The laboratory production of asphalts from animal and vegetable materials

Sept., 1899. ]

Laboratorl, l~rodnclivn o f Asphalts.

205

disposal, driving motors or air engines of various kinds, clipping horses, coal or eulm conveyors, lighting, agitating syrup in sugar refineries, beating eggs, raising beer, automatic fire-extinguisher service, propelling torpedoes and torpedo boats, sand-papering, a~rating fuel, refining asphalt, excavating cesspools, finishing silk ribbon, for dry dock and canal lock service, agitating acids, ventilating in mines, cotton compresses, vulcanizing wood, temperature regulators, raising sunken vessels, driving printing presses and other individual tools, operating clocks, etc.

CHEMICAL

SECTION.

.%/aled llZeetinAq held Frhrnacv iS, zS99.

"THE L A B O R A T O R Y P R O D U C T I O N OF A S P H A L T S FI~OM A N I M A L .xYI~ V E G E T A B L E M A T E R I A L S . ~ BY WM. C. DAY.

By carrying out operations of distillation at the ordinary atmospheric pressure upon animal and vegetable matter, both separately and mixed, I have succeeded during the past year in producing three different materials, all of which present in different degrees the properties characteristic of asphalts. Two of these materials quite closely resemble asphalts occurring in nature, namely, gilsonite and elaterite, as found in Utah. Postponing for the present a consideration of the reasons which led to these experiments, I will first give a description of the work done and a statement of the results obtained since the publication last summer of a preliminary paper+ on the same subject. The first experiment was to distil from an iron retort a mixture of fresh fish (herring from the Delaware) and fat pine wood, partly in the form of sawdust and partly in Published by permissiou of the U. S. G e o l o g i c a l Survey. I " P r o c . Amer. Philos Soc.," ~ 7 , 171.

206

D a r ."

[J. F. I.,

sticks. T h e r e t o r t was connected with a short glass tube by m e a n s of a j o i n t of plaster-of-paris and asbestos ; this tube was connected at the o t h e r end by a similar j o i n t with a small iron gas pipe four feet long, placed upon a combustion furnace, by which it could be m a i n t a i n e d at a red heat. The retort was h e a t e d by gas f u r n a c e s and the distillation was carried to complete carbonization of the organic matter. An o r d i n a r y Liebig's condenser served to condense the mixed oil and w a t e r as it issued from the red-hot gas pipe. T h e distillation p r o d u c t consisted of w a t e r of a yellowishred color, and a dark, nearly black, mobile oil, which for the g r e a t e r part floated upon the water, a l t h o u g h toward the close of the'distillation a little oil would u s u a l l y sink t h r o u g h the water. Twelve operations of distillation c o n s u m e d 9,882 grams of wood and 8,17o g r a m s of fish, and yielded 3,oio cubic c e n t i m e t e r s oil, of specific g r a v i t y o9837 , and 8,240 cubic c e n t i m e t e r s water. T h e average distillation shows, therefore, the figures 823"5 g r a m s wood, 680"8 g r a m s fish, 250"8 cubic c e n t i m e t e r s oil and 686"7 cubic c e n t i m e t e r s water; these a v e r a g e figures were a p p r o x i m a t e d in each single distillation. T h e oil was s e p a r a t e d from the w a t e r a n d t h e n dried by s t a n d i n g over chloride of calcium. A c o m b u s t i o n of this oil, u s i n g copper oxide and lead c h r o m a t e , gave the followin K resu]ts: o'3~o4 g r a m oil gave 0"9593 g r a m CO2 and 0"2794 gram t I~(), or I'er Cellt Carboll Hydrogen

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

84"28

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

lo'{,o

The dried oil was then s u b j e c t e d to distillation b y i t s e l f i:: a hard glass r e t o r t provided w i t h t h e r m o m e t e r . A few drops of oil, a c c o m p a n i e d by a little moisture, came over at go ° C. : the t e m p e r a t u r e rose r a p i d l y to I2o ~, at which point distillation proceeded rapidly, g i v i n g a distillate lemon yellow in color and s l i g h t l y t u r b i d from moisture. T h e receiver was c h a n g e d at t 8' o~, w h e n the distillate app<.'ared darker in color b u t free from moisture. The receiver

S e p t . , 1899. ]

Laharatorr Prodzlctialt of Asp/za#s.

2o 7

was c h a n g e d at 245 °, 3~5 ° and 340 ° , at w h i c h last point t he t h e r m o m e t e r was r e m o v e d ; a f t e r this t he distillation was c o n d u c t e d to a b o u t 425 ° as n e a r l y as could be j u d g e d by the r a t e at w h i c h t he t e m p e r a t u r e had been rising. A t 315 ° a g r e e n i s h fluorescence a p p e a r e d . W h e n the boiling was s t o p p e d the c o n t e n t s of t he r e t o r t consi st ed of a mobile, h o m o g e n e o u s , black l i qui d c o n t a i n i n g no solid part i cl es of any kind. W h e n the r e t o r t cooled this oil solidified to a black, s h i n i n g mass, s h o w i n g c o n e h o i d a l fracture, b r i t t l e and p u l v e r i z i n g to a b r o w n i s h - c o l o r e d p o w d e r s l i g h t l y d a r k e r than th e p o w d e r of U t a h gilsonite, which, in appearance, it closely r e s e m b l e d ; in fact, it was only by t he r o u n d e d surface of th e artificial p r o d u c t t h a t t he two could be disting u i s h e d b y inspection. A n u m b e r of distillations w ere mad e with e s s e n t i a l l y the s a m e e x p e r i e n c e as j u s t described, ex cep t t h a t th e m a t e r i a l o b t a i n e d the first t i m e was s l i g h t l y sticky to th e to uc h and e n t i r e l y soluble in carbon bisulphide, while th e s am pl es o b t a i n e d s u b s e q u e n t l y were not at all sticky, and were not e n t i r e l y soluble in the bisnlohide. S u b j e c t e d to c o m b u s t i o n , t h e s a m p l e r e s u l t i n g from the first distillation g a v e t he f o l l o w i n g r e s u l t : o'221i g r a m s u b s t a n c e g a v e o'7~oo g r a m C )2 and o't54o g r a m tL(), or Pet" Cent. Carbon . . . . . . . . . . . . . . . . . . . . . . . . . Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . .

S7'57 7'74

T w o c o m b u s t i o n s of t he artificial gi l soni t e finally m a d e in q u a n t i t y g a v e the following results : I. 0"2529 g r a m sul~stance g a v e o'8o3~ g r a m CO., and o'I 599 g r a m H.,O. II. o"3oi5 g r a m s u b s t a n c e g a v e o'9564 g r a m C(). and o'I938 g r a m t[:O. I. P e r Cent. Carbon . . . . . . . . . . . . . . . . . . . . . Hydrogen . . . . . . . . . . . . . . . . . . .

S6"6t 7"o2

11. Per Ce/lt. S~,'5 t 7"to

T w o n i t r o g e n d e t e r m i n a t i o n s by K e j h l d a h l ' s m e t h o d , using in the first case I" 195)0 g r a m s s ubs t ance, and i n the second o'9824, g a v e nitro,~en I"95 and t'86 per cent., respect i vel y.

208

Din, ."

[j. F. I.,

T w o determinations of sulphur by Peckham's method ~ resulted as follows : [. 2"o218 grams substance gave o"o136 gram B a S Q . II. I'9988 grams substance gave o'o114 gram BaSO4. II. Per Cent.

I.

Per Cent. S . . . . . . . . . . . . . . . . . . . . . . .

0"092

o'o78

According to the figures obtained, the composition of the artificial gilsonite appears to be as follows : For the sake of comparison, the figures for natural Utah gilsonite are also given here, as well as elsewhere. Carbon . Hydrogen Nitrogen Sulphur . (hcygen

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

( b y dif.) . . . . . . . . . . . . . . .

Artificial. Per Cent.

Natural. Per Cent.

86"56

85'83

7"06 I "91 0"08

m'59 2 '59 0"26

4"39 Ash,

I CO'O0

o'63 o'Io

lOO o o

W h i l e the differences in composition b e t w e e n these two materials are not great, still they can by no means be regarded as insignificant, particularly as regards those in the cases of hydrogen and oxygen. It is true, however, that much greater differences b e t w e e n two natural asphalts taken from sources in the same neighborhood have been found. Determinations of solubility in the f o l l o w i n g solvents were made : Carbon bisulphide, turpentine, ether, gasoline and absohlte alcohol. T h e method employed was to treat a w e i g h e d portion of the substance with the solvent until no further action took place, and then w e i g h the undissolved residue on a t a r e d filter. CARBON BISULPHIDE. I.

W e i g h t of s u b s t a n c e t a k e n . . . . . . . . . . . . . . . . " " undissolved residue . . . . . . . . . . . . . . .

0'5505

.... dissolved substance . . . . . . . . . . . . . . . Per c e n t . s o l u b l e i n C S 2 -~- 8 0 " 7 4 .

("4445

*fourmll.~,'oc. C h e m . I n d . , I ~ L

N o . I 2 , 1897.

o'Io6o

Laboratory

Sept., I8 9%]

Pr&ttlctioJ~ o f A s p h a / / s .

2o 9

II.

W e i g h t of s u b s t a n c e t a k e n . . . . . . . . . . . . . . . . " " umtissolved residue . . . . . . . . . . . . . . .

o'697(, ,vi293

.... dissolved substance . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e in CS~ --: 8t'44.

o'5677

TURPENTINE°

W e i g h t of s u b s t a n c e t a k e n . . . . . . . . . . . . . . . . .... undissolved residue . . . . . . . . . . . . . . .

o'9o41 o'456S

.... dissolved substance . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e in t u r p e n t i n e 49'47.

04473

F.TH]~,R.

W e i g h t of s u b s t a n c e t a k e n . . . . . . . . . . . . . . . . .... undissolved residue . . . . . . . . . . . . . . .

¢,'577~, ~,lqo.!

.... substance dissolved . . . . . . . . . . . . . . . P e r cen t. s o l u b l e in e t h e r = 67"o 3.

~v >~72

GASOLINE. W e i g h t of s u b s t a n c e t a k e n . . . . . . . . . . . . . . . . " " undissolved residue . . . . . . . . . . . . . . .

)'55~9 o'2,',45

.... substance dissolved . . . . . . . . . . . . . . . P e r cent. s o l u b l e in g a s o l i n e ~--- 16"7t.

o 2~¢)1

~. E S O I , UTI,: A I , C O H O L .

'5547

W e i g h t of s u b s t a n c e t a k e u . . . . . . . . . . . . . . . . . . " " undissolved residue . . . . . . . . . . . . . . .

~'2~6e

.... substance dissolved . . . . . . . . . . . . . . . I ' e r ceut. s o l u b l e in a l c o h o l = 48"4o. All or less the

the

solutions

marked

natural

obtained

greenish

were

o-2553

characterized

fluorescence,

which

by

is also

a more true

oiis(mite. \( TI()N

tH e S O l , V E N T S ,

>;,Avent.

Utah Gilsonlte.

Artificial G i l s o n lie.

Carbon Bisulphide . . . . . . . . . .

I first laroduet, 1c,<)'o~ 99"50 "[ seeon(1 " SJl l

Turpentine Jdther . . . (;asoline . Alcohol . .

97"34 73.o8 63.08 34"8I

While differences

the

. . . .

. . . .

. . . .

. . . .

. . . .

above

. . . .

. . . .

table

in solubility,

VOL, CX I ~ ' v' l I l .

No. 885 .

. . . .

. . . .

. . . .

. . . .

. . . .

. . . .

shows every

. . . .

in some one

of

the

. . . .

. . . .

. . . .

cases

. . . .

. . . .

. . . .

. . . .

quite

solvents

49"-17 ()7.o3 1~.7 18"4o notable exercises r4

of

210

Day :

[J. F. I.,

in each case a p r o n o u n c e d effect, all figures b e i n g a b o v e 3° per cent., and g e n e r a l l y n e a r l y 50 per cent. or more. T h e action of c o n c e n t r a t e d nitric acid u p o n the n a t u r a l and the a r t i f c i a l material is peculiar, and of e x a c t l y the s a m e character. T h i s action consists in c o m p l e t e l y dissolving the material w i t h copious e v o l u t i o n of b r o w n f u m e s and the p r o d u c t i o n of a dark-red solution, which, u p o n dilut. ing with water, yields a flocculent p r e c i p i t a t e m u c h resemb l i n g freshly p r e c i p i t a t e d ferric hydroxide. In the course of an i n v e s t i g a t i o n of U t a h gilsonite,* carried o u t some years since, I s e p a r a t e d from the oils distilled from the mineral certain basic c o m p o u n d s s u g g e s t i v e in odor of the pyridine or quinoline series. T h e s e b o d i e s were o b t a i n e d b y the e x t r a c t i v e action of dilute s u l p h u r i c acid upon the oils. F r o m such solution t h e y are t h r o w n down by alkalies as floceulent precipitates. T h e s a m e kind of s u b s t a n c e s were o b t a i n e d from the oil which, b y distillation, yielded the artificial gilsonite. The m e t h o d of t r e a t m e n t a d o p t e d to e x t r a c t t h e s e basic substances was to shake the oil w i t h dilute s u l p h u r i c acid and then pass s t e a m into the m i x t u r e c o n t a i n e d in a large flask until oil no longer distilled off with steam. On neutralizing the residual acid with caustic soda solution, a precipitate looking and smelling like t h a t from gilsonite oil was obtained. T h e p r e c i p i t a t e was a l t e r n a t e l y redissolved in sulphuric acid and r e p r e c i p i t a t e d b y alkali a n u m b e r of times, and then, after w a s h i n g with water, w a s left on a filter to dr3". On drying, however, the m a t e r i a l l a r g e l y disappeared, t h u s s h o w i n g its volatility, w h i c h the solid a p p e a r a n c e when freshly p r e c i p i t a t e d h a d failed to s u g g e s t . It is evident, however, t h a t the presence of these basic c o m p o u n d s affords a n o t h e r e l e m e n t of similarity b e t w e e n the natural and the artificial product, and also b e t w e e n t h e s e bodies and California p e t r o l e u m . D I S T I L L A T I O N OF FISIt

ALONE.

T h e i n t e r e s t i n g c h a r a c t e r of the p r o d u c t o b t a i n e d by distilling a m i x t u r e of fish and wood, and the similarity -~Journal Frank/D1 Znslilule, 1 G O , 221.

Sept., I899.]

Laboratory Production o f Asphalts•

2II

b e t w e e n this a n d U t a h gilsonite, s u g g e s t e d t h e a d v i s a b i l i t y of c a r r y i n g o u t t h e s a m e ki nd of e x p e r i m e n t s w i t h fish alone and also w i t h wood alone. A c c o r d i n g l y , a n u m b e r of c h a r g e s of t h e s a m e k i n d of fish w e r e distilled, u s i n g t h e s a m e appar a t u s as was e m p l o y e d for t h e m i x t u r e of w ood and fish. In all 4,585 g r a m s of fish w e r e distilled, y i e l d i n g 700 cubic c e n t i m e t e r s of oil a nd 2,830 cubi c c e n t i m e t e r s water• T h e d is tillate c o n s i s t e d of a yel l ow e m u l s i o n difficult to b r e a k u p ; th e d i s t i l l at e f r o m t h e fish and w ood m i x e d g a v e no e m u l s i o n at all, b u t p r e s e n t e d a well-defined line of sepa r a t i o n b e t w e e n t h e oil and water. T h e e m u l s i o n was sepa r a t e d in to oil a nd w a t e r b y h e a t i n g u p o n t h e w a t e r - b a t h , t h e oil b e i n g e v e n t u a l l y b r o u g h t to t he s u r f a c e of t he water. Mu ch a m m o n i a was p r o d u c e d d u r i n g t he distillation. A n a t t e m p t was m a d e to d r y t h e oil b y al l ow i ng it to stand o v e r ch lo ri de of c a l c i u m for a n u m b e r of days, b u t it could n o t be p e r f e c t l y dr i e d in this way. Success in d r y i n g was finally a t t a i n e d onl y b y a s p i r a t i n g a c u r r e n t of d r y air • t h r o u g h t h e oil while it was h e a t e d u p o n t he water-bath. On a t t e m p t i n g to distil t h e fish oil f r o m a retort, as was done w i t h t h e oil f r om t h e m i x t u r e of fish and wood, such v i g o r o u s an d expl os i ve " b m n p i n g " was e n c o u n t e r e d as to c a r r y t h e c o n t e n t s of t he r e t o r t o v e r m e c h a n i c a l l y so t h a t it • was f o u n d i m p o s s i b l e to distil it in this way. T h e appearance of m o i s t u r e d u r i n g this a t t e m p t to distil an oil w hi ch had b e e n t h o r o u g h l y dr i e d m a d e it e v i d e n t t h a t t he w a t e r was f o r m e d d u r i n g t he distillation. T h e oil was t r a n s f e r r e d from t h e r e t o r t to an iron c r u c i b l e and h e a t e d c a u t i o u s l y until th e s t a g e of w a t e r f o r m a t i o n was passed, and t h e n h e a t e d m o r e s t r o n g l y . A f t e r h e a t i n g for a t i m e t he contents of th e cruci bl e w e r e allowed to cool, w h e n a v e r y sticky, t h i c k semi-liquid m a s s r e m a i n e d . It looked and s m e lled m o r e like a m a l t h a f r o m M o n t a n a t h a t I had examined a few y ear s since t h a n a n y t h i n g else I could c o m p a r e it to. T h e m a t e r i a l was agai n h e a t e d Jn t he crucible, boi l i ng it f r e e l y : on c o o l i n g agai n a solid was o b t a i n e d , black in color and elastic, so t h a t if b e n t n e a r l y d o u b l e it w o u l d fly back to its o r i g i n a l s h a p e like a thick piece of I n d i a rub.

212

]Pat' ."

[J. F. I.,

her. I t c o u l d b e e a s i l y cut, b u t n o t p u l v e r i z e d , a l t h o u g h if s t r u c k a b l o w w i t h a h a m m e r it w o u l d b r e a k w i t h conchoidal fracture. D e t e r m i n a t i o n s of c a r b o n , h y d r o g e n a n d n i t r o g e n w e r e made with the following results : I. 0'2366 g r a m s u b s t a n c e g a v e 0'6638 g r a m CO~ and o"I933 g r a m H..O. II. 0"2333 g r a m s u b s t a n c e g a v e o"6618 g r a m COo and o ' I 9 t 6 g r a m H,,O. III. 0"2233 g r a m s u b s t a n c e g a v e b y K e j h l d a h l ' s m e t h o d a m m o n i a c o r r e s p o n d i n g to 4"19 p e r cent. of n i t r o g e n . I V . 0"8896 g r a m s u b s t a n c e g a v e a m m o n i a c o r r e s p o n d i n g to 4"27 p e r c e n t . n i t r o g e n . \r. 2.0402 g r a m s s u b s t a n c e g a v e 0"0287 g r a m BaSO4. *~rI. I'9!)54 g r a m s s u b s t a n c e g a v e 0"0276 g r a m B a S O v Carbon

. . . . . .

Hydrogen . . . . . Nitrogen . . . . . Sulphur . . . . . .

I.

II.

76'5I

77"36

9'08 ---

III.

9'I2 ---

IV, "

.

.

.

.

4"19 --

V.

.

.

.

.

4"27 --

--

oo"t9

VI.

--

oo'I 9

T h i s m a t e r i a l , if c o o l e d d o w n , b e c a m e h a r d e r a n d less .~usceptible of b e n d i n g ; t h e s a m e k i n d of c h a n g e s e e m e d to r e s u l t also as t h e m a t e r i a l b e c a m e older, as a f t e r s o m e m o n t h s it b e c a m e h a r d e r and m o r e b r i t t l e . T h e f o l l o w i n g r e s u l t s of a n a l y s i s w e r e o b t a i n e d u p o n a s a m p l e of e l a t e r i t e f r o m U t a h . T h i s m a t e r i a l in l u m p f o r m was h a r d a n d not at all c a p a b l e of b e i n g b e n t ; it was, however, q u i t e flexible w h e n s a w e d i n t o t h i n slabs. T h e perc e n t a g e s of c a r b o n a n d h y d r o g e n f o u n d are n o t f a r rem o v e d f r o m t h o s e of t h e a s p h a l t f r o m fish alone. I. 0"2993 g r a m s u b s t a n c e g a v e 0"8024 g r a m CO., a n d o'255o g r a i n H.O. II. o'i995 g r a m s u b s t a n c e g a v e 0"5404 g r a m CO~ and o"I698 g r a m tI._.O. Carbon

.

.

.

.

.

.

.

.

.

.

.

Hydrogen . . . . . . . . . . . . . . . . . . .

.

.

.

.

.

.

.

.

.

I.

II.

73.ii

7388

9.46

9"45

F u r t h e r i n v e s t i g a t i o n of t h i s m a t e r i a l is n o w b e i n g ear. r i e d out. A c c o r d i n g to D a n a ' s " M i n e r a l o g y , " p. 734, elate r i t e a n a l y z e d b y J o h n s t o n c o n t a i n s 84 to 86 p e r cent. car-

Laboratorl' ProdJtction o f Asphalts.

Sept., I899. ]

2I 3

bon, and I2"3 to I3"2 per cent. h y d r o g e n . I am u n a b l e to give the a u t h o r i t y for calling the U t a h material elaterite, but in c o m p o s i t i o n it e v i d e n t l y r e s e m b l e s m u c h more nearly the material o b t a i n e d from fish t h a n it does the elaterite described b y Dana. ] ' h e m u c h lower p e r c e n t a g e of carbon t h a n is c o n t a i n e d in g i l s o n i t e is n o t e w o r t h y . T r e a t m e n t of oil o b t a i n e d from fish alone with dilute sulphuric acid g a v e a s o l u t i o n of basic n i t r o g e n c o m p o u n d s w h i c h could be precipitated by alkalies, just as in the case of oil from natural or artificial gilsonite, q'he odor of these basic s u b s t a n c e s was of the same character, w h a t e v e r the source. T h e f o l l o w i n g d e t e r m i n a t i o n s of the s o l u b i l i t y of the asphalt from fish alone were made: CAR|~ON

Weight of

B I ~ U l-~l't{IDI~.

substance

used

undissolved

.

.

.

.

.

.

.

.

.

.

.

.

. . . . . . . . . . . . . . . . .

dissolved

Per cent. soluble in

CSz =

Weight of substance

used

.

.

.

.

.

.

.

.

.

.

.

. . . . . . . . . . . . . . .

~v2999 o'c)954 o'2045

68"I9. TI-1 )- I ' E N T [ N ~ ; .

.

.

.

.

.

.

.

.

Per cent.

.

.

.

.

. . . . . . . . . . . . . . . . .

undissolved dissolved

soluble

in

o'3~63

. . . . . . . . . . . . .

,v~655

. . . . . . . . . . . . . . .

,~'j4c~S

turpentine

~

~7"36.

I~Tt[ER.

W e i g h t of substance .

.

.

.

.

.

.

.

.

.

.

.

.

.

0'2662

. . . . . . . . . . . . .

o'IoS7

. . . . . . . . . . . . . . .

o'1575

undissolved

.

.

used

.

dissolved

Per cent. soluble in ether

~

.

.

.

.

.

.

.

.

.

.

.

5917. (',~SOlA y E .

Weight of . .

. .

. .

. .

.

Per cent.

substance

used

.

undissolved

.

. . . . . . . . . . . . . . . . .

dissolved

.

soluble

in

gasoline

o.3733

. . . . . . . . . . . . .

o'24i 9

. . . . . . . . . . . . . . .

o'x314

---~ 3 5 ' ~ 9 .

.~l~so r.u'rJ,: A L C O t r O L . \\;eight . "

.

of substance .

.

.

.

used

. . . . . . . . . . . . . . . . .

undissolved

"

"

Per cent.

soluble

dissolved in alcohol

=

o.4239

. . . . . . . . . . . . .

¢~'2,,74

. . . . . . . . . . . . . . .

~," 2165

5 I "o7.

2I 4

Daj, ."

[J. F. I.,

DISTILLATION OF WOOD ALONE. T h e same kind of rich and h e a v y pine as was used in m i x t u r e w i t h fish was s u b j e c t e d to d i s t i l l a t i o n by itself. In all 4,588 g r a m s were used, y i e l d i n g I,I5O cubic centim e t e r s of oil and 89° cubic c e n t i m e t e r s water. It is i n t e r e s t i n g to note here the m u c h larger proportion of oil o b t a i n e d t h a n r e s u l t e d from the d i s t i l l a t i o n of fish alone. T h e distillation was a c c o m p a n i e d by the p r o d u c t i o n of a thick, w h i t e smoke, w h i c h could n o t be condensed. T h e distillate was s t r o n g l y acid. T h e oil, after drying, s h o w e d a specific g r a v i t y of o'992. It was s u b j e c t e d to distillation by itself, collecting the same fractions as were t a k e n in the case of the distillation of oil from wood and fish. T h e first fraction, 9 °0 - - I45 °, was light-yellow in color, and s l i g h t l y t u r b i d f r o m m o i s t u r e ; the second, I45 ° _ 18o ° , was darker y e l l o w ; t h e third, i8o ° - - 2 4 5 % was greenishblack; the last one showed green fluorescence. A f t e r distilling off s o m e w h a t more t h a n h a l f the oil, the black, b u t perfectly mobile liquid, was allowed to cool, w h e n it solidified to a black s h i n i n g mass, v e r y brittle and s h o w i n g conchoidal fracture. W h i l e t h e g e n e r a l color was black, inspection of a t h i n edge along a line of f r a c t u r e showed a purple color, such as could n o t be seen w i t h the m a t e r i a l f r o m wood and fish. T h e specific g r a v i t y was f o u n d to be I'O825. W h e n pulverized, the powder, in the course of several days, w o u l d c e m e n t t o g e t h e r and re-form a hard, rigid mass. D e t e r m i n a t i o n s of carbon, h y d r o g e n and n i t r o g e n gave the following results : 0"2078 g r a m s u b s t a n c e g a v e 0"6568 g r a m COs and o'I549 g r a m H20. o'9362 g r a m s u b s t a n c e g a v e a m m o n i a c o r r e s p o n d i n g to 0"26 per cent. nitrogen. 0"8884 g r a m s u b s t a n c e gave a m m o n i a c o r r e s p o n d i n g to 0"33 per cent. nitrogen. l ) e t e r m i n a t i o n s of s u l p h u r g a v e only traces. I.

Car b o 1 1 . 86"20

Hydrogen, 8"28

Nitrogen. --

II,

--

--

0'26

III.

--

--

0"33

Laboratory Production o f Asphalts.

Sept., I899. ] The

following

determinations

of solubility

were

2I 5 made

CARBON BISULPHIDE. I.

Weight of substance used "

"

"

. . . . . . . . . . . . . . . . .

undissolved

~'36¢,4

. . . . . . . . . . . . .

o'oo5 o

. . . . . . dissolved . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e i n CSz ---~ 9 8 " 6 I .

~"355-1

1I.

W e i g h t of s u b s t a n c e u s e d . . . . . . . . . . . . . . . . . . . . . . .

undissolved

o'3,%8

. . . . . . . . . . . . .

o'~w 3

" " " dissolved . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e in CS:, = 99'92.

~'3S65

'fVRPENTINI,;. I.

W e i g h t of s u b s t a n c e u s e d . . . . . . . . . . . . . . . . . . . . . . . undissolved . . . . . . . . . . . . . . . . . . . dissoh'ed . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e i n t u r p e n t i n e = 96'55.

o'449S o'o155 ~v4343

II.

Weight of substance used . . . . . . . . . . . . . . . . . . . . . . .

undissolved

. . . . . . . . . . . . .

. . . . . . dissolved . . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e i n t u r p e n t i n e = 96"04.

o'421,~ o'o~67 v4o51

ETtlER. [.

W e i g h t of s u b s t a n c e u s e d . . . . . . . . . . . . . . . . . . . . . . . undissolved . . . . . . . . . . . . .

0"3589 o'or53

. . . . . . dissolved . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e i u e t h e r --~ 95"45.

(v3436

II.

W e i g h t of s u b s t a n c e u s e d . . . . . . . . . . . . . . . . . " . . . . undissolved . . . . . . . . . . . . .

0"4o84 o'oi3o

" " " dissolved . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e in e t h e r = 96"81.

("3954

(~ASOLINE. I.

W e i g h t of s u b s t a n c e used . . . . . . . . . . . . . . . . " " " undissolved . . . . . . . . . . . . . .

0"5342 o'o44t

" " " dissolved . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e in g a s o l i n e ~ 91 "74.

o'49ol

:

216

.Day ..

[J. F. L,

IL

W e i g h t of s u b s t a n c e u s e d . . . . . .

. . . . . . . . . . . . . . . . .

undissolved

0"3582

. . . . . . . . . . . . .

o"o412

. . . . . . dissolved . . . . . . . . . . . . . . P e r c e n t . s o l u b l e in g a s o l i n e = 88"49.

o317o

ALCOHOL.

Weight of substance used . . . . . . . . . . . . . . . . . . . . . . . undissolved . . . . . . . . . . . . .

0"5548 o'213o

" dissolved . . . . . . . . . . . . . . . P e r c e n t . s o l u b l e i n a l c o h o l ~ 6i"6o.

o'3418

Hi~'h solubility is c h a r a c t e r i s t i c of this m a t e r i a l in all cases.

A q u a n t i t y of the oil from wood alone was t r e a t e d with d i l u t e sulphuric acid for the purpose of t e s t i n g for basic oils. No trace of these oils could be precipitated, however, b y n e u t r a l i z i n g the acid with s o d i u m hydroxide. In connection with the p r e s e n t i n v e s t i g a t i o n a complete analysis of U t a h gilsonite has been m a d e w i t h results that are s o m e w h a t lower in carbon and in s u l p h u r t h a n those o b t a i n e d and p u b l i s h e d a few years since. ":'~ I n s t e a d of u s i n g finely-powdered lead c h r o m a t e t o g e t h e r w i t h copper oxide, as was the case in the first analysis, a large q u a n t i t y of coarse g r a n u l e s of lead c h r o m a t e were e m p l o y e d with results t h a t s h o w e d b e t t e r a g r e e m e n t . In this c o n n e c t i o n it s h o u l d be r e m a r k e d t h a t the use of copper oxide in h y d r o c a r b o n c o m b u s t i o n s has not infreq u e n t l y given trouble in the form of irregularities in the figures for carbon. Professor P e c k h a m , in a recent conversation, called m y a t t e n t i o n to a r e m a r k m a d e to h i m by \Varren to the effect t h a t copper forms c a r b i d e s which are oxidized with difficulty, and hence, according as these are formed or oxidized in s u c c e e d i n g combustions, the figures for c a r b ) n will vary. T h i s point is now b e i n g investigated. Certain it is, however, t h a t a s p h a l t s are t r o u b l e s o m e substances in e l e m e n t a r y analysis. T h i s s t a t e m e n t is thoro u g h l y borne out by a s t u d y of the l i t e r a t u r e of these bodies. ~ f f ~ m m ~ l Frank~in I1ls/ilu/e, 1 6 0 ,

22 r.

Laboratory Pro(&ction of Asphalts.

Sept., 1899.1

el7

T h e following are the results of analysis of U t a h gilsonite : I, o'2738 gram s u b s t a n c e gave 0"2603 gram HzO and o"863I gram CO.,. II. o'2oi 7 gram substance gave o'i93o gram HX) and 0"6336 gram C().,. III. 1"o347 grams s u b s t a n c e g a v e a m m o n i a by Kejhl. dahl's m e t h o d corresponding to 2"65 per cent. nitrogen. IV. o'9363 gram substance gave a m m o n i a corresponding to -"53 per cent. nitrogen. V. e'165I grams s u b s t a n c e g a v e 0"039° gram B a S O , VI. e'ool 7 grams substance gave o'o388 gram BaSO,. Carbon.

Itydr()gen.

Nitrogen.

"~5"98

[0'56

--

m'62

. . 2"65

I. . . . . . . . . . . II . . . . . . . . . . III . . . . . . . .

S5"67 . .

.

.

.

.

Sull)hur. .

.

.

IV . . . . . . . . . . .

--

--

2"53

--

V. . . . . . . . . . .

--

--

--

o,~'25

\'I . . . . . . . . . . .

-.

.

.

T a k i n g the averages of composition appears to be: Carbon

.

() "-'7

these results, the percentage

. . . . . . . . . . . . . . . . . . . . . . . . . . .

Hy.drogen

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

85'b3 1~,'59

Nitrogen

. . . . . . . . . . . . . . . . . . . . . . . . . .

Sulphur

. . . . . . . . . . . . . . . . . . . . . . . .

Oxygen Ash::

. . . . . . . . . . . . . . . . . . . . . .

"~'3

. . . . . . . . . . . . . . . . . . . . . . . . . . .

"~)

!by dif. I

2" 5'~ ~,'-'(,

[¢ K~'Cf)

* Quoted fronl p a p e r o,1 gilsonite,,/vurmll ].)',~nkUn lu.~/flu/e, 160,221.

TABL]:~ G I V I N G A N A L ~ ' T I C A L RI,~SUI,'I'S. N a m e of ,%tl)stance. Oil

from

wood

fish

Carbon, t l y d r o g e n . N i t r o g e n ,

. . . . .

54"25

i(~'c*i)

tion . . . . . . S7'57 Artiticial gilsonite

7"74

Artificial

Sulphur.

Oxygen.

AM1.

and undtnl,

uudtm,

nndtln,

none

gilsonite

from first prepara-

made Utah

finally

Asphalt alone Utah

.

from

alone

. S5"S 3

from

.

.

.

.

.

t'9I

o'ob

4"39

"

2"59

0'26

o'63

o Io

76'93

9"1()

4'iS

o'19

9'60

none

• 73"[I

9"45

t'9o

3"I7

12"37

trace none

wood

. . . .

nigrite

7'o6 io'59

.

fish

. . . . .

elaterite

Alphalt Utah

, • $6"56

gilsonite

.

.

.

>;6'2o

S'28

o'29

trace

5"23

. 33'5~

~'6()

undtm.

~,'42

undtm.

,,'J2

Day:

218 Utah nigrite . . . . . . . . . .

Fixed Carbon, 36.33

[J. F. Volatile ~Iatter. 63"55

Ash. o' I2

The specific gravities of various substances, determim in the course of the present investigation, are given in tl following table : SPECIFIC GRAVITIES. Oil o b t a i n e d f r o m p r i m a r y d i s t i l l a t i o n of fish a n d wood, t e m p e r a t u r e 26 ° C . . . . . . . . . . . . . . . . . . . . . . o'9837 F i r s t f r a c t i o n of a b o v e oil, 8o-145 ° C. w h e n d i s t i l l e d b y itself, t e m p e r a t u r e 25"8 ° C . . . . . . . . . . . . . . . . . . . . o'842 Last f r a c t i o n in s a l l l e d i s t i l l a t i o n , 34 °0 C., t e m p e r a t u r e 25"9 ° C., i ' o o 2 U t a h g i l s o u i t e , t e m p e r a t u r e 26 ° C . . . . . . . . . . . . . . I' o354 A r t i f i c i a l g i l s o n i t e , t e m p e r a t u r e 26 ° C . . . . . . . . . . . . 1"I713 A s p h a l t o b t a i n e d f r o m w o o d alone, t e m p e r a t u r e 26 ° C . . . . i'oS25 A l p h a l t o b t a i n e d f r o m fish alone, t e m p e r a t u r e 26 ° C . . . . . 1"o59o Oil f r o m wood a n d fish, vo utile w i t h s t e a m , t e m p e r a t u r e 26 ° C., 0'8940 Oil o b t a i n e d in p r i m a r y d i s t i l l a t i o n of wood, t e m p e r a t u r e 26"4' (2. . . . . . . . . . . . . . . . . . . . . . . . . . O'992o TABLE OF SOLUBILITIES IN VARIOUS SOLVENTS, Carbon Bisulphide, Absolute Name of substalme, all.* Turpentine. Ether, Gasoline. Alcohol, Artificial gilsonite .... 81"o 9 49"47 67'o3 46"7I 4S'4o Utah gilsonite . . . . 99"5 o 97"34 73"o8 63"o8 34"81 A s p h a l t f r o m fish a l o n e : . 68. I 9 47"36 59'~7 35"19 51"o7 A s p h a l t f r o m w o o d a l o n e 99"26 96"29 96"13 9o'12 6.1"6o

*This determination involved no weighings, as when the solution was filtered nothing insoluble remaint,d behind on the filter.

The foregoing experiments s u g g e s t e d themselves as the result of a number of years of experimental work upon asphalts from a number of natural sources in the W'estern part of the United States and a study of the literature of natural hydrocarbons, solid, liquid and gaseous, and the synthetical experiments which have been carried out by Warren, Engler and Sadtler. From the chemical.geological standpoint the writings of Peckham have been very suggestive, advocating, as they have done, the idea that bitumens are distillates together with water of organic matter, which has accumulated in strata of all ages in the earth. Utah gilsonite is the natural material to which the writer has given most experimental study. This mineral contains very little oxygen and sulphur, almost no ash, but a notable quantity of nitrogen, which shows itself in distillation pro-

Sept., 1899.]

Laboratory ProductioJt of Asphalts.

,_I9

ducts in the form of basic s u b s t a n c e s similar in a general w a y to the p y r i d i n e and quinoline series, and of the s a m e character as the basic s u b s t a n c e s o b t a i n e d b y P e e k h a m and Salath~ from California petroleum, and freely c o m m e n t e d upon b y P e e k h a m in a n u m b e r of papers b y him. T h e s e n i t r o g e n c o m p o u n d s s u g g e s t animal origin of the bodies c o n t a i n i n g them. It seemed, however, to the writer that a material h a v i n g exclusively animal origin w o u l d be likely to contain a larger proportion of o x y g e n than is contained in such m a t e r i a l as n a t u r a l gilsonite, and that in l a b o r a t o r y e x p e r i m e n t s to r e p r o d u c e a s p h a l t s low in oxygen, v e g e t a b l e m a t e r i a l should be p r e s e n t at the s a m e time, and that o p p o r t u n i t y should be afforded for the o x y g e n containing distillates from oils and animal s u b s t a n c e s to react at a fairly high t e m p e r a t u r e w i t h the a b u n d a n t g a s e o u s hydrocarbons p r o d u c e d b y distilling wood or in general v e g e t a b l e material. T h e result of such reaction b e t w e e n bodies of the n a t u r e j u s t described w o u l d be to eliminate o x y g e n from the oily distillate b y c a u s i n g it to form w a t e r and carbon dioxide w i t h the h y d r o g e n and carbon of g a s e o u s hydrocarbons. T h i s idea was s t r e n g t h e n e d b y the fact that in h i s e x p e r i m e n t s to p r o d u c e petroleum-like s u b s t a n c e s and paraffine from linseed oil S a d t l e r * noticed the odor of acrolein and referred to it as follows: " A t first the odor of acrolein was v e r y p r o n o u n c e d and powerful, showing t h a t the glycerine of the glycerides c o m p o s i n g the oil was b e i n g d e c o m p o s e d ; later the odor was more that of a cracked p e t r o l e u m oil, s h o w i n g that the linoleic and o t h e r aids of the oil were u n d e r g o i n g decomposition." On another page the s a m e w r i t e r says: " O f course the fractions m u s t be o b t a i n e d on a sufficiently large scale to a d m i t of t h o r o u g h p u r i f y i n g before the c h a r a c t e r of the hydrocarbons can be studied. A t p r e s e n t t h e y contain impurities, such as aldehyde-like and p o s s i b l y k e t o n e products. T h e y reduce a m m o n i a c a l silver solutions and indicate t h u s the presence of these impurities." T h e following facts, b a s e d upon a consideration of the " Proc. A m e r . Philos. S o t . , " 3 6 , 93.

220

Day :

[J. F. I.,

c h a r a c t e r of the distillates o b t a i n e d from the mixed animal and v e g e t a b l e m a t t e r , the fish alone and the w o o d alone, tend to s h o w the correctness of the writer's position in an attempt to p r o d u c e an a s p h a l t low in oxygen. T h e table of ultimate analyses given b e l o w s h o w s that there is less than half as much o x y g e n in the a s p h a l t from wood and fish mixed as in that from fish alone. U L T f ~ I A T ~ ANAI, YSES. Ash. Utah gilsonite

. . . o'ro

Utah elaterite • • • -Artificial gilsonite from w o o d a n d fish

. . --

Asphalt from wood Asphalt

f r o m fish

.

Carbon.

H y d r o g e n . ,Sulphur. N i t r o g e n . Oxygen,

85'83

m'59

o'26

73"49

9"46

undtm,

2"59

o'63

undtm.

~7'o 5 4'39

86"56

7"06

0'08

I"9t

. --

86'20

8"28

trace

0"29

5"23

. --

76"93

9 'Io

o'I9

4"23

9"55

T h e following table, g i v i n g the yields of w a t e r and oil in the various distillations, is also of interest, as showing the effect of w a t e r f o r m i n g reactions b e t w e e n hydrocarbons and o x y g e n c o m p o u n d s , which, doubtless, took place in the hot t u b e t h r o u g h w h i c h the vapors were p a s s e d before condensation. Material Used, G t ares. Fish. 8, t 70

Wood. 9,882 -

-

4,588

1,585 -

-

Oil Produced, Cubic Centimeters.

VCater Produced, Cubic Centirlleters.

3,oio

8, 240

700

2,830

:,:5o

89o

If the wood and fish, w h e n distilled together, had yielded oil and w a t e r in the same proportion as w h e n each was dis: tilled by itself, then there should have been a yield of 3,724 cubic c e n t i m e t e r s of oil from the mixture, i n s t e a d of the 3,o¢o cubic c e n t i m e t e r s a c t u a l l y produced, and, instead of 8,24o cubic c e n t i m e t e r s of water, t h e r e should h a v e b e e n only 7,3~ cul)ic centimeters. T h e q u e s t i o n of the origin of asphalts is one that cannot be intelligently d i s c u s s e d apart from that of the origin of petroleum, or, more b r o a d l y still, a p a r t from the origin of the b i t u m e n s in general, w h i c h include n a t u r a l hydrocarbons in all states of matter, solid, liquid and gaseous. Of these three states, liquid p e t r o l e u m has, for a v a r i e t y of

S e p t , i899. ]

Laboratory Production of Aspha/ts.

22~

obvious reasons, received the m o s t a t t e n t i o n scientifically and technologically. T h e connection quite g e n e r a l l y believed at p r e s e n t to exist b e t w e e n p e t r o l e u m and the a s p h a l t s is expressed in Dana's " M i n e r a l o g y , " p. 75~, as follows: " T h e more solid kinds g r a d u a t e into the pit asphalts, or mineral tar, and t h r o u g h these there is a g r a d a t i o n to petroleum. T h e fluid kinds c h a n g e into the solid by the loss of a vaporizable portion on exposure, and also by a process of oxidation, which consists, first, in a loss of h y d r o g e n , and finally in the oxvgenation of a portion of the mass." If it be accepted as true t h a t p e t r o l e u m and the asphalts are related, as the q u o t a t i o n j u s t m a d e would indicate, then it follows, of course, t h a t a n y view as to the origin of petroleum also applies to the asphalts. A s t u d y of the literature concerning theories as to the origin of p e t r o l e u m reveals a n u m b e r w h i c h differ f u n d a m e n t a l l y from each other, and which are based l a r g e l y upon geological evidence. It does not seem necessary here to give detailed consideration to .these h y p o t h e s e s in view of the t h o r o u g h m a n n e r in which they have been r e c e n t l y s u m m e d up and reviewed by Messrs Sadtler, P e c k h a m , M a b e r y Phillips and D. T. Day in a series of papers ~ read before the A m e r i c a n Philosophical Society, F e b r u a r y 5, I897. T h e c o m p r e h e n s i v e r,:su~m"given by Boverton R e d w o o d in his work on petroleum also c o n t r i b u t e s to m a k e f u r t h e r detailed review superfluous at t h i s tim~. It seems, however, t h a t the p r o p r i e t y of a t t e m p t i n g to make any one of these theories cover the entire q u e s t i o n of the origin of p e t r o l e u m is very questionable in view of the fund a m e n t a l differences in c h a r a c t e r and properties b e t w e e n petroleums of different sources, which, bv the work of Schorlemmer, W a r r e n , Mabery, Beilstein and 1,2urbatow, Markownikoff, S c h u t z e n b e r g e r and Jonine, Zaloziecky and others, have been shown to exist. T h e following q u o t a t i o n from Boverton R e d w o o d ' s work is of i n t e r e s t in this connection. R e f e r r i n g to his r/sumc'of theories, he says : " From the " Proc. Amer. Philos. S o t . , " l~ll, 93-

222

Day :

EJ. F. I.,

a c c o u n t g i v e n in this section, it will b e seen t h a t t h e r e has been an a b u n d a n c e of s p e c u l a t i o n as to the origin of bitumen, and that, in r e g a r d to s o m e of t h e theories, a c o n s i d e r able a m o u n t of e x p e r i m e n t a l proof has been forthcoming. P r o b a b l y , on the whole, the H 6 f e r - E n g l e r v i e w s at present h a v e t h e l a r g e s t n u m b e r of adherents, and in respect, at any rate, to certain d e s c r i p t i o n s of p e t r o l e u m , are t h e most w o r t h y of acceptance. _At the s a m e time, a careful s t u d y of the s u b j e c t leads to the conelusion t h a t s o m e p e t r o l e u m is of v e g e t a b l e origin, and it therefore follows t h a t no theory is applicable in all cases." W h e n we consider, for example, the s t r i k i n g differences in c h a r a c t e r b e t w e e n California p e t r o l e u m and Pennsylvania petroleum, to w h i c h P e c k h a m , in a n u m b e r of different papers, has e a r n e s t l y called attention, the force of the last s e n t e n c e q u o t e d from R e d w o o d will u n d o u b t e d l y be keenly appreciated. C o m m e n t i n g u p o n t h e H 6 f e r - E n g l e r theory, Professor P e c k h a m ~ says : " D r . Engler, therefore, considers t h a t s o m e c h a n g e in t h e animal r e m a i n s m u s t h a v e taken place in the earth, w h e r e b y all n i t r o g e n o u s and o t h e r matters, save fats, were removed, the p e t r o l e u m b e i n g formed from this fat alone b y the c o m b i n e d action of pressure and heat, or b y p r e s s u r e only. " I n s u m m i n g up the e v i d e n c e as to origin, H 6 f e r expresses the belief that p e t r o l e u m is of animal origin, and has been f o r m e d w i t h o u t the action of excessive heat, and observes t h a t it is found in all s t r a t a in w h i c h animal r e m a i n s h a v e been discovered. " C o m b i n i n g these t w o s t a t e m e n t s , we arrive at this con. clusion as the H g f e r - E n g l e r theory, t h a t b i t u m e n s are of animal origin, f o r m e d at low t e m p e r a t u r e s from fats alone b y the c o m b i n e d action of p r e s s u r e and heat. " S t e a m is left o u t of this formula, and it is, therefore, i n a d e q u a t e . T h e r e is no evidence w h a t e v e r that a n y portion of the crust of the e a r t h has ever been s u b j e c t e d to the c o m b i n e d action of heat and pressure w i t h o u t the presence of s t e a m or hot water, and in m y j u d g m e n t the s t e a m has * " Proe. Amer. Philos. S o c . , " 3 1 I , lO6.

Sept., 1899.]

LaSoratorr Production off A'sp/lalts.

223

been a v e r y p o t e n t factor in d e t e r m i n i n g not only the formation, b u t the t r a n s f e r e n c e of b i t u m e n s . " T h e writer, from his experience in the p r o d u c t i o n o f asphalts, as a l r e a d y d e s c r i b e d in this paper, feels like endorsing m o s t heartily the views of P e c k h a m in regard to the necessity of s t e a m as a factor in the production of such asphalts, at least, as have been m a d e the s u b j e c t of experimental study. T h e following is a q u o t a t i o n from Professor P e c k h a m ' s paper on " T h e Genesis of B i t u m e n s as R e l a t e d to Chemical Geology, ''~ which s u m s up the m o s t i m p o r t a n t features of his v i e w s as to the genesis of b i t u m e n s . T h e l a b o r a t o r y results w h i c h I h a v e so far o b t a i n e d seem to be quite fully in accordance with the conclusions which P r o f e s s o r Peckham has reached. " U p o n this h y p o t h e s i s , that b i t u m e n s are distillates, all of the v a r i a t i o n s o b s e r v e d in b i t u m e n s of different geological ages are easily explained. T h e earliest forms of animal and v e g e t a b l e life are a d m i t t e d to have been nearly d e s t i t u t e of pitrogen; hence, w h e n these forms a c c u m u l a t e d in s e d i m e n t s which, borne d o w n b y deposits a b o v e them, i n v a d e d an isothermal t h a t a d m i t t e d of their distillation, t h e y m u s t have b e e n disti!led, in the presence of steam, at the lowest possible t e m p e r a t u r e ; t h e y m u s t have been distilled u n d e r a g r a d u a l l y increasing pressure, the e x t e n t of which de'pended u p o n the p o r o s i t y of s e d i m e n t s a b o v e t h e m up to the surface. T h e y m u s t also h a v e been distilled u n d e r a gradually increasing t e m p e r a t u r e , which w o u l d h a v e been largely controlled b y the pressure. W h i l e the t e m p e r a t u r e and p r e s s u r e w o u l d have, in e v e r y instance, been the least possible, with s t e a m always present, these physical conditions would, on a c c o u n t of the v a r y i n g p o r o s i t y and consequent v a r y i n g resistance of the o v e r l y i n g mass, have produced v e r y g r e a t effects in some instances, and v e r y slight effects in others. .As a consequence, we have in natural bitumens, as in artificial distillates, materials v a r y i n g in density from n a t u r a l gas to solid a s p h a l t u m . ~Loc oil.

224

f)~J'"

I.I.F. 1.,

" I f these d i s t i l l a t e s p r o c e e d e d from m a t e r i a l s t h a t would yield paraffine, these p e r m a n e n t and stable c o m p o u n d s from marsh gas to solid paraffine r e m a i n e d in the receptacles that n a t u r e had p r o v i d e d for t h e m until t h e y were released by t h e drill. If, however, the distillates p r o c e e d e d from s e d i m e n t s of a different geological age, c o n t a i n i n g animal and v e g e t a b l e r e m a i n s more h i g h l y organized, t h a t would yield different series of h y d r o c a r b o n s , w i t h c o m p o u n d s of nitrogen, then a v e r y different b i t u m e n w o u l d be stored in these receptacles. S e c o n d a r y reactions would convert these p r i m a r y distillates into a g r e a t v a r i e t y of substances. " T h e c o n t e n t s of the original reservoirs, borne d o w n and invaded b y heat, m i g h t b e c o m e involved in a second distillation at an increased pressure and t e m p e r a t u r e . F r a c t u r e s of these reservoirs from excessive pressure m i g h t lead their c o n t e n t s to the surface along lines of c o n t a c t of strata or with w a t e r c o n t a i n i n g sulphates, b y w h i c h an originally pure h y d r o c a r b o n would be c o n v e r t e d into a s u l p h u r bitumen. A nitro-hydrocarbon, r e a c h i n g the surface under these conditions, might, b y the c o m b i n e d action of evaporation and reaction with sulphates, pass t h r o u g h all the varying d e g r e e s of d e n s i t y from p e t r o l e u m to maltha, and be. come finally solid a s p h a l t u m , and this, t h r o u g h the lapse of time and a b u n d a n c e of material, on a scale of v a s t magnitude." W h i l e it is true that most of the theories that h a v e been a d v a n c e d to explain the origin of b i t u m e n s h a v e been directly concerned with the liquid v a r i e t y ordinarily known as petroleum, and s e e m at least to have been b a s e d upon study, w h e t h e r geological or chemical, of this v a r i e t y to the exclusion of the solid form g e n e r a l l y k n o w n as asphalt, still it is true that s o m e theories have been a d v a n c e d to explain directly the formation of asphalts, aside from and independently of their possible relation to liquid p e t r o l e u m s . T h u s the T r i n i d a d a s p h a l t was looked u p o n b y Wall ~ as h a v i n g r e s u l t e d from the g r a d u a l d e c o m p o s i t i o n of vegetable m a t t e r found i m b e d d e d in it. T h i s view is, however, "Q. J. G. Sot.," l ~ , 46o.

Sep-..,1899.l

l.ahora/,~rl' l~ro,Zzlc[1oll ,li .-l.~/~ho'./A~.

225

no m o r e tenable than the idea that the material originated from a n i m a l r e m a i n s w h i c h h a v e been found clearly indicated f r o m a s t u d y of the c o m p o s i t i o n of the asphalt. W h e n we c o n s i d e r t he a m o u n t and t he c h a r a c t e r of the s t r ictly c h e m i c a l work t h a t has be e n done upon the a s p h a l t s or solid b i t u m e n s , it m u s t be a d m i t t e d t h a t t h e y h a v e been d e c i d e d l y n e g l e c t e d as c o m p a r e d with t he liquid formE v e n e l e m e n t a r y anal ys e s arc, in m a n y cases, unreliable, and t h e r e is muc h need of p a i n s t a k i n g and p e r s i s t e n t s t u d y in this field. W h e n we c o n t e m p l a t e the m a r k e d differences b e t w e e n b i t u m e n s f r o m d i f f e r ent sources, it h a r d l y seems r e a s o n a b l e to b eliev e t h a t a n y otle t h e o r y as to t he origin of t hese bodies can co v er all t he act ual occurrences. It wouht seem t h at h e a t and pressure, s i ngl y and c o m b i n e d , and of v a r i o u s intensities, a c t i n g with water, b o t h as liquid and a s steam, upon th e s ame f u n d a m e n t a l m a t e r i a l , w h e t h e r animal or v e g e t a b l e , s h o n h t p r o d u c e a v a r i e t y of c a r b o n a c e o u s substances d if f er in g from each o t h e r q u i t e p r o f o u n d l y in physical and c h e m i c a l p r o p e r t i e s . A g a i n , s i m i l ar or identical conditions p r e v a i l i n g with d i f f e r e n t kinds of m at eri al , w h e t h e r animal or v e g e t a b l e , or m i x t u r e s ,~f the t w o , shouhl also yield p r o d u c t s of v a r i o u s kinds. W h e n , therefore, we consider th e g r e a t possibilities of v a r i a t i o n in c o m b i n a t i o n s of n a t u r a l forces, and also e q u a l l y g r e a t possibilities of varialcion in th e n a t n r c ~f the o r g a n i c m a t e r i a l upon w hi ch t hese forces m a y act, it is not s u r p r i s i n g t h a t we find,.as we d,,, in v a r i o u s p ar ts of t he ear t h, c o m p l i c a t e d and i n t i m a t e carb o n a e e o u s m i x t u r e s , gaseous, liquid and solid, which are usually s u m m e d up u n d e r t he g e n e r a l he a di ng, b i t u m e n s . T h e facts and figures g i v e n in this c o m m u n i c a t i o n speak for the, nselves. S u m m e d up, t h e y show t h a t t h r e e asphal t i c s u b s t a n c e s h a v e been o b t a i n e d by o p e r a t i o n s of distillation, p r i m a r i l y in p r e s e n c e ~,f s t e a m f r om n a t u r a l animal and v e g e t a b l e mater i al , b o t h s e p a r a t e l y and com bi ned. T h e m a ter ial o b t a i n e d from the m i x t u r e of fish and wood, and called artificial gilsonite, so closely r e s e m b l e s t he g i l s o n i t e from U t a h t h a t it is i m p o s s i b l e b y i n s p e c t i o n to tell the two m a t e r i a l s apart. T h e m a t e r i a l o b t a i n e d from fish alone also VOL. CXLVIII. No. 885. ~

226

.D~y.

[J. F. I

r e s e m b l e s w h a t has b e e n called ( w i t h q u e s t i o n a b l e p r o p r i e t y e l a t e r i t e f r o m U t a h . W h i l e t h e s e t w o pairs of substance: differ f r o m each o t h e r to a g r e a t e r or less e x t e n t in r e s p e c to th e v ar io u s parallel t r e a t m e n t s to w h i c h t h e y h a v e beer s u b j e c t e d , an d while t h e y also differ s o m e w h a t in chemical c o m p o s i t i o n , as well as in p h y s i c a l s ol ubil i t y, specific gray. ity, streak, etc., t h e s e di f f e r ences are all 9z degree and not in a n y single case bz ~,htd. I am now e n g a g e d in t h e s t u d y of an a s p h a l t k n o w n as nigrite, w h i c h occurs n e a r the g i l s o n i t e of U t a h . T h e diff e r e n c e s b e t w e e n t h e s e two b i t u m e n s are t h r o u g h o u t more striking than any that I have observed between the natural a n d th e artificial s u b s t a n c e s c o n s i d e r e d in this paper. In conclusion, I take p l e a s u r e in a c k n o w l e d g i n g t he benefit a n d th e s a t i s f a c t i o n I h a v e d e r i v e d f r o m a s t u d y of t h e papers p u b l i s h e d by P r o f e s s o r P e c k h a m , p a r t i c u l a r l y t h e two e n t i t l e d " T h e G e ne s i s of B i t u m e n s as R e l a t e d to Chemical t ; e o l o g y "* an d " On t he N a t u r e and O r i g i n of P e t r o l e u m . " t i am i n d e b t e d to m y assistant, Mr. E u g e n e L e a m y , for able a s s i s t a n c e t h r o u g h o u t t h e e n t i r e work, and to one of m y f o r m e r pupils, Miss G e o r g i a P o r t e r , for t he n i t r o g e n determinations. SVCARTI[MORE COLLE('E,

PA.. February I8, 1899.

+ "Proe. Amer. Philos. Sot.," ~7, ioS. f Ibid, 36, lO3.