658
T H E J O U R N A L OF I N D U S T R I A L AA‘D E-YGINEERING C H E M I S T R Y
cast iron kettle filled with water and held down tightly by means of a chain fixed t o the ground. It can hold 400-500 lbs. of the dried herbs from which a I . 2-1,6 per cent yield of the oil is obtained. The advantages of the ‘‘ Seiro ” are : the larger charg-
Vol. 5 , No. 8
pot is filled with oil and then it can be removed by closing the opening with a finger tip while under water. Water in the trough is made to flow back into the kettle from time to time for replenishing it. As a rule, the end of a distillation is determined by practice from the appearance of the distillate dropping into the receiver. I n this way one entire process is carried out in about three hours, charging and’ discharging requiring each about thirty minutes. Such distillations are usually repeated three or four times per day. The crude oil is separated from water, filtered and then put into cans. Two cans are packed as one set, in a box. The product is sold to commission merchants or directly to exporters and through those channels i t is exported from Yokohama or Kobe. The separation of menthol is carried on in the hands of exporters before the goods are shipped either to Europe or America. The distillation residue is used as forage for domestic animals or is burned in order to save the ash as fertilizer. IMPERIAL TOKYOUNIVERSITY CAREPROF.T. KAMOI JAPAN
ON JAPANESE PEPPERMINT OIL By YEINOSUKE SHINOSAKI Received May 24, 1913 DISTILLING PEPPERMINT OIL BY SEIRO(OLDTYPEO F STILI.) AT NOTSUKEUSHI FARM
ing, less labor for charging and discharging than the still referred to before. On the other hand, it has the following defects: the distillation is incomplete on account of some oil remaining in the “Seiro;” besides, the life of the still is only about four years. (4) By the hanging vat. The “Seiro” has been lately improved and provided with a false bottom of metal netting, the other parts remaining the same. At the end of the distillation the still (Seiro) is hoisted by means of a rope attached t o a series of pulleys and then the distillation residue is discharged. The operation was made easier by the use of this kind of improved still. Such use of the hanging vat is said to have additional advantages; namely, the charge of material is larger, discharging easier and durability prolonged (about ten years). The author thinks that it is the best type of still employed among the distillers of peppermint oil. As a receiver, the socalled ‘‘ Mizukiri-Kame ” is employed, which is a pot of stoneware with a small opening on the bottom. The pot stands in the beginning of distillation, ina small trough filled with water. As theoil distilsandaccumuRBCENER“MIZUKIRI-KAME” lates in the pot, water in the pot is gradually displaced through the opening on the bottom into the trough until finally the entire
The peppermint oils examined by the author are those which are produced a t the Kitami Branch of the Agricultural Experiment Station of Hokkaido and the Odakogetsu Peppermint Oil Trade Association in the Okayama prefecture. I . HOKKAIDO PEPPERMINT OIL OF ENGLISH AND GERMAN ORIGIN
Peppermint of Mitcham, England and Hamburg, Germany which were imported into Japan a few years ago, have been put on trial cultivation and dis-
Plantation..
. , . . . . . . . . . .. . .
Germination.. . .
German origin 1910 Nov. 10 1911 May 12
Year
Japanese origin (KitamiAkamaru)
English Origin
1910 1911
Yay 26 June 1
May 23 May 7
May 25 May 5
Flowering , . . . . . . . . . . . . . . . . 1910 1911
Sept. 4 Sept. 7
May 7 May 7
Sept. 4 Sept. 13
1910 1911
Sept. 23 Sept. 16
Hay 7 May i
Sept. 13 Sept. 13
.
Cutting..
Length of peppermint at cutting t i m e . . , , . , . . , . , , , , 1910
.
..
1911
Weight of cutting per 1 ton (0.245 acre). . , , . , , , , . . , , , 1910 1911
Weight of dried herb per 1 ton. 1910 1911
Weight of oil from dried herb, per 1 ton ....... . . . . . . , , , . 1910 1911
Yield of o i l . , , . . , , . . . . . . ,
,, ,
1910 1911
5 3 . 9 3 cm 7 9 . 0 8 cm.
4 2 1 . 1 kg. 1 7 1 6 . 6 kg. 124.13 kg. 3 9 9 . 9 kg.
975 grams 2 5 5 . 0 grams 0.79% 0.63%
88.48 62.42
559 1 1161.2 143.0 199.57
78i 5 1687.5 0.52 0.84
5i.27 66.05
771.0 1158.3 214.88 279.15
2625 2775 1.23 0.99
tillation a t the Katami Branch. Mr. S. Yanada, Director of the Branch, has published the foregoing results of the trial. The results determined by the author are as follO\TS
--
:
-
German origin
English origin Japanese I 1910 1911 origin 1910 1911 Dii . . . . . . . . . . 0,9638 0.9105 0.8989 0.9228 0,9132 Ng. . . . . . . . . 1.6117 1.4672 1.4602 1.4717 1.6573 q,...... . . . . . . . . . -42.25 -28.92 -52.25 -63.60 AcidNo . . . . . 19.53 Nil Nil 4.42 7.06 Menthyl acetate, percent. . . . 24.94 11 .os 6.35 26.50 13.65 Ester menthol, 8.69 5 .OO 20.88 I O . 75 per cent. . . . . 19.65 Free menthol, 57.61 64.30 66.00 64.65 per cent. . . . . 66.06 Total menthol, 66.30 69.30 66.88 75.60 percent. . _ . 85.71 Solubility (70% alcohol a t 20' C . ) , . . . . . . . 2 . 5 vols. insol. in 2 . 8 vols. insol in 3 vols 15 vols. 15 vols. KO. 1
Dis. .
............................... x g . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
0.9005 1 ,4600 an.... . . . . . . . . . . . . . . . . . . . . . . . . . . . -33,750 .4cid S o . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Si1 Menthyl acetate, per c e n t . , , . , . . , . , , . , . 2.79 Ester menthol, per cent.. . . . . . . . . . . . . . . . . 2 2 Free menthol, per cent. . . . . . . . . . . . . . . . . 69 23 il.43 Total menthol, per c e n t . , . . . . . . . . . . . . . . . . Solubility (70 per cent alc. a t 20" C . ) . . . . . . 2 6 vols.
.......
96.87
662.50
135.00
97 . 8 8
300.00
78.75
82.25
318.75
i8.76
S1,62
251.25
56.25
...
375 . O O
82 .SO
98.76
453.76
120.00
92.13
The properties of the oil are found as follows: No. 3
so.4 0.8991 1 ,4600 --24.00' 1.45 3.68 2.9 66.20 69.10 2 . 7 vols.
0 9010 1 ,6602 --31 800 0 7 4 32 3 6 68.20 71.60 2 . 7 rols
3.7
KO. 5 0.9010 1.5598 -33.60' 2.00 3.31 2.61 66.26 68.85 2 , s vols.
0.8977 (24' C.) -40 2.8 13.55 11.05
The analytical results are:
Dzo Ng aD Normal 0.8982 1.4607-34.00° oil Leaf oil . . . 0 . 9 0 2 s 1.4600 -33.33'
......
Menthyl Ester ace- mentate thol Acid Per Per No. cent cent 1 . 5 3 4.10 1.04 4 . 5 6
Solubility (70 per cent alcohol a t 20' C.1.. . . . . .
111. H O K K A I D O P E P P E R M I S T OIL O F J A P A S E S E O R I G I N
I. OIL FROM HERBS DRIEDB Y I r A R I O U S 31ETHODS.The experiments carried out a t the Kitami Branch
Free menthol Per cent
Total menthol Per cent
3 . 2 3 iS.17 3 . 5 1 67.91
81.40 71 41
Normal oil 2 6 1.01s
Leaf oil 2 . 6 vols.
3. FALLEK LEAFOrL.-The oil obtained by the distillation a t the Katami Branch has a pale yellow color.
3 vols.
B 0,9140 1 ,6667 -54. i 5 Si1 8.11 6.39 46.55 52.94 Insol. in 15 vols.
-
Weight of oil from 3i5 kg. of dried herb. . . . . . . . . . . 322.5 kg. \\'eight of oil from 375 kg. of dried leaf.. . . . . . . . . . 217.5 kg.
79.14 2.06 82.23
The analyses of other samples which were produced in 191I (the yield of oil is unknown) are:
No. 6 0.9020 1 ,6607 -39.60 Nil 5.20 4.10 70.10 74.10 2 . 5 vols
2 . LEAF. ~ S D SORMAL OIL.-The report on the yield of the two kinds of oil a t the Kitami Branch is:
Japanese origin
D .....................
.............
KO.4. Drying on shelf indoors Sep. 24 (under direct sunlight). No. 5. Drying by hanging in series of sheaves indoors (under direct sunlight). . . . . . . . . . . . . . Sep. 24 No. 6. Drying by hanging in series of sheaves indoors (in the Sep. 24 shade) . . . . . . . . . . . . . . . . . . . . . .
66.52 70.22 2 . 5 vols
German peppermint has a reddish violet stem and its leaf is longer than that of Japanese origin. The oil examined by the author was obtained from the production in 1909. The distillation was carried out from the end of June t o the beginning of July, 1910,and the yield of oil was only 0.8per cent, while that of Japanese peppermint is I , 6 per cent. The oil is dark brown and has a sa-eet taste. I n the following table of the author's experimental results, the nature of the oil of Japanese origin is given for the comparison:
-4 Dls. . . . . . . . . . . . . . . . . . . . . . . . . . 0.9035 &-2o D., . . . . . . . . . . . . . . . . . . . . . . . . . 1.6610 aT). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -34.02 Acid X o . . . . . . . . . . . . . . . . . . . . . . . . . . 0.81 Menthyl acetate, per cent.. . . . . . . . . . . 4.30 Ester menthol, per cent.. 5.46 Free menthol, per c e n t . . . . . . . . . . . . . . . 75.76 Total menthol, per cent.. . . . . . . . . . . . . 79.20 Solubility (70 per cent alcohol a t 20' C.) 2 .9 vols.
No. 1. Drying on shelf (out of Sep. 24 doors).. . . . . . . . . . . . . . . . . . . . . h-o. 2. Drying on roof forniing shelf (out of doors). . . . . . . . . . . Sep. 24 No. 3. Drying by hanging in series of sheaves under the eaves of north direction.. . . . . . . . . . . Sep. 2 4
Nil 4.70
11. OKAYAM.4 P E P P E R M I N T OIL O F G E R M A S ORIGIN
................
Kg. of dry Grams of oil herb from from 37.5 kg. Cutting 375 kg. , time Cuttings Dry herbs Cuttings
No. 2 0.9012 1 ,6599 -32.50'
..
German origin 0.9161 (15' C . ) O D . , . . . . . . . . . . . . . . . . . . . --IS. 15 Acid X o . . . . . . . . . . . . . . . . 3.45 Sap. S o . . . . . . . . . . . . . . . . 33.46 Ester N o . . . . . . . . . . . . . . . . . . . 30.01 Free menthol, per cent.. . . . . . 36.07 Ester menthol, per c e n t . , , , . , 8.36 Total menthol, per cent.. . . . . 58.61 Solubility (70 per cent alcohol at 2 O ' C . ) Insol.
to determine the yield of oil by the various drying methods are as follows:
D20
Ng
(ID
0.9000 1.6600 -21.15'
Acid No. 0.76
Menthyl Ester Free Total ace- menmen- menSolubiltate thol tho1 tho1 ity (70 Per Per Per Per percent alc. cent cent cent cent at 20° C.) 13.44 75.59 75.37 85 96 2 . 6 ~ 0 1 ~ .
4 . COMMERCIAL PEPPERMINT OIL.-(a) A\70r~iiul Oil. The oil examined by the author (its origin is unknown), perhaps of Hokkaido. has a pale brown color.
Dlo S2 D" 0.9000 1.6601 -33.85'
Jlenthyl Ester acementate thol Acid Per Per No. cent cent 2.18 3.18 3.0
Free Total men- men- Solubilthol thol ity (70 Per Per per cent alc. cent cent a t 2 O 0 C.) 71 20 74.20 2 . 8 vols.
( b ) " P e p p e r m i n t Oil" mid "Purified Peppcriiiiutt Oil." -The samples which \Yere presented a t t h e GummiCompetitive Exhibition in I 910 had the following constants :
660
mann carefully tested the accuracy of the method ‘by having different analysts send him small samples Dgo. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.9010 0.8990 of beer, together with a statement of their density. 1,657’) Na”. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4586 .D. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -39.60’ -37.30’ From this and the refractometer reading taken by himAcid N o . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.52 3.60 self, Ackermann calculated the percentage of alcohol 9.09 11.4i Menthyl acetate, per cent. . . . . . . . . . . . and extract with the aid of his machine. Some of the Ester menthol, per cent. . . . . . . . . . . . . . 7.16 9.03 45 ,3A Ester menthol, per c e n t . . . . . . . . . . . . . 58.04 results obtained are discussed below. I t must be Total menthol, per c e n t . . . . . . . . . . . . . 54.41 65.20 stated that this calculating apparatus was based upon 3 rols. Solubility (70percent alcoholat 20°C.. 3 vols tables which had been worked out from analytical IMPERIAL TOKYO UNIVERSITY data obtained by means of the pycnometer, and the T.KAMOI CAREPROF. JAPAN corrected alcohol and extract tables of Karl Windisch.1 -During the same year Bartha published a formula for determining the extract and alcohol in beer from THE USE OF THE IMMERSION REFRACTOMETER I N the specific gravity and the refractometer reading EXAMINING AMERICAN BEERS MADE FROM of the same. I n his article Barth published the reMALT AND UNMALTED CEREALS’ sults of 16 analyses, and to these we shall again refer B y ROBERTSCHWARZ below. The application of the immersion refractometer In 1910 Danzer3 published a series of tables (also to the analysis of numerous chemical solutions and based upon the alcohol and extract tables of Karl food products has attracted the attention of many in- Windisch) from which the alcohol and extract of any vestigators, and during the past 1 2 years quite a few beer could be calculated from the same determinaanalytical methods based upon the use of this instru- tions as those used in Ackermann’s method. As ment, together with valuable tables, have been pub- these tables are quite readily accessible, and the callished in various chemical journals. A considerable culations involved very simple, they put the refractopart of this work has been done by fermentation metric method of beer analysis within the reach of chemists, who quickly recognized the fact that the all chemists. immersion refractometer was especially well adapted The results published by Ackermann,4 and also for the analysis of the products obtained by the those given by Barth,s show but small differences wine grower, the distiller and the brewer. It is to the between the percentage of alcohol and extract as dework done in the last mentioned field that the author termined by the refractometer and the pycnometer. desires t o call special attention. It is therefore somewhat surprising that the former Tornoe,* in 1897, published a method for the analysis method has not come into more general use by brewof beer which was partially based upon determining ing chemists. Particularly here in America, has the the index of refraction, using sodium light and a spe- immersion refractometer failed to receive from the cially constructed type of differential refractometer. brewing chemists the attention which it so justly This method, while fairly rapid and quite accurate, deserves. Although the author has never found any direct did not, however, find wide application. written statement to the effect that the method, as The introduction of the Zeiss immersion refractompublished by Ackermann, could not be applied to eter, which is so extremely simple to manipulate, gave typical American beers which are brewed from a mixfresh impetus to the study of optical methods for the ture containing 60-70 per cent malt and 40-30 per cent examination of liquids such as beer. I n 1903, Ackeradjuncts (in most instances unmalted cereals), some of mann and Spindlers published a method for determining our brewing chemists have informally expressed the the extract by the formula E = (J - J’) 6 7 j o . in belief that the results obtained with the refractometer which J = index of refraction of the beer, J’ = index on such American beers would not be sufficiently acof refraction of the distillate, and 6750 a n empirically curate to permit the use of this instrument. determined factor. I n this method the index of reThe writer, therefore, decided t o investigate this fraction of the beer and the distillate are calculated matter and examined, with the aid of the refractomfrom the immersion refractometer reading of these eter and the Danzer tables, 47 samples of beer and liquids. ale which iyere also analyzed by another chemist, I n 190j Ackermann4 constructed a calculating ma- using the official method, namely, distillation and dechine with which to determine the percentage of alcohol termination of the specific gravity of the distillate and extract in beer from the density of the decar- and residue with the pycnometer. Attention must bonated beer, taken at I j / I j O C. and its refractori- be called to the fact that in calculating the percenteter reading a t 17.5’ C. It is not the purpose ol ages of extract and alcohol equivalent to the various this paper to discuss the above publication other than densities found, the tables of Karl Windisch, and to say that this method is far simpler and much more not those given in Bulletin N o . 107, revised, Bureau rapid than the official pycnometer analysis. ,lcker- of Chemistry. LT.S. Dept. of Agriculture, were used. “Peppermint oil”
“Purified peppermint oil”
Paper presented before the S e w York Section of the .lniericAn Chemical Society, Chemists’ Club, June 6, 19!3. 2 . f,d. ges. Brauuesen, 20, 373 (IS97 Ibzd., 26, 441 (1903:. 2. 1.d. ges. Brauwesen. 28, 33 (1905
These tables have been published in numerous journals and text books. I b i d . , 28, 303 \1905:8. 3 2 . f d. ges. B r a u z e s e u , 32 (1910 . .I See reference 3 j See reference 4. 1
2
