2. Twenty-four grammes of hyposulphite of sodium in a liter of water.
3. A ten per cent. solution of iodide of potassium. Dissolve 0.1 to 0.2 gramme of the volatile oil in 10 cubic centimeters of chloroform, and add first 15 cubic centimeters of the iodine-mercuric chloride solution; let stand three or four hours, and, in case the mixture gets discolored, add a few more centimeters of solution. Now add 10 to 15 cubic centimeters iodide of potassium solution, dilute with 150 cubic centimeters of water, and titrate with hyposulphite till the mixture remains clear for about a minute. The iodide of potassium solution must be added before the water, and the relative proportions between this solution and the iodine-mercuric chloride solution must be 15 to 20 cubic centimeters. The quantity of iodine solution consumed is calculated to iodine for 100 parts and the figure thus obtained is designated as the "iodine number."
Barenthin has in this manner determined the iodine number of several volatile oils; other experimenters, however, for instance, Kremel and Davies,[4] have found different numbers for the same oils, so that this method requires further thorough examination before it can be classed as available.
VI. A. Kremel has endeavored to utilize titration or saponification with alcoholic potash lye for the examination of volatile oils. In his experiments he was guided by the following points: A series of volatile oils contains partially free organic acids, like oils of bitter almonds and cinnamon, and partially aldehydes or other combinations. Now it seems not impossible, that up to a certain limit, the quantities of these combinations in the separate volatile oils remain constant, thus presenting the opportunity of testing the respective oils as to their quality and purity by saponification. In some cases these combinations are the chief bearers of the specific odor, and hence the determination of the "saponification number" becomes of double value. It is, of course, self-evident that not every volatile oil can be saponified, and Kremel admits that, even where saponification takes place, it is not in every case a sure test.
The execution of the method is as follows: Dissolve 1 gramme of the oil to be examined in 2 to 3 cubic centimeters of 90 per cent. alcohol freed from acid, compound the solution with a few drops of phenol-phthalein solution, and titrate the free acid with ½ normal alcoholic potash lye. The milligrammes of caustic potash used are designated the "acid number." After having thus determined the content of acid, add to the same solution 10 cubic centimeters of the same potash lye, heat for ¼ hour upon the water bath, and then titrate back the excess of potash lye with ½ normal hydrochloric acid. In this manner the "saponification number" is obtained. (In some cases when the final reaction is not plainly perceptible, it is advisable to correspondingly dilute with water after heating the alcoholic fluid.) The saponification number, less the acid number, gives the "ether or ester number."
Kremel has in this manner examined a large number of volatile oils and partially obtained surprising results. Rose oil gives a saponification number of 12, and geranium oils one of 40 to 50. While lavender oils give very high saponification numbers, oil of lemons does not. Artificial oil of bitter almonds shows higher saponification numbers than the natural oil. By further compounding the saponified portions of the latter with acid, a crystalline precipitate of benzoin is formed, the quantity of which amounts to from 40 to 50 per cent. of the oil used. Such a precipitate, but only in very small quantities, is also formed in peach kernel oil, but not in other similar oils nor in artificial oil of bitter almonds.
VII. F. R. Williams has recently endeavored to utilize for testing volatile oils Maumené's test, which is based upon the increase in temperature produced in oils by concentrated sulphuric acid, and which gives valuable points for the examination of some fat oils. Of course, the large quantities of oil otherwise prescribed cannot be used. While for the examination of fat oils 50 grammes of oil are mixed with 10 cubic centimeters of concentrated sulphuric acid in a beaker glass wrapped around with cotton, Williams could use only six cubic centimeters of volatile oil. They were brought into a very small beaker glass enveloped in cotton. After reading off the temperature, twelve cubic centimeters of concentrated sulphuric acid were added and the whole stirred with the thermometer until the temperature no longer rose. Numbers were in this manner obtained which might in some cases, for instance, cassia oil, furnish guiding points for judging the purity of the oil.
Planchon proposes the following procedure in order to recognize a volatile oil:—
A. The oil is specifically lighter than water.
1. The substance is solid and only melts at 347° F.: Camphor.