1098
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 C H E M I S T R Y
11-In addition t o t h e western hemlock bark, t h a t of t h e western larch a n d western pine seems t o yield extract satisfactory both in quantity and quality. 111-Of t h e deciduous species examined, the dogwood alone appears suitable for use in extract manufacture but only as a dye. LABORATORY OF INDUSTRIAL CHEMISTRY OF WASHINGTON UNIVERSITY SEATTLE, WASHINGTON
SATURATED HYDROCARBONS IN BASKING-SHARK LIVER OIL BY MITSUMARU TSUJIMOTO Received July 25, 1917
Basking-shark (Japanese: "Uba-zam6"), Cetorhinzis maximus (Gunner), ( C e f o r h i n i d a e ), is t h e largest of all living sharks and indeed of all fishes. It reaches a length of 14 meters and has a n enormous weight. This shark is a dull and sluggish animal of t h e arctic seas, being occasionally found off t h e coast of Japan. T h e liver of basking-shark is very heavy, often weighing as much as I t o n and yielding some j cwt. of oil.* Three authentic samples of basking-shark liver oil examined by t h e writer were pale yellow t o orangeyellow liquids of low specific gravity and contained 41.92-55.51 per cent of unsaponifiable matter. They a , highly unsaturated contained squalene, C ~ O H S O hydrocarbon found by t h e writer in certain Japanese shark liver oils.2 This is important as an instance showing t h a t t h e occurrence of squalene is not limited t o t h e liver oils from t h e sharks belonging t o t h e family Squalidae. The experimental details concerning squalene will, as t h e writer hopes, be published shortly in another paper, together with the results of t h e experiments performed on t h e liver oils obtained from some twenty-three species of Japanese sharks. I n t h e present paper, t h e writer describes t h e remarkable occurrence of saturated hydrocarbons in a sample of basking-shark liver oil. Of t h e three samples of t h e oil above referred to, t h e one from t h e Province Hidachi had t h e following properties:
. .. ....... ................. ....... .......... ......... ........... .. ....... ...... ......... ....... .......
Specific gravity at 1S0/4O C . . Acid value.. Saoonification-value Toaine value (WijsJ Refractive index at 20° C . . Butyto-refractometer at 20' C Unsapcmitiable matter.
0.8839 1.09 102.45 178.30 1,4773 78.2 41.92 per cent
The unsaponifiable matter was, for t h e most part, a liquid. One hundred grams of t h e oil were distilled under 5 mm. pressure. At t h e temperature of 170190' C. (the temperature of t h e oil bath, 250--270° C.), I O g. (or I O per cent) of a pale yellow liquid distilled over. It had t h e refractive index 1.4775 a t 20' C. This substance was, therefore, different from squalene. On changing t h e receiver and raising t h e temperature L. E. Andes, "Animal Fats and Oils." 1898, p. 194. *THISJOURNAL. 8 (19161, 889. Spinacene, a hydrocarbon found by I
C. Chapman
17.. Chcm. SOC.,66 (1917), 111], in a Portuguese shark liver oil appears to be identical with squalene. The writer has already prepared squalene hexahalogen hydrates of the general formula CaoHao6HX. which crystallize well and serve for the convenient identification of squalene.
Vol. 9, No.
12
of t h e oil bath t o 29c-315~C., a further distillate was obtained a t t h e boiling temperature of 244-260' C., amounting t o 2 5 g., or 2 5 per cent of the original oil. This latter distillate was found t o consist mainly of squalene. The first distillate was washed with aqueous NaOH solution t o remove free f a t t y acids, and then 8 g. of this purified substance were distilled under 13 mm. pressure. It distilled over a t 160-166' C., mainly a t 164' C. (the temperature of t h e oil bath, 2 0 0 - 2 0 5 ' C , ) , leaving a small residue. The distillate was a colorless, mobile liquid which did not solidify even when cooled t o below o o C. I t had the specific gravity 0.7868 a t 15' C., 0.781j a t 20' C.,0.7789 a t 2 8 ' C. (water a t 4' C. = I), and t h e refractive index 1.4398 a t 20' C. Its iodine value was determined t o be only 4.40, so t h a t i t was nearly saturated. It dissolved in alcohol; when mixed with concentrated sulfuric acid, t h e acid layer turned brown, and on raising t h e temperature t o about 100' C., t h e coloration became darker, b u t the distillate on the upper layer was not readily a t tacked. N o insoluble hydrochloride was formed b y passing dry HC1 into t h e well-cooled ethereal solution of t h e substance. When heated under 766 mm. pressure, t h e substance began t o boil a t about 294' C., and mainly distilled over a t 296' C. The distillate thus obtained had the refractive index 1.439: a t z o o C.,which was nearly identical with t h a t of the original substance. 0.2011 g. original substance (distilled under 13 mm. pressure) gave 0.6223 COS and 0.2700 HzO: C
=
84.39 per cent; H
=
15.02 per cent.
Molecular weight determined by t h e depression of t h e freezing point of benzene solution, (I) 26j, ( 2 ) 252, mean 259. C 8 4 , 8 9 per cent CtrHsa requires.. ClsHai requires.. 84.96 CioH4o requires. . . . . . . . . . . . 84.98
........... ...........
H Mol. wt. 15.11 per cent 240.3 15.04 254.3 15.02 268.3
The substance was, therefore, a hydrocarbon or a mixture of hydrocarbons, the percentage of carbon a n d hydrogen amounting t o 99.4 per cent. I t s elementary composition corresponded t o any of t h e above-mentioned three paraffins. It is not safe t o say t h a t t h e substance was a single chemical compound, b u t judging from.its boiling point and molecular weight, it appears t o be very probable t h a t it consisted mainly of C18H38 or an octadecane. But as t h e normal octadecane is a solid a t t h e ordinary temperatures, t h e substance must be a t least a n iso-octadecane. I t s comparatively low boiling point may be attributed t o this cause. A quite similar relation has already been observed between solid triacontane and t h e , hydrogenation product of squalene, C S ~ H ~a Zliquid not solidifying even a t --zoo C.' Melting Boiling Point Point OC. OC. (mm.) 2 2 . 5 303 (760) 28 181.5 (15) 317 (760) Normal Nonadecane, ClpH40.. 32 193 (15) 330 (760)
COMPOUXD Normal Heptadecane. C1,Hse.. Normal Octadecane, ClaHa s...
.
1
LOG. cit.
Spec/Bc Gravity -/4'C. 0.7768 (22.5' C.) 0.7768 (28' c.) 0.7774 (32' C.)
Dec., I917
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
Employing t h e i t 2 formula, t h e specific refraction of t h e saturated hydrocarbon of t h e basking-shark liver oil is 0.3283, a n d t h e molecular refraction (adopting t h e formula C18H38)83.4. The calculated molecular refraction for C18H38(adopting Eisenlohr’s numbers) is 8 j . 3 . The saturated hydrocarbons i n t h e sample of t h e basking-shark liver oil were not due t o some adulteration, inasmuch as their properties differed considerably from petroleum or other hydrocarbons, more especially from Japanese petroleum which consists chiefly of naphthenes. Then, t h e occurrence of about I O per cent of saturated hydrocarbons in a shark liver oil is a fact hitherto unknown. However, t h e hydrocarbons appear not t o be t h e essential constituents of baskingshark liver oil, since they m-ere not found in t h e other two samples of t h e oil examined b y t h e writer. IMPERIAL INDUSTRIAL LABORATORY YETCHIU-SHIMA. TOKYO, JAPAN
SOME DATA ON SPERM OILS USED FOR BURNING PURPOSES By ABRAHAMG. BLAKELEYA N D
EDMUXD A. REILLY
Received September 10, 1917
A considerable quantity of sperm oil is used as a burning oil in Miners’ Safety Lamps of t h e Davy type. Some trouble experienced with a shipment of supposedly pure sperm oil led t h e writers t o conduct a n investigation, results of which are given in Table I. Abbreviations:
...
R-2 R-3 BW B W 45 38 0.876 0.877 1 ,4649 1.4649 260 260 295 300 128.9 130.2 86.4 89.6 0.20 0.21 42 51 46 35 30 25 107 105 9.3 94 110 111 82 83 48 48 59.8 59.6 39.1 39.9
F-1 N W 45
__
F-2 B W 45
F-3 B W 38
E-l N-2 N W R W Below 38 0.883 1.4649 260 290 142.2 89.3 1.34 39 36 31 109 93 127 80 47 63.0 35.4
N-3 B W 42
F-4 N-4 S-1 T-2 R W ’ E W B (a) (b) 42 .... .... .... .... 0.883 0.879 0.884 0.881 1,4669 1.4665 1,4593 1,4600 265 250 250 270 300 295 285 300 133.8 130.8 145.7 142.7 85.3 85,6 64.7 62.4 0.19 0.23 1.42 1.37 43 . . . . .... .... 38
38 114 96 118 88 46
....
.... .... . . . . 37 37 29 .... 111 . . . . .... 86 . . . . .... .... .... .... .... 63.7 35.2
60.1 36.3
0.896 0.897 0.897 0.895 0.894 0.896 0.899 0.896 0 . 8 9 4 0.895 1.4609 1.4600 1.4595 1.4595 1.4595 1.4587 1.4600 1.4585 1.4580 1.4609 208.9 206.2 201.6 201.2 194.3 204.3 198.8 201.3 188.6 197.7 82.2 86.5 86.6 87.7 91.8 88.1 86.0 84.8 85.9 85.6 11.5 10.5 12.9 10.6 13.2 10.1 7.9 9.6 6.2 7.7
0.893
0.895
0.895
186.8 86.7 11.0
224.8 64.9 12.0
222.8 66.2 12.0
1.4450 1.4455 1.4495 1.4490 1,4490 1.4461 1.4484 1.4465 1.4464 1.4383 65.9 70.2 68.9 72.3 73.2 71.4 74.1 74.1 72.5 71.6 25.5 25.0 23.5 24.0 22.5 24.0 20.0 23.5 25.0 23.2 216.0 203.3 202.9 193.4 200.1 204.6 197.9 197.3 215.4 189.6 ( a ) Sample representing shipment. ( b ) Oil which gave trouble.
............
T h e Flake Test indicates t h e temperature at which occurs a separation of solid matter. This test corresponds t o t h e “cold test” of t h e sperm oil manufacturer. T h e cloud test indicates t h e temperature a t which t h e lower half of t h e sample becomes opaque. T h e pour test indicates t h e temperature at which a sample of oil in cylindrical form of specified diameter a n d length will just flow under specified conditions.’ The iodine values were determined b y t h e Hanus method. T h e melting points were determined b y t h e ordinary capillary t u b e method. 1
N o glycerol was found in any sperm oil tested. Samples R - I , R - 2 , and R-3 (received Dec. I , 1916) were supplied by t h e same manufacturer. The manufacturer stated t h a t t h e oil was probably taken from one or two different lots of Atlantic Ocean Sperm Oil. T h e oil was all from t h e Sperm or Cachalot Whale. The head and body oils were thoroughly mixed. T h e “boats catch this oil in moderately warm waters, say from about as far north as t h e Azores t o as far south as t h e coast of Brazil.” Samples R - 2 and R-3 were the entirely satisfactory as burning oils. Sample R-I, Natural Winter Oil, was not satisfactory for burning. Samples F - I , F-2, a n d F-3 (received December 11, 1916) were all supplied b y a second manufacturer. The oils were from t h e Sperm or Cachalot Whale, and mere mixtures of head and body oils. No further information was available. Samples F-z and F-3 were entirely satisfactory as burning oils. Even Sample F - I , t h e Natural Winter Oil (containing 2 . 2 8 per cent free oleic acid), gave fairly good results, although showing a slight tendency t o incrust t h e wick. Samples S - I ,N-2, N-3. and N-4 (received January 4, 1917) were supplied b y a third manufacturer. T h e manufacturer stated t h a t t h e oils were all from t h e same cargo. T h e oil is bought from t h e whalers in original casks. The oil in these casks, in refining, is p u t into a press, and in one pressing there may be three or four different casks of oil. These casks may contain head and body oil from two or three different
TABLEI N W, Katural Winter; B W, Bleached Winter; E W B. Extra Winter Bleached
DESCRIPTION OF S A M P L E SAMPLE No.:. . . . . . . . . . . . R - 1 K W Kind of Oil:. “Cold Test“:. . . . . . . . . . . . 45 Specific Gravity a t 15.6‘ C ............... 0.882 1,4649 Refractive Index a t 15.6’ C 245 Flash Point, C. . . . . . . . . . 285 Fire Point, O C.. ........................ Saponification Value.. . . . . . . . . . . . . . . . . . . . 142.1 Iodine Value ( H a n u s ) .. . . . . . . . . . . . . . . . . . . 8 6 . 6 3.60 Per cent Free Acid (calculated as oleic). 52 Flake Test, F.. ....................... 46 Cloud Test. F . . ....................... 35 Pour Test, F.. . . . . . . . . . . . . . . . . . . . . . . . . 110 VISCOSITY( T a s l i a b u e ) : a t 70’ F.. . . . . . . . 91 a t 212’ F 117 VISCOSITY( S a y b o l t ) : a t 100’ F . . . . . . . . . 82 a t 130’ F... . . . . . . a t 210’ F.. . . . . . . . 52 63.1 PERCEXTAGES: F a t t y Anhydrides 35.2 Alcohols. . . . . . . . . . FATTY ACIDS: Specific Gravity a t 15.6‘ C . . . . . . . . . . 0.899 Refractive Index a t 15.6‘ C . . . . . . . . . . 1.4623 216.2 Neutralization Value. Iodine Value ( H a n u s ) .. . . . . . . . . . . . . . . 88.8 13.6 Titer Test, C.. .................... ALCOHOLS: R e f r a c t i v e h d e x a t 6 0 ° C . . . . . . . . . . . 1.4475 Iodine Value ( H a n u s ). . . . . . . . . . . . . . . . 6 7 . 4 Melting Po,int. O C . . . . . . . . . . . . . . . . . . . 27.0 Saponification Value of Acetate . . . . . . . 193.2 1 Low acidity.
............
1099
Proceedings of the A . S. T. M., 16 (1915), P a r t 1, pp. 281-282.
33.6
....
63.9 24.0 189.5
....
59.9 37.8
....
41.4 39.3 34.0 35.0 198.3
whales. T h e cargo from which t h e four samples were prepared consisted of some 16,000 gallons of oil of “very fine quality.” T h e oil is all strictly pure sperm oil from t h e Sperm or Cachalot Whale. Sample N - I represents t h e Natural Winter Oil. Sample N-2 represents t h e same oil after “caustic” bleaching t o reduce free acid. Sample N-3 represents Sample N-I bleached by filtering through fuller’s earth t o make i t of light color. Sample N-4 represents Sample N-3 “caustic” bleached; t h a t is, this sample h a d been treated both t o reduce color a n d to reduce acidity. Samples N-3
