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INDUSTRIAL AND ENGINEERING CHEMISTRY
closures, he will make no reference to his ability as a connoisseur of one of the products of the art in which he has developed such outstanding refinements. Dr. Metager has another habit in which careful observers have found peculiar scientific interest. I refer to his flair for the fiddl-r music-as the case may be. Under normal conditions this weakness is not evident, and many of you who have known him for years have never suspected that he might be a rival of Fritz Kreisler under the right conditions. His reaction to the fiddle seems to occur only in the liquid phase. Added interest attaches to the fact that the reaction goes from fiddling to music as the concentration of the essential liquid reaches a certain optimum degree. Strangely enough, the temperature does not seem to be a factor in
Vol. 27, No. 1
this reaction. He fiddles in summer or winter with equal success, depending entirely upon the relative concentrations in the essential liquid phase. In closing, I cannot resist the opportunity of expressing the belief that every acquaintance, friend, former student, assistant, and associate, constituting together a large section of the men identified with this profession, is tremendously pleased to see this honor conferred upon Dr. Metzger. It is a deserved recognition of what he has accomplished, both for himself, for the university with which he was so long connected, and for the industries to which he has so generously contributed his scientific results. It is a tribute to his abundant energy, his outstanding ability, and his genius for hard work.
Traces from Tons F. J. METZGER Air Reduction Company, Inc., U. S. Industrial Alcohol Company, and U. S. Industrial Chemical Company, New York, N. Y.
T
HE late W. F. Hillebrand, noted analyst and for many tive, requirements. First, the operation must be continuyears chief chemist of the Bureau of Standards in ous in order that the processing of sufficient raw material Washington, once replied when asked what he meant may be accomplished. Second, the research and developby a ‘%race:” “It is that quantity which passes into the deep ment end of such a problem must be carried out on a comparatively large semi-works scale in order to obtain accurate recesses of remote decimals.” There are problems of chemical research and development data which may later be translated into terms of full-plant involving the production in large quantity of products or operation. In some cases, unless research operations are substances where the only adequate supplies of raw ma- carried out on a semi-plant or even full-plant scale, results terials are those containing only such “traces” of the product may be entirely negative. To carry out such a program of research reauires adeauate sought; in other words, processes are involved that require f a c i l i t i e s , well-rouhded thehandling of very large combination of p r o p e r l y tonnages in order t o obtrained scient,ists and engitain reasonable production. neers, and financial support An outstanding a c h i e v e commensurate with the unment, for instance, is the dertaking. extraction of radium from radium-containing m a t e rials. I n t h i s c a s e t h e RECOVERY OF RAREGASES pitchblende w i t h which FROM AIR M m e . C u r i e worked conSome of our own detained less than one part velopments in recovering p e r m i l l i o n of r a d i u m , traces, particularly in the and she obtained only a field of the rare gases of the f r a c t i o n of a g r a m of atmosphere, will b e m e n r a d i u m per t o n of o r e tioned briefly and some reftreated. erence will be made to the Another good example is way in which such a probof quite recent accomplishlem is approached. ment-the e x t r a c t i o n of The following table gives bromine from sea water by t h e boiling points a n d the Dow Chemical Comquantities of the elements pany. Industry demanded c o n t a i n e d i n t h e atmossuch large q u a n t i t i e s of phere. The quantities for bromine that the only logithe major constituents are cal raw material w a s s e a quite accurate. The figw a t e r w h i c h contains 67 ures f o r t h e m i n o r conp a r t s per million. These stituents, however, must be “ p a r t s p e r million” have t a k e n a s approximations been corralled i n t o “ t o n s only. It will be noted that per day.” KRYeON t h e e l e m e n t hydrogen is In w o r k of t h i s k i n d a XENON q u e s t i o n e d ; this will be t h e r e a p p e a r t o b e two FIGURE 1. FUNDAMENTAL OPERATIONS OF SEGREGATINGT H E referred to later. ATMOSPHERIC GASES e s s e n t i a l , if not impera-
a
i
Jsnuary, 1935
1 N D U S 1' H I A L
A
N D E N G I 'L
1:. E
K I U G C H 13 31 I 5 1' It
113
'1
SEW-PLANT SCALE EUUIPMEXT
Nitioae~ Oxygen
Aleon Eydrogea Neon Heiiuin Krypton
xerlon
-195.814
78.039 20.99$
-252.54
0.94 1 part& l0WO (1) I ~5'nno 1 pert jn Z 0 b . W
--1S3.983 -1xs.84
-240.3
-2fi8.98
-152.9 -107.1
,"
lpe.rt!n%WOOW 1 part m li,oob,ooo
... ... ... 1Ib. iII.44 tons
1 Ib. in 725 tons 1Ib. in 173 ton8 1 lb. in 120s tons
Oxygcn and nitrogen were the first of these constituenta to be sought, as such, for industrial uses, and large-scale rcquiniinent,sfor these products came a b u t a third of a century ngc In the earlier Sedges the processes employed for supplying the oxygen demand were of various kinds, some based on purely chemical nietliods, otliers on the electrolysis of water. ,it the same time, nietliods involving tlie liquefaction and iraetionatioir nf the cnnstit,uentsof tire air were being studied. At the urescnt time tlie cliemical methods h a v e ,pasL& entirely out. of the picture, and there are left t w o general processeselectrolytic snd liquefaction -,it11 the latter process supplying nearly all of the industrial oxygeii consumed. These liquefaction proce s s e s for the production of oxygen have been developed t o a high degree of perfection, and today the recognized s t a n d a r d of purity of tlie commercial gas in cylinders is 9 9 . 5 per cmt, the balitnce being argon wi:,h a. l i t t l e nitroeen. Tlie d e m a n d f o r uitrogeii came for i ~ iire eoiincr:tirm aibh t,lie various processes of nitrogen fixation. These fixation processes have now been firmly estallished. Kitrogen can readily he produced frroin tlie air by liquefaction n~idrectification a t B purity of ii9.8 to 99.9 per oent. Aa installation of nitropen i?quip>enterected during the war a t Muscle Shoals r/
had a capacity of fifteen million culr~cfeet of pure nitrogen per day. About fifteen or twenty years ago inquiry began to be made for some of the rare gases of the atmosphere for use in industry, the requests coming largely from niauufacturers of electric light& Those interested in air liquefactlon undertook the research and development work for the production of these rare gases. Cavendish in 1785 was the first to suspect that the atmosphere contained gases other than pblogisticated air (nitrogen) and dephlogisticated air (oxygen). His publistred statement, "If there is any part of the phlogktirated air of our atmosphere which differs from the rest and cannot be reduced to nitrous acid, we may safely conclude that it is not more than */,m part of the whole." This was a remarkably close estimate. Cavendish had actually isolated a mixture of these rare gases. However, one hundred wars or more e l a p s e d b e f o r e Cavendish's o b s e r v a t i o n was cirtrified, and it remained for Sir William Ramsay, Lord Rayleigh, Travers, and others (1894-1898) to separate and identify the five rare gases. The discovery of these rare gases attracted considerable attention, a n d much l a b o r a t o r y and scientific investigation of their properties followed. Hovever a further period of nearly t w e n t y y e a r s elapsed before any apprer.iable a p p l i c a t i o n was discovered or a demand created for the production of one of theu-iianiely, n r e o n . .kt the time. no m&od had heen perfected for its production on a Scale coirimensurate with the probaiJle uses. The underlying principle involved in the production of oxygen and nitrogen from the atmospliere by liquefaction methods is shown in Figure 1. There is also iudicatcd the Inay he w r e m t e d manner in whiclr each of the rare ga L_
L14
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(1
J ' K I i I ,A I.
h
N 1) l i
u c; I N E IE I1 I u G
C H ) ? : M I S T I( Y
Vol. 27, .\io. I
40 ti, 50 ~ I I Y1:ctit neoii with 12 tu 15 per cent helium, the tic., will I):iIaiice i ~ i n giiit.rogm. Further separation of this neontion, coiirsc of Ar,w ilirritigli nixtiire to pwduce cadi in a pure state is accomplished differ considerably it, the sea twiintic ahsorption and reniporization from activated the production of tlicse pa i:liarCwa,I traps employiiig liquid air ur liquid nitrogen for similar in all of them. Since eoritirruous ,separations by a i r liquefaotiaii oii at cooling. Jfetnllic calcium or alkali metals mav also be iiscd for the removal wiall s c a l e nil1 not fiiiiction properly if of minute traces of impurities if present, at all, and large-scale a s in t h e c a s e of exlieritneiitation is arg
