ANALYTICAL EDITION Fieldner, Jones, and Holbrook, U. S. Bur. Mines, Tech. Paper 320,5 (1925). Francis, U. S. Patent 1,668,362,May 1, 1928. Francis, U. S. Patent 1,850,499,March 22, 1932. La Condamine, French Patent 552,978,May 11, 1923. Neumann and Strahuber, Arch. Eisenhtittenw., 2,557-74 (1929). Ott, Gas- u. Wasserfach, 71,590 (1928); 72, 862 (1929); 74,970 (1931);Gas Age-Record, 63,112 (1929). Pfeifer, Gas- u. Wasserfach, 51,523 (1908).
Vol. 6 , No. 1
(13) Shepherd, Bur. Standards J. Research, 6, 121-67 (1931); Am. Gas J., 134, No.4, 49 (1931); No. 5, 67 (1931). 9,5 (1916). (14) U.S.Bur. Standards, C~TO. (15) Vossieck and Sohmitz, Chem. Fabrik, 3, 529 (1930). (16) White, J . Am. Chem. Soc., 22, 343-9 (1900). (17) Williams, J. IND. ENQ.CHEM.,4, 380-2 (1912);M e t . & Chem. Eng., 10,382-4 (1912). RECEIVED October 19, 1933.
Extraction of Triethanolamine Oleate from Aqueous Solution FRANK M. BIFFENAND FOSTER DEESNELL, Foster D. Snell, Inc., Brooklyn, N. Y.
I
N T H E extraction of oil from a soap and oil emulsion,
irregular results obtained indicated some abnormality. Further investigation showed that the soap was triethanolamine oleate and that the variable results were due to decomposition of the soap in extraction. Such decomposition is not unexpected, since triethanolamine oleate is a salt of a weak acid and a weak base. The extractions were carried out with ethyl ether and all results were higher than anticipated. The acidity of the extracted material proved to be higher than normal for the type of oil being extracted. The importance of this behavior is increased by the widespread technical application of triethanolamine oleate as an emulsifying agent and for other purposes. Normally, soaps other than those of abietic acid are not decomposed by extraction of an aqueous solution with ethyl ether. This method of separation of oils, etc., from soap solutions is therefore widely used.
A 200-cc. portion of the soa solution was extracted with 3 successive 50-cc. portions of et! 1 ether. In each case shaking was carried out for approximatey 2 minutes under similar conditions by the same chemist. T t e composite ether extractions were washed 3 times with 20-cc. portions of water. The ether was then evaporated, and the extract weighed, dissolved in alcohol, and titrated with 0.5 N sodium hydroxide. From this titration the amount of oleic acid extracted from the triethanolamine oleate was calculated to terms of percentage. In the case of experiments 3 and 6 the excess of oleic acid was allowed for before this calculation. The results are summarized in Table I. The original commercial oleic acid contained 97.25 per cent of oleic acid as oleic acid. The acidity of the extract varies from 95.0 t o 97.0 per cent by weight, and is highest in the experiments where recovery of the oleic acid was most complete. More dilute qolutions give a more nearly quantitative extraction. A determination of nitrogen on the extract from
FROM TRIETHANOLAMINE OLEATESOLUTIONS TABLEI. OLEIC ACID EXTRACTED
CONCENTRATION EXPERI- OR TRIETHANOLEXCESE TRIMENT
1 2 3 4 5 6
AMINE
EXCEES
OLEATE ~ T H A N O L A M I N E OLEIC ACID
M
M
0.1 0.1
0:05
0.1 0.01 0.01 0.01
0:05
..
..
M
..
0:05
..
0:65
COMBINED OLEIC ACID PRESENT
’ OLEICACID PUREOLSICACID EXTRACTED BY TITRATION C O R R l C T E < COMMERCIAL WEIQHT OF CORREXJTED PO^ FOR FREE OLEIC ACID EXTRACT FREEOLEICACID OLEIC.kCID KECOVH~RED
Grams
Grams
Grams
%
%
5.808 5.808 5.SO8 0.5808 0.5808 0.5808
3.4702 2.4746 6.1986 0.4265 0.4916 0.6900
3.3050 2.3500 2.8910 0.4135 0.4746 0.2660
95.2 95.0 95.4 97.0 96.6 97.0
58.5 41.7 54.7 73.2 84.0 68.5
The tentative explanation reached was that triethanolamine oleate was giving up oleic acid because of its instability. To verify this, a 10 per cent neutral triethanolamine oleate solution was extracted with ethyl ether under conditions normal for extraction of soap. A recovery of 85 per cent of the oleic acid present was obtained and the composition of the extract confirmed by titration. To express this phenomenon quantitatively, a series of experiments was carried out in which triethanolamine oleate was produced in solution alone, in the presence of excess triethanolamine, and in the presence of excess oleic acid. I n preparing these solutions, commercial triethanolamine and commercial oleic acid (olive elaine) were titrated and then combined in proportions to give the solutions outlined in Table I. The extractions were carried out as follows:
experiment 1 showed that less than 0.1 per cent of the triethanolamine had been extracted with the oleic acid. Table I indicates the possibility that all of the oleic acid could be recovered by further extractions. The results of 6 extractions instead of 3 showed recoveries as follows: Experiment 1, 76.32 per cent; experiment 4,93.73 per cent; experiment 6, 81.84 per cent. This indicates that further extraction may approach 100 per cent of the oleic acid present, particularly in dilute solution. It is to be concluded that normal conditions of separation of oils from soap solutions, in which the soap is triethanolamine oleate, will not apply and that either prolonged extraction with correction for the free fatty acid content is necessary, or that, preferably, a method other than extraction from aqueous solution without acidifying should be used.
CONDITIONS TO PRESERVE PUBLICATIONS. Light, adverse temperature and humidity, acid pollution of the air, and lowgrade paper appear to be the main deteriorative agents to be guarded against in libraries and other book depositories, according to a re ort prepared by the Bureau of Standards. Sulfur $oxide gas is a potential destroyer of all classes of paper, but tests demonstrated that this condition can be com-
pletely removed by washing the air with alkaline wash water. The destructive effect of light is emphasized. The removal of dust and the maintenance of a medium degree of tem erature and humidity are recommended. Extensive tests of opd newspapers showed that many made from crude fibers such as ground wood were badly deteriorated, whereas papers composed of chemically purified fibers were found to be in good condition.
RECEIVED August 26, 1933
