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Using classical methods to start quantum mechanical calculations for microporosity and mesoporosity

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Abstract

One primary measurement of open porosity uses physical adsorption isotherm, amount adsorbed versus gas pressure. Classical treatments, including the BET, cannot fit the isotherm for its full range, therefore standard curves have been created from non-porous materials for comparison. This classical method yields three output parameters, two surface areas, pore and external, relative to the standard. The third output is moles of material needed to fill the pores. A modern treatment using quantum mechanics and thermodynamics, call χ/ESW, yields seven physical quantities. However, the calculation requires a non-linear least squares routine, with initial parameters to find a minimum. In this paper the possibility of using the answers from the classical method as a first approximation is explored, with no need for a standard since χ/ESW treatment is used as a self-standard. Within limits, this works well for microporosity but mesoporosity presents some problems with one of the parameters.

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Code availability

Open literature codes available in reference Condon (2020).

Notes

  1. This is a modification of Gurvich rule in this publication given with the insight of χ/ESW.

  2. The QM treatment preceded the ASP but was difficult to get published, whereas the ASP seem more classical and was somewhat acceptable, but theoretically incorrect.

  3. This is NOT the original Henry's law which applies to solutions! The extrapolation from 0.05 P/Pvap used simply because some researchers could not measure in low (UHV) pressures. It is in no way mathematically or thermodynamically related.

  4. See Chapter 5 section “Thompson” (The publications of these experiments were rejected by multiple journals.).

  5. Defined here as micropores: adsorption in pores without the surface tension effect to fill the pores in any way except by continued surface adsorption and mesopores: partially filling the pores by surface adsorption and the quickly finish by the tensile strength of the outer interface formation.

  6. The pore distribution observation is tied up with the filling of “layers.” The quotes indicate that the definition of layers is different from the normal layer-by-layer description. Some hint of the meaning here is given below in Case B.

  7. Note of caution: In this reference Eq. 14 is missing a γ on the left side. Equation 13 is OK.

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  1. Roane State Community College, Harriman, TN, USA

    James Condon

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Condon, J. Using classical methods to start quantum mechanical calculations for microporosity and mesoporosity. Adsorption 26, 1291–1299 (2020). https://doi.org/10.1007/s10450-020-00267-8

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