Thermodynamics of the magnetite-ulvöspinel (Fe3O 4-Fe2TiO4) solid solution

American Mineralogist

Volumn 97, Issue 8-9, 2012, Pages 1330-1338

  Lilova, Kristina I ^a   Pearce, Carolyn I ^b   Gorski, Christopher ^c   Rosso, Kevin M ^b   Navrotsky, Alexandra ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b PACIFIC NORTHWEST NATIONAL LABORATORY   (United States)

^c SWISS FEDERAL INSTITUTE OF AQUATIC SCIENCE AND TECHNOLOGY   (Switzerland)

Author keywords

Calorimetry; Enthalpies of mixing; Magnetite ulv spinel solid solution; Titanomagnetite

Indexed keywords

CALORIMETERS; CALORIMETRY; DROPS; ENTHALPY; IRON OXIDES; MAGNETITE; MIXING; POSITIVE IONS; TEMPERATURE;

CATION DISTRIBUTIONS; ENTHALPIES OF FORMATION; ENTHALPY OF MIXING; HIGH TEMPERATURE OXIDE MELT SOLUTION CALORIMETRY; QUADRATIC FORMALISM; SPECTROSCOPIC PROBES; SPINEL SOLID SOLUTIONS; TITANOMAGNETITES;

SOLID SOLUTIONS;

CALORIMETRY; CATION; ENTHALPY; EXPERIMENTAL MINERALOGY; HIGH TEMPERATURE; ILMENITE; MAGNETITE; MOLYBDATE GROUP; SPINEL; THERMODYNAMICS; TITANOMAGNETITE;

EID: 84866620708     PISSN: 0003004X     EISSN: 19453027     Source Type: Journal    
DOI: 10.2138/am.2012.4076     Document Type: Article

References (91)

1. Akimoto, S. (1954) Thermo-magnetic study of ferromagnetic minerals contained in igneous rocks. Journal of Geomagnetism and Geoelectricity, 6, 1-14.
2. Anovitz, L.M., Treiman, A.H., Essene, E.J., Hemingway, B.S., Westrum, E.F. Jr., Wall, V.J., Burriel, R., and Bohlen, S.R. (1985) The heat-capacity of ilmenite and phase equilibria in the system iron-titanium-oxygen. Geochimica et Cosmochimica Acta, 49, 2027-2040.
3. Arenholz, E. and Prestemon, S.O. (2005) Design and performance of an eight-pole resistive magnet for soft X-ray magnetic dichroism measurements. Review of Scientific Instruments, 76, 083908.
4. Banerjee, S.K. (1991) Magnetic properties of Fe-Ti oxides. In D.H. Lindsley, Ed., Oxide Minerals: Petrologic and Magnetic Significance, 25, p. 107-128. Reviews in Mineralogy, Mineralogical Society of America, Chantilly, Virginia.
5. Barth, T.F.W. and Posnjak, E. (1932) Spinel structures: with and without variate atom equipoints. Zeitschrift fÜr Kristallographie, 82, 325-341.
6. Akimoto, S. (1954) Thermo-magnetic study of ferromagnetic minerals contained in igneous rocks. Journal of Geomagnetism and Geoelectricity, 6, 1-14.
7. Anovitz, L.M., Treiman, A.H., Essene, E.J., Hemingway, B.S., Westrum, E.F. Jr., Wall, V.J., Burriel, R., and Bohlen, S.R. (1985) The heat-capacity of ilmenite and phase equilibria in the system iron-titanium-oxygen. Geochimica et Cosmochimica Acta, 49, 2027-2040.
8. Arenholz, E. and Prestemon, S.O. (2005) Design and performance of an eight-pole resistive magnet for soft X-ray magnetic dichroism measurements. Review of Scientific Instruments, 76, 083908.
9. Banerjee, S.K. (1991) Magnetic properties of Fe-Ti oxides. In D.H. Lindsley, Ed., Oxide Minerals: Petrologic and Magnetic Significance, 25, p. 107-128. Reviews in Mineralogy, Mineralogical Society of America, Chantilly, Virginia.
10. Barth, T.F.W. and Posnjak, E. (1932) Spinel structures: with and without variate atom equipoints. Zeitschrift fÜr Kristallographie, 82, 325-341.
11. Basta, E.Z. (1959) Some mineralogical relationships in the system Fe2O3-Fe3O4 and the composition of titanomaghemite. Society of Economic Geologist, 54, 698-719.
12. Bauminger, R., Cohen, S.G., Marinov, A., Ofer, S., and Segal, E. (1961) Study of the low temperature transition in magnetite and the internal fields acting on iron nuclei in some spinel ferrites, using Mössbauer absorption. Physical Review, 122, 1447-1450.
13. Berman, R.G. (1988) Internally-consistent thermodynamic data for minerals in the system sodium oxide-potassium oxide-calcium oxide-magnesium oxide-iron oxide (FeO)-iron oxide (Fe2O3)-alumina-silica-titania-water-carbon dioxide. Journal of Petrology, 29, 445-522.
14. Bosi, F., Halenius, U., and Skogby, H. (2009) Crystal chemistry of the magnetite-ulvöspinel series. American Mineralogist, 94, 181-189.
15. Bragg, W.H. (1915) The structure of magnetite and the spinels. Nature, 955, 61.
16. Brown, N.E. and Navrotsky, A. (1994) Hematite-ilmenite (Fe2O3-FeTiO3) solid solutions: the effects of cation ordering on the thermodynamics of mixing. American Mineralogist, 79, 485-496.
17. Carel, C. and Vallet, P. (1981) First-order transition of magnetite at 1160 °C. Bulletin de la Societe Scientifique de Bretagne, 52, 55-59.
18. Chevallier, R., Bolfa, J., and Mathieu, S. (1955) Titanomagnétites et ilménites ferromagnétiques. Bulletin du Société Français Minéralogie et Cristallographie, 78, 307-346.
19. Cornell, R.M. and Schwertmann, U., Eds. (2003) The Iron Oxides: Structure, properties, reactions, occurrences and uses, 664 p. Wiley-VCH, Darmstadt.
20. Della Giusta, A., Princivalle, F., and Carbonin, S. (1987) Crystal structure and cation distribution in some natural magnetites. Mineralogy and Petrology, 37, 315-321.
21. Eriksson, G., Pelton, A.D., Woermann, E., and Ender, A. (1996) Measurement and thermodynamic evaluation of phase equilibria in the Fe-Ti-O system. Berichte der Bunsen-Gesellschaft, 100, 1839-1849.
22. Fabrichnaya, O.B. and Sundman, B. (1997) The assessment of thermodynamic parameters in the Fe-O and Fe-Si-O systems. Geochimica et Cosmochimica Acta, 61, 4539-4555.
23. Forster, R.H. and Hall, E.O. (1965) A neutron and X-ray diffraction study of ulvöspinel, Fe2TiO4. Acta Crystallographica, 18, 857-862.
24. Fujino, K. (1974) Cation distribution and local variation of sity symmetry in solid solution series, Fe3O4-Fe2TiO4. Mineralogical Journal, 7, 472-488.
25. Gottschalk, M. (1997) Internally consistent thermodynamic data for rock-forming minerals in the system SiO2-TiO2-Al2O3-Fe2O3-CaO-MgO-FeO-K2O-Na2O- H2O-CO2. European Journal of Mineralogy, 9, 175-223.
26. Gorski, C.A. and Scherer, M.M. (2010) Determination of nanoparticulate magnetite stoichiometry by Mössbauer spectroscopy, acidic dissolution, and powder X-ray diffraction: A critical review. American Mineralogist, 95, 1017-1026.
27. Gorter, E.W. (1957) Chemistry and magnetic properties of some ferrimagnetic oxides like those occurring in nature. Advances in Physics, 6, 336-361.
28. Groenvold, F. and Sveen, A. (1974) Heat capacity and thermodynamic properties of synthetic magnetite (Fe3O4) from 300 to 1050 K. Ferrimagnetic transition and zero point entropy. Journal of Chemical Thermodynamics, 6, 859-872.
29. Hamdeh, H.H., Barghout, K., Ho, J.C., Shand, P.M., and Miller, L.L. (1999) A Mössbauer evaluation of cation distribution in titanomagnetites. Journal of Magnetism and Magnetic Materials, 191, 72-78.
30. Hemingway, B.S. (1990) Thermodynamic properties for bunsenite, NiO, magnetite, Fe3O4, and hematite, Fe2O3, with comments on selected oxygen buffer reactions. American Mineralogist, 75, 781-790.
31. Hill, R.L. and Sack, R.O. (1987) Thermodynamic properties of Fe-Mg titaniferous magnetite spinels. Canadian Mineratogist, 25, 443-464.
32. Holland, T.J.B. and Powell, R. (1998) An internally consistent thermodynamic data set for phases of petrological interest. Journal of Metamorphic Geology, 16, 309-343.
33. Ilton, E.S., Boily, J.F., Buck, E.C., Skomurski, F.N., Rosso, K.M., Cahill, C.L., Bargar, J.R., and Felmy, A.R. (2010) Influence of dynamical conditions on the reduction of U(VI) at the magnetite-solution interface. Environmental Science and Technology, 44, 170-176.
34. Itoh, S. (1999) Phase equilibria in the titanium-iron-oxygen system in the temperature range of 1173 to 1373 K. ISIJ International, 39, 1107-1115.
35. Itoh, S., Azakami, T., Kikuchi, A., and Nagasaka, T. (2003) Thermodynamic and phase diagram studies of Ti-Fe-O system. Metals, Materials and Processes, 15, 95-110.
36. Jensen, S.D. and Shive P.N. (1973) Cation distribution in sintered titanomagnetites. Journal of Geophysical Research, 78, 8474-8480.
37. Kakol, Z., Sabol, J., and Honig, J.M. (1991) Cation distribution and magnetic properties of titanomagnetites Fe3-xTixO4 (0 < x < 1). Physical Review B, 43, 649-654.
38. Kale, G.M. and Jacob, K.T. (1992) Chemical potential of oxygen for iron-rutile-ilmenite and iron-ilmenite-ulvöspinel equilibria. Metallurgical and Materials Transactions B, 23, 57-64.
39. Kawai, N. (1956) Exsolution of titanomagnetites and its effect on rock magnetism III. Proceedings of the Japanese Academy, 32, 46-68.
40. Kawai, N., Kume, S., and Sasajima, S. (1954) Magnetism of rocks and solid phase transformations in ferromagnetic minerals. Proceeding of the Imperial Academy of Japan, 30, 538-593.
41. Lagarec, K. and Rancourt, D.G. (1997) Extended Voigt-based analytic lineshape method for determining N-dimensional correlated hyperfine parameter distributions in Mössbauer spectroscopy. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 129, 266-280.
42. Levitskii, V.A., Popov, S.G., Chentsov, V.N., and Karlin, V.V. (1976) Thermodynamic properties of double oxide systems. Thermodynamic stability of ferrous oxide-titanium dioxide system compounds during their indirect reduction. Zhurnal Fizicheskoj Himii, 50, 2494-2499.
43. Lilova, K., Xu, F., Rosso, K., Pearce, C., Kamali, S., and Navrotsky, A. (2011) Oxide melt solution calorimetry of Fe2+-bearing oxides and application to the magnetite-maghemite (Fe3O4-Fe8/3O4) system. American Mineralogist, 97, 164-175.
44. Lindsley, D.H. (1981) Some experiments pertaining to the magnetite-ulvöspinel miscibility gap. American Mineralogist, 66, 759-762.
45. Linton, J., Navrotsky, A., and Fei, Y. (1998) The thermodynamics of ordered perovskites on the CaTiO3-FeTiO3 join. Physics and Chemistry of Minerals, 25, 591-596.
46. Liu, J., Pearce, C.I., Qafoku, O., Arenholz, E., Heald, S.M., and Rosso, K.M. (2012) Tc(VII) reduction kinetics by titanomagnetite (Fe3-xTixO4) nanoparticles. Geochimica et Cosmochimica Acta, in press.
47. Lykasov, A.A., Gollai, A.V., and Pavlovskaya, M.S. (2006) Phase equilibria and the thermodynamic properties of spinel solutions in the Fe-Ti-O system. Russian Journal of Physical Chemistry, 80, 1767-1769.
48. MacChesney, J.B. and Muan, A. (1959) Studies on the system iron-oxide-titanium oxide. American Mineralogist, 44, 926-945.
49. - (1961) Phase equilibria at liquidus temperatures in the system iron oxide-titanium oxide at low oxygen pressures. American Mineralogist, 46, 572-582.
50. Mackay, A.L. (1961) Topochemistry of the iron oxides and hydroxides. Reactivity of Solids: Proceeding of the 4th International Symposium, Amsterdam, 1960, 571-583.
51. Mehta, A., Leinenweber, K., Navrotsky, A., and Akaogi, M. (1994) Calorimetric study of high pressure polymorphism in FeTiO3: stability of the perovskite phase. Physics and Chemistry of Minerals, 21, 207-212.
52. Mogensen, F. (1946) A ferro-orthotitanate ore from Sodra Ulvtin. Geologisk Forening Stockholm Fdrhandlinger, 68, 578-588.
53. Navrotsky, A. (1977) Progress and new directions in high temperature calorimetry. Physics and Chemistry of Minerals, 2, 89-104.
54. - (1997) Progress and new directions in high temperature calorimetry revisited. Physics and Chemistry of Minerals, 24, 222-241.
55. Navrotsky, A. and Kleppa, O.J. (1967) Cation distributions in simple spinels. Journal of Inorganic and Nuclear Chemistry, 29, 2701-2714.
56. Néel, L. (1955) Some theoretical aspects of rock-magnetism. Advances in Physics, 54, 191-243.
57. Nishikawa, S. (1915) The structure of some crystals of the spinel group. Proceedings of the Mathematical and Physical Society of Tokyo, 8, 199-209.
58. Okudera, H., Kihara, K., and Matsumoto, T. (1996) Temperature dependence of structure parameters in natural magnetite: single crystal X-ray studies from 126 to 773 K. Acta Crystallographica, B52, 450-457.
59. O'Neill, H.St.C. and Navrotsky, A. (1984) Cation distribution and thermodynamic properties of binary solid solutions. American. Mineralogist, 69, 733-753.
60. O'Neill, H.St.C., Pownceby, M.I., and Wall, V.J. (1988) Ilmenite-rutile-iron and ulvöspinel-ilmenite-iron equilibria and the thermochemistry of ilmenite (FeTiO3) and ulvöspinel (Fe2TiO4). Geochimica et Cosmochimica Acta, 52, 2065-2072.
61. O'Reilly, W. (1984) Rock and Mineral Magnetism, 220 p. Blackie, Glasgow.
62. O'Reilly, W. and Banerjee, S.K. (1965) Cation distribution in titanomagnetites (l-x)Fe3O4-xFe2TiO4. Physics Letters, 17, 237-238.
63. Pattrick, R.A.D., Van der Laan, G., Henderson, C.M.B., Kuiper, P., Dudzik, E., and Vaughan, D.J. (2002) Cation site occupancy in spinel ferrites studied by X-ray magnetic circular dichroism: developing a method for mineralogists. European Journal of Mineralogy, 14, 1095-1102.
64. Pearce, C.I., Henderson, C.M.B., Telling, N.D., Pattrick, R.A.D., Charnock, J.M., Coker, V.S., Arenholz, E., Tuna, F., and van der Laan, G. (2010) Fe site occupancy in magnetite-ulvöspinel solid solutions: A new approach using X-ray magnetic circular dichroism. American Mineralogist, 95, 425-439.
65. Peretyazhko, T., Zachara, J.M., Heald, S.M., Jeon, B.H., Kukkadapu, R.K., Liu, C., Moore, D., and Resch, C.T. (2008) Heterogeneous reduction of Tc(VII) by Fe(II) at the solid-water interface. Geochimica et Cosmochimica Acta, 72, 1521-1539.
66. Price, G.D. (1981) Subsolidus phase relations in the titanomagnetite solid solution series. American Mineralogist, 66, 751-758.
67. Robie, R.A. and Hemingway, B.S. (1995) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 Pascals) pressure and at higher temperatures. U.S. Geological Survey Bulletin, 2131, 461 p.
68. Rossiter, M.J. and Clarke, P.T. (1965) Cation distribution in ulvöspinel Fe2TiO4. Nature, 207, 402.
69. Rumble, D. (1977) Configurational entropy of magnetite-ulvöspinel and hematiteilmenite. Carnegie Institution of Washington Year Book, 76, 581-584.
70. Sauerzapf, U., Lattard, D., Burchard, M., and Engelmann, R. (2008) The titanomagnetite-ilmenite equilibrium: new experimental data and thermooxybarometric application to the crystallization of basic to intermediate rocks. Journal of Petrology, 49, 1161-1185.
71. Schmahl, N.G., Frisch, B., and Hargarter, E. (1960) Phase relations in the Fe-Ti-O system at 1000 °C. Zeitschrift fÜr Anorganische und Allgemeine Chemie, 305, 40-54.
72. Senderov, E., Dogan, A.U., and Navrotsky, A. (1993) Nonstoichiometry of magnetite-ulvöspinel solid solution quenched from 1300 °C. American Minerologist, 78, 565-573.
73. Shomate, C.H., Naylor, B.F., and Boericke, F.S. (1946) Thermodynamic properties of ilmenite and selective reduction of iron in ilmenite. Bureau of Mines, Report of Investigations, 3864, 19 p. U.S. Department of the Interior, Washington, D.C.
74. Simons, B. and Woermann, E. (1978) Iron-titanium oxides in equilibrium with metallic iron. Contributions to Mineralogy and Petrology, 66, 81-89.
75. Stølen, S., Glöckner, R., Grønvold, F., Atake, T., and Izumisawa, S. (1996) Heat capacity and thermodynamic properties of nearly stoichiometric wustite from 13 to 450 K. American Mineralogist, 81, 973-981.
76. Sundman, B. (1991) An assessment of the iron-oxygen system. Journal of Phase Equilibria, 12, 127-140.
77. Takai, S., Akishige, Y., Kawaji, H., Atake, T., and Sawaguchi, E. (1994) Low-temperature heat capacities and Verwey transition of magnetite. Journal of Chemical Thermodynamics, 26, 1259-1266.
78. Taylor, R.W. and Schmalzriedh, H. (1964) The free energy of formation of some titanates, silicates and magnesium aluminate from measurements made with galvanic cells involving solid electrolytes. Journal of Physical Chemistry, 68, 2444-2449.
79. Trestman-Matts, A., Dorris, S.E., Kumarakrishnan, S., and Mason, T.O. (1983) Thermoelectric determination of cation distributions in Fe3O4-Fe2TiO4. Journal of the American Ceramic Society, 66, 829-834.
80. van der Laan, G. and Thole, B.T. (1991) Strong magnetic-X-ray dichroism in 2p absorption-spectra of 3d transition-metal ions. Physical Review B, 43, 13401-13411.
81. Vandenberghe, R.E. and De Grave, E. (1989) Mössbauer studies of oxidic spinels. Mössbauer Spectroscopy Applied to Inorganic Chemistry, 3, 159-182.
82. Verhoogen, J. (1962) Oxidation of iron-titanium oxides in igneous rocks. Journal of Geology, 70, 168-181.
83. Verwey, E.J.W. and de Boer, J.H. (1936) Cation arrangement in a few oxides with crystal structures of the spinel type. Recueil des Travaux Chimiques des Pays-Bas et de la Belgique, 55, 531-540.
84. Verwey, E.J.W. and Haayman, P.W. (1941) Electronic conductivity and transition point of magnetite ("Fe3O4"). Physica, 8, 979-986.
85. Vincent, E.A., Wright, J.B., Chavallier, R., and Mathieu, S. (1957) Heating experiments on some natural titaniferous magnetites. Mineralogical Magazine, 31, 624-655.
86. Wechsler, B.A., Lindsley, D.H., and Prewitt, C.T. (1984) Crystal stucture and cation distribution in titanomagnetites (Fe3-xTixO4). American Mineralogist, 69, 754-770.
87. Westrum, E.F. and Groenvold, F. (1969) Magnetite (Fe3O4) heat capacity and thermodynamic properties from 5 to 350.deg.K, low-temperature transition. Journal of Chemical Thermodynamics, 1, 543-557.
88. Xirouchakis, D. and Lindsley, D.H. (1998) Equilibria among titanite, hedenbergite, fayalite, quartz, ilmenite, and magnetite: Experiments and internally consistent thermodynamic data for titanite. American Mineralogist, 83, 712-725.
89. Yang, S.J., He, H.P., Wu, D.Q., Chen, D., Liang, X.L., Qin, Z.H., Fan, M.D., Zhu, J.X., and Yuan, P. (2009) Decolorization of methyleneblue by heterogeneousFentonreaction using Fe3?xTixO4 (0 ≤ x ≤ 0.78) at neutral pH values. Applied Catalysis B: Environmental, 89, 527-535.
90. Zachara, J.M., Heald, S.M., Jeon, B.H., Kukkadapu, R.K., Liu, C.X., McKinley, J.P., Dohnalkova, A.C., and Moore, D.A. (2007a) Reduction of pertechnetate [Tc(VII)] by aqueous Fe(II) and the nature of solid phase redox products. Geochimica et Cosmochimica Acta, 71, 2137-2157.
91. Zachara, J.M., Serne, R.J., Freshley, M., Mann, F., Anderson, F., Wood, M., Jones, T., and Myers, D. (2007b) Geochemical processes controlling migration of high level wastes in Hanford's vadose zone. Vadose Zone Journal, 6, 985-1003.