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 .
72
MINERAL. OIL-ROSIX OIL.
Feb., 1911
LIXSEED OIL-CASTOR OIL,
a 0
z
2
J .
.y
h 0
0
5 4921 4928 4927 4926 4925 4924 4923 4922 4818
100
98 95 80 50 20
0 2 5 20 50 80
5
95
2 0
98 100
0.8977 0 . 0 3 ., 0.8996 0.9006 0.9125 0,9347 , 0.9586 , 0.9712 0.9731 0.9750 0 . 0 0
..
..
.. . .
..
1.0
.. ... ... ,
I
.
.
...
...
. ..
2.0
186 217 6.2 7.5 184 217 180 210 7.1 162 196 9.8 148 185 17 142 177 18 134 162 21 132 159 2 1 . 8 130 158 20
171.6 170 168 160 150 142 140.8 139.8 139.6
4810 4809 4808 4807 4806 4805 4804 4803 4802
100
98 95 80 50 20 5 2 0
0 2 5 20 50 80 95 98 100
0.9286 0.9290 0.9294 0.9344 0.9432 0.9534 0.9583 0.9597 0.9599
1 . 3 0 195.68 1 . 3 0 194.90 1 . 3 0 194.40 1.58 192.18 1 . 8 6 189.72 2 . 3 6 187.20 2.78 184.09 2 . 7 8 185.50 2 . 8 6 183.52
294 334 101 293 334 98 293 334 100 290 329 92 283 320 91 277 316 7 3 . 5 274 311 7 3 . 5 273 306 47 271 304 58
132 134 136 178 393 1043 1677 1946 2146
LINSEEDOIL-ROSINOIL.
COTTONSEEDOIL-LIPSEED OIL.
i
4983 4998 4999 5000 5001 5002 5003 5004 4810
100
98
0 2
95
5
80 50 20 5 2 0
20 50 80 95 98 100
0.9184 0.9188 0.9201 0.9209 0.9232 0.9268 0.9280 0.9284 0.9286
0 08 0.08 0.11 0.31 0.64 0.98 1.12 1.15 1.30
196.1 196.0 195.0 197.2 194.4 193.9 194.7 196.2 195.7
299 299 299 298 297 294 294 294 294
340 71 340 69 340 7 4 . 5 340 79 340 77 5 336 9 7 . 5 337 102 336 IO5 334 101
175 165.6 162 158.4 146.4 140 132.6 132 132
4810 4825 4824 4823 4822 4821 4820 4819 4818
100 98 95 80 50 20 5 2 0
0 2 5 20 50 80 95 98 100
0.9286 0.9290 0.9301 0.9370 0.9510 0.9644 0.9720 0.9741 0.9750
-
1.30 1.14 1.14 0.92 0.58 0.19 0.03 0.00 0.00
195.7 190.8 184.7 151.7 96.0 40.8 13.6 7.7 2.0
294 334 101 246 334 102 220 322 93.5 172 215 84 146 172 86 139 160 5 2 . 5 132 162 31 131 159 26 130 158 20
132 130 124 116 112 112 120 124 139.6
CASTOR OIL-ROSIS OIL.
.”
COTTONSEEDOIL-CASTOROIL
4983 4991 4992 4993 4994 4995 4996 4997 4802
100 98 95 80 50 20 5
2 0
0 2 5
20 50 80 95 98 100
0.9184 0 . 0 8 0.9193 0 . 0 8 0.9206 0.17 0.9266 0 . 5 0 0.9392 1 . 5 4 0.9512 2.01 0.9577 2 . 5 0 0.9591 2 . 5 3 0.9599 2 . 8 6
196.1 197 4 195.3 194 3 190.3 185 9 181.9 183.2 183.5
299 298 297 292 285 276 273 271 271
340 340
...
332 325 320 317 315 304
17 76 65 67.5 73 72 64 64 58
175 176 180 243 500 1204 1889 2070 2 146
4811 4812 4813 4814 4815 4816 4817 4818
98 95 80 50 20 5 2
2 5 20 50 80 95 98
0
100
0.9611
0.9613 0.9620 0.9658 0.9736 0.9744 0.9748 0.9750
2.86 2.69 2.36 1.64 0.61 0.14 0.08 0.00
178.82 175.26 147.57 96.37 37.53 10.37 5.23 2.0
245 314 216 285 160 215 137 180 132 165 130 162 130 162 130 158
56 54
1977 1855 56 1320 57.5 647 39.5 259 27 142 21 140 20 139.6
1,J . KESSLER, YANDEVENTER A N D DUNCANAVES., ST LOUIS, Mo. LABORATORY O F
A COMPARISON OF METHODS OF DETERMINING UNSAPONIFIABLE MATTER I N WOOL OILS. B y A-GGUSTVSH. GILL AND A. E. SHIPPEE. Received December 23, 1910.
COTTOXSEED OIL-ROSIN OIL
4983 5005 5006 5007 5008 5009 5010 5011 4818
100 98 95
80 50 20 5 2 0
0
2 5 20 50 80 95 98 100
0.9184 0.9186 0.9205 0,9284 0.9447 0.9641 0.9731 0.9739 0.9750
0.08 0.08 0.08 0.03 0.03 0.00 0.00 0.00 0.00
196.1 299 192.7 252 1 8 8 . 8 212 158.1 168 9 8 . 0 142 366 132 1 1 . 6 130 4 . 3 130 2 . 0 130
340 338 315 205 165 150 145 143 148
71 69.8 69.5 67.5 58.5 45.5 35.5 27.5
20
175 172 169 160
146 140.8 141 140 139.6
There are two methods in common use for determining unsaponifiable matter in wool oils, the usual extraction method with gasoline, and the method by difference. In the latter method the free acid is determined, then the combined fatty acids, these latter calculated as olein, added to the free acid, and this sum subtracted from 100,giving the unsaponifiable matter. As this method is more rapid, and is quite extensively used, it seemed advisable to compare it with the other. Procedure: Extractiow Method.-The free fatty acids, unsaponifiable matter and saponification number were determined according t o the procedure given in Gill’s “Oil Analysis.”
GILL AND S H I P P E E ON WOOL OILS G U M M I N G ON O X I D A T I O N .
~
Procedure: Di8erential Method.-Ten grams of the oil are weighed into a 2 5 0 cc. Erlenmeyer flask, dissolved in neutral alcohol, heated to 65-70 O , and titrated with iV/6 alcoholic potash, using phenolphthalein as an indicator. This operation gives the free fatty acids. From this point two processes are available: ( I ) To the solution of soap and neutral fat is added 2 5 cc. of N / 2 alcoholic potash, the solution boiled, IOO cc. of water added and the boiling continued. Finally the excess of alcoholic potash was titrated for with hydrochloric acid. The sum of these two figured as oleic acid and the triglyceride of oleic acid, respectively, gives the saponifiable matter. The unsaponifiable matter is the difference in weight between the sample taken and this amount. ( 2 ) After titrating for the free acids, an excess of alcoholic potash is added and the solution boiled. When saponification was complete, the alcohol was removed by adding 600 cc. of water and boiling, water being added as it evaporates. The fatty acids were then precipitated with dilute sulphuric acid. The boiling was continued till the fatty acids formed a clear liquid on top of the aqueous solution. They were then separated in a separatory funnel and washed till the washings were free from mineral acid. The fatty acids were then dissolved in neutral ‘alcohol, heattd to 65-70’, and titrated with, N / 2 alcoholic potash. The difference between this result and the free acid figured as the triglyceride of oleic acid and the free acid figured as oleic acid in the saponifiable matter; the difference between the sum of the free acid and saponifiable matter and the weight of oil taken is the unsaponifiable matter. The extraction method suffers from the disadvantage of incomplete extraction by gasoline, of the solubility of soap therein, from the difficulty of complete removal of the solvent used in extracting the oil, and of losing any volatile constituents of the unsaponifiable matter. The errors in the differential method come from assuming that all the acids and neutral fats consist of oleic acid and its triglyceride, and in the second modification from a loss of fatty acids in manipulation and their solubility in hot water. From this it would seem that the method of finding the unsaponifiable matter by difference is sufficiently accurate for industrial purposes and is to be preferred to others on account of the greater rapidity and ease of manipulation. The following table shows the results obtained by the two methods: the average difference between the two methods is less than the difference between two determinations by the same method, except with oil No. 3. Description of oil. Scotch wool.. Wool o i l . .
SP. gr..LUnsapon. Matter 15 5’ C. b y ext. b y diff. . . . . . . . . 0.908 65.7 65.4 0.908 91.7 90.9 n.0.911 58.5 56.6 Eng. oleine, 42 per cent. sapon 0.911 59.4 59.2
.......
..............
Per cent. Sap. free acid value as oleic. 73 12.8 17 3.3 88 41.3 80
40.7
.
0.910
31.2
31.0
140
65.2
..............
0.910
65.2
65.3
69
32.6
sapon.. .... Woololeine,35 per cent.
sapon
73
ON T H E LIABILITY OF WOOL OILS TO GUM ON OXIDATION. By AUGUSTUS H. GILL AND A.
E. SHIPPEE
Received December 23, 1910.
Besides the determination of the amount of unsaponifiable matter, free acid, and the flash point of wool oils, it is desirable to know if they gum on exposure to the air. An excellent opportunity for this is offered by their exposure on the textile fibers in the course of manufacture. Richardson and Hansonr have used an apparatus in which a current of air was drawn over the hot oil. Although primarily designed for cylinder oils i t gives useful information with wool oils. The apparatus consists of a copper oven ioff x ioff x 7 f f , all joints brazed, which constitutes the oil or water jacket. This jacket surrounds a chamber 5” x 7 N x in height. The tray measures 4” x 6 * l Z f fx r / 2 f f deep. The inner chamber is sukounded by halfinch copper tube in eight coils; the last coil enters the chamber a t the back of one corner and the exit is a t the opposite corner diagonally and is connected with a half-inch copper exit tube, which is connected with a suction pump. The air is measured by a meter joined to the first coil of copper pipe surrounding the chamber, so that the meter is a t the room temperature. A tube leads from the center of the chamber to the outside, and is fitted with a thermometer. The chamber is closed by an asbestos board outside of which is a copper plate, held firmly over the mouth of the chamber b y two thumb-screws. Procedure: ten cc. of the oil are placed in the chamber in a shallow pan 4N x 6’/,” x I/~“. Air a t 100’ is drawn over the oil a t the rate of from 3 to 5 cubic feet in four hours, which was the length of a run. The tendency of an oil to oxidize and gum is indicated by its increase in viscosity. The pans first tried were made of tinned iron. These were unsatisfactory because the metal was so thin that a level surface could not be obtained and consequently the oil did not cover the bottom of them in an even film. By using a pan made of iron about I / , ~ ’ ’ thick which had a level, rigid bottom, this difficulty was removed. The machine was leveled by placing I O cc. of oil in it and, after allowing i t to stand for an hour, noting a t what point the bottom was not covered by oil. After one or two trials the apparatus could be adjusted so that every part of the bottom was covered with a layer of oil. Since there are 168 sq. cm. area, I O cc. would form a layer 0.06 cm. thick; therefore, the apparatus was considered level enough when this condition was reached. In order that the pan might be placed in the same position each time, a mark was made on one corner and it was placed against two sides of the chamber, always having the marked corner opposite to the one touching the sides. I n order to test the viscosity after oxidation a special form of apparatus was necessary, the amount of oil oxidized being far too small for the ordinary forms. The only method which seemed feasible was that of allowing the oil t o flow through an orifice. A tube 1
J. SOC.Chem. I s d . , 24,
315 (1905).
