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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
I k g . of pulverized N a O H . W h e n t h i s h a s been well s t i r r e d i n , a d d s h r e d d e d asbestos g r a d u a l l y , cont i n u i n g t h e s t i r r i n g u n t i l t h e m i x t u r e n o longer a p p e a r s c a p a b l e of w e t t i n g more asbestos. T h e whole mass is t h e n h e a t e d i n a n air b a t h at 150 t o 180’ for 4 hrs. D u r i n g t h e early p a r t of t h e h e a t i n g , a d d i t i o n a l q u a n tities of asbestos a r e a d d e d f r o m t i m e t o t i m e u n t i l i t p r e s e n t s t h e s a m e a p p e a r a n c e a s before h e a t i n g . After cooling, i t is g r o u n d i n a coffee mill u n t i l m o s t of i t passes a Io-mesh sieve. A t u b e filled with t h i s a b s o r b e n t t a k e s u p 8 t o I O g. of c a r b o n dioxide, corresponding t o 160 t o 2 4 0 c a r b o n d e t e r m i n a t i o n s , using t h e full f a c t o r weight o n a steel c o n t a i n i n g 0 . 5 p e r c e n t c a r b o n . RESEARCH LABORATORY, MIDVALESTEELCOMPANY PHILADELPHIA
LABORATORY TABLE TOPS AGAIN By HILTON IRAJONES Received August 17, 1916
I039
boiling h o t . Moreover, i t is so poor a c o n d u c t o r of h e a t t h a t e v e n t h i c k glass c o n t a i n i n g h o t liquids m a y b e s e t u p o n i t w i t h o u t b r e a k i n g . T h i s does a w a y with t h e use of s u b e r i t e m a t s s u c h as a r e required o n s t o n e , tile or glass t o p s . T h e asbestos s l a t e t o p h a s everyt h i n g t o c o m m e n d i t , a n d a f t e r four years of use I h a v e y e t t o discover a single f a u l t . DAXOTA WESLEYAN UNIVERSITY MITCHELL, SOUTHDAKOTA
A SIMPLE MERCURY SEALED ETHER STILL By 0 . C SMITH A N D D. G. M O R G A N Received June 27, 1916
T h e h e a t e r H was c o n s t r u c t e d f r o m a s h e e t of galvanized i r o n a n d a n electric light socket f i t t e d i n t o t h e b o t t o m . T h e corks which a r e i n s e r t e d i n t o t h e necks of t h e flasks a t D a n d E s h o u l d be close-grained a n d fit t i g h t l y so as t o hold t h e m e r c u r y a t F a n d G. I t is n o t difficult t o m a k e a m e r c u r y - t i g h t fit if c a r e is used i n selecting t h e corks a n d t h e y a r e c o a t e d with a little vaseline before inserting. Before using, t h e flasks
M u c h h a s been w r i t t e n a b o u t various s o r t s of l a b o r a t o r y t a b l e tops-wood, alberene a n d tile a d v o c a t e s h a v e all h a d t h e i r s a y . I n t h e p a s t t w e n t y y e a r s I h a v e worked a n d condlucted classes o n e v e r y s o r t of top-glass, tile, Cement, s l a t e , alberene s t o n e a n d wood. W h e n I c a m e t o D a k o t a Wesleyan I f o u n d a n e w one. F i v e y e a r s ago D r . Sterling T e m p l e , n o w of t h e Univ e r s i t y of M i n n e s o t a , installed t h e t a b l e s here. T h e t o p s a r e o r d i n a r y soft pine flooring o n which is l a i d t w o s h e e t s of t a r p a p e r , a n d t h i s is covered w i t h l a r g e s h e e t s of asbestos slate, t w o t o a t a b l e . I t is onee i g h t h i n c h i n thickness. T h e asbestos s l a t e is screwed o n , t h e holes being c o u n t e r - s u n k a n d filled a b o v e t h e screw h e a d w i t h asbestos c e m e n t . T h e t a b l e s e v e r y y e a r h a v e been t r e a t e d with a gasoline s o l u t i o n of paraffin c o n c e n t r a t e d enough so t h a t i t would s e t t o a jelly consistency when cold. T h i s s o l u t i o n is b r u s h e d on h o t . W e h a v e f o u n d t h i s m e t h o d of paraffining m u c h b e t t e r a n d quicker t h a n t h e old ironing in p r o cess. T h i s paraffin t r e a t m e n t h a s given t h e t o p s a polished a p p e a r a n c e b u t is really u n n e c e s s a r y a n d a d d s n o t h i n g t o t h e i r i m m e d i a t e serviceability o r life. T h i s asbestos t o p is so m u c h b e t t e r t h a n a n y o t h e r t o p I h a v e ever seen t h a t I a m s u r e i t would be e x t e n sively used if i t s a d v a n t a g e s were more widely u n d e r s t o o d . It h a s low first cost, long life, a n d a n y one c a n u p u t i t on. I feel c e r t a i n o u r t a b l e t o p s will be i n good s h o u l d b e washed with e t h e r t o r e m o v e t h e excess s h a p e t w e n t y y e a r s hence. T h e y a r e fully now as . as good vaseline. T h e glass t u b e s A , B , C are a b o u t j , 5, I O when first installed. T h e asbestos t o p w i t h t h e tar--.mm,, respectively, in d i a m e t e r . T h e reflux c o n d e n s e r p a p e r b e n e a t h i t h a s elasticity, a n d 1 find t h e r e is I prevents t h e escape of ether, e v e n less glassware b r o k e n o n i t t h a n o n a wooden To r ~ m c v et h e e t h e r f r o m t h e receiving flask J lift top. A1berene stone is Objectionable f o r u p t h e condenser I a n d i n s e r t a small s i p h o n t h r o u g h A , beginners for t h i s reason. T h e asbestos s l a t e t o p is OgLAHoMA AGRICULTURAL EXPERIMENT STATIoli e n t i r e l y unaffected b y acid or alkali e v e n t h o u g h STTLLWATER
i ADDRESSES A CENSUS OF THE ARTIFICIAL DYESTUFFS USED IN THE UNITED STATES‘ By THOMAS H. NORTON
The necessity for a complete enumeration of the artificial coloring matters, regularly consumed by the various manufac1 Address delivered before the American Chemical Society, a t the New York Meeting, during the Symposium on “ ~ Dyestuff ~ M ~~ facture.”
turing industries of this country soon became evident when these branches were threatened in 1914by a dyestuff famine, as a result of the great European war. Those who took into careful consideration the possibility of creating an independent American coal-tar dyestuff industry were obliged to study closely a number of factors bearing upon this ~ ~~ exceedingly i complicated ~ ~ question. ~ -4mong these were such items as the supply of crude materials, the chemists and
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chemical engineers available, the probable attitude of the European interests, hitherto furnishing our synthetic dyes, upon the return of normal international conditions, the requisite fiscal and other legislation essential t o safeguard American enterprise and capital against unfair competition on the part of such foreign rivals, etc. First arid foremost, however, came the factor of quantity. What is the total annual consumption of artificial colors in the United States? How many different dyes are in current use? What is the average annual consumption of each ol these dyes? The necessity of exact information on these three points is self-evident to some. For most, a brief explanation may be helpful. In a general way we know how the great dyestuff industries of Germany and Switzerland are organized. We understand the relations of capital, of technical staff, etc., to output. From an economic standpoint it is necessary to know the total extent of the American market for this class of products, in order to estimate approximately the amount of capital required for a comprehensive industry, the number of trained chemists and engineers needed, and the quantities of coal-tar crudes to be provided. Thew form the main links in the chain connecting the gas works and the coke plant yielding coal tar and the gases laden with benzene and its homologues, with the multitude of mills and shops in which synthetic colors are employed to produce chromatic effects upon textiles, wares of the most varied nature-paper, leather, wood, ink, varnish, fur, feathers, Foods, beverages, etc. While such leading data are of prime importance from a general economic standpoint, of still greatcr ralue are the details concerning the specific products of the synthetic color industry. KECESSITY OF A CENSUS OF DYES
There are nearly I ,000 coal-tar dyestuffs of recognized standing in the tinctorial world; i. e., their chemical composition, or a t least the methods of preparation, are publicly known. About twice as many are regularly manufactured, and enter into international trade, regarding the preparation or the composition of which little or nothing has been published. Many colors of both categories are encountered comniercially in the form of several marks or brands. These rcpresent slight modifications of the primary dye, sometimes in regard t o shade, often in regard to convenience of application. The form in which a dye is prepared for use on cotton may not be the best form for the needs of the silk dyer. The requirements of the feather dyer may be quite different from those of the manufacturer of ink. It is essential that the organizers of a national color industry know, with a certain approximation t o accuracy, how much annually is consumed of each primary dye, and how much of each minor modiiication is employed. Without such data a manufacturer cannot calculate the size and number of the units to be constructed for the production of any given dye, and he is a t an equal loss as to the equipment necessary to manufacture it in the different modifications of current use. Again, the industry is one of great complexity, involving a high degree of coordination and of careful planning to avoid material loss in the way of byproducts. I n the various steps intervening between
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T H E JOURATAL O F I N D U S T R I A L A N D E*VGIiVEERING C H E M I S T R Y
a coal-tar “crude” and a finished dyestuff, each chemical reaction in the sequence is a p t to produce certain percentages of closely allied compounds, isomeric substances as a rule. These latter may possess the same general chemical composition as the product more directly sought. The arrangement o€ the atoms in the molecule is, however, quite different. As a result, physical and chemical properties are totally unlike those characterizing the main substances. Such by-products possess, as a rule, distinct technical and commercial value. One may serve to make an entirely different dyestuff, another may be the raw material for manufacturing a valued medicinal; a third may be employed i n the production of a photographic developer, etc. I t is evident, therefore, that the establishment of a synthetic color industry means an elaborate study of a multitude of interrelated operations, allied furthermore with ntimerous products in a group of closely connected industries, based likewise upon the use of coal-tar crudes. To some extent the changing whims of fashion enter into play. Back of every plan and calculation stands, however, the dominant factor of quantity. I t is now generally recognized that any intelligent effort to build up a comprehensive, self-contained, American coal-tar chemical industry must rest upon the solid foundations of accurate statistical data concerning the American market for artificial colors. In no other way can the creators of such an industry avoid duplication, overlapping, waste, and blundering, tentative struggles to adjust productive mechanism to a vague. indefinite demand. With0u.t such fundamental data the future industry will be heavily handicapped by permanent overhead charges, accumulated as the result of being forced to feel its way in the dark, chemically, mechanically, and commercially. If the coming American Idyestuff industry is to hold its own successfully against foreign competition, it must be free from any unnecessary shackle. It miist start into existence during these years of crimson-splashed struggle for Europe-of golden opportunity for this Republic-at the point where a brusque order to halt has been given the giant factories on the Rhine, the Main, and the Spree. It must utilize to the full all the gathered stores of experience accumulated during the six decades since Perkin’s epochal discovery, and become a world factor in the seventh period of the histor:y of synthetic color, a t whose portal we now stand. To no one is this country more indebted than t o Dr. Bernhard C. Hesse, of New York, for a clear, forcible presentation of the complexity of the synthetic idyestuff industry and of the pressing necessity of accurate data on the domestic consumption of artificial colors. Attention should be directed to his briefer OF INDUSTRIAL AND studies on the subject in the JOURNAL ENGISEERING CHEMISTRY, and t o his more exhaustive paper read before the A’ational Association of Cotton Manufacturers, in April, 1915, and publizihed in the Textile Manzifucturers’ Journal, May I , 1915, p. 60. ACTION O F THE BUREAC OF FOREIGN AND DOMEST1,C COMMERCE
Early in 1915 the embargo came into force, shutting off German dyes from this country. Long before, the relatively small supply of colors from England, France, Belgium and Holland had practically ceased and the somewhat more important source in Switzerland was threatened with paralysis. The Bureau of Foreign and Domestic Commerce in Washington was following with the keenest interest, and even with anxiety, the initial steps taken bravely and resolutely by a small band of far-sighted American men, some mahufacturers, some capitalists-all patriots-convinced that finally the opportunity had arrived to build up a genuinely national coal-tar chemical industry. In the earnest desire to second their efforts and facilitate their plans, as well as to insure the most favorable and economical
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conditions for the rapid evolution of the new industry on a permanent basis, it was promptly recognized, in harmony with the reasoning detailed above, that nothing could be of such direct assistance as a “census” of the dyestuffs consumed normally in this country. Plans were carefully laid to carry out the work as expeditiously, accurately, and fully as the very limited appropriations a t the command of the Bureau for such general purposes would permit. HOW THE CENSUS WAS TAKEN
First of all it was necessary to decide upon the modus operandi. It was suggested by some, who had early recognized the desirability of such a “census,” that the only available method for securing the needed data was to appeal to all consumers of artificial colors for their cooperation. It was thought that a ready response would be given to circular requests €or detailed information regarding the annual consumption of coal-tar dyes by each user of the same. It was proposed, in order to overcome the customary repugnance of manufacturers to communicate facts of this nature, that the replies should be sent to some central financial institution, which would guarantee secrecy in collating the numerical information thus gathered. A careful analysis of the problem showed that any such method of collecting data was impracticable. I t would be impossible to secure a complete list of all users of dyestuffs in scores of trades and manufacturing branches. Assuming that figures could be obtained from all users of colors, their compilation would be a herculean task. Suppose that 5 tons of Congo Red are consumed annually in this country. This amount might be divided up among several thousand consumers, in lots ranging from 5 to IOO pounds. With a somewhat elementary knowledge of human psychology, it was furthermore certain that no replies could be expected from the great majority of the recipients of circular requests. Indifference, suspicion, or pure laziness are serious factors to overcome. BRITISH ATTEMPT TO TAKE A CENSUS OF COLORS
The correctness of this conclusion has recently been abundantly verified by trans-Atlantic experience. British textile and allied interests have been forced to deal with a far more serious “dyestuff famine” than has been the case in the United States. There was a similar determination to build up a genuinely national color industry. The necessity of a dyestuff “census” was likewise recognized as of paramount importance. An influential committee, representing makers and consumers of dyes, took the matter in hand. Appreciating the futility of dealing directly with the multitude of individual users of colors, the committee decided to collect its statistics through the various powerful organizations of trades employing large quantities of dyestuffs and then double the results, thus roughly approximating a t the entire national consumption of the various colors. After months of labor the committee was forced, in h’ovember, 191j , to report a practical fiasco. Replies were secured from but 19 associations or large individual consumers. The figures obtained covered but 3,145 short tons, perhaps I Z per cent of the national consumption. FEATURES AND VALCE O F THE CENSUS
The method adopted by the Bureau of Foreign and Domestic Commerce was much more simple, direct and accurate. As in the case of Great Britain, nearly nine-tenths -of the normal American consumption is derived from European sources. It was decided to use the data based upon the imports of artificial colors into this country during the I Z months ending June 30, 1914-a month before the outbreak of the present war. The remaining tenth is covered by the returns of the Bureau of the Census for the domestic coal-tar dyestuff industry based upon the production of the calendar year 1914. No serious
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SUMMARI’ O F THE MOST I M F O R T A K T COLORS I M P O R T E D B Y U . S. D U R I X G F I S C A L Y E A R 1913-14 T h e abbreviation V.11.denotes “vaf.ious marks ” T h e serial numbers employed correspond t o those found in Schultz’s “Farbstcifftabellen” (edition oi 1914) . S u m b e t s precedrd bj- letters 1-eler to colors regarding the manufacture and chemical composition oi which little or nothiing is known . Azo dyes in this category are indicated by A sulfur colors by S and other dyestuffs of unknown composition by C . Invoice Class I (lo.000 to 100.000 Ibs.) Serial COXXERCIIL Invoice Serial COMMERCIAL T,,~.&~,= s o. PiAME Lhs . Value S o. NAX?? Lbs . Value Serial CO~~A~~RCIAL Value 275c Chrome Fast Black A176 Benzo F a s t Heliotrope NO . ?XAME Lbs . ( V . M . ) . . . . . . . . . . . . 13. 018 8 1541 ( V . R Z . ) . . . . . . . . . . . . 35. 999 $ 10. 532 Nitroso and Nitro Colors A184 Benzo Green (V.M ) 16.506 2. 850 Anthracene Scid 2i7 4 A-aphthol Green . . . . . . 19. 146 8 2. 902 Black . . . . . . . . . . . . . 17.793 4. 715 A191 Benzo Red 10 B, 12 I3 19.420 2. 647 A203 Benzo Rhodiiline Red 279 Benzo Fast Scarlet . . 36. 674 9. 010 Stilbene Colors B, 3 B . . . . . . . . . . . . 11.873 1.813 Bismarck Brown . . . . . 27. 576 5.352 11.295 9 Direct Yellow . . . . . . . . . 71. 399 A210 Brilliant F a s t Blue Palatine C h r o m e 9a Xaphthamine Yellow ( V . M . ) . . . . . . . . . . . . 11.553 3.309 Black . . . . . . . . . . . . 18.985 1. 607 6.7.18 (\‘.&I.). . . . . . . . . . . . 42. I80 A215 C a s h m e r e B l a c k Cotton Yellow . . . . . . . 21.437 6. 161 16.784 79.055 9b Direct Yellow (V.ii1.) 1.881 3 B N . V . . . . . . . . . . 12.269 Renal Brilliant Yellow 12.786 3.290 2. 766 9g Direct Yellow B . . . . . . 29. 123 A227 Diazo Brilliant Scarlet Congo . . . . . . . . . . . . . . 12.040 1. 687 7.464 10 Stilbene Yellow . . . . . . . 50.477 ( V . M . ) , . . . . . . . . . . . 38. 909 14.210 Diazo B l a c k . , . . . . . . . 62. 854 8. 257 6.305 10a Stilbene Y ~ l l o wR X . . 34. 588 A242 Diazo F a s t Black (V. Congo Corinth . . . . . . . 39. 748 6.030 5.914 11 Chloramine Orangc . . . 24. 688 hi.) . . . . . . . . . . . . . . 29.330 7.476 Congo Rubine . . . . . . . 46. 113 6.329 13a Diphenyl Orange G G 13.646 3.938 319 Diamine Scarlet . . . . . . 28. 88: A259 Direct Black (V.M.). 12.048 2.019 9. 027 3.071 14 Diphenyl Chrysoine . . 9. 898 14.703 793 A266 Helio Bordeaux B L . . Oxv Diamine Violet. 11. 514 1. 938 2.988 18 Diphenyl Fast Yellow 9. 656 2.246 A277 Orange R O . . . . . . . . . . 24.288 Be&o Vi0iet.R . . . . . 12.467 1.552 Phenylamine B 1 a c k A285 Diamine Violet K.. . . 327 13.107 2. 840 Pyrazolone Colors 1.619 4 B . . . . . . . . . . . . . . 14.066 333d Develop Black.. . . . . . 17.495 4. 333 6. 034 A286 Pluto Black (V.M.). . 30.010 10.272 334 Diphenyl Blue Black 19 Fast Light Yellow .... 33.514 26.240 4.415 14.580 2.542 A292 Pluto Brown (V.31.). 4. 927 335 h-aphthamine Black . 47.969 19.000 20 Flavazine S . . . . . . . . . . 7. 132 A303 Alphanol Black (V 20a Flavazine (V.hl.). . . . . 62. 375 10.700 337 Befizo Blue., . . . . . . 19.035 7x9 M .) . . . . . . . . . . . . . . . 30. 189 3. 124 9. 750 338 h’aphthamine Blue 22 Xylene Yellow., . . . . . 23.074 11.707 2.455 . A336 A z o Wool Violet 343 Diamine Fast Red . 47.724 17.131 Azo Colors n1.). . . . . . . . . . . . . . . 12.944 3.298 344 Diamine Brown . . . . . . 63. 716 12.457 A346 Diamine Catechine (V . 8. 585 346 Oxamine Red . . . . . . . . 11.636 2.568 33 Chrysoidine . . . . . . . . . 63. 303 14.942 M.) . . . . . . . . . . . . . . . 66. 876 11.366 1.535 348 Diphenyl Brown B N . 13.471 4.015 37 Croceine Orange . . . . . A351 Diamine Fast Blue 7. 159 358 Diphenyl R e d . , . . . . . . 12.808 5.001 38 Orange G . . . . . . . . . . . 48.456 7. 227 V . M . ) . . . . . . . . . . . . . 28. 880 31.674 2. 337 360 Pyramine Orange R . . 21. 329 7. 818 45 Brilliant Lake Red R A355 Diamine Fast Orange 5 .379 362 Oxydiamine Orange . . 19.905 4. 223 56 Auto1 R e d . , . . . . . . . . . 49.847 4. 819 (v.nf,),. . . . . . . . . . . 17.387 4. 112 365 Benzopurpurine (V . 58 Mordant Yellow. . . . . 26. 570 A361 Diamine Jet Black (V . >I.) . . . . . . . . . . . . . . . 2i.ocm 1.442 58, Alizarin Yellorv (I7. 4. 315 M . ) , . . . . . . . . . . . . . . 14.091 M . ) . . . . . . . . . . . . . . . 59.000 7.676 366 Deltapurpurine 5 B . . 20. 284 3. 646 6.204 A362 Diamine Neron BB . . 36. 982 19.133 3. 133 2.634 370 Brilliant Congo . . . . . . 58 Orange 1 3 14 . . . . . . . . i n .974 A367 Diamine Orange (V . 21. 725 3.687 10.998 384a Diamine Blue (V.31.) 61 Victoria Violet., . . . . . 47. 126 17. 068 2.851 ni.) . . . . . . . . . . . . . . . 44. 258 Toluylene Orange . . . . Azo Acid Blue . . . . . . . 8. 544 392 55. 562 13. 236 63 7. 574 A368 Diamine Sky Blue FF 41. 115 5 . 174 9. 375 400 Acid Anthracene Red . 17.560 64 Lanafuchsize . . . . . . . . . 68.055 Oxy Diamine Brown 25. 970 405 A384 36. 000 Benzopurpnrine 10 B . 27. 708 11. 181 Amido Naphthol Red 66a 3.810 (V.lM.). . . . . . . . . . . . 23. 498 8.835 410 Benzazurine (V.M.), . ( 8 .699 21. 018 70 Brilliant Orange 0 . . . . 21.480 A385 Oxy Diamine Carbon 2. 141 416 Brilliant Azurine 5 G . 18.396 3. 206 73 Helio F a s t Red . . . . . . 13.413 7.864 (V.M.), . . . . . . . . . . . 34.388 36. 295 9.287 418 D i a m i n e Brilliant 73a Litho1 F a s t Scarlet . . . A388 Para Diamine Black 6. 293 39. 888 Blue G . , . . . . . . . . . . 11. 592 2. 496 w o o l Scarlet ( V . M . ) . 80a 2. 690 ( V , M . ) , . . . . . . . . . . . 18.634 1.931 419 Chicago Blue R W . , . 15.176 3. 364 82a Ponceau (V.M.) . . . . . . 20. 972 16.224 8.449 A403 Salicine Blue B . . . . . . 2.436 421 Oxamine Blue B . . . . . 14.091 88a Acid .4 n t h r a c e n e Naphthol A414 A in i d o 30. 555 3. 749 Brown (V.hI.1. . . . . 7.932 421a Oxamine Blue (V.11.) 21. 800 10. 760 1.219 4 B. R K . , . . Black 15. 165 Benzaniine Pure Blue 12. 881 5. 663 056 426 3. 96a Chrome Fast Yellow . A418 Azo Acid Black (V . 23. 080 5.366 4. 226 428a Direct Blue (V.M.) . . 21.322 102 Diamond Flavine G . . 19. 500 3. 042 M . ) . . . . . . . . . . . . . . . 10. 383 Trisulfon Brown . . . . . 16. 781 5. 255 Bordeaux B . . . . . . . . . 1. 474 449 112 A430 F a g Mordant Blue B. 1.291 456 Benzo Fast B l u e . , . . . 73. 936 20. 607 112a Claret Red . . . . . . . . . 14.338 17. 000 4. 612 K . . . . . . . . . . . . . . . . 18. 917 Benzo F a s t Blue (V . Geranine . . . . . . . . . 6. 090 456, 118 A437 Najhthalene Blue B, 2. 116 15.353 31.).. . . . . . . . . . . . . . 26. 559 8.439 126a Union Blue (V.M.). . . 28. 000 5. 102 I> I , . . . . . . . . . . . . . . . 40. 345 Direct Deep Black 2. 019 462 Lake Ked P . . . . . . . . 132 A439 \Tictoria S c a r 1e t R , 6.313 5.032 E .\v . . . . . . . . . . . . . 32.830 137 Acid Yellow . . . . . . . . 35.982 22. 400 2. 379 . . . . . . . . . . . . . . 3 R 11. 238 91. 485 22.206 Cotton Black (T’.Ri.). 1. 966 462c Orange I?. . . . . . . . . . . 139 5.091 4444 Direct Green (V.11.). 31. 194 9.044 6.257 462d Union Black ( V . h l . ) .. 61. 218 140 Carcumeine . . . . . . . . . . 39. 269 A451 H e l i g o 1 a n d Black 13.756 469 Chloramine Black . . . . 20.095 5 .278 141 Azo Yellow . . . . . . . . . 59.894 25. 132 4. 151 FFN ............. 20. 114 3. 151 469a Chloramine Black (V. 141a Azo Flavine (V.31.).. A469 Oxyrhronie Brown (V. 2.392 3. 951 10 537 &I.) . . . . . . . . . . . . . . 19.505 141b Indian Yellow ( V . B f . ) i n . 490 2. 235 11.). .............. 2. 585 474 Oxamine Green B . . . . 23. 932 5. 134 146 Azo Fuchsine G . . . . . . 17.819 A472 Oxychrome Yellow (1’. 13.206 1.867 474a Diamine Green (V . 147 Azo Fuchsine 6 B . . . 1.985 M.) . . . . . . . . . . . . . 10.085 7. 395 k1.J . . . . . . . . . . . . . . . 53. 268 8.318 90. 174 151a Orange R 0 . . . . . . . . . i n . 148 1.580 A478 Triazol Blue (V.M.) . . 14.513 476a Benzamine Brown 3 152 permanent Red 4 B . . 44.850 17. 067 2. 854 A485 Triazol Brown (V.M.) G . . . . . . . . . . . . . . . 16.988 2.470 152a Permanent Red (V. Triazol Dark Blue (U . A489 56. 545 7. 403 477a S a p h t h a m i n e Brown 11.). . . . . . . . . . . . 19. 489 2. 647 1U.j . . . . . . . . . . . . . . . 9. 452 (V.M.). . . . . . . . . . . 48. 734 154 P a l a t i n e C h r o m e A515 Brilliant Scarlet 2 R. 4.674 478 Columhia Green . . . . . . 24. 749 4. 723 Brown. . . . . . . . . . . . 18.204 1.425 4 R . . . . . . . . . . . . . . . 12.565 19.313 4. 291 47% Direct Green (V.M.) . 159a Vigoureux Fast Black Chrome A524 Anthraryl 41.905 7. 125 3. 522 485a Benzo Brown ( Y R I . ) . 1 . . . . . . . . . . . . . . . . 16.000 24. 979 6. 385 Blue 2 B. D . , . . . . . 5.207 6.200 490a Cotton Brown (V.M.) 23. 975 160 Fast Brown S . ,. . . . . 67. 531 A527 Croceine Scarlet M O . 5 .465 46.359 161 lors 12. 210 2. 235 Unclassified Azo Col M O O . , . . . . . . . . . . . 2. 427 17.107 163a 15.501 3 .023 AR31 Acid Blue Black . . . . . . 53.404 A 6 Chrome Fast Black 19.874 163b Chrome Blue ( V . M . ) . 12.952 4. 365 Chrome Blue . . . 3.800 (v.nZ). . . . . . . . . . . . 76.451 i n . 172 A532 Acid 164a Diamond Blue R . . . . . 20. 117 14. 050 7.068 Acid Fast Green 8 B . . A533 Columbia Brown (V . 73. 973 9. 420 -4 12 168 Amaranth . . . . . . . . . A541 Diazogene Black (V. 2. 285 3. 073 M .) . . . . . . . . . . . . . . . 20. 793 11.497 168b \Vool Red ( V . M I . , . . 30.042 6. 813 M . ) . . . . . . . . . . . . . . . Columbia F a s t Blue 29. 981 Cochineal R e d . , . . . . . 3 . 669 . 4 16 169 2 .804 A550 Direct Black ABC. C 15.245 18.879 (V.11.). . . . . . . . . . . . 84.661 5.029 . 67.515 173a Litho1 Red (V.13.). 12.178 2.665 Direct Chrome Brown A552 h-aphthogene Blue (V . 85. 003 11. 280 A 28 Mordant Yellow . . . . 177 4. 425 A556 Drazaline Blue (\’.MI 10.831 6. 824 61.). . . . . . . . . . . . . . . 33.847 3.011 16.050 177a Anthracene Y e l l o w . . A566 Draialine Brown (1’. 9. 751 3. 536 A 32 ?-erol ( K n r . ) . . . . . . . . 65. 441 177b Salicine Yellow . . . . . . 23.068 21. 756 4. 979 M . ) . . . . . . . . . . . . . . . 8.376 A 44 Colamine Blue B . . . . 21.704 180 Erichrome Blue Black A593 Drazaline Sky Blue 10.033 1.870 8.485 A 69 Corvan Black (V.M.) B C . . . . . . . . . . . . . . . 43. 880 10. 940 5. 204 FF . . . . . . . . . . . . . . . 4. 843 10.606 A 71 Cotton Black ( V . M . ) , 24. 505 181 Salicine Black C . . . . . 65. 658 16.690 A600 Excelsior Black . . . . . . 59.956 36. 641 4. 381 13.530 A 81 Litho1 Fast Orange R 96.570 184 Eriochrome Black A IO. 981 1. 629 Hydrazol B l a c k . , . . . . A603 10.472 A 88 Oxamine Black (V.M.) 50.032 Chrome 185 Anthracene Chrome A605 Hydrazol 7. 869 A 95 Oxamine Brown (V. Black . . . . . . . . . . . . . . 51.577 7.499 Black CB. D B . . . . . 51.694 22. 569 11.372 A I . ) , . . . . . . . . . . . . . 93. 454 1 5 .038 188 Sulfone Acid Blue R 13.195 2. 420 A612 Chicago Red 111 . . . . . 35. 112 8.813 A102 Oxamine Copper Blue 189 Sulfone Acid Blue B . 12. 677 3. 842 Diphenyl Blue (V.14.) A617 10. 222 1. 941 RR............... 8.410 198 Thiazine Yellow . . . . . . 29. 879 A622 Diphenyl Deep Black 2. 549 A104 Oxamine Dark Blue 13.189 211 Resorcin Brown . . . . . 21. 098 4. 216 W M . ) , . . . . . . . . . . . 23. 810 4. 246 (V.M.), . . . . . . . . . . . 3. 238 14.705 212a Acid Brown (\‘.hl.). . A629 Diphenyl Green (V . 40.763 7. 518 A108 Oxamine Dark Brown 217 Agalma Black 10 B 18. 021 4. 667 &I.). . . . . . . . . . . . . . . 10.599 1. 312 G , R . . . . . . . . . . . . . . 2. 359 13.465 217a Agalma Black (V M.) Brown A664 Chlorantine A122 Palatine Chrome Blue 217c Rlaphthol Blue Black 18. 267 4. 034 (V M . ) . . . . . . . . . . . . 42. 244 4. 679 BB . . . . . . . . . . . . . . . 8. 864 62. 864 (V.X),. .......... A674 Chrome Fast Brown 7. 547 A124 P a l a t i n e C h r o m e 217e Acid Black (\’.XI.).. 47.489 3. 550 (V.M.). . . . . . . . . . . . 12.204 19.665 6.452 Green G . . . . . . . . . 4. 866 23. 371 217g n’ool Black (KhI.),. A682 Chrome Fast Green 7.281 4. 202 A131 Scarlet (V.Iv1.). . . . . . 80.778 217h Acid \Vod Black . . . . 13.518 12.943 6. 670 (\’.XI.) . . . . . . . . . . . . 12. 780 1. 417 Wool Scarlet (V.M.) 32. 624 3. 614 A142 Amido Acid B l a c k . , . 220a A687 Cupranil Brown (V . 18.660 2.031 1.942 A144 Acid Black E, M . . . . 236 Wool Ked . . . . . . . . . . . 13.245 4. 859 M . ) . . . . . . . . . . . . . . . 24.851 4. 228 A147 Acid C p o m e Black 247 Scarlet . . . . . . . . . . . . . . 36. 398 4. 205 A692 Direct Black E . . . . . . 22.223 8.052 2. 967 (V.M., . . . . . . . . . . . . 39. 508 257b Tolyl Blue . . . . . . . . . . 16.750 11.290 2.790 A696 Direct Fast Black B . . 2.234 7. 663 A150 Acid Silk Black R . . . . 12.928 69. 590 265 Sulfon Cyanine Black 10. 108 2. 624 Azo Rhodine 2 B . . . A711 5.765 AI57 Benzo Chrome Black 269 Acid B l a c k . , . . . . . . . . 35 662 58.838 12.827 A719 Direct Sky Blue FF . . 9.804 Blue B . , . . . . . . . . . . 51.315 5.588 272 Brilliant Black . . . . . . . 39. 454 hl i 1 1 i n g A729 Azomine 15.756 3.596 A166 Benzo Dark Green B , 272b Wool Black (V.M.) . . 22. 500 5. 124 Black N 2. 123 1 3 .616 G G . . . . . . . . . . . . . . . 13.038 275a Chrome Black ( V . M . ) 72. 521
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Nov., 1916
T H E J O U R N A L O F I N D U S T R I A L A,VD E N G I N E E R I N G C H E M I S T R Y
S U M M A R Y O F T H E M O S T I M P O R T ' A N T COLORS I M P O R T E D B Y U. S. D U R I N G Invoice Invoice COMMERCIAL Serial COMMERCIAL Value NAME Lbs. hTo. NAME Lbs. Value 739 Immedial Maroon B . 15,496 $2,886 Triphenylmethane Colors 746 Katigene Green (V. 44,595 $10,305 497a Victoria Green.. . . . 9,950 M . ) . . . . . . . . . . . . . . 63,929 409 Brilliant Green (V.M.) 73,904 18,345 750 Kryogene Brown A, G 10,313 972 502 Guinea Green.. . . . . . 14,666 3,362 Unclassified Sulfur Colors 502a Acid Green (V.M.). . 35,305 9,379 503 Neptune Green (V. S 3 Sulfur Blue (V.M.)., 73,434 15,489 M.) , . , . . . . . . . . . . . 40,868 13,825 S 12 Sulfur Brown (V.M.) , 79,691 9,505 505 Light Green (YellowS 18 Sulfur Catchu G, R . , 48,973 5,071 5,960 ish) (V.M.) . . . . . . . . 24,946 S 26 Sulfur Indigo (V.M.). 10,488 2,085 46,461 505a Acid Green (V.M.). 20,176 S 37 Katigene Black Brown 28,971 506 Erioglaucine (V.M.). 86,526 (V.M.). . . . . . , , , . , . 11,006 1,336 M a g e n t a . , . . , , , , . , . 87,102 25,659 512 S 45 Katigene Brown 2 R , 33,653 13,664 516 Crystal Violet. . . . V................ 22,811 2,452 18,219 5,289 516a Violet (V.M.) . . . . . . .. S 49 Katigene Direct Blue 6,018 517 Benzyl Violet.. . . . . . 22,387 B, R F . . . .. . . , , , , .' 11,299 2,305 Ethyl P u r p l e . . . , , . . . 23,101 51,933 018 S 51 Katigene Indigo (V. 18,586 50,563 521 Aniline Blue. . . . . . . . . M.) , . . . . . , , . . . . . . . 42,157 5,924 Acid M a g e n t a . . . . . . . 4,030 19,098 524 S 55 Katigene Khaki G . . , 14,242 1,691 4,362 13,078 527 Acid Violet. .. . . , . . . . S 58 Katigene Red Brown Acid Violet (V.M.), . 5,360 16,106 527a R , 3 R , . . . . . . . . . . . 68,864 9,386 3,229 528 Fast Acid Violet 10 B 12,919 S 62 Katigene Yellow G, 12,806 50,055 530 Acid Violet.. . GG, G R . . . . . . . . . . 55,227 9,318 20,954 65,395 530a Acid Violet (V.M.) S 65 Katigene Yellow 4,185 19,819 530b Formyl Violet (V.M.) Brown (V.M.) . . . . . 36,826 5,617 530c Guinea Violet 4 B, 6 S 75 Immedial Direct Blue 18,854 5,114 B................ (V.M.) . . . . , 73,892 11,145 25,091 11,987 53 1 Eriocyanine . S 76 Immedial Indogene 19,960 6,310 534a Acid Violet (V.M.) (V.M.). . . . . . . . . . 90,077 13,141 31,499 6,275 537a Navy Blue (V.M.) . . S 78 Im-medial New Blue Cotton Blue (V.M.) 45,019 9,809 538a ti................ 37,492 10,016 86,523 31,093 539 Soluble Blue S 84 Sulfur B r o w n . . . . . . 12,735 1,926 14,467 4,916 543c Acid B l u e . . . . S 86 Thion Brown (V.M.) . 18,579 2,824 10,229 40,848 545 Patent Blue A , . S 97 Thiogene Blue (V.M.) 14,344 2,261 10,765 2,305 545a Neptune Blue (V.M.) S l O O Ttiogene Brown (V. 545c Brilliant Acid Blue IVI.I . . . . . . , . 97,551 10,601 3,525 (V.M.). 10,120 S l o g Thiogene Deep Blue. 13,106 3,049 15,757 546 Cyanol . . . . , . . . . , , . . 40,015 S155 Pyrogene Brown (V. Azurol 551 ErbEhrome M . ) . . . . . . . . , , , , 63,450 6,689 21,070 14,480 B L . .. . . . . . . . . . . 5168 Sulfur Bronze.. . . , .. 15,152 1,392 SI77 Cross Dye Drab N . . . 15,758 1,324 Diphenyl-Naphthyl-Methane Cola'IS 564 Naphthalene G r e e n . . 22,144 5,904 Anthraquinone and Allied Col.ors 566 Wool Green S . . . . . 33,863 13,526 G o 1d 760 Indanthrene 566b Cyanol Green (V.M.) 10,988 2,193 Orange G . . . . . . . 20,092 10,088 Xanthone Colors G o 1d 761 Indanthrene Orange.. , . . . . . . . 50,496 2,052 571 Rhodamine 6 G . 37,460 18,495 D ark 763 Indanthrene 58,339 573 Rhodamine B . . . . . 23,777 Blue B O . . . . . . . . . 11,096 2,516 16,940 576 Rhodamine 3 G . . . . . 6,858 72,227 765 Indanthrene Green B , 16,377 580a Fast Acid Violet (V. Violet 767 Indanthrene 13,975 M . ) . . . . . . . .. . . . . . . 19,811 R R . . . . . . . . . . . , . , 68,419 21,516 13,183 587 Eosine.. . . . . . . . . . . . 35,511 768a Indanthrene Black B, 587a Eosine (V.M.). . . . . . . 21 017 7,891 BB. .. . . , . . . . . . . , , 50,034 12,876 587b Bromo-Flu o r e s c e i c 7741, Alizarin Black (V.dM,) 61,187 19,239 Acid.. . . . . . . 38,000 18,397 779 Alizarin Orange (V. 590a Acid Eosine.. 17,499 7,388 M.) . . . . . . . . . . . . . 14,239 3,184 15,404 599 Galleine.. . . . . . , , , , 8.817 53,154 24,784 780 Alizarin R e d . . , . . . . . , Acridine Colors 780a Alizarin Red (V.M.) . 28,775 3,708 785, Alizarin (V.M.), . . . . , 49,021 5,379 606c Patent Phosphine. . . , 28,627 17,881 790a A?t&acene Blue (V. 606g Leather Flavine.. . , . . 24,153 8,235 N L .) . . . . . . . . . . . . 22,444 7,174 19,704 607 Rheonine.. . . . . . . . . 5,261 800 Anthracene Blue WB, 15,403 608 Euchrysine. , . . . . . . . 5,343 WG. . . . . . . . . . . . . . 54,712 9,228 609b Diamond Phosphine. 30,336 5,897 18,575 803 Alizarin Blue W X , A . 6,453 609c Corioflavine. . . . . . 40,343 13,438 79,679 804 Alizarin Blue S , , , , , , 69,871 Quinoline and Thiobenzenvl Colc)rs 804a Alizarin Blue SB, 942 12,409 6,158 804c Alizarin Sky Blue B , , 19,471 24,555 612 Quinoline Y e 11 o w 805 Alizarin Green S . , , . 15,885 (spirit-soluble) , , . 79,553 2,497 28,170 807a Patent Alizarin Black 613 Quinoline Y e I1 o w (V M.). . . . . . . . . . . . 61,500 10,049 (water-soluble) ,, 15,324 7,072 808 Alizarin Green S . , , . , 11,096 2,337 616 Primuline.. . . . . . . . . 56,212 8,478 810a Helindone Yellow C G 20,744 6,954 617 Columbia Yellow (V. 820 Algol Brilliant Violet M.) . . . . . . . . .. . . . . . 86,090 10,165 R................ 12,784 617a Diamine Fast Yellow 3,623 827 Indanthrene Claret B 28,728 9,923 (V.M.).. .. . . . . 88,688 12,972 Violet 832 Indanthrene 618 Thioflavine T.. . , , , , . 31,714 17,683 R N . . . .. .. . . . . . , , , 11,667 5,181 Oxazine and Thiazine Colors 883 Algol Olive R . . . . . . . 13,334 2,850 B 1u e 84 1 Indanthrene 627 Gallocyanine.. , , , , , , . 78,283 27,227 GGS. . . . . . . . . . . . 10,163 649 Cotton Blue (V.M.) , , 32,509 4,284 9,675 Yellow 849 Indanthrene 660 Methylene Green (V. G, G P . . . . . . . . 4,353 12,683 M . ) , . . . . . . . . . . . . . 30,812 13,196 Violet 849a Indanthrene 661 Thionine Blue (V.M.) 18,618 7,873 Yellow G P . . . . . . . 62,509 20,738 663 New Methylene Blue B 1u e 850a Indanthrene ( V . M , ) . ,. . . . . . . . . , 30,392 12,127 WR. .. . . . . . . . . , , , 31,658 667 Indochromine (V.M.) 19,060 4,272 12,430 85la Alizarin Direct Blue Azine Colors (V.M.). . . . , . ., . 10,201 11,878 856a Alizarin Rubinol R , , . 10,917 672 Azo C a r m i n e . . . . , . . 17,500 11,826 5,453 859 Cyananthrol R . . . , . , , 18,792 679 Safranine (V.M.). . , . 59,921 27,555 21,273 862 Alizarin Blue Black 681 New Fast Gray (V. B,3B............ 54,706 61,370 M.) , . . . . . . . . . . , . . . 29,507 10,436 697 Induline, Soluble in Indigo a n d Its Derivatives Spirit (V.M.). . . . . . 25,342 5,016 699 Induline, Soluble in 877 Indigo E x t r a c t . . . . . . . 19,329 6,377 Water (V.M.). . . ... 21,775 5,514 879 Indigo M L B . .. . . , . . . 53,610 11,604 705a Indocyanine B, 2 R F 23,138 5,205 881 Ciba Blue 2 B . . . . , , , 7,423 16,880 886 Brilliant Indigo G D , , 12,057 1,747 Sulfur Colors 888 Indigo M L B , T . . . . . 12,730 1,598 708 Sulfaniline Brown 0, 90 1 Ciba Violet B . , . . . . . 19,830 6,975 R . . . . . . . . . . . . . . . . 11,327 1,158 904 Helindone Brown G . 12,936 6,710 710 Immedial Yellow D 907 Ciba Scarlet G . , , , , 22,265 11,479 (V.M.). . . . . . . . . . . 13,395 2,266 910 Helindone Pink (V. 725 Immedial Brown (V. M . ) . . .. . . . , . . . . . . 39,393 47,117 M . ) . . . . . . . . . . . . . . . 23,887 2,558 913 Helindone Orange R . 14,489 5,841 726 Pyrogene Blue (V.M.) 10,934 2,582 918 Helindone Red 3 B . . 27,874 10,042 734 Pyrogene Yellow M 0 18,515 5,102 920 Helindone Violet B, 735 Pyrogene Indigo (V. 2 B, R . . .. 28,607 18,945 M.) . . . .. . . . . . . . . . . 22,661 6,652 923 Ursol, , . . . . . . . . . . . 53,720 15,779
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I043
F I S C A L Y E A R 1913-14-(continued) Serial COMMERCtAL Invoice hTAME Lbs. Value No. Unclassified Coal-Tar Colors Include imported artificial colors, the composition or manufacture of which are not known and which have not been mentioned among the unclassified azo colors and sulfur colors u 20 Guinea Bordeaux (V. M . ) . . . . . . . . . . . . . . . 23,252 $3,233 4,647 U 24 Indo Violet B . . . . . . . 23,060 Metachrome Blue B, u 27 14,301 G................ 3,996 U 31 Metachrome Brown 7,271 . . 57,313 BL, B R L 1,246 u 61 Scarlet 33446.. . . . 13,344 U 78 ChLome Fast Blue 4 n . . . . . . . . . . . . . . 23,585 .. 5,198 U 86 Columbia Fast Black 82,040 15,756 UlOO 11,235 2,039 Y 2............... u 1 0 9 Brilliant Scarlet V. 23,382 2,688 10,789 3,241 u121 U138 Fast Acid Marine Blue H B B . . . 25,567 6,212 13,974 2,766 U145 Japan Black (V.M.) 19,442 4,779 U151 Jet Black APX, R R . 10,218 43,807 U155 Kraft Brown L Y 2 . 4,843 U158 Leather Black BO, C R 16,433 U163 Oil Black 6 B, 28,603 HG. ... , .. . . 4,258 926 U180 Pigment Black.. . . . . . 22,448 U183 Quercitron Substitute 2,422 16,812 WBL, V . . . . . . . . . 2,809 U192 Thiazine Brown R . . . 12,105 U206 Acid Chrome Blue 3 G , 2 R , 5 R . . . . . . . 25,633 6,553 994 U217 Blue 27071.. . . . . . . 14,775 15,290 949 U238 Claret Lake B L . . . . . 20,610 3,790 U246 Half Wool Blue 3 R . . U271 Wool Fast Blue BI,, 19,238 6,331 GL . . . . . . . . . . . . . . . u 2 7 9 Brilliant Lanafuchsine 1,757 11,289 U283 41,082 4,317 11,784 3,063 u 2 9 0 1,eather B ac 44,676 8,484 U293 30,099 6,238 E304 15,445 1,649 U321 Carpet Red B, 4,959 G329 Cotton Brown (V.M.) 15,079 u 3 3 2 Cotton Marine Blue 4676. . . , . . . . . . . . . . 79,035 10,902 21,665 5,116 u 3 3 3 Cotton Orange (V.M.) 8,438 u 3 3 5 Direct Black (V.M.) . 42,277 57,224 14,318 U336 Direct Blue ( V . M . ) . . 4,799 u 3 3 7 Direct Brown (V.M.). 21,828 Fast U361 Naphthamine 34,203 10,671 Black, S E , S D E , VE 24,372 3,101 TJ378 29,634 3,363 U385 23,020 6,854 U391 40,736 6,333 u393 16.038 2,359 u394 20,255 5,488 u395 12,584 3,429 u397 17,465 2,629 u399 u 4 2 3 Alizarin Pure Blue . . 31,000 7,349 DPH U440 Hansa Yellow G, 5 G, 4,559 R . . . . . . . . . . . . . . . . 11,014 L-460 Paratol Chrome Yellow L.. . . . . , . . . . , . 17,336 1,238 8,271 U465 Paratol Scarlet 3 B . . . 41,000 8,536 U470 Rosazeine B B 5 6 G 17,509 4,246 U5lO Cresol Blacd (V.M.) . . 37,322 15,766 6,575 U526 Chrysolarine A , . , , , , , 4,789 u 5 5 3 Black B H , H B . . . . 21,239 U570 Developed Black B, N-, R , W . . . . . . . , . . 36,475 9,501 6,117 U610 Erio Violet BC, R L C 21,345 10,527 2,367 C682 Sepia Black F W . . . . . E687 Solfigene Deep Black (V.M.) . . . . . . . . . 61,949 9,509 3,627 U695 Blue ( V . M . ) .. . . . . . . . 13,667 U701 Calcutta Blue 2 . . . , . 26,669 4,669 U708 Meridian Blark AB, AN. . . . . , . . . . . . . , , 15,157 3,316 U711 Omega Chrome Cya3,019 nine R . . . . . . . . . . , . 21,001 U716 Alpha Black JC, 6 B N . . . . , . . . . . . . . 12,100 2,949 3,430 U731 Cachou (V.M.). . . . , . 56,991 18,979 1,986 u 7 4 4 Alizadine Black M . . . 10,047 2,126 U770 X L Blue (V.M.). . . . .
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Class I1 ~1'00.000 . . to 200.000 lbs.) Chrysoidine R . , . , , , , 105,946 16,852 11,118 Alizarin Yellow.. . . . . 144,761 10,116 Orange 11.. . . . . . . . . . 127,550 Azo R u b i n e . . . . . . , . . . 160,252 23,409 26,945 Salicine Black (V.M.) 177,203 23,447 Eriochrome Black T . 129,550 Naphthylamine Black 12,240 ( V . M . ) .. . . .. . . . . . . 122,581 217f Amido Black (V.M.) . 105,005 10,062 15,169 220 Palatine Black. , , , . , 148,203 16,868 220b Wool Black (V.M.). . 110,244 227 Brilliant Croceine, , . . 123,058 20,333 21,118 257 Sulfon Cyanine . . , 128,944 266 hTaphthylamine Black 152,141 21,903 34 48 145 163 181b 183 217d
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Serial
h-0 261)a 284
455a 462f A169 A382 A387 495 543 558
565a 606 659
698
JOCRiVTAL O F 11VDC‘STRldL A S D E S G I l V E E R I N G CHEiVIlSTRY
1”E
I044
S U M M A R Y O P THE MOST cOMMERCI.4L NAME Lbs. Xaphthol Black (V. 131,890 Bismar 170,882 148,406 171,211 116,560 112,095 . . 145,738 Columbia Black (V. M.) . . . . . . . . . . . . . . , 143,956 Carbide Black (V.M.) 190 304 Benzo Fast Black I,. . 100:268 Oxy Diamine Black (V.M.) 146,629 Oxy Dia M.), . . . . . . . . . . . . . . 139,118 bfalachite G r e e n . . . . 178,831 Patent B l u e . . . . . . , . . 114 631 Victoria Blue R . . . . . , 109:627 Wool Blue (V.M.) . , . 173,904 Phosphine.. . . . . . . . . , 101,858 Methylene Blue (V. M.). . . . .. . . . . . . . . 185,738 Nigrosine, Soliible in 186,540 Spirit ( V . M . ) . . . . .
.
~
,
I M P O R T A N T COLORS I M P O R T E D BY U. S. D U R I N G Invoice Serial COMMERCIAL Invoice Value No. NAME 1,bs Value 774 Alizarin Black S S R $19,436 N R . . . . . . . .i . .’. . . ,’ 136,461 fs 9,936 31,241 782 Alizarin Brown (V.M.) 110,211 30,907 789 Anthracene Blue WR. 107,778 13,622 40,466 19,634 807 Alizarin Black S... . . 198.491 19,902 32,417 80% Alizarin Green (V.M.) 124 095 5R,491 12,635 838 Indanthrene Blue R S . 187:379 56,532 11,831 C 64 Amine Black (V.M.). 146,163 14,390 U390 Wool Black (V.M.). . . 118 791 26,125 U799 Black (V.11.) . . . . . . . . 138:805 20,453 14,781 31,607 22,846 Class 111 (200,000 to 300,000 lbs.) 24,836 26,832 43,363 49,945 33,117 18,406 30,442
72,611) 23,433
7 23 134 157 173 174a 303a 436 463 515 536 748
Naphthol Yellow., . . . Tartrazine.. . . . . . . , . . Metanil Yellow. , . , . , Diamond Black.. . . , , Litho1 Red R . . . Scarlet.. , . , . . . . Paper Yellow Columbia Bla Cotton Black RlethyI Violet Alkali R l u e . , . , . . . . . . HydronBlue (G, R ) . ,
interference in the output of American colors occurred until after the beginning or 191j. With the cordial cooperation of the Secretary of the Treasury, all the invoices for the year in question were sent by the collectors of customs a t the various ports of entry t o a central point, where the essential data were transcribed. These include weight, value and price. Some 37,500 different transcripts, each covering these three items, were necessary. These entries are found under j,674 heads, each representing a distinct commercial designation. It must not be inferred, however, that this number of different colors comes into consideration. Many standard dyes are manufactured by several firms in the same country as well as in various countries. Frequently, some or all of the competing manufacturers use entirely different trade names for identical wares. Thus, the red color, known chemically as sodium a-naphthalene azo-a-naphthol-disulfonate, is manufactured under the name of Palatine Red by the Badische Co, The Bayer Co. sells it under the name of Naphthorubine. Primuline is encountered commercially as Polychrornine, Thiochromogen, Aureoline and Sulfine. Malachite Green, a favorite color, is found under 38 different designations, few representing even slight yariations in the exact chemical composition. The reduction of this extensive vocabulary to the limits of the list given in the census has required highly specialized editing. It is hoped that the arrangement and the full use of synonyms are such as to render the published results of the greatest utility, not only t o all engaged in the manufacture of artificial dyestuffs, and especially in planning for the establishment of a comprehensive American color industry, but also to all dealers in the wares and t o all consumers of dyeing materials. ,4Li three of these categories have hitherto been indebted to the painstaking labors of several prominent German color chemists, notably of Gustar Schultz and Paul Julius, for complete and detailed classifications of the coal-tar dyes in current use. The carefully elaborated “Farbstofftabellen,” devised by the two authors, reached a fifth edition in 1914. These “tables,” divided into groups according to chemical relationship, give for every artificial dye of known composition or preparation the commercial designation, the scientific name, the chemical formula, the most advantageous process for technical production physical and chemical properties, methods of application, tests and full references to patents and literature. They have for years been the nude mecum, of all connected with the manufacture of colors, their commerce, and their manifold uses. It has remained for a bureau of our Government t o supplement the work of the German duo, by adding the all-important factor of quantity. The complete exposition of the exact amounts of the many synthetic dyes required to meet the almost niimherless needs of a population of over IOO,OOO,OOO, portrays
250,409 266,781 284 606 285:047 214,448
24,702 53,137 46,614 37,055 18,550
290,902 248,567 255,063 286,531 292,729
41,563 34,602 63,183 117,365 33,356
Yo1 8, SO.11
F I S C A L Y E A R 1913-14-(concluded) Serial COJIMERCL4L No. KAME Lbs. 778 Alizarin (Synthetic). . 202,392 806a Alizarin Black (V.M.) 229,500
Invoice Value $20,465 33,275
Class IV (300,000 to 400,000 Ibs.) 274 275 363 A396 -4432 700
351,582 341,724 300,473 349,380
a e r . . . . . . , . . . . . 394,718 803a Alizarin Blue (V.M.). 302,319 Class V (400,000 to 500,000 Ibs.) 333 Oxamine Black. ... . . . 417,423 493 Auramine.. . . . . . . . . . 449,276 842 I n d a n t 11 r e n e Blue G C D . . . . . . . . . , . 478,980
55,020 45,233 44,567 11,682 58,903 69,712 57,464 107,887 169,780
Class VI (over 500,000 lbs.) 462a Direct Deep Black E. 862,601 110,009 A 46 Zambesi Black ( V . M . ) 629,359 107,669 720 Su1f.w Blacks (V.M.).5,615,458 558,909 874 Indigo, Synthetic . . . . .8,507,359 1,090,733
approximately the relative demands of all other nations with highly organized textile and allied interests. The young American dyestuff industry, now in a position to expand rapidly and l o embrace in its scope the great majority of the colors in currcnt use, will naturally find in it a sure guide for coordinating the diverse phases of manufacture, establishing the capacity of units, and shaping all plans for harmonious expansion. More than this, it will be of almost equal value to those seeking to create the national coal-tar industries of Great Britain, France, Russia and Italy. Even the newly organized industry in Japan may profit from its summaries, although in a less pronounced degree, on account of the widely divergent taste for colors between the Orient and the Occident. Should China plan to manufacture her own coal-tar dyes, but little help could be secured from this compilation in formulating schemes for installing plants. Synthetic indigo constitutes two-thirds of the Chinese consumption of artificial colors. It enters to the extent of 14 per cent into the Japanese iniports of dyestuffs, and forms but I O per cent of the American consumption. One of the first results of the compilation of this census was to show how exceedingly vague an idea of the extent t o which synthetic dyes are consumed in the United States prevailed in commercial and manufacturing circles. Those most closely in touch with the branch have estimated hitherto that the annual American consumption of coal-tar colors did not exceed 20,ooo tons. As a matter of fact, it is nearly one-half again this amount-more exactly, 29,000 short tons. SUMMARY OP THE MOST IMPORTANT COLORS IMPORTED
It has seemed desirable, in the interest of American chemists who are now studying closely the problems connected with the creation of a national dyestuff industry, t o prepare a summary of the more important synthetic colors currently imported into this country and compiled systematically, in the complete census of dyes consumed in the United States, now in press. The list prepared (pages 1042, 3 and 4) includes practically all colors, the annual importation of which, during the fiscal year 1913-14, exceeded in amount 10,000 Ibs. These colors, for the sake of classification, are divided into six groups, according to the amount of the importation. PRICES OF DYES
The values of the different colors imported from Europe are taken directly from the invoice entries. The prices varied but little during the course of the fiscal year 1913-14. They are on file in the Bureau of Foreign and Domestic Commerce. It did not seem necessary to reproduce them in full in the enumeration of colors. The average price for the year, in the case of any dyc., is easily ascertained by a simple act of division. I n most cases the values stated represent the lowest possible estimate of wholesale cost which can be placed upon the wares iu question. The hulk of the importations is shipped from the great
Nov., 1916
T H E J t 3 L T R N A L O F I N D U S T R I A L A-YD E N G I N E E R I N G C H E M I S T R Y
manufacturing firms of Germany, Switzerland and England, to their agents in this country. The latter are ordinarily incorporated American companies, bearing essentially the same names as the European houses which they represent, and may be practically under the control of the latter, if not financed by them directly. Under these circumstances and in view of the exceptional difficulty of ascertaining market values for the highly differentiated gradations of quality in thiz thousands of brands of artificial colors, there was a strong temptation to place the lowest possible values upon wares subject t o an ad valorem duty of 30 per cent. It is doubtful in many cases, therefore, whether the values published in the following lists are fully equal to those against which American manufacturers of colors would contend, should all the factors, falling under the head of “unfair competition,” be eliminated in the international trade in synthetic dyes. I n these values there is a slight element of variability and uncertainty, based upon the lack of uniformity in invoicing colors. In some cases-probably the majority-the prices and values are net, not covering charges for containers and packing, freight, and insurance to seaport, consular certification, minor shipping charges a t point of departure and a t seaport. Wares shipped by the “Badische Co.,” the Berlin “Actien-Gesellschaft,” the “Cassella Co.,” the “Griesheim-Elektron,” and the “Chemikalienwerk-Griesheim” are usually invoiced in this manner. Other firms, such as the “Bayer Co.,” the “Sandoz Co.,” “Carl Jager,” and “Beyer and Kegel,” ‘nclude in their prices the cost of containers and packing, freight and insurance to seaport, consular certification, and minor shipping charges. In other words, their prices are f . o. b. ocean steamers a t Hamburg, Bremen, Rotterdam, Antwei-p, etc. It has not been possible, on account of time limitations, to estimate this small factor in the case of each shipment and make the accompanying correction in value so as to have actual uniformity in the basis of valuation. The element of quantity is the dominant feature in this work, and in view of what is stated above, very elaborate calculations of values would be of doubtful utility.
1045
This represented $0.00497 on each dollar of value, or about 0.5 per cent on the value. Shipments by another company, located on the Rhine, averaged 0.3 per cent. Packing-There is some diversity in the average cost of containers. This item ranges from $0.00459 to $0.00863 per lb. (net) of color in a number of large invoices. A fair average would be $0.00651 per net lb. Some of the more expensive colors are shipped in tin boxes, packed in cases holding IOO lbs. (net). Cases cost $0.48. The charges for tins are as follows: I lb., 4 8c.; j Ibs., 9.6c.; I O lbs., 15.5c.; 25 lbs., 32c. Kegs, containing IOO Ibs., cost usually $o.gj, but range in value from $0.63 to $1.14. Casks hold ordinarily about 500 lbs. The net contents range, however, from 41j to j 9 j lbs. I n four large shipments the average net weights were 442, 469, 480, and j31 lbs. The general average was 480 lbs. The average price of casks is $1.90. They range, however, in cost from $1.55 to $3.24. On an average the importation of European colors to New York costs S0.014per net lb. for packing and transportation (packing $0.0065, transportation $o.0075), and $7 per $1,000 of value for insurance and incidental charges (insurance Sj, shipping charges and consular certification $ 2 ) . American consumers of coal-tar colors, who may wish to compare the prices paid by them two or three years ago for European wares with the prices based upon the values furnished in this report, can add to the prices calculated from these values the cost of the above items. In addition there comes the duty of 30 per cent ad aalorem on all artificial colors, except indigo and its derivatives, and colors made frcm anthracene (largely alizarin) and carbazole, which were exempt from duty under the late tariff. This duty is levied upon the combined cost of a dye and its containers. Furthermore, the normal cost of handling, storing, and distributing, in the importing houses, is to be added. The difference between the sum total of these various items and the current price for a given color represents the profit made by the importer.
COST OF PACKISG, FREIGHT, ISSURBNCE, ETC.
ARTIFICIAL COLORS MANUFACTURED IN THE UNITED STATES
I t is well, however, to know with some approximation to exactness the extent and nature of the charges incident to the importation of European coal-tar colors into the United States. They are as follows: Consular certi$cation-A f’ee of $ 2 . j o for all invoices covering shipments, the value of which exceeds $100. Freight to seaport-This is quite variable, depending upon the distance to be traversed and whether rail or water transportation is employed. Rates per lb. (net) of color are $o.ooIzj from Berlin; $0.ooj6 to $0.0071 from Basel; $0.0008 to $0.00216 for points on the Rhine. Insurance, ~ T Ziransit ‘0 seaport-Rates vary from $0.0007 to $0.0016 for each dollar of invoice value. Shipping charges-The item appears occasionally and ranges from $I to $ 2 for each $1,000 of an invoice. Ocean freight-Customary rates from European ports, such as Hamburg and Antwerp to New York, were, prior to the war, $9.7j per metric ton (gross weight) for most of the coal-tar dyes, and $7.91 for ceitain categories, such as sulfur black and other sulfur colors. Several large invoices of colors showed an average rate for ocean freight per net lb. of dyestuff, of $0.00471, ranging from $0.0041~5 to $0.00539. Through freight from Frankfort to New York on a large and varied assortment of artificial dyes was a t the rate of $0.00755 per net lb. of colors. On an average, I lb. of color (net) is represented by 1.165 lbs. gross weight, the tare per lb. ranging from 0.155 to 0,174 lb. on shipments of some size Marine insurance-Insurance on large shipments of dyes from Frankfort to New York, covering both inland and marine insurance, was equivalent to $0.000916 per lb. (net) of colors.
The manufacture of coal-tar colors in the United States has been in existence for some 37 years. Prior to 1915 it had never become a factor of importance in supplying the American market. The reasons for this slowness of development have been presented in detail in the monograph published in 1915 by the Bureau of Foreign and Domestic Commerce, entitled “Dyestuffs €or American Textile and Other Industries” (Special Agents Series N o . 96). The American manufacture was confined almost entirely to the “assembling” into finished dyes of coal-tar intermediates imported from Europe, chiefly from Germany. In its entirety it represented less than one-tenth of the activity to be encountered in any one of the larger companies producing synthetic colors in Germany and Switzerland. STATUS OF THE DOMESTIC PRODUCTION IN 1914 The status of the industry for the calendar year 1914 is shown by the following tabular statement prepared by the Bureau of the Census. Number of establishments Persons engaged in manufacture. Salaried employees Wage earners (aver Primary horse pow
............... .............
.............
..............
Services. Salaries, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Materials..
.
............
............
7 528 130 398 1,376 83 386 212 8 ’529’070 $ 273’633 $ 255’437 $1 936’982 $3:596: 795 6,619,729 $2,470,096
All other (including medicinal coal-tar products t o value of $174,508).. .................................. Value added by manufacture.
............................
$1 126 699 $1:659:813
The scope and extent of the manufacture carried on prior to the war by the seven American companies engaged in this branch
T H E J O U R N A L O F I N D U S T R I A L A N D EJVGIXEERING C H E M I S T R Y
I 046
are summarized under their respective na.mes. S o attempt has been made to estimate the annual output of the individual colors made in the American factories, as it fluctuated largely from year t o year. I n nearly all cases the character of the manufacture has been vastly affected by the conditions prevailing since 1914.. As a rule the rariety of colors has been diminished while the output has been vastly augmented. The number oT employees has been notably augmented I n geceral, it hss been quintupled. I n one case the force is 50 times greater than in 1914. TEE SCHOELLKOPF .4NILINE AND CHENICAL WONKS (INC.)
This firm, located a t Buffalo, ?X. Y , , was founded in 1879, and is the oldest American company in this industry. A number of dyestuffs in current use originated in its laboratories. It has shown a commendable degree of enterprise in maintaining its position for over a third of a century, frequently under conditions of a most discouraging nature. It has also earned the grateful recognition of a multitude of American consumers of dyes by swiftly enlarging the capacity of its works so as t o alleviate materially the severity of the dyestuff famine to which our textile and allied interests have been exposed. The annual output of this firm constituted about one-half of the American production of coal-tar dyes. The following colors were currently manufactured before the wa,‘;. The serial numbers correspond to those given in Schultz’s Farbstofftabellen:” STILBEKU A S D PYKAZOLOK& DYES
9 9 23
Direct Yellow F Direct Yellow 2 R F XVool Yellow extra conc. T R I P H E ~ Y L - M E T H A N E DYES
512 512 513 521 521 524 536 536 537 532 53
Fuchsine Fuchsine T R Fuchqine h-B Spirit Blue, red shades Spirit Blue, green shades Acid Magenta Alkali Blues, red shades Alkali Blues, green shades Paper Blues, red shades Paper Blues, green shades Paper Blue 6 G super
587
Eosine
679 680 684 699 700
Safranine Y extra Safranine 6 B Brilliant Safranine R Piigrosines from aniline (indulines) Iiigrosines from nitrobenzi,1
31 32 33 33 34 36 36a 37 38 64 66 68 70 82 83 94 95 105 110 112 126 134 141 141 143 145 147 151 161
Oil Yellow -4 Oil Yellow 2625 Chrysoidine Y extra Chrysoidine crystals Chrysoidine 3 R Oil Orange 23 11 Oil Yellow 2338 Croceine Orange Y Crystal Orange 2 G Buffalo F a s t Crimson G Buffalo F a s t Crimson R Oil Yellow 2681 Croceine Orange K Xylidine Scarlet Cumidine Scarlet Bufialo Flamine B Buffalo Flamine G Sudan Brown S Bufialo Rubine Azo Bordeaux Indoine Blue Metanil Yellow Azo Yellow Azo Yellow A 5 W Resorcin Yellow Orange A Buflalo F a s t Fuchsine B Orange R F a s t Red conc
I
X A l T H O K E DYES AZINES
AZO DYES
azo DYES ( , a n c l u d e d ) Fast Red S conc Azo Rubine extra Wool Red 40 F Brilliant Scarlet 3 R Bufialo Fast Blue R Buffalo Fast Blue B Resorcin Brown Leather Orange Buffalo Bliick h-B Buffalo Black PY extra 227 Croceiue Scarlet M O O 257 Buffalo Cyanine R 257 Buffalo Cyanine 3 R 261 Buffalo Black 8 B, 10 B, R 266 Buflalo Black A D 268 Buffalo Black EX 269 Buffalo Black 4 B 2 i 2 Buffalo Black 2 B 275 Bufialo Chrome Black B W N 283 Bismarck Brown Y 284 Biimarck Brown 53 303 Brilliant Tiellow C 307 Congo Red 4 B 311 Erie Orange 2 R 312 Bufialo Direct Garnet R 313 Buffalo Direct Crimson B 320 Bordeaux extra 326 S i a g a r a Violet 2 B 326 S i a g a r a Blue R 327 h-iagara Violet 3 R 333 Diazine Black H extra 336 Niagara Blue G W , HX?‘,R W 337 S i a g a r a Blue B, 2 B 342 Buffalo Direct Yellow C G extra 343 Pu’iagara F a s t Red F D 344 Erie Direct Brown 3 R E 362 Buffalo Direct Orange R 363 Buffalo Direct Red 4 B 375 Buffalo Direct Violet 4 R 386 Xiagara Blue B R 392 Buffalo Direct Orange Y 394 Buffalo Direct Yellow C R R extra 40.5 Buffalo Direct Cardinal 7 B 410 Buffalo Direct Blue G extra 424 Niagara Blue 6 B 426 Niagara Blue 4 B 43 6 Panama Black R extra 436 Panama Black 3 G extra 44 1 Niagara Black Blue R 462 Erie Direct Black G extra 463 Erie Direct Black R extra 464 Erie Direct Green ET 464 Erie Direct Green TVT 474 Erie Direct Green M T 477 Erie Direct Brown G R 4 i 7 a Erie Direct Brown GB 488 Erie Direct Brown R F , 2 R F 161 163 168 169 188 189 211 21: 211 220
THE HELLER AND MER2 CO.
hi^ firm, located at Kewark, N , J,, stands second in point of seniority and importance, Its allnual outout of coal-tar colors was estimated a t slightly less than one-qujrter of the country’s production. It has catered very largely to the nee& of the paper trade. I n addition to organic dyestuffs, it has manufactured large quantities of mineral colors, notably ultramarine. The equipment for the production of coal-ta,r dyes has been largely augmented during the past year.
V O ~8, . NO.I I
The following artificial colors were currently manufactured in 1914 (serial numbers of Schultz’s Farbstofftabellen) : AZO DYES
TRIPHENYL-31ETHAlE DYES
5 12 515 536 537 538 539
33 Chrysoidine 145 Orange I1 283 Bismarck Brown
Fuchsine Methyl Violet alkali Blue Soluble Blue Methyl Blue iZcid Blue
X.4NTHONE
DYES
587 Eosine AZINES
698 Nigrosine, spirit-soluble 700 Kigrosine, water-soluble
THE B.4YER CO. (INC.)
This company owns works a t Rensselaer, N. Y., where several of the staple colors and medicinal products of the Farbenfabriken vormals Priedr. Bayer & Co., of Lererkusen, Germany, are manufactured on a scale of some importance. The output of coaltar dyes prior t o the war constituted somewhat less than onefifth of the entire production. The expansion during the past year and a half has not been as pronounced as in the case of the other establishments. Prior to the war the company manufactured the following colors: A Z O DYES
TRIPHEXYL-YETHAKE DYES
33 Chrysoidine 283 Bismarck Brown
w.
BECIIER’S
512 Fuchsine 536 Alkali Blue 537 Soluble Blue
AZIKES
698 hligrosine, spirit-soluble 699 Induline 700 Nigrosine, water-soluble
XKILIKE A N D CHEMICAL WORIG
(IXC.)
This company, founded in 1912, is located a t Brooklyn, hT.Y. Prior t o the war it specialized on alizarin substitute colors. The annual output was modest, estimated a t about 180 tons. During the past 18 months the plant has been rapidly enlarged. To-day it is second in importance as a Factor in the domestic co!or industry. The following colors were manufactured regularly prior to 1915: XANTHONE rims
-420 DYES
48 83 145 163 166 188
Alizarin Yellow FF Ponceau 3 R Orange I1 Azo Rubine IVB Fast Red A Acid Fast Blue SR
189 217 333 337 342 410 426
Acid Fast Blue S B Acid Black 10 B Diazo Black BHiY Direct Blue W B B Direct Yellow WH Benzazurine W B Direct Sky Blue B
599 Chrome Blue R , powder a nd paste OXAZINE DYES
626 Chrome Blue B, paste and powder
THE CESTRAL DYESTUPF CO.
This company, located a t Kewark, N. J., was founded in 1898. The output was not large, possibly 4 per cent of the country’s production. I t included, however, several dyes of importance for the textile industries. The plant has been notably enlarged during the past year. Prior t o the war the following colors were currently manufactured : AZO DYES
31 Amido-azobenzene 33 Chrysoidine 37 Crosceine Orange 68 Amido-azo-toluene 112 Bordeaux B 145 Orange I1
AZINES
161 163 168 174 223 232 283
697 Enduline 698 Nigrosine
E‘ast Red Azorubine -4maranth Scarlet Sudan I11 Sudan I V Bismarck Brown
THE CONSOLIDATED COLOR AKD CHEMICAL CO.
This company, located also a t Newark, N. J., manufactured for some years prior t o the war less than IOO tons annually of colors. The following colors for textile works were currently produced. 58 Alizarin Yellow R .
168 Fast R e d
144 Naphthol Orange
I n addition, a certain variety of colors for pigments, especially alizarin, para and scarlet lakes, and for use in paper making, were regularly manufactured. During the past year the plant has been greatly enlarged. It is a t present an important center of production. HUB DYESTUFP AND CHEMICAL CO.
This company, located a t South Boston, Mass., manufactured on a modest scale, fcr a few years, prior t o 1915, 58 Alizarin Yellow R. IJIPORTATIOK
OF
COAL-TAR CRCDES
ASD
INTERMEDIATES
-1s stated above, the synthetic colors manufactured in the United States prior to 1915 were made almost exclusively from intermediate coal-tar products imported from Europe. Gerlnany was the chief source A considerable amount, however, was of British origin. -A single lloteworthy exception is found in the case of aniline. The A4merican manufacture of this all-important intermediate was organized in 1910. The annual output had attained about q~~ short tons in 191q-the product of a single establishment.
Nov., 1916
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 CHEMISTRY
A t present aniline is regularly manufactured by over 30 companies and the annual output is in excess of 16,000 short tons. I n connection with the preceding enumeration of the artificial dyes currently produced in the United States prior to the war, it is of considerable importance to know what coal-tar crudes and intermediates were imported for use in their manufacture and, further, the quantity and value of each crude and intermediate. This information is furnished in the following tabular statement based upon the importations for the fiscal year ending June 30, 1914' IMPORTS OF COAL-TARCRUDES,FISCAL YEAR 1913-14 Benzene ....................................
............................. ...............
Pounds 131,211 199,088 30,681 3,880,108
...... ......
................
8,393,216
Phenol (carbolic acid). Phenol, ref. . . . Cresol. . . . . . . . Creosote oil (gallons). . . . . . . . . . . . . . . . .
404,361 59.271.677 . , Total,
Value $4,247 7,892 1,722 70,428 32,175 531,535 109,146 16,139 3.822.919 . . 4,596,203
D I A M I N E S A N D DERIVATIVES Phenylene-diamine ........................... p-Phenylene-diamine m-Toluylene-diamine . . . . . . . . . . . . . . m-Toluylene-diamine-sulfonic acid (1
................. Salicylic acid, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acetyl-salicylic acid. . . . . . . . . . . . . . . . . . . . . . . . . . Resorcin Hydroqu Pyrogallol. ............................ Gallic a c i d . . . . . . . . . . Naphthols ( aand 8 ) a Naphthol.. . . . . . . . a-Naphthol-5-sulfonic acid (L or Cleve's acid; 1 5 )..................................... a-Na~hthol-3,6,8-trisulfonic acid (1,3,6,8). . . . . . . &Naphthol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0-Naphthol-monosulfonic acid (constitution unknown) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . j3-Naphthol-7-sulfonic acid ( F salt; 2 7). . . . . . . . . Naphthol-6,8-disulfonic acid .(G a,dd; 2 , 6 , 8 ) . . . 1,8-Dioxy-naphthalene-4-sulfonic acid. 8-Oxy-naphthoic acid. . . . . . . . . . . . . . . . . . . . . . . . 8-Oxy-naphthoic anilide (Naphthol AS). . . . . . . . . AMIDO-PHENOLS A N D DERIVATIVES o-Amido-phenol ............................. Sodium picramate.. ......................... Oxv-nitraniline .............................. Diamido-phenol .............................. 9-Amido-phenol .............................. 9 -Amido-pheno! hydrochloride. p-Amido-salicylic acid. Methyl-p-amido-phenol sulfate. . . . . . . . . . . . . . . . . 1,8-Amido-naphthol-3,6-disulfonic acid ( H acid; 1,8,3,6),. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,5-Amido-naphthol-7-sulfonic acid. . . . . . . . . . . . . ALDEHYDES A N D QUIXOA'ES Benzaldehyde. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Oil of bitter almonds (benzaldehyde). . . . . . . . . . . Anthraquinone, ..............................
..........
~~
An exceedingly small part of the above-mentioned coal tar crudes was utilized in the manufacture of artificial colors. The creosote oil was emplpyed in the preservation of timber. The phenol served chiefly as a disinfectant and antiseptic. The chief use of naphthalene was in the familiar form of "moth balls." During the calendar year 1913, according to official German records, the following coal-.tar crudes were imported into the United States from Germany : Naphthalene, 7,900 short tons; carbolic acid (pure and crude), 1,320 short tons; cresol, 2 2 0 short tons; creosote oil, 17,600 short tons. IMPORTS OF
COAL-TARINTERMEDIATES. FISCAL YEAR 19 13-14
................ ........................
DEVELOPERS REDUCERS A N D INDICATORS
F a s t Blue Develbper A D (amido-diphenylamine) Oxamine Developer H . . ...................... Orange Developer R.......................... Developer Z (phenyl-methyl pyrazolone) Phenolphthalein . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
........
Total
T h e values given are net invoic,?values of European manufacturers and do not include cost of containers, etc. Pounds Value IXTERMEDIATES NITRO C O M P O U N D S
o-Nitro-toluene.. ... Dinitro-toluene . . . . . . . . . . . . . . . . . . . . . . .
...............
........................
$59,835 10,399 359 2,969 36 660 13,242 165 1,037 67,638 135 3,415 4,200 6,524 9,??? ~
=,Io"
Ethyl-p-toluene-sulfonic ester, . . . . . . . . . . . . . . . . . P R I M A R Y A M I N E S A N D DERIVATIVES
Aniline oil.. . . . . . . . . . . . . . . . Aniline salts. . . . . . . . . . . . . . .
........... ...........
Toluidine. . . . . . . . . .
1,087,911 164,650 6,670 42,482 547,701 57,242 2,247 3,527 506,961 500 10,874 10,513 20,737 3;>222
...................
Xylidine. . . . . . . . . . . . . . . . . . . p-Phenetidine . . . . . . . . . . . . . . .
51,701
3,083,467 1,060 5,568 108, 4,477 835 309, 595
222,728
24,686 174
4,7i:
:; :: : 1
l:;;z;i 500 2,832
or Badische acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-Xaphthylamine-@-sulfonic acid ( 8 or Bronner's acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-h7aphthylamine-disulfonicacid ( a or R acid; amido-R-salt' 2 3 6 ) . . . . . . . . . . . . . . . . . . . . . . 8-Naphthylamine;di'sthfonic acid (y or G acid; amido-G-salt; 2,6,8) SECONDARY AMINES
Dimethyl-aniline . . . . . . . ... Diphenylamine ........................... ... Ethyl-a-napht hylamine .................... Ethyl-8-naphthylamine. . . . . . . . . . . . . . . . . . . . Phenyl-a-naphthylamine-8-sulfonic acid. . . . . . . . . 9-Tolyl-a-naphthylamine-8-sulfoIiic acid. . . . . . . . . .
I
.
1 1 1
278,896 63,574 1,102 21 ,444,772
5,493 5,246 5,073 232265
15,597 659 l9 16,628
izi
1 , 257
14, 161
2 7 , 361
1:
1
;:z
lg;z:i : ;9"
2,316
495
46,267
4,495
3,603
230
48,642 55,556 1,102 375 9,139 1,097
7,045 9,042 338 190 2,860 568
37,907 11,088 133,355 2,277 55,245 10,656
$ 7,704
18,821 22,841 61,624 66,596 23,615 61,635 70,469 44,089
4,425 11,873 18,175 25,140 20,476 20,429 4,193 2,271
25,126 6,443 1,030,268
5,026 1,344 74,238
32,852 1,996 11,624 2,178 2,359 1,997
5,998 382 1,404 1,056 972 1,218
625 5,207 200 441 10,631 652 9,188 10,582
223 1,485 32 391 1,684 189 2,996 13,658
96,296 1,153
22,168 445
12,950 7,525 25,193
2,757 21,954 4,676
100 11,096 701 1,397 14,076
39 2,119 376 377 14.090
3,414 25,582 835 16,991 4,217
10,165.896 $1,082,775
SUMMARY OF IMPORTS OF COAL-TAR PRODUCTS,
1913-14
The coal-tar crudes and intermediates listed above, with the exception of aniline oil and salts, several acids, such as carbolic acid and salicylic acid, alizarin and colors derived from alizarin, anthracene and carbazole, indigo and its derivatives, and a few other compounds, such as antipyrine, aspirin, saccharin, and phenolphthalein, are included in the following summarized statement of the imports for consumption into the United States of coal-tar products, for the fiscal year ending June 30, 1914, published by the Bureau of Foreign and Domestic Commerce. Imports designated by an asterisk (*) are for the period July 1 t o October 3, 1913. Those designated b y a dagger (t) are for the remainder of the fiscal year. COAL-TAR PRODUCTS R a t e of d u t y Value Anthracene and anthracene oil.. . . . . . . . . Freet $32,175 .OO Colors or dyes, n. s. p. f . , . . . . . . . . . . . . . . 30 per cent 7,537,869.55. Do. (for use of the United States). . . Free 54.00 Dead or creosote oil (59,271,677 gallons). Free 3,822,919.00 All other, not medicinal and not colors or dyes, known as benzol, toluol, naphthalin, xylol, phenol, cresol, toluidine, xylidin, cumidin, binitrotoluol, binitrobenzol, benzidin, tolidin, dianisidin, naphthol, naphthylamine, diphenylamin, benzaldehyde, benzylchloride, resorcin, nitrobenzol, and nitrotoluol; naphthylaminsulfoacids, naphtholsulfoacids and amidonaphtholsulfoacids and their sodium or potassium salts; amidosalicylic acid, binitrochlorbenzol, diamidostilbendisulfoacid, metanilic acid, paranitranilin, and dimethylanilin. Free* 288,799.00 Distillates n . s. p. f , not medicinal and not coldrs or dyes, benzol: naphthol, resorcin, toluol, xylol. 5 per cent? 138,636.00 N o t medicinal and not colors or dves. known as toluidine, xylidin, cumibin; binitrotoluol, binitrobenzol, benzidin, tolidin, dianisidin, naphthylamine, diphenylamin, benzaldehyde, benezyl chloride, n i t r o - b e n ~ o l ,and nitrotoluol; naphthylaminsulfoacids, naphtholsulfoacids, and amidonaphtholsulfoacids and their sodium or potassium salts; amidosalicylic acid, binitrochlorbenzol, diamidoytilbendisulfoacid, metanilic acid, paranitranilin, a n d dimethylanilin. IIO per cent* 398,996.00
:;$ 7,579
..................................
I047
I048
T H E JOURN.4L O F I h i D U S T R I A L A N D ELVGI.VEERING C H E M I S T R Y
COAL-TAR PRODUCTS R a t e of duty Do. (for use of the United States). . . Free Saphthalene, phenol, and cresol.. . . . . . . . Free? All preparations of, not colors o r dyes, and not medicinal, n. s. p. f . . . . . . . . . . . . . . . 20 per cent* All other products or preparations of, not colors or dyes, n. s. p f . . 15 per centt Do. (for use of the United States). .... Free?
Value 40,741.00 195,713.00 162,864.00
............
Total coal-tar products
............
{gt%able
496,548.13 18,082.00
$ 4,398,483.00
8,734,913.68
IMPORTS OP ISTERMEDIATES FROM GERMANY
The official records of exports of intermediates from the German Empire to the United States show that the following quantities, in short tons, were shipped during the calendar year 1913: ilniline oil and . .................................. Naphthol a n d n e.................................. Anthraquinone nitrobenzene phthalic acid, resorcin, toluidine, etc Benzoic acid, s h c y l i c acid, ahd their sodium salts . . . . . . . . . Total (short tons). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2,640 660 1,067 . 297
__
4,664
THE MARKS O F COAL-TAR COLORS
The great diversity of marks employed by the different manufacturers of artificial dyes is a source of confusion and bewilderment to many, especially to those in the United States now taking an active interest in the evolution of a domestic coal-tar chemical industry, and but slightly familiar with the commercial features or this most complicated of all the varied branches of technology. As the subject has never been treated to any extent in the literature devoted to this industry, it seems desirable to furnish some information of a general character, as explanatory of the symbols used to discriminate between the different shades of dyestuffs. Several of the managers and chemists of the leading firms in S e w York City devoted to the sale in this country of the dyes, tabulated in the census, have kindly responded to inquiries in this connection. The following excerpts from their letters furnish a fairly good portrayal of the few conventional leatures, and the general lack of uniformity characterizing the use of marks for coal-tar colors: T h e customary designation of dyestuffs as practiced by t h e manuFacturers, their representatives, and t h e free-lances in t h e dyestuff business does not appear t o be governed by any set formula. I n t h e early days of the artificial-dyestuff industry when dyes were few, the manufacturers designated distinct differences in h a d e b y t h e letters B , R, and G , signifying blue, red, a n d yellow (gelb). Our French confreres used t h e corresoondinc B. R T (iaune). and V (vert). which became familiar t o dvers Lnd d$&iff u%. ” As dyes- multiplied,”differences in shade became more numerous and it became necessary t o alter or t o augment, as t h e case might be, t h e distinguishing marks. Consequently t h e marks 2 B, or 2 R , or 2 G etc. became common and continue t o this day. Xb uniformity, however, exists between t h e corresponding marks of different concerns. For example Chicago Blue 6 B, t h e lightest and bri-htest of the substantive blues,’is designated in t h e schedule of another fir; as 7 B, while among the products of still another firm it is indicated as el3 rL,.
Such marks serve t o distinguish in a great measure t h e brands of different houses. One skilled in the a r t of buying and selling dyestuffs can, without great difficulty, distinguish a competitor’s types among a variety of designations. As far back as 1888 I went into this matter of type designations, discussed it with prominent dye agents, and was supplied by them a t t h e time with comprehensive lists of their dyes and t h e meaning of their distinguishing letters. These demonstrated conclusively t h a t each firm selling dyes m-as a law unto itself, so f a r as t h e commercial designation of its products was concerned. M a n y individuals in and out of t h e textile industry and dabblers in tinctorial chemistry have entertained t h e idea t h a t there was a key t o a prescribed code of type designations which, in t h e hands of one possessing i t , would unlock t h e numerous combinations of dyes required by individual customers, but this is not so. Wr have, for example, a familiar instance of one oi the smaller dyestuff firms, which designates its dye mixtures b y numbers preceded b y letters. These letters indicate t h e mixture books, Volume A, Volume B, Volume C, etc.. a n d t h e number is t h a t of the mixture. I n order t o dnpllcate t h e mixture as in t h e case of a physician’s prescription, one simply goes t o t h e volume ‘indicated by the letter and picks out the corresponding number. For all time t h a t number holds good for one particular customer. A’o real trade secret is divulged by communicating this bjt of informalion. ,, , ’PhP e. s.. not mean extra. whatever “extra 1s. .....Iettrr .......X ...d.o.. ....npressarilv ..... I n t h e codes of some firms probabfi i t does mean “extra,” presumably higher strength or greater brilliancy or solubility. I n other cases it ,may designate t h e region where certain dyes are sold. S Y , for example, mdlcates brands of colors prepared especially for t h e American market (Piew York). ’The whole subject of dye designations is so complex t h a t it becomes a hopeless problem t o untangle. General references t o i t in literature are scarce, for t h e reason t h a t there is nothing definite t o say upon the subject. It is much like patent medicines; t h e medical trade has not formulated a code t o designate such remedial agents. Some dyestuffs are differentiated from others by appended letters t o indicate their source, or t h e materials of which they are prepared. For instance, one of t h e well-known commercial types of Methylene Bluespecifically Methylene Blue SZ-of no particular merit as t o shade, possesses
V O ~8, . SO.T I
properties peculiar t o itself on account of having been prepared free from zinc (sans zinc). From t h e foregoing it is easily realized t h a t the matter of commercial designations of dyes is very complex. While there are standards i . e . established types of individual dyes, such as those enumerated in th; Schultz tables. from which millions of cornhinations are oossihle. c v w v dyestuff firm has thousands and^ t h o u s a n d s - o f ~ t h e s ecom6inations their books. Each is necessarily designated by some intelligible and comprehensive system in order t o guard against errors and mistakes in compounding when called for. M a n y well-known types of “straight” dyes a s produced b y t h e manufacturer are, per se, of little value when used alone. Their value is brought out when used in combination with other dyes, and this is the strong point of many valuable mixtures t h a t under no circumstance can be replaced by “straight” dyes. While we prefer t o use straipht or unmixed colors, we are frequently compelled t o make use of mixtures, the value of which for dyeing purposes f a r outweighs the usefulness of t h e individual components when used separately. Such mixtures, of necessity, must be designated by different letters or numbers, t o prevent confusion. A common instance of this is t h e very extensive series of combination shades of great value produced with the fast reds and azo scarlets, which may! or may not b i modified in tone by the judicious admixture of acid violets.--L. J . M. h
a
d.
*.
There is no uniform practice and not much of a system in the marks which are used t o distinguish t h e different brands of dyestuffs. T h i s fact may seem rather strange, h u t i t may be readily understood if one realizes t h a t all dyestuff concerns have manufacturing and selling ends of t h e business-two loosely connected departments. T h e dyestuff is sent from t h e manufacturing department t o the dyehouse, which is connected with t h e selling department. Xoth t h e dyehouse and t h e selling department are kept in ignorance regarding the chemical nature of any new product which is brought out. T h e same has, thereforc, t o he classified according t o its shade and its dyeing properties. T h e result is t h a t in many cases the dyer identifies a color with a group of others having similar dyeing properties but which in fact, are chemicallv entirely different. T h e leading principle in nami& t h e colors is less one ofgeneral classification t h a n t o [urnish i h e salesman of a special factory with some hint as t o the dyeing properties of any given color. in most cases it is understood, for instancr, that t h e letter B stands equivalent t o XB, denotes a s;jll bluer for “bluish.” Hence, 2 X , which shade. G means greenish” or ellowish;” R , “reddish;” V, violet.” Apart from these fen- cases of un r m practice the marks are open t o ail kinds of explanation. T h e mark L, for instance, may mean “soluble,” or “fast t o light,” or even may stand for Ludwigshaven, which means t h a t t h e color in question is identical with a well-known product of the, Badische Co. a t Ludwigshaven. I n the same way C may stand for Cassella” (Leopold Cassella & Co. Frauklurt); H for “Hoechst” (Farbwerke vorm. hleister, Lucius & Brkujng, Hoechst a. 31.); E for “Elberfeld” (Farbenfabriken vorm. Frie,$. Bayer & Co., Leverkusen, formerly a t Elberfeldl; a f t Anilin-Fabrikation, and B or A for Berlin” ( ~ ~ ~ t i e n - G e s e l l s c l i fur Berlin). A l l refer t o types against which t h e competitive products have been standardized. The word “extra” indicates eithet;,a special shade or a special concentration. I t is a rule with us t h a t our extra” marks are more concentrated than the single brands, which otherwise bear the same name and mark. T h e letter X is used by other firms in t h e same way a s onr “extra,” for higher concentrations, without, however, giving a n v definite information r~. r m r d i n c the orODortionate streneth. M a l y iug‘geshonshave been L a d e in order t o do away with this rather confusing habit of classification, b u t so far without success. T h e reason is t h a t the selling staff on t h e one hand, and the millman on the other hand, are not expected t o possess much chemical or coloristic knowledge. Such knowledae only mould enable them t o benefit from a more complicated and scientific-systek--A. M~ * * : + e I t is a pretty well-established practice among dye manufacturers t o use certain marks and letters in connection with t h e name of any color. .ill dyestuffs may be said t o vary in shade from red t o yellow or irom blue t o yellow, and this variation from t h e standard type is designated by t h e letters X G R etc. Tal‘;, ibr instance, X e t h y l Violet, which varies in shade from 3 R t o 6 B. T h e 3 R indicates a reddish shade nearly approaching Magenta, and 6 B indicates a bluish shade nearly approaching a product like Victoria Blue B, It follows from this t h a t 3 R means a tint redder t h a n 2 R,3 B means a tint bluer than 2 E . and 6 B denotes a still bluer shade t h a n 3 B. Te!, letter G is generally t h e abbreviation for the German word which means yellow T h e French word for yellow is “jaune.” “Gelb Consebuently, French, Belgian, and sometimes Swiss firms use t h e letter J where Germans use G. English and Amerlcans employ for t h e same purpose t h e letter Y . 2 G means t h e same thing as if the letter G is repeated twice, and 3 G means t h e same as if it were repeated three times. As t o the use of t h e letter X and the word ,‘,‘extra, these two desiguations are by no means alike. T h e word “extra is ordinarily used t o indicate a quality superior t o the regular type. This is sometimes shortened simply to t h e letter X. More generally X indicates t h a t t h e product in question is reduced 10 per cent below the standard typc. X X in t h a t case would mean t h a t i t is reduced 20 per cent below the standard type. T h e mark W indicates t h a t a dye IS employed preferably for “wool,” and H n ’ refers t o “half wool” or union fabrics. T h e mark S indicates frequently a bisulfite compound, a s in t h e case of Alizarin Blue S S R , and SW, Sometimes i t denotes a sulfonic acid, as when used with’ilizarin Red S , SA, and W S , or Fuchsine S, S S , SN,and ST.-E, C. I ‘ . WASHINGTON, D. C.
CONDITIONS AFFECTING THE ESTABLISHMENT OF T H E NITRATE INDUSTRY I N T H E UNITED STATES’ By LAWRENCI:XDDICKS
The general problem of the establishment of the nitrate in; dustry in the United States is complicated by the existence of several more or less conflicting and unrelated factors which fact in large measure accounts for the present confusion as to the relative merits of the various available processes for the production of nitric acid. These factors may be stated as difficulties in 1 Read before t h e 53rd Meeting of the American Chemical Society, September 25-30, 1916
