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 .
736
E. Coarsely ground, ball-milled for two hours. Wood reduced to pqwder ; bark reduced to small scales. These samples were extracted in a Soxhlet with acetone, and then by carbon bisulfid, the extracts dried a t I O O O C. and weighed. The table shows the results. Carbon bisulfid extract, rubber.
- ------
Acetone extract, resin. ,PA__
Preparation.
A. B. C. D.
E.
(1)
(2)
Av.
Var.
(1)
(2)
Coarselyground.. 9.91 9 . 8 4 9.88 0.07 9.77 10.95 Medium f i n e . , . . . .&9.16 8.84 9 . 0 0 0 . 3 2 9.34 9.44 Finely ( ? ) ground 9.90 9 . 7 4 9.82 0.16 7.33 8 . 7 1 Medium ground, s i f t e d . , , , , , , . , 9.97 10.77 10.42 0.88 8 . 6 8 9 . 8 8 Coarsely ground, ball-milled.. . . 9.63 9 . 5 4 9 . 7 4 0 . 2 1 7.88 9 . 2 9
.
.
-4v. Var.
10.41 1.18 9 . 3 9 0.10 8 . 0 2 1.38 9.28 1.20 8.58 1.41
An examination of these results reveals: 1st. T h a t none of the methods of preparation are perfect. 2nd. That the regrinding system, (B) when carefully carried out, gives best results. 3rd. That the rubber content seems inversely proportional to the degree of fineness. This is probably due to a more even distribution of the rubbery (barky) portion throughout the entire mass. I n coarsely ground sample the barky portions, due to gravity, a r c usually on top and an undue proportion gets into the assay charge. 4th. That the tendency of the bark particles on account of their rubber content, as determined by the initial grinding or crushing, is to amalgamate in opposition to heavy milling or ball-milling and sifting combined, and that a cutting system CHAS. P. Fox. is demanded.
RECENT INVESTIGATIONS OF FATS AND OILS. I n the first number of THE J O V R N A L ~ I contributed a brief account of some work, carried out by Professor Paal, of Erlangen, on the catalytic reduction of fats and oils. The number of letters on the subject which I have received suggests that a further report on some subsequent investigations may prove to be of interest. The method of experiment consisted in emulsifying the fat or oil with an aqueous solution of gum arabic adding a little colloidal palladium, also dissolved in water. The remainder of the vessel was filled with hydrogen and i t was shaken a t the ordinary temperature, until the volume of gas remained constant. The relative quantities of fat and palladium which were employed differed within rather mide limits, in one case, which may be taken as fairly typical, the ratio of metal: fat was I : 500. I n their most recent communication Paal and Roth2 describe experiments with castor, croton, olive, sesame, cottonseed and linseed oils and with butter fat, lard and oleomargarin (from beef suet). I n some cases complete reduction was only attained by a second or even a third treatment with hydrogen and colloidal palladium. The reduced fats and oils are in general, colorless solids, which melt a t definite temperatures, ranging from about 45-7oo. The compounds from croton and castor oils fail to exhibit any physiological activity. As a rule these reduction products are without taste or odor, but that from butter has a pleasant nutty flavor and a faint odor of the mother substance is noticeable in the castor oil derivative. 1VOl.
2
1, 47
Be?., a,1541.
Oct., 1909
One of the most interesting points brought out in the course of the work is the lack of connection between the quantity of iodine and that of hydrogen with which a given fat or oil can combine. It has been generally supposed that the additive power of a fat for hydrogen, iodine, or iodine chloride was dependent on the double (ethylene) linkages which were present. This, however, is by no means the only factor to be considered and i t is necessary to recognize clearly that the addition of hydrogen and of iodine are quite independent reactions \+hich proceed on parallel, but by no means on identical lines. All the fats and oils mentioned above absorbed more hydrogen than the quantity calculated from their iodine numbers and the excess was quite considerable, amounting to over zjyo in the case of linseed oil, to more than joy0 in that of lard and, with the cottonseed oil, to almost 1007~. The reduced fats, although containing this excess” of hydrogen are, in some cases, still capable of combining with iodine. The product from sesame oil and also that from oleomargarin, for example, have iodine numbers of z and I z , respectively. This compound from sesame oil (iodine number 2 ) exhibits Baudouin’s test only very feebly, After remaining during eight months the fat gives the Baudouin color quite strongly, although its iodine number is not changed. I t is evident that the particular substance which is present in sesame oil, and on which the Baudouin test depends, is reduced by the hydrogen but is regenerated, to some extent a t least, on exposure to air. The reduced fat from cottonseed oil fails to show either the Becchi or the Halphen tests. I n general, these reduced fats are quite stable in air and exhibit no sign of rancidity. I n another paper,’ Paal and Hartmann show that a minute quantity of colloidal palladium solution is able to bring about the combination of ethylene and hydrogen. The liquid was shaken in a closed vessel, containing the two gases, a t the ordinary temperature. The union of the gases was quantitative. This result is of considerable interest in connection with the reactions involved in the reduction of fats and oils. The problem of the fats has been attacked in another manner by Quensell,* who has synthesized a number of the glyceryl esters of stearolic acid and also those of behenolic acid. From some of these esters he has prepared a number of halogen addition compounds. The first molecule of halogen is added by the acid radicle without difficulty, but combination with a second molecule takes place only slowly and in presence of light. I n these respects the glyceryl esters resemble the free acids. I n dealing with the diacylated glycerols, Quensell unfortunately fails to state which of the isomers, HOCH,CHOXCH,OX or XOCH,CH(OH)CH,OX (X = C,,H,,O or C,,H,,O), he employed in his experiments with halogens, so that the value of his results is lessened. J. BISHOPTINGLE. ‘I
MCMASTER V N I V E R S ITORONTO, ~. CANADA, Aug , 1909.
CORRECTED QUALITY FIGURES. I n the July number of THIS JOURNAL, the writer criticizes Turner’s rule for getting quality figures as being Ber , 42, 2239. 2
I b z d . , 48, 2440
.VOTES A V D CORRESPONDENCE. wrong in principle and giving, therefore, misleading results, and proposed a rule of his own which, however, upon further study, is seen to be also wrong (although to a lesser degree) when any factor happens t o be abnormally low, and he therefore begs to Substitute the following: Find \\hat per cent. the elastic limit of the steel under consideration is of the very best elastic limit that could be possible (always thereafter adhering to this best elastic limit as a standard, and so also of the other factors), what per cent. the shock or alternation figure is of the best, what per cent. the hardness is of the best. Add them together and divide by three. According to this rule the quality figures given in the above-mentioned paper come as follows: Standard, elastic limit, zoo Shock, 20. Hardness, 600. QUENCHEDVANADIUMNICKEL STEELS Ni6 Ni6
Vanadium Chrome S t e e l s . - ~ o . 15, 0.5568; No. 17, 0 . 5 2 0 3 ; XO. 2 3 , 0 . 6 0 8 3 ; NO. 24, 0 . j 3 3 3 ; NO. ~ 7 o , 6170. Nickel Chrdme Steels.-No. 9, 0 . 3 8 5 8 ; No. P I , o 3907;
No. 2 8 , 0.4810.
GEORGEAUCHY.
A MODIFIED KJELDAHL CONNECTING BULB. A modification of the Kjeldahl connecting bulb, which is not only useful b u t also tends toward greater accuracy in ammonia determination, is represented in the drawing. This was designed primarily for ammonia determinations in water but will, no doubt, find favor in other ammonia determinations as well. The drawing speaks for itself, so there is little need for a n explanation of the modified apparatus, Chemists making an ammonia determination in water with a Kjeldahl flask connected to a condenser by a Kjeldahl bulb pursue
Quality figure.
Composltlon C0.20 C O 20
73 7
V a 5 0....... Va70 .
. .
................
0 5570 0 4433
QUENCHEDCHROMIUM, ETC. NICKEL STEELS
c 0.20 c 0.20 c 0.20
Ni6 Ni5 Ni6
c0.20
Xi5
c 0.20 c 0.20 c 0.20 c 0.20 c 0.20 c 0.20 c 0.20 c 0.20
Ni6 Ni 6 Ni5 Xi6 Ni 6 Ni6 Ni6 Ni6
C r 0 . 5 0 ....................... C r l . O. . . . . . . . . . Cr 1 . 0 ........................ Cr 3 . 0 ........................ W2.0. ... .... W o 3 0 ........................ Wo 30 Mo 1 . 0 . . .............. Y o 0.50.. .............. Mo2.0 Si 0 . 5 0 . . . . . . . . . . . . . . . . Si 0 . 8 0
........................
.................
......................
0.5653 0.6583 0.5422 0.5055 0.6050 0.5900 0.5939 0.5072 0.6030 0.5317 0.5839 0.6133
QUENCHEDVANADIUMNICKEL STEELS. Va30.0 ................ \'a 1 . O . . .....................
c 0.20 c 0.20
Ni2 Xi 2
c 0.20
Ni2
Si 1 . 5
Ni2
SiO.50.
0.4603 0.5252 0.6131
Ni6 Ni 6
Va50.0.... \'a 7 0 . 0 . . . . . . . . . . .
0.3693 0.3609 0.3897
0.5600 0.4636
QUENCHEDSILICON NICKEL STEELS.
c 0.20 c 0.20 c 0.20 c 0.20 c 0.20
........................
I I!'
NORMALCHROMIUMNrc
c 0.20 c0.20 c 0.20
c 0.20
c 0.20 c 0.20
Ni5 Si6 Xi6
Cr 1 . 0 ..... Cr 1 . 0 Cr 2 . 0 . .......................
........................
0.5628 0.4639 0.5467
NORMALTUNGSTEN NICKEL STEELS. X i 6 W1.0.... 0 4517 X i 6 W 2 . 0 ........................ 0,4100 Ni6 W 6 . 0................. 0.4319 NORMALMOLYBDENUM NICKEL STEELS. YoO.50 . . . . . . . . . . . . . . . Mo 1 . 0 . . . . . . . . . . . . . . . . Mo 2 . 0 ....................... Mo 5 . 0 .
c 0.20 c 0.20 c 0.20 c 0.20
Ni6 Ni6 Ni6 Ni 6
c0.20 c 0.20 c 0.20 c 0.20 c 0.20
Ni6 Ni6
S i O . 5 0 ....................... 3i0.8
Ni 5
Si 2 . 0
0.5203 0.5064 0.4561 0.4311
XORMALSILICON NICKEL STEELS. 0.5094 0.3144 0.2822 0.2722 0.3511
A4r. Turner's T e s t s . S t a n d a r d , 200,000 elastic limit. alternations. Not comparable with preceding.
2000
a method which is capable of greater experimental error than i t should be. I n an effort to lessen this experimental error, the above modification mas made. m4th the old style of bulb i t was necessary, after freeing the apparatus of ammonia, to remove the rubber stopper containing the connecting bulb and pour i t through the neck of the flask, the sample of water to be analyzed. The stopper had to be removed again when introducing the alkaline permanganate for the determination of the albuminoid ammonia. This makes possible the introduction of ammonia into the apparatus which has previously been carefully freed of ammonia. With the modified connecting bulb, the opening in the bulb
