Hostname: page-component-848d4c4894-pjpqr Total loading time: 0 Render date: 2024-06-27T19:43:55.442Z Has data issue: false hasContentIssue false

The nature of structure-bonded H2O in illite and leucophyllite from dehydration and dehydroxylation experiments

Published online by Cambridge University Press:  01 January 2024

Victor A. Drits
Affiliation:
Geological Institute of the Russian Academy of Science, Pyzevskij per. D.7, 109017 Moscow, Russia
Douglas K. McCarty*
Affiliation:
Chevron ETC, 3901 Briarpark, Houston, TX, 77063, USA
*
*E-mail address of corresponding author: dmccarty@chevron.com

Abstract

Thermogravimetric analysis combined with mass spectrometry was used to study H2O bound to samples of illite-1M, illite-2M2 and leucophyllite-1M. Samples were heated in a helium atmosphere at different temperatures and after heating at each given temperature were cooled to 35°C. Each cycle in the mass 18 spectrum of each illite sample contains a low-temperature peak at 60–80°C, a medium-temperature peak at 340–360°C, and a high-temperature peak at a temperature that is very close to the maximum temperature of sample heating of a given cycle. Within each heating-cooling cycle, the sample weight at the beginning of cooling is lower than that at the end of the same cooling stage because of H2O resorption. However, the number of H2O molecules released during each medium-temperature heating cycle is equal to the number of H2O molecules resorbed during the corresponding cooling stages.

The weight losses, under medium-temperature heating, of the illite samples are related to dehydration when H2O molecules located in K-free sites of the illite interlayers are removed. The medium-temperature peak is reproducible for each cycle because during each cooling stage the illite interlayers resorb the same number of H2O molecules that were lost during the preceding dehydration.

Two distinct features are characteristic of leucophyllite during heating-cooling treatments. First, the number of H2O molecules resorbed during cooling is significantly greater than the number of H2O molecules lost during dehydration. Second, the medium-temperature peaks in the spectrum appear only in the last five cycles and the maximum-peak temperature is 450–460°C. These data indicate that the heating-cooling treatments are accompanied by partial rehydroxylation. This rehydroxylation occurs during each coolingstage when a small number of resorbed H2O molecules are trapped in the interlayers, although most migrate into the octahedral sheet of the 2:1 layers and reform as OH groups. The crystal chemical factors responsible for the dehydration and rehydration as well as for the rehydroxylation reactions are discussed and speculation about the origin of the low- and medium-temperature H2O losses is presented.

Type
Research Article
Copyright
Copyright © 2007, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bailey, S.W. and Bailey, S.W., (1984) Crystal chemistry of the true micas Micas Washington, D.C Mineralogical Society of America 1360 10.1515/9781501508820-006.CrossRefGoogle Scholar
Besson, G. and Drits, V.A., (1997) Refined relationships between chemical composition of dioctahedral fine-grained mica minerals and their infrared spectra within the OH stretching region. Part I: Identification of the OH stretching bands Clays and Clay Minerals 45 158169 10.1346/CCMN.1997.0450204.CrossRefGoogle Scholar
Bish, D.L. Duffy, C.J., Stucki, J.W. Bish, D.L. and Mumpton, F.A., (1990) Thermogravimetric analysis of minerals Thermal Analysis in Clay Science Bloomington, Indiana The Clay Minerals Society 95157.Google Scholar
Drits, V.A., (2003) Structural and chemical heterogeneity of layer silicates and clay minerals Clay Minerals 38 403432 10.1180/0009855033840106.CrossRefGoogle Scholar
Drits, V.A. Besson, G. and Muller, F., (1995) Structural mechanism of dehydroxylation of cis-vacant 2:1 layer silicates Clays and Clay Minerals 43 718731 10.1346/CCMN.1995.0430608.CrossRefGoogle Scholar
Drits, V.A. Środoń, J. and Eberl, D.D., (1997) XRD measurement of mean crystallite thickness of illite and illite/smectite: Reappraisal of the Kübler index and the Scherrer equation Clays and Clay Minerals 45 461475 10.1346/CCMN.1997.0450315.CrossRefGoogle Scholar
Emmerich, K. Madsen, F.T. and Kahr, G., (1999) Dehydroxylation behavior of heat-treated and steam-treated homoionic cis-vacant montmorillonites Clays and Clay Minerals 47 591604 10.1346/CCMN.1999.0470506.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Malikova, N. Plançon, A. Sakharov, B.A. and Drits, V.A., (2005) News insights in the distribution of interlayer H2O molecules in bi-hydrated smectite from X-ray diffraction profile modelingof 00l reflections Chemistry of Materials 17 34993512 10.1021/cm047995v.CrossRefGoogle Scholar
Grim, R.E. (1968) Clay Mineralogy: International Series in the Earth and Planetary Sciences (Press, F., editor). McGraw-Hill Book Company, New York, 596 pp.Google Scholar
Guggenheim, S., Farmer, V.C. and Tardy, Y., (1990) The dynamics of thermal decomposition in aluminous dioctahedral 2:1 layer silicates: A crystal chemical model Proceedings of the 9th International Clay Conference, Vol. 2: Surface chemistry, structure and mixed layering of clays France Strasbourg 99107.Google Scholar
Guggenheim, S. Chang, H.Y. and Koster van Groos, A.F., (1987) Muscovite dehydroxylation: High-temperature studies American Mineralogist 72 537550.Google Scholar
Güven, N., (2001) Mica structure and fibrous growth of illite Clays and Clay Minerals 49 189196 10.1346/CCMN.2001.0490301.CrossRefGoogle Scholar
Heller, L. Farmer, V.C. Mackenzie, R.C. Mitchell, B.D. and Taylor, H.F.W., (1962) The dehydroxylation and rehydroxylation of triphormic dioctahedral clay minerals Clay Minerals Bulletin 5 5672 10.1180/claymin.1962.005.28.02.CrossRefGoogle Scholar
Heller-Kallai, L. and Rozenson, I., (1980) Dehydroxylation of dioctahedral phyllosilicates Clays and Clay Minerals 28 355368 10.1346/CCMN.1980.0280505.CrossRefGoogle Scholar
Hower, Y. and Mowatt, G.S., (1966) The mineralogy of illites and mixed-layer illite-montmorillonites American Mineralogist 5 825854.Google Scholar
Jonas, E.C. (1955) Clays and Clay Minerals (Swineford, A., editor). National Academy of Sciences — National Resource Council, Washington, publication 395, p. 66.Google Scholar
Jonas, E.C. Grim, R.E. and MacKenzie, R.C., (1957) Differential thermal analysis usingcontrolled atmosphere The Differential Thermal Investigation of Clays London Mineralogical Society 389403.Google Scholar
Koster van Groos, A.F. and Guggenheim, S., (1987) High-pressure differential thermal analysis (HP-DTA) of the dehydroxylation of Na-rich montmorillonite and K-exchanged montmorillonite American Mineralogist 72 11701175.Google Scholar
van Koster Groos, A.F. and Guggenheim, S., (1990) Dehydroxylation of Ca- and Mg-exchanged montmorillonite American Mineralogist 74 627636.Google Scholar
Mackenzie, R.C., (1957) The Differential Thermal Investigation of Clays London Mineralogical Society 456 pp.Google Scholar
Mackenzie, R.C. and Miller, B., (1982) Down-to-earth thermal analysis Thermal Analysis Chichester, UK Wiley Heyden Ltd 2536.Google Scholar
Mackenzie, R.C. Walker, G.F. and Hart, R., (1949) Illite from Ballater Mineralogical Magazine 28 704713 10.1180/minmag.1949.28.206.06.CrossRefGoogle Scholar
McCarty, D.K. and Reynolds, R.C., (2001) Three-dimensional crystal structures of illite-smectite minerals in Paleozoic K-bentonites from the Appalachian Basin Clays and Clay Minerals 49 2435 10.1346/CCMN.2001.0490102.CrossRefGoogle Scholar
Muller, F. Drits, V.A. Plançon, A. and Besson, G., (2000) Dehydroxylation of Fe3+, Mg-rich dioctahedral micas: (I) structural transformation Clay Minerals 35 491504 10.1180/000985500546963.CrossRefGoogle Scholar
Muller, F. Drits, V.A. Tsipursky, S.I. and Plançon, A., (2000) Dehydroxylation of Fe3+, Mg-rich dioctahedral micas: (II) cation migration Clay Minerals 35 505514 10.1180/000985500546972.CrossRefGoogle Scholar
Muller, F. Drits, V.A. Plançon, A. and Robert, J.P., (2000) Structural transformation of 2:1 dioctahedral layer silicates during dehydroxylation-rehydroxylation reactions Clays and Clay Minerals 48 572585 10.1346/CCMN.2000.0480510.CrossRefGoogle Scholar
Slonimskaya, M.V. Drits, V.A. Finko, V.I. and Salyn, A.L., (1978) The nature of interlayer water in fine-dispersed muscovites Izvestiya Akademii Nauk SSSR, seriya geologicheskaya 10 95104 (in Russian).Google Scholar
Sokolova, T.N. Drits, V.A. Sokolova, A.L. and Stepanova, K.A., (1976) Structural and mineralogical characteristics and formation conditions of leucophyllite from salt deposits Litologiya I poleznie iscopaemie 26 8095 (in Russian).Google Scholar
Środoń, J. Elsass, F. McHardy, W.J. and Morgan, D.J., (1992) Chemistry of illite-smectite inferred from TEM measurements of fundamental particles Clay Minerals 27 137158 10.1180/claymin.1992.027.2.01.CrossRefGoogle Scholar
Tsipursky, S.I., Kameneva, M.Y. and Drits, V.A. (1985) Structural transformation of Fe3+-containing 2:1 dioctahedral phyllosilicates in the course of dehydration. 5thMeeting of the European Clay Groups (Konta, J., editor) Prague, pp. 569577.Google Scholar
Udagawa, S. Urabe, K. and Hasu, H., (1974) The crystal structure of muscovite dehydroxylate Japanese Association of Mineralogy, Petroleum and Economic Geology 69 381389 10.2465/ganko1941.69.381.CrossRefGoogle Scholar
Wardle, R. and Brindley, G.W., (1972) The crystal structures of pyrophyllite-1Tc and of its dehydroxylate American Mineralogist 57 732750.Google Scholar