Calculation of pore size distribution

Use of the Kelvin equation for calculation of pore size distribution... 

In the pioneer work of Foster the correction due to film thinning had to be neglected, but with the coming of the BET and related methods for the evaluation of specific surface, it became possible to estimate the thickness of the adsorbed film on the walls. A number of procedures have been devised for the calculation of pore size distribution, in which the adsorption contribution is allowed for. All of them are necessarily somewhat tedious and require close attention to detail, and at some stage or another involve the assumption of a pore model. The model-less method of Brunauer and his colleagues represents an attempt to postpone the introduction of a model to a late stage in the calculations. 

Various methods have been devised for incorporating the bv correction into calculations of pore size distribution. Some of them involve the length of the pores and the area of their walls others the area of the walls only and yet others avoid the direct involvement of either the length or the area. Up to the present, virtually all the procedures have been restricted to nitrogen as the adsorptive. 

Calculation of pore size distribution (Method of Pierce, also of Orr and DallaValle )... 

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

The time is perhaps not yet ripe, however, for introducing this kind of correction into calculations of pore size distribution the analyses, whether based on classical thermodynamics or statistical mechanics are being applied to systems containing relatively small numbers of molecules where, as stressed by Everett and Haynes, the properties of matter must exhibit wide fluctuations. A fuller quantitative assessment of the situation in very fine capillaries must await the development of a thermodynamics of small systems. Meanwhile, enough is known to justify the conclusion that, at the lower end of the mesopore range, the calculated value of r is almost certain to be too low by many per cent. 

Each of the procedures described in Section 3.6 for the calculation of pore size distribution involves a value of the pore area y4f for each successive group of pores. In the Roberts procedure 6A, can be immediately obtained from the corresponding pore volume and pore radius as (for... 

Fig. 3J3 Calculation of pore size distribution in ink-bottle" pores, from mercury intrusion-extrusion experiment." (After Reverberi. )...

In writing the present book our aim has been to give a critical exposition of the use of adsorption data for the evaluation of the surface area and the pore size distribution of finely divided and porous solids. The major part of the book is devoted to the Brunauer-Emmett-Teller (BET) method for the determination of specific surface, and the use of the Kelvin equation for the calculation of pore size distribution but due attention has also been given to other well known methods for the estimation of surface area from adsorption measurements, viz. those based on adsorption from solution, on heat of immersion, on chemisorption, and on the application of the Gibbs adsorption equation to gaseous adsorption. 

Calculations of Pore Size Distributions in Nanoporous Materials from Adsorption and Desorption Isotherms... 

COMPARISON WITH EXPERIMENTS AND CALCULATION OF PORE SIZE DISTRIBUTIONS... 

The most common method used for the determination of surface area and pore size distribution is physical gas adsorption (also see 1.4.1). Nitrogen, krypton, and argon are some of the typically used adsorptives. The amount of gas adsorbed is generally determined by a volumetric technique. A gravimetric technique may be used if changes in the mass of the adsorbent itself need to be measured at the same time. The nature of the adsorption process and the shape of the equilibrium adsorption isotherm depend on the nature of the solid and its internal structure. The Brunauer-Emmett-Teller (BET) method is generally used for the analysis of the surface area based on monolayer coverage, and the Kelvin equation is used for calculation of pore size distribution. 

Hysteresis in the adsorption-desorption isotherms (Fig. 4) is a common observation for supports with a large fraction of small pores. It results from desorption from the meniscus at the end of a filled pore. The vapor pressure above the liquid at the pore mouth defines the pore radius in the Kelvin equation. Therefore, it is the desorption branch of the isotherm that is preferred in calculations of pore size distributions. 

Dollimore D and Heal GR. Improved method for calculation of pore size distribution from adsorption data. J. Appl. Chem. USSR, 1964 14(3) 109. 

CALCULATIONS OF PORE SIZE DISTRIBUTIONS FROM ADSORPTION AND DESORPTION BRANCHES... 

The novel approach for calculation of pore size distributions, which is reported in the current study is based on recent developments in the materials science and in the theory of inhomogeneous fluids. First, an application of experimental adsorption data for well-characterized MCM-41 silicas enabled proper calibration of the pore size analysis. Second, an application of a modem theory to describe the behavior of inhomogeneous fluids in confined spaces, that is the non-local density functional theory [6], allowed the numerical calculation of model isotherms for various pore sizes. In addition, a practical numerical deconvolution method that provides a "best fit" solution representing the pore distribution of the sample was implemented [7, 8]. In this paper we describe a deconvolution method for estimating mesopore size distribution that explicitly allows for unfilled large pores, and a method for creating composite, or hybrid, models that incorporate both theoretical calculations and experimental observations. Moreover, we showed the applicability of the new approach in characterization of MCM-41 and related materials. 

Others already employed local adsorption isotherms obtained from density functional theory in their calculations of pore size distributions for MCM-41 [16-17]. However, desorption data were used, which imposes two severe limitations on the results of calculations. 

Historically, the calculation of pore size distributions in porous materials has been primarily based on various forms and modifications of capillary theory... 

Innes, W.B. (1957). Use of a parallel plate model in calculation of pore size distribution. Anal. Chem., 29, 1069-73. 

Davies, G.M., Seaton, N.A., and Vassdiadis, V.S. (1999). Calculation of pore size distributions of activated carbons from adsorption isotherms. Langmuir, 15, 8235-45. 

The basic description of a mesoporous sample requires two types of determinations X-ray diffraction and gas adsorption/dcsorption isotherm. The latter are usually represented as the amount of gas adsorbed by the sample as the function of relative pressure. This information characterizes pore size distribution. Nitrogen adsorption/desorplion isotherm at 77 K is most often used and relatively convenient to carry out. The adsorption of noble gases is used if accurate in-depth pore characterization is attempted, especially quantitative. The calculation of pore size distribution from the isotherms is carried out using appropriate formulas such as Kelvin and IIorwath-Kawazoe equations (e.g. as in Ref. 5 and [6]), which involve assumptions and approximations. A more detailed and rigorous treatments have been developed, as for example KJS (Kruk-Jaroniec-Sayari), which is relatively simple and accurate [42]. In practice, the diameter of mesopores can be quickly estimated directly from the position of the capillary condensation or, if not vertical, the p/p0 of the inflection point. The conversion table of p/po values to pore diameters can be found in Ref. [43] and is partially reproduced here in Table 2. 

Such equations are the key to calculations of pore size distributions of meso-porous solids, via the Barrett, Joyner and Halenda (BJH) method, as explained by Thomas and Thomas. ... 

Various mathematical approaches to calculation of pore size distribution have evolved during the past centu. ... 

Chapter 2 provides a simple formula for calculating the basic forces or potentials for adsorption. Thus, one can compare the adsorption potentials of two different molecules on the same site, or that of the same molecule on two different sites. The calculation of pore size distribution from a single adsorption isotherm is shown in Chapter 4. The effects of pore size and shape on adsorption are discussed in both Chapters 2 and 4. Chapter 3 aims to provide rules for sorbent selection. Sorbent selection is a complex problem because it also depends on the adsorption cycle and the form of sorbent (e.g., granules, powder, or monolith) that are to be used. The attributes sought in a sorbent are capacity, selectivity, regenerability, kinetics, and cost. Hence, Chapter 3 also includes a summary of equilibrium isotherms, diffusion steps, and cyclic processes. Simple sorbent selection criteria are also presented. 

Calculation of pore size distribution by capillary cohesion method. Capillary cohesion method for the calculation of pore size distribution including the classical BJH method based on Kelvin equation for the analysis of pore size distribution DH method and its improved modificatory non-Model (ML method ) for the calculation of medium pore size distribution MP method DR equation HK equation CA equation density functional theory method for the calculation of micropore size distribution, and so on, have been introduced in many monographs.As for the adsorption experimental technology, the instrumental automation of static capacity way has been achieved and the d3mamic way has become common method. In particular, the apparatus of the static capacity way is small, and equipped with a variety of computer simulation softwares, and thus becomes a universal and standardized analytical instrument. 

Recent progress in the theory of adsorption on porous solids, in general, and in the adsorption methods of pore structure characterization, in particular, has been related, to a large extent, to the application of the density functional theory (DFT) of Inhomogeneous fluids [1]. DFT has helped qualitatively describe and classify the specifics of adsorption and capillary condensation in pores of different geometries [2-4]. Moreover, it has been shown that the non-local density functional theory (NLDFT) with suitably chosen parameters of fluid-fluid and fluid-solid interactions quantitatively predicts the positions of capillary condensation and desorption transitions of argon and nitrogen in cylindrical pores of ordered mesoporous molecular sieves of MCM-41 and SBA-15 types [5,6]. NLDFT methods have been already commercialized by the producers of adsorption equipment for the interpretation of experimental data and the calculation of pore size distributions from adsorption isotherms [7-9]. 

Test Method for Single-Point Determination of the Specific Surface Area of Catalysts Using Nitrogen Adsorption by the Continuous Flou Method Practice for Calculation of Pore Size Distributions of Catalysts from Nitrogen Desorption Isotherms... 

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