I.17D r S T R I A L Ah-D EA-GISEERIKG CHEJIISTRY
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Vol. 15, KO. 12
Notes on t h e Oil from Kauri Copal’ By Augustus H. Gill and D. Nishida MASSACHUSETTS I N S T I T U T E OF TBCRNOLOGY, CAMBRIDGE, MASS.
OR
varnish-making by the American method gum copal is heated over an open coke fire at a temperature of about 330” C. until from 10 to 25 per cent is driven off up the chimney. By the English process a cover arranged with a condensing outfit connected to suction is used. This collects much of the oil, which is known as copal oil. It has been used to mix with turpentine, but it does not give good results on paint and varnish films. According to Vaube12 it can be detected in the turpentine residue by its odor and bromine number. Other investigators report as follows:
F
Scheiblers subjected “copal from Manila” to dry distillation and noted two distinct stages in the process, but has nothing to say about the composition of the distillate. Tschirch4 states that the dry distillation of hard copal yields formic, acetic, and succinic acids among the products of the 9composition. Friedburgs noticed that certain copals yielded a distillate having an odor suggestive of limonene, but he was unable to isolate the latter, and he did not state what variety of copal had this property. Wallacha subjected kauri copal to destructive distillation and succeeded in isolating pinene and dipentene, but said nothing about the quantities of them. Guedras’ also reported almost the same result as that obtained by Wallach. Neither the results obtained by Wallach or Guedras, however, are obtained from the technical kauri copal oil, but from the laboratory products. Schmolling8 examined kauri and manila copal oils, which are obtained technically in varnish-making, and found that they are soluble in the usual organic solvents except petroleum ether, and that they have the following characteristics: Kauri CoDal
spirit. When the oil was spread out on a glass plate in thin layers and exposed to the air, it gradually solidified and a resinous film was produced within 5 or 6 days. The oil had the following characteristics:
.
ecific gravity a t Z O O C. 0.9667 8 a s h i n g point, b y Pensky e r . . . . . . . . . . . . . . . 85’ t o 86O C. Specific rotation, [a]”,” .............................. 4-3 O, 40’ Specific viscosity a t 20° C. 11.8 Refractive index’at 25’ C. 1.5128 Acid value (free k i d ) mg. ...................... 69.0 Saponification value. ,’, , 83.0 Iodine value, by Hanus method, 15 minutes. 114.0
..
...................
The raw oil was treated with 10 per cent potassium hydroxide solution to remove acids, washed with water, dehydrated with anhydrous sodium sulfate, and by distilling it under diminished pressure a straw-yellow colored transparent oil was obtained, giving a yield of 52 per cent. T h e refined oil thus obtained had the following characteristics: Specific gravity at 20’ C . .... Specific rotation Specific viscosity a t 20° C Refractive index a t 25’ C.”. Iodine value, by Hanus met
[a12
........................ ......................
Fraction
I I1 I11
Manila Copal
R E S U L T S OF
Fraction
I
I1
I11 IV
1.9 288.9
17.4 230.4
FRACTIONATION
--Kauri Copal-Temperature OC. Per cent 21.0 125 to 155 155 t o 157 38.5 157 t o 170 24.7 Over 170 15.8
-Manila Copal? Temperature OC. Per cent 26.0 To 155 155 to 165 26.0 165 t o 170 12.3
....
....
From the Fraction I1 of kauri copal oil he obtained much crystalline pinene nitrosochloride; he also found from Fraction I V limonene-like substances, but no other terpenes, nor any of their characteristic derivatives, were isolated. The aqueous portion of the distillate gave reactions for formic and acetic acids.
RESULTS OF PRESENT STUDY The sample used for this examination was a by-product of varnish-making with kauri copal and had the commercial name “Gum Spirits.” It was a dark yellow, viscous liquid, almost insoluble in water, but very soluble in 96 per cent alcohol, glacial acetic acid, ether, chloroform, carbon bisulfide, carbon tetrachloride, benzene, and petroleum 1 Received f
July 10, 1923.
2. angew. Chem., 33, 1165 (1920).
Ann., 118, 338 (1860). Arch. Pharm., 240, 202 (1902). 6 J. A m . Chem. Soc., ‘22, 285 (1890). 8 Ann., 271, 380 (1892). Chem. Z l g . , 26, 1132 (1902). 8 I b i d . , 29, 955 (1905). 8 4
.... ....
0.9280 +2”, 46‘
....
104.0
The refined oil had the same drying property as the raw oil and gave the color reactions of rosin oil with the Lieberman starch test. When distilled under 15 to 16 mm. pressure the following fractions were obtained:
Residue Ester value. Iodine value..
.
Temperature
c.
u p t o 120 120 t o 200 200 t o 250
....
‘
Per cent
4.3
53.0 41.3 1.4
These figures are quite different from those described by SchmKlling. Fraction I was a slightly yellow-colored liquid ’closely resembling turpentine as regards its odor, specific gravity, refractive index, and rotation; it was fractionated a t atmospheric pressure a t temperatures up to 165” C., 165” to 180” C., and 180” to 200” C. About half of it came over a t the middle temperatures. Pinene was found in Fraction I and limonene in Fractions I1 and 111,using Wallach’sg method of the nitrosochlorides. No aldehydes or ketones could be identified by the bisulfite method. Fraction I1 had characteristics suggesting sesquiterpenes, such as boiling point, specific gravity, etc., but the fact that the fraction formed no crystalline compounds with amyl nitrite or with dry hydrochloric acidlo would seem to show there are no sesquiterpenes contained in this fraction. Fraction I11 closely resembled diterpenes or polyterpenes by its boiling point, specific gravity, and fluorescence, or these characters are almost the same as those of colophene and diterpilene, but the chemical characteristics of both colophene and diterpilene have been little studied; therefore no methods for exact identification have been obtained. Schultze‘l had treated ordinary rosin oil with concentrated sulfuric acid and obtained saturated hydrocarbons with the yield of 36 per cent of refined rosin oil, in which he found Ann., 245, 241 (1888). Allen, “Commercial Organic Analysis,” Vol. IV, p. 186. 11Ann., 859, 129 (1908). 0
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I N D U S T R I A L A N D ENGINEERING CHEMISTRY
December, 1923
octahydroretene, and confirmed this by treating the saturated oil with sulfur with which octahydroretene was dehydrogenated, and obtained crystals of retene. Experiments were carried out following Schultze's directions. At first the mixture of Fractions I1 and 111was treated with concentrated sulfuric acid, and saturated compounds were obt,ained, with a yield of about 19 per cent of the refined oil. This saturated kauri copal oil has some resem-
1277
blance to the saturated resin oil which has been described by Schultze, but is quite a different substance because it gives neither retene by treating with sulfur, nor trimellitic acid by oxidizing with dilute sulfuric acid and manganese dioxide; therefore, in order to confirm this composition some other method is necessary. Nothing was learned by treatment with nitric acid or oxidation with alkaline permanganate.
A New Method of Gas Analysis' By Rudolph Geberth 1452
EAST1 7 ST., ~ BROOKLYN, ~ N. Y.
0 OVERCOME objections to the chemical methods of making quantitative determinations of gases, as employed by the manufacturers of commercially used gases, a n apparatus has been designed by Samuel Ruben, a physicist, of New York, based upon principles of resonance, by which such determinations as to binary gases are made with great accuracy and speed. Broadly considered, the apparatus involves the principle that mechanical energy impulses, such as sound waves, produced by a vibrating element, differ in character with the condition of the gas through which they are transmitted. By "condition" is meant either a physical property, as density, or its chemical composition.
T
When the column is in resonance with the sound wave length, the load upon the fork is a t a maximum and is sharply so indicated by the ammeter. The dial reading, then, which is in accord with that of the ammeter, indicates the resonance length of the gas column. The accompanying curve shows the relation between the length of chamber and the ammeter readings. (Fig. 2) The resonance length of a known gas is indicated by the relation between the velocity and the frequency of sound through that gas; or the resonance length L is equal to the wave length X of the sound source. =-a
VO =
FIG. APPARATUS FOR GASANALYSIS
The accompanying illustration (Fig. 1) shows the complete apparatus, consisting of a closed cylinder, adjustable as to length, through which the gases are passed, and having a t one end a diaphragm coupled to a tuning fork, electrically maintained, together with a current-measuring instrument. One of the cylinders is closely movable within the other by means of a rack and gear arrangement, and has a graduated dial attached to the gear shaft for indicating gas column length. A thermometer projects into the chamber for temperature corrections. The tuning fork is oscillated a t a constant rate by an electromagnet having a carbon transmitter as a variable resistance. As the column is brought close to the resonance point, the ammeter, in series with the electromagnet, indicates a very sharp current rise. The input current of the driving element depends upon the amplitude of the fork vibration as controlled by the diaphragm, its force of reaction against the fork varying according to the condition of the gas in respect to its resonance length.
* Received December 12. 1922
y,x = L
9; V, d1.4$ (1 + =
at) ; V, =
VO 2 / l f a t
where p equals pressure; d, density; a, temperature expansion coefficient, 0.003665; t, operating temperature; VO,velocity a t O C.; f, frequency. As the tuning fork maintains a n oscillation of constant frequency, ordinary pressure changes do not affect the resonance length of the gas; but as its velocity varies with temperature, correction therefor must be made. From the accompanying curve (Fig. 2) it may be noted that the resonance amplitude is very perceptibly reduced by a slight variation in the length of column, as indicated by the ammeter, At the frequency employed in various devices, a change of 0.01 per cent from the resonance length causes the column to be thrown out of resonance from the maximum amplitude indicated by the meter. Thus, a change in the density of the
0
4
8
12
16
20 24 28 32 36 46 44 Cenf i m e fers
FIG. 3-RELATION BETWEEN LENGTHOF CHAMBER AND AMMETEX os TUNINGPORKDRIVSRCIRCUIT READINQS
gas sufficient to cause a change in the resonance length of 0.01 per cent is readily indicated; and if the resonance length of one of the gases in the binary mixture is known, its quantitative relation t o the other known element can be determined.
