Surfactants:

Surfactants are compounds that lower the surface tension (or interfacial tension) between two liquids
or between a liquid and a solid. These may act as detergents, wetting agents, emulsifers, foaming
agents and dispersants. Some common examples of surfactants are:
Soaps (free fatt acid salts)
Fatt acid sllfonaates (tie moost comomoona of iici is sodilmo lartl sllfate or SaS)
Etioxtlated comopolnads, slci as etioxtlated proptlenae gltcol
aecitiina
Poltgllconaates, basicallt a glorifed naamoe for siort-ciaina starcies
Surfactants are usually organic compounds that are amphiphilic, meaning they contain both
hydrophobic groups (their tails) and hydrophilic groups (their heads). Therefore, a surfactant contains
both a water-insoluble (or oil-soluble) component and a water-soluble component. Surfactants will
diffuse in water and adsorb at interfaces between air and water or at the interface between oil and
water, in the case where water is mixed with oil. The water-insoluble hydrophobic group may extend
out of the bulk water phase, into the air or into the oil phase, while the water-soluble head group
remains in the water phase.
Surfactants adsorb preferably at interfaces where they fnd the energetcally most favourable conditons
due to their two-part structure. At a water surface, for example, the surfactants orient themselves in
such a way that the head group resides in the water and the hydrocarbon chain points to the gaseous
phase. Thus surfactants can mediate between two phases as they can form strong interactons with both
of them. The interfacial tension consequently decreases. The additon of surfactants hence facilitates
the mixing of non-polar and polar phases, which is used in the detergent industry for example.

Surfactants at an interface

Classification of Surfactants:
The tails of most surfactants are fairly similar, consistng of a hydrocarbon chain, which can be branched,
linear or aromatc. Fluoro surfactants have fluorocarbon chains. Siloxane surfactants have siloxane
chains. Many important surfactants include a polyether chain terminatng in a highly polar anionic
group. The polyether groups ofen comprise ethoxylated (polyethylene oxide-like) sequences inserted to
increase the hydrophilic character of a surfactant. Polypropylene oxides conversely, may be inserted to
increase the lipophilic character of a surfactant. Surfactant molecules have either one tail or two; those
with two tails are said to be double-chained.

Surfactants are classifed depending on their solubility as: hydrophilic and hydrophobic (lipophilic)
surfactants. Hydrophilic surfactants are soluble in water whereas hydrophobic (lipophilic) surfactants
are soluble in lipids. Ionic surfactants are generally hydrophilic surfactants, but nonionic surfactants can
be either hydrophilic or lipophilic, depending on the balance of the hydrophilic group and lipophilic
group. In other words, the solubility of nonionic surfactants depends on the balance between the
hydrophilic group's capacity of atractng water and the lipophilic group's capacity of atractng oil.
Surfactants can be classifed according to the charge of their polar head group: anionic, catonic,
zwiterionic and nonionic surfactants.
(i) Anionic Surfactants:
Anionic surfactants have a negatvely charged head group such as sulfate (-OSO3-), sulphonate (-SO3-),
phosphate, and carboxylates (-COO−). Prominent alkyl sulfates include ammonium lauryl sulfate, sodium
lauryl sulfate (sodium dodecyl sulfate, SLS, or SDS) and the related alkyl-ether sulfates sodium laureth
sulfate (sodium lauryl ether sulfate or SLES) and sodium myreth sulfate. Others include:
Doclsate (diocttl sodilmo sllfoslccinaate)
Perflorooctanaesllfonaate (PFOS)
Perflorobltanaesllfonaate
Alktl-artl etier piospiates
Alktl etier piospiates
Carboxylates are the most common surfactants and comprise the carboxylate salts (soaps), such
as sodium stearate. More specialized species include sodium lauroyl sarcosinate and carboxylate-based
fluorosurfactants such as perfluorononanoate, perfluorooctanoate (PFOA or PFO).
Anionic surfactants are the most widely used type of surfactants for laundering, dishwashing liquids and
shampoos. They are partcularly good at keeping the dirt, once dislodged, away from fabrics. Commn
anionic surfactants are used: alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates and soaps.

An alkylbenzene sulfonates An alkyl ether sulfates

A soap

(ii) Cationic Surfactants:

Cationic surfactants have a positvely charged head group. These surfactants show surfactant propertes
over the whole pH range. Many applicatons of catonic surfactants are based on their adsorpton
behaviour on negatvely charged surfaces. Typically quaternary ammonium compounds are used as
hydrophobic agent, hydrotropes, antstatc and sofening agent (fabrics). The range of ester and amide
based quaternary ammonium compounds comply with the European detergent regulatons.

Methylquatschlorode Ethylquats ethosulphate Benzylquats Epichlorohydrin quats

or methosulphate
(iii) Zwiterrionic Surfactants:
Zwiterionic surfactants (amphoteric) have a head with two oppositely charged groups (positve and
negatve charge). These surfactants have both catonic and anionic centers atached to the same
molecule. The catonic part is based on primary, secondary or tertary amines or quaternary ammonium
catons. The anionic part can be more variable and include sulfonates, as in sultaines CHAPS (3-[(3-
cholamidopropyl)dimethylammonio]-1-propanesulfonate) and cocamidopropyl. Betaines such
as cocamidopropyl betaine have a carboxylate with the ammonium. The most common biological
zwiterionic surfactants have a phosphate anion with an amine or ammonium, such as
phospholipids phosphatdylserine, phosphatdylethanolamine, phosphatdylcholine and sphigomyelins.
(ii) Nonrionic Surfactants:
Nonionic surfactants have no charged groups in its head group. These surfactants have covalently
bonded oxygen-containing hydrophilic groups, which are bonded to hydrophobic parent structures. The
water-solubility of the oxygen groups is the result of hydrogen bonding. Hydrogen bonding decreases
with increasing temperature, and the water solubility of non-ionic surfactants therefore decreases with
increasing temperature.
Nonrionic surfactants are less sensitve to water hardness than anionic surfactants, and they foam less
strongly. The differences between the individual types of non-ionic surfactants are slight, and the choice
is primarily governed having regard to the costs of special propertes (e.g., effectveness and efciency,
toxicity, dermatological compatbility, biodegradability) or permission for use in food. Nonionic
surfactants do not dissociate into ions in aqueous solutons.

Micelle:
Surfactants are interfacially actve compounds. They consist of a polar head group and a non-polar
hydrocarbon chain. The polar part of the molecule can interact strongly with polar solvents, like water
and is therefore also called the hydrophilic part (head). The non-polar part, on the other hand, can form
strong interactons with non-polar solvents, like oil and is therefore also called lipophilic or hydrophobic
part (tail).

Schematic structure of a surfactant

A micelle or micella is an aggregate of surfactant molecules dispersed in a liquid colloid. A typical micelle
in aqueous soluton forms an aggregate with the hydrophilic head regions in contact with surrounding
solvent (the outside surface of the micelle), sequestering the hydrophobic single-tail regions in the
micelle centre (forms the core).

Schematic diagram of a micelle Spherical micelles

The lipophilic tails of the surfactant ions remain inside the oil because they interact more strongly with
oil than with water. The polar "heads" of the surfactant molecules coatng the micelle interact more
strongly with water, so they form a hydrophilic outer layer that forms a barrier between micelles. This
inhibits the oil droplets, the hydrophobic cores of micelles, from merging into fewer, larger droplets
(emulsion breaking) of the micelle. A micelle consists of a core and a shell, where hydrophobic end
groups form the core and hydrophilic head groups form the outer shell Micelles represent the simplest
associaton structures frequently formed by amphiphles in aqueous solutons.
The compounds that coat a micelle are typically amphiphilic in nature, meaning that micelles may be
stable either as droplets of aprotc solvents such as oil in water, or as protc solvents such as water in oil.
However, if the solvent is aprotc (organic), then the components of the micelle are reversed called
reverse micelle. The polar heads are interior and the hydrophobic chains are exterior.

Micelle Reverse micelle

Micelles can vary in shape from spherical rod-like or ellipsoidal structures depending on their
compositon

Critical Micelle Concentration (CMC):

The critical micelle concentration (CMC) is defned as the concentraton of surfactants (amphiphilic
molecules) above which micelles are formed. Micelle nanopartcles range in size from 5 to 100 nm. The
CMC is an important characteristc of a surfactant. At this concentraton, these molecules start to form
the micellar structure, assembly driven by the decrease of free energy.
The value of the CMC for a given dispersant in a given medium depends on temperature, pressure and
(sometmes strongly) on the presence and concentraton of other surface actve substances and
electrolytes. Micelles only form above critical micelle temperature or Kraf temperature. Below the
Kraf temperature, micelles cannot form. For example, the value of CMC for sodium dodecyl sulfate in
water (no other additves or salts) at 25 °C, atmospheric pressure, is 8x10−3 mol/L. With increase in
concentraton of surfactant there will be decrease in surface tension.
Upon introducton of surfactants (or any surface actve materials) into the system, they will initally
partton into the interface, reducing the system free energy by:
lo erinag tie enaergt of tie inaterface (calcllated as area tmoes slrface tenasiona)
remoovinag tie itdropiobic parts of tie slrfactanat fromo conatact iti ater
Subsequently, when the surface coverage by the surfactants increases, the surface free energy (surface
tension) decreases and the surfactants start aggregatng into micelles, thus again decreasing the
system's free energy by decreasing the contact area of hydrophobic parts of the surfactant with
water. Upon reaching CMC, any further additon of surfactants will just increase the number of micelles
(in the ideal case).

Increasing concentration of surfactant in water slowly forming a layer on the surface and eventually forming
micelles at or above the CMC

.
Surface tension of a surfactant solution with increasing concentration, formation of micelles
There are several theoretcal defnitons of CMC. One well-known defniton is that CMC is the total
concentraton (Ct) of surfactants under the conditons:
F
Ct3 = d3 x
d
F
Ct = d x
√3

d
Where,
a, b are proportonal constants and F is Functon of surfactant soluton
F = a[micelle] + b[monomer]
Significance of CMC:
Knowledge of the CMC is very important when using surfactants. As the surface tension does not reduce
further above the CMC, in many processes the CMC specifes the limitng concentraton for meaningful
use. When the formaton of micelles is desirable, e.g. when cleaning, the CMC is a measure of the
efciency of a surfactant. Variables for the scientfc characterisaton of the surface adsorpton can also
be derived from the CMC. Examples include the area per molecule and the surface excess. The last-
mentoned variable can be used to help determine the adsorpton coefcient from measurements made
with a bubble pressure tensiometer.