Nov., 1 9 1 j
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
you could invariably find a news item stating t h a t the dye works are practically shut down for want of even simple dyes. 1
I t is a t once amusing and pitiable t o note the superficiality with which these investigations have been conducted. Three weeks ago in the -Ye;,, I-ork T i m e s there appeared a statement that L: corporation was rormetl and \-ery shortly there would lie no dearth of the barium chemjcals necessary for the manufacture of mordants and paper glazing material, and t h a t a great deal of credit should be given to this concern as being the first concern t o manufacture the barium chemicals in the United States, and this just exactly one year after the industry with which I am connected has been steadily turning out hundreds [if carloads. It may be true t h a t I have not trumpeted from thc housetops t h a t the concern which we started was supplying material with great regularity- and of chemical uniformity, and our own Goveriiment did not know it. On the other hand, last Spring a friend of mine sent me a clipping from the German commercial reports giying a full description of the materials t h a t we are making, and an item concerning myself, for the investigator had stated t h a t many German chemists would recognize my name as having been president of a section of the Eighth Iuternational Congress of Applied Chemistry. This was last Spring, and now our own wide-awake Government is noting t h e fact t h a t soon there will be a barium industry started in the trniteti States. One of the L-ery serious drawbacks concerning the new barium industry in the T-nited States is the inability to obtain raw materials and equipment. There isn’t a steel factory in the United States t h a t is not working overtime a t high prices on appliances which are designed to kill people, and as long as this condition obtains we peaceful manufacturers who want new rotaries and new apparatus will simply have to abide our time and pay exorbitant prices until we can obtain parts of new equipment. To give you a striking example, we needed in one of our works a set of bevel gears made of a special metal, and after waiting twelve weeks, because there was no shop in the country which would pay any attention’to us, we finally had to devise gears ourselves as a makeshift. . Nor does this apply to machinery alone, for no one could take any contract on any of the barium salts like the chloride, nitrate or sulfate and hope to deliver a n y part, because it is absolutely out of the question to obtain acids. The people with whom we have dealt for our acids for years are simply either refusing to give us any materials or supplying us with ridiculously small lots a t enormous prices, for there are other channels which buy larger quantities and pay more than the peaceful manufacturer can afford.
I mentioned before that industrial chemistry was 51 per cent business and 49 per cent chemistry, and these figures will serve for a n example. I was often asked why we located a t Sweetwater, Tennessee, and while I did not have very much time to look around I found t h a t t h a t was the logical and strategic location for coal, labor, water and ore, for all of these materials combined are perhaps more reasonable a t t h a t locality than anywhere else I know of. I n the lantern slides, which I will show you later, you will see a graphic description of the method by which the ore is mined, and in order to make a success of this enterprise the works should be located within such a radius of the mine t h a t the ore can be delivered a t a reasonable rate. The great and only question with reference to the barium industry is, shall this industry live after the European war is over, and I could not. answer t h a t categorically without some explanation. I t depends entirely upon our own Government, If, on account of the economic conditions which I have described, foreigners are prevented from underselling us, we shall be able to live. Our own manufacturers should get together and understand t h a t the underlying principle of successful business is to have a profitable business, for no argument is necessary on this point other than t o prove t h a t when you have a growing and
995
going manufacturing concern, in order to have peace and success you must he able to pal- your men a living wage, and you must be able t o pay them regularly, for the shut-down of auy works in any community, particularly in a small one, produces disastrous results. Innocent women and children are made to sut-fer through it, so that in the greed ol obtaining business manufacturers must understand that cut-throat methods lead to I m l results for all parties coiicerned. I hope that when this war is over the barium industry will be firmly established and protected, as the economic conditions in this country would demand. LVhat a remarkable difference there is lietweeii the enterprise in Japan as compared to the ITnitcd States. Japan ha.; suffered from a lack of cheniicals and dyestuffs just 3 s much :IS we have, and both Houses of the Japanese Government have voted to subsidize all corporations anti firms who iir- aiiout to engage in the manufacture of chemicals and dk-estuifs that were the O ,other not formerly made in Japan to thc extent of S ~ , , ~ O O , O O half to be subscribed by thc manufacturers themselves. I t is understood that the subsidy granted is for ten years in order t h a t the new manufacturing concerns may pay :L dividend of at least 8 per cent. I n addition to this i t i.; understood t h a t the Japanese Government has protected these manufacturers in the form of a high tariff. And t h a t is the country to whom we have been sending missionaries in order to convert them from their archaic beliefs and notions. The old order of things could be reversed and Japan could now send missionaries to this country. I t seems to me t h a t it is a great pity that nothing has been done up to now to protect the a-hnerican manufacturer, for a subsidy from the Government is out of all reason, even though this is a t present the richest Government in the world and Japan rated as one of the poorest. As I said before, we cau hope t o succeed only iT our Government will help 11s from being destroyed by outside influences. 320
FIFTH
AvE., N E W
YOKK
NOTES ON T H E EUCALYPTUS OIL INDUSTRY OF CALIFORNIA By 1’. W. TOMPKISS Received April 26, 1915
Euculypius globulus oil produced in California
has bccn characterized, since the Pure Food and Drug Act, by its noxiconformity to the U. S . P . solubility standard in three volumes of 70 per cent alcohol by volume, a guarantee now required by wholesale druggists. While this difficulty can be readily overcome by appropriate fractionating, it is a t the expense of a certain portion of the oil and a cost not favorably comparable with Australian conditions of production, with which we must compete. A feature developed during an investigation of the industry begun in 1912 satisfactorily explains the wide variation occasionally encountered in California oils. A considerable proportion of the trees cut are topped or stumped and the subsequent growth develops a very prolific and dense foilage. Since this new wood is sometimes recut, its influence on the oil derived exclusively from mature trees was determined. Two sections were found where the new foilage (all globulus) was fairly accurately established as being five years old and was from topped trees while the other was a lot of one year sucker shoots from tree stumps. Each batch of 400 pounds imith a minimum of terminal twigs) was separately distilled and is compared with an oil from trees about 30 years old, with salient characteristics briefly determined as follows : OILS
FROM
ElLiUlyfilzlS
Yield, per c e n t . . . . . . . . . . Sp. gr. -25O. , , , , . , , . . . . Sol. 70 per cent alcohol b y Sol. 7 0 p e r cent alcohol b y
globulus. ALL F R O M 1 year . , . . , . . , , , 0 .09 . . . . . . . . . . 0.890 w t . , , . , , , . 15 vols. v o l . , . . . . . . Insoluble
SAN
I.’RAKCISCO
CO.
5 years
30 y e a r s 0.21 0.84 0.906 0.908 1 . 5 vols 3 . 2 5 vols. 45 vols. 15 vols.
Obviously the young growth furnishes much less oil in proportion to its age, and its inferior quality would have an un-
996
T H E J O l ’ R S L I L OF IND1’STRI.IL
desirable influence on any run. Aside from a very marked difference due to locality, observed in oil from mature trees, this young growth would apparently account for the abnormal character of California oils noted from time to time. What age the new growth must attain before its oil fully matures, would be an interesting subject for those having the opportunity to investigate. However, the greatest difficulty the California industry has to contend with, aside from the decreased oil recovered, in order to bring its product u p t o present U. S. P. solubility, lies in the fact ipractically speaking) t h a t Eucalyptus globulus is the only species available in quantities for oil production a t t h e present time, whereas in Australis more productive species requiring no treatment are almost exclusively worked for export. This suhject is best illuminated by quoting some correspondence with Richard T. Baker’ in part as follows: “There is, however, an erroneous opinion commercially as to the percentage content of cineol in the oil of E . gZobuZus and we have species growing naturally in Australia, the oils of which are much richer in cineol than t h a t species, and also yield a much greater quantity’ of oil. These oils are now largely exported from Australia, particularly t h a t of E . poiybractee and are without doubt often sold as the oil of E . g l o b d u s as indicated by the records of their sale. I n fact, there is a t the present time very little oil of E . globulus distilled in Australia, as i t cannot compete against the more prolific oil-yielding species which are richer in cineol. “ I t is not usual to fractionate the oil of E u c d y p t u s globulus and the other rich eucalyptol oils so as t o remove terpenes and thus endeavor t o increase the eucalyptol content, as this is unnecessary with these species. Rectification by steam distillation is all t h a t is necessary. There are species, however, the oil of which can be much improved by fractional distillation and the oil of the S e w South Wales form of Eucalyptus a m y g d a l i m can be, and is so increased in eucalyptol, by separating the large fraction boiling a t about the temperature of eucalyptol; the other portions of the oil are then used for industrial purposes other t h a n pharmaceutical. 4 s a rule fractional distillation, on a large scale, is not practiced to any great extent in Australia in preparing eucalyptus oils for market.” I n addition t o this unequal basis of competition they now employ, in Australia, digesters of much greater capacity than are used here, some of these taking over 3 to 4 tons of green leaves t o the charge. h most interesting feature was developed in the fact t h a t the raw globulus oil from Australia does not conform to L-,S. P.solubility, unless fractionally distilled like our own, though with less loss. Notwithstanding the popular idea that the raw riustralian globulus oil is soluble in 3 volumes of 70 per cent alcohol by volume, it is in reality not so. Through the kind assistance of b l r . Baker this valuable comparison was made possible and in submitting the first sample (broken in transit) h l r . Baker stated in part: “After considerable difficulty I have a t last been able to obtain a sample of the oil of Eucalyptus globulus which has lieen forwarded, etc.” “The oil was without doubt distilled from Eucalyptus globulus and is typical of the oil of this species as grown in Tasmania.” The second samplc also from t h e Island of Tasmania was received with the comment: “ I have after considerable trouble secured another sample of Eucalyptus globulus oil,” etc. Compared with the average raw California globulus oils from San Francisco County, and normal extremes observed from properly distilled leaves (mature) of several localities, the Australian sample gave the following, compared with Baker and Smith’s observations of the N e w South \Vales growth: 1 Curator of t h e technical museum of Sydney. Baker nnd Smith-“A Research on the Eucalyptus with Particular Reference t o Their Essential Oils” published b y t h e Government of Australia in 1902.
1-\’D
ESGI4EERISG CHEMISTRY
YARIOIIS SAMPLES OF O I L S
T‘ol.
;,
So.
11
AUSTRALIA (TasCALIFORXIA (mature growth) mania) S.U’1 Extremes Average Our Baker,p observed S. F. Co. sample Smith 0.901 t o 0.909 0.906 0.9123 0.913 t 1 1 . 4 t o +7.0 +8.0 +3.9 +9.2 1.7 to 1.4 vols. 1.5 l.? 1.5 35 to 13 vols. 15 8 ?
(2.
S p gr. - 2 i 3 ... Rotation l a l T ( a ) S0l.iO7~ alc.bywt. Sol.iO%alc.byvol. Per cent cineol (U. S.P . M e t h o d ) . . 47 to 54 Phellandrene test S e g a t i v e
52 Neg.
54
Neg.
(a) Burke andScalione, THISJOCJRNAL, 7 (1915). 206, found from trees a t Berkeley, Cal.
Ahout 50 Neg. [CY]:+ 14.4
Inasmuch as most oils from Australia are soluble in 1.8 t o volumes of 7 0 ppr cent alcohol by volume, it would lead t o the conclusion, particularly in view of hlr. Baker’s statement and our examination of the Tasmania globulus oil, t h a t this species is not represented in the products received here. Merely in support of its scant production, is the fact t h a t of some ten commercial Yarieties of eucalyptus oil representing the Australian exhibit a t the P. P. I. E., Ezicnlyptus globulus is the species conspicuously absent. I t could hardly be considered guess work to assume t h a t the raw globulus oil of Australia is in reality a s variable in 70 per cent alcohol by volume as our own, when we compare the constants of the Tasmania sample and those found by Baker and Smith, with over twice the specific rotation and 0.3 cc. less soluble in 70 per cent alcohol by weight, a very great factor of influence on the solubility in j o per cent alcohol by volume. Probably the greatest relief home industry could receive, would be by appropriate modifications of U. S. P. requirements in the coming edition, which would permit within reasonably practical limits the use of our globulus oil. The limitations should be sufficiently broad to include normal variations, particularly the solubility in 70 per cent alcohol by “volume.” Among the proposed requirements are: specific gravity a t 2 j O -0.gOj t o 0 . 9 2j (same as a t present) ; soluble in 4 volumes of 7 0 per cent alcohol (undoubtedly meaning jo per cent by volume) ; and containing not less than 7 0 per cent cineol by the resorcin method. However, if 7 0 per cent cineol is t o constitute the minimum limit, then a gravity as low as 0.90j is unnecessary. The proposed solubility in 4 volumes of 70 per cent alcohol by volume with oils containing a minimum of 7 0 per cent cineol when the present U . S. P. calls for solubility in 3 volumes with not less than j o per cent cineol, reverses the needs, since the solubility increases as the cineol increases. T h a t is, if by increasing the solubility to 4 volumes, a mort liberal scope is intended, the 7 0 per cent cineol makes this increase unnecessary and would he a solubility more in keeping with present U. S. P. requirements for j o per cent cineol. If, on the other hand, a gravity of 0.90j (about that of California’s) is meant to include the conditions of a broader range of oils, then the solubility in either 3 or 4 volumes of 7 0 per cent alcohol by volume is entirely inadequate; nor could a natural oil of this gravity contain as much as 70 per cent cineol. 2.2
SUMMARY
I-Appropriate fractional distillation will render California eucalyptus oil up to present U. S.P. requirements, but a t t h e expense of about 15 per cent of the original volume as determined by the present official method. The quality is further improved by the use of caustic soda. 11-Seither Australian nor California globulus oils . in the raw state or redistilled in a current of steam are soluble in 3 or 1 volumes 70 per cent alcohol by volume, without fractionating, though this variety is not the competitive species we have t o deal with in the Australian trade. 111-If the phosphoric acid method is retained as official in the coming U. S. P. the minimum per cent of cineol should remain as a t present, 50 per cent. If the resorcin method is
Iiov., 191j
T H E J O r R N A L OF ILVDL'STRI.lL
adopted the minilnum per cent of cineol could be placed a t 60 per cent without materially interfering with the California industry, but the proposed 70 per cent would entail a loss of a t least 30 per cent of the original volume to bring i t up to this figure if determined by the phosphoric acid method, and about I ,j per cent loss if the cineol is determined by the resorcin method. Il.--The solubility in 7 0 per cent alcohol by volume should lie increased to a t least 18 instead of 4 volumes, if the average raw California oils redistilled in a current of steam without
fractionating (Australian practice) are t o be included on a n equal basis with the foreign importations. \'--The by-product oil of refining as well as the crude (if sufficiently reasonable and in quantities) might be utilized for the separation of metallic sulfides by the flotation process, as extensively applied in -1ustralia and to some degrce hcrc with the foreign oil. LABORATORIES C U R T I S AXD T O M P I i l s s 108 FROKT Sr., SAX FRANCISCO
CURRENT INDUSTRIAL NEWS MARKET CONDITIONS Active inquiry, alarming advances and continued scarcity have been noted for many chemicals and raw materials during the past month. A combination of peculiar circumstances that is unprecedented has resulted in a very sensitive market. Conditions prevailing are such t h a t quotations seldom hold for more than a day. llanufacturers having a surplus of some articles are selling a t a handsome profit and small fortunes have been realized by speculators. Manufacturers in many lines have been compelled to alter their formulae to allow for the use of substitutes where the necessary materials are abnormally high or impossible to obtain. These unusual conditions are justly attributed t o the European war but there are some features only remotely connected with the hostilities of nine nations and some causes entirely independent of the European situation. The cessation of all shipments from Germany is probably the largest single factor although home requirements and embargoes have prevented England, France, Russia and Italy from permitting or making normal exportations of many commodities. The war has re' sulted in a scarcity of freight room o n ocean \-essels, higher rates for freight and insurance, and a general uncertainty. Contracts for the manufacture of esplosives for the entente Allies are responsible for the scarcity and high prices noted for carbolic, picric and nitric acid, nitrate of soda, glycerine, ether, benzol, toluol, aniline oil and many other coal-tar derivatives. Nitrate of soda in normal times enters commerce principally for fertilizer. During the early months of the war, large stocks were held a t most receiving and shipping points; with a large portion of foreign markets closed, operations in Chile mere brought almost to a standstill and prices were very low. As the war continued the demand for nitrate increased and operations a t producing points were increased t o normal with quotations slowly advancing. About a month ago unusually large purchases in Chile were credited t o explosive interests and great strength developed. Then came the last big slides in the Panama Canal and the subsequent announcement t h a t Canal traffic would be suspended indefinitely. This resulted in the market reaching $3.00, the highest point in several years. Cargoes will no\$-come "round the Horn" and increased freights and the growing scarcity will probably result in further advances. Glycerine was not attracting any particular attention in the markets a month ago and C. P. was available a t 2 6 cents and "dynamite" a t 25 cents. To-day i t is difficult for any buyer to secure supplies, except subject to delays, although the current quotation is 60 cents per pound for both C . P. and dynamite grades. One consumer was in the market a few days ago for I ,.jOO,OOC) pounds. The high prices and active demand h a w resulted in a n increased production and this is proving the most profitable business t o most of the soapmakers. 1-egetable oils are being purchased in large quantitieq for this purpo liiiseed oil appears to be the only- one not profitahlc.. Inability to securc supplies of potash salts has resulted in xncl obnorinal price\ for tnally chemical e o ~ n p o u ~ ~ d s thc e1irni11;~-
1
tion of some from the market. Dealers and brokers have verily scoured every corner of thc globe in search of old stocks of German potash, so t h a t now little muriate or sulfate i.; to be had except from third hands who naturally look for a substantial profit. Muriate of potash, however, is available in a limited way a t Sz4j to Szjo per ton. Scarcity of the various forms of potash has found the soda compounds being substituted to such a degree that sharp a& vances are common. Yellow prussiate of potash is to-day selling a t 87 cents per pound as compared with I I ' I cents bcfore the beginning of the war. Red prussiate of potash commands $2.60 to $ 2 . 7 5 per pound as compared with 2 1 cents in Jiily, 1914. These advances result in such an increased use of soda compounds t h a t prussiate of soda is to-day selling a t 44 to 45 cents per pound, as compafed with 8l 2 to 8:' cents during July, 1914. Bichromate of potash is held a t 2 1 cents per pound as compared with a normal price of 7 cents or less. Bichromate of soda is selling a t 1 5 to I G cents and quoted a t 1 4 to 14' for winter deliveries as compared with 43 1 cents belore the wzr. Chlorate of potash is to-day bringing 37 to 35 cents per pound as against the old price of i1i to 7' 2 cents. Chloratc of soda sells to-day a t 2 2 to 23 cents per pound on spot with contracts for future deliveries commanding 11to 16 cents f . 0 . 11. work.;, as compared with 7' '4 t o 8 cents a little more than a year a g o .
In July, 1914, aniline oil was selling at IO^,'^ to I I cents per pound while to-day one can sell a t 9 j cents to S r . j o per pound, according t o urgency of the consumer's requirements. Aiiiliiiv salts a t present command S 1 . 3 j to S I . ~ O per pound whereas 9 cents was the average price fifteen months ago. Benzol is now selling a t So to 90 cents; not long ago inany orders WI-C filled a t S I . 2 j to $1.40; just a little o\-er a year a g o , plentii'al supplies could be had a t 2 2 cents. The foregoing are only a few instances of thv up\vard trend: further reference to a price current of July, 1914, s h o w the pricr of oxalic acid a t 7 l / 4 to 7 l , P cents; this week sales were recorded a t 4 j and 46 cents and quotations are as high as 50 cents. \Ye have depended on Germany and other foreign sources to supply us with oxalic. Lead products were very high for a time but present levels are close to normal. Zinc products are high and scarce but Quicksilver sells to-dal- a t not as high as a few months ago. $93 to $95 per flask as against a normal figure of 3 7 5 . One of the principal reasons for the extreme high prices is that manufacturers ha\-c contracted for their entire output and consumers not fortunate in holding a contract for regulardeliveries are a t the mercy of second hands who arc reaping profits while they may. H o w long present conditions will prcvail is a question t h a t interests many. The duration of European hostilities is the most important factor although this may be overcome, to a degree, by more generous supplies of needed raw materials. Further ad\-ances are predicted and are to be expected for many articles. X sudden cessation of thc war would result in declines b u t well-posted factors claim that i t would be many months before the old levels were restored But few commodities have reniainctl Inictically uiichallge(l
