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 . ANALYSES O F M I N E - A I R SAMPLES
34
35 36
37 38
39
Vulcan mine. co,. Face of workings, main entry, 600 f t . i n. . . . . . . . . . . . . . . . . . . . . . . . . . . No. 9-B upraise, 25 ft. from entry 0.6 Cross-cut between 8-B and 9-B upraises.. . . . . . . . . . . . . . . . . . . 0 . 4 Rockvale mine Room 28, C dip.. . . . . . . . . . . . . . . 0 . 2 1st dip, 5th south, off C dip. . . . . . . . . Main return in main south, 1,500 ft. fromshaft . . . . . . . . . . . . . . . . . . . .
(Contimed)
0.
N.
CH,.
20.5 20.1
78.9 78.7
0.6 0.6
20.5
78.5
0.6
moisture, and possibly b y the removal of the resulting mud from the mine. I.YTVERSITY
.
20.0 19.8
78.6 78.9
1.2 1.3
19.7
79.1
1.2
The dust samples from the Standard and the Summit mines, which are probably representative samples of dusts from the Boulder County field, show a fairly high percentage of moisture. This would tend to make these dusts safer than those of the southe m fields, which are very dry. However, it would be dangerous t o trust t o this for safety from explosions, since we have not enough data on this question as yet. These dusts from the ribs and timbers and from the roadways usually contain considerable fire clay, but the results from experiments a t the Pittsburg testing station on similar coal dusts containing a high percentage of fire clay have shown that even such dusts are dangerous. The dusts in the mines in the southern part of the state are without doubt very dangerous. A similar dust having a composition, moisture 3.41, volatile matter 17.98, fixed carbon 47.22, ash 21.39, was tried in the explosion gallery of the Pittsburg testing station. The dust exploded from the effect of a blownout shot of 5 0 0 grams of black powder, and propagated the flame through the entire length of the dusted gallery, and 2 7 feet beyond the dust zone. Similarly, a road dust, rich in rock dust, giving the following analysis, moisture 2.75, volatile matter 15.45,fixed carbon 24.85, ash 56.95, exploded and propagated the explosion 2 0 feet beyond the dust zone. All the dusts in the tables except Nos. 1 2 , 24 and 2 5 would be far more likely to explode than the samples experimented upon a t Pittsburg, as may be sedn by comparing the analyses. An interesting dust is N o 14,which was taken from a sheltered place on the ribs of the third north entry of the Delagua mine, and which had not been dis-' lodged b y the explosion. This may be taken as a fair sample of the Delagua mine dust, which, without doubt, contributed its share t o the explosion of October 8th. This dust varies little in composition from the dust found in the other mines of that part of the state. I t is a pleasure to say that, in the Cokedale mine, there was very little dust; in fact, no suitable sample for analysis was found. I n the Somerset mine there was practically no dust, though, after some trouble, a sample was obtained. Of the mines visited, almost all were in danger from coal dust, and it is fair t o assume t h a t the great majority of the mines of the state are in the same condition. This matter should be remedied by proper legislation, requiring that the dust be rendered harm' less by means of the addition of a large amount of The intake is contaminated by air from some old workings.
Aug., 1911
[CONTBIBUTlUh
OF
COLORADO.
P R D X D I V I S I O N O F D R U G S . BUREAU O F C H E M I S T R Y ,
u . s . D E P T . O F AGRICULTURE
]
T H E Q UANTI'IATIVE DETERMINATION OF KETONES IN ESSENTIAL OILS. By E K . N E L S O N . Received June 7. 1911.
While we have general methods for the estimation of alcohols, esters, phenols and aldehydes in oils, such a method seems t o be n-anting in the case of ketones. Some sukstances of this class, as for example, camphor, do not react with sodium bisulphite. Others, while they may react with bisulphite, can not be even approximately estimated by its use. The methods of Sadtlerr and LabbC,* while valuable in many cascJ could not be accepted as general methods because the reactions involved are not characteristic of all ketones. All the ketones usually found in essential oils, however, do react with hydroxylamine to form oxims. The method of Walthers depending upon tile transformation of the ketone into oxim on boiling with a standard alcoholic solution of hydroxylamine hydrochloride in the presence of alkali, and the determination of the amount of the reagent th.us consunied. b : ~ titration of the excess on completion of the reaction, seemed to offer advantages as a general method for the analysis of ketone-bearing oils. Walther experimented on the estimation of citral and carvone, but does not speak of having tried the method on other ketones, or aldehydes. The following work was undertaken t o test the accuracy of Walther's method on ketones in general. The ketones used were prepared from the oils in which they occur, or were obtained in some cases on the market and purified. I n every case the method was carried out the same way. The standard hydroxylamine solution was prepared b y dissolving 2 0 grams hydroxylamine hydrochloride i n 30 cc. water and adding 1 2 5 cc. aldehyde-free a l w hol. One t o two grams of the substance were boiled in a water bath under a reflux with 35 cc. of this reagent and 2 grams sodium bicarbonate, cooled, 6 cc. HC1 added, through the condenser, followed by water and the mixture made dp t o 500 cc. The solution was filtered and in a n aliquot part of the filtrate the free acid was neutralized by running in N / 2 NaOH, using methyl orange. Phenolphthalein was then added and the hydroxylamine left in excess of that required to form oxim was titrated with N / I O NaOH. The results in the following table were obtained: Considering the nature of the work and the difficulty of preparing absolutely pure materials t o start with, these results may be considered as fairly satisfactory except in the case of fenchone. As this is a rather rare ketone, however, and as it is present in but few oils and in those only in small amount, a method for its estimation is not so necessary. 5
a 3
A m . J . Pharm., 76-84; J . SOC.Chem. Ind Bull. SOC.Chim., 23, 283. Pharm. Centrh., 41-613.
~
23, 303.
Aug., 1 9 1 1
T H E J O U R N A L OF I N D C S T R I A L AhTD EA-GINEERIA'G CHE31ISTRY.
Carvone. . . . . . . . . . . . . . . Carvone. . . . . . . . . . . . . . . Carvone. . . . . . . . . . . . . . . Carvone, . . . . . . . . . . . . . . Pulegone. . . . . . . . . . . . . . Pulegone. . . . . . . . . . . . . . Camphor. . . . . . . . . . . . . . Camphor. . . . . . . . . . . . . . Camphor. . . . . . . . . . . . . . Camphor.. . . . . . . . . . . . . Thujone . . . . . . . . . . . . . . Thujone . . . . . . . . . . . . . . Menthone. . . . . . . . . . . . . Fenchone . . . . . . . . . . . . . Fenchone. . . . . . . . . . . . . Benzaldehyde. . . . . . . . . . Benzaldehyde. . . . . . . . . .
2.3508 2 ,3343 2.2819 1.9493 2.2852 2.3228 1.025 1.0626 2 ,0509 1.7177 2.2793 2.2903 2.1416 0.9026 1.1823 2.5447 2.5278
605.5 605.5 605.5 607.8 605.5 605.5
455.5 454.5 455.0 479.5 452.5 451.5
.....
..... .....
.....
..... 604.6 604.6
459.0 458.0
578.2 578.2 606.7 606.7
527.3 540.6 375 .O 376.0
.....
96.18 97.51 99.41 99.12 101,77 100.77 92.3 97.13 99.08 101.5 97.1 97.3 97.5 85.7 50.6 96.5 96.7
I/:,
1 1 '/P
'/n 1 '/?
1 2 2 3/2
1 1 2 1 '/2
1
In the case of spearmint oil the Walther method was tried in comparison with the estimation of the carvone by absorption in boiling sodium bisulphite solution as well as by the LabbC method. RESULTSON CARVONE; SPEARMINT OIL. Sample.
Labbe method.
Absorption b y Walther method. boiling NaHS03.
1
54.7
58.4 53.1
55 .o
2
61 . 3
65.5 66.4
67.5
61.43 60.7
61 5
3
A sample of tansy oil, assayed by the Walther method, gave thujone = 68.56 and 65.42 per cent. A sample of wormwood oil gave thujone = 33.15 per cent. and 31.24 per cent. Pennyroyal oil gave 81.87 per cent. ketone by this met.hod calculated as C,,EI,,O. A mixture of pulegone with a t least two other ketones is present in pennyroyal oil. A sample of rosemary oil gave 30.33 and 30.24 per cent. ketone calculated as camphor. The Walther method can not be recommended for the assay of any particular ketone-bearing oil until the influence on the reagent of other substances in the oil has been determined by working on known mixtures, and comparison, when that is possible, with other methods. This work will require time. For the present it seems that the assay of oils in which carvone, camphor, pulegone or thujone is the main constituent can be carried out with fair accuracy by this method, a t least affording a criterion of the purity of such oils. THE MANUFACTURE OF AMMONIA IN BY-PRODUCT COKE
OVENS. B y Louis CLEVELAND JONES Received March 9, 1911.
Nitrogen is to me the most intensely interesting element of all the eighty with which we chemists have t o deal. It is present in only small quantities within the solid earth's crust but in tremendous quantities in the atmosphere, enough if condensed upon the
589
earth's surface to submerge us all in a liquid layer only a little lighter than water and twenty feet deep. A sea of liquid nitrogen over all the surface of the earth gives you an idea of the abundance of this substance. Uncombined, nitrogen is the most inactive and harmless material tha can be imagined. It can be mixed in all proportions with oxygen and hydrogen and yet retain its passive characteristics. Combined, however, chemically with 2 . 5 parts of oxygen (another harmless even life-sustaining element) it forms fuming nitric acid which would consume the human body with almost explosive violence. Combined with three parts hydrogen it forms ammonia gas, a volatile alkali almost as dangerous a substance as its oxygenated cousin. I n other compounds it forms the most sensitive explosives, set off by the gentlest breath of air, or if we wish, explosives the most powerful and a t the same time the most useful. Man cannot live without nitrogen in his food, yet combined in a particular manner with carbon (another harmless substance) it becomes one of the deadliest poisons known. Combined, however, with carbon in another way but in the same proportion it is physiologically harmless. In yet another way nitrogen combined with hydrogen, oxygen and carbon produces all that wonderful galaxy of colors of which aniline and nitro compounds are the base. Uncombined, i t requires the subtlest means (nitrifying bacteria) or else the most strenuous (the electric arc) to bring it into chemical union, but when once combined with other elements it forms tKe most stable of chemical compounds. To illustrate the sources and uses of the particular nitrogen compound, ammonia, which we are discussing to-night, I have prepared two tables. Table I shows some general sources of ammonia; I1 indicates some of the principal forms in which it is obtained and their general uses. T A B L E 1 .-SOURCES OF .~YJIOXIA By-product coking of coal. By-product of producer gas manufacture. From distillation of peat. From distillation of shale. Blast-furnace gases. Distillation of bones and leather. Hz and osmium Synrhetically produced from Nz From nitrides of metals, titanium nitride. From calcium cyanamide and steam. Found in alkali lakes and maters from volcanic rocks Electric sparking of N? + H?. Sewage and urine.
+
In these two tables there is material for many days' discussion, but I propose t o speak only of the production of ammonia in by-product ovens. Production of Ammonia in B y - p r o d u c t Coking of Coal.-The yield of ammonia as sulphate in the actual coking operation varies from 18-28 lbs. per ton of dry coal. These look like rather small figures (about 5 lbs. NH,) to be obtained from 2 0 0 0 Ibs. of coal, but the total annual production from by-product coke ovens in the United States alone amounts to the immense total as sulphate of ammonia, to about 75,000 tons; or a t 2 5 tons to a car, 3,000 carloads, and a t 50 cars each would equal 160 train loads, or a solid trainload 2 2 miles long. The total production
