BET surface area measurements

Adsorption vs Absorption

Adsorption

is the adhesion of atoms, ions or molecules of gas, liquid, or dissolved solids to a surface.
This

process creates a film of the adsorbate on the surface of the adsorbent. It differs from absorption, in which a fluid permeates or is dissolved by a liquid or solid.

Langmuir equation is the fractional coverage of the surface, P is the gas pressure or concentration, is a constant. 1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equivalent. 2. Adsorbed molecules do not interact. 3. All adsorption occurs through the same mechanism. 4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate do not deposit on other, already adsorbed, molecules of adsorbate, only on the free surface of the adsorbent.

Brunauer, Emmett and Teller Theory

Often molecules do form multilayers, that is, some are adsorbed on already adsorbed molecules and the Langmuir isotherm is not valid.

S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309.

Basic assumptions 1. the same assumptions as that of Langmuir but allow multi-layer adsorption 2. the heat of ads. of additional layer equals to the latent heat of condensation 3. based on the rate of adsorption=the rate of desorption for each layer of ads. the following BET equation was derived
P / P0 1 c 1 = + ( P / P0 ) V ( 1 P / P0 ) cVm cVm

Where P - equilibrium pressure P0 -saturate vapour pressure of the adsorbed gas at the temperature P/P0 is called relative pressure V - volume of adsorbed gas per kg adsorbent Vm - volume of monolayer adsorbed gas per kg adsorbent c - constant associated with adsorption heat and condensation heat

Applications of BET surface area measurements: Its main application is in catalysis

1. Calculation of surface areaof a solid material 2. Pore Size of Porous materials 3. Pore Volume of Porous materials

Sorption isotherm measurement volumetric methods

Choice of Gas and Temperature

Gases
Nitrogen Argon Krypton Carbon dioxide Others

Temperatures
Liquid Nitrogen Liquid Argon Dry ice/acetone Water/ice Others

 Five types of physisorption isotherms are found over all solids

I

II

Type I is found for porous materials with small pores e.g. charcoal. It is clearly Langmuir monolayer type, but the other 4 are not Type II for non-porous materials

amount adsorbed

III

IV

Type III porous materials with cohesive force between adsorbate molecules greater than the adhesive force between adsorbate molecules and adsorbent Type IV staged adsorption (first monolayer then build up of additional layers)
1.0

relative pres. P/P0

Type V porous materials with cohesive force between adsorbate molecules and adsorbent being greater than that between adsorbate molecules

Nitrogen adsorption-desorption isotherm of SBA-15

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