Chapter III:
SURFACE PHENOMENA
I. BASIC DEFINITIONS AND CONCEPTS
1. Surface area
v A molecule in the bulk: interact equally with
other molecules → net force applied = 0.
v A molecule on the surface
→ Fliquid – liquid > Fliquid – gas → net force applied ≠ 0
Excess surface free energy due to
the existence of a free surface
Gs = s.S
Gs: Excess surface free energy
S: Surface area
s: the factor
I. BASIC DEFINITIONS AND CONCEPTS
2. Surface free energy
Gs = s.S If S = 1 then Gs = s Free energy of a surface area unit
Surface free energy of several Surface free energy of
liquid surface several solid surface
Matter Surface Interaction Matter Surface Interaction
free between free between molecule
energy molecule energy
(mJ/m2) (mJ/m2
Mecury 485.0 Metal - metal Poly- 28 Van der Waals
Water 72.8 Hydrogen bond propyl interaction
ene
n-octanol 27.5 Week hydrogen
bond Ice 83 Hydrogen bond
Octan 12.0 Week Van der PbI2 130 Week covalent
Waals bond
interaction SiO2 462 Covalent bond
Gold 1500 Metal - metal
The stronger bond, the higher surface energy
I. BASIC DEFINITIONS AND CONCEPTS
3. Relationship between surface free energy and particle size
Systems with high surface energy:
Materials with capillary system Materials with small particle size
(E.g. pore material, zeolite…) (E.g. colloidal system, nanomaterials)
II. SURFACE TENSION AND DETERMINATION METHODS
1. Definition of surface tension
Gs = s.S
v Definition 1: the energy of a surface area unit
v Definition 2: a work to bring molecules from bulk phase to the
surface to create extra surface
𝑱 𝑵. 𝒎 𝑵
Unit: = =
𝒎 𝟐 𝒎 𝟐 𝒎 Gas
Liquid
Solid
v Definition 3: the force applied on a unit length of the line of
intersection between liquid phase and solid phase
II. SURFACE TENSION AND DETERMINATION METHODS
2. Determination methods
a. Capillary rise method
𝟏
At equilibrium: f = P 𝝈 = 𝒓𝒉𝒅𝒈
𝟐
If comparing with a standard liquid (surface tension so
and density do):
𝝆𝒉
𝝈 = 𝝈𝐨
𝝆𝐨𝒉𝐨
Schematic
Measure h and ho diagram of the
rise of a liquid
II. SURFACE TENSION AND DETERMINATION METHODS
2. Determination methods
b. du Noüy – ring method
Dynamometer
Assume: the liquid totally wets
the metal ring.
- Immerse the metal ring on
the liquid
- Detach the ring from the Metal ring
liquid surface → Fmax at the
moment of detachment
Surface tension force: Fmax = f = s.2p(r1 + r2)
𝑭𝒎𝒂𝒙 𝑭𝒎𝒂𝒙 force
𝛔= =
𝟐𝝅 𝒓𝟏 + 𝒓𝟐 𝟒𝝅𝒓
Where: r1 is the inner radius of the ring
r2 is the outer radius of the ring
Measurement of interfacial
When the ring is very thin: r1 ≈ r2 ≈ r tension by ring method
II. SURFACE TENSION AND DETERMINATION METHODS
2. Determination methods
c. Maximum bubble pressure method
- Air gas bubble is blown at
constant rate through a
capillary
- The internal pressure of a
spherical gas bubble P is
measured → The
maximum pressure Pmax
Bubble Pressure Tensiometer
𝟐𝛔
𝑷𝒎𝒂𝒙 =
r
Where: r: radius of the capillary
III. SURFACTANT
1. Structure of surfactant
vDefinition: a substance that significantly reduces surface/interface
tension
vStructure: hydrophilic head and hydrophobic tail
Hydrocarbon radical Polar group
(hate water) - hydrophobic (like water) - hydrophilic
vE.g: detergent, fatty acid
III. SURFACTANT
2. Types of surfactant
a. Anionic surfactant: the polar group has negative charge
E.g. carboxylate, sulfonate, sulfate.
Sodium dodecyl sulfate
III. SURFACTANT
2. Types of surfactant
b. Cationic surfactant: the polar group has positive charge
E.g. ammonium salt
Cetyltrimethylammonium bromide (CTAB)
III. SURFACTANT
2. Types of surfactant
c. Non-ionic surfactant: the polar group has no charge
E.g. poly(ethylene glycol)
Decaethylene glycol mono dodecyl ether
III. SURFACTANT
2. Types of surfactant
d. Amphoteric surfactant: 2 polar groups have positive and negative
charge
E.g. polypeptides, aminoacids
N-Dodecyl-β-alanine
III. SURFACTANT
3. Effect of surfactant on the surface tension of a liquid
Ø Surfactant molecules concentrate on the surface
Reduce surface area
→ Reduce surface tension of liquid
Ø Concentration of surfactant increases, surface tension decreases
Ø Szyszkowski equation:
sC = so – aln(1+bC)
III. SURFACTANT
4. Application of surfactant
vFoam maker
vDefoam agent
vDetergent
vEmulsifier
vDeform emulsion
IV. SORPTION. GIBBS’S ISOTHERM
Ø Surfactant concentrates on
the surface
Ø Sorption of surfactant on
surface:
𝑪 𝒅𝝈
𝜞=−
𝑹𝑻 𝒅𝑪
ln (surfactant concentration)
