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CONTENT
PHYSICAL CHEMISTRY 2
1. Surface phenomena
▪ Surface tension
CHAPTER 4:
▪ Wetting phenomena
SURFACE PHENOMENA & ADSORPTION ▪ Capillary action

2. Adsorption
▪ Adsorption on gas/solid interface

Assoc. Prof. Dr. Nguyen Van Dung

▪ Adsorption on liquid/solid interface

Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, VNU-HCM ▪ Adsorption on gas/liquid interface
Email: [email protected]

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SURFACE RESIDUAL ENERGY SURFACE RESIDUAL ENERGY

The molecules inside the phase and those on its

surface are subjected to different interaction forces.
→ Have a difference in energy
→ Have surface residual energy dES (dGS)
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SURFACE RESIDUAL ENERGY SURFACE TENSION

Under reversible isothermal conditions:

= dGS/dS

Surface tension: or (dyne/cm)

1 dyne = 10-5 N, 1 dyne/cm = 1 mN/m

✓ Surface residual energy on one unit of surface J/m2

✓ Force acts on 1 cm of surface

✓ Tangent to the phase interface

Surface residual energy is a
measure of the excess energy
present at the surface of a
material in comparison to its bulk.

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SURFACE TENSION NO SURFACE TENSION BETWEEN GAS-GAS

 G 
-As = dS = dGs =   dGs = dS + Sd
 S T , P

If = const, spontaneous process If S = const, spontaneous process

dG < 0 → dS < 0 → S reduces dG < 0 → d < 0 → reduces
Ex: Flocculation reduces S. Ex: Adsorption reduces surface area.
Soap bubbles are spherical. Surfaces become dirty.
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GAS–LIQUID SURFACE TENSION LIQUID–LIQUID SURFACE TENSION

For air, 25 oC, [dyn.cm-1]

✓ Water: 72.75
✓ Benzene: 28.28
✓ CCl4: 26.80

At 20 oC, benzene–water, = 35.00 dyn.cm-1

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GAS–SOLID & LIQUID-SOLID SURFACE TENSION EFFECT OF TEMPERATURE ON SURFACE TENSION

 
  0
 T  S , P ,n i
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EFFECT OF TEMPERATURE ON SURFACE TENSION EFFECT OF PHASE NATURE ON SURFACE TENSION

T (oC) H2O C6H6 CH3OH C2H5OH As temperature increases,

0 75.6 31.6 29.5 24.0 suraface tension decreases. Surface tension of water with various compounds at 20 oC
Because when temperature (dyn/cm)
25 71.9 28.2 27.1 21.8
increases, molecular
50 67.9 25.0 24.6 19.8 Air Isopentane Benzene Hexane
thermal activities also
70 63.5 21.9 22.0 increase, and as a result, 72.8 49.6 32.6 51.1
intermolecular cohesive
Ramay – Shields equation
force decreases, and finally
Vm2 / 3 = k (Tc − T − 6.0) surface tension decreases.
TC: critical temp. at = 0
Vm: molar volume of liquid
k = 2.1 erg/K = 2.2.10-7 J/K

Van Der Waals – Guggenheim equation:

= o(1-T/Tc)n ; Metal: n = 1; Organic liquids: n = 11/9

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MEASUREMENT OF SURFACE TENSION WETTING PHENOMENA

Read in textbook When a liquid comes into contact with a solid in a bulk, gaseous
phase, according to Young’s equation, there is a relationship between
▪ Capillary method
the contact angle θ, the surface tension of the liquid σlg,
▪ Du Noüy ring method the interfacial tension σsl between liquid and solid and the surface free
▪ Wilhelmy plate method energy σsg of the solid: σsg = σsl + σlg cosθ

▪ Liquid drop weight method 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
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WETTING PHENOMENA 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).
Wetting Non-wetting  Those interactions are described by cohesion and adhesion forces,
- Adhesion forces > Cohesive forces - Cohesive forces > adhesive forces which are intermolecular forces. The balance between the
- The molecules of the liquid tend to - The molecules of the liquid tend to cohesive forces of similar molecules, such as between the liquid
interact more with solid molecules interact more with each other than molecules (i.e., hydrogen bonds and Van der Waals forces), and
then liquid molecules. with the solid molecules.
the adhesive forces between dissimilar molecules, such as
- Fliquid-solid > Fliquid-liquid - Fliquid-solid < Fliquid-liquid
between the liquid and solid molecules (i.e., mechanical and
-< 90o -> 90o electrostatic forces), will determine the contact angle created in the
solid and liquid interface.

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CAPILLARY ACTION KELVIN EQUATION

The phenomenon of rise or fall of liquids in a capillary tube

Pr 2Vm 2 cos 
RT ln = h=
P0 r gr

 = surface tension
Pr = P at a curved interface of radius r
P0 = P at flat interface
Vm = molar volume of liquid
 = density

- Convex meniscus: positive radii, r > 0, Pr > P0

Capillary diameter: din < 2 mm - Concave meniscus: negative radii, r < 0, Pr > P0

Wetting creates meniscus (liquid-air interface): convex meniscus

As r increases, P r is toward P0, and the droplets grow into bulk liquid.
or concave meniscus
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ADSORPTION ADSORPTION

Adsorption: concentrate adsorbates on the surface of the adsorbents.

Release (desorption) Adsorbate

Uptake
Adsorbent

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ADSORPTION ADSORPTION AND ABSORPTION

Adsorption is the adhesion of atoms, ions or molecules from a gas,

liquid or dissolved solid to a surface.

This process creates a film of the adsorbate on the surface of the

adsorbent.

This process differs from absorption, in which a fluid (the absorbate)

is dissolved by or permeates a liquid or solid (the absorbent).

 Adsorbent: materials on which the adsorption occurs

 Adsorbate: substances are attracted on the adsorbent’s surface

 Reason: the non-equilibrium interaction forces of surface’s

molecules
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TYPES OF ADSORPTION CHEMISORPTION AND PHYSISORPTION

Property Physisorption Chemisorption

At low temperature, boiling point
Adsorption
of adsorbates (Xe: T < 100 K;
temperature
CO: T < 200 K)
Adsorption
40 – 800 kJ/mol 5 – 40 kJ/mol
enthalpy
Activated energy Low High
Van der waals force Chemical bonding
Weak force
Properties Irreversible process
Reversible process
Multi-layers Mono layer
Selectivity Low High
Weak van der Waals force, Strong chemical bonds
hydrogen bond

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ADSORPTION CAPACITY ADSORPTION ISOTHERMS

Adsorption capacity is the amount (mole, mass, volume) of

adsorbate taken up by the adsorbent per unit mass of the
adsorbent.
Adsorption capacity:  or x (mol/g, g/g, mg/g, mL/g)

Factors affect adsorption:

✓ Conc.
✓ Temp.
✓ Nature

Type I, II, IV: stronger interaction

Type III, V: weaker interaction
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GAS/SOLID ADSORPTION LANGMUIR ADSORPTION MODEL

Langmuir isotherm (for non-dissociation model) K.P K.P

= V = Vm 
1 + K.P 1 + K.P
Assumptions P 1 P
Linear form: = +
- Uniform surface V K.Vm Vm
- Monolayer adsorption
V, Vm: volume/maximum volume of adsorbed gas on the adsorbent (mL/g)
- No interaction between adsorbed species and no movement
of the adsorbed species K.P P 1 P
x = xm  = +
1 + K.P x K. xm xm
P: Pressure of the gas on the adsorbent
K.P x, xm : adsorption capacity, maximum adsorption capacity (g/g)
= : Surface coverage
1 + K.P
K: Adsorption constant • IF P is low (K.P << 1) → V, x are directly proportional to P
• IF P is high (K.P >> 1) → V, x → max.

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LANGMUIR ADSORPTION MODEL FREUNDLICH ADSORPTION ISOTHERM

The data given below are for the adsorption of CO on charcoal at 273 K.
1
Confirm that they fit the Langmuir isotherm, and find the constant K and the
x = b P 1/ n ln x = ln b + ln P
volume corresponding to complete coverage (Vm). In each case V has been n
corrected to 1.00 atm. Amount of charcoal is 1.00 g.
x: adsorption capacity
P (kPa) 13.3 26.7 40.0 53.3 66.7 80.0 93.3
P: pressure of gas on the adsorbent at equilibrium
V (cm3) 10.2 18.6 25.5 31.5 36.9 41.6 46.0
b, n: constant

Application:
- For gas/solid adsorption: 1/n = 0.1 - 0.5
- For liquid/solid adsorption: (replace P by C), 1/n = 0.2 - 1
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BET THEORY SPECIFIC SURFACE AREA

Vm  NA  A
S=
Assumptions: V.m
 Physical adsorption forms multi-layers. The first
layer is formed by Van der Waals force; the next S: specific surface area (m2/g)
layers are formed by gas condensation. Vm: the monolayer volume of the adsorbate gas (mL)
 Adsorbed species interact only with the below N: Avogadro number (6.022 x 1023)
and above species, not the beside ones. A: the cross-sectional area of the adsorbate gas (m2)
P / PO 1 C −1 V: the molar volume of the adsorbate gas (mL/mol)
= + .( P / PO ) m: the mass of the adsorbent
V (1 − P / PO ) Vm C Vm C
Vm can be determined from Langmuir or BET isotherms!!

0.05 P/Po 0.3

0 P/Po

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LIQUID/SOLID ADSORPTION ADSORPTION OF NON-ELECTROLYTES

 Similar to gas/solid adsorption, except for the competition Basic rules:

of the solvent during the adsorption, which leads to the
▪ Adsorption capacity increases as the C-chain length
complexity of liquid-solid adsorption.
increases. However, adsorption capacity decreases rapidly
 Freundlich & Langmuir models can be applied for liquid- at certain C-chain lengths for porous adsorbents due to the
solid adsorption (replace P by C).
space constraint.

▪ The direction of adsorption is to equilibrate the polarity of

Adsorption capacity (mol/g)
nA: Adsorbate (mol) the phases. The greater the polarization difference, the
nA C −C V stronger the adsorption.
= = o m: Adsorbent (g)
m m Co: Initial adsorbate C (mol/L)
C: Adsorbate C at t (mol/L)
V: Adsorbate solution (L)
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ADSORPTION OF ELECTROLYTES ADSORPTION OF ELECTROLYTES

▪ Ion-exchange: Typical ion-exchange adsorbents are anionite (containing

Basic rules:
amine → anion exchange) and cationite (containing carboxyl, sulfonate
1. For similar valence ions, large ion radii are adsorbed at first → cation exchange)
due to a thin hydration layer and large polarization. ▪ Characteristics: High selectivity because this is chemical adsorption. An
irreversible process is possible, but the rate is slow, especially for the
▪ Li+ < Na+ < K+ < Rb+ < Cs+
inner part of the adsorbents. The pH of the solution may change due to
▪ Mg2+ < Ca2+ < Sr2+ < Ba2+ the release of H+.

▪ Cl- < Br- < NO3- < I- < CN-

2. High-valence ions are adsorbed first.

▪ K+ < Ca2+ < Al3+ < Th4+

3. Priority is given to ions or molecules that are contained in

the crystalline structure of the adsorbents.

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ADSORPTION AT LIQUID-GAS INTERFACES GIBBS ADSORPTION ISOTHERM

solution  solvent 
d

1
  = Surface excess (mol/m2)
Electrolytes Gibbs surface excess =− .
Surfactant: bRT dln C
✓ Small solubility
solvent solution
✓ Focus on the interface : Gibbs surface excess (mol/m2)
✓ Adsorption on the interface ( > 0) b = 1 for non-ionic surfactants and ionic surfactants in excess
✓ Spontaneous adsorption Surfactant electrolyte;
C b = 2 for 1:1 ionic surfactants in the absence of added electrolytes
(solution < solvent)
Electrolytes: C: molar surfactant concentration
Non-polar tail: ✓ High solubility : surface tension
Hydrocacbon groups ✓ Concentrate in bulk phase R: universal gas constant
→ Negative adsorption ( < 0) T: absolute temperature
Polar tail: –COOH, –OH, ✓ Non-spontaneous adsorption
–NH2, –CHO groups (solution > solvent)
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ADSORBENTS APPLICATIONS OF ADSORPTION

Common adsorbents: activated carbon, silica gel, bentonite, zeolite, ✓ Catalysis (chemical, biological)
some polymers
✓ Chromatography method
▪ Non-porous adsorbents
✓ Adsorbs harmful emissions in the air (H 2S, NH3, VOCs, odors).
▪ Porous adsorbents
✓ Adsorbs toxic inorganic substances in wastewater (heavy metal
▪ Ion-exchange adsorbents ions, arsenic, chromate)
✓ Adsorbs toxic organic substances in wastewater (colorants,
surfactants, antibiotics, pesticides).

Water purification: Removal of low-concentration contaminants

Wastewater treatment: Removal of high-concentration

contaminants