O N NITRO-SACCHAROSE.
147
allow of any determination of the conductivity, though this would be an interesting point to examine, in view of the high conducting power of tlie commercial metal, and the probability that the value would be notably raised by the removal of impuritiee. An imperfect attempt was made to measure the expansion by change of temperature, using for the purpose determinations of specific gravity in water at widely different temperatures, and correcting for expansion of water and glass, but the quantity of material wae too small to make the result trustworthy. It was also attempted to estimate roughly the fusibility, by placing equally heavy beads of the purr and the commercial aluminum in front of a fine blowpipe jet, this jet being fixed in position and fed with air by a steady water blast. From the difference of distance a t which the beads could be just fused it seemed probable that the pure metal was a litt]r> less fusible than that of commercial character Under the same conditions of heating the former seemed to oxidize on the surface with rather more ease than the latter. On the other hand, the pure metal seemed to present perceptibly greater resistance to the prolonged action of solvents-acidq and alkaliesthan the impure. VNIV. OF VIRGINIA, J d y 15, 1882.
C O N T R I B U T I O N S F R O M THE LABORATORIES O F THE SCHOOL O F MINES, COLVMBIA COLLEGE. XXX1.-ON
NITRO-SACCHAROSE.
By ARTHURH. ELLIOTT,P h . B., F, C. S. This curious body has already been investigated by Sobrero in 1847,* Schoenbein,f A d & W. Knopl and others; and no definite conclusions as to its constitution appear to have been brought out b y their labors. Having to make some experiments upon this body I thought it would not be uninteresting to give an account of some refiults which I obtaiiwd in the course of my work. These experiments include the action of a number of solvents, the action
*
Comptes Rendus Vol. 24, p. 247.
t Pogg. Ann. Vol. 70, p. 100. $ .Jour. fur prak. Chem, Vol. 56, p. 334.
148
O N NITRU-SACCHAROSE.
of ammonium sulphydrate, and also the action of a strong solution of ferrous chloride. I n the preparation of nitrosaccharose, pure crystals of cane sugar w used and reduced t o a powder fine enough t o pass through a sieve with 100 holes to the linear inch, after which it was dried in a water-bath. A number of methods mere used to nitrate the sugar, and a brief clc&1jtion of these niay p i o w useful. In the first case the following metliocl \\'ab iised. 5~ grms of sulphuric acid (81). gr. 1.84) nncl 23 grnis of nitric acid (&p.gr 1 5 3 ) were mixed together, and t h e rni\tiire cooled to 15" C -25 grmq. of the finelj powdered sugar were now slowly qtirrecl into the acid mixture, the temperature rose t o 3W' C.,the misturc Leiiig constantly 5tirred for 15 minutes The clot thus formed was thrown into cold water (about 1 litre) and the acid niixtiire was alsn arldetl. T h e nitrosaccharose thus formed u as collected together into one mass, and after washing and squeezing in plenty of colt1 watcxr it weighed 24.4 grms. T h e material thus obtained was a soft, silky looking, wax-like body, plastic,'and adhering t o the fingers y h e n removed from water. A t 30° C. it is soft enough t o flow like melted pitch It could not be washed free from acid When heated on :L water bath it melted ant1 began to decompose giving off red fumes A n attempt was made tu neutralize it with potassic carlionate, but the action was very energetic and most of the material dissolved in water. Another lot of nitrosaccharose was made using 25 grms. of sugar 400 grms. of sulphuric acid (sp. gr. 1.64) and 150 grms. of nitric acid (hp. gr. 1.53). following the same method of adding the sugar as mentioned before. T h e mixture had a temperature of 1 5 O C. before adding the sugar and ioze 100 C during the experiment. In this case tIie arid mixture containing the clot of nitrosaccharose was poured into cold water and the mixture of acids atid water became so hot that red fumes were elolved. T h e resulting mass after washing and squeezing weighed only 28 grms. The mass was melted on a water-bath under water, and \ $ M e in this condition potnssiuni carbonate was added and the whole well htirred I t was ~ to stand in water then \\ aslied froin excess of alkalies and a l l o ed several clays, changing the water daily After :L time it began t o give an acid reaction, showing decomposition. It I+ as \ra\hed with a little alcohol and allowed t o clrj . A third lot of nitrosaccharose was made, using the same acids and sugar i n the following proportions: sugar, 22 grnis., sulphurio
@#
SIT ItO-S ACCH ARO 4 E.
149
Acid, 17G grms., nitric acid, 66 grms. The SIlgiIr was added as usual, and the resulting mixture was poured into water in small portions, cooling the water after each addition; the nitrosxccharose thus obtained after washing and squeezing weighed 21 grnis. It waq washed with water and a weak solution of potassic carbonate. The rest of the treatment was exactly like that followed in the seccmd case. Yet another quantity of nitrosaccharose was made, using a large yrixiitity of sugar. Eight hundred grnis. of sulphuric acid (sp. gr. 1.S1,and 300 grnis. of nitric acid (sp. gr. 1.53), were used wit11 95 grin\ of sugar. When half the sugar had been added to the acid rniiture, the whole was cooled, the rest of the sugar added and the completed niixture allowed to stand one hour with frequent stirring. 'l'hcs acids were now poured off the nitrosaccharose, and the latter, when washed and kneaded tlioroughly with water, weighed 135 grriis. W'lie~ithe mass was first removed from the acid mixture i t had thc consistence of soft butter, but as the washing and squeezing progressed it became inore and more resinous and white. A further kneading i i i water hot enoiigh to bear the hand in it, using tn-rj lots of about oiie litre each, and finally in water containingone per cent of potassic carboiinte, reduced the well-squeezed mass to 101)grrns 'l'hi< last method appear': to give the best result in the matter of wa4iing, but the material slowly tlecomposer, the water in which i t is kept becomes acid and smells faintly of hydrocyanic acid. Nevertheless the nitroeaccharose made by either of the methods changes so slowly that I have kept it under water for over a year n-ithont any great change in appearance or bulk, beyond the acid reaction mentioned above. AIctio?zof A'olveibts oii N,trosacchcc?.ose.-The following solvents were used upon nitrosaccharose, both at ordinary temperature and also by heating in a water-bath: Water- Cold, soluble; hot, soluble. Absolute alcohol- CoM and hot, soluble. Alcohol, 93 per cent.-Same as absolute. Alcohol, 80 per cent.-- CoZd, slowly soluble; hot, soluble. Alcohol, 50 per cent.- Cold, insoluble; hot, soluble. Ether- Cold and hot, soluble. Chloroform- Cold and hot, soluble. Be~zole- C'old, insoluble; hot, slowly soluble. Carbon &sulphide- CoZd, insoluble; hot, insoluble.
Sulphuric acid (sp. 81'.1.g4)- C'oLtZ aiid /tot, soluble. Acetic acid (glacial)--C'ottZ aiid hot, Z I ~ I I I I I I V . Turpentine- Cold and h u t , i11sol~i1ilt~. Wood iiaplitha--CoZd arid kat, ~oIii1)lt~. ,; Ariiylic alcoliol- L'dcl, partly ~ ~ 1 ~ 1 1 k~ 1~ c l ~soluble. ('arbolic. aci(1- C'O/C(,],art Iy ~ o l u l ~ l /t /~o:f , soluble. h'itrolciizole--- old and / , o f , ~ o i i ~ l ) l c ~ . r, 1oluol- (,'old, iiiso1ul)le; l i o t , 1i:~i.ii y ~~1111ble. 1:'~ -- ('ulil a i i t l hot, insoluble. Petroleum naphtlia ( 7 i '.-;(;Asti3al oil-- R( ' d ( lant1 / t o / , i i ~ s ~ ~ l u l ~ l e , > I i n c d sperm-- C'ultl and hot, i ~ s o l i t b l ~ ~ . Olive oil- Clold, insolul~lc~; hot, > t i l i i l i ; c > . Sperm oil- (,'old, insolulile; h o t , bolulilc. Potassic hydrate ( 1 in 11) ;-C'old, iiisolublc; h D f , partly soluble. Ammonia hydrate- Cold, insoiriiile ; /tot, partly soluble. Nitric acid (conc.)-- Cold :mil h v t , solublc. Ilydrochloric acid (cone,)-- L'ol(!,pat~Iy soluble ; /~ut,slowlysoluble. Stannous ,.liloride, dec:onil)oses i t . Feriviis siilpliatc., ~l(:coinposesit. Ferroiis cliloritle, deconipow.; it Amnion ia s u 1p 11y tl r at e, I lccom 1' sc h i t . ISora, j 5 per cent. solution - I ' o i i / :inti h u t , iiisoliible, Acetic ether- Cold aiid hot, soliil)l(~. Acetone- (:old and hol, solublc. G 1ycwin e- Cold, ii I sol i i L 1e ; h ot , z I1Ii I b 1e. Kitroglycerine- Cold, slowly soluble; hot, re:idily soluble. IVliile trying the action of thebc sulvcnts the following facts were noticed. \Vhen h'eatcd with water it decomposes as it dissolves. On heating with turpentine a slightly yellow fluid is obtained. Carbolic acid is rcddencd, both cold and hot. Toluol, both cold and hot, gi\-es :I red color. IVith olive oil mutual decomposition takes place on lie-ating. Sperm oil acts like olive oil. Potassic hydrate gives a brown solution when heated. Ammonic hydrate, even in t h e cold gives a yellowish-brown color. Nitric acid, decomposes it on heating giving red fumes. Hydrochloric acid, botli cold and hot decomposes nitrosaccharose. Stannous chloride is decomposed giving a white precipitate, even in the cold. Ferrous sulphate, also chloride, decomposes nitrosacc?iarose, even in the cold, giving brown precipitates. Ammonic sulphydrate, both hot and cold, decompbses this body, giving a liver colored solution, with separation of sulphur. ( )
O N NITRO-SACCHAROSE.
151
Action of' Eerrous Chloride upon Nitrosaccharose.-Solution of ferrous chloride waR prepared 10 C.C.of which contained 1.4 grms of iron in the ferrous state. Nitrosaccharose was dissolved in 93 per cent. alcohol and the solution mixed with ferrous chloride solution mentioned above. After heating on a water-bath excess of potassic hydrate was added, the solution filtered and the precipitate washed. Two samples of this so!ution were taken ; oiie was used to estimate glucose direct with Fehling's solution ; the other was heated with acid to invert f he sugar, and then, after neutralizing, the glucose was determined as in the first case. They both gave 11.7 per cent. of glucose on the original amount of iritrosaccharose taken, showing that, as might have been expected, heating with ferrous chloride solution inverts all the sugar in nitrosaccharose. This action should be compared with the reducing action of ammonic sulphhydrate mentioned further on. It should be mentioned here that the ferrous chloride contained no free acid, since it was made by adding a large excess of iron to hydrochloric acid and heating till action ceased, a large quantity of iron remaining undissolved which was left in the solution to keep it saturated. T o determine the amount of oxidation produced by the nitrosaccharose upon the ferrous chloride, several experiments were niade. I n the first case the nitrosaccharose was treated with ferrous chloride and hydrochloric acid in an atmosphere of carbonic acid. The excess of ferrous chloride remaining after the action, was determined with standard solution of potassic dichromate. ,705 grm. of nitrosaccharose oxidized .553 grm. of iron, which is equal to 30 6 per cent. of NO, in nitrosaccharose. I n another experiment the nitrosaccharose was dissolved in ether and the ether solution was shaken u p with pure calcic carbonate. After filtering, the calcic carbonate was washed with ether and the filtrate and washings evaporated to dryness. The residue was washed with water and contained only a trace of calcic nitrate, hence nitrosaLcharose contained little free acid. The water-washed residue was now disholved in ether and treated with ferrous chloride solution and hydrochloric acid on a water bath, the excess of ferrous salt being determined with potassic dichromate as in .previous experiment. .572 grm. of nitrosaccharose oxidized .646 grm. of iron which is equal to 41.6 per cent. of NO, in nitrosaccharose. Another experiment in which the treatment with calcic carbonate was omitted and the ether solution treated a t once with ferrous chloride and hydrochloric acid, gave the following results : .563 grm. of nitrosaccharose oxi-
152
ON NITRO-SACCHAROSE.
S O T E S ON R O S E OIL.
153
percentage of NO, found by oxidizing ferrous chloride, we obtain the following results: The average of the first and second determinations of sugar by reducing with ammonic sulphhydrate (28.4 and 28.7) gives 28.55 per cent. of cane sugar in nitrosilccliarose. The average of two determinations of NO, in nitrosaccliarose (41.6 and 41.3)gives 41.45 per cent. of NO, in that body. Adding these together we have 70.00 per cent. as a total; the balance of the percentage consists of water, some free aeids, anti probably other compoiinds resulting from the action of the acids upoii the sugar. Calculating the deterniiiied constituents to per cent., we have cane wgar, 40.78, to NO, 59.21, or a ratio of 1 molecule of cane sugar to S molecules of NO, (exactly 1 t,, S 009) From these figures it wonld appear that nitrosaccliaroae is formed by replacing eight atonis of hydrogen in a niolecule of sugar by eight niolecules of Assuming that NO,, giving the formula C, H, il (N0,)S 0 , this is the correct formula for nitrosaccliarose, the theoretical percentage yield of its constituents ~voulclbe sugar 41.20, NO, 59.75. When wc (.ompare these figure3 with those actually obtained above, and remember that the nictliods used are not capable of great ex~ctiiessin results, it appears most probable that the above ip the true formula for nitrosaccharohe.
XXXI1.-NO'L'ES
ON EOSE OIL. AND F X R ~ I N A SANDS, XD A. B., Ph. B. During the Spring of 1SS1, Messrs. C . P. Sawyer and W.W. Share, two students of the class of 1Y81,of the School of Mines, at the suggestion of Prof. C. F. Chandler, undertook to investigate bone oil, and repeat some of the work of Anderson," C. G. Willianis,t Voh1,f Church, and Owen$, Schwanert, /I UnverdorbenT and €Lunge.**
BY ARTHUR13. ELLIOTT, Pli. B., F. C. S.,
*PhiZ. Mog.. (3) vol. xxxiii. p. 174; (4) vol. ii. 11. 457 ; (4) vol. ix pp. 145 and 214. Tvane. Roy. isoc &din,., vol. xvi. p. 4; vol. xx. (2) 1.' 247; vol. xxi. (1) p. 219 ; vol. xxi. (4) 1'. 571. tohem &c. Jour.,(Lon.), sol. vii. p. 9.; f'iae. &oy. &e.. vol. xiii. p. 305; VOI. xii. p. 311. SJaAresb., 1859, p. 742. SJuhreab., 1850, 0. 369. Phil. Mag., (4) vol xx. 11. 110. !Ani. '0. Phawn.. . vol. cxs. 11. ?;!I. .TPagg.Ann., vol. xi. 111). 59. OS; vol. viii. 111). 25C, 480. *"r./gs. Ann., vol. xxxi. pp. 63. 67. Chwi. G'ctz., 1855. p. SOY.
