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
I4
Jan.,
1912
SAMPLES FROM ALCOHOL DISTILLATION. Grams per 100 liters (based on original sample). Lab.
No.
Description. Gallons. Distillate No. 1 2000 Distillate No. 2 2000 M i x t u r e o f above after filtering through cha r c o a 1 -average of kettle 4000
36814 36815 36816
Beer still samples.
.
Proof. Degrees. 101 101
Acids. 21.6 21.6
Esters. 22.3 22.3
101
20.4
22.3
Higher alcohols.
Aldehydes.
100.2 86.2
120 I20
0 .o 0.0
86.2
125
0.0
Higher alcohols.
Aldehydes.
Furfurol.
Furfurol
SAMPLES FROM COLUMN. Sample 1,ab. No. 36817 36818 56819 36820 36821 36822 36823 36824 36825 36826 36827 36828 36829 36830 3683 1 36832 36833 36834 36835 36836 36837 36838
... ...
...
NO.
Descriptioii.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
Low wines Low wines Low wines Heads Heads Heads Heads Heads Heads Heads Heads Heads Middle run Middle run Middle run
.. .. ..
Tails Tails Tails Tails Low wines Low wines Low wines Fusel oil Fusel oil Water-clean out
Time taken. 10.13 A.M. 10.25 10.45 11.01 11.45 12.35 1.15 P . M . 2.15 3.15 4.15 5.40 6.40 8.45 2.00 A . M . 7.30 8 .OO 9.13 10.10 11.05 11.50 12.06 P . M . 12.30 12.38 Begins 1.00 Ends
Proof, Degrees. 185 185 180 185 187 189 190 191 191 191 191 191 191 191 191 190 190 190 187 182 172
Acids. 32.6 18.0 27.6 54.0 48.0 45.6 63.6 60.0 54.0 42.0 36.0 32.4 15.6 12.0 8.4 9.6 8.4 3.6 9.6 16.8 10.8 8.4
...
Esters. 70.4 79.2 82.7 78.6 71.6 45.2 38.2 31.1 25.8 24.1 17.6 21.1 21.1 19.4 24.6 28.2 24.6 14.1 28.2
17.6 22.9 40.5
SAVPLESFROM CHAMBERSOF COLUMN.
36816 Lab. No.
Average of kettle when charged. No. of chambers from bottom.
36855 4 36856 5 36857 6 36858 7 36859 9 36860 11 3686 1 13 36862 15 36863 17 36864 19 36865 21 36866 23 36829 at condenser finished alcohol
Higher alcohols.
Proof.
Acids.
Esters.
101%
20.4
22.3
86.2
164.4 170.8 174.4 180.4 183 .O 184.8 186.0 187.2 188.4 189.1 190.2 190.7
6.0 6.0 4.8 15.6 8.4 13.2 8.4 7.2 7.2 7.2 13.2 10.8
10.6 12.3 12.3 61.6 35.2 70.4 52.8 44.0 65.1 22.9 24.6 44.0
336.2 292.9 148.8 111.0 54.3 58.1 41.4 35.2 15 .o 17.6 14.1 17.6
190.8
15.6
21.1
16.3
proportion distilled a t less than IzB', proving t h a t the Allen-Marquardt method estimates only about 50 per cent. of the total higher alcohols present in this particular sample. Preliminary fractionation of a sample of salable fusel oil from this distillation proves i t t o contain a t least 7 5 per cent. of amyl alcohol, boiling a t 128'1 3 2 O ; therefore, as the Allen-Marquardt method estimates practically all of this alcohol, then the proportion of the lower boiling point, higher alcohols, in this sample 36838 must be greater than in the marketable fusel oil. On account of the small samples taken a n d the
6000 6400 4800 2320 2200 800 426 370 96 42 13 7.2 1.8 1.1 1.2 1.3 1.3 1.3 trace 1 .o 1 .o 2.2
0.0 0.0
...
......
... ...
0.0 0.0 0.0 0.0 0.0
0.0
... ..* 0.0 ...
0.0
0.0
...
0.0
...
SAMPLES FROM CHAMBERSOF COLUMN.
Grams per 100 liters (original samples).
Lab. No.
47.5 38.7 36.0 32.0 19.4 19.4 19.4 19.0 17.6 22.9 19.4 17.6 16.3 18.0 16.3 15.0 21.1 25.0 122.3 840.0 2650 .O 16.3y0
Grams per 100 liters calculated to 100 proof.
Aldehydes.
125
faint faint faint faint faint faint faint faint faint faint faint faint
Furfurol. Acids. 0.0
trace trace trace trace trace trace trace trace trace trace trace trace
1.8
20.2
Esters.
Higher Furalcohols. Aldehydes. furol.
22.1
85.4
0.0
3.6 3.5 2.7 8.6 4.6 7.1 4.5 3.8 3.8 3.8 6.9 5.6
6.4 7.2 7.1 34.1 19.2 38.0 28.4 23.5 34.5 12.1 12.9 23.0
204.6 171.5 85.3 61.5 29.7 31.4 22.3 18.8 7.9 9.3 7.4 9.2
0.0
8.2
11.1
0.0 0.0
... ...
...
.*. ...
0.0
...
...
...
9.0
124
0.0
0.0
0.0
... ... ... ... ... ... ...
... ... ... ... ... ... ...
...
...
...
... ... ...
...
... ... ...
limited time available, I can not a t this time complete the work along these lines, but hope t o carry it t o completion a t some future time.
PURE LINSEED OIL. By E. J. SHEPPARD. Received October 20. 1911.
The majority of writers on the subject of linseed oil state t h a t linseed invariably contains admixed seeds and straw as impurities; but, with the exception of the article b y Ketel and Antusch,I there is no data 1
Z.ongew. Chem.. 1896, 581.
Jan., 1 9 1 2
THE J O CRiZ;,lL OF IiVD U S T R I A L A N D E l Y G I N E E R I N G CHE!VI.CTRY.
available of the precise effect of these impurities on the constants of the oil. Church, however, calls attention t o the injurious effect of weed seeds on the color of the oil. The following investigation was undertaktn in order to establish t h e exact influence of these impurities on t h e oil.
IS
pletely freed of impurities by screening and by hand picking. Portions of the clean seed were analyzed and the data obtained are shown in Table I. On pressing the clean seed, oil sample C was obtained. Samples I , 2 , 3 and 4 are considered as representativc nf seed used for crushing in this country; 5 , 6 ant1 7
Fig. 1 .
It was thought best t o obtain the oil by the pressure method rather than b y the extraction method as employed b y Ketel and Antusch. The accompanying drawings and photographs (Fig. I ) show the details of construction of the special press designed and built for this purpose b y Professor A. H. Sabin: A , in Fig. 2 , is a cast-iron base. B is a piece of steel tubing. C, in Fig. 3, is a perforated steel plate, the grooves of nhich serve as channels for the oil; in use it is placed with grooves down. D is a solid piece of shafting; this serves as a piston. I n practice,
were imported in a small quantity, but are believed to be representative-no authentic factory samples of oil could be obtained. The average weight per seed was obtained on 4000 full-sized seeds; these were afterward used for the specific gravity determination. TABLEI. Oil in h-onAverage Oleagi- oleagitotal weight nous im- nous im- impurities. Oil. SP. n. per purities. purities. ~. 1 5 S 0 c . seed. Per Per Per Per Seed. cent. 15.5’C. hlg. cent. cent. cent. 1.1388 4.61 1.50 1.69 10.0 1-American. . . . . . . 39.67 ,. . 4.53 1.01 1.05 .. 2-American. . . . . . . 3 9 . 4 0 14.1 1.1415 5.58 0.58 5.64 3-La Plata.. . . , , . , . 36.98 14.9 1.1326 5.41 4.85 5.03 4-Calcutta. . . . . , . . 4 0 . 8 2 5-Bombay. . . . . , . . 4 1 . 2 3 1.1182 7.88 0.81 2.80 .. 6 - S . Russia (Kertch).. . . . . 3 9 . 1 1 1.1375 5.74 5.05 1.71 .. 7-X. Russia 1.1458 4.19 3.31 1.97 .. (Riga). . . . . . . . 36.95
.
.%.
-
J c ~ < i a( $ 1
Fig. 2 .
a piece of wire gauze fitting inside of B is placed on C ; this prevents the charge from wedging in the holes of the plate C. Samples of seed, as used for pressing, were taken a t an oil-mill together with samples of the oil pressed therefrom-Samp’les A. Portions of the seed as received were pressed in the special press and gave samples B. About 300 grams of the seed were com-
The per cent. of oil was obtained b y the extraction method. The percentages of impurities refer, of course, t o the amounts present in the seed as received. I n the case of the Calcutta seed, the percentage of total impurities is a trifle high, as the average of 11 recent samples was 6.90 per cent.-containing 15.1 per cent. oil. The oil in the clean Calcutta seed averaged 41.01 per cent. Andes1 is evidently in error on the average weight of a seed. Wijs’ figures2 on the amount of impurities present in various seeds are correct in some cases. I t is a remarkable fact t h a t the percentages of impurities in the Calcutta and Russian seeds do not confirm the statements of most writers on the subject t h a t “Calcutta and Baltic seeds are freer from foreign seeds than the American and La Plata seeds, and that, consequently, the oils are of better quality.” Apparently, this prejudice regarding the presence of “Drying Oils,” page 58 Andes. I b i d . , page 318.
T H E J O U R N A L OF f N D U S T R I A L A N D EAiGt.VEERI~\’G C H E M I S T R Y .
16
foreign seeds in commercial American linseed is unfounded. In preparing the oil, the seed was ground in a coffeemill, placed in a Mason jar and steam introduced, the jar covered and placed in a steam oven for 2 hours. On removal, the meal was a t once packed in cloth and placed in the press, the piston inserted and, using the screw of a filter-press, pressure was applied, the oil draining through the outlet tube into a bottle wired t o the press. The first test-run showed t h a t only slightly more oil was left in the cake than in regular factory practice. Table I1 contains the analytical results obtained on the oils. I n all cases, the oil was filtered through paper before making a determination. Sample 2A is a n extraction process oil; all the other factory samples are oils manufactured b y the old process hydraulic method.
.es
D”
,
Fig. 3
Analyses: I A and 2A give the results obtained recently on the factory samples of oil, while IA, and 2A, are the results obtained two years ago on the same samples, indicating t h a t no change in the constants determined took place in the oils. Samples IB,I C and 2C were pressed in the laboratory from seed kept 2 1 / ~ years in closed Mason jars. TABLE11. SB. gr. 15.5’C.
NO.
1
2
3
4
5 6 7
Oil. American-A American-At American-B American-C American-A American-A, American-C La Plata-A La Plata-B La Plats-C Calcutta-A Calcutta-B Calcutta-C Bombay-C S . Russian (Kertch)-C N. Russian (Riga)-C
15.5’ C. 0.9346 0.9347 0.9347 0.9346 0.9330 0.9331 0.9330 0.9316 0.9316 0.9317 0.9329 0.9327 0.9327 0.9316 0.9317 0.9354
No.
at 25’ C. (Hanus.) 187.5 1.4802 1.4800 187.9 1.4800 187.6 187.5 1.4800 185.9 1.4800 186.1 1.4797 1.4800 186.5 1.4782 171.4 1.4782 171.8 171.1 1.4783 1.4790 178.9 1.4792 179.3 1.4793 180.5 1.4790 176.9 1.4795 177.0 1.4815 196.4
published giving the analysis of oils from picked seed, with the exception of Thomson and DunlopI who obtained 205.4 as the iodine no. on oil from picked Riga seed, but they used the Wijs method. Ketel and Antusch’ give data of the effect on the oil of varying amounts of dotter and rape seeds added to clean linseed, but they used the extraction method for obtaining the oil; while, in a later articles they admit the possibility of a lower iodine no. in extracted oil, they state that to their knowledge this has never been actually tested. I t may.also be mentioned t h a t the amounts of dotter and rape seeds added are considerably out of proportion to those actually present in the commercial seed examined. Mastbaum states4 that “expressed oil has a higher iodine no. than extracted oil.” The comparative analysis of zA and 2C would seem to indicate, however, that this is not necessarily so. I t is worthy of note t h a t high percentages of nonoleaginous and low percentages of oleaginous impurities, as in the La Plata seed, do not affect the constants, but do affect the color of the oil. On the other hand, with the Calcutta seed, the variation in iodine no. can hardly be due t o experimental error-more likely t o the high per cent. of oleaginous impuritieswhereas the color is only slightly affected. The green color of the Riga oil must be due t o some coloring matter present in the seed itself. The typical analyses quoted in Table I1 fall well within the limits set b y Wijs when the usual difference between the Hanus iodine no. and the Wijs no. is considered. From a consideration of the results it appears that I . Oil pressed from clean linseed does not differ materially from commercially pure linseed oil. 2 . The dark green color of the La Plata oil is due t o the non-oleaginous impurities. 3. A high per cent. of oleaginous impurities does not affect the color appreciably, but does affect the iodine no. slightly. 4. The technical manufacture of oil b y the extraction process does not lower the iodine no. 5 . The constants of the oil pressed from the seed which had been kept 2 1 / ~ years in a closed container do not appear t o be affected b y the aging of the seed. LABORATORY NATIONAL LEADCOMPANY, BROOKLYN. N. Y .
Iodine Ref. index
Jan., 1 9 t a
Color. yellow yellow yellow yellow yellow yellow yellow green green orange yellow yellow yellow yellow orange green
So far as the writer knows, no figures have been
ARSENIC IN GLASS.. B y S. R . SCHOLES. Received November 13, 1911.
I n Hovestadt’s excellent work on “Jena Glass” arsenic oxide (As,O,) is listed among the constituents of many of the glasses described, in quantities of from 0 . 2 to 0.4 per cent. The English edition of this book contains a note by Everett, the senior translator. Analyst, 1906, 282. cit. 3 Z . artgew Chem., 1897, 210. 4 Ibid., 1896, 719. 1
2 LOC.
