Abstract
The paper reports results of an experimental thermochemical study (in a heat-flux Tian-Calvet microcalorimeter) of montmorillonite from (I) the Taganskoe and (II) Askanskoe deposits and (III) from the caldera of Uzon volcano, Kamchatka. The enthalpy of formation Δ f H 0el (298.15 K) of dehydrated hydroxyl-bearing montmorillonite was determined by melt solution calorimetry: −5677.6 ± 7.6 kJ/mol for Na0.3Ca0.1(Mg0.4Al1.6)[Si3.9Al0.1O10](OH)2 (I), −5614.3 ± 7.0 kJ/mol for Na0.4K0.1(Ca0.1Mg0.3Al1.5Fe 3+0.1 )[Si3.9Al0.1O10](OH)2 (II), −5719 ± 11 kJ/mol for K0.1Ca0.2Mg0.2(Mg0.6Al1.3Fe 3+0.1 ) [Si3.7Al0.3O10](OH)2 (III), and −6454 ± 11 kJ/mol for water-bearing montmorillonite (I) Na0.3Ca0.1(Mg0.4Al1.6)[Si3.9Al0.1O10](OH)2 · 2.6H2O. The paper reports estimated enthalpy of formation for the smectite end members of the theoretical composition of K-, Na-, Mg-, and Ca-montmorillonite and experimental data on the enthalpy of dehydration (14 ± 2 kJ per mole of H2O) and dehydroxylation (166 ± 10 kJ per mole of H2O) for Na-montmorillonite.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Minerals, Ed. by F. V. Chukhrov (Nauka, Moscow, 1992), Vol. 4 [in Russian].
M. Kawano and K. Tomita, “X-ray Studies of Rehydratation Behaviors for Montmorillonite,” Clay Sci. 7(5), 277–287 (1989).
A. F. van Groos and S. Guggenheim, “Dehydratation of K-Exchanged Montmorillonite at Elevated Temperatures and Pressure,” Clays Clay Miner. 34(3), 281–286 (1986).
A. F. van Groos and S. Guggenheim, “Dehydroxylation of Ca- and Mg-Exchanged Montmorillonite,” Am. Mineral. 74, 627–636 (1989).
G. Dios Cancela, F. J. Huertas, E. Romero Taboada, F. Sanches-Rasero, A. Hernadez Laguna, “Adsorption of Water Vapor by Homoionic Montmorillonites: Heats of Adsorption and Desorption,” J. Colloid. Int. Sci. 185, 343–354 (1997).
M. Sakizci, B. E. Alver, O. Alver, and E. Yorukogullari, “Spectroscopic and Thermal Studies of Bentonites from Unye, Turkey,” J. Mol. Struct. 969, 187–191 (2010).
H. Gailhanou, J. C. Miltenburg, J. Roges, J. Olives, M. Amouric, E. C. Gaucher, and P. Blanc, “Thermodynamic Properties of Anhydrous Smectite MX-80, Illite IMt-2 and Mixed-Layer Illite-Smectite ISCz-1 as Determined by Calorimetric Methods. Part I: Heat Capacities, Heat Contents, and Entropies,” Geochim. Cosmochim. Acta 71, 5463–5473 (2007).
P. Vieillard, “A New Method for the Prediction of Gibbs Free Energies of Formation of Hydrated Clay Minerals Based on the Electronegativity Scale,” Clays Clay Miner. 48(4), 459–473 (2000).
O. Vidal and B. Dubacq, “Thermodynamic Modeling of Clay Dehydration, Stability and Compositional Evolution with Temperature, Pressure, and H2O Activity,” Geochim. Cosmochim. Acta 73, 6544–6564 (2009).
H. W. van der Marel and H. Beutelspacher, Atlas of Infrared Spectroscopy of Clay Minerals and Their Admixtures (Elsevier, Amsterdam-Oxford-New York, 1976).
J. Modejova and P. Komadel, “Baseline Studies of the Clay Minerals Society Source Clays: Infrared Methods,” Clays Clay Miner. 49(5), 410–432 (2001).
J. Modejova and P. Komadel, “Information Available from Infrared Spectra of the Fine Fractions of Bentonites,” in The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides, Ed. by J. Theo Cloprogge, CMS Workshop Lectures, 13, 65–98 (2005).
V. C. Farmer and J. D. Russell, “The Infra-Red Spectra of Layer Silicates,” Spectrochim. Acta 20, 1149–1173 (1964).
I. A. Kiseleva, L. P. Ogorodova, N. D. Topor, and O. G. Chigareva, “Thermochemical Study of the CaO-MgO-SiO2 System,” Geokhimiya, No. 12, 1811–1825 (1979).
R. A. Robie and B. S. Hemingway, “Thermodynamic Properties of Minerals and Related Substances at 298.15 K and 1 bar (105 Pascals) Pressure and at Higher Temperatures,” U.S. Geol. Surv. Bull., No. 2131, (1995).
M. V. Eirish, Z. N. Eirish, V. M. Bezzubov, N. V. Evdokimova, and E. N. Permyakov, “Crystal Chemical and Structural Features of Montmorillonite and Their Influence on the Properties of Bentonite Clays,” in Bentonites (Nauka, Moscow, 1980) [in Russian].
M. V. Eirish and A. A. Dvorechenskaya, NGR Spectroscopic Study of the Setting and Role of Fe3+ Ions in the Structure of Clay Minerals: A Change in the State of Fe3+ Ions during the Dehydration and Dehydroxilation of Montmorillonite, Geokhimiya, No. 4, 597–605 (1976).
M. Onal and Y. Sarikaya, “Thermal Behavior of a Bentonite,” J. Therm. Anal. Calorim. 90, 167–172 (2007).
I. A. Kiseleva, A. Navrotsky, I. A. Belitsky, and B. A. Fursenko, “Thermochemical Study of Calcium Zeolites-Heulandite and Stilite,” Am. Mineral. 86, 448–455 (2001).
A. Navrotsky and W. J. Coons, “Thermochemistry of Some Pyroxenes and Related Compounds,” Geochim. Cosmochim. Acta. 40, 1281–1295 (1976).
I. A. Kiseleva, “Thermodynamic Properties and Stability of Pyrope,” Geokhimiya, No. 6, 845–854 (1976).
L. P. Ogorodova, L. V. Melchakova, I. A. Kiseleva, and I. A. Belitsky, “Thermochemical Study of Natural Pollucite,” Thermochim. Acta 403 251–256 (2003).
L. P. Ogorodova, I. A. Kiseleva, L. V. Mel’chakova, M. F. Vigasina, and E. M. Spiridonov, “Calorimetric Determination of the Enthalpy of Formation of Pyrophyllite” Russ. J. Phys. Chem. 85(9), 1492–1494 (2011).
H. Gailhanou, Determination Eperimentale des Proprietes Thermodynamiques et Etude des Nanostructures de Mineraux Argileux, These de Docteaur (Universite aix Marseilles, 2005).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © L.P. Ogorodova, I.A. Kiseleva, L.V. Melchakova, M.F. Vigasina, V.V. Krupskaya, 2013, published in Geokhimiya, 2013, Vol. 51, No. 6, pp. 541–551.
Rights and permissions
About this article
Cite this article
Ogorodova, L.P., Kiseleva, I.A., Melchakova, L.V. et al. Thermochemical study of natural montmorillonite. Geochem. Int. 51, 484–494 (2013). https://doi.org/10.1134/S0016702913040058
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0016702913040058