Solid / gas interface

• When a gas or vapor is brought into contact with a

solid, part of it is adsorbed on the solid.

• Eg: in heterogeneous catalysis

• The gas adsorption on solid surfaces has been

studied theoretically
• - Langmuir adsorption isotherm
• - Brunauer, Emmett and Teller (BET) isotherm
 Heat of adsorption
• Adsorption is a spontaneous process
• ΔG < 0
• The freedom of molecules are limited after the
adsorption on to a surface
• ΔS < 0

• Δ H = ΔG + TΔS < 0
• - adsorption is an exothermic process

• Enthalpy of adsorption: Heat energy liberated

when 1 mole of gas is adsorbed on the surface
• Gas molecule should collide with the solid surface
in order to get adsorbed
• The rate of collision (u) for a ideal gas molecule on
unit area of the surface in a unit time is given by
p
u=
2 πmKT

• p – is the pressure of the gas

• m – mass of a gas molecule
• K – Boltzmann constant
• T – Temperature

• All the molecules which collide with the surface are

not adsorbed on the surface
 Sticking probability
• The fraction of molecules that adsorbed on the
surface is given by Sticking probability (s)

• s = rate of adsorption / rate of collision (u)

• Rate of adsorption = s x u
•
sp
Rads =
2 πmKT
 Factors which influence the sticking probability
1. Activation energy for adsorption

Energy

Ea

R
ΔHa <0
ΔHa P exothermic

Reaction coordinates

2. Sticking probability ∞ e (-Ea/RT)

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

• θ - is the fraction of surface covered by the molecules

• Therefore fraction unoccupied ∞ (1-θ)

• Possible adsorption sites ∞ (1-θ)

• For a non-dissociative adsorption

• 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.

• 4. Efficiency of energy transfer

• - Adsorption is an exothermic process
• - the evolved energy should efficiently
• removed from the system
• - if not the adsorbed molecules could desorb by taking
• liberated heat of adsorption
•
5. Surface heterogeneity
• - There are lots of defects, irregulaties and
• deformations on solid surfaces: not uniform
A uniform
surface
• Surfaces
with
defects
• Point defects : vacancies, impurities,
interstitials

• Dislocations: are linear defects around

which some of the atoms of the crystal
lattice are misaligned
• Screw dislocation
• edge dislocation
Lattice planes showing an Screw dislocation
edge dislocation (line in blue).
• - adsorption at sites with defects are different from the
• adsorption at the rest of the sites

• - surfaces have certain sites with are more effective in

• adsorption than other sites
• - Called active sites of heterogeneous surfaces

• - associated with different energies and different

• rates of adsorption
• The Langmuir Isotherm
• - was developed by Irving Langmuir in 1916

• - describe the relationship between θ and the

pressure of the gas above the surface (P) at a fixed
temperature.
• Assumptions used in Langmuir isotherm

1. Every adsorption site is equivalent

2. Ability of a particle to bind at and adsorption site is
independent of whether near by sites are occupied
or not
3. There is a dynamic equilibrium between the
substrate and the adsorbate:
Rate Forward reaction = Rate back ward reaction
4. Adsorption occur by collision of gas molecules with
vacant sites during their random motion
5. Each site can accommodate only one adsorbate
species (monolayer adsorption)
6. Ideal gas behavior is assumed for the gaseous
phase
• S * + M (g) S–M
• S* , represents a vacant surface site

• Rate of adsorption = Ka P (1-θ)

• Rate of Desorption = Kd θ

• 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 )

mass of gas adsobed (m)

θ=
mass of the gas required to fill all the adsorption sites on the surface m m

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).

P/Torr 0.19 0.97 1.90 4.05 7.50 11.95

V/cm3 0.042 0.163 0.221 0.321 0.441 0.471

I. Confirm that the above data fit the Langmuir Isotherm

II. Calculate the value of Langmuir constant (b) and adsorption
volume corresponding to complete monolayer coverage
(Vm).
• 1 bar = 1 X 105 Pa

• 1 atm = 760 torr = 1.013 25 X105 Pa

• 1 Torr (mmHg) = (1.013 25 X105 / 760) Pa

• = 1.333 224 X102 Pa

Pascal (Pa) = Nm-2 = kgm-1s-2

 1 1 1 1
= ⋅ +
v bvm p vm

0.1900 0.9700 1.9000 4.0500 7.5000 11.9500

p
0.0420 0.1630 0.2210 0.3210 0.4410 0.4710
v

1/p 5.26316 1.03093 0.52632 0.24691 0.13333 0.083682

1/v 23.8095 6.13497 4.52489 3.11526 2.26757 2.123142

 Scale ---?---------
30
25
1/v = 4.1566x(1/p) + 1.9495
1/v (cm-3)

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:

(a) Derive the Langmuir absorption isotherm for θ, the

equilibrium fraction of sites occupied by absorbate on a
surface. Give your result in terms of ka and kd, the rate
constants for the absorption and desorption processes
and the pressure of adsorbate, P.
(b) Suppose two species, A and B, adsorb on the surface
with adsorption and desorption rate constants kaA, kaB,
kdA and kdB. Find an expression for θ = θA + θB in terms
of the rate constants and the pressures.

θA = KaA P/ (KdA + KaA P)

θB = KaBP/ (KdB + KaB P)

Question 3:

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.

(b) Calculate the collision rate, if the vessel contains

propane instead of hydrogen under the same
conditions.

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.

(i) Confirm that they fit the Langmuir isotherm

(ii) Find the Langmuir constant (K) and the

volume corresponding to complete monolayer
coverage.

P/Torr 100 200 300 400 500 600

V/cm3 10.3 19.3 27.3 34.1 40.0 45.5