The oils employed in adulterating olive oil, and to which regard must be had in testing it, are the following: Cotton seed oil, sesame, peanut, sun flower, rape, and castor oils. The tests for the two last named have hitherto never presented any difficulty, as rape seed is easily detected, owing to the sulphur in it, by saponifying it in a silver dish, and castor oil by its solubility in alcohol. But in recent times another product has come into the market called sulphur oil or pulpa oil, obtained by extracting the pressed olive cake with sulphide of carbon. This also gives a sulphur reaction when saponified, while it resembles castor oil by its solubility in alcohol. When this oil is mixed with ordinary olive oil, it can easily deceive any one who uses the ordinary tests.
My method of testing olive oil is as follows:
First, the so-called elaidine test is made, and then the test with nitric acid. About 5 c. c. (a teaspoonful) of the oil is mixed in a test tube with its own volume of nitric acid, spec. gr. 1.30, and shaken violently for one minute. At the expiration of this time the oils will have acquired the following colors: Olive oil, pale green; cotton seed oil, yellowish brown; sesame, white; sun flower, dirty white; peanut, rape, and castor oils, pale pink or rose.
As soon as the color has been observed, the test glass is put in a water bath at the full boiling temperature and left there five minutes. It was found that the action of nitric acid upon cotton seed and sesame oil was the most violent, sometimes so violent as to throw the oil out of the glass. At the end of another five minutes after the test tube is taken out of the water bath, the following colors are seen: olive and rape oils are red; castor oil is golden yellow; sun flower oil, reddish yellow; sesame and peanut, brownish yellow; cotton seed, reddish brown.
After standing 12 to 18 hours at about 60° Fahr. the olive, rape, and peanut oils will have solidified; sun flower, castor, and cotton seed will be like salve (sticky), while sesame will remain perfectly liquid. Mixtures of olive oil with small quantities of cotton seed or sesame are distinguished by this characteristic--that, although the whole mass, which is darker in color than olive oil, solidifies at first, at the end of 24 or 36 hours a brown oil will be found floating upon the surface of the solid mass, while the lower strata exhibit the yellow color of pure olive oil. Oil of rosemary has no effect when shaken with cold nitric acid, and imparts to it only a slightly darker color on heating. Oils treated with lye act just like pure oils.
Far the purpose of determining the melting point of the fatty acids, 10 grammes of oil were saponified with 5 grammes of caustic potash on the water bath; some water and alcohol being added. After all the alcohol had been expelled the soap was dissolved in hot water, and the fatty acids separated from the clear solution by adding hydrochloric acid. After prolonged heating these acids will swim on the salt solution as a perfectly clear oil, a portion of which is then put into a little, narrow, thin walled tube and allowed to solidify. The point at with it melts and solidifies is determined by putting this tube in a beaker glass filled with water and warming with a small flame. A thermometer is placed in the fatty acids and moved gently about during the observation, and the point accurately observed at which the whole mass becomes perfectly clear, and also when the mercury bulb begins to be clouded. It was found that the acids from pure olive oil melt between 26½ and 28½° C. (= 80° to 83° Fahr.) and solidify at a point not lower than 22° C. (72° Fahr.). The melting point of the fatty acids in the oils used to adulterate olive oil differs considerably from this. The melting and solidifying points of the acids in cotton seed, sesame, and peanut oils lie considerably higher, those of sunflower, rape, and castor oils decidedly lower than those of olive oil.
The melting and solidifying points of these acids are as follows:
Cotton seed melts at 38.0°C. solidifies 35.0°C.
Sesame do. 35.0 do. do. 32.5 do.
Peanut do. 33.0 do. do. 31.0 do.
Sunflower do. 23.0 do. do. 17.0 do.
Rape do. 20.7 do. do. 15.0 do.
Castor oil do. 13.0 do. do. 2.0 do.
The above figures differ so much from those of olive oil, that adulteratious carried to the extent that they are in trade can easily be detected by the aid of an estimation of the melting point, for a Gallipoli olive oil, mixed with 20 per cent. of sunflower oil, melted at 24° C. and solidified at 18° C. (of course, the fatty acids are meant). A Nizza oil, mixed with 20 per cent. cotton seed oil, melted at 31½° C. and solidified at 28° C. A Gallipoli oil with 33-1/3 per cent. of rape oil melted at 23½° C. and solidified at 16½° C. When 0.50 per cent. of rape is added, it melts as low as 20° and solidifies at 13½° C., etc.
In testing the solubility of the fatty acids in alcohol and acetic acid, I employ the method proposed by David (in Comptes Rendus, 1878, p. 1416) for estimating stearic acid.