Hostname: page-component-586b7cd67f-t7fkt Total loading time: 0 Render date: 2024-11-23T02:20:32.476Z Has data issue: false hasContentIssue false
  • English
  • Français

Surface enthalpy of goethite

Published online by Cambridge University Press:  01 January 2024

Lena Mazeina  and
Alexandra Navrotsky
Lena Mazeina
Affiliation:
Thermochemistry Facility and NEAT ORU, University of California at Davis, Davis, CA 95616, USA
Alexandra Navrotsky*
Affiliation:
Thermochemistry Facility and NEAT ORU, University of California at Davis, Davis, CA 95616, USA
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

High-temperature oxide-melt solution calorimetry and acid-solution calorimetry were used to determine the heat of dissolution of synthetic goethite with particle sizes in the range 2–75 nm and measured surface areas of 30–273 m2/g (27–240 × 103 m2/mol). Sample characterization was performed using X-ray diffraction, Fourier transform infrared spectroscopy, the Brunauer, Emmett and Teller method and thermogravimetric analysis. Water content (structural plus excess water) was determined from weight loss after firing at 1100°C. Calorimetric data were corrected for excess water assuming this loosely adsorbed water has the same energetics as bulk liquid water. The enthalpy of formation was calculated from calorimetric data using enthalpies of formation of hematite and liquid water as reference phases for high-temperature oxide-melt calorimetry and using enthalpy of formation of lepidocrocite for acid-solution calorimetry. The enthalpy of formation of goethite can vary by 15–20 kJ/mol as a function of surface area. The plot of calorimetric data vs. surface area gives a surface enthalpy of 0.60±0.10 J/m2 and enthalpy of formation of goethite (with nominal composition FeOOH and surface area = 0) of −561.5±1.5 kJ/mol. This surface enthalpy of goethite, which is lower than values reported previously, clarifies previous inconsistencies between goethite-hematite equilibrium thermodynamics and observations in natural systems.

Keywords

Enthalpy of FormationGoethiteSurface Enthalpy
Type
Research Article
Information
Clays and Clay Minerals , Volume 53 , Issue 2 , April 2005 , pp. 113 - 122
Copyright
Copyright © Clay Minerals Society 2005

References

Barany, R. (1965) Heats of formation of goethite, ferrous vanadate and manganese molybdate. US Department of the Interior, Bureau of Mines, Report of Investigation 6618.Google Scholar
Brunauer, S. Emmett, P.H. and Teller, E., (1938) Adsorption of gases in multimolecular layers Journal of the American Chemical Society 60 309–319 10.1021/ja01269a023.Google Scholar
Cohen, D.R. Shen, X.C. Dunlop, A.C. and Rutherford, N.F., (1998) A comparison of selective extraction soil geochemistry and biogeochemistry in the Cobar area, New South Wales Journal of Geochemical Exploration 61 367–370 10.1016/S0375-6742(97)00052-6.Google Scholar
Cornell, R.M. and Schwertmann, U., (1996) The Iron Oxides: Structure, Properties, Reactions, Occurrence and Uses Germany VCH 573 pp.Google Scholar
Crespo, M.T. del Villar, L.P. Quejido, A.J. Sánchez, M. Cózar, J.S. and Fernández-Díaz, M., (2003) U-series in FeU-rich fracture fillings from the oxidised cap of the ‘Mina Fe’ uranium deposit (Spain): implications for processes in a radwaste repository Applied Geochemistry 18 1251–1266 10.1016/S0883-2927(02)00248-2.Google Scholar
Diakonov, I. Khodakovsky, I. Schott, J. and Sergeeva, E., (1994) Thermodynamic properties of iron oxides and hydroxides. I. Surface and bulk thermodynamic properties of goethite (α-FeOOH) up to 500 K European Journal of Mineralogy 6 967–983 10.1127/ejm/6/6/0967.Google Scholar
Dixon, J.B., (1991) Roles of clays in soils Applied Clay Science 5 489–500 10.1016/0169-1317(91)90019-6.Google Scholar
Duff, M.C. Coughlin, J.U. and Hunter, D.B., (2002) Uranium co-precipitation with iron oxide minerals Geochimica et Cosmochimica Acta 66 3533–3547 10.1016/S0016-7037(02)00953-5.Google Scholar
Ferrier, A., (1966) Influence de l’état de division de la goethite et de l’oxyde ferrique sur leurs chaleurs de réaction Revue de Chimie minérale 3 587.Google Scholar
Hiemstra, T. and Van Riemsdijk, W.H., (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model Journal of Colloid and Interface Science 179 488–508 10.1006/jcis.1996.0242.Google Scholar
Kaiser, K., (2003) Sorption of natural organic matter fractions to goethite (α-FeOOH): effect of chemical composition as revealed by liquid-state 13C NMR and wet-chemical analysis Organic Geochemistry 34 1569–1579 10.1016/S0146-6380(03)00120-7.Google Scholar
Kosmulski, M. and Maczka, E., (2004) Dilatometric study of the adsorption of heavy-metal cations on goethite Langmuir 20 2320–2323 10.1021/la0356957.Google Scholar
Kosmulski, M. Saneluta, S. and Maczka, E., (2003) Electrokinetic study of specific adsorption of cations on synthetic goethite Colloids and Surfaces A: Physicochemical and Engineering Aspects 222 119–124 10.1016/S0927-7757(03)00241-3.Google Scholar
Langmuir, D., (1971) Particle size effect on the reaction goethite = hematite + water American Journal of Science 277 788–791.Google Scholar
Lehmann, M. Zouboulis, A.I. and Matis, K.A., (2001) Modeling the sorption of metals from aqueous solutions on goethite fixed-beds Environmental Pollution 113 121–128 10.1016/S0269-7491(00)00174-3.Google Scholar
Li, P. Miser, D.E. Rabiei, S. Yadav, R.T. and Hajaligol, M.R., (2003) The removal of carbon monoxide by iron oxide nanoparticles Applied Catalysis B: Environmental 43 151–162 10.1016/S0926-3373(02)00297-7.Google Scholar
Lower, S.K. Tadanier, C.J. and Hochella, M.F., (2000) Measuring interfacial and adhesion forces between bacteria and mineral surfaces with biological force microscopy Geochimica et Cosmochimica Acta 64 3133–3139 10.1016/S0016-7037(00)00430-0.Google Scholar
Lützenkirchen, B.J. Balmès, O. Beattie, J. and Sjöberg, S., (2001) Modeling proton binding at the goethite (α-FeOOH)–water interface Colloids and Surfaces A: Physicochemical and Engineering Aspects 179 11–27 10.1016/S0927-7757(00)00712-3.Google Scholar
Majzlan, J., (2002) Thermodynamics of iron and aluminum oxides Davis, CA, USA University of California at Davis PhD dissertation.Google Scholar
Majzlan, J. Navrotsky, A. and Casey, W.H., (2000) Surface enthalpy of boehmite Clays and Clay Minerals 48 699–707 10.1346/CCMN.2000.0480611.Google Scholar
Majzlan, J. Grevel, K.D. and Navrotsky, A., (2003) Thermodynamics of iron oxides. II. Enthalpies of formation and relative stability of goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and maghemite (γ-Fe2O3) American Mineralogist 88 855–859 10.2138/am-2003-5-614.Google Scholar
Majzlan, J. Navrotsky, A. and Schwertmann, U., (2004) Thermodynamics of iron oxides: Part III. Enthalpies of formation and stability of ferrihydrite (∼Fe(OH)3), schwertmannite (∼FeO(OH)3/4(SO4)1/8), and ε-Fe2O3 Geochimica et Cosmochimica Acta 68 1049–1059 10.1016/S0016-7037(03)00371-5.Google Scholar
Manceau, A. and Charlet, L., (1994) The mechanism of selenate adsorption on goethite and hydrous ferric oxide Journal of Colloid and Interface Science 168 87–93 10.1006/jcis.1994.1396.Google Scholar
McHale, J.M. Auroux, A. Perrota, A.J. and Navrotsky, A., (1997) Surface energetics and thermodynamic phase stability in nanocrystalline aluminas Science 277 788–791 10.1126/science.277.5327.788.Google Scholar
McHale, J.M. Navrotsky, A. and Perrotta, A.J., (1997) Effects of increased surface area and chemisorbed H2O on the relative stability of nanocrystalline γ-Al2O3 and α-Al2O3 Journal of Physical Chemistry 101 603–613 10.1021/jp9627584.CrossRefGoogle Scholar
Navrotsky, A., (1997) Progress and new directions in high temperature calorimetry: revisited Physics and Chemistry of Minerals 24 222–241 10.1007/s002690050035.Google Scholar
Navrotsky, A., (2003) Energetics of nanoparticle oxides: interplay between surface energy and polymorphism Geochemical Transactions 4 34–37 10.1186/1467-4866-4-34.Google Scholar
Navrotsky, A., Schwartz-Christian, J.A. and Putyera, C.-K., (2004) Environmental nanoparticles Dekker Encyclopedia of Nanoscience and Nanotechnology New York Marcel Dekker 1147–1155.Google Scholar
Navrotsky, A. Rapp, R.P. Smelik, E. Burnley, P. Circone, S. Chai, L. and Bose, K., (1994) The behavior of H2O and CO2 in high-temperature lead borate solution calorimetry of volatile-bearing phases American Mineralogist 79 1099–1109.Google Scholar
Ottley, C.J. Davison, W. and Edmunds, W.M., (1997) Chemical catalysis of nitrate reduction by iron (II) Geochimica et Cosmochimica Acta 61 1819–1828 10.1016/S0016-7037(97)00058-6.Google Scholar
Pitcher, M.W. Ushakov, S.V. Navrotsky, A. Woodfield, B.F. Li, G. Boerio-Goates, J. and Tissue, B.M., (2005) Energy crossovers in nanocrystalline zirconia Journal of the American Ceramic Society 88 160–167 10.1111/j.1551-2916.2004.00031.x.Google Scholar
Ranade, M.R. Navrotsky, A. Zhang, H.Z. Banfield, J.F. Elder, S.H. Zaban, A. Borse, P.H. Kulkarni, S.K. Doran, G.S. and Whitfield, H.J., (2002) Energetics of nanocrystalline TiO2 Proceedings of the National Academy of Science 99 6476–6481 10.1073/pnas.251534898.Google Scholar
Robie, R.A. and Hemingway, B.S. (1995) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 pascals) and at higher temperatures. US Geological Survey Bulletin, 2131, 461 pp.Google Scholar
Schwertmann, U. and Cornell, R.M., (2000) The Iron Oxides in the Laboratory: Preparation and Characterization New York VCH 10.1002/9783527613229.Google Scholar
Sudakar, C. Subbanna, G.N. and Kutty, T.R.N., (2003) Effect of anions on the phase stability of γ-FeOOH nanoparticles and the magnetic properties of gamma-ferric oxide derived from lepidocrocite Journal of Physics and Chemistry of Solids 64 2337–2349 10.1016/S0022-3697(03)00270-1.Google Scholar
Von Gunten, H.R. Roessler, E. Lowson, R.T. Reid, P.D. and Short, S.A., (1999) Distribution of uranium- and thorium series radionuclides in mineral phases of a weathered lateritic transect of a uranium ore body Chemical Geology 160 225–240 10.1016/S0009-2541(99)00062-5.Google Scholar
Zar, J.H., (1974) Biostatistical Analysis Englewood Cliffs, New York Prentice-Hall, Inc.Google Scholar