VOL.
XXII
[AUGUST,1go0.1
No. 8.
THE JOURNAL OF
THE
AMERICAN CHEMICAL SOCIETY. T H E CHEI71STRY OF CORN OIL. BY HERXANNT.VULTEA N D HARRIETWINFIELDGIBSON. Received M a y 7, :goo.
DETERIlINATlON OF T H E CONSTANTS.
T
HE samples of corn oil, the determination of whose con-
stants has been reported in the present article, are here designated as Nos. I. 11, and 111. OiZ No. I is a commercial article, bought of a reputable dealer and intended for use in the manufacture of cheap paints. It has been kept in a corked tin can for six to seven years. It is of a bright, golden yellow color, is free from foots, and has a pronounced grain-like odor. Oil No. I1 is a sample freshly prepared by hydraulic pressure and is of undoubted purity. Its color is somewhat lighter and its grain-like odor more marked than that of oil No. I. Oil No. III is a product of the mash of distilleries. It is golden brown in color and from ten to twelve years old. T h e properties of this oil have been so affected by the process of manufacture that it is practically distinct from the other samples examined. For this reason and because this method of manufacture is now obsolete, its examination was dropped at an early stage.
454
HERhfAXN T. VC'LTE A S D H A R R I E T W I N F I E L D G I B S O N . D E T E R M I N A T I O N O F PHYSIC.4L COXSTANTS.
Specific Gravitrt,.
A.
Both the Sprengel tube and the Westphal balance were used in making this determination, although but little reliance can be placed on the latter beyond the second place of decimals. Results Obtained : OIL No. I. W t . water y,.j'C. Grams.
Wt. oil 15.5'C. Grams.
Sp. gr. r5.j' C .
Sp. gr.
0.9216 0.9213 0.9210 0.92 r3 0.921
0.8722 0.8715 0.8710 0.8716 0.895
OIL No. 11. . . ... 2.0130 1.8547 1.7554 . .... .... .... 2.1788 2.0072 1.8958 Average for Sprengel tube. . Westphal balance.. . . . . .. . . . . . . . . .
0.92136 0.92124 0.9213 0.921
0.87203 0.87011 0.87107
OIL K O . 111.' 1.0037 0.9288 0.8789 . 1.5718 1.4551 1.3780 Average for Sprengel tube. . . .. . . ... Westphal balance. . . . . . ..
0.9253 0.9257 0.9255 0.9255
0.8746 0.8767 0.8756
....... ...... 1.5265 2 .. ..... ...... 1.6404 3 ....... ...... 1.3602 I
1.4068 1.5113 1.2528 Average for Sprengel tube. . Westphal balance. . . . . . ..
. .. ..
I 2
Wt. oil at xcd C. Grams.
1.3315 1.4297 1.1848
. . . . ... . . . . .. . . . . . . . . . .. .
.. . . . . .
. . . .. . . . . . . . . . . . .. .. a
I 2
. . . .... . .... .
.......... ..
. . . . . .. . . .. . . . . . . . . . . .. .
100'
C.
. . .. . .
. . .. . .
Comparison with Results of Other Observers. SP g r . a t 15 C.
0.8360 0.9160 0.9170 0.9200 0.9215 0.9216 0.9215-0.9244 0.9220 0.9239 0.9238-0.9262 0.9243 0.9244 0.9245 0.9262 1 2
Observer
Rokitianski' Curtmann BowersL Shuttleworth Schaedler Procter De Segri and Fabris Trimble HartJ Hopkins Duliere Smith DeNegri' Mills
Reference
ph. RUSS. ( I @ $ ) , 712-713. Chem. Centrbl.,59, 1193. Pharm. J., Xov., 1889. Pharm.J., 16,1095. J . SOL.Chew. Ind., 1 1 , 504. J . SOC. Chem. Znd., 17, 11. Zischr. anal. Chem., 33,547-72. A m . ] . Pharm., 58, 265. Chent. Ztg., 17, 1522. This Journal, Dec., 1898. J . Phann. (1897), 217. J. SOC.Chem. Znd., 1 1 , 504-5. Chetn. Zig., 22, 961-976. J . SOC.Chem. Znd., I I , 504-5.
Fifteen-year-old sample of oil from mash of distillery Petroleum ether extract. 3 D a r k brown oil.
THE CHEMISTRY OF CORN OIL.
455
B.
Viscosity. This determination was made by means of a Boverton-Redwood viscosimeter and the instrument standardized for both distilled water and rape oil at 20’ c. Results Obtained: Av. time Tempera- of flow. ture. Seconds.
............ 20° ...................20° ................... 20’ .................. 20°
Distilled water.. Rapeoil Oil No. I OilNo. I1
Viscos. water.
29 405.5 283.7 297.7
Viscos. water.
.....
1.00
....
100.00
9.79 10.27
70.42 73.89
Comparison with ResuZts of Other Observers : Temperature. 180 C.-IgO 150 c.
c
Viscos. water.
....
Viscos. rape.
Observer.
61.1
Smith 19.2 Andes Viscosity of almond oil Shuttleworth Viscosity greater than olive Bowers
...
Reference.
J . SOC. Chem. Id.,XI, 504. “Veg. Fats and Oils.” Pharm.]., 16,1095. Pharm. J., Nov., 1889.
C. Index of Refraction. T h e instrument used for this determination was Abbe’s refractometer.
Results Obtained: OILNo. I. Temperature.
.......................... 150 c. .......................... 15’ C. 200 c. 3 .......................... 200 c. 4 .......................... Average for .............. 15’ C. Average for .............. 205 C. I 2
A.
T.
1.4768 I.4766 I,4762 I.4760 1.4767 1.4761
35.8 36.0 35.9 35.9 35.9 35.9
1 .4765 1 e4767 1.4766
35.8 36.0 36.0 35.9
1.4767 I,4766 1.4764 1.4765
36.2 36.2 36.3 36.2
OIL KO. 11.
.......................... 150 c. 2 .......................... I50 c. C. 3 .......................... Average for .............. 1 5 O C. I
1 5 O
I,4766
OILNo. 111.
....................... 19.50 c. 2......................... 200 c. 3......................... 20.50c. Average for ............. 20° C. I..
456
T. V U L T E A N D
H&RMANN
H A R R I E T W I N F I E L D GIBSON.
Comparison wiih Resulis of Other Observers : Temperature Ijo
Refractive index
C.
1.476j
DETERlIINATION
OF
Observer
Reference
J . SOL.Chein. I d . ,17,
Proctor CHEXICXL
11.
CONSTANTS-QUANTIThTIVE.
A . Free Acid. T h e method given in Allen’s “ Commercial Organic Analysis,” I1 ( I ) , 104, was used in this determination, substituting a mixture of g parts neutral alcohol and I part ether for the methylated spirit. T h e percentage of free acid was calculated to oleic acid. Results Obtained : OIL No.
I.
Wt. oil. 1.01. N/’m Grams. KOH. cc.
I
2
................ 10.6617
................
7.0 4.8
7.2552
Free acid. Degrees acidity. Per cent
3.65 3.71 3.70
1.851
4.0
2.26
1.136
j.2
2.23
1.121
2.25
1.128
4.03 3.97 4.00
20.64
10.387 10.385 10.356
36.83 36.83 36.83
..........................
Average.
Acid value.
1.851 1.8j1
6.56 6.62 6.59
OIL s o . 11. I 2
................ 9.9294 ................ 13.0816
-4verage.. ......................... OIL
................ 2 ................ 1
s o . 111.
4.2351 6.2726
Ij.6 23.1
20.66
........................ 20.65 Comparison wiih Results of Oiher Obseruers Average..
Free acid Per cent
Observer
Hart Lloyd Spiiller De Segri
0.75 US8 0.00
5.65
B.
Reference
Cheiir. Ztg., 17, I 522. Chevt. Centvbl., 59, 257. Ding. poly. I., 264, 626. Chettz. Ztg., 22, 961-976.
Iodine Absorjiion Hub1 Figure.
Necessary Solutions.I . HgCl, in 95 per cent. alcohol, 60 grams per liter. 2. Iodine in 95 per cent. alcohol, 50 grams per liter. T h e alcohol used was purified by oxidation with potassium permanganate and subsequent distillation over calcium carbonate. T h e distillate was rejected until no discoloration was
457
THE C H E M I S T R Y OF C O R N OIL.
shown on heating a small portion with a lump of solid potash for ten minutes. 3. N/IO sodium thiosulphate. 4. Twenty per cent. solution of potassium iodide in distilled water. 5 . Solution of boiled starch as indicator. Process.-Thin Erlenmeyer flasks, having accurately fitted ground-glass stoppers and flaring mouths, thus forming a gutter between flask and stopper, were used for this operation. Equal parts of solutions I and z were mixed twenty-four hours before each test and allowed to.stand in the dark until needed. About 0.250 gram oil was weighed into a test flask, the oil dissolved in I O cc. chloroform, and 25 cc. of the mixed Hubl solution added. T h e excess of Hubl solution was afterward found to be about roo per cent. T h e flask was then stoppered, the gutter filled with potassium iodide solution, and the whole set away in the dark for twenty-four hours. A blank was run for every determination. After twenty-four hours the stopper was removed, sufficient potassium iodide solution added to the contents of the flask to prevent any precipitation of mercuric iodide and enough distilled water to make the bulk convenient for titration. T h e liquid was then titrated with N / I O sodium thiosulphate, starch indicator. Resulfs Obtained: OIL No. I. Wt. oil.
Gram.
Vol. hypo. cc.
I ................. 0.1986 18.9 0,.2466 23.7 2. 26.0 3 ................. 0.2677 22.0 4. ................ 0.22835 Average Hub1 figure.. ...............
................
I. 2.
OIL No. 11. 26.2 0.2441 23.3 0.2697 25.7 0.3070 29.I
................ 0.2708
................
3 .................
...............
4.. Average Hubl figure..
Wt. iodine.
Gram.
Iodine absorption Per c e n t
0.235323 0.295088 0.323725 0.273921
118.44 119.66
0.322183 0.2go108 0.319990 0.326232
118.97 118.85 118.65 118.02 118.62
120.93
119.95
...............119.74
................ ..............
458
HERMANN
T. VULTE
A N D H A R R I E T WISFIELD GIBSON.
OIL s o . 111.
...............
Wt. oil. Grani
Val hypo cc
W t iodine. Gram
0.2199 20. I 0.2 j0264 2 . . ............... o.aSgj 26.2 0.326215 0.291352 3 ................. 0.2559 23.4 22.2 0.276471 4 ................. 0.2453 Average Hub1 figure.. .............................. I..
Comparison wiih Resulis of Other Observers Hub1 figure
75 .8 I I I . 2-123
115.17 116.3 117 119.6 119.4-119.9 121.7-122.7 I22
I22 I 2 1.5-123. I
122.55 122.9
Observer.
Iodine absorption. Per cent. I
13.80
112.72
113.85 112.70 113.27
:
Reference
Rokitianski De Segri and Fabris De Negri Smethani Hart Hazura Spiiller Lane Hehner Wallenstein Hopkins Duli&re Xills
P%.RUSS. (1894), 712-713. Ztsrh?,. m a / . Chem., 33, 547-72.
Chem. Ztg., 22, 961-976. A t t a b s t , la, 191-193. Chem . Ztg-., I 7, 1522 . Zfschi-.nngew. Chem. (1888),696. Ding. po(s. I., 264, 626. J . Cheiit. Soc. ( 1S93 1. A, 153. /,Soc. Chtvn. Zxd., 16,87. C h e w Zig. ‘1894), 18, ( i i ) , 119. This Journal, Dec., 189s. f f%lZ?’lU. (Is97 1, 217. f.Sor. Chem. Zmi., 1 1 , 504.
C. Sapon$caiion Vulue (Koettsforfer Figure), T h e method here employed was that given in Allen’s “Commercial Organic Analysis,” I1 ( I ) ,j6-j7. The alcohol employed was prepared as described under ‘ ‘ Iodine Values,” and a blank run side by side with the test for each determination. Reszdfs Obtuined : OIL KO.1. Wt oil. Pol N /HCI Grams cc
.......... 2.0127 6.95 ........... 2.5187 8.60 3 ........... 2.4600 8.4j Xverage ....................... I
2
Koettstorfer fig
Sapou equiv
Ether value
193.71 191.55 192.70 192.65
289.61 292.88 291.13 291.21
190.o1 187.85 189.00 188.95
290.57 289.85 293.24 291.22
190.S2 191.30 189.06 190.39
294.81 290.28 292.55
169.64 172.61 171.13
OIL K O . I1
........... 3.S356 13.20 ........... 5.2317 I8.0j 3 ........... 2.5611 8.75 Average ....................... I 2
193.07 193.55 191.31 192.64
OIL KO. 111.
I
2
........... r.gjoo 6.75 ........... 2.2206 7.6j Average .......................
190.29 193.26 191.78
THE CHEMISTRY O F CORN OIL.
459
Comparison with Results of Other Observers : Koettstorfer fig.
Sapo?. equiv.
Observer.
306.9 182.81 188.1-189.2 298.3-296.6 298.4-290.7 188-193 296 189.5 290.07 I934 282.6 198.5 198.8-203 282.2-276.4
Reference.
De Negri Chem. Ztg., 22, 961-976. Spiiller Ding. Po&.]., 264, 626. De Negri and Fabris Zischr. anal. Chem., 33,547. Hart Chem. Ztg., 1 7 , 1522. Mills J . Soc. Chem. Ind., 1 1 , 504. Smetham A n a l . , 18, 191-193. Duliere J. Pharm. (1897)~ 217.
D. Insoluble Fatty An'ds ( f f e h n e rFzkure), From 2 to 4 grams of oil were dissolved in ether in a beaker. Fifty cc. of alcoholic potash (made by dissolving about 2 0 grams potassium hydroxide in 500 cc. purified and redistilled 95 per cent. alcohol) were added to the ethereal solution and the whole heated on a water-bath until saponification was effected. T h e liquid was then diluted with hot distilled water and heated until the ether and alcohol were entirely expelled. T h e aqueous soap solution thus formed was broken up with dilute hydrochloric acid and heating continued until the insoluble fatty acids formed a clear oily layer. T h e fatty acids were then washed with boiling distilled water until the filtrate was neutral to methyl orange. An unusual amount of washing was found necessary with this oil, owing to the large proportion of an acid difficultly soluble in hot water. About 1500 cc. of wash-water were used and, as will be seen by the results, the amount of insoluble acids found to be unusually low. ResuZts Obtained: OIL No. I. Wt. oil taken. Grams.
I .................. 2 ..................
3
..................
4.6700 2.6092 2.3161
Wt. insol. fatty acids. Grams.
4.3256 2.4121 2.1609
.............................
Average Hehner value.. OIL No. 11. I 3.5853 3.2678 2 3.2331 3.0142 3 .................. 2.6079 2.4079 Average Hehner value.. .............................
.................. ..................
Hehner value.
-
92 63 92.45 93.29 92.79 91.14 93.23 92-33 92.23
460 HERMAPI" T. VULTE
ASD HARRIET WINFIELD
GIBSON.
OIL KO. 111. Wt oil taken. Grams
I
2
Wt insol. fatty acids
Hehner value.
3.5102
88.12 S8.30 88.21
Grams.
.................. .................. 3.9832 2.8297
2.4995
Average Hehner value. ..............................
Comparison with Results of Other Observers : Hehner value
93.40 93.57 94.70 95.70 96.70
Observer
Reference
Hoppe-Seyler Hopkins Spiiller Hart Lloyd
Bull. SOC.Cltiwz. (1866), [2], 6, 342. This Journal, Dec., 1898 Ding. POLY.I., 264, 626. Chem. Zfg., 17, 1j22. Chein. Ceatibi., 59, 1193.
E. Volatile Acids (Reichert Figure). Precisely 2.5 grams oil were saponified as in the Koettstorfer process, evaporating off the alcohol completely. Fifty cc. distilled water, containing I cc. phenolphthalein indicator, were then added to the dried soap and the whole heated on the waterbath until the soap was completely dissolved. While still warm the aqueous soap solution was titrated with Nl2 sulphuric acid, overrunning 2 cc. T h e total volume of liquid was now 60-65 cc. T h e decomposed soap solution mas then slowly distilled into a similar flask, containing 5 0 cc of N I O potassium hydroxide and I cc. phenolphthalein indicator. A large percentage of a solid fatty acid also distilled over in white flakes, but was held back by a small wetted filter, placed in the neck of the receiving flask. When about 50 cc of the liquid in the distilling flask had gone over, 50 cc. of distilled water were added to the residue and the distillation repeated. T h e contents of the receiver were then titrated back with Niro hydrochloric acid and the " Reichert figure ' ' calculated from the amount of volatile acids thus recovered from the two distillations. Results Obtained : OIL KO.I. Vol. S / r o HCI.
I
2
....................
....................
453 45.6
Reichert figure
Xverage ............................ OIL s o . 11. I .................... 46.0 2 .................... 45.6 Average. ...........................
Wt K O H f o r loo g . oil.
Gram
4.2 4.4 4.3
0.94248 0.95736 0.96492
4.0
0.89760 0.98j36 0.94248
4.4 4.2
46 1
T H E CHEMISTRY OF CORN O I L .
OIL No. 111. Vol. N / I O HCl.
1 2
Reichert figure.
.................... .................... 39.9 40.3 Average.. ..........................
Wt. KOH for 100 g. oil. Grams.
2.26644 2.17668 2.22156
10.1
9.7 9.9
Comparison wifh Results of Other Observers : Reichert value.
Observer.
0.33 2.5’ 6.7’
Spiiller Smith Morse Hopkins
0.0
Reference.
Ding. poly.
I.,264, 626.
/. SOC.Chem. Ind.,11, 504. A? H . Expt. Sta. BUZZ.(1892), 16,1g. This Journal, Dec., 1898.
F. Acetyl Value. T h e method used was that given in Allen’s “ Commercial Organic Analysis,” I1 ( I ) ,64-65, the ‘‘ Filtration Process” being the one employed. Results Obtained :
OIL No. I.
Wt.oil.
Grams.
I 2
............. 2.3420 ............. 2,0092 Average
VOl.
N/HCl. cc.
VOl.
Koettstorfer fig.
N / I O KOH.
cc.
Acetyl value.
210.8
4.5 4.1
10.78 11.45
8.8 7.6
............................
212.2
211.5
..
2’3.7
3.7 3. 1
11.12
OIL No. 11. I 2
............. 1.8641
7.1 ............. 1.4686 5.5 Average ............................
210.1 21 1.9
..
11.14 11.84 11.49
Comparison with Results of Other Observers : Koetts- Acetyl value torfer fig. (filtr.).
201.5 200.9
8.25 7-90
Observer.
Reference.
Lewkowitsch Allen’s Lewkowitsch Allen’s
‘‘ Corn. Org. Anal.,” Vol. 11, 68. (‘
Corn. Org. Anal.,” Vol. 11,68.
G . GCycerol. Hehner’s dichromate method, as given in Allen’s ‘‘ Commercial Organic Analysis,” I1 ( I ) , 316-317, was employed for this determination. Results Obtained : OIL No. I. Wt. oil. Grams.
Vol. K,CrlO,. cc.
Wt. glycerol. Grams.
I . .......... 2.6092 27.57 0.276395 24.46 0.245217 2 ........... 2.3361 Average ............................................ 1 2
Calculated. IOO parts oil require 0.56 p a r t KOH. Calculated. Reported as 3.2 p e r cent. volatile acids.
Glycerol. P e r cent.
10.59 I O . 50
10.545
462
H E K R I A F N T. V U L T E A X D H A R R I E T T V I K F I E L D GIBSON.
Wt. oil. Grams.
I.. 2.
......... 2.5jOI
OIL No. 11. Vol. K,Cr20,. cc. 26.3j
Wt. glycerol. Grams.
Glycerol. Per cent.
0.264359 0.212635
10.29 Io,4r
.......... 2.0425 21.21 Average ............................................
'0.35
H. Phytosterol. T h e process of Foster and Reichelmann, as given in the Analyst (r897), 131,was employed in this determination. T h e crude phytosterol, resulting from the evaporation of the ethereal extract, was estimated as unsaponifiable matter.
Results Obtained: Wt. oil.
Grams.
TVt. ether residue. Gram.
Oil KO.I ..............55.3945 0.7691 Oil No. I1 ............. 49.I 123 0.7036 Xverage .............................................
Unsap. matter. P e r cent.
1.39 1.43
1.41
Cona,barison with Results of Other Observers : Unsap. matter. Per cent.
Observer.
Spiiller Hart Hopkins
I.3j I.5; 2.S6
Reference.
Ding. poly.]., 264, 626. Chem. Ztg., 17, 1522. This Journal, Dec., 1898.
D E T E R M I N B T I O N O F C H E X I C A L COKSTXNTS-MISCELLAKEOUS.
A.
Color Reactions with Sul,bhuric Acid.
2'. Heidenreich's Test. -Two drops concentrated sulphuric acid were allowed to fall into the center of 2 0 drops of oil on a watchglass. T h e oil and acid were then stirred together with a glass rod. Before stirring, all three oils gave a rayed ring of mahoganyred on golden brown background. After stirring, oils I and I1 gave a dark red-brown, while oil 111 gave a dull claret, all of honey-like consistency. II. Carbon Disulfihide Test.-One drop concentrated sulphuric acid was added to a solution of a few drops of oil in carbon disulphide ; the mixture was well shaken and allowed to stand. All three oils gave a fine violet after twenty-four hours. B.
Color Reactions with Nitric Acid.
I. Hauchecorne's Test.-From 3 to 5 parts oil by volume were shaken with1 part nitricacid (sp. gr. 1.32). Themixturewasthen
THE CHEMISTRY O F CORN OIL.
463
heated on the water-bath for five minutes and allowed to stand. Oils I and I1 gave an orange-yellow oily layer of consistency of thick honey. Oil I11 gave a mahogany-red layer of much less viscosity. 11. Massie’s Test.-Three parts oil by volume were shaken with I part nitric acid (sp. gr. 1.42) for two minutes and allowed to stand. Oils I and I1 gave a bright mahogany-red oily layer of great viscosity. Oil I11 gave a dark, reddish brown layer of less viscosity. Comparison with Results of Other Observers : H,8O4.
“ 0 8 .
. . .. . . .. ..
Observer.
Reference.
Duliere J. Pharm. (1897), 217. . ..... .. .. Dark red Hart Chem. Ztg-., 17, 1522. Reddish (Massie) Black-brown Shuttleworth Pharm. I., 16, 1095, Reddish yellow Green Brannt “An. and Veg. Fats and Oils.”
Yellow-orange
. .....
C.
Silver Nitra te Reduction Tests.
I. Becchi’s Test-Process of Pearmain a n d Moor.-Ten cc. of oil were shaken with 2 cc. of a reagent prepared by dissolving I gram silver nitrate in roo cc. 9 j per cent. alcohol, then adding 2 0 cc. ether and I drop of nitric acid, T h e mixture was then placed in boiling water for ten minutes. All three oils gave a dark brown coloration. 11. Brullk’s Test.-Twelve cc. of oil were shaken with 5 cc. of a solution prepared by dissolving 2 . 5 granis silver nitrate in roo cc. of g j per cent. alcohol. T h e mixture was then heated in boiling water twenty minutes. All three oils were colored intensely black. Comparison with Results of Other Observers : Becchi.
Slightly darkened Faint brown
Brulle.
.....
Black
Observer.
Reference.
Hart Chew. Ztg., 17, 1522. De Negri Chem. Ztg., 22, 961-976.
D. Elaidin Reaction (Poutet’s Method) . One cc. of mercury was dissolved in 1 2 cc. of cold nitric acid (sp. gr. 1.42);z cc. of the freshly prepared green solution were added to j o cc. of oil contained in a wide-mouthed, stoppered bottle, the contents of the bottle violently shaken and the agitation
464
HERMANN
T. VULTE
A N D HARRIET WINFIELD
GIBSON.
repeated every ten minutes for two hours. T h e oil was then allowed to stand undisturbed in a warm room. ResuZfs Obtained.-All three oils. After two hours, orange-yellow deposit, pasty in consistency and small in amount. Orange-red, viscous liquid above. After two weeks, little change except in gradual darkening of color and decrease in viscosity of supernatant liquid.
Comparison with Results of Other Observers : Result of test.
Observer
Reference.
Pasty or buttery mass Smith Orange-yellow color ; partial solidification. Shuttlemorth Orange-yellow ; no solidification. Dulihe Much olein ; between olive and cotton-seed oils. Lloyd
J . SOC.Chem. Znd., 11, 504. Phnvm. J , , 16, 1095.
J . Phnrm. (~Sgjj, 217. Chem. Cenfl-bl.,59, 1193.
E. Rise i n Tem$erafure with Szilphuni- Acid. In making this determination, Archbutt’s method for the Maumene, test, as given in Allen’s “Commercial Organic Analysis,” I1 ( I ) , 76-77, was employed. T h e sulphuric acid used was of 1.842 sp. gr. Results Obtained : Initial temp.
Distilled water.. ........... z j c C. Oil KO.I .................. z j o C. Oil No. 11 ................. 2 3 O C.
Av. rise in temp. Specific temp. 42O
C.
IO0
r - 0
c.
17S.6 I 76.2
/3
74’ C.
Comparison with Resulfs of Other Obseraers; MaumenC figure.
Observer.
5 6 O C.
60.5’ C. 79O c. 84O C.-8go C. 89O C.
Spiiller Hart Jean. De Xegri and Fabrisl Millsp
Reference.
Ding. poly. J., 264, 626. Chem. Ztg., 1 7 , 1522. J . SOC.Chem. Znd., 11, 504. Zfscltr. n?tnl. Chepn., 33, 547-72. J . SOC.Chem. Id.,11, 504-5.
E . Heat of Bromination. T h e process of Hehner and Mitchell, as given in Allen’s ‘ I Commercial Organic Analysis,” I1 ( I ) ,80, was followed in making this determination. Six readings were taken for each sample. T h e calculated iodine value was found by multiplying the bromine thermal value by 5 . 5 . 1 3
Obtained by use of Jean’s thermelaeometer. 15 g r a m s oil j cc. H,SO,.
+
THE CHEMISTRY OF CORN OIL.
465
Results Obtained: Br. Therm. Val.
Oil No. I ........... 21.9~C. Oil No. I1 .......... 2 1 . 8 ~C.
Hub1 No.
Calc. I. No.
119.74 118.62
120.45 119.90
Comparison with Results of Other Observers : Br. Therm. Val.
21.5
Calc. I. No.
Observer.
118.25
Hehner
/.
Reference.
SOC.Chem. Ind.,16,87.
G. SolubiliQ in Glacial Acetic Acid ( Valenfa’s Test). I n this determination the method of Allen’s “ Commercial Organic Analysis,” 11 ( I ) ,40, was followed. Three cc. of oil and of acid were employed.
ResuZts Obtained : Oil No. L-74’ Oil No. II.-80° Oil No. III.-44’
C., average of six tests. C., average of five tests. C., average of five tests.
Comparison with Results of Other Observers : Turbidity temp.
6 5 O C.
Observer.
De Negri1
Reference.
Chem. Ztg., aa, 961-976.
H. Oxygen Absorption (Livache Test) . Finely divided lead powder was obtained by precipitating metallic lead from lead acetate by means of zinc, washing the precipitate rapidly with water, alcohol, and ether, in the order named, and drying it in a desiccator. Approximately I gram of lead powder, prepared as above, was spread in a thin layer on a large watch-glass and a few drops of oil added by means of a pipette, care being taken to keep the drops of oil separate. T h e amount of oil taken was accurately determined and was not allowed to exceed 0.6 gram. T h e watch-glass was then exposed to light but protected from dust and allowed to remain,, at the ordinary temperature, until it ceased to gain in weight. All samples tested were examined at the same time and under the same conditions. 1
Obtained by the use of Jean’s thermelaeometer.
466
HERMANN
T. VULTE A N D H A R R I E T W I N F I E L D G I B S O N .
Results Obtairied : I.
OIL XO. Wt. oil. Gram
Total gain Gram
0.5'93
0.0310
0.3313
0.0172
Gain. Per ceut.
Time required Days
7
5.97
IO
5 . '9
OIL s o . 11.
S U M 31A RE'.
TABLEO F PHYSICAL CONSTANTS. Specific gravity. ..... 1 5 . 5 ~C. Specific gravity.. .... IOOO C. Viscosity (water) .... zoo C. Viscosity (rape) .... 20° C. Index of refraction.. 15O C. Index of refraction.. zoo C. Melting-point . . . . . . . . . . . . .
Oil
Oil
NO I1
NO.I
0.9213 0.8711 IO. j j
73.89 1.4766
...... ......
0.9213 o 8716 9.79 70.42 1.4767 1.4761
Oil s o . 111.
Insol. fat acids.
0.9255 0.8756
0.8j29
..... .....
.....
......
~ 2 . C. 4 ~
TABLEO F CHEMICAL CO~VSTANTS-QUANTITATIVE. Oil No. 11.
Per cent. ash ..................... Acid value.. ................ 2 . 2 5 Per cent. free acid .......... I . 128 Degrees acidity ............. 4.00 Per cent. iodine absorption.. 118.62 Koettstorfer figure .......... 192.64 Saponification equivalent.. .. 291.22 Ether value.. ............... 190.39 Hehner value.. ............. 92.23 Reichert figure.. ............ 4.2 Wt, KOH per 100 grams oil.. 0.942488 Koettstorfer of acetic oil. .... 21 1.9 Acetyl value. ............... 11.49 Per cent. glycerol. .......... 10.35 Per cent.unsaponifiab1e matter I 4 3
Insol. f a t acids.
Oil No.I
Oil No I11
0.065 3.70 1.851 6.59 119.74 192.65 291.21 188.95 92.79 4.3 0.96492g 211.5
0.0655 20.65 10.386 36.83 113.27 191.78 292.55 171.13 88.21 9.9 2.22156 g
......
......
......
11.12
10645
1.39
...... ...... ......
......
......
...... I 20.98
'99.15 281.72
......
...... ...... ......
...... ...... ......
THE C H E M I S T R Y O F C O R N OIL.
h
:8: : 0 : : 0:
467
