CHEMISTRY OF SURFACTANTS
The
Surfactants
-derived from the words Surface
Active Agents
-compounds that lower the surface
tension (interfacial tension) between two
substances
STRUCTURE
Amphipatic: have two distinctly different
characteristics, polar and non polar
non polar tail polar head
(hydrophobic) (hydrophilic)
Non polar tail: usually a hydrocarbon chain but may be a
fluorocarbon or siloxane chain of appropriate length
Polar head: may be either ionic or nonionic
Formation of Micelles
Specific functions of surface
active agents include removing soil (scouring), wetting,
rewetting, softening, retarding dyeing rate, fixing dyes, making
emulsions, stabilizing dispersions, coagulating suspended
solids, making foams, preventing foam formation and
defoaming liquids.
The surface tension of a liquid is an internal pressure
caused by the attraction of molecules below the surface for
those at the surface of a liquid. This molecular attraction creates
an inward pull, or internal pressure, which tends to
restrict the tendency of the liquid to flow and form a large
interface with another substance.
The surface tension (or inter-facial tension if the interface is
not a surface) determines the tendency for surfaces to establish
contact with one another. Therefore, surface tension is
responsible for the shape of a droplet of liquid. If the surface
tension is high, the molecules in the liquid are greatly attracted
to one another and not so much to the surrounding air.
Chemically, surfactants are amphipathic molecules. That
is, they have two distinctly different characteristics, polar and
non polar, in different parts of the same molecule. Therefore,
a surfactant molecule has both hydrophilic (water-loving) and
hydrophobic (water-hating) characteristics. Symbolically, a
surfactant molecule can be represented as having a polar
head and a non polar "tail" as shown below.
The hydrophobic group in a surfactant for use in aqueous
medium is usually a hydrocarbon chain but may be a fluorocarbon
or siloxane chain of appropriate length.
hydrophilic group is polar and may be either ionic or nonionic.
Since surfactant molecules have both hydrophilic and
hydrophobic parts, the most attractive place for them in water
is at the surface where the forces of both attraction and repulsion
to water can be satisfied. One other way that surfactants
interact to satisfy natural forces of attraction and repulsion
between molecules is by formation of micelles. Surfactant
molecules aggregate in water forming micelles (see Figure I).
Micelles consist of hydrophobic interior regions, where
hydrophobic tails interact with one another. These hydrophobic
regions are surrounded by the
hydrophilic regions where the heads of
the surfactant molecules interact with
water.
At very low concentration in water,
surfactant molecules are unassociated.
At higher concentration of surfactant in
water, micelles form, The concentration
at which micelles form is called the
critical micelle concentration (CMC).
The surface tension of water undergoes
a precipitous decrease, and the detergency
of the mixture increases dramatically
at the CMC.
Micelles are formed at the critical micelle
concentration (CMC), which is detected as
an inflection point when physicochemical
properties such as surface tension are plotted
as a function of concentration (Figure 4.7).
The main reason for micelle formation is
the attainment of a minimum free energy state.
The main driving force for the formation of
micelles is the increase of entropy that occurs
when the hydrophobic regions of the surfactant
are removed from water and the ordered
structure of the water molecules around this
region of the molecule is lost.
Most micelles are spherical and contain
between 60 and 100 surfactant molecules.
The surfactant industry is dominated by several types: alkylbenzene
sulfonates,
alcohol ethoxylates, sulfates and ethersulfates.41 These are the major
components of
laundry detergents, household, and personal care products and account for
over half
of all use of surfactants.
The applications of surfactants in industry area are quite
diverse and have a great practical importance.
In some usage surfactants are defined as molecules
capable of associating to form micelles. These compounds are termed from solution. While many physical and compositional properties influence
surfactants, surfactant
amphiphiles, surface-active agents, tensides, or, in the very old literature, adsorption, for a given practical application, usually the main factor that is
paraffinchain manipulated is the type of surfactant used. There are a number of areas of
salts. The most commonly used term, surfactant, was originally registered application
as a where surfactant adsorption is important including ore flotation, improved
trademark for selected surface-active products 48 and later released to the oil
public recovery, in situ and ex-situ soil remediation, cleaning applications
domain.49 (detergency), surfactant
based separation processes, and wetting. Surfactant adsorption may occur
due
to electrostatic interaction, van der Waals interaction, hydrogen bonding,
At a specific, higher, surfactant concentration, known as the critical and/or
Fig. 2 Organization of surfactant molecules in a micelle. From Hiemenz and solvation and desolvation of adsorbate and adsorbent species.
Rajagopalan.28
(Reproduced with permission from Principles of Colloid and Surface Chemistry,
Dekker.)
Annu. Rep. Prog. Chem., Sect. C, 2003, 99, 348 9
micelle concentration (cmc), molecular aggregates termed micelles are
formed. The
cmc is a property of the surfactant and a number of other factors including
the
temperature, pressure, and the presence and nature of additives, since
micellization
is opposed by thermal and electrostatic forces.

The cmc values are important in virtually all of the process industry
surfactant
applications, from mineral processing to formulation of personal care
products and
foods, to drug delivery systems, and to new surfactant remediation
technologies. In
these processes, surfactant must usually be present at a concentration higher
than the
cmc because the greatest effect of the surfactant, whether in interfacial
tension lowering,
37 emulsification, suspension stabilization, as a delivery vehicle, or in
promoting
foam stability,38 is achieved when a significant concentration of micelles is
present.l A high foam is desired e.g.

For manual dish-washing detergents, hairshampoos or detergents

formanual textile washing)

The cmc is also of interest because at concentrations above this value the
adsorption
of surfactant at interfaces usually increases very little. That is, the cmc
frequently
represents the solution concentration of surfactant from which nearly
maximum
adsorption occurs.

Surfactant adsorption and surface properties

Surfactant adsorption is a consideration in any application where
surfactants come in
contact with a surface or interface. Adsorption of surfactants may lead to
positive
effects, as in surface wettability alteration, or be detrimental, as in the loss
of surfactants