(I) Chemistry of Soap

Main Ingredients
Chemically speaking, soap is the result of a chemical process called saponification, which occurs when acids in
the form of animal fat or vegetable oil are combined with an alkaline base to produce soap and glycerin.

Water + Alkaline + Fatty Acid = Soap + Glycerin

(1) Water: Pure water, such as rain water or distilled water, is ideal for soapmaking. Tap water on the
other hand, typically contains minerals such as calcium or magnesium which can combine with the alkali
to produce insoluble fatty acid salts, or soap scum.

(2) Alkaline: Until 1791, the main source of alkaline was the ashes of kelp (a seaweed) and barilla (a
plant).In 1791, French chemist LeBlanc invented a process to make inexpensive and readily available lye
(sodium hydroxide NaOH) which is an excellent alkaline base for soapmaking. Lye is a harsh and caustic
material which must be handled with care. When dissolved in water, it produces fumes which are as
caustic as the solution itself, however, it’s completely consumed during the saponification process.

(3) Fatty Acids: The fats (from animal) and oils (from vegetables) are the differentiating ingredients of the
soapmaking process. Until 1904, most soaps were made with tallow (the rendered fat of cattle) and lard (the
rendered fat of pig). The invention of hydrogenation process in 1904 allowed conversion of liquid vegetable
oils to solid or semi-solid fats (such as margarine) and thus releasing the soap industry from its reliance on
tallow and lard. Tallow soap is a very hard soap which does not lather well. To produce a finer soap,
vegetable oils must be added. The mildest soaps are made entirely from vegetable oils without any
animal fat. Highest quality soaps are made exclusively from more expensive vegetable oils such as olive
oil, coconut oil, or palm oil.

Scent
Most soaps include additional ingredients, such as scents and colors, for enhanced variety and character.
However, most allergic reactions are caused by natural or synthetic colorants and fragrances.

Scents, typically added just before soap is poured into the mold to minimize exposure to heat and lye, are
produced in one of the following three ways:

(a) Perfume oils are produced using the enfleurage technique. In this method the fresh flower petals
are sealed in lard between two glass panes. For several weeks, the old petals are removed daily and
new ones are applied, until the lard is saturated with perfume oil. The lard is then melted and frozen
into a paste which is mixed in alcohol to dissolve the perfume oil. The alcohol is then removed by
distillation, leaving a fragrance oil.

(b) Essential oils, used by most soapmakers, are typically produced using the less expensive
distillation process. Since a large quantity of strongly-scented petals is required, they must be both
abundant and easily accessible – for example, one hundred pounds of rose blossoms produce about ¼
ounce of rose fragrance, while the same amount of lavender blossom yields about two pounds of
lavender oil.

(c) Synthetic scents, similar to those used in candle making, can be added to the liquid soap also.
Finely powdered aromatic spices such as cinnamon, cloves, and nutmeg, when mixed with a little oil,
can be added to the finished liquid soap just before pouring into moulds. Likewise, pure flavoring
essences such as vanilla and almond can be added in small quantities.
Color
Due to highly alkaline conditions of soapmaking, adding colors with consistent results is more difficult than
adding scents. Food coloring, with the exception of yellow, is not very stable and tends to be bleached and
distorted by saponification. Vegetable dyes, traditionally used to color fabric, are highly unstable in the presence
of alkali and will produce unpredictable results. It is possible, however to use powdered spices such as turmeric,
saffron and curry which produce various shades of cream to peach. Cinnamon and cloves yield a wide range of
colors from caramel to deep chocolate. Synthetic aniline dyes, similar to those used in candle making, will
adequately color soap. However, there have been some concerns expressed about the toxicology of such dyes.
Most traditional soapmakers don’t add any color.

Fillers and other stuff

Besides colors and scents, soapmakers often add a variety of fillers. Bran, cornmeal, maize, and oatmeal are
common fillers in cosmetic bars. Gently abrasive, they are intended to stimulate the skin. To prevent or delay
degeneration of such additives in soap, small amounts of antioxidants may be added to soap. Natural
antioxidants are wheat germ oil or Vitamin E oil. Many soap recipes include ingredients from natural cosmetics
such as oatmeal face mask, beeswax, paraffin and lanolin cleansers. Whether the properties of these
ingredients remain unchanged after saponification is open to question.

To make mass-produced hard tallow/lard soap appropriate as a face cleanser emollients or superfats can be
added to soap. Vaseline, lanolin, and cold cream are all softening agents. Coconut oil is another superfat that is
often used for its quick, abundant, though somewhat thin, lather.

(II) Chemistry of Soap Cleaning

The cleaning process of soap takes place in two steps. The soap’s ability to remove dirt depends on its
efficiency as (i) a surfactant (surface-active agent) and (ii) an emulsifying (suspensive) agent.

Surprisingly, water is not a good substance to wet other objects with - the strong mutual attraction of water
molecules inhibits it from coming into full contact with solid objects placed in it. One of the most important
functions of soap as a surfactant is to reduce water’s surface tension and thus enabling it to evenly spread
and wet the object. After accelerating the wetting process, the soap molecule works as an emulsifying agent.
A soap molecule looks something like a caterpillar with the head being hydrophilic (attracted to water). The body
segments of this caterpillar are attracted to oil and are hydrophobic (water-repellent). As a result, the head (attached
to water) and the tail (attached to greasy dirt) form a link between the dirt and water. The dirt is dislodged by mild
agitation and held by soap in suspension until it’s flushed away.

Soap molecules do not always restrict themselves to unions with greasy dirt. When used in hard water, soap
reacts with compounds of magnesium, calcium, and iron to form new materials which don’t dissolve and appear
as soap scum. Synthetic detergents were devised primarily to eliminate the problem of soap scum.

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Revision: Dec 2010