K R E I K E N B A U M ON C O N S T A N T S OF C H I N E S E WOOD O I L . color. On dilution and standing several hours the solution became pale lavender, while a dark olivegreen semi-solid floated on top. This sample of unsaponifiable matter began to soften a t about 75' C., b u t was not sufficiently liquid to flow a t 1 2 j O C. It contained considerable ash not readily soluble in water, b u t soluble in dilute acid. The ash was found to contain some lime. The low saponification value obtained by us was probably not due to insufficient saponification, as the wax was digested for five hours in very strong solution of caustic soda prepared by dissolving sodium in alcohol admixed with a n equal volume of purified gasoline. The wax acids separated from the soaps obtained in the saponification were dark brown, softer than the original wax and free from ash. The wax was prepared ash-free by dissolving in boiling glacial acetic acid and pouring the hot filtered solution into a n equal volume of cold dilute hydrochloric acid. After thoroughly washing the wax obtained in this manner with water, some of its chemical constants were determined and are given in the table with those of the wax as examined in the original state. The cause for the differences there shown is not apparent. The dried and filtered commercial wax yielded on combustion the following average of two closely agreeing determinations :
................................
Carbon, per cent Hydrogen, per cent
80.30
............................. 12.69 A sample of sugar cane wax analyzed by Dumas' was found by him to contain 81 per cent. carbon and 14.16 per cent. hydrogen. H e regarded this substance as an alcohol of the formula C,,H,,O. It will be observed that the candelilla wax is somewhat similar to the cane wax in its ultimate composition. The probabilities are, however, that candelilla wax like carnauba wax is a mixture of an alcohol, a n ester, and some free fatty acid. If, however, an alcohol is present it should be possible to acetylate the unsaponifiable matter. We attempted the acetylation by the Benedict-Lewkowitsch method, but obtained negative results.
CONSTANTS OF CHINESE W O O D OIL. By
ADOLPH KREIKENBAUM.
Received March 1 1 , 1910.
Chinese wood oil is a comparatively new article in general commercial use. It is now very much used in the manufacture of varnishes. I n the following work only the results of the determinations of the constants are given and a discussion of the analytical features added. The literature offers comparatively little definite regarding the constants of the oil and a t most a considerable con* Quoted by Browne in Bull. 91, Louisiana Experiment Station.
20.5
fusion of figures together with a wide range given for the various constants.' I n some cases individual analyses upon some sample of unknown or doubtful source is submitted and in other cases it is evident that a confusion of products is a t fault in that Japanese wood oil and Chinese wood oil have been classed alike,2 being in the opinion of the writer two separate and distinct products. This opinion is based upon references found in literature3 and not from original knowledge. The values given by Lewkowitsch in the tahle of constants for Chinese wood oil are evidently some Chinese wood oil and some Japanese wood oil figures. The values given for the specific gravity of Chinese wood oil by Lewkowitsch himself agree with the results obtained in this work. It seems that a distinction should be observed between the two products, Chinese wood oil and Japanese wood oil by all chemists, because the two oils are evidently separate and distinct substances, and the indiscriminate interchange of the figures of the two oils under one synonym Tung oil causes an unnecessary confusion and hardship for the analytical chemist, who may be compelled to make use of published data for reference. The value of the work embodied in this article and the results obtained and submitted in their entirety are due to the fact, that the determinations of ' t h e constants have been made upon exact and carefully taken average samples of large commercial shipments of Chinese wood oil. This has been done for two years and the samples examined thus show how uniform a product the Chinese wood oil of commerce is. The investigation also reveals the fact that each constant varies but very slightly with the exception of the free acid value. The complete figures for each sample will tell their own story best. All of the following specimens of the oil represent a n average of regular commercial shipments. Several fluid ounces of the oil were taken from each barrel, emptied into a single container, mixed thoroughly and preserved in a tightly stoppered bottle filled close up to the cork and the bottles preserved in a dark, cool cupboard near the floor. More specific details are given directly under the various specimens. The column marked A g e in the analysis tables indicates the time elapsed between the receipt of the shipment and the date the particular analysis was made.
Number
I.
Shipment received October, I 907. Represents average of about IOO barrels which bore the same brand. Filled one-gallon can full, tightly stoppered; kept in cool place. October, 1908,transferred some of this Tach, Chemistry and Technology of Mixed Paints, ed. 1907, p. 9 9 ; Chem. Engr., 9, 186. * A n a l y s t , 23, 113, 118. I b i d 3 23, 113, 118; Kametaka, J. S. C.I., 27, abstract of J. Coll. Science I m p . Univ. Tokyo. 1908, P. 25 ; Lewkowitsch, Chem. Tech. and Anal. Oils, Fats and Waxes.
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY.
2 06
oil into a 16-oz. bottle and filled nearly to the cork. Determinations made from this bottle sample : 15.5
Spec. grav. I'
"
0.9416 0.9422
15,5
Pycnometer.
Sapon. No.
'15.5 5.5
2 yrs.
"
Free acid 4.8 mgs. K O H .
13 mos. 24
... . . .
...... ......
......
...... ...... ...... ......
191.5 1 1 9 1 . 8 192'2 170,8} 171,6 172.4
Hfibl
i i ~ : ~ } 1 7 0 ,,, 9
13
,'
18
"
16
I'
164,5}165.0 165.5
''
3
"
16
"
170.0 169,5 1 1 6 9 . 7
I'
4
I'
17
"
"
21 ''
212'2 )210.8 209.4
18
Hanus 30 min. 16
208.1
"
...... 208'3}208.6 ...... 209 196.0 196.0
solution days old. Hub1 solution days old.
3 0 " 30
"
12
'I
30
'I
12
I'
'I
'I
Y
"
0.9427
15.5
0.9435
-
Spec. grav.
0.9432
15.5 15 .5
24
15.5 15.5
24
,
Free acid 2.3 mgs. KOH.
13 24
"
15 hrs,
13
,,
18
16
I'
Iodine..
. ..
.....
.....
.....
190.6
173.0) 172,6 172.2 168'3)169.8 171.3
i2::) i2: :)
163.9 169.4
169'6}i69.3 169.1
.....
..... ... . .'
Hiibl "
/'
"
3 '
