University of Science and Technology of Hanoi

Department of Fundamental and Applied Sciences

Dr. Nguyen Duc Anh

Department of Fundamental and Applied Sciences (FAS)
nguyen-duc.anh@usth.edu.vn
0904888819

September 2019
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Contents

Content L T P
I. Introduction 2 0 0 [1] C.1
II. Basic Theory of surfactants (cont.) 4 0 0 [1] C.2
III. Types of surfactants 2 0 4 [1] C.4-6
IV. Applied theory of surfactants 4 0 0 [1] C.3
V. Surfactants in materials synthesis 2 0 0
VI. Formulation of detergents 4 0 4 [2] C.2 - 7
VII. Formulation of cosmetics 4 0 4 [3]
VIII. Toxicology and Ecotoxicology 2 0 0 [2] C.19

Experiment 1: Determine CMC of surfactants using different methods

Experiment 2: Controlling of viscosity of detergents
Experiment 3:
Something about me

Reference books
University of Science and Technology of Hanoi
Department of Fundamental and Applied Sciences

Dr. Nguyen Duc Anh

Department of Fundamental and Applied Sciences (FAS)
nguyen-duc.anh@usth.edu.vn
0904888819

September 2019
SURFACTANTS
 BASIC TERMINOLOGY

Hydrophilic: A liquid/surface that has a high affinity to water.

Hydrophobic: A liquid/surface that has very low affinity to water

Lipophilic: A liquid/surface that has a high affinity to oil.

Lipophobic: A liquid/surface that has a very low affinity to oil.

Phobic=Scared Hydrophobic
+
Hydro=Water
Philic=Friendly Hydrophilic

Phobic=Scared Lipophobic
Lipo=Oil +
Philic=Friendly Lipophilic
BASIC TERMINOLOGY

Lyophilic in oil

Hydrophobic Lipophilic

Lyophobic in water

Phobic=Scared Lyophobic
Lyo=Dissolve +
Philic=Friendly Lyophilic

Lyophobic in oil

Hydrophilic Lipophobic
Lyophilic in water
SURFACTANT STRUCTURE

Hydrophobic region
-Surfactants are molecules that preferentially
adsorb at an interface, i.e. solid/liquid (froth
flotation), liquid/gas (foams), liquid/liquid
(emulsions). Hydrophilic region
Amphipathic molecule
- Surfactants have amphipathic structure
- Characterized by two distinct regions
in structure
Properties of surfactants

- Tail or hydrophobic group

Little affinity for bulk solvent. Usually hydrocarbon (alkyl/aryl) chain in aqueous solvents. Can be linear or
branched.
- Head or hydrophilic group
Strong affinity for bulk solvent. Can be neutral or charged.
 SURFACTANT CLASSIFICATION
• Generally classified by Hydrophilic
group

Ionic Surfactants

+ Cationic Surfactants

- Anionic Surfactants

+- Amphoteric Surfactants

Neutral Surfactants
SURFACTANT CLASSIFICATION

Typical hydrophilic
groups
Typical hydrophobic
groups
SURFACTANT IN SOLUTIONS

Various formation of surfactants with concentration

What happen if you have a higher amount of surfactant than water ?

Properties and other criteria influencing surfactant choice

Typical properties Additional properties

• Wetting
• Foaming/defoaming • Corrosion inhibition

• Emulsification/demulsification • Substantivity to fibres and surfaces

• Dispersion/aggregation of solids • Biocidal proper ties

• Solubility and solubilisation • Lubricity

• Adsorption • Stability in highly acidic or alkaline media

• Micellisation • Viscosity modification

• Detergency
• Synergistic interactions with other surfactants
Additional criteria to
be met in specific
applications

Defining the properties required to meet a specific application need, the choice of surfactant is narrowed down
 Other regional criteria: Regulations or directives

• Use of a surfactant may be banned in defined applications in one region of the world, such as the EU and not
elsewhere.
• The surfactantmust belisted on the regionalinventory of approved chemicals, e.g. EINECSin Europe, TSCA in the
United States, etc., to be used in that region.
• In cleaning applications and in uses resulting in discharges of effluent to the environment, the surfactant will be
required to meet biodegradability criteria but test methods and biodegradability ‘pass levels’ vary worldwide.
• Customers may insist on compliance with specific regulations, usually governing permitted use levels (based on
toxicological data), even though there is no legal requirement as such (e.g. compliance with FDA, EPA, BGA
regulations).
• Specific by-products in some surfactants may give rise to concern on toxicological grounds and permitted by-
product levels and/or use of levels of that surfactant may be restricted in particular formulations, e.g.
nitrosamine levels in diethanolamides when used in personal care formulations.
 SURFACTANT APPLICATIONS

First applications
- Recorded first soap: 2800 B.C for Babylonian
- The Gauls and the Romans combined goat's tallow and the
ashes of the beech tree to produce both hard and soft soap
products ~ 80 A.D – Namely “Sapo”
- Savon de Marseilles
- Synthetic soap

- Soaps
 SURFACTANT
APPLICATIONS
THE BASIC THEORY OF SURFACE ACTIVE AGENTS
Term of definitions

• Surfactants are molecules that preferentially adsorb at an interface, i.e. solid/liquid (froth
flotation), liquid/gas (foams), liquid/liquid (emulsions).

• Significantly alter interfacial free energy (work needed to create or expand interface/unit
area).

• Surface free energy of interface minimized by reducing interfacial area.

Term of definitions – Surface activity
The term interface indicates a boundary between any two immiscible phases
The term surface denotes an interface where one phase is a gas, usually air.
Surface tension

Surface tension is a tension force per length acting The surface of the liquid where it is in
in all directions along the surface, and its common contact with another phase, the
molecule will experience cohesive
units are mN/m or dyn/cm.
forces toward the bulk but also some
weaker adhesive forces toward the
adjacent phase.
The interfacial free energy is the minimum amount of
work required to create or expand that interface an unit
of area. its common units are mJ/m2 (equivalent to
mN/m).

W =γ×Δ
min L interfacial area

+ Young equation: γLVcosθ = γSV – γSL describe balance of surface tensions

between the liquid and solid (γSL), liquid and gas (γLV), and solid and gas (γSV)

What kinds of interaction forces affected on surface tension ? What factors affected to surface tension?
Interfacial tension The interfacial tension between phases A and B, γAB, is
expressed by:

γAB = γA + γB − 2ψAB
γA, γB and ψAB are surface tension of A, surface tension of B, and
Interfacial tension is the interaction energy between A and B per unit area, respectively.
tension that is present at
the interface of two
immiscible phases and it
has the same units as What if:
surface tension. + Miscible phases of ethanol and water?
+ Surface tension?
+ Arrange the order of interfacial energies of
surface tension, miscible solution and immiscible
mixture.
Surface and interfacial tension measurements

Du Nouy ring method Wilhelmy plate Spinning drop

A horizontally arranged capillary filled with a bulk phase and a
specifically lighter drop phase is set in rotation. The diameter or
curvature of the drop which is elongated by centrifugal force
correlates with the interfacial tension.

Vonnegut's equation: The interfacial tension (σ) can be

calculated from the measured drop diameter (d=2r) with
a given speed of rotation (ω) and with known densities
(ρ) of the two phases.
L = sum of circumstances L = Wetted length
θ : Contact angle θ : Contact angle The differences?
 Dynamic surface tension

The dynamic surface tension (SFT)

or interfacial tension (IFT) is the value of
the SFT or IFT referred to a particular
surface age or interface age.

Immediately after the surface is produced, the SFT or IFT has the same value as the pure liquid(s). The value then
reduces until an equilibrium value is reached. The time required for this depends on the diffusion rate and
the adsorption rate of the surfactant.

•Bubble pressure method: The maximum internal pressure of a gas bubble which is formed in a liquid by means of a capillary is
measured.
•Drop volume method: The volume of a drop of liquid produced at a vertical capillary is measured at the moment of its
detachment. This method is mainly used for measuring the interfacial tension.
•Interfacial rheology: Measurement of the progression of the SFT or IFT on a drop, the surface area of which changes in sinusoidal
cycles. The measurement reveals the viscoelastic behavior of the surface or interface of a surfactant solution, which often
correlates to the stability of foams or emulsions. The analysis is carried out using drop shape analysis on a pendant drop or by
measuring the Laplace pressure on a spherical drop.
Surface tension in the presence of surfactants

https://www.youtube.com/watch?v=zMzqiAuOSz0

https://www.youtube.com/watch?v=b_UnAsmPwSw
Surface tension in the presence of surfactants
Surfactants usually act to reduce interfacial free energy rather than to increase it

Lowering interfacial tension phenomenon

Without surfactants With surfactants

Phenomena resulted from surfactants
Two phenomena result from these opposing forces within the same molecule.

Adsorption
Adsorption

Aggregation
The aggregation process is so-called
‘micellisation’ and the aggregates are
known as ‘micelles’
Adsorption

• Adsorption vs. Absorption

Adsorption
• The process of accumulation at
an interface

Absorption
• The penetration of one
component throughout the body

31
 Adsorption
The adsorption mechanisms of surfactant at interfaces have been extensively studied in order to understand
their performance in many processes such as dispersion, coating, emulsification, foaming and detergency.

+ liquid–gas (foaming)
+ liquid–liquid (emulsification)

+ liquid–solid

(dispersion, coating and

detergency).
Wetting agents Dispersing agents
Adsorption at the solid/gas and liquid/gas surfaces

• Two general types of adsorption

• Physical adsorption
• Adsorbate is bound to the surface through the weak van der Waals forces

• Chemical adsorption (Chemisorption)

• Involves the stronger valence forces

• Usually involves an ion-exchange process

33
 Adsorption Classification
1) Physical adsorption 2) Chemical adsorption
• The gas molecules adhere to the surface of the solid • Results from a chemical interaction between the
adsorbent as a result of intermolecular attractive forces adsorbate and adsorbent. Therefore formed bond is
(van der Waals forces) between them much stronger than that for physical adsorption
• Heat liberated during chemisorption is in the range of
• The process is exothermic: the heat liberated is in the
20-400 kj/g.mole
order of the the enthalpy of condensation of vapor (2-20
• It is frequently irreversible. On desorption the chemical
kJ/g.mole)
nature of the original adsorbate will have undergone a
• The process is reversible (recovery of adsorbent material change.
or adsorbed gas is possible) by increasing the • Only a monomolecular layer of adsorbate appears on
temperature or lowering the adsorbate conc. the adsorbing medium
• Physical adsorption usually directly proportional to the
amount of solid surface area
• Adsorbate can be adsorbed on a monolayer or a number
of layers
• The adsorption rate is generally quite rapid

34
 Adsorption Isotherm
• The amount of gas/solute adsorbed per unit of adsorbent at equilibrium is measured against the partial
pressure/concentration of the adsorbate in thegas/liquid phase at certain temperature gives equilibrium
adsorption isotherm

x: Amount of adsorbate
m: Amount of adsorbents
x/m = mg/g or g/g

• The equilibrium concentration adsorbed is very sensitive to T

• There are many equations proposed to fit analyticaly the various experimental
isotherms
35
Adsorption isotherms

The adsorption of gases and solutes is usually described through isotherms, that is, the amount of adsorbate
on the adsorbent as a function of its pressure (if gas) or concentration (for liquid phase solutes) at constant
temperature.

Freundlich Langmuir
• Adsorption isotherms
• Langmuir equation

• Monolayer adsorption

• Freundlich equation

• Multilayer adsorption

The concentration of solute adsorbed

onto the solid phase

36
 Adsorption of surfactant on liquid/gas and liquid/liquid interfaces

The amount of surfactant adsorbed per unit area of interface (Γ) at surface saturation  surfactant adsorption
isotherm
Adsorption isotherms are used to relate the bulk surfactant concentration (C) to Γ

Langmuir adsorption isotherm

Γmax : maximum surfactant
adsorption at infinite
dilution in mol cm−2

a is a constant in mol cm−3

Γmax
C/Γ

Γ
δ is the thickness of the adsorption
layer, G0 is the free energy of
adsorption at infinite dilution, R is ideal
gas constant and T is the absolute
temperature C
Adsorption at liquid–solid interface
Langmuir adsorption isotherm
Surfactants adsorb on solid surfaces due to
hydrophobic bonding, electrostatic interaction,
acid–base interaction, polarization of π electrons
and dispersion forces.
Ns: The moles of surfactant adsorbed per unit mass of
the solid
+ Ns: The moles of surfactant adsorbed per Ns,max: The maximum moles of surfactant adsorbed per
unit mass of the solid unit mass of the solid
C: Concentration of surfactants
V: Volume of liquid phase a: a constant related to free energy of adsorption
m: mass of adsorbent

+ The surface concentration of surfactant on solid

surface, Γ (mol/area)
C/Γ

As is the surface area per unit

mass of the solid adsorbent

C
Adsorption at liquid–solid interface
The characteristics of surfactant adsorption isotherm on solid
surface are generally analysed by the plot of log Ns versus log
C or the plot of log Γ versus log C.

These plots show four region isotherms:

+ Region 1: the adsorption at low surfactant concentration.
Slope = 1. Surfactants molecules are freely adsorbed.
+ Region 2: Slope > 1 . Surfactant molecules move toward the
solid surface and form hemi-micelle or monolayer
+ Region 3: the slope of the isotherm decreases since the rate
of bilayer formation decreases
+ Region 4: the plateau adsorption occurs due to micelle
formation in the bulk liquid and slope of the isotherm levels off
Factors affecting adsorption

1. Solubility of adsorbate

2. pH

3. Nature of adsorbent

4. Temperature

43
Factors affecting adsorption
Factors affecting adsorption
Solubility of the adsorbate
• Lundelius’s Rule
• Adsorption of a solute is inversely proportional to its solubility.

• The greater the solubility, the stronger are solute-solvent

bonds

• Solute-solvent bonds must first be broken for adsorption.

 The smaller the extent of adsorption!

pH
• Adsorption increases as the ionisation of the surfactants is
suppressed.
• The extent of adsorption reaches a maximum when the molecules is
completely uninonised.
44
Nature of the adsorbent
Factors affecting adsorption

• Surface area of the adsorbent

• The most important property affecting
adsorption

• Extent of the adsorption is proportional to the

specific surface area.

• Adsorbent-adsorbate interactions

• Particular adsorbents have affinities for

particular adsorbates

• Ex) Digoxin - Antacids

45
 Temperature Factors affecting adsorption

• Adsorption is generally an exothermic

process
• Increase in temp  Decrease in
the amount adsorbed

• Small variations in temp tend not

to alter the adsorption process to
a significant extent
Explain this graph ?

46
 Self-assembly of Surfactants

Concentration

Free Molecules

Micelles

Cylindrical
Versicles

Micelles: Small aggregates

formed by the self-assemblage of
surfactants Lamellar
Self-assembly of Surfactants

Critical Micellar Concentration (CMC)

The critical micelle concentration (CMC) is defined as the

concentration of surfactants above which micelles form
and all additional surfactants added to the system will
form micelles
• In dynamic equilibrium with free molecules in solution
• Association colloids

• Driving force for micelle formation

• To attain a state of minimum free energy

• Remove the hydrophobic group from

the aqueous environment

49
Micellar structure

• Critical packing parameter (CPP)

• Consider the geometry of the surfactant molecule

𝑣
𝐶𝑃𝑃 =
𝑙𝑐 𝑎
v: volume of one chain
a: cross-sectional area of surfactant head group
lc: extended length of the surfactant alkyl chain

n = number of C in hydrophobic tail

Sometimes n = number of C - 1

• CPP determines the preferred association structures assumed for each molecular shape.
50
• CPP ≤ 1/3
• Single hydrophobic chain

• Simple ionic or large nonionic head group

 Spherical micelle

• 1/3 < CPP ≈ 1

• Additional second alkyl chain

 Bilayer (non-spherical structures)

• Form vesicles

51
• 1 < CPP
• In nonaqueous media, reverse (or inverted) micelles may form.

52
 Micellar structure of ionic micelles
Gouy-Chapman layer

• Stern layer Stern layer

• For most ionic micelles, the degree of ionization (α) is
between 0.2 ~ 0.3; 70~80 % of the counter-ions may be
bound to the micelles
• Gouy-Chapman electrical double layer
• Outer surface of the Stern layer
• Contain 20~30 % counter-ions to neutralize the charge on
the micelle
• In highly concentrated solution
• The micelles elongating to form cylindrical structures with
many ionic systems.

54
• Larger than ionic micelles
• Absence of an electrical work for additional monomer
into ionic micelle

• Frequently asymmetric

• Hydrophobic core surrounded by a shell of

oxyethylene chains
• The palisade layer (highly hydrated)

55
 Factors affecting the CMC and size

• Structure of the hydrophobic group

• Nature of the hydrophilic group

• Type of counter-ions

• Addition of electrolytes

• Temperature

56
Structure of the hydrophobic group
Factors affecting CMC and size

• Compounds with rigid aromatic or heteroaromatic ring structures

• Purines, pyrimidines, etc.

 Face-to-face stacking of molecules one on top of the other

 Do not exhibit CMC

• Length of Hydrocarbon chain

• Increase length  Increased hydrophobicity  Decreased CMC  Increase size

m: the number of carbon atoms in the chain

log [CMC] = A – B.m
A and B: constants for a homologous series

57
Structure of the hydrophobic group
Factors affecting CMC and size

• Effect of substituents on hydrophobicity can be roughly estimated.

Hydrophobicity

58
 Nature of the hydrophilic group
Factors affecting CMC and size

• Ionic surfactants
• Electrical works and interaction to
solvents lead to a high CMC, low
aggregation numbers
• Nonionic surfactants
• Not involve any electrical work

 Much lower CMC and higher

aggregation number

• Increase in the ethylene oxide chain

length An aggregation number is a description of the number of molecules
present in a micelle once the critical micelle concentration (CMC) has
 Make more hydrophilic and the been reached
59
CMC increases
 Type of counter-ions
Factors affecting CMC and size
• Cationic surfactant
• Cl- < Br- < I-

• Anionic surfactant
• Na+ < K+ < Cs+

Increase in micellar size

• The weakly hydrated ions can be adsorbed more readily

in the micellar surface
 Decrease the charge repulsion between the polar groups

60
 Addition of electrolytes
Factors affecting CMC and size
• Reduction of repulsion forces by electrolytes
 Lower CMC and higher micellar size

Decrease Increase

61
 Temperature
Factors affecting CMC and size
• Cloud point
• Temperature over which aqueous solutions of nonionic surfactants
become turbid

• Reversible process of phase separation

Increase in the micellar aggregation number

Mechanism Change in micellar interactions

The dehydration process

* J. Chromato. A, 2000, 902, 251-265 62

R. Carabias-Martinez, E. Rodriguez-gonzalo,, and B. Moreno-Cordero
 Temperature
Factors affecting CMC and size
• Comparatively small effect on ionic surfactants

Ionic surfactant

Nonionic surfactant

63
* Physiochemical Principles of Pharmacy 4th edition Alexander T Florence and David Attwood
CMC determination
The CMC is a useful tool for the selection of surfactants for specific applications or properties. For example,
surfactants with a low CMC are less of an irritant than those with high CMC.
The CMC can be determined by measuring the changes in physical properties such as electrical conductivity,
turbidity, surface tension, interfacial tension, solubilization and auto diffusion.
General Structural Features and Behavior of Surfactants

Hydrophilic groups – Effects of charges

Most natural surfaces are negatively charged.

Explain..
Cationic surfactants will be used for?
In case of positively charged surfaces ?
What if we use non-ionic (neutral surfactants) ?
If surfaces covered by polar and non-polar groups?
General Structural Features and Behavior of Surfactants
Hydrophobic groups
1. Straight-chain, long alkyl groups (C8–C20)
2. Branched-chain, long alkyl groups (C8–C20)
3. long-chain (C8–C15) alkylbenzene residues
4. Alkylnaphthalene residues (C3 and greater-length alkyl
groups)
5. Rosin derivatives (rosin is obtained from plant resins)
6. high-molecular-weight propylene oxide polymers
(polyoxypropylene glycol derivatives)
7. long-chain perfloroalkyl groups
8. Polysiloxane groups
9. lignin derivatives
General Structural Features and Behavior of Surfactants
Hydrophobic groups
+ Length of the Hydrophobic Group

(1) decreases the solubility of the surfactant in water and increases its
solubility in organic solvents
(2) causes closer packing of the surfactant molecules at the interface
(provided that the area occupied by the hydrophilic group at the
interface permits it)
(3) Increases the tendency of the surfactant to adsorb at an interface
or to form aggregates, called micelles
(4) Increases the melting point of the surfactant and of the adsorbed
film and the tendency to form liquid crystal phases in the solution
(5) Increases the sensitivity of the surfactant, if it is ionic, to
precipitation from water by counterions.
General Structural Features and Behavior of Surfactants
Hydrophobic groups
Branching, Unsaturation
(1) Increases the solubility of the surfactant in water or in
organic solvents (compared to the straight-chain, saturated
isomer)
(2) Decreases the melting point of the surfactant and of the
adsorbed film,
(3) Causes looser packing of the surfactant molecules at the
interface (the cis isomer is particularly loosely packed; the
trans isomer is packed almost as closely as the saturated
isomer) and inhibits liquid crystal phase formation in
solution
(4) May cause oxidation and color formation in unsaturated
compounds
(5) May decrease biodegradability in branched-chain
compounds
(6) May increase thermal instability.
General Structural Features and Behavior of Surfactants
Hydrophobic groups
Aromatic Nucleus

(1) increase the adsorption of the surfactant onto polar

surfaces
(2) Decrease its biodegradability
(3) Cause looser packing of the surfactant molecules at the
interface. Cycloaliphatic nuclei, such as those in rosin
derivatives, are even more loosely packed.
 Hydrophile Lipophile Balance

The relationship (or balance) between the hydrophilic portion of the nonionic surfactant to
the lipophilic portion

• It was invented in 1954 by William C. Griffin of the

Atlas Powder
Company ( bought by ICI in 1971 )

• As a guidance to good emulsification performance

• HLB values are calculated for nonionic surfactants

• The HLB value is an indication of the solubility of the surfactant

Hydrophile Lipophile Balance
Surfactant properties based on HLB value

The HLB value can be used to predict the surfactant properties

of a molecule