The percentage of free fatty acid is of even greater importance in the soap industry. The amount of glycerine yield is dependent upon the percentage of free fatty acid and is one of the criterions of a good fat or oil for soap stock.
PREVENTION OF RANCIDITY.
Since moisture, air, light and enzymes, produced by the presence of organic impurities, are necessary for the rancidity of a fat or oil, the methods of preventing rancidity are given. Complete dryness, complete purification of fats and oils and storage without access of air or light are desirable. Simple as these means may seem, they can only be approximated in practice. The most difficult problem is the removal of the last trace of moisture. Impurities may be lessened very often by the use of greater care. In storing it is well to store in closed barrels or closed iron tanks away from light, as it has been observed that oils and fats in closed receptacles become rancid less rapidly than those in open ones, even though this method of storing is only partially attained. Preservatives are also used, but only in edible products, where their effectiveness is an open question.
CHEMICAL CONSTANTS OF OILS AND FATS.
Besides the various physical properties of oils and fats, such as color, specific gravity, melting point, solubility, etc., they may be distinguished chemically by a number of chemical constants. These are the iodine number, the acetyl value, saponification number, Reichert-Meissl number for volatile acids, Hehner number for insoluble acids. These constants, while they vary somewhat with any particular oil or fat, are more applicable to the edible products and are criterions where any adulteration of fat or oil is suspected. The methods of carrying out the analyses of oils and fats to obtain these constants are given in the various texts[2] on oils and fats, and inasmuch as they are not of great importance to the soap industry they are merely mentioned here.
OIL HARDENING OR HYDROGENATING.
It is very well known that oils and fats vary in consistency and hardness, depending upon the glycerides forming same. Olein, a combination of oleic acid and glycerine, as well as oleic acid itself largely forms the liquid portion of oils and fats. Oleic acid (C18H34O2) is an unsaturated acid and differs from stearic acid (C18H36O2), the acid forming the hard firm portion of oils and fats, by containing two atoms of hydrogen less in the molecule. Theoretically it should be a simple matter to introduce two atoms of hydrogen into oleic acid or olein, and by this mere addition convert liquid oleic acid and olein into solid stearic acid and stearine.
For years this was attempted and all attempts to apply the well known methods of reduction (addition of hydrogen) in organic chemistry, such as treatment with tin and acid, sodium amalgam, etc., were unsuccessful. In recent years, however, it has been discovered that in the presence of a catalyzer, nickel in finely divided form or the oxides of nickel are usually employed, the process of hydrogenating an oil is readily attained upon a practical basis.
The introduction of hardened oils has opened a new source of raw material for the soap manufacturer in that it is now possible to use oils in soap making which were formerly discarded because of their undesirable odors. Thus fish or train oils which had up to the time of oil hydrogenating resisted all attempts of being permanently deodorized, can now be employed very satisfactorily for soap manufacture. A Japanese chemist, Tsujimoto[3] has shown that fish oils contain an unsaturated acid of the composition C18H28O2, for which he proposed the name clupanodonic acid. By the catalytic hardening of train oils this acid passes to stearic acid and the problem of deodorizing these oils is solved.[4]
At first the introduction of hardened oils for soap manufacture met with numerous objections, due to the continual failures of obtaining a satisfactory product by the use of same. Various attempts have now shown that these oils, particularly hardened train oils, produce extraordinarily useful materials for soap making. These replace expensive tallow and other high melting oils. It is of course impossible to employ hardened oils alone, as a soap so hard would thus be obtained that it would be difficultly soluble in water and possess very little lathering quality. By the addition of 20-25% of tallow oil or some other oil forming a soft soap a very suitable soap for household use may be obtained. Ribot[5] discusses this matter fully. Hardened oils readily saponify, may be perfumed without any objections and do not impart any fishy odor to an article washed with same. Meyerheim[6] states that through the use of hydrogenated oils the hardness of soap is extraordinarily raised, so that soap made from hardened cottonseed oil is twelve times as hard as the soap made from ordinary cottonseed oil. This soap is also said to no longer spot yellow upon aging, and as a consequence of its hardness, is able to contain a considerably higher content of rosin through which lathering power and odor may be improved. Hardened oils can easily be used for toilet soap bases, provided they are not added in too great a percentage.