Detergent and Soap

Soaps are metallic salts of fatty acids (saturated or unsaturated) containing from 8 to
22 carbon atoms. It’s a natural cleansing agent. There may be various kinds of
metallic salt (There may be Pb, Mg, Ca or other metallic salts) but sodium and
potassium salts are used as detergents. Commercially soap is produced by boiling
natural fats/oils with aqueous solution of sodium or potassium hydroxide. This
reaction is called Saponification.

(The potassium soaps tend to be softer and more soluble in water than the corresponding sodium
soaps).

But as detergents only Na or K salt of higher fatty acids, soap is made on a

commercial scale by boiling natural oil or fatty oil which is used for soap
manufacturing,

The following oils are used in soap manufacturing:

 Cotton seed oil

 Coconut oil
 Oliver oil
 Soya bin oil
 Palm oil
 Ground nut oil
Chemistry of Soap Manufacturing:
(1) Fat Saponification Process:

Fat Saponification Process

Sodium soaps are sparingly soluble in strong sodium chloride solution. The mixture
of soap and glycerol in aqueous solution obtained by saponification is saturated with
common salt where the soap is precipitated. As soap is lighter than glycerol it’ll rise
to the surface. Then it’s skimmed off i.e. the best parts from the surface is
removed.To remove excess alkali or salt solution it’s washed with cold water. Then
it’s cast into cakes/bars and dried. The liquor is evaporated under reduced pressure
and glycerol is recovered by distillation.

(2) Fatty Acid Neutralization Process:

Fatty Acid Neutralization Process

In this process alkalinity can be controlled as we add in known concentrations)

(3) Fatty Methyl Ester Process:

Fatty Methyl Ester Process

(Glycerin found in this process are more pure than other processes)

Functional Properties of Soap:

(1)Solubility:

 An increase in the size of monovalent cation (base) increases solubility & an

increase in the size of di/tri valent cation decreases solubility
 Carbon chain length of soap increases, solubility decreases but cleansing power
increases.
 The presence of unsaturation results in an increase in solubility.

In general, with the increase of solubility the softness and mushiness property of soap also
increases.

(2) Lathering & Cleansing Attributes:

 The use of fatty acids of C-10 to C-12 chain length is most preferred for
lathering attributes.
 The use of fatty acid of C-16 to C-18 chain length is most preferred for
cleansing attributes.
The most suitable soap is made from the combination of coconut (C-10 to C-12 ) and
tallow( C-16 to C-18 ) from the view point of lathering and cleansing attributes .

***The effectiveness of a soap solution as a detergent will be influenced to a marked

degree by –

 Nature of the fatty acid

 Conditions of temperature
 Concentration in which it is to be used

Disadvantages:
1. Doesn’t work on hard water
2. Doesn’t work on acidic solution
3. Doesn’t work in the presence of sodium ion as excess sodium ion precipitates
soap.

Soap manufacturing process:

Soap is made on a commercial scale by boiling natural oil or fatty oils with aqueous
solution of sodium or potassium hydroxide.

C17H35COOCH2 CH2OH

C17H35COO CH + 3NaOH CHOH + 3C17H35COONa

C17H35COOCH2 CH2OH
Sodium soaps are sparingly soluble in strong sodium chloride solution. The mixture
of soap and glycerol in aqueous solution obtained by Saponification in therefore
saturated with common salt when the soap is precipitated and rises to the surface
where it can be skimmed off. It is washed with cold water and is cast cakes or bars
and dried.

Most exception for K - salt because addition of NaCl salt cause precipitation of the
Na - salt of fatty acid.

C17H35COOK +NaCl = C17H35COONa + KCl

KCl made the fatty acid into K – fatty acid. Thus the glycerol is not separated.

Properties of Soap:

 Soap dissolve very slowly in cold water but rapidly in hot water.
 Soap dissolves in hot alcohol but is only sparingly soluble in other organic
solvents such as acetone, ether, or petroleum.
 Soap reacts with hard water.
2C17H35COONa + CaSO4 (C17H35COO)2Ca + Na2SO4
 The number of carbon atom in the aliphatic chain of soap is very important
 Less than 9 Carbon - No detergency power
 17 Carbon – Extremely good detergent
 Above 17 Carbon – Poor solubility

Selection of soap:

 Soap should contain at least 62% of fatty acid and between 6.5% and 8.5%
combined alkali expressed as Na2O.
 No free fat, unsaponifiable oil or free caustic should present, free caustic alkali
denotes careless in manufacture but sodium carbonate or silicate are often
added purposely to make the soap harder or to improve its detergent action.
  Salts such as Sodium Chloride and Sodium Sulphate should only be present in
small quantity.
 It should show high degree of surface affinity.
 The most important factors which determine the properties of soaps in the
number of carbon atoms in the aliphatic chain. If there are less than 9 carbon,
the soap will have virtually no detergent power.

Detergent:

Basic detergents are surface active compound. The compounds which get orient at the
interface (between water and air) and reduce interfacial tension/surface are called
active compound or detergent.

The substance that consists the removal of dirt. The removal is affected by
emulsification or dissolution of the dirt particles and the substance normally has the
power of suspending the dirt in cleaning liquid.

Detergency:
The compounds which can remove dirt/oil from a material & keep it in solution by
the means of suspension are called detergents. This property is called detergency. It’s
a property of a compound which is closely related with surface tension.

A satisfactory detergent must possess the following properties:

1. Good wetting characteristics in order that the detergent may come into intimate
contact with the surface to be cleaned.
2. Ability to remove or to help remove dirt into the bulk of the liquid.
3. Ability to solubilize or to disperse removed dirt and to prevent it from being re-
deposited on to the cleaned surface.
Classification of Detergent:
Detergent is classified on the basis of ionic nature-

Detergent

Ionic Non ionic

Anionic Cationic Amphoteric

Anionic detergent:
When the detergents are ionized into anions and cations but the anion is dominating
ion in the solution. Therefore the surfactant is called an anionic surfactant or
detergent.

When Sodium stearate is dissolved in water, it ionizes as follows:

CH3(CH2)16COONa CH3(CH2)16-COO- + Na+

H2O

Among the ions, anions CH3(CH2)16COO- is comparatively very large to Sodium

ion. So anion acts as dominating ion here. This Sodium stearate is called anionic
stearate.
Cationic detergent:
When the detergents are ionized into anions and cations but the cation is dominating
ion in the solution. Therefore the surfactant is called a cationic surfactant or
detergent.

CH2(CH2)14-CH3 CH2(CH2)14CH3

+ + Cl-
N N

Cl

Among two ions cation is very large compound to the chloride ion. Therefore cation
acts as a dominating ion in case of cationic surface active agents.

Nonionic detergent:
Surface active agent which are soluble in water and get oriented at the surface of the
solution and reduce when dissolve in water hence they are called nonionic detergent.
CH3(CH2)16-COOH + 6CH2 CH2 CH3(CH2)16-COO(CH2-CH2-O)6H

Stearic acid O Nonionic detergent

Ethylene oxide

Amphoteric detergent:

Detergents when dissolved in water, ionizes and produce large segments carrying
both anionic and cationic ions (these segments are called zwitter ions). Thus amino
carboxylic acids in which amino and carboxylic groups are present at the molecular
chain ends dissolved in water to give zwitter ions.

H2N(CH2)n-COOH H3N+-(CH2)n-COO-
H2O
Advantage of nonionic detergent:
 They are available in liquid form. Their lack of affinity for textile fibers make them easily
washable from textile material.
 Stable over a wide range of PH
 Being nonionic in nature, they are compatible with many dyes and surfactants and they may
be used in many formations.

Mechanism of Detergent:

Let’s consider an oil drop on a fabric

 The shape of the oil drop will depend on the following 3 forces:

TL =The surface tension between the oil drop and surrounding aqueous phase

TS= The surface tension between the fabric & surrounding aqueous phase

TLS = The surface tension between the fabric and oil drop

We can see that if TLS + TL increases in relation to TS the area of contact

between oil and fabric will decrease. This will lead the shape of the oil to be
like a sphere with the decreasing of contact angle (Ө)

When the forces are in equilibrium, their relationship is expressed by Young’s

equation neglecting gravity effect:

TL = TS – TLS [When θ = 0°]

 The value of cosӨ varies from +1 (Ө=0 degree) through 0 (Ө=90 degree) to -
1(Ө=180 degree)

Here, 3 cases are considerable-

As we can see there are 2 liquid phases (water and oil) now which liquid phase
will displace the other one can be known by the contact angle. If the angle is
more than 90 degree than the value of cosӨ is negative which means TLS > TS
so obviously the water phase will start to displace the oil phase which is in
contact with the fabric.

***To remove oil/dirt from a fabric, the soap solution must increase the
contact angle which must be more than 90 degree
Mechanism of Detergent:(Alternate )

When a fiber covered with a layer of oil or wax, is immersed in a warm aqueous
solution of soap and it will be seen that the film bounces up and ultimately collects
itself into spherical globules which are very easily detached.

TL

TS TLS

In a drop of oil, reticular in foam, adhere to a fiber, its actual shape will be
determined by the inter action of the following three forces-

TL = The surface tension between the drop and the surrounding in aqueous phase.

TLS = The surface tension between the fiber and the oil.

TS = The surface tension between the fiber and the water plane any solute which it
may contain.

In the figure, any increase in (T LS + TL) in relation to TS will decrease the area of
contact between the oil and fiber. The result of this the shape of the oil drop will
approach more and more to that of a sphere.

θ is the contact angle which is drawn at the contact point of solid surface and oil drop.
When the forces are equilibrium their relationship-

TS = TLS + TL Cos θ

Cos θ = (TS – TLS)/TL

TL = TS – TLS [When θ = 0°]

To fulfill this condition, the solid surface must be covered with that phase of the
lowest surface tension. If TS is greater than TLS, Cosθ will be positive and θ will be
less than 90°. If θ is greater than 90° the value of Cos θ will be negative and then T LS
will be greater than TS. It indicates that the aqueous phase will displace the oil.
For Hydrophobic impurities:
Here are two images to understand the concept clearly -

Roll up:
  The Hydrophobic tails saturates the dirt/oil & fabric.
 Fibre water & oil water surface tension decreases.
 The surface tension between fibre and oil is unchanged so from the equation
(1) we will get a negative value of cosӨ that means the contact angle is now
more than 90 degree
 This unchanged surface tension between fibre and oil & repulsion between the
negative charges of fibre water and oil water interface will cause the oil to
reduce it’s surface area by rolling up
 The oil begins to lift from the fibre& is removed into the solution where it’s
suspended by electrostatic repulsion.
 The oil/dirt won’t be re-deposited because of the negative charged repulsion
between oil/dirt water &fibre water interfaces

For Hydrophilic (polar) impurities:

 The hydrophilic head orients itself to the polar dirt

 A second layer is formed where the hydrophobic tail orients itself to the first
layer of tails
 The rest of the mechanism is similar to the previous system

Working Principle of Surfactant:

A surfactant molecules is divided into two ion when dissolved in water-

1. Hydrophilic (Head)
2. Hydrophobic (Tail)

Hydrophobic (tail) are water avoiding and try to get away of the water i; e. they
protruding away from the water surface.
And hydrophilic (head) try to dissolve in water and just dipping at the water surface.
As a result the hydrophobic (tail) reduces the surface tension and the surface
characteristics altered.

- - --- - - - -
- - - - - - -
- - - - -
- - - - - - -
- - - - - -

As for example, Sodium Stearate (C17H35COONa) dissolved in water and divided

by following two segments-

C17H35COONa C17H35COO- + Na+

The aliphatic chain (C17H35) is hydrophobic (tail) and repelled the water. The
electronegative (COO-) carbonilic ion is hydrophilic (head) and just dipping at the
water surface. As a result, the hydrocarbon chains (tail) reduces the surface tension
and creates a force opposite to the inward pull on the water molecules. So, we can say
that soap is a surface active compound which reduces surface tension of water.Then
the most of ion get oriented on the surface between the water and air.

When the fatty acid components of the (soap/detergent) compounds is of low

molecular weight, the hydrophilic (head) can pull the hydrophobic (tail) into the
water, but the high number of carbon atoms prevents this force oppositely.
Differentiate between soap and detergent:
S.L Soap Detergent

1. Soap can give effective cleaning action Detergent can give effective cleaning
to soft water only. action to both soft and hard water.

2. Soap is generally used for cleaning It is used in textile purpose.

agent in domestic purpose.

3. All soaps are detergent All detergents are not soap

4. Soap is Pb, Mg, Ca or other metallic Detergents are only Na or K salt of higher
salts. fatty acids.

5. Production cost is high Production cost is cheap

Micelle:
As the concentration of surfactant in a solution is increased it becomes energetically
favorable for the individual molecules, or monomers, to combine together to form
large aggregates, or micelles, which shield the hydrophobic components from the
solution. It’s a group of surfactant molecules associated in a cluster.

Here, a stearate ion is represented -

(The long alkaline chain is the hydrophobic and carboxylate ion is the hydrophilic part)
Structures of Micelle:

Only (a) & (d) is of our concern as we only find these two structures in surfactant solution.
CMC:
The concentration above which micelle formation becomes appreciable is termed as
the Critical micelle concentration (C.M.C.)

At low surfactant concentration the surfactant molecules arrange on the surface.

When more surfactant is added the surface tension of the solution starts to rapidly
decrease since more and more surfactant molecules will be on the surface. When the
surface becomes saturated, the addition of the surfactant molecules will lead to
formation of micelles. This concentration point is called critical micelle
concentration.

1. At very low surfactant concentration only slight change in surface tension is

detected.
2. Addition of surfactant decreases the surface tension drastically
3. At CMC point, surface becomes saturated and the addition of surfactant
molecules do not effect on the surface tension.
Factors Affecting CMC:
(1)No. of Carbon Atom:
Increasing hydrophobic part (no. of carbon atom) will result in a decrease of c.m.c. In
aqueous medium, the c.m.c. of ionic surfactants is approximately halved by the
addition of each CH2 group .For non-ionic surfactants this effect is usually even more
pronounced. This trend usually continues up to about the C16member. Above the
C18 member the c.m.c. tends to be approximately constant. This is probably the
result of coiling of the long hydrocarbon chains in the water phase.

(2)Thermal Agitation:
Micelle formation is opposed by thermal agitation and c.m.c.’s would thus be
expected to increase with increasing temperature but not always.
(3)Addition of Electrolytes:
With ionic micelles, the addition of simple electrolyte reduces the repulsion between
the charged groups at the surface of the micelle. The c.m.c. is, therefore, lowered .

(4)Addition of Organic Molecules:

Organic molecules may influence c.m.c.’s at higher additive concentrations by virtue
of their influence on water structuring. Sugars are structure-makers and as such cause
a lowering of c.m.c., whereas urea and formamide are structure-breakers and their
addition causes an increase in c.m.c.

Micelles containing more than one surfactant often form readily with a c.m.c. lower
than any of the c.m.c.’s of the pure constituents.