October, 1931
I N D U S T R I A L A N D ENGINEERING CHEMISTRY
1135
Comparison of Physical Characteristics of French and American Commercial Pine Gum, Rosin, and Turpentine' Arthur R. Hitch CHEMICALLABORA roRY, GILLICAN-CHIPLEY Co
HIS work was undertaken in order to obtain a direct comparison of certain of the physical characteristics of the French commercial crude pine gum, rosin, and turpentine with those of the corresponding American NavalStores products of commercial pine gum, especially those produced in southeastern Georgia. For this study a shipment of commercial crude French gum, rosin, and turpentine was received directly from the Bordeaux region in France. Data on the American materials were obtained from products produced in southeastern Georgia. The French crude pine gum was shipped in 50-gallon (189.5liter) wooden barrels and was supposed to be representative of both medium and poor-quality gum. The French rosin shipment was made up of two grades, one corresponding to American Isaac, I, and one to American Nancy, N, grade. The French commercial turpentine was received in galvanized drums. The results given in this article for the American pine gum were obtained from a compilation of data on one-year operation of the plant of the Better Rosin Corporation, Cogdell, Ga. Data on turpentine and rosin given herein were taken from representative samples of the Downing Company yards, Brunswick, Ga., the Better Rosin Corporation, Cogdell, Ga., and the Pineland Products Company, Savannah, Ga.
T
Methods of Analysis
,
SAVANNAH, GA.
as well as the grade, melting point, and optical rotation. The melting point was determined by the capillary-tube method and the optical rotation calculated at 20' C. on a 5 per cent solution of the rosin in a standard straight-run gasoline, using a 100-mm. tube. GRaDE OF ROSIN I N CRUDEGuni-The turpentine was distilled off from clean gum under vacuum with steam. Results of the analyses are shown in Table I. T a b l e I-Analytical Results FREKCH
AMERICAN
M F D I U V Q U A L I T Y GUM
Crude G u m Some scrape, chips, Much scrape, chips, needles, thin consisetc., thick consistency, light color tency, yellowish color Odor Like limonene Pleasant, aromatic Suspended material, % 0.74 3.4 Clean G u m H K Grade 70.4 73.4 Rosin, % 18.8 20.5 Turpentine, % ' 10.8 6.0 Water % -24.5 -21.7 s p . roiation a t 200 C. Turpentine from Previous Gum 0,8700 0.8670 Sp. gr. a t 20' C. 1.4690 Refractive index a t 20' C. 1.4714 -34.1 -18.8 Sp. rotation at02O0 C. Boiling point C. 154.8 155 0 Engler distillation, % ' below 170' C. 90.5 96.0 Rosin from Previous C u m H Grade K 56.0 Melting point, C. 56.5 165.1 Acid number 162.0 +1.4 Optical rotation (5% gasoline s o h ) +1.0 Character
POOR
QUALITY G U M
CRUDEGuw-The gum was thoroughly mixed in the barrels Crude G u m Much scrape, chips, Very much scrape, and representative 5-kg. samples taken for analysis of the Character dirt, thick consischips, dirt, very tency, yellowish thick consistency percentage of foreign suspended matter (dirt, chips, etc.) color brownish color contained therein. The gum was dissolved by warming in Odor Like limonene Pleasant, aromatic 3.17 5.4 approximately its own weight of turpentine and then filtered Suspended material, % Clean G u m through a previously weighed paper filter on a large Buchner Grade F I 70.5 69.4 Rosin, yo filter. The material remaining on the paper was washed free Turpentine, 17.8 19.0 70 12.8 10.2 from gum with warm turpentine followed by several washings Water, % Turpentine from Previous G u m with acetone. The residue was dried and weighed, and the 0.8730 0 8695 $p. gr. a t 20' C. percentage of suspended foreign matter calculated. 1 4735 Refractive index a t 20' C . 1 4725 -21 6 rotation at02O0 C. -34 2 CLEANGLTM-(1) Perczntage Rosin and Turpcntine. -4 Sp. 155 5 Boiling point, C. 154 8 94.5 large representative sample of the crude gum was thoroughly Engler distillation, % below 170' C. 89.0 Rosin from Previous G u m cleaned by filtering through cotton. It was then distilled I F with steam at atmospheric pressure to its rosin content, the Grade Melting point, C. 57 0 56.5 163 0 164.5 number turpentine being collected. The rosin and turpentine were Acid Optical rotation (5% gasoline s o h ) + 10 4-1.5 analyzed as given in Table I. C O X X E R C I A L TURPENTINES 0 8678 0.8668 ( 2 ) Percentage TVuter. Since pine gum cannot lie filtered Sp. gr. a t 20' C. 1.4685 index a t 20' C. 1.4705 through ordinary filter medium on a small scale without Refractive -19.4 Sp. rotation a t 20' C. -36.6 Boiling point C. 155.0 155.0 altering its water content somewhat, it was filtered through a Engler distillation, R below 170' C. 93.0 95.5 very fine (300-mesh) copper screen and analyzed fer water COMMERCIAL ROSINS Ha and sediment, a oorrection being made for the sediment. A Grade I N point, C. 56.0 56.5 55 s large sample of this filtered gum was then distilled without Melting 164 4 Acid number 161.0 163.5 rotation (5% steam in the Engler apparatus carrying the distillation up to Optical gasoline s o h ) +l.O +l.O +1.3 200° C. a Average of 20 samples. TURPENTINE-Engler distillations and determinations of Summary and Conclusions specific gravity, refractive index, and optical rotation were made. d direct comparison has been made of certain physical Rosm-The acid number (milligrams of potassium hydrox- characteristics of the French commercial crude pine gum, ide required to neutralize one gram of sample) was determined, rosin, and turpentine with those of the corresponding American commercial products produced in southeastern Georgia. 1 Received June 20, 1931.
INDUSTRIAL AND ENGINEERING CHEMISTRY
1136
I n this work it has been shown that the percentage of foreign suspended matter and water is much less in French than in American pine gums of the same class. The turpentine yield, on the dry basis, from French gum is approximately 1 per cent higher than that for American gum of the same class. The specific gravity and refractive index of the French is slightly higher than for the American turpentine. The odor of the French gum and turpentine is decidedly different from that of the American. The French has a distinct odor of limonene, while the American has a pleasant aromatic odor. Both the French and the American pine gum and turpentine are strongly levorotatory, the French being somewhat more so than the American. The strong levorotatory characteristics of the American turpentine obtained from the pine gum used in this investigation show this gum to be mostly of the slash variety. Results obtained from the turpentine
Vol. 23, No. 10
and rosin derived from French pine gum correspond closely to those obtained from the regular commercial French turpentine and rosin samples. The initial boiling range of the French turpentine is slightly lower than that of the American, but the French contains more of the higher boiling components as shown by the Engler distillation test. The acid number of the French rosins is slightly lower than that of the American rosins of the same grade. Both French and American rosins show dextrorotatory readings. Crystallization tests on all of the French rosins studied in this investigation show them to be identical in their tendency to crystallize. This tendency of the French rosins to crystallize is much greater than that of the American gum rosins, but less than that of the ordinary wood rosins. The French rosin samples examined were clearer and freer from suspended particles than the average American gum rosin.
Vitamin A Content of Body Oils of Pacific Coast Salmon' R. W. Truesdai12and L. C. Boynton3 DEPARTMENT OF CHEMISTRY, UNIVERSITY OF WASHINGTON, SEATTLE,WASH.
R
EFERENCES to bioz
Five samples of salmon body oils are prepared under standardized conditions fromi five common species of salmon. The vitamin A content of these body oils is determined by the biological assay recommended by Sherman and Munsell, and for comparison a medicinal cod-liver oil is used as a control. Ninety-three mg. of chinook oil, 186 mg. of sockeye oil, 226 mg. of silver oil, 227 mg. of humpback oil, 221 mg. of chum oil, and 1 mg. of cod-liver oil are fed per animal per day. The results obtained show chinook and sockeye oils to contain more vitamin A than silver, humpback, or chum oils. All the salmon body oils tested are found to be decidedly inferior to a medicinal cod-liver oil of high grade as a source of vitamin A.
liver oils and fish body oils are numerous. Holmes and Pigott (2) reported body oil of sockeye s a l m o n as not being comparable in vitamin A potency with medicinal cod-liver oil. R e c e n t l y Nelson and Manning (3) reported a commercial salmon oil to be about one-third as rich in this factor as a medicinal cod-liver oil of known high vitamin A content. They further state, "But medicinal cod-liver oils have been tested in this laboratory which contain no more vitamin A than the sample of salmon oil." The purpose of the present biological tests was to secure quantitative data upon the relative vitamin A content of body oils of the five common species of Pacific Coast salmon, genus Oncorhynchus (Table I), widely used as food. The oils were compared with a high-grade medicinal cod-liver oil,' used as a standard of comparison throughout. Considerable variation in the vitamin A potency of the different oils was anticipated since the several species differ greatly in their color and fat content.
These fish were received well iced and unopened, and p within 24 h o u r s after the c a t c h t h e edible flesh was rendered for an hour at 80" to 85" C. The oil was immediately expressed, separated f r o m w a t e r , filtered, and sealed in ground-glass stoppered containers which were kept in a refrigerator during the entire period of experimentation. Certain common physical and chemical constants of the oils were determined and are recorded in Table 111.
NAME Chinook Sockeye Silver Humpback Chum
OIL Table I-Biological a n d C o m m o n Names of Different Species Chinook spring king red salmon Oncorhynchus fschavylscha Sockeye,' bluebs'ck, Aiaska red Oncorhynchus ncrka Silver, coho, medium red, silversides Oncorhynchus kilsufch Oncorhynchus gorbuscha Humpback, pink Chum, keta, dog, calico Oncorhynchus kcfa
Materials Studied
Table I1 relates data pertaining to the fish which were the best obtainable during the periodic salmon runs. Received May 1, 1931. Department of Chemistry, Pomona College, Claremont, Calif. Medical School, University of Rochester, Rochester, N . Y. 4 Control number 25338235 M, furnished through the courtesy of the E. L. Patch Co. 1 f
Table 11-Description of Fish Used NUMBER APPROXIOF TOTAL MATE FISH WEIGHT AGE LOCALITY CAUGHT Pounds Years 1 23 4 Off Cape Flattery 4 20 4 South of San Juan Islands 5 31 5 Off Whidby Island 5 30 2 Off Whidby Island 4 40.5 3 Between Everett and Port Townsend
Table 111-Physical and Chemical Constants of Oils REFRACTIVE SAPONIFREE SP. G R INDEX FICATION IODINE FATTY Av. BODY 25' C:' 25' C: VALUE NUMBER" ACID FAT(6)
%
%
0.9144 0.9145 0.9195 0.9187 0.9160
1.4728 1.4763 1.4784 1.4778 1.4780
169.1 168.6 188.2 167.9 187.9
131.5 160.6 135.8 148.0 136.1
0.56 0.21 0.14 0.26 0.42
13.41 8.58 8.49 8.20 6.15
Cod-liver 0.9182 5 Hanus method.
1.4787
185.5
155.1
0.59
.. .
Chinook Sockeye Silver Humpback Chum
Specifications of the U. S. Pharmacopeia X for the chemical and physical constants of cod-liver oil are: specific gravity, 0.918 to 0.927 a t 25" C.; saponification value, 180 to 190; iodine number, 140 to 180; free fatty acid, not more than 1.41 per cent; and unsaponifiable matter, not more than 1.5 per cent. The latter constant was not deter-
