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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 ere 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 Received June 30. 1916
By Itr. V. CRUESS
F. FL05SrEDER
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. _
.
A
u
Dec., 1916
T H E J O U R N A L O F I N D U S T R I A L A N D E N GI ilr E E RI N G C H E M I S T R Y
ANALYSESOF EXPERIMENTAL SWEETWINES: After Storage the Wines were Analyzed and Tasted with the Following Results Volatile Total Wine Alcohol Acid Acid Sugar OBSERVATIONS 0.030 7.5 Excellent “sherry” flavor li89(u) 1 8 . 2 0 0.80 1966b 19.9 0.406 1.20 2 . 7 “Tourne” bacteria. Spoiled 1821 18.40 O.Oi6 1.10 11.40 Condition and flavor excellent 1973 18.30 0.060 1.00 1 4 . 4 0 Good “port” flavor (a) At one time during fermentation Wine 1789 reached 20.1 per cent alcohol but the addition of syrup later reduced this somewhat.
Experiment r966b shows t h a t raisins m a y be used instead of grape syrup t o increase t h e sugar in t h e fermenting must a n d t o invigorate t h e yeast. I t also indicates t h e danger of spoilage of such wine unless precautions are taken t o get it clear after fermentation a n d store i t in full containers. I n spite of its alcohol content of 19.9 per cent, this wine was completely spoiled b y t h e growth of “tourne” bacteria (Bacterium manizitopaeum). It is a well-known fact t h a t fortified wines of 19 per cent alcohol or over are not readily attacked b y this organism although i t is found living in wines of over 2 0 per cent alcohol. It is possible t h a t alcohol formed b y fermentation i n t h e wine is less toxic t h a n t h a t distilled a n d added t o t h e wine; t h a t is t o s a y , perhaps aldehydes or other compounds formed during distillation may increase t h e toxicity of t h e alcohol t o the organisms of wine. Experiments made in 1915 on this point bear out t h e above statement. The authors also have results of experiments showing t h e effect of a number of additions of syrup during fermentation: ( a ) one addition of s y r u p ; ( b ) three additions of s y r u p ; (c) four additions (tables omitted). These tests a n d d a t a obtained from a number of similar experiments indicate t h a t t h e number of additions of syrup does not materially affect t h e result if t h e additions are made before t h e yeast has become weakened. MAXIMUM
ALCOHOL
FORMED
BY
BURGUNDY
WINE
YEAST B Y h-ORMAL FERMEXTATIONS
I n t h e following experiment, musts varying from 28.3 Balling t o 4 3 . 9 Balling were made u p b y t h e addition of grape syrup t o grape must. T h e different lots were inoculated a n d kept at room temperature until fermentation ceased. T h e y were t h e n analyzed for alcohol content. RESULTSIN BALLINGDEGREES MUST I I1 I11 IV Jan. 14 ....................... 31.0 35.7 39.8 43.9 Jan. 17 . . . . . . . . . . . . . . . . . . . . . . . 11.0 35.5 38.5 41.6 Jan. 18 . . . . . . . . . . . . . . . . . . . . . . . 5.4 35.5 .... 4 1 . 6 Jan. 19 . . . . . . . . . . . . . . . . . . . . . . . 4.0 34.5 37.5 41.6 J a n . 2 0. . . . . . . . . . . . . . . . . . . . . . . 1.8 34.5 26.7 Jan. 24 . . . . . . . . . . . . . . . . . . . . . . . . . . . 25.5 26.7 Tan. 29 . . . . . . . . . . . . . . . . . . . . . . . . . . . 15.6 .... . . . . . . . . . . . . Jan. 31 . . . . . . . . . . . . . . . . . . . . . . 13.7 24.0 29.6 Feb. I . . . . . . . . . . . . . . . . . . . . . 13.0 22.8 27.4 Feb. 9 . . . . . . . . . . . . . . . . . . . . . . Mar. 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Apr. 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . 13.0 ........ ANALYSISOF WIXES I-Iv, -APRIL 5 , 1916 WINE I I1 I11 IV 15.2 11.4 11.3 Alcohol(percentj . . . . . . . . . . . . . . l i . 2
....
F r o m these results, it may be seen t h a t musts of 35 Balling a n d above are not fermented t o give very
high yields of alcohol (see 11, I11 a n d IV). T h e alcohol yield in I is remarkable a n d is about 0.6 per cent higher t h a n is usually obtained with this yeast as a maximum b y t h e usual “straight” fermentation of sweet must. I t is probable t h a t high concentrations,
1125
e. g., 3 j per cent Balling or over, interfere seriously with t h e growth of t h e yeast, giving a smaller crop of yeast or a weaker yeast t h a n normally develops in musts of lowe’r sugar concentration. The formation of 17.2 per cent alcohol b y a single straight fermentation of must of 31 Balling has little practical value for unfortified sweet wine because t h e addition of s y r u p will be necessary after fermentation a n d would reduce t h e alcohol content so t h a t t h e wine would be liable t o spoilage. Therefore, the syruping method of fermentation is better because i t gives high alcohol yields a n d also gives a wine with sufficient sugar for a sweet wine of Port or sherry type. U S E OF S A K 6 YEAST
Sak6 yeast is used in Japan for t h e fermentation of rice mash i n t h e manufacture of Japanese sakC beer. It is accredited with t h e ability t o form 2 2 per cent alcohol i n rice mash. Wine yeast is described i n t h e literature as being able t o form in must not more t h a n 16.5 per cent alcohol b y volume. T h e sake yeast was grown in grape must several generations t o accustom i t more or less t o t h e new medium. Straight fermentation a n d fermentations t o which syrup was added were tried with this yeast b u t 1 j . 2 per cent alcohol was t h e maximum formed. SAKB YEASTALCOHOL YIELDS Per cent Alcohol by “straight” fermentation.. ........................... 13.3 Alcohol by “syruped” fermentatron, one addition of syrup.. . . . . . . . 1 5 . 2 Alcohol by “syruped“ fermentation, two additions of syrup.. . . . . . 14.6
Apparently t h e sak6 yeast does not become easily ac’climated t o grape must. TESTS TO D E T E R M I N E N A T U R E O F THE SUBSTANCE I N GRAPE S Y R U P WHICH STIMULATES YEAST TO HIGH ALCOHOL FORMATIOX
I n v e r t sugar syrup, made b y hydrolyzing cane sugar with HC1 a n d neutralizing with KOH, was added t o must during fermentation b u t gave no increased alcohol yield. Ammonium salts gave no definite effect. T h e dealcoholized extract from fermented must did not give t h e desired result. Evidently growth of yeast a n d fermentation use u p t h e invigorating substance. T h e ash of must gave no definite result. Phosphates seemed t o increase t h e alcohol yield, b u t not markedly so. The experiments on this point are so far more or less negative a n d indefinite. SUMMARY A N D CONCLUSIONS
I-In four small scale fermentations representing five or more gallons each, wines of over 18 per cent alcohol were made b y fermentation of grape must b y “Burgundy” wine yeast a n d t h e addition of grape syrup during fermentation. One of these wines reached 19.9 per cent alcohol. 11-The maximum alcohol obtained by a “straight” fermentation with t h e same yeast was 1 7 . 2 per cent; i n most cases, t h e maximum was 16.6 per cent or less b y this method. The fact t h a t t h e syruping method i n practically all cases gave wines of 18 per cent alcohol or over shows t h a t t h e exceptionally high yields are due t o t h e addition of t h e syrup. 111-Tests made to throw light o n t h e character of t h e invigorating compound of t h e syrup showed
T H E J O U R N A L OR 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
1126
t h a t i t was not t h e sugar of t h e syrup, b u t did not give a n y definite evidence as t o what t h e compounds causing the increased activity of t h e yeast might be. IV.-Partially dried grapes may be used instead of syrup during fermentation t o increase t h e sugar content and invigorate t h e yeast. Therefore, no expensive evaporating system is necessary in t h e application of t h e new method. ‘IT-Where the wine made by t h e new method was not filtered and carefully handled, it was spoiled b y t h e growth of “tourne” bacteria. Where i t was racked clear or filtered after fermentation and kept in wellfilled packages, it kept well and developed a n agreeable “rancio” or “sherry” flavor. Whether t h e method will become important commercially remains to be seen. It was applied on a large scale during t h e past season b y several large companies in California, b u t t h e results of this work are not available for publication. VITXCULTURE DIVISIOI UNIVERSITY OF CALIFORNIA, BERKELEY
TOTAL CARBON IN SOIL BY WET COMBUSTION By C. J. SCHOLLENBERGER Received August 23, 1916
The determination of total carbon in soil is necessary in certain soil investigations. Of t h e several methods used, t h a t of combustion in a furnace! absorption and weighing of the carbon dioxide obtained is probably the most accurate, provided t h e necessary precautions are observed. T h e latter include not only t h e complicated purifying and drying train common t o all gravimetric carbon determinations, b u t a second combustion tube n-ith copper oxide or some similar arrangement t o insure complete oxidation of volatile carbon compounds which may be distilled off before a temperature sufficiently high €or complete combustion has been attained. -4 further precaution necessary in t h e case of soils high in carbonate carbon is a determination of carbonate in the residue after the ignition. In this connection it may be well t o cail attention t o the fact t h a t the wet combustion-volumetric method described b y Ames and Gaitherl is capable, with slight changes, of affording results which compare very favorably with those obtained from a furnace combustion and gravimetric determination. The changes referred t o consist in t h e use of a mixture of phosphoric and sulfuric acids, instead of sulfuric acid alone, with chromic anhydride as t h e oxidizing agent, in t h e substitution of barium hydroxide for sodium hydroxide as t h e alkaline absorbent for carbon dioxide, and in the replacement of the .modified Camp absorption t u b e described in the original article b y Meyer’s absorption apparatus or Truog’s bead together with changes in procedure made necessary by t h e changes in reagents employed. T h e apparatus used and t h e method of operation are practically the same as those described in t h e article first cited, with the changes as noted; t h e absorption apparatus being filled with t h e alkaline absorbent, a gentle suction is turned on t o facilitate the 8
THISJOURIAL,
* dbid., 7
6 (1914), 561.
(1915), 1045.
Vol. 8 , NO. 1 2
addition of t h e reagents. T o t h e sample ( I t o 3 g.) in t h e boiling flask is added I O cc. of the oxidizing mixture made as follows: chromic anhydride 8 j g. dissolved in 1 0 0 cc. water and diluted t o 2 5 0 cc. with 8 j per cent phosphoric acid. The I O cc. portion of oxidizing mixture is followed b y z j cc. 85 per cent phosphoric acid and b y Z j cc. concentrated sulfuric acid. T h e mixture is heated rapidly a t first, b u t with a lower flame when t h e reaction is well started; after t h e chromic acid is largely decomposed, a more intense heat may be used, b u t very hard boiling is unnecessary; the heating should be continued about 3 0 min. after boiling begins. A current of purified air is aspirated through the apparatus in volume just sufficient t o prevent t h e hot acid mixture being forced up t h e stem of t h e separatory funnel for addition of reagents. T h e apparatus should be so arranged t h a t the condensed water will run down the outside of the stem of this funnel and not drop directly into the hot acid; this simple precaution will prevent much trouble and breakage of apparatus. The partial substitution of phosphoric for sulfuric acid reduces t o a negligible quantity the fuming noticed when sulfuric acid alone is used; heavy fumes of sulfuric acid are objectionable, not only for t h e reason t h a t they cause a consumption of the alkaline absorbent, b u t because they prevent complete absorption of carbon dioxide. Phosphoric acid alone was tried, but invariably gave results too low; a certain amount of sulfuric acid is absolutely necessary t o insure complete oxidation. The determination is completed b y titrating the barium carbonate as described by Cain1 or b y titrating the excess of barium hydroxide as described b y Truog.2 The latter method, while not absolutely accurate under all conditions, as was pointed out in a former article3 is sufficiently so for most purposes a n d is very much more rapid and convenient; with either method, t h e solutions used should be standardized against a sample of known carbon content. Blanks should be r u n for carbon in reagents, etc. PER CENT TOTAL CARBON I N SOIL BY SEVERAL hcETHODS Sample 1 2 3 4 Furnace combustion, Gravimetric., . . , 0 . 9 4 2 . 6 9 1 . 1 3 0.88 Wew wet combustion, Volumetric, B a ( 0 H ) z . . . . . . . . . . . . . . . . . . . ~. . . 0.94 2 . 6 6 1 . 1 3 0.87 Old wet combustion, Volumetric, NaOH. . . . , . . . . . . . . . . . . . . . . 0 . 9 0 2 . 6 2 1.10 0.80 Parr method.. . . , . . . . . . . . . . 0 . 8 3 2 . 6 6 1.10 0.97
.. . . .. . . . .. . . .
..
.
5 2.95
2.84 2.72
,.
I n t h e table are presented results obtained on five samples of soil by the gravimetric method (com6ustion with copper oxide in combustion tube, absorption and weighing of carbon dioxide). by the wet combustion-volumetric method as modified, titrating excess barium hydroxide without removal of carbonate, b y t h e met combustion-x-olumetric method as originally described, and b y the Parr method of combustion in bomb with sodium peroxide and measurement of carbon dioxide in gas burette. The results tabulated are from the averages of a t least two closely agreeing determinations. OHIO
1
AGRICVLTVRAL EXPERIMENT STA’IIOY WOOSTER, OHIO
THISJOURNAL, 6 (19141, 465.
* Ibid., 3
7 (1915), 1045. I b i d . , 8 (1916), 427.
