322
T H E J O U R N A L O F I N D U S T R I A L A N D ENGIiVEERING C H E M I S T R Y
V d . 7, No.
4
column, 60 per cent of t h e oil distilled between 161" t h e crystals obtained began t o soften a t 147', melted a n d 16;", and 35 per cent between 1 6 j " and 167'. a t 150-151', a n d were completely liquid a t 157'. T h e above data show t h a t t h e volatile oil is entirely Another portion of the rosin was first Crystallized twice different from ordinary gum turpentine. from alcohol. containing I O per cent concentrated hydrochloric acid a n d then recrystallized repeatedly IDEiiTIPICATION O F CONSTITUENTS a-PIxEm-Repeated fractionation yielded 48 g. from 95 per cent alcohol. When allowed t o crystallize (9.6 per cent) boiling between I 57' a n d 160' a n d having slowly the abietic acid was obtained as large triangular 0 0 The oil gave crystals. The crystals finally obtained began t o melt t h e constants d150 0.86 j 6 , ~ ~ 2 -30.17'. and were completely liquid a t 167'. a low yield of pinene nitrosochloride, which was trans- a t 157-158' formed t o the nitrolpiperidine compound melting at Using a n alcoholic solution t h e abietic acid had t h e specific rotation [a], -85.46" calculated from the 119". following values : CAMPHENE-Between 160' and 1 6 2 ' ' 50.5 g. (10.1 a ..,.. . . . . . . . 6.74' $9.433 per cent) of oil were obtained having t h e following L.... . . . . . . . . 1 d 0.8357 properties: d l 5 0 0.8671, ~ ~ 2 -29.31~. 9 0 The oil was The silver salt was obtained by neutralizing a n treated with a mixture of glacial acetic acid and sulfuric acid in t h e usual way. The oil recovered by alcoholic solution of t h e acid with sodium hydroxide steam distillation after saponification would not crystal- and adding t h e calculated quantity of &NO, in a large lize on cooling in a freezing mixture. On distilling volume of alcohol. The silver salt vas filtered off, t h e oil and rejecting t h e portions boiling below 190'~ washed repeatedly with alcohol, then with ether and Analysis of the silver salt follows: t h e residue readily crystallized on cooling. After dried a t 70'. removing t h e crystals with t h e aid of a force filter and 0.4685 g. silver salt gave 0,1234 g. A g 26.34 per cent Ag Calculated for silver abietate, Ag(CzoHzaOz), 26.37 per cent Ag recrystallizing four times from petroleum ether t h e isoborneol melted a t 207-zo9 ', resolidifying on slow c ONC L US1 0 N 8 cooling a t 208". A fifth crystallization did not raise The volatile oil of the sand pine (Pilzus clausa, t h e melting point. Sarg.) has approximately the following composition : fl-PINENE-The fl-pinene fractions constituted about I-a-pinene, I O per cent; k-camphene I O per cent; I-@7 j per cent of t h e oil, so t h a t this terpene is t h e major pinene 75 per cent; losses by polymerization, etc., j constituent. A portion of t h e P-pinene was oxidized per cent. with alkaline potassium permanganate. Ten grams of The "rosin" contains 4.0 per cent resene while the the sodium nopinate obtained yielded on further oxi- remainder consists mainly of abietic acid. dation 2 grams of nopinone whose semicarbazone FOREST P R O D U C T 5 LABOBATORY melted a t 189". MADISON, WISCONSIN Since t h e oil consisted so largely of &pinene i t was thought possible t o isolate this terpene in a fairly pure state. After I O fractionations over metallic sodium, THE CONDITIONS OF NATURAL GAS IN THE EARTH'S STRATA' two fractions were obtained t h a t showed fairly constant BY G E O R G E A. BUEEELb boiling points. Below will be found t h e properties Received November 28, 1914 of the two fractions and of one of t h e synthetic ppinenes prepared by Wallach: I n this paper are recorded some observations a n d 200 Calculated experiments regarding t h e liquid or gaseous occurB. p. nD200 d25jE [a]D M found for CioHic I= rence of natural gas in t h e earth's strata. This ques43.54 44.19 1.4772 0.8700 -26.00° ( l ) . , . , .. 164-165O 43.54 44.23 tion has been a subject for conjecture in t h e past, 1.4984 0.8709 -23.73' ( 2 ) ....._ 16.5-166' but t o date, in t h e case of most natural gases, no exact Wallach'sl synthetic P-pinene : Calculated d a t a have been available from which t o draw definite d22° aD M found for CioHii B. p. *D22' conclusions, because t h e exact composition of natural 0.8660 -22O20' 44.13 43.54 163-164O 1.4724 gases has not been known, Knowing (I) t h e composiFraction 2 was about four times as large in quantity tion of a natural gas, ( 2 ) rock pressures t h a t prevail as Fraction I . The values obtained for all t h e con- in natural-gas strata, (3) temperatures t h a t prevail stants are higher t h a n those recorded by Wallach, a n d in natural-gas strata, and (4) t h e temperature and this had been t h e author's general experience in t h e pressures t h a t are necessary for t h e liquefaction of t h e examination of various essential oils in which /?-pinene gaseous paraffin hydrocarbons, one can obtain evidence was t h e chief constituent. T o determine whether this regarding t h e liquid or gaseous occurrence of natural condition was due t o t h e presence of camphene, j o gas in t h e earth. The vapor pressures of some of t h e g. of Fraction 2 were treated with t h e mixture of paraffin hydrocarbons are shown in t h e following glacial acetic acid and sulfuric acid. No isoborneol, tables. The d a t a were taken from Landolt a n d Bijrnhowever, could be detected. stein's "Physilialische Chemische Tabellen*'' Rosm-The rosin, grade G, h a d a n acid No. of 1 7 2 . 5 The results of a complete analysis including the a n d a saponification number of 178.7. It yielded 4.01 quantity of each paraffin hydrocarbon as found by per cent of resene soluble in petroleum ether. liquefaction and fractionation follows. For compariThe rosin crystallized very readily from acetone 1 Paper presented a t the Spring Meeting of the American Chemical or alcohol. After t e n crystallizations from acetone, Society, Cincinnati, Ohio, April 6-10, 1914, by permission of the Director E
1 Ann.,
363 (19081,1.
of the Bureau of Mines.
+
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
Apr., 1915
-
TABLEI-VAPOR
PRESSURES OF SEVEN PARAFRIN HYDROCARBONS Critical Critical Boiling temperapressure pointture NAME Formula O C. ' C. Lbs. Atmos. Methane CH4 -160 -99.5 735 50 Ethane CZHD 93 35 662 45 CsHs 45 97 647 44 Propane N-Butane C4HIO 1 N-Pentane CsHu 36.4 N-Hexane CBH14 68.4 .. N-Heptane . . . . . . . ClHl0 98.4 ... ..
.........
........... .......... ........ ....... ........
-
...
... ... ...
... ... .
I
.. ..
.
TABLE11-VAPOR PRESS ~ U R E SOF METHANE,ETHANE A N D PROPANE ETHANE(U) PROPANE($ METHANE(U) Atm. PI. at C. Atm. Pr. a t C. Atm. PI. at C. 50 - 95.5(u) 44 ;;(a) 26.3 -105.8 4 52 . 3 3 9 21.4 -110.6 23.3 0 7.1 12.5 4.8 11 -126.8 18.3 -11 -2 14.5 -21 6.2 -138.5 2.7 -19 2 . 2 4 -153.8 1.8 -33 11 -31 1 -165(b) 1 -93(b) 1 -45(b) t u ) Critical constants. ( b ) Boiling point.
E'"'
son, the results of a eudiometric analysis of the natural gas are also included: TABLE111-ANALYTICALRESULTSOBTAINED BY T w o METHODS Liquefaction Eudiometric PERCENTAGES and fractionation analysis Methane ........................... 84.7 79.2 Ethane.. 9.4 19.6 Propane.. 3.0 Butane (chiefly). 1.3 Nitrogen ........................... 1.6 i:2
........................... ..........................
....................
Totals
...........................
-
.. -
100.00
100.00
Included in the above analysis is 0.03 per cent carbon dioxide. It is scarcely necessary to state t h a t the eudiometric determination shows only approximately t h e quantity of hydrocarbons in a natural-gas mixture. From the fractionation analysis a n d other d a t a one can calculate t h e pressures t h a t would be required t o liquefy t h e different constituents a t particular temperatures. T o s t a r t t h e liauefaction of t h e methane there would be required a pressure of a t least
(z)
735 =
868 lbs. per sq. in. a t -95. 5' C. T h a t is, in order t o p u t 735 lbs. pressure on t h e methane there would be required a pressure of 868 lbs. on t h e mixture; as liquefaction proceeded a n d t h e partial pressure of t h e methane decreased proportionally greater pressure would be required t o continue the liquefaction. T o liquefy the ethane there would be required a . .
pressure of a t least
(2)
662 = 7064 lbs., a t 35 O C.
T o liquefy t h e propane a t 97' C., there would be required a pressure of
- 647 (jooo)
= 21,567 lbs.
These
'
calculations were made a t t h e critical temperatures a n d pressures of t h e paraffin hydrocarbons. The critical constants for butane have not been determined. E a r t h temperatures increase about I O C. for each 60 or 7 0 f t . of depth. This is a thermal gradient t h a t has been determined b y measuring temperatures in many bore holes, although increases in temperatures different from the foregoing have been determined b y some investigators. If the initial temperature is 20' C., a n d an increase of I ' C. for each 7 0 ft. takes place, strata dt a depth of 2000 f t . (not an uncommon depth for a gas well) should have a temperature of 48' C. Methane may be dismissed as ever occurring in t h e liquid condition because even a t -95.5' C. there is required a pressure of a t least 735 lbs. per sq. in. t o liquefy i t when it occurs in t h e pure state. Mixed
3 23
with other gases, so t h a t its partial pressure is less t h a n one atmosphere, there are required proportionally greater pressures a t a n y particular temperature. The critical temperature of ethane is 3 5 ' C., which is not far from gas-strata temperatures. However, t h e pressures required t o liquefy the ethane in Pittsburgh natural gas a t the critical temperature is 7064 lbs. a n d is far above gas-strata pressures. It is questionable whether pressures as high as 1500 lbs. have ever been measured in a gas well. 1000 lbs. per sq. in. is high. The vapor pressure of liquid propane a t z z o C. is 132 lbs. (9 atmospheres). Vapor pressures a t temperatures closer t o gas-strata temperatures t h a n this have not been determined. T o liquefy t h e propane in Pittsburgh natural gas a t 2 2 ' C. there would b e required a pressure of
(5)
IOO =
44001bS.
This is
also a pressure much greater t h a n is found in naturalgas strata. Vapor pressures of butane a t different temperatures other t h a n the boiling point have not been determined. At I O C. (boiling point) there would be required a pressure of about 1153 lbs. t o liquefy t h e butane in Pittsburgh natural gas. At higher temperatures there would be required greater pressures. Hence, t h e butane in Pittsburgh natural gas can also be dismissed as occurring in the liquid condition in the earth. I n view of t h e above considerations, it can be stated t h a t the essential constituents of Pittsburgh natural gas never occur in t h e strata in the liquid form, because rock pressures are not high enough, rock t e m peratures are not low enough, a n d the quantities of the more easily condensable constituents in the gas mixture are not great enough for this condition. T h e natural gas used in Pittsburgh is typical in composition of gas t h a t is supplied t o many cities t o the extent of billions of cubic feet per year. The condition of natural gas in t h e earth is of importance, for, if present therein as a liquid, i t would be possible for a single subterranean reservoir t o furnish a much larger supply of gas t h a n if present in the gaseous condition. The foregoing vapor pressures a n d percentage composition of the gas are also instructive as showing t h e pressure t h a t would have t o be applied t o liquefy t h e various constituents in a compressor plant. As somewhat different from the natural gas mentioned above, which is contained in rock s t r a t a under heavy pressure, there may be mentioned those natural gases t h a t issue from t h e casing heads of oil wells under slight pressure, or are withdrawn from t h e casing heads a t pressures less t h a n atmospheric. These gases frequently contain, besides some of t h e gases already mentioned, enough of the vapors of t h e liquid paraffin hydrocarbons t o warrant t h e installation of a plant for the condensation of gasoline. The question arises as t o t h e liquid or gaseous condition of these casing-head gases in the earth. T h e quantities of t h e more easily liquefied gases are much higher t h a n in t h e so-called d r y gases, but, on t h e other hand, t h e pressures in the rock strata from which t h e y issue or are drawn are almost invariably much lower,
.
3 24
T H E J O L T R N A L O F I N D r S T R I A L A N D E N G I X E E R I N G CHEillIS2‘RY
t h a t t h e chances of them occurring in the liquid condition are small. No account is taken herein of gases t h a t are closely associated under heavy pressure with oil in t h e sands. Under such condition there is a solution of gases in the oil t o a great extent. T h e natural gas used in Pittsburgh is not associated with oil in t h e earth’s strata. SO
J*ol. 7r No, 4
THE UTILITY OF SULFUROUS ACID AND PURE YEAST IN CIDER VINEGAR MANUFACTURE By W. V. CRUESS,J. R. ZION A N D A. V. SII~REDI
Received January 4, 1915
A study of methods of alcoholic fermentation of
apple juice destined t o be made into vinegar in various California factories showed t h a t in almost every case no a t t e m p t was made t o control the microorganisms CHEMICAL LABORATORY BURBAU OF MIKES. PITTSBURGH of fermentation. A brief description of the various ways of handling the cider stock will no doubt be of interest. THE ANALYSIS OF CHROME YELLOWS AND GREENS I n one of the largest factories t h e cull apples and By A. CI~vdlu peels and cores f r o m apple driers are ground or “ g r a t e d ” Received January 22, 1915 ‘Froin inquiries received a t this laboratory, it ap- in a n Ohio apple grater as soon as received. The juice pears t h a t the determination of the composition of is pressed out with heavy screw presses driven by a chrome yellows and chrome greens is not well under- motor and cog gearing with a capacity of 60 tons per stood in m a n y color and paint works; and the excellent day. The juice goes t o 20,000 gallon tanks. The publications of t h e Bureau of Standards on the analysis first t a n k of t h e season is started with a large starter of inks help only in a degree. The method here given of compressed yeast. When this t a n k is in fermentais the result of a great deal of work and experience tion, about one-third of its contents is used t o s t a r t with these colors, and has given excellent >atisfaction. t h e next t a n k . T h e third t a n k is started from t h e second, and so on through t h e whole series of tanks. Sl E T 1%0 D Over joo,ooo gallons are made in this way during a X O I S T U R E 4 N D L E A D CARBOXATE-lljeigh Out acseason. Examination of the fermented juice showed .zurately about I gram of the yellow or green into a i t t o be ( ( d r y ; ” t h a t is, practically free from unfersmall beaker, a n d d r y for 4 hours a t r o j - - ~ ~ o O C . mented sugar, b u t i t was shown b y microscopical Calculate t h e loss in weight as water. Add 5 0 cc. of examination t o contain large numbers of lactic acid j o per cent acetic acid t o t h e d r y substance in t h e bacteria and the large t a n k s soon developed a heavy beaker, mix thoroughly, and let stand over night. growth of mycadernta (wine flowers) after alcoholic Filter through a tared Gooch, wash with hot water, fermentation. The lactic bacteria develop a ((mousey” dry, cool and weigh. Calculate t h e loss from d r y weight flavor and the mycoderma rapidly oxidizes alcohol as lead carbonate. t o COZ and HZO without forming any corresponding L E A D S U L F A T E A N D CHROhIATE-lveigh Out accurately amount of acetic acid.’ Laboratory tests demonstrated about I g., wash into a z j o cc. beaker. add 50 cc. mater t h a t mycoderma isolated from cider was capable a n d 5 0 cc. of 2 5 per cent caustic soda and boil for 5 of destroying all of the alcohol of a fermented orange or I O minutes. Filter through a tared Gooch, wash juice containing 4.5 per cent alcohol in three weeks. thoroughly with hot water, cool t h e filtrate a n d make The gravity of heavy mycoderma growth may be seen up t o 2 5 0 cc. Save t h e residue. T o j o cc. of t h e solufrom these figures. tion add a n excess of hydrochloric acid and 5 cc. alAnother large factory stores its cull apples, peels cohol and boil until the chromate is reduced t o chromic and cores in a large wooden bin. Often this material chloride. Add a n excess of barium chloride, boil, undergoes a fermentation, resembling silage fermentalet settle, filter on an ashless paper, wash, burn a n d tion, before i t can be crushed. The juice after crushing weigh as barium sulfate. Calculate t o per cent lead and pressing is allowed t o undergo spontaneous fersulfate, mentation in go,ooo-gallon tanks. Wild yeasts, T o 50 cc. of t h e above solution add an excess of lactic bacteria a n d mycoderma develop profusely, nitric acid, heat t o boiling a n d a d d zj cc. boiling satgiving a very cloudy cider. Occasionally a t a n k urated solution of potassium bichromate. Boil I < I sticks” with some unfermented sugar, b u t in genminute, let settle filter through a tared Gooch, wash, era1 the fermentations are complete. d r y and weigh. Calculate a s per cent lead chromate. A third factory (until 1914) crushed its apples and F r o m this amount subtract the lead sulfate and lead allowed t h e crushed apples t o undergo spontaneous carbonate, both calculated t o lead chromate, and call fermentation 3 or 4 days before pressing. This the difference actual lead chromate present. R E S I D U E - F ~t ~h e~ Gooch containing the residue from method gave a high yield of juice, due to the softening %he solution for lead sulfate and chromate with hot effect of the fermentation. Beginning with this season, this factory used pure “ B u r g u n d y ” wine yeast on the T : I hydrochloric acid, let s t a n d I O minutes, filter a n d wash with hot water. Repeat twice, wash thor- crushed apples with good results. T h e yeast was oughly, dry and weigh. Calculate remaining residue propagated according t o Bullethz 230 of t h e University as per cent barytes or china clay according t o base. of California Experiment Station. No sulfurous acid P U R E BLUE-The s u m of all the previous determina- is used on the crushed apples, consequently t h e fertions is subtracted from 100,and the difference called mented cider shows a strong tendency t o develop mycoderma. g u r e blue. The above factories all use t h e generator process LABOR~TORIES OF MORRISHERRXANN AND C O M P ~ V Y 878
M T . P R O S P E C T .4VEKUE
NETV4RK XEI% JERSEY
1
A. V. Sifredi, Thesis for X. S., Univ. Calif., Dec., 1914.
