Feb., 191 j
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TABLE11-COMPARISONOF LIQUID-AIRSEPARATION AND COMBUSTION ANALYSISMETHODS FOR GASOLINE VAPORIN AIR Sample Number 1 2 3 4 5 Mm. H g Mm. H g Mm. Hg Mm. H g hfm. Hg LIQUID-AIRSEPARATION Barometric pressure.. . . . . . . . . . . . . . . 744 748 744 744 740 Partial pressure of gasoline vapor, . . . . 8 19 23 67 110 23 X 100 = 3 09 ‘K?L!L!O = 9.04 nOXL!oO ‘14.85 oE 748 = 2.40 = 1.08 P E R CENT GASOLINE VAPOR , . , . , . , , 744 744 744 740 COMBUSTION ANALYSIS cc. cc. cc. cc. cc. 46.80 28.89 40.96 50.60 Volume of sample t a k e n . . . . . . . . . . . . 40.10 46.80 72.44 69.08 Oxygen a d d e d . . . . . . . . . . . . . . . . . . . . . 101.33 110.04 90.70 93.60 Total v o l u m e . . .................... 88.65 90.75 84.94 88.55 After combustion. . . . . . . . . . . . . . . . . . 4.95 10.58 25.10 2 15 Contraction. . . . . . . . . . . . . . . . . . . . . . . 77.97 54.44 82.46 85 85 After KOH absorption. . . . . . . . . . . . . . 6.19 12.78 30.50 2.70 COzproduced ..................... 6.19 X 100 12.78 X 100 2 . 7 0 x 100 ~- 8.86 30.50 X 100 14.83 = 2.65 = 1.07 PER CENT GASOLINE V A P O R... . . . . . 5 X 46.80 5 X 28.89 5 X 40.96 5 X 60.5
sxxo
~
is a mixture of liquid paraffin hydrocarbons including other paraffins t h a n t h e pentanes. I t was found, however, t h a t t h e results obtained i n t h e combustion analysis b y calculating t h e d a t a as pentane checked very well with t h e results obtained b y separating t h e gasoline vapor with liquid air. I n other words, t h e pentanes are distilled in largest quantity a t first when gasoline is exposed t o t h e air. Pentane reacts with oxygen as follows: CSHI:! 8 0 2 = jCOz 6Hz0 T h e contraction is 4 volumes a n d t h e carbon dioxide j volumes. Hence t h e carbon dioxide produced b y burning a sample of gasoline vapor can be divided by 5 t o obtain t h e gasoline vapor present in air or t h e contraction can be divided b y 4. T h e authors used t h e first method in t h e d a t a presented in this paper. T h e analyses in Table I1 show t h e d a t a obtained b y burning t h e gasoline-vapor-air-mixture in oxygen, a n d b y separating t h e gasoline vapor with liquid air. It will be observed t h a t t h e combustion d a t a , i. e., t h e contraction a n d CO?, agree very well with the reaction t h a t occurs when pentane reacts with oxygen. I n other words, t h e constituents t h a t evaporated from t h e gasoline in greatest quantity were t h e pentanes.
+
+
S U M MARY
T w o methods for t h e determination of gasoline vapor in air are shown. One has t o d o with t h e cooling of t h e sample with liquid air, t h e removal of t h e air with a vacuum p u m p , a n d t h e measurement of t h e partial pressure of t h e gasoline vapor. Another method has t o do with t h e burning of t h e gasoline vapor with air or oxygen a n d calculating t h e percentage present from t h e carbon dioxide or contraction. One c a n tell closely enough for most purposes, how t o calculate t h e combustion d a t a from t h e ratio between t h e carbon dioxide a n d contraction. CHEMICAL LABORATORY, BUREAUOF MINES PITTSBURGH
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THE COLORING PRINCIPLE OF MYRICA RUBRA-ITS AZO-, SULFIDE AND NITRO-DYESTUFFS B y SADAEICHI SATOW Received November 28. 1914
I n Japan, t h e bark of myrica rubra has been used f o r yellow or black dyeing from ancient times; i t is f o u n d in t h e districts adjacent t o warm-water currents a n d not in those influenced by cold currents. There are two varieties of i t in Japan, one producing a larger sized fruit t h a n t h e other; t h e larger fruit yields a greater quantity of coloring principle having t h e stronger tinctorial power.
While investigating t h e coloring principle of this variety, t h e author used a new process of separation of pure coloring principle which seems simpler and more effective t h a n former processes. The method used was as follows: One pound of t h e extract of t h e bark of myrica rubra was crushed t o bean size, boiled with I j liters of water for several hours and set aside for four days; t h e brown solution was decanted off, t h e m u d d y precipitate once more boiled with I O times its volume of water a n d filtered by suction while hot. After standing for a time, t h e glucoside of t h e coloring principle was deposited from t h e filtrate in rhombic crystals. T h e dark yellowish muddy residue was treated with twenty times its volume of acetone a n d filtered; t o t h e brown filtrate a solution of lead acetate was added until t h e appearance of a reddish brown precipitate which was filtered off. T h e brownish yellow filtrate was distilled in a flask a n d t h e acetone evaporated off for t h e crystallization of the coloring principle. On concentrating t h e solution, fine greenish yellow needle crystals were easily obtained; these were washed several times in distilled water, t h e n collected on a porous tile a n d recrystallized from acetone solution; t h e pure crystals were slightly greenish yellow a n d monoclinic in form. The yield t h u s obtained was nearly j per cent of t h e extract, or 1l/2 per cent of t h e bark. T h e crystals analyzed as follows in percentages: G.
O F SAMPLE As anhvdride COz 1 . . . . . . . . . . . . . 0,5463 1.1323 2 0,2746 0,5701 3 . . . . . . . . . . . . . 0.3477 0.7195 Theoretical for CjsH~oOs,.
No.
.............
H20
0.1623 0.0828 0.0960
............................
C 56.53 56.62 56.43 56.60
H 3.30 3.35 3.06 3.14
T h e author determined t h e molecular weight of t h e coloring principle b y both t h e cryoscopic a n d chemical methods. Anhydride of the coloring principle was dissolved in absolute alcohol a n d t h e rise of boiling point was determined b y means of Beckmann’s apparatus. G. of Iio. anhydride 1 . . . . . . . . . . . . . 0,1712 2 . . . . . . . . . . . . . 0,2176
G. of alcohol 21.4395 26.6512
Rise of Molecular temperature weight 0.26O 314 0.30‘ 316
The sulfate of t h e coloring principle having been decomposed by boiling water, sulfuric acid was determined as barium sulfate, a n d t h e deposited coloring principle collected a n d weighed. hlo.
G . of the sulfate
. . . . . . . . . . . 0.3874 2 . . . . . . . . . . . 0,4886 1
G. of Bas04 0.2167 0.2724
G. of coloring principle 0,2963 0.3740
Molecular weight 318.7 319.8
T h e pure glucoside having been decomposed by sulfuric acid, t h e weights of coloring principle and rham-
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nose were determined, a n d t h e molecular weight was calculated. G. of glucoside 2.2142
G. of coloring principle 1.4068
G. of rhamnose 0.8074
Molecular weight 317.2
According t o these results t h e molecular formula of t h e coloring principle is C15Hj008 (mol. wt. 318). It has one molecule of water of crystallization, which is dehydrated partially in a desiccator a n d perfectly above 13jO C. It is acetylated b y acetyl chloride in its pyridine solution; t h e crystals of t h e acetyl derivative were obtained pure from its acetic acid solution. T o determine t h e number of hydroxyl groups, t h e a u t h o r saponified t h e acetyl derivative with concent r a t e d sulfuric acid a n d t h e deposited coloring principle was collected a n d weighed. G. acetyl derivative 1 . . . . . . . . . . . 1.0907 2 . . . . . . . . . . . . 0,7376
NO.
G. coloring principle 0,6049 0.4102
Per cent coloring principle 55.46 55.61
Theoretical percentage requires for: C~HaOs(CeHa0)a.. . . . . . . . . . . . . 60.23 CisHaOa(CzHa0)s... . . . . . . . . . . . 55.79 C I L H ~ O ~ ( C ~ H .~.O . .) .Y. ,. .. . . . .51.96
Hence t h e coloring principle has six hydroxyl groups. B y alkali fusion, i t decomposes into gallic acid, phloroglucinol, oxalic acid a n d carbon dioxide. According t o t h e above investigations, t h e yellow coloiing principle separated b y this process should be identical with “myricetin” which A. G. Perkin has already investigated; in fact, t h e two substances have both similar a n d dissimilar properties. For instance, t h e former dissolves partially in glacial acetic acid, a n d still i t s lead compound does not become yellower b y boiling. T h e a u t h o r also discovered i t t o react noticeably with nitrous acid. When a n alcoholic solution of t h e coloring matt,er is added t o a nitrous acid solution, a deep reddish purple coloration is produced, which, on standing, fades away gradually t o a yellowish color. It dyes brownish yellow, orange-yellow, orangebrown, a n d black, with alumina, tin, chrome, a n d iron mordants, respectively; on comparing their fastnesses, t h e black b y iron (which is extraordinarily fast a n d resists practically all tests) ranks first; t h e chrome stands second. For brightness a n d deepness of color shades, t h e single-bath method is superior t o t h e twob a t h method, especially with alumina, tin, a n d chrome mordants. T h e a u t h o r prepared several new dyestuffs b y introducing myricetin into azo-, sulfide-, a n d nitrodyestuffs. Observing t h e constitution of t h e myricetin, i t m a y easily be seen t h a t i t can be employed as a component of azo-dyes; m a n y kinds of azo-dyes were prepared from myricetin a n d aromatic bases, all of which have hues varying from orange t o brown. Applying t h e formation of t h e ingrain colors, t h e a u t h o r effected a new process of batik dyeing; i. e., a piece of cloth was dipped into a n alcoholic solution of myricetin a n d dried without washing. A mixture of resin a n d Japan-wax was then lacquered over both surfaces of t h e cloth; when cooled, i t was cracked b y t h e hands, a n d dipped into a diazotized solution t o develop t h e color. I n this way, a n y desired color
Vol. 7 , NO.
2
m a y be obtained without a n y danger ofmelting either resin or wax. Besides this t h e author also discovered a process which enables t h e operator to dye several kinds of shades b y a single process, never repeating t h e cracking a n d dyeing as in t h e usual batik process. This new process consists only of immersing a piece of fabric, which has already been cracked upon t h e resin surface, in dilute alcohol for a few seconds, before i t is dipped into t h e diazotized solution. Then t h e whole surface of resin a n d wax is dissolved by alcohol deeply or thinly according t o t h e condition of t h e cracking; a n d t h u s when t h e cloth is developed b y a diazotized solution, several gradations or shades of color are produced after their respective degrees of dissolution by alcohol. In this way, b y t h e a r t of cracking, there may be obtained very interesting depths of shades of color by a mere single process. The author has also prepared three new sulfide dyestuffs b y melting myricetin: I-with polysulfide of soda a n d free sulfur; a-by adding metallic salts t o t h e polysulfide melting; a n d 3-by direct melting with sulfur. I. POLYSULFIDE xELTING-One molecular weight of myrecitin was thrown into t h e solution of three molecular weights of Na&, a n d t h e mixture was heated in a n oil b a t h for ten hours a t 115-13o0 C., a n d t h e n for seven hours a t I jo-180’ C., under a reverse condenser. T h e syrupy mass was dissolved in hot water a n d sodium sulfide added; t h e filtrate was slightly acidified with dilute hydrochloric acid a n d a n excess of sodium chloride added; t h u s t h e brown sulfide dyestuff was salted o u t , a n d t h e n washed a n d dried. The dried dyestuff is a black powder which dissolves in hot water without t h e aid of sodium sulfide. It dyes cotton directly t o a deep sepia color which does not require a n y after-treatments, a n d it m a y also be topped with basic colors with quite good fastnesses. 2.
POLYSULFIDE
MELTING
WITH
METALLIC
SALTS-
Copper sulfate, manganese sulfate a n d ferrous sulfate were added a n d t h e polysulfide melting was carried out under conditions quite similar t o Case I ; t h e dyestuff containing copper sulfate has t h e stronger tinctorial power a n d a bluish brown shade; manganese sulfate a n d ferrous sulfate give dyestuffs of weaker dyeing power a n d of a bluish gray shade. 3. DIRECT X E L T I N G WITH suLFuR-One part of flowers of sulfur a n d four p a r t s of myricetin were thoroughly mixed a n d heated for five hours a t z o o - a ~ oC~. ; t h e brown mass was dissolved in caustic soda a n d acidified with dilute hydrochloric acid; a brown-yellow precipitate of t h e dyestuff was produced which was collected a n d dried. It dissolves in hot water a n d dyes animal fiber yellowish brown, directly in i t s acid b a t h . T h e author also prepared a n interesting direct yellow dyestuff b y nitrating t h e sulfonic acid of myricetin with fuming nitric acid. One p a r t of myricetin was dissolved in t w e n t y p a r t s of fuming sulfuric acid and warmed t o 80’ C. on a water bath. T o t h e deep brownviolet solution, kept cold b y means of a freezing mixture, t e n parts of fuming nitric acid were added slowly, drop b y drop, while stirring t h e solution a n d keeping t h e temperature below 10’ C. After t e n hours,
Feb., 1915
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
i t was diluted with water, neutralized with caustic soda a n d then shaken with ether t o extract t h e nitrodyestuff; a yellow needle crystalline mass was obtained after t h e ether h a d evaporated. T h e compound has explosive properties a n d readily dissolves in water. This aqueous solution dyes animal fibers directly a bright yellow with a remarkable tinctorial power a n d even appearance. Thus, a n insoluble, naturally yellow, mordant coloring matter. myricetin, was converted into several other useful soluble dyestuffs, t h a t have m a n y new a n d different hues b y converting i t into azo-dyes, sulfide-dyes, a n d nitro-dyes. CHEMICAL INSTITUTE, SCIEKCECOLLEGE IMPERIAL UNIVERSITY, SENDAI,JAPAN
115
b y heating under pressure t o a temperature of I j o o C., a n d then immediately converted t o sugar by active diastase, since on standing cold t h e y revert t o hemicelluloses. M y attention was first called t o t h e new enzyme which is t h e subject of this paper, on determining t h e yield of extract from barley malt between t h e temperatures of melting ice and boiling water as shown in Table I a n d Fig. 11. TABLE I-YIELD
OF EXTRACT FROM O N E SAMPLE O F WESTERN BARLEY MALT Malt was Crushed 25' Seck., Mashed with Three Times I t s Weight of Water and Each Temperature Was Maintained 30 hlin. in Water Bath. Highest Yield by Laboratory Method = 68.91 Per Cent. TEMPERATURE TOTAL YIELD TEMPERATURE TOTAL YIELD F. C. Windisch F. C. Windisch 32 0 14.35 140 60 51.67 50 10 17.28 149 65 65.80 68 20 18.45 158 70 70 59 86 30 19.16 167 75 71.50 104 40 20.60 176 80 72.15 113 45 24.50 185 85 71.50 122 50 26.60 194 90 70.60 126.5 52.5 31.01 203 95 68.80 131 55 35.61 212 100 67.00 I
ON A STARCH-FORMING ENZYME FROM MALT: ITS ACTION ON HEMICELLULOSES AND ITS COMMERCIAL APPLICATION TO BREWING By CHARLESB. DAVIS Received December 2, 1914
The chemistry of enzymes or unorganized ferments teaches one t o believe without seeing, for on account of reactions, a n d products of reactions, we have every reason t o believe t h a t enzymes exist, a n d yet-who has ever seen a n enzyme? This "something" cannot be produced b y chemical means a n d is of unknown chemical composition. Enzymes inhabit every p a r t of t h e animal a n d vegetable organism, a n d in t h e vegetable world are employed t o render insoluble matter soluble a n d diffusible. For example, starch is carried througho u t t h e plant, building up its fabric, reappearing a t different stages as cellulose, gum a n d lignin, a n d is again converted back t o starch as reserve material in t h e seed. E. Roux a n d L. LIaquenne' have shown t h a t at highly elevated temperatures, e . g., 120-150' C., products were formed from hemicelluloses having cell structure similar t o ordinary starch; these could not be gelatinized in hot water a n d reverted t o hemicellulose on cooling t h e solution. All of this work has been disputed by Fernback. Roux and Maquenne do not claim t h a t their results were brought about by a n enzyme, nor could one have been present a t t h e temperatures used in their experiments. H. C. Schellenberg2 speaks of t h e action of fungi on hemicellulose, b u t since t h e writer's experiments were carried o u t in t h e presence of I per cent toluol or chloroform his results are due entirely t o enzymic hydrolysis a n d not t o vital organisms. Ling3 has shown b y microphotographs t h a t t h e cell walls of t h e endosperm of barley are not dissolved b y t h e enzymes during malting. Hemicelluloses together with mineral matter cons t i t u t e t h e cell walls of yeast, also t h e envelopes or cellulosic skeletons of t h e endosperm a n d starch granules (Fig. I ) , a n d are a t present converted t o sugar either b y boiling with dilute mineral acid or 1 Comfit r e n d . , 1904, 49-51, 213-4, 375-7 Also 1905, 440-2, 943-6. 1259-61 and 1303-8 2 W o c h f u r Brau , 25 (1908), 539 3 Roux and Maquenne, Brewers' Journal, 40 (1904), 741-1.
Table I a n d Fig. I1 show t h a t although diastase is coagulated a n d destroyed a t j j C., there is a marked activity a n d conversion between t h e temperatures O
1 SECT1 O N FROM A GRAl N OF BARLEY
FIG.I X 250
7 5 " a n d 85' C., a n d t h a t t h e worts or extract show a blue starch reaction by iodine due t o transformation of hemicelluloses t o starch by t h e "hemicellutase." SEPARATION
OF THE
STARCH-FORMING
EYZYIIE FROM
MALT
Three hundred grams of ground barley malt a n d g. of water were macerated with I per cent toluene, a n antiseptic, a t 6 0 " t o j o " F. for 4l/2 hrs. T h e liquid pressed o u t was ( ~ j og.) heated in a water b a t h t o 81' C. t o destroy t h e diastase, a n d t h e separated clots were filtered off after j min. heating. T h e resultant clear liquid, when cooled t o j o " F., measured 3 7 5 cc., equivalent t o about I j o g. of malt. This was precipitated with I j,Ooo cc. of 9 5 per cent alcohol a n d allowed t o s t a n d 2 4 hrs. The precipitate was filtered off, washed with alcohol and water (4 : I ) , dissolved joo
