COLLOID CHEMISTRY

Dr. Ngo Thanh An

Low Pressure High
Silica structure

Zeolite structure
    g

P
    g    RT  ln 
o
g
 Po 
Where go is the standard chemical potential of the vapor phase, that is, the chemical
potential at the reference pressure po. Differentiating at constant adsorbed phase
concentration and applying Gibbs – Helmholtz relation

  
 T  H
T T2
 H   ln P 
H go
 2   2  R 
T T  T  q

  ln P  H go  H s Hg  Hs H s
    
 T  q
2
RT RT 2 RT 2

Since for an ideal vapor phase, the partial molar enthalpy 𝐻𝑔𝑜 is independent of
composition and identical to the molar enthalpy Hg. Hs is the enthalpy change
on adsorption.

H s
ln p  const 
RT
Ⅰ Microporous (Active carbon, Zeolite)

Ⅱ Non-porous （Metal powder)

Ⅲ Non porous and weak adsorption interaction

Ⅳ Mesoporous （Silica gel）

Ⅴ Porous and weak adsorption interaction

Ⅵ Energetically uniform surface

Micropore
～2nm
Mesopore
2nm～50nm
Macropore
50nm～
23
• Type I arises when only one type
of site:
• Initially surface fills randomly
• Eventually saturates when surface
filled (or pores filled with a porous
material)

24
• Type III arises when there are
strong attractive interactions
leading to condensation
• Initially, no adsorption
• Pressure increases lead to
nucleation and growth of islands
• Eventually liquids condense on the
surface

25
• Type II arises when the is more
than one adsorption site
• Initial rapid adsorption
• Saturates when first site filled
• Second rise when second site fills
• Second site could be a second
monolayer, a second site on the
surface. In porous materials, it
can also be a second type of pore.

26
• Type V is another case for
attractive interactions
• Initially no adsorption
• Next nucleation and growth of
islands or liquid drops
• Coverage saturates when no more
space to hold adsorbates

27
• Type IV occurs when there are
multiple phase transitions due to
a mixture of attractive and
repulsive interactions
• Can also arise in multilayer
adsorption where adsorption on
second layer starts before first
layer saturates

28
Mechanism of Adsorption on Non-porous Surfaces

n n n

0 p/p
0

1 0 p/p
0

1 0 p/p
0

n n n

0 t/nm 0.548 0 t/nm 0.548 0 t/nm 0.548

s 1 s 1 s 1
Adsorption on Mesoporous Samples: Capillary Condensation

n n n

0 0

p/p 1 0 0

p/p 1 0 p/p
0

n n n

0 0

p/p 1 0 p/p
0

1 0 p/p
0

1
Capillary condensation is the "process by which multilayer
adsorption from the vapor [phase] into a porous medium
proceeds to the point at which pore spaces become filled with
condensed liquid from the vapor [phase]. The unique aspect of
capillary condensation is that vapor condensation occurs below
the saturation vapor pressure Psat of the pure liquid

 Pv  2Vm
ln   
 Psat  RTr
Where:
Pv: equilibrium vapor pressure; Psat: saturation vapor pressure;
r: radius of capillary; : liquid/vapor surface tension; Vm: liquid molar volume;
R: ideal gas constant; T: temperature
The relation of equilibrium vapor pressure to the saturation vapor pressure can be thought of as a
relative humidity measurement for the atmosphere. As Pv/Psat increases, vapor will continue to
condense inside a given capillary. If Pv/Psat decreases, liquid will begin to evaporate into the
atmosphere as vapor molecules

System A → Pv=0, no vapor is present in the system

System B → Pv=P1<Psat, capillary condensation occurs and liquid/vapor equilibrium is reached
System C → Pv=P2<Psat, P1<P2, as vapor pressure is increased condensation continues in order
to satisfy the Kelvin equation
System D → Pv=Pmax<Psat, vapor pressure is increased to its maximum allowed value and the
pore is filled completely
This figure is used to demonstrate the concept that by increasing the vapor pressure in a given
system, more condensation will occur. In a porous medium, capillary condensation will always
occur if Pv ≠ 0.
 Adsorption in Micropores

n n n

0 p/p
0

0.25 0 0

p/p 0.25 0 p/p

0

n n

0 p/p
0

1 0 0

p/p 0.25
Figure 4.5 Langmuir’s model of the structure of the adsorbed layer. The black dots
represent possible adsorption sites, while the white and mauve ovals represent adsorbed
molecules.

40
Extent of adsorption usually given by fractional coverage
N is often
number of surface sites occupied (Ns )
 equivalent to
total number of surface sites (N) number of surface
atoms of the
V substrate

V
when   1 we have monolayer coverage

Associative (or non-dissociative) adsorption is when a

molecule adsorbs without fragmentation
Dissociative adsorption is when fragmentation occurs during
the adsorption process
• Molecules in gas and surface are in dynamic equilibrium
G (g) +  (surface) ↔ G-
• Isotherm describes pressure dependence of equilibrium
• Langmuir isotherm proposed by Irving Langmuir
• (1932 Noble Prize)
• Adsorption saturates at 1 monolayer
• All sites are equivalent
• Adsorption is independent of coverage

ratea  ka PA N * rated  kd NA

KPA
Site conservation
+
Equilibrium
A  , K  ka kd
θA + θ* = 1 rateads = ratedes 1  KPA

42
 KP
G2 (g) + 2 (surface) ↔ 2G- 
1  KP

Ka Pa
A (g) +  (surface) ↔ A- a 
B (g) +  (surface) ↔ B-
1  Ka Pa  Kb Pb
Kb Pb
b 
1  Ka Pa  Kb Pb

Ka Pa
a 
A (g) +  (surface) ↔ A- 1  Ka Pa  Kb Pb
B2 (g) + 2 (surface) ↔ 2B-
Kb Pb
b 
1  Ka Pa  Kb Pb
Assumptions
１ Surface is energetically homogenious.

２ There is no lateral interface between adsorbed molecules.

The adsorption energies in the second and all higher layers are equal
３
to condensation energy of adsorptive.

y x
Assignments
1. Check the fit of Langmuir equation and determine K (equilibrium constant of
adsorption) and V:
P, Torr 100 200 300 400 500 600 700

V, ml 10.2 18.6 25.5 31.5 36.9 41.6 46.1

2. The data given below are for the adsorption of nitrogen on alumina at
77.3 K. Show that they fit in a BET isotherm in the range of adsorption and
find Vm and hence surface area of alumina (m2 /g). At 77.3 K, saturation
pressure, Po = 733.59 torr. The volumes are corrected to STP and refer to
1g of alumina. Given: contact area of one N2 molecule =16.2x10-20m2)

P, Torr 37.67 74.20 114.54 142 185.34

V, ml/g 23.14 28.1 33.1 36.35 41.49