Surfactant (1)

An amphiphilic (also called amphipathic) compound that adsorbs at interfaces

to form oriented monolayers and shows surface activity. An amphiphilic compound
is a molecule that has a hydrophilic (polar) head and a hydrophobic (nonpolar) tail.
Common synonyms for the term “surfactant” include amphiphile, surface-active
agent, and tenside. If a surfactant is placed into contact with both a polar medium,
such aswater, and a nonpolar medium, such as an oil, one part of its molecule has
an affinity for the polar medium and one part that has an affinity for the nonpolar
medium. An example is an organic molecule such as sodium dodecyl sulfate (SDS),
which can be thought of as having a hydrocarbon (dodecyl) tail and a highly polar
(sulfate) head group. If the molecule is placed into a system containing water and
oil, the sulfate head group will have an affinity for the water, while the dodecyl tail
will have an affinity for the oil.
The energetically most favorable orientation for such molecules is at the
interface between the polar and nonpolar media, so that each part of the molecule
can reside in an environment for which it has the greatest affinity. In the case of
SDS in a mixture of oil and water, the SDS molecules will preferentially adsorbat the
water/oil interface, with the polar sulfate.
Surfactant group oriented into the water and the dodecyl tail group oriented
into the oil. Three consequences of the amphiphilic nature of surfactants are their
ability
(1) to adsorb and form layers at interfaces,
(2) to reduce the interfacial tension between fluids, and
(3) to associate to form clusters, called micelles.
When surfactant molecules adsorb at an interface, they provide an expanding
force that acts against the normal interfacial tension. At the interface between water
and air, for example, there exists a natural interfacial tension that arises from
chemical differences between thewater and the air. The interfacial tension acts to
cause the water/air interface to always strive toward a condition that minimizes the
area of contact (interfacial area) between the two phases. This interfacial tension is
what causes a waterdroplet to strive to achieve the shape of a sphere (the shape
having the smallest interfacial area). When a small amount of a surfactant is added
to the water/air system, surfactant molecules adsorb at the interface and reduce the
interfacial tension. This makes it easier for the system to adopt shapes having a
higher interfacial area. A waterdroplet in air that contains some surfactant can more
easily distort and adopt shapes other than spherical. This makes it easier to form
foams. The same thing happens when a small amount of surfactant is added to a
mixture of water and oil. The reduced interfacial tension makes it easier for the
system to adopt shapes having a higher interfacial area. This makes it easier to form
emulsions either of oil-in-water or of water-in-oil.
Many hydrocarbon surfactants can lower the interfacial tension of air–water at
20◦C (68◦F) from 72.8 mN/m to about 28 mN/m. Polysiloxane surfactants can
reduce it to about 20 mN/m, and perfluoroalkyl surfactants can reduce it still further
to about 15 mN/m. Similarly, hydrocarbon surfactants can reduce the interfacial
tension ofwater–mineral oil from about 40 mN/m to about 3 mN/m. In addition to
lowering interfacial tension, adsorbed surfactant at interfaces can strongly influence
other properties, such as interfacial elasticity and interfacial viscosity.
Lung surfactants, including phospholipids and proteins, are an example of
natural surfactants present in the human body. The lung surfactants are necessary
to maintain a low interfacial tension at the alveolar air–water interface and to help
the alveolar spaces change size during the breathing cycle. These interfacial
tensions also change rapidly in response to changes in alveolar radius, and can fall
to values as low as 10 mN/m or less. A deficiency of lung surfactant causes the
interfacial tension to be too high, which causes alveolar collapse at the end of
expiration.
The lung surfactants may also play a role in protecting the lung from injury and
infection caused by inhalation of particles and microorganisms.
As surfactant is added to a multiphase system, the surfactant molecules will
tend to adsorb at the interface(s), forming into an oriented monolayer at the interface
and reducing interfacial tension. However, above a certain concentration, called the
critical micelle concentration (cmc), the surfactant molecules will start to self-
associate and form aggregates called micelles. The value of the cmc depends
primarily on the nature of the surfactant. Other factors being equal, higher molar
masses produce lower cmc values.
Once micelles have been formed, almost all additional surfactant added to the
system will become solubilized in the micelles. In aqueous solution the part of the
surfactant molecules that have an affinity for the nonpolar medium (the tails)
associates in the interior of the micelle, while that part that has an affinity for the
water (the head groups) faces the aqueous medium. Micelles typically contain 20–
100 surfactant molecules each. The insides of the micelles, being filled mostly with
nonpolar tails, have properties similar to an oil phase.
Surfactant types. Depending on the nature of the polar (hydrophilic) part of
the molecule, surfactants are classified as anionic (negatively charged), cationic
(positively charged), nonionic (noncharged), or zwitterionic (able to contain either or
both kinds of charge). A common anionic surfactant is sodium dodecyl sulfate,
CH3(CH2)11SO4−Na+. A common cationic surfactant is cetyl trimethylammonium
bromide, CH3(CH2)15N+(CH3)3Br−, a common type of nonionic surfactant is
polyoxyethylene alcohol, CnH2n+1(OCH2CH2)mOH. An example of a zwitterionic
surfactant is dodecyl betaine, C12H25N+(CH3)2CH2COO−. A soap is a particular
kind of anionic surfactant comprising any of the surface-active fatty-acid salts
containing at least eight carbon atoms. Typically, the molar masses of surfactants
range froma fewhundreds to several thousands of grams per mole.
Although surfactants are not generally considered to be a serious threat to
humans, they can be toxic to aquatic organisms. This can be a concern due to the
large quantity of surfactants used. It has been estimated that the global use of
synthetic surfactants is on the order of several million metric tons per year.

Reference : Encyclopedia of Science and Technology of Surfactant