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The kinetic derivation applies to gas-phase adsorption. However, it has been mistakenly applied to solutions. The multiple-adsorbate case is covered in the competitive adsorption sub-section. The model assumes adsorption and desorption as being elementary processes, where the rate of adsorption r ad and the rate of desorption r d are given by
Irving Langmuir was the first to derive a scientifically based adsorption isotherm in 1918. [14] The model applies to gases adsorbed on solid surfaces. It is a semi-empirical isotherm with a kinetic basis and was derived based on statistical thermodynamics.
The Gibbs adsorption isotherm for multicomponent systems is an equation used to relate the changes in concentration of a component in contact with a surface with changes in the surface tension, which results in a corresponding change in surface energy. For a binary system, the Gibbs adsorption equation in terms of surface excess is
The Langmuir model of adsorption [2] assumes . The maximum coverage is one adsorbate molecule per substrate site. Independent and equivalent adsorption sites. This model is the simplest useful approximation that still retains the dependence of the adsorption rate on the coverage, and in the simplest case, precursor states are not considered.
BET model of multilayer adsorption, that is, a random distribution of sites covered by one, two, three, etc., adsorbate molecules. 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:
This equation is known as Freundlich adsorption isotherm or Freundlich adsorption equation. As this relationship is entirely empirical, in the case where adsorption behavior can be properly fit by isotherms with a theoretical basis, it is usually appropriate to use such isotherms instead (see for example the Langmuir and BET adsorption theories ...
The linear isotherm can be used to describe the initial part of many practical isotherms. It is typically taken as valid for low surface coverages, and the adsorption energy being independent of the coverage (lack of inhomogeneities on the surface). The Henry adsorption constant can be defined as: [2]
Adsorption occurs at the liquid–liquid, liquid–vapor, and liquid-solid interfaces. The transport of molecules to the surface occurs due to a combination of diffusion and convective transport. According to the Langmuir or Avrami kinetic model the rate of deposition onto the surface is proportional to the free space of the surface. [7]