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Surface Phenomena Adsorption
Surface Phenomena Adsorption
Surface phenomena
& Adsorption
Trần Thụy Tuyết Mai Ph. D
Email: TUYETMAI@HCMUT.EDU.VN
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Contents
Surface residual energy
Capillary phenomena
Adsorption
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Surface phenomena
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is a relative measurement of
Surface free energy the energy at the surface.
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Surface tension
Molecules in phases and in the surface
are under different forces energy
differences residual energy on the
surface dES
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Surface residual energy
Cohesion
force
air bromine
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Surface tension gas-liquid
Ex:
For air, 25oC:
[dyn.cm-1]
Water: 72.75
Benzene : 28.28
CCl4 : 26.80
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Surface tension liquid-liquid
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Surface tension liquid-solid
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Factors affect surface tension
Temperature
Nature of phases
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0
Effect of temp. T S , P ,n i
iso-
Air benzene n-hexane
pentane
72.8 49.6 32.6 51.1
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Measurement of surface tension
(read in textbook)
Capillary method
Du-Nouy method
Wihemy method
Liquid drop weighting method
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Wetting phenomena
When a liquid comes into contact with a solid in a bulk, gaseous phase,
according to Young’s equation, there is a relationship between the contact
angle θ, the surface tension of the liquid σlg, the interfacial
tension σsl between liquid and solid and the surface free energy σsg of the
solid: σsg = σsl + σlg ⋅ cosθ
Surface arrangement of 3 phases (solid-liquid-
gas) to minimize the total surface energy σsg
Characteristic parameters:
Wetting/contact angle:
Wetting degree: cos
Wetting energy: 103 - 105 cal/cm2
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The contact angle is an angle that a liquid creates with a solid
surface or capillary walls of a porous material when both
materials come in contact together.
Wetting Non-wetting
- Adhesion Forces (lực ngoại phân - Cohesive forces > adhesive
tử) > Cohesive Forces (lực nội phân forces
tử)
- The molecules of the liquid tend
- The molecules of the liquid tend to to interact more with each other
interact more with solid molecules then with the solid molecules.
then liquid molecules.
- > 90o
- < 90o
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Contact angle
This angle is determined by both properties of the solid and the
liquid and the interaction and repulsion forces between liquid
and solid and by the three phase interface properties (gas, liquid
and solid).
Those interactions are described by cohesion and
adhesion forces which are intermolecular forces. The balance
between the cohesive forces of similar molecules such as
between the liquid molecules (i.e. hydrogen bonds and Van der
Waals forces) and the adhesive forces between dissimilar
molecules such as between the liquid and solid molecules (i.e.
mechanical and electrostatic forces) will determine the contact
angle created in the solid and liquid interface.
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Capillary phenomena: The phenomenon of rise or
fall of liquids in a capillary tube
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Adsorption: Concentrating substances on the
phases’ separating surface
Release (desorption)
Adsorbate
Uptake
Adsorbent
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Types of adsorption
L3
L2
1st layer (L1)
Physisorption
(N0,N1,N2,N3......Ni,...: adsorption sites)
Chemisorption
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Classification of adsorption
Physisorption
Chemisorption
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Chemisorption vs. Physisorption
Chemisorption Physisorption
at low temperature, boiling point of
Ads. Temp. adsorbates (Xe: T< 100 K; CO: T <
200K)
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Gas/solid adsorption
Langmuir isotherm (for non-dissociation model)
Assumptions
- Uniform surface
- Monolayer adsorption
- No interaction between adsorbed species and no
movement of the adsorbed species
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Langmuir isotherm
K.P K.P
v vm
1 K.P 1 K.P
P 1 P
Linear form:
v K. v m v m
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Langmuir isotherm
K.P K.P
x xm
1 K.P 1 K.P
x, xm : adsorption capacity, maximum
adsorption capacity (g/g).
P 1 P
Linear form: P/x
x K. x m x m
0 P
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Langmuir isotherm
K.P K.P
v vm x xm
1 K.P 1 K.P
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Example
The data given below are for the adsorption of CO on charcoal at 273 K.
Confirm that they fit the Langmuir isotherm, and find the constant K and the
volume corresponding to complete coverage (Vm). In each case V has been
corrected to 1.00 atm (101.325 kPa). Amount of charcoal is 1 g
p/kPa 13.3 26.7 40.0 53.3 66.7 80.0 93.3
V/cm3 10.2 18.6 25.5 31.5 36.9 41.6 46.0
Langmuir model
2.5
1.5
P/V
1 y = 0.0091x + 1.196
R² = 0.9984
0.5
0
0 20 40 60 80 100
tuyetmai@hcmut.edu.vn P
Freundlich isotherm
x b P 1/ n 1
ln x ln b ln P
n
x: adsorption capacity; lnx
lnP
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Freundlich isotherm
x b P 1/ n
Application:
- For gas/solid adsorption: 1/n = 0.1 - 0.5
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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.
C* P P P0 P0 C 1
vm P
v
P0 v P0 P v m C * v m C *
P C* P P
(1 )(1 )
P0 P0 P0
P / PO 1 C 1
.( P / PO )
tuyetmai@hcmut.edu.vn V (1 P / PO ) Vm C Vm C
Determination of specific surface area: [m2/g]
vm N A
P / Po
V (1 P / Po )
S0
V .m
vm: Volume of the first adsorbed species (ml)
N: Avogadro number
0 P/P
A: cross section area of the adsorbed species (m2)
o
V: molar volume at the adsorption condition
(ml/mol)
0.05 P/Po 0.3
m: adsorbent weight
P / PO 1 C 1
.( P / PO )
tuyetmai@hcmut.edu.vn V (1 P / PO ) Vm C Vm C
Adsorbents
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Liquid/ solid adsorption
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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.
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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-
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Adsorption for water treatment
Water purification
Removal of low-concentration, toxic
organic compounds such as
benzene, PCBs, TCE…
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Adsorption on liquid-gas interface
• solution solvent electrolytes
• = surface excess (mol/m2)
solvent solution
Surfactant:
Small solubility surfactant
Focuss on the interface
Adsorption on the interface ( > 0)
Spontaneous adsorption (solution < C
solvent)
Electrolytes
high solubility
concentrated in bulk phase
Non-polar tail: negative adsorption ( < 0 )
Polar tail: –COOH; -OH;
hydrocacbon groups,
-NH2; -CHO groups Non-spontaneous adsorption
(solution > solvent)
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Adsorption at liquid gas interfaces
Gibbs adsorption equation
1 d
Gibbs surface excess .
bRT d ln C
: the surface excess concentration (the Gibbs surface excess, mol/m2)
b=1 for non-ionic surfactants and ionic surfactants in excess electrolyte;
b=2 for 1:1 ionic surfactants in the absence of added electrolyte
C: molar surfactant concentration
: surface tension
R: universal gas constant
T: absolute temperature
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tuyetmai@hcmut.edu.vn Catherine D. Taylor, et al, Phys. Chem. Chem. Phys., 2003, 5, 4885–4891