YEAR 12 CHEMISTRY

Soaps & Detergents

The cleaning action of soaps can be described in this way. The carboxylate end (-COO-) of the
soap ion dissolves in water while the long chained hydrocarbon end CxHy preferentially dissolves
in oil or grease. This has the effect of wetting the surface of the oil or grease. Hence soap (and
detergents), link the water and the greasy surface thus removing the oil or grease from the surface
to which it was previously attached. This ion which links the water and the grease is known as a
surfactant. Its charged end (that dissolves in the water) is said to be hydrophilic while the non-
charged hydrocarbon end (that dissolves in the grease) is said to be hydrophobic. The diagram
below indicates how soaps and detergents act.

surface

One of the major factors which inhibit the functioning of soap is that the carboxylate ion reacts
with ions of calcium and magnesium to produce insoluble salts. These insoluble salts form a
scum.

2C17H35COO- + Mg2+ (C17H35COO)2 Mg

stearate ion magnesium stearate
O
To allow the soaps to be effective the
calcium and magnesium ions need CH3 (CH2)n CH2 S O- Na+
to be removed (or the water softened).
O
This requires expensive water softeners
or the use of inexpensive synthetic agents known as detergents. A common group of synthetic
detergents is the alkyl benzyl sulphonates.
While the cleaning action of these detergents is the same as for soap that is the ionic end
dissolves in water and the hydrocarbon chain end dissolves preferentially in the greasy surface,
the synthetic detergents have the advantage that their calcium and magnesium salts are soluble.
This means that the detergents will work in all types of water including samples which contain a
high concentration of soluble salts.

The distinction between the structure of soaps and detergents can best be shown by the formulae
below:

O O

CH2 C CH2 S O-Na+

O-Na+ O
soap structure detergent structure

Detergents are more stable than soaps and persist in the waste water long after use. The
consequence of this has been the fouling of sewerage works and rivers with tremendous masses
of froth.

The increased stability of the detergents was due both to the greater stability of the sulphonate
grouping and the fact that the raw material hydrocarbon chains contained large proportions of
carbon chains that were branched, in contrast to the straight-chain hydrocarbons from animal
fats. Bacteria were slower to break down the branched-chains and so the detergents were not
considered biodegradable. For example, the two benzene sulphonates below have very similar
structure (in fact they are isomers) yet bacteria react very differently to each. Bacteria readily
made a meal of the straight chained isomer while they reject the branched one. Hence, the
former is biodegradable while the latter is not.

CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2 S O-Na+

O
Straight-chained biodegradable sulphonate

CH3CHCH2CH CH2CH CH2 CH S O-Na+

CH3 CH3 CH3 CH3 O

Branched-chained non-biodegradable sulphonate

Biodegradability is a term which always requires careful definition. In essence it means the
process of decomposition of an organic material, and note that it applies only to organic
materials by naturally occurring microorganisms. Such a process is one which obviously
depends both on time, concentration and temperature. The surfactants which were used
previously were biodegradable but only very slowly. They did not degrade quickly enough for
the surfactants to be destroyed in the conventional sewage treatment plant, or to be reasonably
rapidly decomposed in flowing rivers.
The graph below indicates the rate at which soaps and detergents are degraded:

The situation with soaps and detergents can be summarised as follows:

1. Soaps are not an effective cleaning agent in hard water due to the formation of scum.
In addition, it presents other problems such as
(a) a tendency to gel,
(b) deteriorates on storage, and
(c) lacks cleaning power when compared to synthetic detergents.

On the positive side, soaps are cheap and are manufactured from renewable sources
(animal fats and oils, vegetable oils). From an environmental point of view they are
suitable because they are quickly and completely degraded by bacteria.

2. Detergents are extremely effective cleaning agents but present certain problems from an
environmental viewpoint.

(a) Branched-chain detergents are not completely or quickly biodegradable and

hence foam up in water system,
(b) Detergents also provide additional phosphates to the water system. This can
eventually lead to massive water pollution through the eutrophication process.