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
6j S ACTION
OF
SULFUR
MONOCHLORIDE
ON
G A S ENGINE
THE
PwsrcAL
OILS
I n testing several gas engine oils with sulfur monochloride, the procedure was adopted of adding I cc. of sulfur monochloride t o 5 cc. of t h e oil in a testtube, mixing thoroughly, allowing t o stand in the cold for 15 minutes, and then comparing the results with those obtained on an oil of known refinement. Several gas engine oils foundon the market were tested and i t was found t h a t t h e specially refined oils showed b u t a slight wine-colored tinge, whereas those not so carefully selected and refined changed t o a deep wine color in some cases, and almost black in others. I n t h e latter cases, t h e evolution of small bubbles of hydrochloric acid gas was clearly visible after half a n hour, and these were shown t o be such by testing with ammonia and comparing with a blank test. T h a t is t o say, t h e reaction in t h e case of the oils was found t o be evidently identical, as t o t h e evolution of hydrochloric acid gas, with the reaction in t h e case of t h e bituminous and t a r r y matter. It was also found t h a t the more rapid the development of color in the case of t h e oils, the more vigorous t h e evolution of hydrochloric acid gas. Finally, if t h e gas engine oils were arranged in order, beginning with those t h a t showed least color change in t h e same time interval, a n d proceeding t o those t h a t developed the darkest color, it was found t h a t this order was the same as t h a t in which t h e oils were placed b y Gill’s gumming test1 beginning with those showing least gum formation a n d proceeding t o those showing t h e most gum, or tar. Since hydrogen is removed from t h e hydrocarbon molecule b y t h e action of t h e sulfur monochloride and, since, as is well known, t h e removal of hydrogen (as water vapor or steam by t h e agencies of heat and atmospheric oxygen) constitutes a large p a r t of t h e process of carbonization of lubricating oils. i t would seem t h a t sulfur monochloride might be used t o measure t h e relative “sensitiveness” of the hydrogen in hydrocarbon oils, t h a t is t o say, as a measure of t h e relative stabilities of those oils. The matter is being further studied, in order t o show, if possible, whether the action of sulfur chloride on bituminous matter, t a r r y substances and paraffin oils, is due, as appears very likely, t o the presence of unsaturated hydrocarbons. SUMMARY
I-It has been shown t h a t sulfur chloride acts on bituminous matter, t a r r y substances and hydrocarbon oils, giving hydrochloric acid gas as one product of the reaction. 11-Sulfur monochloride, undiluted, is propose& as a reagent for testing the comparative stabilities of transparent lubricating oils. 111-Sulfur monochloride in carbon disulfide is proposed as a reagent for investigating t h e nature of bitumens and hydrocarbon oils. MASSACHUSETTS INSTITUTEOF TECHNOLOGY, BOSTON ~~
1
Gill, “Handbook of Oil Analysis.” 7th Ed., p. 43.
1701. 9, No. 7
TESTING OF PAPER AS AFFECTED BY HUMIDITY By Ross CAMPBELL Received April 23, 1917
-4s a result of reading t h e article on the “Influence of Humidity on t h e Physical Constants of Paper” by Kress a n d Silverstein, in THIS J O U R N A L , g (I917), 2 7 7 , it was decided t o contribute t h e d a t a on t h e same subject which was collected in this laboratory by E. J. Goldstein during t h e summer of 1916. APPARATUS
Unfortunately, we were not blessed with the excellent equipment described in the above-mentioned article. We had no method of temperature control and were forced t o control t h e humidity by regulating a Comins Sectional Humidifier head b y hand. The humidity was determined by means of a recording wet and dry bulb thermometer and a sling psychrometer. Even with this very crude control, it was found t h a t t h e relative humidity did not vary more t h a n two or three points, a t most, nor the temperature more t h a n I O . The tensile strengths of the specimens were determined by means of a hand-operated Schopper tensile-strength test machine. The test strips were 180 mm. long. Resistances t o folding were determined by means of a motor-driven Schopper folding machine. Times of penetration were determined by floating the samples on a n ink bath. PROCEDURE
About 8.00 A . M . t h e test room was closed and t h e humidifier started. The sheets of paper t o be tested had been Rung in t h e test room t h e night previous. It was found t h a t t h e humidity could be brought t o t h e desired point by 1.00P . M . and t h a t , owing t o t h e gradual increase of t h e humidity, t h e weight of t h e sheets t o be tested was constant a t about t h e same time. The testing was then begun. All t h e tests of a given kind, on a given sample were, of course, run on t h e same day. OBJECT OF TESTS
The object of t h e tests which form the subject of this article was t o determine how closely i t would be necessary t o control the humidity in order t o have physical tests comparable from day t o day. I n addition it was desired t o see whether the different grades, as fines, bonds, etc., varied in t h e same way. PAPERS TESTED
The papers tested were t h e company‘s regular commercial output. They varied, as is shown in the table, from high-grade, loft-dried bond and ledger, t o a relatively low-grade, machine-dried, fine. Samule A B C
D E
F G H
&L
KIND Bond Ledger Bond Bond Fine Bond Envelope Bond Blueprint Bond Blueprint
FOLIOWT. FURNISH (PERCENTAGES)THICKNESS in Lbs. per Rag Soda Sulfite In. 500 sheets 25 Few i5 0.00384 20 .. 15 0.00385 20 85 .. 10 0.00360 20 90 50 0,00320 20 so .. Trace 25 i5 0.00362 24 5 80 0,00338 20 15 Few 25 i5 0.00410 28 10 75 0.00405 20 15 50 0.00406 16 50 90 .. IO 0.00492 19 50 0,00509 24 50
..
..
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 C H E M I S T R Y
J u l y , 1917
RESULTS OF PHYSICAL TGSTIKG OF PAPERWITH VARYINGHUMIDITY Av. rel. Humidity A B C D E F G H J K L PENETRATION ( N E W STANDARD): SECS. ........................................... 54 61 99 316 862 686 387 722 1320 810 902 . . . . 438 64 S4i ' j i s ' 2 S i .i4i . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726 500 496 343 206 48 179 65 70 882 544 379 556 1326 846 996 403 89 367 733 402 269 446 1079 555 820 554 307 79 288 75 615 398 278 423 974 569 760 558 292 74 258 81 830 664 387 556 1362 826 1062 4.01 91 326 86 ............................................ 90 462 432 215 412 729 549 613 356 227 63 171 92 98
RESULTSOF
Av. Rel. Humidity 54 61 64 65 70 75 81 86 90 92 98
.... ....
............................................
54 61 64 65 70 75 81 86 90 92 98
MULLEN:LBS. 26.1 43.5 35.8 23.5 19.1 20.6 10.2 28.6 22.9 25.8
....
54 61 64 65 70 75 81 86 90 92 98
9 . 9 28.5 2 2 . 6 2 3 . 8 3 3 . 6
............................................
26.1 26.6 26.3 23.3 20.6
43.5 41.6 41.4 38.0 34.3
36.3 36.2 38.2 33.4 28.4
22.4 21.9 21.2 19.8 18.6
18.1 18.0 19.1 15.8 12.5
18.6 19.5 18.9 16.2 14.3
10.1 10.5 9.5 8.8 7.7
29.1 26.6 26.9 24.8 21.9
22.8 22.3 30.8 21.3 20.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18.6 1 8 . 1 2 i . 8 22.7 14.9 9 . 1 1 2 . 6 6 . 2 1 6 . 8 20.9
23.8 24.3 24.0 21.7 20.3
....
14.6
35.0 32.8 31.3 27.6
.... .._.
25.6
POLDING, CROSS,DOUBLEFOLDS 54 61 64 65
io
75 81 86 90 92 98
89
402
555
44
11
25
7
111
95
262
....
82 64 104 62 64
372 557 355 361 358
887 407 737 533 583
37 37 34 27 29
8 10 21 6 6
22 23 25 21 15
5 6 6 6 5 ,"3
134 67 76 68 49
Cs0 56 57
212 189 168 172 167
249 217 296 188
54
222
377
17
4
38
811
554
61
13
28
4
76
109 92 88 76 47
2124 2457 3580 4140
1028 1318 1430 1980
71 94 78 64
13 2i 11 12
33 39 29 32
5 6 6 5
147 211 163 155
46
9
35
4
142
"ii
.... 55
60
.... 62
.... 185 .., .
139 360
....
53 51 239
FOLDING MACHINE, DOUBLEFOLDS 54 61 64 65 70 75 81 86 90 92 98
54 61 64 65 70 75 81 86 90 92 98
.......................................... 114 460 620 42 13 23 6 84 71 193 342 ............................................
....................
I
....................
I
TESTING OF
P A P E R WITH VARYING
HUMIDITY
E F G H J TENSILE STRENGTH, CROSSK G . D
C
L
K
....
4.21 4.62 4 . 4 6 3 . 2 8 3.25 3.06 2.89 4 . 2 1 3.42 3.53
............................................ ............................................
4.02 4 . 2 3 4 . 6 6 2 . 9 6 3.14 2.99 2.69 4 . 0 0 3 . 2 6 3 . 5 7 4.73 3.83 3.80 3.71 3.22 2.65
4.09 4.03 3.83 3.67 2.46
4.03 4.32 3.69 3.83 2.59
2.85 2.90 2.61 2.43 1.74
2.86 2.76 2.58 2.33 1.84
2.63 2.55 2.45 2.39 1.78
2.57 2.35 2.45 2.25 1.58
3.59 3.62 3.31 3.29 2.37
2.89 2.96 2 78 2.61 1.93 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.12 1.86 2 . 1 9 2.67 1 . 9 3 1.78 1.54 1 . 6 6 1.72 2 . 6 0
3.05 3.20 2.97 2.93 2.02
148 586 676 207 483 329 171 534 451 292 542 . . . 156 . . . . 411 3:'9 279
....
6.70 8.69 7.78 5 . 7 8 6 . 2 7 6.09 4.03 7.35 6.14 6 . 5 4
....
1.99
............................................
6 . 9 1 8 . 6 5 7 . 9 4 5 . 8 8 6 . 1 2 5 . 6 2 3 . 8 1 7 . 3 9 5.97 6 . 2 8 7.78
............................................
6.06 6.40 5.76 5.58 4.13
7.80 7.86 z.70 i.28 5.34
7.25 7.25 6.76 6.53 4.81
5.37 5.14 5.13 4.61 3.32
5.89 5.64 4.66 5.10 3.67
5.34 5.17 4.69 4.63 3.41
3.49 3.31 3.17 3.04 2.19
6.38 6.52 6.38 5.98 4.82
5.38 5.59 6.72 5.07 4.05 ................................ 3.87 3 . 7 7 4 . 3 3 4.67 3 . 3 4 3 . 8 0 2 . 8 8 2 . 2 8 3.61 4 . 2 9
5.99 5.58 5.40 5.22 3.88
....
3.69
5.8 5.1 6.2 6.3 6.8
8.0 9.1 7.9 9.7 9 . 0 9.7 9 . 2 10.2 9.111.6
6.5 5.2 5.6 7.6 7.0
2.9 3.7 4.8 3.1 3.5
7.5
9 . 9 10.4
8.5
3.;
2.2
3.6
3.1
2.0
1.2
1.7
0.9
2.1
2.0
2.6 2.7 2.5 2.7 2.8
4.3 4.7 4.5 5.1 4.6
4.0 3.9 4.2 4.8 4.2
2.5 2.5 3.0 3.1 2.9
1.4 1.7 2.0 1.6 1.5
1.9 1.9 1.8 1.9 2.1
1.0 2.3 1.1 2.6 1.1 2.5 1.2 2.7 1.1 2.6
3.1
4.6
4.4
3.4
1 . 6 2.1
2.5 2.5 2.6 2.7 2.9 3.0 3.9
6
0
......................
4.8 5.1 5.6 6.4 5.8
3.2 3.1 3.8 3.6 3.3
5.4 6.1 6 . 0 5.9 6.6 6.3 6.8 6.7 6.1 6.8 .......... 7.0 6.5 4.0 7.0 9.2
.... ....
2.1
....
................................ 1.3
2.9
$
st D
u
G I
t .o
c D
4PI
I
J K
per Cu. ,FA
//
/2
9.3
2 . 8 2.8 2.7 3.0 2 . 6 3.0 3.0 3.5 3 . 3 .... .... 3.6 3.2 . . . .
L
10
8.0 8.4 8.4
............................................ 2 . 3 4 . 0 3 . 5 2 . 3 1 . 5 1.7 1 . 0 2 . 1 2 . 0 2 . 3 2.7 ............................................
83
9
7.8
8.1
....
Q
8 Grains Moisfure
._..
6.3 7.5 8.1 8.5 8.0
4
7
....
5.03
4.4 6.6 4.8 5 . 6 . . . . ............................................ 4.2 6.5 8 . 0 5.1 3 . 1 4.3 2.5 5.0 4.9 6.7 6.7 ............................................
%
6
7.32 6.74 6.55 6.28
STRETCH, CROSS,PER CENT 7.9 4.8 2.6 4.0 2.4 4.5
40
h
.... ....
3.34
I
I
4.69 4.34 4.21 3.89
....
STRETCH, MACHINE, PER CENT 54 61 64 65 70 75 81 86 90 92 98
............................................ 58 1260 7.54 77 15 24 5 75 195 388 292 .................................. 55 2090 899 72 9 31 5 161 ic,i ' i s < '4%
.... jjie i i i b
B
TENSILE STRENGTH, MACHINE, KG.
............................................
27.2 4 3 . 9 37.2 23.1 18.9 2 0 . 4
PHYSICAL
A
659
I
7
I
70,
I
80
I
?a
Per cent Relative Hum/dify
I
loo
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
660
IFOLRING-
1FOLDING-CROSS] 800
I
I
I
Vol. 9 , No. 7
I
MACHINE] 45001
xc
700
xc
600.
xc
I
xc
'50
'30
60 70 80 90 Per cen f Relafive Humid+
/00
I
I
70 80 9a per cent Re/u f i v e Humidify 6U
I
100
60
Per tenf Re/af i v e Hum id;+
70
80
90
I
/oo
July, 1917
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 C H E M I S T R Y RESULTS
T h e results obtained are given in t h e accompanying set of tables a n d plots. Before making t h e plots, two preliminary sets were made, one using relative and t h e other absolute humidities. It was found t h a t the results could be plotted against t h e relati1 e humidity only, except in the case of t h e penetration tests, where t h e results yielded a curve only when plotted against t h e absolute humidity. It will be noted t h a t t h e results here given agree with those obtained b y Kress a n d Silverstein in t h e case of t h e Mullen test plot only. These variations may have been due t o t h e higher grades of’ paper used in our tests, b u t this seems rather doubtful, as no such variations were observed over t h e range of qualities tested here. I t was found impossible t o draw a curve for “penetration” for sample “ H ” owing t o t h e wide variations noted between different tests a t t h e same humidity. I n t h e “folding-cross” tests no curve could be drawn for “C,” t h e points being as shown on t h e drawing. T h e “folding-machine” tests for B a n d C were so far beyond t h e range of t h e other samples t h a t their curves are presented on a different scale. SUMMARY
The magnitude of most of t h e tests decreased 40 t o j o per cent as t h e relative humidity increased from j o t o 98 per cent. T h e stretch in t h e machine direction increased about 30 per cent a n d in t h e cross direction about 40 t o j o per cent under t h e same circumstances. The results of t h e folding tests in t h e machine direction tended t o reach a maximum :it about 80 per cent relative humidity in all except two cases. I n t h e cases of samples “B” a n d “C,” t h e curve plotted from t h e results of this test increased 1;ery rapidly with t h e increase of relative humidity a r d tended t o become asymptotic t o about t h e g j per cent humidity line. T h e time of ink penetration decreased 4 0 t o 5 0 per cent as t h e absolute humidity increased from 6 grains per cubic foot of air ( j j per t e n t relative humidity at 8 0 ” F.) t o 11 grains per cubic foot (100 per cent relative humidity a t 80’ F.). Special attention is called t o curves “E;” a n d “K.” These samples wrre t h e same in every way except t h a t ‘(B” was t u b sized a n d “K” was not. The advantages of a good t u b size are very clearly shown. RESEARCH L A B O R A T O R Y , AMERICAN KRITKNG PAPERCOMPANY HOLYOPE,
MASSACHUSETTS
THE OCCURRENCE OF GERMANIUM IN MISSOURl AND WISCONSIN BLENDES’ By G . H. BUCHANAN
Of t h e fifty or more elements which we usually distinguish as rare, few are more worthy of t h e distinction t h a n t h e element germanium. Discovered in 1886 by Winkler in a new silver mineral, argyrodite, a n d identified by him as t h e eka-silicon of Mendelbef, i t has dropped back into oblivion since t h e days of 1 Presented a t the .Symposium on the Chemistry and Metallurgy of Z i n c , 54th Meeting American Chemical Society, Kansas City, April 10 t o 14, 1917.
661
this classic work, until to-day it is one of our least known elements. With b u t few exceptions our entire knowledge of t h e properties of t h e element is due t o Winkler. According t o Urbain,‘ t h e material worked over by R’inkler for t h e preparation of germanium was a mixture of argyrodite with other minerals, and did not contain more t h a n 0 . 3 6 per cent of argyrodite. Since t h e germanium content of argyrodite is 6 t o 7 per cent, t h e germanium content of his raw material could only have been between 0 . 0 2 a n d 0 . 0 3 per cent. From this material Winkler obtained 8 0 kilos of mixed metallic sulfides which yielded I j 6 g. pure germanium. Argyrodite, t h e richest source of t h e element heretofore known, has proved exceedingly rare, a n d during t h e thirty years t h a t have elapsed since t h e work of Winkler only a very few additional sources of t h e element have been brought t o light. Kriiss has reported t h e presence of 0 .I per cent germanium in euxenite. I t s occurrence in samarskite, tantalite a n d niobite has been reported a n d denied, a disagreement which is not surprising in view of t h e complexity of these minerals. Two other sources have been more recently discussed. Urbain2 by spectroscopic methods detected germanium in 38 out of 64 blendes from various localities. Taking jjo kilos of one of these, a Mexican blende, he obtained from i t j g. pure germanium. Bardet,3 also by spectroscopic methods, detected traces of germanium in certain French mineral waters. Since t h e recovery of germanium from blendes by t h e method of Urbain was long and costly, he believed t h a t t h e residues from these mineral waters might yield sufficient germanium t o provide for t h e needs of scientific study. From IOO kilos of residues, representing zjojooo liters of mineral water, he obtained 60 mg. GeOn. A more recent report of t h e occurrence of germanium is due t o W. F. Hillebrand and J . -4. S ~ h e r r e r :in ~ a paper on “ T h e Recovery of Gallium from Speltcr in t h e United States,” mention is made of a n examination for germanium of a number of blenldes, carried on a t t h e Bureau of Standards by Dr. K. Burns. By t h e use of t h e spectroscope germanium mas identified in several of these, notably in a Missouri sulfide. A short paper by t h e writer was published in THIS J O U R N A L in July, 1916, p. j S j , relating t o t h e identification of germanium in zinc-bearing materials. At t h a t time i t mas not possible t o give details as t o t h e origin of t h e rich germanium-bearing material. I t is t h e purpose of t h e present paper to discuss t h e nature of this material, which now appears t o be t h e richest source of the element known During t h e summer of 191j there was brought t o t h e writer’s attention a n oxide of zinc which had been prepared from spelter residues by the American process. A chemical examination revealed the presence of considerable quantities of a n unusual constituent, which was identified as t h e element germanium. The identification tests consisted in a distillation of 1 1
a 4
Comfit. rend., 150, 1758. I b i d . , 149, 602. I b i d . . 158, 1278. THISJOURNAL, 8 (1916). 2 2 5 .
