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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 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.
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 langmuir is defined by multiplying the pressure of the gas by the time of exposure. One langmuir corresponds to an exposure of 10 −6 Torr during one second. [1] [2] For example, exposing a surface to a gas pressure of 10 −8 Torr for 100 seconds corresponds to 1 L.
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
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 pressure swing adsorption (PSA) process is based on the phenomenon that under high pressure, gases tend to be trapped onto solid surfaces, i.e. to be "adsorbed". The higher the pressure, the more gas is adsorbed. When the pressure is dropped, the gas is released, or desorbed.