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
NH3 + charcoal N2 + silica

Monolayer I III II

Multilayer

Br2 + silica

Benzene + Fe2O2

H2 O + charcoal

V Condensation in pores/capillaries

IV

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

Vads

= a p Vm 1 + ap

Vads

p Vads 1 { aVm p

1 Vm

p = p + 1 Vads Vm a Vm
Apr 2004

NH3 on Charcoal
Dr Mark Osborne

Langmuir Derivation
Vads p Vm a = volume of gas adsorbed / mass of adsorbate at p = vapour pressure of absorbate gas = volume of absorbate at full monolayer coverage = 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) a p = (1 + a p) Vads/Vm At low p: At high p: medium p:
Apr 2004

or a p a p Vads/Vm = Vads/Vm so so so Vads = a p Vm / (1 + a p) Vads = a p Vm (linear with p) Vads ~ Vm (saturation)

(1 + a p) ~ 1 (1 + a p) ~ ap

curvature dependent on a hence temperature T

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 Hence Brunauer, Emmett and Teller BET model (1938)

CO on Pd(111) V/Vm

} HL enthalpy of adsorption for subsequent layers

H1 enthalpy of adsorption for monolayer Balancing evaporation and condensation rates between layers:

Vads =
Apr 2004

cp0pVm (p0-p)[p0+p(c-1)]
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 p vs 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 where p2 = p1VA/(VA+VB) measured with and without the solid surface get isotherm from Vads vs p2/p0 and Vm from p2/Vm(p0-p2) vs p2/p0 get mass adsorbed Mm = x Vm where is density of liquid N2 From mass how might we determine BET surface area?
Apr 2004

A @ P1

B ~ 10-4

A + B @ P2

Solid

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/ R = 6/ D where = mass/4R3/3 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