Heat capacity of γ-Fe2SiO4 between 5 and 303 K and derived thermodynamic properties
Source abstract
Abstract
A multi-anvil device was used to synthesize 24 mg of pure γ-Fe2SiO4 crystals at 8.5 GPa and 1,273 K. The low-temperature heat capacity (Cp) of γ-Fe2SiO4 was measured between 5 and 303 K using the heat capacity option of a physical properties measurement system. The measured heat capacity data show a broad λ-transition at 11.8 K. The difference in the Cp between fayalite and γ-Fe2SiO4 is reduced as the temperature increases in the range of 50–300 K. The gap in Cp data between 300 and 350 K of γ-Fe2SiO4 is an impediment to calculation of a precise Cp equation above 298 K that can be used for phase equilibrium calculations at high temperatures and high pressures. The Cp and entropy of γ-Fe2SiO4 at standard temperature and pressure (S°298) are 131.1 ± 0.6 and 140.2 ± 0.4 J mol−1 K−1, respectively. The Gibbs free energy at standard pressure and temperature (ΔG°f,298) is calculated to be −1,369.3 ± 2.7 J mol−1 based on the new entropy data. The phase boundary for the fayalite–γ-Fe2SiO4 transition at 298 K based on current thermodynamic data is located at 2.4 ± 0.6 GPa with a slope of 25.4 bars/K, consistent with extrapolated results of previous experimental studies.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: High-pressure geophysics and materials · Crystal Structures and Properties · Geological and Geochemical Analysis
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (30)
Show source-provided references
1. Akaogi M, Ito E, Navrotsky A (1989) Olivine-modified spinel–spinel transition in the system Mg2SiO4–Fe2SiO4: calorimetric measurements, thermochemical calculation, and geophysical application. J Geophys Res 94:15671–1568510.1029/JB094iB11p15671 ↗
2. Akimoto S, Fujisawa H, Katsura T (1965) Olivine–spinel transition in Fe2SiO4 and Ni2SiO4. J Geophys Res 66:1969–197710.1029/JZ070i008p01969 ↗
3. Akimoto S, Komada E, Kushiro I (1967) Effect of pressure on the melting of olivine and spinel polymorphs of Fe2SiO4. J Geophys Res 68:679–68610.1029/JZ072i002p00679 ↗
4. Akimoto S, Matsui Y, Syono Y (1976) High-pressure crystal chemistry of orthosilicates and formation of the mantle transition zone. In: Strens RGJ (eds) The physics and chemistry of minerals and rocks. Wiley, New York, pp 327–363
5. Akimoto S, Yagi T, Inoue K (1977) High temperature–pressure phase boundaries in silicate systems using in situ X-ray diffraction. In: Manghnani MH, Akimoto S (eds) High-pressure research: application in geophysics. Academic, New York, pp 585–60210.1016/B978-0-12-468750-9.50045-0 ↗
6. Dachs E, Bertoldi C (2005) Precision and accuracy of the heat-pulse calorimetric technique: low temperature heat capacities of milligram-sized synthetic mineral samples. Eur J Mineral 17:251–25910.1127/0935-1221/2005/0017-0251 ↗
7. Dachs E, Geiger CA (2006) Heat capacities and entropies of mixing of pyrope–grossular (Mg3Al2Si3O12–Ca3Al2Si3O12) garnet solid solutions: a low-temperature calorimetric and a thermodynamic investigation. Am Mineral 91:8894–900610.2138/am.2006.2005 ↗
8. Ehrenberg H, Fuess H (1993) Analytical interpretation and simulation of the static magnetic properties of synthetic α-Fe2SiO4. J Phys Condens Matter 5:3663–367210.1088/0953-8984/5/22/017 ↗
9. Fabrichnaya O (1998) The assessment of thermodynamic parameters for solid phases in the Fe–Mg–O and Fe–Mg–Si–O systems. Calphad 22:85–12510.1016/S0364-5916(98)00016-9 ↗
10. Fei Y, Saxena SK (1986) A thermochemical data base for phase equilibria in the system Fe–Mg–Si–O at high pressure and temperature. Phys Chem Miner 13:311–32410.1007/BF00308348 ↗
11. Fei Y, Mao H, Mysen BO (1991) Experimental determination of element partitioning and calculation of phase relations in the MgO–FeO–SiO2 system at high pressure and high temperature. J Geophys Res 96:2157–216910.1029/90JB02164 ↗
12. Furnish MD, Bassett WA (1983) Investigation of the mechanism of the olivine–spinel transition in fayalite by synchrotron radiation. J Geophys Res 88:10333–1034110.1029/JB088iB12p10333 ↗
13. Gopal ESR (1966) Specific heats at low temperatures. Plenum, New York10.1007/978-1-4684-9081-7 ↗
14. Inoue K (1975) Development of high temperature and high pressure X-ray diffraction apparatus with energy dispersive technique and its geophysical applications. Ph.D. thesis, Tokyo University, Tokyo
15. Jacobs MHG, de Jong BHWS (2005) An investigation into thermodynamic consistency of data for the olivine, wadsleyite and ringwoodite form of (Mg,Fe)2SiO4. Geochim Cosmochim Acta 69:4361–437510.1016/j.gca.2005.05.002 ↗
16. Jacobs MHG, de Jong BHWS, Oonk HAJ (2001) The Gibbs energy formulation of α, γ, and liquid Fe2SiO4 using Grover, Getting and Kennedy’s empirical relation between volume and bulk modulus. Geochim Cosmochim Acta 65:4231–424210.1016/S0016-7037(01)00694-9 ↗
17. Kudoh Y, Takeda H (1986) Single crystal X-ray diffraction study on the bond compressibility of fayalite, Fe2SiO4 and rutile, TiO2 under high pressure. Physica B 139–140:333–33610.1016/0378-4363(86)90591-7 ↗
18. Lashley JC, Hundley MF, Migliori A, Sarrao JL, Pagliuso PG, Darling TW, Jaime M, Cooley JC, Hults WL, Morales L, Thoma DJ, Smith JL, Boerio-Goates J, Woodfield BF, Stewart GR, Fisher RA, Phillips NE (2003) Critical examination of heat capacity measurements made on a quantum design physical property measurement system. Cryogenics 43:369–37810.1016/S0011-2275(03)00092-4 ↗
19. Marumo F, Isobe M, Akimoto S (1977) Electron-density distributions in crystals of γ-Fe2SiO4 and γ-Co2SiO4. Acta Crystallogr B 33:713–71610.1107/S0567740877004531 ↗
20. Robie RA, Hemingway BS (1972) Calorimeters for heat of solution and low-temperature heat capacity measurement. U.S. Geol Surv Prof Paper 755, 32 pp10.3133/pp755 ↗
21. Robie RA, Hemingway BS (1995) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 Pascals) pressure and at higher temperatures. US Geol Surv Bull 2131:461
22. Robie RA, Finch CB, Hemingway BS (1982) Heat capacity and entropy of fayalite (Fe2SiO4) between 5.1 and 383 K: comparison of calorimetric and equilibrium values of the QFM buffer reaction. Am Mineral 67:463–469
23. Santoro RP, Newnham RE, Nomura S (1966) Magnetic properties of Mn2SiO4 and Fe2SiO4. J Phys Chem Solids 27:655–66610.1016/0022-3697(66)90216-2 ↗
24. Sato Y (1977) Equation of state of mantle minerals determined through high-pressure X-ray study. In: Manghnani MH, Akimoto S (eds) High-pressure research: application in geophysics. Academic, New York, pp 307–32310.1016/B978-0-12-468750-9.50028-0 ↗
25. Sung CM, Burns RG (1976) Kinetics of high-pressure phase transformations: implications to the evolution of the olivine–spinel transition in the downgoing lithosphere and its consequences on the dynamics of the mantle. Tectonophysics 31:1–3210.1016/0040-1951(76)90165-7 ↗
26. Watanabe H (1982) Thermochemical properties of synthetic high-pressure compounds relevant to the earth’s mantle. In: Manghnani MH, Akimoto S (eds) High-pressure research in geophysics. Center for Academic Publications, Japan, pp 441–46410.1007/978-94-009-7867-6_34 ↗
27. Xie ZD, Sharp TG (2004) High-pressure phases in shock-induced melt veins of the Umbarger L6 chondrite: constraints of shock pressure. Meteorit Planet Sci 39:2043–205410.1111/j.1945-5100.2004.tb00095.x ↗
28. Xie ZD, Tomioka N, Sharp TG (2002) Natural occurrence of Fe2SiO4–spinel in the shocked Umbarger L6 chondrite. Am Mineral 87:1257–126010.2138/am-2002-8-926 ↗
29. Yagi T, Akaogi M, Shimomura O, Suzuki T, Akimoto S (1987) In situ observation of the olivine–spinel phase transition in Fe2SiO4 using synchrotron radiation. J Geophys Res 92:6207–621310.1029/JB092iB07p06207 ↗
30. Yong W, Dachs E, Withers AC, Essene EJ (2006) Heat capacity and phase equilibria of hollandite polymorph of KAlSi3O8. Phys Chem Miner 33:167–17710.1007/s00269-006-0063-4 ↗