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How does bet work?

Adsorption is defined as the adhesion of atoms or molecules of gas to a surface. It should be noted that adsorption is not confused with absorption, in which a fluid permeates a liquid or solid. The amount of gas adsorbed depends on the exposed surface are but also on the temperature, gas pressure and strength of interaction between the gas and solid. In BET surface area analysis, nitrogen is usually used because of its availability in high purity and its strong interaction with most solids. Because the interaction between gaseous and solid phases is usually weak, the surface is cooled using liquid N 2 to obtain detectable amounts of adsorption. Known amounts of nitrogen gas are then released stepwise into the sample cell. Relative pressures less than atmospheric pressure is achieved by creating conditions of partial vacuum. After the saturation pressure, no more adsorption occurs regardless of any further increase in pressure. Highly precise and accurate pressure transducers monitor the pressure changes due to the adsorption process. After the adsorption layers are formed, the sample is removed from the nitrogen atmosphere and heated to cause the adsorbed nitrogen to be released from the material and quantified. The data collected is displayed in the form of a BET isotherm, which plots the amount of gas adsorbed as a function of the relative pressure. There are five types of adsorption isotherms possible.

Type i isotherm

Type I is a pseudo-Langmuir isotherm because it depicts monolayer adsorption ( [link] ). A type I isotherm is obtained when P/P o <1 and c>1 in the BET equation, where P/P o is the partial pressure value and c is the BET constant, which is related to the adsorption energy of the first monolayer and varies from solid to solid. The characterization of microporous materials, those with pore diameters less than 2 nm, gives this type of isotherm.

The isotherm plots the volume of gas adsorbed onto the surface of the sample as pressure increases. Adapted from S. Brunauer L. S. Deming, W. E. Deming, and E. Teller, J. Am. Chem. Soc. , 1940, 62 , 1723.

Type ii isotherm

A type II isotherm ( [link] ) is very different than the Langmuir model. The flatter region in the middle represents the formation of a monolayer. A type II isotherm is obtained when c>1 in the BET equation. This is the most common isotherm obtained when using the BET technique. At very low pressures, the micropores fill with nitrogen gas. At the knee, monolayer formation is beginning and multilayer formation occurs at medium pressure. At the higher pressures, capillary condensation occurs.

The isotherm plots the volume of gas adsorbed onto the surface of the sample as pressure increases. Adapted from S. Brunauer, L. S. Deming, W. E. Deming, and E. Teller, J. Am. Chem. Soc. , 1940, 62 , 1723.

Type iii isotherm

A type III isotherm ( [link] ) is obtained when the c<1 and shows the formation of a multilayer. Because there is no asymptote in the curve, no monolayer is formed and BET is not applicable.

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Source:  OpenStax, Physical methods in chemistry and nano science. OpenStax CNX. May 05, 2015 Download for free at http://legacy.cnx.org/content/col10699/1.21
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