T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING C H E M I S T R Y
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and contained bones. it was not entirely eaten. “On the whole, then, these experiments [and others’ described in the report b y Atwater but omitted here]* bear unanimous and convincing testimony in favor of the easy digestibility and high nutritive value of animal foods in general and of fish guano in particular when fed t o sheep and swine. How far they could be made profitable for other herbivorous animals than sheep has not yet been tested. I n the nature of the case there is no reason why they should not be as nutritious for neat cattle as for sheep. As Voit has justly observed, all mammals are a t one period of their lives, when living upon milk, carnivorous. * * * “ I n short, we have every reason, from practical experience, from actual experiment, and from what we know of the nature of the case, to believe that the immense amount of animal waste produced in this country from our slaughter houses, and especially from our fisheries, can be utilized with the greatest ease and profit t o supply the most pressing need of a most important part of our agriculture, nitrogenous food for stock.” “The ingredients of fish may be made more available for plant food and their value for manure increased by * * * feeding to stock, thus putting it through a process similar to t h a t by which Peruvian guano has been formed. I n this way i t can be used t o enrich the manure made on the farm, and thus made one of the best aids to successful farming.” Concerning the utilization of fish.scrap as cattle feed, Henry, in ‘Feeds and Feeding’ says: “Dried Fish.-Along the coasts of Europe the waste parts of fish, as well as of fishes not used for human food, are fed in dried form to animals. Spier of Scotland reports no bad influence on milk when reasonable quantities of dried fish are fed to dairy cows. Nilson found t h a t 80 parts of herring cake could replace I O O parts of linseed cake in the ration for cows. The better grades of dried fish meal should be used for feeding farm animals. “Flesh M e a l , Fish Scrap.--In a trial by Schrodt and Peters, bran and rape cake were gradually replaced by equal quantities of flesh meal until the allowance of the latter reached 2 . 2 pounds per head daily. It was found that the customary shrinkage in live weight when in full milk flow did not occur, and there was a n increase in the total quantity of milk as well as in the total solids and fat. Flesh meal effected a saving of 2 Ibs. of feed per head daily, and the cows learned t o relish it highly. “According t o Kuhn, milk and butter of normal quality were produced on a daily allowance of 2.3 lbs. of fat-free fish scrap supplied with a variety of other feed, no deleterious effects resulting.” The universally affirmative results of all the recorded experiments with fish scrap as a cattle feed leaves little room for doubt as t o its efficiency. It is, indeed, surprising that its use as a feed has not been
*
1 By Wolff, Wildt, Kellner, and m’eiske, described in “Die Landwirthschaftlichen Versuchs-Stationen.” “J. f . Landwirthschaft”and “Landswirthschaftliche Yahrbiicher.” 1 8 7 6 and 1S77. * Note inserted by w.riter, J . W .T.
Vol.
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more generally introduced. This is doubtless due to the lack of exploitation on the part of the manufacturers, the ones most vitally interested financially. I t will be recalled that in the beginning of the cotton-seed oil industry, the expressed cake was a by-product which found use only in the fertilizer industry. I t s subsequent exploitation as a cattle feed gave it a much enhanced value. To-day it is produced in immense and constantly increasing quantities, and the portion of i t which enters the mixed fertilizer is much less than the amount used as cattle feed. We venture t o predict that, in t h a t particular, the history of fish scrap will parallel that of cottonseed meal; that the time will soon come when i t will be recognized by both manufacturer and farmer that its preparation and use as a cattle feed is more profitable to both than when employed only as a stimulation for growing plants. And fitting, indeed, i t would be t h a t even a small part of the millions of pounds of combined nitrogen carried seaward annually by the rivers should be returned and, after a short cycle, again be rendered suitable for man’s consumption. L’.
s.
BUREAUOF SOIIS DEPARTMENT OF AGRICULTURE wASFIINGTONs
D.c.
SOME ANALYSES OF FISH SCRAP’ E. G . PARKER Received March 13. 1913
By J. R . LINDEMUTH AND
A small number of samples of fish scrap were taken, for the most part in person, b y J. W. Turrentine, of this Bureau, during the fall of 1 9 1 2 . No attempt was made t o obtain a complete series from all the plants of the Atlantic coast, but those obtained may be regarded a s typical. The samples were gotten from open heaps of scrap in the storage houses, or from bags by means of samplers, or by opening the bags. They were shipped in canvas sample sacks. Before analysis, the entire sample was ground t o a powder that would pass a sieve of 16 apertures per linear inch. LVIethods of A.izalysis.-Samples of 2 grams were dried to constant weight in a n electric oven a t a temperature of about 100’ C. The loss in weight was recorded as moisture. I n this connection i t should be said t h a t it is believed t h a t possibly some oil also was lost in this operation. Oil was determined by extracting with carbon tetrachloride a 2-gram sample, previously dried t o constant weight. For the extraction a Soxhlet apparatus was employed. Following the extraction, the sample was again dried t o constant weight and the loss taken as oils. I n the determination of nitrogen, the official, modified Gunning method was applied, and in t h a t of phosphoric acid, the official gravimetric method was used. The results are recorded in the subioined table. The eleventh analysis is reported in thk table merely for convenience. I t is the analysis of pulverized crab shells used as a filler for mixed fertilizers. The particular adaptability O f this material for that purpose is brought out by the analysis. 1
Published by permission of the Secretary of Agriculture.
T H E JOURNAL 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
May, 1913
389
TABLEI Nitrogen Phos. (PaOs) Moisture Oils DESCRIPTION Per cent Per cent Per cent Per cent From Eubanks Tankard Co. Dry scrap (from 6 sacks) 8.93 6.17 6.48 5.91 From Taft Fish Co. Dry scrap (sample from 525 tons) 8.96 '7.75 6.18 6.81 From Carter's Creek Fish Guano Co. Dry scrap, dried in hot air ard steam driers (from one sack) Fall product 7.70 5.22 11.68 6.62 Cape Charles, Va. From Atlantic Fish & Oil Co. Dry scrap, ground (from 3 sacks) 9.29 6 . 12 7.86 5.38 Cape Charles, Va. From Atlantic Fish & Oil Co. Dust from grinders 8.80 5.21 7.17 7.55 Beaufort. N.C. From Beaufort Fish-scrap & Oil Co. Dry scrap, hydraulic presses, sample from heap 8 . 2 2 S .95 6.13 8.57 Morehead City. N. C. R. W. Taylor. Dry scrap from open heap 8.49 5.95 9.12 8.23 Morehead City, N. C. From Chas. S. Wallace. Scrap, dry, from hydraulic presses 7.76 9.65 8.15 7.56 Lenoxville, N. C. From C. P. Dey. Ground scrap, sulz dried, hydraulic presses. Sample from heap 7 . 8 1 S .85 7.46 7.89 Lenoxville, N. C. From C. P. Dey. Scrap, dry, ground, hydraulic presses. Sample from heap 8.29 9.00 7.00 5.40
No.
LOCATIOK 1 Kilmarnock, Va. 2 Taft. Va. 3 Irvington. Va. 4 5 6 7
8 9 10
AVERAGES ON MOISTURE-FREE FISH SCRAP
11 Crisfield, Md.
From L. E. P. Dennis & Son.
Ground crab shells, used as filler
9.13
i.25
0.00
7.09
3.82
4.55
6.95
2.11
bromate method (Koppeschaar's solution) are equally rapid, accurate, and satisfactory, under proper condiWASHINGTOK, D. C. tions of acidity and phenol concentration, in forming THE EFFECT OF TEMPERATURE, ACID CONCENTRATION the white, flocculent, insoluble tribromphenol. The hypobromite solution is shown t o have the disadvantage AND TIME ON THE BROMINATION OF PHENOL FOR QUANTITATIVE DETERMINATIONS of being unstable when not carefully sealed or kept B y L. V. REDMAN, A. J. WEITH AND I?. P. BROCK in air-tight bottles, and as a consequence requires Received February 26, 1913 restandardization every day. The diluting of the The rapid introduction into commerce of synthetic phenol solution has entirely prevented the influence plastic resistives made from phenol and compounds of the yellow tribromphenolbromide and the formation containing mobile methylenes has made the rapid of the red tetrabromphenoquinone, which have been and accurate determination of phenols of great im- noted as sources of error by earlier investigators.' portance. This paper deals with the simplest of the Errors from these sources were consequently avoided. series, C,H,OH, and will be followed later by methods There remains, however, t o perfect a method for for the determination of the higher homologues. determining phenol, a n investigation into : The fact t h a t seventy-two investigators have con( a ) The effect of acid concentration during the tributed research papers on the determinationof phenols bromination period. is indicative of the trouble experienced in making ( b ) The length of time required for the liberation accurate assays of phenol. Previous investigators of the iodine b y the bromine. have worked upon the theory t h a t the bromination (6) The necessary excess of free bromine t o be used. of phenol is a slow rate reaction and requires time for ( d ) The effects of temperature. completion. To this end they have employed small ( e ) The excess of potassium bromide necessary in volumes of rather concentrated solutions, with con- the bromide-bromate solution. siderable excess of bromine during the bromination The only equipment required for the investigation period. The result is a precipitate of tribromphenol, was a mechanical shaker,%several half-liter grounddense, and almost granular in structure, having often stoppered bottles and standardized burettes. the yellow color of the tribromphenolbromide or The solutions used were a s follows: N / I O sodium containing the separate red specks of tetrabrompheno- thiosulfate, N / I O bromide bromate, N / I O phenol, quinone. As these products1 are not completely 2 0 per cent potassium iodide, hydrochloric acid reduced b y hydriodic acid, the determinations often (sp. gr. 1.2) and a starch solution made by stirring varied b y one or more per cent. 5 grams of starch into a liter of water, heating slowly A complete bibliography of the earlier work is t o until a clear solution is obtained, and allowing the be found in Lloyd's paper' and references to the more gelatinous material t o settle out. recent investigations are found in the researches of The thiosulfate solution was prepared by dissolving Wilkie." I 2 5 grams of sodium thiosulfate (Na,S,0,.5H,O) in Recently, Rhodes and Redmans have shown t h a t if 5 liters of water; 2.76 grams:of:potassium bromate and the concentration of the phenol be approximately 4 3 grams of potassium bromide per liter of solution N / I O Oduring the bromination period, the precipitate constituted the bromide-bromate solution ; a later is a light flocculent, white mass through which the solution in which the potassium bromate was 2 . 7 6 solution can diffuse easily and a s a consequence on grams per liter but the bromide was reduced to 15 thorough shaking the reaction is completed in one grams per liter was found t o be quite as satisfactory minute's time; there is no rapid return of the blue as the 4 3 grams'?per liter. The higher bromide concolor after titration, such as Koppeschaar mentions tent was introduced in the earlier methods to prevent as incident a t times in his method; and from their the formation of tribromphenolbromide,3 but in the numbers a s published the results are accurate t o two dilute solutions is quite unnecessary, as is shown later or three parts in a thousand. These authors have in this paper. The phenol solution was made from the shown t h a t Lloyd's hypobromite and the bromide1 Beckurts, Arch. Pharm., 6, 24, 561 (1886): J . SOC.Chen. I d . , 6, BUREAUO F SOILS
u. s. DEPARTMENT O F AGRICULTURE
'
1
Jour. A m . Chem. SOC., 47, 16 (1905).
* J . SOC.Chen. I d . , 30, 398
(1911); 31, 208 (1912). THISJOURNAL, 4, 655 (1912).
546 (1886). 2 THISJOURNAL, 4, 656 (1912). a Lloyd, Jour. A m . Chem. S O C .27, , 15 (190.5).
