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Adsorption of toluene, methylcyclohexane and neopentane on silica MCM-41

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Abstract

Adsorption-desorption isotherms of toluene, methylcyclohexane and neopentane were determined on a silica MCM-41 material of pore diameter ∼3.4 nm over the temperature range 258 K to 308 K (278 K for neopentane). The isosteric enthalpies of adsorption were determined from the isotherms at the various temperatures. It was found that the isotherms of toluene and methylcyclohexane have a similar variation with the temperature, exhibiting hysteresis at 268 K and at lower temperature, while the adsorption of neopentane is reversible at all temperatures. The three organic adsorptives interact differently with the silica surface and the isosteric enthalpies of adsorption indicated that methylcyclohexane has the weakest interaction and toluene the strongest. A slight increase in the adsorption enthalpy at the beginning of the capillary condensation step is observed with methylcyclohexane and neopentane but not with toluene.

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Abbreviations

a m :

Molecular cross sectional area

A s :

Total surface area

A ext :

External surface area

D ch :

Hysteresis critical diameter

D p (g):

Geometric pore diameter

D p (H):

Hydraulic pore diameter

L :

Avogadro’s constant

M :

Molar mass

n ads :

Adsorbed amount

p/p o :

Relative pressure

q st :

Isosteric heat of adsorption

R :

Gas constant

T :

Temperature

T ch :

Hysteresis critical temperature

V ads :

Adsorbed volume

V p :

Pore volume

ρ l :

Density of the liquid

ρ sil :

Silica density

References

  • Bambrough, C.M., Slade, R.C.T., Williams, R.T., Burkett, S.L., Sims, S.D., Mann, S.: Sorption of nitrogen, water vapor, and benzene by a phenyl-modified MCM-41 sorbent. J. Colloid Interface Sci. 201, 220–222 (1998)

    Article  CAS  Google Scholar 

  • Beck, J.S., Vartuli, J.C., Roth, W.J., Leonowicz, M.E., Kresge, C.T., Schmitt, K.D., Chu, C.T.W., Olson, D.H., Sheppard, E.W., McCullen, S.B., Higgins, J.B., Schlenker, J.L.: A new family of mesoporous molecular-sieves prepared with liquid-crystal templates. J. Am. Chem. Soc. 114, 10834–10843 (1992)

    Article  CAS  Google Scholar 

  • Branton, P.J., Hall, P.G., Sing, K.S.W., Reichert, H., Schüth, F., Unger, K.K.: Physisorption of argon, nitrogen and oxygen by MCM-41, a model mesoporous adsorbent. J. Chem. Soc., Faraday Trans. 90, 2965–2967 (1994)

    Article  CAS  Google Scholar 

  • Branton, P.J., Hall, P.G., Sing, K.S.W.: Physisorption of alcohols and water vapour by MCM-41, a model mesoporous adsorbent. Adsorption 1, 77–82 (1995)

    Article  CAS  Google Scholar 

  • Branton, P.J., Sing, K.S.W., White, J.W.: Adsorption of carbon tetrachloride and nitrogen by 3.4 nm pore diameter siliceous MCM-41. J. Chem. Soc., Faraday Trans. 93(13), 2337–2340 (1997)

    Article  CAS  Google Scholar 

  • Carrott, P.J.M., Roberts, R.A., Sing, K.S.W.: Adsorption of neopentane by nonporous carbons and silicas. Langmuir 4, 740–743 (1988)

    Article  CAS  Google Scholar 

  • Choma, J., Kloske, M., Jaroniec, M., Klinik, J.: Benzene adsorption isotherms on MCM-41 and their use for pore size analysis. Adsorption 10, 195–203 (2004)

    Article  CAS  Google Scholar 

  • Franke, O., Schulz-Ekloff, G., Rathouský, J., Stárek, J., Zukal, A.: Unusual type of adsorption isotherm describing capillary condensation without hysteresis. J. Chem. Soc., Chem. Commun. 724–726 (1993)

  • Gregg, S.J., Sing, K.S.W.: Adsorption, Surface Area and Porosity, 2nd edn. Academic Press, New York (1982)

    Google Scholar 

  • Grün, M., Unger, K.K., Matsumoto, A., Tsutsumi, K.: Ordered mesoporous MCM-41 adsorbents: novel routes in synthesis, product characterisation and specification. In: McEnaney, B., Mays, T.J., Rouquérol, J., Rodriguez-Reinoso, F., Sing, K.S.W., Unger, K.K. (eds.) Characterization of Porous Solids IV, pp. 81–89. Royal Society of Chemistry, London (1997)

    Google Scholar 

  • He, Y., Seaton, N.A.: Heats of adsorption and adsorption heterogeneity for methane, ethane, and carbon dioxide in MCM-41. Langmuir 22, 1150–1155 (2006)

    Article  CAS  Google Scholar 

  • Inoue, S., Hanzawa, Y., Kaneko, K.: Prediction of hysteresis disappearance in the adsorption isotherm of N2 on regular mesoporous silica. Langmuir 14, 3079–3081 (1998)

    Article  CAS  Google Scholar 

  • Kresge, C.T., Leonowicz, M.E., Roth, W.J., Vartuli, J.C., Beck, J.S.: Ordered mesoporous molecular-sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710–712 (1992)

    Article  CAS  Google Scholar 

  • Kruk, M., Jaroniec, M., Sayari, A.: Application of large pore MCM-41 molecular sieves to improve pore size analysis using nitrogen adsorption measurements. Langmuir 13, 6267–6273 (1997a)

    Article  CAS  Google Scholar 

  • Kruk, M., Jaroniec, M., Sayari, A.: Adsorption study of surface and structural properties of MCM-41 materials of different pore sizes. J. Phys. Chem. B 101, 583–589 (1997b)

    Article  CAS  Google Scholar 

  • Kowalczyk, P., Jaroniec, M., Terzyk, A.P., Kaneko, K., Do, D.D.: Improvement of the Derjaguin-Broekhoff-de Boer theory for capillary condensation/evaporation of nitrogen in mesoporous systems and its implications for pore size analysis of MCM-41 silicas and related materials. Langmuir 21, 1827–1833 (2005)

    Article  CAS  Google Scholar 

  • Morishige, K., Nakamura, Y.: Nature of adsorption and desorption branches in cylindrical pores. Langmuir 20, 4503–4506 (2004)

    Article  CAS  Google Scholar 

  • Morishige, K., Shikimi, M.: Adsorption hysteresis and pore critical temperature in a single cylindrical pore. J. Chem. Phys. 18, 7821–7824 (1998)

    Article  Google Scholar 

  • Morishige, K., Tateishi, M.: Accurate relations between pore size and the pressure of capillary condensation and the evaporation of nitrogen in cylindrical pores. Langmuir 22, 4165–4169 (2006)

    Article  CAS  Google Scholar 

  • Morishige, K., Fuji, H., Uga, M., Kinukawa, D.: Capillary critical point of argon, nitrogen, oxygen, ethylene, and carbon dioxide in MCM-41. Langmuir 13, 3494–3498 (1997)

    Article  CAS  Google Scholar 

  • Neimark, A.V., Ravikovitch, P.I., Vishnyakov, A.: Bridging scales from molecular simulations to classical thermodynamics: density functional theory of capillary condensation in nanopores. J. Phys.: Condens. Mater. 15, 347–365 (2003)

    Article  CAS  Google Scholar 

  • Qiao, S.Z., Bhatia, S.K., Nicholson, D.: Study of hexane adsorption in nanoporous MCM-41 silica. Langmuir 20, 389–395 (2004)

    Article  CAS  Google Scholar 

  • Rathouský, J., Zukal, A., Franke, O., Schulz-Ekloff, G.: Adsorption on MCM-41 mesoporous molecular sieves, part 2: cyclopentane isotherms and their temperature dependence. J. Chem. Soc., Faraday Trans. 91(5), 937–940 (1995)

    Article  Google Scholar 

  • Ravikovitch, P.I., O’Domhnail, S.C., Neimark, A.V., Schüth, F., Unger, K.K.: Capillary hysteresis in nanopores: theoretical and experimental studies of nitrogen adsorption on MCM-41. Langmuir 11, 4765–4772 (1995)

    Article  CAS  Google Scholar 

  • Ravikovitch, P.I., Wei, D., Chueh, W.T., Haller, G.L., Neimark, A.V.: Evaluation of pore structure parameters of MCM-41 catalyst supports and catalysts by means of nitrogen and argon adsorption. J. Phys. Chem. B 101(19), 3671–3679 (1997)

    Article  CAS  Google Scholar 

  • Ravikovitch, P.I., Haller, G.L., Neimark, A.V.: Density functional theory model for calculating pore size distributions: pore structure of nanoporous catalysts. Adv. Colloid Interface Sci. 77, 203–226 (1998)

    Article  Google Scholar 

  • Ravikovitch, P.I., Vishnyakov, A., Neimark, A.V., Ribeiro Carrott, M.M.L., Russo, P.A., Carrott, P.J.: Characterization of micro-mesoporous materials from nitrogen and toluene adsorption: experiment and modeling. Langmuir 22(2), 513–516 (2006)

    Article  CAS  Google Scholar 

  • Reid, R.C., Prausnitz, J.M., Poling, B.E.: The Properties of Gases and Liquids. McGraw-Hill, New York (1986)

    Google Scholar 

  • Ribeiro Carrott, M.M.L., Candeias, A.J.E., Carrott, P.J.M., Ravikovitch, P.I., Neimark, A.V., Sequeira, A.D.: Adsorption of nitrogen, neopentane, n-hexane, benzene and methanol for the evaluation of pore sizes in silica grades of MCM-41. Micropor. Mesopor. Mater. 47, 323–337 (2001)

    Article  CAS  Google Scholar 

  • Rouquérol, F., Rouquérol, J., Sing, K.: Adsorption by Powders and Porous Solids. Academic Press, London (1999)

    Google Scholar 

  • Russo, P.A., Ribeiro Carrott, M.M.L., Padre-Eterno, A., Carrott, P.J.M., Ravikovitch, P.I., Neimark, A.V.: Interaction of water vapour at 298 K with Al-MCM-41 materials synthesised at room temperature. Micropor. Mesopor. Mater. 103, 82–93 (2007)

    Article  CAS  Google Scholar 

  • Schlangen, L.J.M., Koopal, L.K., Stuart, M.A.C., Lyklema, J., Robin, M., Toulhoat, H.: Thin hydrocarbon and water films on bare and methylated silica: vapor adsorption, wettability, adhesion, and surface forces. Langmuir 11, 1701–1710 (1995)

    Article  CAS  Google Scholar 

  • Schreiber, A., Reinhardt, S., Findenegg, G.H.: The lower closure point of the adsorption hysteresis loop of fluids in mesoporous silica materials. In: F. Rodríguez-Reinoso, B. McEnaney, J. Rouquerol, K. Unger (eds.), Studies in Surface Science and Catalysis—Characterization of Porous Solids VI, pp. 177–184 (2002)

  • Sonwane, C.G., Bhatia, S.K.: Analysis of criticality and isotherm reversibility in regular mesoporous materials. Langmuir 15, 5347–5354 (1999)

    Article  CAS  Google Scholar 

  • Tanchoux, N., Trens, P., Maldonado, D., Di Renzo, F., Fajula, F.: The adsorption of hexane over MCM-41 type materials. Colloids Surf. A: Physicochem. Eng. Aspects 246, 1–8 (2004)

    Article  CAS  Google Scholar 

  • Trens, P., Tanchoux, N., Maldonado, D., Galarneau, A., Di Renzo, F., Fajula, F.: Study of n-hexane adsorption in MCM-41 mesoporous materials: a scaling effect approach of capillary condensation processes. New J. Chem. 28, 874–879 (2004)

    Article  CAS  Google Scholar 

  • Zukal, A.: Adsorption and pore condensation of krypton on mesoporous silicas at 77 K. Micropor. Mesopor. Mater. 92, 220–226 (2006)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Centro de Química de Évora and Departamento de Química, Universidade de Évora, Rua Romão Ramalho, 59, 7000-671, Évora, Portugal

    Patrícia A. Russo, M. Manuela L. Ribeiro Carrott & Peter J. M. Carrott

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  1. Patrícia A. Russo
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  2. M. Manuela L. Ribeiro Carrott
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  3. Peter J. M. Carrott
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Correspondence to M. Manuela L. Ribeiro Carrott.

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Russo, P.A., Ribeiro Carrott, M.M.L. & Carrott, P.J.M. Adsorption of toluene, methylcyclohexane and neopentane on silica MCM-41. Adsorption 14, 367–375 (2008). https://doi.org/10.1007/s10450-007-9099-0

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  • DOI: https://doi.org/10.1007/s10450-007-9099-0

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