INTERNATIONA
L
minor irregularities in column packing can increase the E H T P by an order of magnitude. Glueckauf suggested that for given operating conditions one should b e able to use the ratio ( E H T P t h e o r e t i c a l ) / ( E H T P observed) as a parameter by means of which different techniques of column packing can be compared quantitatively with regard to their perfection. To make ion exchange operations more efficient he outlined different aspects which must be considered. Chemical conditions must b e such that substances to be separated distribute between exchanger and solution in such a manner that distribution coefficient ratios are as large as possible. Operat ing conditions should be adjusted so that the E H T P is small enough, and the total number large enough to attain desired performance. Glueckauf showed that the E H T P is not only a function of the column and that it can vary with the flow rate, but that it is often also a function of t h e dis tribution factor of the species and of the ratio of exchanger capacity to solution concentration. Chelating Resins. In a survey of structure and properties of ion exchange resins, K. W. Pepper and D . K. Hale, Chemical Research Laboratory, Teddington, called particular attention to potentialities of chelating resins. Resins containing functional groups possessing chelating or complexing properties should show greatly increased selec tivity, which need not necessarily b e obtained at the expense of a reduction in exchange rate, declared Pepper. H e called attention to a Norwegian synthesis of resins of this type. Picryl chloride reacts with nitrated and re duced polystyrene and the product is then nitrated. The resin behaved as a cation exchanger with an affinity for potassium several times greater than that shown by conventional cation ex changers, he continued. Resins with greater physical and chemical stability can be prepared from chloromethylated, crosslinked polysty rene, said Pepper. After amination with ammonia or a primary amine, the co polymer is treated with chloroacetic acid in slightly alkaline solution. R CH2C1 4- NH, -> R CH,> NH,C1 R OH, NH 2 + 2C1CH 2 C0 2 H -* R-CH r N(CH. 2 C0 2 H), -f 2ΗΓ1 An alternative method for prepara tion of this chelating resin has been worked out by S. L. S. Thomas at Teddington. The Thomas procedure in volves reaction of the chloromethylated copolymer with iminodiacetonitrile, fol lowed by hydrolysis of the product. 1898
These resins have a high affinity for copper, Pepper remarked. Cuprammonium
Waste
Recovery.
Ammoniacal "blue water" and "spin ning acid" from the cuprammonium process are now being treated in ion exchange columns. Previous practice involved recovery of copper by means of a chemical precipitation process. Now copper is absorbed from the cupric ammonium sulfate solution on ion ex changers a n d t h e exchanger regener ated with sulfuric acid in t h e form of waste "spinning acid," explained Franz Gerstner, Farbenfabriken Bayer. Bay er's Lewatit D N has proved to b e a suitable exchanger for this purpose, he said. It is a condensation product from phenol formaldehyde and bisulfite,
with anchored iom exchange active groups, he w e n t on to explain. Emphasizing irrtproved economics resulting from the u s e o f ion exchang ers, Gerstner said that while about two tons of calciusm sulfate and 2.5 tons of ferrous sulfate p e r tons of fiber produced, as well sts almost the entire free ammonia from the spinning solu tion, were previously discharged in the waste water, tttese chemicals have now almost completely disappeared, except for residual aanmcmia. At Bayer's Domiageri Works, the average concentration of copper in waste water is aboiat 5 milligrams per liter. A dilution of 1:10,000 is achieved, leading t o a concentration of only 0.5 ^ g . / l .
Molecular Rearrangement Full understanding of organic reaction mechanisms and molecular orientations not yet in sight LONDON.—Conclusive evidence to support precise reaction mechanisms and well defined molecular orientations is not easily obtained. This point be came crystal clear during lively discus sion following a symposium on Mo lecular Rearrangements in Organic Chemistry, held here recently. T h e symposium, viewed as a follow-up on an earlier program in Manchester on Dynamic Stereochemistry ( C&EN, April 19, p a g e 1582), was sponsored by the chemistry department of Queen Mary College. The role of acid catalysis in the con cept of anionotropy was emphasized by E. A. Braude, University of London. H e described a reinvestigation of the rearrangement of α-phenylallyl p-nitrobenzoate into cinnamyl p-nitrobenzoate in presence of isotopically labeled pnitrobenzoic acid in chlorobenzene solu tion. The reaction occurs by two dis tinct paths, said Braude. Both reactions are acid catalyzed, but one involves an internal rearrangement, and one a bimolecular reaction with the added acid. No free allylic cations are involved as intermediates, concluded Braude. It was his opinion that the bimolecular process was of the S n 2' type, and that free allyl cations are probably not in volved in anionotropy. Criticizing Braude's conclusions on t h e grounds that free ions could not in any case occur in the solvent used, UCLA's Saul Winstein declared that t h e work described was consistent with initial formation of an ion pair, which can either rearrange by "internal col lapse," or react with p-nitrobenzoic acid. Winstein's comment initiated a lively CHEMICAL
floor discussion on the distinction be tween ion pair mechaanisrns a n d mecha nisms involving cycdic transition states. Conclusion appeared t o be that ion pairs and covalently bound cyclic in termediates are no»! qualitatively dis tinct, b u t form extremes in a graded series. Reactions of allyl. alcohol derivatives with thionyl chlori.de w e r e described by another UCLA ρσ-ofessor, William G. Young. Under conditions where inter vention of chloride ion i s avoided, said Young, reactions rproceed with rear rangement via cyclic transition states. In the presence of chloride ion, an al ternative Sw2 reaction leads to unrearranged chloride. E i t h e r unrearranged chloride or rearranged chloride can be obtained by suitable choice of reaction conditions. An S„i reaction could also be observed in iomizing solvents, he concluded. Aromatic Systems, Difficulties in determining whether or not rearrange ments in aromatic systems are intra molecular were emrphasized b y M. J. S. Dewar, University of L o n d o n . If they are, he said, classioal mechanisms will not suffice, for rearr-angernents often oc cur between widelv separated centers. Dewar outlined! trie ττ-complex mechanism for such processes, and ap plied the idea to rearrangements of N-bromoacetanilide and of hydrazobenzenes. Citing n e w experimental evi dence, Dewar smggested that the N-bromoacetanilide reaction was intra molecular. The general classification of reactions in which groups migrate from side chain to nucleus in an a r o m a t i c system were outlined by E . D. Hughes, UniAND
ENGINEERING
NEWS
INTERNATIONAL versity of London. The main types of mechanism, h e said, were an intermolecular process of S a i or Sn2 type, a n d an intramolecular process, giving o-substituted aniline derivatives via cyclic transition states. As an example of his first type, H u g h e s referred to the rearrangement of N-phenylhydroxylamine and of N-nitranilines. T h e reaction of aniline with sulfur trioxide was cited as an ex ample of the second type of mechanism. H y d r o g e n Shifts. Investigations of 1:3 and 1:2 hydrogen shifts in carbonium ions w e r e described by Winstein. Referring to earlier work by Roberts and L e e , establishing the ex istence of 1:3 hydrogen shifts in the nonclassical norbornyl carbonium ion, h e reported t h a t the hydrogen shift does not accompany formation of the ion, but occurs in a subsequent step. Experiments at U C L A in the cyclohexane series have demonstrated the possibility of anchimeric assistance of ionization by adjacent hydrogen atoms. T h e ionization of appropriate cyclohexyl esters, said Winstein, occurs more rapidly than would be anticipated and with a 1:2 shift of hydrogen. U.S.S.R. Joins U N E S C O T h e Russians last week came to T h e H a g u e , w h e r e a meeting of U N E S C O was opening, a n d took the seat which has been open to them from the begin ning of the organization. Question u n d e r consideration by the body at T h e H a g u e is the preservation of historical monuments during time of warfare. Heretofore U.S.S.R. has spurned membership. Decision to join was m a d e last month in a letter from Molotov to U N E S C O Director General, Luther E v a n s , and last week Soviet Ambassador Malik signed t h e constitu tion of U N E S C O in the British Foreign Office. U.S.S.R. is asking that East Germany and Communist China be allowed to join U N E S C O . According to the London Times, hope is now revived that Poland, Czechoslovakia, and Hun gary, who resigned from U N E S C O in December 1952, may reconsider their decision. I C I Produces PTFE Fluon, which is brand name of polytetrafluoroethylene ( P T F E ) , is being manufactured by Imperial Chemical Industries' n e w London plant. Said to be the only completely fluorinated high polymer, it has a wide range of working temperature from —100° to 250° C , and in special circumstances, to 300° C. It also possesses extreme chemical inertness and solvent resist ance, good mechanical properties, firs,. V O L U M E
3 2,
NO.
19
>
»
class electrical properties, and u n i q u e low friction and nonstick characteristics. Properties allow its application i n the electrial industry for valve bases, crystal holders, parts of condensers and and other electrical components for use at high frequencies and high ambient temperatures, hermetic seals for con densers and transformers, insulation for motors and transformers, covered wire and cable, spacers and connectors, in sulating tapes, and sheets. Polymer is available as a granular white powder which can be fabricated by special techniques into a variety of forms—block and rod, extruded sleev ing and cables, film, and many others. Union C a r b i d e Buys G e m e c , L t d . Goodwill, undertaking, and assets of Gemec, Ltd., have been acquired by Union Carbide, Ltd., London, a n d will continue manufacture and supply of chemicals as Gemec Chemical Co., division of Union Carbide, Ltd. I t a l y Builds Furfural Plant Italians are building Europe's largest plant for production of furfural at Gioia Tauro in Calabria, a southern province. Enterprise is cooperatively o w n e d b y 140 olive growers, w h o expect to open the plant in July, with full-scale opera tions producing 6 metric tons a day. Half of total cost, estimated at $1,750,000, was covered by a public works loan repayable over 10 years from 1955 onwards. N e w plant is fully automatic. Raw material is "sansa," t h e residue left after complete extraction of the oil from
the olives, formerly burned as a fuel. In view of difficulties experienced b y other Italian furfural producers in meet ing U. S. competition in the export market, special care has been taken to ensure economical operation of the new plant. Special research station attached to t h e plant will work on development of new outlets. India Opens S a l t Research Institute Prime Minister Nehru opened the Central Salt Research Institute at Bhavanagar, Western India, last month, the twelfth in the chain of national research laboratories. Nehru said it was in t h e fitness of things that salt, which was the cause of all revolutions in the world, should be chosen for research. Mata Prasad, director of the institute, announced that it would conduct in vestigations on recovery of chemical from bitterns obtained both from sea and lake brines as well as on their utilization in manufacture of other im portant substances. Work will b e car ried out in divisions of inorganic and physical chemistry and of chemical engineering. Germans Bid f o r Mexico T r a d e W e s t German T r a d e Fair recently staged in Mexico City sold more than $12 million worth of exhibits and re portedly contracted more than $100 million in future sales. Because of longterm credit offered by E u r o p e a n s , United States manufacturers are wit nessing the loss of substantial a m o u n t of business to them. Serious discussion
H o w Things G o in t h e N e t h e r W o r l d
An anhydrite mine in Billingham, England, has a canteen 800 feet under ground for the men who toil in the underground workshops and service the mine vehicles and equip ment. Meals are served in the canteen, and all who work in the mine gather there to see films on safety and other subjects. Room is about 18 χ 24 feet and is located on a gallery whose openings have been bricked up. Most of the walls are left rough-hewn. The room is on two levels. On the lower level the men wash things used for a meal at sinks along one wall. The end wall holds a cinema screen. Lighting is through two rows of louvres in a false ceiling in the roof MAY
10,
1954
1899
INTERNATIONAL is going o n of the n e e d for long-term credit protection of U. S. exports. W h i l e t h e Germans w e r e reportedly q u o t i n g p u r c h a s e terms of one to three and e v e n four years, most U. S. m a n u facturers selling in M e x i c o d e m a n d pay m e n t within 3 0 to 6 0 days for lack of any long-term financing facilities. O n e year is virtually the outside limit offered by U . S. exporters, and it is rare. Likelv o u t c o m e will be r e n e w e d pressure o n the U. S. Export-Import Bank to loosen up on credits to finance longer term p a y m e n t s abroad for U. S. goods.
Sweden Expands Fertilizer Industry Ljuiigaverk chemical works of Stock holm's Superfosfat Fabriks, S w e d e n , is b e i n g e x p a n d e d . Existing plant for pro duction of synthetic a m m o n i a by Fauser process and for manufacture of urea is to be substantially extended; output capacity for a m m o n i u m nitrate will b e d o u b l e d and that of urea resins i n creased by 5 0 ' f. In line with the country's p o s t w a r policy to d e v e l o p further the fertilizer industry, superphosphate requirements
of over 5 0 0 , 0 0 0 tons are n o w met in full by i n d i g e n o u s producers. Of t h e n i t r o g e n consumption of about 8 5 , 0 0 0 t o n s a year, only a third is being sup p l i e d b y domestic producers, most of t h e rest c o m i n g from N o r w a y and Chile. S w e d e n also possesses a small syn t h e t i c a m m o n i a plant of Koping which w a s erected by the cooperative societies d u r i n g the war. Small-scale production of a m m o n i u m sulfate from by-product a m m o n i a at the s t a t e - o w n e d oil shale w o r k s at Kvarntorp has m a d e a useful contribution to t h e country's fertilizer suprjly, and plans h a v e b e e n drawn for erection at the same p l a c e of a large unit for production of 2 0 , 0 0 0 tons ( X ) a year. S w e d i s h policy is to p r o d u c e suffi c i e n t foodstuffs within t h e country to f e e d her population; therefore d e m a n d for c h e m i c a l fertilizers will increase steadily, probably necessitating further a d d i t i o n s to productive capacity.
Uranium Plant in India Uranium-thorium plant at T r o m b a y , India, is e x p e c t e d to b e g i n producing l a t e this year. It will process residual c a k e left over from m o n a z i t e after ex traction of rare earth and phosphate. S o m e of the thorium thus obtained will b e turned into nitrate for u s e in the in d i g e n o u s gas mantle industry and the rest will b e retained by the Indian A t o m i c Energy C o m m i s s i o n . Uranium w i l l b e purified for use in a reactor, w h i c h India h o p e s to h a v e in about t w o years. Commission is also setting u p a plant to process uranium to a s t a t e of atomic purity.
Stauffer has been supplying chemicals to the rubber industry, since the early days of vulcanization. With an expected produc tion of over 1 5 0 0 thousand long tons for the next year, this industry depends o n Stauffer for the heavy chemicals important to rubber processing and manufacturing. Stauffer has Carbon Disulphide, for cold vulcanization and manufacture of rubber Stauffer
accelerators, Sulphurs and Crystex Insolu ble Sulphur, for all types of vulcanizing, Caustic Soda, Chlorine, Sulphur Chlorides, and Acids» For processing chemicals, Stauffer as sures its users of continuous supplies. Since 1 8 8 5 Stauffer has been furnishing industry with dependable products and
Products:
Aluminum Sulphate* Borax Boric Acid Boron Trichloride Carbon Disulphide Carbon Tetrachloride Caustic Soda Chlorine Citric Acid Copperas* Cream of Tartar
Ferric Sulphate* Fire Extinguisher Fluid Insecticides and Fungicides Muriatic Acid* Nitric Acid* Perchlorethylene Potassium Nitrate Rochelle Salt Silicon Tetrachloride
Sodium Hydrosulphide Sodium Silico Fluoride* Sodium Sulphate* Sulphur (processed) for all uses Sulphur-Rubber maker s Su Iphur-lnsolu ble (in CSg) (specialpurpose rubbermaking)
Sulphur Chlorides Sulphuric Acid Superphosphate * Tartar Emetic Tartaric Acid Titanium Tetrachloride Titanium Trichloride Solution "Zol" Dry Cleaning Fluid* (•West Coast Only)
STAUFFER CHEMICAL COMPANY 3 8 0 Madison Avenue, N e w York 17, Ν. Υ . 221 N . La Salle Street, Chicago 1 , III. · 3 2 6 So. M a i n Street, Akron 8, Ohio · 824 Wilshlre Boulevard, Los Angeles 14, Calif. · 636 California Street, San Francisco 8 , Calif. · North Portland, Oregon · P. O . Box 7 2 2 2 , Houston 8, Texas · Weslaco, Texas · Apopka, Florida
1900
C H E M I C A L
N e w Zealand Company to Produce Oil f r o m C o a l Projects are p l a n n e d i n Southland, N e w Zealand, for production of oil f u e l s a n d by-products from coal. Capi tal investment for d e v e l o p m e n t of a d e e p coal mine is estimated at over $ 1 8 million, that for the projected 5 0 0 0 barrel-per-dav oil refinerv, about $ 3 3 , 6 0 0 , 0 0 0 . ' Plans call for production of gasoline. Diesel oil, solvents, jet f u e l , a n d w a x e s . Initial o u t p u t w o u l d c o v e r a b o u t a third of the country's r e q u i r e m e n t s . Sol D e v e l o p m e n t Co., L t d . , is negotiating w i t h overseas engi n e e r i n g contractors w i l l i n g to prepare t h e necessary d e t a i l e d technical data, s u r v e y s , and reports.
C&EN Foreign Correspondents Con tributing to This Issue: G. ABRAHAMSON, Italy, Sweden A. P. S O M , BHtain, India, New Zea land A N D
ENGINEERING
NEWS
