表面化学Chemical_Adsorption_(_Chemisorption_)教材教学课件.pptVIP

2.7 Adsorption and desorption;Some Terminologies;Adsorption - the process in which a molecule becomes adsorbed onto a surface of another phase (note - to be distinguished from absorption which is used when describing uptake into the bulk of a solid or liquid phase) Coverage - a measure of the extent of adsorption of a species onto a surface (unfortunately this is defined in more than one way ! ). Usually denoted by the lower case Greek theta, q Exposure - a measure of the amount of gas which a surface has seen; more specifically, it is the product of the pressure and time of exposure (normal unit is the Langmuir, where 1?L = 10-6 Torr s ). ;Coverage;Physical Adsorption ( Physisorption ) ;Chemical Adsorption ( Chemisorption );Physisorption + Molecular Chemisorption ;The energy of adsorption is negative, and since it corresponds to the energy change upon adsorption it is better represented as DE(ads) or DEads There is clearly no barrier to be overcome in the adsorption process and there is no activation energy of adsorption ;There is of course a significant barrier to the reverse, desorption process - the red arrow in the diagram below represents the activation energy for desorption. The magnitudes of the energy of adsorption and the activation energy for desorption can also be equated i.e. Eades = DE (ads)?;Physisorption + Dissociative Chemisorption ;Eades - Eaads = - DEads;;;Adsorption Kinetics - The Rate of Adsorption ;The rate of adsorption is governed by : 1. the rate of arrival of molecules at the surface 2. the proportion of incident molecules which undergo adsorption. ;We also can express the rate of adsorption (per unit area of surface) as a product of the incident molecular flux, F , and the sticking probability , S . ?Rads = S?F [molecules m-2 s-1 ];The flux of incident molecules is given by the Hertz-Knudsen equation F = P / (2pmkT)1/2 [ molecules m-2 s-1 ] where??P - gas pressure [ N m-2 ],?m - mass of one molecule [ kg ] , k - Boltzmann const