In conjunction with a high temperature, lead dissolves in oil at the expense of the glycerine, which is decomposed into acrolein, while lead linoleate is formed.
When litharge is heated with linseed oil, the action is somewhat similar, the substances formed being acrolein, lead linoleate, and linoleic acid.
If we consider the action of red lead on trilinolein, we have not only the formation of these lead linoleates, but an excess of oxygen available for the oxidation of glycerine to acrolein and acrylic acid, or to acetic and formic acids.
These equations serve to show the effect of lead and lead oxides in what may be termed the initiation of the chemical action upon the oil. Subsequent changes, no doubt, depend upon the conditions which obtain at the time, notably upon the temperature and upon access of air to the oil. It is probable that acid linoleates are formed, and that compounds formed from the polymerisation of linoleic acid result eventually.
Whatever doubt there may be as to the action of lead salts, there can be none whatever as to that of manganese compounds. In the first place, manganous oxide is a powerful base, which readily dissolves in oil; manganic oxide is also readily soluble, yielding fatty acid salts of manganese, and causing oxidation of glycerine. Manganese borate and manganese oxalate are both soluble in oil, the former much more readily than the latter, but they are both salts of little stability at high temperatures in contact with oils. They both dissolve by the aid of heat, forming fatty acid salts of manganese. Borate liberates boric acid under these circumstances, but oxalate yields a mixture of carbon monoxide and carbon dioxide.
Of manganese oleate and linoleate nothing more may be said than that both are extremely soluble in oil, and both easily oxidised from colourless to brown compounds when submitted to the action of air.
The chief adulterants of linseed oil and of boiled oil are cotton-seed oil, rosin oil, and linoleic acid. Cotton-seed, which is to some extent a drying oil, can act as such when mixed with linseed, but when added to olive oil, it behaves as a non-drying oil. In fact, its behaviour is anomalous, and of such a character that it greatly facilitates its extensive use as an adulterating material for the more expensive oils.
Rosin oil is a deleterious adulterant, but one which may be more readily detected than cotton-seed oil. Rosin is added to boiled oil to hasten its drying; this also is an injurious substance. Of late years glycerine has become an article of greater value than formerly, and this may account for the manufacture of linoleic acid and its use as an adulterant of oleic acid and of linseed oil.
Lastly, it may be mentioned that certain samples of “pale boiled oil” have been found to contain what is practically a raw oil mixed with dryers. Although such oils will dry, their efficiency is nothing like so great as that of an oil “boiled” with a blast of air at a suitable temperature, and, moreover, such oils are deficient in body.
In bleaching vegetable oils, it is necessary to consider the nature of the colouring matters naturally contained in them. These consist of a mixture in varying proportions of the colouring matters known to exist in the leaves of plants, but which, in the case of oils, are derived from the fruit or seeds from which the oils are expressed. There can be no doubt that these substances are closely allied in chemical constitution; they all possess an intensely powerful colouring property, by which is meant that though the colour of some of them may not be dark, yet a very minute weight is capable of imparting a tint to a very large quantity of material.