Adsorption Isotherms

Surface coverage of adsorbate is a function of adsorptive gas

or vapour pressure = adsorption isotherm (constant temp)
5 types classified by Brunauer in 3 categories

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)

Langmuir (1916) recognised the rapid decrease in attractive

force as 1/R6 with increasing:
“Our present conception of the structure of atoms andmolecules makes it
impossible for us to conceive of any appreciable force which one atom or
molecule can exert directly on others at distances greater than two or three
Angstrom units” I Langmuir, Trans. Farad. Soc. 1921, 17, 4

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)

Langmuir model assumes:

1) Only one adsorbed molecular layer

2) Adsorption is localised (lattice model)
3) ∆Hads is independent of surface coverage

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)

Apr 2004 Dr Mark Osborne

 Continued
p (1-Vads/Vm) exp(-Ea/RT) = k Vads/Vm exp(-Ed/RT)

p = k exp(-Ed/RT) Vads/Vm / (1-Vads/Vm)

1/a = k exp[-(Ed-Ea)/RT] = k exp[-(∆

∆Hads)/RT]

a p = Vads/Vm / (1-Vads/Vm) or a p – a p Vads/Vm = Vads/Vm

a p = (1 + a p) Vads/Vm so Vads = a p Vm / (1 + a p)

At low p: (1 + a p) ~ 1 so Vads = a p Vm (linear with p)

At high p: (1 + a p) ~ ap so Vads ~ Vm (saturation)

medium p: curvature dependent on “a” hence temperature T

Apr 2004 Dr Mark Osborne

 Adsorption with Dissociation
Rate of adsorption depends additionally on probability of each
dissociated atom finding a vacant site i.e (1-Vads/Vm)2
Rate of desorption depends additionally on frequency of atom
encounters to form desorbing gas i.e (Vads/Vm)2
Equating adsorption and desorption rates leads to
(a p)1/2 = (Vads/Vm)/ (1-Vads/Vm)
(a p)1/2 – (a p)1/2 Vads/Vm = Vads/Vm
(a p)1/2 = [1 + (a p)1/2] Vads/Vm
Vads = (a p)1/2 Vm / [1 + (a p)1/2]
Surface coverage now depends more weakly on pressure (p1/2)

Apr 2004 Dr Mark Osborne

 BET Model of Adsorption
Langmuir fails to account for multilayer
adsorption and dependency of ∆Hads on
surface coverage i.e more difficult to
adsorb gas in between adsorbed molecules
∆Hads decreases with coverage V/Vm CO on Pd(111)
Hence
V/Vm
Brunauer, Emmett and Teller BET model (1938)

} ∆HL enthalpy of adsorption for subsequent layers

∆H1 enthalpy of adsorption for monolayer

Balancing evaporation and condensation rates between layers:

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)

When c > 1 (|∆

∆HL| < |∆
∆H1|)
BET describes type II isotherm
Then at low p: (p0 – p) ~ p0
BET reduces to Langmuir

When c <= 1 (|∆

∆HL| > |∆
∆H1|)
BET describes type III
Apr 2004 Dr Mark Osborne
 Monolayer capacity from BET
BET c > 1 most general isotherm so how do we get Vm without
adsorption curve reaching an asymptotic limit?

Plotting
p vs
p
Vads(p0-p) p0

~ linear 0.05 <= p/p0 <= 0.35

Gradient = (c-1) Intercept = 1

V mc V mc

So Vm = 1
(gradient + intercept)

Intercept often small << gradient and typically leads to errors

of only 5-10% of calculated monolayer capacity Vm
Apr 2004 Dr Mark Osborne
 Determination of Surface Area
Usually use N2 @ 77 K (b.p) to determine surface capacities
since cheap, inert and produces well defined ‘knee’ (saturation)
on many surfaces
Using volumetric analysis determine
Vads = (p2-p2’)x(VA+VB)p2’ VS p2 A @ P1 B ~ 10-4

where p2 = p1VA/(VA+VB) measured

with’ and without the solid surface A + B @ P2

get isotherm from Vads vs p2/p0 Solid

and Vm from p2/Vm(p0-p2) vs p2/p0
get mass adsorbed Mm = ρ x Vm where ρ is density of liquid N2
From mass how might we determine BET surface area?
Apr 2004 Dr Mark Osborne
 BET Surface Area
Determine number of molecules adsorbed = Mm/MN2 from mass
of monolayer per molecular mass of absorbate

From real gas Van der Waals constant b (N2=3.9x10-5 m3/mol)

can calculate area per molecule ~ (b/NA)2/3 = 16.2x10-20 m2 N2

So for a non-porous, planar solid substrate

BET area = number of molecules adsorbed x area per molecule

expressed as area per unit mass of solid substrate (m2/g)

For a particulate substrate (powder) area related to grain size

Area per unit mass = 3/ρ R = 6/ρ D where ρ = mass/4π πR3/3 is

the solid density and assumes monodisperse spherical particles
Apr 2004 Dr Mark Osborne
 Low Pressure Isotherms
What about the dependence of ∆Hads on surface coverage Vads?

In general ∆Hads becomes less negative as Vads increases

Suggests most energetically favourable sites are occupied first

Temkin Isotherm - assumes ∆Hads changes linearly with p

Vads = k ln (n p) or Vads = k ln n + k ln p

Freundlich Isotherm - assumes ∆Hads exponential with p

Vads = k p1/n or log Vads = log k + n log p

Apr 2004 Dr Mark Osborne

 Anomalous Isotherms
Stepwise isotherms associated with the formation of complete
monolayer before each subsequent multilayer commences
e.g. Krypton @ 90 K on carbon graphitised at 3000 K
The isotherm shows two distinct steps corresponding to the
complete formation of the first and second monolayer
Favoured if ∆Hads remains more exothermic
near completion than ∆HL for commencing
the next layer

Apr 2004 Dr Mark Osborne