Chapter 4

Surface phenomena
&
Adsorption
Surface phenomena
Surface residual
energy

3
 Surface residual energy

• Molecules in phases
and in the surface are
under different forces
 energy differences
 residual energy on
the surface dES
 Surface tension
• For reversible, isothermal
condition:
 = dES/dS

•  - erg/cm2 (dyn.cm/cm2) – surface

tension- energy needed to generate
a unit surface area.
 Surface tension
Properties:
• Value: dES/dS
• Direction: tangent of the interface of
the two phases and reducing the
surface area.
No surface tension between gas-gas
 Surface tension gas-liquid

Ex:
For air, 25oC:
[dyn.cm-1]
Water: 72.75
Benzene : 28.28
CCl4 : 26.80
 Surface tension liquid-liquid

Ex: at 20oC, benzene– water: 35,00 dyn.cm-1

Surface tension gas-solid
Surface tension liquid-solid
Factors affect surface tension
- Temperature
Increase temperature  surface tension
decrease.
Increase temperature  surface tension liquid-
air decreases almost linearly.

- Nature of the phases: the more different the

polarity of the two phases is, the large the
surface tension between two phase become.
 Effect of temperature

T / oC H2O C6H6 CH3OH C2H5OH

0 75.64 31.6 29.5 24.0

25 71.94 28.2 27.1 21.8

50 67.91 25.0 24.6 19.8

70 63.5 21.9 22.0 -

Effect of temperature
Ramsay – Shields equation:

Vm2 / 3  k (Tc  T  6)

TC: Critical temperature (at which: = 0)

Vm: liquid molar volume
k: const ; k = 2,1erg/K = 2,1.10-7J/K
 Effect of temperature

Van Der Waals – Guggenheim equation:

 = o(1-T/Tc)n

metals: n = 1; organic compounds: n = 11/9

Effect of temperature
Nature of the phases

Surface tension of water with various

compounds at 20oC (dyn/cm)

iso-
Air n-hexane benzene
pentane
72.8 51.1 49.6 32.6
Measurement of surface tension
(read in textbook)

• Capillary method
• Du-Nouy method
• Wihemy method
• Liquid drop weighting method
 Wetting phenomena
Surface arrangement of 3 phases (solid-liquid-gas) to
minimize the total surface energy Es.
Characteristic parameters:
• Wetting/contact angle: 
• Wetting degree: cos
• Wetting energy: 103 - 105 cal/cm2

Wetting is an exothermic process. At equilibrium,

follows Young relation: RK = LR + LK.cos
 Wetting phenomena

rk 

rl

Reason: replace the solid-gas tension (large) by

solid-liquid tension plus liquid-gas tension

Wetting angle
・ < 90o : the liquid wets the solid ,
・ > 90o : the liquid doesn’t wet the solid
 Capillary phenomena/action

• Wetting creates meniscus (liquid-air

interface): convex meniscus or concave
meniscus.

• Thompson – Kelvin equation

- Convex meniscus:
(positive radii: r > 0)
𝑟
𝑅𝑇𝑙𝑛𝑃𝑃0 = 2𝜎𝑉
𝑟
- Concave meniscus:
(negative radii: r = -r’ < 0)
𝑃𝑜
𝑅𝑇𝑙𝑛 𝑃𝑟 = 2𝜎𝑉 𝑟′
• Ex: water
𝑟
– Convex meniscus: r= 10-5 cm, 𝑃𝑃0 = 0.01
𝑃0
• 𝑉: liquid molar volume
– Concave meniscus : r= 10-5 cm, 𝑃𝑟
= 0.01
Adsorption
Oil Adsorption by cellulose aerogel
Cellulose aerogel prepared
from Rice straw
 Adsorption

• Adsorption: Concentrating substances on the

phases’ separating surface.

• Adsorbent: materials on which the adsorption occurs.

• Adsorbate: substances which is attracted on the
adsorbent’s surface (the phases’ separating surface).

• Reason: the non- equilibrium interaction forces of

surface’s molecules.
Release Adsorbate

Uptake
Adsorbent
Physical adsorption – chemical adsorption
• Physical ads. force: Van der Waals force
Weak interaction force, forming multi-layers, non-selective,
reversible, low activation energy, easy for desorption, low
enthalpy (> -10 kcal/ mol), occurring at low temperatures.

• Chemical ads. force: stable chemical bonds,

Strong interaction force, forming mono-layer, selective,
irreversible, high activation energy, difficult for desorption,
high enthalpy (similar to a chemical reaction, -10 to -200
kcal/ mol), occurring at high temperatures.
 Physical adsorption Chemical adsorption

Force van de Waal Chemical bond

No. of layer many one
Enthalpy (H) -10 to -40 kJ/mol <- 40 kJ/mol
Selectivity low high
Temperature low high
Gas/solid adsorption
Langmuir isotherm
• Assumptions
- Uniform surface
- Monolayer adsorption
- No interaction between adsorbed species and no
movement of the adsorbed species

K.P P: pressure of the gas on the adsorbent.

 : surface coverage
1  K.P K: adsorption constant
 Langmuir isotherm

K.P K.P
 v  vm 
1  K.P 1  K.P
P 1 P
Linear form:  
v K. vm vm

V, Vm: volume/ maximum volume of

adsorbed gas on the adsorbent (ml/g).
 Langmuir isotherm

K.P K.P
 x  xm 
1  K.P 1  K.P

P 1 P
Linear form:  
x K. xm xm

x, xm : adsorption capacity, maximum

adsorption capacity (g/g).
 Langmuir isotherm
K.P K.P
v  vm  x  xm 
1  K.P 1  K.P

• IF P is low (K.P << 1)  v, x are directly proportional to P

• IF P is high (K.P >> 1)  v, x  max.
 Freundlich isotherm

x  b P 1/ n

1
• Linear form: lg x  lg b  lgP
n
x: adsorption capacity;
P: pressure of gas on the adsorbent at
equilibrium;
b,n: constant.
 Freundlich isotherm

x  b P 1/ n

Application:
- For gas/solid adsorption: 1/n = 0.1 - 0.5

- For gas/solid adsorption: (replace P by C)

1/n = 0.2 - 1
 Multi-layer adsorption isotherm BET

Assumptions:
• Physical adsorption forms multi-layers. First
layer is formed by Van der Waals force, next
layers formed by gas condensation.

• Adsorbed species interact only with the

below and above species, not the beside
ones.

C*  P
vm 
P0
v P P0 P0 C1
P *
C P P    P
(1  )(1   ) v P0  P vm  C * vm  C *
P0 P0 P0
• Determination of specific surface area: [m2/g]

vm  N  A
S0 
V .m

vm: Volume of the first adsorbed species (ml)

N: Avogadro number
A: cross section area of the adsorbed species (m2)
V: molar volume at the adsorption condition
(ml/mol)
m: adsorbent weight
 Adsorbents
• Solid adsorbents: selective adsorption,
heterogeneous catalysis, catalyst’s supports, Gas-
chromatography, water treatment/purification

Non-porous Porous Ion-exchange

adsorbents adsorbents adsorbents
 Liquid/ solid adsorption

• Similar to gas/solid adsorption, except

the competition of the solvent during the
adsorption which lead to complexity of
the liquid/solid adsorption

• Freundlich, Langmuir, BET can be

applied for liquid/solid adsorption
(replace P by C)
 Molecule adsorption
(adsorption of non-electrolytes)
• Basic rules:
Rule of molecule weight: adsorption capacity increase
as increasing the C-chain length. However, adsorption
capacity decrease rapidly at certain C-chain length for
porous adsorbents due to the space constrain.

• Basic rules:
Rebindia’s rule: Direction of adsorption is to equilibrate
the polarity of the phases. The greater polarization
difference results in the stronger adsorption.
 Adsorption of electrolytes
Rules:
1. For similar valence ions, large ion radius are adsorbed
at first due to thin hydration layer and large polarization:
• Li+<Na+<K+<Rb+<Cs+
• Mg2+<Ca2+<Sr2+<Ba2+
• Cl-<Br-<NO3-<I-<CN-
2. High valence ions are adsorbed firstly:
K+< Ca2+<Al3+<Th4+

3. Priority is for ions/molecules which contain in the

crystalline structure of the adsorbents.
 Adsorption of electrolytes
• Ion-exchange:
Typical ion-exchange adsorbent are anionit (containing
amino, piridin  anion exchange), cationit (containing
caboxyl, sulfo  cation exchange)

• Characteristics: high selectivity because this is a

chemical adsorption. Irreversible process is possible, the
rate is slow, especially the inner part of the adsorbents.
The pH of the solution may change due to the release of
H+.
 Adsorption in water treatment technology
Water purification
Removal of low-concentration,
toxic organic compounds such as
benzene, PCBs, TCE…

Removal of odor, color

compounds, such as H2S,
ammonia….

Waste water treatment

Removal of non-biodegradable
organic compounds such as:
Khử chất độc hữu cơ không
phân hủy sinh học, ex:
Herbicides, phenols, antiseptic,
aromatic nitrogen compounds,
surfactant, dyes.