APT., 1915
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
perience showed, not as quickly, over 7 j per cent as over IOO per cent HzS04. With cheese t h e percentage of moisture obtained over I O O per cent HzS04 is about t h e same as t h a t by drying t o constant weight a t IOOOC. Flour shows another example of t h e increase in weight of some materials on heating, due t o a certain amount of oxidation. Skertchlyl has pointed out inconsistencies of this kind which he found while drying biscuits. As has been suggested by several authors, exposing a substance over varying concentrations of HzSOa a n d finding t h e concentration a t which i t neither gains nor loses weight indicates t h e concentration of H2S04 which has t h e same vapor pressure as t h e material. I n this way flour had a vapor pressure of about 15. o mm. and cane-sugar syrup of about 2 1 . o mm. Hempe12 has shown t h a t the rate a t which substances dry depends upon t h e rate a t which water vapor is transferred. Since air saturated with water vapor is less dense t h a n unsaturated air, Hempel puts t h e HzS04 in the upper p a r t of t h e desiccating jar. Similarly, if air currents can be formed in t h e jar, t h e drying will go much faster. T o show this point, samples of maple syrup were dried over 95 per cent H2S04 a t room temperature in two desiccators; in one a small motor was introduced a n d t h e air stirred vigorously during t h e experiment. I n one a n d onehalf hours as much moisture was removed with stirring as was removed without stirring in six hours. Several portions of A1203 were prepared for comparison with t h e other desiccants. The A1203 used in t h e preliminary trials was prepared from “technical” Alz(S04)3 b y dissolving t h e salt in water a n d precipitating t h e Al(OH), with T\iT&OH. The alumin u m hydroxide was filtered off and dehydrated in t h e glass tube of a combustion furnace with the smoky flame. The &03 employed in the later experiments was made in t h e same way, except t h a t “ C . P.” Alz(S04)3was used in t h e preparation a n d t h e Al(OH)3 was washed many times t o remove a n y impurity which might lead t o erroneous results. Preliminary experiments comparing A1208 with CaClz showed t h a t in nine days a t laboratory temperature and pressure, a sample of coffee yielded 0 .z per cent more moisture over Al2O3 t h a n over CaC12. I n t h e same length of time a sample of sugar yielded t h e same weight of moisture over either. The percentage of moisture in this case, however, was very low. Trials were made, also, by placing weighed dishes of A1203 over H z S 0 4 a n d &So4 over A1203 t o see which would increase in weight more rapidly. The moisture introduced b y opening t h e desiccator was enough t o vitiate t h e results somewhat, b u t the A1203 increased in weight faster t h a n t h e &Sod. The following table shows t h e percentage of moisture obtained with three common materials dried over t h e three desiccants a n d kept in a thermostat a t 2 j o C . Each percentage shown is t h e average result of duplicate experiments in individual desiccators over t h e same weight of desiccant. 1
J . SOC.Chem. I n d . , Jan., 1913.
* Ber., 23 (1890), 3566.
TABLE 11-PERCENTAGES SUBSTANCE FLOUR &SO4 Time AlaOa 95 Days per cent 1 8.42 8.42 2 9.51 9.56 3 10.30 10.33 4 10.67 10.61 5 11.08 10.96 6 11.21 11.13 7 11.46 11.33
8
10 11 13
.........
ii:i5
11.75
ii:& 11.64
ii:i5
11.15
DIFFERENTDESICCANTS CuSOa.5HzO COFFEE &SO4 AlzOa 95 CaClz Der cent AhOa CaCh 14.12 15.08 15.22 1.31 1.17 18.76 19.47 16.84 1.98 1.82 23.73 25.51 21.31 2.66 2.38 28.11 2 8 . 7 4 25.40 3.11 2.92 29.36 29.46 28.77 3.30 3.11 29.43 29.45 29.32 3.44 3.22 29.53 29.54 29.42 3.54 3.32 3.66 3.46 2 6 : i 3 2 6 : i 4 29:42 .. . . 3146 26:53 26:54 26:42 ..
O F MOISTUREB Y
CaClz 8.47 9.21 10.06 10.35 10.62 10.75 10.96
321
..
The time values in Table I1 are given roughly in days, which intervals are close enough t o show t h e points in question. Some of t h e moisture in t h e blue vitriol was lost in grinding t h e sample. The work in Table I1 was repeated in vacuum desiccators a t a pressure of about one-tenth atmosphere a n d a t laboratory temperatures. As before, three substances, flour, blue vitriol a n d tea, were dried over t h e three desiccants. Although there was some difficulty in obtaining desiccating jars with t h e same power for “holding” t h e vacuum, t h e average results were in t h e same order as in t h e above table. For small amounts of moisture A1200 appears t o be somewhat superior t o either HzS04 or CaC12, when used in this way’, while with CuS04.gHz0, which has a larger percentage of moisture, there seems t o be but little choice between A1203 and 95 per cent HzS04. CaClz seems t o be inferior t o either of t h e others. I t is possible t h a t H z S 0 4methods of drying may give better results when t h e acid has frequent agitation, a n d when two or three charges of fresh acid are added during a determination. A1203 has t h e further advantages t h a t one need not guard against slopping, burns, etc., as when using HzS04 a n d t h a t this oxide can be reheated when i t becomes saturated with water and used again and again. UNIVERSITY OF
MISSOURI,COLUMBIA
THE OLEORESIN OF SAND PINE By A. W. SCEOROER Received December 28, 1914
The sand pine (Pinus clausa, Sarg.) is practically confined in its range t o t h e State of Florida. It is a small tree whose branches extend t o t h e ground, t h e height being usually I j to 2 0 feet, while a diameter of I foot is rarely exceeded. The’ material examined was obtained on t h e Florida National Forest from near Ocala, Florida. OLEORESIN-The oleoresin contained considerable water a n d small trash of such a nature t h a t a n unusually low-grade rosin for virgin “gum” was obtained. Analysis gave t h e following results: Volatile oil. ............................. Rosin (Grade G). ........................ Trash.. W a t e r . . . ...............................
.................................
Per cent 18.93 72.30 2.67 6.10
VOLATILE oris-The volatile oils obtained from two samples of oleoresin were practically identical. Their properties were as follows: 1 io
( 1 ) ........................... (2) ...........................
d@ 0.8725 0.8723
nD150 1.4768 1.4767
aD200
-22.49 -22.80
On fractional distillation with a rz-inch ,Hempel
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 j6, ~ ~ 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 E
two fractions were obtained t h a t showed fairly constant boiling points. Below will be found t h e properties of the two fractions and of one of t h e synthetic ppinenes prepared by Wallach:
STRATA'
BY
GEORGE
A. BUEEELb
Received November 28, 1914
I n this paper are recorded some observations a n d experiments regarding t h e liquid or gaseous occurB. p. nD200 rence of natural gas in t h e earth's strata. This ques1.4772 ( l ) . , . , .. 164-165O 1.4984 tion has been a subject for conjecture in t h e past, ( 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 200 d25jE 0.8700 0.8709
1 Ann.,
363 (19081,1.
Calculated [a]D M found for CioHic I= 43.54 44.19 -26.00° 43.54 44.23 -23.73'
of the Bureau of Mines.
+
