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The Langmuir adsorption model deviates significantly in many cases, primarily because it fails to account for the surface roughness of the adsorbent. Rough inhomogeneous surfaces have multiple site types available for adsorption, with some parameters varying from site to site, such as the heat of adsorption.
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 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.
Because of this, adsorption of molecules onto polymer surfaces can be easily modeled by the Langmuir or Frumkin Isotherms. The Langmuir equation states that for the adsorption of a molecule of adsorbate A onto a surface binding site S, a single binding site is used, and each free binding site is equally likely to accept a molecule of adsorbate: [1]
The sticking probability is the probability that molecules are trapped on surfaces and adsorb chemically. From Langmuir's adsorption isotherm, molecules cannot adsorb on surfaces when the adsorption sites are already occupied by other molecules, so the sticking probability can be expressed as follows:
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:
The Langmuir-Rideal mechanism is often, incorrectly, attributed to Dan Eley as the Eley-Rideal mechanism. [5] The actual Eley-Rideal mechanism, studied in the thesis of Dan Eley and proposed by Eric Rideal in 1939, was the reaction between a chemisorbed and a physisorbed molecule. [6]
The simplest mathematical model to explain the Vroman Effect is the Langmuir model using the Langmuir isotherm. [9] [10] More complex models include the Fruendlich isotherm and other modifications to the Langmuir model.