misture, the pores if sufficiently larger in diameter than the liquid molecules, fill with quid. At equilibrium, because of differences in the extent of physical adsorption among liquid molecules, composition of the liquid in pores differs from that of bulk liquid surrounding adsorbent panicles. The observed exothermic heat effect is referred to as the hear of wetting, Which is much smaller than the heat of adsorption fora sas. AS with gases, the extent of equilibrium adsorption of a given solute inereases with concentration and decreases with en perature. Chemisorption ean ako occur with liquids. ‘Table 15.2 lists, for six major types of solid adsorbents: the nature of the adsorbent and representative values of the mean pore diameter, dy: particle porosity (intemal void frac- tion), €p: particle density, py: and specific surface area, Sy. In addition, for some adsorbents, the capacity for adsorbing ‘water vapor ata partial pressure of 4.6 mmHg in air at 25°C is listed, as taken from Rousseau [9]. Not included is specific pore volume, Vp, which is given by y, p= 10 (1s) Also not included in Table 15.2, but of interest when the adsorbent is used in fixed beds, are bulk density, py. and bed porosity (external void fraction), e), which are related by (154) In addition, the true solid particle density (also called the Sraine densi) sa Be compe rm Sir eeu gait (ass) Surface Are omd the BET Equation Specie sue area ofan aorbent Sy is measured by adsorbing gaseous nitrogen, using the well-accepted BET. ‘method (Brunauer, Emmett, and ‘Teller (11). Typically, the BET apparatus operates at the normal boiling point of N: (195.8°C) by measuring the equilibrium volume of pure Nz physically adsorbed on several grams of the adsorbent at number of different values of the total pressure in a vacuum of 5 to at least 250 mmHg. Brunauer, Emmett, and Teller derived an equation to model adsorption by allowing for For- ‘mation of multimolecular layers. They assumed that the heat of adsorption during monolayer formation (Aya) is con- tant and that the heat effect associated with subsequent ers is equal to the heat of condensation (AMcoq). The BET aR F we a () where P = total pressure, Po = vapor pressure of adsorbate at {est temperature, v = volume of gas adsorbed at STP (°C, 760 mmHg), vn, = volume of monomolecular layer of gas adsorbed at STP, and ¢ = a constant related to the heat of adsomption ~ expl(AFfoy1 ~ AHyiQ/RT1 Experimental data for v as a function of P are plotted, according to (15-6) as P/[uPy — P)] versus P/Po, from, which vy and ¢ are determined from the slope and intercept Of the best straight-line fit ofthe data, The value of S, is then ‘computed from (15-6) enn y= Suna as) where Nq = Avogadro's number = 6,023 x 10® molecules mmol, V = volume of gas per mole at STP conditions (0°C, Tat) = 22.400 em'Ymol, and exis surface area per adsorbed molecule. If spherical molecules arranged in close two- dimensional packing are assumed, the projected surface area i: ois 11 Gin) where M = molecular weight of the adsorbate, and py = den- sity of the adsorbate in glem*, taken as the liquid at the test temperature (158)