3 grammes of cacao butter are dissolved in 6 grammes of ether at 10° C. Should the resulting solution be clear, this is an indication that no wax is present. The solution is then introduced in its test tube into water at 0° C. and the length of the time which transpires before it begins to become cloudy or to deposit flocculent matter, observed, also the temperature when the solution again becomes clear.
If the solution becomes turbid before ten minutes have elapsed the cacao butter is not quite pure. Pure cacao butter becomes turbid in from 10 to 15 minutes at 0° C. and clear again at from 19-20° C.; an admixture of 5 percent of tallow renders the solution turbid at 19-20° C. in 8 minutes and it becomes clear again at 22° C.; 15 per cent of tallow give a turbid solution in from 4-5 minutes at 0° C. that becomes clear again at 22·5-28·5 ° C. Filsinger[178] has suggested a modification of Björklund’s test. In his method 2 grammes of the fat are dissolved in a graduated tube in a mixture of 4 parts of ether (S. G. 0·725)) and 1 part of alcohol (S. G. 0·810). Pure cacao butter should remain clear after some lapse of time, whereas foreign fats and more especially tallow preparations cause a separation. But Lewkowitsch[179] maintains that this test is not be relied on, as genuine kinds of cacao butter will crystallise out from the ether alcohol solution at 9° C. and some at 12° C.
Yet we are nevertheless of the opinion that liquid fats are of no great moment at the present time, for they always involve a considerable lowering of the melting point and so greatly impair the fracture of the chocolate. Fats such as tallow, or the like, must be used, and these are detected both by their flavour and by Björklund’s test. Adulteration is therefore very rarely met with in the German chocolate industry, thanks to these facts and the rigid self-control practised by the Association of German Chocolate Manufactures and the sharp supervision exercised by the inspectors of articles of consumption in that country. The only regularly occurring adulterations are connected with the preparation of Cocoa powder and consist in substitutions of finely ground cacao husk; the detection of which still remains most difficult and uncertain; and even here it is rather the Dutch firms which are culpable; and generally speaking it is a trick of smaller manufacturers, who consider such an admixture as quite the normal procedure.
Determination of Theobromine and Caffeine
6. Determination of Theobromine and Caffeine. Methods for the ascertainment of the quantity of theobromine are so numerous that it would be impossible here to enter into the detail of their advantages and disadvantages. Of the different processes adopted in the determination of the cacao diureide perhaps only Eminger’s is worthy of consideration at present, and this is described fully in the following paragraphs, as best corresponding to our present knowledge of the subject and its requirements, and most deserving recommendation to chemists and food analysts on account of its reliability.
For the practical testing of cacao preparations the splitting up of the diureide has no special advantage and so we can at once proceed to treat of the compound particle, though rather inclined to maintain that the diureide has very little importance on the whole, for it establishes no basis from which we can judge of the quality of the various products.
The procedure in Eminger’s process is as follows:
10 grammes of powdered bean of cacao preparation are placed in a weighed glass flask, then stirred up with 100 grammes of petroleum ether and allowed to settle. The petroleum ether is next carefully poured off, without disturbing the sediment, and the treatment repeated several times. After the last decantation, the residue is well drained, then dried in the flask and weighed. The difference in weight of the residue and the former figure represents the amount of fat. An aliquot portion of the residue (about 5 grammes) is then boiled with 100 grammes of a 3-4 percent strong sulphuric acid in a flask connected with a reflux condenser, until cacao red is given as a resultant, a task which occupies three quarters of an hour. The contents of the flask are then poured into a beaker, and neutralised, whilst hot, with barium hydroxide. The whole is then mixed with sand in a basin and evaporated to dryness; afterwards the dry residue is introduced into a Soxhlet apparatus on a paper cone, and there extracted for 5 hours with 150 grammes of chloroform. The latter is carefully distilled off and the residue dried for a period of one hour at 100° C. As previously stated, the separation of the two diureides is not necessary and in commercial analyses it is sufficient to state the amount of each separate substance after the removal of fat by means of some suitable solvent. But should the splitting up be desired, then Eminger’s method should be adopted, which depends on the solubility of caffeine in carbon tetrachloride.[180] With that object, the mixture of fat, theobromine and caffeine is treated in the flask with 100 grammes of carbon tetrachloride and repeatedly agitated for one hour. After filtration, the carbon tetrachloride, which now contains fat and caffeine, is distilled off. The theobromine left undissolved in the flask and the filter used to filter the carbon tetrachloride solution are then extracted with boiling water, the solution is filtered and evaporated to dryness, the residue representing theobromine. The separation of caffeine and theobromine can also be effected by cautious treatment with caustic soda, so dissolving the theobromine and leaving the caffeine untouched in its entirety.[181] (Cf. Riederer.)
Determination of Starch
7. Determination of Starch. This can only be of importance in rarer instances, as the starch naturally present in raw cacao generally varies between 9 and 10 percent, and there is no chemical method of separating foreign matter from cacao starch. But should the necessity arise, a determination can be carried out as follows.