T H E J O U R N A L OF I . V D U S T R I A L A N D Eil;GINEERILIZ’GC H E M I S T R I ’ .
812
temperature 8, of the asbestos grate, 8 of the heating gases, and 01, = 2 1 2 , the temperature of the vessel. H , A and T have the usual significance.
H
H
/*=AT(O-O,,) -___-
’’
e
AT(8-8,,)
$1
H
=
(O1-8,,)
AT(%--81)
Hence,
P’ -
Plate.
Thickness.
A, , . . . . . A,. . ... A , . .. . . .
A.. . . . . . A ,.,....
.,. . . . B... . . . , R .. . . . .. B . ,. , . . . c . .. . . . . n . .. . . . , E. . . . . , . E . . ... . . €3
,
1 3/41! Q/,
fINERAL
FlaskNo . . . . . . 5 Heat N o . . . . . . 1 Evaporation, percent . . . . . 4 7 . 1 “Varnish.” per cent . . . . . . . . 0 . 1 6 Insoluble, per cent . . . . . . . . 2 . 2 2 Total residue, per cent ... . . 2 . 3 8
12 3 49.2
2 6 35.1
40.0
9 8l
32.9
8 10
11
12
2 13
51.0
60.2
38.4
Avs.
..
0.27
0.20 0.46
0.35
..
0.25 0.27
2.15
1.96
1.83
2.34
2.72
2.51
2.25 2.25
2.37
2.23
2.03
2.80 3.07
..
2.53 2.52
Il 3
OIL CONTAINING ROSINOIL,
5
7
81
65.5
41.7
IO
12
14
36.7
34.4
53.5
Evaporation,
per cent. . . . . 4 4 . 1
.
0.19
S O . 4.--XIINERAL
Flask No,,,,,. Ilent NO. . . . . . . 1
OIL CONTAINIWC ROSIN
7 5
47.2
56.1
AX.^.
.,
per
.. . . .. .
0.40
0.20
0.18
..
0.07 0 . 2 1
cent . . . . . . . . 1 . 8 4 2 . 0 2 2 . 1 0 2 . 5 9 Total resid::e. per cent ... . . 2 . 1 8 2 . 1 8 2 . 2 4 2 . 9 9
1.79
1.90
1.76
1 . 1 9 1.90
1.99
2.08
..
1.26 2.11
cent
lnso‘ub’e,
1
per
0.34
0.16
0.14
In hent No. 8 there was some difficultv in regulating the temperature
T H E JOUR,\’AL
814 NO.
s.-XfINERAL
OF I N D U S T R I A L -4-VD ElZ‘GI,”V’EERIiYG C H E M I S T R Y .
OIL CONTAINING RAPESEEDOIL.
F l a s k s o...... 5 12 2 9 8 11 2 ... 2 3 5 7 9 10 12 14 Avs. H e a t KO... Evaporation, per cent . . . . . 3 6 . 4 5 0 . 1 4 8 . 6 4 4 . 6 34 4 4 3 . 2 45 1 26.8 .. “Varnish.” per 0.67 1 .37 c e n t . . . . . . . . 1.39 1 . 3 5 1.45 1 . 3 6 1 . 5 5 1 . 8 5 . . Insoliible, per 0.01 0 . 0 1 0 . 0 2 0 . 0 1 0.02 0 . 0 1 0.01 0.02 0.01 per cent...
..
1.40
1.36
1.47
1.37
1.57
1.86
..
0.69 1.38
The reason for the apparently low percentage of 4‘insoluble” and the high percentage of “varnish” is that the flocculent precipitate a t first thrown out of the heated oil by the petroleum ether collected, on standing, in small, hard lumps on the bottom of the flask and could not be washed out. No. 6 , containing lard oil, showed a tendency in the same direction, but the residue was easily dislodged by a strong stream of petroleum ether from a wash-bottle. NO. 6.-MINERAL . . 6 H e a t No . . . . . . 2 Evaporation, per cent... . . 4 2 . 0 “Varnish,” per
...
Insoluble. per cent. . . . . . . . Total residue. per cent . . . . .
1 4
51.6
OIL CONTAININGLARDOIL. 8 5
3 7
52.2
49.2
10 9
1 11
43.6
49.0
1
2 12
3 14
45.2
33.9
Avs.
..
0.08 .0.03
0.04
0.06
0.24
0.02
..
0.18 0.09
0.31
0.31
0.33
0.61
0.46
0.32
0.55
0.28 0.40
0.39
0.34
0.37
0.67
0.70
0.34
...
0.46 0.49
h’0. 7.-h?,INERAL
OIL CONTAINING TALLOW.
Flask h‘o . . . . . . 7 2 9 4 11 2 5 4 H e a t No.. . . . . 2 4 . 6 7 9 11 13 14 Avs. Evaporation. p e r c e n t . . . . . 4 5 . 5 38.1 4 7 . 9 4 6 . 6 41.9 4 6 . 8 4 0 . 2 3 5 . 6 .. “Varnish,” per per c e n t , . , 0 . 1 0 0 . 0 6 0.07 0 05 0 . 1 2 0 . 1 3 0 . 0 9 0 . 2 9 0 . 1 1 Insoluble, per cent.. . . . . . 1 . 3 5 1.27 1 38 1 47 1 43 1 49 1 . 2 5 1 31 1.37 Total residue, percent 1 45 1 33 1 45 1 52 1 55 1 62 1 34 1 60 1 48
The percentages of “insoluble” here given are not corrected for the amount ( 0 . 2 0 per cent.) thrown out by petroleum ether before the oil was heated. A second sample of engine oil, purporting to be the same as S o . I , was obtained, since no more of the latter was available, and it seemed advisable to make some determinations on several mixtures not thought of a t first. The descriptions of these new mixtures follow: No.8. New sample of mineral oil. No. 9. Mineral oil, to every I O grams of which was added 0 . 2 j gram of Syrian asphalt dissolved in 2 5 cc. of xylene. The solution was always added after the oil was weighed, and the solvent driven off by heating of the stcam-bath, a t the same time blowing a gentle current of air into the flask. Before heating t o 2 5 0 ° , petroleum ether threw out 1.35 per cent. of insoluble. No. IO. Mineral oil, to every I O grams of which 0.01 gram of sulphur dissolved in I cc. of xylene was added. In this case the solvent was not driven off before heating. No. 1 1 . A I O per cent. solution of 5 5 ” paraffin in mineral oil. This could be poured about as well as a heavy cylinder oil. No.12. A I O per cent. solution of linseed oil in mineral oil.
Nov., 191 I
No. 13. Mineral oil and soap. To every I O grams of the oil there was added before heating 0.50 gram of finely powdered “ivory” soap, dried a t 100-105~. No. 14. Mineral oil oxidized by the combined action of air and sunlight, as described in an earlier paper.1 The oil was placed in a crystallizing dish, in a layer about 1.5 cm. deep, covered with a second dish and exposed outside a southern window from February zIst until March ~ 3 r d . Every day or two the oil was thoroughly stirred.
NO. r j . A mixture of the mineral oil with “Kahlbaum” ferric oxide. In each I O grams of the mixture there was 0.086 gram of the oxide. No. 16. Mineral oil oxidized in flasks, but atherwise like No. 14. The oxidation was carried out in this way in order to determine the gain in weight. The average for four flasks, all of which gained nearly the same amount, was 0.92 per cent. This figure represents absorbed oxygen minus carbon dioxide and a little water. The contents of the four flasks were mixed before determining the carbonization. Nearly all of the insoluble oxidation product remained on the walls of the flasks, The results obtained on heating these oils under the same conditions as for oil I t o 8 are here given. NO.
8.-sECOND
Flask 12‘0. ...... Heat S o . . . . . . . . . . . . . . . . . . Evaporation. per c e n t . . . . . . “Varnish,” per c e n t . . . . . . . . Insoluble, per c e n t . , . . . . . . . Total residue, per c e n t . . . . . .
SAZIPLE OF
MINERAL OIL.
5 9 7 lnew11 1 1 2 4 8 9 12 4 1 . 1 3 4 . 6 4 3 . 6 6 0 . 1 4 9 . 1 44..0 0 . 2 2 0 . 6 6 0 . 1 6 0 . 4 9 0 . 3 1 0.37 2.08 2.73 1.98 3.18 2.50 2.58 2.30 3 . 3 9 2 . 1 4 3 . 6 7 2 . 8 1 2 . 9 5
NO. g.-?vfINERAL OIL CONTAINING
-4~s.
..
0.35 2.51 2.86
ASPHALT.
.....
5 6 8 9 5 2 4 ..... 1 4 9 10 12 .4vs. , . . , . 46.1 31.0 38.3 37.9 30.6 34.4 . . “Varnish,” p e r c e n t . . . . . . . 0 . 3 1 0 . 2 9 0 . 2 1 0 . 2 2 0 . 3 5 0 . 3 6 0 . 2 9 Insoluble, per cent. . . . . . . . . 4 . 9 5 4 S 5 4.40 4 . 5 5 4 . 6 6 4 . 8 4 4 . 6 6 Total residue, per c e n t . , , . . , 5.26’ 4 . 8 4 4 . 6 1 4 . 7 7 5 . 0 1 5 . 2 0 4 . 9 5
The percentages of insoluble here given are not corrected for the amount thrown out of the oil when petroleum ether is added before heating. As mentioned above, this was 1.35 per cent. The percentages given are figured on the basis of I O grams of oil. No. ~ ~ . - - U I N E R A L OIL COSTAINIXGSULPHUR
Flask No . . . . . . . . . . . . . . . . . . 7
Heat S o . . . . . . . . . . . . . . . . . . . E\-aporation. per c e n t . , . . . . “Varnish.” per c e n t , . . . . . . . Insoluble. per c e n t . . . . . . . . . Total residue. per c e n t . , , , . .
1 36.4 0.37 2.81 3,18
NO. I I.-MINERAL
~
6 12 10 4 5 9 65.2 36.0 3 3 . 4 0.54 0.56 0.27 3.34 2.57 1.89 3.88 3.13 2,16 I
6 3 10 12 37.0 34.7 0.19 0.29 2 . 1 4 2.39 2 . 3 3 2.68
OIL CONTAINING
I.INSEED
1 2 6 8 ................... 3 3 7 10 , . 50.5 3 3 . 0 4 8 . 6 3 6 . 0 “Varnish.” per cent. . . , . 6.10 5.29 6 . 3 1 6 . 7 2 . . 0 . 0 2 0 . 0 3 0 . 0 1 0.01 Insoluble, per c e n t . . . . Total residue, per c e n t . , . . . . . . . . . . . 6 . 1 2 5 . 3 2 6 . 3 2 6 . 7 3
Bull. Bur. Standards. 7, 227 (1911);
1 11 39.0 0.41 3.23 3.63
Xvs.
..
0.30 2.70 3 .OO
OIL,
Flask No ........................
1
.. 0.37 2.52 2.89
CONTAINING L PARAFFIN.
Flask KO........................ 8 4 5 7 , . , , , . . , , , , . , 1 3 7 10 Heat N o . . . . . t . , . . . . . . . . . 39.9 42.0 40.8 39.0 Evaporation, “Tlarnish,”percent. . . . . . . . . . . . . . - 0 . 3 7 0 . 1 5 0 . 1 5 0 . 4 0 Insoluble, per cent. . . . . . . . . . . . . . 2 . 5 9 2 . 3 9 2 . 3 3 2 . 9 5 Total residue, per cent., . . . . . . . . . . 2 . 9 6 2 . 5 4 2 . 4 8 3 . 3 5 NO. 12.-MINERAL
Avs.
T H I S JOURNAL.
2 11 48.1 7r09 0.01 7.10
Avs.
..
6.30 0.02 6.32
2, 451 (1910)
T H E JOiYRAV-4L OF I-\\-DCSTRIAL . 4 S D E - Y G I - Y E E R I S G C H E X I S T R Y .
n’ov., 1911
The petroleum ether threw out a thick, tarry deposit t h a t adhered t o the bottom of the flask. This was necessarily counted in with the true “varnish.” NO. 13.->IINERAL
OIL COXTAINING S O A P . ,
The contents of the flasks formed, after heating, a nearly solid cake, which could be broken up only with difficulty with petroleum ether. The residue was so fine-grained and gummy that it could not be filtered off. N O . 14.-!VfIKERAL
OIL
OXIDIZED IN
Flask No ......................... H e a t KO., ...................... Evaporation, per cent. ........ “Varnish,” per cent. . . . . . . . . . Insoluble, per cent. . . . . . . . . . . . . . . Total residue, per cent ........
No.
9 5 47.7 0.34 5,69 6 03
CRYSTALLIZING
DISHES
10 7 4 3 5 7 8 11 Avs. 44.6 42.1 51.6 44.9 .. 0 . 3 0 0 31 0 . 1 6 0 . 2 6 0 . 2 8 6.06 5 . 6 4 5.87 6.76 6.00 6 . 3 6 5 . 9 5 6 . 0 3 7.03 6 . 2 8
MINERAL OIL CONTAINING FERRIC .OXIDE.
Flask N o . . . . . . . . .
.......
3 11 2 3 4 3 5 8 8 11 Avs. . . . . . . . 35.5 51.5 5 7 . 1 42.4 4 4 . 3 . . . . . . . . . 1.11 0 . 5 7 1 . 5 9 0 . 6 0 1 . 2 3 1 . 0 2 rFe2OI) 7 . 3 0 4 . 9 1 6 . 5 8 5 . 0 5 8 . 6 6 6 . 5 0 Total residue, per cent. . . . . . . . . . . . 8 . 4 1 5.49 8 . 1 7 5 65 9 . 8 9 7 . 5 2
.......
The insoluble was corrected for ferric oxide by washing out the Gooch crucible with benzene. With one exception, the weight of the residue was about 2 mg., or 0 . 0 2 per cent., greater than the amount of ferric oxide known to be in I O grams of the unheated oil-ferric oxide mixture. Hence the percentages of insoluble given above are somewhat too low. The exact amount of the discrepancy must be greater than 0 . 0 2 per cent., however, for a small part of the oxide remained in the ring of “varnish” adhering t o the walls of the flasks. There wer?, besides, traces t h a t could not be removed from the bottoms of the flasks even ‘with the most careful washing with petroleum ether. NO. 16.-lfINERAL
OIL
OXIDIZED I N
Flask h-o., ..................... ....... H e a t h-0.. . . . . . . . . . . . . . . . . . . . . . ....... Evaporation, per cent. . . . . . . . . . . . . . . . . . . . . . . . “Varnish,” iler cent. . . . . ............... Insoluble, per cent. . . . . . . . . . . . . . . . . . . . . . . . . . . Total residue, per c e n t . . . . . . . . . . . . . . . . . . . . . . . .
FLASKS
8 . 12 4 7 9 12 Avs. 4 2 . 9 4 0 . 8 56 . O .. 0.44 0.18 0.31 0.31 7.30 6.12 7.65 7.02 7 . i 4 6 . 3 0 7 .96 7 . 3 3
I n order t o determine whether or not any “varnish” or insoluble is formed in the absence of air, Io-gram samples of each of the oils numbered 5 , 6 , 7 and 8 were heated in flasks with the mouths covered with ground glass plates. They were heated t o 2 5 0 ’ for 5 hours. I n no case was there any “varnish” formed on the walls, and only traces of insoluble were thrown out by petroleum ether. The “loss by evaporation” represents largely the oil which condensed on the glass .plates and dripped off or was wiped off the necks of the flasks before they were weighed. Sample... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Evaporation. per c e n t , . . . . . . . . . . . . . . . . . . . . . . . DISCUSSION
5 3 56
6
5.42
7 8 4 . h4 5 30
O F RESULTS
In considering the percentages of insoluble obtained on heating any given sample of oil, it is evident that there are causes of variation that may or may not be capable of elimination. A frequent source of annoyance was the sudden changes in the temperature
81.5
of the air-bath. I n all of this work two thermometers, which gave almost identical readings when heated side by side in an oil-bath, were used on opposite sides of the air-bath with their bulbs on a level with the oil in the flasks. They were only 8 cm. apart, yet would often differ 10’ in their readings. Frequently they would be not more than a degree apart for a n hour or more, and then one or both would show a change in temperature; or first one and then the other would show a higher reading. The copper bath, with a double bottom and sheathed on the sides with a double layer of asbestos with a 3 mm. air-space between, was heated by a burner with a “rose” top giving a uniformly spreading flame. The flasks were only about one centimeter apart a t their widest part and the thermometer bulbs were between opposite pairs of flasks. I t seemed, therefore, as if the reactions of cracking and oxidation, which are endothermic(and exothermic respectively, might have something to do with the sudden variations. I t is also possible that air currents might have caused more or less of the products of combustion from the burner, and hence varying amounts of oxygen, t o encircle the necks of the flasks on one side of the bath and thus lower or raise the amounts of insoluble formed. I t is hoped t o eliminate this possible source of variation and also the irregular heating by means of a n electrically heated bath now being made. The results given in the present paper show, as did those published before, that there is no apparent connection between the amounts of insoluble, evaporation and “varnish.” As to catalytic action, influencing the amount of insoluble, which was hinted a t in the earlier paper, a tabulation of the present results fails to give any certain evidence of it. I n the following table are brought together the average values for “varnish,” insoluble and total residue for each of the mixtures. There are also given the averages calculated after striking out the most widely variant values, with the exception of those for KO. 15, all of which differed so much among themselves that a recalculation would mean nothing. ’L‘ABLE S H O W I N G AVERAGE
All values included.
-___-__ Sam“Varnish.” ple. Contains: 1 . Min. oil.. . . . . . 0 . 3 3 2. Soap . . . . . . . . . 0 . 1 1 3 . Rosin . . . . . . . . 0 . 2 7 4 . Rosinoil , . . , . 0 . 2 1 5 . Rapeseed oil ... 1 . 3 7 6. T.ard o i l . . . . . . 0 . 0 9 7 . iallow . . . . . . . 0 . 1 1 8. Min oil ( Z ’ , , 0 . 3 5 9. A s p h a l t . . . . . . 0 . 2 9 10. S u l p h u r . . . . . . 0 . 3 7 11. Paraffin., . . , . 0 . 3 0 1Zi Linseed o i l . , . 6 . 3 0 14. Oxidized min. oil., . . . . . . . . . 0.28 15. T;enOs.,. . . . . . 1.02 16. Oxidized min. oil . . . . . . . . 0.31
,.
Insolubie
RESULTS.
--
Aberrant values omitted. ,
Total residue.
“Varnish.”
Insol’I’otal uble. residue.
2.26 2.06 2.25 1.90 0.01 0 40 1.37 2.51 4 66 2.52 2.iO 0.02
2.59 2.17 2.52 2.11 1.38 0.49 148 2.86 4.95 2 89 3.00 6.32
0.32 0.13 0.24 0.17 1.42 0.05 0.09 0.35 0.29 0.31 0.39 6.38
2.21 1.93 2.30 1.90 0.01 0.31 1.37 2.60 4.66 2.59 2.44 0.02
2.53 2.06 2.54 2.07 1.43 0.36 1.46 2.95 4.95 2.90 2 83 6.40
6.00 6.50
6.28 7.52
0.30
5 82
..
6.12
..
7.02
7.33
0.31
7 32
, .
7.63
Comparing the results of Nos. I t o 7 , it is evident t h a t , with the exception of adding rosin, the admixture
816
T H E JOL,’RLYAL OF ILL’DUSTRIAL A.VD E-VGIIYEERING CHELZIISTRY.
Nov., 1911
of other oils to the mineral oil has caused a greater THE FLUORESCENT TEST FOR MINERAL AND ROSIN OILS. or less diminution in the amount of insoluble and of B y PERCYH. WALKERA N D E. W. BOUGHTON. total residue. The same is also true of the “varnish,” Received Sept. 23, 1911. for, as already explained, the apparently high values The 0ute.rbridge method’ of detecting and estimating obtained for No. 5 were caused b y the adherence mineral and rosin oils in fatty oils, b y taking advantage of the insoluble precipitate t o the bottom of the of the fact t h a t the fluorescence, which is a property flask. of some oils, is very much magnified b y examining Considering Nos. 8 to 16, we see t h a t the addition the oil in the light of a n inclosed arc, introduces a n of asphalt increases the percentage of insoluble. entirely new method of oil-testing. The author This is true even if we correct the figures given in the of this method has made the interesting discovery table b y the amount precipitated b y petroleum that samples of oil which in sunlight show no fluorether before the mixture is heated. This is equivalent escence, when examined b y the light of an inclosed to 1.35 per cent. calculated on the basis of I O grams arc frequently show a very strong fluorescence. He of oil. further states that the examination of a large number The addition of sulphur, contrary t o expectation, of vegetable oils failed t o show a trace of fluorescence caused no marked difference. The same is true of in any of them, while all samples of heavy mineral the addition of paraffin. Linseed oil, as was t o be and rosin oil, whether debloomed or not, showed strong expected, enormously increased the amount of total fluorescence in the proper light. Based upon this observation, he proposes t o rapidly detect and deresidue. The oil which was exposed t o the action of sun- termine mineral or rosin oil in fatty oils b y matching light and air in flasks was, presumably, more com- the fluorescence of the oil under examination with t h a t pletely oxidized than that in the crystallizing dish, of a prepared set of standard mixtures. Outerbridge’s statement t h a t fluorescence is very for it was in a thinner layer and, besides, the flasks greatly magnified b y making the observation in the were rotated each day so as to spread the oil on the light of an inclosed arc has been verified in this laborawalls. I t is not surprising t h a t the figures obtained tory. I n addition to the lights used b y Outerbridge, on heating this oil are higher than those for No. 14. The results obtained with the mixture containing the uviol light was tried but found t o be in no way ferric oxide are interesting, especially in connection equal to the inclosed arc, which is far superior for with the statement of Worrall and Southcombe,‘ this purpose t o any other source of light. Fluorescence in an oil does not, however, prove that the horny or granular deposit a t times found in steam cylinders is Fe,O, or Fe,O, cemented to- the presence of mineral or rosin oil. Of the 1 6 samples gether by oil. One would not expect t o find much of pure linseed oil furnished by Committee D-Iof the rusting in the cylinder or carbureter of a gas engine, American Society for Testing Materials, Nos. 3, 5 , but i t is not impossible that the fine metallic powder 6, I O , 1 2 , 13, 14 and 16 showed no fluorescence, Nos. I , z and 1 1 showed slight fluorescence and Nos. resulting from the wearing of the piston and of the cylinder walls may become oxidized and then further 4, 7 , 8, 9 and 1 5 showed marked fluorescence. A number of samples of other fatty oils of known purity, the carbonization of the lubricant. some of which were cold-pressed from the seed in the CONCLUSIONS. Bureau of Chemistry, showed marked fluorescence, I t has been shown that the addition of various in some cases as marked as t h a t of many pure mineral oils and other substances t o a straight mineral oil oils. affects the amount of carbonization, as measured In order t o test the delicacy of the method, a sample by the percentage of precipitate thrown out by pe- of kerosene, which alone showed very strong fluorestroleum ether, in various ways. Lubricants con- cence in the light of the arc, was mixed with linseed taining soap in quantity (see No. 13), rosin and as- oil S o . 3. This mixture, containing I per cent. of phalt, or which have been exposed to the action of kerosene, which could easily be detected b y its odor, sunlight and air, are to be avoided. showed a slight fluorescence, but it was not so marked One must not conclude, however, from the low as that shown b y linseed oil No. 4 without any addition results obtained with mixtures containing tallow, of other oil. The pure linseed oil No. 3 was then lard oil, etc., that the addition of these oils is t o be heated to 300’ C. and after cooling was found to be recommended. The presence of the fatty acids re- strongly fluorescent. The same development of strong sulting from the decomposition of the oils may greatly fluorescence was observed in a sample of pure olive increase the corrosion of the cylinder and in actual oil, which, before heating, showed no fluorescence. practice cause a s much carbonization as the addition The examination of a number of turpentines demonof ferric oxide would do. strated t h a t while many of these samples show no I t is intended in the near future t o make a series fluorescence, some containing mineral oil also show of determinations by heating the above mixtures, none, and some samples of undoubted purity show and possibly others, with polished strips of iron, marked fluorescence. I t appears, therefore, that while brass and other metals. i t is interesting t o know t h a t the inclosed arc is a very B U R E A U OF STANDARDS. WASHINGTON, D.
c.
1
J. SOC.Chem. I d . .
19, 525 (1900).
1 “A Novel Method of Detecting Mineral Oil and Rosin Oil in Other Oils.” B y A. E. Outerbridge. Jr. Proceedings, Fourteenth Meeting American Society for Testing Materials.
’
