An alkali is a soluble salt of an alkali metal like sodium or potassium. Originally, the alkalis used in soapmaking were obtained from the ashes of plants, but they are now made commercially. Today, the term alkali describes a substance that chemically is a base (the opposite of an acid) and that reacts with and neutralizes an acid.
The common alkalis used in soapmaking are sodium hydroxide (NaOH), also called caustic soda; and potassium hydroxide (KOH), also called caustic potash.
How Soaps are Made
Saponification of fats and oils is the most widely used soapmaking process. This method involves heating fats and oils and reacting them with a liquid alkali to produce soap and water (neat soap) plus glycerine.
When the alkali is sodium hydroxide, a sodium soap is formed. Sodium soaps are "hard" soaps. When the alkali is potassium hydroxide, a potassium soap is formed. Potassium soaps are softer and are found in some liquid hand soaps and shaving creams.
The carboxylate end of the soap molecule is attracted to water. It is called the hydrophilic (water-loving) end. The hydrocarbon chain is attracted to oil and grease and repelled by water. It is known as the hydrophobic (water-hating) end.
How Water Hardness Affects Cleaning Action
Although soap is a good cleaning agent, its effectiveness is reduced when used in hard water. Hardness in water is caused by the presence of mineral salts - mostly those of calcium (Ca) and magnesium (Mg), but sometimes also iron (Fe) and manganese (Mn). The mineral salts react with soap to form an insoluble precipitate known as soap film or scum.
Soap film does not rinse away easily. It tends to remain behind and produces visible deposits on clothing and makes fabrics feel stiff. It also attaches to the insides of bathtubs, sinks and washing machines.
Some soap is used up by reacting with hard water minerals to form the film. This reduces the amount of soap available for cleaning. Even when clothes are washed in soft water, some hardness minerals are introduced by the soil on clothes. Soap molecules are not very versatile and cannot be adapted to today's variety of fibers, washing temperatures and water conditions.
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