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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 that 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. In 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. In 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
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rank, the measurement of low-temperature oxidation should be a promising method for use in coal classification studies or a t least its application is logically justified in principle. Numerous methods for studies of this kind have been proposed employing nitric acid, potassium chlorate, etc., as oxidizing agents. That of Francis and Wheeler (2), using Hoffmeister’s reagent (a mixture of hydrochloric acid and potassium chlorate) applied to a dozen coals and lignites from Wyoming, Colorado, Montana, and Utah in determining the “reactivity index” or reducing effect of the ulmins, gave a scale of values ranging from 80.0 for a Wyoming lignite with 31 per cent bed moisture to 48.0 for a Utah coal with a moisture content of 3.8 per cent. The method of Heathcoat (3) and Francis (1) which seems to promise a high degree of precision involves first the extraction of the sample with pyridine to dissolve the relatively inert bitumens and the digestion of the solid residue (consisting of lignins or ulmins) d h a measured excess of standard potassium permanganate solution near the boiling temperature for one hour. The filtrate and washings are then titrated with standard sodium oxalate, and the reducing effect is finally calculated and expressed as the permanganate number or the milliliter volume of potassium permanganate solution used in treating 0.5 gram of coal for one hour under the conditions specified. THIS method, with only minor modifications, was used 0 in the present work on a large range of coals from lignites of Wyoming and Montana to the Pocahontas and anthracites of West Virginia and Pennsylvania, with the results shon-n in Figure 1. Conspicuous among these graphs are those of samples 1 to 3, representing coals of Upper Cretaceous or Tertiary age with extremely high permanganate numbers as well as inherent moisture. Samples 4 and 5 from Page and Taylor Counties of Iowa in the Nodaway of the Upper Des Moines of the Pennsylvanian are characterized by high bed moisture and by a high weathering index (i. e., they disintegrate readily on exposure to dry air); Campbell of the U. S. Geological
I
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3 4 s 67
a9
1011 I Z : ~ I ~ I ~ I G I ~ I ~ I ~ ~ D Z I ~ ~ Z ~ M ~ ~ ~ ~ ~ ~
SAMPLE
NUMBER
FIQURE 1. CHEMICAL PROPERTIES OF COALS (Thermal values are in B. t. u.)
Survey has classed them as sub-bituminous. Samples 6 to 14, inclusive, embrace the commercial coals of Iowa of the lower Des Moines series which, in general, are satisfactorily resistant to weathering, of fair storing quality, and distinctly agglutinating according to the coking test. Samples 15 to 21 come from the major seams of Illinois, mainly from the south OF COALS USEDI N PERMANGANATE NPMBER where the coal rank was profoundly affected by crustal m o v e TABLEI. SOURCES STUDIES ments incident to the Ozark uplift. The rest are from the Name or No. lorn-er strata of the Pennsylvanian in the Appalachian region Rank County State of Seam NO. where diastrophism in the mountain-making period produced ...... S.Dak. 1 Lignite what might be termed an “accelerated aging” effect on the Mont. Powell ..... .. 2 Lignite Subbituminous Campbell wyo. Roland-Smith 3 coal. Iowa Nodaway Page 4 Bituminous Results in general seem to show marked correlation between Taylor Iowa Nodaway 5 Bituminous permanganate number and coal rank; they are presented as -4ppanoose Iowa Mystic 6 Bituminous tentative data without prejudice. Further studies are being Bituminous Appanoose Iowa Mystic 7 made along the same lines. Dallas Iowa ... . , , , 8 Bituminous 9 10
11 12 13 14
15 16
17 18 19 20 21 22 23 24 25 26 27 28 29
30
Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Bituminous Semi-bituminous Semi-bituminous Bituminous Anthracite Anthracite
Appanoose Appanoose Monroe Mahaska Polk Monroe Henry Jackson W-illiamson Saline Sangamon Fulton Franklin Hopkins Christian Claiborne Perry Raleigh Fayette Mingo
......
Luzerne
Iowa Iowa Iowa Iowa Iowa Iowa Illinois Illinois Illinois Illinois Illinois Illinois Illinois Western Ky. Western Ky. Tenn. Eastern Ky. W. Va. W. T’a. IT. Va. Pa. Pa.
Mystic Mystic
Literature Cited
..... . , . . ... .~. . . . . . ,
, , ,
La Salle No. 2 Murphysboro No. 6 No. 5 No. 6 No. 6 No. 6 K O . 11
Empire Jellioo Hazard No. 4 Beckley New River Dorothy
... ....
Northern field
(1) Francis, W., Fuel, 12, 128 (1933). (2) Francis, W., and Wheeler, R. T‘, J . Chem. SOC, 1928, 2967; 1933,586. (3) Heathcoat, F., Fuel, 12,4 (1933). RECEIVED June 4, 1936. Presented before the Division of Gas and Fuel Chemistry at the 91st Meeting of the American Chemical Society, Kansae City, & l o , April 13 to 17, 1936
