A.W.

Marczewski 2002 A Practical Guide to Isotherms of ADSORPTION on Heterogeneous Surfaces Reload Adsorption Guide Adsorption in mesopores See an example of surface area / pore volume analysis report BJH scheme details and pore filling graphics NOTE Adsorption in mesopores according to the classical Kelvin model (below) occurs i n vapours. Liquids require a different approach (e.g. DFT). Mesopores | Hysteresis loops | Kelvin equation | Pore size | Pore/meniscus shape | BJH Adsorption in mesopores (usually pores of 2 - 50m - IUPAC - or sometimes 2 - 100 nm in diameter). Typical adsorbates are N2 (nitrogen vapours at the temperature of liquid nitroge n bath at atmospheric pressure, approx. 77-78K - depending on liquid N2 purity a nd pressure) and vapours of benzene, C6H6 , at room (i.e. 25C) temperature. Krypto n is often used for low pressure isotherms. Other gases like CH4, CO2 are also u sed. Adsorption in a so called "mesopore range" is a combination of physical adsorpti on on mesopore walls (described by one of theoretical or experimental isotherm e quations like HJ or FHH or other - sometimes with wall curvature corrections) wi th physical condensation of adsorbate in pores, where meniscus reached a critica l radius. It is assumed that in this "mesopore" range all micropores are already filled-up and monolayer is filled, too. Generally, experimental isotherms measured on mesoporous solids display hysteres is loops (adsorption and desorption go along different paths) in the mesopore re gion. However, hysteresis is observed only when the menisci in the adsorption an d desorption "paths" are different in shape/diameter. Such situation is typical for open-ended cylindrical mesopores, bottle-shaped (ink bottle), or spaces betw een parallel sheets (slits). If cylindrical pore is closed at one end and does n ot contain any narrows, the adsorption isotherm will not diplay hysteresis loop. The same is true for conical pores. For typical adsorbates the opening/closing of hysteresis loop is found at: For N2 at 78K (liquid nitrogen bath at std. pressure): xhist = p/ps 0.40 For benzene at room temperature (25C or 298K) : xhist = p/ps 0.175. As the true pore diameter is a sum of 2 adsorbed layer thicknesses and meniscus diameter, the methods of data analysis use meniscus radii calculated from Kelvi n equation (or its modifications including e.g. influence of menicus radius on a dsorbate surface tension - e.g. by Dubinin) and statistical layer thickness of a dsorbate (often given by Harkins-Jura (HJ) or by Halsey / Frenkel-Halsey-Hill (F HH) equations). Very often in simple data analysis specific expressions for N2 adsorption are us ed: tHJ and tHalsey, respectively - see also above). Those simple equations (i.e . HJ and FHH) are also used in a so called t-plot method which is a simple metho d of determination of total micropore adsorption and external (i.e. mesopore + m acropore) surface area. A better method is an s-plot which compares adsorption dat a on porous solid with experimental isotherms measured on a similar in nature/ch emical structure - but non-porous (or having much less micro- and mesopores) - a dsorbent. Calculations of mesopore size distribution depend on many factors: Mesopore shape: Cylindrical mesopores: Evaporation occurs at lower pressures than condensation in the same pore (hyster esis): pevap(rpore) < pcond(rpore) Adsorption on cylindrical walls acc. to Kelvin eq. with: rcond = rK,cyl = rx , ry = + For desorption, the meniscus is spherical, i.e.: rcond = rK,sph = rx = ry

(see below) Spherical mesopores Kelvin eq. with: rcond = revap = rK,sph = rx = ry Bottle shaped mesopores Condensation (ads. branch) occurs acc. to Kelvin eq. for spherical pore, i.e. wi th: rcond = rK,sph = rx = ry where this radius is the radius of inner pore space rK,sph = rsph,in Evaporation (des. branch) occurs at the much lower pressure determined by the ra dius of spherical meniscus formed in a narrow bottleneck: revap = rK,sph = rneck Slit-shaped mesopores Adsorption on "flat" pore walls Desorption occurs on slit openings with cylinrical meniscus (along slit edge), i .e. acc. to Kelvin eq. with: devap = 2 rK,cyl = rx , ry = + Other, e.g. conical pores (no rapid condensation at any fixed pressure, condensa tion and evaporation along the same path) Mesopore filling model / pore distribution calculation scheme: Barret-Joyner-Halenda (BJH) simplified BJH Dubinin (like BJH, but takes into account the dependence of N2 surface tension o n meniscus radius) Density-Functional Theory (DFT) Commented example of surface area/pore volume analysis report of experimental a ctivated carbon RIB (Norit b.v., Amsterdam, Netherlands) - adsorption/desorption isotherms of N2 at 78K measured with ASAP 2405N automatic sorption analyzer (Mi cromeritics, USA). Original text report (black text) includes pictures and addit ional explanations (blue) / comments (green) from myself. Mesopores | Hysteresis loops | Kelvin equation | Pore size | Pore/meniscus shape | BJH