I 140
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 N G I N E E R I N G C H E M I S T R Y
nickel crucible. T h i s indicates t h a t t h e discrepancy at first observed was due t o s o m e u n d e t e c t e d e r r o r i n m a n i p u l a t i o n with t h e p l a t i n u m crucible fusion, r a t h e r t h a n t o i n a d e q u a c y of t h e nickel crucible. Although, as s h o w n , correct results a r e o b t a i n e d b y using a nickel crucible, i t c a n n o t b e claimed t h a t nickel is as satisfactory as p l a t i n u m . T h e nickel crucibles a r e decidedly a t t a c k e d b y t h e fusion mixt u r e , so t h a t t h e life of a crucible is r a t h e r s h o r t . The i n n e r surface of t h e crucible soon becomes r o u g h and P i t t e d , m a k i n g it s o m e w h a t difficult t o r e m o v e the mass cleanly. T h e fused mass is always colored green by dissolved nickel, a n d i t does n o t slake a n d disint e g r a t e as well as t h o s e f r o m p l a t i n u m crucibles. But,
Vol.
1 1 , No. 1 2
as also m e n t i o n e d b y Ames and Gaither,l poor slaking does n o t affect t h e final result. SUMMARY
I t is f o u n d t h a t t h e s a m e result for soil p o t a s s i u m is o b t a i n e d w h e t h e r t h e soil is fused i n a p l a t i n u m o r a nickel crucible. Nickel crucibles a r e a t t a c k e d b y the J. Lawrence S m i t h fusion m i x t u r e a n d a r e therefore n o t a s satisf a c t o r y as p l a t i n u m crucibles. SOILLABORATORY p+h
LOUISIANA AGRICULTURAL EXPERIMENT STATION “, :BATON R ~ ~ LOUISIANA ~ E ,
____ 1 LOC.
cit.
ADDRESSES AND CONTRIBUTED ARTICLES CHEMICALS RECEIVED BY THE BUREAU OF CHEMISTRY DURING THE WAR*
by means of morphine were futile. All samples of carbon tetrachloride examined contained carbon disulfides. Other liquid organic reagents have been of less excellent quality. B y H. E. Buc Good methyl alcohol is obtainable, but not without a t least For a good many years the Bureau of Chemistry has been traces of acetone. Amyl alcohol of good quality is not to be regularly examining all the stock chemicals purchased. Without had. Not only does it contain appreciable amounts of pyridine going into a detailed account of this work, initiated by Dr. I,. but the boiling range is very wide. This is also true of amyl F. Kebler and carried on under his charge, i t may be said that acetate. Pure benzene seems to be non-existent. Thiophene during the period of half a dozen years preceding the war the and carbon disulfide are always present, and quite often the chemical reagents on the market, mostly of American make, boiling range points to the presence of homologs. were quite generally of excellent quality. During the first year “Absolute” organic chemicals (free from water, etc.) are of the war, according to our records, there was no marked change. generally unobtainable. This is true of acetic acid, methyl Since that time, however, the Bureau has had considerable alcohol and ethyl acetate, which are occasionally desired in difficulty in procuring good chemicals belonging to certain absolute or nearly absolute condition. We prepare our own classes, and we have been occasionally disappointed with chemabsolute ethyl alcohol (not less than 99.8 per cent), having icals belonging to types that generally come quite pure. started to make it ourselves long before the war, owing to the The writer’s experience covers a period of four years, 1915fact that we were unable to procure a dependable grade. 1300 samples were examined. 1919. During that time about I n the case of absolute ether, for the most part the products Of these about 150 shipments were found to be more or less sent to us are good. Occasionally we are obliged to reject unsatisfactory. During a similar preceding period of four years, samples which show turbidity when treated with sodium. Our 1911-1915, during which a like number of chemicals were tested, experience with the preparation of this product, which a t one only about 50 were unsatisfactory. Too much importance time we did ourselves, indicates the necessity of thoroughly should not be attached to the proportion of 150 to 50 as the washing out the alcohol in the preliminary stage. A heavy test kinds of chemicals tested were not exactly parallel. On the for aldehyde seems always to accompany the turbidity obtained other hand, in the latter period, in addition to the above 150, with sodium. a number of tests were made of samples submitted by dealers. Acetic acid (99.9 per cent) complying with the dichromate When these were found unsatisfactory, the agents or manufactest requirement is now unobtainable; but even before the war turers were so informed, thus diminishing the number of shipthis grade was not easy to get. The best grade which we can ments of unsatisfactory chemicals. It should also be added obtain a t present, and that from only one firm, is labeled 99.5 that the shortcomings of the chemicals tested in the war period per cent, but is actually a little higher. Samples that have were more serious than those recorded in the pre-war period. reached’us from other firms rarely go above 99.0per cent. A more detailed comparison between the two periods is hardly ALKALI SALTS-This embraces a number of common and necessary. The main purpose of this paper is to point out the important reagents. For the most part they are of good quality, present situation in regard to ordinary reagents, as shown by but certainly not dependably so. We have on record sodium the examinations made in the Bureau of Chemistry. For the purpose of this discussion the chemicals may be divided into chloride with quite a little magnesium present, and ammonium chloride leaving a high residue on ignition. several classes which differ widely in quality. “Anhydrous” alkali carbonates seldom have less than 8 to LIQUID INORGANIC CHEMICALS-Hydrochloric, Sulfuric, nitric, I Z per cent of water. Sodium and potassium hydroxides, parand phosphoric acids, and ammonia, generally have met our ticularly the latter, a t one time gave us considerable trouble. requirements. The quality coming in now is fair, except for too strong a test LIQUID ORGANIC CHEMICALS-The ordinary alcohol, ether, for chlorides. Incidentally, it should be said that the strength acetone chloroform, carbon tetrachloride, carbon disulfide, of these chemicals is higher than is commonly supposed. Sodium and glycerin have been found satisfactory for practically all chemical purposes. On evaporating large quantities of ether hydroxide comes about 97 per cent potassium hydroxide, hardly ever falls below 86 per cent and occasionally goes above go per the penetrating odor of formaldehyde is often perceived in the last portions. However, attempts to identify formaldehyde cent. Potassium permanganate, long a source of worry to our purchasing office, now comes in good quality, in spite of a rather 1 Presented before the Division of Industrial and Engineering Chemistry novel appearance and color. Occasionally, however, it bears at the Philadelphia Meeting of the American Chemical Society, September more than traces of chloride. 2 t o 6. 1919.
Dec., 1919
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
OTHER SOLUBLE SALTS-while seldom very bad, these are often contaminated with foreign metals, especially with alkali salts, reaching to tenths of one per cent. The mercury salts almost always leave an appreciable residue on ignition, mostly, if not entirely, iron. Zinc salts frequently contain 0.1 to 0.2 per cent of lead. Hydroxylamine and phenylhydrazine salts are grossly impure, bearing a large proportion of inorganic salts, reaching as high as 24 per cent. The following are a few instances of poor chemicals in the above class: Bari.um acetate, 0 . 2 6 per cent calcium, etc. Cob:rlt nitrate, 0 . 8 0 per cent chlorine Hydroxylamine, hydrochloride, 2 1 . 0 per cent residue on ignition Mercuric acetate, 9 . 0 per cent residue on ignition Nickel sulfate, 1 . 0 0 per cent alkali salts Zinc oxide, 0.22 per cent lead Zinc sulfate, 0 . 3 per cent alkali salts
INSOLUBLE PRODUCTS-This heading is meant to include all difficultly soluble products. It is in this class that we have made the largest proportion of rejections. Here an acceptable chemical is the exception; a poor chemical is the rule. A number of instances follow : Animal charcoal, 25.0 per cent residue on ignition Barium carbonate, 3 . 8 per cent soluble matter Calcium oxide, 22.8 per cent loss on ignition; iron sulfate present Calcium, 2.8 per cent foreign metals Copper carbonate, 4.4 per cent soluble matter Cupi.ic oxide, chlorine present Lead carbonate, 7.0 per cent soluble matter Lead chromate, 7.0 per cent soluble matter, largely acetate Lead chromate, 9.0 per cent soluble matter Lead peroxide, 3 0 . 0 per cent soluble matter “ANAI,YZED” CHEMICALS-At no time has it been our purpose to verify the label “analysis.” Our object was merely to pass on the suitability of the chemicals for our work. It is only incidentally that we have noted discrepancies numerous enough and large enough to warrant our distrust of all label analyses, except those of one firm, from which, however, we have received only a comparatively small number of samples.
SUMMARY
during the last four years about 1300 shipments of chemicals from a large number of dealers and manufacturers have been tested in the Bureau of Chemistry. The greater part of the reagents bore an analysis on the label. 2-Most of the chemicals examined are satisfactory. Occasionally impurities are found often enough in chemicals from practically all manufacturers to make it necessary to test all shipments. 3-The standard acids, ammonia, alkali salts and alkali, and most of the organic solvents are generally satisfactory. 4-The soluble salts other than alkali salts are generally acceptable but are seldom of a high degree of purity. 5-Certain organic solvents and solids are either unobtainable or unsatisfactory. 6-The insoluble products are generally unfit for use in analytical work. BUREAU OF CHEMISTRY
u. s. DEPARTMENT O F AGRICUkTURE WASHINGTON, D . C.
REPORT ON THE PRODUCTION OF SYNTHETIC ORGANIC CHEMICALS IN THE RESEARCH LABORATORY OF THE EASTMAN KODAK COMPANY FOR THE YEAR 1918-19191 By C.
E. K. MEES
The preparation of synthetic organic chemicals was commenced by the research laboratory of the Eastman Kodak Company in Presented before the Division of Industrial and Engineering Chemistry, American Chemical Society, Philadelphia, Pa., September 4, 1919.
1141
September 1918 in order to supply the demand for these chemicals by research workers in the United States. Proposals for the work were submitted a t the Cleveland Meeting of the AMERICAN CHEMICAL SOCIETY in September 1918, and there approved by the Divisions of Organic and Industrial Chemistry. A report was presented by Dr. Clarke a t the Buffalo Meeting of the AMERICAN CHEMICAL SOCIETY in April 1919; the present report represents experience in the working of the department for a period of eleven months. Much assistance in the undertaking has been received from the American chemical manufacturers, who have willingly supplied not only materials which they had on the market, but in many cases intermediates which they prepared for their own use. Much assistance has also been received from university laboratories. The University of Illinois has supplied a considerable number of the chemicals prepared under the direction of Dr. Adams. Professor Turner, of the University of Missouri, and Prof. H. I. Jones, of the University of Oklahoma, have also supplied a number of substances. Recently, Professor Acree, of the New York State College of Forestry, in Syracuse, has undertaken to prepare pure sugars and indicators. A wider extension of this collaboration is to be desired. If investigators who in the course of their researches make new or interesting organic compounds would prepare and sell small quantities in excess of their needs, samples for experimental or comparison purposes could then be supplied to other workers. Most substances sold have, however, been prepared in the laboratories of the Eastman Kodak Company and all materials listed under the name of Eastman Organic Chemicals have been tested there. The first list of chemicals was issued in January 1919, a second in March, and the most recent list in August 1919-this containing the names of 550 substances, of which 268 were prepared in the laboratory. Up to September I , 1919, a total of 348 preparations had been undertaken. Substances are listed in three degrees of purity: The “Eastman chemicals” are those of the highest purity which can be obtained. The “practical chemicals” are those which are of sufficient purity for ordinary synthetic work, and in most cases these can be substituted in preparations for the Eastman chemicals, especially as information can always be given as t o the impurities which these “practical chemicals” contain. The “technical chemicals” are those which are available on the market in bulk only but are retailed in small quantities for the convenience of both manufacturer and consumer. The financial situation of the work up to date is not very satisfactory. The total loss in the twelve months during which the department has been running is $14,822, this figure not containing any charges for rent or overhead of any kind, and representing only the apparatus, supplies and labor used in the department. This loss covers the whole of the working period and thus includes the first months, during which production was very low. It also includes depreciation in the value of materials bought, which is mainly due to the lowering of prices during the last twelve months. Many materials can now be purchased for much less than they cost during the war, and it has been necessary to write off the value of the stock to cover this depreciation. The investment in the stock is very considerable. The large number of chemicals held in stock and the considerable average value which they represent makes a very heavy investment necessary. At the present time the sales of materials are rising rapidly; but it is not anticipated that the department will meet its expenses during the next year, even with some increase in the prices, which will be necessary. The main cost is in the labor used for the preparations and is due primarily to the small scale on which the material can be prepared as well as to the new experimental work which is necessary in order to add new preparations. About twenty
