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Water isotherm models for 4A (NaA) zeolite

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Abstract

The adsorption data of Gorbach et al. (Adsorption 10(1): 29–46, 2004) and Morris (J. Colloid Interface Sci. 28: 149–155, 1968) for the adsorption of water on 4A zeolite pellets is re-analyzed. Model isotherms are derived considering a two site hypothesis, one for the α cage and one for the β cage. Four simple model isotherms are fitted to the data. Both a dual site Toth or dual site Langmuir isotherm model fit the data adequately.

The optimized standard enthalpy and entropy of adsorption parameters derived from the data are surprising for the β cage. The optimized standard enthalpy of the β cage is 1/3rd of that observed calorimetrically, and the standard entropy of adsorption is positive, a physical impossibility. Substituting the calorimetric enthalpy of adsorption corrected the standard differential entropy of sorption values resulting in the standard entropy of sorption values varying significantly with temperature. This variation is postulated to be due to either water of hydration formation, or clathrate formation, or the formation of clusters of water such as dimers, trimers, etc.

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Abbreviations

f i :

fractional size of site i

K ci :

dimensionless equilibrium constant ci, c β for cage β and c α for cage α respectively

K i :

equilibrium parameter i, 1 for cage β and 2 for cage α respectively, mbar1

H i :

Henry constants, for cages β and α respectively, g/g.mbar

H oi :

pre-exponential Henry parameter, g/g.mbar

m max  :

maximum number of terms in Ruthven model, ≡v/β H

m i :

Toth equilibrium parameter, for cages β and α respectively, units

\(MW_{\mathrm{H}_{2}\mathrm{O}}\) :

molecular weight of water

n :

number of data points in regression calculations

n max  :

maximum molecules of water puc

N o :

Avogadro’s number

p :

pressure, mbar

q :

adsorbed phase concentration, g/g

q sat :

saturated adsorbed phase concentration, g/g

q sat crystal :

saturated adsorbed phase concentration for pure 5A crystals, g/g

R :

gas constant, kJ/mol.K

t i :

toth heterogeneity parameter, dimensionless

T :

temperature, K

T C :

critical temperature, K

V β :

volume of β cage, Å3

V α or v :

volume of α cage, Å3

V cell :

volume of pseudo unit cell of 5A, 1870 Å3

y i,exp  :

experimental data point, g/g

y i,th :

theoretical data point, g/g

Z:

zeolite

References

  • Avgul, N.N., Kiselev, A.V., Mirskii, Ya.V., Serdobov, M.V.: Heat of adsorption of water vapor by NaX and NaA zeolite. Zurnal Fiz. Khimii 42(6), 1474–1479 (1968)

    CAS  Google Scholar 

  • Barrer, R.M.: Zeolites and Clay Minerals. Academic Press, London (1978)

    Google Scholar 

  • Breck, D.W.: Zeolite Molecular Sieves. Wiley, New York (1974)

    Google Scholar 

  • Carter, J.W., Hussain, H.: The simultaneous adsorption of carbon dioxide and water vapor by fixed beds of molecular sieves. Chem. Eng. Sci. 29, 267–273 (1974)

    Article  CAS  Google Scholar 

  • Cointot, A., Cruchaudet, J., Simonot-Grange, M.-H.: Reseau d’Isotherme de l’eau par la zeolithe synthetique 4A. CR Acad. Sci. Paris 266(16), 1220–1222 (1968)

    CAS  Google Scholar 

  • Cui, Y.-P.: Experimental research of adsorption-desorption amount equilibrium properties in a zeolite water system. Tienranqi Huagong 2693, 11–14 (2001)

    Google Scholar 

  • Deininger, D., Fruede, D., Geschke, G., Pfeifer, H., Przyborowski, F., Schirmer, W., Stach, H.: Results of studying proton magnetic resonance in zeolites. In: Dubinin, M.M. (ed.) Adsorbenty, Ikh Poluch., Svoistva Primen., Tr. Vses. Soveshch. Adsorbentam, pp. 113–115. Nauka, Leningrad (1969)

    Google Scholar 

  • Do, D.D.: Adsorption Analysis: Equilibria and Kinetics. Imperial College Press, Singapore (1998)

    Google Scholar 

  • Dubinin, M.M., Isiriikyan, A.A., Sarakhov, A.I., Serpinskii, V.V.: Energy of adsorption of gases and vapors on microporous adsorbents. II Heat of adsorption of water on formed synthetic zeolite NaA. In: Izvestiya Akademii Nauk SSSR. Seriya Khimicheskaya, vol. 11, pp. 2355–2360 (1969)

  • Dubinin, M.M., Isirikyan, A.A., Mirzai, D.I.: Infrared spectroscopic study of adsorption complexes in zeolites. 1. NaA-H2O adsorption system. In: Izvestiya Akademii Nauk SSSR. Seriya Khimicheskaya, vol. 8, pp. 1699–1705. Inst. Fiz. Khim., Moscow (1974)

    Google Scholar 

  • Dubinin, M.M., Isirikyan, A.A., Mirzan, D.I.: Adsorption complexes in zeolites studied by ir spectroscopy. II. Adsorption systems NaA-water-d2, NaA-water-d2-water-d, and NaA-water-water-d. In: Izvestiya Akademii Nauk SSSR. Seriya Khimicheskaya, vol. 3, pp. 521–527. Inst. Khim. Fiz., Moscow (1975)

    Google Scholar 

  • Fedorov, V.M., Glazun, B.A., Zhilenkov, I.V., Dubinin, M.M.: Dielectric properties of water adsorbed by zeolites. I. Dielectric losses in the system NaA zeolite crystals- water, at low primings. In: Izvestiya Akademii Nauk SSSR. Seriya Khimicheskaya, vol. 11, pp. 1930–1934. Agr. Inst., Voronezh (1964)

    Google Scholar 

  • Fedorov, V.M., Glazun, B.A., Dubinin, M.M., Zhilenkov, I.V.: Dielectric properties of water adsorbed by zeolites. III. Dielectric losses in the system zeolite crystals NaA-water at the average fillings. In: Izvestiya Akademii Nauk SSSR. Seriya Khimicheskaya, vol. 7, pp. 1129–1135. Agr. Inst., Voronezh (1966)

    Google Scholar 

  • Glazun, B.A., Dubinin, M.M., Zhilenkov, I.V., Rakityanskaya, M.F.: Dielectric behavior of water absorbed on zeolites of various ion-exchange forms. In: Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, vol. 6, pp. 1193–1196. Voronezhsk. Sel’skokhoz. Inst., Voronezh (1967)

    Google Scholar 

  • Gorbach, A., Stegmaier, M., Eigenberger, G.: Measurement and modeling of water vapor adsorption on zeolite 4A-equilibria and kinetics. Adsorption 10(1), 29–46 (2004)

    Article  CAS  Google Scholar 

  • Hino, M.: Infrared studies on water adsorption systems with the use of HDO. I. Molecular sieves 13X and 4A. Bull. Chem. Soc. Jpn. 50(3), 574–579 (1977)

    Article  CAS  Google Scholar 

  • Jury, S.H., Horng, J.S.: The molecular sieve 4-A water vapor sorption therm. AIChEJ 19(2), 371–372 (1973)

    Article  CAS  Google Scholar 

  • Kononyuk, V.F., Sarakhov, A.I., Dubinin, M.M.: Dilatometric study of NaA zeolite during adsorption of water vapors. Dockl. Akad. Nauk SSSR 98(3), 638–640 (1971) (Phys. Chem.)

    Google Scholar 

  • Kononyuk, V.F., Sarakhov, A.I., Dubinin, M.M.: Change in the linear dimensions of synthetic zeolite granules during the adsorption of water vapor. In: Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, vol. 8, pp. 1691–1697. Inst. Fiz. Khim., Moscow (1972)

    Google Scholar 

  • Mikhailova, M.V., Meerson, L.A., Astakhov, V.A., Klyushkova, G.S.: Sorption of water vapors of NaA zeolite at elevated temperatures. In: Dubinin, M.M. (ed.) Issled. Adsorbtsionnykh Protsessov Adsorbentov, pp. 132–134. Akad. Nauk Uzbekskoi SSR, Inst. Khimii, Tashkent (1979)

    Google Scholar 

  • Morris, B.: Heats of sorption in the crystalline linde-A zeolite-water vapor system. J. Colloid Interface Sci. 28, 149–155 (1968)

    Article  CAS  Google Scholar 

  • Myers, A.L.: Characterization of nanopores by standard enthalpy and entropy of adsorption of probe molecules. Colloids Surf. A: Physiochem. Eng. Aspects 241, 9–14 (2004)

    Article  CAS  Google Scholar 

  • Qin, G.-L., Zhou, R.-X., Ni, Z.-X.: Adsorption of water vapor on molecular sieves. Cuihua Xuebao 1(3), 181–186 (1980)

    CAS  Google Scholar 

  • Ruthven, D.M.: Principles of Adsorption and Adsorption Processes. Wiley, New York (1984)

    Google Scholar 

  • Simontot-Grange, M.H., Prillard, S., Belhamidi-El-Hannouni, F.: Heat capacity of water adsorbed in zeolites and clay minerals. In: Collection Colloques et Seminaires (Institut Francais du Petrole), 42 (Interact. Solid-Liq. Poreux), pp. 159–170 (1985)

  • Singh, V.P., Ruthven, D.M.: Adsorption of moisture on molecular sieve adsorbents at low humidity. Res. Lab., Ontario Hydro, Toronto, ON, Can. Report (F-84026), 50 pp. (1984)

  • Ulku, S., Balkose, D., Alp, B.: Dynamic heat of adsorption of water vapor on zeolite tuff and zeolite 4A by flow microcalorimetry. In: Balkose, D., Zaikov, G.E. (eds.) Modern Advances in Organic and Inorganic Chemistry, pp. 159–172. Nova Science, New York (2005)

    Google Scholar 

  • Valenzuela, D.P., Myers, A.L.: Adsorption Equilibrium Data Handbook. Prentice-Hall, New York (1989)

    Google Scholar 

  • Vergnaud, J.M., Mange, M., de la Hargrove, M.G., Ray-Coquais, B.: Physiochemical study of water adsorption on type 4A molecular sieves. Bull. Soc. Chim. France 5, 1279–1283 (1965)

    Google Scholar 

  • Zhdanov, S.P., Khvoshchev, S.S., Samulevich, N.N.: Synthetic, Zeolites: Crystallization, Structural-Chemical Modification, and Adsorption Properties. Khimiya, Moscow (1981), 261 pp. (Sinteticheskie Tseolity: Kristallizatsiya, Strukturno-Khimicheskie Modifitsirovanie i Adsorbtsionnie Svoistva)

    Google Scholar 

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  1. Department of Chemical Engineering, American University of Sharjah, PO Box 26666, Sharjah, United Arab Emirates

    Kevin F. Loughlin

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Loughlin, K.F. Water isotherm models for 4A (NaA) zeolite. Adsorption 15, 337–353 (2009). https://doi.org/10.1007/s10450-009-9189-2

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