586
.
THE JOURiZ‘AL OF I X D U S T R I A L A N D ENGINEERING CHELMISTRk’.
agriculturist in the quality of the material in the more concentrated commercial fertilizers such as those used in this experiment. I n the following respects the best comparison of the different materials is afforded by the growth of the last crop, namely: the soil itself had become more depleted of its nitrogen; the cumulative effects of three applications of nitrogen were exerted; there was scarcely any evidence that the phosphorus associated with the nitrogenous materials exerted any influence; and the grain was allowed to ripen. On the basis of the last crop, only five of the twelve fertilizers (Nos. I , z , 6, 8 and 9) yielded in each of the two respective pots, less total crop and grain than was produced in either of the pots in which blood was applied. Although the insoluble nitrogen in fertilizers I and 2 , particularly, was less available than the nitrogen in blood, there is reason for the belief that it was largely from bone and meat tankage instead of from such low-grade material as garbage tankage, peat, and leather. The directors of certain northeastern stations announced in March, 1910,their intention t o have the fertilizers collected in 1911 for inspection, examined b y some uniform laboratory method as to the availability of their organic nitrogen ; and they appointed a committee of station chemists t o recommend a method. I t was very opportune that the vegetation results under discussion had already been secured on the insoluble organic nitrogen of certain fertilizers, and that some of the identical material was on hand. This material was submitted, without any information concerning the crop results, t o Mr. C. H. Jones, of the Vermont Agricultural Experiment Station, for the determination of availability b y the alkaline permanganate method. The agreement was very satisfactory, but it was considered unfortunate that probably none of these particular fertilizers were made up of low-grade materials. Subsequently, however, a few decidedly low-grade fertilizers were likewise compared, with gratifying results ; the vegetation tests are not fully completed and will not be published a t this time. The alkaline permanganate method was the one adopted March 4, 1911,b y the agricultural experiment stations of New York, New Jersey and the New England States for “examining the activity of the organic forms of nitrogen,” and a circular was printed which includes the details of the method. I n the last column of the accompanying table we have included the results secured by Mr. Jones with the method as adopted. The agreement is quite good even without full recognition of the fact that the limit of error in vegetation experiments must be placed rather wide. Even the hird crop (oats) equaled 49 grams on the check pots, although the pots to which blood was added yielded j5 grams more; this is taken to represent a range in availability from o to 8 0 ; it is evident, therefore, that even a variation of 3 . 4 grams in the weight of the crop from two parallel pots represents a difference of j in availability.
Aug., 1911
With two kinds of crops even on the same soil, the degree of availability will vary considerably, and on different soils the variation may be expected t o be still greater. It is probable, for example, that an experiment with rye on an acid soil, in which the predominating microflora is composed of fungi a n d yeasts, would result in quite a different availability from one with barley on a neutral or alkaline soil in which bacterial growth is the more prominent. Two nitrogenous materials might exhibit very different relative availability, depending upon which of the above-mentioned conditions existed. An availability test even with a single kind of plant and soil may comprise the following: one manuring and one planting; one manuring, and more than one planting; or more than one manuring and as many plantings. I t should be understood, therefore, that a difference of a t least ten per cent. in the availability as determined by pot experiments is not of much significance, especially when no standard conditions have been adopted for carrying on vegetation tests. The degree of availability of a substance, whether determined by vegetation or chemical tests, should be considered only as a n approximation which is useful in distinguishing between materials of quite different qualities.
----_-
T H E NATURE OF SOME COAL DUSTS AND MINE AIR FROM COLORADO MINES. B y JOHN B . EKELEY. Received M a y 2 , 1911
I n November, 1910, Governor John F. Shafroth appointed a commission, consisting of Victor C. Alderson, president of the State School of Mines; James Dalrymple, state coal mine inspector; R. D. George, state geologist and professor of geology a t the University of Colorado; and John B. Ekeley, professor of chemistry a t the University of Colorado, t o inquire into the condition of the coal mines of Colorado, and the causes of the many accidents in those mines, and to suggest remedial legislation for the consideration of the Eighteenth General Assembly of the State. The following tables give the analyses of samples of coal dusts and of mine air taken during the investigation trip made by the Coal Mine Commission. The coal dust samples were passed through 20-, 100-,and zoo-mesh sieves, and the fractions analyzed. I n the fractions passing through the 200-mesh sieve, the analyses show a slight error, because the very fine dust undoubtedly lost some moisture during the screening operation. However, the results for this fine dust are very interesting, because they show that in all cases the composition was approximately the same as in the coarser portions. The analyses show that the non-carbonaceous part of the dust was of about the same state of division as the coal dust itself. The air samples were collected b y allowing water t o run out from completely filled glass bulbs, which were then closed air-tight. This is the method used by Mr. Chamberlin, of the United States Geological Survey. The small amount of water remaining on
T H E JOITRi'L'AL OF INDUSTRIAL A N D EA-GINEERING C H E M I S T R >-.
Aug., 1911
the inner walls of the bulbs absorbs carbon dioxide so t h a t the amounts of carbon dioxide shown in the analyses are a fraction of a per cent. too low. The striking fact shown by the analyses is the presence, in most cases, of a small amount of methane, even in samples where none was expected. Since it is known t h a t a small amount of methane may act as a primer in an explosion of coal dust, these facts are significant.
ANALYSES OF COAL DCST (Confznued). No.
Summit mine.
1
2
3
Standard mine. hiain north entry, 250 f t . from hoisting shaft. Road d u s t . Same as No. timbers.
1.
Mesh 2o
loo 1200
Dust from
Fifth northwest room 8. 25 f t . from working face. 20
4
Fifth southwest.
5
Intersection of main south a n d first southwest entries. Road dust.
6
No.
7
7. parting Road dust.
main
i
20 100 200
south.
'
Main south a t intersection of 20 100 third east. Dust from timbers and ribs. 1200
9 10
11 12
13
20
Dust from main slope 600 it. in. from timbers and ribs. Main slope between second and third entries. Road dust. Rope parting in main slope between 4 t h a n d 6th south. Road dust.
i
20 100 200
7th south, 500 ft. from main slope. Trolley. Double parting between 7th a n d 8 t h cross-cut of 7th south. Road dust. Trolley. Dust from timbers and ribs be.tween 1st and 2nd cross-cut in 7th south.
Fine dust from ribs 3rd north e n t r y , not dislodged b y explosion. Primero mines.
15
1st east mine. Dust from ribs, 700 ft. from entrance.
16
1st north mine. in A-12.
Dust from ribs
i::: i ;:: 20
21
22
Main entry, 300 f t . in. from ribs.
23
Main entry, opposite 8th B , upraise. Ribs.
Main slope 500 f t . in.
9.7 8.5 8.0
27.7 34.0 40.6 43.4 43.5 44.7
15.8 12.4 10.1
24.6 22.2 22.3
27.2 21.9 26.8
22.4 34.5 40.8
25
16.9 14.8 14.3
26.1 26.7 27.0
44.3 43.5 42.4
12.7 15.0 16.3
Dust from road in 5 t h south. Same place as No. 24.
26
13.8 10.5 9.1
24.0 25.3 25.1
35.9 31.2 29.5
26.3 33.0 36.3
Dust from timbers, main south entry, 1,500 f t . from shaft.
16.8 13.7 12.7
23.8 22.1 24.5
37.5 22.0 28.0
21.9 31.2 34.8
11.9 11.1 8.9
22.1 20.2 22.8
20.1 21.5 29.1
35.9 37.1 39.2
25.7
48.7 49.2 51.5
20.6 20.7 21.5
2.4 1.7 1.4
27.8 28.3 26.3
46.2 46.4 48.4
23.6 23.6 23.9
2.1 1.6 1.3
23.8 24.4 23.6
34.9 36.8 39.9
39.2 36.2 35.2
1.8 1.8 1.4
17.9 18.9 19.0
30.6 31.8 33.2
49.7 47.5 46.4
1.9 1.8 1.6 2.2 1.8 0.8
9.6 12.8 13.0
16.0 19.9 22.2 32.8 33.9 34.4
72.5 65.5 63.2 43.3 43.2 42.8
1.8 1.5 1.3
28.9 28.6
21.7 21.1 22.0
21.0 20.0 22.1
39.9 40.3 39.2
36.7 37.4 37.6
20
1.0 1.0 0.5
24.4 24.8 25.3
47.9 46.4 47.2
26.7 26.2 26.1
20
2.4 1.7 0.6
20.5 18.1 21.7
48.0 54.6 42.1
24.7 25.6 26.6
3.3 3.8 1.8 5.3 5.2 2.3
25.0 23.1 28.2 25.4 22.9 27.9
33.2 36.3 33.2 36.2 38.5 34.7
38.5 36.8 36.8 33.1 33.4 35.1
9.0 8.6 5.6
39.1 33.5 34.9
33.0 38.5 30.2
18.9 19.4 19.3
Roof and
ribs. 18
200 20
8 t h north off main entry.
Ribs.
Danville mine. 19
Main slope 600 ft. from entrance.
Ribs.
Dust
33.3 30.1 28.5 25.1 27.2 26.0
2.4 2.3 1.1
18.0 16.8
21.0 21.0
54.1 54.3
6.9 7.9
7.8 6.4
26.8 24.3
49.3 49.4
16.1 29.9
Coarse. quite damp stuff from ribs.
Rockvale mine.
..
..
20
6.2 6.0 3.5
20
{ ;:: c 100 20
{
Dust from ribs of 5th south.
24
..
..
25.9 27.9 33.0
49.1 47.0 43.7
19.8 19.1 20.8
11.5 6.4 1.6
25.8 33.6 32.9
54.2 49.5 43.6
9.5 11.5 12.9
15.4 12.2 3.1
10.2 12.8 17 9
20.9 19.6 11.6
53.5 56.4 57.4
9.8 9.2 5.0
13.4 13.8 17.3
7.2 5.7 2.9
19.7 21.2 26.1
19.1 21.7 19.0 39.6 39.0 34.9
49.7 55.3 58.7 33.5 34.1 36.1
' Iio": 200 2o
{
ANALYSES OF hIINE-AIR SPLZIPLES. CO?.
Standard mine.
Fifth northeast, Main intake' north side. . . . . . . . . . . . . . . . . . . 0 . 2 5 Fifth northwest, room 8 . . . . . . . . . . . . Fifth southwest, 30 min. after shot 0 . 6 1 Ninth southwest, 100 f t . from main e n t r y . . . . . . . . . . . . . . . . . . . . . . Main south, 7 t h double parting . . . . .
9 10
Hastings mine. Main slope, 300 f t . from m o u t h . . 7th south double parting.. . . . . . . . . . . 1st dip off 7th south, shot night before. . . . . . . . . . . . . . . . . 7th south a t 7th crossing.. . . . . . . . . . Face of 7th south, pillar w o r k . . . . . . . . .
11 12
Primero 1 s t east mine. Room 8, B-9, west.. . . . . . . . . . . . Intersection B-9 east and main-air
6 7 8
....
................. 13
,000 f t . from fan
..
0.4 0.7
Primero 1 s t north mine. 14 Room 3 , first blind -4-12.. . . . . . . . . . . . 0.1 15 Room6.A-11. . . e 16 Main air course, -4-7, overcast.. . . . . . . . . . . . . . . . . . . Cokedale mine. 17 Room 10, 2nd B west, pillars 18 Face of 5 t h west C . . ......... 19 Main return under 4 t h south undercast.. . . . . . . . . . . . . . . . . . . . . . . . 20 21 22 23
Pictou mine. Face of room 5, 4 t h cross off 8 t h south. .......................... Bottom of slope, face. . . . . . . . . . . . . . . ...... Face of 10th n o r t h . . . . Back entry, interme air course, 7th s o u t h . . . . . . . . . . . . . . . . .
0.
N.
CHI.
17.4 20.8 19.7
82.35 79.2 79.69
.... ....
20.5 20.0
79.04 80.0
0.46
19.7 20.4
80.3 78.5
20.4 20.4 20.4
79.6 79.6 79.6
20.6
79.4
....
20.6 19.9
79.0 79.4
....
20.6 20.5
79.2 79.4
0.2
20.2
79.8
. . .a.
20.0 19.8
79.3 79.4
0.7 0.8
20.0
79.6
0.4
19.7 20.5 19.7
80.3 78.4 79.9
1.1 0.4
19.4
78.8
1.8
.... ....
.... 1.1
....
.... ....
....
....
....
Danville mine. Face of main slope.. . . . Main slope just above 7 above fire.. . . . . . . . . . . . . . . . . . 0 . 3
18.5
81.1
0.4
20.5
79.2
....
26 27 28
Summit mine. hlain return, 100 f t . from s Room 11 off 7 t h southwest Face of 7th southwest.. . . .
19.9 20.1 20.0
80.1 78.9 79.7
0.8 0.2
29 30 31 32 33
Somerset mine. Room 40, 6 t h west.. . . . . . . . . . . . . . . . Room 2, 9 t h west.. . . . . . . . . . . . . . . . . Main entry, 9 t h w e s t . . . . . . . . . . . 0 , l Face of main slope.. . . . . . . . . . . . . . . . Main return, 75 f t . from f a n . . ... 0 . 2
20.5 20.2 20.4 20.1 20.6
78.1 78.8 79.5 78.7 78.8
24 25
Pictou mine. 17
i
100 ZOO
Somerset mine.
25.8 24.4 23.9 21.8 20.8 21.3
Delagua mine. 14
4
B u g dust, 8 t h southwest.
Hastings mine.
8
Xois- T'olatile Fixed ture. matter. carbon. Ash.
Vulcan mine.
Vois- Volatile Fixed ture. matter. carbon. Ash, 13.2 11.5 8.0
Mesh.
(' 20
20
AUALYSESOF COAL DUST. No
587
.........
....
1.4 1 .o
....
1.2 0.4
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.
