FISH OIL Changes in Physical and Chemical Properties during Heat-Bodying LINCOLN T. WORK, CHARLES SWAN, ALBERT WASMUTH, Columbia University, New York, N. Y.,AND JOSEPH MATTIELLO, Hilo Varnish Corporation, Brooklyn, N. Y.
HE paint and varnish industry has in recent years used increasing quantities of fish oil in its products. There is, however, little available information as to the changes in physical and chemical properties which take place in the process of heatbodying as practiced in this industry. I n the study reported here a coinmercial batch of fish oil was heat-processed a t a temperature commonly used with linseed oil. Samples taken at intervals were tested to ascertain their physical and chemical properties and their tendency to cause livering. Menhaden oil, which was used in this investigation, comes from a fish of the herring type which is found in schools off the S o r t h American Atlantic coast. The composition of this oil as given by Hilditch (4) is:
FIGURE 1. HEATING Cmms
Per cent Saturated acids: Myristic Ci4H?aO? 5.9 Palmitic: c ~ B H ~ ? o ~ 16 3 Stearic, CisHasOl 0 6 r n s a t u r a t e d acids: Palmitoleic, C1eH~o09 1.55 Linoleic, CiaHnO? 39.6 Clo acids (CZOH40 - ~ 0 2 ) 19.0 ( 1 O j a CX acids (C22H44 - yOpj 1 l . i (10)" The acids of the Czo and Czz series are in a s t a t e of extreme unsaturation, and their probable "average" saturation is indicated b y the figures in parentheses. These number6 are the approximate values of I and y so far as are known a t present.
The Menhaden fish oil used had the following characteristics: Sp. gr. (25' C.) Acid h-o. Iodine No.
0.928 2.6 179.2
Octabromide So. Saponification So.
56.1 200.0
.4 batch of 250 gallons of this oil was heat-processed a t 296" C. i 5 G 0 F.) for 12 hours, at which time a viscosity of 53 poises had been attained. The batch reached 296" C. in about 2.75 hours and was then maintained between 293" and 301" C. (560" and 574' F.) for the remainder of the day. It was reheated the following day in a similar manner. Samples were withdran-n at intervals of 15 minutes during the period of bodying. They were tested for viscosity, specific gravity, acid number, iodine number, octabromide number, saponification number, glyceride number, cloud point, and accelerated livering test.
Methods of Test VISCOSITY was determined with the Gardner-Holdt bubble viscometer a t 25 * l o C. Results are expressed in poises.
FIGURE 2.
VARIOUSPROPFIRTIXIS us. VISCOSrrY
O
SPECIFICGRAVITY was determined by the plummet method. Results are expressed as a ratio between the density of oil a t 25" C. and the density of water a t 25" C. ACID NUMBERwas determined by titration with 0.20 AT alcoholic potassium hydroxide, using phenolphthalein as indicator; the oil had previously been refluxed in benzene and alcohol for 30 minutes, Results are expressed as milligrams of potassium hydroxide required to neutralize the acid in one gram of oil. SAPONIFICATION NUMBER(3) was determined by titrating the excess alkali with 0.5 N sulfuric acid using thymolphthalein as indicator after the saponification of the oil by refluxing for one hour with a known amount of standard alcoholic potassium- hydroxide. GLYCERIDE NUMBERis the difference between the saponification number and the acid number, and represents the milligrams of potassium hydroxide required to saponify the glycerides in- one gram of oil.IODINE NUMBERwas determined by the oHanut method, the mixture being allowed to remain in a dark chamber a t 23 * 2 C. for one hour. Results are expressed as the number of centigrams of iodine absorbed by one gram of oil. OCTABROMIDE NUMBERwas determined according to the method outlined by Hoback (6), the free fatty acids having been prepared after the method of Jamieson ( 6 ) . It can be defined as the percentage of octabromide obtained. CLOUDPOINTwas tested in accordance with the method of the American Society for Testing Materials ( I ) , which is also an American standard. Results are 1022
INDUSTRLiL AND ENGINEERING CHEMISTRY
SEPTEMBER, 1936 expressed in both Fahrenheit' and Centigrade degrees, the temperature t o which the oil must be cooled t o become cloudy. LIrER IN G ACCELERATED TESTwas performed in accordance with t h e m e t h o d of Mat.tiello and Work (8). The peacock blue and zinc oxide pigments were of the same grades described by them. The peacock blue pastes were made by using 20 grams of bodied oil and 20 grams of pigment. Equivalent amounts of zinc oxide (52.5 grams) were used with t h e s a m e weight (20 grams) of oil. The pastes were heated at 180" F. (82' C.) for the limiting time of 72 hours. Observation was made as t'o whether or not the pastes had livered after this treatment ,
1023
I A commercial batch of 250 gallons of Menhaden fish oil was heatprocessed at 296" C. (565" F,),and the following properties were measured on samples taken at frequent intervals: viscosity, specific gravity, acid number, iodine number, octabromide number, saponification number, glyceride number, surface tension, and cloud point. The variation of each of these properties with respect to viscosity is presented in graphical form. Fish oil behaves similarly t o linseed oil under the conditions of heat processing employed except that the saponification and glyceride numbers decrease with an increase in viscosity. Up to a viscosity of 53 poises and an acid number of 9.9 no livering is encountered when bodied fish oil is ground with zinc oxide or peacock blue.
Results
There was no significant change in viscosity during the cooling or the warming periods between the first and second days. Since viscosity is a dominant variable in the practical relation of oil to paint, and since it is also a good indication of the
The physical and chemical constants of bodied fish oil are reported in Table I. Figure 1 shows the time-temperatute and viscoeity-time curves for the total processing period.
AND CHEMICAL CONSTANTS OF BODIED FISH OIL TABLEI. PHYSICAL
Sample so. 0 1
Time 7:30 : 45
8:on 8 4
: 15 : 30
5
:45
?
9:oo : 15 :30 : 45
8 $1
Heating Period Ho!krs 0 0.23
0.2. 0
1 3
1 1.2:
1,s
I.i5
2
- . -.> 5 .i
Temprrature c. OF 21 io 93 200
250 333 419
480
121 167 215 249
494 510 528 532
257 266 276 278
Viscosity Poises 0.5 0.5
Sp. Gr.
0.5
0,929 n . 924 0.930 0.926
0.5
..
0,932 0.930 0.936 0 93;
..
10 11 12 13
10:oo :15 :30 :45
2.22.t3 3 3.25
557 563 568 569
14 15 16 17
11:oo : 15 :30 :45
3.5 3.75 4 4 25
566 573 562 574
29i 301 294 301
18 19 20 21
12:oo : 15 :30 :45
4.5 4.75 5 5.25
566 569 664 568
297 298 296 298
10.7
22 23 24 25
l:oo
: 15 :30 :45
5 . 213.
569 559 563 559
16.7
a.
298 293 295 293
26
8:
i.25
574 568 566 563
301 298 297 295
17.6
28 29
2:oo : 15 :30 : 45
30 31 32 33
3 00 : 15 : 30 : 45
7.5 7.75 8 8.25
574 564 568 568
301 296 298 298
22.7
34
4:OO
8.5
564
296
35 36
7:30 :45
s,5 8. i 5
60 223
106
37 38 39 40
9:oo
9 9.25 9.5 9.75
308 395 463 525
153 202 240 274
41 42 43 44
9:oo
10 10.25 10.5 10.75
546 551 560 564
286 288 293 296
45 46
1o:oo
: 15
11 11.25
11.5-
:46
ll,r3
294 294 294
43:0
:30
566 662 561 562
297
47 48 19
11:oo
12
56 1
294
27
:15 :30 :45
: 15 :30 :45
6 6.25 ;5
16
n.928 0,92i
0 6
292 295 298 298
1 . 3:3
. 7
b .
3.4
..
5.9
s:s .. 14'0
..
16:4
..
Iodine
No.
2.5
2.6
... ..
2.6
2.5
...
3.0 I
.
179.2
...
1ji:i lfi.6 166:4
.
3.2
...
15;7:4
0 939 0,948
3.4
li4.9
0 ,' 9 i 2
3.8
1-0'6
0:958
4.6
iii:o
0.95;
5,3
1is:1
0 :963
4.3
108: 3
0:961
6.3
iii:3
...
...
... ...
...
...
0 : 964
6.5
0,'964
7.0
...
...
109:1
iio:n
0:966
7.7
iii:o
0 :968
7:9
10i:4
.. ..
0 : 968
8.3
..
0 : 96s
29.3
...
.. ..
0.970
.. .. ..
Octabro-
inide S o
Saponification S o .
Glyceride NO.
Cloud Point
" F
6
' -
.Icid S o
...
...
.. .. ..
... ...
...
109: 1
... ... ...
104.2
...
56.1
.. ..
200. n
...
197.5
...
... ...
199: 5
47.4
...
1%:8
.. ..
11' '3
...
..
191.5
193:s
190: 4
..
, . .
..
... ...
... ...
,
...
.
. .
...
, . .
..
192.9
13s:o
, . .
. .
.. .. , .
..
.. .. .. .. ..
..
.. ..
..
.. ..
. .
...
...
...
...
192 :i
185:5
...
. . ... ... . . 19i: 1
...
,.
... ...
31
36
..
... ...
... ... ... ...
...
I . .
183:8
...
15.6
.. ..
..
..
.. .. .. ..
.. ..
..
..
, . , . .
.. ..
...
...
..
... ... ...
..
...
... ...
0,969
8.7
99.9
,.
192.4
183.7
0.970
...
8.9
108:s
0.970
9.2
99.2
0 : 974
103:2
49:i
...
9.5
.... *. ....
.. ..
53.1
0 ,S i 0
9.9
100.6
..
...
...
... ...
...
...
...
..
*.
... ... ...
.... .. .. .. .. ...
I
..
... ...
....
.
. .
...
3216
.. ..
..
103: 2
...
..
..
1s:9
8.7
...
..
6ti
i:9
...
ii.1
60
...
.. ..
L' 2.2
..
0.970 3 i .'6
56
..
52
... . . ...
..
..
-11
..
...
..
..
11
, .
, .
194.3
..
' c.
-1
...
..
..
30
...
... ... ...
..
.. , .
I .
..
, .
68
.. ..
20 ti
INDUSTRIAL AND ENGINEERING CHEMISTRY
1024
extent of processing, the other constants have been plotted against viscosity (Figure 2). The curves follow, in general, the trend of the linseed oil curves (2, 8) except that both the saponification and the glyceride numbers fall with increase in viscosity, whereas with linseed oil both rise with increased viscosity, The data on the octabromide number are not as complete as they should be. This number fell from 56.1 to 12.9 during the interval required to bring the oil up to the desired temperature. It might be expected that the decrease in the octabromide number would be reflected in an equivalent decrease in iodine number. This expectation was not borne out by the results. The decrease in octabromide number from the raw oil to the ninth sample was 43.2 per cent. The molecular weight of the clupanodonic acid may be taken as 330; that of its octabromide (really decabromide) is 1129. Therefore, 0.432 gram of octabromide formed would be equivalent to 0.126 gram of acid per gram of oil. Theoretically 1 gram of clupanodonic acid would absorb 3.95 grams of iodine. The decrease in iodine absorption from sample 0 to 9 is 0.24 gram of iodine per gram of oil. This corresponds to 0.061 gram of acid. Thus the iodine number indicates only about one-half the decrease in unsaturation t h a t the octabromide test shows. A similar discrepancy is reported by Long (7) who found that in the case of linseed oil bodying, the iodine number measured only one-third the decrease in unsaturation shown by the hexabromide number of linolenic acid. The rapid decrease in octabromide number as against relatively slow decrease in iodine value could indicate either rearrangement of the highly unsaturated acids to isomeric forms whose bromides are soluble, or rupture of these acids to lower carbon-chain groups which yield essentially the same iodine value but indicate a lower octabromide number because of soluble bromides. I n the tests for livering, none of the pastes which were made with peacock blue or with zinc oxide in these bodied
VOL. 28, NO. 9
fish oils has livered. The most highly bodied sample had a viscosity of 53.1 poises and an acid number of 9.9. The results in this case compare with those of alkali-refined linseed oil bodied in a similar manner. With linseed oil bodied at this temperature, zinc oxide pastes have livered with oil of 65 poises or higher, whereas peacock blue livered with an oil of 75 poises or higher. ilt 53 poises the acid number of the fish oil is approximately one unit lower than the acid number of the linseed oil now being used for comparison. Hence it appears that fish oil presents no greater livering tendency than linseed oil when bodied a t 296’ C. (565’ F.).
Acknowledgment The authors desire to thank C. J. Schumann, president, and the Hilo Varnish Corporation for aid in the processing of samples.
Literature Cited (1) Am. Soc. Testing Materials, Standards, Part 11, p. 761 (1933). (2) Caldwell, B. P., and Mattiello, J , IND.ENQ. CHEM.,24, 158
(1932). (3) Gardner, H. A., “Physical and Chemical Examination of Paints. Varnishes and Lacquers,” 7th ed., Washington, Inst. Paint and Varnish Research, 1935. (4) Hilditch, T. P., “Industrial Chemistry of Fats and Waxes,” New York, D. Van Nostrand and Co., 1927. ( 5 ) Hobrtck, W. H., Oil Paint Drug Reptr., 123, No. 24 (1933); 124, No. 3 (1933). (6) Jamieson, G. S., “Vegetable Fats and Oils,” A. C. S. hionograph Series No. 58, New York, Chemical Catalog Co. (1932). (7) Long, J. S., Knauss, G. H., and Smull, J. G., IND.ENCI. CHEU.. 19, 62 (1927). (8) Mattiello, J., and Work, L. T., Natl. Paint, Varnish Lacquer Xssoc., Sei. Sect., Circ. 502 (1936). RECEIVED May 8, 1936. Condensed from theses submitted to the Department of Chemical Engineering, Columbia University, by Charles Swan rnd Albert Kasmuth.
RANK OF COALS A s Indicated by Oxygen Absorption H. L. OLIN AND W. W. WATERMAN
0
NE of the major current projects of Com-
mittee D-5 on Coal and Coke of the American Society for Testing Materials is the drafting of specifications for the classification of coal. As a result of intensive work by the Bureau of Mines, supported to a considerable extent by cosperating laboratories, much progress has been made and a t present two tentative methods are under consideration, D388-34T and D389-34T for rank and grade, respectively. The fundamental criteria of rank under the proposed code involve data on thermal values on the moist and fixed carbon on the dry basis, both computed to mineral-matter-free coal. I n designating grade, these figures are qualified by data on thermal value, ash content, ash fusion temperature, and sulfur content, based on the asreceived sample, and by the results of empirical tests of weathering resistance and coking tendency. Doubtless the approximate analyses and physical tests employed constitute collectively the most effective measures possible for drawing the classification boundaries in broad outline. It is entirely possible, however, that in the long scale of coal rank extending from lignite to anthracite some specific and purely chemical property may be traced in ascending or descending order of magnitude and correlated with the
University of I o w a , Iowa City, Iowa
chemical age of the coal-in other words, its rank. Among these perhaps none is more conspicuous than the readiness with which freshly exposed coals absorb oxygen even a t ordinary temperatures, especially in the finely divided state; the measure of the degree to which such chemical change takes place in coals of widely different quality and geological age rvas the objective of the present study.
e
THROUGH the fundamental studies of Parr and others, the sensitivity of lignins to oxygen and their relation to the bituminic fraction and t o the coking properties of the coal have been clearly established. As the aging process in coal formation goes on through geologic time, it appears that in the chemical changes involved in polymerization the lignins lose not only their inherent oxygen but much of their power for absorbing it from outside sources, and we find that as a result the coals not only undergo less damage in storage piles but make better cokes. If, then, the extent to which oxygen attacks the coal structure is a natural function of its age or
