Dec., 1916
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
zur Schwefelbestimmung in Eisen und Stahl.” Simplification of previous one as i n 2. angew. Chem. Vol. 22 page 2044. 1910-G. Preuss. i.angew.’ Chem., Vol. 23, page 1980. “Apparate zur Bestimmung des Kohlenstoffs, Arsenes und Schwefels in Eisen und Stahl.” Improved evolution apparatus. 1910-G. Preuss. Chem. Ztg., Vol. 34, page 840. “Neuer Schwefelbestimmungapparat.” A very tompact out5t. 1910-A. Riidisule’s Book: “Die Untersuchungsmethoden des Eisens und Stahls.” Published by M. Drechsel, Bern. Sulfur determination on pages 1 to’ 48. 175 references partly arranged. 1910-W. Trautman. Z . anal. Chem., Vol. 49, page 360. “Schwefelhestimmung in Molybdan- und Wolfram-Metal1 und in deren Eisenlegierungen.” Direct oxidation li’ith uxygen at a red heat. 191 1-Bureau of Standarc$. Circular No. 14. From Department of Commerce, Washington. Analyzed Irons and Steels-Methods of Analysis.” 5th edition in 1916. Oxidation and evolution methods. 1911-T. G. Elliott. Chem. News, Vol 104, page 298. “The Volumetric Estimation of Sulfur in Iron and Steel.” Before evolution of HzS anneals at 800° with KaFe(CN)R. Results on 5 samples. 1911-T. G. Elliott. J . Iron S t e e l Inst., Vol. 83, page 412. “The Volumetric Estimation of Sulfur in Iron and Steel.” Optimum temperature for annealing: results on 5 samples. 1911-Giolitti and Marcantonio. Rass. m i n . , Vol. 35, page 67. From Chem. Abs., Vol. 5, page 3548. Arnold and Hardy method for rapid sulfur determination. 1911-D. A. Wennman. Z . angew. Chem., Vol. 24. page 1861. “Neuw Apparate zur Schwefel- und Kohlenstoffbestimmung in Eisen und Stahl.” Improved apparatus .for evolution method. 1911-D. A. Wennman. Chem. Ztg., Vol. 35, page 596. “Neuer Schwefelbestimmungsapparat.” Improsed apparatus for evolution method. 1911-D. A. Wennman. Chem. Ztg., Vol. 35, page 863. “Apparate zur Schwefelbestimmung in Eisen und Stahl.” Patented evolution apparatus. 1912-Bauer und Deiss’s Book: “Probenahme und Analyse von Eisen und Stahl.” J. Springer, Berlin. Gives three of best methods. 1912-A. A. Blair’s Book: “The Chemical Analysis of Iron.” 7th Ed., Pub. by Lippincott’s, Philadelphia. The leading American treatise on the subject. 1912-L. Brandt. Slahl u. Eisen, Vol. 31, page 1935. “Zur Schwefelbestimmung in Eisen und Stahl.” Discusszon and cut of absorption bulbs for evolution method. 1912-The Chemists’ Committee of t h e U. S. Steel Corporation. 8th Internal. Congr. A p p l . Chem., Vol. 1, page 91. “The Methods of the United States Steel Corporation for the Commercial Sampling and Analysis of Pig Irons.” Customary evolut$n and oxidation processes given. 1912-C. Krug’s Book: Die Praxis des Eisenhiittenchemikers.” J. Springer, Berlin. Page 11.31- gives methods for sulfur. 1912-Spang. Chem. Ztg. Vol. 36, page 392. “Vereinfachter Apparat zur Bestimmung des Skhwefels in Eisen und Stahl. Improved evolution apparatus. 1912-Treadwell and Hall’s Book: “Analytical Chemistry, Vol. 11, Quantitative Analysis.” Wiley and Sons, New York. Pages 350 to 364 on sulfur determination. T h i s i s 3rd edition; 4th edition i n 1914. 1912-Vita and Massenez. Stahl u. Eisen, Vol. 32, page 2089. “Eine neue Schwefelbestimmung in Roheisen und Stahl.” Oxidation of H2.S f r o m evolution method with permanganate titration. 1913-H. Beckurts’s Book: “Die Methoden der Massanalyse.” F. Vieweg & Sohn, Braunschweig. Methods for sulfur determination begin on page 298. 1913-Wm. W. Clark. Met. Chem. Eng., Vol. 11, page 256. “The Determination of Sulfur in Ferro-Vanadium.” Wet or dry oxidation method
ARMOUR INSTITUTE OF TECHKOLOGY CHICAGO
1113
A MODIFICATION OF PRICE’S METHOD FOR THE SEPARATION OF THE SEVEN PERMITTED COAL-TAR DYES TO INCLUDE TARTRAZINE’ By CLARENCEESTES Received July 31, 1916
Food Inspection Decisions 76, 117 a n d 129 of t h e United States Department of Agriculture have been amended b y Food Inspectioqz Decision 164, so t h a t hereafter, t h e following 8 coal-tar dyes may be used t o color food products, subject t o t h e provision of Food Inspection Decisiofas 76, 117 a n d 129: 107Amaranth, j6-Ponceau g R , j17-Erythrosin, 8 ;-Orange I, 4-Kaphthol Yellow S, 43 ;-Light Green S F Yellowish, 692-Indigo Disulfonic Acid, a n d gd-Tartrazine. A method for t h e separation of t h e first seven coalt a r dyes, when occurring in mixtures, has been worked out by Price, which depends upon t h e solubility or insolubility of t h e dyes in various solvents, b u t so far as t h e writer is aware, there has not been published a method for t h e separation of t h e eight permitted coal-tar dyes. I wish, therefore, t o give a modification of Price’s scheme t o include t h e new permitted coal-tar dye Tartrazine. * T H E R E A G E K T S are t h e same as those given b y Price with t h e addition of glacial acetic acid a n d concentrated hydrochloric acid. PROCEDCRE-Assuming t h a t t h e dyes occur together in a food product a n d it is desired t o separate a n d identify t h e m , it is first necessary t o separate t h e dyes from t h e food products b y slightly acidifying a n aqueous solution of t h e material with hydrochloric acid; t h e n a d d a piece of white woolen cloth, which has been freed f r o m grease, a n d boil until most of t h e color has been removed. Remove t h e dyed cloth a n d rinse thoroughly in boiling water t o remove a n y foreign material which may be adhering t o t h e fiber. The dyes are stripped from t h e cloth b y immersing in a very dilute solution of ammonia a n d boiling. When stripping of t h e dye f r o m t h e cloth is complete, acidify a n d repeat t h e dyeing process with a new piece of cloth if fruit colors are present; remove t h e cloth after t h e second stripping a n d evaporate t o dryness on a water bath. This leaves t h e dyes in a pure dry condition ready for t h e separation. R u b a small quantity of t h e dyes in a n evaporating dish with about 2 5 cc. of supersaturated solution of ammonium sulfate, filter, a n d wash t h e residue with small portions of t h e supersaturated solution of ammonium sulfate hntil t h e washings are no longer colored red. T h e filtrate a n d washings will contain Amaranth, Tartrazine a n d a small quantity of Naphthol Yellow S. T h e Naphthol Yellow S is separated from Amaranth a n d Tartrazine by extracting several times with ethyl acetate until i t is no longer colored yellow. The ethyl acetate extract containing t h e Naphthol Yellow S is discarded, as it will be separated in a pure s t a t e later. Amaranth a n d Tartrazine are separated from the ammonium sulfate b y extracting with acetone. The acetone solution is diluted with water and evaporated on a steam b a t h until t h e acetone has been expelled. 1
180.
U S Department of Agriculture, Bureau of Animal Industry, Bull.
1124
v01. 8, SO.I Z
T H E JOUR.hTAL O F I , V D C S T R I A L A N D E N G I N E E R I J G C H E M I S T R Y
SCHEME FOR THE SEPARATION OF THB EIGHTPERMITTED COAL-TARDYES: t o avoid the tax California mine malters last Amaranth, Tartrazine, Erythrosin, Naphthol Yellow S , Light Green S F Yellowish, Orange I, Indigo Disulfonic Acid and Ponceau 3 R entirelv or t o decrease t h e amount of brandv used in R u b a small quantity of t h e mixed dyes in a n evaporating dish with grapes Of high sugar fortification’ B y O n e supersaturated solution of (r\TW4)&0.1, filter and wash with t h e supersaturated solution of (NHa)?SOauntil t h e washings are no longer red content were used. By employing selected pure yeast, FILTRATE contains A,maranth, Tartrazine and a small RESIDUE conguantily Gf Na$hthol Yellow s. Shake with acetic ether tains Erythropotassium rnetabisulfite t o eliminate wild yeasts 01“ Acetic ether re- (NHa)zSOa SOLUTION contains A m a szn, Naph?anth and Tarjvaz{ne,which are reYellow s, bacteria, and b y keeping the temperature the fertholYellow S. moved b y shaking with acetone. menting must d0n.n b y artificial cooling t o t h e opti~ ~ k ~ e l L f ~ ~ ~ ; This solution Dilute t h e acetone solution with HzO IS discarded and drive off t h e acetone. Supermum for fermentation, wines of approximately 15 saturate t h e aqueous solution containing Amaranth and Tartrazine andIndigodiper cent alcohol were produced. Where SO much alcowith NaC1, filter, and wash with s u l b n i c acid. They aye whol is formed b y fermentation, only a small amount supersaturated NaCl solution until ai,ated accordfiltrate is no longer yellow ing to need be added in the form of fortifying brandy t o FILTRP.TE contains RESIDUE contains Tartranine. Add Amaranth. Add produce wines of the required alcohol content. Where excess of conc. excess of conc. H C ~or glacial HCI or glacial t h e wine is t o be fortified, it must not contain more acetic a.cid and acetic acid a n d 1 d us t h a n I j per cent alcohol b y volume before fortificashake .ivith aceshake with aceu. s, Depl: tone. Dilute tone. Dilute a4gr. tion t o comply with the S. Revenue Regulations. t h e acetone sothe acetone solution with lution with By a second method, sweet wines of high alcohol Hz0. Drive off 1120. Drive off
z ~ :2 : ~
$::&c i z t:ot ~~~~~
C.
t h e acetone a n d l‘artrazine re-
t h e acetone and Amaranth remains
mains
content were made without fortification. The method consists in adding grape syrup t o the must during fermentation. I t is claimed t h a t wines of over 18 per cent alcohol were produced in this way. To obtain data O n this process, the follo.\ying ‘Our experiments were carried o u t (tables omitted).
T h e aqueous solution containing Amaranth and Tartrazine is supersaturated .vc-.th sodium chloride, filtered, a n d residue and filter paper TTTashed with t h e supersaturated solution of sodium chloride until EXPERIMENT 1789-SWEET WINE, SHERRY TYPE, NOT FORTImrashings are no longer colored yellow. The filtrate FIED, SYRUP ADDED D r R I S G FERAIENTATIOP?-\7ery ripe SelTlillOTl washings contain ~ ~ ~Tvhilet h e ulidissolved ~ ~ ~ i ~ ~ , grapes of 27.3 Balling or Brix degree were used. The juice was portion contains Amaranth. Tartrazine’ is separated allowed to settle 24 hrs. to clear partially and it was then inin the pure state f r o m the by oculated with pure Burgundy %.ine yeast; 7 j mg, of SOa per adding an excess of either glacial acetic acid or con- liter were used before of the juice to check growth of centrated hydrochloric acid and extracting with ace- wild yeasts during this period, The fermentation Tvas carried tone. T h e acetone is evaporated off on a steam bath, out a t a room temperature of 2 1 - 2 5 ~c. in 3 S-gal, keg, Grape which leaves t h e Tartrazine’ in a pure condition. syrup of 60 per cent Balling was added near the end of fermentaAmaranth is obtained in a pure state b y adding t o tion. The wine was racked after fermentation and stored in t h e residue a n excess of either glacial acetic acid or glass demijohns. concentrated liydroch]oric acid and extracting with EXPERI.\.IENT 182 1-SWEET WINE, PORT TYPE, WITHOUT FORTIacetone. ~h~ is evaporated on a FICATION, SYRUP ADDED DURISG FERMENTATION-This lot was bath, which leaves t h e Amaranth in a pure condition. made in the laboratory in a 5-gal. barrel. Red grape juice from USIVERSITY OF K.4NS.4S LAWRENCE, K.4NSP.S ~~~~
SWEET WINES OF
~~
HIGH ALCOHOL CONTENT WITHOUT FORTIFICATION3 E &I. BROWXAKD F. FL05SrEDER
By Itr. V. CRUESS
Received June 30. 1916
Port wine, as made in California, normally contains over 20 per cent alcohol b y 1-olume and California sherry over 18 per cent. Under ordinary conditions, t h e must, or crushed grapes, is allowed t o ferment until 6 t o I O per cent alcohol is formed and t h e alcohol content is then increased t o the desired point by the addition of 180 proof (90 per cent) grape brandy. Until t h e past season, a tax of 3 cents per proof gallon was paid o n this fortifying brandy. Owing t o t h e necessity for increased revenue, the U. S. Government in 191 j increased t h e t a x from 3 cents per proof gallon t o jj cents per proof gallon. If the fortified sweet wines v-ere t o be made in t h e usual n-ay under this heavy t a x , t h e cost of production would he prohibitive. T w o methods v e r e used by -4n extraction of about 98 per cent has been made. For t h e reactions which are used t o identify the separated colors, see Allen’s “Commercial Organic Analysis,” Vol. V, 4 t h Ed. 3 This interesting treatise is given in full with t h e exception of much of t h e tabulated matter which t o our regret could not be included on account of lack of space. T h e comment on this tabulated matter makes t h e article snfficiently clear in itself. [EDITOR’Si i o r e . ]
experimental juice made a t Davis in 1914 was used. A syrup made by boiling down a mixture of red juice and raisin juice to 65 per cent Balling was added during fermentation. The wine was roughly filtered after fermentation and stored in a filled and corked demijohn, EXPERIMEST 1966b -SWEET WISE, SHERRY TYPE, NOT FORTIPIED, RAISIXS ADDED DURING FERMENTATION-This experiment was carried out a t the University Farm a t Davis. Ripe Semillon grapes were crushed and pressed. The juice was given 7 j mg. SO? per liter and allowed to settle 24 hrs. It was racked and inoculated with pure yeast: IOC lbs. Semillon grapes were sun-dried to 63 lbs., crushed, and added to the fermenting must near the end of the fermentation. The mixture was later pressed and fermentation allowed to proceed a t room temperature for a time and the final fermentation was carried out in a room kept a t zj ’ C. The wine was stored several weeks a t this temperature to subject it to extreme conditions favorable to spoilage. EXPERIMEST 1973-SWEET WIXE WITHOUT FORTIFICATION, PORT TYPE, SYRUP ADDED DURING FERMEKTATION---ThiS Wine TVaS made in practically the same way as Wine 1821. Grape syrup from Burger grapes and made by vacuum evaporation on a commercial scale was used to add during fermentation. Only one addition of syrup was made. The wine was racked clear after fermentation and stored in a well-filled j-gal. demijohn.
T h e results reported below demonstrate t h a t a sound sweet wine of over 18 per cent alcohol can be made b v t h e addition of s v r u ~durinp fermentation. prorided the mine is filtered or racked clear after fermentation and stored in clean, well-filled containers. _
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