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INDUSTRIAL A N D EN 'GINEERING CHEMISTRY TABLE XIII-SUMMARYOB 1,ossEs OB MATERIAL (Concluded)
B-Necessary Losses (concluded) 4) Coloring matter 3) Unsaponifiable
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Total Total necessary losses C-Undesirable losses (conversion of primary DrOdWt t o by-product) )il saDonified (less rrlvcerol~
=3.
Per cent
Trace Trace
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Solution of Tin and Antimony Oxides'
.....
11,822.7 13,470.4
By Ernest0 Stelling
2.693
3.066
Vol. 16, KO. 4
Y A L E UNIVERSITY. N E W H A V E N ,
W
CONN.
HEN tin and antimony are converted into oxides by evaporation with nitric acid, they become insoluble, and in order t o dissolve them for further examination or for separation, it is common practice to use some method involving a fusion, which takes some time and offers difficulty Total 12,440.9 2.826 in getting the oxides entirely in a soluble form. D-Undesirable losses (irrecoverable) It has been found that when these oxides obtained as above (1) Neutral oil absorbed by bleaching materials 785.0 0.179 are digested with water containing some sulfur dioxide they (2) Saponified neutral oil absorbed by bleach Trace ..... 3) Neutral oil wasted in pressing 2,439.5 0.553 become readily soluble in hot hydrochloric acid. This observa4 Neutral oil lost in deodorizing 396.4 0.093 tion may have some interest in connection with the analysis eutral oil washed out of acid oil None ...., Free fatty acid washed out of acid oil None ..... of alloys containing these metals. 7) Glycerol washed out of acid oil 804.1 0.183 (8) Coloring washed out of acid oil Trace ..... The experiments were performed by using various amounts __ (0.2, 0.5, 1.0 gram) of powdered tin and antimony and mixtures 1,008 Total 4,424.0 of equal parts of both metals. Each sample was treated with Total undesirable losses 16,864.9 3.834 10 cc. of concentrated nitric acid and 10 cc. of water. Some of TABLEX ~ ~ - - ~ A B I l L A T I O NOf LOSSESCLASSIFIED AS (1) RECOVERABLEthese were evaporated to dryness on a steam bath, while others AS BY-I~RODUCT, A N D (2) IRRECOVERABLE were further heated to a dull redness. The oxides obtained K%. Per cent were treated with 50 cc. of a strong solution of sulfur dioxide RECOVERABLE AS BY-PRODUCT A-Necessarv losses and digested from 3 to 5 minutes a t about 60" C. Ten cubic 1) Moistire and volatile 490.0 0.114 f21 Gasoline-insoluble I centimeters of concentrated hydrochloric acid were added and (3j Free fatty acids 11 332.7 2.579 $race the solution was boiled until no more sulfur dioxide was evolved. 4) Coloring matter Trace o) Unsaponifiable matter ..... The solution thus obtained was perfectly clear. The digestion B-Undesirable losses (1) Neutral oil saponified (less glycerol) 4,940.0 1.124 with sulfur dioxide changed the appearance of the oxides, caus(2) and (3) Neutral oil mechanically held soap stock and wash water 6,182.7 1.405 ing them to become more dense and settle more readily. 1,072.7 (4) Neutral oil scrap from pressing 0.242 On testing the solutions of tin and antimony chloride obtained 245.5 (5) Neutral oil scrap from deodorizer 0.055 it was found that both of the metals were in the higher valence, Total recoverable as by-product 24,263.6 5.519 so that reduction by the sulfur dioxides does not occur in either 2-IRRECOVERABLE A-Necessary losses case. This is further confirmed by the fact that the amount (1) Moisture and volatile 1,647 7 0.373 of sulfate present in traces as an impurity in the water con(2) Gasoline-insolu ble Trace 3) Free f a t t y acid ..... taining sulfur dioxide is not increased by the solution of the Trace 4) Coloring matter ..... B-Undesirable losses oxides. This was found by determining sulfate photometrically (1) Neutral oil absorbed by bleaching ma785.0 0.179 in the solution before and after the oxides were treated. On terials (2) Saponified neutral oil absorbed by bleachthe other hand, sulfur dioxide is taken up by the oxide, as shown Trace ing materials ..... 2,439.5 0.553 (3) Neutral oil lost in pressing by the following experiment: The residues obtained by treating 395.5 0.093 (4) Neutral oil lost in deodorizing None the oxides of tin and antimony with sulfur dioxide water were ( 5 ) Neutral oil washed out of acid oil Nohe ..... (6) Free f a t t y acid washed out of acid oil filtered and washed thoroughly. The residues were then treated 804.1 0.183 (7) Glycerol washed out of acid oil Trace ..... ( 8 ) Coloring washed out of acid oil with bromine and dilute hydrochloric acid. After the bromine 6,071.8 was removed the solution gave a strong test for sulfate. If the 1.381 Total irrecoverable oxides, after treatment with sulfur dioxide, are boiled until the 30,335.4 6.900 Total losses sulfur dioxide is removed from solution, they are no longer 409,087.2 93.100 Net refined oil obtained soluble in hydrochloric acid. As the compound was not crystalline, it was thought useless to analyze it. Chemical literature CONCLUSIONS already contains too many formulas of imaginary compounds. 1-The yield of hard butter was good, but considerably The following procedure is recommended for the treatment below theoretical possibilities. of an alloy containing tin or antimony or both: 2-The yield of acid oil was satisfactorily low in relation to Treat 1 gram of the borings with 20 cc. of concentrated the free fatty acid content of the crude oil. nitric acid and 10 cc. of water. Evaporate to dryness over a 3-The shrinkage was low for this class of operation, but flame or a steam bath. Add 10 cc. of dilute nitric acid and warm. Filter and wash with dilute nitric acid. The filtrate might be reduced to a still lower figure by redesigning the will contain all the metals except the tin and antimony, which pressing department in such a way as to reduce the losses of are retained as oxides on the filter paper. Up to this point this is a regular procedure for alloys. Wash the oxides into a oil therein. with 50 cc. of a strong solution of sulfur dioxide and 4-Other shrinkage losses besides that of glycerol have beaker digest from 3 t o 5 minutes a t 60" to 70" C. Heat to boiling, been reduced to absolute minimum, until such time as the add about 10 cc. of concentrated hydrochloric acid, and boil refiner of coconut oil can obtain his raw material absolutely until all sulfur dioxide is removed. If necessary to remove free from water, setMings, and other unsaponifiable impuri- traces of the oxides from the filter paper, this can be treated in a similar manner. Tin and antimony will now be in solution ties. as chlorides of the higher valence in the presence of traces of sulfate, which is a convenient form for further treatment. &-Glycerol losses can be reduced in proportion to reduction in the percentage oi neutral oil saponified and hydrolyzed ACKNOWLEDGMENT in the refining processes. The writer wishes to express thanks to Professor H. W. Foote 6-Refiners of edible oils may, with profit, investigate the sources of small losses of material in their manufacturing for his valuable suggestions and for his criticism of this paper. 1 Received February 16, 1924. operations. 4940
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