Oct.,
1911
Y’tl;; JOUR,VAL OF I N D U S T R I A L AiYD E N G I N E E R I N G C H E M I S T R Y .
and until the !+acts : re questioned, there is no “point at issue.” Very l . l k < l ythe effects which all pigments have on oil, whet1,c.r as stimulators or inhibitors of oxidation or any otlirr ;x-ocess, are due t o catalytic or contact action; I do n o t “feel” t h a t , as Mr. Gardner does, but I think i t ; so we will not quarrel. I think all pigments have some effect on oil, not depending on their fineness but on their chemical qualities; and t h a t i t is incorrect t o call one inert to oil if it has a noticeable effect on i t , whether t o retard drying, like gypsum or lampblack, or t o hasten the destruction of the film, like CaCO, or BaSO,. We do not regard spongy platinum, as used in making H,SO,, as an inert substance, although it does not dissolve or undergo a chemical change. All pigments are, b y definition, nearly or quite insoluble in oil; PbO and oil form a cement rather than a paint. PbO is considerably soluble in oil; and it is likely (but not certain) t h a t the minute amount of P b which was found in oil which had been mixed with white lead was from a t.race of PbO in the pigment. I can in no other way understand why oil stops dissolving lead when the basic carbonate (containing hydrate) is present in unlimited amount. I n practice we add P b or hln compounds to white lead paint to make it dry, in about the same amount t h a t we do t o other paints; for all practical purposes the quantity of P b dissolved is of no account. It is the same way with red lead; true red lead does not combine with oil in the way Mr. Gardner describes; t h a t with which he experimented probably contained as much as 2 0 or 30 per cent. of PbO. Orange lead, which is red lead nearly or quite free from PbO, will remain uncombined with oil for years, and good ordinary red lead made b y modern methods will do so for a month or more. When saying t h a t white lead is alkaline, Mr. Gardner doubtless means basic; lead is not an alkali metal. If he has any evidence, or knows of any, t h a t white lead or zinc saponify oil a t ordinary temperatures, he should publish i t ; i t would be new and important; also how I O per cent. of a chemically inactive substance can hinder saponification. A. H.SABIN.
To the Editor of the Journal of I9zdustrial and E+t z e e r i q Citeniistry. SIR: I n the July number, 1 9 1 1 ,of THISJ O U R I ~ A L there is a description b y Mr. George P. Meade of a continuous sampler for condenser waters from evaporators. There is an advantage in such an apparatus, it seems t o me, for taking samples of condenser water throughout a strike. Where the entrainment is likely t o vary much, as in vacuum-pan boiling, i t - is quite necessary t o take a continuous sample or a great many samples throughout the strike, in order t o make an accurate determination of the entrained sugar. But this is the only case, I believe, in which a n apparatus of this kind is of any especial advantage. In multiple-effect evaporators the entrainment is usually quite constant, so t h a t a few samples taken intermittently are as of much value as a continuous
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sample. There are, moreover, some objections t o the use of a sampler of this kind. It is quite as important in determining the loss of sugar t o know the amount of water leaving the condenser as t o know the percentage of sugar in it, and it is usually necessary t o determine this from the temperatures of the water entering and leaving the condenser. In order t o do this the temperature of the sample must be taken immediately as i t is drawn from the tail-pipe, or . a thermometer must be inserted into the pipe. It is also important that the sample of water shall be evaporated and polarized very soon after i t is taken since, on account of its being such a dilute solution and warm, the sugar in it will ferment quickly. A continuous sampler may therefore very easily be misused. I n view of these considerations, it seems t o me t h a t a short piece of pipe, with two valves or corks on i t , which can be used on either the vertical or horizontal part of a tail-pipe, is more generally applicable and more likely t o give accurate results than a continuous sampler. R. S . SORRIS. HONOLKLU. July, 1911.
THE DETERMINATION OF CAMPHOR,
The extensive use of camphor in medicine and the fact t h a t the Pharmacopoeia includes preparations which must contain definite quantities of camphor make it imperative t h a t there should be a reliable method of assay. There have been in vogue for some time procedures depending on the rotation of a n alcoholic, benzol, or oil solution and on the loss b y evaporation, but they are open to objection, and in certain instances the results might easily be misinterpreted. Artificial camphor is without rotatory power, natural camphor might contain a portion of the levo body, the rotation varies with the strength of the solvent, and fixed oils themselves on heating often undergo loss or gain in weight. These are a few of the reasons which call for a method based on a more substantial foundation. Camphor, being of ketonic character, forms with hydroxylamin a well defined oxim, C,,H ,,NOH, and advantage has been taken of this property in assaying camphor preparations, the procedure being based on Walther’s carvone* estimation and on the work of Nelson,z who determined in essential oils by the hydroxylamin method a number of ketones including camphor. The procedure is simple and may be applied directly t o spirits of camphor. Of the sample 2 j cc. are measured into an Erlenmeyer flask of r o o cc. capacity, 2 grams of sodium bicarbonate are added, and then, accurately, from a burette, 3 j cc. of a hydroxylamin solution ( 2 0 grams NH,OH.HCl 30 cc. H,O 1 2 j cc. absolute alcohol aldehyde-free). The flask is connected with a reflux condenser, and heated to gentle boiling for two hours; it is then cooled t o 25’ C., treated with a mixture of 6 cc. hydrochloric acid ( 1 . 1 2 specific gravity 6 cc. water), transferred t o a 500 cc. volumetric flask,
+
+
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Phnrnr. Cenlrulhdle. 41, 613 (1900). U . S. Dsgt. Agr., Bureau of Chemistry, BILL/.137. p. 186.
792
T H E J O U R N A L OF I i V 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 .
rinsing out the condenser and flask with water, and finally made up to volume; 5 0 cc. portions are filtered off and titrated as follows: Methyl orange is added and the mineral acid neutralized with normal alkali, then phenolphthalein is added and the hydroxylamin hydrochlorid titrated with tenth-normal alkali. A blank must be run,using the same amount of hydroxylamin solution and 2 5 cc. of alcohol t o correspond with the spirits of camphor, the difference in titrations representing the hydroxylamin converted into camphor oxim. Each cubic centimeter of tenthnormal sodium hydroxid is equivalent to 0.01509 H. C. FULLER. gram of camphor.
r.s
DEPARTMENT O F AGRICULTURE, BUREAUOF CHEMISTRY
GENERAL NOTES. Professor Charles L. Parsons, Secretary of the American Chemical Society. has been appointed Chief Chemist of the Mineral Division of the Bureau of Mines, and has been placed in charge of the work in mineral technology. Professor Parsons will take immediate charge of the investigations along the lines of conservation development and use of the mineral products of the country and make special studies of the processes used in their manufacture. As soon as the plans for the development of this work are completed headquarters will be established in Washington.
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Dr. F. G. Cottrell has resigned his professorship in the University of California in order t o accept the position of Physical Chemist with the U. S. Bureau of Mines, with headquarters for the present a t the Aston House and Appraiser’s Building, San Francisco. Up t o the present time the work of the Bureau of Mines has centered around the coal mining industry, b u t this year it is beginning in a modest way some work aimed directly a t the metalliferous field. Professor Cottrell’s work will start with the general fume investigation, b u t i t is felt, in view of the interest of the mining and metallurgical communities, t h a t appropriations will be made later which will make possible the growth and development of work in the metallurgical industry.
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Statistics compiled by the United States Geological Survey show t h a t the production of spelter or metallic zinc from ore for the first six months of 1911 was 140,196 short tons, a gain of more than 5 , 0 0 0 tons over half the record output of 1910. Of this production, 5,135 tons was made from foreign ore. Spelter stocks were reduced from 23,232 tons to 17,788 tons. Imports remained about the same but exports were nearly double those of half the preceding year. The apparent consumption of spelter was 135,497 tons, an increase of more than 1 2 , 0 0 0 tons over the half of 1910 b u t about the same as in half of 1909. The average price of spelter a t St. Louis for the period was 5.36 cents per pound, the London average being 0 . 2 cent less per pound. During the
Oct., 1 9 r r
latter part of May and the first part of June the average London price was about 0.1 cent higher than the corresponding St. Louis prices. Under this stimulus the May exports of spelter, zinc ore, and dross were largely increased over those of the preceding months. The Bureau of Standards has recently issued Circular No. I I , entitled “The Standardization of Bomb Calorimeters.” It contains some very valuable suggestions and instructions relative t o the manipulation of bomb calorimeters and also points out the important features t o be considered with respect t o the type and construction of bombs, water equivalent, and method of calculating results. The Bureau is now prepared t o furnish standard combustion samples of about j o grams each of sugar, naphthalene, benzoic acid, etc., accompanied by a certificate giving the heat of combustion of the sample, a t $2 each. They are also prepared t o determine the water equivalent of any type of calorimeter including corrections to the accompanying thermometers. This question is of very great importance, and every chemist who has anything t o do with the use of calorimeters should avail himself of the opportunity of a t lea’st securing a standard sample and have the thermometers properly standardized. Cement production in the United States during 191o has been officially reported upon b y Mr. Ernest F. Burchard, of the United States Geological Survey. These figures compared with those for 1909 are as. follows : Barrels. 1909.
S a t u r a l and puzzolan . . . . .
Portland. . . . , . . . . . . . . . . . .
Total.. . . . . . .
. . . . ,. . .
1,698.284 64,991.431 66.689.7 15
1910 1,235,190 75,699,485
-__ 76,934,675
Prof. James R. Finlay in his report t o the State Tax Commission on the Lake Superior copper mines places their total value at $69,815,000. The Calumet and Hecla mines are appraised a t $31,400,000, and, it is estimated, have a life of twenty years. The tailings dump of this company contains 37,000,ooo tons of rich conglomerate sands with a value of $4,500,000. Six lodes support profitable operations : the Kearsarge, Osceola, Pewabic, Isle Royale and Baltic amygdaloidal beds and the Calumet conglomerate bed. The Lake Superior district stands alone as a low cost producer of copper.
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The price of platinum has continued t o advance and a t present quotations an ounce of the refined metal is worth 2 ’ l P ounces of gold. Moreover, the tendency is still upward and further advances are expected. Advices from Russia indicate t h a t the present season will see a decrease rather than an increase in the output from the older placers of the Urals. The Fidelity Chemical Corporation of Houston, Texas, has been incorporated with $60,000 capital
