Nitrogen isotherm

Fig. XVII-29. Nitrogen isotherms the volume adsorbed is plotted on an arbitrary scale. The upper scale shows pore radii corresponding to various relative pressures. Samples A, Oulton catalyst B, bone char number 452 C, activated charcoal F, Alumina catalyst F12 G, porous glass S, silica aerogel. (From Ref. 196).

Comparison of BET areas from nitrogen isotherms with independent values... 

Molecular area, a ,(Ar), of argon at 77 K on nonporous oxides (Argon BET plots constructed withp (liquid) BET surface areas calculated from nitrogen isotherms, with a (Na) = 16-2 A )... 

Thus, if the specific surface of the reference material is known (e.g. from the nitrogen isotherm) the specific surface of the test sample can be calculated from the ratio of the slopes of the a -plots. The specific surfaces of all the... 

The method may be illustrated by reference to a study of the effect of compaction of a non-porous powder. The nitrogen isotherm on a silica... 

Since they all necessitate a knowledge of the value of r, and of both r and either directly or indirectly, all as a function of p p°, these data are given in tabular form for reference (Table 3.2). If required, intermediate values of t may be obtained to sufficient accuracy by graphical interpolation, and the corresponding values of r can be calculated with the Kelvin formula. The values of r refer to the most commonly used model, the cylindrical pore, so that r " = r + t. The values of t are derived from the standard nitrogen isotherm for hydroxylated silica and though the values do differ... 

Calculation of pore size distribution (Roberts Method"). Worked example from desorption branch of nitrogen isotherm on... 

It was noted earlier (p. 115) that the upward swing in the Type IV isotherm characteristic of capillary condensation not infrequently commences in the region prior to the lower closure point of the hysteresis loop. This feature can be detected by means of an a,-plot or a comparison plot (p. 100). Thus Fig. 3.25(a) shows the nitrogen isotherm and Fig. 3.25(h) the a,-plot for a particular silica gel the isotherm is clearly of Type IV and the closure point is situated around 0 4p° the a,-plot shows an upward swing commencing at a = 0-73, corresponding to relative pressures of 013 and therefore well below the closure point. 

Striking confirmation of the conclusion that the BET area derived from a Type IV isotherm is indeed equal to the specific surface is afforded by a recent study of a mesoporous silica, Gasil I, undertaken by Havard and Wilson. This material, having been extensively characterized, had already been adopted as a standard adsorbent for surface area determination (cf. Section 2.12). The nitrogen isotherm was of Type IV with a well defined hysteresis loop, which closed at a point below saturation (cf. F, in Fig. 3.1). The BET area calculated from it was 290 5 0 9 m g , in excellent agreement with the value 291 m g obtained from the slope of the initial region of the plot (based on silica TK800 as reference cf. p. 93). 

Experimental findings in the intervening years have tended to support and extend this concept. The results obtained by Ramsay and Avery in their studies of the effect of compaction on the nitrogen isotherms of two finely divided powders, one of zirconia and the other of silica, are especially instructive in the present context. As in earlier studies (cf. Chapter 3) the isotherm on the original powder was of Type II, but on compaction it first became Type IV with a well defined hysteresis loop, which moved... 

To test the Brunauer approach, it was necessary to use standard isotherms of nitrogen having the same c-constants as the experimental isotherms of Table 4.7. Since nitrogen isotherms with c > 10 have not been reported in the literature, theoretical isotherms corresponding to the c-values of Table 4.6 were calculated by Brunauer s modification of Anderson s equation, and standard a,-curves were constructed from them. The corresponding a,-plots appear in Fig. 4.15 they are no longer parallel... 

Fig. 4.15 a,-plots for the adsorption of nitrogen on a sample of microporous titania, before and after nonane treatment. Curve (A), before nonane pre-adsorption curves (B), (C), (D) after nonane pre-adsorption, followed by outgassing at (B) 250° (C) 150°C (D) 25°C. The a,-plots were based on standard nitrogen isotherms having the same c-values as the isotherms of... 

It is, however, possible to use a Type 111 isotherm of an adsorptive G, say, on a solid S for the evaluation of the specific surface of S, provided a standard sample of the solid is available to enable one to construct a standard a,-curve of G on S. The area of the standard sample must be known, usually from the nitrogen isotherm. 

Although a correlation between BET surface areas from 77 K nitrogen isotherms and methane uptake at 298 K and 3.5 MPa has been shown for many carbon adsorbents, [11, 20], deviations from this relationship have been observed [20]. However, as a primary screening process for possible carbonaceous adsorbents for natural gas, this remains a useful relationship. It should be noted that this correlation only seems to be applicable for active carbons. 

Barrett, E.P., Joyner, L.G., and Halenda, P.P. 1951. The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J. Am. Chem. Soc. 73 373-80. 

Figure 17.11. Nitrogen isotherm for activated alumina determined at the boiling point of liquid nitrogen...

E. P. Barrett, L. G. Joyner, and P. P. Halenda, The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms, J. Am. Chem. Soc., 73, 373-380(1951)... 

Figure la Nitrogen isotherm of a polymer templated material at 77 K (sample 5) 10 100 1000... 

The nitrogen adsorption / desorption isotherms (Fig. 2) are typical of well-defined porous frameworks that are characteristic of either supermicroporosity (MSU-1) or a small mesoporosity (MSU-4) without any textural porosity [14]. In these two compounds, the silica walls (deduced from x-ray diffraction and nitrogen isotherms) are quite thick (< 20 A) [5],... 

Specific surface areas of the materials under study were calculated using the BET method [22, 23]. Their pore size distributions were evaluated from adsorption branches of nitrogen isotherms using the BJH method [24] with the corrected form of the Kelvin equation for capillary condensation in cylindrical pores [25, 26]. In addition, adsorption energy distributions (AED) were evaluated from submonolayer parts of nitrogen adsorption isotherms using the algorithm reported in Ref. [27],... 

Both types of molecular sieves, MCM-36 and MCM-41, demonstrate large BET surface area and high static sorption capacity (see Table 2). Considerable qualitative differences are observed in N2 isotherms, which are shown in Figure 3. The nitrogen isotherm for MCM-41, prepared with cetyltrimethylammonium cation, is type IV [9] and shows the characteristic reversible steep capillary condensation at p/p0 = -0.4 corresponding to the pore opening -40 A [1]. MCM-36 also shows the type IV isotherm with almost linear and reversible uptake increase up to - p/p0 = 0.5, followed by a hysteresis loop. This profile of adsorption/desorption is typical for layered materials with slit-like porosity generated between layers [9],... 

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