Nitrogen isotherm, desorption branch

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

Fig. 4.29 Adsorption isotherms of water vapour on caldte, after being balt-milted for different periods (A, B, C) and on precipitated calcium carbonate (D). Period of milling (A) 1000h (B) ISOh (C) 22h outgassing temperature 2S°C. Isotherms A, B and C (but not D) all showed extensive low-pressure hysteresis, but for clarity the desorption branch is omitted. The amount adsorbed is referred to 1 m of BET-nitrogen area. ...

Fig. 4 Nitrogen adsorption-desorption isotherms at 77 K of heat-treated NH4 -exchanged MSU-Ge-2 (solid circles, adsorption data open circles, desorption data). The hysteresis observed at P/Po > 0.8 is due to the voids between the agglomerated particles. (Inset) BJH pore size distribution calculated from the adsorption branch of the isotherm...

Fig. 11 Nitrogen adsorption-desorption isotherms of mesoporous (a) NU-GeSi-1, (b) NU-GeSi-2, (c) NU-GeSi-3, and (d) NU-GeSi-4 materials. Inset. BJH pore size distribution calculated from the adsorption branch...

Nitrogen adsorption - desorption isotherms were obtained from a volumetric adsorption analyzer ASAP 2010 manufactured by Micromeritics. The samples were first degassed for several hours at 350°C. The measurements were then carried out at -196°C over a wide relative pressure range from 0.01 to 0.995. The average pore diameter and the pore size distribution were determined by the B JH method from the adsorption branch of isotherm [18],... 

The nitrogen adsorption-desorption isotherms were obtained at 77K by AutoSorb-1 -C (Quantachrome). Prior to measurement, the samples were outgassed at 300°C for 3 h. The specific surface areas of the samples were determined from the linear portion of the BET plots. Pore size distribution was calculated from the desorption branch of N2 desorption isotherm using the conventional Barrett-Joyner-Halenda (BJH) method, as suggested by Tanev and Vlaev [15], because the desorption branch can provide more information about the degree of blocking than the adsorption branch. 

Figure 6. The pore size distributions of enlarged MCM-41 materials [2-3] calculated from adsorption (dotted lines) and desorption (solid lines) branches of nitrogen isotherms by the NLDFT method.

Figure 7. The pore size distribution of wide-pore material [4] (sample 4 in Table 1) calculated from adsorption and desorption branches of nitrogen isotherm by the NLDFT method.

The adsorption isotherm of N, on FSM-16 at 77 K had an explicit hysteresis. As to the adsorption hysteresis of N-, on regular mesoporous silica, the dependencies of adsorption hysteresis on the pore width and adsorbate were observed the adsorption hysteresis can be observed for pores of w 4.0nm. The reason has been studied by several approaches [5-8]. The adsorption isotherm of acetonitrile on FSM-16 at 303K is shown in Fig. 1. The adsorption isotherm has a clear hysteresis the adsorption and desorption branches close at PIP, = 0.38. The presence of the adsorption hysteresis coincides with the anticipation of the classical capillary condensation theory for the cylindrical pores whose both ends are open. The value of the BET monolayer capacity, nm, for acetonitrile was 3.9 mmol g. By assuming the surface area from the nitrogen isotherm to be available for the adsorption of acetonitrile, the apparent molecular area, am, of adsorbed acetonitrile can be obtained from nm. The value of am for adsorbed acetonitrile (0.35 nnr) was quite different from the value (0.22 nm2) from the liquid density under the assumption of the close packing. Acetonitrile molecules on the mesopore surface are packed more loosely than the close packing. The later IR data will show that acetonitrile molecules are adsorbed on the surface hydroxyls in... 

Nitrogen adsorption/condensation is used for the determination of specific surface areas (relative pressure < 0.3) and pore size distributions in the pore size range of 1 to 100 nm (relative pressure > 0.3). As with mercury porosimetry, surface area and PSD information are obtained from the same instrument. Typically, the desorption branch of the isotherm is used (which corresponds to the porosimetry intrusion curve). However, if the isotherm does not plateau at high relative pressure, the calculated PSD will be in error. For PSD s, nitrogen condensation suffers from many of the same disadvantages as porosimetry such as network/percolation effects and pore shape effects. In addition, adsorption/condensation analysis can be quite time consuming with analysis times greater than 1 day for PSD s with reasonable resolution. 

Nitrogen adsorption/condensation measurements were performed using an Autosorb-1 analyzer to calculate sample surface area and pore size distribution. BET analysis at 77 K was applied for extracting the monolayer capacity from the adsorption isotherm and a N molecular cross-sectional area of 0.162 nm2 was used to relate tne monolayer capacity to surface area. PSD s were calculated from the desorption branches of the isotherms using a modified form of the BJH method [18]. Mercury intrusion measurements were performed using an Autoscan-33 continuous scanning mercury porosimeter (12-33000 psia) and a contact angle of 140°. 

Figure 4.16 Pore size distribution obtained from the desorption branch of the nitrogen adsorption isotherm for the film formed from the two-weefc-aged, four-component sol (see Figure 4.14). Median pore diameter is 3.8 nm. (Reprinted...

The nitrogen adsorption-desorption isotherm and the pore-size distribution plots of the sample CPN-2 are shown in Figure 3. According to the classification of lUPAC [11], the isotherm should be ascribed to be of type IV. The BET surface area of the example sample is 215.39m. The pore size distribution (Fig. 3b) can be calculated from the desorption branch of the isotherms. The most probable pore size of the sample is 5nm and the pore volume of the pores with a diameter less than 606A at relative pressure of 0.967 is 0.2376cm /g. 

Pore size Pa and Pd were calculated from nitrogen sorption isotherm based on BJH model from adsorption branch and desorption branch, respectively. 

Figure 3-3. Nitrogen adsorption isotherm. 1, Adsorption branch 2, desorption branch.

Characterization of products. N2-adsorption-desorption isotherms were recorded at liquid nitrogen temperature after outgassing at 200-250 C for 2hr. Surface areas were calculated using the BET-equation and pore volumes were estimated to be the liquid volume adsorbed at a relative pressure of 0.995. Pore-size distributions were calculated from the desorption branches of the isotherms using parallel plates as a geometrical model. X-ray diffraction analyses were performed on samples oriented in order to amplify the 001-reflexions. 

Textural Parameters. Adsorption-desorption isotherms of N2 at 77K were determined in a Micromeritics ASAP 2010 with a micropore system. Prior to measurement, the samples were outgassed at 140 C for at least 16 h. The specific surface area was determined by the BET method, assuming that the area of a nitrogen molecule is 0.162 nm [12]. Micropore volume was calculated by the t-plot method using the Harkins and Jura [13] thickness. We used model isotherms calculated from density functional theory (DFT) to determine the pore size distributions and cumulative pore volume of the pillared samples by taking the adsorption branch of the experimental nitrogen isotherm, assuming slit-like pores [14]. 

Important trends in N2 isotherm when the PS beads are used as a physical template are shown in Table 1 and Fig. 2. In Table 1, PI is the alumina prepared without any templates, P2 is prepared without ]4iysical template (PS bead), P3 is prepared without chemical template (stearic acid), and P4 is prepared with all templates. For above 10 nm of pore size and spherical pore system, the Barrett-Joyner-Halenda (BJH) method underestimates the characteristics for spherical pores, while the Broekhoff-de Boer-Frenkel-Halsey-Hill (BdB-FHH) model is more accurate than the BJH model at the range 10-100 nm [13]. Therefore, the pore size distribution between 1 and 10 nm and between 10 and 100 nm obtained from the BJH model and BdB-FHH model on the desorption branch of nitrogen isotherm, respectively. N2 isotherm of P2 has typical type IV and hysteresis loop, while that of P3 shows reduced hysteresis loop at P/Po ca. 0.5 and sharp lifting-up hysteresis loop at P/Po > 0.8. This sharp inflection implies a change in the texture, namely, textural macro-porosity [4,14]. It should be noted that P3 shows only macropore due to the PS bead-free from alumina framework. 

Bulk Si/Al ratios were determined by AAS. Surface areas and pore volumes were determined by N2 absorption isotherms measured at liquid nitrogen temperature using a Micromeritics ASAP 2000M (Table 1). The zeolites were degassed under vacuum at 150°C for the as-s)mthesised and 450°C for the modified zeolites for at least 3 hours. The total surface area was derived using the BET equation [12], the micropore volume and the external surface area (ESA) were estimated by means of the t-plot method of Lippens et al [13] and the total and mesopore volumes were calculated by Barrett-Joyner-Halenda anaylsis of the desorption branch of the N2 isotherm [14]. 

Canonical ensemble density functional theory (CEDFT) has been employed for predicting hysteretic adsorption/desorption isotherms in nanopores of different geometries in the wide range of pore sizes (1 - 12 nm). It is shown that the CEDFT model qualitatively describes equilibrium and spinodal transitions and is in a reasonable quantitative agreement with experiments on well-characterized MCM-41 samples. A DFT-based method for calculating pore size distributions from the adsorption and desorption branches of nitrogen adsorption isotherms has been elaborated and tested against literature data on capillary condensation in MCM-41 samples with pores from 5 to 10 nm. 

Essential progress has been made recently in the area of molecular level modeling of capillary condensation. The methods of grand canonical Monte Carlo (GCMC) simulations [4], molecular dynamics (MD) [5], and density functional theory (DFT) [6] are capable of generating hysteresis loops for sorption of simple fluids in model pores. In our previous publications (see [7] and references therein), we have shown that the non-local density functional theory (NLDFT) with properly chosen parameters of fluid-fluid and fluid-solid intermolecular interactions quantitatively predicts desorption branches of hysteretic isotherms of nitrogen and argon on reference MCM-41 samples with pore channels narrower than 5 nm. 

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