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Kinetics of Desorption of Water, Ethanol, Ethyl Acetate, and Toluene from a Montmorillonite

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Clays and Clay Minerals

Abstract

Desorption processes of low-molecular-weight compounds from the surface of smectites into the gas phase determine a number of processes, e.g. those involved in drug delivery and the release of herbicides. The desorption has not been investigated thoroughly and is not well understood. The present study was undertaken in order to understand better the factors influencing these desorption mechanisms. Starting with a very pure standard (Na+-rich) montmorillonite (Kunipia-F), which was exchanged against cations with different hydration properties (Ca2+, Li+, phenyltrimethylammonium, hexyltrimethyl-ammonium), the experiments explored the rate of desorption of volatiles with different chemical functionalities (water, ethanol, ethyl acetate, and toluene). The desorption was monitored by thermogravimetry and differential scanning calorimetry under isothermal conditions, and by ramping the temperature at a constant rate. The experiments were compared with numerical calculations based on finite-element methods and with analytical models. These data point to a two-step mechanism where the desorption follows the curve of the equilibrium desorption isotherms of those molecules on the montmorillonite. The bulk-like volatiles (i.e. volatiles with release kinetics close to that of the bulk liquids) were desorbed in a first step. With a decrease in the degree of coverage of the volatile on the montmorillonite, the desorption was increasingly dominated by the strength of interaction between the volatile and the interlayer cations of the montmorillonite.

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References

  • Altshuller, A.P. and Cohen, I.R. (1960) Application of diffusion cells to the production of known concentrations of gaseous hydrocarbons. Analytical Chemistry, 32, 802–810

    Google Scholar 

  • Ambrose, D. and Sprake, C.H.S. (1970) Thermodynamic properties of organic oxygen compounds. XXV. Vapor pressures and normal boiling temperatures of aliphatic alcohols. Journal of Chemical Thermodynamics, 2, 631–645

    Google Scholar 

  • Arnikar, H.J., Rao, T.S., and Karmarkar, K.H. (1967) Electrodeless discharge as detector in gas chromatography III. Study of inter-diffusion of gases. International Journal of Electronics, 22, 381–385.

    Google Scholar 

  • Arocha, M.A., Jackman, A.P., and McCoy, B.J. (1996) Adsorption kinetics of toluene on soil agglomerates: Soil as a biporous sorbent. Environmental Science & Technology, 30, 1500–1507.

    Google Scholar 

  • Bérend, I., Cases, J.M., François, M., Uriot, J.P., Michot, L., Masion, A., and Thomas, F. (1995) Mechanism of adsorption and desorption of water vapor by homoionic montmorillonites: 2. The Li+, Na+, K+, Rb+, and Cs+-exchanged forms. Clays and Clay Minerals, 43, 324–336.

    Google Scholar 

  • Besley, L.M. and Bottomley, G.A. (1974) Vapour pressure of toluene from 273.15 to 298.15 K. Journal of Chemical Thermodynamics, 6, 577–580.

    Google Scholar 

  • Bharadwaj, R.K. (2001) Modeling the barrier properties of polymer-layered silicate nanocomposites. Macromolecules, 34, 9189–9192.

    Google Scholar 

  • Boek, E.S., Coveney, P.V., and Skipper, N.T. (1995) Monte Carlo molecular modeling studies of hydrated Li-, Na-, and K-smectites: Understanding the role of potassium as a clay swelling inhibitor. Journal of the American Chemical Society, 117, 12608–12607.

  • Bourg, I.C., Sposito, G., and Bourg, A.CM. (2006) Tracer diffusion in compacted, water-saturated bentonite. Clays and Clay Minerals, 54, 363–374.

    Google Scholar 

  • Bray, H.J. and Redfern, S.A.T. (1999) Kinetics of dehydration of Ca-montmorillonite. Physics and Chemistry of Minerals, 26, 591–600.

    Google Scholar 

  • Bridgeman, O.C. and Aldrich, E.W. (1964) Vapor pressure tables for water. Journal of Heat Transfer, 86, 279–286.

    Google Scholar 

  • Cases, J.M., Bérend, I., François, M., Uriot, J.P., Michot, L.J., and Thomas, F. (1997) Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite; 3. The Mg2+, Ca2+, and Ba3+ exchanged forms. Clays and Clay Minerals, 45, 8–22.

    Google Scholar 

  • Cebula, D.J., Thomas, R.K., and White, J.W. (1981) Diffusion of water in Li-montmorillonite studied by quasielastic neutron scattering. Clays and Clay Minerals, 29, 241–248.

    Google Scholar 

  • Chang, F.-R.C., Skipper, N.T., and Sposito, G. (1995) Computer simulation of interlayer molecular structure in sodium montmorillonite hydrates. Langmuir, 11, 2734–2741.

    Google Scholar 

  • Chang, M.-L., Wu, S.-C., Chen P.-J., and Cheng, S.-C. (2003) Infrared investigation of the sequestration of toluene vapor on clay minerals. Environmental Toxicology and Chemistry, 22, 1956–1962.

    Google Scholar 

  • Clausen, P., Andreoni, W., Curioni, A., and Hughes, E., (2009a) Adsorption of low-molecular-weight molecules on a dry clay surface: An ab initio study. Journal of Physical Chemistry C, 113, 12293–12300.

    Google Scholar 

  • Clausen, P., Signorelli, M., Schreiber, A., Hughes, E., Plummer, J.G.P., Fessas, D., Schiraldi, A., and Månson, E.J.A. (2009b) Equilibrium desorption isotherms of water, ethanol, ethyl acetate, and toluene on a sodium smectite clay. Journal of Thermal Analysis and Calorimetry, 98, 833–841.

    Google Scholar 

  • Clausen, P., Watzke, B., Hughes, E., Plummer, J.G.P., and Månson, E.J.A. (2011) Evaporation kinetics of volatile liquids and release kinetics of water from a smectite clay: Comparison between experiments and finite element calculations. International Journal of Engineering Science, 49, 1125–1140.

    Google Scholar 

  • Crider, W.L. (1956) The use of diffusion coefficients in the measurement of vapour pressure. Journal of the American Chemical Society, 78, 924–925.

    Google Scholar 

  • Duval, F.P., Porion, P., Faugere, A.-M., and Van Damme, H. (1999) Microscale and macroscale diffusion of water in colloidal gels. A pulsed field gradient and NMR imaging investigation. Journal of Physical Chemistry, 103, 5730–5735.

    Google Scholar 

  • El-Nokaly, M.A., Piatt, D.M., and Charpentier, B.A. (1993) Polymeric Delivery Systems: Properties and Applications. ACS Symposium Series, American Chemical Society.

    Google Scholar 

  • Fairbanks, D.F. and Wilke, C.R. (1950) Diffusion coefficients in multicomponent gas mixtures. Industrial and Engineering Chemistry, 42, 471–475.

    Google Scholar 

  • Ferrage, E., Lanson, B., Sakharov, B.A., and Drits, V.A. (2005) Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties. American Mineralogist, 90, 1358–1374.

    Google Scholar 

  • Frezzotti, A., Gibelli, L., and Lorenzani, S. (2005) Mean field kinetic theory description of evaporation of a fluid into vacuum. Physics of Fluids, 17, 012102, (doi: 10.1063/1.1824111).

    Google Scholar 

  • Fujii, N., Ichikawa, Y., Katsuyuki, K., Suzuki, S., and Kitayama, K. (2003) Micro-structure of bentonite clay and diffusion coefficient given by multiscale homogeneization analysis. Materials Science Research International, 9, 117–124

    Google Scholar 

  • Gilliland, E.R. (1934) Diffusion coefficients in gaseous systems. Industrial and Engineering Chemistry, 26, 681–685

    Google Scholar 

  • Girard, F., Antoni, M., Faure, S., and Steinchen, A. (2006) Evaporation and marangoni driven convection in small heated water droplets. Langmuir, 22, 11085–11091.

    Google Scholar 

  • Grismer, M.E. (1987a) Kinetics of water vapor adsorption on soils. Soil Science, 143, 367–371.

    Google Scholar 

  • Grismer, M.E. (1987b) Vapor adsorption kinetics and vapor diffusivity. Soil Science, 144, 1–5.

    Google Scholar 

  • Hendricks, S.B., Nelson, R.A., and Alexandre, M. (1940) Hydration mechanism of the clay mineral montmorillonite saturated with various cations. Journal of the American Chemical Society, 62, 1457–1464.

    Google Scholar 

  • Hensen, E.J.M. and Smit, B. (2002) Why clays swell. Journal of Physical Chemistry B, 106, 12664–12667.

    Google Scholar 

  • Hippenmeyer, B. (1949) Die Diffusion von Wasserdampf in Wasserstoff, Stickstoff und deren Gemischen. Angewandte Physik, 1, 549–557.

    Google Scholar 

  • Ibrahim, S.H. and Kuloor, N.R. (1961) Diffusion in binary gas system. British Chemical Engineering, 6, 862–863.

    Google Scholar 

  • Keyes, B.R. and Silicox, G.D. (1994) Fundamental study of the thermal desorption of toluene from montmorillonite clay particles. Environmental Science & Technology, 28, 840–849.

    Google Scholar 

  • Kraehenbuehl, F., Stoeckli, H.F., Brunner, F., Kahr, G., and Müller-Vonmoos, M. (1987) Study of the water-bentonite-system by vapour adsorption, immersion calorimetry and X-ray techniques, I. Micropore volumes and internal surface areas, following Dubinin’s theory. Clay Minerals, 22, 1–9.

    Google Scholar 

  • Kretschmer, C.B. and Wiebe, R. (1949) Li quid-vapor equilibrium of ethanol-toluene solutions. Journal of the American Chemical Society, 71, 1793–1797.

    Google Scholar 

  • Landau, L.D. and Lifschitz, E.M. (1987) Fluid Mechanics. 2nd edition, Pergamon Press, Oxford, UK.

    Google Scholar 

  • Lugg, G.A. (1968) Diffusion coefficients of some organic and other vapors in air. Analytical Chemistry, 40, 1072–1077.

    Google Scholar 

  • Lusti, H.R., Gusev, A.A., and Guseva, O. (2004) The influence of platelet disorientation on the barrier properties of composites: a numerical study. Modelling and Simulation in Materials Science and Engineering, 12, 1201–1207.

    Google Scholar 

  • Malikova, N., Cadene, A., and Marry, V. (2006) Diffusion of water in clays on the microscopic scale: modeling and experiment. Journal of Physical Chemistry B, 110, 3206–3214.

    Google Scholar 

  • Marry, V., Malikova, N., Cadène, A., Dubois, E., Durand-Vidal, A., Turq, P., Breu, J., Longeville, S., and Zanotti, J.-M. (2008) Water diffusion in a synthetic hectorite by neutron scattering—beyond the isotropic translation model. Journal of Physics: Condensed Matter, 20, 104205–104215.

    Google Scholar 

  • Mato, F. and Cimavilla, J.M. (1983) Determinacion de coeficientes binarios de difusion en fase gaseosa mediante el metodo experimental de Stefan. Anales De Quimica, 79, 445–448.

    Google Scholar 

  • Meier, L.P. and Kahr, G. (1999) Determination of the cation exchange capacity (CEC) of clay minerals using the complexes of copper(II) ions with triethylenetetramine and tetraethylenepentamine. Clays and Clay Minerals, 47, 386–388.

    Google Scholar 

  • Michot, L.J., Bihannic, I., Pelletier, M., Rinnert, E., and Robert, J.-L. (2005) Hydration and swelling of synthetic Nasaponites: Influence of layer charge. American Mineralogist, 90, 166–172.

    Google Scholar 

  • Morodome, S. and Kawamura, K. (2009) Swelling behavior of Na- and Ca-montmorillonite up to 150ºC by in situ X-ray diffraction experiments. Clays and Clay Minerals, 57, 150–160.

    Google Scholar 

  • Morrissey, FA. and Grismer, M.E. (1999) Kinetics of volatile organic compound sorption/desorption on clay minerals. Journal of Contaminant Hydrology, 36, 291–312.

    Google Scholar 

  • Nagata, I. and Hasegawa, T. (1970) Gaseous interdiffusion coefficients. Journal of Chemical Engineering of Japan, 3, 143–145.

    Google Scholar 

  • Nakashima, Y. (2000a) Effects of clay fraction and temperature on the H2O self-diffusivity in hectorite gel: A pulsed-field-gradient spin-echo nuclear magnetic resonance study. Clays and Clay Minerals, 48, 603–609.

    Google Scholar 

  • Nakashima, Y. (2000b) Pulsed field gradient proton NMR study of the self-diffusion of H2O in montmorillonite gel: effects of temperature and water fraction. American Mineralogist, 85, 132–138.

    Google Scholar 

  • Nakashima, Y. (2002) Diffusion of H2O and I- in expandable mica and montmorillonite gels: contribution of bound H2O. Clays and Clay Minerals, 50, 1–10.

    Google Scholar 

  • Nakashima, Y. (2003) Diffusion of H2O in smectite gels: obstruction effects of bound H2O layers. Clays and Clay Minerals, 51, 9–22.

    Google Scholar 

  • Nakashima, Y. (2006) H2O self-diffusion coefficient of water rich MX-80 bentonite gels. Clay Minerals, 41, 659–668.

    Google Scholar 

  • Navier, C.L.M.H. (1822) Mémoire sur les lois du mouvement des fluides. Mémoires de lAcadémie des Sciences de l’Institut de France, 6, 389–440.

    Google Scholar 

  • Nelson, E.T. (1956) The measurement of vapour diffusivities in coal-gas and some common gases. Journal of Applied Chemistry, 6, 286–292.

    Google Scholar 

  • Norrish, K. (1954) The swelling of montmorillonite. Discussions of the Faraday Society, 18, 120–134.

    Google Scholar 

  • O’Connell, J.P., Gillespie, M.D., Krostek, W.D., and Prausnitz, J.M. (1969) Diffusivities of water in nonpolar gases. Journal of Chemical Physics, 73, 2000–2004.

    Google Scholar 

  • Ochs, M., Lothenbach, B., Shibata, M., and Mikazu, Y. (2004) Thermodynamic modeling and sensitivity analysis of porewater chemistry in compacted bentonite. Physics and Chemistry of the Earth, 29, 129–136.

    Google Scholar 

  • Poinsignon, J., Estrade-Szwarckopf, H., Conard, J., and Dianoux, A.J. (1989) Structure and dynamics of intercalated water in clay minerals. Physica B: Physics of Condensed Matter, 156-157, 140–144.

    Google Scholar 

  • Polak, J. and Mertl, I. (1965) Saturated vapour pressure of methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, and ethyl propionate. Collection of Czechoslovak Chemical Communications, 30, 3526–3528.

    Google Scholar 

  • Polubesova, T., Rytwo, G., Nir, S., Serban, C., and Margulies, L. (1997) Adsorption of benzyltrimethylammonium and benzyltriethylammonium on montmorillonite: Experimental studies and model calculations. Clays and Clay Minerals, 45, 834–841.

    Google Scholar 

  • Sato, H. and Suzuki, S. (2003) Fundamental study on the effect of an orientation of clay particles on diffusion pathway in compacted bentonite. Applied Clay Science, 23, 51–60.

    Google Scholar 

  • Schwertz, FA. and Brow, J.E. (1951) Diffusivity of water vapor in some common gases. Journal of Chemical Physics, 19, 640–646.

    Google Scholar 

  • Salles, F., Beurroies, I., Bildstein, O., Jullien, M., Raynal, J., Denoyel, R., and Van Damme, H. (2008) A calorimetric study of mesoscopic swelling and hydration sequence in solid Na-montmorillonite. Applied Clay Science, 39, 186–201.

    Google Scholar 

  • Shih, Y.-H. and Wu, S.-C. (2004) Kinetics of toluene sorption and desorption in Ca- and Cu-montmorillonites investigated with Fourier transform infrared spectroscopy under two different levels of humidity. Environmental Toxicology and Chemistry, 23, 2061–2067.

    Google Scholar 

  • Siepmann, J., Ainaoui, A., Vergnaud, J.M., and Bodmeier, R. (1998) Calculation of the dimensions of drug-polymer devices based on diffusion parameters. Journal of Pharmaceutical Sciences, 87, 827–832.

    Google Scholar 

  • Skipper, N.T., Lock, P.A., Titiloye, J.O., and Swenson, J. (2006) The structure and dynamics of 2-dimensional fluids in swelling clays. Chemical Geology, 230, 182–196.

    Google Scholar 

  • Suzuki, A., Sato, H., Ishidera, T., and Fujii, N. (2004) Study on anisotropy of effective diffusion coefficient and activation energy for deuterated water in compacted sodium bentonite. Journal of Contaminant Hydrology, 68, 23–37.

    Google Scholar 

  • Steinberg, S., Fairley, J.P., and Kreamer, D. (1994) Slow vapor-phase desorption of toluene from several ion-exchanged monmorillonites. Journal of Soil Contamination, 3, 249–264.

    Google Scholar 

  • Swenson, J., Bergman, R., and Howells, W.S. (2000) Quasielastic neutron scattering of two-dimensional water in a vermiculite clay. Journal of Chemical Physics, 113, 2873–2879.

    Google Scholar 

  • Tambach, T.J., Bohuis, P.G., Hensen, J.M., and Smit, B. (2006) Hysteresis in clay swelling induced by hydrogen bonding: accurate prediction of swelling states. Langmuir, 22, 1223–1234.

    Google Scholar 

  • Tamura, K., Yamada, H., and Nakazawa, H. (2000) Stepwise hydration of high-quality synthetic smectite with various cations. Clays and Clay Minerals, 48, 400–404.

    Google Scholar 

  • Tuck, J.J., Hall, P.L., Hayes, M.H.B., Ross, D.K., and Poinsignon, J. (1984) Quasi-elastic neutron-scattering studies of intercalated molecules in charged-deficient layer silicates: part 1. Journal of the Chemical Society Faraday Transaction 1: Physical Chemistry in Condensed Phases, 80, 309–324.

    Google Scholar 

  • Tuck, J.J., Hall, P.L., and Hayes, M.H.B. (1985) Quasi-elastic neutron-scattering studies of intercalated molecules in charged-deficient layer silicates: Part 2. Journal of the Chemical Society Faraday Transactions 1: Physical Chemistry in Condensed Phases, 81, 833–846.

    Google Scholar 

  • Veith, S.R., Hughes, E., and Pratsinis, S.E. (2004) Restricted diffusion and release of aroma molecules from sol-gel-made porous silica particles. Journal of Controlled Release, 99, 315–327.

    Google Scholar 

  • Ward, C.A. and Fang, G. (1999) Expression for predicting liquid evaporation flux: statistical rate theory approach. Physical Review E, 59, 429–439.

    Google Scholar 

  • Zabat, M. and Van Damme, H. (2000) Evaluation of the energy barrier for dehydration of momionic (Li, Na, Cs, Mg, Ca, Ba, Alx(OH)yz+ and La)-montmorillonite by a differentiation method. Clay Minerals, 35, 357–363.

    Google Scholar 

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  1. Laboratoire de Technologie des Composites et Polymères (LTC), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015, Lausanne, Switzerland

    Pascal Clausen, Christopher J. G. Plummer & Jan-Anders E. Månson

  2. Riedtlistrasse 67, 8006, Zurich, Switzerland

    Lorenz Meier

  3. Ver-Chez-Les-Blanc, Nestlé Research Center, 1000, Lausanne 26, Switzerland

    Eric Hughes

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  1. Pascal Clausen
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  2. Lorenz Meier
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  4. Christopher J. G. Plummer
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Correspondence to Pascal Clausen.

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Clausen, P., Meier, L., Hughes, E. et al. Kinetics of Desorption of Water, Ethanol, Ethyl Acetate, and Toluene from a Montmorillonite. Clays Clay Miner. 61, 361–374 (2013). https://doi.org/10.1346/CCMN.2013.0610414

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  • DOI: https://doi.org/10.1346/CCMN.2013.0610414

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