Abstract
Adsorption of Xe, Kr, Ar, N2, O2, H2 CH4, CO2, He, and freons by PAU-10 and ACC microporous carbon adsorbents as well as by A and X zeolites was investigated over a wide range of pressures (0.1 Pa – 20 MPa) and temperatures (77, 120–600 K). The amount of gases, vapors and liquids adsorbed by microporous adsorbents increases steadily with increasing pressure and does not change dramatically if phase transitions occur in the adsorptive. Isosteres of adsorption constructed as a curve of ln P against f(1/T) a retain a linear form over a wide range of pressures and temperatures. The slope of isosteres does not vary on going through the critical temperature of the gaseous phase. At high pressures, due to non-ideality of the gaseous phase and non-inert behavior of the adsorbent the differential molar heat of adsorption is dependent on temperature. At high fillings of micropores the differential molar isosteric heat capacities of adsorption systems show maxima that indicate the occurrence of structural rearrangements in the adsorbate.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Bakaev V.A., “Ob Odnoy Vosmozhnoy Formulirovke Termodinamiki Sorbzionnogo Ravnovesija,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 12, 2648–2653 (1971) (in russia). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 12, 2648–2653 (1971) (Engl. Transl.)].
Bakaev V.A., Molekuljarnaja teorija fisicheskoy adsorbzii, Dissertazija doktora fis.-mat. nauk,IFC AN SSSR, Moskva, 1989.
Bangham, D.H., “The Gibbs Adsorption Equation and Adsorption on Solids,” Trans. Faraday Soc., 33, 805–809 (1937).
Bangham, D.H. and N. Fakhoury, “The Expansion of Charcoal Accompanying Sorption of Gases and Vapours,” Nature, 122, 681–687 (1928).
Bangham, D.H., N Fakhoury, and A.F. Mohamed, “The Swelling of Charcoals. P. II, Proc. Roy. Soc., A138, 162–167 (1932).
Bangham, D.H., W Fakhoury, and A.F. Mohamed, “The Swelling of Charcoals. P. III.,” Proc. Roy. Soc. A147, 152–157 (1934).
Barrer, R.M. and R. Papadopoulos, Pros. Roy. Soc. London, A326, 1566, 315, 1972.
Beresin, G.I. and A.A. Koslov, “Termodinamika Deformazii Adsorbenta Pri Adsorbzii,” Doklady Akademii Nauk SSSR, 253(2), 373–376 (1980) (in russia).
Bering, B.P., A. Myers, and V.V. Serpinsky, “Problemi Inertnosti Adsorbentov,” Doklady Akademii Nauk SSSR, 193, 119–122, (1970) (Russ.).
Breck, D.W., Zeolite Molecular Sieves, A Wiley-Interscience Publ., New York, 1974.
Bülow M., D. Shen, and S. Jale, “Measurement of Sorption Equilibria Under Isosteric Conditions. The Principles, Advantages and Limitations,” Applied Surface Sciece. 196, 157–172 (2002).
Cheung, T.T.P., “Low-Temperature (144 K) Xe NMR Studies of Zeolites,” J. Phys. Chem., 94, 376–380 (1990).
Chkhaidse, E.V., A.A. Fomkin, V.V. Serpinsky, G.V. Tsit sishvili, and M.M. Dubinin, “Adsorbzija Metana na Mikroporistom Uglerodnom Adsorbente v Dokriticheskoy i Sverchkriticheskoy Oblastjach,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 4, 929–931, (1986), (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 4, 929–931 (1986), (Engl. Transl.)].
Chkhaidse E.V., A.A. Fomkin, V.V. Serpinsky, and G.V. Tsitsishvili, “Adsorbzija Metana Na Zeolite Na X v Dokriticheskoy I Zakriticheskoy Oblastjach,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 5, 974–978 (1985) (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 5, 974–978 (1985), (Engl. Transl.)].
Chkhaidze E.V., A.A. Fomkin, V.V. Serpinsky, and G.V. Tsitsichvili, “Adsorption of Methane on Na X Zeolite Over Wide Ranges of Temperature, Pressure and Filling,” Preprints of the Workshop “Adsorption of Hydrocarbons in Microporous Adsorbents-π,” pp. 93–99, Eberswalde, GDR, 1982.
Dolino, G, D. Bellet, and C. Faivre, “Adsorption strains in porous silicon,” Phys. Rev.Ser.B, 54(24), 17919–17929 (1996).
Dubinin, M.M., “Physical Adsorption of Gases and Vapors in Micropores,” in Progress in Surface and Membrane Science, vol. 9, pp. 1–70, Academic Press Inc., New York, London, 1975.
Dubinin M.M., A.A. Fomkin A.A., I.I. Seliverstova, and V.V. Serpinsky, “Direct Determination of the Density of Adsorbates in Zeolite Micropores,” in Proceedings of the 5-th International Conference on Zeolites, pp. 468–476, Elsiver, Naples, 1980.
Fiedler, K., H. Stach, and W. Schirmer, “Theoretische Unersuchungen zum Adsorptionsgleichgewicht vom unpolaren Adsorptiven an Zeolithen von Faujasittyp,” Theorie der Adsorption an Zeolithen, Akademie-Verlag, Berlin, 17, 5–21 (1982).
Flood, E.A. and R.D. Heyding, “Stresses and Strains in Adsorbent-Adsorbate Systems.” Pt I //Can. J. Chem.-1954.-V32.-p. 660. (a) 1955.-V33.- p. 979; (b) 1957.-V. 35.-p. 48; (c) 1957.-V. 35.-p. 887; 1963.-V. 41.-p. 1703.
Fomkin A.A., “Adsorbzija Ar na Zeolite Na X,” in Adsorbzija v mikroporach, M.M. Dubinin, and V.V. Serpinsky (Eds.), pp. 98–99, Nauka, Moskva, 1983 (Russ.).
Fomkin A.A., V.A. Avramenko, I.I. Seliverstova, and V.V. Serpinsky, “Adsorbzija Gasov, Parov i Jidkostey v Mikroporach Kak Edinoe Javlenie,” Doklady Akademii Nauk SSSR, 288(3), 678–681 (1986) (Russ.).
Fomkin, A.A. and A.L.Pulin, “Adsorption Deformation of Zeolite Na X at High Pressures Xenon,” Russian Chemical Bulletin, International Edition, V. 45(2), 321–323 (1996).
Fomkin, A.A., N.I. Regent, and V.A. Sinitsyn, “Adsorption Deformation in Microporous Carbon Adsorbent-Benzene System and Porous Structure of Adsorbents,” Russian Chemical Bulletin, International Edition, V. 49(6), 1012–1016 (2000).
Fomkin A.A. and V.V. Serpinsky, “Issledovanie Adsorbzii Chlortriftormetana na Zeolite Na X v Shirokom Intervale Davleny i Temperatur,” Izvestija Akademii Nauk SSSR, Serija Chimicheskaja, 9, 2108–2110, (1974), (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 9, 2108–2110 (1974), (Engl. Transl.)].
Fomkin, A.A., I.I. Seliverstova, V.V. Serpinsky, and B.P. Bering, “Fisicheskaja Adsorbzija Gasov Na Zeolitach v Shirokich Intervalach Ismeneniya Davleniy I Temperatur,” in Adsorbenti, ich poluchenie, svostva i primenenie, T.G. Plachenov and M.M. Dubinin (Eds.), pp. 109-112, Nauka, Leningrad, 1978, (Russ.).
Fomkin, A.A., V.V. Serpinsky, and B.P. Bering, “Issledovanie Adsorbzii Ksenona Na Zeolite Na X v Shirokom Intervale Davleniy,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 1244–1248, (1975), (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 1244–1248 (1975), (Engl. Transl.)].
Fomkin, A.A., I.I. Seliverstova, and V.V. Serpinsky, “New Method of Determining the Volume of Adsorbent Micropores,” in Proceedings of an International Symposium “Zeolites: Synthesis, Structure, Technology and Application, Elsevier, Portorose, Yugoslavia, pp. 443–451, 1985.
Fomkin, A.A., A.V. Tvardovski, I.I. Seliverstova, and V.V. Serpinsky, “Temperaturnaja Savisimost Adsorbzii Gelija Na Zeolitach Na X i Na A,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 7, 1469–1473 (1987) (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 7, 1469–1473 (1987) (Engl. Transl.)].
Gerard, N., G. Weber, V. Francois, M.T. Mesnier, J.F. Mazue, and C. Paulin, “Conception D'une Chambre de Diffraction RX Haute Temperature Pour 1'etitude de 1'Adsorption D'un Gaz Par Un Solide Sous Haute Pression,” J. de Phys. Ser. IV., 8, Pr5, 421–428 (1998).
Guggenheim, E.A., Modern thermodynamics by the Methods of Willard Gibbs, Methuen & Co Ltd., London, 1933.
Gusev, V.Y. and A.A. Fomkin, “Thermodynamics of High-Pressure Tian—Calve Adsorption Calorimetry and the Heats of Adsorption of Xe on Na X Zeolite Over the Temperature Range 299–467 K,” Adsorption Science and Technology, 8(2), 75–85 (1991).
IUPAC Manual of Symbols and Terminology, Appendix 2, Pt.1, Colloid and surface Chemistry. Pure Appl. Chem., 31, 578, 1972.
Kharitonov A.B., A.A. Fomkin, A.A. Pribiylov, and V.A. Sinitsyn, “Adsorption of Carbon Dioxide on Microporous Carbon Adsorbent PAU-10” Russian Chemical Bulletin, International Edition, V. 50(4), 591–594 (2001).
Kington, G.L. and J.G. Aston, “Heat of Adsorption of Nitrogen on Titanium Dioxide (Rutile) at 77.3 K,” J. Am. Chem. Soc., 73(5), 1920–1936 (1951).
Kononyuk, V.F., A.I. Sarachov, and M.M. Dubinin, “Ob Ismenenii Lineynich Rasmerov Granul Sinteticheskich Zeolitov Pri Adsorbzii Parov Vody,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 8, 1691–1697 (1972), (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 8, 1691–1697 (1972) (Engl. Transl.)].
Krasilnikova, O.K., A.I. Sarachov, and M.M. Dubinin, “Ismenenie Lineynich Rasmerov Granul Zeolita Na X Pri Adsorbzii Kriptona,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 7, 1479–1485, (1979) (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 7, 1479–1485 (1979) (Engl. Transl.)].
Landau, L.D. and E.M. Lifshiz, “Statisticheskaja Fisika,” Nauka, Moskva, 1964, (Russ.).
Mechan F.T., “The Expansion of Charcoal on Sorption of Carbon Dioxide,” Proc. R. Soc., A115, 199–205 (1927).
Moelwyn-Hughes, E. A. Physical Chemistry, Pergamon Press, London, 1961.
Pulin. A.l., A.A. Fomkin, V.A. Sinitsyn, A.A. Pribylov, “Adsorption and Adsorption-Induced Deformation of Na X Zeolite Under Pressures of Carbon Dioxide,” Russian Chemical Bulletin, International Edition, V. 50(1), 60–62 (2001).
Shechovzova, L.G. and A.A. Fomkin, “O Dvuch Sposobach Opisanija Adsorbzionnogo Ravnovesija,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 1, 19–23 (1992) (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci., 1, 19–23 (1992) (Engl. Transl.)].
Seliverstova I.I., A.A. Fomkin., and V.V. Serpinsky, “Issledovanie Adsorbzii Kriptona i Ksenona Na Zeolite Na X,” Izvestija Akademii Nauk SSSR, Serija chimicheskaja, 1, 201–204 (1978) (Russ.). [Bull. Russ. Acad. Sci. USSR, Div. Chem. Sci. 1, 201–204 (1978), (Engl. Transl.)].
Seliverstova I.I., A.A. Fomkin, and V.V. Serpinsky, “Adsorption of One-Component Liquids by Microporous Adsorbent” Preprints of the Workshop “Adsorption of Hydrocarbons in Microporous Adsorbents-π,” pp. 39–46, ZIFC, Eberswalde, GDR, 1982.
Tvardovski A.V., A.A. Fomkin., Yu.I. Tarasevich, I.G. Polyakova, V.V. Serpinski, and I.M. Guseva, “Investigation of Cation-Substituted Vermikulit Deformation upon Water vapor Sorption,” J. Coll. Inter. Science, 164 114–118 (1994).
Tvardovski, A.V., A.A. Fomkin, Yu. I. Tarasevich, and A.I. Zhukova, “Hysteresis Phenomena in the Study of Sorptive Deformation of Sorbents,” J. Coll. Inter. Science, 191, 117–119 (1997).
Tvardovski, A.V., A.A. Fomkin, Yu. I. Tarasevich, and A.I. Zhukova, “Adsorptive Deformation of Organo-Substituted Laminar Silicates,” J. Colloid Inter. Science, 212, 426–430, (1999).
Tvardovski, A.V., A.A. Fomkin, Yu.I. Tarasevich, and A.I. Zhukova, “Sorptive Deformation of Organo-Substituted Laminar Silicates and Hysteresis Phenomena,” J. Colloid Inter. Science, 241, 297–301 (2001).
Vargaftik, N.B., Spravochnik po teplofisicheskim svoystvam gasov i jidkostey, Nauka, Moskva, 1972 (Russ.).
Warne, M.R., N.L. Allan, and T. Cosgrove, “Computer Simulation of Water Molecules at Kaolinite and Silica Surfaces,” Phys. Chem. Chem. Phys.,V.2, 16 3663–3668 (2000).
Yakovlev, V. Yu., A.A. Fomkin, and A.V. Tvardovsi, “Adsorption and Deformation Phenomena at the Interaction of CO2 and a Microporous Carbon Adsorbent,” Journal of Colloid and Interface Science, 268, 33-36 (2003).
Yates, D.J.C. “A Note on Some Proposed Equation of State for the Expansion of Rigid Porous Solids on the Adsorption of Gases and Vapors,” Proc. Roy. Soc., 65, 80–84 (1952).
Yates, D.J.O. “The Expansion of Porous Glass on the Adsorption of Non-Polar Glasses,”Proc. Roy. Soc., A224, 525–531 (1954).
Young, D.A. and D.E. Smith, “Simulations of Clay Mineral Swelling and Hydration: Dependence upon Interlayer Ion Size and Charge,” J. Phys. Chem. Ser. B., 104(39), 9163–9170 (2000).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Fomkin, A.A. Adsorption of Gases, Vapors and Liquids by Microporous Adsorbents. Adsorption 11, 425–436 (2005). https://doi.org/10.1007/s10450-005-5636-x
Issue Date:
DOI: https://doi.org/10.1007/s10450-005-5636-x