perirrrental work are shoaii iir IK'itSiire 2. Suine of tho materials treated ill the apparatus urp dcscrilied below.
Linseed oil with 0.02 per cent of Sobslt; light-treated 4 hours. The e f i r d was only a slight thickenmg. The oil was still liquid. Linsced o i l with 0.02 pcr cent cobalt; light-treated 24 hours. Thc oil was oridieed arid polymerized to a solid m318ss resembling thc type OF scrim oil used in the linoleum industry. The skins Forming in the chaiincls wcre scraped off the entire length as thin, clastic rihbons. Tune oil without drier; light~treatedlor 1 bours. Orily slight thickening action. Tune oil with U.(E per cent cobalt; light~treatcd1 hours. Formcd a solid. polymcrieed, and oxidized mass resembling the scrim oil used in the linoleum industry but VF extremely light color. Possibly a very light colorcd linolcum could he Gadr from such a pioduct. Vcry resilient. Perilla oil with 0.02 per cent cobalt; light-treated For 21 houri. Formed a d i d mass resembling swim oil but of darker color than that produced from linseed or tung oil. Tunc o i l with 0.05 p ~ cent r flowers of sulfur: light-treated 3 Itours. Pormed a solid, wax-like mass consisting largely of heta-elPostearin. Material w r y hard, resembling hydrogenated fats in appearance.
Fieure I-Laboratory Cabinet for liradlatinb 0118 \Ishen in use. tiir open ciid of drum is closed with a c o v e i provided wilh s cobalt viewing glass.
It was found that very rriucli quicker effectscould he obtained if there was added to the oil about 0.02 per cent of nxt.ailic cobalt as a catalyst for the oxidation and polymerizatioii effect,s. The cobalt was added in organic hare form. Some of the solid nroducts obtained in this ex~~
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l k e r e i v e d Fcbruury 13, 1930. To he presroted before the Division and v,r,,ish Chcrni.;,iy hf the 79th of f'lrernicnl Society, Atlanta, Ga., April 7 t o 11, 1930.
.As r i o t c d a b o ~ etlic , pr:rilla atid Iiuseed oils r,oiitaiiiing 0.02 ,;vrmrit of eoGalt, 11ci~a111csolid in 24 hours, wliweas thc tung oil rontaining tlrc smii? aniount of cobsit hrt;arnt~solid in 4 /tours. Thesc thrm produet,s w r e extrartetl with hot aeetoiie. From t.iicrri there, wcre &ract,cd 20, 32: and Iti per cent, respectively, of unp~ilynisrized products. The polymerized, spongelike residue which was insoluble in aeetone was then (lried and used to detennjnc the amount 01petroleum distillate (mineral spirits) which could be alisorhed. Tile perilla absorbed 70 per cent, the linseed 80 per cent, and the tung oil 160 per cent of the iniiieral spirits beforc the surfaces of the particles actually appeared to he wet. While from this preliminary re,mrch, figurt%s are not available which would indie& the possibility of producing these solid products from oil through the. use of light in an PCO-
noniical uiaiincr, it is ljeliercd that such results iniglit follow The speed wit11 which sucl2 oils may be produced and their light color might make the process feasible, even though the cost should he somewhat greater than the present cost of heat or air treatment. The added fact that ultra-violet light is now used for treating water for drinking and hathing purposes would indicate possibilities in this direction for industrial
I S D C S T R I A L AND ENGINEERING CHEMISTRY
April, 1930
products such as oils. Certain food products, such as cheese and cereals, are irradiated to induce the development of vitamins. This would suggest the possibilities of an apparatus such as that shown in Figure 1 for the treatment or some vegetable oils which after irradiation might have
379
valuable medicinal properties. Tung oil, which is now toxic, might in the presence of sulfur produce a form of betaeleostearin which would be non-toxic. Apparently metallic salts, such as cobalt, when in solution in oil greatly stimulate the effect of light.
Free Water Necessary to Change Beta Anhydrous Lactose to Alpha Hydrous Lactose' R. W. Bell BUREAC O F DAIRYI N D U S T R Y ,
T
HREE forms of lactose have been isolated-alpha anhydride, alpha hydrate, and beta anhydride. Mixtures of these forms have also been isolated. The ordinary lactose of commerce, the monohydrate, is prepared by crystallizing from solution a t temperatures below 93" C. The other forms change to the hydrate below 93" C. in the presence of small amounts of water, indicating that this is the stable, solid form a t ordinary temperatures. The degree of stability of the beta anhydride is of commercial importance, since its change t o the alpha hydrate results in a product having a lower initial solubility and an apparently less sweet taste. Information regarding the amount of free water required to bring about this change and the conditions under which water is adsorbed is therefore of value. Experimental PREPARATION O F h R E CRYSThLLlNE BETA . h H Y D R O U S LACTOSE-Seven hundred cubic centimeters of hot distilled water were added to 1200 grams of c. P. alpha hydrous lactose and the mixture was heated t o boiling with stirring. All the sugar dissolved. Evaporation of the water was continued with stirring until a thick mush had formed. Glycerol heated t o 130" C. was added and the mixture poured quickly into a running centrifuge that had been heated with live steam, after which the collected crystals were washed with hot alcohol and centrifuged to remove any liquid that might be present. The method is essentially that of Hudson and Brown ( I ) with the addition of a stirrer as used by Schmoeger ( 2 ) . That the sugar so obtained was pure crystalline beta anhydrous lactose was proved by its specific rotation of 35.5 degrees to the right with sodium light a t 20" C. and by the fact that a Bidwell-Sterling toluene-distillation determination for moisture (,?) showed that it contained only a trace of water.
D. C.
WASHINGTON,
t o 2 crystals deep and was evenly distributed over the bottom of each container. The six dishes were placed in a desiccator over distilled water and held a t 30" C. The increase in weight of each sample due to the adsorption or condensation of water on the crystals is given, together with other data, in Table I. That the values given for bound water, and therefore for free water, are essentially correct is proved by the results obtained for bound water by calculation from the specific rotation of the samples. The specific rotation of alpha hydrous lactose mas taken to be 88 degrees dextro with sodium light a t 20 degrees and that of beta anhydrous lactose to be 35.5 degrees in the same direction. The specific rotation of the samples, other factors being constant, has a definite relationship to the relative amounts of the two forms
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Taible I-( Zhange of Beta Anhydrous Lactose t o Alpha Hydrous Lactose with Sorption of .Moisture THEOTIME
ININ-
RETICAL
INCREASE
INCREASE CREASE
DIFFERENCE BETWEEN D E T N . FOR
Figure 1-Change i n Rotation of Pure Crystalline BetaLactose with Sorption of Water
BOUND
IN CREASE IN IN SPECIFIC IN WATERA N D DESIC- IN FREE BOUKD ROTA- BOUND THEORETI- of sugar present. CATOR WEIGHT WAIER WATER TIOK WATER CAL .4MOVNT percentage of beta Days Per rent Per cent Per cent Degrees Per cent Per cent
Saw PLE
0
7 9 9 11 11
1.27 1.89 3.22 4.00 4.69 5.41
0.43 0.34 0.49 0.57 1.06 0.96
0.84 1.55 2.73 3.43 3.63 4.45
43.66 n2.34 61.41 70.03 73 61 79 72
0.78 1.61 2.47 3.29 3 63 4.21
+0.06 -0.06 +0.26 + O . 14 0.00 f0.24
CHAKGE TO ALPHA HYDROUS L.icro.;s-The pure crystalline anhydrous sugar was sifted through an 80-mesh wire screen and 0.5 to 0.6 gram weighed into each of six glass weighing dishes. These dishes were 5 cm. in diameter and were fitted with ground-glass covers. The layer of sugar was 1 1
Received March 5 , 1930.
The converse is also true, and after the and alpha present had been determined from the specific rotation, the percentage of theoretical bound water was calculated by multiplying the percentage of alpha by 0.05, which is the proportion of water of crystallization in each molecule of the hydrate. It was found by experimeiitation that the amount of free water obtained by drying each sample in a vacuum oven a t 70" C. for 5 hours was practically the same as the value arrived a t by subtracting the theoretical bound water from the increase in weight of the samples or the total amount of water present. Figure 1 gives curves illustrating some of the data in Table I.
