Adsorption

Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid permeates or is dissolved by a liquid or solid. Note that adsorption is a surface-based process while absorption involves the whole volume of the material. The term sorption encompasses both processes, whiledesorption is the reverse of adsorption. Similar to surface tension, adsorption is a consequence of surface energy. In a bulk material, all the bonding requirements (be they ionic, covalent, or metallic) of the constituent atoms of the material are filled by other atoms in the material. However, atoms on the surface of the adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract adsorbates. The exact nature of the bonding depends on the details of the species involved, but the adsorption process is generally classified as physisorption(characteristic of weak van der Waals forces) or chemisorption (characteristic of covalent bonding). It may also occur due to electrostatic attraction. Adsorption is usually described through isotherms, that is, the amount of adsorbate on the adsorbent as a function of its pressure (if gas) or concentration (if liquid) at constant temperature. The quantity adsorbed is nearly always normalized by the mass of the adsorbent to allow comparison of different materials.

Langmuir
The Langmuir equation (also known as the Langmuir isotherm, Langmuir adsorption equation or Hill-Langmuir equation) relates the coverage or adsorption of molecules on a solid surface to gas

pressure or concentration of a medium above the solid surface at a fixed temperature. The equation was developed by Irving Langmuir in 1916. The equation is stated as:

or theta is the fractional coverage of the surface, P is the gas pressure or concentration, alphais a constant. The constant is the Langmuir adsorption constant and increases with an increase in the binding energy of adsorption and with a decrease in temperature.

In 1916, Irving Langmuir published a new model isotherm for gases adsorbed to solids, which retained his name. It is a semi-empirical isotherm derived from a proposed kinetic mechanism. It is based on four assumptions: 1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equivalent. 2. 3. Adsorbed molecules do not interact. 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.

The Langmuir isotherm is nonetheless the first choice for most models of adsorption, and has many applications in surface kinetics (usually called Langmuir-Hinshelwood kinetics) and thermodynamics.

Langmuir suggested that adsorption takes place through this mechanism: , where A is a gas molecule and S is an adsorption site. The direct and inverse rate constants are k and k -1. If we define surface coverage, , as the fraction of the adsorption sites occupied, in the equilibrium we have:

or

where is the partial pressure of the gas or the molar concentration of the solution. For very low pressures and for high pressures is difficult to measure experimentally; usually, the adsorbate is a gas and the quantity adsorbed is given in moles, grams, or gas volumes at standard temperature and pressure (STP) per gram of adsorbent.

BET

Often molecules do form multilayers, that is, some are adsorbed on already adsorbed molecules and the Langmuir isotherm is not valid. The concept of the theory is an extension of the Langmuir theory, which is a theory for monolayer molecular adsorption, to multilayer adsorption with the following hypotheses: (a) gas molecules physically adsorb on a solid in layers infinitely; (b) there is no interaction between each adsorption layer; and (c) the Langmuir theory can be applied to each layer The modified Langmuir's mechanism is: A(g) + S AS A(g) + AS A2S A(g) + A2S A3S and so on

The Langmuir isotherm is usually better for chemisorption and the BET isotherm works better for physisorption for non-microporous surfaces.

Langmuir isotherm (red) and BET isotherm (green)

Desorption
Desorption is a phenomenon whereby a substance is released from or through a surface. The process is the opposite of sorption (that is, either adsorption and absorption). This occurs in a system being in the state of sorption equilibrium between bulk phase (fluid, i.e. gas or liquid solution) and an adsorbing surface (solid or boundary separating two fluids). When the concentration (or pressure) of substance in the bulk phase is lowered, some of the sorbed substance changes to the bulk state. I

After adsorption, the adsorbed chemical will remain on the substrate nearly indefinitely, provided the temperature remains low. However,as the temperature rises, so does the likelihood of desorption occurring. The general equation for the rate of desorption is:

, where is the rate constant for desorption, is the concentration of the adsorbed material, and is the kinetic order of desorption. Usually, the order of the desorption can be predicted by the number of elementary steps involved: Atomic or simple molecular desorption will typically be a first-order process (i.e. a simple molecule on the surface of the substrate desorbs into a gaseous form). Recombinative molecular desorption will generally be a second-order process (i.e. two hydrogen atoms on the surface desorb and form a gaseous H2 molecule). The rate constant may be expressed in the form

where is the "attempt frequency" (often the Greek letter ), the chance of the adsorbed molecule overcoming its potential barrier to desorption, is the activation energy of desorption, is the Boltzmann constant, and is the temperature.