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The adsorption rate is dependent on the temperature, the diffusion rate of the solute (related to mean free path for pure gas), and the energy barrier between the molecule and the surface. The diffusion and key elements of the adsorption rate can be calculated using Fick's laws of diffusion and Einstein relation (kinetic theory).
Let us assume that the adsorption rate R ads,i-1 for molecules on a layer (i-1) (i.e. formation of a layer i) is proportional to both its fractional surface θ i-1 and to the pressure P, and that the desorption rate R des,i on a layer i is also proportional to its fractional surface θ i:
The Hertz–Knudsen equation describes the non-dissociative adsorption of a gas molecule on a surface by expressing the variation of the number of molecules impacting on the surfaces per unit of time as a function of the pressure of the gas and other parameters which characterise both the gas phase molecule and the surface: [1] [2]
The adsorption sites (heavy dots) are equivalent and can have unit occupancy. Also, the adsorbates are immobile on the surface. The Langmuir adsorption model explains adsorption by assuming an adsorbate behaves as an ideal gas at isothermal conditions. According to the model, adsorption and desorption are reversible processes.
where A is the reactant and S is an adsorption site on the surface and the respective rate constants for the adsorption, desorption and reaction are k 1, k −1 and k 2, then the global reaction rate is: = = where: r is the rate, mol·m −2 ·s −1
The Freundlich equation or Freundlich adsorption isotherm, an adsorption isotherm, is an empirical relationship between the quantity of a gas adsorbed into a solid surface and the gas pressure. The same relationship is also applicable for the concentration of a solute adsorbed onto the surface of a solid and the concentration of the solute in ...
Source: [2] If a solid body is modeled by a constant field and the structure of the field is such that it has a penetrable core, then = ′ [ ()] ′ [ ()]. Here ′ is the position of the dividing surface, = is the external force field, simulating a solid, is the field value deep in the solid, = /, is the Boltzmann constant, and is the temperature.
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