Basics of

Surfactants
Surfactants
(Surface Active Agents)

Definition

Amphiphilic (schizofrenic) compounds with

the following key properties:

Adsorption at surfaces/ interfaces

Aggregation at certain concentrations

and temperatures
 Chemical Structure

Water: Hydrophobic part Hydrophilic part

Oil: Lipophilic Lipophobic

The balance between the two parts is decisive for

the properties of the surfactant!!
 What Is a Surfactant?

Surface tension

Inorganic
electrolytes
0

Organic solutes
Amphiphilic solutes
Concentration
 Surfactants

Surface active molecules

Air
orientate themselves in the
interface between two phases.
Water

When the surface is saturated

with surfactants they start to
form spherical globules in the Air
water, which are called Oil
micelles.

Interfacial tension
Water
 Types of Surfactants

The Hydrophobe The Hydrophile

Fatty acids Nonionic types
Ethoxylates
Fatty amines
Glucosides
Alkyl phenols Cationic types +
Fatty alcohols Quaternary, tertiary and
Etc. primary amines
_
Anionic types
Acids, phosphonic groups
Sulphonates etc
_
Amphoteric types +
Glycinates, propionates
Betaines
 Functions of Surfactants

Dispersing Conditioning
Aggregation Emulsification
Hydrophobation Colloid stabilization
Wetting Water retention
Disinfection
Anti-corrosion
Rheology control
Foaming/Defoaming
Thickening
 Applications of Surfactants

Important group of compounds in biological

systems:
Cell membranes: phospholipids
Emulsification of fat: bile salts

Wide range of industrial applications

We focus on Cleaning & Biocides!

 Why Use Surfactants in Cleaning?

The main tasks of surface active agents for cleaning are to:

9 reduce the surface tension of water to get

wetting properties and to release soil from surfaces.

9 emulsify fatty material

9 disperse solid particles and pigment (dirticles)

 What is Surface Tension?

The work/force needed to create more surface area!

The stronger bonds the higher surface tension and
the more energy needed.
Surface Tension (in mN/m) of
Some Liquids at 25oC

Mercury 480
Water 72
Blood 56-61
Ethanol 22
n-Hexane 18
 The Influence of Surfactants
on Surface Tension

The surfactants orientate

themselves in between the water
molecules and disturb their
Weaker hydrogen hand-holding. The force is then
bond lowered.

For some surfactants the surface

tension can be reduced to ~30
mN/m or even lower.
 Wetting

Bad wetting, high Good wetting, low

surface tension, big surface tension, small
contact angle contact angle

Air

Water

Contact angle reduction is the key!

 Youngs Equation(1805)

Vapour L/V = surface/ interfacial tension

Liquid

Solid S/L S/V

S/V = S/L + L/V . cos

For any non-wetting conditions: cos <1, thus

S/V < S/L + L/V for non-wetting conditions!

S/V S/L
The contact angle is given by: cos =
L/V
 Substrate

Type of material
Critical Surface Tension (CST), C
Material mN/m
Glass >73
301 Stainless steel 44
Polyethylene 31
Polypropylene 28
Teflon 18
Water 72

To wet a surface, the surface tension of the

liquid should be below the CST => C >L/V
Kinetics of Wetting

air
new liquid/air
interface old liquid/air
interface

solid

New liquid/solid interface

To ensure a good wetting you need

9 a low surface tension

9 a high diffusion rate
 Wetting Properties of
Amine Oxides

Wetting time, sec

3000
Wetting properties
2000 CnH2n +1N(CH3)2O according to DIN 53901
1000
HT 1 g amine oxide/l, 25oC

500
400
300 MC = middle cut coco
200 HT = hydrogenated tallow
100
MC
50
40
30
8 10 12 14 16 18 n
 Real Soil

Pigment: Grease:
* Dust * Mineral Oil
* Graphite * Vegetable Oil
* Carbon Black * Animal Fat
* Etc
 Removal of Oily/ Greasy Soils

The hydrophobic (lipophilic) chain

is attracted by the soil and
penetrates it.

The surfactants force the soil to

open and to detach from the
surface.

The soil is detached from the

surface.
 Oily Soil on Different Substrates

Intitial Water
Oil
Final
O/W
Oil
Solid O/S S/W
Energy needed to remove oily soil

Wadhesion = O/W S/W O/S

+
Hydrophobic solid: S/W higher O/S lower Wadhesion higher
Hydrophilic solid: S/W lower O/S higher Wadhesion lower

L
O/W same in both cases

Conclusion: More difficult to remove oily soil from more

hydrophobic surfaces (e.g plastic surfaces)
 Solubility versus Degreasing

When surfactants are highly water soluble:

the driving force for the surfactants to leave the water phase and
penetrate the oil phase (grease) is low
few molecules leave the water phase
high surfactant concentrations are required

When surfactants are poorly water soluble:

the driving force to go to the oil phase is strong
many molecules leave the water phase
low concentrations do great job

Best surfactant to remove oils and fats is nonionic.

 Phase Diagram of a Nonionic

90 W + L1 Cloud curve

Cloud
L1
Temperature, oC

point
60
Clear micellar
solution V1

30 H1 L

S
I1
0 25 50 75 100
Composition, wt% C12EO8 (aq)
 Cloud Point and Cleaning

Residual oil, g/m2

10.0
Original oil level 6.23 g/m2
5.0
NP-10 NP-12
2.0

1.0

0.5

0.2
Cloud points
0.1
20 40 60 80
Temp, oC
 Pigment Removal

Most particles and surfaces are given a negative surface

potential in water

An increase of the pH means and increase of the

repulsion between pigment and surface

OH - OH - OH -
 Pigment Removal

Pigment removing capacity on cotton at different pH,

without surfactant
40

20

0
2 4 6 8 10 12 14
 Pigment Removal

Repulsion of the head groups

avoid coalescenece and
precipitations of the particles.

Surfactants adsorbing on hydrophobic particles

CMC (Critical Micelle Concentration)

Interfacial tension

Equivalent conductivity
Osmotic pressure
Surface tension

CMC Concentration
 CMC (Critical Micelle Concentration)

Below the CMC, the molecules are

free, swimming around seeking
areas to attach and forming mono-
molecular layers to (adsorb)

Above the CMC, they form the

mono-molecular layer. When all the
area has been covered they stick to
one another instead, forming the
micelles. The more you add, the
more micelles you form.

The surface tension now does not

decrease with increased surfactant
addition. The micelles form and
disintegrate 1000 times per second
Below CMC Above CMC
 How CMC Can Be Affected ?

The aggregation (CMC) depends on for example:

9 Type of surfactant ionics higher, longer tails lower

9 Temperature ionics small increase, nonionics

decrease with temperature

9 Salts usually reduction with increase (salt)

9 Co-surfactants increase or decrease; in some mixtures

a synergistic reduction of CMC
 CMC for Some Surfactants

Surfactant CMC/mM at 25oC

Anionic
n-C10H21SO4-Na+ 33,0
n-C12H25SO4-Na+ 8,20
n-C14H29SO4-Na+ 2,05

Nonionic
C12H25(OC2H4)3OH 0,052
C12H25(OC2H4)5OH 0,064
C12H25(OC2H4)8OH 0,109
 Structures of Micelles

Spherical Rod-shaped or Lamellar

cylindrical

The structure and shape of a micelle depends on:

Temperature
Concentration
Type of surfactants
Electrolytes
Other water soluble organic compounds (e.g. alcohols)
 Conclusions CMC and Micelles

Micelles make insoluble material soluble in water.

The structure of the micelles can affect the viscosity of
the solution.
Micelles are reservoirs of surfactants.
If not above CMC, the cleaning solution gets
depleted of surfactants and cleaning power is lost!!
Important Cleaning Parameters

Mechanical
treatment

So me
il Ti

a tion Te
m
r
ent pe
ra
nc tur
Co e

Foam/
no foam