Chapter 4-PhyChem 2 - Surface Phenomena Adsorption

CHAPTER 4:
Surface phenomena
& Adsorption
Trần Thụy Tuyết Mai Ph. D
Email: TUYETMAI@HCMUT.EDU.VN
1
Contents
 Surface residual energy
 Capillary phenomena
 Adsorption
tuyetmai@hcmut.edu.vn 2
Surface phenomena
tuyetmai@hcmut.edu.vn
is a relative measurement of
Surface free energy the energy at the surface.
Surface tension
Molecules in phases and in the surface
are under different forces  energy
differences  residual energy on the
surface dES
Surface residual energy
Cohesion
force
Intermolecular interactions in a liquid lower the internal energy.

Molecules at the surface of the liquid experience fewer
attractions from other liquid-phase molecules compared with
molecules in the bulk liquid phase and so have a higher average
energy than molecules in the bulk liquid phase.  it requires
work to increase the area of the liquid–vapor interface.
https://www.nanoscience.com/techniques/tensiometry/surface-interfacial-tension/#measurement
Surface energy  G 
(for one component system)    
 S T , P
Surface energy dGs (erg/cm2);

1 erg = 10-7 J
The surface tension of a
= Energy needed to generate
a unit surface area (energy to liquid, γlg or  , is defined as
increase the size of surface) the energy (in Joule) needed
(reversible & isotherm) to create 1 m2 of new liquid-
gas interfacial area.
dGs = dS + Sd
Spontaneous process + (constant S)
Ws = dS = dGs  d < 0
 Adsorption reduces surface area
Spontaneous process + (constant )  dS < 0
 Flocculation reduces surface area
No surface tension between gas-gas
air bromine
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
 Nature of phases
  
  0
Effect of temp.  T  S , P ,n i
Table 1: Surface tension (mN/m) of chemicals with

temp.
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
Ramsay – Shields equation TC: critical temp. ( at  = 0)
Vm: molar volume of liquid
Vm2 / 3  k (Tc  T  6.0) k: constant ; k = 2.1erg/K = 2.2.10-7J/K
Van Der Waals – Guggenheim eq.:

 = o(1-T/Tc)n ; 14
Metal: n = 1; inorganic compounds: n = 11/9
Effect of phase nature
Surface tension of water with various

compounds at 20oC (dyn/cm)
iso-
Air benzene n-hexane
pentane
72.8 49.6 32.6 51.1
15
Measurement of surface tension
(read in textbook)
 Capillary method
 Du-Nouy method
 Wihemy method
 Liquid drop weighting method
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: 103 - 105 cal/cm2
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
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.
Capillary phenomena: The phenomenon of rise or
fall of liquids in a capillary tube
mặt khum lõm mặt khum lồi

ống mao dẫn
mặt khum
thủy ngân
Wetting creates meniscus

(liquid-air interface): convex
meniscus or concave meniscus
Capillary diameter: din < 2mm
https://www.google.com/search?q=convex+meniscus+or+concave+meniscus&rlz=1C1CHBF_
enVN842VN842&tbm=isch&source=iu&ictx=1&fir=A59g0P7oblTy8M%253A%252CPbcMc
Y3bBzm6JM%252C_&vet=1&usg=AI4_Rj_oYVYqpiP20SPxTt_WvR9Aio5A&sa=X&ved=2
tuyetmai@hcmut.edu.vn ahUKEwiC5oLnsLPkAhVYfH0KHfRuAksQ9QEwAHoECAIQAw#imgdii=N0TU6w0OcbWe 20
FM:&imgrc=XoaS3jSWbp-XUM:&vet=1
Thompson – Kelvin equation
mặt khum lồi bán kính dương
- Convex meniscus: (positive radii: r > 0)

𝑃𝑟 ഥ
2𝜎 𝑉
𝑅𝑇𝑙𝑛𝑃0 = 𝑟
mặt khum lõm bán kính âm
- Concave meniscus: (negative radii: r = -r’ < 0)

𝑃𝑜 2𝜎𝑉ഥ
𝑅𝑇𝑙𝑛 𝑃𝑟
= 𝑟′
ഥ liquid molar volume
• 𝑉:
• Ex: water
𝑟
– Convex meniscus: r= 10-5 cm, 𝑃𝑃0 = 0.01
𝑃0
– Concave meniscus : r= 10-5 cm, 𝑃𝑟
= 0.01
ADSORPTION
Adsorption: Concentrating substances on the
phases’ separating surface
chất hấp phụ
 Adsorbent: materials on which the adsorption occurs.

chất bị hấp phụ
 Adsorbate: substances which is attracted on the adsorbent’s
surface (the phases’ separating surface).
 Reason: the non- equilibrium interaction forces of surface’s
molecules
Lý do: Các lực tương tác không cân bằng của bề mặt các phân tử
tuyetmai@hcmut.edu.vn [2] http://slideplayer.com/slide/9199010/ 23

Adsorption: Concentrating substances
on the phases’ separating surface
Release (desorption)
Adsorbate
Uptake
Adsorbent
Types of adsorption
L3
L2
1st layer (L1)
Physisorption
(N0,N1,N2,N3......Ni,...: adsorption sites)
Chemisorption
Classification of adsorption
Physisorption
Chemisorption
Chemisorption vs. Physisorption
Chemisorption Physisorption
at low temperature, boiling point of
Ads. Temp. adsorbates (Xe: T< 100 K; CO: T <
200K)
40 – 800kJ/mol 5 – 40 kJ/mol, low enthalpy

Adsorption enthalpy
Activated energy low (> -10 kcal/ mol)
Van der Waals force
Chemical bonding
Weak interaction force
Properties Irreversible process
forming multi-layers,
Mono layer
reversible process
Selectivity High non-selectivity
Adsorption capacity: or x (mol/g hay ml/g)
& adsorption isotherms
 Factors affect adsorption :
 Conc.
 Temp.
 Nature
Type I, II, IV:

stronger interaction.
Type III, V: weaker
interaction.
Gas/solid adsorption
Langmuir isotherm (for non-dissociation model)
 Assumptions
- Uniform surfacebề mặt đồng nhất
- Monolayer adsorption hấp phụ một lớp
- No interaction between adsorbed species and no

movement of the adsorbed species
áp suất của khí trên bề mặt chất hấp phụ
K.P P: pressure of the gas on the adsorbent.

 : surface coverage hấp phụ bề mặt
1  K.P K: adsorption constant hằng số hấp phụ
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
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
x, xm : adsorption capacity, maximum
adsorption capacity (g/g). khả năng hấp phụ
P 1 P
Linear form:   P/x
x K. x m x m
0 P
Langmuir isotherm
K.P K.P
v  vm  x  xm 
1  K.P 1  K.P
tỉ lệ thuận
 IF P is low (K.P << 1)  v, x are directly proportional to P

 IF P is high (K.P >> 1)  v, x  max.
Example
than cuir
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; khả năng hấp phụ lnx
P: pressure of gas on the áp suất của khí trên

bề mặt chất hấp
phụ tại cân bằng
adsorbent at equilibrium;
b, n: constant.
lnP
Freundlich isotherm
x  b P 1/ n
Application:
- For gas/solid adsorption: 1/n = 0.1 - 0.5
- For liquid/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 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
 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.
Quy luật khối lượng phân tử: khả năng hấp phụ tăngkhi tăng chiều dài chuỗi C. Tuy nhiên, sự hấp phụcông suất giảm nhanh
chóng ở độ dài chuỗi C nhất định đối vớichất hấp phụ xốp do hạn chế về không gian
• 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.
Hướng hấp phụ cân bằngđộ phân cực của các pha. Sự phân cực lớn hơnkhác nhau dẫn đến sự hấp phụ mạnh
hơn.
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+ Đối với các ion có hóa trị tương tự, bán kính ion lớn bị hấp phụlúc đầu do lớp
ngậm nước mỏng và độ phân cực lớn:
 Mg2+<Ca2+<Sr2+<Ba2+
 Cl-<Br-<NO3-<I-<CN-
2. High valence ions are adsorbed firstly:

K+< Ca2+<Al3+<Th4+ Ion hóa trị cao bị hấp phụ trước hết:
3. Priority is for ions/molecules which contain in the

crystalline structure of the adsorbents. Ưu tiên dành cho các ion/phân tử chứa trongcấu
trúc tinh thể của chất hấp phụ
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+.
Đặc điểm: tính chọn lọc cao vì đây là mộthấp phụ hóa học. Quá trình không thể đảo ngược là có thể,tốc độ
chậm, đặc biệt là phần bên trong củachất hấp phụ. Độ pH của dung dịch có thể thay đổi dogiải phóng H+
Adsorption for water treatment
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:
Herbicides, phenols, antiseptic,
aromatic nitrogen compounds,
surfactant, dyes.
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 độ hòa tan cao
 concentrated in bulk phase 
Non-polar tail: negative adsorption (  < 0 )
Polar tail: –COOH; -OH;
hydrocacbon groups,
-NH2; -CHO groups Non-spontaneous adsorption
(solution > solvent)
44
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
45
tuyetmai@hcmut.edu.vn Catherine D. Taylor, et al, Phys. Chem. Chem. Phys., 2003, 5, 4885–4891

Chapter 4-PhyChem 2 - Surface Phenomena Adsorption

Uploaded by

Copyright:

Available Formats

You might also like

Chapter 4-PhyChem 2 - Surface Phenomena Adsorption

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 4-PhyChem 2 - Surface Phenomena Adsorption

Uploaded by

Copyright:

Available Formats

CHAPTER 4:

Intermolecular interactions in a liquid lower the internal energy.

Surface energy dGs (erg/cm2);

Ex: at 20oC, benzene– water: 35.00 dyn.cm-1

Table 1: Surface tension (mN/m) of chemicals with

0 75.64 31.6 29.5 24.0

Van Der Waals – Guggenheim eq.:

Surface tension of water with various

mặt khum lõm mặt khum lồi

Wetting creates meniscus

- Convex meniscus: (positive radii: r > 0)

- Concave meniscus: (negative radii: r = -r’ < 0)

 Adsorbent: materials on which the adsorption occurs.

tuyetmai@hcmut.edu.vn [2] http://slideplayer.com/slide/9199010/ 23

40 – 800kJ/mol 5 – 40 kJ/mol, low enthalpy

Type I, II, IV:

- Monolayer adsorption hấp phụ một lớp

- No interaction between adsorbed species and no

áp suất của khí trên bề mặt chất hấp phụ

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

V, Vm: volume/ maximum volume of

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

P: pressure of gas on the áp suất của khí trên

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

 Adsorbed species interact only with the

 Solid adsorbents: selective adsorption, heterogeneous

Non-porous Porous Ion-exchange

 Similar to gas/solid adsorption, except the

 Freundlich, Langmuir, BET can be applied for

2. High valence ions are adsorbed firstly:

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

 Characteristics: high selectivity because this is a

Removal of odor, color compounds,

Waste water treatment

You might also like