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Langmuir equation : ウィキペディア英語版
Langmuir adsorption model

The Langmuir adsorption model explains adsorption by assuming an adsorbate behaves as an ideal gas at isothermal conditions. At these conditions the adsorbate's partial pressure, p_A, is related to the volume of it, V, adsorbed onto a solid adsorbent. The adsorbent, as indicated in Figure 1, is assumed to be an ideal solid surface composed of series of distinct sites capable of binding the adsorbate. The adsorbate binding is treated as a chemical reaction between the adsorbate molecule A_ and an empty site, S. This reaction yields an adsorbed complex A_ with an associated equilibrium constant K_
: A_\,\,\, + \,\,\, S \,\,\, \rightleftharpoons \,\,\, A_
From these assumptions the Langmuir isotherm can be derived (see below), which states that:
:\theta_A = \frac = \frac
where \theta_A is the fractional occupancy of the adsorption sites and V_m is the volume of the monolayer. A continuous monolayer of adsorbate molecules surrounding a homogeneous solid surface is the conceptual basis for this adsorption model.
The Langmuir isotherm is formally equivalent to the Hill equation in biochemistry.
==Background and experiments==
In 1916, Irving Langmuir presented his model for the adsorption of species onto simple surfaces. Langmuir was awarded the Nobel Prize in 1932 for his work concerning surface chemistry. He hypothesized that a given surface has a certain number of equivalent sites that a species can “stick”, either by physisorption or chemisorption. His theory began when he postulated that gaseous molecules do not rebound elastically from a surface, but are held by it in a similar way to groups of molecules in solid bodies.
Langmuir published two papers that proved the assumption that adsorbed films do not exceed one molecule in thickness. The first experiment involved observing electron emission from heated filaments in gases.
The second, a more direct proof, examined and measured the films of liquid on an adsorbent surface layer. He also noted that generally the attractive strength between the surface and the first layer of adsorbed substance is much greater than the strength between the first and second layer. However, there are instances where the subsequent layers may condense given the right combination of temperature and pressure.
The most important empirical data came from a set of experiments that Langmuir ran to test the adsorption of several gases on mica, glass and platinum. The experiments began at very low pressures (~100 bar) in order to more easily measure the change in quantities of free gas and also to avoid condensation. He then ran the experiments at different temperatures and pressures, which proved the pressure dependence demonstrated below.

抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)
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