PRODUCTION themselves so that the anmine grouping is away fron* the granules, leaving it free to associate itself ^with another granule t o foarrn an amixse phosphate, especially if t h e second particle is. in completely cocated. The studies of Baarsoo and his as sociates indicate that use o*f fatty amines may make additional drying unneces sary. Many producers fciave felt that serious caking and b a g set would be prevented if rJbeir product were dried to within 0.5% or "less moisture. But even this would still not prevent these hygroscopic materials from absorbing air moisture during storage, Labora tory work indicates that some moisture in the fertilizer will improve spreading and efficiency of the fatty amine. Temperahrre of t h e granules must be high enough to keep tfcie formulation liquefied after it is addeol, and the for mulation itself must be heated prior to addition t o the mixer t o provide it in
completely liquid form. Mixing can also be critical. In an actual fertilizer plant test, a screw conveyor did not give rigorous enough rnixing. Addi tion of a short cylindrical mixing drum into the process line immediately after the rotary dryer would give rigorous tumbling and mixing. Preliminary trials with single nutrient materials such as sodium nitrate, am monium nitrate, and superphosphates have been sufficiently successful to en courage the company to plan further tests on these materials. As Baarson points out, studies of Ar mour's anticaking agent are not yet complete. Still remaining to be done are more plant-scale evaluations and greenhouse tests to evaluate any affects it may have on a growing plant's ability to utilize the fertilizer. On the latter point, Baarson said his own lawn thrived this summer on the treated materials.
Diborane Discovery Search for diffusion foil turns up permeation proc ess which may help diborane purification
It's b e t t e r t o g e t it f r o m
Sure, when, you need .an un common organic (or an un commonly pure one) in morethan-test-tube and less-thantank-car quantities, try Eastman Organic Chemicals Department, Distillation Products Industries, Rochester 3, Ν. Y.
there a r e some 3 5 0 0 Eastman O r g a n i c Chemicals f o r science a n d industry
DISTILLATION PRODUCTS INDUSTRIES is a division of
EASTMAN KODAK COMPANY
4690
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SEPT. 2 4,
Removing ni trogen a n d hydrogem from dibor a n e (B 2 H e ) by fractional distulatiom at l o w tem p e r a ture, the usual method is costly- enough and slow enough to make it at key drawback to that conapound's u s e as a rocket fuel. Relief could come, however, from Michigan State University where Ralph K. Bîrdwhistell, ^nd coworkers (Consolidated Vultee Aircraft Corp.) find that diborane peraneates certain plastic memoranes a t room temperature much faster than the otmer two gases. For one set of conditions, for example, diborane permeated a silicone rubber membrane ( Silastic-Dow Chemical) almost twice as fa*st as hydrogen and 4.6 times as fast as nitrogen. This might well "be the basis for a n efficient separation method whidh, as an added advantage, might b e naade part of a continuous diborane production system. Also, the phenomenon o r others like it might prove useful int unrelated industrial gàus separatioris, Birdwhistell told the E>ivision of ^Physical & Inorganic Chemistry. The MSU group h a d set out to find a membraae that w o u l d allow differential diffusion of diborane from the nitrogen antcl hA'dro^en v/hicb are " c p ^ or formed in its manufacture. Thev
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Eastman . . .
1956
hoped that, with the right membrane, the differences in molecular weight of diborane (27.69) and the other two gases might be enough to make such a purification method economical. Also, there was a chance that diborane would dissociate during diffusion to
R. K. Birdwhistell, with apparatus he used in finding possible n e w process for purification of diborane
;>ÉBÉc*9«éÉriÎU
BUTADIENE Processes Improved Here •**f>V
*«v\„*
nance. In t h e aggregate, these and bther KelloggA 1 ^Sf^tnantthe naturaI;supRly40jI^xhemical;;and:rubbet:^f engineering studies now i n progress p r o m i s e ^ tjfefecornpanies arereviewingtheir productionrfacilittes^ m a r k e d economies i n butadiene processing.- ^ %0y P ^ ^ o ç b u t a d i e n e — m a i n constituentof;GB-S, thegen-f;: :\ M: W ^ K ë l l à g g ' s experience'with butadièhefprol^K&erai?pu rpose ·* synthetic fru bbèr.C As ÎI eacl î ng l, éngi- "ieduction (andIf recovery^includes^ the^ènglné'ëpÏÏgV^ g^?3neers /and builders of petrochemical pjànts,/The r < andvponstruction of complete*plants,; as'.Well^aTs^V f l g ^ M f- \Nl \Ke\togg^Compà ny· h a s$ been ;co nd ucti ng ex-: *Jndivîdliai extraction ù^its^ÀisSl**MÎ,*\/V. Kellogg is % &5 5ί : tensive economic and engineering studies toward . experienced i n engineering and erecting naphtha,7 cracking u n i t s overseas for t h e simultaneous p r o : o ^lijincreasing th e f f i c i e n c y of-butadiene processes.. : a u c t i o n o f ethylene and butadiene. / £bnsid^rabie.^rWuIts;h1aVje:been achieved in im^^jDroying r niechaniçàl desîgn^,;în utilizing new and : We w e l c o m e t h e opportunity to review with y o u r ? ; f||;f more? ëfficîenfeequipmëht^andin reducing operate engineers t h e improved economics of Kellogg^#r ^#mg^costs~mcluding\ utilities,^labor -and;mainteengineered butadiene plants: Λ g y \ ^With^world* d e m a n d for r u b b e r increasing f a s t e r
lotograph shows section of petrochemical process? engineering division at M. W . Kellogg's New York headquarters
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t i n t LtmE veviiiiviiiilbi Specifications Ethylene Dichloride
85-87%
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13-15% .01-.03% 25 max. UO-1.23
Substantial quantities available for im mediate tank car or tank wagon shipments. Inquiries invited.
Chemicals for Industry
ROHM & H A A S COMPANY Washington Square
Philadelphia 5, Pa.
Number IS in Advances in Chemistry
PHYSICAL PROPERTIES OF CHEMICAL COMPOUNDS A systematic tabular presentation of accurate data on the physical properties of 511 organic cyclic compounds compiled by R. R. Dreisbach of t h e Dow Chemical Co. These comprehensive and basic data were determined for specially prepared, high purity compounds. I n adclition to the precisely measured properties the author has calculated new values for many constants based upon his new experimental values 523 pages plus index cloth bound—$5.S5 per copy order from: Special Publication Dept. American Cbemioal Society 1155 Sixteenth Street, N.W. Washington 6, D. C.
C&EN
SEPT. 2 4,
1956
and nitrogen in the various plastics might explain their different rates of diffusion, but no present theory ex plains either these solubility differences or the diffusion rates found for the three gases. To approach the solubility idea from a different angle, the MSU group hopes to substitute liquid membranes for some of the plastic ones. They may use silicone oils, for instance, in place of the silicone rubber. Since the plastics they're working with are quite diverse, both chemically and struc turally, they plan not to try others until they learn more of why the pres ent ones behave as they do. Temperature effects were not checked, but since diborane is heatsensitive, the important point for the process at hand was that it took place at room temperature. If some kind of solubility mechanism proves important, then temperature would very likely be important too. Pressure effects were not checked either, but within the range used (10 to 500 millimeters), diffusion rates for all three gases ap peared to vary linearly with pressure.
Sensitive Cellulose Testing Improvements in testing techniques open the door to effective study of cellulose and its reactivity in rayon processing; carbon-14 found useful
Series
edited by the staff of industrial and Engineering Chemistry
4692
borane, a small amount of which nor mally exists in equihbrium with it. If borane were the diffusing molecule, chances of success would b e better. It turned out that diborane was ap parently the diffusing molecule and that it diffused through nickel and brass foils at about the same rate as nitrogen. Since the two have similar molecular weights, the results agreed with diffusion theory (Graham's Law), which says that a molecule's rate of diffusion through a membrane varies inversely with its molecular weight. Agreement with theory, however, meant that diborane and nitrogen couldn't be separated economically by diffusion through nickel or brass foils. • Plastics Surprise. Next came the plastic membranes, made of ordinary commercial stock, which included a vinyl, cellulose acetate, cellulose acetate butyrate, polyethylene, trifluorochloroethylene, a cement for cellulosic sheets, and the silicone rubber. Diffusion of diborane, nitrogen, and hydrogen through all the plastic membranes varied widely from Graham's Law. Differences in solubility of diborane
The study of cellulose and its reactivity has been blocked con siderably in the past by the lack of sufficiently sen sitive control tests. One of the big gest obstacles in the way of good analyt ical tests for cellulose is the usual micro size cellulose samples available. Like its fellow carbohydrates, cellulose is ex tremely difficult to isolate from solution and still more difficult to estimate. From the locks of data presented at this year's American Chemical So ciety meeting, all is not black—sci entists told the Division of Cellulose Chemistry that they are successfully adapting extremely sensitive tests for the study of cellulose and cellulose reactivity. For the study of cellulose, an ex tremely sensitive method is now being applied—the C 1 4 labeling process. The cellulose sample is tagged with a car bon-14 labeling reagent. Carrier ma terial is added (nonradioactive counter part of the radioactive material). Re
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sult: formation of a sufneiendy large crystal sample that can be analyzed for reactivity. H. S. Isbell and coworkers of the National Bureau of Standards say that they have found two C 1 4 labeled re agents, sodium cyanide and methyl
W. J. Alexander of Rayonier. co-experi menter with D . K. Smith, detects manganese with polarographic analysis
