Surfactants: Surface Active Agents

Surfactants are surface active agents, which literally means active at surface. Surfactants are those compounds which
lower the surface tension (or interfacial tension) by their tendency to get adsorbed at surface and interfaces. Interface
is a link of any two immiscible phases and the term surface is used when any one phase is a gas, i.e., air. Some
examples of surface and interface are as follows:
Solid – Vapour (surface)
Solid – Liquid (interface)
Solid – Solid (interface)
Liquid – Vapour (surface)
Liquid – Liquid (interface)
The extent of work required to expand the interface is termed as interfacial free energy per unit area and is usually
termed as interfacial tension. The surface tension of water is equal to the interfacial free energy per unit area of the
boundary between water and the air above it. When thatboundary is covered by surfactant molecules, surface tension
(or the amount of work required to expand the interface) is reduced Fig. 1. Denser the surfactant part at the interface,
greater will be the reduction in surface tension.

Figure1
Adsorption of surfactant
at thesurface of water

Surfactant may absorb at all surfaces and interfaces given above. Generally, we have interfaces which have water
as the liquid phase. Various examples for the different interfaces and products are given in Table 1.

Table 1 Examples of interface involving a liquid phase

Interface Type of system Product

Solid – liquid Suspension Sand in water
Liquid – liquid Emulsion Milk, Cream
Liquid – Vapour Foam Shaving cream

As we have seen, the fundamental property of the surfactants is their tendency to accumulate at interface. The
concentration of surfactant at a boundary usually depends on the surfactant structure and on the nature of the two
phases which are in contact at the interface. Therefore, no universally good surfactant is potent for all uses. The
choice depends on the application. A good surfactant should have weak solubility to the bulk phases. Some
surfactants (and several surface active macromolecules) are only soluble at the oil-water interface. Such compounds
are hard to carry but are very efficient in reducing the interfacial tension.

Composition and Structure: Surfactants are Amphiphilic

The word amphiphile first introduced by G.S. Hartley, is taken from the Greek word amphi, which means
‘both’. Mainly these amphiphilic organic compounds consist of contain 2 parts, one part i.e., the lyophilic part which
is soluble in a specific fluid while the other part which is insoluble is the lyophobic part. The hydrophilic part is
denoted as the head group and the hydrophobic part is referred as the tail (see figure 2). In case of water as a fluid,
the water soluble part is called hydrophilic and water insoluble part is called hydrophobic.
 Fig 2. Diagrammatic illustration of a surfactant

The hydrophobic part is usually linear or a branched chain of 8 to 18 carbons, which can be aliphatic, aromatic, or
a mixture of both the structures. The sources of hydrophobic part are generally fats, oils, petroleum fractions, short
synthetic polymers, or relatively high molecular weight synthetic alcohols. The chain branching degree, the polar
group position and the chain length are parameters of importance for the surfactant physiochemical properties. The
surfactant polar part may be ionic or non-ionic, which give the primary classification to the surfactants which we
will discuss in Section 5. The choice of polar group and comparative size of the hydrophobic and polar groups are
important factors in determining the properties and surfactant physiochemical behavior in water.
A surfactant usually contains one polar group. In recent times, there have been considerable research interest in
certain dimeric surfactants, which contain two hydrophobic tails and two head groups linked together with a short
spacer. These species are termed as Gemini surfactants or doubled chain surfactant. They show several interesting
physicochemical properties, such as high efficiency in lowering surface tension and very low CMC. A typical
Gemini surfactant is shown in Figure 3.
(a) (b)

Fig 3. (a) Gemini surfactant (b) Dimer of sodium dodecylsulfate

Natural Surfactants:
Nature’s own surfactants are termed as polar lipids. These are abundant in all living organisms. In the biological
system, the surface active agents play the same role as surfactants in technical systems: to overcome solubility
problems, as emulsifiers, as dispersants, to modify surfaces, etc. Some examples of this in biological system are:
bile salts are extremely efficient solubilizers of hydrophobic components in the blood, while mixtures of
phospholipids pack in ordered bilayers liquid crystal of surfactants and such structures constitute cell membranes,.
The importantexample of a phospholipid is lecithin: phosphatidylcholine.,illustrated in fig. 4. Lecithin is extracted
from phospholipid-rich sources such as soybean and egg.

Fig 4. lecithin: phosphatidylcholine

Dynamics of surfactants in solution

One characteristic feature of surfactant is their tendency to dissolve in water and adsorb at interface of air and water
or at the interface of oil & H2O (a case where H2O is mixed with oil). The hydrophobic group which is water
insoluble may extend out from the water phase which is in bulk with the air or with the oil phase. Whereas water
soluble head group is linked with the water phase. The alignment at the surface of surfactant improves the water
properties –air or water-oil interface. In addition to this, surfactants have a special property that of having a
monomer in solution which tends to form aggregates known as micelles. The Micelle formation or the process
micellization is an alternative mechanism of adsorption where the hydrophobic group is removed from the water at
the interface, thereby reducing the system’s free energy. It is an important process as surfactant molecules when
present in micelles form behave differently in comparison to free monomers in solution. Only surfactant monomers
take part on the surface, whereas the lowered interfacial tension and the dynamic phenomena i.e., wetting and
foaming is checked by concentration of free monomers in the solution. The micelles formation is considered as a
reservoir for the monomers surfactant. The exchange rate of a surfactant molecule between micelle and bulk solution
may vary by many orders of magnitude depending on the size and structure of the surfactant. The dynamics of
surfactant in solution is shown in figure 5.

The middle figure corresponds to reverse micelle?

Fig 5. Dynamics of surfactant in solution

In micelle the surfactant hydrophobic group is linked with the interior of the cluster and the polar head group is
linked with the solvent. The micelle, therefore, is a polar aggregate of high water solubility and without much
surface activity. When a surfactant adsorbs from aqueous solution at a hydrophobic surface, it normally orients its
hydrophobic group towards the surface and exposes its polar group to the water. The surface becomes hydrophilic
and, as a result, the interfacial tension of the surface and water is reduced. Adsorption at hydrophilic surface often
result in more complex surfactant assemblies.

Classification of Surfactants

The classification of primary surfactants is made on the basis of the charge on the polar head group. If the charge
is negative, the surfactant is termed as anionic; if the charge is positive, it is termed as cationic. If a surfactant
contains a head with two oppositely charged groups, it is knownas zwitterionic. We can categorize surfactants into
the classes - anionic, cationic, nonionic and zwitterionic.

Fig 6. Surfactants classification according the composition of charges on them.

Anionic surfactants

Anionic surfactants consist of anionic functional groups at their head, i.e., sulfate, sulfonate, phosphate, and
carboxylate. We use anionic surfactants in greater volume than other surfactant class, and they are used in most
detergent formulations and the best detergency is obtained by alkyl and alkyl-aryl chains in the C12-C18 range.
Soaps which are the largest single type of surfactants are anionic surfactants obtained by saponification of natural
oils and fats. Soap is a gene name indicating the metal salt of an alkali carboxylic acid originated from animal fats
or vegetable oils. Soap bars are usually based on fatty acids mixtures produced from tallow, coconut and palm oil.
Over the last 50 years, soaps have been replaced with more efficient substances like alkylsulphates, alkyl sulphonates
and alkyl benzene sulphonates.
Anionic surfactants are very sensitive to hardness of water. The counter ions most commonly used are sodium,
potassium, ammonium, calcium and various protonated alkyl amines. Sodium and potassium impart solubility in
water, whereas calcium and magnesium give solubility in oil. Amine / Alkanol amine salts give products which are
both oil and water soluble.

Table 2. Few examples of Anionic surfactants

Classifications Examples
Alkyl sulfates • Ammonium lauryl sulfate
• Sodium lauryl sulfate (SDS, sodium dodecyl sulfate)

Alkyl-ether sulfates • Sodium laureth sulfate or sodium lauryl ether sulfate (SLES)
• Sodium myreth sulfate.
Sulfonate • Dioctyl sodium sulfosuccinate, perfluorooctanesulfonate (PFOS)
• Perfluorobutanesulfonate
• Linear alkylbenzenesulfonates (LABs).
Alkyl carboxylates • Sodium stearate
• Sodium lauroylsarcosinate
Carboxylate-based • Perfluorononanoate
fluorosurfactants • Perfluorooctanoate (PFOA or PFO).

Cationic surfactants

In this category the hydrophilic part is positively charged. This group contains no wash activity effect, but it
fastens to the surfaces where they may give softening, antistatic, soil repellent, and antibacterial or corrosion
inhibitory effects. The various typical applications are their use as softeners (fabric softeners) and antistatic. The
counter ion of cationic surfactants is generally a halide or methyl sulfate. The primary, secondary, or tertiary
amines are pH dependent: (Primary and secondary amines are positively charged with pH < 10).

Table 3. Some common examples of cationic surfactants

Permanently Charged quaternary ammonium cation

• Hexadecyltrimethyl ammonium bromide • Cetrimonium bromide

• Dioctadecyldimethylammonium
bromide(DODAB)

• Cetylpyridinium chloride (CPC) • Cetyltrimethylammonium bromide

(CTAB)
• Benzethonium chloride (BZT) • Cetyltrimethylammonium chloride
(CTAC)
Nonionic surfactants

A surfactant of uncharged hydrophilic part is non-ionic. These substances are suitable for cleaning purposes and
are insensitive to water hardness. They have a wide application among cleaning detergents and they include groups
like fatty alcohol polyglycosides, alcohol ethoxylates etc.
The long chain alcohols show some surfactant properties. Most prominent among these are fatty alcohols, cetyl
alcohol, stearyl alcohol, and cetostearyl alcohol (consisting predominantly of cetyl and stearyl alcohols), and oleyl
alcohol.

Table 4. Some common examples of nonionic surfactants

Polyoxyethylene glycolalkyl Polyoxypropylene glycol alkyl Glucoside alkyl ethers:
ethers (Brij): ethers:
CH3–(CH2)10–16–(O-Glucoside)1–
CH3–(CH2)10–16–(O- C2H4)1–25–OH: 3–OH
CH3–(CH2)10-16–(O-C3H6)1–25–OH • Decylglucoside,
 •Octaethyleneglycol • Lauryl glucoside
monododecyl ether • Octylglucoside
• Pentaethylene glycol
monododecyl
Ether
Polyoxyethylene glycol Polyoxyethylene-glycol alkylphenol Glycerol
octylphenol ethers C8H17–(C6H4)– ethers: alkyl esters:
(O-C2H4)1– • Glycerylla
25–OH: C9H19–(C6H4)–(O-C2H4)1–25–OH: urate
• Triton X-100 • Nonoxynol-9

Polyoxyethylene-glycol Sorbitan alkyl esters: Block copolymers of

sorbitan alkyl esters: • Spans polyethyleneglycol and
• Cocamide MEA, polypropylene glycol:
• Polysorbate • cocamide DEA • PoloxamersPolyet
• Dodecyldimethylamine hoxylated tallow
oxide amine (POEA)

Zwitterionic surfactants

Zwitterionic surfactant consists of two oppositely charged groups. Zwitterions are often known as ‘amphoterics’ but
these terms are not same. An amphoteric surfactant is one that converts to net cation via Zwitterion to net anion by
going from low to high pH. Neither the acid nor the base site is permantly charged, i.e. the compound is only
Zwitterionic over a limit pH range. At the iso- electric point, the physicochemical behavior often resembles that of
non-ionic surfactants. Below and above the iso-electric point there is gradual shift towards the cation and anion
character, respectively.
Zwitterion is a group that is followed by their excellent dermatological properties. They cause low eye and skin
irritation. Therefore, these are suitable for use in shampoo and various personal care (cosmetic) products.
Zwitterionic (amphoteric) surfactants consists of both cation and anion centers attached with the same molecule.
The cation part depends on primary, secondary, or tertiary amines or quaternary ammonium cations. The anion part
can vary and it include sulfonates, i.e. CHAPS (3-[(3 Cholamidopropyl)dimethylammonio]-1-propanesulfonate).
Other anionic groups are sultaines. Sultaines are the inner sulfonic acid salt of a strong inorganic acid and are
commonly termed as‘sulfobetaines.’ They are similar to betaines, which are inner carboxylic acid salt of a weak
organic acids. Both molecules are considered zwitter-ionic at pH7 where the nitrogen at the hydrophobic tail is
quaternary (cationic); the polar head groups are anionic and add to the hydrophilic properties of the molecule. The
nitrogen which is quaternary always positive, these molecules do not get anionic nature at any pH and they are not
truly amphoteric, although they are commonly referred to some common types of Zwitterionic surfactants that are
N-alkyl derivatives of simple amino acids, such as glycine (NH2CH2COOH), betain (CH3)2NCH2COOH) and amino
propionic acid (NH2CH2CH2COOH). Betaines, e.g. cocamidopropylbetaine. Phosphates: lecithin.
Application of Surfactants

The surfactant plays an important role in cleaning, wetting, dispersing, emulsifying, foaming and anti-foaming
agents with many practical applications and products, including a wide variety of consumer products which are
given below:
⚫ Shampoos, Dish detergents, Laundry detergents, Conditioners, Fabric softeners, Diapers, Contact lens
cleaners, Cosmetics, Toothpastes, Biocides (sanitizers), Fabric softeners
Surfactants are also widely used in the following industries:
⚫ Emulsions, Paints. Adhesives, Recycled papers deinking, in flotation, washing and enzymatic processes,
Heavy and tertiary oil recovery, Ore flotation, Dry cleaning, Pesticide and herbicide applications, Water
repellency
⚫ Others: Ski waxes, snowboard wax, Pipelines, liquid drag reducing agent, Laxatives, Ink
Micelle

A surface active agent (surfactant), when sent in less concentration in a system, assimilate at the surfaces or
interfaces extremely by varying the surface or interfacial free energy. When molecules of surfactant are water
soluble at the concentrations more than the critical micelle concentration (CMC), they form aggregates
termed as micelles, that are having importance in science and pharmacy because they are having competency
of increasing the dissolution of mildly soluble substances in water. In a micelle, the hydrophobic tails
attached to the inner core to decrease their link with water, while hydrophilic heads remain at the outer
surface to maximize their interaction with water. They are movable structures and are repeatedly formed and
dissociated in solution (they must not be thought of as solid spheres). There exist a state of equilibrium
between micelle and free molecules of surfactant in solution. This is illustrated in the figure as shown.

Fig. 7 Representative model of the reversible monomer-micelle in thermodynamic equilibrium. The head of
surfactant is represented by dark circle (hydrophilic portion) and the curved dark lines represent the tail of
surfactant (hydrophobic moieties).

A pile of the molecules of surfactant called micelle spread in a colloid of liquid. In liquefied solution, an
ideal micelle forms an aggregate with the hydrophilic "head" regions which interacts with the surrounding
solvent that is forming an outer shell, the sequestering the non-polar or hydrophobic single-tail regions at
centre of micelle.

Hence, the micelle nucleus, which is consists of long non polar tails, resembles an oil or gasoline drop that
we see in the figure. The non -polar tail length , the nature and the size of the polar or ionic head, the
acidity of the solution, the temperature, and the presence of salts that are added are the essential factors in
determining the kind of the product obtained. If these domains are changed, it is viable to change the shape
and size of the micelles. A number of amphiphilic molecules form an aggregate gives aggregation number;
it is the way to explain the size of the micelle.
Fig. 8. (a) Representation of a micelle in aqueous solution.
(b) Representation of a spherical micelle for dodecyl sulphate.

The process of micellization in water execute mild balancing of intermolecular forces containing
hydrophobic, steric, electrostatic, hydrogen bonding and van der Waals interactions. The leading force
which results from the hydrophobic effect is formed with the non-polar surfactant tails, and the leading
adversing repulsive force which results from the interactions i.e steric and electrostatic between the surfactant
polar heads as represented in figure. Whether micellization occurs and, if, at which flocking of monomeric
surfactant, build upon the uniformity of the the forces promoting micellization and some of those opposing
it. We can mention l that it builds on the balancing of two main effects i.e the readiness of the non polar tails
to reject the contacts with water and the repulsion between the polar or charged heads, an effect of
destabilizing at the aggregated process. Hydrocarbon tails reject the interactions with the solvent molecules
which is moving toward the aggregate/micelle interior, which have low water capacity. Inspite of this , the
repulsion between the charged heads on the micelle surface is governed by the existence of oppositely
charged ions (counter-ions). The suitable association of the non polar tails in the micelle interior occur
through the hydrophobic interaction, that is the prevailing effect in the formation process of these aggregates.

Fig. 9
Amphiphilic molecules structure micelles in water, as well as in non-polar organic
solvents. In such cases, micelle aggregates are called inverse micelles because the situation is
inverted as respect to water as depicted in the fig .In this case, hydrocarbon tails are exposed
to the solvent, whereas the polar heads indicate towards the micelle interior so as to remove
the contacts with the non-polar solvent.

Fig. 10
Reverseible micelles are able to control huge amount of water in its interior. In this way,
a "pocket" is formed which is only suitable for the dissolution and transportation of polar
solutes through a non polar solvent.

Critical Micelle Concentration (CMC)

It is explained as the concentration of surfactants above which micelles are formd and all additional
surfactants are added in the system so as to go to the micelles. The CMC is the accurate flocking of surfactants
at which aggregates become thermodynamically soluble in an liquid solution. There is no high density of
surfactant below the CMC which immediately precipitate into a separate t phase. Above the CMC, the
solubility of the surfactant in the aqueous solution go beyond.. The energy which is required to keep the
surfactant in the solution is no longer in the e lowest energy state. To decrease the system free energy the
surfactant is precipitated out which is depicted in the fig. Now when we go from frame 1→4, with increase
of surfactant concentration in water, slowly a layer is formed at the surface and eventually micelles are
formed at or above the CMC.

Fig. 11

You must be wondering how the CMC of surfactants is determined? It is done by establishing inflection
points for pre-determined surface tension of surfactants in solution. The design of inflection point against the
surfactant concentration will give picture of the critical micelle concentration by representing the
stabilization of phases.

In the setup as depicted in Fig 12. three phases ae shown which are
1. At very low concentrations of surfactant less changes in surface tension are detected.
2. Additional surfactants decreases the surface tension.
3. Surface become full weighted , no more change in the surface tension.

Determination of CMC of the Surfactant

The CMC for a surfactant can be obtained by measuring physical properties, such as surface tension (γ),
conductivity (κ) ( ionic surfactants), osmotic pressure (π), detergency, etc. When these properties are setup
as a function of surfactant concentration (or its logarithm, in case of surface tension), a sharp rupture is seen
in the curves attain by signalling the formation of micelles at this point
(explain figure)
Another important parameter that featured is the aggregation number, Nagg, that correlates to the average
number of monomers of surfactant in each micelle. Normally, in a micelle solution the aggregation number
is relatively constant for a broad range of total concentration (up to 100 times the CMC), with increasing
number of micelles. Infact, under undisturbed conditions micelles can grow with the aggregation number
which differs with the surfactant concentration.

Fig. 13: Change in the physical properties of detergency, conductivity (κ), osmotic pressure (π) and surface
tension (γ) of an aqueous solution of surfactant which is depicted as a function of surfactant concentration.
The break in the curve of each property indicates the Critical Micelle Concentration (CMC).

Micellar Shape and Size

Micelles are the labile entities which are outlined by the non-covalent combination of single surfactant
monomers. Therefore, they may be spherical, cylindrical, or planar (discs or bilayers) as depicted in
Figure the shape and size of micelle can be controlled by changing chemical structure of the surfactant as
well as by altering solution conditions such as temperature, overall surfactant concentration, surfactant
composition (in the case of mixed surfactant systems), ionic strength and pH. Depending on the
type of surfactant and the solution conditions, the spherical micelles can grow one-dimensionally in
cylindrical micelles or two-dimensionally to bilayers or discoidal micelles. The growth of micelle is
controlled generally by the heads of surfactant , as the two i.e (one-dimensional and two-dimensional) growth
requires taking the surfactant heads closer to each other to reduce the available area per surfactant molecule
at the micelle surface, and also e the bend of the micelle surface Surfactant aggregates:
Fig. 14. Surfactants self-assemblies.

Self-assembly of surfactant leads to a domain of different structures as we will discuss now:

(a) Spherical micelles with its interior is formed of the hydrocarbon chains and the polar head group
surface which is covering water . The radiusof the hydrocarbon core is close to alkyl chain length .
(b) Cylindrical micelles with its interior is formed of the hydrocarbon chains and polar head groups
surface water surface . The cross-section of hydrocarbon core is identical r to that of spherical micelles. The
micelle length is fluctuating so these micelles are polydisperse.
(c) Surfactants bilayers which is build up of lamellar liquids crystals have surfactant- water system
having a hydrocarbon core of thickness of 80% of the length of two extended alkyl chains.
(d) Reversed or inverted micelle has core of water that is covered by the polar head groups surfactants.
The alkyl chains together with a non-polar solvent make up the continuous medium. Like normal micelle
they can reproduce into cylindrical form.
(e) A bicontinuous structure having the surfactant molecules assembled into connected films.
(f) Vesicles are built from bilayer like those of the lamellar phase and are featured by two distinct water
compartments, one producing the core and one the external medium. Vesicles may have different shape and
there are also reversed-type vesicles.

In particular, depend on the type of surfactant and on the solution conditions, spherical micelles which are
one-dimensionally can grow to cylindrical micelles or two-dimensionally to bilayers or discoidal micelles.
The growth of micelle is controlled basically by the surfactant heads, as both one-dimensional and two-
dimensional growth require the surfactant heads closer to each other to reduce the available area per
surfactant molecule at the surface of the micelle , and also the bend of the micelle surface. For all the micelle
structures in aqueous media, the surfactant molecules are turned with their polar heads in the water phaseand
their tail away from it.

Structure and Composition

(a) The inner part of the micelle, i.e a hydrophobic core is formed of the hydrocarbon chain of the
surfactant molecule. It’s radius is approximately of the range of fully extended hydrophobic chain shown in
the fig
 (b) A Stern layer covering the core, is part of electrical double layer, which have coordinated shell of
hydrophilic head groups with (1 - α )N counter ions, where α is the degree of ionisation and N is the
aggregation number (number of molecules in the micelle). the degree of ionisation for most of the ionic
micelles is between 0.2 and 0.3; that is, 70 - 80% of the counter ions may be treated as they are bound to
the micelles .
(c) The Gouy-Chapman portion of electrically two layer is diffused and surrounds the Stern layer, it
comprises of the N counter ions that are needed to neutralise the charge on the micelle. The thickness of the
double layer is the ionic strength function the solution and is can be highly reduced in the presence of
electrolyte.

Fig. 15.

Resource of the above material: e Pathshala Modules