I S D U S T R I A L AND ENGINEERING CHEMISTRY
August, 1927
T a b l e 11-Constants of Boiled Oils CLEANSEED DOCKAGE SEED Lot 119 Lot 121 179 8 175 7 Iodine number 0 9416 0 943 Specific gravity 4 12 4 95 Acid number 1 48 (182) 1 48 (17s) Refractive index Drying time, hours 9 9 5 Lot 120 Lot 123 Iodine number 181.4 l 7 i .4 Specific gravity 0.9394 0 9412 Acid number 3.6 4.37 1 . 4 8 (145) Refractive index 11 Drying time, hours 10
As would be expected. the iodine number, acid number, and refractive index vary with the specific gravity of the boiled oil, but a higher iodine number persists with the oils made from clean seed and the difference in drying time is very noticeable. Tests on Blown Oils Further portions of the oil were made u p as oils aged by blowing a t temperatures ranging from 300" to 240" F. (149" to 116" C.), but to as nearly the same final specific gravity as factory conditions allow. The differences given in Table 1x1 show the effects of heat and air upon the refractive index and acid number. The refractive index is much more sensitive t o heat than to oxidation and oil with a high original index will show a high final index. T a b l e 111-Constants BLOWISG EKTEMP ATURE o -r.
O .F .
149
300
138
280
127
260
116
240
LOT
SEED
33 41 34 42 35 43 36 44
Clean Dockage Clean Dockage Clean Dockage Clean Dockage
of Blown Raw Oils
REBRAC-IODINE ACID SAPONIFISPECIFIC TIVE NUM- NUXCATIOK GRAVITY INDEX BER EER NUMBER 0,9509 0.9516 0.9516 0.9504 0.9504 0.951 1 0.9511 0.9606
169.4 167.2 169.1 168.3 170.7 168.1 1.48(264) 1 7 0 . 4 1.48(247) 1 6 9 . 3
1.48(330) 1.48(289) 1.48(291) 1.48(271) 1.48(263) 1.48(260)
2.37 2.75 2.73 2.89 2.70 3.32 2.65 3.12
19.5.9 193.8 194.9 193.2 195.7 195.3 195.4 195.3
I n general, further heating intensifies differences in the blown raw oils, as shown in Table IV. Tubes of oil from the eight batches were heated a t the same time in an oil bath with a double bottom and tubes kept a t the same distance from the sides of the bath. of B l o w n R a w Oils H e a t e d for 90 M i n u t e s at 560-600O F. (293-316' C . ) CLEANSEED DOCKAGE SEED Refractive Refractive BLOWING TEMPERATURE Index Viscosity Index Viscosity C. F. Poises Poises 1.49(239) 57 1.49(20!2) 52 149 300 1,49(2201 46 1.49(111) 28 138 280 1.49(224) 65 1.49(082) 20 127 260 1 49(265) 76 1.49(150) 31 116 240
T a b l e I\-Constants
897
Tests on Varnish Oils
In order to make a further study of bodying qualities the remainder of the original raw oils was made into a neutral varnish oil, thoroughly bleached to produce an oil of the mater-white class, and refrigerated so that it would stand in melting ice for 12 hours without showing any cloudiness. Some data concerning these varnish oils are given in Table T', and the results of varnish tests made on them in Table VI. T a b l e V-Constants CONSTANT Varnish Oil: Iodine number Refractive index Color Supreme (water-white class) : Iodine number Refractive index Color Arctic supreme: Iodine number Refractive index Color
of V a r n i s h Oils C L E A N S E E D DOCKAGESEED 189.8 1.48(033) 7.7 R
185.6 1.48(023) 7.3 R
189, i 1.48(041) 3 3 R
185.7 1 , 48(026) 3.4 R
191,6 1.48(046) 3.2 R
186.7 1.48(034) 3.3R
T a b l e VI-Varnish T e s t s CLEAN SEED A-LIGHT
VARNISH.
TIME, 90 MINUTES, H E A T , 560-600'
DOCKAGE SEED F
(293-316'
C )
Varnish 1.49(141) 1 49(098) Supreme 1.49(122) 1 49(030) Arctic supreme 1 49(067) 1 49(026) B-HEAVY VARNISH. T I M E , 160 M I N U T E S , HEAT, 66C-6Oo0 F. (293-316' C ) 1 49(398) 1 49(362) Varnish 1 49(379) 1 49(280) Supreme 1 49(294) 1 49(274) Arctic supreme
Table V I suggests an interesting relationship between the viscosity of a heat-treated oil as shown by the refractive index and the higher melting point fats and the iodine number of the original oil. It indicates that of two oils with the same proportion of high melting point fats the one with the higher iodine number will body faster. Conclusion
The investigation shows the variations which may be expected in oils made from the same crop from the same district, if greater or less amounts of dockage seeds are allowed to remain mixed with the flaxseed a t the time of crushing, and further, that these variations cause differences which will affect the processes of the linseed-oil consumer. Thus far all the writers' work with pure linseed oils and linseed oils containing a proportion of dockage oil demonstrates that there is an appreciable difference in their constants, that these differences are maintained in the refined oils made from them and are often magnified in later blowing and heat treatments.
Absorption of Ultra-Violet Light b y Paint Vehicles By George F. A. Stutz NEWJERSEYZINCCOMPANY, PALMERTON, PA.
I
N X recent paper' the results are given of an investigation of the action of ultra-violet radiations on wet paint vehicles. Included is a determination of the degree to which various paint vehicles absorb the ultra-violet light. In the present paper this absorption determination is extended to the case of the dry films of a number of vehicles. The nature and amount of this absorption is of particular importance, because of the action of the ultra-violet portion of sunlight in "weathering," or decomposing, vehicle films; and also because of the growing use of strong sources of ultraviolet light in accelerated weathering apparatus. To further aid in this study, the change in the absorption caused by StUtZ, THIS JOCRN.AI., 18, 1235 (1926).
exposure of the films to sunlight and the mercury arc is also determined. Method
Because of the relatively high opacity of all vehicles to ultra-violet light, it is necessary to examine them in very thin films. A film thickness of 0.02 mm. or less is required in most cases in order that sufficient light will be transmitted to make accurate measurements possible. Most satisfactory results were obtained by flowing out thin films of the vehicles on transparent plates. For this purpose plates of fused quartz and Corning glass G 980 A were used. The vehicles were allowed to dry in diffused daylight, in the laboratory,
Vol. 19, No. 8
IXUUSTRIAL A N D ENGIiVEERING CHEMISTRY
898
and no attempt was made to control tlie humidity conditions. The film tliickuess was determined by meails of a 1Zandall-Stickney micrometer thickness gage. This ineasurement is only accurate to within about 10 per cent, the extreme thinness, as wcll as the non-uniforniity, of the films making a more accurate deterniii~rttioi~impossible. The quarts spectrophotometer described in the previous paper was used to measure the ultra-violet transnrission of
pigure l-specfrugrams
the filius. At least four different thicknesses of each filni were used. The degree of absorption was calculated using the relationship I = lolo-"' wl,ere I
=
iirte,,sity
light
of transmitted
I,
= intensity of incident light 1 = film thickness in centimeters k = cocfficient of ahsorption
of Tungaten Spark under Wafer, Taken fhrovah Films of Vehicle Appreximately 0.02 mm. 'Thick
Tsble 1-Ultra.Vlolcf Absorption by Oils T n n ~ s ~ i s s i o,AT x 0.01 ULM.THIFYNLSS LN PBR C Z N A~T U'AVS I.ENGIX: AUII D"YS
nnrosuxr"
wet him
5
115 115
...
5'c:\ ~ ,
WVri 61111
...
5
115 115 40 40
2400
2300
98.7 98.5 76.7 91.6
48.2
35.0 H.1
97.11 lIS.4 72.4 86.1
34.4 18.2 10.9 17.0
29.4 18.0 10.9
6.0 10.0
10.0
3023
3655
2968
2804
wet
film 5
115
115 40 40
wet film 6 115 115
5.u: v.
17.8 26.9
Y / W LINSiiED
In's;..
76 7 98.0
85.2 68.0
10.9 35.5
3.0 14.1
97.3 97.5 69.1 87.1 64.1 88.3
85.7 74.0 32.5 65.1 26.7 55.0
94,o 98.4 76.7 91.8
83.0 84.1 53.7 78.5
21) 5 51.2
28.5 48.0
22
...
u. v.
... 5.u: v. 16'S;n.
... 5.u:
v.
+ s PEL C S N T i.iQUT"
+
115
I1 5 3 years 3 years U'et
film 5
115 115
3 yeair 3 years
... 5.c:
2ai.:
v. v.
... 5.c:v.
za'u: v.
7 2 . IJ 72.4 70.n sa3
10.6 50.9 98.0 !IS. S 65.2 74.1 27.0 44.7
25.1 34.7
2.5.4 44.6 2.28 25.4 80.0 58.3 29.2 32.4 5.9
13.8
PBX CSNT L I P U i D
7 ~ 8 11.5
+
22.6 24.3 17.8 30.0
1.7%
22.1
16.2
17.u 14.2 26.3 1. P6 17.2
I.TNSBiiD, YISEOSITY 9 POLSIIS
8.1 s.O 6.5 17.0 0.77 10.9
3.2 3.1 2.55 8.38 0.59 9.6
0.80 0.51
0.43
, .L
0.55
6.9 7.5 4.0
76.1 36. I1 i8.0 16.6 4.8 12.6
3.5 3.5 0.4 1.4
46.4 30.9
43.0
5
... 48 u. v.
88.1 88.9
46.7 49.6
41.7 45.0
34.3 38.5
85.5
39.6 54.0
2S.5 44.2
WOOD
on, *mil
PSXII,L*
91.8
48.U: V.
88.1 85.7
71.6 59.3
68.1 84.8
r 2.2 51.6
v.
94.4 95.3
76.5 68.4
64.1
55.0 37.4
0.%8 2.5
27.5 14.9 12.5 23.0
28.4 14.4 11,s 21.6 2.3 3.3
34.9 22.1 17.8
38.6 19.3 15.5 29.2
3.0 6.2
84.3 0.50 0.2 0.2 7.0 0.41 4.5 3.7 3.5 2.9 2.7 0.2
1.3
0.50 0.2 0.2 6.8 0.48 3.9
3.5 3.2 2.8 2.8 0.2 0.90
0.80 1.10
0.64
0.80 0.41
5.25 12.5
3.05 7.60
1.6% 6.50
1.49 5.75
3.2 13.6
1.8 9.60
8.50
1.72
1.68 5.95
16.9 33.4
8.50 29.3
2.04 22.4
0.50 19.5
20.9 44.7
16.3 42.8
9.9 33.0
2.0 28.4
OLL
8.6 22.1
v.
0.65 3.2
DRIBB
16.3 21.5
46.8 60.5
3.8
0.70
24.4 C,,INI
15.8
D*if_X
.
73.5
48'ii:
8.0
13.8
+
4 s . u : i'.
84.5
5
15.5
24.5
DXlZ*
1.2 1.0 0.85 2.1 4.9 5.1 1".!l 6,5 h 1 . 6 A i . l N B K L Y ' N l i " (alirni..awnrrin) I.lh-SliCD s PLX cxai *)RICK 65.1 60.8 51.6 81 .6 s4.2 15~8 2 1 . 1 3 9 . 8 6100 61.5 14.0 15.1 18.2 32.8 24.2 27.1 3 9 . 3 3 2 . 0 53,4 57 11 4.7 7.1 9.2 19.0 19,0 X.5 11.1 44.0 43.0 18.9 ,,cm K*PINl?D LiNSLii" 5 P I E f*NT L,Q"il> "XiBK 78.5 66.6 64.0 56.6 70 2 30.6 37.2 50.7 70.0 70.8 21.1) 2 8 . 0 2 4 . 5 37.8 45.0 38.0 42.0 69. I 66.1 49.0
5
5
18.7 21.5
2.4 12.3
A I X ~ I I L O W Nii"ilili"
wet fl1nr
2536
27.5
K I W LIIVSllB"
2 yenis 2 year5
2655
Howr
TRBIIE" POPDYSBKD OIL
21.6 41.0
.IRBITBD SOY EB*N
48'u:
62.0
29.0 49.0
"IL
INDUSTRILIL AND ENGINEERING CHEMISTRY
August, 1927
From the average value of k, determined a t the several thicknesses, the percentage transmission of a film 0.01 mm. thick was calculated. These values are recorded as a measure of the transparency of the films. The figures are given at a film thickness of 0.01 mm., because the differences existing between the several vehicles are best shown a t this thickness. The exposure of the films to ultra-violet light was carried out in a cabinet held a t 40" C. by blowing through it a current of cool air. The films were placed 30 cm. (12 inches) from a 15-cm. (6-inch) Cooper-Hewitt quartz 'Uviarc. The exposures to sunlight were made on clear days in iiugust, 1926. Results
To show that the ultra-violet absorption by oil films is continuous, the spectrograms shown in Figure 1 were taken. The source of light is a tungsten spark under water, giving a continuous spectrum down to 2140 The light from this source was passed through a film of the vehicle approximately 0.02 mm. thick and dispersed in a Hilger E-4 quartz 2
Fulweiler and Barnes, J. Franklin l n s t , 194, 83 (1922)
IJC
2655
spectrograph. The increase in opacity of linseed oil on drying is shown, as we11 as the relative opacities of raw, heatbodied, and air-blown oils. The transmission values, as determined with the quartz spectrophotometer, for linseed and other oils, are recorded in Table I. Values for the wet films of several of the oils are also given, corresponding to the results previously recorded. Nole-The values of K recorded in the previous paper are relatively high in some cases, owing t o an inaccuracy in the determination of the thickness of the wet films.
Curve 1 shows the transmission of three typical linseed oils. Curve 2 gives the transmission of several other paint oils. Different samples of any one kind of oil vary somewhat in ultra-violet transparency. The results given are characteristic of oils of the several classes and types named. The results for varnishes are recorded in Table 11, and Curve 3 shows the transmission of several of these varnishes. The seven varnishes used are the ones on which Nelson and Schmutz have reported accelerated weathering r e s ~ l t s . ~ s Nelson and Schmutz, Proc. Am. SOC.Tesling Malerials, 24, Pt. 11, 920 (1924).
1
I
2536
899
2968 3023 3131 WIY€.LENGTH OF LIGHT IN A. U.
2804
Curve 1 - T r a n s m i s s i o n
3655
Curves f o r Dry L i n s e e d Oil F i l m s , Age 5 Days
WAYE.LENGTH Of LIGHT IN A U. Curve 2-Transmission
Curves for D r y Oil F i l m s , Age 5 D a y s
AGE-2 OAYS
536 Curve 3 - T r a n s m i s s i o n
WIVE.lENGTH OF LIGHT IN A. U, Curves for D r y Varnish F i l m s , Age 5 D a y s
2655
2804
Curve 4 - T r a n s m i s s i o n
2968 3023 3131 31 WAYEiENGTH OF LIGHT IN A. U. Curves for Dry L a c q u e r F i l m s , Age 2 D a y s
INDUSTRIAL AND ENGINEERING CHEMISTRY
900 No.
GUM
AGE Days 5 7 5 7 5 7 5 7
Tung
Linseed
EXPOSURE 3655 Hours
7
10
10
0
1
5
0
25
.. ..
Limed rosin
A-2
Limed rosin 507,; Congo 50%
A-5
Ester 50%; Kauri 50%
A-3
No. 1 Kauri
A-7
5 14 35 .. 7 48 Limed rosin 5 72 28 .. 7 48 55.8 Ester 5 36 0 .. 85.8 7 48 66.5 By length in oil is meant the number of gallons of oil per 100 pounds of gum.
48 4S
48 48
Ester 50%; Congo 50%
A-4 Q
3131
3023
2968
2804
2655
2536
2400
2300
31.3 15.7 25.4 18.3 25.1 15.7 37.1 31.8 29.5 28.2 25.1 17.5 47.3 22.6
24.8 13.3 21.6 14.6 21.6
18.0 9.8 14.3 10.1 12.0 7.6 23.4 17.1 16.4 14.1 13.1 10.0 28.8 15.1
6.3 2.6 4.90 2.7 3.6 1.6 9.2 7.2 6.1 3.6 4.3 4.5 10.7 4.93
0.73 0.56 0.40 0.44 0.23
0.19 0.20 0.05 0.08 0.08 0.03 0.28 0.9 0.02 0.36 0.04 0.67 0.23 0.40
0.17 0.16 0.03 0.05 0.07 0.03 0.20 0.35 0.03 0.16 0.06 0.36 0.40
0.20 0.16 0.04 0.05 0.06 0.03 0.20. 0.40 0.03 0.15 0.05 0.25 0.23 0.10
.
A-1
A-6
Vol. 19, No. 8
Table II-L?ltra-\’iolet Absorption by Varnishes LENGTHIN OIL^ U. V. TRANSMISSION AT 0.01 MM. THICKNESS IN PER CENTAT WAVELENGTH: 83.2 59.4 75.3 54.5 79.4 58.6 75.8 67.6 75,s 50.8 75.2
10.6
29.8 23.8 25.1 22.0 20.5 14.4 43.3 21.1
0.18 1.3
2.1 0.20 1.0 0.33 1.40 2.3 1.32
0.1s
Absorption by Lacquers U. V. TRANSMISSION A T 0.01 MM. THICKNESS IN P E R CENT No. COMPOSITION EXPOSURE A T WAVELENGTH: 3655 3131 3023 2968 2804 2655 2536 ’ Hours 1 177, 1 / z sec. R. S.a cotton, 83T0 solvents . . 100.0 9 4 . 0 8 8 . 0 8 2 . 0 5 2 . 7 2 8 . 5 2 4 . 5 48 45.5 10.5 7.5 6.5 3.4 1 . 0 0.32 2 14.17, * / z sec. R. S. cotton, 16.6% tricresyl phosphate, 69.3% solvents 97.0 89.5 83.6 78.0 31.0 0.51 0.50 4s 16.1 1.70 1.60 1.45 0.04 0 . 0 3 0 . 0 3 3 10.770 1 / z sec. R. S.cotton, 12.770 tricresyl phosphate, 10.9% ester gum, 65.770 solvents .. 94.4 38.9 29.0 21.9 2.00 0.53 0.50 48 8.80 0.31 0.18 0.10 0 . 0 2 0 . 0 1 0.01 4 9.8% 1/2 sec. R. S. cotton, 11.5% tricresyl phosphate, 9.67, dammar gum, 69.17, solvents .. 96.6 87.1 80.3 73.3 3 0 . 5 0.4 0.3 48 18.6 2.1 1.7 1.3 0.35 0.07 0 . 0 6 10.3Y0 1 / z sec. R. S. cotton, 12.1% tricresyl phosphate, 5.27, dammar, 5.2% ester, 67.27, 5 solvents .. 66.8 96 0 60.8 52.0 48 14.6 20 n 0 . 3in 2 1.66 1.35 0 . 9 5 08 . 295 0.. 31.. .. 86.6 39.1 28.0 17.4 5.19 2.48 3.08 6 Commercial brushing 1.08 0 . 5 6 0 . 7 0 48 22.4 3.13 2.43 2.07 .. 81.4 54.8 49.0 36.1 16.2 1.12 0.83 7 Commercial brushing 48 12.4 1.08 1.01 0.64 0 . 1 6 0.11 0 . 1 0 Same as No. 3 with sample of pale ester gum 93.1 59.2 49.9 31.5 5.75 1 . 5 3 1.33 48 2 0 . 3 1 . 8 6 1 . 3 2 1 . 2 2 0 . 4 1 0 . 0 5 0 . 0 5 ., 70.9 38.5 34.2 9 Same as No. 3 with sample of dark ester gum 24.0 5 . 1 3 1.88 1 . 8 0 48 26.0 3.35 2.60 1.32 0.70 0.61 0 . 3 5 a R. S.-regularly soluble.
Table 111-Ultra-Violet
..
~~
Results for lacquer films are given in Table I11 and Curve 4. Lacauers No. 6 and No. 7 are clear brushing lacauers furnishe4 through the courtesy of Mr. Hopkins, ofuthe Murphy Varnish Company. Mr. Hopkins also furnished the samples of pale and dark ester gum used in lacquers No. 8 and No. 9. Discussion
Several conclusions may be drawn from the results on oils.
A raw or untreated linseed oil is quite transparent. A heatbodied oil is more opaque. A heavy-bodied, air-blown oil is still more opaque. I n general, then, in the case of a bodied oil the ultra-violet light is absorbed almost entirely a t the surface. A raw linseed oil, however, allows the light to penetrate a considerable distance before it is completely absorbed. On exposure to the mercury arc, or to sunlight, a film of raw linseed oil becomes more transparent (bleaches). A film of air-blown oil also bleaches, though not so much as the raw oil film. A heat-bodied oil film, however, shows but little change and may even become more opaque on exposure to the ultra-violet light. This leads to the conclusion that, in the case of a raw oil, a material is produced on drying and aging, which is acted on by ultra-violet light in such a way as to convert it into some other material more transparent to ultra-violet light. I n the case of a heat-treated oil an opaque material is produced on drying and aging, which is not changed t o a more transparent form when acted-on by ultra-violet. Instead, the ultra-violet light may accelerate the formation of the opaque material. An air-blown oil would seem to contain some of each of these materials since it is rendered somewhat more transparent by exposure to the ultra-violet light. Perilla oil becomes more transparent on exposure t o the
ultra-violet light. China wood oil also becomes slightly more transparent. Poppy and soy bean oils become more opaque in the near ultra-violet and more transparent in the far ultraviolet. All the varnishes measured are quite opaque. Moreover, on exposure to ultra-violet light they become more opaque (yellow). The tendency to yellow is least in the case of a long oil varnish high in linseed oil and is greatest in the case of a short oil varnish high in China wood oil. Apparently the gums present are largely responsible for the yellowing of the varnish as well as its high initial opacity. The results for lacquers show that clear nitrocotton is quite transparent. The addition of a plasticizer renders it more opaque a t the shorter wave lengths. This is true of all the plasticizers commonly used. The further addition of gum renders the lacquer still more opaque. Also, ester gum is much more opaque than dammar. Exposure of the lacquer film to ultra-violet light or sunlight results in the formation of a deep yellow color and a corresponding tremendous increase in opacity to ultra-violet light. It will be noticed that practically all vehicles have high absorption a t the shorter wave lengths, below the limit of the sun’s spectrum. Therefore, whenever a vehicle film j s exposed to a source of short ultra-violet radiations (2800 A. or less) the energy is practically all absorbed a t the surface. This accelerates decomposition, hardening, and similar reactions a t the surface only, the underlying film not being affected. On the contrary, when exposed to sunlight, the radiations, being above 2900 i., are sometimes able to penetrate a considerable distance into the film before being completely absorbed. This difference should be considered in interpreting accelerated weathering results where the light source used is one rich in the short wave lengths beyond the limit of the sun’s spectrum.
INDUSTRIAL A N D ENGINEERING CHEMISTRY
August, 1927
Acknowledgment The author wishes to acknowledge the assistance and criticisms of the members of the Research Division of the New
90 1
Jersey Zinc Company, and the aid rendered by his assistant, c. Hall, in making the observations.
Action of Cathode Rays on Drying Oils By J. S. Long and C. N. Moore LEHICHUNIVERSITY,
T
BETFILEHEM,
P A . ,A N D GENERALELSCTRIC COMPANY,
HE production of high-voltage cathode rays outside of
the generating tube has been described by Coolidge' and some experiments with these rays outside of the generating tube are described by Coolidge and In a description of this work3 it was mentioned that castor oil exposed to the rays was changed to a solid. The relations which occur when drying oils are thickened by heating are quite different than those when the oil is thickened by the action of ultra-violet light, and these differ from the actions when the oil is oxidized by blowing. It was believed that this thickening by the action of high-voltage cathode rays might be of service in indicating the types of reactions occurring in the process of thickening and that during raying there might be actions which did not take place in other methods of bodying. Accordingly, series of samples of linseed, perilla, and China wood oils were prepared as described. Some or all of the constants-specific gravity, refractive index, iodine number, molecular weight, and hexabromide number-were determined on these samples. The samples were than rayed and the constants again determined. The results produced by the raying are given in Table I to 111. Table I-Effect
of T i m e of E x p o s u r e to C a t h o d e R a y s on L i n s e e d and
P e r i l l a Oils REFRACTIVE IODINE MOLECULAR HEXABROMIDE EXPOSURE INDEX PI-UMBER WEIGHT NUMBER Mtnufes S E T 1-LIHSEED
0 1 2 3 5 10
1.4776 1,4778 1.4780 1,4782 1.4786 1.4799
0
1.4804 1.4805 1.4806 1.4808 1.4812 1.4819
S E T I-PERILLA
1 2 3
5 10
OIL
187.6 187.4 187.4 187.6 185.5 181.0
762 781 832 870 883 967
37.6 22.6 22.3 24.3 19.5 21.6
785 810 817 834 878 925
47.8 42.2 41.1 38.8 37.0 31.2
OIL
205.5 205.5 202.6 202.3 198.7 195.3
T a b l e 11-Linseed 011-50 Seconds' Exposure t o C a t h o d e R a y s AFTER REFRACTIVE INDEX MOLECULAR WEIGHTIODINEUMBER HEATINGBefore After Before After Before After Hours S E T 2-HEATED
a
1 2
2 5
1.4776 1 4836 1.4890 1.4903
1.4810 1 4842 1.4895
...
A T 253O C.
970 1096 1728 2330
S E T 3-BLOWN 0
3 9
1.4781 1.4790 1.4796
1.4788 1.4800 1.4820
S E T 4-HEATED
1 0 1.25 1.5 1.75 a
1,4830 1.4857 1.4892 1.4904 1.4915
A T 138'
788 833 893 A T 253'
1038 1209 1540 1617 1840
J . Fvankiin Insl., 202, 693 (1926). I b i d . , 202, 722 (1926). 8 J . Chem. Educ.. 3. 13G9 (1026). 1
2
177.2 148 117.5
147' 112.6
C.
818 929 1025
184.0 175.6 160.5
183.7 173.2 159.3
C. W I T H U M B E R
1046 1220 1571 1658 1904 Gel Time required t o raise oil t o temperature used.
0.5
1.4825 1.4855 1.4886 1.4901 1,4910
856 1132 1989 Insoluble gel
155.2 142.2 135.9 132.0 129:s
144.2 128.8 120.3 114.7 103.2
SCHENECTADY,
N. Y.
a n d C h i n a Wood Oils-50 S e c o n d s ' E x p o s u r e to C a t h o d e Rays REFRACTIVE I X D E XMOLECULAR WISIGHTIODINEh T HEATING Before After Before After Before After Hours
T a b l e 111-Perilla AFTER
S E T b P E R I L L A OIL H E A T E D A T 293'
1.4806 1.4869 1,4900 1.4917
1.25 1.75 2.25 2.76
1.4811 1.4873 1.4906 1,4920
S E T 7-PERILLA 4
0.5 0.92 1.10 1.24
1.4808 1.1850 1.4888 1,4906
C.
891 1207 1527 1959
201.4 157.4 143 4 134.1
196 6 155.3 142.5 Gel
OIL A I R - B L O W N >IT 283' C.
1.4812 1.4852 1.4892 1.4910
S E T 8-CHINA
790 1123 1388 1719 Solidified 785 1078 1440 1753 Solidified
864 1131 1524 1857
W O O D OIL H E A T E D AT 190'
0 1.5148 1.5144 873 888 0.5 1.5134 1.5132 991 1020 1.0 1.5116 1.5114 1098 1160 1.5 1.5103 1.5100 1371 1453 2 1994 Gel a Time required t o raise oil t o temperature used.
200 161.2 151.6 131.7 C.
.. .
1si:l 146.1
195.7 162.5 142.1 131.8 157 157 153.8 145.6
Materials
Perilla oil of suitable purity for research work was kind7y furnished by Maximilian Toch. It had the following characteristics when used in this work: Specific gravity a t 15.5'/15 5' C. Refractive index a t 25' C. Iodine number, U'ijs (30 minutes) Hexabromide number Acid value Molecular weight
0 1 205 47 3 765
935s 4804 8 08
Linseed oil derived from selected northwest seed was treated to remove the break, chilled to 6.6" C. to separate part of the saturated glycerides, and filtered cold. This oil showed the following characteristics when used in this work: Specific gravity a t 15.9°/15.50 C. Refractive index a t 25' C. Iodine number, Wijs (30 minutes) Hexabromide number Acid value Molecular weight
0.9395 1.4776 187.6 37.6 4.38 760
The China wood oil had the following characteristics: Specific gravity a t 15,5°'15,50 C. Refractive index a t 2 5 O 'c. Iodine number, Wijs Browne heat test minutes
0,9405 1.5160 163 9.5
Preparation of Sets of Samples
SET 1-Two and a half cubic centimeters of linseed oil were placed in a glass Petri dish of 10 cm. diameter. T h e dish was fastened to a shaft inclined at an angle of 27 degrees and rotated at about 60 r. p. m. The center of the Petri dish was 5 cm. from the window of the cathode ray tube. In all cases the tube was operated at 250,000 volts (maximum) and 1 MA. The oil spread itself quite evenly over the bottom of the Petri dish in a layer about 0.3 nim. thick. Five samples were exposed 1, 2, 3, 5 , and 10 minutes. SET 2-Six hundred grams of linseed oil were heated a t 293" C. in a 1000-cc. three-neck Pyrex flask with mechanical stirring at 200 r. p. m. Air carrying moisture equivalent to 62.6 per cent relative humidity a t 25" C. was passed over
~
~
