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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
d.
a
*.
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 for “bluish.” Hence, 2 X , which equivalent t o XB, denotes a s;jll bluer ellowish;” R , “reddish;” V, violet.” shade. G means greenish” or 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; and B or A for Berlin” ( ~ ~ ~ t i e n - G e s e l l s c l i fur a f t Anilin-Fabrikation, 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 “Gelb which means yellow T h e French word for yellow is “jaune.” 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
NOV. , I9 I 6
T H E J O U R N A L OF I N D U S T R I A L A N D E X G I N E E R I N G C H E M I S T R Y
properly evaluating ( I ) mili.tary necessity, ( 2 ) the forced-sale price of Chilean nitrate, ( 3 ) certain technical difficulties, (4) the attitude of the Government regarding water power development, and (5) that of the farmer toward changes in fertilizer practice. The standard method of manufacturing nitric acid by digesting sodium nitrate with sulfuric acid is very satisfactory. The investment in plant is reasonable, the process is simple and the end-product is nitric acid in quite concentrated form. As sulfuric acid and nitre are easily transported, such a plant may be operated anywhere, while nitric acid is a t best an undesirable article of freight. It has been long evident and for a little while generally appreciated that were we to have ;a war with a first-class power about half our navy would be engaged in protecting our line of communication with Chile instead of protecting our coasts, and, as nitric acid is indispensable in the manufacture of explosives, this has given the government a special interest in the development of a process requiring no imported supplies. This introduces the question of military necessity, which is a need for a prompt supply of concentrated nitric acid in enormous quantities upon a sudden demand and in a time of commercial isolation. In view of the tremendous expenditure of explosives in the European war it is hard to stipulate our maximum need, but considering only defensive warfare and that distance from possible enemies would make the assembling of a nation’s entire land fighting force against us very unlikely, the estimated requirements are much more than the probable consumption of nitric acid as such in peace times a t present. This means that if the Government undertakes to guarantee its requirements by building and operating a plant it will cripple industry in two directions-first by marketing nitrates a t forced-sale prices in time of peace in order to keep the plant in shape and justify the investment, and second by stopping commercial exploitation of one or more of the processee for producing nitrates now in private hands. The alternative is to stock a large quantity of Chilean nitrate, which is easily stored, until the day when commercial rivalry develops the best process. Thus the military argument instead of stimu1,ating work on the production of nitrates has an unpleasant possibility of strangling it. If we dismiss the military preparedness issue we are a t once confronted with another problem-how low can the price of Chilean nitrate be driven by domestic competition? Nitre is generally considered to command a price of a little over zc. per lb. in this country in normal times and the total available supply in Chile is estimated a t thirty years more or less, so that progressive exhaustion would tend to send.the price up as the years pass. On the other hand these nitrate fields have enjoyed such a natural monopoly of. the market that they have never had to meet real competition. It must be remembered that about onefourth of the assumed saleprice goes to the Chilean Government as an export duty, that increased trade with South America may drive down freight rates for return cargoes, and that improved mining and leaching methods may lower costs. Finally the life of the district is constantly being extended by including leaner deposits than formerly thought workable, so that it is quite possible that the forced-sale value of Chilean nitre may prove to be surprisingly low. Then we come t o the processes, of which there are a surprising number considering the difficulties of the problem. They may be classified tCchnically as chemical, electrochemical and biochemical; or by source, as utilizing the nitrogen in the atmosphere or that in coal; or finally as producing nitric acid directly by the combustion of atmospheric nitrogen or indirectly by the oxidation of ammonia. Altogether there are some ten distinct processes, most of which have enthusiastic advocates in this country, and I have been solemnly assured by the representatives of three that each has been the method relitd upon by Germany these last
I049
two years, which probably simply means that that blockaded country has found it necessary to use every source of nitrogen available to meet the combined demands for explosives and fertilizers. The mostdirect process is of course the oxidation of atmospheric nitrogen in the electric furnace upon which so much work has been done in Norway. This is an enormous consumer of power but no greater than the standard process for the reduction of aluminum per ton of product. The hopeful part of this process to me is its low efficiency, but z or 3 per cent of the nitrogen in a given volume of air being oxidized a t last accounts. On the other hand the efficiency is high when the equilibrium of the reaction under the conditions of operation is considered. We know, however, that greater efficiencies are possible with mixtures &her in oxygen than the atmosphere; this is interesting when coupled with the fact that oxygen obtained as a by-product in the cyanamid process is a t present thrown away. Other ways of obtaining conditions affording an increased yield may be discovered and an improved efficiency lowering the power cost would give the arc process a commanding position, the raw materials being free and present everywhere in unlimited quantities. The cyanamid process appears to be fully developed and the high efficiencies obtained in every step of the process would seem to preclude the possibility of any great lowering of the cost in the future. I t has the advantage, however, of making several useful intermediate products and in fact from the nitrate point. of view cyanamid may be considered simply as a raw material for the production of nitric acid. The Haber process for the synthesis of ammonia seems to have surmounted great obstacles abroad. It makes no demands for power beyond a reasonable quantity of coal and the records olp the patent office indicate that serious attempts are being made to make the working conditions less extr‘eme. Passing over the various. processes based on nitrides or cyanides and similar compounds, of which cyanamid has been the only notably successful instance so far, we have the biochemical action which is the basis of the “saltpeter plantations” of the East Indies.1 Wood ashes, animal refuse, stable products and earthy material are piled up and allowed to stand for several years, when i t is found that the outer crust contains potassium. calcium and magnesium nitrates which can be leached out. This bacterial action is worthy of systematic study. Finally we have the large and steadily increasing outplrt of ammonium sulfate from the by-product coke ovens in various parts of the country. Unfortunately little or no work seems to have been done on the oxidation of crude ammonia to nitric acid, and it is hard to form any just opinion of the magnitude of the difficulties reported in the poisoning of catalyzers by iml;urities. Truth to tell when ammonia is available as a market product, but little commercial interest has been shown in the further step to nitric acid owing to its limited market, and only the arc processes enter the field by compulsion. Practically all of the processes have to meet the problem of concentrating dilute nitric acid and all but the arc processes must contend with the more formidable one of the economical oxidation of ammonia. The electrochemical processes have the power cost problem in addition and altogether we have the elements of a first-class family quarrel in selecting the method best adapted to our local needs. If the Government keeps hands off for two or three years the quarrel will go merrily on and result in the survival of the fittest. The water power problem has a very serious bearing on this whole matter. In fact it is possible to range the arc process, the cyanamid process and the Haber process in any order we desire as to cost by suitably varying the cost of power. Unless water power is available it seems certain that no electrochemical process can survive and the hhole legislative situation regarding 1
Remsen‘s “Inorganic Chemistry,” p. 488.
T H E JOCR-VAL O F I N D U S T R I A L A N D ENCIAVEERING CI’EMISTRY
I O j0
the use of water rights in this country has been impossible for ten years. Until this has clarified, the chemical processes, which a t present have the advantage, always have to face the possibility of a truce between the conservationists and the liberals which may turn the field abruptly over to the electrolytic methods. Finally w e have the American farmer to deal with. He insists on being supplied with a complete fertilizer, which can be put on in a single application and fed through drills which cuts out any hygroscopic material This means that nitrogenous products must either be sold to a fertilizer manufacturer or made the basis of a fertilizer manufactory. In order to get around this, various bucolic advisory staffs have been organized by competitive interests and the farmer is being shown one week why ammonia is better than nitrate and the next why nitrate is better than ammonia, and so on Said farmer has by this time probably reached my own conclusion, that the whole problem is both interesting and complex, if not convincing, but when he finally makes up his mind i t may have much t o do 17-ith the establishment of the nitrate industry in these United States. 126
LIBERTY
STREET
KEW YORK C l T Y
WHY OUR CHEMICAL IMPORT STATISTICS SHOULD BE OVERHAULED’ B y BERKHARD C. HESSE
On three previous occasions2 I have pointed out in more or less detail the need of a revision of our chemical import statistics, more particularly in reference t o the need of a finer subdivision of the itemization of the entries and have indicated how this might be accomplished. Assurances of enthusiastic and sympathetic cooperation have been received irom a number of technical and commercial associations and organizations, as well as from the Department of Commerce and from the United States Geological Survey. Many high executive officers of domestic chemical manufacturing and merchandising enterprises have assured me of their belief and faith in the great potential good residing in such an effort, and editors of our leading trade publications such as the Oil, Paiizt and Drug Reporter, of New York, and the Paint,Oil and Drug Review, of Chicago, have in sincere and emphatic editorials seriously commended this endeavor t o the thoughtful consideration of their readers and have urged intelligent and prompt cooperation. It is, therefore, only reasonable to assume that these proposals bear, on their surface a t least, evidence of potential constructive good for the country a t large. It now remains for us to realize this supposed potential good. T o this end the cooperation of all the sections of the American Electrochemical Society and of the American Chemical Society has been solicited and there is plenty of evidence of a whole-hearted desire on the part of all t o contribute all they can and to cooperate t o the extent of their opportunities and ability. As a result of considerable correspondence with sectional secretaries and of conversations with a number of local councillors during the holding of the Second Kational Exposition of Chemical Industries last month, it has seemed to me that after all I had not succeeded in clearly bringing out the crux of the situation, so that all were clear as to just what was wanted and as to how it might be done, although quite a number of sectional secretaries did fully get the ideas and suggestions conveyed by my publications and have proceeded accordingly. In view of the situation as a whole, it may be vxll to say what are not the objects of this project, since many seem to have Presented at t h e Joint Meeting of the New York Sections of the American Chemical Society, American Electrochemical Society and the Society OF Chemical Industry, Chemists’ Club, October 13, 1916. 2 Tnrs J O U R N A L , 7 (19151, 58; 8 (1916), 672 and 749.
T-ol. 8,SO.1 1
obtained enlarged notions of its scope, which would be unworkable. I . We are not now concerned with exports in any sense. 2. We are m t now concerned with prices or quantities in any sense. 3. We are not now concerned with locus of import or consumption. 4. T e are n o t concerned a t any time with the namcs of users or importers. What we are after is the names, and the names only, of those things that in normal times come to us from abroad a.nd are used by or can be made by a branch of our chemical industry. For example, what material of construction or what chemical raw materials come to us from abroad which our domestic chemical industry in any branch thereof needs? What materials that can be made by a branch of our domestic chemical industry are imported? It must be noted that quantities, prices-unit or otherwiscand locus of consumption are wholly irrelevant and immaterial, and any attempt t o superimpose those data upon the simple request for names only of materials, etc., will very likely lead to confusion and embarrassment and probably refusal. It is merely a gzmlilaiive list we are now after. S o w , why should we want such a list and why bother you with the labor of finding that list out? That is a question that I have been frequently asked. The answer to that is that the person does not live mho can formulate a sure-enough definition of a product of or for chemical industry that will be intelligible t o any one and that would answer our purposes. Obviously our government cannot feasibly list separately each of the thousands upon thousands of different articles that enter our ports, and if it did so list them many of them would,not be used. Just think of the sized volume that such a list mould require ! Since a verbal definition is out of question the only refuge is in illustration. S o w , your answer, like others, may very well be: “Tell the government we want all products of and for chemical industry listed item by item. Give them a copy of all chemical catalogues and tell them we want t o know all about each item in those catalogues.” Now the answer to that kind of an answer is that it is no answer a t all. Self-evidently, we as American commercial, industrial or manufacturing chemists cannot possibly be interested in every chemical listed in every chemical catalogue, and moreover, we are interested and deeply so in many things that never are mentioned in any chemical catalogue of any kind. For the same reasons we cannot refer the government to any one of the numerous Buyers’ Guides. We cannot give the government a blanket list for thc simple reason that there is no such list. England, France, Germany, Sweden, Canada, Switzerland, Italy and the United States, each and all have a different oflicial notion of where products of and for chemical industry begin and end. Our own government’s list is not adapted to our best service and I am sure that none of the other governments’ lists would be satisfactory. I have compiled such a composite list which has been published in a t least €our placesi Your next question will probably be: ‘%’hat will you do with that list after you get it?” TQthat the answer is that the Central Committee, of which I am chairman, will, if the response is satisiactory, compile all of the submitted material into a composite list and ask the government to give us the quantities and values imported monthly, quarterly or annually as may appear best suited to our needs. Then you will say: “Be sure and get a good classification; have it logical and scientific; the present classifications are so illogical and so unscientific.” The answer to that is that we cannot, in reason, ask the government to alter its mode of 1 THIS JOVRXAI,, 8 (1916), 749; M e t . b’ Chem. E n p . , 15 ( l 9 1 6 ) , 143; Oil, Paint and Drug Repouter, July 31, 1916, p . 16; Paint, Oil apid Drug Review, A u g . 16, 1916, p . 11.
