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Monolayer
NH3 + charcoal N2 + silica
I
III II
Multilayer
Br2 + Benzene H2 O +
silica + Fe2O2 charcoal
V IV
Condensation in
pores/capillaries
Apr 2004 Dr Mark Osborne
Interpretations of Isotherms
Pre 1916 adsorbed layers described qualtitatively as either:
Condensed liquid film (2D liquid)
Compressed gaseous layer (2D gas)
hence
“Molecules striking a surface already covered also condense but usually
evaporate much more rapidly than from the first layer. Hence except when
the vapour is nearly saturated, the amount of material adsorbed on a plane
surface rarely exceeds that contained in a layer one atom (or molecule) deep”
I Langmuir, Phys. Rev. 1915, 6, 79
Apr 2004 Dr Mark Osborne
Langmuir Isotherm
Langmuir postulate of monolayer correct for chemisorption and
physisorption at high T and low P (multilayers are reduced)
Monolayer adsorption p 1
Vads Vads Vm
Vads = a p Vm
1 + ap
1
p = p + 1
aVm
{
Vads Vm a Vm
p NH3 on Charcoal p
Apr 2004 Dr Mark Osborne
Langmuir Derivation
Vads = volume of gas adsorbed / mass of adsorbate at p
p = vapour pressure of absorbate gas
Vm = volume of absorbate at full monolayer coverage
a = constant dependent on temperature
Rate of adsorption depends on:
collision rate of adsorbate with surface ∝ p
probability of striking vacant site = (1-V/Vm)
activation energy for adsorption = exp(-Ea/RT)
Rate of desoption depends on:
fraction of surface covered = V/Vm
activation energy for desorption = exp(-Ed/RT)
constant of proportionality k
Then at equilibrium:
p (1-V/Vm) exp(-Ea/RT) = k V/Vm exp(-Ed/RT)
a p = (1 + a p) Vads/Vm so Vads = a p Vm / (1 + a p)
Vads = cp0pVm
(p0-p)[p0+p(c-1)]
Apr 2004 Dr Mark Osborne
Properties of the BET Curves
p = 1 + (c-1) p
Vads(p0-p) c Vm c Vm p0
Where p0 = vapour pressure of bulk liquid of adsorbate
Vm = monolayer capacity (as in Langmuir)
c = exp[(∆
∆HL – ∆H1)/RT] (equivalent to “a” in Langmuir)
Plotting
p vs
p
Vads(p0-p) p0
So Vm = 1
(gradient + intercept)
Vads = k ln (n p) or Vads = k ln n + k ln p