Surface Chemistry: Adsorption
Surface Chemistry: Adsorption
Adsorption
Sorption: movement of a material from one phase to another.
only on the surface: adsorption
gas
Adsorbed molecules
solid
Adsorption of gas molecules
Absorption
Adsorption
1.
2.
3. 4. 5.
slow process requires porous structure attainment of equilibrium takes some time
Chemisorption
involves the formation of chemical bonds between adsorbed molecule and solid surface, and often the breaking of preexisting bonds in the adsorbed molecule. In some cases the chemisorption step requires an activation energy.
physisorption
involves forces similar to the van der Waals forces that lead to condensation of vapors to liquid.
Chemical Adsorption The forces operating are similar to those of chemical bond. Strong adsorption It is slow process
It is irreversible Unimolecular layer is formed It is in the range of 80240 kJ/mol. High
It is 20 to 40 kJ/mol. Low
Non specific
Specific
isotherm
Adsorption increases with increase of pressure under low pressure. While at high pressure, adsorption attains maximum value.
adsorption isotherm:
an expression that gives the fraction of a surface that is covered by adsorbed molecules in equilibrium at constant temperature as a function of pressure or concentration.
2. The residual valency force is effective only one molecule thick. 3. It consists two opposing forces, namely condensation and evaporation (desorption). 4. When adsorption starts condensation is highest, while desorption is smallest.
As the surface becomes covered, the rate of condensation decreases, while the evaporation increases. Ultimately a dynamic equilibrium is set up. Let is fraction the total surface covered, then (1-) is fraction of surface still bare
rads k1 (1 ) P
Rate evaporation r2
At Equilibrium r1 = r2
rdes k2
k1P aP k2 k1P 1 aP
a (adsorption coefficient) :
kaP bP w k 1 aP 1 aP
w bP
p 1 ap w b b y c mx
p w
a b
bP
1 b
3) the heat of the layer other than the first layer is the condensation heat; 4) desorption only occur at the layer exposed to the gas
For the isotherms the multi layer adsorption is responsible for a condensation of large amount of adsorbate. Then the derivation is more complicated than Langmuir but going in similar lines we obtain:
P 1 c 1 P 0 ( P0 P)V Vm c Vm c P
Where P and P0 equilibrium pressure and saturation pressures of adsorbate at adsorption temparature. V is adsorbed gas quantity in volume units Vm is the monolayer adsorbed gas quantity
Surface area
P ( P0 P)V
c 1 Vm c
1 Vm c
P P0
BET Plot
Where
N- Avogadro no