Constrictions in micropores

Adsorption is invariably an exothermic process, so that, provided equilibrium has been established, the amount adsorbed at a given relative pressure must diminish as the temperature increases. It not infrequently happens, however, that the isotherm at a given temperature Tj actually lies above the isotherm for a lower temperature Ti. Anomalous behaviour of this kind is characteristic of a system which is not in equilibrium, and represents the combined effects of temperature on the rate of approach to equilibrium and on the position of equilibrium itself. It points to a process which is activated in the reaction-kinetic sense and which therefore occurs more rapidly as temperature is increased. 

Wynne-Jones and Marshfound somewhat similar results with a number of carbons made by pyrolysis of eight organic polymers at a series of temperatures. The isotherms of Nj at 77 K and of COj at 195 K were measured, and the apparent surface area calculated by the usual BET procedure. (Owing to the microporous nature of the solids, these figures for area will be roughly proportional to the uptake at saturation and therefore 

The uptake, expressed as a volume v, of liquid, of nitrogen and of butane by a number of coal samples, at a pressure slightly below saturation on the Type I isotherms  

Further information as to the width of constrictions can be obtained from measurement of the heat of immersion of the solid in a range of liquids 

Values of the uptake at saturation, of butane, carbon dioxide and nitrogen, by a sample of carbon, expressed as a volume of liquid v,. The carbon had been burnt off to different extents by heating in oxygen at 500°C on a sorption 

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The swelling of the adsorbent can be directly demonstrated as in the experiments of Fig. 4.27 where the solid was a compact made from coal powder and the adsorbate was n-butane. (Closely similar results were obtained with ethyl chloride.) Simultaneous measurements of linear expansion, amount adsorbed and electrical conductivity were made, and as is seen the three resultant isotherms are very similar the hysteresis in adsorption in Fig. 4.27(a), is associated with a corresponding hysteresis in swelling in (h) and in electrical conductivity in (c). The decrease in conductivity in (c) clearly points to an irreversible opening-up of interparticulate junctions this would produce narrow gaps which would function as constrictions in micropores and would thus lead to adsorption hysteresis (cf. Section 4.S). 

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