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Active citronellalsemicarbazone, CloHls : N N H C O N H z , Wurtzilitel (elaterite or mineral rubber) from U t a h melts a t 82.5", t h e racemic f o r m a t 96'. From t h e was first described by Wurtz, who showed t h a t it is optical rotation of the aldehyde fraction of Pinus a distinct mineral. T h e name elaterite h a d been used j e f f y e y i i t is possible t h a t t h e semicarbazone contained previously by Dana a n d other mineralogists t o describe a small amount of t h e active form resulting in t h e low three different minerals of specific gravities ranging melting point obtained. from 0.90j t o 1.223. T h e region in which wurtzilite Colophony.-A sample of " ww " colophony had t h e is found covers a n area of about IOO square miles befollowing properties: Acid no. 147.6; sapon. no. 178.1. tween Indian Canyon a n d Sam's Canyon, branches of T h e rosin contained 12.j per cent of resene obtained Strawberry Creek, about 3 0 miles due north of Price, in the form of a yellow, very sticky, viscous syrup. Utah. T h e colophony crystallized from acetone after standing Ozocerite (mineral wax) has been known for many in t h e cold for several weeks, differing in this respect years on account of t h e economic value of the large from t h e colophony of Pinus s a b i n i a n a . The crystals deposits in Galicia, Austria. T h e only other deposit obtained after five recrystallizations from acetone known t o be of commercial value is t h a t in Utah. softened a t 130' a n d melted a t 137-So. When fol- This deposit begins about two miles west of Colton, lowed by a crystallization from a mixture of acetone U t a h County, a n d extends t o about four miles west of a n d hydrochloric acid t h e y softened a t 136' a n d melted Soldier Summit, a distance of 1 2 miles. The belt a t 145-6 O , becoming completely liquid a t I j I '. is 2 miles wide. This area may be divided into three T h e resin crystals obtained from t h e crude oleo- parts? ( I ) near Colton, on the north side of the resin melted a t 170-171'. The silver salt of the acid Price River valley; (2) t o the east of Soldier Summit was prepared a n d analyzed as follows: where the railroad crosses t h e crest of t h e plateau; 0.3926 gram of silver salt gave 0 . 1 0 2 7 gram Ag = 26.16 a n d (3) near Midway Station, on t h e north side of t h e per cent Ag. canyon, near the source of Soldier's Creek. Silver abietate, Ag(C20H2902), requires 26.37 per cent Heretofore rock asphalt has usually been called bituminous sandstone, b u t t h e former name is growing Ag. in popularity, especially in Utah. The largest deposit SUMMARY T h e volatile oil of Pinus monoQhylla contains So- in the state lies south a n d east of Vernal, north of t h e 85 per cent d-a-pinene; 4-5 per cent I - or i-limonene; White River a n d between Ashley a n d Uinta valley^.^ 4-6 per cent d-cadinene ; losses b y polymerization, This deposit attains a thickness (in places) of twenty etc., 4.j per cent. T h e colophony contains 7.22 per feet, b u t a t present it is too far from a railroad for cent resene a n d resin acids isomeric with abietic acid. successful commercial exploitation. Another deposit T h e volatile oil of Pinus j e f f y e y i contains a b o u t occurs in Spanish Fork Canyon, southeast of Thistle, 9j per cent n-heptane a n d 5 per cent of a n aldehyde, a n d still other immense deposits are found ( I ) in t h e apparently citronellal. T h e colophony contains I 2 . 5 tributaries of Whitmore Canyon, near Sunnyside, per cent resene a n d resin acids isomeric with abietic (2) a t t h e head of Willow Creek, a tributary of the Green River, in the Book Cliff Mountains, and (3) acid. in the Laramie sandstones near Jensen, on the Green FORESTPRODUCTS LABORATORY MADISON, WISCONSIN River. A deposit of bituminous l i m e s t o n e occurs a t t h e head of t h e right-hand branch of Tie Fork, THE HYDROCARBONS OF UTAH1 a canyon entering Spanish Fork Canyon, 2 miles By CARLOSBARDWBLL, B. ARTHURBBRRYMAN, THOMAS B. BRIGHTON west of Clear Creek Station. An area underlaid b y AND KENNETHD. KUHRB bituminous limestone, about 50 miles long east a n d Received September 20, 1913 west by I O miles wide north a n d south, lies just north About fifteen kinds of hydrocarbons occur in U t a h ; of Colton a n d south of Strawberry Creek, extending t h e five of these occurring most abundantly-gilsonite, from Antelope Creek on the east t o Thistle on the west.4 tabbyite, wurtzilite, ozocerite a n d rock asphalt-are HISTORICAL t h e ones selected for this investigation. I n reviewing the literature of these substances one Gilsonite2 (uintaite) was first described by Blake in 1885. He gave i t t h e name uintaite because of finds t h a t a great deal has been published concerning its occurrence in t h e Uinta Mountains. Later the gilsonite a n d ozocerite, but not much about wurtzilite, name gilsonite was adopted because S. H. Gilson, tabbyite a n d rock asphalt. Day,5 working with gila prospector, brought i t into prominence as a n article sonite, a t t e m p t e d to isolate "such single hydrocarbons of commerce. T h e deposits of gilsonite are limited or their derivatives as would give some information t o t h e Uncompahgre Indian Reservation in Uinta as t o t h e real nature of the mineral itself." He gives County, being found in a n area extending along the a n outline of the physical characteristics, solubilities, etc., of gilsonite, a n d describes t h e character of t h e 40th parallel for about 60 miles. Tabbyite receives its name from a n Indian chieftain, residue from each solvent as well as the nature of t h e T a b b y . The deposits are in T a b b y Canyon, a branch dissolved portion. Proximate a n d ultimate analyses of the Duchesne, about 8 t o 9 miles south a n d west 1 Wurtz, I b i d . , 49, 59 (1890). Taff and Smith, U. S. Geol. Survey, Bull. 286, 369 (1905). of Theodore, Uinta County. 1This work was done at the suggestion and under the direction of Dr. W. C . Ebaugh, to whom the authors' thanks are due. Blake. Eng. M i n . J . , 40, 431 (1885).
, 115 (1888). Wigglesworth, Trans. Am. I n s t . .%fin. ~ n g . 17, * Eldridge, V . 2 . Geol. Survey, 17th A n n . Rept., 1896, 915, el s e q . ; ZZnd A n n . R e p t . , 1900-01, 332. 6 Day, J. Frank. I n s l . , Sept., 1895, 221, et seq
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are given. From a study of t h e distillation products of gilsonite he concludes t h a t the oil obtained belongs t o t h e paraffin series of hydrocarbons, a n d is made u p of a number of distinct substances, just as is petroleum. He obtained from the distillate volatile with steam, oils which seem t o correspond t o those described by Peckham’ as obtained from California bitumens. These h a d a n odor similar t o quinoline, a n d t o him this was a n evidence of t h e relationship of California bitumen a n d of gilsonite a n d of their animal origin. D a y gives also t h e results of treatment with nitric acid a n d descriptions of t h e products a n d their properties, concluding t h a t some members of the naphthalene series are present. Eldridge2 described t h e location of t h e hydrocarbon deposits a n d t h e geology of t h e district. He states t h a t t h e cracks in which gilsonite is found were formed b y the gentle folding t h a t produced t h e Uinta Valley syncline. H e describes t h e properties of the gilsonite coming from near t h e surface where, through atmospheric agencies, it has lost its luster a n d become pencillated in structure. From a study of conditions he concludes t h a t t h e gilsonite found its way into t h e fissures as a plastic mass, coming from below under pressure, a n d though of high viscosity, sufficiently fluid t o be pressed between t h e grains constituting t h e wall rocks. H e frankly confesses his lack of ability t o suggest t h e condition under which t h e gilsonite existed prior t o its flow into t h e cracks. An analysis of gilsonite b y Day is quoted as follows: Percentages Volatile matter.. ...... 56.46 43.43 Fixed carbon ..................................... 0.10 Ash or ........................ 8 8 . 3 0 ........................................ 9.96
.............................................. ..........
.......... Oxygen and nitrogen (undetermined).
.............
...............
0.10 0.32
L ~ c k e Blake14 ,~ Raymond,6 a n d Wurtz6 describe t h e uses of gilsonite, its solubilities, methods for “fluxing” it, etc. T h e earlier analyses of asphalts gave rather large percentages of oxygen, b u t this was probably because t h e presence of sulfur had not been recognized a n d t h e oxygen was supposed, with t h e carbon a n d t h e hydrogen, t o make up t h e ash-free bitumen. Nevertheless some analyses which report sulfur a n d nitrogen also report small amounts of ~ x y g e n . ~ By some authorities, as Richardson a n d Peckham, oxygen is considered as foreign t o natural asphalts. I n t h e first reference,t o wurtzilite, Blake8 describes it from a physical standpoint, noting its occurrence, hardness, color, specific gravity, fusibility, electrical properties, etc. H e explains t h e difference between wurtzilite a n d g i l s ~ n i t e ,a~n d shows t h a t t h e U t a h wurtzilite is a n entirely distinct mineral from t h e elaterPeckham, A m . J . Sci., 48, 111, 250. Eldridge, U.S. Geol. Survey, ZZnd A n n . Refif., 1900-01, 330. a Locke, Trans. A m . Inst. M i n . Eng., 16, 162 (1887). 4 Blake, Eng. M i n . J . , 40, 431 (1885). 5 Raymond, Trans. A m . Inst. M i n . Eng.. 17, 113 (1888). 6 Wurtz, Eng. M i n . J., 48, 114 (1889). Sadtler. THISJOURNAL, 6, 393 (1913). D Blake, Eng. M i n . J . , 48, 542 (1889). Blake, Trans. A m . I n s f . M i n . Eng., 18, 497 (1889). 1
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ite of Dana a n d other mineralogists. Wurtzl confirms t h e conclusions of Blake. U t a h ozocerite is very similar in properties t o t h a t f r o m Galicia, b u t as it contains less oily material and is firmer, it is more valuable. M a n y popular accounts2 of its mode of preparation, uses, etc., are t o be found, b u t nothing concerning its chemical composition, distillation products, etc. With t h e exception of occasional references t o t h e location of bituminous sandstones in Utah, nothing could be found about rock asphalt. U S E S O F UTAH HYDROCARBONS
An investigation of t h e uses of U t a h hydrocarbons shows t h e m t o be surprisingly numerous a n d varied. M a n y of our commonest articles are made from these substances. Before the discovery of gilsonite in Utah, European a n d Asiatic asphalts were shipped into the United States; now, because of its abundance a n d purity large quantities of U t a h asphalt are shipped t o foreign countries. T h e production of gilsonite during t h e last t w o years has increased rapidly, due t o t h e greater number of articles made from it. I n 19103 the production was 30,000 tons; i n 1912, over jo,ooo tons. It is worth about $20.00 a ton, f . 0. b. Utah. Wurtzilite is little used because of its insolubility. About 1,000tons are produced annually. Ozocerite is of greater value t h a n gilsonite, t h e price in New York being I j t o 28 cents per pound.4 No d a t a could be found as t o the production of ozocerite, b u t a t present t h e demand far exceeds t h e supply. Perhaps t h e most extended use t h a t has been made of U t a h asphalts is i n t h e paving industry. Gilsonite has been used in paving t h e streets of many i m p o r t a n t ~ i t i e s e, .~ g., Michigan Avenue, Chicago, where it is said t o be giving satisfaction under t h e most exacting requirements. Rock asphalt was used3 in paving Second South Street between West Temple a n d First West Streets, Salt Lake City, a n d t h e surface is now in fair condition, although i t has h a d practically ‘no repairs during its 16 years of service. Another i m p o r t a n t use for U t a h hydrocarbons is in the manufacture of varnishes a n d paint^.^ Only the purest a n d best materials are used for these purposes, the refined hydrocarbons being dissolved in turpentine a n d linseed oils. Wurtzilite has been used in t h e manufacture of a varnish in which t h e particles are simply held in suspension, b u t do not enter into solution. Some of t h e uses of t h e individual U t a h hydrocarbons are as follows: Gilsonite.5-Paving industry, electrical insulators, roofing papers a n d compounds, water-proofing wooden a n d steel pipes a n d masonry aqueducts, preventing electrolytic action o n iron plates of ship bottoms, 1 Wurtz, Eng. M i n . J . , 49, 106 (1890). 2 Higgins, Salt Lake Mining Review, 14, 11-5 (Oct., 1912). Culmer, Salt Lake Tribune (Dec. 29, 1912); Taff and Smith, U. S. Geol. Survey. Bull. 286, 369 (1905). ’ 8 Culmer, Address, Univ. of Utah, Nov. 15, 1912. Higgins, S i l t Lake M i n . Rev., 14, 11-5 (Oct. 15. 1912). 5 Locke, Trans. A m . Inst. M i n . Eng., 16, 162 (1887); New Internatl. Encyc. Article on “Asphalt;” Culmer. loc. c i t . ; Richardson and Parker, U. S . Geol. Survey, M i n . Resources of U.S., 1898, 627-69; Taff and Smith, U. S. Geol. Survey, BdZ. 286, 369 (1905).
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T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
coating barb wire fencing, coating sea walls of brick or masonry, lining t a n k s for chemicals, coating poles, posts a n d ties, toredo-proof pile coating, smokestack paint, lubricant for heavy machinery, substitute for rubber, as binder pitch for culm in making briquettes and egette coal. Tabbyite.-Compounds with Para rubber t o manufacture floor mats, rubber paints a n d roofings; as a filler for rubber in automobile tires, etc. W 24 rt z id it e .- T' ar nishes , roofing compound , et c . 0zocerite.'-Electrical insulator (said t o have about four times the specific resistance of paraffin), altar candles, substitute for beeswax, ointments, pomades. salves, water-proofing, waxed paper, wax dolls a n d figures, telephone receivers, phonograph records, electroplating, water-proof crayons, shoe polish, buttons, ceresine, floor polishes and waxes, water-proofing cartridges, sealing wax, etc. R o c k Asfihalt.-Paving industry. E X PE R I M E NTA L R E S U L T S
T h e results of t h e first tests made upon eight samples of hydrocarbons are given in Table I.2 They are
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classes,' aiz., those soluble i n 6 2 O naphtha (malthenes) a n d those insoluble in carbon tetrachloride b u t soluble in carbon disulfide (carbenes). Our solubility tests were made by allowing one-gram samples, finely ground, t o be in contact with excessive amounts of t h e solvents for 1 2 t o 18 hours, filtering upon ignited asbestos in a Gooch crucible, washing with t h e pure solvent, drying a t 100' C. a n d reweighing. Great difficulty was found in filtering some of t h e samples, especially t h e Trinidad asphalt. Table I1 gives t h e ultimate composition of t h e samples TABLEI1 Substance Carbon . . . . . Hydrogen . . . Sulfur.. . . . . . Xitrogen , , . . Ash . . . . . . . . .
Trin. 51.06 5.84 4.22 0.66 35.70
Ber. ii.52 8.90 4.70 0.89 5.32
Gils. 85.25 10.55 0.52 2.21 0.89
Tab. Wur. 1 Wur. 2 81.32 76.90 i 9 . 4 0 10.40 11.20 10.55 4.34 4.00 1.24 2.10 2.10 2.18 3.36 1.50 4.65
Ozok. R . A 85.35 9.55 13.86 1.10 0.78 0.29 0.31 0.36 0 . 0 4 88.05
as determined b y t h e ordinary combustion method, with lead chromate and copper oxide in t h e combustion tube. Great care must be taken in starting a combustion t o prevent t h e too rapid distillation of t h e volatile components present in t h e samples. Nitrogen was
TABLE I Original substance Trin. Loss 212" F., 1 hr., per cent. . . . . . . . . 0.073 Loss 325' F . , 7 hrs., per c e n t . . , , . , . 1.717 Penetration residue. . . . . . . . . . . . . . . . . 0 New sample loss 400°, 7 hrs.. . . . . . . . 5.25 Penetration residue. . . . . . . . . . . . . . . . . 0 Bitumen sol. in CSr. . . . . . . . . . . . . . . . 60.36 Org. matter insol. in CS,. . . . . . . . . . . . 3.94 Inorg. or mineral matter. . , . , , , , , , , , 35.70
Ber. 0.1765 6.63 30 9.71 0 90.93 3.74 5.32
Gils. 0.353 0.217 0 0.85 0 99.64 0 0.36
Bit. sol. in 62' naphtha. . . . . . . . . . . . . 41 .OO This is per cent of total bit.. , , , , , , , , 68.00 Carbenes: bit. insol. in CCla Bit. more sol. in CC14.. . . . . . Original loss on ignition. . . . . . . . . . . . . 64.30 Fixed carbon.. . . ... Sulfur on original.. . . . . . . . . . . . . . . . . 4.72 Specific gravity 78' F . . . . . . . . . . . 1.372 Streak., . . . . . . . . . . . . . . . . . . . . dark brown Luster. . . . . . . . . . . . . . . . . . Fracture, , , . . , . , , , , , , . , , . . . .conchoidal Hardness. . . . . . . . . . . . . . . Odor.. . . . . . . . . . . . . . . . . . . . . . . . . . . . tarry 203 Softens O F.. ...................... Flows ' F . . . . . . . . . . . . . . . . . . . . . . . . . 266 Penetration a t 78' F . . . . . . . . . . . . . . . . 0
34.40 38.85 0
61.70 61.85 0.18
.
0
1.37 94.68 39,60 4.iO 1 .05 nearly black glossy conch.
