Skip to main content
Log in

Kinetic derivation of common isotherm equations for surface and micropore adsorption

  • Published:
Adsorption Aims and scope Submit manuscript

Abstract

The Langmuir equation is one of the most successful adsorption isotherm equations, being widely used to fit Type I adsorption isotherms. In this article we show that the kinetic approach originally used by Langmuir for 2D monolayer surface adsorption can also be used to derive a 1D analogue of the equation, applicable in ultramicropores with single-file diffusion. It is hoped that such a demonstration helps dispel the idea that the Langmuir isotherm equation cannot apply to some micropores as more than a mathematical correlation. We furthermore seek to extend the insight provided by the simple kinetic derivation of the Langmuir equation to other isotherm equations capable of modelling Type I isotherms. The same kinetic approach is thus also used to derive the Volmer, Fowler–Guggenheim and Hill–de Boer equations, both for surface (2D adsorbed phase) and micropore adsorption (1D and 3D adsorbed phases). It is hoped that this will help make more intuitively clear that these equations can be used as phenomenological models in some instances of adsorption in micropores.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • Afonso, R., Gales, L., Mendes, A.: A surface thermodynamic approach to adsorption in ultramicropores with single-file diffusionthermodynamic approach to adsorption in ultramicropores with single-file diffusion. Micropor. Mesopor. Mater. 225, 543–551 (2016)

    Article  CAS  Google Scholar 

  • Albayati, T., Doyle, A.: Shape-selective adsorption of substituted aniline pollutants from wastewater. Adsorp. Sci. Technol. 31, 459–468 (2013)

    Article  CAS  Google Scholar 

  • Bertsekas, D.P., Tsitsiklis, J.N.: The Bernoulli and Poisson Processes, 2nd edn, pp. 295–338. Athena Scientific, Nashua (2008). (book section 6)

    Google Scholar 

  • de Boer, J.H.: 1st edn, pp. 1–53. Oxford University Press, London (1953a)

  • de Boer, J.H.: The Adsorption Isotherm in the Case of Two-Dimensional Condensation, 1st edn. Oxford University Press, London (1953b). (book section VIII)

    Google Scholar 

  • de Boer, J.H.: The Assumption of a Constant Heat of Adsorption. The Quantity: Unimolecular and Multimolecular Adsorption, 1st edn. Oxford University Press, London (1953c). (book section V)

    Google Scholar 

  • de Boer, J.H.: Ideal Two-Dimensional Gases, 1st edn. Oxford University Press, London (1953d). (book section VI)

    Google Scholar 

  • Do, D.D.: Fundamentals of Pure Component Adsorption Equilibria. Series on Chemical Engineering, pp. 11–48. Imperial College Press, London (1998). (book section 2)

    Google Scholar 

  • Dwass, M.: The Poisson Process. W. A. Benjamin, New York (1970). (book section 11.12)

    Google Scholar 

  • Fowler, R., Guggenheim, E.A.: Surface Layers, pp. 421–451. Cambridge University Press, Cambridge (1949). (book section X)

    Google Scholar 

  • Hill, T.L.: Statistical mechanics of multimolecular adsorption. ii. Localized and mobile adsorption and absorption. J. Chem. Phys. 14, 441–453 (1946)

    Article  CAS  Google Scholar 

  • Hill, T.L.: Statistical thermodynamics of the transition region between two phases. ii. One component system with a plane interface. J. Chem. Phys. 20, 141–144 (1952)

    Article  CAS  Google Scholar 

  • Langmuir, I.: The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 40, 1361–1403 (1918)

    Article  CAS  Google Scholar 

  • Lapizco-Encinas, B.H., Pinto, N.G.: Effectiveness of the h-root method for determining adsorption isotherms of protein–salt systems in open micro-channels. J. Chromatogr. A 1036, 61–72 (2004)

    Article  CAS  Google Scholar 

  • London, F., Polányi, M.: Über die atomtheoretische deutung der adsorptionskräfte. Naturwissenschaften 18, 1099–1100 (1930)

    Article  CAS  Google Scholar 

  • Mishra, V., Balomajumder, C., Agarwal, V.: Design and optimization of simultaneous biosorption and bioaccumulation (SBB) system: a potential method for removal of zn(ii) ion from liquid phase. Desalin. Water Treat. 51, 3179–3188 (2013)

    Article  CAS  Google Scholar 

  • Nguyen, C., Do, D.D.: Adsorption of supercritical gases in porous media: determination of micropore size distribution. J. Phys. Chem. B 103, 6900–6908 (1999)

    Article  CAS  Google Scholar 

  • Ross, S.M.: Exponential Random Variables, 3rd edn, pp. 175–181. Elsevier Academic Press, Burlington (2004)

    Google Scholar 

  • Timmermann, E.O.: Multilayer sorption parameters: bet or gab values? Colloids Surf. A 220, 235–260 (2003)

    Article  CAS  Google Scholar 

  • Volmer, M.: Thermodynamische folgerungen aus der zustandsgleichung fur adsorbierte stoffe. Z. Phys. Chem. 115, 253–261 (1925)

    CAS  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the projects POCI-01-0145-FEDER-006939 - Laboratory for Process Engineering, Environment, Biotechnology and Energy - LEPABE and NORTE-01-0145-FEDER-000005 - LEPABE-2-ECO-INNOVATION, funded by FEDER funds through COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI) and Programa Operacional Regional do Norte (NORTE2020) and by national funds through FCT - Fundação para a Ciência e a Tecnologia; project PTDC/EQU-EQU/114944/2009 and scholarship SFRH/BD/43821/2008. We kindly thank fruitful discussions with Daniel Ferreira, Roberto Magalhães and Emanuele Rodaro.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Adélio Mendes.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Afonso, R., Gales, L. & Mendes, A. Kinetic derivation of common isotherm equations for surface and micropore adsorption. Adsorption 22, 963–971 (2016). https://doi.org/10.1007/s10450-016-9803-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10450-016-9803-z

Keywords

Navigation