568
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
dioxide formed, since thew are independent variables. A straight line has been drawn between the ordinate value of 100 (the point where no oxidation can be detected) and an abscissa point arbitrarily selected so that the poorest experimental values found so far for each of the selected oxidation criteria will fall between 15 and 20. Although based on experimental data for oils of low oxidation resistance, this range can be widened or negative values can be used, if oil? of lower oxidation stability are found or more severe conditions of oxidation are used. Also, more extensive work on oxidation may make it desirable to include other factors in the scale-for instance, a peroxide value. When the ordinate is used to represent carbon dioxide formation, viscosity increase or sludge formation, the scale reading is called “COZ factor”, “viscosity factor”, or “sludge factor”, respectively. A calculated numerical mean of the three factorb is called “oxidation index”, expressed in per cent oxidation units. Table IX gives the experimental values of the selected oxidation criteria for six of the nine oils, together with the corresponding oxidation scale units.
Yol. 36, No. 6
LITERATURE CITED
Am. Soo. for Testing Materials, Designation I9 445-;39T, Method B. Balsbaugh, J. C., Larsen, R. G., and Oncley, J. L., INU.Ewo. CHEM.,30, 287 (1938).
Burk, R. E., Hughes, E. C., Scovill, W. E., and Bartleaon, J. D., Petroleum Div., B.C.S.,Atlantic City, 1941. Davis, L. L., Lincoln, B. H., Byrkit, G . D., and Jones, W. A , , IND. ENG.CHEM., 33, 339 (1941).
Denison, G. H., Jr., private communication, .June, 1943. Dornte, R. W., and Ferguson, C. V., IXD.ENG.CHEW.,28, 863 (1936).
Dorntc. R. W., Ferguaon, C. V., and Haskins, C. P.,Ibid., 28, 1342 (1936).
Fenske, M .R., Stevenson, C. E., Lawson, N. D., Herbolvheixnet G., and Koch, E. F., Ibid., 33, 516 (1941). Fenske, M. E., Stevenson, C. E., Rusk, R. A., Lawson, N. D., Cannon. &I. R., and Koch. E. F., IND.ENQ.CHEM.,ANAL ED., 13, 5 1 (1941).
b’uchs, G. H.
von,
and Diamond, H., IND.ENO.CHEM.,34, 927
(1942).
Fuchs, G, H. yon, Wilson, N. B., and Edlund, K. R., IND. ESG. CHEM.,ANAL.ED., 13, 306 (1941). Gruse, W. ih., and Livingstone, C . J., J.Inst. Petroleum, 26, 413 (1940).
Hall, F. W., Levin, H., and McMillan, W. A., IND.EXG.CHEW., ANAL.ED., 11, 183 (1939).
ACKN0WLEP)CMENT
Appreciation is expressed to S. S. Kurtz, Jr., for many helpful ‘suggestions and to Herbert L. Johnson and other associates in the laboratory for assistance in this work.
Viscosities and
Haus, E., Oel KohEe Erdoel Teer, 14 (E)299, , 321 (1938). Hirsohler, A . E., Petroleum Div., A.C.S., Mcmphis, 1942. Lamb, G. G., Loane, C. M.,and Gaynor, J. W., IND. ENO. CHEM.,ANAL.ED., 13, 317 (1941).
Rogers, ?’ H., and Shoemaker, B. H., Ibid., 6,419
(1934).
ensities of
HYDROGEN
S
HELNIUT WAKEHAM AND FRANK C. MAGNE Southern Regional Rmearch Laboratory, U. S. Department, of Agriculture, New Orleans, LEI. little information has appeared in the literanumber values, free fatty acid contents, melting and solidification ture on the viscosities of cottonseed oils or hydrogenated ranges, and refractive indices of the oils are shown in Table 1. cottonseed oils. Strevens ( 7 ) published the value of Iodine numbers were obtained by the wijs method. The melt. 0.994 poise a t 15.5’ C. for a pale cottonseed oil which was identiing and solidification ranges were determined on samples cooled fied only by B density of 0.925 a t 60” F.;he pointed out that for in sealed capillaries 24 hours before measurement in a melting a wide variety of oils the greater the iodine number, the lower the viscosity at a given temperature. Rawitsch (6) and Boekenoogen ( 2 ) measured the TABLE 1. PROPERTIES OF COTTONSEED OILS USED IN \‘ISCOSlTY AND DENSITY viscosities of unhydrogenated cottonseed oils ovei DETERMINATIONS the temperature range between 20’ and 90’ C., Free Fatty Acid Calcd. as % and Bauer and Markley ( 1 ) reported the viscosiOleic ties a t 98.9” C. of hydiogenated cottonseed oils Itefraotive Before AfterIodine measmeashaving iodine numbers ranging from 6.8 to 58.9. No. Melting Solidification -&!!Z-ureureSample No, (Wijy) Range, 6. Range, C. C. n~ ment ment As yet, however, no complete study has been pub-6.7 to -2.4 -4.4tO -9.6 40 0.06 10 112 1.4658 0.08 lished of the variations of viscosity and density 40 1.4651 20 - 5 . 6 to f 4 . 2 - 4 . 4 to - 9 . 9 0.09 0.10 108 with iodine number and temperature for cotton40 - 2 . 5 t o -8 1.4656 0 . 0 3 - 3 . 0 to f 1 . 9 0.26 101 40 19.6to 14.0 1.4619 0.05 0.27 16.8to 23.5 78 seed oil. Increased processing and utilization of 50 3 3 . 3 t o 28.1 1.4568 5-A d 32.4to 39.1 0.08 0.11 66 40 6-Bd 35.5to 27.6 1 .4604 0 . 0 8 0.09 32.2to 41.6 65 domestic vegetable oils have emphasized the need 50 34.8to 27.4 1.4566 35.4to 41.0 0.09 0.15 7-Bd 65 for such data which may be used in the design of 43 30.7to 27.8 1.4590 0.05 0.09 66 8-C l d 50 0.09 0.06 3 2 1.9 6to 4 3 9 2 . 7 5 3 3 . 9 t o 2 7 . 6 1 . 4 5 6 7 9-C ld 68 processing equipment. 50 1.4555 32.5to 28.4 0.05 0.09 35.6to 42.3 10-C 2d 61 49 1.4558 32.2to 29.1 0.09 0.08 34.7to 42.9 i l - C 2d 61 Samples of hydrogenated cottonseed oils were 40 34.8to 31.6 1.4589 0.08 0.42 37.0to 42.3 12 c 56 prepared in this laboratory from a commercial re0.74 60 50.8to 48.2 52.9to 57.1 1 ,4490 0.17 I3 28 5 3 . 3 t o 5 1 . 2 1.23 6 0 . 6 t o 6 1 . 6 .... 14 6 fined and deodorized cottonseed oil. Properties of 0 Comniercially refined oils from two different refineries of Southern Cotton Oil Co. these.oils were compared with those of commercially 6 U.S.P.grade sold under the label of B . R. Elk & Co., Inc. refined unhydrogenated cottonseed oils from three Hydrogenstid in Southern Regional Research Lab. from a refined oil of 102 iodine number. different sources. These oil samples were suppled Commercially hydrogenated by Southern Cotton Oil Co. A, B , and C refer t o batchee A, B , and C, respectiveiy. Batch C was hydrogenated t o two different iodine numbers. mented with commercially hydrogenated oils of routine batches obtained from a local processor Iodine O
2:
C
C
O
INDUSTRIAL AND ENGINEERING CHEMISTRY *
lune, 1944
TABLE 11. Sample No. Iodine No. Tpp., C. 29.9 37.0 67.5 100.8 141.8 200.2 233.8
1
112
DENSITIESOF HYDROGENATED COTTONSEEDOILS 2 108
4 78
3 101
6 65
12 56
13 28
Density 0.9112 0 9068 0:8869 0 8654 0'8389
0.9105 0 9061 0:8863 0 8649 0:8383 0:8011 0.7998
........
0.9130
::::
.......
0:8993 0.8837 0.8798 0.8783 0:8+65 0:8;50 0 8621 0 8584 0 8570 0 8540 0.8533 0'8360 0'8319 0'8308 0:8280 0 8273 017988 017947 017938 0.7908 0:7902 0.7768 0.7723 0,7693 0.7683
0:963l
018883 0 8667 0:8405 0,.8050 0.7845
14 6
....
COTTONSEED OILS TABLE 111. VISCOSITIES OF HYDROGENATED Sample No. IodineNo. Temp., O
e.
28 R 37 $ 0
47.6 67.5 94.7 124.3 141.8 151.2 179.9 203.5 225.6 244.4
1
112
2 108
3
5 66
4'
78
101
11 61
12 56
13 28
Viscosity, Centipoise8
r
45.3
45.6.
32.4
32.8 23.2 13.7 7.30 4.65 3.64 3.22 2.36 1.89
22.8 13.4 7.15 4.61
am 3.18 2.32
1.88
.. .. .. .. .. ..
60.8 -_._
2k:k 14.5 7.85 4.69 3.71 3.26 2.40 1.90 1.58 1.41
. . . . . . . . . . . . . . .
41.7 28.5 15.8 8.36 4.98
...
3.37 2.45 1.94
30:s 17.2 8.65 5.18 4.01 3.45 2.48 1.96
3i:b
17.3 8:99 5.22 4.02 3.50 2.49 1.96
32:k 17.6 9.01 5.22
...
3.52 2.53 1.99 1.63
...
Ki
9.57 5.49 4.18 3.65 2.64
... .. .. .. .. .. . . . .. .. . . . . . ... ..
point apparatus similar to that described by Hershberg ( 4 ) , with the exception that an infrared reflector drying lamp controlled by a variable transformer served as the heating element. Refractive indices were obtained for the oils a t temperatures above their melting points. The viscometers were of the Ostwald type as modified by Zeitfuchs (8). The technique employed was essentially that described by Craxton (3) except that a thermostatically controlled oil bath was used to m a h a i n the temperature of the viscometers with an accuracy of 0.1 C. The mercury regulators were of the metastatic, preset type and could be rapidly interchanged when a new bath temperature was desired. Individual viscometers were used for each oil; runs were made in the shortest possible time (about 15 minutes at the high temperatures) which would permit attainment of temperature equilibrium and determinations of flow time. Viscometers were removed from the bath immediately after the determination to minimize possible thermal decomposition and polymerivation of the cottonseed oils at the temperature of the bath. Calibration values of the viscometers were determined with a, standard sucrose solution (40% by weight) and were later checked with standard viscosity oib supplied by the National Bureau of Standards. Densities of the oils were measured by a pycnometer with the game bath used for the viscosity determinations.
569
against the iodine numbers for each temperature to give a family of smooth isotherms from which densities were read off for hypothetical oils of 0, 40, 60, 80, and 100 iodine number. These values were then plotted aB density us. temperature for each of the hypothetical oils to give the family of curves shown in Figure 1. Densities of cottonseed oils with various degrees of. unsaturation may be read directly from this chart by interpolation. An equation relating the density and temperhture for a cottonseed oil was calculated from t,he data. in Table 11:
14
di
- 0.000638 (12
- ti)
6
where dl B .d dpare densities corresponding to centigradc temperatures t l and t 2 , respectively. Calculated densities for any second temperature obtained by this relation ... from a known density for a cottonseed oil agreed within 26:; about 0.1 % with experimental values. The mean 10.22 ... coefficient of cubical expansion for cottonseed oil is, 4.48 therefore, 0.000764 over the temperature range 0 3.88 2.73 230" C. 2.08 1.70 Table I11 contains the experimentally measured 1.46 viscosities of nine cottonseed oils with different iodine numbers. These data were plotted to obtain a family of curves of viscosity us. temperature for oils of different. iodine numbers. From these curves viscosities were read off for every 10' C. of temperature for each oil, and the resulting data plotted as viscosity vs. iodine number on a semilog scale to give a family of smooth isotherms as shown in Figure 2. Table IV compares viscosity data of Rawitsch (67, Boekenoogen (21,and Bauer and Markley (1) with values obtained
Experimentally determined densities are shown in Table I1 for oils of different iodine numbers. The densities were plotted
*75
0
50
IO0
TEMPERATURE
150
IN DEGREES c.
_200 _-
2 __56-
Figure 1. Donsities of Hydrogenated Cottonseed Oils
IODINE NUMBER Figure 2.
Viscosities of Hydrogenated Cotton seed Oils
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
570 TABLE Iv.
COMPARISON O F PUBLISHED VISCOSITIE5 WITH DAT.4 FROM FIGURE 2 \. iscosity, Centipoise3 _ _ _ _ _
Temp.. O c . 30 50 60
Author Rawitsch (61
Iodine
NO.
115 115 115 115 115 215 105 105 105
90 80 90
Boekenoogen ( 2 )
30 40 50
Bauer end Markley ( 1 )
98.9 98.9
. ,
6.8
45.6 56.3
98.9
Published 42.0 21 .6 16.0 11.6 9.4 7.5 44.6 30.6 22.1
From Fig. 2 40.0 21 .o 16.0 12.4 9.5 7.7 45.0 31.5 22.4
9.4 8.6 8,3
9.3 8.5 8.3
_
AND DENSITIES OF UNDEODORIZED AND TABLE V. VISCOSITIES
DEODORIZED HYDROGENATED COTTONSEED OILS FROM DIFFERENT
RATCHES
Janiple S o . Batch No. Deodoiized Iodine h o e
6 B
No
7 B
65
Yes 65
1O:Ol
1O:OS
7.01 3.49 2.51 1.88
7.07 3.48 2.51 1.87
!.
No 66
8 c 1 No 66
9 c 1
c 2
Yes
No
66
10
61
I1
c 2 Yes 61
Vol. 3Q No. 6
generality stated by Strevens ( 7 ) and confirmed 'by Kaufmanii and Funke (6)that the viscosity at a given temperature decreases with increasing iodine number. _ .The ~ effect of thermal change such as decomposition or pol) rnerization of the oils upon viscosity values should be small brcause of the short time the oils were kept hot for the high teirrperature measurements. Bauer and Markley ( 1 ) showed thsr heating a cottonseed oil of iodine value 50.2" to 230" C. for 2 hours increased the viscosity by about 3%. Fatty acid contenth of the oils removed from the viscometers after the complete ten1 perature range had been covered were found to have increased in some cases as shown in Table I. Some unavoidable inaccuracies due to thermal change are therefore to be expected, ailti the viscosities reported in Tables I11 and V may he in error bi about 1yo,especially at the higher temperatures. Table V compares the viscosities and densities of samples 3 t I J I I, inclusive. These data indicate, in general, that cottonseed oil5 from different batches but with similar iodine numbers have essentially the same viscosities and densities. A refining treatment, such as deodorization in which little change in composition probably occurs, does not affert these properties to a n y appreciable extent I
59,s 88.5 l06.6 152.3 179.9 210.0
20.95 10.01 5.78 3.47 2.49 1.85
59 . 5 88 . 5 106 . 6 152 . 3 179 . 9 210 .o
0,8848 0,8664 0.8546 0.8248 0.8055 0.7853
. I . ;
0.8663 0.8546 0.8253 0.8071 0 7883 ~
20.25 9.72 6.77 3.36 2.38 1.82
20.97 10.02 7.00 3.48 2.49 1.87
___Density-----. , . . 0.8822
0.8664 0.8661 0.8546 0.8545 0.8258 0.8244 0.8077 0.8069 0.7882 0,7886
22.78 10.48 7,l5 3.56 2.54 1.88
22.72 10.18 6.91 3.47 2.49 1.85
---0.8834 0.8663 0,8546 0,8250 0.8071 0.7879
0.8832 0.8649 0.8531 0.8237 0.8054 0.7858
0.8838 0.8654 0.8536 0.8241 0.8057 n.7861
GCKNOWLEUGMEh'l
The authors art: indebted to S. To Bauer of this laborarory for supplying hydrogenated cottonseed oil samples; to \I Gtansbury and D. @. Heinzelman for determining the iodine numbers, free fatty acid contents, and refractive indices; and to J. J. Ganucheau of the Southern Cotton Oil Company for sirpplying many of the oil samples used. LITERATURE
by interpolation and extrapolation from Figure 2. The kinematic viscosities of Bauer and Markley were converted to absolute viscosities by multiplying by densities read from Figure I , The agreement shown in Table IT' seems to show that the data here reported may be used as an indication of the viscosity of any refined or hydrogenated cottonseed oil of which the iodine nurnber is kn0.IT-n. Furthermore, the curve%in Figure 2 t'ollo\~ the
Craxton, F. c.,I X D . E N G . CHEM., ANAL. E D . , 14, 593-5(1948) Hershberg, E. B., Ibid., 8, 312 (1936). Xrtufmann, H. P., and Funke, S., Fette u. SeiferL, 45, 255 (1W-4) Rawitsch, G . B., Kolloid-Z., 76, 341-5 (1936). Strevens, J. L., J. Soc. Chem. I d . ,33, 109-11 (1914). Zeitfuohs, E. H.,Natl. Petroleum S e w s , 31, 2621 (1939); I'roc. A m . Petrolewn Inst.. 111, 20, 104 (1939)
INHIBITION of F
ING In Solvents >)
Containing SYDNEY ROSS
T
AND
.J.
crrm
Bauer, S.T.,and MarkIey, K. S., Oil & S o a p , 20, 1 (1943). Boekenoogen, H. A., Chern. Weekblad, 34, 759 (1937).
))
Foamers
w. MCBAIN, Stanford [Jriitersity, Calif.
HE foaming of liquids is a, frequent, c a u w of trouble in industrial and laboratory processes. Methods of preventing or reducing the amount of foam may be divided into t\vo groups--mechanical and chemical. The former employ pulsating strea,ms of gas above the liquid, perforated spiral canals, wntrifuges, continuous pumping of liquid from bottom to top of rontainer, change of pressure, heating elements, ultraviolet r a p , x-rays, canal rays, supersonic waves, rotating fans or disks or adjustable gratings above the liquid surface, sharp rorners in the design of the apparatus, etc., with varying degrees of success. h o n g chemical methods the addition of small quantitic+ of caprylic alcohol, amyl alcohol, octyl alcohol, linseed oil, castor oil, rapeseed oil, trimethylcyclohexanol, phenyl ether, isonmyl'isovalerate, milk, etc., has been recommended for various
aqueous ioammg syatemb. .1r11ong the intlu~trial procesws where i t has been found necessary to use foam preventive measures are purification of beet juice&, manufarture of glue, sepnration of cream, production of steam in boilers, preparation of paper and coated papers, heat dehydratioii of c r u d e oils and tars, purification of sewage, and thr boiling. v : + ( ~ i i i r n i wapnratinn, distillation. or filtering of many solutiorr~. The present paper reports a h e r r ~ 5of experinwnts to determine the effect of incorporating certim agents in different ~ ~ 1 1 defined systems capable of forming foam. The object of t h e investigation 1s to uncover some operative factors in the inhibition of foaming by means of antifoaming additives. ,1 knowledge of those factors would k~ of out importance
