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• Δ H = ΔG + TΔS < 0
• - adsorption is an exothermic process
Energy
Ea
R
ΔHa <0
ΔHa P exothermic
Reaction coordinates
T S and Ea S
Desorption
Energy
Ea Ed
R
P
ΔHa
Reaction coordinates
ΔHa + Ea = Ed (activation energy for desorption)
-Physically adsorbed surface (Ea ≈0) will need lower
activation energy for desorption than chemisorbed surface
-Chemisorbed molecules require a higher temp. for
desorption
2. Collision at an unoccupied site
• s = σ (1-θ) e (-Ea/RT)
• σ – is the condensation coefficient
• θ s
• 3. Steric factor
• - colliding molecule should collide
• with proper orientation, in
• order to get adsorbed.
• At Equilibrium State
• Ka P (1-θ) = Kd θ
• Rearrangement gives the following expression for the
surface coverage of non-dissociatve gas adsorption
• θ = Ka P/ (Kd + Ka P)
• If b = Ka /Kd
• Therefore θ = b P/ (1 + b P)
• θ May be defined in terms of volume or relative masses
of adsorbing species
v bp
Volume of adsoption (V) =
θ= vm 1 + bp
volume required to cover the surface completely (Vm )
m bp
=
mm 1 + bp
v bp
For non dissociative adsorption =
vm 1 + bp
1 1 p 1 1
=v m b ⋅ − b = ⋅ p+
p v v vm bvm
1 1 1 1
= ⋅ +
v bvm p vm
• Question 1:
• The data below are for the chemisorption of hydrogen on
copper at 25ºC (V is the volume of gas adsorbed
corresponding to the standard temperature and pressure).
20
15
10
5
0
0 1 2 3 4 5 6
1/p (torr-1)
1 1 1 1
= ⋅ +
v bvm p vm
1 1 1 1
= ⋅ +
v bvm p vm
1
= 4.1566 Torr cm-3
bvm
1
= 1.9495 cm-3 Find Vm
vm
Question 2:
Pr 2 Mγ
ln =
P ∞ RTρr
1. (a) Calculate the rate of molecular collisions per square
meter of surface in a vessel containing hydrogen at 25
ºC at a pressure of 100 Pa.
p
u=
2 πmKT
•The data below relate to the adsorption of N2 on
rutile (TiO2) at 273 K. In each case V has been
corrected to standard temperature and pressure.