Surfactants:

It reduces the surface tension of a solvent.

Due to surface tension wetting of fibre surface does not take place
thoroughly and quickly.
Surfactant not removes the surface tension but it reduces it.
Widely used in scouring.
Chemically surfactants are long chain of organic compounds contain both
hydrophobic and hydrophilic component.
The concentration at which no further reduction in surface tension occurs
is known as critical micelle concentration.
The good surfactant should have hydrophobic and lyophilic balance
(HBL).

Classification:

1. Anionic.
2. Cationic.
3. Non-ionic.
4. Amphoteric.

Cationic surfactant:
Unsuitable for use as detergent or wetting agents.
The hydrophobic part of the molecule of the cationic surfactant is the
organic ammonium or pyridinium compound containing one or more
hydrophobic residues as shown below.

Cationic surfactants are mainly used as softeners, leveling agents,

retardants in dyeing, water repellent bacteria growth inhibitors and
emulsifiers.
Non-ionic surfactants:
They do not contain an ionisable group and have no electrical charge.
They do not contain an insoluble group.

1. EO-PO ethers
2. EO-PO esters
3. Thioethers.
4. Sorbitan ethers.

Non-ionic surfactants are free from precipitation and redeposition onto

the fabric and can be safely used.
It also permits the caustic to act as a lime soap detergent.

Advantages:
1. Excellent compatibility.
2. Good watters and rewetters.
3. God emulsifiers.
4. Excellent oil solubility.

Amphoteric surfactants:

Amphoteric surfactants are may be of cationic,anionic or non-ionic

depending upon the pH of the aqueous solution.

Effect of pH on Ionic nature of surfactants:

Structure pH ionic
I-RNH2+CH2CH2COOH acidic cationic
RNH2CH2CH2COOH Isoelectric range non-ionic
 Amphoteric surfactants offers an excellent degree of
lubrication,corrosion,inhibitor and wetting action and provide a
protectice colloid for silk and wool.
Major use is in scouring and dyeing of protecting chafting, crack and
crows feet.
They are comparatively expensive and some of them are not heat stable
and hence can not use at elevated temperature.

Anionic surfactants:

Anionic surfactants are those which bear a negative charge and mirate the
anode or positive charge in solution.

1. Sodium stearate (soap)

2. Alkyl sulphates
3. Phosphate esters
4. Alkyl sulphonates.
Surfactant as a wetting agent:

Interfacial tension b/w textile fibre and the liquor are high hence wetting
may be effected.
One of the functions of surfactant is to reduce surface tension.
Water surface tension is 72 dynes/cm. It is possible to bring down the
surface tension of water from 72 dynes/cm to 28 dynes/cm.

A lone oxygen atom in the water contains a pair of electrons which is

balanced correspondingly large positive charge in the hydrogen atom.
The structure of the water has a great dipole moment and also the
molecule stick to another when water is in the liquid phase.
It is a mixture of clusters of tetrahedral linked water molecules and a
single molecule occupying space b/w the cluster.
The energy of the hydrogen bond is even greater than that of any other
molecular interaction.
All these factors either alone or together make the wetting of textile
difficult.
When surfactant soap is dissolved in water the hydrocarbon chain (tail),
tries to get away from water medium due to its hydrophobicity to the
surface.
The hydrophilic grouping just dip in the water at the surface and sodium
cation is in the vicinity of negatively charged carboxyl heal.
Thus structure of the water distorted and decreases the free energy of the
system.
In other means micelles with their hydrophobic grouping directed
towards the interior of the cluster and their hydrophilic group directed
towards the solvent.
 Wetting agent also displaces the air from the microphores of the cotton
by the water.
Liquid spread as a continuous film instead of remaining as drops.
If is less than 90 degree , the oil will tend to spread over the fibres.
If is greater than 90 degree the oil will tend to form a globe which
easily detached from fibres.
The surfactant reduces the values of cos .

Surfactant as detergent:
The function of the detergent is to remove the dirt and dust particles and
other constituents.
Detergent keeps the soil in dispersed or suspended form in scouring
solution and prevents redeposition on the fabric.
When detergent is added, the soil hydrophobe either dissolves into the
soil or orient along the fabric surface.
 Micelle is due to unfavorable interactions.
The polar "heads" of the micelle, due to favorable interactions with
water, form a hydrophilic outer layer that in effect protects the
hydrophobic core of the micelle.
The compounds that make up a micelle are typically amphiphilic in
nature, meaning that not only are micelles soluble in protic solvents such
as water but also in aprotic solvents as a reverse micelle.

Because of the hydrophile, the edges tend to associate with water and
thus the removal of soil from the fabric starts.
The oil disperses as droplets and the dirt is held in suspension with the
droplets. The suspended soil particles with its shealth of oriented soap
molecules assume a net negative charge similarly to the globe of soap.
The electrostatic charge of repulsion b/w particles and the fibre play a
major role in redeposition.
CMC (carbomethyl cellulose) and PVP (pyrolidon) can act as anti
redepositing agents.
The most important consideration in scouring is the critical micelle
concentration CMC of the surfactant.
The detergency is at maximum while surface tension and inter facial
tension are at their minimum.
CMC concentration is that how much amount of detergent is required.

Surfactant as emulsifier:
 An emulsion is a mixture of two or more immiscible (unblendable)
liquids.
Emulsions are part of a more general class of two-phase systems of
matter called colloids.
The terms colloid and emulsion are sometimes used interchangeably,
emulsion tends to imply that both the dispersed and the continuous phase
are liquid.

In an emulsion, one liquid (the dispersed phase) is dispersed in the other

(the continuous phase).
An emulsifier (also known as an emulgent) is a substance which
stabilizes an emulsion by increasing its kinetic stability.
In some cases, particles can stabilize emulsions as well through a
mechanism called Pickering stabilization.

Theory of surface activity and detergency:

Surface activity generally related to the balance b/w hydrophobic and
hydrophilic portions of the molecule.
If hydrophobic characteristic of the surfactant is increased, aqueous
solubility decreases and oil solubility increases.
The balance b/w the hydrophobic and hydrophilic moieties of the
surfactant is critical factor in determining its major characteristics.
This is referred as HBL value and is generally use in expressing the
characteristics of a surfactant and it is of particular value in describing
the emulsion formation.
For some general purpose the HBL can be used qualitatively (referring,
for instance to low, medium or high HBL).
Quantifying scale:
Covers a range of values from zero to 20 hydrophobic and hydrophilic
portions.
The value of 10 approximately representing the point at which
hydrophilic and hydrophobic portions are in balance.

Examples:-

1. HBL 4-6

Hydrophobic group presents.

Suitable for water-in oil emulsions.

2. HBL 7-9

Good wetting properties.

3. HBL 8-18

Typical for surfactant to give oil-in water

emulsion.