Dissolve 5 grams of soap in 50 cubic centimeters of 50 per cent. alcohol. Should any free fatty acids be present neutralize them with standard alkali. Wash into a separatory funnel with 50 per cent. alcohol and extract with 100 cubic centimeters of gasoline, boiling at 50 degrees to 60 degrees C. Wash the gasoline with water, draw off the watery layer. Run the gasoline into a weighed dish, evaporate the alcohol, dry and weigh the residue as unsaponified matter. The residue contains any hydrocarbon oils or fats not converted into soap.
SILICA AND SILICATES.
The insoluble silicates, sand, etc., are present in the ignited residue in the determination of insoluble matter. Sodium silicate, extensively used as a filler, however, will only show itself in forming a pasty liquid. Where it is desired to determine sodium silicate, 10 grams of soap are ashed by ignition, hydrochloric acid added to the ash in excess and evaporated to dryness. More hydrochloric acid is then added and the mass is again evaporated until dry; then cooled; moistened with hydrochloric acid; dissolved in water; filtered; washed; the filtrate evaporated to dryness and again taken up with hydrochloric acid and water; filtered and washed. The precipitates are then combined and ignited. Silicon dioxide (SiO2) is thus formed, which can be calculated to sodium silicate (Na2Si4O9). Should other metals than alkali metals be suspected present the filtrate from the silica determinations should be examined.
GLYCERINE IN SOAP.
To determine the amount of glycerine contained in soap dissolve 25 grams in hot water, add a slight excess of sulfuric acid and keep hot until the fatty acids form as a clear layer on top. Cool the mass and remove the fatty acids. Filter the acid solution into a 25 cubic centimeter graduated flask; bring to the mark with water and determine the glycerine by the bichromate method as described under glycerine analysis.
When sugar is present the bichromate would be reduced by the sugar, hence this method is not applicable. In this case remove the fatty acids as before, neutralize an aliquot portion with milk of lime, evaporate to 10 cubic centimeters, add 2 grams of sand and milk of lime containing about 2 grams of calcium hydroxide and evaporate almost to dryness. Treat the moist residue with 5 cubic centimeters of 96 per cent. alcohol, rub the whole mass into a paste, then constantly stirring, heat on a water bath and decant into a 250 cubic centimeter graduated flask. Repeat the washing with 5 cubic centimeters of alcohol five or six times, each time pouring the washings into the flask; cool the flask to room temperature and fill to the mark with 96 per cent. alcohol, agitate the flask until well mixed and filter through a dry filter paper. Take 200 cubic centimeters of the nitrate and evaporate to a syrupy consistency over a safety water bath. Wash the liquor into a stoppered flask with 20 cubic centimeters of absolute alcohol, add 30 cubic centimeters of absolute ether 10 cubic centimeters at a time, shaking well after each addition and let stand until clear. Pour off the solution through a filter into a weighed dish and wash out the flask with a mixture of three parts absolute ether and two parts absolute alcohol. Evaporate to a syrup, dry for one hour at the temperature of boiling water, weigh, ignite and weigh again. The loss is glycerine. This multiplied by 5/4 gives the total loss for the aliquot portion taken. The glycerine may also be determined by the acetin or bichromate methods after driving off the alcohol and ether if so desired.
SUGAR IN SOAP.
To determine sugar in soap, usually present in transparent soaps, decompose a soap solution of 5 grams of soap dissolved in 100 cubic centimeters of hot water with an excess of hydrochloric acid and separate the fatty acids as usual. Filter the acid solution into a graduated flask and make up to the mark. Take an aliquot containing approximately 1 per cent. of reducing sugar and determine the amount of sugar by the Soxhlet method.[18]
GLYCERINE ANALYSIS.
The methods of analyzing glycerine varied so greatly due to the fact that glycerine contained impurities which acted so much like glycerine as to introduce serious errors in the determinations of crude glycerine. This led to the appointment of committees in the United States and Europe to investigate the methods of glycerine analysis. An international committee met after their investigations and decided the acetin method should control the buying and selling of glycerine, but the more convenient bichromate method in a standardized form might be used in factory control and other technical purposes. The following are the methods of analysis and sampling as suggested by the international committee: