems), the source (self-absorption
resulting from decay), and the sample (thicknessbroadening,next-nearest-
neighboureffects, and dynamic processessuchas relaxation).
Relative area(0 - Relative proportion of subspectrumarea to the total area. Each site nor-
mally contributes a subspectrum(e.g. a quadrupoledoublet) whose areais
approximatelyrelatedto the relative abundanceof that particular site within
the absorber.
McCAMMON 335
Type Reference
Book Bancroft, G.M. Miissbauer Spectroscopy. An Introduction for Inorganic Chemists and Geo-
chemists. McGraw Hill, New York, 1973.
Cranshaw, T.E.. Dale, B.W., Longworth, G.O. and Johnson, C.E. Miissbuuer Spectroscopy and
its Applications, CambridgeUniversity Press,Cambridge, 1986.
Dickson, D.P. and Berry, F.J. (eds.) Miissbauer Spectroscopy, Cambridge University Press,
Cambridge, 1986.
Gibb, T.C. Principles of Miissbauer Spectroscopy, Chapmanand Hall, London, 1977.
Gonser, U. (ed.) Mfissbauer Spectroscopy, Topics in Applied Physics, Vol. 5, Springer-Verlag,
Berlin, 1975.
Greenwood, N.N. and Gibb, T.D. M&sbauer Spectroscopy, Chapmanand Hall, London, 1971.
Giitlich, P., Link, R. and Trautwein, A., MSssbauer Spectroscopy and Transition Metal
Chemistry, Springer-Verlag, Berlin, 1978.
Hawthorne, F.C. (4.) Spectroscopic Methods in Mineralogy and Geology, Rev. Mineral. Vol. 18,
Mineralogical Society of America, 1988. See Chapter on Mossbauer Spectroscopy, F.C.
Hawthorne, pp. 255340.
Mitra, S. Applied MBssbauer Spectroscopy, Theory and Practice for Geochemists and
Archeologists, PergamonPress,Oxford, 1992.
Robinson, J.W. (ed.) Handbbok of Spectroscopy, Vol. 3, CRC Press, Inc., Boca Raton, USA,
1981. SeeChapter on MossbauerSpectroscopy,J.G. Stevens(ed.), pp. 403-528.
336 MijSSBAUER SPECTROSCOPY
TABLE 3. (continued)
Type Reference
Journal Analytical Chemistry (American Chemical Society, Washington DC) contains biennial reviews
(starting in 1966) of Mossbauerspectroscopy,seefor example Vol. 62, pp. 125R-139R, 1990.
Hyperfine Interactions (J.C. Baltzer AG, Basel) publishes proceedingsfrom various Mossbauer
conferences,seefor exampleVol. 68-71, 1992.
MossbauerEffect Referenceand Data Journal (MossbauerEffect Data Center, Asheville, NC) con-
tainsreferencesand Mossbauerdata for nearlyall Miissbauerpaperspublished.
Data Resource Stevens,J.G., Pollack, H., Zhe, L., Stevens,V.E.. White, R.M. and Gibson, J.L. (eds.) Mineral:
Data and Mineral: References, MdssbauerHandbook Series, MdssbauerEffect Data Center,
University of North Carolina, Asheville, North Carolina, USA, 1983.
MossbauerMicro Databases(MtissbauerEffect Data Center, Asheville, NC) cover many topics in-
cluding Minerals. Databasesare set up to run on IBM-compatible microcomputersand can be
searchedusing variousoptions.
Mlissbauer Effect Data Center Mtjssbauer Information System (maintained by the MUssbauer
Effect Data Center, Asheville, NC) containsextensivebibliographic and Mossbauerdata entries
compiled from the Mossbauer literature. Searchesof the databaseare possible; contact the
MossbauerEffect Data Center for details.
Amphibole structure
W2i.-rFedi8O&H)2 RT 1.16(l) 2.76(l) 0.07 MFe2+ uo71
1.13(l) 1.81(l) 0.93 vrFe2+
F%2Mgo.sSis&d0Hh RT 1.16(l) 2.79( 1) 0.69 vrFe2+ [531
1.07(l) 1.55(l) 0.31 MFe2+
McCAh4h4ON 337
TABLE 6. (continued)
TABLE 6. (continued)
Kyanite
(~o.98FeO.ozhsios RT 0.38(2) 0.99(2) WI
Mica groupb
Ko.sNao.J~Si3WW2 RT 1.21(l) 2.99(l) 0.08 r411
X=All.Pe0.2Mg0.1 1.14(l) 2.12(l) 0.05
0.36(l) 0.86( 1) 0.87
RT 1.12(l) 2.63(l) 0.38 1391
0.19(l) 0.56(l) 0.62
RT 1.02(l) 2.52(l) 0.59 1761
1.06(l) 2.08( 1) 0.33
0.31(l) 0.80( 1) 0.08
C~A127Sid40@Hh RT 1.06(l) 2.34(l) 0.30 WI
X=Mg2.3Alo.+o.l 0.28( 1) 0.66( 1) 0.70
Olivine
F@iO, 310K 0.89(2) 1.91(2) 0.48 r1111
0.95(2) 2.39(2) 0.52
CaFeSi04 400K 0.84(2) 1.33(2) 0.70 [I111
0.19(4) 1.23(4) 0.30
310 K 0.94(2) 1.98(2) 0.51 r1111
0.99(2) 2.36(2) 0.41
0.23(4) 0.70(4) 0.08
Fe2+o.~e3+Si04 290 K 1.13(l) 2.75(2) 0.41 Km
0.39( 1) 0.91(2) 0.59
Orthoclase
~b.95FQ.osSidh RT 0.46(l) 0.68(l) 1191
Osumilite
XMgl.4Feo.9AL.4Sil0.3030 RT 1.20(l) 2.35(l) 0.68 WI
X=Ko.9Nao.1 1.14(l) 1.86(l) 0.32 channel Fe2*
Perovskite structure
RT 1.12(l) 1.58(l) XnFe2+
Mgo&eo.~SQ 0.92 WI
quenched from 25 GPa, 165OT 0.44(5) 0.98(5) 0.08 Fe3+
Pyrophyllite
FezMgo.1Ab.,SbO,o(OH), RT 0.36(l) 0.18(l) 0.85 wFe3c
0.43(4) 1.22(8) 0.07 vFes
0.14(4) 0.59(8) 0.08 IvFeN
Pyroxene structure
FeSi03 RT 1.18(l) 2.49( 1) 0.54 1381
1.13(l) 1.91(l) 0.46
77 K 1.30(l) 3.13(l) 0.50
1.26(2) 2.00(l) 0.50
77 K 1.29(l) 3.06( 1) 0.20 WI
1.28(l) 2.16(l) 0.80
RT 1.19(l) 2.22( 1) [381
RT 0.42( 1) 1.07(l) 0.50 WI
0.14(l) 1.62(l) 0.50
NaFeSi,o, RT 0.39( 1) 0.30(1) MFes WI
McCAMMON 339
TABLE 6. (continued)
1.00(l) VFe3+/vIFe3+ PI
a see [45] for a detailed discussion of calcic amphibole data d spectral data were fitted using a relaxation model
b spectra are more realistically described with hyperfine c site distribution depends strongly on thermal history,
parameter distributions, see [98] see e.g. [112]
’ see [59] for a compilation of data f small amount of additional component present
340 MCjSSBAUER SPECTROSCOPY
Arsenopyrite
FeAsS RT 0.26(3) 1.15(3) [@I
Berthierite
FeSb$& RT 0.83(2) 2.69(2) u71
Bornite
Cu5FeS4 RT 0.39( 1) 0.22( 1) PI
Chalcopyrite
CUFeS2 RT 0.25(3) 35.7(5) WI
Cobaltite
(Co,Fe)AsS RT 0.26(l) 0.45( 1) WI
Cubanite
CuFe& (or-rho) RT 0.43( 1) 1.2 33.1(5) WI
CuFe& (cubic) RT 0.72( 1) 0.20(l) 0.46 r491
0.22( 1) 0.54
Ldlingite structure
FeAs2 RT 0.3q 1) 1.65(l) WI
FeSbz RT 0.45( 1) 1.28(2) u 191
Marcasite structure
FeS2 RT 0.27( 1) 0.51(l) r1191
FeSq RT 0.39( 1) 0.58( 1) u191
FeT% RT 0.47( 1) 0.5q 1) [I191
Pentlandite
Fe4.2Coo.lNids RT 0.36(l) 0.32( 1) 0.82 1691
0.65( 1) 0.18
Pyrite
FeS2 RT 0.31(l) 0.61(l) u191
Pyrrhotite
F%.89s 285 K 0.69( 1) - 0.48 30.2(5) 0.41 [701
0.68( 1) - 0.59 25.7(5) 0.36
0.67( 1) - 0.45 23.1(5) 0.23
Sphalerite
Zno.d%osS RT 0.67(3) 0.54 [431
0.67(3) 0.60(10) 0.46
Stannite
Cu2FeSnS4 RT 0.57( 1) 2.90(l) [491
Sternbergite
4TezS3 RT 0.39(2) 1.07(2) 27.8(2) W91
Tetrahed-ite
CUs.9Ag,Fe,.,Sb4S~2.8 RT 0.58( 1) 2.28( 1) 0.60 WI
0.37( 1) 0.33( 1) 0.40
Thiospinel minerals
FeNi,S, RT 0.29( 1) 0.54( 1) W51
FeCr2S4 RT 0.59( 1) o.@-w 0.93 wa
0.58( 1) 0.7q 1) 0.06’
=3S4 RT 0.55( 1) 3 1.0(5) 0.66 ml51
0.26(l) 31.1(5) 0.34 “‘Fe3
342 MijSSBAUER SPECTROSCOPY
TABLE 8. (continued)
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Subject Index
actinides, bulk moduli, 13 1 black-body emission, dependence on temperature and thermal pressure,
activation energy, apparent, crystals, wavelength at different 78
238 temperatures, 300 elastic moduli, 68
activation energy, diffusion, 274 bonding properties, minerals, 291 mantle mineral data, 85
activation volume, apparent, crystals, borates thermal expansivity, specific heat,
238 mineral data, 3-4 elastic constants, and
Al-27 NMR spectra, 307,3 14-3 18, 322 shock wave equation of state, 160 velocities, 72
silicate glasses, 324 Coble creep, crystals, 240
albite calcite, spectra, 296 coesite, phase diagrams, 249
phase diagrams, 249-252 calcium aluminates, Al-27 NMR data, 3 18 compression curves, shock waves, 172
viscosity, 214 calcium oxide convective flow
alkali feldspar, phase diagrams, 250 dimensionless parameters, Debye mantle, 227
alloys, shear viscosity, 221-224 temperature and thermal pressure, mantle viscosity, 229
aluminates 76 coordination number, NMR spectra, 307
NMR spectra, 325 elastic moduli, 65 core, outer, viscosity, 218-226
See also calcium-aluminates mantle mineral data, 83 correspondence principle, elasticity,
aluminosilicates, layer thermal expansivity, specific heat, 228
Al-27 NMR data, 3 1.5 elastic constants, and corundum
Si-29 NMR data, 3 11 velocities, 73 phase diagrams, 25 1
aluminum oxides carbides, shock wave equation of state, See also aluminum oxide
dimensionless parameters, Debye 152-153 creep, climb-controlled, crystals,
temperature and thermal pressure, carbon-bearing minerals, bulk moduli, 239-240
75 117-118 creep, glide-controlled, crystals, 239
elastic moduli, 69 carbonates creep, power-law
mantle mineral data, 85-86 bulk moduli, 117-l 18 dislocations, 240
O-l 7 NMR data, 320 high-temperature electrical mantle viscosity,
thermal expansivity, specific heat, conductivity, 189 creep, quasi steady-state, crystals, 237
elastic constants, and mineral data, 3 crystals, 237
velocities, 70 Mbssbauer spectra, 342 See also diffusion creep; dislocation
amorphous materials shock wave equation of state, 160 creep; Harper-Dom creep;
bulk moduli, 134 thermal expansion, 32 Herring-Nabarro creep
NMR spectra, 303.322-325 chain silicates creep mechanism, mantle viscosity, 227
amphiboles bulk moduli, 105-107 cristobalite, phase diagrams, 249
diffusion, 277 mineral data, 6 critical resolved shear stress, yield
Mossbauer spectra, 336-337 O-17 NMR data, 321-322 strength, 245
andalusite, Mossbauer spectra, 337 charge transfer band, 297 cross-slip, dislocations, 240
andesite, shear viscosity, 215 chemical diffusion, 271 crystal-field absorptions, 297
anelasticity, melts, 209-217 chemical shift, NMR spectra, 304,306 crystallographic data, minerals, l- 17
anorthite, phase diagrams, 249-25 1 chemical shift anisotropy, NMR spectra, crystals
Arrhenius equation, diffusion, 274 306 plastic rheology, 237-247
Arrhenius law, crystals, 238 chlorite, Mossbauer spectra, 337 See also cubic crystals; hexagonal
asymmetry parameter, NMR spectra, 307 chloritoid, Mossbauer spectra, 337 crystals; orthorhombic crystals;
augite, phase diagrams, 255 clay minerals, Mossbauer spectra, 337 trigonal crystals
clinoenstatite, phase diagrams, 253-254 crystal structure, mineral data, 1-17
babingtonite, Mossbauer spectra, 337 clinopyroxene cubic crystals, elastic moduli, 46-48
basalt, diffusion, 274,282-283 phase diagrams, 254,256 cyclosilicates
Beer-Lambert law, absorption, 295 plastic properties, 244 bulk moduli, 107-l 10
beta-spinel, plasticity, 245 closure temperature, diffusion, 274 mineral data, 5-6
bibliography, Miissbauer spectroscopy, cobalt silicate See also ring silicates
335-336 dimensionless parameters, Debye
349
350 INDEX
Debye temperature, mantle minerals, electrical properties, minerals, 185-208 See also magnesium silicate
7.5-79 electronic transitions, minerals, 291 framework silicates
deformation-mechanism maps, plastic elements, Group I, bulk moduli, 122-123 bulk moduh, 104-105
deformation, 241 elements, Group II, bulk moduli, 123 0- 17 NMR data, 322
deformation mechanism, mantle elements, Group III, bulk moduli, 126 See also tektosilicates
viscosity, 227 elements, Group IV, bulk moduli, 126- 128 fusion, enthalpy, 25
diamond-anvil cell elements, Group V, bulk moduh, 128
equations of state, 98-101 elements, Group VI, bulk moduli, 128- 129 gamma-spinel, plasticity, 245-246
high-pressure minerals, 245-246 elements, Group VII, bulk moduli, 129 garnet, grossular
dielectric permittivity, 185 elastic moduh, 46 dimensionless parameters, Debye
diffusion, 304 shock wave equation of state, 146-152 temperature and thermal pressure,
multicomponent, 273 enstatite 76
dislocations, 240 phase diagrams, 254-257 elastic moduh, 65
olivine, 243-244 phase relations, 25 mantle mineral data, 83
diffusion plastic properties, 244 phase diagrams, 257
silicates, 269-290 enthalpy thermal expansivity, specific heat,
See also chemical diffusion mantle minerals, 90 elastic constants, and
diffusional flow, mantle viscosity, 227 minerals, 2 l-23 velocities, 73
diffusion coefficients phase transformations, 23-27 thermoelastic properties, 93-94
silicates, 270-273 entropy garnet, majorite
See also chemical diffusion; mantle minerals, 90 phase diagrams, 253
effective binary diffusion minerals, 2 l-23 plasticity, 245
coefficients; interdiffusion; phase transformations, 23-27 garnet, pyrope-rich
multicomponent diffusion; epidote, Mossbauer spectra, 337 dimensionless parameters, Debye
phenomenological diffusion equations of state temperature and thermal pressure,
coefficients; self-diffusion shock waves, 143-174 76
coefficient; thermodynamic static compression measurements, elastic moduli, 65
factor; tracer diffusion 98-142 mantle mineral data, 83
coefficient See also Mie-Gruneisen equation of phase diagrams, 256-257
diffusion creep state thermal expansivity, specific heat,
crystals, 239 elastic constants, and
dislocations, 240 fayalite velocities, 73
diopside crystal field absorption spectra, 299 garnet
phase diagrams, 253-257 phase diagrams, 256 diffusion, 280
plastic properties, 244 see also iron silicate elastic moduli, 47-48
dislocation creep, crystals, 239 Fe-57 Mossbauer spectra, 337
dislocations, crystals, 239 line positions for 14.4 ke V phase diagrams, 248,256-257
dynamic topography, mantle viscosity, transition, 335 gases, shock wave equation of state,
229 Miissbauer spectroscopy, 332-335 144-145
dynamic yielding, shock waves, 174-175 feldspars geochemistry, 304
Al-27 NMR data, 3 15 geodetic studies, core viscosity, 219
Earth-forming minerals diffusion, 275-276 geoid, mantle viscosity, 227
phase diagrams, 248-268 log electrical conductivity vs. geoid anomaly, positive mass anomaly,
spectra, 29 l-302 partial pressure, 205 231
Earth rotation, mantle viscosity, 23 1 phase diagrams, 248-252 geoid inversion, mantle viscosity,
effective binary diffusion Si-29 NMR data, 312 232-234
coefficients, 273 viscosity, 214 geomagnetism studies, core viscosity,
elastic constants, isotropic, mantle feldspathoids 220
minerals, 69-74 Al-27 NMR data, 3 15 geophysics, 304
elasticity, geological materials, 45-63 diffusion, 279 germanates, phase transitions, 25
elastic limit, crystals, 237 log electrical conductivity vs. Gibbs free energy, vs. temperature, 23
elastic moduli, isotropic, P and T partial pressure, 205 glasses
derivatives, 57-58 Si-29 NMR data, 312 bulk moduli, 134
crystals, 46-56 ferropseudobrookite, phase diagrams, 259 diffusion, 269-290
mantle minerals at high temperature, ferrosilite, phase diagrams, 255 elasticity, 45-63
64-97 Fick’s laws, diffusion, 270-27 1 elastic moduli, 56
melts, 209 forsterite heat capacity, 20
electrical conductivity, 185 heat capacity, 19 NMR spectra, 322-325
minerals, 29 1 phase diagrams, 254-256 phase transitions, 2 12
point defects, 187-188 thermoelastic properties, 92-93 shock wave equation of state, 166- 168
INDEX 351
glass transition, heat capacity, 20-21 iron-sulfur alloys, liquid, shear thermal expansivity, specific heat,
grain-boundary sliding, crystals, 239 viscosity, 223 elastic constants, and
grandidierite, Mossbatter spectra, 337 iron-titanium oxides, phase diagrams, velocities, 69
Grlineisen ratio, 173 248,258-260 thermoelastic properties, 92
iron magnesium silicate
halides bulk moduli, 13 1 dimensionless parameters, Debye
bulk moduli, 120-122 Mossbauer spectra, 342 temperature and thermal pressure,
elastic moduli, 47 phase diagrams, 248,262 77
high temperature electrical iron alloys, bulk moduli, 13 1- 133 elastic moduli, 67
conductivity, 189-190 iron silicate mantle mineral data, 84-85
log electrical conductivity vs. elastic moduli, 68 thermal expansivity, specific heat,
partial pressure, 204 mantle mineral data, 85 elastic constants, and
mineral data, 8-9 thermal expansivity, specific heat, velocities, 7 1
shock wave equation of state, 153-1.55 elastic constants, and magnetite, phase diagrams, 258-260
hardening, crystals, 237 velocities, 72 manganese oxide
Harper-Dom creep, crystals, 240-241 isopleths, phase diagrams, 249-262 dimensionless parameters, Debye
heat capacity, minerals, 18-21 temperature and thermal pressure,
hedenbergite, phase diagrams, 255 jadeite, phase diagrams, 249 78
Helmholtz free energy, mantle minerals, elastic moduli, 66
86-87 kamacite, Miissbauer spectra, 342 mantle mineral data, 83-84
hematite, phase diagrams, 258-260 kinks, crystals, 239 thermal expansivity, specific heat,
Herring-Nabarro creep, crystals, 240 Kroger-Vink notation, point defects, elastic constants, and
hexagonal crystals, elastic moduli, 48 187-188 velocities, 72
high-pressure minerals, I antle, 245-24; kyanite, Miissbauer spectra, 338 manganese silicate
high-pressure silicates dimensionless parameters, Debye
mineral data, 8 lanthanides, Lik moduli, 130-131 temperature and thermal pressure,
0- 17 NMR data, 322 leucite, phase diagrams, 250,252 78
hollandite, phase diagrams, 250 liquid alloys, shear viscosity, 221-224 elastic moduli, 68
Hugoniot equation of state, minerals, liquid metals theory, core viscosity, mantle mineral data, 85
143 221 thermal expansivity, specific heat,
hydrides, bulk moduli, 133-134 liquids elastic constants, and
hydrostatic pressure, plastic bulk moduli, 134 velocities, 72
deformation, 241 diffusion, 269-290 mantle
hydrous minerals, thermal expansion, heat capacity, 20 high-pressure minerals, 245-246
31-32 NMR spectroscopy, 303 viscosity, 227-236
hydroxides phase transitions, 2 12 mantle minerals, elastic constants,
bulk moduli, 11 l-l 17 lithosphere, strength, 228 64-97
mineral data, 3 longitudinal viscosity, vs. frequency, MAS, See magic angles spinning
Miissbauer spectra, 340 211 melting, entropy, 23-27
O-17 NMR data, 321 lunar glass, shock wave equation of melts
shock wave equation of state, 159 state, 168 elasticity, 45-63
elastic moduli, 55-56
ices, bulk moduli, 133 magic angles spinning, NMR spectra, 303 electrical properties, 185-208
ilmenite, phase diagrams, 253,259-260 magnesiowuestite NMR spectra, 304.322-325
ilvaite, Mossbatter spectra, 337 phase diagrams, 256 viscosity and anelasticity, 209-217
infrared spectroscopy, Earth-forming plasticity, 245 See also amorphous materials;
minerals, 29 l-302 magnesium aluminum oxide glasses; liquids; silicate melts
insulators, 186 dimensionless parameters, Debye metal cations, effect of octahedral
interdiffusion, 271 temperature and thermal pressure, coordination on d-orbitals, 298
intervalence transitions, 297 79 metallic compounds, elastic moduli, 46
inverse problems, mantle viscosity, elastic mod&, 66 metallic conductors, 186
231-232 thermal expansivity, specific heat, metals, transition, bulk moduli, 124-126
iron, liquid, shear dynamic viscosity, elastic constants, and mica, Mijssbauer spectra, 338
222 velocities, 70 Mie-Gruneisen equation of state, shock
iron-nickel alloys, liquid, shear magnesium oxide waves, 175
viscosity, 222-223 dimensionless parameters, Debye minerals
iron-oxygen alloys, liquid, shear temperature and thermal pressure, crystallographic data, 1 - 17
viscosity, 224 75 elasticity, 45-63
iron-silicon alloys, liquid, shear elastic moduli, 65 electrical properties, 185-208
viscosity, 224-225 mantle mineral data, 82-83 equations of state, 98-142
352 INDEX
relaxation mode, melts, 209 Miissbauer spectra, 336-339 climb-controlled creep, 240
relaxation time nuclear magnetic resonance plastic properties, 244
melts, 209 spectroscopy, 303-331 sulfates
vs. temperature, 2 12 phase transitions, 19-27 mineral data, 4
resonant frequency, 303 shock wave equation of state, 162- 166 MSssbauer spectra, 342
rheology, non-Newtonian, melts, 215 thermal expansion, 33-38 shock wave equation of state, 160
rheology, plastic, crystals, 237-247 vibration of tetrahedra, 293 thermal expansion, 33
rheology, mantle viscosity, 227 vibrations, 297 sulfides
rhyolite See also amphiboles; chain silicates; bulk moduli, 118- 120
diffusion, 274,28 l-282 clinopyroxene; cobalt silicate; elastic moduli, 47
shear viscosity, 2 15 feldspars; feldspathoids; mineral data, 9- 10
ring silicates framework silicates; iron Mossbauer spectra, 341-342
bulk moduli, 107-l 10 silicate; magnesium silicate; thermal expansion, 33
See also cyclosilicates manganese silicate; olivine; superplastic deformation, crystals, 239
ringwoodite, See also gamma-spine1 orthopyroxene; orthosilicates;
ruby, crystal-field effects, 298 pyroxenes; ring silicates; sheet taenite, MSssbauer spectra, 342
rutile, phase diagrams, 259 silicates; silica polymorphs; talc, Miissbauer spectra, 339
sorosilicates tectosilicates, See tektosilicates
sanidine, phase diagrams, 250 sillimanite tektosilicates, mineral data, 7-8
sapphirine, phase diagrams, 256 Miissbauer spectra, 339 tellurides
sealevel variations, ice models, 229 phase diagrams, 256 bulk moduli, 118-120
seismic tomography, mantle viscosity, smectite, Mossbauer spectra, 339 Miissbauer spectra, 341-342
229 Sn- 119, Mossbauer spectroscopy, 332-335 temperature, shock waves, 175
seismological studies, core viscosity, sodium chloride tetragonal crystals, elastic moduli, 50
220 dimensionless parameters, Debye thermal expansion
selenides, Mossbauer spectra, 341-342 temperature and thermal pressure, geological materials, 29-44
self-diffusion coefficient, 27 1 79 mantle minerals, 69-74
semiconductors, I86 elastic moduli, 66 thermal expansivity, geological
serpentine mantle mineral data, 84 materials, 29
Mossbauer spectra, 339 thermal expansivity, specific heat, thermal pressure, mantle minerals, 75-79
phase diagrams, 248,261 elastic constants, and thermobarometry, 248
shear stress, critical resolved, velocities, 74 thermochemical properties, minerals, 18
crystals, 239 sorosilicates thermodynamic factor, diffusion, 273
shear viscosity, vs. frequency, 211 bulk moduli, 107-l 10 thermodynamic properties
sheet silicates mineral data, 5-6 mantle minerals, 84-94
bulk moduli, 110-l 11 specific heat, mantle minerals, 69-74 minerals, 18-28, 172- 174
diffusion, 277 spine1 thermoelastic dimensionless parameters,
mineral data, 6-7 Al-27 MAS spectra, 3 19 mantle minerals, 75-82
shock waves, minerals, 143-l 84 elastic moduli, 47 thermoelastic properties,
Si-29 NMR spectra, 307-3 13 high temperature electrical high-temperature, mantle
silicate glasses, 322-324 conductivity, 192 minerals, 9 1-94
silica analogs, Al-27 NMR data, 3 15 mantle mineral data, 83 tholeiite, shear viscosity, 215
silica polymorphs Mossbauer spectra, 339 tin, Miissbauer spectra, 343
diffusion, 275 phase diagrams, 253,255-256 titanates, phase transitions, 25
phase diagrams, 248-249 plasticity, 245 titanite
shock wave equation of state, 16 1- 162 See also beta-spinel; gamma-spinel; diffusion, 28 1
Si-29 NMR data, 3 12 ulvospinel Mossbauer spectra, 339
silicate melts spin quantum number, 303 tracer diffusion coefficient, 271
high temperature electrical standard materials, shock wave equation transmission electron microscopy
conductivity, 201 of state, 168-171 high-pressure minerals, 245-246
longitudinal viscosity vs. shear static compression tests, equations of plastic deformation, 241
viscosity, 210 state, 98- 142 quartz, 242
silicates, crystalline staurolite, Mossbauer spectra, 339 tridymite, phase diagrams, 249
Al-27 NMR data, 314-318 stishovite, phase diagrams, 249, 253 trigonal crystals, elastic moduli, 49
Si-29 NMR data, 308-3 13 strain, vs. time, 210 tungstates, Mossbauer spectra, 342
silicates stress-strain curve
crystallographic properties, 4-8 crystals, 237 ulvospinel, phase diagrams, 259-260
diffusion, 269-290 plastic solid, 238
high temperature electrical stress creep curve, plastic solid, 238 velocity, mantle minerals, 69-74
conductivity, 192-200 stress exponent vibrational spectroscopy
354 INDEX
minerals, 29 1-297 See also longitudinal viscosity; wuestite, phase diagrams, 258-260
See also infrared spectroscopy; Raman Newtonian viscosity; shear
spectroscopy viscosity; volume viscosity X-ray diffraction data, minerals, 1-17
vibrational spectrum, minerals, 291 viscous flow, 304
virtitication, enthalpy, 25 volume viscosity, vs. frequency, 211 yield point, quartz, 24 1
viscoelasticity, melts, 209 yield stress, crystals, 237
viscosity, dynamic, outer core, 218-226 wadsleyite, Miissbauer spectra, 339 yoderite, Mossbauer spectra, 339
viscosity, Newtonian, crystals, 237 water-weakening, quartz, 241
viscosity, non-Newtonian, crystals, 237 water zeolites
mantle, 227-236 high pressure electrical conductivity Al-27 NMR data, 3 16
mantle models, 230 vs. density, 206 S-29 NMR data, 3 12
melts, 209-217 phase relations, 27 zircon, diffusion, 28 1
pressure dependence, 214 silicate glasses, 324-325
temperate dependence, 2 13-2 14 wollastonite, phase diagrams, 257