1. The ash of cocoa powder (containing 33-1/3 percent of fat) is never more than 5·5 percent.
2. The maximum amount of alkali (calculated as potash) is 1·2 percent.
3. The ash soluble in water is always less than that insoluble in water. A reverse proportion shows a larger amount of alkali, that is, alkali has been added.
In addition to the importance of determining the amount of alkali in cocoa powder, it is very desirable that analytical chemists should agree as to the methods to be adopted, since the determinations of alkali seldom agree and may differ as much as 0·3 percent.[168] The method of calculating the results should also be defined, that is to say, an agreement should be arrived at as to whether the alkali should be expressed as K2O, K2CO3 or Na2CO3.[169]
Cacao which has been rendered miscible by means of ammonia, sometimes contains a small amount of ammonia, probably in combination with an organic acid. To detect it, the Cocoa powder should be distilled with water, which gives an alkaline distillate, as the ammonia salt would be decomposed at the temperature of boiling water. The ammonia can be volumetrically determined in the distillate with sulphuric acid.[170]
Determination of the Fatty Contents
5. Determination of the Fatty Contents. In this operation 5 grammes of the finest powdered bean i. e. the finest cocoa powder (in the case of chocolate, which must be finely flaked, 10 grammes) should be mixed with an equal quantity of evenly grained quartz sand in a warmed mortar, and then transferred per filter to a Soxhlet’s apparatus, wherein it can be extracted with ether for from 10 to 12 hours at a stretch. The previously weighed carboy, which now contains the fatty contents in solution, is placed on a water bath, and the ether extracted as far as possible, after which the fatty residue remaining is dried by first introducing the vessel in a water oven and afterwards allowing it to stand for 2 hours in a dessicator. The increase of weight in the flask is due to ether extract, consisting almost exclusively of fat. It is true that small proportions of theobromine will have been simultaneously dissolved (perhaps about 0·1 g.) but no special significance need be attached to them. If it should seem advisable to avoid even this slight drawback, petroleum ether with a boiling point of 50° C. should be employed instead of the ordinary variety.
Welmans[171] has further described a quick and practical method for determining fat in cacao and its preparations, which is not only of value as a check on the extraction method, but also serves as a determination of the constituents soluble in water. It is carried out as follows:
5 grammes of Cocoa powder or cacao mass, which need not be very fine, or 10 grammes of chocolate are stirred for some minutes in a separator or cylinder with 100 ccm of ether (saturated with water) until coherent particles are no more visible, that is to say, until the factory degree of fineness has been attained. In two minutes all will have gone to powder even if the chocolate has not been rubbed down but is in pieces; 100 ccm of water (saturated with ether) are then added, and the mixture agitated until a complete emulsion takes place. With powdered cacao, especially those kinds rich in fat, that occurs in ½ to 1 minute, and with chocolate in 2 minutes. It is then allowed to rest until the emulsion separates, which at the ordinary temperature of 15-20° C. usually occurs in 6-12 hours in the case of chocolate, and 12-24 hours with cacao. The greater part of the water separates first and, usually, amounts to 90-98 ccm with chocolate and 70-86 ccm with cocoa. The powdery portion of the cocoa or chocolate floats on the surface of the aqueous layer at the bottom of the ether layer. Only husk, sand, particles of cacao beans, added starch, etc. accumulate at the bottom of the separator and are to be removed with the aqueous layer, which in the case of chocolate contains the sugar, but usually no trace of fat. The ether layer, which freely separates from the emulsion in the time mentioned, is quite clear and from 25 to 50 ccm can generally be pipetted off and an aliquot part poured into a measuring cylinder or graduated tube, or into a 25 or 50 ccm flask. If the ether solution of fat is not sufficient in quantity, the separation can be effected after removing the aqueous liquid by twirling round the separator. The turbidity soon disappears and the non-fatty particles quickly sink to the bottom. The ether solution of fat can also be examined aräometrically, as with milk fat, by Soxhlet’s aräometric method, after forcing it by means of an india rubber ball, into a pipette or burette, but the constants to be used in that case have not been ascertained. After the ether has been distilled off, in the normal manner, the weight obtained must be calculated for 100 ccm and a small correction made. For example, if 50 ccm of the ether solution of fat give a residue of 0·8 gramme, then 100 ccm represents 1·6 gramme. But this 1·6 gramme has not been obtained from 100 ccm of the original (water saturated) ether, but from 100-x ccm, x representing the number of cubic centimetres corresponding to 1·6 gramme of cacao butter and, as the specific gravity of cacao butter is nearly = 1; the equation becomes (100-1·6): 100 = 1·6: x; x = 160/98·4 = 1·627 gramme; so that the 5 grammes of substance would contain 1·627 gramme of fat or 32·54 percent.
The remaining aqueous solution contains the whole of the constituents of cacao or chocolate which are soluble in water. It is measured into a graduated cylinder and its volume ascertained. Then, after the entire amount has been evaporated to dryness, the residue is calculated on a percentage basis. The following procedure, however, is preferable. 10 ccm of the liquid are evaporated and the residue well dried in a vacuum before it is weighed. Multiplying the ascertained weight by 10, we obtain the amount of cacao or chocolate soluble in water and present in 5 and 10 grammes of either substance respectively. The amount of sugar in the aqueous extract can be determined in the following manner. 50 ccm of the extract are heated in a water bath and thus separated from ether; afterwards 2 ccm of lead acetate are added and the whole immediately transferred to a special kind of filter paper. The solution is now polarised in the usual way and the number of grammes of sugar thus ascertained converted into ccm by division (1·55 being the unit) and then the result subtracted from 100, which gives the volume of water present in 100 ccm of sugar solution, and so by further division until the percentage of sugar in chocolate is finally obtained. If the polarisation yields more sugar than the weight of the total residue, it is an indication that dextrine is present as an adulteration. The quantitative determination of dextrine, which is sometimes added to cocoa powder as well as to chocolate, for like gelatine and tragacanth it holds water together and so ensures a saving of fat, is best carried out in P. Welman’s polarising method.[172]