6 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Aliquot A Liebermann- Storch test for the detection of lanolin Group III Cold Acetone Insoluble (wax, lanolin, and hydrocarbon containing fraction) Aliquot B* Concentrated sulfuric acid __ Paraffinic Fraction Non-paraffinic- sulfuric acid digestion mixture * Should the analyst so desire he may determine the waxes by the Zweig and Taub method. Figure 4. soluble portion can be further fractionated by treatment with naphtha in which dye, castor oil and certain other oils are insoluble. Group V, if it is present, may consist of a variety of compounds, many of them esters. However, elaboration on this fraction is beyond the scope of this paper. Its softening point, consistency at room temperature and saponification value give helpful clues concerning its composition. Further analysis of Group I is of no interest. Impurities are precluded, certified colors only being permissible. Matching color does not require chemical analysis. Figure 3 deals with Group II, the aqueous fraction. The bromo acids generally found in lipstick are not water soluble. Any trace which might appear in the aqueous layer may be removed by decolorizing with charcoal. This fraction is then divided into three small (A, B, C) and one large ali- quot (D). Aliquot A is spot tested for the presence of primary alcohols (6). Aliquot B is subjected to the periodate test in order to detect the presence of propylene glycol (7). Aliquot C is tested with barium silicotungstate to detect the presence of polyols (8). If the test for a primary alcohol is positive and neither glycol nor polyols are present, it is probable that the alcohol is tetrahydrofurfuryl alcohol. I do not know of any test which is specific for the tetrahydrofurfuryl radical or its alcohol. If no primary alcohol is detected Aliquot D should be saponified for the purpose of de- tecting the presence of a water-soluble ester such as tetrahydrofurfuryl acetate. Approximate quantitative determinations (85-95%) of these water- soluble compounds may be ascertained, as follows: To determine propylene glycol: Add to a fresh sample of lipstick, a hydrocarbon such as xylol and carry out an azeotropic distillation. The propylene glycol separates from the hydrocarbon in the distillate and is measured volumetrically. The Dean-Starke (9) distilling apparatus is most suitable for this operation. Confirmatory tests such as boiling point,

SEMIQUANTITATIVE ANALYSIS OF LIPSTICK 7 refractive index, specific gravity, and solubility in solvents may be ascer- tained. To determine polyols: They may be determined by weighing the yel- low precipitate which forms with barium silicotungstate, or, by weighing the residue after the water has been driven off. Determinations of the physical constants on the residue will further confirm its identity. To determine tetrahydrofurfuryl alcohol: Carry out a vacuum dis- tillation on a fresh sample of lipstick. The initial distillate should contain the low boiling THFA and some perfume. Determine the volume of the mixture. Shake this fraction with water and determine the volume of the water-insoluble fraction. The difference in volume should represent the volume of THFA. Upon evaporating off the water in the water-soluble fraction its identity can be confirmed by its physical constants. Figure 4 deals with Group III. The cold acetone insoluble residue is the "wax" fraction. A Liebermann-Storch test for the detection of lanolin is performed on Aliquot A. Although the waxes can be identified and determined by the Zweig and Taub method, the most significant factor concerning this acetone-insoluble fraction is what percentage of it is par- affinic in nature. Treatment of Aliquot B with concentrated sulfuric acid will show the percentage of aliphatic hydrocarbon present. Group (Hydrophylic oils) Dilute with trichlorethylene and filter through aluminum oxide Elute with trichlorethylene, benzene-acetone, and meth- anol, respectively Trichlorethylene Benzene-Acetone Methanol Eluate Eluate Eluate (castor oil) (dye) Figure 5. Figure $ deals with Group IV. This naphtha-insoluble portion will contain the dye and castor oil, if present. Using aluminum oxide, the castor oil will be eluted with benzene-acetone or ethyl ether and the dye subsequently with methanol. As stated previously, Group V is beyond the scope of this paper. The method of analysis which has been described quickly divides the mass into major fractions thus permitting the examination of only those portions which are of interest. Nevertheless, this method affords the op- portunity for an exhaustive analysis, if desired. Harry (10) has defined a realistic and practical evaluation of analysis of an unknown in these words: