1212
VOL. 28, NO. 10
INDUSTRIAL AND ENGINEERING CHEMISTRY
throughput at high efficiencies is small. The efficiency of the unpacked columns drops off rapidly as the rate of boiling increases. 2. The single-turn, So. 26 wire helices ( 1 ) result in high efficiency (eight plates) even a t relatively high rates of boiling. This type of packing gives higher efficiencies than any other studied. 3. The continuous spiral packing used in the 6-mm. column is not as efficient as the single-turn helices. At low rates of boiling the unpacked column is a little more efficient than the spiral packed. 4. rlt the same rate of boiling, the empty 3-mm. column is no more efficient than the 6-mm. column. The 3-mm. column, however, does give higher efficiencies a t very low rates of boiling-i. e., conditions under which the larger column cannot be satisfactorily operated. 5. The effect of insulation is as follows: At high rates of boiling the effectiveness of the insulation seems to make but little difference in efficiency. At somewhat lower rates of boiling the better insulated column has the lower efficiency. However, the better insulated columns can be operated at velocities below those possible with poorly insulated columns, and under such conditions the better insulated columns have greatest efficiency, 6. The results with qpiral packing in the 3-mm. column re-
quire further investigation because of the unusual way in which efficiency varies with rate of boiling.
Experience in operating the columns leads t'o the following conclusions : 1. Operation of the columns becomes more and more dificult as the rate of boiling becomes very low because the slightest variation in the insulation of the column or heat input to the pot destroys the equilibrium in the column. For successful operation at very low rates of boiling the columns should be insulated almost as well as a calorimeter. Under such conditions efficiencies as high as thirty plates per foot seem possible. 2 . The 3-mm. column is so difficult to operate smoothly that its further use is probably undesirable unless further work with packed rolumns shows substantial advantages over the 6-mm. column.
Literature Cited 1) l ~ v u d k eQuiggle. , and Tongberg, ISD. Exo. CHEK, 24, 410 (1932).
2 ) hlcCahe and Thiele, Ibid.. 17, 605 (1925). RECEIVED July 16, 1936. Presented before the Division of Petroleum Chemietry at the 92nd Meeting of the American Chemical Society, Pittaburgh. Pa . Yeptember 7 t o 11, 1926.
ANIMAL AND VEGETABLE OILS Viscosity-Temperature Characteristics Viscosities in centistokes at 100" and 210" F. were determined for some thirty animal and vegetable oils of various types. Other properties of the samples are listed. In general these products show high viscosity indices and low gravity indices. LTHOGGH >tattered data expressed in various units at many different temperatures exist for the yiscosities of animal and vegetable oils, apparently no coinparatiye collection has been made. I n the present investigation, viscosities at 100" and 210" F. (37.78" and 98.89' C.) have been found in fundamental units for about thirty common animal and vegetable oils possessing other physical and chemical characteristics as listed. From the combined data, viscosity indices, gravity indices, and viscosity-gravity constants were found. The oils are classified in groups according to the scheme used by Mitchell (9).
Oil Specimens The oils used were obtained from several sources and are believed t o be true samples. The olive oil, the second castor oil, and t h e second lard oil obtained from the Department of' Agricultural and Biological Chemistry had been tested for the addition of foreign substances. Although the other samples were not so examined, specimens from different sources were found in each case to be remarkably uniform in their properties. The last three rosin oils listed are certain cuts from the fractionation of the commercial rosin oil whose properties are not included in this report.
A. R. RESCORLA A N D F. L. CARNAHAN The Pennsylvania State College, State College, Pa.
Methods and Apparatus Seutralization and saponification numbers were obtained by methods much the same as the A. S. T. hl. procedures (1). Specific gravities at 20" C. (68" F.) relative t o water at 4" C. 39.2' F.) were found b y pycnometers; division of these values by the factor 0.999 gave specific gravity a t 60" F. 15.6" C.) This factor was derived from the experimental Yalues shown in Table I and represents the ratio between -pecific gravity a t 68" and a t 60" F. for eight oils of different classes. The corresponding value for petroleum oils is 0.9968 '3'). Refractive indices a t 68", loo', and 130" F. (20', 37.78', .tnd 54.44' C.) were evaluated by an Abb6 refractometer. TABLE
1. VARIATION O F SPECIFIC GR.4vrr.i WITH TEMPER.~TURE FOR SOMEFIXED OILS
Ratio Sp. Gr. 6S0/ Sp. Gr., Chtnge in Sp. G I 15.6'/4' C . Sp. Gr. mi 1 O o / 4 O C . 37.78'/4O C. Per C. Per ' F. (Calod.) 60' F. Almond 0.9188 0.9141 0.00026 0.00015 0,9200 0.998; Rapeseed 11.9114 0.9078 0.00037 0.00021 0.9023 0.9990
-
-Sp,
R e f i n d.__
Gr. -
--
perilla 0.9329 Castor 0.9619
0.9294 0.9580
0,00019 0.00022
0 00011 0.00012
0.9338 0.9629
0.9990
kernel U.9190 Yeat'sfoot 0.9158 3ardine 0.9384 Sperm 0.5829
0.9154
0,00020
0.00011
0.9198
0,9990
0.9105 0.9351 0.8800
0..00029 0,00018 0.00016
0.00016 0.00010 0.00009
0.9171 0.9392 0.8536
0.9986 0,9991 0.9992
Pllrn -
0.9990
Kinematic viscosities at 100" and 210" F. (37.78" and 98.89" C.) in centistokes were determined by the use of modified Ostwald pipets (4, 11). Viscosity-temperature change is expressed in terms of the kinematic viscosity index #$), The Saybolt viscosities were obtained from a conversion table (8). From the Saybolt viscosity at 100" F. and the specific gravity a t 60" F., the gravity index ( 7 ) may be found ilr +he viscosity-gravity constant (6) calculated.
INDUSTRI 41. hl;D ELGINEERIUG CHE91ISTHJ
OCTOBER, 1936
1213
-
T LBLE 11. Oil
P H Y s I C i L i T D CHE\llC4L .Icid No.
Oil G i o u p
CH 4R 4CTERISTICS
S a o o n i - y - b n Gr -&a15.6' 20'. 4' C: tion So. 4 O C . 'ralcrl
n 9200
1.4710 1.4760 1.4728 1.4725 1.4652 1.4720 1.4755 1.4790 1.4800 1.4836 1.4830 1.4750 1.5180 1.4790 1.4787 Solid Solid Solid 1.4679 1.4700 1.4675 1.4810 1.4810
.. 143 .,
0.9295 U.914i lJ.9364 0.9058 IJ.9067 0,9295 0.9304 0.922; 0.9236 0 , 9 2 0 5 0.9214 0.9186 0.9195 0.9135 0 9144
1.4820 1.4785 1.4806 1.4785 1.4805 1.4770 1.4745 1.4701 1.4660
119
0 8777
V.87b6
1.4658
Sperm , , 0,8774 Sperm 0:kO 54 0.8829 Sperm .. . 0.8774 Sulfonated castor ,. U.894b Rosin l6:6 . . 0.994:i Narrow-boiling cut .. 0 964h Kosin S a r i ow-boiling cut .. , , 0.9i4: Kcisin Xarr ow-boiling cut .. ., 0 9814 0 Estlapolated on . i, J . T . 11.chart f i u : n value determined
0.8782 0.8836 0.8782 0.9956 0,9953
1.4652 1.4642 Solid 1 4619 1.5395
2.85
Olive Olive Rape Rape Rape Cottonseed Cottonseed Linseed Linseed Linseed Linseed Linseed Linseed Castoi Castor Coconut Coc (,nu t Coconut Lard Lard Lard Whale Whale
o:io
0.34 14: i 4 3.50 1.20 3.42 1.36 0.56 2.76 5.26 0.81 0'01
196 191 179 176 185 198 208 199 193 198 196 193 197 188 193 243
194 199 191
0.9186 0.9158 0.9106 0.9114 0.9237 0.9187 0.9228 0,9258 0.9297 0.929; 0.9329 0.9207 0.9375 0.9619 0.9606 0.9226 0.9235 0,9190 11,9138 0.8968 0.9158 0.9384 0.9276
213 193 ,.
0 9356
0 l!)234 9 0 PO5
:L39 I 3 83 0.57 0.47
2.38
Whale Whale Whale Whale Whale \\-hale Khale Sperm Speriii
0 85
9'6
0.7::
,.
11.30
.
Sperin
6.23
201 106
.
LO7 196
0.9286 0.9138
.
Consideration of Data The collected data are shown in Table 11. \
(1.9656 1.5330 I>.
9;:'l
1,5399 1.3451
1,
__
-~
___
OF h I M i L %YD V E G F r I B L E OILS
-
-
Kiiieniatic _--3ayholt ~ I S - Grab-. Viscosity Yisositv cobity ity 100' F. 210' F. l ( l U a F. %IO3 F. Index I n d e x L'rnliCentistokes stokes 1,4670 1.4621 43.20 8.74 201 54.0 159 30 46.68 9.09 216 55.2 156 :35 1:4687 1:4660 5 0 . 9 1 10 36 235 59.5 145 52 1.4684 1.4661 50.64 10.32 234 59.4 145 52 9.46 209 56.9 45.13 38.88 8.39 191 32.7 1:4678 114645 162 166 25 12 1.4710 1.4688 28.49 7.60 134 50.1 185 - 5 1.4751 1.4719 29.07 1 2 2 137 48.8 178 -15 1.4750 1.4729 29.60 d.33 139 49.2 175 -20 1.4791 1.4754 25.24 6.86 120 47.6 190 -20 1.4788 1.4758 26.00 6.89 123 47.8 187 -30 1.4703 1.4660 33.31 7.68 156 50.3 172 I0 1.5118 1,5090 1 1 5 . 2 15.46 531 i8 5 132 5 1.4742 1.4700 293.4 20.08 1.168 97.7 86 -60 301.5 20.43 1400 99.2 86 -60 114530 114498 L'9.79a 6 . 0 6 140'" 45.2 I56 0 1.4530 1 4480 28.58* 5 . 8 3 135Q 14.5 U I55 1.4530 1.4498 30.92" 6 60 1~~. 4.9 4fi 5 18 I56 1.4636 1.4605 44.41 !.SI 206 54.2 I58 41 31.66 i.24 148 48.9 171 68 1:4637 1.4600 43.15 !.XI 200 53.1 178 38 1.4760 1.4741 27.86 , 06 131 4 8 . 3 182 --40 1.4769 1.4752 28.22 7.14 13Y 48 6 182 --a0
--Refractive Index-68' F. 100' F. 130' F.
0 9167 0 9115 0.9123 0,9246 0.9196 0,9237 0.9267 0 9306 0.9306 0 9338 0.9216 0 9384 0.9629 0.9615 0.9235 0.9244 0 9198 0.9147 0 8977 0.9171 0.9392 1.1.9285
Almond Olive Rapeseed Rapeseed Xf us t ard Cottonseed Soybean Raw hempeeed Linseed Raw perilla Refined perilla Sunflower China wood Castor Castor Coconut Coconut Palm kernel 1,ard Lard Seat's-f oot Sardine Sardine Cold-pressed sardine Cod liver Menhaden Porpoise body Whale Refined whale Satural ahale Sperm deodorized Sperm deodorized Sperm winterpressed Cold-test-bleached sperm Sperm Spermaceti oil Turkey-red oil Rusin Rosin
._
~
-
~
1.4772
1.4754
1
2
1:4749
1:4760 1 0
1:4752 1,4700
1.4660
.. ..
1.4648
1.4619
1,4592
,
1:4602
,
.... .., . . . ..
.
,
1:45ib ,
1 1.5330
_
.
. .
26.89 32.79 28.75 30.74 29.50 31.4i
~
127 158 135 ~ 2 7 144 7 26 139 7,48 147
48.0 50.7 48.9 49.0 48.9 49.7
, 3 2 7.~0
7.5.3
152
in11
,53.21 51.36
9.79 8.6(!
246 238
57.5 53.5
5 :34
io
98.9 110
4.70
88.2
43.u 44.1 41 0
~
6.96 7.80 i.26
20.,311
2 2 99 17 8:i
5
1,53011 1 4 1 . 7
0.877 0.883 0.888 0.891 0.896 0.898 0.900 0.882 0.888 0.912 0,910 0.885 0,886 0.880 U.869 0.853 0.872 0.902 0,890
100
*6
0.835
191
6 !
0.835
183 19:i 17X -169
.,,
14.72
-
.I4 4 h
-119
. .
4 4 11
-1'i.i
,
0.865 0.865
0.872 0.865
, , , ,
,
0.877 0.873
39 42
153 141
'2IJ,42
.-
V7n. .
cosityGravity Constant
4
87 ( 9 0.831 0.841 ti5 0.866 , , 0.943
. .
.
I1
94u
I1
!44i
U.955
:a1
i-iuitie
dt
temperatures other than 100" and 210" F. ma>-he tound troii~ the A. S. T. 11.T.iscositv-teirIperature chart ( 2 1 OI f r tlir equation log log (Kl- 0 8 ) = A log T + B where f i l - = viwosity in centi-tohea at abs. temp, 1' A , B = conatants ~~~
+
It has long been known that fixed oils possess flat 11 temperature curves. Kinematic viscosity indice- ( culated as a measure of this property vary irorn 86 for castoi oil to 193 for a sample of sperm oil. Excepting the rosin oils from consideration, the products of 20 to 50 centistokes at 100" F exhibit a roughly linear relation between viscosity and viscosity index, the more viscous oils showing t h e lower indiceb. For mineral oils refined by conventional inethocit t h e gravity index ( 7 ) is approximately the same as the viscosity index. This is far from the case for fixed oils, the viscosity index being 100 to 200 points higher. This circuinstance may be taken as a manifestation of the very great differences in chemical structure of these two classes of oil. The effect of a complex ring structure is evidenced by the viscosity index of -169 for a commercial rosin oil and of -4 t o -183 for rosin oil cuts of increasing viscosity. Viscosity-temperature and viscosity-gravitx relations should be useful supplements to the other meam used for the identification of fixed oils. However, in cases where other physical properties of oils are nearly identical, the
Viscosities may be also; for exainple, this is true of olive oil and lard oil (dainple l ) ,for the differentiation of which special tests have been tlerisecl (10).
Acknowledgment The oil samples iiir-e>tigatecl rrere iurnished by the ti. H. Lewis Company, the Murray 011 Products Company, the Scientific Oil Compounding Company, and the Department of Agricultural and Biological Chemistry of the college. The experimental data were Iargel? obtained by K. El. Dashem H. R. Guest.
Literature Cited Am. J o e . Testing lIaterials, Standards (Petroleun~Products and Lubricants), p11. 210 am1 258 (19%). Ibid., p. 311. I b i d . , p. 317. Cannon, M. R., ; l i d E'emke, 11. R . , Oil Gas J.,33, NO, 47, j:! (1935) : 34, S o . 47, 46 (1938). Hersh, R. E., Fisher, E . K . , and F c n s k e , M. R . , IXD. ENG. CHEM., 27, 14.11 (19%). Hill, J. B., and Coats. H. €3.. Ibid.. 20. ti41 119383. McCluer, W. B., and Fenske, M.R., i h i d . , 2 4 , l i i l (1Y:jP). Ibid.. 27, 82 (19363. Mitchell, C. A , 'in Allen's "Commercial Organic .halysis," 5th ed.. Vol. 11, p 109, Philadelphia, P. Blakiston'a Son & Co., 1924. Ibid., p. 153. Willihnganr, E. -i.,McCluer, JF-. H., E'eiiske, M. R., end McGren-, R. V.,ISD. ESG.CHEX,;\rial. Ed., 6 , 231 (1934). RECEIVED July 28, 1936.
