definitely settled.
Hydrolysis can be brought about by water alone, if sufficient time is allowed, but as the process is extremely slow, it is customary in practice to accelerate the reaction by the use of various methods, which include (i.) the application of heat or electricity, (ii.) action of enzymes, and (iii.) treatment with chemicals; the accelerating effect of the two latter methods is due to their emulsifying power.
The most usual method adopted in the manufacture of soap is to hydrolyse the fat or oil by caustic soda or potash, the fatty acids liberated at the same time combining with the catalyst, i.e., soda or potash, to form soap. Hitherto the other processes of hydrolysis have been employed chiefly for the preparation of material for candles, for which purpose complete separation of the glycerol in the first hydrolysis is not essential, since the fatty matter is usually subjected to a second treatment with sulphuric acid to increase the proportion of solid fatty acids. The colour of the resulting fatty acids is also of no importance, as they are always subjected to distillation.
During the last few years, however, there has been a growing attempt to first separate the glycerol from the fatty acids, and then convert the latter into soap by treatment with the carbonates of soda or potash, which are of course considerably cheaper than the caustic alkalies, but cannot be used in the actual saponification of a neutral fat. The two processes chiefly used for this purpose are those in which the reaction is brought about by enzymes or by Twitchell's reagent.
I. Application of Heat or Electricity.--Up to temperatures of 150�� C. the effect of water on oils and fats is very slight, but by passing superheated steam through fatty matter heated to 200��-300�� C. the neutral glycerides are completely decomposed into glycerol and fatty acids according to the equation--
C{3}H{5}(OR){3} + 3H.OH = C{3}H{5}(OH){3} + 3ROH.
The fatty acids and glycerol formed distil over with the excess of steam, and by arranging a series of condensers, the former, which condense first, are obtained almost alone in the earlier ones, and an aqueous solution of glycerine in the later ones. This method of preparation of fatty acids is extensively used in France for the production of stearine for candle-manufacture, but the resulting product is liable to be dark coloured, and to yield a dark soap. To expose the acids to heat for a minimum of time, and so prevent discoloration, Mannig has patented (Germ. Pat. 160,111) a process whereby steam under a pressure of 8 to 10 atmospheres is projected against a baffle plate mounted in a closed vessel, where it mixes with the fat or oil in the form of a spray, the rate of hydrolysis being thereby, it is claimed, much increased.
Simpson (Fr. Pat. 364,587) has attempted to accelerate further the decomposition by subjecting oils or fats to the simultaneous action of heat and electricity. Superheated steam is passed into the oil, in which are immersed the two electrodes connected with a dynamo or battery, the temperature not being allowed to exceed 270�� C.
II. Action of Enzymes.--It was discovered by Muntz in 1871 (Annales de Chemie, xxii.) that during germination of castor seeds a quantity of fatty acid was developed in the seeds, which he suggested might be due to the decomposition of the oil by the embryo acting as a ferment. Schutzenberger in 1876 showed that when castor seeds are steeped in water, fatty acids and glycerol are liberated, and attributed this to the hydrolytic action of an enzyme present in the seeds. No evidence of the existence of such a ferment was adduced, however, till 1890, when Green (Roy. Soc. Proc., 48, 370) definitely proved the presence in the seeds of a ferment capable of splitting up the oil into fatty acid and glycerol.
The first experimenters to suggest any industrial application of this enzymic hydrolysis were Connstein, Hoyer and Wartenburg, who (Berichte, 1902, 35, pp. 3988-4006) published the results of a lengthy investigation of the whole subject. They found that tallow, cotton-seed, palm, olive, almond, and many other oils, were readily hydrolysed by the castor-seed ferment in the presence of dilute acid, but that cocoa-nut and palm-kernel oils only decomposed with difficulty. The presence of acidity is essential for the hydrolysis to take place, the most suitable strength being one-tenth normal, and the degree of hydrolysis is proportional to the quantity of ferment present. Sulphuric, phosphoric, acetic or butyric acids, or sodium bisulphate, may be used without much influence on the result. Butyric acid is stated to be the best, but in practice is too expensive, and acetic acid is usually adopted. The emulsified mixture should be allowed to stand for twenty-four hours, and the temperature should not exceed 40�� C.; at 50�� C. the action is weakened,
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