Brunauer-Emmett-Teller surface area determination

In practice, the amount of solid molecules on the surface being exposed to the solution is difficult or even impossible to quantify. Instead, the solid surface area to solution volume ratio is often used to quantify the amount of solid reactant. Therefore, experimentally determined second-order rate constants for interfacial reactions have the unit m s h As the true surface area of the solid is very difficult to determine, the BET (Brunauer-Emmett-Teller) surface area is fte-quentiy used. The maximum diffusion-controlled rate constant for a particle suspension containing pm-sized particles is ca 10 m s and for mm-sized particle suspensions the corresponding value is I0 m s h Unfortunately, the discrepancy between the true surface area and the BET surface area and the non-spherical geometry of the solid particles makes it impossible to exactly determine the theoretical diffusion-controlled rate constant. 

Brunauer-Emmett-Teller surface area BET measurements were conducted using a micrometries adsorption equipment (Quantachrome instrument, model Nova 2000, USA) determining nitrogen (99.99% purity) as the analysis gas and the catalyst samples were slowly heated to 300 for 3 hours under nitrogen atmospheric. Prior to analysis each precursors and catalyst and after reaction catalysts measurements specific surface area was evacuated at -196°C for 66 minutes. 

In addition to actual synthesis tests, fresh and used catalysts were investigated extensively in order to determine the effect of steam on catalyst activity and catalyst stability. This was done by measurement of surface areas. Whereas the Brunauer-Emmett-Teller (BET) area (4) is a measure of the total surface area, the volume of chemisorbed hydrogen is a measure only of the exposed metallic nickel area and therefore should be a truer measure of the catalytically active area. The H2 chemisorption measurement data are summarized in Table III. For fresh reduced catalyst, activity was equivalent to 11.2 ml/g. When this reduced catalyst was treated with a mixture of hydrogen and steam, it lost 27% of its activity. This activity loss is definitely caused by steam since a... 

In their pioneering studies of silica sols, Alexander and Iler (4) employed low-temperature nitrogen adsorption to determine the surface areas of the colloidal particles after removal of the aqueous medium. The Brunauer-Emmett-Teller (BET) areas were found to be only slightly larger than the values obtained from the particle size distributions as determined by light scattering and electron microscopy. These remarkable measurements indicated little change in the particle size or shape after the stabilized silica sols were carefully dried. 

To obtain the monolayer capacity from the isotherm, it is necessary to interpret the (Type II) isotherm in quantitative terms. A number of theories have been advanced for this purpose from time to time, none with complete success. The best known of them, and perhaps the most useful in relation to surface area determination, is that of Brunauer, Emmett and Teller. Though based on a model which is admittedly over-simplified and open to criticism on a number of grounds, the theory leads to an expression—the BET equation —which, when applied with discrimination, has proved remarkably successful in evaluating the specific surface from a Type II isotherm. 

A vast amount of research has been undertaken on adsorption phenomena and the nature of solid surfaces over the fifteen years since the first edition was published, but for the most part this work has resulted in the refinement of existing theoretical principles and experimental procedures rather than in the formulation of entirely new concepts. In spite of the acknowledged weakness of its theoretical foundations, the Brunauer-Emmett-Teller (BET) method still remains the most widely used procedure for the determination of surface area similarly, methods based on the Kelvin equation are still generally applied for the computation of mesopore size distribution from gas adsorption data. However, the more recent studies, especially those carried out on well defined surfaces, have led to a clearer understanding of the scope and limitations of these methods furthermore, the growing awareness of the importance of molecular sieve carbons and zeolites has generated considerable interest in the properties of microporous solids and the mechanism of micropore filling. 

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. 

The intrinsic dissolution rates of pharmaceutical solids may be calculated from the dissolution rate and wetted surface area using Eq. (36) or (37). For powdered solids, two common methods are available the powder intrinsic dissolution rate method, and the disc intrinsic dissolution rate method. In the former method, the initial dissolution rate of one gram of powder is determined by a batch-type procedure as illustrated in Fig. 13A. The initial wetted surface area of one gram of powder is assumed to equal the specific surface area determined by an established dry procedure, such as monolayer gas adsorption by the Brunauer, Emmett, and Teller (BET) procedure [110]. 

EA = elemental analysis IR = infrared spectroscopy PXRD = powder X-ray diffraction BET = Brunauer-Emmett-Teller method (specific BET surface area) and BJH = Barrett-)oyner-Halenda method (determination of pore volume and diameter), both determined by nitrogen physisorption ... 

The most definitive surface area measurements are probably those made by nitrogen adsorption using the BET theory. Neither the Brunauer, Emmett and Teller (BET) theory nor equation (11.5), used to calculate surface area from mercury intrusion data makes any assumptions regarding pore shape for surface area determinations. When these two methods are compared there is often surprisingly good agreement. When... 

Measurement of Surface Area. The Teachability determined by these methods is usually reported as g/cm day. The total surface area of particulate material can be assessed 1) by assuming a particle shape e.g.spherical) and estimating the number of particles, or 2) by measurements using the Brunauer-Emmett-Teller (BET) nitrogen adsorption technique ( ). Unfortunately, the BET method measures the area of surfaces to which nitrogen has access this is not necessarily the same as the area to which a solution has access. Access by solutions requires much larger pore areas. 

The Brunauer-Emmett-Teller (or BET) adsorption isotherm applies only to the physisorption of vapours but it is important to heterogeneous catalysis because of its use for the determination of the surface areas of solids. The isotherm is given by the following equation,... 

Surface area determined by krypton physisorption calculated by the Brunauer-Emmett- -Teller equation. ... 

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. 

Surface areas are determined by physisorption. The most common procedure to determine surface area is to measure how much N2 is adsorbed onto a certain amount of material. The uptake is measured at a constant low temperature (i.e., 80 K) as a function of N2 pressure, and is usually very well described by the Brunauer-Emmett-Teller (BET) isotherm. After determining the number of N2... 

The Brunauer-Emmett-Teller (BET) gas adsorption method has become the most widely used standard procedure for the determination of the surface area of finely-divided and porous materials, in spite of the oversimplification of the model on which the theory is based. 

The observed roughness factors (ratio of true to geometric surface) of the surfaces employed in this study varied from 1.2 to 1.4 (Table IV). This checked with electron microscope pictures of alumina and silica replicas from electropolished single crystal copper surfaces. It is unlikely that the surface areas determined by the Brunauer-Emmett-Teller analysis are too high by 50% or even by 25%, because in several cases this would lead to a roughness factor of less than unity. 

The area is an important surface parameter for catalytic studies. It is needed to evaluate the rate constant of the surface reaction from the kinetics as well as to allow a fair comparison to be made of the effectiveness of different catalysts. Areas are commonly determined by nitrogen or krypton gas adsorption interpreted by the Brunauer-Emmett Teller (BET) isotherm [30, 32], A number of other methods has been proposed and utilised including microscopy, isotopic exchange, chromatography, gas permeability, adsorption from solution, and negative adsorption (desorption) of co-ions [30, 33]. 

The appearance of Langmuir s comprehensive review of the nature of adsorption (1916, 1918) prompted several investigators to consider the possibility of using gas adsorption for surface area determination. Early attempts were made by Williams (1919) and Benton (1926), but these led to inconclusive findings. The first significant advances were made by Brunauer and Emmett (1935, 1937) and their work prepared the way for the development of the Brunauer-Emmett-Teller (BET) theory in 1938. 

Other methods that have been used to determine specific surface areas of cements include the Wagner turbidimeter (W16) and BET (Brunauer-Emmett-Teller) gas adsorption. The former, as eonventionally used, gives very low results beeause of a false assumption that the mean diameter of the particles smaller than 7.5 pm is 3.8 pm, which is much too high. The BET method gives results two to three times higher than the air permeability... 

In principle, isotherms at low partial pressures of the sorbate may be used to determine specific surface areas by the Brunauer-Emmett-Teller (BET) method (G64). In this method, it is assumed that molecules of the sorbate are adsorbed on surfaces that can include the walls of pores, provided that the distance between molecules on opposing walls is large compared with molecular dimensions. From a plot derived from the isotherm, and given the effective cross-sectional area of the sorbate molecule, the specific surface area of the sorbent and the net heat of adsorption are obtained. Using water as sorbate, specific surface areas of about 200 m per g of D-dried paste have typically been obtained for mature cement pastes of normal w/c ratios... 

Specific surface area was calculated from the Brunauer-Emmett-Teller (BET) equation for N2 adsorption at 77 K (Micromeritics, ASAP 2010) [10], The t-method of de Boer was used to determine the micropore volume [11]. The pore size distribution curves of micropores were obtained by the Horvath-Kawazoe (H-K) method [12]. 

We now cite the types of experimental data in the literature, by which an analysis of surface adsorption effects is carried out. One common experiment involves measuring adsorption isotherms. By weighing or by volumetric techniques one determines as a function of equilibrium gas pressure the amount of gas held on a given surface at a specified temperature. Usually this quantity varies sigmoidally with rising pressure P, as sketched in Fig. 5.2.1 for a variety of temperatures 7). By standard methods that rely on the Brunauer, Emmett, Teller isotherm equa-tion one can determine the point on the isotherms at which monolayer coverage of the surface is complete it is usually is located fairly close to the knee of the isotherm. From the cross sectional area of the adsorbate molecules and from the amount needed for monolayer coverage one may then ascertain more or less quantitatively the surface area of the adsorbent. As-... 

There are three different gas adsorption methods usually employed to obtain surface fractal dimension. In the first method, the particles are fractionated into narrow particle size distribution and the Brunauer-Emmett-Teller (BET) surface area is measured for each size fraction. Ds can then be determined from Eq. (7) ... 

The present article deals primarily with the elucidation of the surface nature of common metallic and oxidic catalysts, and with statistical-mechanical investigations of the chemisorption equilibrium on these catalysts. The surface areas of these catalysts as determined by the Brunauer-Emmett-Teller method have been taken into consideration. It was shown that a number of certain metallic catalysts such as nickel, cobalt, and platinum and also oxide catalysts of the spinel type act as an array of homogeneous active sites. There is no reason to believe that a few limited regions of the surfaces of these catalysts, such as corners, edges, lattice defects, etc. are particularly important for their catalytic activity. This conclusion is in accordance with the poisoning experiments of Maxted et al. There is some evidence that the surfaces of these catalysts... 

The most relevant characteristic of porous materials is the disposal of a high effective surface/volume relationship, usually expressed in terms of their specific surface area (area per mass unit), which can be determined from nitrogen adsorption/desorption data. Different methods are available for determining the specific surface area (Brunauer-Emmett-Teller, Langmuir, and Kaganer), micropore volume (f-plot, ttj, and Dubinin-Astakhov), and mesopore diameter (Barrett-Joyner-Halenda Leroux et al., 2006). Table 1.1 summarizes the values of specific surface area for selected porous materials. 

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