The Determination of Small Surface Areas by Krypton Adsorption at Low Temperatures

Beebe, Ralph A.; Beckwith, John B.; Honig, J. M.

doi:10.1021/ja01225a048

Cited by 130 publications

(58 citation statements)

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“…For carbon dioxide and krypton the extrapolated vapor pressures for the super-cooled liquids at the temperature of the bath have been used in calculating P/Po. The validity of this latter procedure has been discussed by various authors (Beebe et aL, 1945;Gregg and Sing, 1967, pp. 84 and 90l. It is~used here since more linear plots were obtained in applying the BET theory than when the measured saturation vapor pressure was used.…”

Section: Isothermsmentioning

confidence: 99%

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Gas Sorption in Clay Mineral Systems

Aylmore

1974

Clays and clay miner.

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Abstract--Sorption isotherms for four gases (N2, A, Kr and CO2) , commonly used in specific surface area and pore structure measurements, have been accurately determined on a number of clay mineral and oxide systems.Specific surface areas obtained by application of the BET theory to these isotherms illustrate the extent to which the apparent cross-sectional areas for these sorbed gases vary with surface structure, exchangeable cation and microporosity.V-n plots for nitrogen adsorption on these materials using nitrogen adsorption on crystalline materials of large crystal size as a standard isotherm provide appreciable ranges of linearity in each case. The specific surface areas obtained from these straight line plots agree well with the corresponding BET values. The linearity of these plots for illite clays indicates the absence of capillary condensation and that adsorption in slit-shaped pores takes place largely by the formation of physically adsorbed layers on the surfaces.Much larger BET specific surface areas were obtained from carbon dioxide sorption at 196K on goethite, hematite and gibbsite than from nitrogen, argon and krypton sorption at 78"K. It is suggested that enhanced sorption of CO2 into microporous regions of the oxides, inaccessible to the other gases, occurs in a similar fashion to that frequently observed for coal and charcoal materials. V-n plots for CO2 sorption in these materials using that for an illite clay as a standard isotherm, support this conclusion.Considerably lower BET specific surface areas were obtained for CO 2 sorption on kaolinite than were obtained for nitrogen, argon and krypton sorption. The shape of the V-n plots for CO., sorption on kaolinite compared with illite suggest that an initial specific adsorption of CO2 on the kaolinite is followed by a change in state with the completion of this layer, allowing normal multilayer formation to proceed.

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Section: Isothermsmentioning

confidence: 99%

“…and hence a marked reduction in the volume of unadsorbed gas which has to be corrected for (Beebe, Beckwith and Honig, 1945;Sing and Swallow, 1960). Krypton adsorption also offers the benefit that its inertness makes it unlikely that it will interact specifically with the solid surface.…”

Section: Introductionmentioning

confidence: 99%

Gas Sorption in Clay Mineral Systems

Aylmore

1974

Clays and clay miner.

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“…Krypton at 77 K (well below its bulk triple point of 115.8 K) is the adsorbate of choice for measuring the surface area of low surface area solids [1]. At this temperature, the adsorption isotherm on homogeneous graphite surfaces is stepped, clearly indicating that adsorption proceeds by a layering mechanism, and for these reasons the system has attracted much attention both experimentally and theoretically.…”

Section: Introductionmentioning

confidence: 99%

On the 2D-transition, hysteresis and thermodynamic equilibrium of Kr adsorption on a graphite surface

Diao

Fan

et al. 2015

Journal of Colloid and Interface Science

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The adsorption and desorption of Kr on graphite at temperatures in the range 60 K to 88 K, was systematically investigated using a combination of several simulation techniques including: grand canonical Monte Carlo (GCMC), canonical kinetic-Monte Carlo (C-kMC) and the Mid-Density scheme (MDS). Particular emphasis was placed on the gas-solid, gas-liquid and liquid-solid 2D phase transitions. For temperatures below the bulk triple point, the transition from a 2D-liquid-like monolayer to a 2D-solid-like state is manifested as a sub-step in the isotherm. A further increase in the chemical potential leads to another rearrangement of the 2D-solidlike state from a disordered structure to an ordered structure that is signalled by (1) another sub-step in the monolayer region and (2) a spike in the plot of the isosteric heat versus density at loadings close to the dense monolayer coverage concentration. Whenever a 2D transition occurs in a grand canonical isotherm it is always associated with a hysteresis, a feature that is not widely recognized in the literature. We studied in details this hysteresis with the analysis of the canonical isotherm, obtained with C-kMC, which exhibits a van der Waals (vdW) type loop with a vertical segment in the middle. We complemented the hysteresis loop and the vdW curve with the analysis of the equilibrium transition obtained with the MDS, and found that the equilibrium transition coincides exactly with the vertical segment of the C-kMC isotherm, indicating the coexistence of two phases at equilibrium. We also analysed adsorption at higher layers and found that the 2D-coexistence is also observed, provided that the temperature is well below the triple point. Finally the 2D-critical temperatures were obtained for the first three layers and they are in good agreement with the experimental data in the literature.

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“…Secondly, the isotherm appears to meet the p/p 0 * 1 axis at a finite value in the region of 3.5 layers. The adsorption at high saturations of solid layers is little understood, but the latter effect has been observed before with other gases, for example, carbon dioxide (Brunauer and Emmet, 1937) and krypton (Beebe, Beckwith, and Honig, 1945). As the result of this effect, the data at the high saturations cannot be represented by a power law similar to Equation (1).…”

Section: The Adsorption Of Argonmentioning

confidence: 94%

Quarterly Rept. No. 28 for March 1953 to Sponsors of the Institute for the Study of Metals

METALS¹

1953

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The Determination of Small Surface Areas by Krypton Adsorption at Low Temperatures

Cited by 130 publications

References 0 publications

Gas Sorption in Clay Mineral Systems

Gas Sorption in Clay Mineral Systems

On the 2D-transition, hysteresis and thermodynamic equilibrium of Kr adsorption on a graphite surface

Quarterly Rept. No. 28 for March 1953 to Sponsors of the Institute for the Study of Metals

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