Mar., 1915
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
20;
amounts of carbon dioxide and traces of organic VANATIONS OF THE PHYSICAL CHARACTERISTICS OF A PETROLEUM RESIDUUM WITH INCREASING compounds,l soon after exposure t o air the weight2 PERCENTAGES OF GRAHAMITE of the film a t any stage of t h e drying process is depenBy H. ROSSBACHER dent on the resultant of t h e gain due t o oxygen abReceived November 23, 1914 sorption and these losses. The drying process is a I n the technology of asphaltic materials the fluxing continuous one and there can be no definite point on of asphaltites such as Grahamite and Gilsonite in a n y of t h e curves a t which this process may be termed complete. We are, however, inclined t o agree with asphaltic or semi-asphaltic petroleum residuum plays Lippert t h a t the highest point on t h e curve may be a very important r6le. It is well known t h a t the effect advantageously used in judging the relative rates of increasing the proportion of the asphaltite is t o raise of drying. When this maximum is reached the film is the melting point and lower t h e penetration of t h e tough and elastic, the surface may be termed “dry” product. The object of this paper is t o present a a n d we are probably justified in saying t h a t the most graphic representation of the alteration of the physical rapidly drying oil film reaches its maximum weight in characteristics of a sample of Mexican residuum o n fluxing with it increasing percentages of Grahamite. the shortest space of time. DESCRIPTION OF E X P E R I M E N T S The curves indicate clearly t h a t the addition of the Typical samples of Mexican residuum and Grahamite three elaeostearates greatly increases the rate of drying of linseed oil. The three sets of curves are quite were taken (Table I ) ; the flux was weighed into a similar and indicate very similar drying properties. copper beaker of about 2 j 0 cc. capacity and heated t o The film containing the manganous soap probably 475-485’ F. and t h e finely powdered Grahamite was dries most rapidly.3 I t s maximum gain in weight is added with stirring. Stirring and heating a t t h e TABLEI-MATERIALSUSEDIN EXPERIMENTS t h e lowest of t h e series. The litharge and lead elaeoGRAHAMITE RESIDUUM stearate drying curves resemble each other very closely Sp. gr. 7 7MEXICAN O F . . ........... 1 ,0039 Sp. gr. 77’ F. 1.1822 ...... Per cent although the latter shows a somewhat greater .gain Shutte 77 F . ............ 78” CSI insoluble.. ........... None Fixed carbon 53.77 during t h e first stage of the drying process. The general CCh insoluble.. ........... 0.31 per cent Ash 1.17 8 8 O Be. naphtha insoluble.. 2 1 . 5 0 per cent CSz insoluble (hot) 0 . 8 3 similarity of these curves leads us t o the conclusion Flash point.. ............. 457a F . CClr cold 95.65 insoluble hot 74.75 t h a t t h e drying action depended solely on the presence Fire point.. ..............505 F. 8 8 O Be. /cold 99.46 naphtha Evaporation loss: of the lead, and was quite independent of t h e non- 20 hours at 485O F . . ....... 13.4 per cent insoluble hot 97.12 metallic radical in the drier. The cobalt soap-oil above temperatures were continued until the solution film has drying properties similar t o those of the oil film treated with lead soap, but loses more rapidly was complete. About a n hour was the average time t h a n t h e latter after the maximum gain in weight required, varying, of course, with the percentage of asphaltite t o be fluxed. Percentages of Grahamite has been reached. from o t o 3 0 were used (Table 11), the coarseness I n conclusion we beg t o thank the Standard Varnish of the product in t h e latter case indicating t h a t the Works of Staten Island, Tu’. Y., for supplying the Chinese limit of solubility was being approached. wood oil used in this work. The “Ring and Ball” melting points noted in Table CHEMICAL LABORATORY, UNIVERSITYOF MISSOURI I1 and Fig. I were determined by the method developed COLUMBIA in t h e Chicago laboratory of the Barrett Manufacturing 1 Klein has very recently shown that Gardner’s results do not prove Company. The melted sample is poured into a brass the presence of carbon monoxide in the vapors given off by drying linseed cylinder 6/8 inch high, exterior diameter 13/16 in., oil films. Cf. THISJOURNAL, 1, 99. interior diameter 3/4 in.: copper wire is soldered t o t h e 2 Cf. Sabin, I b i d . , 3, 81. * This point is more clearly indicated in an unpublished set of curves cylinder for suspending it in t h e bath. When t h e representing the results of drying tests with the same linseed oil treated sample has cooled t o room temperature i t is cut off with these soaps at 250-70’. The curves are somewhat steeper than level w i t h , t h e top of t h e cylinder and a brass ball those given herein.
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T H E J O U R N A L OF IiVDUSTRIAL A N D ENGINEERIYG CHIIMISTRY
TABLE 11-PRODUCTS
O B T A I W E D B Y FLDXING GR.4HAMITE W I T H RESlDUtJM
MEXICAN
--
PERCENT
MELTING POINT O F .
MATERIALS 7 h _ , CHARACTER AND Fixed R i n g and Ball Barrett OF MIXTURES Carbon Ash Water Glycerine Bir PRODUCT M Mexican 17.26 tr. 104.7 residuum 117.3 Too soft Semi-fluid Too R 485” F: 20 21.22 0 . 0 4 hard 191.5 179.0 Tough hr. residue Per cent 70loss on M. Gr. fluxing .,. . . 130.3 A 95 5 145.4 133 . O ~&ogeneous B 90 10 181.4 162.0 Homogeneous 20.34 0 . 0 8 ) c 85 15 2 : i s 212.0 187.0 Homogeneous 2i:?2 0:24 Ton 238 3 229.0 Homogeneous D 80 20 1 . 9 0 E 75 25 1 . 1 5 . . hard 257 .O 241.0 Homogeneous ,. Fairly homo26.62 0 . 2 4 j F 70 30 1.25 Brittle
..
Vol. 7 ) NO. 3
material or on t h e penetration a t one specified temperature. The flattening out of t h e temperaturepenetration curves far below t h e so-called melting points emphasizes this point. A series of determinations plotted as in Fig. 2 may be of assistance in many
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3 / 8 in. in diameter a n d weighing 3l/2 g. is placed on top of t h e sample which is then suspended in a 600 cc. beaker containing 400 cc. of glycerine, t h e bottom of t h e cylinder being I in. from t h e bottom of t h e beaker. A thermometer is suspended in t h e bath with the bottom of t h e bulb flush with t h e bottom of t h e cylinder. The b a t h is heated at t h e rate of 7’ C. per minute with constant stirring. The temperature registered at t h e time the sample touches t h e bottom of t h e beaker is recorded as the melting point of t h e material. T h e rate of heating exercises a marked effect on t h e melting point and must be watched closely t o obtain concordant results. The reflux solubilities and t h e air melting points were made as described by S. R.Church.’ The various other tests noted were made according t o t h e methods
cases in predetermining and comparing t h e values of new “mixes.” KoTE-The writer is indebted to &Ira S. Drucker for t h e preparation of t h e graphs which accompany this article. TECIIWICAL DEPARTMENT, MORRISA K D COMPANY UNIOXSTOCK BARDS, CHICAGO
1NVESTIGATIONS ON T H E OIL OF EUCALYPTUS GLOBULUS OF CALIFORNIA By CHARLESE. BURKEA N D CHARLESC. SCALIONE Received December 21, 1914
recommended by Prevost Hubbard2 and by Clifford Ri~hardson.~ CONCLUSIONS
I-Fig. I shows a fairly regular increase of melting points of t h e fluxed products with increasing percentages of t h e asphaltite. 11-It is of interest t o note in Fig. 2 , t h a t t h e temperature-penetration curve of t h e residue from a 485’ F.-20 hour evaporation test of t h e original residuum follows very closely t h e curve given by t h e sample containing I; per cent of t h e asphaltite. 111-The writer believes t h a t too much emphasis is often placed on the melting point of a n asphaltic 1 2
3
THrs
JOURNAL, 3 (1911). 227, 6 (2913). 195. “Dust Preventives a n d Road Binders.” “ T h e Modern Asphalt Pavement.”
For many years considerable interest has been taken in California, in t h e Eucalyptus globulzts (Blue gum), a tree which, while a native of Australia, has been transplanted and thrives well on many parts of t h e Pacific Coast. The fact t h a t t h e tree grows very fast, and yields a hard wood makes it a tree particularly desirable in these localities which are almost destitute of hard woods. Many difficulties have been met in seasoning t h e wood which has a great tendency t o warp a n d check, b u t these have been largely overcome by experienced lumbermen and i t is now easily possible with certain precautions t o prepare from t h e Eucalyptus a good clean lumber, which for hardness and tensile strength compares very favorably with oak or hickory. I n Australia one of t h e valuable products of t h e tree has been the oil which is obtained by the distillation of t h e leaves; this oil finds extensive use in the arts a n d in medicine and is imported in large quantities annually from Australia into t h e United States. The United States Pharmacopeia describes the oil as: “A colorless or pale yellow oil, having a characteristic or aromatic and somewhat camphoraceous odor, and a pungent, spicy, and cooling taste. Specific gravity, 0.905 t o 0 . 9 2 5 a t 2 5 ’ C. Soluble in all proportions in alcohol; also soluble in three volumes of 70 per cent alcohol. I t s alcoholic solution should be neutraI t o litmus. It is dextrogyrate. the anglc of rotation being not more t h a n + I O ’ in a I O O mm. t u b e
