November, 1930
INDUSTRIAL AND ENGINEERING CHEMISTRY
Hydrodictyon with some Ulothrix and Rotifera and a few Spirogyra. Bacteriological Data The bacteriological data plotted in Figure 5 show plainly the effect of the drought on the data for 1930. The average total counts and the B. coli counts are all higher for the lowwater season. Here again one notes the gradual self-purification of the river in the section from Henry to Chillicothe and in the lake region from Chillicothe to Peoria. The reader’s attention is called to the fact that the counts are plotted logarithmically against time rather than distance. This takes care of the slow flow found in the Peoria Lakes. The counts are seen to rise quite rapidly upon the addition of the Peoria and Pekin wastes.
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The Super-Power Company of Pekin has found the river immediately below Pekin so polluted that they have had to resort to chlorination to keep down sphaerotilus growbhs so that they could use the river water in their condensers. Literature Cited (1) Boruff and Buswell, Illinois S t a t e Water Survey, Bull. 28 (1929). (2) Boruff and Buswell, Paper read before Division of Water, Sewage, and Sanitation a t t h e Atlanta Meeting of t h e American Chemical Society (not published). (3) Greenfield, Illinois S t a t e Water Survey, Bull. 20 (1925). (4) Hoskins, Ruchhoft, and Williams, U. S. Pub. Health Service, Bull. 171. ( 3 ) Standard Methods for t h e Examination of Water and Sewage (1925). (6) U. S. Department of Interior and U. S. Department of Agriculture reports.
New Commercial Emulsifying Agents’ H. Bennett GLYCOP R O D U C T S COMPANY, INC.,BUSH
M
AKY of the trials and tribulations encountered in the manufacture of technical emulsions have been
caused by the use of ancient formulas, all of which specify the preparation of the emulsifying agent in situ. Because of variations in strength of the reactant ingredients and chemical interaction with other materials present and through variations in time, temperature, and contact, it is often impossible to get the same results in duplicate batches. I n order to overcome these variations the newer trend is to use a previously prepared, practically anhydrous emulsifying agent of definite concentration. I n this manner it is quite simple t o make excellent emulsions, which can be duplicated without difficulty. Two such emulsifying agents which are being produced commercially are trihydroxyethylamine stearate and ammonium linoleate (paste). 1
Received June 5, 1930.
TERMINAL
BLDG.N O , 5, BROOKLYN, N. Y.
Trihydroxyethylamine Stearate Emulsions Trihydroxyethylamine stearate is a waxlike product of amber color, possessing a faint fatty odor. It is soluble in water and hydrocarbons and can be melted without decomposition. The method used in making an emulsion is as follows : Dissolve 14 parts of trihydroxyethylamine stearate in 72 parts of mineral oil heating to 60-70° C. Add 150 parts of water slowly with vigorous stirring and continue stirring until homogeneous. This will give a rich, creamy emulsion of great stability. The above formula with the addition of a perfume makes an excellent liquid cold cream. I n place of mineral oil other vegetable or animal oils may be used. Hydrocarbons, such as benzene, gasoline, naphtha, kerosene, etc., are emulsified in the same manner. Waxes and hard fats are likewise emulsified except that the water added must be heated above the melting point of the wax or fat. Water-insoluble
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INDUSTRIAL AND ENGI NEERING CHEMISTRY
solids may be emulsified in the same way by first dissolving them in a water-insoluble solvent. For example, p-dichlorbenzene is dissolved in solvent naphtha and then emulsified as above. Of course, the amount of emulsifying agent may be reduced considerably depending on the nature of the emulsion. By dissolving trihydroxyethylamine stearate in boiling water, viscous opalescent solutions are obtained, which are being used in preparing hand lotions which assume a pearly appearance on cooling. If a milky lotion is desired, a little mineral or other oil is melted with the trihydroxyethylamine stearate and the hot water is added slowly with vigorous beating.
Vol. 22, No. 11
I n emulsifying waxes the ammonium linoleate (paste) is dissolved in water and heated above the melting point of the wax that is to be emulsified. The wax is melted in a separate container and poured slowly into the heated water solution with vigorous stirring. If this method is followed exactly, using the proportions given above, excellent stable wax emulsions will be formed. Such emulsions make excellent polishes, waterproofing, lubricating, and filling compounds. Formula 1 is an excellent oil polish. Formula 16 gives an automobile or furniture polish of outstanding luster and extreme durability. It will not show finger marks. I t does not require the hard rubbing necessary with most commercial wax polishes. Ammonium Linoleate Emulsions Many synthetic reactions require contact between an Ammonium linoleate (paste), which is a relatively low aqueous solution and a liquid or solid phase insoluble in priced product, is finding many novel applications. To pre- water. The speed and completeness of the reaction are pare the emulsion the required amount of ammonium linoleate dependent on intimate contact. For example, if we try to paste is completely dissolved in water and the oil to be hydrolyze ethylene dichloride with an aqueous solution of emulsified is added slowly with vigorous stirring until emulsi- sodium hydroxide, we see that the two phases are immiscible fication is complete. and even vigorous agitation does not bring sufficient intimate The following table shows the amounts of oil, water, and contact. By emulsifying the ethylene dichloride with amammonium linoleate required: monium linoleate paste and water, a very fine dispersion is created which promotes hydrolysis under proper conditions Formulas for Ammonium Linoleate Emulsionsa of heat and pressure. If one of the reactant materials is a (All parts by weight) solid having a melting point above 100’ C., it should first AMMONIUX LINOLEATE be dissolved in an inert organic solvent and then emulsified NO. MATERIAL EMULSIFIED WATER PASTE according to the method given above. Parts Parts Paris 1 Mineral oil .. 90 10 These emulsions, for synthetic processes, must be agitated 2 90 90 8 Kerosene 3 Naphtha 90 100 7 violently during the course of reaction. Although acids, 4 Benzene 90 100 7 salts, and alcohol are usually detrimental to the stability of Gasoline 5 90 100 7 Cottonseed oil 6 90 90 11 emulsions, they can be used if violent agitation is kept up 90 7 Linseed oil 150 8 Ufl 8 Olive oil .. 60 10 continuously. 10 Castor oil 12 90 80 In many cases where chemical bleaching changes the struc11 10 Pine oil 90 90 12 China wood oil 12 90 SO ture of oils, fats, waxes, resins, etc., or leaves an undesirable 13 Peanut oil SO 90 12 Coconut oil 14 90 80 12 residue, the color can be lightened by emulsification with amParaffin wax 90 320 24 15 monium linoleate paste. The emulsion is made as previously Carnauba wax 16 90 12 420 Asphaltum 40 17 8 200 outlined and then a large excess of water is added while 1s Beeswax 90 500 12 Glyco wax 19 90 500 12 vigorous agitation is continued. A small amount of any acid 20 Ozokerite 90 400 14 or electrolyte is then added and stirring is continued until 21 Turpentine 90 100 S 22 Nitrobenzene S 90 100 the emulsion “breaks.” On standing the oil, fat, wax, resin, 90 8 o-Dichlorbenzene 23 100 Methyl salicylate 24 90 100 8 etc., rises to the top and can be drained off. It is then The cost of these emulsions can be reduced hy decreasing the amount “whizzed” and dried if the moisture occluded is objectionable. of emulsifier used, the minimum being determined by experiment. In crude materials the insoluble matter usually settles out the Emulsions made according to the above formulas are bottom in the settling tank. Rosin soaps are used extensively as emulsifying agents in useful as sprays, disinfectants, insecticides, lubricants, cleaners, etc. Khen volatile hydrocarbons are thus emul- the manufacture of disinfectants, water paints, paper coating, sified. their flash points are raised sufficiently to make them etc. They are usually made when needed, and the method is non-inflammable aud thus reduce fire hazards. Noreover, slow and cumbersome and duplicate batches show great their vapor tensions are so reduced that they do not evaporate variations. By the use of ammonium linoleate paste all this so readily and the resultant loss by volatilization is reduced is avoided and heating, with the resultant fire hazard, foamto a minimum. The formula given for making iiiineral- ing, etc., are eliminated. Ammonium linoleate paste also furnishes a convenient oil emulsions is typical of the usual oil polish for furniture or autoinobiles. If desired, a varying amount of tripoli or method for the preparation of metallic soaps which are exair-floated silica may be added to produce a silver or other tensively used in waterproofing textiles, stucco, etc., and metal polish. In the case of metal polishes the use of am- driers in paints and varnishes. The technic is quite simple. monia and the evil-sinelling oleic acid is eliminated by usiiig The ammonium linoleate is dissolved in water by vigorous agitation and is heated just below the boiling point. I n anthese formulas. Good stable wax emulsioiLs lIa\.e bcen the despair of many other kettle a concentrated solution of lead acetate is brought chemists. Many have tried and but fen have succeeded. to a boil. This solution is added slowly to the ammonium The quest is continued bevause was is used in many indus- linoleate solution with vigorous stirring. The insoluble tries arid would be used in many niore were it not fur the lead linoleate floats to the top and is washed and dried in difficulties involved in applying this class of msterial.~. the usual way. Solutions of aluminum, magnesium, calSince waxes are usually solids, they must be melted or cium, barium, titanium, copper, zinc, nickel, cobalt, and dissolved. The former procedure is not usually economical manganese salts precipitate the corresponding metallic soaps. because the wax hardens quickly and unevenly. In dis- Since the ammonium linoleate is an especially light-colored solviiig tlie waxes inflammable solvents must be heated product, the precipitated soaps are usually lighter in color than the usual commercial products. \lit11 tlie was, with resultant fire hazards.
