I
108
T H E JOrRLXAL OF I N D l - S T R I A L A N D ENGINEERING C H E M I S T R Y
geneous, consisting of a liquid oil and a crystalline body. It resembled crude paraffin. I t had an iodine value of 1.7 and melted a t 2 2 ' C. G L Y C E R I N E 0 LE AT E
Oleic acid (56.4 g.) a n d 18.4 g. glycerine were heated for 5 hrs. a t 240' C. with continuous stirring. The oily product was washed several times with warm water a n d dried. I t s acid number was 0.6. It was dark in color, very viscous and not uniform in appearance. I n cool weather a crystalline body formed which rendered t h e ester opaque. T h e iodine number of t h e product was 69.4. Pure glycerol mono-oleate has an iodine number of 71.3. H Y D R O G E S A T I O N O F G L Y C E R Y L OI,EATE-The ester was hydrogenated in t h e usual way. Treatment with hydrogen for about 2 hrs. a t 180 t o zoo' C. gave a product which melted a t 59' C. and possessing an iodine number of 6.5. T h e hydrogenated product was similar in appearance t o a good grade of hardened cottonseed oil, except t h a t it was somewhat darker in color. BENZYL OLEATE
Oleic acid ( j 6 g.), 49 g. benzyl alcohol a n d I g. concentrated sulfuric acid were boiled under reflux for 6 hrs. T h e product was steam-distilled until the distillate came over odorless. T h e oil was then treated with alkali t o remove t h e free oleic acid, dried and distilled a t 2 5 t o 40 mm. pressure. The oil came over largely a t 2 7 5 l o 2 8 5 " C. I t was light yellow in color and practically odorless. I t s acid value was 0.7, and t h e iodine value was 62.3. The iodine value of pure benzyl oleate is 68.2. I n another case, the same amounts of benzyl alcohol and oleic acid were used b u t t h e amount of sulfuric acid was reduced t o 0.j g. T h e mixture was heated for jl/, hrs. a t 14 j t o I j o o C. T h e product was steam-distilled, washed free from acid and dried. I t had a n acid number of 8.7. Treatment with sodium hydroxide solution reduced t h e acid number t o 0.4. The ester was of a dark brown color, almost odorless and had a n iodine value of 54.5. H Y D R O G E K A T I O N O F B E K Z Y L OLEATE-Hydrogenation i n t h e presence of finely divided reduced nickel gave a product which had a n iodine value of 6.3 and a melting point of 28' C. B E H A I I O R O F O L E I C A C I D WITH P H E K O L , R E S O R C I K A N D
BETA-NAPHTHOL Oleic acid (28.2 9.) and 37.6 g. phenol were boiled f o r 4 hrs. under reflux. The product was then washed with boiling water until it was free from phenol. T h e acid number of t h e dried oil was 201. Oleic acid (28 g.) a n d 2 2 g. resorcin were treated for 4 hrs. at 180 t o zoo" C. A considerable amount of t h e resorcin was lost b y sublimation, T h e product darkened considerably. I t was purified b y washing with h o t water a n d drying. I t s acid value was 197. Betanaphthol when heated with oleic acid for several hours t o 200' C. failed t o combine with it. OLEIC A C I D AND A K I L I N E
Aniline (24.4 g.) and 37 g. oleic acid were heated a n d e r a reflux condenser for 4 hrs. a t 170 t o 190' C.
YO^. 8. NO. 1 2
The mixture darkened considerably. It was steamdistilled until t h e distillate was free from aniline. The acid number of t h e steam-distilled product was 30.5. It became solid on standing. The substance was treated with a solution of sodium hydroxide and washed free from alltali and sodium oleate. T h e acid number of t h e product was reduced t o 3.6. T h e product melted a t 3 4 " C. It was dark brown in color and had a greasy feel. H Y D R O G E N A T I O N O F T H E PRODUCT-The material was hydrogenated for z hrs. a t 190 t o 200" C. in t h e presence of I per cent finely divided reduced metallic nickel. The hydrogenated product was filtered in t h e hot oven. I t had a n iodine number of 3 0 . 3 . T h e iodine value of the unhydrogenated substance was 69.5. T h e iodine value of oleic anilide is 71.6. T h e product melted a t 76" C. and was very hard and brittle. This and other allied bodies are being made t h e subject of further investigation in this laboratory. S U $1 M A R Y
I-The esters of oleic acid with methyl, ethyl, propyl, iso-butyl. amyl and benzyl alcohols and also glycerine were prepared. These bodies were of oily consistency a n d liquid a t room temperature. 11-These esters were hydrogenated in a liquid state in the presence of finely divided reduced nickel and products were obtained t h a t were practically saturated. 111-The nature of t h e alcohol did not seem t o affect t o a n y great extent t h e rate or degree of hydrogenation of t h e oil. IT'--A product derived b y heating oleic acid and aniline was found t o hydrogenate readily t o form relatively a very hard product. 92 GREEA-~COOD AVBPI'UE ~IONTCLA XEIV I R , JERSEY ~
-_
WATER ABSORPTION BY VULCANIZED FIBER By ROLLING. MYERS Received August 3, 1916
The writer conceived t h e idea of using vulcanized fiber for a golf ball covering, i. e., as a substitute for t h e more expensive g u t t a percha or rubber. T h e TABLEI
Expt. NO.
.. z..... 1.. .
Color and
Texture Hard Red
3..... 4..... 5.."..
GRAMS WEIGHT Time After Per cent Immersed ImWater Inches Hours Original mersion Absorbed 0.591 0.866 46.53 4 1 X 1 X l/32 0.890 48.58 0.599 0.558 0.810 46.16 0.569 0.846 48.66 2.5 X 2.5 X 1/18 5.5 6.700 9.490 41.64 45.07 9.72 1,222 1.704 39.44 4 1 x 1 X :/Le 1.254 1.751 39.63 1.275 1.742 36.62 1.285 1 ,766 37.46 1 X 1 X liis 4 1.341 1.785 33.10 1.208 1.610 33.27 1.327 1.764 32.93 1.300 1.725 36.69 3.7 X 1 . 1 X ~ / I 7.360 9.790 33.08 2 X 2 X1/n 4 6.995 51 06 1 x 1 X'/1e 1.721 2:3jl 37:76 1.254 1.772 41.30 1.829 2.599 42.09 1.546 2.178 40.87
Size in
.
6.....
7... . 8.....
9
., .. . . .. . ... IS..... 19... . . 10.
11..
Flexible
12.... 13. " . . 14,.~. . 15 . . . ~ .Hardgray 16.... 17.. .
I
.
AVERAGEABSORPTIOH(PSRCENTAGBS) FOR 4 HOURSIMMERSION Dimensions Hard Red Flexible Red Hard Grav 1 X 1 X'/sn in. 47.98 51.06 1 X 1 X l j in. ~ 38.25 3i:j4 40,50
Dee., 1916
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
undeniable toughness of this substance, combined with its sufficiently high resiliency, were properties entirely in its favor. Considerable water is absorbed, however, when i t is placed in this liquid for any length of time. This property is decidedly objectionable, since t h e fiber shows a marked decrease in its resiliency a n d toughness. I n order t o measure t h e actual quantity of water absorbed, t h e following experiments were made with materials furnished b y t h e American Vulcanized Fiber Co. These are summed u p in Table I. Three other experiments made on rate of absorption are summarized in Table 11. Expt. No.
1.... , . 2. . . . . 3. . . ., .
.
TABLEI1 Color Weight PERCENTAGE IICREASE and taken 1st 2nd 3rd 4th Texture Size Grams hr. hr. hr. hr. Total Hard Gray 2 X 2 Xl/az 4.235 25.92 17.24 6.42 3.52 53.10 4.082 11.14 10,20 6.53 3.23 31.13 Hard Red 2 X 2 XI,” 6.901 17.40 7.13 7.37 5.83 37.73
The results indicate t h a t t h e greatest part of t h e water absorbed is during t h e first hour. From then on there appears t o be a steady decrease until t h e experiment was finished. The absorption is completed in 7 t o 8 hours, possibly. The total increase in absorption agrees quite well with t h a t observed in Table I , excepting t h e value obtained in Expt. 3 ; no reason can be given for this divergence. The writer decided t o treat t h e fiber with various substances t o see if he could not reduce t h e degree of mater absorption, and by so doing annul t h e effect of this property to such an extent as t o make this TABLEI11 (A) Saturated with 5 per cent alum solution, then in 8 to 9 per cent ammonia solution, finally in water and then dried. (C) First saturated with water, then placed in boiled linseed oil, which is heated slowly from the ordinary temperature to 135-140’ C. for an hour or two. The fiber was then taken out and allowed to dry. (D) The fiber was placed in a nearly boiling saturated agar-agar solution for 2 or 3 hrs., then taken out and dried. (E) Saturated with 15 per cent NaOH solution for 2 or 3 hrs., then exposed to the action of carbon disulfide vapor in a tight jar for about 48 brs.; finally washed with dilute hydrochloric acid and dried. (F) Placed in about 70 per cent sulfuric acid, then washed and dried. (G) Saturated with a strong solution of zinc sulfate solution, then placed in 8-9 per cent ammonia water, washed a little and dried. (H) Saturated with a mixture of blood albumen, borax, magnesium sulfate and glycerine, then exposed t o the action of steam and dried. (I) Saturated with a hot 1.5 per cent gelatin solution, then exposed to the action of hot formaline vapor and dried. (J) The wet fiber was placed in hot molten paraffin, then heated to 115-120’ C. for 1 or 2 hours, then removed and allowed to cool. (K) The moist fiber placed in a mixture of Burgundy pitch, paraffin and linseed oil, which is heated to 105-110° C. for 1 or 2 hrs., then taken out and cooled. Per Time cent of Method of Water ImExpt. Treat- Color and Size in Ab- merNo. ment Texture inches sorbed sion REMARKS Hard Red l/g x 1.25 16.44 5 . 5 No change 1 A dia. hemisphere shell 2 B Hard Gray 2.5 X 2 X’/ia 41.07 6 . 0 No change 3 Piece from Ex. 2 38.47 4 . 0 No change No change Retreated 43.05 ... No change 4 c Hard Red 2 x 2 x1/16 9.76 4 . 0 Brittle 5 17.80 No change 6 D Hard Gray 2 X 2 X1/a2 Hard Red 7 5.50 . . . N o change 2 x 2 X‘/Ifi 45.45 8 E Hard Gray 2 x 2 x1/1fi 9 41.40 4 . 0 A slight in44.45 6 . 0 10 F crease in flexi50.08 4 . 0 11 G bility appar35.84 12 H Hard Red ‘/le Irreg. ent in shape Hard Gray 13 35.53 . . . 14 I 37.73 Brittle 8.66 . . . No change 10.88 . . . Brittle Piece from 13 Retreated 17 Piece from 15 Retreated 21.32 . . . Brittle Piece from 16 Retreated 18 16.56 . . . Brittle Hard Red 2 X 2 X1/16 19 K 17.86 . . . No change
... ...
...
E
’
...
I 109
material of value for a golf ball cover. Table I11 is a summary of t h e results of these later experiments. These preliminary experiments indicate t h a t t h e objectionable property of absorbing relatively large quantities of water can be done away with t o a large extent, perhaps completely. The final mechanical difficulty of covering the elastic rubber core with t h e treated fiber in such a way as t o eliminate any tendency of cracking or of t h e tearing away of the latter from t h e core, would require further experimentation t o be overcome. TULANE UNIVERSITY
OF
LOUISI.4NA, NEWORLEANS
A BOILING METHOD FOR THE DETERMINATION OF WATER-SOLUBLE ARSENIC IN LEAD ARSENATE By GEORGEP GRAYAND A W . CHRISTIE Received July 18, 1916 IKTRODUCTION
Some 3000 tons of arsenic trioxide have been annuaIIy produced in t h e United States during recent years a s a by-product in smelters of t h e western states and am equal amount is also imported under normal conditions.’ Probably the largest use of this “white arsenic” is in t h e preparation, of lead arsenate used solely in t h e control of leaf-eating insects. T h i s commodity is usually supplied t o t h e consumer in t h e form of a paste containing 40 t o j o per cent water, 1 2 t o 16 per cent arsenic pentoxide, and 30 t o 4 0 p e r cent lead oxide. Of recent years, however, t h e dried powder is coming into favor t o some extent. The acid and basic salts of lead and arsenic acid, and possibly t h e neutral salt, are believed t o comprise t h e various brands on t h e market. Most commercial lead arsenates are probably mixtures rather t h a n a n y pure salt. I n order t o compound an arsenical which may b e safely applied t o growing plants without fear of defoliation and yet will poison the insects, many factors must be taken into consideration. The most important thing t o be considered is t h a t t h e arsenical must b e as free from water-soluble arsenic as can be economically produced on a commercial scale. The grower has a right t o demand this protection for his orchards a n d crops for t h e reason t h a t arsenic in water-solubEe jorm is one of t h e most violent plant-poisons known. It h a s been shown t h a t certain pure salts of lead and arsenic acid are exceedingly insoluble in ~ a t e r . * ’ ~ Com’~ mercial lead arsenates, however, usually contain a small amount of water-soluble arsenic as an impurity which has not been washed out during the process o f manufacture. The majority of lead arsenates which are being offered for sale in California a t t h e present time are reasonably free from impurities. Occasionally, however, a sample is received by t h e Insecticide a n d Fungicide Laboratory of t h e University of California 1 F. I ,. Hess, “The Production of Antimony, Arsenic, Bismuth, a n d Selenium in 1912,” 1913, “The Mineral Resources of the United States,” E. S. Geological Survey. 2 R. H. Robinson and H. V. Tartar, “The Valuation of Commercial! Arsenate of Lead,” THISJOURNAL, 7 (1919, 499; “The Arsenates of Lead,” Ore. Agr. Exp. Sta., Bull. 13.9 (1915); 4 H. V. Tartar and R. H. Robinson, “The Arsenates of Lead,” J . Am. Chem. Soc., 36 (1914), 1843. J
