1094
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
chloroform by passing in chlorine gas assisted b y sunlight or even b y t h e light from 1 5 0 watt tungsten lamps. The temperature cannot rise above t h e boiling point of t h e liquid a n d no catalysts are necessary. T h e formation of carbon tetrachloride is avoided b y chlorinating until only about I O per cent of the methylene chloride has been reacted upon and then separating the chloroform b y distillation. Methyl chloride up t o 40 per cent has been found in the gases removed from the ice chamber during t h e first few minutes after starting t o chlorinate natural gas. I t is easily isolated by compression or by solution in water or other solvents and this method presents a commercial method for its manufacture. I t s use would probably be greatly increased b y t h e development of a cheap and easy method of production. RESEARCH LABORATORIES
THEGOODYEAR TIRE& RUBBBRCOMPAXY AKROW. OHIO
THE RELATION BETWEEN THE TOXICITY AND THE VOLATILITY OF CREOSOTE OILS By
ERXESTBATEMAK
Received October 18, 1916
During t h e last few years considerable attention has been given by various workers on creosote oils and other wood preservatives t o t h e question of toxicity. J. M . Weiss,' Dean and Humphrey and Flemings3 and others have accumulated considerable d a t a on this subject. T h e two most important sources of oils used for wood preservation are coal t a r and water-gas t a r . T h e oils obtained from these b y distillation are usually called creosotes or distillates. In t h e course of a study of t h e literature on t h e toxicity of these oils t h e writer was struck b y t h e fact t h a t it depended a great deal on t h e boiling point, or, more properly speaking, on t h e volatility of t h e oils used, whether or not coal-tar creosote was more toxic t h a n water-gas t a r distillates. For instance, J. M. ST7eiss showed t h a t American creosote ( ; i per cent distilling a t 270' C.) was slightly more toxic t h a n German creosote (36 per cent distilling a t 2 7 0 ' c.) but t h a t they both were more toxic t h a n water-gas t a r distillate ( j o per cent distilling a t 270' C,). I n another article he shows t h a t n-atergas t a r distillate S o . 2 1 ( j o per cent distilling a t 270' C.) was more toxic t h a n coal-tar creosote No. I O (8.5 per cent distilling below 2 7 0 ' C.),Dean and Downs showed t h a t coal-tar creosotes marked "A" (58 per cent distilling a t 300' C.) and "B" (distillation limits not gi\yen) and water-gas t a r distillate marked "C" (78 per cent distilling a t 3 0 0 ' C . ) had about t h e same toxicity, while water-gas t a r distillate marked "D" (distillation limits not given) v a s slightly more toxic t h a n all three. B u t all four of above oils were more toxic t h a n expressed anthracene oil (distillation limits not given b u t certainly much less volatile t h a n t h e other oils). Humphrey and Fleming show t h a t water-gas t a r distillate No. 2 2 3 5 ( 6 2 per cent disJ . SOC.Chem. ItLd., 30 (1911), 190 a n d 1348. 2 Proc. Interitat. Congr. ,499. Chem., 1912. Department of Agriculture, Bull. 227; THISJ O U R N A L , 6 (1914), 128; 7 (1915), 6 5 2 . 1
Vol. 8, No.
12
tilling below 2 7 j oC . ) is much more toxic t h a n Fraction I V coal-tar creosote (4.7 per cent distilling below 2 7 j " C.) or Fraction V coal-tar creosote (0 distilling below z i j " C.) and t h e carbolineum N o . 1843 (6.1 per cent distilling below 2 7 j" (2.). On t h e other hand, they also show t h a t all t h e coal-tar produc,ts tested were more toxic t h a n water-gas t a r distillate No, 1 x 0 1 (16.3 per cent distilling below 2 7 5 ' C.). A study of all of the toxicity d a t a available show t h a t out of these apparently conflicting results a very definite and logical order can be established if t h e volatility of t h e oils in question is coordinated 'with their toxicity. I t is the purpose of this paper t o show this relation. For all practical purposes the percentage of oil distilling below 2; j' C. is a good measure of t h e comparative volatility of creosote oi1.l This point has been taken as a measure of t h e volatility of t h e creosotes and a curve has been plotted using this figure as one coordinate and t h e killing point against Fomes annosus (Humphrey and Fleming) as t h e other coordinate. ,4s a result, two curves are obtained-one for coal-tar creosote and t h e other for water-gas t a r distillates. These are shown in t h e accompanying cut. D a t a from other sources could not be included because different organisms have a somewhat different action. IW
u
1(1
i 1
v 60
5
n
1
40
20
0
PCRCEYI lllPUlRED TO KILL
A careful s t u d y of tests using other organisms, however, shows t h a t t h e general finding is the same, although t h e numerical values may be quite different. T h e accuracy of these curves ha5 been proved in a measure in t h e following manner:' Creosotes whose toxicity has not hitherto been tested rrere analyzed and their toxicity mas predicted from their T olatility, with the following results: KILLINGPOIKT
(As estimated Kinds of from curvej Creosote Coal-tar oil No. 1 . . . . . . . . . . . . . . . . . . . . . 0.670 Coal-tar oil No. 2 . . . . . . . . . . . . . . . . . . . . . 0.75% Coal-tar oil No. 3 . . . . . . . . . . . . . . . . . . . . . 1 .O% Water-gas t a r oil h-0 1 . . . . . . . . . . . . . . . . 17 ,0yO
( A s determined
bv test)
T h e above indicates t h a t t h e killing point can be determined as accurately from a consideration of t h e distillation as i t can be from toxicity tests, provided t h a t t h e authenticity of t h e oil is without question. The cur\-es are of considerable interest aside from merely predicting the toxicity. They suggest-Jirst, a possible method of determining the purity of oils, perhaps b y some short test as the Rideal-Walker test on t h e high boiiing fractions; and s c c o u d : t h a t much See Forest Service, Circ. li2. M y thanks are due t o Miss R u b y Tiller and LIrs. R u t h Fleming, Bssistants in Pathology, Bureau of Plant Industry, of this laboratory, for supplying me with t h e d a t a on toxicity which were necessary t o prove t h e correctness of t h e relationship here shown 1 2
Dec., 1916
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 CHEMISTRY
of t h e toxicity of t h e hydrocarbon boiling t a r acids will be followed future.
coal-tar creosote is derived not oils a n d solids b u t from t h e and t a r bases. These lines of u p by this laboratory in t h e
from high work near
FOREST PRODUCTS LABORATORY MADISON, WLSCONSIN
OZOKERITE FROM THE THRALL OIL FIELD] By
E. P. SCHOCH
Received August 5 , 1916
I095
Ceresine is distinguished from paraffin by means of its lesser solubility in carbon tetrachloride, carbon bisulfide, and chloroform:’ I O O cc. portions of carbon tetrachloride dissolved 3.08 g. of Thrall ceresine, and 24. I j g. of “Texaco” paraffin, respectively. The melting point of ozokerite2 varies “from below 60’ C. in t h e poorer grades t o 68-7 j oC. in the normal quality, but may go as high as 84’ C. (marble wax).’’ T h e Thrall ozokerite (unrefined) had a melting point of 79. j’ C., while t h e refined material (the Thrall ceresine) melted a t 7 j ’ C. The melting point of paraffin of t h e same consistency varies from 50 t o 58’ C., a n d t h a t of “Texaco” paraffin was found t o be j j ’ C. Thus melting point determinations indicate t h a t the Thrall ozokerite is of fine quality. The specific gravity2 of paraffin (solidification point 44-58’ C.) is 0.867-0.915 a t I j o C., and of ceresine (solidification point 56-84’ C.) i t is between 0.912 and 0.943. The Thrall ceresine had a specific gravity of 0.926 t o 0.928. Various investigators have found t h a t the indices of refraction of paraffins with melting points 50-58’ C., range from 1.4220 t o 1.4275 a t 90” C., while the indices of refraction of pure ceresine range from 1.4212 t o 1.4334, and even t o 1.441s’. The index of refraction of the Thrall ceresine was 1.4414 to 1.4420 a t 90’ C. The purity of ceresine (particularly t h e absence of paraffin in it) is established by “fractional” dissolution and precipitation which, with a mixture of ceresine and paraffin, yields consecutive precipitates and a non-precipitable residue containing different proportions of ceresine t o paraffin. This variation in the proportions of ceresine t o paraffin can be ascertained by taking t h e indices of refraction of t h e consecutive precipitates and of t h e non-precipitable residue. With a pure ceresine, t h e indices of refraction of all t h e different precipitates should be well above the index of refraction for paraffin. On dissolution in chloroform, and precipitation with alcoh01,~t h e Thrall ceresine gave, on an average, t h e following indices of refraction:
Ozokerite owes its use and value t o t h e fact t h a t it combines t h e great chemical inactivity or resistivity of paraffin with t h e p’hysical properties of beeswax, namely, t h e property of being “doughy” or “kneadable.” I t s value is enhanced b y t h e fact t h a t its melting point is higher t h a n t h a t of paraffin or of beeswax. Ozokerite and ceresine are used industrially in t h e manufacture of candles, in cable insulation, in shoe, stove and floor polishes. They are rather expensive -particularly a t t h e present time because ozokerite is mined chiefly in Galicia. One New York firm! which buys large amounts of this material, stated t h a t before the war Galician ceresine was worth 2 j cents per lb., and t h a t a t present i t was probably worth three times t h a t amount. 0zokerit.e is found in t h e Caucasus, and in t h e Wasatch Alo.untains, Utah. Some dark brown, ‘waxy material, which is obtained together with crude petroleum a t Thrall, Texas, has recently been analyzed in the Chemical Division of t h e Bureau of Economic Geology, and has been recognized as being ozokerite of a n exceptionally good quality, as t h e following d a t a show: The crude material is soft, sticky, and of a dark brown color, with a sp. gr. of 0.87 j. It has a strong odor of crude petroleum. Hea$ed t o remove t h e latter, t h e crude material loses 14.72 per cent in weight u p t o 100’ C., and 8.42 per cent more (or a total of 23.14 per cent) up t o 180’ C. For refining, this heated material was treated with 18 per cent of its weight of concentrated sulfuric acid First Precipitate Second Precipitate Residue and the mixture heated a t 180--20o’ C. until SO2 1.4470 1.4420 1 4400 ceased t o be evolved. Then the mass was mixed with This indicates t h a t the Thrall ceresine is totally free animal charcoal and “extracted” sawdust, t h e mixture from paraffin. heated for 2 0 min., then cooled and extracted with A sample of Galician ozokerite, secured in t h e open gasoline. On evaporating the gasoline, a material of t h e consistency of beeswax varying in color iron1 orange- market for purposes of comparison, showed itself t o yellow t o white was obtained. The white samples be less “doughy” or kneadable t h a n the Thrall ozokerwere practically free from t h e odor of petroleum, so ite, and yielded a more flaky or brittle ceresin t h a n t h a t the color in t h e yellow samples was probably due t h e Thrall ceresine. I t s melting point was low (jj’ t o t h e presence of a tra,ce of t h e original impurities. C . ) ; its index of refraction, 1.4420 a t go’ C. This The amount of refined rqaterial thus obtained varied sample seems t o be of a less desirable material t h a n from j 4 t o 77, per cent of the weight of t h e crude t h e Thrall ozokerite, but we do not know t h a t i t is material employed. Such refined ozokerite is tech- a fair sample of Galician ozokerite. These determinations show, beyond t h e question nically known as cevesine. Since t h e material might be either paraffin or ozoker- of a doubt, t h a t t h e “Thrall” material is ozokerite, ite, a comparison with paraffin of t h e same consistency free from paraffin, and of a fine quality. RVREAUOF ECONOXIC GEOLOGY A N D TECHNOLOGY or hardness was made. The Thrall ozokerite is perAUSTIN, TEXAS fectly “doughy” and can be “kneaded,” while paraffin is “flaky” and brittle. 1 Lewkowitsch’s, “Analysis of Oils, Fats and Waxes.” Published by permission of the Director of t h e Bureau of Economic Geology a n d Technology of the Cniversity of Texas.
3
Holde-Mueller’s “Examination of Hydrocarbon Oils.” Holde-Mueller, p. 246.
