T H E JOL7RLI7ilLOF I - Y D L - S T R I A L AiYD EAYGILYEERIA'\-GC H E M I S T R Y . the failure to find milk sugar also indicated t h a t no milk or cream had been used in their production. The analysis of the fat indicated t h a t i t was soy bean oil, and a s soy beans contain a large percentage of protein, it mas a t once suspected t h a t this was one of the numerous products made from them. It is a well known fact t h a t in China and Japan soy beans have been used for hundreds of years, not only t o produce a n edible oil, but in the production of many other food products. TKO hundred grams of soy bean meal, ground from the \+-hole bean in the laboratory, were thoroughly mixed in 1000 cc. of cold mater. After standing twelve hours fermentation set in and continued for three days. No effort was made to ascertain the nature of this fermentation. At the end of this time the mash, upon which a mold had started t o grow, was strained through cheese cloth; a heavy, milky liquid was obtained. Kumerous methods were tried t o coagulate the suspended and dissolved protein, such a s the addition of acids, rennet, and heat. Heating upon the steam bath seemed to give the most satisfactory results as the dissolved material coagulated and settled out upon standing. The coagulated mass was filtered, giving a product
I
t h a t was identical in appearance, taste and odor with the two samples examined. The dried product was analyzed showing the similarity beyond any doubt. Laboratory S o . 44288
... . ... . . . . . .
Proteins. Per cent.
Fat. Per cent.
.Per4sh. cent.
59.46
11.86
5.19
B y L. M. DESNIS.
Received October 14, 1912.
I n the analysis of commercial grades of sodium carbonate there early arose a demand for a rapid and convenient method for the determination of carbon dioxide, which was met in 1868 b y the apparatus designed b y Schlosing and Rolland.1 I n 1874 Orsat patented a device* t h a t was based directly upon the principle of the apparatus of Schlosing and Rolland, and t h a t attracted considerable attention a t the time and rapidly came into general use. Because of its compactness and ease of manipulation, the Orsat apparatus has been and still is very generally employed by gas analysts. I n its original form, however, and even in some of the later mod.ifications, it possesses certain inherent faults, and the unsatisfactory character of the analytical results t h a t are obtainable with the various forms is evidenced by the large number of changes in its construction that are constantly being brought forward in chemical journals. The chief objection t o the apparatus is the incompleteness of the absorption of such gases as oxygen and carbon monoxide. The researches of Gautier and Clausmann, Bendemann, Hankus, Hempel, Nowicki, Hahn, Dennis and Edgar, and others, have demonstrated t h a t the complete removal of oxygen by alkaline pyrogallol and of carbon monoxide by cuprous chloride can be effected only when the absorbent and the gas are 1 2
Aniiales de chimie et de bhysique, 4 serie, 14, 55 (1868). Chem. N e w s , 29, 176 (1874).
Sugar. Sone
The investigation proved t h a t the product submitted for examination could not be classed as filled cheese, although a very good substitute. Cheese prepared from soy beans must be consumed within a few days as i t deteriorates very rapidly. While making this investigation I confirmed the work of J. Ruhiah,l who found sucrose present in soy beans. The beans t h a t I used contained 4 . 4 per cent. sucrose.
As thousands of tons of soy beans are used annually in making oil, i t does not seem improbable t h a t a method could be found which would make the recovery of the sucrose possible without reducing the yield or injuring the quality of the meal for feeding purposes. I t would be a source of profit from a n industrial product that is now entirely wasted. LABORATORY BUREAUO F INTERNAL REVENUE, WASHINGTON, D. C.
LABORATORY AND PLANT A N E W FORM OF ORSAT APPARATUS.
Dec., 1 9 1 2
I
shaken together, or when the gas is, in some manner, brought into prolonged and intimate contact with the absorbent. With most of the suggested forms of the Orsat absorption pipette, the removal of oxygen and carbon monoxide is quite incomplete unless the gas is allowed to stand in contact with the absorbent for a very considerable length of time, or is passed back and forth many times between the burette and pipette. Failure t o recognize this inadequacy of the apparatus frequently results in the incomplete removal of oxygen, and, as a consequence, a decrease in volume is observed when the gas mixture is next passedinto the cuprous chloride pipette. I n very many cases the analyst has, in this manner, been led into reporting carbon monoxide in a gas mixture, such as flue gas, when in fact no carbon monoxide is present, the decrease in volume being due solely t o the absorption, by cuprous chloride, of oxygen t h a t still remains in the gas mixture. I n recent years several interesting and some valuable suggestions for increasing the completeness and rapidity of absorption in the Orsat apparatus have appeared in chemical journals. Bendemann proposesa that two pipettes be used for the absorption of oxygen by alkaline pyrogallol and two for the removal of carbon monoxide by cuprous chloride. This would undoubtedly lessen the errors of the determinations but would hardly remove them entirely. More worthy of consideration are the proposed modifications of the form of the absorption pipette to bring 1 2
See Chemical Abstracts. 4, 1789, 1912, J . f . Gasbeleuchiung, 49, 8 5 3 (1906).
Dec., 1912
T H E JOL-R.\7A4L OF I.YDCSTRI.4L A S D ESGI-\-EERI.\-G
gas and liquid into intimate contact. Mos of these are based upon the construction described in 1899 by E. Hankus1 and shown in Fig. I . The gas enters the
CHEJIISTRI'.
899
t h a t , upon experiment, 15-as found to be obtainable with the Friedrichs Gas Washing Bottle,I led the writer to employ the same principle in the construction of an absorption pipette for the Orsat apparatus, the form of pipette that was finally adopted being that shown in Fig. 1. The gas mixture enters the pipette
B 11
JI L
lf
w FIG.1.
B
if
w FIG.2 .
FIG. 3
pipette through il,passes downward through the capillary and, by impinging on the plate B . is broken up into minute bubbles which then pass upward through the absorbing liquid. The gas is brought back into the burette by turning the stopcock through an angle of 180' and lowering the level bottle of the burette. I n 1911 the Chemists' Committee of the United States Steel Corporation describedl and copyrighted drawings of a n absorption pipette (Fig. 2) t h a t is quite similar t o the form proposed twelve years earlier by Hankus, but is slightly less efficient than the Hankus pipette (see results below) since it permits the gas to escape freely in large bubbles from the lower end of the capillary tube. The pipette devised b y Nowicki3 and iin;roved by Heinz4 (Fig. 3) yields more complete absorption than t h a t of Hankus. The gas passes downward through the straight capillary tube .4 and then rises in small bubbles through the spiral tube S, which insures long and thorough contact between the gas and absorbent. A short tube, D , is attached to the lower end of the spiral, and fresh absorbing liquid is drawn upward through this opening when the gas bubbles rise through the spiral. Experience has shown, however, t h a t when this form of abwrption pipette is used for the determination of oxygen with alkaline pyrogallol, the gas is frequently trapped in the spiral. Moreover, the pipette is so fragile that i t is often broken in transportation, which renders i t unsuitable for use in a portable apparatus. The very rapid and complete absorption of gases
' Oestevu. Chem. Z f g . , 47, 8 1 (1899); J . GasbeleuchtzL?ig,49, 367 (1906). .Wef. and Chem. Errg., 9, 303 (1911). Oesteru. Z e i f . f . B e v g . - H i i f f . ,S3, 337 (190.5). J . f. Gasbeleuchfung, 49, 367 (1906).
FIG.4.
through the capillary .4 (the stopcock being in position I ) , and, passing downward through the capillary, escapes a t B . I t then rises. and in so doing follows the spiral S. The rising gas carries some of the absorbing liquid with it, and this liquid then flows down on the inside of the cylinder C and mixes with the main body of the absorbent again a t D . After the gas has risen through the spiral and has collected in the space F ,the stopcock is turned through 180' to position I1 and the gas is then drawn back into the burette. An experimental comparison of the different forms of Orsat pipette here illustrated has been made by h4r. F. H. Rhodes. I n the first series of comparative determinations, oxygen in atmospheric air was absorbed by means of a n alkaline solution of pyrogallol. The absorbent was prepared by dissolving one part by weight of pyrogallol in three parts by weight of water and adding one volume of this solution to four volumes of a solution of potassium hydroxide prepared by dissolving one and one-half parts by weight of potassium hydroxide in one part by weight of water. One hundred cc. of air were measured off in a Hempel burette, and this x.as then connected with the pipette under examination, and the gas sam2. aital. Cham., 50, 175 (1911 I .
900
T H E J O U R N A L OF I N D U S T R I A L A N D EIVGIi\TEERIXG
ple was passed back and forth between the absorption pipette and the burette until all of the oxygen in the sample had been absorbed. The air was passed into the several pipettes a t a uniform speed. The absorption pipettes t h a t were tested were: ( a ) The usual form of Orsat pipette, which is filled with glass tubes t o increase the absorbing surface ; ( b ) The Hankus pipette (Fig. I ) ; (6) The absorption pipette recommended by the Chemists' Committee of the United States Steel Corporation (Fig. 2 ) ; ( d ) The Nowicki-Heinz spiral absorption pipette (Fig. 3) ; and ( e ) The new form of pipette here described (Fig. 4). The sample of air was passed over into each absorption pipette in one minute. I t was then immediately drawn back into the burette and again passed into the absorption pipette a t the same speed as before. This was continued until all of the oxygen was absorbed. The results given in the tables are the averages of numerous determinations.
CHEMISTRY.
Dec., 1912
back, and then passed in a second time in one minute. I n the absorption of carbon monoxide the same time intervals were found t o give complete absorption of the gas unless the amount of carbon monoxide exceeded 2 5 per cent. I n such case i t was found necessary to pass the gas mixture three times into the pipette, the first time in two minutes, and the second and third times in one minute each. The results were as follows : TABLE111. I. Oxygen. . . . . . . . . . .
11.
111.
16.2 16.3 22.9 22.8
13.2 13.2 37.3 37.4
It thus appears that with this form of absorption pipette both oxygen and carbon monoxide can be removed as completely and as rapidly as is possible with the Hempel absorption pipette in which the gas and absorbent are shaken together.
A further error in analyses made with the usual forms of the Orsat apparatus results from the incorrect position of the measuring burette.' After the (b) (c) U. S. ( d ) Nonricki(e) ( a ) Orsat removal of the absorbable constituents of the gas Hankus steel Heinz Pipette Time usual pipette. committee. pipette. new form. form. (minutes). mixture, the capillary tube t h a t connects the burette 1 8.0 11.2 9.0 20.6 18.6 with the pipettes remains filled with the combustible 2 13.3 16.5 14.2 20.8 20.4 residue; consequently, when a portion of this residue 16.7 19.1 17.2 20.9 20.9 3 is measured off in the burette and is passed to the com20.1 18.8 4 18.7 20.5 19.8 19.5 5 bustion apparatus through the capillary tube above 20.7 20.2 20.2 6 the pipettes, it will carry with it the combustible gas 20.8 20.6 7 20.4 20.9 20.9 20.8 8 remaining in that capillary. This difficulty may be 20.9 9 avoided by filling the connecting capillary with the confining liquid (water) in the manner suggested I n the analyses here tabulated, the sample of air by Pfeifer,* or more simply by placing the burette was first passed into each pipette in two minutes,. between the absorption pipettes and the combustion that is, a t half the earlier speed. I t was then immeapparatus in the manner recommended by Hahn.3 diately drawn back into the burette and passed a Since the Orsat apparatus is chiefly employed for second time into the pipette in one minute. the determination b y absorption in liquid reagents of TABLE11. carbon dioxide, oxygen, and carbon monoxide, i t is, in the opinion of the writer, preferable to limit the ap( a ) Orsat (b) ( c ) U. S. ( d ) Xowicki(e) steel Heinz Pipette usual Hankus Time paratus to the determination of these three gases form. pipette. committee. pipette. new form. (minutes). and to construct i t in such manner as to render it 15.6 12.3 20.7 20.6 2 10.3 easily possible to connect the burette when so de1 minute more 17 . 2 18.3 17.2 20.9 20.9 sired with suitable special apparatus for the deterThe above results render it evident t h a t the com- mination of hydrogen and hydrocarbons. The applete absorption of oxygen from air can be effected paratus is thus rendered smaller, more easily portable, with the first three forms of pipette only by repeated and less fragile, and the combustion results, with passage of the gas sample into the pipette and back proper apparatus, will usually be much more accurate into the burette. The Nowicki-Heinz pipette and than with the imperfect devices contained in the many the spiral pipette here proposed seem to be of nearly forms of the Orsat apparatus now upon the market. equal efficiency, but the former is open t o the objecA further drawback in the usual forms of Orsat tions already noted. apparatus is to be found in the rubber bulbs that are To ascertain the efficiency of the new spiral pipette attached to the level cylinders of the pipettes to proin the absorption of carbon monoxide, mixtures of tect the various reagents from the air. These bulbs this gas 'with known amounts of air were prepared; rapidly deteriorate, and after short use fail to accomoxygen was determined in one spiral pipette by ab- plish the purpose for which they are intended. sorption with a n alkaline solution of pyrogallol and I n the hope of remedying some, if not all, of the decarbon monoxide in a second spiral pipette by abTABLEI.
sorption with an ammoniacal solution of cuprous chloride. I n the absorption of oxygen the gas mixture was passed into the pipette in two minutes, mas drawn
1
See Hahn, Zezf. d . Verezns deuischer Ingenieure, 1906; J . f Gasbeleuch-
f u m g , 49, 367 (1906). 2 J f . Gasbeleuchtung, 51, 523 (1908). 3 L O G . CZt
.b
Dec.,
1g12
T H E JOL+Rl-AL OF I-VDliSTRI.4L AaYD Ez17GISEERIL\'G C H E X I S T R Y .
fects of the Orsat apparatus t h a t have been enumerated above, the writer has designed the modification shown in Fig. 5 . 1
r' FIG.
5.
The burette B has a capacity of somewhat more than 100 cc. and is graduated from a point near the bottom upward to the stopcock J . The stopcock is a three-way stopcock, the position of which is shown by means of a black glass 4 fused to its outer surface. The capillary tube connecting J with the pipettes and with the stopcock K has an external diameter of j mm. and an internal diameter of I mm. I n fusing on the branch capillaries that extend downward t o the three pipettes, the internal diameter of the capillary should, a t no point, be much greater than I mm. if the apparatus is properly made. The three absorption pipettes, E , F and G, are of the form already described, and are filled, respectively, with solutions of potassium hydroxide, alkaline pyrogallol, and ammoniacal cuprous chloride. They are connected with the capillary tube from the burette by means of pieces of soft, black rubber tubing of I , j mm. thickness of wall. and these rubber tubes are held in place by xire hooks that pass through the blocks behind the joints, and have threaded ends upon which small set screws are placed. This method of attachment renders it easily possible to remove all the glass parts from the frame. Into the open ends of the three level tubes of the pipettes are inserted T h e appnriltus is manufactured b y Greiner and Friedrichs, Stutzerbach i n Thiirinpen, Germany.
901
one-hole rubber stoppers, and through the openings of these stoppers pass the branch tubes from the tube 55,that is 7 mm. external diameter and I mm. thickness of wall. This tube passes downward and is joined by a piece of rubber tubing to the upper side of the stopcock attached to the cylindrical vessel T , which in turn is connected with V by the glass tube shown by the dotted line. After the pipettes have been filled with the several reagents, the stoppers connecting the level tubes with the tube SS are inserted in place and the protecting reservoir I'T is. half filled with water. As the gas is driven over from the burette into the pipette and is drawn back into the burette, the water in V T rises and falls, but protects the reagents a t all times from contact with the air. The level bottle L is held in place by a clamp when the apparatus is in transport. After the absorbable gases have been removed from the gas mixture, the combustible residue may be burned, if so desired, by connecting the capillary M , which has a n external diameter of 6 mm. and a bore of I m m . , with a combustion pipette or other suitable device. The case containing the apparatus is 5 7 cm. high, 27 cm. wide and 16 cm. deep. The panels forming the front and back of the case are removed when the apparatus is in use. As illustrative of the speed, accuracy, and uniformity of the results yielded by this apparatus, the following analyses of a mixture of carbon dioxide, oxygen, and carbon monoxide may be cited. A single passage of the gas mixture in one minute into the first absorption pipette serves to completely remove the carbon dioxide. In the determination of oxygen and carbon monoxide each gas ivas twice passed into the absorption pipette, the first time in tn-o minutes, the second time in one minute. TABLEI V . Carbon dioxide, per cent. .. . . . . Oxygen, per cent . . . . . . . . . . , . . . Carbon monoxide, per c e n t . . . . .
I.
11.
111.
IV.
3.1
3.2
3.1
6 0
3.1 6.0
22.5
22.6
5.9 22.6
5.9 22.7
CORKELLUSIVERSITY, ITHACA, N. Y.
THE STORMER VISCOSIMETER AND THE VALUE O F VISCOSITY DETERMINATIONS BY ITS USE. By GILBERTRIGGA K D J. L. CIRPEUTER.
Received Oct. 9, 1912.
The Stormer viscosimeter is the instrument proposed for use in bringing paints to a common viscosity, and for the comparison of the viscosities of difierent paints. I t may be briefly described as follows: A weight attached to a string falls vertically from the instrument. The string pays out over a vertical pulley as the weight falls, and unTvinds from about the shaft of a large toothed wheel, this m-heel lying in a horizontal plane. The large wheel fits into a small Tear on the shaft of the viscosimeter cylinder. When Lnelarge wheel is caused to revolve by the falling weight, this shaft is turned, and the cylinder attached to its lower end is revolved in whatever liauid .
A
