July, 1917
T H E J O U R N A L OF INDL’STRIAI. A N D ENGINEERING CHEMISTRY
for Sept. 1917 (Vol IO, page 203), and in it he contends that salammoniac is not a chloride of ammonium hut a muriate of ammonia. According t o the old view muriatic acid and ammonia both contained oxygen while hydrochloric acid and ammonium were oxygen-free. The muriates upon heating were supposed t o be converted into chlorides by the expulsion of water. Ure sublimed dry sal ammoniac over hot metals and obtaining water concluded that the latter was due t o a combination of the hydrogen and oxygen in the sal ammoniac molecule. Sal ammoniac was therefore a muriate and not a chloride. The fallacy of this conclusion was pointed out by Thomson (in Vol. I Z of his A m a l s , p. 381) who by a natural intuition picked the winning side in the chloridic argument, as he did in the atomic controversy, years before most of his contemporaries. Although Ure in after years realized the correctness of Thomson’s view, he had the satisfaction of knowing that he went astray in good company. Berzelius believed up to 1820 in a hypothetical element muriaticum, which, upon combining with two atoms of oxygen, produced the anhydride of muriatic acid; this anhydride, upon further oxidation, as by means of manganese peroxide, yielded oxy-muriatic acid gas or chlorine Berzelius also believed in another hypothetical element nztricum, the oxide of which was nitrogen and which oxide in combination with hydrogen gave ammonia. Relics of these old views still survive in chemical nomenclature. The contribution of Ure. who was assisted in his experiments by Gmelin, a pupil of Berzelius, will always be worth reading, for it illustrates the difficulties with which early experimenters had to contend. As Kopp remarks in his account of the chloridic controversy, “it is interesting to note how correct observations led t o incorrect conclusions.” The tributes which Granville and Ure both pay to.Vauquelin only confirm what others have written about one of the best loved and most honored chemists of France. The readiness with which English scientists, after the bitter Napoleonic wars, could give expression t o such feelings of admiration shows the strength of the bonds which unite the great international brotherhood of science, and a t the time of the present crisis should fill us with hope for the future. 80 SOUTHSTREET, ~ - E WYORKCITY C. A BROWNS May 16. 1917
TWO LETTERS ON THE INCOMPLETE HYDROGENATION OF COTTONSEED OIL Editor of the Journal of Industrial and Engirieering Chemistry: I n a very interesting article entitled “Incomplete Hydrogenation of Cottonseed Oil,” by Hugh K. Moore, et al., published in the May 1917 number of THISJOURNAL, the following statement occurs on page 461 under the caption “Response to Halphen Test: The amount of hydrogenation which is required to render the oil just incapable of responding to the test has not to our knowledge been investigated.” A very limited amount of experimental data is given and a conclusion is drawn on page 462: “The degree of hydrogenation necessary to destroy the response of Cottonseed Oil to the Halphen test has been shown t o be a drop of about four units in the iodine number.” There are so many variable factors which would have an effect on this conclusion that it seems a rather broad statement to make on the limited evidence submitted. I t is rather interesting to the writer that the statement is made in the article that “the amount of hydrogenation which is required to render the oil just incapable of responding to the test has not to our knowledge been investigated,” in view of United States Patent 1,187,999, application for which was filed by the writer on August 31, 1915, and issued on June 20, 1916, in which the following statement appears in the specification: “ I n carrying out my new process for the manufacture of the
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product, a fatty oil, for instance, choice or prime yellow cottonseed oil, is placed in a closed vessel and caused to be chemically combined with hydrogen in the presence of a catalyzer. Any of the known processes of hydrogenation, or any active catalyzer may be employed, which does not leave any residual catalytic impurities in the product after careful filtration. A temperature of 150 to zoo’ C. has been satisfactorily employed, and the time required to produce the desired result after attaining this temperature, is from five to thirty minutes, depending upon the activity and proportion of the catalyzer employed. I n practice the time or degree of hydrogenation desired are determined by preliminary experiment on the oil and catalyzer used in an experimental apparatus. In carrying on such preliminary test the hydrogenation process is continued until a sample of the oil fails to respond to the Halphen reaction and the desired degree of crystallization takes place when the oil is chilled. “Depending upon the particular oil treated by the process, the iodine value of the finished product varies from about 90 to 102. Its titre (as determined by the Wolfbauer method) has been slightly increased during the process to the extent of from about 0 . I to 0 ,j O C. over that of the original oil treated. The color of the treated product is usually somewhat lighter than the original oil. On cooling the product it in part readily crystallizes, thereby making separation of the stearin from the oil much easier and more effective for ‘winter pressing’ for salad oil than is the case with ordinary cottonseed oil. The new product responds negatively t o the Milliau test for cottonseed oil.” Other parts of the specification and also the claims of this patent treat further on this subject. Inasmuch as a copy of this patent was sent to the Berlin Mills Company and was investigated by their patent attorney, it is somewhat surprising to the writer to find a t this time an article published by the research laboratory of this company over the name of the company, in which the abovequoted statement occurs. ARTHURLOWENSTEIN CHICAGO,June 6 , 1917
......... Editor of the Journal of Industrial and Engineering Chemistry: In reply to Dr. Arthur Lowenstein’s criticism of a section in our article on “The Incomplete Hydrogenation of Cottonseed Oil,” we wish to state that U. S.Patent 1,187,999 was familiar to us a t the time the section in question was written; neither a t that time nor a t the present time, however, could we regard the disclosures of the patent as constituting anticipation of our work. The fundamental statement of the patent, as quoted above by Dr. Lowenstein, is as follows: “ . . . . . . the hydrogenation process is continued until a sample of the oil fails to respond to the Halphen reaction and the desired degree of crystallization takes place when the oil is chilled.” There is no warrant for assuming from the language of the patent that when the Halphen test is just destroyed the proper amount of crystallizable material has just been produced; in fact it would appear that a considerable degree of choice may be exercised in the production of this stearine after the Halphen test response is gone. The iodine number of the product of the patent is not stated to be that of a product in which the response to Halphen test has just been destroyed, but is that of a product in which both conditions have been met. The breadth of the range given, go102, indicates that “the desired degree of crystallization” upon chilling, is subject to considerable variation, according to the object in view. The other distinguishing mark given in the patent, namely, a range of increase in titre, likewise fails to disclose any definite knowledge of the degree of hydrogenation necessary to destroy the response to the test; its indication is ambiguous, like that of the iodine number. We have not experimented with t h e Wolfbauer method, since its use is uncommon in this country, but it is certain that the range of 0 . I to 0.5 C. represents a very
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y large range in actual hydrogenation, as measured by change in iodine number. It is noteworthy that our experiments invariably showed a decrease in titre, as measured by the A. 0. A. C. method, before any increase began, so that to increase the titer 0.1t o 0.5’ C. above that of the original oil required a drop of iodine number to about 7 0 . We wish t o point out that if, as Dr. Lowenstein asserts, there are “many variable factors which would have a n effect on this conclusion,” there exists no published evidence to that effect. It seems probable to us that temperature is the only factor which would have such a n effect, and the temperature 150 t o 160’ C. was specified in the experiment in question. We are therefore unable t o agree with Dr. Lowenstein’s implication that U. S. Patent 1,187,999 anticipates our disclosure. It is quite possible that other investigators have carried out the same work a t a n earlier date, b u t we believe ourselves t o have been the first to publish the results of such work. BERLIN H. K. MOORE NEW HAMPSEZIRE G. A. RICHTER June 12, 1917 W. B. VANARSDEL
AN EXPLOSION OF AN ATTILINE STRIPPER Recently a stripper employed on aniline waters exploded and as the cause has not been ascertained, it is thought that a description of same may be of interest to manufacturers of aniline and similar compounds. DESCRIPTION OF STRIPPER
The stripper is a 3/&. steel tank 7 ft. in diameter and 8 f t . in. deep, flat bottom and plate cover on top, all S/a-in. steel. To stiffen the cover, two 64x1. I-beams (12l/~lbs.)16in. between centers were riveted on the cover. The cover was bolted t o the flange with about forty 3/4 in. X 1 1 / ~in. bolts. The bolt holes are spaced about 6 in. a p a r t on three-quarters of the circumference and 12 in. on centers on the remaining quarter. The bottom has a 21/2-in. outlet with a plug cock which runs to the sewer. The top has a zI/z-in. inlet with a cross. The cross has a 2-in. inlet with a valve and a 11/2-in. inlet with a valve. On the top of the cross was a 3/,-in. level safety valve and a gauge. The stripper has a closed coil of 2-in. pipe, for the purpose of heating, 8 turns, welded, connected in through the side with cast-iron elbows and nipples t o the coil. There is a 11/2-in. valve and line feeding the top of the coil with steam and the bottom drains through a a/&. steam trap. On the cover was a manhole and a 6-in. vapor line outlet running up vertically for 6 ft. to a zl/Z-in. coil in a 4 ft. X 6 ft. wooden tank. The vapor line, coil and coil-outlet have no valve. The coil discharges into a steel separator, 5 ft. X 6 ft. The aniline is drawn off the separator. OPERATION JUST PRIOR TO THE EXPLOSION The stripper was filled with aniline waters up t o just 30 in. from the top of the stripper, by means of a steam siphon from the wooden tank in t h e yard which is used as a reservoir for aniline waters. At 4:30 P.M., April 21, 1917, the cover was placed on the manhole of the stripper and the steam turned on the coil between 4:45 and 5:15 P.M. by a workman. The stripper is operated by simply distilling the aniline waters, condensing the aniline and water in a coil and running same into a separator. About 5:45 P.M. the stripper exploded. A workman was IO t o 20 ft. from the stripper when it went up and was splashed with water, undoubtedly from the stripper: the water was warm, not hot, and he was not burned. RESULTS OF THE EXPLOSION The cover of the stripper was blown off with considerable force, breaking all the bolts which held it on by tension. The cover was bent and the flange of the stripper bent. The cover landed on the edge of the floor beside the stripper.
Val. 9, No. 7
The entire contents of the stripper ( 1 6 ~ 0gallons) were thrown out, leaving a layer of r1/2 in. of iron sludge in the bottom of the stripper. A hole 20 ft. X 25 ft. was t o m through the roof and an 8-ft. I-beam bent 18 in. out of line. The wire glass windows which were near were broken. The stripper was not damaged very much. The same cover was replaced and except ’ for a few fittings was satisfactory for service again. After the explosion the inlet valve t o the coil was found wide open 53/,1 turns. The condenser was clear. The two valves on inlets t o the cross on the cover were closed. COMMENTS
The aniline waters were analyzed with the following results: SAMPLE: Feed Water as put into Stripper Aniline.. 3.13 per cent Acidity (as HsSO4). 0 , 0 0 5 per cent Nitro Compounds., , None
. . . . . . .. . . .
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Liquid from Bottom of Strlpper after Explosion 3.07 per cent 0 . 0 9 per cent None
The explosion behaved as though a layer of explosive had been placed on the bottom of the stripper. It is almost inconceivable that the explosion could have been caused by steam because the I ~ / in. Z steam inlet is the only supply. If this were led into the stripper through a break in the coil, the contents of the stripper would probably have been heated t o boiling before exploding. Even then, i t is difficult t o see how the steam a t 115 lbs. would create such a sudden and violent explosion, entering as it did, and with the exit condenser coil wide open. We would be pleased t o receive opinions as t o the probable causes of this explosion, which we are a t present unable to explain. CO., INC., NBWARIC, NBW JnRSEY MARDEN,ORTH& HASTINGS per RICHARDS. BICKNELL April 30, 1917
BUREAU OF STANDARDS’ ANALYZED SAMPLES The Bureau of Standards, Washington, D. C., now has ready for distribution its High Phosphorus Standard Analyzed Iron E No. 7, which is typical of the irons from the Alabama area. The analysis is: carbon, 2 . 1 7 ; graphite, 1.82; combined carbon, 0.38; silicon, 2 . 2 I ; titanium, o , o g g ; phosphorus, 0.862 ; sulfur, 0.05 I ; manganese, 0.444; copper, 0 . 0 2 I ; chromium, 0.014; nickel, 0.016; andvanadium, 0.073. Therenewal No. Iz-b, of the Basic Open Hearth Steel approximately 0.4 Carbon, is also ready. Until printed certificates can be secured, the above samples will be issued with provisional certificates without details of analysis, or description of methods. A new sample of Bessemer steel with approximately 0.I per cent carbon to replace No. 8-a is now in process of analysis. DECENNIAL INDEX OF CHEMICAL ABSTRACTS The intention of offering the Decennial Index of Chemical Abstracts in bound form has been reconsidered. There has been so little demand, and members who are binding their volumes have so many different bindings, that it was considered unwise, and, in fact, almost impossible t o offer a binding which would suit the members of the Society. CHAS.I,. PARSONS June 8, 1917 ALCOHOL AND WATER IN ETHER-CORRECTION I n the article under the above title, THIS JOURNAL, 9 (19171, 52 I , in the table on page 5 2 2 , the first “0.25 per cent Water” in the last group of figures should read ‘‘0.025”. R. L. PERKINS NITROGEN INDUSTRIES LITERATURE-CORRECTION In printing the ‘‘Literature of the Nitrogen Industries, 1912 t o 1916,” in the April issue of THIS JOURNAL, pages 424 to 438, we omitted t o state that this material was reprinted from the January, February and March, 1917, issues of the General Electric Review.- [EDITOR 1
